CN1078221C - Polyether ester amide elastomer and method for producing elastic fiber - Google Patents

Abstract

The invention provides a method for preparing polyether ester amide elastomer and elastic fiber, which comprises heating polyether glycol, diacid and lactam reactant in a dissolving tank respectively, injecting the reactants into a high-efficiency static stirrer through a gear pump after melting, carrying out esterification prepolymerization reaction of the polyether glycol and the diacid and ring-opening prepolymerization reaction of the lactam in the high-efficiency static stirrer, introducing a prepolymerization product obtained from the high-efficiency static stirrer into a film evaporator for high polymerization reaction for 3-30 minutes to obtain the required elastomer, and carrying out melt spinning by using the elastomer as a raw material to produce the polyether ester amide elastic fiber, thereby achieving the effects of improving production capacity and reducing production cost.

Description

Polyether ester amide elastomer and method for producing elastic fiber

The invention relates to a manufacturing method of polyether ester amide elastomer and elastic fiber, especially a method for producing polyether ester amide elastomer by continuous process, and using polyether ester amide elastomer as raw material to produce melt-spun fiber A method for elastic fibers; belonging to the field of methods and technologies for manufacturing artificial fibers.

Polyether-ester amide (Polyether-ester Amide) elastomer is one of the most noticed high-performance thermoplastic elastomers, which is mainly used in advanced sports equipment, electrical appliances and pipes, etc. Mechanical strength, high (low) temperature stability, and excellent formability make it widely used.

At present, the traditional elastic fiber production method is the most famous dry method of DuPont. These production methods must first synthesize polyurethane (PU) elastomers, and then squeeze out the spinning nozzle in the form of a solution, and then use Heated nitrogen blows away the solvent, leaving the elastomer to form elastic fibers; this method involves solvent [such as: dimethyl formamide (dimethyl formamide DMF) or dimethyl acetamide (dimethyl acetamidfe DMAC)] volatilization problem, All cause harm to human body and environment, make it need huge investment on solvent recovery, and then cause the elastic fiber cost that produces according to this kind of method to be too high, be unfavorable for promotion and competition in the market.

In recent years, the technology of producing elastic fiber by melt spinning has been developed in Japan. The main achievements include: Nisshinbo, Kanebo and Kuraray produce elastic fiber by melt spinning of polyurethane (PU), and Teijin and Unitika use polyether ester (PU) to produce elastic fiber. Polyether-ester) elastomer is melt spun to produce elastic fiber, which is different from DuPont's dry production method. The process of producing elastic fiber by melting method has no problem of solvent recovery, so the production cost is relatively low, but on the other hand Due to the poor heat resistance of PU and polyether ester, its physical properties will be greatly reduced after high-temperature melt spinning. At the same time, the elastic fibers produced will also undergo heating, dyeing and finishing steps in the subsequent processing procedures. , must accept changes such as high temperature and hydrolysis, so the melt spinning method developed by Japan is quite limited in use, and its physical properties are far lower than DuPont's elastic fibers.

The main purpose of the present invention is to provide a kind of manufacturing method of polyether ester amide elastomer (Polyether-ester amide elastomer) with continuous processing technology, polyether glycol (Polyetherglycol), diacid (diacid) and lactam (lactam) ) The reactants are heated in their melting tanks respectively, and after melting, they are respectively injected into a high-efficiency static agitator by a gear pump, and the esterification prepolymerization of polyether diol and diacid is carried out in this high-efficiency static agitator and Lactam ring-opening prepolymerization reaction, and the prepolymerization product obtained from the high-efficiency static agitator is introduced into a thin film evaporator for high polymerization reaction for 3 to 30 minutes. To increase production and reduce manufacturing costs.

Based on the above-mentioned purpose, the production of the continuous polyether ester amide elastomer in the present invention is to pre-polymerize in the tank type, then heat the pre-polymer in a short time with a thin film evaporator, and remove the water with a high vacuum. Unreacted substances and oligomers. The product is cut into pellets through the outlet below the thin film evaporator. The present invention has improved the shortcoming of batch reactor, and its flow process characteristic is as follows:

(1) According to the requirements of the physical properties of the finished product, the ratio of poly(tetramethylene ether) glycol (PTMG for short), ε-caprolactam (CPL for short) and adipic acid (AA for short) can be directly adjusted, and the application is quite easy .

(2) Use a high-efficiency static mixer to mix PTMG, CPL and AA and pre-polymerize by heating. The first-in-first-out mode is adopted. The viscosity of the pre-polymer can be determined by the time it stays in the reactor, and then the quantitative pump will The prepolymer is sent to a thin film evaporator.

(3) Use a thin-film evaporator to heat the prepolymer quickly. When the film is formed, use a high vacuum to quickly remove the water, unreacted substances and oligomers of the esterification reaction, so that the high-polymerization reaction can be carried out in a short time. completed within.

(4) Thin-film evaporator is used for high-polymerization reaction, adopting the first-in-first-out mode, and the viscosity of the product can be controlled according to the residence time.

(5) The product after high polymerization is exported from the lower part of the thin film evaporator, sent to the water tank for cooling through the gear pump, and stretched into strips and pelletized by the pelletizer.

A further object of the present invention is to provide a method for producing polyether ester amide elastic fibers from the elastic body produced in the above-mentioned manner.

Based on the above-mentioned purpose, the production of polyether ester amide elastic fiber related to the present invention is that the polyether ester amide elastic body in the previous process is used as a raw material, heated and melted by a drying extruder, and sent into a two piece (two piece) spinning nozzle. Fibers are produced, oriented at high speed by double intermediate wheels, and then coiled by a coiler; the characteristics of the process flow of the present invention are as follows:

(1) Using polyether ester amide elastomer to make elastic fibers is different from Japanese polyurethane elastic fibers and polyether ester elastic fibers.

(2) The melted elastomer passes through the double-piece spinning nozzle, resulting in double orientation opportunities and increasing the strength of the fiber.

(3) The ratio of the elongation rate of 1 to 4 times by the double middle interrogating wheel causes high fiber orientation, promotes crystallization, and increases the strength of elastic fibers.

(4) Coiling elastic fibers with high-speed spinning (1500-3000 m/min), which is different from low-speed spinning of polyurethane elastic fibers (less than 1500 m/min), which not only increases production and reduces costs, but also due to High speed spinning results in increased strength.

The invention has the advantages of low production cost, high efficiency and good product quality.

The present invention is a kind of manufacture method of producing polyether ester amide elastomer with continuous process, it is characterized in that: polyether glycol (Polyether glycol), diacid (diacid) and lactam (lactam) reactants are melted in it respectively The tank is heated, and after melting, it is injected into a high-efficiency static agitator by a gear pump; the esterification prepolymerization of polyether diol and diacid and the ring-opening prepolymerization of lactam are carried out in the high-efficiency static agitator , and the pre-polymerized product obtained from the high-efficiency static mixer is introduced into a thin-film evaporator for high-polymerization reaction for 3 to 30 minutes.

Among them, polyether diol, diacid and lactam are PTMG, CPL and AA respectively, and the molar ratio of AA to PTMG is 1.01-1.06 to 1, and the molar ratio of CPL to PTMG is 5-20 to 1.

Wherein, the molecular weight of the PTMG used is from 500 g/mole to 3000 g/mole.

Wherein, the high-efficiency static agitator is maintained at a temperature of 200° C. to 260° C., a vacuum of 10 torr to normal pressure, and a residence time of reactants therein for 1 to 4 hours.

Wherein, the thin film evaporator is maintained at a temperature of 240° C. to 280° C., a vacuum of 0.1 torr to 50 torr, and a residence time of reactants therein of 3 to 30 minutes.

A method for producing polyether ester amide elastic fibers using polyether ester amide elastomers as raw materials, characterized in that the polyether ester amide elastic fibers are produced by melt spinning using the polyether ester amide elastomers as raw materials.

Among them, the molten elastomer is extruded through two series of spinning nozzles to be oriented twice.

Wherein, for the two spinning nozzles connected in series, the specification of the first spinning nozzle is L/D=2, and the specification of the second spinning nozzle is L/D=3.

Wherein, the spun yarn coming out from the second spinning port is cooled and extended 1 to 4 times through two intermediate wheels.

Wherein, a high-speed coiler is used to coil the stretched spinning yarn, and the coiling speed is 1500 m/min to 300 m/min.

The present invention has the following drawings:

Fig. 1 is the block diagram of the preparation process of the relevant polyether ester amide elastomer of the present invention.

Fig. 2 is the schematic diagram of the preparation process of the polyether ester amide elastomer of the present invention.

Figure 3 is a schematic diagram of a thin film evaporator.

Fig. 4 is a schematic cross-sectional view of a thin film evaporator on line 4-4 in Fig. 3 .

Fig. 5 is the block diagram of the production process of the relevant polyether ester amide elastic fiber of the present invention.

Fig. 6 is a schematic flow chart of melt spinning.

Fig. 7 is a schematic diagram of the double-piece spinning mouth in Fig. 6 (the ratio is 3:1, and the unit of dimension is mm).

The numbers in the figure are as follows:

1 PTMG melting tank 2 CPL melting tank 3AA melting tank

4 High efficiency static mixer (static mixer) 5 Thin film evaporator

6 motor 7 material inlet 8 heat medium outlet

9 Extraction outlet 10 Blade 11 Heating medium inlet

12 Inner barrel 13 Jacket 14 Gear pump

15 Polymer export 16 Particle drying equipment 17 Extrusion machine

18 Spinning group 19 Cooling air box (Quench duct)

20 Spin tube (Spin tube) 21 The first intermediate wheel 22 The second intermediate wheel

23 Winding machine 24 The first piece of spinning 25 The second piece of spinning mouth

The polymer, English name, and abbreviation of the present invention are as follows: Chinese name English name abbreviations Polyether-bster amide eteher TPAE ε-Caprolalalactic ADIPIC Acid AA polyethyl Poly (Tetra Methylne Ether) Glycou PTMG Polyurethane Pu polyettic ether elastomer Play (Ether-ASTER) Elaster TPEE Dimethyl FormorMamide Dimethyl Acetmide Dmac

Hereby give embodiment and describe in detail as follows in conjunction with accompanying drawing:

The present invention is a manufacturing method of polyether ester amide elastomer and elastic fiber; wherein, the production method of polyether ester amide elastomer is shown in Figure 1 and 2, and is explained as follows according to the production process:

A. Reactant preparation:

First, the main reactants, such as PTMG, CPL and AA, are heated in their melting tanks 1, 2 and 3 respectively, and the molar ratio of AA to PTMG is 1.01-1.06 to 1, and the molar ratio of CPL to PTMG is 5-20 1. The molecular weight of the PTMG used in the present invention is from 500g/mole to 3000g/mole, which can be adjusted according to the physical requirements of the product. At the same time, the stabilizer required for the reaction and the catalyst in the first stage are also metered by the gear pump (not shown in the figure) into the melting tank 1, 2, 3 and fully mixed.

B. Prepolymer Preparation:

After the reactants are melted in the corner melting tanks 1, 2, and 3, they are injected into the high-efficiency static mixer 4 by the gear pump respectively. The injected amount and ratio can be adjusted by the gear pump according to the required physical properties. The principle is from top to bottom. The reactants are heated to start the esterification reaction. At the same time, the water generated by the esterification drives the ring-opening reaction of CPL (caprolactam). After appropriate time control, the prepolymer is gradually formed, and the The lower outlet is injected into the thin film evaporator 5; the temperature used in the pre-polymerization stage is 200°C to 260°C, the vacuum degree is 10torr to normal pressure, and the reactant entry and exit time is 1 to 4 hours.

C. Synthetic preparation of polyether ester amide elastomer:

The pre-polymer is injected into the thin film evaporator 5 through the gear pump, and the catalyst required for the high polymerization reaction is also sent into the thin film evaporator 5 by the micro gear pump (not shown in the figure); as shown in Figure 3 and Figure 4, The structure and basic principle of the thin film evaporator 5 is to send the prepolymer into the inner cylinder 12 from the feed port 7, cooperate with the motor 6 to drive the blades 10 of the array coaxial device to rotate at a high speed, and put the prepolymer between the blades 10 and the inner cylinder. 12 walls are scraped into a thin film, and then the heated heat medium is sent from the heat medium inlet 11 into the jacket 13 to heat the film in the inner cylinder 12 to promote its reaction. At the same time, the inner cylinder 12 is vacuumed to an extremely low pressure state. When the pre-polymer is in a thin film, reduced pressure, and heated state, the pre-polymerized by-products and moisture can be quickly extracted from the outlet 9 of the extract, and a small part of unreacted substances and oligomers are also extracted from the outlet 9 of the extract At this time, the high-polymerization reaction proceeds rapidly, the esterified product produced by pre-polymerization and the CPL ring-opened product are quickly combined, and the viscosity of the product is also rapidly increased at the same time. According to the required physical properties, the pre-polymer can be highly polymerized within 3 to 30 minutes. ; Among them, the temperature used for high polymerization is 240°C to 280°C, the vacuum degree is 0.1torr to 50torr, and the time for the reactants to enter and exit is 3 to 30 minutes.

The chemical reactions involved in the preparation of B and C above can be seen in FIG. 8 . Finally, the product is sent out from the polymer outlet 15, quenched by cooling water, and then pelletized by a pelletizer to complete the preparation of the polyether ester amide elastomer; wherein, the finished product of the polyether ester amide elastomer can be Nylon6 , Nylon11, Nylon12 and Nylon66 and other elastomers.

For the production method of polyether ester amide elastic fiber, please refer to Figures 5, 6, and 7, and the descriptions are as follows according to the production process:

a. Polyether ester amide elastomer drying:

Please refer to Figures 5, 6, and 7. The polyether ester amide elastomer prepared by the previous process is used as a raw material, and it is placed in the material drying equipment 16 for drying. Since the glass transition point of the polyether ester amide elastomer is lower than room temperature, it is therefore When drying, the temperature should not be too high. The temperature setting can be adjusted according to the CPL content of the elastomer itself. At the same time, dry nitrogen is used to assist in taking away the water. The drying time is 24 to 48 hours. After drying, the water Part content should be the most appropriate below 300ppm.

b. Extruder setting:

According to the difference in composition, the melting point of polyether ester amide elastomer is 195°C to 205°C, so the temperature of the extruder 17 is set at 220°C to 240°C, the pressure is set at 160-200kg/cm ² , and the speed is set at 2～50rpm, set according to the spinning specification.

c. Spinning group setting:

The present invention uses a double-piece spinning nozzle group 18 (the output end of the double-piece spinning nozzle group is sequentially connected with a cooling fan 19 and a spinning tube 20), and the specification of the first spinning nozzle 24 is L/D=2 , the specification of the second spinning port 25 is L/D=3, so that the melted elastomer has two chances of orientation to increase the strength.

d. Intermediate wheel speed setting:

The rotational speed ratio of the first intermediate wheel 21 and the second intermediate wheel 22 is 1/1 to 1/3, so as to extend the orientation of the fiber, improve the crystallinity and increase the physical properties of the fiber; wherein the two intermediate wheels 21, 22 The extension ratio is 1 to 4 times.

e. Finished product volume:

Due to the high viscosity and melting point of polyether ester amide elastomer, it is suitable for high-speed spinning, and the actual operation can reach 1500 m/min to 3000 m/min, which can effectively increase the yield and reduce the cost, while the general PU elastomer only It can operate at a low speed (300m/min-700m/min), and its production capacity is quite low; therefore, the elastic fiber produced by the present invention has low cost, and its physical and chemical properties surpass that of PU elastic fiber.

Please refer to Table (1) and Table (2), which respectively list the typical reaction formula and reaction conditions of the present invention, as well as the physical properties of elastomers and elastic fibers.

To sum up, the present invention uses an original continuous process to develop polyether ester amide elastomers, which have stable quality and can be adjusted in diversity, and greatly reduce production costs with high-efficiency production methods; in addition, the present invention uses production Based on the polyether ester amide elastomer, melt-spun elastic fiber has been developed, which not only has excellent quality, low production cost, but also has no environmental problems, and can improve market competitiveness.

Table 1: Typical reaction formula and reaction conditions Feed rate (g/min) The molar ratio of pre-polymerization Film High Polymerization example PTMG (g/mole) PTMG AAA CPL PTMG/AA/CPL Reaction time/temperature/vacuum degree(hour)(℃)(torr) Reaction time/temperature/vacuum degree(hour)(℃)(torr) 1 1000 22.0 3.3 12.4 1/1.03/5 3.5/240/60 10/260/1 2 1000 16.5 2.5 18.7 1/1.03/10 3.5/240/60 10/260/1 3 1000 13.3 2.0 22.4 1/1, 03/15 3.5/240/60 10/260/1 4 1000 11.1 1.7 24.9 1/1.03/20 3.5/240/60 10/260/1 5 1000 33.0 5.0 18.6 1/1.03/5 2.4/240/60 10/260/1 6 1000 24.8 3.7 28.1 1/1.03/10 2.4/240/60 10/260/1 7 1000 19.9 3.0 33.7 1/1.03/15 2.4/240/60 10/260/1 8 1000 16.7 2.6 37.3 1/1.03/20 2.4/240/60 10/260/1 9 2000 24.5 1.9 6.9 1/1.05/5 4/240/40 10/260/1 10 2000 20.2 1.5 11.6 1/1.05/10 4/240/40 10/260/1 11 2000 17.3 1.3 14.7 1/1.05/15 4/240/40 10/260/1 12 2000 15.1 1.1 17.1 1/1.05/20 4/240/40 10/260/1 13 2000 39.2 3.0 11.1 1/1.05/5 2.5/240/40 10/260/1 14 2000 32.3 2.4 18.6 1/1.05/10 2.5/240/40 10/260/1 15 2000 27.7 2.1 23.5 1/1.05/15 2.5/240/40 10/260/1 16 2000 24.2 2.9 26.2 1/1.05/20 2.5/240/40 10/260/1 17 1000 22.0 3.3 12.4 1/1.03/5 3.5/240/60 20/260/1 18 1000 16.5 2.5 18.7 1/1.03/10 3.5/240/60 20/260/1 19 1000 13.3 2.0 22.4 1/1.03/15 3.5/240/60 20/260/1 20 1000 11.1 1.7 24.9 1/1.03/20 3.5/240/60 20/260/1 twenty one 2000 33.0 5.0 18.6 1/1.05/5 4/240/40 20/260/1 twenty two 2000 24.8 3.7 28.1 1/1.05/10 4/240/40 20/260/1 twenty three 2000 19.9 3.0 33.7 1/1.05/15 4/240/40 20/260/1 twenty four 2000 16.7 2.6 37.3 1/1.05/20 4/240/40 20/260/1

Table 2: Physical properties of elastomers and elastic fibers Physical properties of elastomer Physical properties of elastic fiber example Relative viscosity (0.5%) IN O-chlorophenol 25℃ Melting point °C Tensile strengthkg/ ^cm2 Elongation% Danny (4f) Strength g/d Elongation% 100% elongation recovery Silk Relative Viscosity (0.5%) IN O-chlorophenol 25℃ 1 1.93 191 550 632 100 1.10 526 93.9% 1.87 2 2.05 193 587 597 100 1.17 497 94.4% 1.93 3 2.07 199 613 425 100 1.22 354 96.5% 1.94 4 2.13 209 680 320 100 1.36 269 99.5% 1.97 5 1.87 190 510 617 100 1.02 514 93.7% 1.84 6 1.96 191 547 583 100 1.09 486 94.2% 1.89 7 2.03 195 602 410 100 1.20 372 96.6% 1.92 8 2.05 206 632 310 100 1.26 285 99.0% 1.93 9 1.78 183 470 780 100 0.94 650 92.7% 1.73 10 1.81 187 487 653 100 0.97 544 93.4% 1.80 11 1.97 193 503 597 100 1.00 497 93.8% 1.89 12 2.01 195 530 530 100 1.06 441 94.5% 1.91 13 1.70 181 420 760 100 0.84 633 92.5% 1.69 14 1.74 183 450 589 100 0.91 491 93.4% 1.71 15 1.89 185 495 537 100 0.99 448 94.1% 1.78 16 1.97 190 517 495 100 1.03 413 95.1% 1.89 17 1.95 192 560 568 100 1.12 473 95.3% 1.88 18 2.10 194 591 503 100 1.18 419 95.7% 1.95 19 2.13 201 617 410 100 1.23 341 96.8% 1.97 20 2.20 208 695 280 100 1.39 254 99.0% 2.00 twenty one 1.89 187 490 793 100 0.98 660 92.3% 1.85 twenty two 1.93 192 503 701 100 1.01 584 93.2% 1.87 twenty three 2.07 195 523 623 100 1.05 519 93.7% 1.94 twenty four 2.10 199 554 587 100 1.11 490 94.2% 1.96

Polymerization equation of the present invention is as follows: (1) prepolymerization reaction

(1) Esterification reaction

(2) Esterification prepolymerization reaction

(3) Ring-opening reaction of caprolactam

(4) Caprolactam prepolymerization reaction (2) High polymerization reaction

(5) Polyamide reaction

(6) Generation of high-polymerization polyether ester amide segmental copolymer (polyester reaction)

E＋zE→(1＋z)E＋zHO Note: ①[A].[B].[C].[D].[E] are the products of reaction formula (1)(2)(3)(4)(5).

②X.Y.Z is a positive integer.

Claims (10)

1. A method for producing polyether ester amide elastomers with a continuous process, characterized in that: it heats polyether glycol, diacid and lactam reactants in its melting tank respectively, and after melting, it is heated by a gear pump Inject into a high-efficiency static agitator respectively; In this high-efficiency static agitator, carry out the esterification prepolymerization reaction of polyether diol and diacid and the lactam ring-opening prepolymerization reaction, and will from this high-efficiency static agitator The obtained pre-polymerized product is introduced into a thin-film evaporator for high-polymerization reaction for 3-30 minutes. 2. the manufacture method of polyether ester amide elastomer according to claim 1 is characterized in that: wherein polyether diol, diacid and lactam are respectively PTMG, CPL and AA, and the mol ratio of AA to PTMG is 1.01 to 1.06 to 1, and the molar ratio of CPL to PTMG is 5 to 20 to 1. 3. The manufacturing method of polyether ester amide elastomer according to claim 1, characterized in that: the molecular weight of the PTMG used therein is from 500 g/mole to 3000 g/mole. 4. The manufacturing method of polyether ester amide elastomer according to claim 1, characterized in that: wherein the high-efficiency static mixer is maintained at a temperature of 200°C to 260°C, a vacuum of 10torr to normal pressure, and the reaction The residence time of the substance in it is 1 to 4 hours. 5. The manufacturing method of polyether ester amide elastomer according to claim 1, characterized in that: wherein the thin film evaporator is maintained at a temperature of 240°C to 280°C, a vacuum of 0.1torr to 50torr, and the reactants in The residence time therein is from 3 to 30 minutes. 6. A method for producing polyether ester amide elastic fibers using polyether ester amide elastomers as raw materials, characterized in that: using the polyether ester amide elastomers as raw materials, melt spinning produces polyether ester amide elastic fibers fiber. 7. The manufacturing method of polyether ester amide elastic fiber according to claim 6, wherein the melted elastomer is extruded through two spinning nozzles connected in series to be oriented twice. 8. The manufacturing method of polyether ester amide elastic fiber according to claim 6, characterized in that: among the two spinning ports connected in series, the specification of the first spinning port is L/D=2, and the second spinning port is L/D=2. The specification is L/D=3. 9. The manufacturing method of polyether ester amide elastic fiber according to claim 8, characterized in that: wherein the spinning from the second spinning port is cooled and stretched 1-4 times through two intermediate wheels. 10. The manufacturing method of polyether ester amide elastic fiber according to claim 9, characterized in that: wherein a high-speed coiler is used to coil up the stretched spinning, and the coiling rate is 1500 m/min to 300 m /point.

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