KR101644068B1 - Polytrimethyleneterephthalate Composite Fibers Using materials from biomass and Method Preparing Same - Google Patents

Abstract

The present invention relates to a polytrimethylene terephthalate having a high viscosity and a low viscosity polytrimethylene terephthalate formed by polymerizing biomass-derived terephthalic acid and biomass-derived 1,3-propanediol in a side-by-side form, And a polytrimethylene terephthalate conjugate fiber using a raw material derived from a biomass.

Description

TECHNICAL FIELD [0001] The present invention relates to a polytrimethylene terephthalate conjugate fiber using a biomass-derived raw material,

The present invention relates to a polytrimethylene terephthalate conjugate fiber using a raw material derived from a biomass and a method for producing the same, and more particularly, to a polytrimethylene terephthalate conjugate fiber using a raw material derived from a biomass having self- And a manufacturing method thereof.

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 method of collecting biomass energy such as methane, ethanol, and hydrogen by pyrolyzing or fermenting an organism in terms of biomass or biomass. The amount of biomass increases with the production of biomass, which is the amount of accumulation that subtracts the amount of respiration, loss of decay, In the ecosystem, the biomass of the low-nutrient biomass is high, and the biomass of the high-order biomass is low.

Biomass is a cycle of material circulation in the biosphere of the earth that decomposes microbes into microbes and reduces them to minerals. Instead of these microbes, humans use them as energy or organic materials.

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, which is a polyester-based compound, can be prepared by esterification and condensation polymerization of terephthalic acid or an ester-forming derivative thereof with 1,3-propanediol. The raw materials terephthalic acid and 1,3- Techniques for obtaining propanediol from biomass are being developed.

In this connection, U.S. Patent No. 8,415,496 discloses a technique for synthesizing terephthalic acid from a biomass, muconic acid, and replacing terephthalic acid, which was heretofore a petrochemical-based raw material, as a raw material derived from biomass .

On the other hand, 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.

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.

Particularly, since CHDCA is an obstacle to obtaining high-purity terephthalic acid, an additional purification process is required, and an unevenness content in terephthalic acid has an undesirable influence on the physical property variation of the synthesized PTT. Therefore, There are also difficulties in obtaining suitable spinning conditions in which yarn is not spun when spinning terephthalate.

In addition, when biomass-derived raw materials are used in the manufacture of conjugated fibers in a side-by-side cross-sectional shape, it is more preferable to synthesize polytrimethylene terephthalate using the biomass-derived terephthalic acid, .

Accordingly, there is a need to develop a composite fiber which exhibits uniform properties without spoiling the processability and exhibits excellent spontaneous crimping properties.

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 polytrimethylene terephthalate conjugate fiber having spontaneous crimping property by using a raw material derived from biomass.

Another object of the present invention is to provide a composite fiber of polytrimethylene terephthalate spontaneously crimping property using a raw material derived from a biomass having an equivalent level of fairness when spinning polytrimethylene terephthalate synthesized from a raw material obtained from petrochemicals .

It is another object of the present invention to provide a composite fiber of polytrimethylene terephthalate spontaneously crimping property using a raw material derived from biomass which is not different from that of polytrimethylene terephthalate produced from petrochemical raw material.

The present invention relates to a biodegradable polytrimethylene terephthalate which is formed by polymerizing terephthalic acid derived from biomass and 1,3-propanediol derived from biomass and a low viscosity polytrimethylene terephthalate A polytrimethylene terephthalate composite fiber using a mass-derived raw material is provided.

Also, the content of CHDCA (Cychlohexanedicarboxylic acid: C ₈ H ₁₂ O ₄ ) in the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate is 1 to 2.5 mol% Methylene terephthalate composite fiber.

The high viscosity polytrimethylene terephthalate has an intrinsic viscosity of 0.85 to 1.05 g / d, and the low viscosity polytrimethylene terephthalate has an intrinsic viscosity of 0.80 to 0.90 g / d. A polytrimethylene terephthalate composite fiber is provided.

Also, the intrinsic viscosity difference between the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate is 0.05 to 0.10, and the polytrimethylene terephthalate conjugate fiber using the raw material derived from the biomass is provided.

The intrinsic viscosity difference between the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate satisfies 0 < K &lt; / = 0.09 as calculated by Equation (1) And a trimethylene terephthalate conjugate fiber.

 [Equation 1]

In the formula, [η] _H is the intrinsic viscosity of the high viscosity polytrimethylene terephthalate, and [η] _L is the intrinsic viscosity of the low viscosity polytrimethylene terephthalate.

The polytrimethylene terephthalate conjugate fiber has a strength of 2.5 to 3.5 g / de and an elongation of 45 to 65%. The polytrimethylene terephthalate conjugate fiber comprises the biomass-derived raw material.

The present invention also relates to a process for producing a high-viscosity polytrimethylene terephthalate having an intrinsic viscosity difference of 0.05 to 0.10, which is formed by polymerizing biomass-derived terephthalic acid and biomass-derived 1,3-propanediol, A melting step; A spinning step of spinning the molten high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate in a side-by-side manner; And a stretching step of stretching the spun conjugated fiber. The present invention also provides a method for producing a PTT conjugate fiber using the biomass-derived raw material.

As described above, the present invention relates to a side-by-side polytrimethylene terephthalate composite fiber using a high-viscosity, low-viscosity polytrimethylene terephthalate using a raw material derived from a biomass, and has an effect of having spontaneous cementing property in a subsequent relaxation heat treatment process have.

Further, the polytrimethylene terephthalate conjugate fiber using the raw material derived from the biomass of the present invention has an effect in that it has no difference in physical properties from the polytrimethylene terephthalate prepared from a petrochemical raw material.

Hereinafter, a preferred embodiment 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 &quot; about, &quot;&quot; substantially, &quot;&quot; etc. &quot;, when used to refer to a manufacturing or material tolerance inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The present invention relates to a composite fiber having a spontaneously crimping property by coextruding a high viscosity polytrimethylene terephthalate and a low viscosity polytrimethylene terephthalate using a raw material derived from a biomass in a side-by-side cross-sectional shape.

The high viscosity and low viscosity polytrimethyleneterephthalate (PTT) are formed by polymerizing biomass-derived terephthalic acid and biomass-derived 1,3-propanediol.

In the present invention, the term "derived from biomass" refers not to raw materials produced from petrochemical origin but to organic raw materials obtained from natural biomass, and terephthalic acid and 1,3-propanediol synthesized from biomass can be used have.

As described above, polytrimethylene terephthalate formed by polymerizing terephthalic acid derived from biomass and 1,3-propanediol derived from biomass has high viscosity and low viscosity polytrimethylene terephthalate .

The inventors of the present invention confirmed in Korean patent application No. 2013-0152141 that the CHDCA content influences the uniformity of the production of polytrimethylene terephthalate, and that the CHDCA content varies depending on the content thereof. When the CHDCA content is within a certain range, And it was confirmed that it is possible to produce polytrimethylene terephthalate using raw material derived from biomass which is not different from that of polytrimethylene terephthalate prepared from the raw material obtained from conventional petrochemicals.

Accordingly, the content of CHDCA (Cychlohexanedicarboxylic acid: C ₈ H ₁₂ O ₄ ) in the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate is preferably 1 to 2.5 mol%, more preferably 1 to 1.5 mol %.

The intrinsic viscosity of the high viscosity polytrimethylene terephthalate is 0.85 to 1.05 g / d,

The low viscosity polytrimethylene terephthalate preferably has an intrinsic viscosity of 0.80 to 0.90 g / d, and the intrinsic viscosity difference between the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate is preferably 0.05 to 0.10 will be.

When the difference in intrinsic viscosity between the high viscosity and low viscosity polytrimethylene terephthalate is less than 0.05, the shrinkage ratio of the high viscosity and low viscosity polytrimethylene terephthalate may be small and the crimp ratio of the composite fiber may be decreased. The intrinsic viscosity difference between trimethylene terephthalate exceeds 0.1 and there is no large difference in crimp ratio, and the physical properties of the composite fiber may be deteriorated.

In particular, the difference in intrinsic viscosity between the high viscosity and low viscosity polytrimethylene terephthalate is preferably 0 <K? 0.09, as determined by the following formula (1).

 [Equation 1]

In the formula, [η] _H is the intrinsic viscosity of the high viscosity polytrimethylene terephthalate, and [η] _L is the intrinsic viscosity of the low viscosity polytrimethylene terephthalate.

Even if the combination of the high viscosity and low viscosity polytrimethylene terephthalate has a small viscosity difference, it is also possible to control the melting point difference and the composite ratio between the two components during spinning, so that even when the polymer having the viscosity difference as described above is used, Lt; RTI ID = 0.0 &gt; polytrimethylene terephthalate &lt; / RTI &gt;

The high-viscosity polytrimethylene terephthalate and the low-viscosity polytrimethylene terephthalate of the polytrimethylene terephthalate conjugate fiber are preferably formed in a weight ratio of 30:70 to 70:30.

The control of the melt viscosity difference between the two components can be achieved by varying the thermal history of each component melt or by adjusting the high viscosity component and the low viscosity component ratio by varying the temperature condition of the extruder of each component. Preferably, the spinning temperature is preferably controlled within the range of 240 to 270 DEG C so that the difference in melting point between the high viscosity and the low viscosity is 1000Poise or less.

It is preferable that the PTT conjugate fiber has a strength of 2.5 to 3.5 g / de and an elongation of 45 to 65%.

If the strength is less than 2.5 g / de, the strength is low, and yarn may be generated in the spinning process, and the workability may be lowered when fabric is manufactured. If the strength is more than 3.5 g / have.

In addition, if the elongation is less than 45%, a rounding may occur during the spinning process, and if the elongation exceeds 65%, the uniformity may be lowered.

The polytrimethylene terephthalate composite fiber using the raw material derived from the biomass of the present invention, which is formed of the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate, has a high viscosity polytrimethylene terephthalate having an intrinsic viscosity difference of 0.05 to 0.1 A melting step for melting the phthalate and the low viscosity polytrimethylene terephthalate, a spinning step for complexly spinning the molten high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate side by side, And a stretching step.

The polytrimethylene terephthalate conjugate fiber made of the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate using the raw material derived from the biomass can be produced in the same manner as a general polytrimethylene terephthalate conjugate fiber, In the step, the melting temperature may be adjusted according to the melting point of the high viscosity and low viscosity polytrimethylene terephthalate.

The spinning speed may be in the range of 1000 to 4000 m / min. In the spinning step, the spinning temperature may be 50 to 80 ° C. The spinning ratio may be suitably adjusted according to the purpose of use of the polytrimethylene terephthalate composite fiber You will be able to control it.

After the stretching step, the polytrimethylene terephthalate composite fiber may be subjected to a relaxation heat treatment to give spontaneous vulcanization, and the heat treatment may be performed at 180 to 240 ° C.

The polytrimethylene terephthalate composite fiber using the raw material derived from the biomass according to the present invention has a high viscosity and a low viscosity polytrimethylene terephthalate as a side-by-side composite fiber, Crimp is generated due to the difference in shrinkage ratio of trimethylene terephthalate, and thus has spontaneous crimping property.

Hereinafter, examples of the method for producing the PTT conjugated fiber using the biomass-derived raw material according to the present invention will be described, but the present invention is not limited to the examples.

Examples 1 to 4

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 200 ° C for 1 hour to prepare an esterified oligomer.

The esterified oligomer was subjected to polycondensation reaction with the TBT catalyst containing 90 ppm of the final polymer on the basis of the metal content by gradually raising the temperature to 255 ° C so that the final reduced pressure became 0.1 mmHg.

High viscosity polytrimethylene terephthalate and low viscosity polytrimethylene terephthalate were prepared by varying the termination power value and the intrinsic viscosity of the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate of Examples 1 to 4 and the content of CHDCA Are shown in Table 1.

The high-viscosity polytrimethylene terephthalate prepared above and the low-viscosity polytrimethylene terephthalate were spinned at a rate of 2000 m / min using a side-by-side spinning nozzle at 260 ° C., and then subjected to a drawing rate of 1.5 times and a drawing temperature of 55 ° C. , And stretched at a heat treatment temperature of 220 캜 to prepare a PTT fiber using the raw material derived from the biomass of the present invention.

Comparative Example

The polytrimethylene terephthalate conjugate fiber was prepared in the same manner as in Example 1 except that terephthalic acid and 1,3-propanediol obtained through petrochemical were used and prepared without containing CHDCA.

Table 1 shows the spinnability and yarn properties of the PTT fibers of Examples 1 to 4 and Comparative Examples.

* Intrinsic Viscosity (IV): Each polymer is dissolved sufficiently in 1% concentration in ortho-chlorophenol at 120 ° C and then measured at 30 ° C in a thermostatic chamber using Ube Rod type viscometer.

* Robust: Measured 5 times under conditions of sample length 200mm and cross head speed 400mpm using Instron instrument under constant temperature and humidity conditions of temperature 20 ℃ and humidity 65%.

* 30% elongation elasticity recovery rate of fabric (FR ₃₀ ,%): After preparing three pieces of 5.5 cm × 30 cm each in the direction of warp and weft, the width of the test piece was set to 5 cm in the tensile tester, Let the specimen stretch. After elongation to 30% elongation at a rate of 100% / min with a low-speed elongation measurement method (JIS L 1018-70), the elongation at the same time in the opposite direction of the stress- (ε) and measure the mean value of each direction of light and weft.

Fraction CHDCA content
(mole%) Intrinsic viscosity Radiation fairness Yarn properties High viscosity Low viscosity General envoy yield
(%) burglar
(g / de) Shindo
(%) FR ₃₀
(%) Example 1 One 1.0 0.9 4 99.2 2.91 55.4 96 Example 2 One 1.0 0.85 6 98.9 2.85 56.5 93 Example 3 1.5 1.0 0.9 5 98.8 2.87 53.6 92 Example 4 1.5 1.0 0.85 5 99.0 2.95 54.1 96 Comparative Example 0 1.0 0.9 4 99.3 2.98 56.3 95

As shown in Table 1, it can be seen that the PTT fibers of Examples 1 to 4 have almost no difference in spinnability and yarn properties from the PTT fibers of the comparative example.

Therefore, the polytrimethylene terephthalate conjugate fiber using the raw materials derived from the biomass of the present invention can be used in place of the conventional polytrimethylene terephthalate conjugate fiber, thereby enhancing the eco-friendliness.

Claims (7)

The high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate formed by polymerizing the biomass-derived terephthalic acid and the biomass-derived 1,3-propanediol are formed as the side-by-side type,
Wherein the content of CHDCA (Cychlohexanedicarboxylic acid: C8H12O4) in the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate is 1 to 2.5 mol%. delete The method according to claim 1,
Wherein the high viscosity polytrimethylene terephthalate has an intrinsic viscosity of 0.85 to 1.05 g / d, and the low viscosity polytrimethylene terephthalate has an intrinsic viscosity of 0.8 to 0.90 g / d. Methylene terephthalate composite fiber. The method according to claim 1,
Wherein the intrinsic viscosity difference between the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate is 0.05 to 0.10. The polytrimethylene terephthalate conjugate fiber using the raw material derived from the biomass. The method according to claim 1,
Wherein the intrinsic viscosity difference between the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate satisfies the K value 0 <K? 0.09 calculated by the formula (1). The polytrimethylene terephthalate Phthalate Composite Fiber.
[Equation 1]

In the formula, [η] _H is the intrinsic viscosity of the high viscosity polytrimethylene terephthalate, and [η] _L is the intrinsic viscosity of the low viscosity polytrimethylene terephthalate. The method according to claim 1,
Wherein the polytrimethylene terephthalate conjugate fiber has a strength of 2.5 to 3.5 g / de and an elongation of 45 to 65%. The polytrimethylene terephthalate conjugate fiber according to claim 1, A melting step of melting a high viscosity polytrimethylene terephthalate and a low viscosity polytrimethylene terephthalate having an intrinsic viscosity difference of 0.05 to 0.10 formed by polymerizing biomass-derived terephthalic acid and 1,3-propanediol derived from biomass;
A spinning step of spinning the molten high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate in a side-by-side manner; And
And a stretching step of stretching the spun conjugated fiber,
Characterized in that the content of CHDCA (Cychlohexanedicarboxylic acid: C8H12O4) in the high viscosity polytrimethylene terephthalate and the low viscosity polytrimethylene terephthalate is 1 to 2.5 mol%, and the production method of the polytrimethylene terephthalate conjugate fiber using the raw material derived from the biomass .