JPS5948014B2 - Manufacturing method of modified polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyethylene terephthalate, and its purpose is to produce a polyester having good dye affinity, flame retardancy, and pilling resistance.

0-Generally, polyethylene terephthalate has high crystallinity;
Although it has excellent mechanical properties, it has the disadvantages of low affinity for dyes, low pilling resistance, and easy flammability.

As one method for improving these drawbacks, a method of adding phosphoric esters is known. In the conventional method of adding a phosphoric acid ester, the phosphoric acid ester often distills out of the reaction system during polyester production, particularly during the polycondensation reaction, which is undesirable as it causes process fluctuations. For this purpose, methods have been proposed in which a part of the phosphoric ester is made into a metal salt, or a phosphoric ester derivative is made into a polymer through a polycondensation reaction. It could not be said that the color tone and spinnability were sufficiently good. The present inventor has arrived at the present invention as a result of studies aimed at improving the above-mentioned drawbacks when using phosphoric acid esters. That is,
The present invention uses terephthalic acid or dimethyl terephthalate (dimethyl terephthalate) and ethylene glycol as main raw materials to produce polyethylene terephthalate through an esterification reaction or transesterification reaction, followed by a polycondensation reaction. The esterification rate of the esterification reaction product is 90% or more, preferably 95% or more, and the intrinsic viscosity measured at 30°C when the product is dissolved in an equal weight mixture of phenol and tetrachloroethane is 0.06. ~0.30
db1 is preferably 0.08 to 0.25 d1/g, when dimethyl terephthalate is used, the transesterification reaction rate of the transesterification product is 95% or more, preferably 98% or more, and the product is At the stage where the intrinsic viscosity measured by the same method as above is 0.06 to 0.30 dV', preferably 0.08 to 0.25 d1/9, the general formula 0=P-0R2 (to Rl, R2, \).

R3 is an organic residue having either one OH group or COOH group, and even if Rl, R2, and R3 are the same,
Or they may be different.

) and the general formula 0=PG91 (R.
, R, is an organic residue having either one OH group or COOH group, and R4 and R5 may be the same or different. M1 is either a lithium atom, a potassium atom or a sodium atom. ) de/--14
Compound B shown and the general formula 0=P-0M3(R6\halo ** is an organic residue having either one 0H group or COOH group, M2 and M3 are a lithium atom, a ryorium atom, or Any sodium atom, and M2 and M3 may be the same or different.

) to the terephthalic acid component.
Compound 0.1-2.0 mol%, preferably 0.3-1
．． 0 mol%, B compound 0.1 mol% or more, C compound A
It is 1/3 to 3 times the equivalent of the compound, and at the same time, the A compound,
Compound B and compound C are added so that the total amount is 0.3 to 10 mol%, preferably 0.5 to 5 mol%, and the polycondensation reaction is carried out in the presence of an antimony-based catalyst and/or a germanium-based catalyst. This is a method for producing modified polyester characterized by the following. The three types of phosphoric acid esters used in the present invention are known compounds, and are also used to modify polyester. However, the feature of the present invention is that these three types of phosphoric acid esters are prepared under specific conditions. The purpose of this invention is to stably produce a modified polyester with good color tone and excellent dye affinity, flame retardancy, and pilling resistance, which were completely unexpected by conventional methods, by simultaneously using them in specific proportions.

R, , R2, R3, R4, R, and R6 in the general formula representing compound A, compound B, and compound C in the present invention are:
It is an organic residue having either one 0H group or COOH group. Specifically, the reaction causes an increase in diethylene glycol production and coloring, and if the reaction is carried out at a stage where the intrinsic viscosity is 0.06 d or less, it is a phosphorus compound. If it is added at a stage when the residual rate of is low and the intrinsic viscosity is greater than 0.30 d1/l,
This may lead to the formation of insoluble foreign substances and fluctuations in the process, leading to a decrease in spinnability.

In addition, when using dimethyl terephthalate and ethylene glycol as the main raw materials, adding compounds A, B, and C at a stage where the transesterification reaction rate is lower than 95% may lead to a decrease in the polycondensation reaction rate, or If it is added at a stage where the intrinsic viscosity is lower than 0.06 dVT, the residual rate of the phosphorus compound will be low, but if it is added at a stage where the intrinsic viscosity is higher than 0.30 dθ1, as mentioned above, the formation of unparalleled foreign substances and the spinability due to process fluctuations will occur. This will lead to a decrease in These A, B and C compounds may be added separately or simultaneously, but preferably they are added simultaneously. The total amount of A, B and C compounds added is 0 relative to the terephthalic acid component.
．． If it is less than 3 mol%, the effect of improving dye affinity, flame retardancy and pilling resistance is too small, and if it is less than 10 mol%
If the amount is more than that, it is not preferable because the color tone of the obtained product may deteriorate, process fluctuations may occur, and spinnability may deteriorate. At the same time, A, B and C compounds are, as mentioned above, A compound 0.1~
It is necessary to use the compound B in an amount of 2 mol % or more, the amount of the compound B in an amount of 0.1 mol % or more, and the compound C in an equivalent amount of 1/3 to 3 times that of the compound A. When using only one or two of these three types of compounds, there may be variations in the process, deterioration of color tone, and decrease in spinnability. Moreover, Ml in the general formula,
M2 and M3 must be selected from among alkali metals such as lithium, sodium, and potassium; metal atoms other than these are not preferred because they tend to form insoluble foreign substances. The polycondensation catalyst used in the present invention must be selected from antimony-based catalysts and/or germanium-based catalysts, and specifically, antimony trioxide, antimony acetate, antimony glycolate, antimony metal, germanium dioxide, Examples include germanium tetrachloride, germanium tetraethoxide, germanium tetrabutoxide, and germanium hydrogen phosphite. The polyester in the present invention is one in which most of the repeating structural units are composed of ethylene terephthalate, such as isophthalic acid, phthalic acid, adipic acid, sebacic acid, P-oxybenzoic acid, propylene glycol, tetramethylene glycol, neopentyl Copolymerized components such as glycol, 1,4-cyclohexanedimethanol, polyethylene glycol, trimethylolpropane, pentaerythritol, trimesic acid, sodium 3,5-dicarboxybenzenesulfonate, methoxypolyethylene glycol, and functional derivatives thereof; , a matting agent such as titanium dioxide, an antioxidant, an ultraviolet absorber, a pigment such as a fluorescent whitening agent, and the like.

There are two methods for producing polyester: a batch method and a continuous method, and the present invention is applicable to either method.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these examples.

In the examples, "I-part" indicating the amount added means all parts by weight. The R value is a value that represents the color tone of polyester, and is calculated from the formula: R (%) - 4R45 from the reflectance R45O and R55O at wavelengths of 450 mμ and 550 mμ measured with a tungsten light source using a Hitachi self-recording spectrophotometer EPR-2.
The value was determined using 0-3R350, and the larger the value, the better the whiteness. The K value is a value indicating the dye affinity of polyester, and Eastman
2% by weight of POlyester RedB was used for the fiber, and 2% by weight of Score Roll 400 was used as a dispersant for the dye liquor.
9/l at a bath ratio of 1:50 and a temperature of 98°C.
The dye exhaustion rate when dyed for 20 minutes is expressed as a weight percentage. Pilling resistance is determined by using IC for polyester knitted fabrics.
The grade is determined by a standard photograph after 5 hours of operation in accordance with the provisions of JISL-1076 using an I-pilling tester, and the higher the value, the better the pilling resistance is. [η] is a value representing the intrinsic viscosity (dl/9) measured at 30° C. by dissolving polyester in a mixture of equal weights of phenol and tetrachloroethane.

The flame retardant property is expressed by the LO value determined by the oxygen index method of JIS-7201-1972, and the larger the value, the better the flame retardant property. Spinnability is expressed as a grade determined based on the frequency of yarn breakage during spinning under the conditions described in each example. First grade spinnability is 0 to 2 yarn breakages during spinning, and second grade is 3 to 2 times. 5 times, 3rd grade is determined to be 6 to 10 times, and 4th grade is determined to be unspinning after 11 times or more. Examples 1 to 6 and Comparative Examples 1 to 12 100 parts of dimethyl terephthalate, 8 parts of ethylene glycol
0 parts and 0.03 parts of zinc acetate were put into the reactor, and the reaction temperature was 1.
The methanol produced by heating to 60 to 220°C was distilled off.

When the transesterification reaction rate and [η] reach a predetermined value,
0=PN-0CH2CH20H as the A compound, 0=P(0(CH2CH2O)3H as the B compound, /υI, 40=P-0Na as the C compound, respectively, in predetermined amounts of \-.--1,.-1) At the same time, 0.04 part of antimony trioxide and 0.06 part of titanium dioxide were added.

Next, the temperature was raised while distilling off excess ethylene glycol, and when it reached 240°C, the pressure was gradually reduced, and finally the temperature reached 280°C and 1 nHy or less, and [η] was 0.
．． The polycondensation reaction was carried out until it reached 58±0.02. The polyester thus obtained was extruded and spun from a spinneret installed at the bottom of the reactor, followed by roller stretching at 75°C, and then constant length heat treatment at 130°C, resulting in 75 denier/36 fibers. A polyester filament was obtained. When a knitted fabric was made using this and its dyeability, flame resistance and pilling properties were measured, the results shown in Table 1 were obtained. Examples 7-8, Comparative Examples 13-14 100 parts of dimethyl terephthalate, 80 parts of ethylene glycol, 0.0 parts of zinc acetate.
03 parts were placed in a reactor and heated to a reaction temperature of 160 to 220°C, and the generated methanol was distilled off.

When the transesterification reaction rate and [η] reach a predetermined value,
As compound A, 0=P-0-(as compound 1B\V
TlrT-T- n )3H' 0=P-0(CHCH2O)3H,C as a compound, /
"゛゛0=V-0K--1" were added in predetermined amounts, and then 0.02 part of germanium dioxide was added, followed by continued heating to distill off excess ethylene glycol.

Next, the pressure was gradually reduced, and finally the temperature was 280°C.
Achieving Hy or less [η] is 0.58 + 0.02d1
A polycondensation reaction is carried out until the polyester becomes 1/9, and the resulting polyester is extruded from a spinneret installed at the bottom of the reactor and spun, followed by roller stretching at 75°C, and then further stretched at 130°C.
A constant length heat treatment was carried out at .degree. C. to obtain 75 denier/36 polyester filaments. A knitted fabric was prepared using this, and its dyeability, flame resistance, and pilling properties were measured, and the results shown in Table 1 were obtained. Example 9 and Comparative Examples 15-19 100 parts of terephthalic acid, 60 parts of ethylene glycol, 0.2 parts of titanium dioxide, and 0.03 parts of antimony trioxide were placed in a reactor, and the pressure was 2-3 kg/Cd gauge pressure, 230-25
The esterification reaction was carried out at 0°C, and the produced water was distilled off.

When the esterification rate and [η] reach a predetermined value, as compound A/0=P-0(CH2CH2O)3H, as compound B\/0=P-0(CH2CH2O)3H, as compound C\
/O=P-0K were added in predetermined amounts, respectively, and then heating was continued to distill off excess ethylene glycol.

Next, the temperature was gradually increased to 280°C, and the pressure was reduced.
Achieving 1nH9 or less, [η] is 0.58±0.0
The polycondensation reaction was carried out until it reached 2d1/9. The polyester thus obtained was extruded from a spinneret installed at the bottom of the reactor and spun, followed by roller stretching at 75°C, and then constant length heat treatment at 130°C, resulting in 75 denier/36 polyester fibers. Got filament. A knitted fabric was made using this, and its dyeability, flame retardancy, and pilling properties were measured and are shown in Table 2. Example 10 Terephthalic acid 1
00 parts of ethylene glycol, 60 parts of ethylene glycol, and 0.03 parts of ammonium trioxide are placed in a reactor, and the esterification reaction is carried out at 2-3 kg/Clll gauge pressure and 230-250°C, and the water produced is distilled. I left.

When the esterification rate is 96% and [η] 0.12, O = sieve 1'1)-COOH as the A compound, O-Pg0CH2CH20H as the /B compound, and O as the C compound /0L'1. -P-0Li \ 1▼ each? ≦▼? A4'0 Added in amounts of 0.6 mol%, 1.2 mol%, and 0.2 mol% based on the total terephthalic acid component, and further added 0.5 part of methoxypolyethylene glycol with a molecular weight of 2000. After that, heating was continued to distill off excess ethylene glycol, and then the pressure was gradually reduced to a final temperature of 280°C.
1m7! Reach LH9 [η] is 0.55 + 0.02
The polycondensation reaction was carried out until dIV9.

Claims (1)

[Claims] 1. When producing polyethylene terephthalate by esterification reaction or transesterification reaction and subsequent polycondensation reaction using terephthalic acid or dimethyl terephthalate and ethylene glycol as main raw materials, if terephthalic acid is used, ester The esterification rate of the reaction product is 90%.
Above, the product is dissolved in an equal weight mixture of phenol and tetrachloroethane and the intrinsic viscosity measured at 30°C is 0.06 to 0.30 dl/g. The transesterification reaction rate of the exchange reaction product is 95% or more, and the intrinsic viscosity of the compound measured by the same method as above is 0.06 to 0.30 d.
At the l/g level, there are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼(R_1, R_2, R_3 are OH groups or CO
An organic residue having one OH group, which may be the same or different. ) and the general formula ▲ mathematical formula, chemical formula, table, etc. M_1 is a lithium atom,
Either a potassium atom or a sodium atom. )
There are compound B represented by the general formula ▲ mathematical formula, chemical formula, table, etc. Atom or sodium atom, which may be the same or different.
The compound is 0.1 to 2.0 mol%, the B compound is 0.1 mol% or more, the C compound is 1/3 to 3 times equivalent of the A compound, and the A
The total amount of the compound, B compound and C compound is 0.3 to 10
A method for producing a modified polyester, characterized in that the polycondensation reaction is carried out in the presence of an antimony-based catalyst and/or a germanium-based catalyst.