CN115477752B

CN115477752B - Polyester amide, polyester amide fiber and preparation method

Info

Publication number: CN115477752B
Application number: CN202110604715.8A
Authority: CN
Inventors: 刘修才; 王学利; 郭娟子; 孙莉娜
Original assignee: Cathay R&D Center Co Ltd; Donghua University; CIBT America Inc
Current assignee: Cathay R&D Center Co Ltd; Donghua University; CIBT America Inc
Priority date: 2021-05-31
Filing date: 2021-05-31
Publication date: 2023-11-17
Anticipated expiration: 2041-05-31
Also published as: CN115477752A

Abstract

The application discloses a polyester amide, a polyester amide fiber and a preparation method thereof. The preparation method of the polyesteramide comprises the step of carrying out polycondensation reaction on the PA56 salt derivative shown in the formula II and ethylene terephthalate. The polyester amide molecular chain prepared by the method has good flexibility and hydrophilicity, and the polyester amide fiber prepared by the polyester amide has good dyeing performance, especially can realize good dyeing effect at a lower temperature, and has high dyeing M rate and low evenness.

Description

Polyester amide, polyester amide fiber and preparation method

Technical Field

The application relates to a polyester amide, a polyester amide fiber and a preparation method thereof.

Background

Polyethylene terephthalate (PET) has benzene rings, high molecular modulus, rigid whole PET molecular chain and good mechanical property and dimensional stability. However, since the crystallinity of the PET macromolecules is high and the PET macromolecules lack hydrophilic groups, the fiber made of PET has poor hygroscopicity and dyeing property, the moisture regain of the fiber is only about 0.4%, and the fabric has poor hand feeling.

The existing method for modifying the moisture absorption of the surrounding polyester fiber at home and abroad mainly comprises blending modification, preparing a fiber section anisotropic structure, surface coating/finishing, copolymerization modification and the like, and the three modification methods respectively have the problems of poor compatibility, small improvement of the moisture absorption, non-lasting modification effect and the like, and have unsatisfactory spinning effect. In addition, due to the poor dyeing performance of PET fibers, in order to achieve a higher dye-uptake, it is often necessary to dye at a higher temperature (e.g. around 130 ℃), whereas high temperature operation is generally dangerous, requires higher dyeing equipment, and wastes energy; and even if dyeing is performed under high temperature conditions, further improvement is required.

Therefore, there is a need to improve the hydrophilicity and flexibility of PET while being able to improve the dyeing properties of PET fibers, especially at low temperature.

Disclosure of Invention

The application aims to overcome the defects of poor hydrophilicity and flexibility of PET and low dye-uptake of PET fibers, especially low dye-uptake under low temperature conditions in the prior art, and provides a polyester amide, a polyester amide fiber and a preparation method thereof. The polyester amide disclosed by the application has higher hydrophilicity and flexibility, and is friendly to fiber spinning equipment; the prepared polyester amide fiber has good dyeing property, can realize better dyeing effect at lower temperature, and has low evenness.

The application solves the technical problems by the following scheme:

the application provides a preparation method of polyesteramide, which comprises the following steps of carrying out polycondensation reaction on PA56 salt derivative shown in a formula II and ethylene terephthalate (BHET) to obtain the polyesteramide; wherein the temperature of the polycondensation reaction is 235-280 ℃.

In the application, the molecular formula of the PA56 salt derivative is C ₁₇ H ₃₀ O ₆ N ₂ The relative molecular mass is 358.

In the present application, the temperature of the polycondensation reaction is preferably 250 to 270 ℃, more preferably 250 to 260 ℃, still more preferably 250 to 255 ℃. Other conditions for the polycondensation reaction may be conventional in the art. The pressure of the polycondensation reaction is generally 50Pa or less. The polycondensation reaction time may be 2.5 to 3.5 hours, preferably 3 to 3.5 hours.

In the present application, the molar ratio of the PA56 salt derivative to the ethylene terephthalate may be conventional in the art, and may be, for example, (0.04 to 0.30): 1, further for example 0.05:1.1, 0.1:1.4, 0.15:1.3 or 0.2:1.2, preferably (0.07 to 0.15): 1, further preferably (0.07 to 0.12): 1, more preferably (0.10 to 0.12): 1.

in the present application, the PA56 salt derivative is commercially available or prepared in a manner conventional in the art. Preferably, the PA56 salt derivative is prepared according to the following steps: reacting PA56 salt with adipic acid;

wherein the molar ratio of the PA56 salt to the adipic acid may be in accordance with conventional molar ratios for reactions in the art, preferably 1: (1 to 1.6), for example, 1:1.4. The PA56 salt is reacted with the adipic acid preferably at a temperature of 145-165 ℃, such as 150 ℃ or 160 ℃. The PA56 salt may be reacted with the adipic acid for a period of time ranging from 10 to 20 hours, preferably from 10 to 18 hours, for example 14 hours.

Wherein the process for the preparation of the polyesteramide generally further comprises a step of separating in step (a) and a step of purifying in step (b).

The steps and conditions for the separation of step (a) and the purification of step (b) may be as conventional in the art. The step of separating may comprise azeotropic distillation to obtain a mixture comprising PA56 salt derivatives. The entrainer used in the azeotropic distillation may comprise xylene and/or trimethylbenzene. The temperature of the azeotropic distillation is 148 ℃ to 160 ℃, for example 150 ℃ or 160 ℃. The azeotropic distillation time is 12 to 20 hours, for example 15 hours or 19 hours. The azeotropic distillation device can adopt an oil-water separation device. Preferably, the reaction of the PA56 salt and the adipic acid side is performed in synchronization with the azeotropic distillation. The volume mass ratio of the entrainer to the PA56 salt can be (6-8): 1 (mL/g), e.g., 7:1 (mL/g).

The step of purifying may include: and mixing the mixture containing the PA56 salt derivative obtained by separation with an alcohol solvent, and performing secondary precipitation to obtain filtrate containing the PA56 salt derivative. The mixing temperature of the mixture comprising the PA56 salt derivative and the alcoholic solvent may be 62-68 ℃, for example 65 ℃. The temperature of the first precipitation in the secondary precipitation may be normal temperature. The temperature of the second precipitation in the secondary precipitation may be 0 to 10 ℃. The alcohol solvent may be ethanol. The number of the purification is preferably 1 to 5, for example 3. Typically, the purification further comprises drying the filtrate containing the PA56 salt derivative. The drying may be by rotary evaporation.

In the present application, the ethylene terephthalate is commercially available or prepared in a manner conventional in the art. Preferably, the ethylene terephthalate is prepared according to the following steps: carrying out esterification reaction on terephthalic acid and ethylene glycol;

wherein, preferably, the molar ratio of terephthalic acid (PTA) to Ethylene Glycol (EG) is 1: (1.2-1.6), e.g., 1:1.4.

Wherein the temperature of the esterification reaction may be 225 to 248 ℃, for example 240 ℃, preferably 230 to 237 ℃. The time of the esterification reaction is preferably 2 to 3 hours.

Wherein, the catalyst of the esterification reaction can be one or more of antimony triacetate, antimony trioxide and ethylene glycol antimony.

In the present application, the polycondensation reaction system may further include additives such as an antioxidant and/or a light stabilizer. The antioxidants may include antioxidants conventional in the art, for example, the antioxidants include one or more of antioxidant 1098, antioxidant 168, diisopropylphenyl diphenylamine, antioxidant N, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, sodium hypophosphite, sodium phenylphosphinate, and trimethyl phosphate. The light stabilizer may include light stabilizers conventional in the art, for example, the light stabilizer includes one or more of zinc oxide, titanium white powder R103, light stabilizer BW-10LD, and ultramarine blue 5008. The addition amount of the antioxidant is 0.001-0.1 wt% of the polyester amide. The addition amount of the light stabilizer is 0.001-5 wt% of the polyesteramide.

In a preferred embodiment of the application, the molar ratio of the PA56 salt derivative to the ethylene terephthalate is (0.10-0.12): 1, the temperature of the polycondensation reaction is 250-255 ℃, the time of the polycondensation reaction is 3-3.5 h, and the pressure of the polycondensation reaction is controlled below 50 Pa.

In a more preferred embodiment of the present application, the molar ratio of the PA56 salt derivative to the ethylene terephthalate is 0.15:1.3, the temperature of the polycondensation reaction is 255 ℃, the time of the polycondensation reaction is 3.5 hours, and the pressure of the polycondensation reaction is controlled to be less than 50 PA.

In the application, the obtained polyesteramide is pre-crystallized according to the conventional mode in the field, for example, the polyesteramide is pre-crystallized for 1 to 3 hours at 132 to 137 ℃, and then dried for 10 to 30 hours at 140 to 147 ℃ by using a vacuum rotary drum to obtain a dried slice, and the dried slice is stored in an aluminum-plastic bag in a sealing way.

The application also provides a polyester amide which is prepared by the preparation method.

In the present application, the viscosity average molecular weight of the polyester amide is preferably 18000 to 22600, more preferably 18070 to 22570, for example 18750, 20120, 22570 or 20470.

In the present application, the crystallinity of the polyesteramide is preferably 24 to 34%, for example 33.97%, 32.73%, 28.97% or 26.88%, more preferably 24 to 29%. The crystallinity test condition can be that the radiation target source is a Cu target, the wavelength is 15.4nm, the voltage is 40kV, and the scanning range is 5-60 degrees.

In the present application, the glass transition temperature (Tg) of the polyesteramide is preferably 45 to 65℃such as 64.5℃59.1℃48.4℃or 46.9℃and more preferably 45 to 49 ℃.

In the present application, the intrinsic viscosity of the polyesteramide is preferably 0.65 to 0.78dL/g, for example 0.67dL/g, 0.71dL/g, 0.78dL/g or 0.72dL/g.

In the present application, the static contact angle of the polyesteramide is preferably 65 to 85 °, for example 82.3 ℃, 77.4 ℃, 73.6 ℃ or 68.1 ℃, more preferably 65 to 74 °.

The application also provides a preparation method of the polyester amide fiber, which comprises the following steps: the polyester amide is prepared into polyester amide fibers.

In the present application, the polyester amide may be prepared into a polyester amide fiber according to a conventional method in the art, for example, by melting and spinning the polyester amide; further, for example, the method further comprises a step of drawing and heat setting. Preferably, the polyester amide is melted and spun in a screw extruder to obtain a pre-oriented yarn, and the pre-oriented yarn is drawn and heat-set to obtain the polyester amide fiber.

The heating mode of the melting can be conventional in the field, for example, a five-zone heating mode by using a spinning screw extruder. In the five-zone heating mode, the temperature of one zone can be 248-255 ℃, such as 250 ℃. The temperature in the second zone may be 270 to 275 ℃, for example 272 ℃. The temperature in the three zones may be 278 to 283 ℃, for example 280 ℃. The temperature in the fourth zone may be 280 to 285 ℃, for example 282 ℃. The temperature in the fifth zone may be 275 to 280 ℃, for example 278 ℃.

Wherein the spinning conditions may be conventional in the art. The temperature of the spinning may be 270-285 ℃, e.g. 278 ℃. The pressure of the spinning process may be 10-15 MPa, for example 12MPa. The spinning speed may be 2500 to 4000m/min, for example 3500m/min.

Wherein the steps and conditions of the draft heat setting may be conventional in the art. The temperature of the drawing heat-set may be 125-135 ℃, for example 130 ℃. The draft heat set may have a draft multiple of 1.2 to 1.7 times, for example 1.5 times.

The application also provides a polyester amide fiber, which is prepared by the preparation method.

The application also provides a polyester amide fiber, wherein the dye-uptake of the polyester amide fiber is more than 80 percent at 100-130 ℃.

In the present application, the dye uptake of the polyester amide fibers at a temperature of 100 to 130℃is more preferably 83 to 99.5%, for example 83.2%, 85.6%, 98.7%, 99.2%, 98.8%, 99.1%, 99.2% or 99.4%. More preferably, the dye uptake at 100℃is 83 to 99.5%. Even more preferably, the dye uptake at 130℃is 98.5 to 99.5%.

In the present application, the dyeing M-ratio of the polyester amide fiber is preferably 99% or more, for example, 99.2%, 99.6% or 99.7%.

In the present application, the polyester amide fiber preferably has a evenness value of 1 to 2%, for example, 1.28% or 1.92%, more preferably 1.28%.

In the present application, preferably, the polyester amide fibers include POY fibers, FDY fibers, or DTY fibers.

In the present application, the polyester amide fiber is preferably produced by the above-mentioned polyester amide fiber production method.

On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the application.

The reagents and materials used in the present application are commercially available.

The application has the positive progress effects that:

1) The polyester amide has low Tg, is easy to dye at the temperature of below 65 ℃ and has good flexibility of a molecular chain.

2) The contact angle of the polyester amide is lower than 90 ℃, and the hydrophilicity is good.

3) The polyester amide fiber has good dyeing performance, and particularly can realize good dyeing effect at a lower temperature; the dyeing M rate is higher.

4) The polyester amide fiber of the application has low unevenness rate.

Drawings

FIG. 1 shows the polyesteramides of comparative example 1 and examples 3 to 6 ¹ H-NMR spectrum.

FIG. 2 is an enlarged view of region A in FIG. 1

Detailed Description

The application is further illustrated by means of the following examples, which are not intended to limit the scope of the application. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.

EXAMPLE 1 preparation of PA56 salt derivatives

The adipic acid is adopted to carry out end capping treatment on the PA56 salt, the reaction formula is as follows, and the molecular formula of the PA56 salt derivative is C ₁₇ H ₃₀ O ₆ N ₂ The relative molecular mass is 358.

a. Mixing PA56 salt, adipic acid and dimethylbenzene, then carrying out reaction, and carrying out azeotropic distillation while carrying out the reaction to remove generated water, thus obtaining a mixture containing the derivative of the PA56 salt; wherein the molar ratio of the PA56 salt to the dibasic acid is 1:1.4, the ratio of the volume of dimethylbenzene to the mass of the PA56 salt is 7:1 (mL/g), the reaction temperature is 160 ℃, the reaction time is 20h, an oil-water separation device is adopted in azeotropic distillation, the azeotropic distillation temperature is 160 ℃, and the azeotropic distillation time is 19h;

b. after the reaction is finished, an alcohol organic solvent (ethanol) is used for purification, and the specific process is as follows: firstly, mixing the reacted mixture with an alcohol organic solvent at the temperature of 65 ℃, cooling to normal temperature, performing first precipitation, precipitating insoluble reactants, filtering to obtain first filtrate, then placing the filtrate into an environment of 0 ℃ for second precipitation, precipitating reactants insoluble in the alcohol organic solvent, and filtering to obtain second filtrate;

c. repeating the step b for three times, and finally, spin-evaporating the filtrate to obtain a product, drying the product, and sealing and preserving the product.

Example 2 preparation of ethylene terephthalate

1mol of PTA and 1.4mol of EG are respectively weighed, and simultaneously the catalyst Sb ₂ O ₃ Putting the mixture into a reaction kettle, wherein the esterification temperature is 240 ℃, and the esterification reaction time is 3 hours, so as to generate ethylene terephthalate;

examples 3 to 6 preparation of polyester amides

The PA56 salt derivative prepared in example 1 and the ethylene terephthalate (BHET) prepared in example 2 are added into a reaction kettle according to the addition amount shown in table 1, and polycondensation reaction is carried out, wherein the reaction temperature in the polycondensation stage is shown in table 1, the polycondensation reaction time is 3.5h, the vacuum degree is controlled below 50PA, and the materials are discharged, granulated and dried after the reaction is finished. Pre-crystallization mode: after pre-crystallization for 1.5h at 135 ℃, drying for 22 hours at 145 ℃ by using a vacuum rotary drum to obtain dried slices, and preserving the dried slices in an aluminum-plastic bag in a sealing way.

TABLE 1

Sample numbering	BHET/mol	PA56 salt derivative/mol	Reaction temperature in polycondensation stage
				Example 3	1.1	0.05	270℃
Examples4	1.4	0.10	260℃
				Example 5	1.3	0.15	255℃
Example 6	1.2	0.20	250℃

Identification data: a Bruker 600 nmr spectrometer was used. The structures of the samples of examples 3-6 were characterized, with the internal standard being Tetramethylsilane (TMS). Weighing 5-10 mg of sample, placing into a sample tube, adding deuterated trifluoroacetic acid (CF) ₃ COOD) reagent is dissolved, after the sample is completely dissolved, the sample tube is put into a probe for testing, ¹ the number of H-NMR scans was 16, and the test results were shown in FIG. 1 and FIG. 2.

The characteristic functional groups in the samples of examples 3 to 6 were analyzed by using a Nicolet 6700 Fourier infrared spectrometer, and the scanning spectrum range was 4000 to 400cm ^-1 Resolution of 4cm ^-1 The number of scans was 10. Detected at 727cm ^-1 Bending vibration peaks of H on the benzene ring appear at the positions; 1718cm ^-1 A stretching vibration peak of-c=o appears at; 873cm ^-1 The telescopic vibration peaks of 2 adjacent H on the benzene ring appear at the position; 1095cm ^-1 And 1244cm ^-1 The stretching vibration peaks of-C-O-C and-COO-respectively appear, and the stretching vibration peaks are characteristic absorption peaks on polyester. And 1656cm ^-1 Where an amide absorption band (C=O stretching vibration) occurs, 1534cm ^-1 Where an amide absorption band (flexural vibration of N-H) appears.

From the above detection results, it is inferred that the structural formulas of the polyesteramides of examples 3 to 6 (5 # to 8# in FIG. 1 correspond to examples 3 to 6 respectively) are as follows:

examples 7 and 8 preparation of polyester amides

Example 7

The only difference from example 5 is the preparation method: the temperature of the polycondensation reaction was 235 ℃. Compared with example 5, the polymerization viscosity of most polymers in the system is low at the same time by the reaction at the temperature, the strength of the obtained polyesteramide is low, and the spinning is easy to break, so that the polyesteramide is not suitable for large-scale spinning.

Example 8

The only difference from example 5 is the preparation method: the temperature of the polycondensation reaction was 280 ℃. The polymer molecules are partially crosslinked due to the higher polycondensation temperature.

Example 9 preparation of polyester amide fibers

Transferring the products stored in examples 3 to 8 and comparative example 1 to a spinning machine, and heating the raw materials to a molten state by using a screw extruder; accurately metering by a metering pump, extruding from a spinneret orifice of a spinneret plate to form the pre-oriented yarn, namely the polyester amide POY fiber. Wherein, the spinning screw extruder adopts five-zone heating, the first zone temperature is 250 ℃, the second zone temperature is 272 ℃, the third zone temperature is 280 ℃, the fourth zone temperature is 282 ℃, the fifth zone temperature is 278 ℃, the spinning box temperature is 278 ℃, the pressure of a spinning component is 12MPa, and the spinning speed is 3500m/min. And then carrying out drafting heat setting on the obtained polyester amide POY fiber at 130 ℃ with the drafting multiple of 1.5 times to obtain the polyester amide FDY fiber.

Comparative example 1 preparation of PET

And (3) carrying out polycondensation reaction on the BHET prepared in the example 2, controlling the reaction temperature at 275 ℃ and the vacuum degree below 50Pa in the polycondensation stage, discharging, granulating and drying after the reaction is finished, thus obtaining the PET. The pre-crystallization was performed in the same manner as in the previous examples.

Identification data: the test was carried out in the same manner as in examples 3 to 6, and it was found from the maps shown in FIG. 1 and FIG. 2 that the structural formula of PET (0 # in FIG. 1) in comparative example 1 was identical to the structural formula of the conventional PET.

Effect example 1

The polyester amides of examples 3 to 6 and comparative example 1 were laminated with PET at 220 to 260℃and a film thickness of about 1mm, and the laminated films were subjected to the following test:

(1) X-ray diffraction (XRD) testing

The crystallization performance of the polymer is studied by adopting a D/max-2550VB+/PC X-ray diffractometer aiming at the phenomenon that the density of the polymer is uneven. The experiment was performed at room temperature, the sample was first vacuum dried in a vacuum drying oven at 80 ℃ for 2 hours, the radiation target source was a Cu target, the wavelength was 15.4nm, the voltage was 40kV, the scan range was 5 ° to 60 °, and the WAXD data tested are shown in table 2.

TABLE 2

Sample numbering	Crystallinity/%
		Comparative example 1	44.20
Example 3	33.97
		Example 4	32.73
Example 5	28.97
		Example 6	26.88

As is clear from Table 2, the crystallinity of the polyesteramides of examples 3 to 6 of the application is between 24.09% and 33.97%, and the crystallinity of the polyesteramide gradually decreases with increasing addition of the modifying monomer, and the amorphous region increases, which is advantageous for dyeing with disperse dyes.

(2) Differential Scanning Calorimeter (DSC) test

A DSC250 differential scanning calorimeter was used. The temperature was raised from room temperature to 300℃at a rate of 20℃per minute, then cooled to 0℃at a rate of 20℃per minute, and then raised from 0℃to 300℃at a rate of 10℃per minute, to give a DSC curve, nitrogen protection, and the test results are shown in Table 3.

TABLE 3 Table 3

Sample numbering	T _g /℃
		Comparative example 1	77.8
Example 3	64.5
		Example 4	59.1
Example 5	48.4
		Example 6	46.9

As can be seen from Table 3, the Tg of the polyesteramides of examples 3 to 6 of the application are lower than the Tg of comparative example 1; the Tg is greatly influenced by the flexibility of the molecular chain, and the better the flexibility of the molecular chain is, the lower the Tg is, so that the low-temperature dyeing is facilitated.

(3) Thermogravimetric analysis (TGA) test

TG4000 thermogravimetry was used. 5-10 mg of the sample is weighed and placed into a crucible, the heating rate is 20 ℃/min, the heating range is 30-700 ℃, the nitrogen is protected, and the test result is shown in Table 4.

TABLE 4 Table 4

As can be seen from Table 4, the polyester amide of examples 3 to 6 of the present application has an initial degradation temperature of 386 to 404℃and a maximum weight loss rate temperature of 424 to 435℃which is far higher than the spinning temperature (about 200 ℃).

(4) Intrinsic viscosity test

The method is carried out according to the national standard GB/T14190-2008 fiber grade polyester chip test method, the capillary diameter of the used black-bone viscometer is 0.8mm, phenol and tetrachloroethane are mixed according to the mass ratio of 1:1 during the test, and the sample is dissolved to prepare a solution with the concentration of 0.005 g/mL. Placing the solvent and each solution to be tested in a constant temperature bath at 25+/-0.1 ℃ for 10min, observing and recording the time for the solvent and each solution to be tested to flow through two scale marks, testing each sample three times, measuring the time error of the former and later times within 0.2s, taking the average value of the three tests, and finally carrying out intrinsic viscosity [ eta ] according to formulas (1-1) and (1-2)]Calculating the viscosity average molecular weight M of the corresponding polymer according to the formula (1-3) _η 。

Wherein: [ eta ]]Is the intrinsic viscosity, unit dL/g; η (eta) _r Is the relative viscosity; η (eta) ₀ Is the viscosity of the pure solvent; η (eta) _sp Is the specific viscosity; t is t ₀ Solvent run-off time in s; t is the solution outflow time in s; c is the solvent concentration in g/mL.

[η]＝KM _η ^α (1-3)

Wherein: m is M _η Is a viscosity average molecular weight; the proportionality constant K is 2.1X10 ^-4 The method comprises the steps of carrying out a first treatment on the surface of the The expansion factor α is 0.82.

TABLE 5

As is clear from Table 5, the intrinsic viscosity of the polyesteramides prepared in examples 3 to 6 of the application was between 0.65 and 0.78dL/g, and the corresponding viscosity average molecular weight was between 18070 and 22570, and it was possible to achieve the spinnability grade of the polyester-based fibers.

(5) Static contact angle test

Kino SL200B dynamic/static contact angle goniometer (Keno industries, inc. of U.S.A.) was used. Samples were adhered to the middle of the slide with double sided tape, test face up, sample size 40mm x 5mm, static contact angle of test samples, 5 sites per sample, and average.

The test results were as follows:

the static contact angle of PET of comparative example 1 was 91.2℃and the static contact angles of the samples of examples 3 to 6 were 82.3℃77.4℃73.6℃and 68.1℃respectively, were greatly reduced compared with the static contact angle of pure PET, and gradually decreased with increasing addition of the modifying monomer, and the polymer was changed from hydrophobic to hydrophilic.

Effect example 2

The polyester amide fibers prepared in example 9 (prepared using the polyester amides of examples 3 to 6 and example 8) were subjected to dye uptake test, dyeing M-rate, and evenness test, and the test results are shown in Table 6.

(1) The method for measuring the dye uptake comprises the following steps: the change in dye liquor concentration before and after dyeing was measured with a spectrophotometer. Dye uptake (%) = (A0-At)/A0 x 100%; wherein A0 is the absorbance value of the characteristic absorption peak of the dye before treatment, and At is the absorbance of the dye At the treatment time t.

As can be seen from Table 6, the dye-uptake of the polyester-amide fibers prepared by using the polyester-amide of examples 3 to 6 is above 80%, even above 99%, which is far higher than that of comparative example 1; the dye-uptake at 130 ℃ is also above 98%, which is still higher than that of comparative example 1, that is to say, the polyester amide fiber of the application not only can ensure the dye-uptake under high temperature, but also can obviously improve the dye-uptake under lower temperature.

(2) Dyeing M rate

The dyeing uniformity of the polyamide fiber prepared by the preparation method is measured by a dyeing uniformity method (ASTMZ 7667-1999), and the M rate is measured by a 5-level standard judgment method. M ratio= (number of fibers with dyeing uniformity of no less than 4.5 grade)/total number of all dyed fibers) ×100%.

As is clear from Table 6, the polyester-amide fibers prepared by using the polyester-amide of examples 3 to 6 all had a dyeing M ratio of 99% or more and a high dyeing uniformity.

TABLE 6

Sample numbering	Dye uptake/%	Dye uptake/%	Dyeing M Rate/%
				Comparative example 1	18.7	96.2	98.5
Example 3	83.2	98.8	99.0
				Example 4	85.6	99.1	99.2
Example 5	98.7	99.6	99.7
				Example 6	99.2	99.4	99.0

(3) And testing the evenness unevenness rate.

The evenness rate: the measurement was carried out according to the method of GB/T14346-93. The test results are shown in Table 7.

As is clear from Table 7, the polyester-amide fibers prepared by the polyester-amide fibers of examples 5 and 8 of the present application have a evenness of not more than 2% and even about 1.2%, which means that the polyester-amide fibers have a high structural uniformity and a good spinning effect.

TABLE 7

。

Claims

1. The preparation method of the polyesteramide is characterized by comprising the following steps of carrying out polycondensation reaction on a PA56 salt derivative shown in a formula II and ethylene terephthalate, wherein the temperature of the polycondensation reaction is 250-255 ℃; the mole ratio of the PA56 salt derivative to the ethylene terephthalate is (0.6-1): 6, preparing a base material;

2. the process for producing a polyesteramide according to claim 1, wherein the pressure of the polycondensation reaction is 50Pa or less;

and/or the polycondensation reaction time is 2.5-3.5 h;

and/or the molar ratio of the PA56 salt derivative to the ethylene terephthalate is 0.15:1.3 or 0.2:1.2;

and/or, the PA56 salt derivative is prepared according to the following steps: reacting PA56 salt with adipic acid;

and/or, the preparation method of the polyesteramide further comprises the following steps: a step of separating in step (a) and a step of purifying in step (b);

and/or the ethylene terephthalate is prepared according to the following steps: carrying out esterification reaction on terephthalic acid and ethylene glycol;

and/or the polycondensation reaction system further comprises an antioxidant and/or a light stabilizer; the antioxidant comprises one or more of antioxidant 1098, antioxidant 168, diisopropylphenyl diphenylamine, antioxidant N, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, sodium hypophosphite, sodium phenyl hypophosphite and trimethyl phosphate; the light stabilizer comprises one or more of zinc oxide, titanium dioxide R103, light stabilizer BW-10LD and ultramarine 5008; the addition amount of the antioxidant is 0.001-0.1 wt% of the polyesteramide; the addition amount of the light stabilizer is 0.001-5 wt% of the polyesteramide.

3. The process for producing a polyesteramide according to claim 2, wherein the polycondensation reaction is carried out for 3 to 3.5 hours.

4. The process for producing a polyester amide according to claim 1, wherein the molar ratio of the PA56 salt derivative to the ethylene terephthalate is (0.10 to 0.12): 1.

5. the process for producing a polyester amide according to claim 1, wherein the molar ratio of the PA56 salt derivative to the ethylene terephthalate is (0.10 to 0.12): 1, the temperature of the polycondensation reaction is 250-255 ℃, the time of the polycondensation reaction is 3-3.5 h, and the pressure of the polycondensation reaction is controlled below 50 Pa.

6. The process for producing a polyesteramide according to claim 2, wherein the molar ratio of terephthalic acid to ethylene glycol is 1: (1.2-1.6);

and/or, the temperature of the esterification reaction is 225-248 ℃;

and/or the esterification reaction time is 2-3 h;

and/or the catalyst for the esterification reaction comprises one or more of antimony triacetate, antimony trioxide and ethylene glycol antimony.

7. The process for producing a polyesteramide according to claim 6, wherein the molar ratio of terephthalic acid to ethylene glycol is 1:1.4;

and/or the temperature of the esterification reaction is 240 ℃.

8. The process for producing a polyester amide according to claim 6, wherein the temperature of the esterification reaction is 230 to 237 ℃.

9. The process for the preparation of a polyesteramide according to claim 2, wherein the molar ratio of PA56 salt to adipic acid is 1: (1-1.6);

and/or the reaction temperature of the PA56 salt and the adipic acid is 145-165 ℃;

and/or the reaction time of the PA56 salt and the adipic acid is 10-20 h;

and/or, in step (a), the step of separating comprises: azeotropic distillation and separation are carried out to obtain a mixture containing PA56 salt derivatives; the entrainer used for azeotropic distillation comprises dimethylbenzene and/or trimethylbenzene; the volume mass ratio of the entrainer to the PA56 salt is (6-8): 1mL/g, wherein the temperature of azeotropic distillation is 148-160 ℃;

and/or, in the step (b), the purifying step includes: mixing the mixture containing the PA56 salt derivative obtained by separation with an alcohol solvent, and performing secondary precipitation to obtain filtrate containing the PA56 salt derivative; the mixing temperature of the mixture containing the PA56 salt derivative and the alcohol solvent is 62-68 ℃; the temperature of the first precipitation in the secondary precipitation is normal temperature; the temperature of the second precipitation in the secondary precipitation is 0-10 ℃; the alcohol solvent is ethanol.

10. The process for preparing a polyesteramide according to claim 9, wherein the molar ratio of the PA56 salt to the adipic acid is 1:1.4;

and/or the PA56 salt reacts with the adipic acid at a temperature of 150 ℃ or 160 ℃;

and/or the reaction time of the PA56 salt and the adipic acid is 10-18 h.

11. The process for preparing a polyesteramide according to claim 10, wherein the PA56 salt is reacted with the adipic acid for 14 hours.

12. A polyesteramide prepared by the process of any of claims 1 to 11.

13. The polyesteramide of claim 12, wherein the polyesteramide has a viscosity average molecular weight of 18000 to 22600;

and/or the crystallinity of the polyesteramide is 24-34%;

and/or, the glass transition temperature of the polyesteramide is 45-65 ℃;

and/or the intrinsic viscosity of the polyesteramide is 0.65 to 0.78dL/g;

and/or the static contact angle of the polyesteramide is 65-85 degrees.

14. The polyesteramide of claim 13, wherein the polyesteramide has a viscosity average molecular weight of 18070 to 22570;

and/or the polyester amide has a crystallinity of 33.97%, 32.73%, 28.97%, or 26.88%;

and/or the glass transition temperature of the polyesteramide is 64.5 ℃, 59.1 ℃, 48.4 ℃ or 46.9 ℃;

and/or the inherent viscosity of the polyesteramide is 0.67dL/g, 0.71dL/g, 0.78dL/g, or 0.72dL/g;

and/or the static contact angle of the polyesteramide is 82.3 ℃, 77.4 ℃, 73.6 ℃ or 68.1 ℃.

15. The polyesteramide of claim 14, wherein the polyesteramide has a viscosity average molecular weight of 18750, 20120, 22570, or 20470.

16. The polyesteramide of claim 13, wherein the polyesteramide has a crystallinity of 24 to 29%.

17. The polyesteramide of claim 13, wherein the polyesteramide has a glass transition temperature of 45 to 49 ℃.

18. The polyesteramide of claim 13, wherein the polyesteramide has a static contact angle of 65 to 74 °.

19. The preparation method of the polyester amide fiber is characterized by comprising the following steps: polyester amide fibers made from the polyester amide of any of claims 12-18.

20. The method of making a polyester amide fiber according to claim 19 wherein the polyester amide is made in a manner comprising: melting, spinning, drafting and heat setting the polyester amide;

the spinning temperature is 270-285 ℃;

the pressure in the spinning process is 10-15 MPa;

the spinning speed is 2500-4000 m/min;

the temperature of the drafting heat setting is 125-135 ℃;

the draft multiple of the draft heat setting is 1.2-1.7 times.

21. The method for preparing the polyester-amide fiber according to claim 20, wherein the method for preparing the polyester-amide fiber from the polyester-amide comprises the steps of melting and spinning the polyester-amide in a screw extruder to obtain a pre-oriented yarn, and then carrying out drafting heat setting on the pre-oriented yarn to obtain the polyester-amide fiber.

22. The method of making a polyester amide fiber according to claim 20 wherein the spinning temperature is 278 ℃;

the pressure in the spinning process is 12MPa;

the spinning speed is 3500m/min;

the temperature of the drafting heat setting is 130 ℃;

the draft multiple of the draft heat setting is 1.5 times.

23. A polyester-amide fiber, characterized in that it is produced by the process for producing a polyester-amide fiber as claimed in any one of claims 19 to 22.

24. The polyester-amide fiber according to claim 23, wherein the polyester-amide fiber has a dye uptake of 98.7% or more at 100 to 130 ℃.

25. The polyester-amide fiber according to claim 24, wherein the dye-uptake of the polyester-amide fiber at 100 to 130 ℃ is 98.7% to 99.5%.

26. The polyester-amide fiber according to claim 25, wherein the polyester-amide fiber has a dye uptake of 98.7%, 99.2%, 98.8%, 99.1%, 99.2% or 99.4% at 100-130 ℃.

27. The polyester-amide fiber according to claim 25, wherein the dye uptake of the polyester-amide fiber at 100 ℃ is 98.7% to 99.5%.

28. The polyester-amide fiber according to claim 25, wherein the polyester-amide fiber has a dye uptake of 98.7% to 99.5% at 130 ℃.

29. The polyester-amide fiber according to claim 24, wherein the polyester-amide fiber has a dyeing M-ratio of 99% or more.

30. The polyester-amide fiber according to claim 29, wherein the polyester-amide fiber has a dyeing M-ratio of 99.2%, 99.6%, or 99.7%.

31. The polyester-amide fiber according to claim 24, wherein the polyester-amide fiber has a evenness of 1 to 2%.

32. The polyester amide fiber of claim 31, wherein the polyester amide fiber has a evenness of 1.28% or 1.92%.

33. The polyester amide fiber of claim 24, wherein the polyester amide fiber comprises POY fiber, FDY fiber, or DTY fiber.