KR20190061563A - Sheath-core type Polyester Composite Fibers Using materials from biomass and Method Preparing Same - Google Patents

Abstract

The present invention relates to a sheath-core type polyester composite fiber. According to the sheath-core type polyester composite fiber using a biomass-derived raw material, a core part is formed of polybutylene terephthalate (PBT) formed by polymerizing a biomass-derived terephthalic acid including CHDCA and a biomass-derived butylene glycol. A sheath part is formed of polytrimethylene terephthalate (PTT) formed by polymerizing biomass-derived terephthalic acid including CHDCA and biomass-derived 1,3-propanediol, or polyethylene terephthalate (PET) formed by polymerizing biomass-derived terephthalic acid including CHDCA and biomass-derived ethylene glycol.

Description

TECHNICAL FIELD [0001] The present invention relates to a sheath-core type polyester conjugate fiber using a biomass-derived raw material,

The present invention relates to a method for producing a cis-core type polyester conjugate fiber using a raw material derived from a biomass, and more particularly, to a method for producing a cis-core type polyester conjugate fiber using a raw material derived from a biomass, which comprises polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) Core type polyester conjugate fiber using a biomass-derived raw material formed of polyethylene terephthalate (PET) and a method for producing the same.

The search for and application of environmentally friendly materials has been progressing steadily as global warming accelerates. Polymers produced from fossil fuels, such as petroleum, are limited in their reserves, and the emission of carbon dioxide is high, so it is urgent to replace them with environmentally friendly materials. However, existing eco-friendly materials have been disadvantageous in that there are many parts that need improvement in order to commercialize them due to hydrolysis, radioactive defect, and hard touch, which are unique characteristics of the material, as products are mainly focused on biodegradability.

Recently, textile products using environmentally friendly materials using biomass have been actively developed and are being launched as products. Biomass is a generic term for organisms that exist in nature, but it can refer to organic materials that can replace petrochemical-derived materials by energy-specific or material cycle cycles.

Petroleum, which occupies a large portion of the present energy source, is expected to be depleted in the near future. Research on biomass utilization has become active in many countries around the world since the second oil crisis began in late 1978 .

Due to these social phenomena, the environment in the textile industry is less burdensome, and a variety of fibers and textile materials are attracting attention using biomass.

For example, polytrimethylene terephthalate (PTT), which is a polyester compound, can be produced by esterification and condensation polymerization of terephthalic acid (TPA) or an ester-forming derivative thereof and 1,3-propanediol, and terephthalic acid And 1,3-propanediol from biomass have been developed.

In this connection, U.S. Patent No. 8,415,496 discloses a method of synthesizing terephthalic acid from a biomass, muconic acid, through the following route, and replacing terephthalic acid, which was a petrochemical-based raw material until now, as a raw material derived from biomass For example.

However, it is generally known that biomass feedstocks degrade fairness when producing the same petrochemical-derived feedstock. It produces impurities that are different from the original petrochemical-derived raw materials and affects fairness or physical properties in existing processes.

In particular, the synthesis of terephthalic acid by the above pathway involves the formation of various byproducts. The largest proportion of byproducts is CHDCA (Cychlohexanedicarboxylic acid: C ₈ H ₁₂ O ₄ ). CHDCA is formed during the synthesis of the divalent acid.

Such CHDCA is a structure in which an aromatic ring of terephthalic acid is substituted with an aliphatic cyclohexane, which is produced in 0.01 to 0.5 mol% in the total terephthalic acid, but its content is not constant and causes other side reactions.

Since the CHDCA has a similar molecular weight, it is an obstacle to obtaining a high purity terephthalic acid (TPA) and requires an additional purification process. When the content of CHDCA in terephthalic acid (TPA) is not uniform, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), the polyester system produced at the time of synthesizing the polyester resin has a large variation in physical properties, which makes it difficult to fabricate the fiber.

In addition, the conventional technology is limited to the technology of making fibers using raw materials derived from biomass, and various types of fibers are required to be developed.

The present invention has been made to solve the problems of the prior art as described above, and it is an object of the present invention to provide a cis-core type polyester conjugate fiber using raw materials derived from biomass excellent in elastic recovery rate by using raw materials derived from biomass.

It is also an object of the present invention to provide a cis-core type polyester conjugate fiber using a raw material derived from a biomass having an equal level of processability when spinning a polyester resin synthesized from a raw material obtained in petrochemical.

It is also an object of the present invention to provide a polyester conjugate fiber and a cis-core type polyester conjugate fiber produced from a petrochemical raw material.

The present invention relates to a cis-core type polyester conjugate fiber, wherein the core portion is formed of polybutylene terephthalate (PBT) formed by polymerizing biomass-derived terephthalic acid containing CHDCA and biomass-derived butylene glycol, (PTT) formed by polymerizing biomass-derived terephthalic acid containing CHDCA and 1,3-propanediol derived from biomass, or ethylene glycol derived from biomass derived from biomass-derived terephthalic acid containing CHDCA Core-type polyester conjugate fiber using a raw material derived from a biomass, which is formed of polyethylene terephthalate (PET).

The present invention also provides a cis-core type polyester conjugate fiber using the biomass-derived raw material, wherein the CHDCA content of the polybutylene terephthalate (PBT) is 1.5 to 4.0 mol%.

When the cis portion is formed of PTT, the difference in CHDCA content between the core portion and the sheath portion is 1.0 to 2.0 mol%. The cis-core type polyester using the biomass-derived raw material Thereby providing a composite fiber.

When the sheath is formed of polyethylene terephthalate (PET), the difference in CHDCA content between the core portion and sheath portion is 2.5 to 3.5 mol%. The sheath-core type polyester conjugate fiber using the biomass- Lt; / RTI >

The present invention also provides a method for producing a cis-core type polyester conjugate fiber, which comprises polybutylene terephthalate (PBT) and CHDCA formed by polymerizing biomass-derived terephthalic acid containing CHDCA and biomass-derived butylene glycol (PTT) formed by polymerizing terephthalic acid derived from biomass derived from biomass and 1,3-propanediol derived from biomass, or polyethylene glycol formed by polymerizing biomass-derived terephthalic acid containing CHDCA and biomass-derived ethylene glycol A melting step of melting terephthalate (PET); A spinning step of spinning polytetramethylene terephthalate (PTT) or polyethylene terephthalate (PET) together with molten polybutylene terephthalate (PBT) as a core part in a cow part; And a stretching step of stretching the spun conjugated fiber. The present invention also provides a method for producing a cis-core type polyester conjugate fiber using the biomass-derived raw material.

 As described above, the present invention uses polytrimethylene terephthalate resin as raw material derived from biomass or polyethylene terephthalate resin as raw material derived from biomass as a cow part as raw material of biomass-derived raw material as a core part, .

In addition, the present invention has a high elastic recovery rate of a polyester conjugate fiber using a raw material derived from a biomass having an equal level of processability in comparison with a polyester resin yarn synthesized from a raw material obtained in petrochemical.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted so as to avoid obscuring the subject matter of the present invention.

As used herein, the terms " about, " " substantially, " " etc. ", when used to refer to a manufacturing or material tolerance inherent in the stated sense, Accurate or absolute numbers are used to help prevent the unauthorized use of the disclosure by the infringer.

The present invention relates to a cis-core type polyester conjugate fiber, wherein the core portion is formed of polybutylene terephthalate (PBT) formed by polymerizing biomass-derived terephthalic acid containing CHDCA and biomass-derived butylene glycol, (PTT) formed by polymerizing biomass-derived terephthalic acid containing CHDCA and 1,3-propanediol derived from biomass, or ethylene glycol derived from biomass derived from biomass-derived terephthalic acid containing CHDCA And is formed of polyethylene terephthalate (PET) to be formed.

In the present invention, the term "biomass-derived material" refers not to raw materials produced from petrochemical origin but to organic raw materials obtained from natural biomass, and terephthalic acid, 1,3-propanediol, ethylene glycol and butylene glycol, A material synthesized from a mass may be used.

At this time, the synthesis of terephthalic acid is accompanied by the generation of various byproducts. The largest proportion of byproducts is CHDCA (Cychlohexanedicarboxylic acid: C ₈ H ₁₂ O ₄ ). CHDCA is formed during the synthesis of the divalent acid.

The present invention relates to a method for producing polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polytrimethylene terephthalate (PTT), wherein the content of CHDCA (Cychlohexanedicarboxylic acid: C ₈ H ₁₂ O ₄ ) The CHDCA content should be adjusted so that the physical properties are not significantly different in a specific range.

In particular, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polytrimethylene terephthalate (PTT) have different melting points, resulting in differences in melt viscosity, which may reduce spinning processability.

In general, polytrimethylene terephthalate (PTT) has higher melting temperature than polybutylene terephthalate (PBT), polyethylene terephthalate (PET) has higher melting temperature than polytrimethylene terephthalate (PTT), and CHDCA has a higher melting point And the melting point of 1.0 mol% is increased to about 100 ~ 300 poise level, so that the melt viscosity can be controlled through the CHDCA content.

In the present invention, the polybutylene terephthalate (PBT) preferably has a CHDCA content of 1.5 to 4.0 mol%, and when the sheath is formed of PTT, the melting point of the core portion and sheath portion In order to reduce the difference, the CHDCA content difference is preferably 1.0 to 2.0 mol%, and when the sheath is formed of polyethylene terephthalate (PET), the difference in CHDCA content between the core portion and the sheath portion is preferably 2.5 to 3.5 mol% something to do.

If the CHDCA content difference is out of the range, the melting point of the core portion and the sheath portion may be significantly different, resulting in frequent occurrence of yarn and yarn phenomena, which may degrade the spinning processability.

It is preferable that the core portion and the sheath portion of the polyester conjugate fiber are formed in a weight ratio of 40:60 to 60:40.

The sheath-core type polyester conjugate fiber of the present invention as usual can produce a fabric having a relatively high tensile strength when the sheath is made of polyethylene terephthalate (PET), and the sheath portion is made of PTT (polyethylene terephthalate) It is possible to produce a fabric having a low drape coefficient and excellent wrinkle recovery property.

The polyester conjugate fiber using the raw material derived from the biomass of the present invention in which the core portion is formed of polybutylene terephthalate (PBT) and the sheath portion is formed of polyethylene terephthalate (PET) or polytrimethylene terephthalate (PTT) A melting step of melting polybutylene terephthalate (PBT) and polyethylene terephthalate (PET) or polytrimethylene terephthalate (PTT), melting the polybutylene terephthalate (PBT) PTT) or polyethylene terephthalate (PET), and a stretching step of stretching the spun conjugated fiber.

Polyester conjugated fibers made of polybutylene terephthalate (PBT) and polytrimethylene terephthalate (PTT) or polyethylene terephthalate (PET) using the biomass-derived raw materials can be produced in the same manner as ordinary polyester conjugated fibers And the melting temperature of the melting step may be adjusted according to the melting point of the core part and the sheath part resin.

The control of the difference in melting point between the two components of the core part and the sheath part may vary the temperature condition of the extruder of each component. Preferably, the core part and the sheath part have a difference in melting point of 1000 Paise The temperature is preferably controlled within the range of 240 to 270 캜.

In the spinning step, the spinning speed may be from 1000 to 4000 m / min. In the spinning step, the spinning temperature may be 50 to 80 ° C. The spinning ratio may be appropriately adjusted according to the purpose of the polyester fiber will be.

Examples of the method for producing the cis-core type polyester conjugate fiber using the raw material derived from the biomass according to the present invention are shown below, but the present invention is not limited to the examples.

Example  One

The terephthalic acid derived from biomass containing CHDCA and the ethylene glycol derived from biomass were put into an esterification reactor and esterification reaction was carried out at a temperature of 250 ° C for 1 hour to prepare an esterified oligomer. The esterified oligomer was subjected to a condensation polymerization reaction together with a conventional polycondensation catalyst while slowly raising the temperature to 280 DEG C so that the final reduced pressure was 0.1 mmHg to obtain a polyethylene terephthalate having a bio-carbon content of 81.6% and a viscosity of 0.64 dl / (PET).

Similarly, the biomass-derived terephthalic acid containing CHDCA and the biomass-derived butylene glycol were introduced into the esterification reactor, and the esterification reaction was carried out at a temperature of 220 ° C for 1 hour to prepare an esterified oligomer. The esterified oligomer was subjected to polycondensation reaction together with a conventional polycondensation catalyst while slowly raising the temperature to 250 ° C so that the final reduced pressure was 0.1 mmHg to obtain polybutylene having a bioc content of 50% and a viscosity of 1.2 g / Terephthalate (PBT) was prepared.

Thereafter, a polybutylene terephthalate (PBT) resin and a polyethylene terephthalate (PET) resin were co-spun in accordance with the cis-core composite ratio shown in Table 1 to obtain a composite material obtained by using a raw material derived from a biomass in a conventional radiator for manufacturing polyester undywn yarn To prepare a cis-core type polyester conjugate fiber.

Example  2

The terephthalic acid derived from biomass containing CHDCA and the 1,3-propanediol derived from biomass were put into an esterification reactor and esterification reaction was carried out at a temperature of 230 ° C for 1 hour to prepare an esterified oligomer.

The esterified oligomer was subjected to polycondensation reaction at 255 DEG C while slowly decompressing the resulting esterified oligomer with a TBT catalyst containing 90 ppm of the final polymer on the basis of the metal content as a final reduced pressure of 0.1 mmHg to obtain a polymer having a bioc content of 82% g / d of polytrimethylene terephthalate (PTT) was prepared.

Similarly, the biomass-derived terephthalic acid containing CHDCA and the biomass-derived butylene glycol were introduced into the esterification reactor, and the esterification reaction was carried out at a temperature of 220 ° C for 1 hour to prepare an esterified oligomer. The esterified oligomer was subjected to polycondensation reaction together with a conventional polycondensation catalyst while slowly raising the temperature to 250 ° C so that the final reduced pressure was 0.1 mmHg to obtain polybutylene having a bioc content of 50% and a viscosity of 1.2 g / Terephthalate (PBT) was prepared.

After that, a polybutylene terephthalate (PBT) resin and a polytrimethylene terephthalate (PTT) resin were combined and spin-coated at a cement-core composite ratio shown in Table 1 to obtain a raw material derived from biomass To prepare a sheath-core type polyester conjugate fiber.

Example  3 ~ 9

The same conditions as in Examples 1 and 2 were used, except that CHDCA content and compounding ratio were varied as shown in Table 1 below.

Comparative Example  1-3

Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polytrimethylene terephthalate (PTT) produced in Examples 1 and 2 were singulated and fiberized.

Core portion Shebu Polymer
Suzy CHDCA
content
(mole%) Melting point
(poise) complex
ratio
(weight%) Polymer
Suzy CHDCA
content
(mole%) Melting point
(poise) complex
ratio
(weight%) Example 1 PBT 0.06 1416 45 PET 0.05 2141 55 Example 2 PBT 0.06 1416 45 PTT 0.03 1698 55 Example 3 PBT 1.5 1738 45 PET 0.05 2141 55 Example 4 PBT 3.0 2063 45 PET 0.05 2141 55 Example 5 PBT 4.5 2322 45 PET 0.05 2141 55 Example 6 PBT 1.5 1738 45 PTT 0.03 1698 55 Example 7 PBT 3.0 2063 45 PTT 0.03 1698 55 Example 8 PBT 3.0 2063 35 PET 0.05 2141 65 Example 9 PBT 3.0 2063 55 PET 0.04 2141 45 Comparative Example 1 PBT 0.06 1416 100 - - - - Comparative Example 2 PET 0.05 2141 100 - - - - Comparative Example 3 PTT 0.03 1698 100 - - - -

◈ Comparison of spinnability and fabric properties of examples and comparative examples

The spinning processability of the polyester conjugate fibers of Examples 1 to 9 and Comparative Examples 1 to 3 prepared above and the fabric properties of the fabric prepared from the fabric were measured and shown in Table 2.

* Tensile Strength: The fabric is made into a 10x15cm rectangle, and then the tensile strength is measured by pulling the center portion of the specimen with a specified size using an Instron tensile tester at a constant speed until it breaks.

* Drape factor: Cut the fabric into a circle with a diameter of 30cm and cut the paper into the same shape. Place a specimen of 18 cm in diameter and cover the cover of the drape tester and place a circular paper. Draw the outline of the projected shadow on the circular paper with the light source. Measure the weight (A) of the circular paper and the weight (B) inside the outline. The larger the drape coefficient, the stiffness of the fabric, and the lower the modulus, the more flexible the fabric.

Drape coefficient (D) = B / A

Wrinkle resilience: Following the AATCC 33-2008 test, the samples are pressurized with 5 N for 5 minutes and record the Wrinkle Recovery Angle (WRA) value of the sample after a recovery period of 5 minutes. The smaller the angle is, the better the recovery by wrinkling is, and the larger the angle, the better the recovery.

division Radiation fairness Fabric Properties Tensile strength (g / d) Drape coefficient Wrinkle recovery (%) Example 1 Bad 3.4 0.40 165 Example 2 Bad 3.3 0.32 173 Example 3 usually 3.1 0.48 162 Example 4 Good 2.7 0.47 166 Example 5 usually 2.5 0.45 160 Example 6 Good 2.5 0.36 171 Example 7 usually 2.7 0.34 167 Example 8 Good 2.6 0.49 166 Example 9 Good 2.9 0.51 168 Comparative Example 1 Good 3.5 0.52 158 Comparative Example 2 Good 3.1 0.63 155 Comparative Example 3 Good 3.3 0.48 163

As shown in Table 2, the composite fiber formed of polyethylene terephthalate (PET) or polytrimethylene terephthalate (PTT) with the core portion made of polybutylene terephthalate (PBT) and the sheath portion made of fabric had a smaller drape coefficient, It is supposed to be flexible and excellent in wrinkle recovery.

In addition, when the sheath is polyethylene terephthalate (PET), the tensile strength tends to be relatively high. In the case of PTT, the elastic restoration is excellent and the drape coefficient is low and the wrinkle recovering property is relatively good can see.

In Examples 4 and 6, which have similar melting points between the core portion and the sheath portion, it is preferable that the content of CHDCA is adjusted so that the melt viscosity of the core portion and the sheath portion are similar to each other,

When the composite fiber is formed of polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), it is preferable that the content of CHDCA is 2.5 to 3.5 mol%.

When the conjugated fiber is formed of polybutylene terephthalate (PBT) and polytrimethylene terephthalate (PTT), it is preferable that the difference in CHDCA content is 1.0 to 2.0 mol%.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. It will be clear to those who have knowledge of.

Claims (5)

In the sheath-core type polyester conjugate fiber,
The core portion is formed of polybutylene terephthalate (PBT) formed by polymerizing biomass-derived terephthalic acid containing CHDCA and biomass-derived butylene glycol,
The sheath is composed of biotite-derived terephthalic acid containing CHDCA and polytrimethylene terephthalate (PTT) formed by polymerizing biomass-derived 1,3-propanediol from biomass and biomass-derived terephthalic acid containing CHDCA and biomass-derived ethylene glycol Core-type polyester conjugate fiber using a raw material derived from biomass, which is formed of polyethylene terephthalate (PET) formed by polymerization.
The method according to claim 1,
Wherein the polybutylene terephthalate (PBT) has a CHDCA content of 1.5 to 4.0 mol%. The cis-core type polyester conjugate fiber using the biomass-derived raw material.
The method according to claim 1,
Core-type polyester conjugate fiber using the biomass-derived raw material, wherein the difference between the content of CHDCA in the core portion and the content of CHDCA in the sheath portion is 1.0 to 2.0 mol% when the sheath portion is formed of PTT (polytrimethylene terephthalate) .
The method according to claim 1,
Core-type polyester conjugate fiber using the biomass-derived raw material, wherein the difference in CHDCA content between the core portion and the sheath portion is 2.5 to 3.5 mol% when the sheath is formed of polyethylene terephthalate (PET).
In the method for producing a cis-core type polyester conjugate fiber,
(PBT) formed by polymerizing biomass-derived terephthalic acid containing CHDCA and biomass-derived butylene glycol, and polymerization of 1,3-propanediol derived from biomass and biomass derived from CHDCA (PET) formed by polymerizing biomass-derived terephthalic acid and biomass-derived ethylene glycol containing polytrimethylene terephthalate (PTT) or CHDCA formed by the steps of: melting the polyethylene terephthalate (PET)
A spinning step of spinning polytetramethylene terephthalate (PTT) or polyethylene terephthalate (PET) with a sheath to melt the polybutylene terephthalate (PBT) as a core part; And
And a stretching step of stretching the spun conjugated fiber. The method of producing a cis-core type polyester conjugate fiber using the raw material derived from a biomass.