A multi-block polymeric high moisture vapor transport material and method of making the same

Abstract

The application discloses a kind of multi-block polymer high moisture-permeable material and preparation method thereof, belong to high polymer material technical field.It includes the following steps: (1) with nylon monomer salt as raw material, water as solvent, prepare nylon prepolymer;(2) with at least one of hexamethylene diisocyanate, isophorone diisocyanate as soft segment monomer, with polytetrahydrofuran ether diol as hard segment monomer, with dibutyl tin dilaurate as catalyst, water as solvent, prepare end isocyanate group polyurethane prepolymer;(3) with nylon prepolymer, polyurethane prepolymer, furan substance, maleimide substance as raw material, crosslinking reaction is prepared multi-block polymer;(4) multi-block polymer is mixed with silane coupling agent modified nano silicon dioxide, biobased plasticizer, natural antioxidant granulation, and multi-block polymer high moisture-permeable material is prepared.The application realizes the synergistic promotion of multi-block polymer high moisture-permeable material mechanical property and moisture permeability.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and more specifically, to a multi-block polymer high moisture permeability material and its preparation method. Background Technology

[0002] Traditional high-permeability materials (such as polyurethane films) generally suffer from insufficient mechanical properties and limited moisture permeability (typically below 5000 g / (d·cm)). 2 Problems such as these exist. Although existing technologies have used composites of nylon and polyurethane to improve these issues, they mostly employ physical blending or simple block structures, which still suffer from weak interfacial bonding and low moisture permeability.

[0003] This invention achieves chemical bonding and micro-phase separation control between nylon and polyurethane through innovative multi-block molecular structure design combined with dynamic cross-linking technology synthesis process, significantly improving material performance. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a multi-block polymer high moisture permeability material and its preparation method.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A method for preparing a multi-block polymer highly moisture-permeable material includes the following steps:

[0007] (1) Nylon prepolymer was prepared by condensation polymerization using nylon monomer salt as raw material and water as solvent;

[0008] (2) Using at least one of hexamethylene diisocyanate and isophorone diisocyanate as soft segment monomers, polytetrahydrofuran ether diol as hard segment monomers, dibutyltin dilaurate as catalyst, and water as solvent, a polyurethane prepolymer with terminal isocyanate is prepared by aqueous emulsification.

[0009] (3) Using nylon prepolymer, polyurethane prepolymer, furan-like substances and maleimide-like substances as raw materials, multi-block polymers are prepared through cross-linking reaction;

[0010] (4) Mix the multi-block polymer with silane coupling agent-modified nano-silica, bio-based plasticizer, and natural antioxidant and granulate to prepare a multi-block polymer high moisture permeability material.

[0011] The present invention is further configured such that, in step (1), the nylon monomer salt is at least one of caprolactam salt, hexamethylenediamine adipic acid salt, and dodecanoic acid salt.

[0012] The present invention is further configured such that, in step (1), the mass ratio of nylon monomer salt to water is 20-40:50.

[0013] The present invention is further configured such that step (1) specifically involves adding nylon monomer salt and water into a high-pressure reactor, and reacting under nitrogen protection at 240-280℃ and 2.0-3.0MPa for 7-9 hours to obtain nylon prepolymer.

[0014] The present invention is further configured such that, in step (2), the mass ratio of polytetrahydrofuran ether diol to soft segment monomer, catalyst and water is 32:7-10:0.1:40.

[0015] The present invention is further configured such that step (2) specifically involves: adding polytetrahydrofuran ether diol and soft segment monomer to water at 60°C, adding an emulsifier for emulsification and dispersion, and then adding a catalyst, dibutyltin dilaurate, to react at 60°C to generate isocyanate-terminated polyurethane prepolymer.

[0016] The present invention is further configured such that the emulsifier in step (2) is castor oil polyoxyethylene ether; the emulsifier accounts for 1-2% of the total mass of the reaction system.

[0017] The present invention is further configured such that step (3) specifically involves: adding nylon prepolymer and polyurethane prepolymer to a reaction vessel at a molar ratio of 1:1; adding furan-like substances and maleimide-like substances; adjusting the pH to 8.0; reacting at 70-75°C; and then heating to 90-95°C to react again to obtain a multi-block polymer.

[0018] The present invention is further configured such that, in step (3), the total mass of the added furan-like substances and maleimide-like substances accounts for 1% of the total mass of the nylon prepolymer and the polyurethane prepolymer.

[0019] The present invention is further configured such that, in step (4), the silane coupling agent modified nano-silica accounts for 4-5% of the mass of the multiblock polymer, the bio-based plasticizer accounts for 3-4% of the mass of the multiblock polymer, and the antioxidant accounts for 1-2.5% of the mass of the multiblock polymer.

[0020] In summary, the present invention has the following beneficial effects:

[0021] The dynamic crosslinking technology synthesis process polymerizes nylon prepolymer and polyurethane prepolymer, realizing the chemical bonding and micro-phase separation control of nylon and polyurethane, forming an alternating arrangement of nylon and polyurethane multi-block molecular structure, and achieving a synergistic improvement in the mechanical properties and moisture permeability of the material. Attached Figure Description

[0022] Figure 1 The infrared spectrum of the multiblock polymer prepared in Example 1;

[0023] Figure 2 The infrared spectrum of the multiblock polymer prepared in Example 2. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] The multi-block polymer high moisture permeability material of the present invention is prepared by the following method:

[0026] (1) Nylon prepolymer was prepared by condensation polymerization using nylon monomer salt as raw material and water as solvent.

[0027] The specific steps are as follows: Nylon monomer salt and water are added to a high-pressure reactor and reacted at 240-280℃ and 2.0-3.0MPa for 7-9 hours under nitrogen protection to obtain nylon prepolymer (molecular weight of 2000-3000Da); the mass ratio of nylon monomer salt to water is 20-40:50.

[0028] The nylon monomer salt is at least one of caprolactam salt, hexamethylenediamine adipic acid salt, and dodecanoic acid salt.

[0029] (2) Using at least one of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) as soft segment monomers, PTMEG (polytetrahydrofuran ether diol) as hard segment monomers, dibutyltin dilaurate as catalyst, and water as solvent, a polyurethane prepolymer with terminal isocyanate is prepared by aqueous emulsification.

[0030] The specific steps are as follows: PTMEG and soft segment monomers are added to water at 60°C, an emulsifier is added for emulsification and dispersion, and then dibutyltin dilaurate catalyst is added and reacted at 60°C for 2-3 hours to generate isocyanate-terminated (-NCO) polyurethane prepolymer. The mass ratio of polytetrahydrofuran ether diol to soft segment monomers, catalyst, and water is 32:7-10:0.1:40; the emulsifier is castor oil polyoxyethylene ether, and the emulsifier accounts for 1-2% of the total mass of the reaction system (TMEG + soft segment monomers + catalyst + water + emulsifier).

[0031] (3) Multiblock polymers are prepared by cross-linking reaction using nylon prepolymer, polyurethane prepolymer, furan-like substances and maleimide-like substances as raw materials.

[0032] The specific steps are as follows: Nylon prepolymer and polyurethane prepolymer are added to a reactor at a molar ratio of 1:1. Furan compounds and maleimides are added at a molar ratio of 1:1 (the total mass of furans and maleimides accounts for 1% of the total mass of the nylon and polyurethane prepolymers). The pH is adjusted to 8.0 using a sodium bicarbonate-sodium carbonate buffer solution, and the reaction is carried out at 70-75℃ for 5-6 hours. The temperature is then increased to 90-95℃ for another 1-2 hours. After the reaction is complete, the mixture is cooled to room temperature, precipitated with acetone, and dried to obtain a multi-block polymer. Furfurylamine is preferred as the furan compound, and bismaleimide is preferred as the maleimide compound.

[0033] Reaction mechanism: The amino groups on the waterborne nylon prepolymer react with the isocyanate of the polyurethane prepolymer to obtain a multi-block polymer. The isocyanate of the polyurethane prepolymer reacts with the amino groups of furan substances to obtain polyurethane with furfurylamine groups. The multi-block polymer with reversible crosslinking is obtained by reacting furan substances with maleimide substances to crosslink the two ends.

[0034] (4) Mix the multi-block polymer with silane coupling agent-modified nano-silica, bio-based plasticizer, and natural antioxidant and granulate to prepare a multi-block polymer high moisture permeability material.

[0035] The specific steps are as follows: a multi-block polymer is extruded and granulated with silane coupling agent-modified nano-silica, bio-based plasticizer, and antioxidant through a twin-screw extruder at 160-185℃ to obtain a multi-block polymer high moisture permeability material.

[0036] The silane coupling agent-modified nano-silica accounts for 4-5% of the mass of the multiblock polymer, the bio-based plasticizer accounts for 3-4% of the mass of the multiblock polymer, and the antioxidant accounts for 1-2.5% of the mass of the multiblock polymer. The bio-based plasticizer is epoxidized soybean oil, and the antioxidant is glyceryl trirosate.

[0037] Example 1

[0038] (1) Sodium hexamethylenediamine adipate and water were added to a high-pressure reactor and reacted at 280°C and 2.5 MPa for 9 hours under nitrogen protection to obtain nylon prepolymer; the mass ratio of nylon monomer to water was 32:50.

[0039] (2) PTMEG and hexamethylene diisocyanate were added to water at 60°C, and castor oil polyoxyethylene ether was added for emulsification and dispersion. Then, dibutyltin dilaurate catalyst was added and the mixture was reacted at 60°C for 2 hours to generate isocyanate-terminated (-NCO) polyurethane prepolymer. The mass ratio of PTMEG to hexamethylene diisocyanate, catalyst, and water was 32:8:0.1:40; the emulsifier accounted for 1.5% of the total mass of the reaction system (TMEG + hexamethylene diisocyanate + catalyst + water + emulsifier).

[0040] (3) Nylon prepolymer and polyurethane prepolymer were added to a reactor at a molar ratio of 1:1. Furfurylamine and bismaleimide were added at a molar ratio of 1:1 (the total mass of furfurylamine and bismaleimide accounted for 1% of the total mass of the nylon prepolymer and polyurethane prepolymer). The pH was adjusted to 8.0 using a sodium bicarbonate-sodium carbonate buffer solution, and the reaction was carried out at 70°C for 5 hours, followed by a further increase to 90°C for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, precipitated with acetone, and dried to obtain the multi-block polymer. The infrared spectrum of this multi-block polymer is shown below. Figure 1 As shown.

[0041] (4) A multi-block polymer, KH550 modified nano-silica, epoxidized soybean oil, and glyceryl trirosinate were extruded and granulated using a twin-screw extruder at 160-185℃ to obtain a multi-block polymer high moisture permeability material. KH550 modified nano-silica accounted for 4.2% of the mass of the multi-block polymer, epoxidized soybean oil accounted for 3% of the mass of the multi-block polymer, and glyceryl trirosinate accounted for 2% of the mass of the multi-block polymer.

[0042] Comparative Example 1

[0043] A multi-block polymer was prepared according to Example 1, and then the multi-block polymer and KH550 modified nano-silica were extruded and granulated using a twin-screw extruder at 160-185°C to obtain a multi-block polymer material. The KH550 modified nano-silica accounted for 4.2% of the mass of the multi-block polymer.

[0044] Comparative Example 2

[0045] A multi-block polymer was prepared according to Example 1, and then the multi-block polymer and epoxidized soybean oil were extruded and granulated using a twin-screw extruder at 160-185°C to obtain a multi-block polymer material, wherein the epoxidized soybean oil accounted for 3% of the mass of the multi-block polymer.

[0046] Comparative Example 3

[0047] A multi-block polymer was prepared according to Example 1. Then, the multi-block polymer, KH550 modified nano-silica, and epoxidized soybean oil were extruded and granulated using a twin-screw extruder at 160-185°C to obtain a multi-block polymer material. The KH550 modified nano-silica accounted for 4.2% of the mass of the multi-block polymer, and the epoxidized soybean oil accounted for 3% of the mass of the multi-block polymer.

[0048] The multi-block polymer high moisture permeability material finally obtained in Example 1, the multi-block polymer materials finally obtained in Comparative Examples 1 and 2, and the multi-block polymer obtained in step (3) of Example 1 were all subjected to film extrusion molding according to the prior art.

[0049] It was found that adding KH550 modified nano-silica (Comparative Example 1), epoxidized soybean oil (Comparative Example 2), or KH550 modified nano-silica and epoxidized soybean oil (Comparative Example 3) to multi-block polymers improved the mechanical properties of the materials, but reduced the moisture permeability (compared to the multi-block polymer obtained in step (3) of Example 1). However, Example 1, through the addition of silane coupling agent modified nano-silica, epoxidized soybean oil, and glyceryl trirosate, ensured both the processing and molding performance of the materials, improved the mechanical properties of the materials, and ensured the moisture permeability. The specific test results are shown in Table 1. The tensile strength and elongation at break were tested according to GB / T 20218-2021 "Biaxially oriented polyamide (nylon) film". Under the conditions of 23℃ and 50% relative humidity, the moisture permeability of the film was tested according to GB / T 1037-2021 "Determination of water vapor permeability of plastic films and sheets by cup weight gain and loss method".

[0050] Table 1

[0051]

[0052] Example 2

[0053] The multi-block polymer was prepared using sodium caprolactam and according to the method in Example 1. The infrared spectrum of the multi-block polymer obtained in step (3) is shown below. Figure 2 As shown.

[0054] The above description is merely a preferred embodiment of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principles of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a multi-block polymer high moisture permeability material, characterized in that, Includes the following steps: (1) Nylon prepolymer was prepared by condensation polymerization using nylon monomer salt as raw material and water as solvent; (2) Using at least one of hexamethylene diisocyanate and isophorone diisocyanate as soft segment monomers, polytetrahydrofuran ether diol as hard segment monomers, dibutyltin dilaurate as catalyst and water as solvent, a polyisocyanate-terminated polyurethane prepolymer was prepared by aqueous emulsification. (3) Using nylon prepolymer, polyurethane prepolymer, furan-like substances and maleimide-like substances as raw materials, multi-block polymers are prepared through cross-linking reaction; (4) Mix and granulate the multi-block polymer with silane coupling agent modified nano-silica, bio-based plasticizer and natural antioxidant to prepare a multi-block polymer high moisture permeability material; Step (3) specifically involves: adding nylon prepolymer and polyurethane prepolymer to a reactor at a molar ratio of 1:1; adding furan and maleimide substances, adjusting the pH to 8.0, and then reacting at 70-75℃, followed by heating to 90-95℃ to obtain a multi-block polymer; in step (3), the total mass of the added furan and maleimide substances accounts for 1% of the total mass of the nylon prepolymer and polyurethane prepolymer. In step (4), the silane coupling agent modified nano-silica accounts for 4-5% of the mass of the multiblock polymer, the bio-based plasticizer accounts for 3-4% of the mass of the multiblock polymer, and the antioxidant accounts for 1-2.5% of the mass of the multiblock polymer.

2. The method for preparing a multi-block polymer high-moisture-permeable material according to claim 1, characterized in that, In step (1), the nylon monomer salt is at least one of caprolactam salt, hexamethylenediamine adipic acid salt, and dodecanoic acid salt.

3. The method for preparing a multi-block polymer high-moisture-permeable material according to claim 1, characterized in that, In step (1), the mass ratio of nylon monomer salt to water is 20-40:

50.

4. The method for preparing a multi-block polymer high-moisture-permeable material according to claim 1, characterized in that, Step (1) is as follows: Nylon monomer salt and water are added to a high-pressure reactor and reacted for 7-9 hours under nitrogen protection at 240-280℃ and 2.0-3.0MPa to obtain nylon prepolymer.

5. The method for preparing a multi-block polymer high-moisture-permeable material according to claim 1, characterized in that, In step (2), the mass ratio of polytetrahydrofuran ether diol to soft segment monomer, catalyst and water is 32:7-10:0.1:

40.

6. The method for preparing a multi-block polymer high moisture permeability material according to claim 1, characterized in that, Step (2) specifically involves adding polytetrahydrofuran ether diol and soft segment monomer to water at 60°C, adding an emulsifier for emulsification and dispersion, and then adding a catalyst, dibutyltin dilaurate, to react at 60°C to generate isocyanate-terminated polyurethane prepolymer.

7. The method for preparing a multi-block polymer high-moisture-permeable material according to claim 6, characterized in that, In step (2), the emulsifier is castor oil polyoxyethylene ether; the emulsifier accounts for 1-2% of the total mass of the reaction system.

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