Biological protein modified polyurethane polymer as well as preparation method and application thereof

Abstract

The invention relates to the technical field of polymer materials of daily hygienic products, in particular to a bioprotein modified polyurethane polymer as well as a preparation method and application thereof. The bioprotein modified polyurethane polymer is prepared from a silk fibroin solution with the solid content of 20%, a modified waterborne polyurethane solution with the solid content of 35% and a compound preparation, and the mass ratio of the silk fibroin solution to the modified waterborne polyurethane solution is 1: (2-10). The addition amount of the composite preparation is 1-3% of the sum of the mass of the silk fibroin solution and the modified waterborne polyurethane solution; wherein the preparation method of the modified waterborne polyurethane solution comprises three steps of preparing a prepolymer, preparing a modified prepolymer and performing post-treatment.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials for daily hygiene products, and in particular to a bioprotein-modified polyurethane polymer, a preparation method and applications. Background Art

[0002] Latex is mainly composed of rubber hydrocarbons, water and a small amount of other non-rubber components. It has the characteristics of good film-forming properties, excellent resilience and strong tensile strength. It is widely used in daily life and medical health care, such as latex mattresses, latex gloves, condoms, etc.

[0003] Currently, common condom materials include natural latex, polyurethane, and polyisoprene. Natural latex is the most traditional material, offering low cost and excellent elasticity, but it can pose allergy concerns. Polyurethane and polyisoprene, commonly used alternatives on the market, can address allergy concerns to a certain extent, but polyurethane is slightly less elastic, and polyisoprene is relatively expensive. Therefore, there is a need to develop a thinner material with excellent tensile properties and good elasticity. Summary of the Invention

[0004] The present application provides a bioprotein-modified polyurethane polymer, a preparation method and an application thereof to solve the problems mentioned in the background technology.

[0005] In a first aspect, a bioprotein-modified polyurethane polymer is provided, characterized in that it comprises:

[0006] A 20% solid content silk fibroin solution, a 35% solid content modified aqueous polyurethane solution, and a composite preparation, wherein the mass ratio of the silk fibroin solution to the modified aqueous polyurethane solution is 1:(2-10), and the addition amount of the composite preparation is 1-3% of the sum of the mass of the silk fibroin solution and the modified aqueous polyurethane solution;

[0007] The preparation method of the modified aqueous polyurethane solution comprises:

[0008] S101, preparing a prepolymer: mixing 40-45 parts of polybutylene adipate, 20-25 parts of isophorone diisocyanate, 5 parts of dimethylol propionic acid, and 0.05 parts of dibutyltin dilaurate, and continuously stirring under a nitrogen atmosphere at 50° C. until the -NCO content reaches 4-5%, thereby obtaining a prepolymer;

[0009] S102, preparing a modified prepolymer: adding 1.2 to 3.5 parts of a modifier to the prepolymer at 70° C. and reacting for 1 hour, cooling to 40° C. and dropwise adding 6 to 8 parts of triethylamine, then adding deionized water and dispersing at a speed of 2000 r / min to form an emulsion;

[0010] S103, post-processing: adding 4-6 parts of a silk fibroin solution with a solid content of 0.5% and 0.1-0.5 parts of a hindered phenol antioxidant to the emulsion, ultrasonically dispersing for 30 minutes, and degassing under reduced pressure to obtain a modified aqueous polyurethane solution.

[0011] Preferably, the modifier comprises 1 to 2 parts of tocopherol polyether and 0.2 to 1.5 parts of triethanolamine.

[0012] Preferably, the tocopherol polyether includes one of tocopherol polyether-10, tocopherol polyether-12 and tocopherol polyether-18.

[0013] Preferably, the composite preparation comprises xanthan gum and biological enzyme in a mass ratio of 1:(0.5-2), and the biological enzyme comprises at least one of laccase, lipase, and catalase.

[0014] Preferably, the biological enzyme is a mixture of laccase and catalase, and the mass ratio of the laccase to the catalase is 1:1.

[0015] Preferably, the post-treatment further comprises adding 0.5 to 1.2 parts of ZnO nanoparticles, wherein the particle size of the ZnO nanoparticles does not exceed 5 nm.

[0016] In a second aspect, a preparation method is provided for preparing the bioprotein-modified polyurethane polymer as described above, characterized in that it comprises the following steps:

[0017] S1, preparing a modified aqueous polyurethane solution;

[0018] S2, mixing the modified aqueous polyurethane solution, the silk fibroin solution and the composite preparation, and ultrasonically dispersing them for 15 minutes, and then vacuum degassing them for 10 minutes to obtain a mixed solution;

[0019] S3. Placing the mixed solution in a mold, pre-drying it at room temperature for 2 hours, and then drying it in an oven at 50° C. for 6 to 12 hours to obtain a bioprotein-modified polyurethane polymer.

[0020] In a third aspect, there is provided a use of any of the above-described bioprotein-modified polyurethane polymers or the bioprotein-modified polyurethane polymers prepared by the above-described preparation method as a composite modified film in condoms.

[0021] The beneficial effects of the technical solution provided by this application include:

[0022] The present application provides a bioprotein-modified polyurethane polymer, a preparation method, and an application thereof. By preparing the modified polyurethane and blending it with silk fibroin, the two are cross-linked to avoid insufficient strength when the polyurethane is used alone, and the amount of polyurethane used can be reduced, thereby improving the tensile strength of the product while maintaining comfort. Silk fibroin, as a natural protein, has good biocompatibility and can effectively broaden the application scope and application scenarios of the bioprotein-modified polyurethane polymer in condoms. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0024] Figure 1 A flow chart of the method for preparing a bioprotein-modified polyurethane polymer provided in this application;

[0025] Figure 2 This is a flow chart of the preparation method of the modified aqueous polyurethane solution provided in this application. DETAILED DESCRIPTION

[0026] To make the purpose, technical solutions, and advantages of the embodiments of this application more clear, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the drawings in the embodiments of this application. Obviously, the described embodiments are part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0027] The present application provides a bioprotein-modified polyurethane polymer, a preparation method and an application thereof, wherein the bioprotein-modified polyurethane polymer comprises a silk fibroin solution with a solid content of 20%, a modified aqueous polyurethane solution with a solid content of 35% and a composite preparation. Specifically, the mass ratio of the silk fibroin solution to the modified aqueous polyurethane solution is 1:(2-10), and the added amount of the composite preparation is 1-3% of the sum of the masses of the silk fibroin solution and the modified aqueous polyurethane solution.

[0028] Furthermore, the preparation method of the modified aqueous polyurethane solution includes:

[0029] S101, preparing a prepolymer: mixing 40-45 parts of polybutylene adipate, 20-25 parts of isophorone diisocyanate, 5 parts of dimethylol propionic acid, and 0.05 parts of dibutyltin dilaurate, and continuously stirring under a nitrogen atmosphere at 50° C. until the -NCO content reaches 4-5%, thereby obtaining a prepolymer;

[0030] S102, preparing a modified prepolymer: adding 1.2 to 3.5 parts of a modifier to the prepolymer at 70° C. and reacting for 1 hour, cooling to 40° C. and dropwise adding 6 to 8 parts of triethylamine, then adding deionized water and dispersing at a speed of 2000 r / min to form an emulsion;

[0031] S103, post-treatment: adding 4-6 parts of a silk fibroin solution with a solid content of 0.5% and 0.1-0.5 parts of a hindered phenol antioxidant (1010) to the emulsion, ultrasonically dispersing for 30 minutes, and degassing under reduced pressure to obtain a modified aqueous polyurethane solution.

[0032] Specifically, in the above S101, the -NCO content refers to the mass percentage of unreacted isocyanate groups (-NCO) in the prepolymer. The -NCO content is verified by infrared spectroscopy to provide reaction sites for the subsequent chain extension reaction.

[0033] In some optional embodiments, the modifier includes 1 to 2 parts of tocopherol polyether and 0.2 to 1.5 parts of triethanolamine.

[0034] Furthermore, the tocopherol polyether includes one of tocopherol polyether-10, tocopherol polyether-12 and tocopherol polyether-18.

[0035] In some optional embodiments, the composite formulation includes xanthan gum and biological enzymes in a mass ratio of 1:(0.5-2), wherein the biological enzymes include at least one of laccase, lipase, and catalase.

[0036] Furthermore, the biological enzyme is a mixture of laccase and catalase, and the mass ratio of laccase to catalase is 1:1.

[0037] In some optional embodiments, the post-treatment further includes adding 0.5 to 1.2 parts of ZnO nanoparticles, wherein the particle size of the ZnO nanoparticles does not exceed 5 nm.

[0038] The present application also provides a method for preparing the above-mentioned bioprotein-modified polyurethane polymer, which comprises the following steps:

[0039] S1, preparing a modified aqueous polyurethane solution;

[0040] S2, mixing the modified aqueous polyurethane solution, the silk fibroin solution and the composite preparation, and ultrasonically dispersing them for 15 minutes, and then vacuum degassing them for 10 minutes to obtain a mixed solution;

[0041] S3. Placing the mixed solution in a mold, pre-drying it at room temperature for 2 hours, and then drying it in an oven at 50° C. for 6 to 12 hours to obtain a bioprotein-modified polyurethane polymer.

[0042] Example 1

[0043] The preparation method of the bioprotein-modified polyurethane polymer provided in this embodiment comprises the following steps:

[0044] S1. Preparation of modified aqueous polyurethane solution:

[0045] S101, preparing a prepolymer: mixing 420 g of polybutylene adipate, 200 g of isophorone diisocyanate, 50 g of dimethylol propionic acid, and 0.5 g of dibutyltin dilaurate, and continuously stirring under a nitrogen atmosphere at 50° C. until the -NCO content reaches 4.5%, thereby obtaining a prepolymer;

[0046] S102, preparing a modified prepolymer: adding 10 g of tocopherol polyether-10 and 10 g of triethanolamine to the prepolymer at 70° C. and reacting for 1 hour, cooling to 40° C. and dropwise adding 70 g of triethylamine, then adding deionized water and dispersing at a speed of 2000 r / min to form an emulsion;

[0047] S103, post-treatment: adding 50 g of a silk fibroin solution with a solid content of 0.5%, 2 g of a hindered phenol antioxidant 1010, and 5 g of ZnO nanoparticles to the emulsion, ultrasonically dispersing for 30 min, and degassing under reduced pressure to obtain a modified aqueous polyurethane solution with a solid content of 35%;

[0048] S2, 450 g of the modified aqueous polyurethane solution prepared in S1, 50 g of a silk fibroin solution with a solid content of 20%, and 12 g of the composite preparation were mixed and ultrasonically dispersed for 15 min, followed by vacuum degassing for 10 min to obtain a mixed solution;

[0049] The composite preparation is a mixture of 6g xanthan gum, 3g laccase and 3g catalase.

[0050] S3. Place the mixed solution prepared in S2 into a mold, pre-dry it at room temperature for 2 hours, and then dry it in an oven at 50° C. for 10 hours to obtain a bioprotein-modified polyurethane polymer.

[0051] Example 2

[0052] The preparation method of the bioprotein-modified polyurethane polymer provided in this embodiment comprises the following steps:

[0053] S1. Preparation of modified aqueous polyurethane solution:

[0054] S101, preparing a prepolymer: mixing 400 g of polybutylene adipate, 200 g of isophorone diisocyanate, 50 g of dimethylol propionic acid, and 0.5 g of dibutyltin dilaurate, and continuously stirring under a nitrogen atmosphere at 50° C. until the -NCO content reaches 4%, thereby obtaining a prepolymer;

[0055] S102, preparing a modified prepolymer: adding 10 g of tocopherol polyether-10 and 2 g of triethanolamine to the prepolymer at 70° C. and reacting for 1 hour, cooling to 40° C. and dropwise adding 60 g of triethylamine, then adding deionized water and dispersing at a speed of 2000 r / min to form an emulsion;

[0056] S103, post-treatment: adding 40 g of a silk fibroin solution with a solid content of 0.5% and 1 g of a hindered phenol antioxidant 1010 to the emulsion prepared in S102, ultrasonically dispersing for 30 min, and degassing under reduced pressure to obtain a modified aqueous polyurethane solution with a solid content of 35%;

[0057] S2, mixing 400 g of the modified aqueous polyurethane solution prepared in S1, 200 g of a silk fibroin solution with a solid content of 20%, and 6 g of the composite preparation, and ultrasonically dispersing the mixture for 15 min, followed by vacuum degassing for 10 min to obtain a mixed solution;

[0058] The composite preparation is a mixture of 4g xanthan gum and 2g laccase.

[0059] S3. Place the mixed solution prepared in S2 into a mold, pre-dry it at room temperature for 2 hours, and then dry it in an oven at 50° C. for 6 hours to obtain a bioprotein-modified polyurethane polymer.

[0060] Example 3

[0061] The preparation method of the bioprotein-modified polyurethane polymer provided in this embodiment comprises the following steps:

[0062] S1. Preparation of modified aqueous polyurethane solution:

[0063] S101, preparing a prepolymer: mixing 450 g of polybutylene adipate, 250 g of isophorone diisocyanate, 50 g of dimethylol propionic acid, and 0.5 g of dibutyltin dilaurate, and continuously stirring under a nitrogen atmosphere at 50° C. until the -NCO content reaches 5%, thereby obtaining a prepolymer;

[0064] S102, preparing a modified prepolymer: adding 15 g of tocopherol polyether-12 and 15 g of triethanolamine to the prepolymer at 70° C. and reacting for 1 hour, cooling to 40° C. and dropwise adding 80 g of triethylamine, then adding deionized water and dispersing at a speed of 2000 r / min to form an emulsion;

[0065] S103, post-treatment: adding 60 g of a silk fibroin solution with a solid content of 0.5%, 5 g of a hindered phenol antioxidant 1010, and 12 g of ZnO nanoparticles to the emulsion, ultrasonically dispersing for 30 min, and degassing under reduced pressure to obtain a modified aqueous polyurethane solution with a solid content of 35%;

[0066] S2, 550 g of the modified aqueous polyurethane solution prepared in S1, 55 g of a silk fibroin solution with a solid content of 20%, and 12.1 g of the composite preparation were mixed and ultrasonically dispersed for 15 min, followed by vacuum degassing for 10 min to obtain a mixed solution;

[0067] The composite preparation is a mixture of 6g xanthan gum, 3.1g laccase and 3g lipase.

[0068] S3. Place the mixed solution prepared in S2 into a mold, pre-dry it at room temperature for 2 hours, and then dry it in an oven at 50° C. for 12 hours to obtain a bioprotein-modified polyurethane polymer.

[0069] Example 4

[0070] The preparation method of the bioprotein-modified polyurethane polymer provided in this embodiment comprises the following steps:

[0071] S1. Preparation of modified aqueous polyurethane solution:

[0072] S101, preparing a prepolymer: mixing 400 g of polybutylene adipate, 220 g of isophorone diisocyanate, 50 g of dimethylol propionic acid, and 0.5 g of dibutyltin dilaurate, and continuously stirring under a nitrogen atmosphere at 50° C. until the -NCO content reaches 4%, thereby obtaining a prepolymer;

[0073] S102, preparing a modified prepolymer: adding 20 g of tocopherol polyether-18 and 15 g of triethanolamine to the prepolymer at 70° C. and reacting for 1 hour, cooling to 40° C. and dropwise adding 70 g of triethylamine, then adding deionized water and dispersing at a speed of 2000 r / min to form an emulsion;

[0074] S103, post-treatment: adding 50 g of a silk fibroin solution with a solid content of 0.5%, 4 g of a hindered phenol antioxidant 1010, and 10 g of ZnO nanoparticles to the emulsion, ultrasonically dispersing for 30 min, and degassing under reduced pressure to obtain a modified aqueous polyurethane solution with a solid content of 35%;

[0075] S2, 500 g of the modified aqueous polyurethane solution prepared in S1, 100 g of a silk fibroin solution with a solid content of 20%, and 18 g of the composite preparation were mixed and ultrasonically dispersed for 15 min, followed by vacuum degassing for 10 min to obtain a mixed solution;

[0076] The composite preparation is a mixture of 6g xanthan gum, 8g laccase and 4g catalase.

[0077] S3. Place the mixed solution prepared in S2 into a mold, pre-dry it at room temperature for 2 hours, and then dry it in an oven at 50° C. for 10 hours to obtain a bioprotein-modified polyurethane polymer.

[0078] Example 5

[0079] The difference from Example 1 is that the method provided in this example does not add ZnO nanoparticles when preparing the modified aqueous polyurethane solution.

[0080] Comparative Example 1

[0081] The difference from Example 1 is that the preparation method provided in this comparative example does not add a composite preparation.

[0082] Comparative Example 2

[0083] The difference from Example 1 is that the preparation method provided in this comparative example does not add a modifier in S1.

[0084] Comparative Example 3

[0085] The difference from Example 1 is that in the preparation method provided in this comparative example, no silk fibroin solution is added to S2, and the amount of the modified aqueous polyurethane solution is adjusted to 600 g.

[0086] Comparative Example 4

[0087] On the basis of Comparative Example 3, no composite preparation is added, and in S1, the polyurethane is not modified, that is, no modifier, silk fibroin solution and hindered phenol antioxidant are added.

[0088] Comparative Example 5

[0089] The difference from Example 1 is that the preparation method provided in this comparative example does not perform the operation of S103 when preparing the modified aqueous polyurethane solution. After the emulsion is formed in S102, the modified aqueous polyurethane solution is directly obtained by decompression and degassing.

[0090] At room temperature, referring to GB / T 7544-2019 “Technical Requirements and Test Methods for Natural Rubber Latex Male Condoms”, the products obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were tested for tearing force, elongation at break, and thickness.

[0091] The comparative data of Examples 1 to 5 of the present application and Comparative Examples 1 to 5 are shown in Table 1.

[0092] Table 1

[0093] sample Breaking force (N) Elongation at break (%) Thickness (mm) Example 1 72.3 1530 0.032 Example 2 77.4 1370 0.041 Example 3 70.5 1544 0.039 Example 4 74.1 1340 0.063 Example 5 72.5 1537 0.033 Comparative Example 1 52.7 1050 0.030 Comparative Example 2 70.6 1336 0.032 Comparative Example 3 73.0 1184 0.050 Comparative Example 4 67.6 1579 0.052 Comparative Example 5 72.6 1440 0.033

[0094] From the examples, as the amount of silk fibroin added increases, the breaking force of the bioprotein modified polyurethane polymer is improved to a certain extent, and the elongation at break is reduced; from the comparison between Comparative Example 2 and Example 1, the addition of the modifier reduces the breaking force, but the elongation at break is improved to a certain extent; Comparative Example 3 does not add silk fibroin compared to Example 1, and only uses modified waterborne polyurethane. The breaking force is slightly improved, the elongation at break is reduced, and the thickness is increased. Combined with Comparative Example 4, it is speculated that the addition of silk fibroin can enhance the physical crosslinking with the modified polyurethane. The single modified waterborne polyurethane lacks a crosslinking network, and the breaking load decreases, but it also retains its own high elastic properties. Further referring to Example 1 and Comparative Example 5, the difference lies in whether silk fibroin is blended when the modified waterborne polyurethane is prepared. The results show that silk fibroin can form crosslinks with the modified polyurethane during preparation, thereby enhancing the load to a certain extent.

[0095] The foregoing is merely a list of specific embodiments of the present application, intended to enable those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application is not limited to the embodiments shown herein, but is intended to conform to the broadest scope consistent with the principles and novel features of the present application.

Claims

1. A bioprotein modified polyurethane polymer, characterized in that: It includes: A 20% solid content silk fibroin solution, a 35% solid content modified aqueous polyurethane solution, and a composite preparation, wherein the mass ratio of the silk fibroin solution to the modified aqueous polyurethane solution is 1:(2-10), and the addition amount of the composite preparation is 1-3% of the sum of the mass of the silk fibroin solution and the modified aqueous polyurethane solution; The preparation method of the modified aqueous polyurethane solution comprises: S101, preparing a prepolymer: mixing 40-45 parts of polybutylene adipate, 20-25 parts of isophorone diisocyanate, 5 parts of dimethylol propionic acid, and 0.05 parts of dibutyltin dilaurate, and continuously stirring under a nitrogen atmosphere at 50° C. until the -NCO content reaches 4-5%, thereby obtaining a prepolymer; S102, preparing a modified prepolymer: adding 1.2 to 3.5 parts of a modifier to the prepolymer at 70° C. and reacting for 1 hour, cooling to 40° C. and dropwise adding 6 to 8 parts of triethylamine, then adding deionized water and dispersing at a speed of 2000 r / min to form an emulsion; S103, post-processing: adding 4-6 parts of a silk fibroin solution with a solid content of 0.5% and 0.1-0.5 parts of a hindered phenol antioxidant to the emulsion, ultrasonically dispersing for 30 minutes, and degassing under reduced pressure to obtain a modified aqueous polyurethane solution.

2. The bioprotein-modified polyurethane polymer according to claim 1, wherein: The modifier includes 1 to 2 parts of tocopherol polyether and 0.2 to 1.5 parts of triethanolamine.

3. The bioprotein-modified polyurethane polymer according to claim 2, wherein: The tocopherol polyether includes one of tocopherol polyether-10, tocopherol polyether-12 and tocopherol polyether-18.

4. The bioprotein-modified polyurethane polymer according to claim 1, wherein: The composite preparation comprises xanthan gum and biological enzyme in a mass ratio of 1:(0.5-2), and the biological enzyme comprises at least one of laccase, lipase and catalase.

5. The bioprotein-modified polyurethane polymer according to claim 4, wherein: The biological enzyme is a mixture of laccase and catalase, and the mass ratio of the laccase to the catalase is 1:

1.

6. The bioprotein-modified polyurethane polymer according to claim 1, wherein: The post-treatment further includes adding 0.5 to 1.2 parts of ZnO nanoparticles, wherein the particle size of the ZnO nanoparticles does not exceed 5 nm.

7. A preparation method for preparing the bioprotein-modified polyurethane polymer according to any one of claims 1 to 6, characterized in that: It includes the following steps: S1, preparing a modified aqueous polyurethane solution; S2, mixing the modified aqueous polyurethane solution, the silk fibroin solution and the composite preparation, and ultrasonically dispersing them for 15 minutes, and then vacuum degassing them for 10 minutes to obtain a mixed solution; S3. Placing the mixed solution in a mold, pre-drying it at room temperature for 2 hours, and then drying it in an oven at 50° C. for 6 to 12 hours to obtain a bioprotein-modified polyurethane polymer.

8. Use of the bioprotein-modified polyurethane polymer according to any one of claims 1 to 6 or the bioprotein-modified polyurethane polymer prepared by the preparation method according to claim 7 as a composite modified film in condoms.

Images