TW202122450A - Copolyester, blend comprising copolyester and method for manufacturing copolyester fibers using the same - Google Patents

Abstract

Provided are a copolyester, a blend comprising the copolyester and a method for manufacturing copolyester fibers using the same. The copolyester is synthesized from a monomer composition comprising adipic acid, itaconic acid and butanediol. A first polymer formed by adipic acid and butanediol and a second polymer formed by itaconic acid and butanediol are bonded with each other through ester bonds, and the mole ratio between the first and second polymers in the copolyester ranges from 90:10 to 50:50. The method provided by the present invention can be used to produce copolyester fibers having high enthalpy and phase change property.

Description

Copolyesters, blends containing copolyesters, and methods for manufacturing copolyester fibers using the blends

The present invention relates to a copolyester, a blend containing copolyester and a method for manufacturing a copolyester fiber using the blend, and particularly relates to a copolyester with phase change characteristics and a blend containing copolyester And a method for manufacturing copolyester fibers using the blend.

Since the advent of polyester fiber, it has been widely used in various fabrics due to its high strength, strong wrinkle resistance, easy dyeing and low cost. Among various fabric materials, a phase change material (PCM) that can absorb heat energy has become one of the popular research and development products in related technical fields. For example, the phase change fiber is a kind of heat storage and temperature regulation functional fiber developed by using the characteristics of releasing or absorbing latent heat and maintaining the temperature during the phase change of a substance.

In the technical field of materials with phase change properties, technical means for embedding low melting point materials with shell materials have been disclosed. However, the phase change enthalpy value of the material obtained by the above technology is not high (△H<5 Joule/g). Therefore, the phase change property of the formed polyester fiber is fixed and difficult to adjust, and it cannot meet various requirements. Required for textiles. In view of the above, in order to further expand the applicability of polyester fibers with phase change properties, there is an urgent need to develop adjustable and high enthalpy values (△H= 10 to 20 joules/g) polyester masterbatch is used to make polyester fibers to meet the needs of various products. Generally speaking, it is a relatively simple process to directly blend a material with phase change properties and a polymer and spin it. However, this technology has problems such as low enthalpy, easy leakage of phase change materials, and low fiber strength. One of the existing technologies is the use of wet spinning, which is applied to polyacrylonitrile fibers and cellulose fibers. In addition, another technology is the microcapsule method, which uses a polymer to coat and seal the phase change material to prevent leakage of the phase change material, and then blend and spin the microcapsule containing the phase change material with the polymer to obtain the phase change fiber. However, this technology has the following shortcomings: the larger phase change material will be filtered out and cannot enter the fiber, resulting in a smaller enthalpy of the fiber phase change.

Accordingly, in the prior art, there is still a need to provide a polyester fiber with phase change properties and a manufacturing method thereof.

In order to solve the above technical problems, the present invention provides a copolyester, a blend containing the copolyester, and a method for manufacturing a copolyester fiber using the blend. The copolyester fiber of the present invention has a desired enthalpy value and can be well applied to various clothing products, such as ski suits, ski boots, gloves, hosiery and other sports clothing.

An embodiment of the present invention provides a copolyester, which is synthesized by copolymerizing a monomer composition, the monomer composition including adipic acid, itaconic acid and butanediol, wherein the In the copolyester, a first polymer formed by the copolymerization of adipic acid and butylene glycol and a second polymer formed by the copolymerization of itaconic acid and butylene glycol are bonded to each other by ester bonds, and the first polymer The molar ratio of one polymer to the second polymer is in the range of 90:10 to 50:50.

In a preferred embodiment, the copolyester has a value between 0.7 g/dL and 1.2 Intrinsic viscosity in the range of g/dL and melting point in the range of 20°C to 60°C.

In a preferred embodiment, the copolyester has a number average molecular weight ranging from 20,000 g/mole to 35,000 g/mole.

Another embodiment of the present invention provides a blend comprising a polymer blend comprising 5 to 50% by weight of the copolyester as described in claim 1 and 50 to 95% by weight Polycaprolactone.

In a preferred embodiment, the polymer blend has an intrinsic viscosity ranging from 0.6 g/dL to 0.8 g/dL.

In a preferred embodiment, the blend further includes a matrix material, and the content of the polymer blend is 10 to 30% by weight, and the content of the matrix material is 70 to 90% by weight.

In a preferred embodiment, the matrix material is polylactic acid, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene terephthalate (PET). PHT) or a mixture thereof.

In a preferred embodiment, the blend has a number average molecular weight ranging from 30,000 g/mol to 50,000 g/mol, a first melting point in the range of 30°C to 40°C, and a medium A second melting point in the range of 140°C to 160°C, and a thermal cracking temperature in the range of 310°C to 340°C.

Another embodiment of the present invention provides a method of manufacturing a copolyester fiber, which includes: using a monomer composition to perform a copolymerization reaction to synthesize a copolyester; the copolyester and polycaprolactone are mixed together to form a copolyester Mixing polymers; and mixing the polymer blends with a matrix material to form a blend. The monomer composition includes adipic acid, itaconic acid and butanediol, Wherein, in the copolyester, a first polymer formed by copolymerization of adipic acid and butanediol and a second polymer formed by copolymerization of itaconic acid and butanediol are bonded to each other by ester bonds And the molar ratio of the first polymer to the second polymer is in the range of 90:10 to 50:50.

In a preferred embodiment, the method for manufacturing a copolyester fiber further includes after forming the polyester pellets, spinning the polyester pellets to obtain a polyester fiber.

In a preferred embodiment, the copolyester has an intrinsic viscosity in the range of 0.7 g/dL to 1.2 g/dL and a melting point in the range of 20°C to 60°C.

In a preferred embodiment, the copolyester has a number average molecular weight ranging from 20,000 g/mole to 35,000 g/mole.

In a preferred embodiment, in the step of kneading the copolyester and polycaprolactone together to form the polymer blend, the polymer blend contains 5 to 50% by weight as requested The copolyester described in Item 1 and 50 to 95% by weight of polycaprolactone.

In a preferred embodiment, in the step of kneading the blend and the matrix material together to form the blend, the content of the blended polymer is 10 to 30% by weight, and The content of the matrix material is 70 to 90% by weight.

In a preferred embodiment, the matrix material is polylactic acid, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene terephthalate (PET). PHT) or a mixture thereof.

The main technical means of the present invention is that the copolyester, the blend containing the copolyester and the method for manufacturing the copolyester fiber using the blend provided in the embodiment of the present invention are achieved by adjusting and controlling different polymers in the copolyester. Between the ratios, and the appropriate content of polycaprolactone and appropriate The content and type of the matrix material and other technical characteristics make the copolyester fiber made with good characteristics and suitable for functional clothing products.

Figure 1 is a micro-differential scanning calorimetry (DSC) analysis diagram of copolyesters provided by some embodiments of the present invention;

Figure 2 is a thermogravimetric analysis (TGA) diagram of the copolyester provided by one of the embodiments of the present invention;

Figure 3 is a micro-differential scanning thermal analysis diagram of copolyester fibers provided by some embodiments of the present invention;

4 is a micro-differential scanning thermal analysis diagram of copolyester fibers provided by other embodiments of the present invention;

Figure 5 is a micro-differential scanning thermal analysis diagram of copolyester fibers provided by still other embodiments of the present invention; and

Fig. 6 is a photograph of a copolyester fiber provided by one of the embodiments of the present invention and its infrared analysis diagram.

The following are specific examples to illustrate the embodiments of the present invention about "copolyesters, blends containing copolyesters, and methods for manufacturing copolyester fibers using the blends" disclosed by the present invention. Those skilled in the art can The content disclosed in this specification understands the advantages and effects of the present invention. The present invention can be implemented or applied through other different specific embodiments, and various details in this specification can also be based on different viewpoints and applications, and various modifications and changes can be made without departing from the spirit of the present invention. In addition, the drawings of the present invention are merely schematic illustrations, and are not drawn according to actual size, and are described first. The following embodiments will further describe the related technical content of the present invention in detail, but the disclosed content is not intended to limit the technical scope of the present invention.

First, the embodiment of the present invention provides a copolyester, which is used to manufacture the copolyester One of the raw materials of fiber. The copolyester of the embodiment of the present invention is synthesized by copolymerization of a monomer composition including adipic acid (AA), itaconic acid and butanediol. For example, in the embodiment of the present invention, in the presence of a catalyst, adipic acid and itaconic acid are reacted with butanediol as the reactants to undergo a copolymerization reaction to form a polyester copolymer with a low melting point.

As mentioned above, in the copolymerization reaction, adipic acid and butanediol are polymerized to form the first polymer: butylene adipate (BA), and itaconic acid and butanediol are polymerized to form the second copolymer : Polybutylene itaconate (BI). Then, in the copolymerization reaction, polybutylene adipate (BA) and polybutylene itaconate (BI) will be randomly arranged and bonded with each other by ester bonds to form a polyester copolymer (polybutylene adipate). Butylene-copolymer-polybutylene itaconate), and this polyester block copolymer is a random copolymer.

In some embodiments of the present invention, in the copolyester, the molar ratio of the first polymer to the second polymer is in the range of 90:10 to 50:50. In other words, the content of the first polymer-butylene adipate is 90 to 50 mol parts, and the content of the second polymer is 10 to 50 mol parts. In the embodiment of the present invention, the content of butylene adipate is 90, 80, 70, 60 or 50 moles, and the content of polybutylene itaconate is 10, 20, 30, 40 or 50. Mo Erfen. By adjusting the ratio between the first polymer and the second polymer in the copolyester within the above range, the copolyester can be made to have desired physical properties, such as intrinsic viscosity and melting point, which are also useful for subsequent formation of blends. The nature of the compound has an impact.

Based on the above, the copolyester provided by the embodiment of the present invention has an intrinsic viscosity in the range of 0.7 g/dL to 1.2 g/dL. In some embodiments, the copolyester has a melting point in the range of 20°C to 60°C. In other words, since the embodiments of the present invention provide The copolyester has a melting point within the above range, and it can absorb heat when it comes into contact with human body temperature. In addition, in some embodiments of the present invention, the copolyester has a number average molecular weight of 20,000 g/mole to 35,000 g/mole.

Next, the embodiment of the present invention also provides a blend. The blend can be used as a raw material for spinning to produce copolyester fibers with phase change properties. In detail, the blend includes a polymer blend, and the polymer blend includes 5 to 50% by weight of the aforementioned copolyester and 50 to 95% by weight of polycaprolactone. In other words, the polymer blend in the blend may be formed by kneading the aforementioned copolyester with polycaprolactone as a matrix.

In some embodiments, the content of polybutylene adipate-co-polybutylene itaconate (copolyester) in the polymer blend is 10, 15, 20, 25, 30 by weight. , And the content of polycaprolactone is 90, 85, 80, 75, 70 weight ratio. Specifically, adding polycaprolactone and kneading with polycaprolactone and copolyester can provide a protective function to the copolyester, and can also adjust the enthalpy value (△Hm) of the polymer blend. Because polycaprolactone has a low melting point and is not easy to flow at high temperatures, polycaprolactone is used as a dispersant (matrix) and a protective agent in the polymer blend.

Next, in some embodiments of the present invention, the blend includes a matrix material in addition to the aforementioned polymer blend. In the blend, the content of the blended polymer is 10 to 30% by weight, and the content of the matrix material is 70 to 90% by weight. Specifically, the content of the polymer blend can be 10, 20, or 30 parts by weight, and the content of the matrix material can be 90, 80, or 70 parts by weight.

As mentioned above, the matrix material can be polylactic acid (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and poly(hexamethylene terephthalate). (PHT) or its mixture. In a preferred embodiment, the matrix material is polylactic acid.

In detail, after forming a polymer blend, the polymer blend can be combined with the matrix The materials are mixed to form a blend. The use of the matrix material and the polymer blend in the blend is used to provide support for the copolyester in the polymer blend and to improve the spinnability of the blend. The formed blend may have a number average molecular weight between 30,000 g/mole and 50,000 g/mole. In one embodiment, the blend may have a first melting point in the range of 30°C to 40°C and a second melting point in the range of 140°C to 160°C. Therefore, the blend is a dual melting point blend. In yet another embodiment, the blend may have a thermal cracking temperature in the range of 310°C to 340°C.

Based on the foregoing, the blend provided by the embodiment of the present invention may be a polyester masterbatch used to manufacture copolyester fibers. Since the copolyester described in the foregoing embodiment is used as one of the main raw materials, the blend can have phase change properties. In some embodiments of the present invention, the enthalpy value of the copolyester fiber with phase change properties ranges from 2.25 to 23.8 millijoules/mg (mJ/mg).

In addition, the blends provided by the embodiments of the present invention are spinnable, and the copolyester fibers produced therefrom can have fiber winding speeds ranging from 1600 to 2400 meters per minute (m/min). In some embodiments, the fiber fineness of the copolyester fiber manufactured from the blend of the present invention as a masterbatch is in the range of 3.09 to 3.86 dtex. In some embodiments, the strength of the copolyester fiber ranges from 0.53 g/den (g/den) to 2.46 g/den. In some embodiments, the elongation of the copolyester fiber is in the range of 30% to 100%. In some embodiments, the temperature of the copolyester fiber with phase change properties decreases by 1 to 3°C under an environment of 40°C to 50°C, as measured by infrared rays.

The embodiment of the present invention also provides a method for manufacturing the copolyester fiber. Said party The method includes the copolymerization of monomer composition to synthesize copolyester; the co-mixing of copolyester and polycaprolactone to form a polymer blend; and the co-mixing of polymer blend and matrix material to form a blend Things.

In fact, the method for manufacturing copolyester fibers provided by the embodiments of the present invention includes using the aforementioned copolyester and blends as raw materials. First, in the step of forming a copolyester, a monomer composition including adipic acid, itaconic acid and butanediol is used as the reactant, and the copolymerization reaction is carried out to form the first polymer and the second polymer.的copolymer. In particular, the first polymer formed by the copolymerization of adipic acid and butylene glycol and the second polymer formed by the copolymerization of itaconic acid and butanediol are bonded to each other by ester bonds, and the first polymer and the second polymer are The molar ratio of the polymer ranges from 90:10 to 50:50. The above-mentioned step of forming a copolyester can be carried out in the presence of a catalyst.

As mentioned above, since the embodiments of the present invention use the aforementioned copolyesters and blends as raw materials, the composition ratios and characteristics of the copolyesters and blends are as described above, and will not be repeated here. Narrative.

Next, the copolyester and polycaprolactone are kneaded together to form a polymer blend. In this step, the polymer blend contains 5 to 50% by weight of copolyester and 50 to 95% by weight of polycaprolactone. In fact, in this step, the product of the copolymerization reaction is further mixed with polycaprolactone as a protective agent and melting point regulator in a specific ratio.

After the polymer blend is formed, the method for manufacturing the copolyester fiber provided by the embodiment of the present invention further includes kneading the polymer blend and the matrix material together to form a blend. In the formed blend, the content of the blended polymer is 10 to 30% by weight, and the content of the matrix material is 70 to 90% by weight. The matrix material can be polylactic acid, polyethylene terephthalate (PET), polyethylene terephthalate Poly(hexamethylene terephthalate) (PHT), polybutylene terephthalate (PBT) or mixtures thereof.

It is worth mentioning that in the method of manufacturing copolyester fibers provided by the present invention, in order to provide sufficient support and spinnability of the copolyester raw materials used to form the copolyester fibers, the copolyester and the The matrix material is blended and kneaded. However, since the physical properties of the copolyester manufactured according to the foregoing steps are quite different from the physical properties of the compound as the matrix material (for example, the melting point between the two is large), before mixing the copolyester with the matrix material, The manufacturing method provided in the embodiment of the present invention is to first knead the copolyester and polycaprolactone, so that the polycaprolactone can be used as a compatibilizing and dispersing aid between the copolyester and the subsequent use of the matrix material.

In detail, if the copolyester synthesized by the copolymerization reaction is directly kneaded with a supporting matrix material, such as polylactic acid, it will make the kneading process difficult and the formed masterbatch has low spinnability.

The following will further illustrate the content of the present invention through specific examples. First, please refer to FIG. 1, which is a differential scanning calorimetry (DSC) image of the copolyester provided by some embodiments of the present invention. Specifically, the graphs of Fig. 1(a), Fig. 1(b) and Fig. 1(c) respectively represent the first heating (1 ^st heating) and the second heating of the copolyester of the embodiment of the present invention. DSC graphs measured during the 2 ^{nd heating and cooling phases.} In each graph, different color curves indicate the molar ratio between the first polymer (BA) and the second polymer (BI) in the copolyester. Among them, the green curve represents BA/BI=7/3, the blue curve represents BA/BI=8/2, the red curve represents BA/BI=9:1, and the black curve represents BA/BI=10/0 (black curve As the control group). It can be seen from Figure 1 that as the molar ratio of the second polymer in the copolyester decreases, the peak in the DSC graph shifts to the high temperature direction, and the adjustable temperature range is 20-60°C.

Next, please refer to Figure 2. Figure 2 is a thermogravimetric analysis (TGA) diagram of the copolyester provided by one of the embodiments of the present invention. It can be seen from FIG. 2 that the copolyesters including the first copolymer and the second copolymer in different ratios have similar TGA curves. Figures 3 to 5 are respectively micro-differential scanning thermal analysis diagrams of copolyester fibers provided by different embodiments of the present invention. Please also refer to Table 1 below. Table 1 below lists the ratios between the polycaprolactone used in the raw materials of different copolyester fibers and the matrix material (polylactic acid is used here), and the correlation measured by DSC analysis data. It can be seen from the results in Table 1 that when the ratio between PLA and PCL is about 1:9, the copolyester has the best enthalpy value.

Next, refer to Figure 6. Fig. 6 is a photograph of a copolyester fiber provided by an embodiment of the present invention and its infrared analysis diagram. Fig. 6(a) shows a photograph of the copolyester fiber made in Example 6, and Fig. 6(b) shows an infrared analysis chart of the copolyester fiber made in Example 6. Please also refer to Table 2 below. Example 6 is a copolyester fiber with directional change properties made by using a blend of PLA/PCL of 8/2. Comparative Example 1 is a copolyester fiber made of a material that only contains PLA as a matrix material without first kneading PCL and copolyester. It can be seen from Table 2 that this The copolyester fibers manufactured in the Ming examples obviously have better properties.

[Feasible effects of the embodiment]

In summary, the beneficial effect of the present invention is that the copolyester, the blend containing the copolyester, and the method for manufacturing the copolyester fiber using the blend provided by the embodiments of the present invention are achieved by adjusting and controlling the copolyester. The ratio of different polymers in the polymer, as well as the selection of appropriate content of polycaprolactone and appropriate content and type of matrix materials and other technical characteristics, make the copolyester fiber made with good characteristics and suitable for functional clothing products in.

In detail, the blend provided by the present invention includes a copolyester with dual melting point properties, and is a polyester masterbatch that can be adjusted and has a high enthalpy value. The copolyester fiber produced by using it has a phase change nature. For example, the copolyester fiber of the present invention can absorb latent heat during the transition between the solid phase and the solid phase while maintaining its own temperature. Therefore, it can be used as a heat storage and temperature adjustment functional fiber and has a wide range of applications.

In addition, the method for manufacturing copolyester fibers provided by the embodiments of the present invention includes first kneading the copolyester and polycaprolactone in a specific ratio, and then mixing the blended polymer formed after the aforementioned kneading with a supporting function. Base materials such as polylactic acid are mixed to greatly improve the copolyester Spinnability of fiber.

Although the embodiments of the present invention are disclosed in the above-mentioned more detailed manner, those with ordinary knowledge in the technical field can understand that various modifications of the present invention can be made without departing from the scope of the present invention defined in the appended patent application. . Therefore, further modifications of the examples of the present invention will not deviate from the technology of the present invention.

Claims (15)

A copolyester, which is synthesized by the copolymerization reaction of a monomer composition, the monomer composition includes adipic acid, itaconic acid and butanediol, wherein, in the copolyester, a A first polymer formed by copolymerization of acid and butanediol and a second polymer formed by copolymerization of itaconic acid and butanediol are bonded to each other by ester bonds, and the first polymer and the first polymer are The molar ratio of the two polymers is in the range of 90:10 to 50:50. The copolyester according to claim 1, which has an intrinsic viscosity in the range of 0.7 g/dL to 1.2 g/dL and a melting point in the range of 20°C to 60°C. The copolyester according to claim 1, which has a number average molecular weight ranging from 20,000 g/mole to 35,000 g/mole. A blend comprising a polymer blend comprising 5 to 50% by weight of the copolyester according to claim 1 and 50 to 95% by weight of polycaprolactone. The blend according to claim 4, wherein the polymer blend has an intrinsic viscosity in the range of 0.6 g/dL to 0.8 g/dL. The blend according to claim 4, which further comprises a matrix material, and the content of the polymer blend is 10 to 30% by weight, and the content of the matrix material is 70 to 90% by weight. The blend according to claim 6, wherein the matrix material is polylactic acid, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene terephthalate Diester (PHT) or its mixture. The blend according to claim 6, which has a number average molecular weight ranging from 30,000 g/mol to 50,000 g/mol, a first melting point ranging from 30°C to 40°C, and a first melting point between 140 A second melting point in the range of ℃ to 160℃, and in the range of 310℃ to 340℃ Thermal cracking temperature within. A method of manufacturing copolyester fiber, which includes: A monomer composition is used for copolymerization to synthesize a copolyester, wherein the monomer composition includes adipic acid, itaconic acid and butanediol, wherein, in the copolyester, adipic acid and A first polymer formed by copolymerization of butanediol and a second polymer formed by copolymerization of itaconic acid and butanediol are bonded to each other by ester bonds, and the first polymer and the second polymer The molar ratio of objects is in the range of 90:10 to 50:50; Kneading the copolyester and polycaprolactone together to form a polymer blend; and The blended polymer and a matrix material are mixed together to form a blend. The method for manufacturing a copolyester fiber according to claim 9, further comprising, after forming the polyester pellets, spinning the polyester pellets to obtain a polyester fiber. The method for manufacturing a copolyester fiber according to claim 9, wherein the copolyester has an intrinsic viscosity in the range of 0.7 g/dL to 1.2 g/dL and a viscosity in the range of 20°C to 60°C Melting point. The method for producing a copolyester fiber according to claim 9, wherein the copolyester has a number average molecular weight of 20,000 g/mole to 35,000 g/mole. The method for producing a copolyester fiber according to claim 9, wherein, in the step of kneading the copolyester and polycaprolactone together to form the polymer blend, the polymer blend includes 5 to 50% by weight of the copolyester as described in claim 1 and 50 to 95% by weight of polycaprolactone. The method for producing a copolyester fiber according to claim 9, wherein, in the step of kneading the blend and the matrix material together to form the blend, the blended polymer The content of is 10 to 30% by weight, and the content of the matrix material is 70 to 90% by weight. The method for manufacturing copolyester fiber according to claim 9, wherein the matrix material is polylactic acid, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly Hexylene terephthalate (PHT) or its mixture.

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