Biomimetic polymer for garment materials and preparation method of biomimetic polymer

Abstract

The invention relates to the technical field of garment materials, and discloses a bionic polymer for a garment material and a preparation method of the bionic polymer. Through the synergistic effect of the bionic micro-nano composite particles and the light / temperature double-response microspheres, the garment fabric is endowed with multiple dynamic functions: based on a photonic crystal structure and bionic shark skin textures, the fabric can realize intelligent optical regulation and control and fluid resistance reduction; the reversible cross-linked network enables the material to have self-repairing capability, and the service life is obviously prolonged; meanwhile, the biological enzyme auxiliary degradation unit is combined with the polylactic acid chain segment, so that efficient and controllable degradation of the fiber in the waste stage is realized, and the bottleneck that a traditional bionic polymer is difficult to recycle is broken through. In addition, the micro-fluidic spinning process enables the distribution uniformity of functional units to be improved by more than 50% by accurately regulating and controlling the sea island structure, and ensures the stable synergy of air permeability, waterproofness, mechanical strength and other properties. According to the invention, high wear resistance is maintained, and environment self-adaption and green and sustainable characteristics are realized at the same time.

Description

Technical Field

[0001] The invention relates to the technical field of clothing fabrics, in particular to a bionic polymer for clothing fabrics and a preparation method thereof. Background Art

[0002] As people's demand for the functionality of clothing fabrics continues to increase, traditional natural fibers and synthetic fibers can no longer meet the diversified demands of modern consumers for comfort, environmental protection, durability, and special functions (such as antibacterial, waterproof, breathable, intelligent adjustment, etc.). In recent years, the application of bionics in the field of materials science has provided new ideas for the innovation of clothing fabrics. Bionic polymers can give fabrics excellent properties by imitating the structure or functional characteristics of organisms in nature. For example, the super-hydrophobic structure of the lotus leaf surface can achieve self-cleaning function, and the mechanical properties of spider silk can be used to prepare high-strength fibers. However, the existing bionic polymers often have problems such as complex process, high cost, and environmental unfriendliness during the preparation process, which limits their large-scale application.

[0003] In addition, traditional clothing fabrics are prone to wear, deformation, fading and other problems after long-term use, and lack adaptability to environmental changes. For example, in a high temperature environment, the air permeability and heat dissipation of the fabric are insufficient; in a low temperature environment, the warmth retention performance is difficult to meet the demand. Therefore, the development of a bionic polymer fabric that is multifunctional, environmentally adaptable and sustainable has become an important research direction in the current textile industry. For this purpose, a bionic polymer for clothing fabrics and a preparation method thereof are proposed. Summary of the invention

[0004] In view of the deficiencies of the prior art, the present invention provides a bionic polymer for clothing fabrics and a preparation method thereof to solve the background technical problems.

[0005] In the first aspect, in order to achieve the above-mentioned purpose, the present invention provides the following technical solution: a bionic polymer for clothing fabrics, comprising the following components: Matrix material: composed of bio-based polyester and polylactic acid copolymer, of which the polylactic acid segment accounts for 20%-40% and 55%-75% of the total polymer mass; Dynamic bionic functional unit: including bionic micro-nano composite particles, light / temperature dual-responsive polymer microspheres and dynamic cross-linking agents, accounting for 15%-25% of the total mass of the polymer; Bio-enzyme-assisted degradation unit: composed of mesoporous silica nanoparticles loaded with cellulase, accounting for 3%-8% of the total mass of the polymer; Interface enhancer: Hyperbranched polymer containing siloxane groups, accounting for 2%-5% of the total polymer mass.

[0006] Preferably, the bionic micro-nano composite particles are a composite with a multi-level bionic structure, comprising: Core: Titanium dioxide / silicon dioxide heterojunction particles that mimic the photonic crystal structure of butterfly wings, with a particle size of 200-500 nanometers; Shell: The polydopamine layer covering the surface of the inner core has a thickness of 10-50 nanometers and is modified with a micro-groove structure that mimics the texture of shark skin.

[0007] Preferably, the light / temperature dual-responsive polymer microspheres are core-shell structures: Core layer: composed of poly N-isopropylacrylamide, with temperature-sensitive phase change characteristics; Shell: composed of azobenzene copolymer, with photoisomerization properties; The particle size of the microspheres is 1-5 microns, and the shell surface is provided with a bionic lotus leaf papillary micro-nano structure.

[0008] Preferably, the dynamic crosslinker is a furan / maleimide type reversible covalent crosslinker based on the Diels-Alder reaction, and its added amount accounts for 0.5%-2% of the mass of the matrix material, and is used to construct a network structure with self-healing ability.

[0009] In a second aspect, a method for preparing a biomimetic polymer for clothing fabric is provided, wherein the method is used to realize the biomimetic polymer for clothing fabric described in the first aspect, and comprises the following steps: Step 1: Under the protection of inert gas, bio-based polyester and polylactic acid are block copolymerized by reactive extrusion, the screw speed is controlled at 200-400 rpm, and the reaction temperature is 190°C-210°C; Step 2: pre-dispersing the dynamic bionic functional unit and the interface enhancer by high shear emulsification technology to form a stable suspension with a particle size of ≤5 μm; Step 3: Co-spinning the copolymer obtained in step 1 and the suspension in step 2 by using microfluidic spinning technology, controlling the flow rate ratio of the two phases in the microfluidic channel to be 1:3-1:5, to obtain a composite fiber with an island structure; Step 4: The fiber is subjected to photo-controlled cross-linking treatment, and ultraviolet light (wavelength 365nm, intensity 50-100mW / cm²) is used to isomerize the azobenzene group and simultaneously trigger the Diels-Alder dynamic cross-linking reaction.

[0010] Preferably, in the microfluidic spinning technology: The sea phase is a bio-based copolymer melt with a viscosity controlled at 500-800 Pa·s; The island phase is a suspension of dynamic biomimetic functional units, and the conductivity is adjusted to 100-300 μS / cm; The spinning electric field strength is 1.5-3 kV / cm, and the fiber diameter ranges from 5-20 μm.

[0011] Preferably, a bioactivation treatment is added after step 4: the fiber is immersed in a phosphate buffer containing cellulase and treated at 40° C.-50° C. for 10-30 minutes to load the biological enzyme into the mesoporous silica nanoparticles.

[0012] Compared with the prior art, the present invention has the following beneficial effects: The present invention endows clothing fabrics with multiple dynamic functions through the synergistic effect of bionic micro-nano composite particles and light / temperature dual-responsive microspheres: based on the photonic crystal structure and bionic shark skin texture, the fabric can achieve intelligent optical regulation and fluid drag reduction; the reversible cross-linking network enables the material to have self-repairing ability, significantly extending the service life; at the same time, the combination of bio-enzyme-assisted degradation units and polylactic acid segments achieves efficient and controllable degradation of fibers in the waste stage, breaking through the bottleneck of traditional bionic polymers that are difficult to recycle. In addition, the microfluidic spinning process improves the uniformity of functional unit distribution by more than 50% by precisely controlling the island structure, ensuring the stable synergy of properties such as air permeability, waterproofness, and mechanical strength. While maintaining high wear resistance, the present invention has both environmental adaptability and green sustainability.

[0013] Other features and advantages of the present invention will be described in the following description, and partly become apparent from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention can be realized and obtained by the structures pointed out in the description, claims and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 The present invention is a flow chart of the method for preparing bionic polymer for clothing fabrics. DETAILED DESCRIPTION

[0015] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this technical field without creative work are within the scope of protection of the present invention.

[0016] See also Figure 1 The present invention provides a bionic polymer for clothing fabric and a preparation method thereof. The following provides multiple embodiments and comparative examples to demonstrate the effects of different raw material ratios and preparation process parameters on the performance of the bionic polymer.

[0017] Example 1: Highly light-responsive fibers Raw material ratio: Matrix material: Bio-based polyester / polylactic acid (7:3), accounting for 70% of the total mass Dynamic functional unit: biomimetic micro-nanoparticles (10%), photoresponsive microspheres (12%), DA cross-linker (1%) Bio-enzyme unit: mesoporous silica loaded with cellulase (5%) Interface enhancer: hyperbranched siloxane polymer (2%) Based on the above raw material ratio, preparation is carried out: Reactive Extrusion: Bio-based polyester and polylactic acid are added into the twin-screw extruder in proportion. Set the temperature zones: feeding zone 180℃ → melting zone 200℃ → reaction zone 210℃ → die head 190℃.

[0018] The screw speed was set to 300 rpm, and reactive extrusion was performed under nitrogen protection.

[0019] The extruded product is copolymer particles with a diameter of 3 mm, which are cooled and used for later use.

[0020] Dynamic functional unit pre-dispersion: The biomimetic micro-nano particles, photoresponsive microspheres, DA cross-linking agent and hyperbranched siloxane polymer are mixed in proportion and added into deionized water.

[0021] A high shear emulsifier (rotation speed 15000 rpm) was used for 30 minutes to form a uniform suspension (particle size ≤ 5 μm, conductivity 200 μS / cm).

[0022] Preparation of composite fibers by microfluidic spinning: The copolymer particles were added into the sea phase hopper of the microfluidic spinning device, the melt temperature was set at 200 °C, and the viscosity was controlled at 650 Pa·s.

[0023] Add the pre-dispersed suspension into the island phase hopper and set the flow rate to 0.5 mL / min.

[0024] The sea phase / island phase flow velocity ratio was adjusted to 1:4 and the electric field strength was 2.5 kV / cm.

[0025] The output fiber diameter is controlled at 12±2μm, forming a sea-island structure (the island phase is evenly distributed inside the fiber).

[0026] Light-controlled dynamic crosslinking: The fiber was passed through a UV curing device (wavelength 365nm, intensity 80mW / cm²) for 3 minutes.

[0027] The photoisomerization of the azobenzene group (cis→trans) was triggered, and the DA cross-linker formed a dynamic network.

[0028] Enzyme loading activation: The fibers were immersed in a phosphate buffer solution (pH=6.8, 50°C) containing cellulase and shaken for 20 minutes.

[0029] The enzyme molecules are embedded in the mesoporous silica carrier to complete the biological activation.

[0030] Performance characteristics: Breathability increased by 50% under light Self-repair efficiency>90% Degradation rate (30 days): 70% Example 2: High temperature responsive fiber Raw material ratio: Matrix material: Bio-based polyester / polylactic acid (6:4), accounting for 65% of the total mass Dynamic functional unit: biomimetic micro-nanoparticles (8%), temperature-responsive microspheres (15%), DA cross-linker (1.5%) Bioenzyme unit: Mesoporous silica loaded with cellulase (6%) Interface enhancer: hyperbranched siloxane polymer (4.5%) Based on the above raw material ratio, preparation is carried out: Reactive Extrusion: Add bio-based polyester and polylactic acid into the twin-screw extruder in proportion, and set the temperature zones: feeding zone 190°C → melting zone 210°C → reaction zone 220°C → die head 200°C.

[0031] The screw speed was set to 350 rpm, and reactive extrusion was performed under nitrogen protection.

[0032] The extruded product is copolymer particles with a diameter of 3 mm, which are cooled and used for later use.

[0033] Dynamic functional unit pre-dispersion: The biomimetic micro-nano particles, the temperature-responsive microspheres, the DA cross-linking agent and the hyperbranched siloxane polymer are mixed in proportion and added into deionized water.

[0034] The mixture was treated with a high shear emulsifier (rotation speed 15000 rpm) for 30 min to form a uniform suspension.

[0035] Preparation of composite fibers by microfluidic spinning: The copolymer particles were added into the sea phase hopper, the melting temperature was set to 210 °C, and the viscosity was controlled at 700 Pa·s.

[0036] Add the pre-dispersed suspension into the island phase hopper and set the flow rate to 0.5 mL / min.

[0037] The sea phase / island phase flow velocity ratio was adjusted to 1:3 and the electric field strength was 3 kV / cm.

[0038] The output fiber diameter is controlled at 10±2μm.

[0039] Light-controlled dynamic crosslinking: The fiber was passed through a UV curing device (wavelength 365nm, intensity 100mW / cm²) for 2 minutes.

[0040] Enzyme loading activation: The fibers were immersed in a phosphate buffer solution (pH=7.0, 45°C) containing cellulase and shaken for 25 minutes.

[0041] Performance characteristics: Shrinkage rate 20% when temperature>32℃ Self-repair efficiency>85% Degradation rate (30 days): 65% Example 3: High mechanical properties fiber Raw material ratio: Matrix material: Bio-based polyester / polylactic acid (8:2), accounting for 75% of the total mass Dynamic functional units: biomimetic micro-nanoparticles (12%), light / temperature dual-responsive microspheres (8%), DA cross-linker (2%) Bio-enzyme unit: mesoporous silica loaded with cellulase (3%) Interface enhancer: hyperbranched siloxane polymer (5%) Based on the above raw material ratio, preparation is carried out: Reactive Extrusion: Add bio-based polyester and polylactic acid into the twin-screw extruder in proportion, and set the temperature zones: feeding zone 170°C → melting zone 190°C → reaction zone 200°C → die head 180°C.

[0042] The screw speed was set to 250 rpm, and reactive extrusion was performed under nitrogen protection.

[0043] Dynamic functional unit pre-dispersion: The biomimetic micro-nano particles, light / temperature dual-responsive microspheres, DA cross-linking agent and hyperbranched siloxane polymer are mixed in proportion and added into deionized water.

[0044] The mixture was treated with a high shear emulsifier (rotation speed 15000 rpm) for 30 min to form a uniform suspension.

[0045] Preparation of composite fibers by microfluidic spinning: The copolymer particles were added into the sea phase hopper, the melting temperature was set to 190 °C, and the viscosity was controlled at 600 Pa·s.

[0046] Add the pre-dispersed suspension into the island phase hopper and set the flow rate to 0.5 mL / min.

[0047] The sea phase / island phase flow velocity ratio was adjusted to 1:5 and the electric field strength was 2 kV / cm.

[0048] The output fiber diameter is controlled at 15±2μm.

[0049] Light-controlled dynamic crosslinking: The fiber was passed through a UV curing device (wavelength 365nm, intensity 60mW / cm²) for 4 minutes.

[0050] Enzyme loading activation: The fibers were immersed in a phosphate buffer solution (pH=6.5, 55°C) containing cellulase and shaken for 15 minutes.

[0051] Performance characteristics: Tensile strength increased by 30% (compared to Example 1) Self-repair efficiency>80% Degradation rate (30 days): 60% Comparative Example 1: No dynamic crosslinker Raw material ratio: Matrix material: Bio-based polyester / polylactic acid (7:3), accounting for 70% of the total mass Dynamic functional units: biomimetic micro-nanoparticles (10%), photoresponsive microspheres (12%) Bio-enzyme unit: mesoporous silica loaded with cellulase (5%) Interface enhancer: hyperbranched siloxane polymer (3%) Based on the above raw material ratio, preparation is carried out: Reactive extrusion: Same as Example 1.

[0052] Dynamic functional unit pre-dispersion: biomimetic micro-nano particles, photoresponsive microspheres and hyperbranched siloxane polymers are mixed in proportion and emulsified.

[0053] Microfluidic spinning: Same as Example 1.

[0054] Photo-controlled cross-linking: same as in Example 1.

[0055] Biological enzyme loading and activation: same as Example 1.

[0056] Performance characteristics: Self-healing efficiency: <10% (without dynamic cross-linking network) Degradation rate (30 days): 70% Comparative Example 2: No bioenzyme unit Raw material ratio: Matrix material: Bio-based polyester / polylactic acid (7:3), accounting for 70% of the total mass Dynamic functional unit: biomimetic micro-nanoparticles (10%), photoresponsive microspheres (12%), DA cross-linker (1%) Interface enhancer: hyperbranched siloxane polymer (7%) Based on the above raw material ratio, preparation is carried out: Reactive extrusion: Same as Example 1.

[0057] Dynamic functional unit pre-dispersion: biomimetic micro-nano particles, photoresponsive microspheres, DA cross-linking agent and hyperbranched siloxane polymer are mixed in proportion and emulsified.

[0058] Microfluidic spinning: Same as Example 1.

[0059] Photo-controlled cross-linking: same as in Example 1.

[0060] Performance characteristics: Degradation rate (30 days): <10% (no enzyme triggering degradation) Self-repair efficiency>90% Comparative Example 3: Traditional melt spinning Raw material ratio: same as Example 1 Based on the above raw material ratio, preparation is carried out: Reactive extrusion: Same as Example 1.

[0061] Conventional melt spinning: Add copolymer pellets into the melt spinning machine, set the spinning temperature to 200°C and the draft ratio to 1:3.

[0062] Photo-controlled cross-linking: same as in Example 1.

[0063] Biological enzyme loading and activation: same as Example 1.

[0064] Performance characteristics: Uneven fiber diameter (20±10μm) Functional units are unevenly distributed, and air permeability is only increased by 20% Self-repair efficiency <50%.

[0065]

[0066] By comparing the preparation process and performance test results of different embodiments and comparative examples, the following conclusions can be drawn: the biomimetic polymer fiber of the present invention shows significant advantages in functionality, environmental adaptability and sustainability. The introduction of the dynamic crosslinker significantly improves the self-repairing ability of the fiber (self-repairing efficiency>90%), while the bioenzyme-assisted degradation unit realizes the controllable degradation of the fiber (30-day degradation rate>60%), solving the problem that traditional biomimetic polymers are difficult to recycle. In addition, the application of microfluidic spinning technology not only improves the uniformity of the fiber (diameter deviation ≤2μm), but also realizes the efficient distribution of functional units, so that the fiber has excellent light / temperature dual response characteristics (air permeability increased by 50% under light, and shrinkage rate of 15% when temperature>32°C). In contrast, the traditional melt spinning process (Comparative Example 3) has obvious deficiencies in fiber uniformity and functional distribution, while the fibers without dynamic crosslinkers (Comparative Example 1) or without bioenzyme units (Comparative Example 2) lose their self-repairing ability and controllable degradation performance, respectively. In summary, the present invention has successfully developed a bionic polymer fiber with high performance, environmental friendliness and multifunctional integration characteristics through multi-level bionic structure design, dynamic response synergy mechanism and green preparation process, providing an innovative solution for the development of future smart clothing fabrics.

Claims

1. A bionic polymer for clothing fabric, characterized in that: Includes the following components: Matrix material: composed of bio-based polyester and polylactic acid copolymer, of which the polylactic acid segment accounts for 20%-40% and 55%-75% of the total polymer mass; Dynamic bionic functional unit: including bionic micro-nano composite particles, light / temperature dual-responsive polymer microspheres and dynamic cross-linking agents, accounting for 15%-25% of the total mass of the polymer; Bio-enzyme-assisted degradation unit: composed of mesoporous silica nanoparticles loaded with cellulase, accounting for 3%-8% of the total mass of the polymer; Interface enhancer: Hyperbranched polymer containing siloxane groups, accounting for 2%-5% of the total polymer mass.

2. The bionic polymer for clothing fabric according to claim 1, characterized in that: The bionic micro-nano composite particles are a composite body with a multi-level bionic structure, including: Core: Titanium dioxide / silicon dioxide heterojunction particles that mimic the photonic crystal structure of butterfly wings, with a particle size of 200-500 nanometers; Shell: The polydopamine layer covering the surface of the inner core has a thickness of 10-50 nanometers and is modified with a micro-groove structure that mimics the texture of shark skin.

3. The bionic polymer for clothing fabric according to claim 1, characterized in that: The light / temperature dual-responsive polymer microspheres are core-shell structures: Core layer: composed of poly N-isopropylacrylamide, with temperature-sensitive phase change characteristics; Shell: composed of azobenzene copolymer, with photoisomerization properties; The particle size of the microspheres is 1-5 microns, and the shell surface is provided with a bionic lotus leaf papillary micro-nano structure.

4. The bionic polymer for clothing fabric according to claim 1, characterized in that: The dynamic cross-linking agent is a furan / maleimide type reversible covalent cross-linking agent based on the Diels-Alder reaction, and its addition amount accounts for 0.5%-2% of the mass of the base material, and is used to construct a network structure with self-repairing ability.

5. A method for preparing a bionic polymer for clothing fabrics, characterized in that: The method is used to realize the bionic polymer for clothing fabrics according to any one of claims 1 to 4, comprising the following steps: Step 1: Under the protection of inert gas, bio-based polyester and polylactic acid are block copolymerized by reactive extrusion, the screw speed is controlled at 200-400 rpm, and the reaction temperature is 190°C-210°C; Step 2: pre-dispersing the dynamic bionic functional unit and the interface enhancer by high shear emulsification technology to form a stable suspension with a particle size of ≤5 μm; Step 3: Co-spinning the copolymer obtained in step 1 and the suspension in step 2 by using microfluidic spinning technology, controlling the flow rate ratio of the two phases in the microfluidic channel to be 1:3-1:5, to obtain a composite fiber with an island structure; Step 4: The fiber is subjected to photo-controlled cross-linking treatment, and ultraviolet light (wavelength 365nm, intensity 50-100mW / cm²) is used to isomerize the azobenzene group and simultaneously trigger the Diels-Alder dynamic cross-linking reaction.

6. The method for preparing a biomimetic polymer for clothing fabric according to claim 5, characterized in that: In the microfluidic spinning technology: The sea phase is a bio-based copolymer melt with a viscosity controlled at 500-800 Pa·s; The island phase is a suspension of dynamic biomimetic functional units, and the conductivity is adjusted to 100-300 μS / cm; The spinning electric field strength is 1.5-3 kV / cm, and the fiber diameter ranges from 5-20 μm.

7. The method for preparing a biomimetic polymer for clothing fabric according to claim 5, characterized in that: After step 4, a bioactivation treatment is added: the fiber is immersed in a phosphate buffer containing cellulase and treated at 40° C.-50° C. for 10-30 minutes to load the bioenzyme into the mesoporous silica nanoparticles.

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