Highly transparent nylon elastomer polymer, preparation method and polymer film

Abstract

The present invention discloses a highly transparent nylon elastomer polymer, a preparation method thereof, and a polymer film. The polymer components are obtained by polymerizing a first monomer and a second monomer in one of the following ways: (1) self-polymerization of a pure para-substituted caprolactam monomer; (2) copolymerization of a para-substituted caprolactam monomer and a caprolactam monomer in different molar ratios; (3) copolymerization of two different para-substituted caprolactam monomers in different molar ratios. By polymerizing a monomer with a structure similar to that of a caprolactam monomer with caprolactam and adopting ring-opening polymerization initiated by water with relatively low requirements for industrial polymerization processes, the present invention overcomes problems such as high residual rate and unstable molecular structure of copolymer products caused by thermodynamic miscibility and polymerization efficiency problems of common modified monomers. At the same time, by restricting the intermolecular hydrogen bond interaction of amide bonds on polyamide macromolecular materials, the aggregation between molecular chains is inhibited to achieve the regulation of the crystallinity and crystal morphology of the polymer, thereby achieving the purpose of preparing a transparent nylon elastomer.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material synthesis, and in particular relates to a highly transparent nylon elastomer polymer, a preparation method and a polymer film. Background Art

[0002] The chemical name of nylon 6 is polycaprolactam, and its structural formula is —[NH(CH2)5CO] n —, is a translucent or milky white thermoplastic resin with excellent self-lubricity, wear resistance and solvent resistance. These excellent properties are mainly derived from the hydrogen bond interaction between adjacent amide bonds in the molecular chain. Therefore, nylon 6 can be used as an engineering plastic and is widely used to make various high-load mechanical parts, electronic and electrical switches and equipment, building and structural materials, transportation vehicle parts, etc. Since polymers are often required to have opposite physical properties such as heat resistance and easy molding, high rigidity and impact resistance in actual use, it is difficult for a single polymer to meet these requirements. For example, the nylon 6-based structure has poor toughness. It will become brittle and break when used in a long-term dry and low-temperature environment. When subjected to external force, it is easy to crack or break. Therefore, nylon 6 usually needs to be toughened and modified.

[0003] The commonly used method to improve the toughness of nylon 6 matrix is through copolymerization or blending modification. Blending modification is to prepare polymer alloys by processing polyamide and elastomer, but most of the current elastomers are non-polar and have low surface energy, which leads to poor dyeability, hydrophilicity, antistatic properties and compatibility with nylon matrix or inorganic fillers, such as polyolefin elastomers, thermoplastic polyurethane elastomers.

[0004] (TPU). Therefore, the nylon alloy prepared by this method has an obvious performance "ceiling". Copolymerization modification is to use a prepolymer polymerized by a dibasic acid with strong crystallinity and a diamine or a prepolymer prepolymerized by ring-opening of a cyclic lactam as a hard segment and a polyester or polyether with a soft molecular chain as a soft segment for block polymerization to obtain a polyamide type thermoplastic elastomer (TPAE). The polyamide type thermoplastic elastomer obtained by copolymerization modification overcomes the problem of compatibility between polyamide and elastomer. On the basis of the characteristics of polyamide such as high temperature resistance, friction resistance, and good dimensional stability, it has more excellent properties through polyether or polyester modification, such as creep stability, low temperature toughness, resilience and impact resistance. However, this method requires solution polymerization and has high requirements for polymerization. Therefore, the development of a polyamide with more excellent properties on the basis of retaining the excellent properties of polyamide, and a polyamide elastomer with relatively simple polymerization process, has also become a hot topic of current research and is of great significance. Summary of the invention

[0005] In view of the above problems, the present invention provides a highly transparent nylon elastomer polymer and a preparation method thereof. By copolymerizing a novel monomer of para-alkyl-substituted caprolactam, the introduction of the alkyl group introduces steric hindrance on the polyamide polymer chain, reduces the intermolecular force between chains, and enhances the toughness of the polymer. At the same time, the introduction of the alkyl chain can also reduce the crystal grain size, thereby enhancing the transparency of traditional nylon materials. Finally, a preparation method of a copolymerized nylon 6 elastomer polymer with both high elasticity and transparency is obtained.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] A highly transparent nylon elastomer polymer, the polymer components of which are obtained by polymerizing a first monomer and a second monomer in one of the following ways:

[0008] (1) The first monomer and the second monomer are the same pure para-substituted caprolactam monomer, and are self-polymerized by the pure para-substituted caprolactam monomer;

[0009] (2) The first monomer and the second monomer are a para-substituted caprolactam monomer and a caprolactam monomer, and are copolymerized by the para-substituted caprolactam monomer and the caprolactam monomer in different molar ratios;

[0010] (3) The first monomer and the second monomer are two different para-substituted caprolactam monomers, and are copolymerized by the two different para-substituted caprolactam monomers in different molar ratios.

[0011] Further, the para-substitution is one of -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH2OH, -CH2CH2OH.

[0012] Further, in the cases of (2) and (3), the different molar ratios of the two monomers are 5% to 85%.

[0013] Further, the repeating unit of the polymer component is represented by the following formula:

[0014]

[0015] Further, in the polymer obtained by self-polymerization, R1 = R2; in the polymer obtained by copolymerization, R1 ≠ R2; where R1 or R2 is one of H, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH2OH, -CH2CH2OH, and R1 and R2 are not both H at the same time.

[0016] Further, in the molecular formula structure shown in formula (1), m and n are both integers, and m + n is between 5 and 1000.

[0017] Furthermore, the tensile strain of the polymer can reach 100%-500%, and the crystallization temperature can be as low as 120-150 degrees Celsius.

[0018] The present invention also provides a method for preparing the above-mentioned highly transparent nylon elastomer polymer, including the following process: mixing a certain molar ratio of a first monomer, a second monomer, and deionized water in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heating to 230-260 °C with mechanical stirring; at the same time, raising the pressure to 0.5-1.0 MPa; then, maintaining for 5 hours in the presence of water to achieve the polymerization of the monomers; then, after keeping the pressure unchanged, continuing the reaction for 1 hour under a nitrogen atmosphere and atmospheric pressure respectively; finally, reducing the system pressure to 40-60 Pa and maintaining for 1 h; after the reaction is completed, naturally cooling the system to room temperature.

[0019] The present invention also provides a polymer film made of the above-mentioned highly transparent nylon elastomer polymer.

[0020] Furthermore, the film has high elasticity, transparency, and a main chain structure consistent with that of nylon 6.

[0021] Furthermore, the polyamide component of the film contains both a homopolymer of para-substituted polyamide and a copolymer of para-substituted polyamide.

[0022] The present invention polymerizes a monomer similar in structure to the caprolactam monomer with caprolactam, and adopts ring-opening polymerization initiated by water with relatively low requirements for industrial polymerization processes, overcoming problems such as high residue rate and unstable molecular structure of copolymer products caused by thermodynamic miscibility and polymerization efficiency of common modified monomers. At the same time, by restricting the intermolecular hydrogen bond interaction of amide bonds on the polyamide polymer material, the aggregation between molecular chains is inhibited to regulate the crystallinity and crystal morphology of the polymer, achieving the purpose of preparing a transparent nylon elastomer. Specific Embodiments

[0023] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be described in detail below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the scope protected by the present invention.

[0024] The polymer composition of the present application invention widely relates to nylon homopolymers and copolymers. The para-substituted caprolactam monomer involved in the present invention cannot be obtained from market sources and can be obtained according to known preparation techniques with a purity > 98%; the caprolactam monomer can be directly obtained from market sources.

[0025] Para-substituted caprolactam, structural formula: R = -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH2CH3, -CH2OH, -CH2CH2OH;

[0026] Taking propylcyclohexanone as an example, the synthesis method of p-propylcaprolactam is as follows: ① Weigh 14.4 g of 4-n-propylcyclohexanone, 14.28 g of hydroxylamine hydrochloride, and 32.64 g of anhydrous sodium carbonate into a beaker. Add 120 ml of methanol and 60 ml of deionized water to the beaker, and stir magnetically for 2.5 h. Then evaporate the methanol solution at 70 °C. After cooling to room temperature, add 120 ml of ethyl acetate and 80 ml of deionized water to the beaker. After vigorously stirring and shaking, let it stand. Take the upper layer solution and rotary evaporate it at 60 °C for 30 min to obtain a white oily substance - 4-n-propylcyclohexanone oxime; ② Take 5 g of 4-n-propylcyclohexanone oxime into a beaker, slowly add 5 ml of 85% H2SO4 (solution A). Add 3 ml of 85% H2SO4 to a three-necked flask, heat to 120 °C, and slowly add solution A dropwise to the three-necked flask under magnetic stirring. After the addition is complete, continue heating for 5 min, then remove the heat source and let it cool naturally to 80 °C. Cool it to 5 - 8 °C in an ice-water bath, and slowly add 25% aqueous ammonia solution to the three-necked flask at a rate of 20 ml / h until pH = 8. Transfer the solution in the three-necked flask to a beaker, add 120 ml of dichloromethane and 80 ml of H2O, shake well and let it stand. Take the lower layer solution and rotary evaporate it at 60 °C to obtain a brown solid - propylcaprolactam;

[0027] The synthesis methods of other p-substituted caprolactam monomers can refer to the synthesis method of p-propylcaprolactam described above.

[0028] Caprolactam, structural formula: Polymerization process equation of the polymer:

[0029]

[0030] When R1 ≠ R2, copolymerization; when R1 = R2, homopolymerization;

[0031] In the preferred specific embodiments of the copolymerization of the present invention, taking the copolymerization of propyl-substituted caprolactam and caprolactam as an example, the propyl-substituted caprolactam monomer in the polymer contains about 0.5% - 85 mol%, and the remaining is the molar amount of caprolactam. More preferably, it is 5 - 45 mol% of propyl-substituted caprolactam monomer, and very preferably, it is 10 - 50 mol% of this propyl-substituted caprolactam monomer mixture. In the preferred specific embodiments of the present invention, taking the polymer of 20 mol% propylcaprolactam and 80 mol% caprolactam as an example, the pressing of splines and the synthesis of films are carried out.

[0032] Specific examples are as follows:

[0033] Example 1

[0034] 10.75 g (0.095 mol) of ε-caprolactam, 0.63 g (0.005 mol) of p-methyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 hours in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 hour under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0035] Example 2

[0036] 10.18 g (0.09 mol) of ε-caprolactam, 1.26 g (0.01 mol) of p-methyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 hours in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 hour under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0037] Example 3

[0038] 9.05 g (0.08 mol) of ε-caprolactam, 2.54 g (0.02 mol) of p-methyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 hours in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 hour under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0039] Example 4

[0040] 5.65 g (0.05 mol) of ε-caprolactam, 6.35 g (0.05 mol) of p-methyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0041] Example 5

[0042] 2.26 g (0.02 mol) of ε-caprolactam, 10.17 g (0.08 mol) of p-methyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0043] Example 6

[0044] 0.56 g (0.005 mol) of ε-caprolactam, 12.07 g (0.095 mol) of p-methyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0045] Example 7

[0046] 10.75 g (0.095 mol) of ε-caprolactam, 0.71 g (0.005 mol) of p-ethyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0047] Example 8

[0048] 10.18 g (0.09 mol) of ε-caprolactam, 1.42 g (0.01 mol) of p-ethyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0049] Example 9

[0050] 9.05 g (0.08 mol) of ε-caprolactam, 2.82 g (0.02 mol) of p-ethyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0051] Example 10

[0052] 5.65 g (0.05 mol) of ε-caprolactam, 7.05 g (0.05 mol) of p-ethyl-substituted ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0053] Example 11

[0054] 2.26 g (0.02 mol) of ε-caprolactam, 11.29 g (0.08 mol) of p-ethyl-substituted ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0055] Example 12

[0056] 0.56 g (0.005 mol) of ε-caprolactam, 13.41 g (0.095 mol) of p-ethyl-substituted ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0057] Example 13

[0058] 10.75 g (0.095 mol) of ε-caprolactam, 0.775 g (0.005 mol) of p-propyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0059] Example 14

[0060] 10.18 g (0.09 mol) of ε-caprolactam, 1.55 g (0.01 mol) of p-propyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0061] Example 15

[0062] 9.05 g (0.08 mol) of ε-caprolactam, 3.10 g (0.02 mol) of p-propyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0063] Example 16

[0064] 5.56 g (0.05 mol) of ε-caprolactam, 7.76 g (0.05 mol) of p-propyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0065] Example 17

[0066] 2.26 g (0.02 mol) of ε-caprolactam, 12.4 g (0.08 mol) of p-propyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0067] Example 18

[0068] 0.56 g (0.005 mol) of ε-caprolactam, 14.73 g (0.095 mol) of p-propyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0069] Example 19

[0070] 9.05 g (0.08 mol) of ε-caprolactam, 3.40 g (0.02 mol) of p-butyl-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0071] Example 20

[0072] 9.05 g (0.08 mol) of ε-caprolactam, 2.86 g (0.02 mol) of p-ethylhydroxy-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0073] Example 21

[0074] 9.05 g (0.08 mol) of ε-caprolactam, 3.14 g (0.02 mol) of p-propylhydroxy-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0075] Example 22

[0076] 10.17 g (0.08 mol) of p-methyl-substituted ε-caprolactam, 2.82 g (0.02 mol) of p-ethyl-substituted ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0077] Example 23

[0078] 10.17 g (0.08 mol) of p-methyl-substituted ε-caprolactam, 3.10 g (0.02 mol) of p-propyl-substituted ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0079] Example 24

[0080] 10.17 g (0.08 mol) of p-methyl-substituted ε-caprolactam, 3.40 g (0.02 mol) of p-butyl-substituted ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0081] Example 25

[0082] 10.17 g (0.08 mol) of p-methyl-substituted-ε-caprolactam, 2.86 g (0.02 mol) of p-ethylhydroxy-substituted-ε-caprolactam and 12 ml of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 hours in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 hour under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0083] Example 26

[0084] 10.18 g (0.08 mol) of p-methyl-substituted-ε-caprolactam, 3.14 g (0.02 mol) of p-propylhydroxy-substituted-ε-caprolactam and 12 ml of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 hours in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 hour under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0085] Example 27

[0086] 11.29 g (0.08 mol) of p-ethyl-substituted-ε-caprolactam, 3.10 g (0.02 mol) of p-propyl-substituted-ε-caprolactam and 12 ml of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 hours in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 hour under a nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0087] Example 28

[0088] 11.29 g (0.08 mol) of p-ethyl substituted-ε-caprolactam, 3.40 g (0.02 mol) of p-butyl substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0089] Example 29

[0090] 11.28 g (0.08 mol) of p-ethyl substituted-ε-caprolactam, 2.86 g (0.02 mol) of p-ethylhydroxy substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0091] Example 30

[0092] 11.28 g (0.08 mol) of p-ethyl substituted-ε-caprolactam, 3.14 g (0.02 mol) of p-propylhydroxy substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0093] Example 31

[0094] 12.41 g (0.08 mol) of p-propyl-substituted ε-caprolactam, 3.40 g (0.02 mol) of p-butyl-substituted ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0095] Example 32

[0096] 12.41 g (0.08 mol) of p-propyl-substituted ε-caprolactam, 2.86 g (0.02 mol) of p-ethylhydroxy-substituted ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0097] Example 33

[0098] 12.14 g (0.08 mol) of p-propyl-substituted ε-caprolactam, 3.14 g (0.02 mol) of p-propylhydroxy-substituted ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0099] Example 34

[0100] 13.60 g (0.08 mol) of p-butyl-substituted-ε-caprolactam, 2.86 g (0.02 mol) of p-ethylhydroxy-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0101] Example 35

[0102] 13.60 g (0.08 mol) of p-butyl-substituted-ε-caprolactam, 3.14 g (0.02 mol) of p-propylhydroxy-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0103] Example 36

[0104] 11.44 g (0.08 mol) of p-ethylhydroxy-substituted-ε-caprolactam, 3.14 g (0.02 mol) of p-propylhydroxy-substituted-ε-caprolactam and 12 mL of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0105] Comparative Example 1

[0106] 22.6 g (0.2 mol) of caprolactam and 2.2 g of deionized water were mixed in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heated to 230 - 260 °C with mechanical stirring. At the same time, the pressure was increased to 0.5 - 1.0 MPa. Then, it was maintained for 5 h in the presence of water to achieve the polymerization of the monomers. Then, the pressure began to stabilize, and the reaction was continued for 1 h under a nitrogen atmosphere and atmospheric pressure, respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction was completed, the system was naturally cooled to room temperature.

[0107] Comparative Example 2

[0108] 23.2 g (0.2 mol) of hexamethylenediamine and 29.2 g (0.2 mol) of adipic acid were placed in a polymerization kettle, 50 g of deionized water was added, and the mixture was heated and continuously stirred under nitrogen protection to obtain a salt solution. After cooling, crystallization, filtration, and drying, nylon salt was obtained; the above nylon 66 salt, catalyst, and deionized water were added to the reaction kettle in proportion. Then, the pressure began to stabilize, and the reaction was continued for 1 hour under nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction, the system was naturally cooled to room temperature.

[0109] Comparative Example 3

[0110] 11.08 g (0.08 mol) of hexamethylenediamine, 3.76 g (0.02 mol) of 3-propylhexamethylenediamine, 9.29 g (0.08 mol) of adipic acid, and 3.16 g (0.02 mol) of 3-methyladipic acid were placed in a polymerization kettle, 30 g of deionized water was added, and the mixture was heated and continuously stirred under nitrogen protection to obtain a salt solution. After cooling, crystallization, filtration, and drying, copolymer nylon salt was obtained; the above copolymer nylon 66 salt, catalyst, and deionized water were added to the reaction kettle in proportion. Then, the pressure began to stabilize, and the reaction was continued for 1 hour under nitrogen atmosphere and atmospheric pressure respectively. Finally, the system pressure was reduced to about 50 Pa and maintained for 1 h. After the reaction, the system was naturally cooled to room temperature.

[0111] Table 1. Composition and Properties of Nylon 6 Matrix Polymer

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120] From the polymer property data obtained in Examples 1-36 and compared with Comparative Examples 1-3, the following conclusions can be drawn: (1) After the copolymerization of caprolactam (or para-substituted caprolactam) and para-substituted caprolactam, the resulting copolyamide 6 (copolymerized nylon 6) has a significantly lower glass transition temperature, and significantly improved toughness and transparency compared with polyamide 6 (nylon 6). In addition, as the proportion of para-substituted caprolactam in the copolymer component increases, its transparency, elasticity / toughness become better, showing typical elastomer characteristics;

[0121] (2) According to the performance requirements of the elastomer, appropriate monomers and ratios can be selected for copolymerization;

[0122] (3) The method of copolymerization using para-substituted caprolactam has obvious advantages over the multi-component binary monomer copolymerization method, and it is easier to obtain nylon elastomers / films with good transparency and high elasticity.

[0123] The above is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of changes or substitutions, which should all be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A highly transparent nylon elastomer polymer, characterized in that, Its polymer component is obtained by polymerizing a first monomer and a second monomer in one of the following ways: (1) The first monomer and the second monomer are para-substituted caprolactam monomers and caprolactam monomers, and are copolymerized by the para-substituted caprolactam monomers and caprolactam monomers in different molar ratios; (2) The first monomer and the second monomer are two different para-substituted caprolactam monomers, and are copolymerized by the two different para-substituted caprolactam monomers in different molar ratios; The para-substitution is one of -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH2OH, -CH2CH2OH; In methods (1) and (2), the different molar ratios of the two monomers are 5% to 85%; The repeating unit of the polymer component is represented by the following formula: （1）； In the copolymerized polymer, R1 ≠ R2; where R1 or R2 is one of H, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH2OH, -CH2CH2OH, and R1 and R2 are not both H at the same time; In the molecular formula structure shown in formula (1), m and n are both integers, and m + n is between 5 and 1000.

2. A method for preparing a highly transparent nylon elastomer polymer as described in claim 1, characterized in that, It includes the following process: Mix a certain molar ratio of the first monomer, the second monomer and deionized water in a steel reactor equipped with a nitrogen inlet under a nitrogen atmosphere and heat to 230-260 °C and mechanically stir; at the same time, raise the pressure to 0.5-1.0 MPa; then, maintain for 5 hours in the presence of water to achieve the polymerization of the monomers; then, after the pressure remains unchanged, continue to react for 1 hour under a nitrogen atmosphere and atmospheric pressure respectively; finally, reduce the system pressure to 40-60 Pa and maintain for 1 h; after the reaction is completed, naturally cool the system to room temperature.

3. A polymer film made of the high-transparency nylon elastomer polymer described in claim 1.

4. A polymer film according to claim 3, characterized in that, The film has high elasticity, transparency, and has a main chain structure consistent with that of nylon 6.

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