CN109929115A - Polyester block copolymer, the production method of polyester block copolymer and polyester fiber - Google Patents

Abstract

The present invention relates to polyester block copolymer, the production method of polyester block copolymer and polyester fibers.The present invention provides a kind of production method of polyester block copolymer comprising makes polyethylene terephthalate and polyethylene naphthalate combined polymerization to form polyester block copolymer in the presence of a catalyst.Catalyst is the compound as composed by cobalt, chromium, manganese and antimony.The molecular weight of poly- polyethylene terephthalate is 19000g/mol~21000g/mol.The molecular weight of polyethylene naphthalate is 18000g/mol~24000g/mol.Thus polyester fiber manufactured by polyester block copolymer has tensile elasticity and recovery characteristic, and tensile elasticity and recovery characteristic can regulate and control easily by the molar ratio for adjusting poly- polyethylene terephthalate and polyethylene naphthalate, therefore the application of polyester fiber can extensively meet needed for miscellaneous product.

Description

Polyester block copolymer, method for producing polyester block copolymer and polyester fiber

technical field

The present invention relates to a polyester block copolymer, a method for producing the polyester block copolymer, and a polyester fiber. In particular, the present invention relates to a polyester block copolymer formed by copolymerizing polyethylene terephthalate and polyethylene naphthalate, a method for producing the same, and a polyester containing the polyester block copolymer fiber.

Background technique

Since the advent of polyester fiber, it can be widely used in various fabrics due to its high strength, good elasticity, strong wrinkle resistance, easy dyeing and low cost. However, polyester fibers containing only a single type of monomer have fixed properties and cannot be easily adjusted, and cannot meet the requirements of various products.

In view of the above, in order to further expand the applicability of polyester fibers, it is urgent to develop other types of polyesters to make polyester fibers to meet the needs of various products.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a polyester block copolymer to produce polyester fibers that meet the needs of various products.

The present disclosure provides a method for fabricating a polyester block copolymer, which includes preparing polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) in the presence of a catalyst. Copolymerization to form a polyester block copolymer, wherein the catalyst is a composite composed of cobalt, chromium, manganese and antimony, and the molecular weight of polyethylene phthalate is 19000g/mol～21000g/mol, polyethylene naphthalate The molecular weight of ethylene formate is 18000g/mol～24000g/mol.

In some embodiments, the concentration of catalyst is in the range of 200 ppm to 1000 ppm.

In some embodiments, the polyethylene naphthalate is 2-10 mole parts, and the polyethylene terephthalate is 90-98 mole parts.

In some embodiments, the intrinsic viscosity of polyethylene naphthalate is in the range of 0.6 g/dL to 0.7 g/dL, and the intrinsic viscosity of polyethylene terephthalate is in the range of 0.6 g/dL ~0.7 g/dL range.

The present disclosure provides a polyester block copolymer, which is formed by copolymerizing polyethylene terephthalate and polyethylene naphthalate, wherein the polyethylene terephthalate is 90-98 The molar part has a molecular weight of 19000 g/mol to 21000 g/mol, and the polyethylene naphthalate is 2 to 10 molar parts and has a molecular weight of 18000 g/mol to 24000 g/mol.

In some embodiments, the polyester block copolymer has an intrinsic viscosity in the range of 0.5 g/dL to 0.7 g/dL.

In some embodiments, the polyester block copolymer has a melting point in the range of 220°C to 260°C.

The present disclosure provides a polyester fiber, which includes a polyester block copolymer, wherein the polyester block copolymer is copolymerized by polyethylene terephthalate and polyethylene naphthalate, wherein the polyethylene terephthalate and polyethylene naphthalate are copolymerized. Ethylene terephthalate is 90 to 98 parts by mole and has a molecular weight of 19000 g/mol to 21000 g/mol, and polyethylene naphthalate is 2 to 10 parts by mole and has a molecular weight of 18000 g/mol to 24000 g/mol.

In some embodiments, the tensile recovery of the polyester fibers is in the range of 50% to 100%.

In some embodiments, the fiber fineness of the polyester fibers is in the range of 3.17 to 3.73 dtex.

Compared with the prior art, the advantages of the present invention are: the present invention will not substantially destroy or reorganize the respective molecular forms of polyethylene terephthalate or polyethylene naphthalate. The two are directly copolymerized to form a polyester block copolymer; and can be regulated by adjusting the molar ratio of polyethylene phthalate and polyethylene naphthalate used to synthesize the polyester block copolymer The obtained polyester fiber has properties such as stretch recovery, so the polyester fiber has wide application and can meet the needs of various products.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further description of the invention as claimed.

Description of drawings

The above and other aspects, features and other advantages of the present invention will be more clearly understood with reference to the description and accompanying drawings, wherein:

1 shows the test results of tensile recovery of polyester fibers of comparative examples and some embodiments of the present disclosure;

Among them, the symbol description:

110, 120, 130, 140, 150, 160: Curves.

Detailed ways

The following disclosure provides many different embodiments or examples for implementing different features of the invention. The composition and arrangement of specific examples are described below to simplify the present disclosure. Of course these are just examples and not intended to be limiting.

In order to solve the problems described in the prior art, the present disclosure provides a polyester block copolymer and a method for making the same. Polyester block copolymers are copolymerized from polyethylene terephthalate and polyethylene naphthalate. The preparation method of the polyester block copolymer includes the following operations: in the presence of a catalyst, using polyethylene terephthalate and polyethylene naphthalate as reactants to form a polyester block copolymer by copolymerization. In detail, after the copolymerization, the polyethylene terephthalate segment and the polyethylene naphthalate segment are randomly arranged and bound to each other by ester bonds to form a polyester block copolymer, and this Polyester block copolymers are random block copolymers. It should be noted that the above-mentioned copolymerization reaction does not substantially destroy or reorganize the molecular forms of polyethylene terephthalate or polyethylene naphthalate, but directly copolymerize the two to form Polyester block copolymer. In other words, in the above polyester block copolymer, the molecular weight of the polyethylene terephthalate block is substantially the same as the molecular weight of the polyethylene terephthalate before the copolymerization reaction, and the polyethylene naphthalate The molecular weight of the ethylene formate block is substantially the same as the molecular weight of the polyethylene naphthalate before the copolymerization reaction.

The molecular weight of polyethylene naphthalate is 18000g/mol～24000g/mol. In some embodiments, the intrinsic viscosity of the polyethylene naphthalate is in the range of 0.6 g/dL to 0.7 g/dL. Polyethylene naphthalate is obtained by copolymerizing p-naphthalene dicarboxylic acid and ethylene glycol. By adjusting the molar ratio of the two, the molecular weight and intrinsic viscosity of polyethylene naphthalate can be regulated.

The molecular weight of polyethylene phthalate is 19,000 g/mol to 21,000 g/mol. In some embodiments, the intrinsic viscosity of the polyethylene terephthalate is in the range of 0.6 g/dL to 0.7 g/dL. Polyethylene phthalate is copolymerized by terephthalic acid and ethylene glycol. By adjusting the molar ratio of the two, the molecular weight and intrinsic viscosity of polyethylene phthalate can be adjusted.

In some embodiments, the polyethylene naphthalate is 2-10 mole parts, and the polyethylene terephthalate is 90-98 mole parts. For example, polyethylene naphthalate is 3, 4, 5, 6, 7, 8 or 9 mole parts and polyethylene terephthalate is 91, 92, 93, 94, 95, 96 or 97 moles.

In some embodiments, the polyester block copolymer has an intrinsic viscosity in the range of 0.5 g/dL to 0.7 g/dL. In some embodiments, the polyester block copolymer has a melting point in the range of 220°C to 260°C.

The catalyst used in the reaction process is a composite composed of cobalt, chromium, manganese and antimony, and the content of each element in the catalyst is, for example: 0.1-0.5 parts by weight of cobalt; 0.1-0.5 parts by weight of chromium; 0.1-0.5 parts by weight parts by weight of manganese; and 1 part by weight of antimony, that is, the weight ratio of cobalt:chromium:manganese:antimony is 0.1-0.5:0.1-0.5:0.1-0.5:1. In some embodiments, the concentration of catalyst is in the range of 200 ppm to 1000 ppm. For example, the concentration of catalyst is 300, 400, 500, 600, 700, 800 or 900 ppm.

The aforementioned polyester block copolymer has spinnability, therefore, the present disclosure provides a polyester fiber comprising the aforementioned polyester block copolymer. For the description of the polyester block copolymer, please refer to the foregoing description, which will not be repeated here.

In some embodiments, the tensile recovery of the polyester fibers is in the range of 50% to 100%. In some embodiments, the fiber fineness of the polyester fibers is in the range of 3.17 to 3.73 dtex. In some embodiments, the strength of the polyester fibers is in the range of 1.6 g/den to 1.9 g/den. In some embodiments, the polyester fibers have an elongation in the range of 120% to 145%.

Notably, polyester fibers containing the aforementioned polyester block copolymers have stretch recovery properties. This may be due to the high degree of physical entanglement of the polyethylene phthalate segment and the polyethylene naphthalate segment in the polyester block copolymer. The tensile recovery of polyester fibers can be regulated by adjusting the molar ratio of polyethylene phthalate and polyethylene naphthalate used to synthesize the polyester block copolymer.

The following examples are intended to describe specific aspects of the present invention in detail and to enable those skilled in the art to which the present invention pertains to practice the present invention. However, the following examples should not be used to limit the present invention.

Experimental Example 1: Synthesis of Polyester Block Copolymer and Properties Test

In this experimental example, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) were copolymerized to form a polyester block copolymer. In Examples 1 to 5, polyethylene terephthalate and polyethylene naphthalate in different mole fractions were used as reactants. The molecular weight of polyethylene terephthalate is 19,000 g/mol to 21,000 g/mol. The molecular weight of polyethylene naphthalate is 18000g/mol～24000g/mol. The reactants used in each example and the intrinsic viscosity and melting point of the resulting polyester block copolymer are shown in Table 1 below.

Table I

Experimental Example 2: Spinning Test

In this experimental example, the polyester block copolymers of Examples 1 to 5 were respectively prepared into polyester fibers by a spinning process, and then the physical properties of the polyester fibers were measured. The polyester fiber of this experimental example is a pre-oriented yarn (POY), and the fiber specification is 120d/36f. The take-up speed of the spinning process was 2400 m/min. The physical properties of polyester fibers are shown in Table 2 below.

Table II

It can be seen from Table 2 that the polyester fibers prepared from the polyester block copolymers of Examples 1 to 5 respectively have good strength.

Next, the physical properties such as tensile recovery and elongation of the polyester fibers prepared from the polyester block copolymers of Examples 1 to 5 were further tested. The test results are shown in Table 3 below.

The tensile recovery rate was measured using a dynamic mechanical analyzer (DMA). The model of DMA is Q800, and the manufacturer that provides DMA is American Business Wurster (TA).

The measurement method of the tensile recovery rate of polyester fibers is as follows: first, the temperature of the test piece of the fiber to be tested is raised to 150°C, and the temperature is maintained for 5 minutes. Next, stretch the test piece of the fiber to be tested with a tensile force of 50 mN for 15 minutes and then release it. The calculation method of the tensile recovery rate is as follows: (deformed length after stretching−recovery deformation length after stretching)/deformed length after stretching×100%.

Please refer to FIG. 1 for the test results of the tensile recovery rate of the polyester fibers of Examples 1 to 5. In addition, a polyester fiber spun only from polyethylene terephthalate is provided here as a comparative example for comparison, which is a pre-oriented yarn with a fiber specification of 120d/36f. The take-up speed of the spinning process was 2400 m/min. FIG. 1 shows the test results of the tensile recovery rate of polyester fibers of Comparative Example and Examples 1-5. The vertical axis is the tensile recovery rate, and the horizontal axis is the time after releasing the test piece of the fiber to be tested. The curve 110 is the test result of the polyester fiber of the comparative example; the curve 120 is the test result of the polyester fiber of the first embodiment; the curve 130 is the test result of the polyester fiber of the second embodiment; the curve 140 is the test result of the polyester fiber of the third embodiment The test results of the fibers; the curve 150 is the test results of the polyester fibers of the fourth embodiment; the curve 160 is the test results of the polyester fibers of the fifth embodiment. It can be seen from FIG. 1 that, at different times, the tensile recovery rates of the polyester fibers of Examples 1 to 5 are higher than those of the polyester fibers of the comparative example, that is, the tensile recovery rates of Examples 1 to 5 are higher than those of the polyester fibers of the Comparative Example. The comparative example has better tensile recovery rate. The following Table 3 only lists the tensile recovery rates after releasing the test pieces of the fibers to be tested in Examples 1 to 5 for 3 minutes and 15 minutes.

Table 3

According to the aforementioned Table 1, in Example 1, the polyethylene naphthalate used for synthesizing the polyester block copolymer has the least content; in Example 5, the polyethylene naphthalate used for synthesizing the polyester block copolymer The highest content of ethylene diformate. Please refer to Table 3 again to know that when the content of polyethylene naphthalate used to form the polyester block copolymer is more, the tensile recovery rate of the polyester fiber formed by the polyester block copolymer is higher. And the tensile recovery rate will also increase, which also means that the polyester fiber is less prone to deformation and has higher rigidity. In addition, Table 3 illustrates that the tensile recovery and elongation of the polyester fibers of the present disclosure can be adjusted by changing the molar ratio of polyethylene terephthalate and polyethylene naphthalate.

To sum up, the present disclosure is based on the polyethylene terephthalate segment having a molecular weight of 19,000 g/mol to 21,000 g/mol and a polyethylene naphthalate segment having a molecular weight of 18,000 g/mol to 24,000 g/mol. It is copolymerized to form a polyester block copolymer, and polyester fibers produced from the polyester block copolymer have stretch recovery properties. In addition, since the stretch recovery can be easily adjusted by adjusting the molar ratio of polyethylene phthalate and polyethylene naphthalate, the polyester fibers of the present disclosure have wide applicability and can satisfy A wide variety of products are required. For example, the polyester fibers of the present disclosure can be used to make impact resistant protective textiles and improve the comfort of textiles.

Although the present invention has been disclosed as above in embodiments, the above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Anyone skilled in the art, without departing from the spirit and scope of the present invention, can make Various equivalent changes and modifications shall fall within the scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope of the appended claims.

Claims (10)

1. a preparation method of polyester block copolymer, is characterized in that, comprises: The polyester block copolymer is formed by copolymerizing polyethylene terephthalate and polyethylene naphthalate in the presence of a catalyst consisting of cobalt, chromium, manganese and antimony and the molecular weight of the polyethylene phthalate is 19000g/mol～21000g/mol, and the molecular weight of the polyethylene naphthalate is 18000g/mol～24000g/mol. 2 . The method of claim 1 , wherein the concentration of the catalyst is in the range of 200 ppm to 1000 ppm. 3 . 3 . The production method according to claim 1 , wherein the polyethylene naphthalate is 2-10 mole parts, and the polyethylene terephthalate is 90-98 mole parts. 4 . 4. The manufacturing method according to claim 1, wherein the intrinsic viscosity of the polyethylene naphthalate is in the range of 0.6g/dL～0.7g/dL, and the polyethylene terephthalate The intrinsic viscosity of the ester is in the range of 0.6 g/dL to 0.7 g/dL. 5. A polyester block copolymer, characterized in that the polyester block copolymer is formed by copolymerization of polyethylene terephthalate and polyethylene naphthalate, wherein the polyethylene terephthalate is copolymerized. Ethylene terephthalate is 90-98 mole parts and has a molecular weight of 19000g/mol-21000g/mol, and the polyethylene naphthalate is 2-10 mole parts and has 18000g/mol-24000g/mol molecular weight. 6. The polyester block copolymer of claim 5, wherein the polyester block copolymer has an intrinsic viscosity in the range of 0.5 g/dL to 0.7 g/dL. 7. The polyester block copolymer of claim 5, wherein the polyester block copolymer has a melting point in the range of 220°C to 260°C. 8. A polyester fiber, characterized in that it comprises a polyester block copolymer, which is formed by the copolymerization of polyethylene terephthalate and polyethylene naphthalate , wherein the polyethylene terephthalate is 90-98 mole parts and has a molecular weight of 19000g/mol-21000g/mol, and the polyethylene naphthalate is 2-10 mole parts and has 18000g/mol Molecular weight of ~24000 g/mol. 9. The polyester fiber of claim 8, wherein the polyester fiber has a tensile recovery in the range of 50% to 100%. 10. The polyester fiber of claim 8, wherein the fiber fineness of the polyester fiber is in the range of 3.17-3.73 dtex.