TW201839035A - Polyamide and method of preparing the same - Google Patents

Abstract

A polyamide includes the following repeat units: [A]p-,-[B]q-and-[C]r-, wherein A, B and C are repeat units derived from A1, B1 and C1, respectively; wherein m is an integer of 2 to 5, and n is an integer of 2 to 6; p, q and r represent mole percentages (mole%) of A, B and C, respectively; r is in a range from 10 to 99 mole% based on the total mole percentages of p, q and r; and the molar ratio of p to q is in a range from 0.9 to 1.1. A method of preparing the polyamide is also provided.

Description

   Polyfluorene and preparation method thereof   

The embodiments of the present invention relate to polyamidoamine and its preparation method.

Nylon 6 is a polyamine made by caprolactam (CPL) polymerization. It has excellent performance in terms of flexibility, elastic resilience, alkali resistance, abrasion resistance, and UV resistance. Because nylon 6 has the above-mentioned good characteristics, nylon textiles woven by nylon 6 worldwide are widely used in clothing, carpets and other industries.

However, because the polymerized nylon 6 contains too many by-products such as cyclic and low molecular weight compounds, a large amount of hot water is required for extraction, which causes problems such as high cost of separating by-products in the extract and reduced yield of nylon 6.

In order to solve the above problems, the currently known prior art is to add Hexamethylenediamine (HMDA) and pure terephthalic acid (PTA) to nylon 6 to perform the co-existence of "HMDA + PTA + CPL" Polymerization to reduce hot water extractability.

However, the polyamide produced by the above-mentioned technology has a problem of a significant decrease in melting point, which will cause a reduction in mechanical properties and limit the scope of product development and application. Furthermore, in the above-mentioned technology, due to the low mutual solubility of the aromatic PTA and the fatty nylon and the large difference in the reactivity between the terminal functional groups of the two, the PTA reaction is incomplete, resulting in the oligomer of the polyamine product. Causes physical instability and increased variability. In addition, the above technology requires the use of hexamethylene diamine (HMDA) as a comonomer. Due to the low boiling point of hexamethylene diamine (HMDA), it is easy to distill, which results in a limited increase in the molecular weight of the product, and the production of hexamethylene diamine has environmental pollution , Limiting the development of subsequent related technologies and applications.

Therefore, a new polyamine is urgently needed to reduce the extractable rate of hot water, at the same time, it can overcome the problems of lowering the melting point of the product, generating oligomers, and limiting the increase of molecular weight.

An embodiment of the present invention provides a polyamidoamine including the following repeating units:-[A] _p -and-[B] _q -and-[C] _r- , wherein A, B, and C are respectively derived from A1 and B1 , C1 repeat unit;

Where m is an integer of 2-5, and n is an integer of 2-6; p, q, and r represent the mole percentages (mole%) of A, B, and C, respectively, and the total mole numbers of p, q, and r are On the basis, r is 10-99 mole%, and the molar ratio of p to q is 0.9 to 1.1.

An embodiment of the present invention further provides a method for preparing polyamide, comprising: reacting monomer A1 and monomer B1 to obtain a salt; and performing a ring-opening reaction on monomer C1, adding the salt, and Performing a melt polymerization reaction to obtain the polyfluorene;

The polyamine includes the following repeating units:-[A] _p -and-[B] _q -and-[C] _r- , A, B, and C are repeats derived from monomers A1, B1, and C1, respectively. Unit; where m is an integer from 2-5, n is an integer from 2-6; p, q, and r represent the mole percentages (mole%) of A, B, and C, respectively, and the total moles of p, q, and r Based on the number, r is 10-99 mole%, and the molar ratio of p to q is 0.9 to 1.1.

In the embodiment of the present invention, a low carbon number diamine is first reacted with PTA to form a low carbon number aromatic diamine. Since the above aromatic diamine has a higher melting point than hexamethylene diamine (HMDA), it can avoid polyfluorene. The molecular weight increase of the amine product is limited. In addition, the polyamide of the embodiment of the present invention can maintain a high melting point, so as to solve the problem that the melting point is greatly reduced after the nylon 6 copolymerization reaction.

In the preparation method of the present invention, first, a diamine having a carbon number of 2-5 is reacted with pure terephthalic acid (PTA) to obtain an aromatic diamine monomer A1. In an embodiment, as shown in the following formula (1), the aromatic diamine monomer A1 is disaminoethylterephthalamide (BATM), which is composed of Ethylene diamine (EDA) and It is made by pure terephthalic acid (PTA) reaction. It should be noted that the compound used in formula (1) is only an example, but the present invention is not limited thereto.

It is worth noting that, compared with the direct use of low-boiling hexamethylene diamine (HMDA) as a reactant in the prior art, in the preparation method of the present invention, a low carbon number diamine is first reacted with PTA to form an aromatic diamine. Because the aromatic diamine has a high melting point, it can avoid that the reactants are easily distilled out because the boiling point is lower than the temperature of the polymerization reaction, which causes the molecular weight of the polyamine product to be limited. In addition, because the above-mentioned aromatic diamine and fatty nylon have high mutual solubility, and the difference in reactivity between the terminal functional groups of the two is small, the generation of oligomers can be avoided, thereby increasing the stability of the product and reducing variation. Sex. In addition, compared with nylon 6, the addition of the above-mentioned aromatic diamine can suppress the generation of cyclic by-products, and can reduce the extractable rate of hot water and increase the yield of polyamine.

Next, the Lactam having a carbon number of 2-6 is ring-opened and reacted with pure terephthalic acid (PTA) to obtain an aromatic diacid monomer B1. In one embodiment, as shown in the following formula (2), the aromatic diacid monomer B1 is biscarboxylpentylterephthalamide (BCTM), which is ring-opened by caprolactam (CPL) and It is made by pure terephthalic acid (PTA) reaction. It should be noted that the compound used in formula (2) is only an example, but the present invention is not limited thereto.

Furthermore, the above-mentioned aromatic diamine monomer A1 and the aromatic diacid monomer B1 are reacted to obtain a monoamine derivative. In some embodiments, the molar ratio of the aromatic diamine monomer A1 to the aromatic diacid monomer B1 is 0.9 to 1.1. For example, the molar ratio of the aromatic diamine monomer A1 to the aromatic diacid monomer B1 is 1. If the molar ratio of the aromatic diamine monomer A1 to the aromatic diacid monomer B1 is less than 0.9, the amine value of the product is lower than the acid value, and the molecular weight increase is limited. If the molar ratio of the aromatic diamine monomer A1 to the aromatic diacid monomer B1 is greater than 1.1, the amine value of the product will be higher than the acid value, and the molecular weight increase will also be limited.

Furthermore, under a nitrogen environment and a condition of about 95-120 ° C / 1.0-2.1 atmosphere (atm) (for example, about 100 ° C / 2atm), the caprolactam (CPL) monomer C1 is subjected to a ring-opening reaction with water. . Next, the amidamine derivative is added, and a melt polymerization reaction is performed at a temperature of about 180-240 ° C (for example, about 210-240 ° C). In some embodiments, based on the total moles of the aromatic diamine monomer A1, the aromatic diacid monomer B1, and the caprolactam (CPL) monomer C1, the caprolactam (CPL) monomer C1 may be It is 10-99 mole%. For example, the caprolactam (CPL) monomer C1 may be 60-99 mole%. If the content of caprolactam (CPL) monomer C1 is less than 10 mole%, the melting point of the product will be too high, the polymer will quickly agglomerate in the reactor, and it will be difficult to stir and unload the caprolactam (CPL) The content of the monomer C1 is more than 99 mole%, which will cause the difference between the physical properties of the product and the nylon 6 to be small, and the purpose of upgrading will be lost.

Finally, the reaction temperature is controlled at about 250-260 ° C. (for example, about 255 ° C.) and the reaction is performed for about 4-7 hours (for example, about 6 hours) to obtain a polyamine.

The polyfluorene obtained according to the above preparation method includes the following repeating units:-[A] _p -,-[B] _q -and-[C] _r- , wherein A, B, and C are derived from monomers A1 and B1, respectively. , C1 repeat unit;

In some embodiments, monomer A1 is an aromatic diamine, and m is an integer of 2-5; monomer B1 is an aromatic diacid, and n is an integer of 2-6; monomer C1 is caprolactam (CPL ). p, q, and r respectively represent mole percentages (mole%) of A, B, and C. In some embodiments, based on the total moles of p, q, and r, r can be 10-99 mole%, for example : R may be 60-90 mole%, and the molar ratio of p to q may be 0.9 to 1.1, for example, the molar ratio of p to q may be 1.0.

In some embodiments, the polyamide may be a random copolymer; in other embodiments, the polyamide may be an alternating copolymer. For example, the arrangement order of the alternating copolymer may be Is-[A]-[B]-[C]-.

In some embodiments, the molecular weight of polyamide is expressed as relative viscosity (RV). The relative viscosity (RV) of polyamide can be 2.0-3.5, for example: 2.40-2.65. It should be noted that the relative viscosity of polyamide can be adjusted as needed, and is not limited to this range.

In some embodiments, the melting point (Tm) of the polyamide can be from 150 ° C to 310 ° C, for example, from 180 to 310 ° C. If the melting point of polyamide is less than 150 ° C, it will cause the degradation of mechanical properties and limit the scope of product development and application. It is worth noting that the polyamidoamine prepared in the embodiment of the present invention can have a high melting point, and therefore the problem of a significant decrease in melting point after the copolymerization reaction of nylon 6 can be solved.

In some embodiments of the present invention, the amount of hot water extractable of the prepared polyamide is lower than that of general nylon 6, which shows that it can improve the yield of the product, reduce costs, reduce energy consumption, and increase the stability of the product processing process. And reduce its variability.

The following provides examples of the preparation of polyamidoamine of the present invention, and examples and comparative examples are given to illustrate its characteristics.

In the following examples and comparative examples, the melting temperature (Tm) (highest peak) and glass transition temperature (Tg) of the copolymer were measured with a differential scanning calorimeter. The analysis conditions of the relative viscosity (RV) of the copolymer are as follows: 0.50 g of nylon copolymer is placed in an analysis glass bottle, and concentrated sulfuric acid (concentration: 96.0 wt%) is added to make a 50 ml solution, and then the temperature is 25 ° C. Next, a relative viscosity (RV) analysis was performed.

Regarding the measurement and analysis methods of the PTA content (mole%) after the polymerization in the following examples, because the ¹ H NMR absorption peak overlap ratio in the fatty region is high, in order to reduce the calculation error, the spectrum is divided into all aromatic systems And the absorption peak regions of all fat systems. In addition, after the copolymer is reacted, the same method of hot water extraction after the polymerization of nylon 6 is used to obtain the extracted copolymer. After the copolymer was dried, the content (mole%) of PTA in the copolymer was analyzed and calculated by nuclear magnetic resonance spectroscopy ( ¹ H NMR).

In the following Examples and Comparative Examples, nuclear magnetic resonance spectroscopy ⁽¹ H NMR) and infrared spectroscopy analysis of the chemical composition in the hot water extract distillate product after polymerization when the polymerization reaction was found that this hot water extraction They are all components of CPL or low molecular weight nylon 6, and there are no aromatic and ethylenediamine (EDA) or ethylenediamine derivatives. This shows that the addition of the aromatic diamine-based component and is not extracted, so that nuclear magnetic resonance spectroscopy ⁽¹ H NMR) may be fat-based absorption peak (less than 5.0 ppm) of the fatty series relative molar hydrogen minus the number B After the relative molar number of hydrogen of the diamine (EDA), the remaining relative molar number of hydrogen of the fat system is contributed by CPL (repeat unit of nylon 6). Therefore, as shown in formula (1), the molar number (mole%) of ethylenediamine (EDA) is equal to 2 times the molar content of BATM. In addition, the ¹ H NMR absorption peak of the aromatic system is the sum of the mole numbers of BCTM (as shown in formula (2)) and BATM (as shown in formula (1)) (added amount is 1: 1 mole ratio) ; Aromatic ¹ H NMR absorption peak (about 8.5 ppm) divided by 4 is the Mohr number (relative mole number) of aromatic PTA; Fat ¹ H NMR absorption peak (about 1.8-4.2 ppm) divided by After 2 is the carbon mole number (relative mole number) of all fat systems. The carbon mols of all fats are then subtracted from the carbon mols of ethylenediamine (EDA) (the ethylene diamine mols are twice the BATM mols), and the remaining carbon mols are The numbers are all carbon moles (relative moles) of CPL (repeated units of nylon 6, each mole of CPL contains 5 moles of CH ₂ ). Therefore, the above carbon moles are divided by 5, ie The molar number content (relative molar number) of CPL (repeated units of nylon 6) was obtained. In summary, as shown in Table 1, the analysis method for the molar percentage content of PTA after polymerization is mole%) is: "relative molar number content of aromatics" / "relative molar number content of aromatics + The relative molar number content of ethylenediamine + the relative molar number content of CPL (repeating units of nylon 6) "= the molar percentage content (mole%) of PTA in the polymer after the polymerization reaction.

The method of measuring and analyzing the content of PTA after the polymerization reaction in the comparative example is the same as the above, except that the ethylene diamine (EDA) is changed to hexamethylene diamine (HMDA). Among them, the molar number (relative molar number) of aromatic PTA is the same as the molar number (relative molar number) of fatty HMDA, and hexamethylene diamine (HMDA) per molar number contains 6 molar numbers of CH ₂ .

In the following examples, it is "BATM + BCTM + CPL". BATM is composed of "EDA + PTA", so the EDA mole number = 2 times the PTA mole number, and the BCTM is composed of "CPL + PTA". Therefore, the CPL mole number in BCTM = 2 times the PTA mole number. And BATM: BCTM = 1: 1, so after all copolymerization reactions, EDA Moore number = PTA Moore number. In the comparative example, it is “PTA + HMDA + CPL”. In order to have a corresponding comparison with the examples, the amount of HMDA added is equal to the number of PTA. In this way, it is possible to make the composition contained in each copolymer, the PTA (aromatic) mole number of the example = the PTA (aromatic) mole number corresponding to the comparative example, and the EDA mole number of the example = Corresponding to the HMDA mole number of the comparative example.

In addition, the ¹ H NMR absorption peak of the aromatic carbon is different from the calculation basis of the fatty system. Each carbon of the aromatic system is bound to only one hydrogen, and each carbon of the fatty system is bound to two hydrogens. Per mole number PTA aromatic system containing a carbon number of moles of 4 NMR showed ¹ H NMR aromatic system so that an absorption peak (about 8.5ppm) divided by 1 is the number of moles of carbon of the aromatic system PTA, is ^an aromatic system The H NMR absorption peak (about 8.5 ppm) divided by 4 is the mole number of the aromatic PTA. At the same time, each carbon of the fat system is combined with two hydrogens, so the ¹ H NMR absorption peak of the fat system is divided by 2 to obtain the carbon mole number of the fat system. Therefore, the "mole number of carbon" of CPL is 5 times the "mole number" of CPL, and the "mole number of carbon" of aromatic PTA is 4 times the "mole number" of aromatic PTA. Since each CPL contains 5 carbon numbers (carbon moles) as shown by NMR, the carbon number content of the CPL / 5 = the content of the CPL. Similarly, because each EDA contains 2 carbon numbers as shown by NMR, the carbon number content of EDA / 2 = the molar number content of EDA.

    [Preparation Example 1] Preparation method of BATM    

Place 6 grams (0.1 mole) of ethylenediamine (EDA) in a 50 ml reaction bottle, add 2.54 grams (0.01 mole) of Bis 2-Hydroxyethyl Terephthalate (BHET), and then add sodium acetate 0.06 g (0.7% of the reactants). After homogeneous mixing, stirring was started under nitrogen. Then, the reaction temperature was raised to 110 ° C for 24 hours, and a white solid was generated in the reaction for 1 hour. The reaction bottle was cooled to room temperature and then filtered, and the white solid was washed with water and methanol and vacuum-dried at 80 ° C to obtain BATM. Nuclear Magnetic Resonance (NMR) spectral analysis was performed on Compound 1 with the following results: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.5 (4H, s); 4.4-4.3 (4H, m); 4.0 (4H , M). IR (cm ^-1 ): 3308 (NH); 3300-2930 (broadband, OH); 2900; 1640-1650 (amidamine); 1570-800.

    [Preparation Example 2] Preparation method of BCTM    

BCTM is made by reacting pure terephthalic acid (PTA) with caprolactam (CPL). The preparation method can be performed according to the steps described in US2015 / 0344414. BCTM was measured with a differential scanning calorimeter, and it was found that its melting temperature (Tm) was 204 ° C (highest peak); and BCTM was analyzed using nuclear magnetic resonance and infrared spectroscopy. The obtained spectral information was as follows: ¹ H NMR ( D ₂ SO ₄ , ppm): 8.53 (4H, phenyl-1, 4-), 4.26 (4H, aromatic-CON-CH _2- , ACA), 3.52 (4H, aliphatic-CH ₂ -CO _2- , ACA), 1.88-2.37 (12H, aliphatic, ACA). IR (cm ^-1 ): 3308 (NH); 3300-2930 (broadband, OH); 2858; 1725 (carbonyl carbonyl of CO ₂ H); 1640 (fluorenamine); 1570-1350; 1300-800.

    [Preparation Example 3] Synthesis of BATM-BCTM salts    

39.2 g (0.1 mole) of BCTM and 25 g (0.1 mole) of BATM were added to a 1 liter 3-neck reaction flask, followed by the addition of 500 ml of pure water and heating to 90 degrees Celsius and reacting overnight. After cooling down every other day, the reaction solution was filtered, wherein the solid obtained after drying the filtrate to remove water was BATM-BCTM salts. The nuclear magnetic resonance (NMR) spectra of the BATM-BCTM salts were measured, and the results were as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.51 (8H, benzene ring); 3.3 (8H, aromatic amidine Linked to CH ₂ ); 2.8 (CH ₂ next to aliphatic amidine); 2.1 (CH ₂ next to carbonyl); 1.4 to 1.2 ppm (CH ₂ on the fatty chain).

    [Example 1] Copolymerization reaction of BATM-BCTM salts (5mole%) and CPL (PTA content = 4.76mole%)    

First, under a nitrogen environment and 100 ° C / 2 atm, 20.4 g (0.18 mole) of caprolactam (CPL) and water (20%) were subjected to a ring-opening reaction to obtain a CPL ring-opening hydrolysis product, aminocaproic acid ( Aminocaproic acid (ACA). Next, 3.2 g (0.005 mole) of BATM-BCTM salt was added, and the calculated PTA content was 4.76 mole%. The melt polymerization reaction is performed at 210 to 220 ° C. The reaction was controlled at 250-260 ° C. and reacted for 6 hours to obtain polyamidoamine (PA-6 / 2T). The polyamine was dried and analyzed to obtain a relative viscosity (RV) of 2.43, and the results of its melting point, hot water extractability, and whether it contains oligomers are shown in Table 1 below. The spectral information of polyamidamine is as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.46 (aromatic, aromatic components of BCTM and BATM), 4.10-4.26 (aromatic-CON-CH _2- ), 4.00- 4.10 (aliphatic-CON-CH _2- ), 3.19-3.21 (aliphatic-CH ₂ -CON-), 1.85-2.37 (aliphatic). ¹³ C NMR (D ₂ SO ₄ , ppm): 176 and 171 (amimine), 130 (aromatic), 43-44, 35, 23-27. IR (cm ^-1 ): 3307 (NH); 2930; 2858; 1630 (broadband, amidine); 1570-1350; 1300-800 (aromatic). In addition, according to ¹ H NMR spectrum calculation, the relative molar number of aromatic hydrogen / the relative molar number of fatty hydrogen = 0.0236. According to the aforementioned measurement and analysis method of PTA content after polymerization, the "aromatic Relative molar number content ”/“ relative molar number content of aromatics + relative molar number content of ethylenediamine + relative molar number content of CPL (repeating unit of nylon 6) ”= in the polymer after polymerization The mole content of PTA was 5.4 mole%.

    [Example 2] Copolymerization reaction of BATM-BCTM salts (10 mole%) and CPL (PTA content = 9.17 mole%).    

First, 15.56 g (0.1375 mole) of caprolactam (CPL) and water (20%) were subjected to a ring-opening reaction in a nitrogen environment and at a temperature of 100 ° C / 2 atm to obtain a CPL ring-opening hydrolysis product aminocaproic acid ( ACA). Next, 5.58 g (0.0087 mole) of BATM-BCTM salt was added, and the calculated PTA content was 9.17 mole%. The melt polymerization reaction is performed at 210 to 220 ° C. The reaction was controlled at 250-260 ° C. and reacted for 6 hours to obtain polyamidoamine (PA-6 / 2T). The polyamine was dried and analyzed to obtain a relative viscosity (RV) of 2.44, and the results of its melting point, hot water extractability, and whether it contains oligomers are shown in Table 1 below. The spectral information of polyamine is as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.46 (aromatic group, aromatic components of BCTM and BATM), 4.10-4.26 (aromatic group -CON-CH _2- ), 4.00- 4.10 (aliphatic-CON-CH _2- ), 3.19-3.21 (aliphatic-CH ₂ -CON-), 1.85-2.37 (aliphatic). ¹³ C NMR (D ₂ SO ₄ , ppm): 176 and 171 (amimine), 130 (aromatic), 43-44, 35, 23-27. IR (cm ^-1 ): 3307 (NH); 2930; 2858; 1630 (broadband, amidine); 1570-1350; 1300-800 (aromatic). In addition, based on ¹ H NMR spectrum calculations, the aromatic hydrogen relative mole number / fat based hydrogen relative mole number = 0.0516. According to the aforementioned measurement and analysis method of the PTA content after the polymerization reaction, the "aromatic type Relative molar number content ”/“ relative molar number content of aromatics + relative molar number content of ethylenediamine + relative molar number content of CPL (repeating unit of nylon 6) ”= in the polymer after polymerization The mole content of PTA was 10.7 mole%.

    [Example 3] Copolymerization reaction of BATM-BCTM salts (16 mole%) and CPL (PTA content = 13.8 mole%).    

First, 19.24 g (0.17 mole) of caprolactam (CPL) and water (20%) were subjected to a ring-opening reaction in a nitrogen environment and at a temperature of 100 ° C / 2 atm to obtain an aminocaproic acid (CPL) ACA). Next, 12.84 g (0.02 mole) of BATM-BCTM salt was added, and the calculated PTA content = 13.8 mole%. The melt polymerization reaction is performed at 210 to 220 ° C. The reaction was controlled at 250-260 ° C. and reacted for 6 hours to obtain polyamidoamine (PA-6 / 2T). The polyamine was dried and analyzed to obtain a relative viscosity (RV) of 2.46, and the results of its melting point, hot water extractability, and whether it contains oligomers are shown in Table 1 below. The spectral information of polyamidamine is as follows: ¹ H NMR (D ₂ SO ₄ ,: 8.46 (aromatic group, aromatic components of BCTM and BATM)), 4.10-4.26 (aromatic group-CON-CH _2- ), 4.00-4.10 ( Aliphatic-CON-CH _2- ), 3.19-3.21 (aliphatic-CH ₂ -CON-), 1.85-2.37 (aliphatic). ¹³ C NMR (D ₂ SO ₄ , ppm): 176 and 171 (amidoamine ), 130 (aromatic), 43-44, 35, 23-27. IR (cm ^-1 ): 3307 (NH); 2930; 2858; 1630 (broadband, amidine); 1570-1350; 1300-800 ( Aromatic group). In addition, calculated from ¹ H NMR spectrum, the aromatic hydrogen relative molar number / fat based hydrogen relative molar number = 0.0721, calculated in accordance with the aforementioned measurement and analysis method of PTA content after polymerization reaction, Obtain "relative molar number content" / "aromatic relative molar number content + ethylenediamine relative molar number content + CPL (repeated unit of nylon 6) relative molar number content" = polymerization reaction The mole content of PTA in the post-polymer was 14.0 mole%.

    [Example 4] Polymerization of BATM-BCTM salts (33.3 mole%) (PTA content = 33.3 mole%).    

First, under a nitrogen environment and 100 ° C / 2atm, 19.26 g (0.03 mole) of BATM-BCTM salt was added, and the calculated PTA content = 33.3 mole% after calculation. And carry out melt polymerization reaction at 210 ~ 220 ℃. Next, the reaction was controlled at 250-260 ° C. and reacted for 6 hours to obtain polyamidoamine (PA-6 / 2T). The polyamine was dried and analyzed to obtain a relative viscosity (RV) of 2.61, and the results of its melting point, hot water extractability and whether it contains oligomers are shown in Table 1 below. The spectral information of polyamidamine is as follows: ¹ H NMR (D ₂ SO ₄ ,: 8.46 (aromatic group, aromatic components of BCTM and BATM)), 4.10-4.26 (aromatic group-CON-CH _2- ), 4.00-4.10 ( Aliphatic-CON-CH _2- ), 3.19-3.21 (aliphatic-CH ₂ -CON-), 1.85-2.37 (aliphatic). ¹³ C NMR (D ₂ SO ₄ , ppm): 176 and 171 (amidoamine ), 130 (aromatic), 43-44, 35, 23-27. IR (cm ^-1 ): 3307 (NH); 2930; 2858; 1630 (broadband, amidine); 1570-1350; 1300-800 ( Aromatic group). In addition, calculated from ¹ H NMR spectrum, the aromatic hydrogen relative mole number / fat hydrogen relative mole number = 0.2925, and after calculating according to the aforementioned measurement and analysis method of PTA content after polymerization, Obtain the "relative molar number content" / "aromatic relative molar number content + hexamethylene diamine relative molar number content + CPL (repeating unit of nylon 6) relative molar number content" = polymerization reaction The mole content of PTA in the post-polymer was 33.7 mole%.

    [Comparative Example 1] A control experiment with a content of caprolactam (CPL) of 100 mole%    

The reaction conditions of Comparative Example 1 are basically the same as those of Example 2. The difference is that Comparative Example 1 uses only the monomer caprolactam (CPL) for the melt polymerization reaction. The results are shown in Table 1 below. The polyamine (nylon 6) was dried and analyzed to obtain the relative viscosity (RV) = 2.40, and the results of its melting point, hot water extractability, and whether it contains oligomers are shown in Table 1 below. The spectral information of polyamines is as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 4.00-4.12 (aliphatic-CON-CH _2- ), 3.18-3.22 (aliphatic-CH ₂ -CON-), 1.87- 2.38 (fat-based). ¹³ C NMR (D ₂ SO ₄ , ppm): 171 (amidamine), 43, 35, 23-27. IR (cm-1): 3307 (NH); 2930; 2858; 1650 (broadband, amidine); 1570-1350; 1300.

    [Comparative Example 2] The content of PTA was 9.0 mole%    

The reaction conditions of Comparative Example 2 are basically the same as those of Example 2. The difference is that the comonomer system added in Comparative Example 2 "caprolactam (CPL) (82mole%), hexamethylene diamine (HMDA) (9.0mole%) And pure terephthalic acid (PTA) (9.0 mole%) ", so the content of PTA is expressed as 9.0 mole%. The results are shown in Table 1 below. The polyamine (PA-6 / 6T) was dried and analyzed. The relative viscosity (RV) was 2.43. The melting point, hot water extraction rate, and the presence or absence of oligomers are shown in Table 1 below. The spectral information of polyamine is as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.46 (aromatic group, aromatic component of BCTM), 4.10-4.26 (aromatic group-CON-CH _2- ), 4.00-4.10 ( Fatty-CON-CH _2- ), 3.19-3.21 (fatyl-CH ₂ -CON-), 1.85-2.37 (fatyl). ¹³ C NMR (D ₂ SO ₄ , ppm): 176 and 171 (amimine), 130 (aromatic), 43-44, 35, 23-27. IR (cm ^-1 ): 3307 (NH); 2930; 2858; 1630 (broadband, amidine); 1570-1350; 1300-800 (aromatic). In addition, based on the ¹ H NMR spectrum calculation, the aromatic hydrogen relative mole number / fat based hydrogen relative mole number = 0.0468. According to the aforementioned measurement and analysis method of the PTA content after the polymerization reaction, the "aromatic type Relative molar number content of "/" relative molar number content of aromatics + relative molar number content of hexamethylene diamine + relative molar number content of CPL (repeating unit of nylon 6) "= in the polymer after polymerization The mole content of PTA was 10.7 mole%.

    [Comparative Example 3] The content of PTA was 13.8 mole%    

The reaction conditions of Comparative Example 3 are basically the same as those of Example 3. The difference is that the comonomer system added in Comparative Example 3 is caprolactam (CPL) (72.4mole%) and hexamethylenediamine (HMDA) (13.8mole%). ) And pure terephthalic acid (PTA) (13.8mole%), so the content of PTA is expressed as 13.8mole%, and the results are shown in Table 1. Polyamine (PA-6 / 6T) is dried and analyzed. The relative viscosity (RV) = 2.39, the melting point, hot water extractability, and whether it contains oligomers are shown in Table 1. The spectral information of polyamines is as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.46 (aromatic group, aromatic component of BCTM), 4.10-4.26 (aromatic-CON-CH _2- ), 4.00-4.10 (aliphatic-CON-CH _2- ), 3.19-3.21 (aliphatic- CH ₂ -CON-), 1.85-2.37 (fatty group). ¹³ C NMR (D ₂ SO ₄ , ppm): 176 and 171 (amidoamine), 130 (aromatic group), 43-44, 35, 23-27 IR (cm ^-1 ): 3307 (NH); 2930; 2858; 1630 (broadband, amidine); 1570-1350; 1300-800 (aromatic group). In addition, based on ¹ H NMR spectrum calculation, the aromatic hydrogen Relative mole number / fat-based hydrogen relative mole number = 0.0645, according to the aforementioned measurement and analysis of PTA content after polymerization After the calculation, the "relative molar number content of the aromatic system" / "the relative molar number content of the aromatic system + the relative molar number content of hexamethylene diamine + the relative molar number content of the CPL (repeating unit of nylon 6) is obtained "= Mole percentage content of PTA in the polymer after polymerization was 14.3 mole%.

    [Comparative Example 4] The content of PTA was 33.3 mole%    

The reaction conditions of Comparative Example 4 are basically the same as those of Example 4. The difference is that the comonomer system added in Comparative Example 4 is caprolactam (CPL) (33.4mole%), hexamethylenediamine (HMDA) (33.3mole% ) And pure terephthalic acid (PTA) (33.3mole%), so the content of PTA is expressed as 33.3mole%, and the results are shown in Table 1. Polyamine (PA-6 / 6T) was dried and analyzed. The relative viscosity (RV) = 2.60, and its melting point, hot water extractability, and whether it contains oligomers are shown in Table 1. The spectral information of polyamide is as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.46 (aromatic group, aromatic component of BCTM), 4.10-4.26 (aromatic group-CON-CH _2- ), 4.00-4.10 (aliphatic group-CON-CH _2- ), 3.19-3.21 (fatty group -CH ₂ -CON-), 1.85-2.37 (fatty group). ¹³ C NMR (D ₂ SO ₄ , ppm): 176 and 171 (amidoamine), 130 (aromatic group), 43-44, 35, 23- 27. IR (cm ^-1 ): 3307 (NH); 2930; 2858; 1630 (broadband, amidine); 1570-1350; 1300-800 (aromatic). In addition, based on ¹ H NMR spectrum calculation, the aromatic Relative Molar Number of Hydrogen / Fat Molar Number of Fat = 0.18530, according to the aforementioned measurement and analysis of PTA content after polymerization After calculation by the method, the "relative molar number content of the aromatic system" / "relative molar number content of the aromatic system + the relative molar number content of hexamethylene diamine + the relative molar number content of the CPL (repeating unit of nylon 6) is obtained. "= Moore percentage content of PTA in polymer after polymerization is 33.8 mole%.

The data for the reported values 1-4 in Table 1 are taken from "Nylon Plastics Handbook", p. 373, Edited by Melvin I. Kohan, Hanser Publishers, Munich Vienna New York 1995.

It can be known from Table 1 that under the condition that the polyamide product is the same mole percentage (for example, Example 2, Comparative Example 2, and Literature Report Value 2 where the polyamide product is about 10 mole%); the polyamide product Example 3, Comparative Example 3, and Literature Report Value 3, all about 14 mole%; Polyamine products of Example 4, Comparative Example 4, and Literature Report Value 4) of about 33 mole%, compared to Comparative Examples and Literature According to the reported values, the polyamides of the examples all have higher melting points, and the melting points of the polyamides of the examples are also reduced less than the nylon 6 of Comparative Example 1. That is, the polyamide obtained in the embodiment of the present invention may have a high melting point to solve the problem that the melting point is significantly reduced after the copolymerization reaction of nylon 6.

Moreover, under the condition that the polyamine product is the same mole percentage, compared with the comparative example and the reported value in the literature, the mole percentage of the PTA content after the polymerization reaction in the examples is less. This is because the melting point of the BATM derivative used in the examples of the present invention is relatively high, which makes it difficult for EDA to distill out during the polymerization reaction, and it is difficult for PTA to separate from the derivative, thereby preventing the molecular weight of the polyamide product from increasing. Restricted.

In addition, under the condition that the polyamine product is the same mole number, compared with the comparative example and the value reported in the literature, the examples all have lower hot water extractability and no oligomers are generated. This is because the BATM derivatives used in the examples of the present invention have high mutual solubility with aliphatic nylons, and the difference in reactivity between the terminal functional groups of the two is small, so the generation of oligomers can be avoided, and the product's Stability and reduced variability.

Claims (17)

A polyamine, comprising the following repeating units:-[A] _p -,-[B] _q -and-[C] _r -wherein A, B, and C are repeating units derived from A1, B1, and C1, respectively; Where m is an integer of 2-5, and n is an integer of 2-6; p, q, and r represent the mole percentages (mole%) of A, B, and C, respectively, and the total mole numbers of p, q, and r are On the basis, r is 10-99 mole%, and the molar ratio of p to q is 0.9 to 1.1.     Polyamine as described in item 1 of the scope of patent application, wherein r is 60-99 mole%.     Polyamine as described in item 1 of the patent application scope, wherein A1 is Polyamine as described in item 1 of the patent application scope, wherein B1 is     The polyamide according to item 1 of the patent application scope, wherein the polyamide is a random copolymer.         The polyamide according to item 1 of the patent application scope, wherein the polyamide is an alternating copolymer.         The polyamide according to item 1 of the scope of patent application, wherein the melting point (Tm) of the polyamide is from 150 ° C to 310 ° C.         The polyamide according to item 1 of the scope of the patent application, wherein the relative viscosity (RV) of the polyamide is 2.0-3.5.         The polyamide according to item 1 of the patent application scope, wherein the polyamide has a lower extractable amount of hot water than nylon 6.     A method for preparing polyamine includes reacting monomer A1 and monomer B1 to obtain a salt. After monomer C1 is subjected to a ring-opening reaction, the salt is added and a melt polymerization reaction is performed to obtain The polyamide The polyamine includes the following repeating units:-[A] _p -,-[B] _q -and-[C] _r -A, B, and C are repeating units derived from the monomers A1, B1, and C1, respectively. ; Where m is an integer of 2-5, n is an integer of 2-6; p, q, and r represent the mole percentages (mole%) of A, B, and C, respectively, and the total mole numbers of p, q, and r As a reference, r is 10-99 mole%, and the molar ratio of p to q is 0.9 to 1.1.     The method for preparing polyamines according to item 10 of the scope of patent application, wherein r is 60-99 mole%.         The method for preparing polyamines according to item 10 of the scope of the patent application, wherein the melt polymerization reaction is performed at a temperature of 180-240 ° C.         The method for preparing polyamines according to item 10 of the scope of patent application, wherein after the melt polymerization reaction, the method further includes: controlling the reaction temperature to 250-260 ° C. and reacting for 4-7 hours.     The method for preparing polyamines according to item 10 of the application, wherein the monomer A1 is .     According to the method for preparing polyamines according to item 14 of the scope of the patent application, the monomer A1 is made by reacting pure terephthalic acid (PTA) with ethylenediamine (EDA).     The method for preparing polyamines according to item 10 of the application, wherein the monomer B1 is .     According to the method for preparing polyamidamine described in item 16 of the scope of the patent application, the monomer B1 is made by reacting pure terephthalic acid (PTA) with caprolactam (CPL).