Wood grain TPU composite material and preparation method and application thereof

Abstract

This invention discloses a wood grain TPU composite material, its preparation method, and its application. The raw materials of the wood grain TPU composite material include the following components measured by weight: 20-30 parts modified plant fiber, 60-70 parts TPU particles, 3-6 parts silane coupling agent, 1-3 parts lubricant, 1 part titanium dioxide, and 0.5-1 parts antioxidant; wherein the modified plant fiber is obtained by modifying plant fiber with cellulase, and the plant fiber length is 1-5 cm, with a fiber diameter of 0.1-1 mm. The TPU composite material of this invention exhibits a clear wood grain after molding, and the addition of modified fiber has minimal impact on the properties of the TPU itself, making it suitable for elastic protective shells and decorative parts.

Description

Technical Field

[0001] This invention belongs to the field of TPU composite material technology, specifically relating to a wood grain TPU composite material, its preparation method, and its application. Background Technology

[0002] TPU, also known as thermoplastic polyurethane elastomer, is a widely used polymer material in daily life. It is obtained by polymerizing isocyanate with polyether or polyester polyol. It possesses excellent elongation at break and resilience, and due to its low glass transition temperature, it maintains good elasticity even at low temperatures. Currently, it is used in many fields, including daily necessities, industrial machinery padding, and the automotive industry. Phone cases and shoe insoles are products we see every day.

[0003] As people's living standards improve, the demand for different material styles has also increased. Styles represented by wood grain have become very popular in the current context of pursuing environmental protection. However, polyurethane, as an elastomer, requires elasticity as a fundamental performance characteristic. The addition of traditional wood flour or plant fibers increases its modulus and alters its properties. Wood grain patterns created through printing, dyeing, or molding appear unnatural.

[0004] The challenge is to find a way to give TPU materials a beautiful and realistic wood grain texture without significantly affecting their basic elastic properties. Summary of the Invention

[0005] The main objective of this invention is to provide a wood grain TPU composite material, its preparation method, and its application, so as to overcome the shortcomings of the prior art.

[0006] To achieve the aforementioned objectives, the technical solutions adopted in the embodiments of the present invention include:

[0007] This invention provides a wood grain TPU composite material, the raw materials of which include the following components measured by weight: 20-30 parts modified plant fiber, 60-70 parts TPU particles, 3-6 parts silane coupling agent, 1-3 parts lubricant, 1 part titanium dioxide and 0.5-1 part antioxidant; wherein, the modified plant fiber is obtained by modifying plant fiber with cellulase.

[0008] Furthermore, the method for preparing the modified plant fiber includes: placing the original plant fiber in a cellulase aqueous solution at a temperature of 40-60℃ and a pH value of 3.5-6.5 and stirring thoroughly.

[0009] This invention also provides a method for preparing a wood grain TPU composite material, comprising:

[0010] Modified plant fibers were prepared by thoroughly stirring raw plant fibers in a cellulase aqueous solution at a temperature of 40-60℃ and a pH of 3.5-6.5.

[0011] The wood grain TPU composite material is prepared by mixing 20-30 parts by weight of modified plant fiber, 60-70 parts by weight of TPU particles, 3-6 parts by weight of silane coupling agent, 1-3 parts by weight of lubricant, 1 part by weight of titanium dioxide and 0.5-1 parts by weight of antioxidant evenly and then extruding.

[0012] Furthermore, the preparation method of the wood grain TPU composite material includes: cutting the original plant fibers into small segments of 1-5 cm, and selecting plant fibers with a diameter of 0.1-1 mm. Then, placing them in the cellulase aqueous solution and stirring thoroughly for 2-5 hours to obtain modified plant fibers.

[0013] Furthermore, the extrusion temperature is 170℃-210℃ and the rotation speed is 20-80r / min.

[0014] The present invention also provides the application of the aforementioned wood grain TPU composite material in elastic protective shells or other elastomeric decorative parts.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] (1) The present invention treats plant fibers with cellulase, which removes the cellulose component that provides mechanical strength while retaining its basic morphology, so that the addition of plant fibers will not significantly change the basic properties of TPU materials.

[0017] (2) The plant fibers selected in this invention are mostly agricultural waste, which are currently mainly returned to the field for burning. This invention not only gives the material a wood grain appearance, but also helps to protect the natural environment. It is applicable to elastic protective shells and other elastomer decorative parts. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic diagram of the wood grain TPU composite material in the embodiments of this application. Detailed Implementation

[0020] In view of the shortcomings of the prior art, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention. The following will further explain and illustrate this technical solution, its implementation process, and its principles.

[0021] One aspect of this invention provides a wood grain TPU composite material, the raw materials of which include the following components measured in parts by weight: 20-30 parts modified plant fiber, 60-70 parts TPU particles, 3-6 parts silane coupling agent, 1-3 parts lubricant, 1 part titanium dioxide, and 0.5-1 parts antioxidant; wherein the modified plant fiber is obtained by modifying plant fiber with cellulase.

[0022] In some preferred embodiments, the method for preparing the modified plant fiber includes: placing the original plant fiber in a cellulase aqueous solution at a temperature of 40-60°C and a pH of 3.5-6.5 and stirring thoroughly.

[0023] In some preferred embodiments, the thorough stirring time is 2-5 hours.

[0024] In some more preferred embodiments, the method for preparing the modified plant fiber includes: placing the original plant fiber in a cellulase aqueous solution at a temperature of 55°C and a pH of 4.8 and stirring thoroughly for 3-4 hours.

[0025] In some preferred embodiments, the plant fiber may include any one or more combinations of palm fiber, coconut fiber, reed, wheat straw, etc., but is not limited thereto.

[0026] In some preferred embodiments, the cellulase includes endoglucanase, exoglucanase, and β-glucosidase.

[0027] This invention utilizes cellulase to eliminate most of the cellulose components that contribute to mechanical strength in plant fibers, leaving only low-modulus, soft lignin and hemicellulose, while preserving the fiber morphology. During the process, the cellulase consists of three types: endoglucanase (C1-enzyme); exoglucanase (Cx-enzyme); and β-glucosidase, also known as cellobiose hydrolase. C1-enzyme acts on the surface of insoluble cellulose, causing the crystalline cellulose chains to break and the ends of long-chain cellulose molecules to become free, thus facilitating hydration of the cellulose chains. Cx-enzyme mainly includes endoglucanase and exoglucanase, which act on the cellulose catalyzed by C1-enzyme to decompose β-1,4 glycosidic bonds. The treated fibers are then blended with TPU material to obtain a wood-grain TPU composite material.

[0028] In some preferred embodiments, the TPU particles may include polyester-type polyurethane particles, but are not limited thereto.

[0029] In some preferred embodiments, the silane coupling agent may include Dow Corning silane coupling agent 6011, but is not limited thereto.

[0030] In some preferred embodiments, the lubricant comprises zinc stearate and / or calcium stearate.

[0031] In some preferred embodiments, the antioxidant may include liquid hindered phenolic antioxidant 1135 or liquid hindered amine antioxidant 5057, but is not limited thereto.

[0032] Another aspect of the present invention provides a method for preparing a wood grain TPU composite material, comprising:

[0033] Modified plant fibers were prepared by thoroughly stirring raw plant fibers in a cellulase aqueous solution at a temperature of 40-60℃ and a pH of 3.5-6.5.

[0034] The wood grain TPU composite material is prepared by mixing 20-30 parts by weight of modified plant fiber, 60-70 parts by weight of TPU particles, 3-6 parts by weight of silane coupling agent, 1-3 parts by weight of lubricant, 1 part by weight of titanium dioxide and 0.5-1 parts by weight of antioxidant evenly and then extruding.

[0035] In some preferred embodiments, the preparation method of the wood grain TPU composite material includes: cutting the original plant fibers into small segments of 1-5 cm, selecting fibers with an average diameter of 0.1-1 mm, and then placing them in the cellulase aqueous solution and stirring thoroughly for 2-5 hours to obtain modified plant fibers.

[0036] In some preferred embodiments, the extrusion is performed at a temperature of 170°C-210°C and a rotation speed of 20-80 r / min.

[0037] Another aspect of the present invention provides the application of the aforementioned wood grain TPU composite material in elastic protective shells or other elastomeric decorative parts.

[0038] The method described in this invention can impart a beautiful and realistic wood grain to TPU material without significantly affecting its basic elastic properties.

[0039] The technical solution of the present invention will be further described below with reference to several embodiments. Non-essential improvements and adjustments made to the process or formulation of the present invention by those skilled in the art based on the above-described invention are still within the scope of protection of the present invention.

[0040] Example 1

[0041] A wood grain TPU composite material is prepared from 3 kg of palm fiber, 6 kg of BASF 1095A TPU, 0.6 kg of Dow Corning 6011 coupling agent, 0.3 kg of zinc stearate lubricant, 0.1 kg of titanium dioxide, and 0.05 kg of antioxidant 1135. Specifically, the palm fiber is cut to 5 cm with an average diameter of 1 mm and placed in a commercial cellulase (Fengrui Biotechnology) aqueous solution. The mixture is stirred for 5 hours at 40°C, pH 6.5, and a rotation speed of 100 r / min. After washing and drying, the treated fiber is mixed evenly with other additives and placed in a twin-screw extruder. The extrusion temperature is 170°C and the rotation speed is 20 r / min to obtain the wood grain TPU composite material.

[0042] Example 2

[0043] A wood grain TPU composite material is prepared from 2 kg of coconut fiber, 7 kg of BASF 1095A TPU, 0.3 kg of Dow Corning 6011 coupling agent, 0.1 kg of calcium stearate lubricant, 0.1 kg of titanium dioxide, and 0.1 kg of antioxidant 1135. Specifically, the coconut fiber is cut to 3 cm with an average diameter of 0.5 mm and placed in a commercial cellulase (Fengrui Biotechnology) aqueous solution. The mixture is stirred for 2 hours at 60°C, pH 3.5, and 100 r / min. After washing and drying, the treated fiber is mixed evenly with other additives and placed in a twin-screw extruder. The extrusion temperature is 210°C and the speed is 80 r / min to obtain the wood grain TPU composite material.

[0044] Example 3

[0045] A wood grain TPU composite material is prepared from 2.5 kg of reed fiber, 6.5 kg of TPU Dawn C1090L, 0.4 kg of coupling agent Dow Corning 6011, 0.2 kg of lubricant calcium stearate, 0.1 kg of titanium dioxide, and 0.1 kg of antioxidant 7057. Specifically, the reed fiber is cut to 1 cm with an average diameter of 0.1 mm and placed in a commercial cellulase (Fengrui Biotechnology) aqueous solution. The solution is stirred for 3 hours at 55°C, pH 4.8, and a rotation speed of 100 r / min. After washing and drying, the treated fiber is mixed evenly with other additives and placed in a twin-screw extruder. The extrusion temperature is 190°C and the rotation speed is 50 r / min to obtain the wood grain TPU composite material.

[0046] Example 4

[0047] A wood grain TPU composite material is prepared from 3 kg of wheat straw, 7 kg of TPU Dawn C1090L, 0.5 kg of coupling agent Dow Corning 6011, 0.05 kg of lubricant calcium stearate, 0.05 kg of lubricant zinc stearate, 0.1 kg of titanium dioxide, and 0.075 kg of antioxidant 7057. Specifically, the wheat straw is cut to 2.5 cm with an average diameter of 0.3 mm and placed in a commercial cellulase (Fengrui Biotechnology) aqueous solution. The mixture is stirred for 4 hours at 45°C, pH 5, and a rotation speed of 100 r / min. After washing and drying, the treated fibers are mixed evenly with other additives and placed in a twin-screw extruder. The mixture is then extruded at 180°C and a rotation speed of 60 r / min to obtain the wood grain TPU composite material.

[0048] The wood grain TPU composite material prepared in the above embodiments can be molded into a material with a visual wood grain feel through processes such as extrusion and injection molding. Figure 1 As shown.

[0049] Comparative Example 1

[0050] A TPU composite material is prepared from 3 kg of palm fiber, 6 kg of BASF 1095A TPU, 0.6 kg of Dow Corning 6011 coupling agent, 0.3 kg of zinc stearate lubricant, 0.1 kg of titanium dioxide and 0.05 kg of antioxidant 1135. Specifically, the palm fiber is cut to 5 cm with an average diameter of 1 mm and mixed evenly with other additives. The mixture is then placed in a twin-screw extruder and extruded at an extrusion temperature of 170°C and a rotation speed of 20 r / min to obtain the TPU composite material.

[0051] Comparative Example 2

[0052] A TPU composite material is prepared from 2 kg of coconut fiber, 7 kg of BASF 1095A TPU, 0.3 kg of Dow Corning 6011 coupling agent, 0.1 kg of calcium stearate lubricant, 0.1 kg of titanium dioxide and 0.1 kg of antioxidant 1135. Specifically, the coconut fiber is cut to 3 cm with an average diameter of 0.5 mm and mixed evenly with other additives. The mixture is then placed in a twin-screw extruder and extruded at an extrusion temperature of 210°C and a rotation speed of 80 r / min to obtain the TPU composite material.

[0053] Comparative Example 3

[0054] A TPU composite material is prepared from 2.5 kg of reed fiber, 6.5 kg of TPU Dawn C1090L, 0.4 kg of coupling agent Dow Corning 6011, 0.2 kg of lubricant calcium stearate, 0.1 kg of titanium dioxide and 0.1 kg of antioxidant 7057. Specifically, the reed fiber is cut to 1 cm with an average diameter of 0.1 mm and mixed evenly with other additives. The mixture is then placed in a twin-screw extruder and extruded at an extrusion temperature of 190°C and a rotation speed of 50 r / min to obtain the TPU composite material.

[0055] Comparative Example 4

[0056] A TPU composite material is prepared from 3 kg of wheat straw, 7 kg of TPU Dawn C1090L, 0.5 kg of coupling agent Dow Corning 6011, 0.05 kg of lubricant calcium stearate, 0.05 kg of lubricant zinc stearate, 0.1 kg of titanium dioxide, and 0.075 kg of antioxidant 7057. Specifically, the wheat straw is cut to 2.5 cm with an average diameter of 0.3 mm and mixed evenly with other additives. The mixture is then placed in a twin-screw extruder and extruded at an extrusion temperature of 180°C and a rotation speed of 60 r / min to obtain the TPU composite material.

[0057] The mechanical properties of the wood grain TPU composite material prepared in the above embodiments and the TPU composite material prepared in the comparative example were compared, and the comparison results are shown in the table below.

[0058]

[0059]

[0060] As can be seen from the table above, after adding cellulase-treated plant fibers to TPU, the material can still maintain a certain elongation at break and hardness. However, after adding untreated plant fibers, the elongation at break of the material drops significantly, and the material becomes rigid and cannot be used as an elastomer material.

[0061] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0062] Although the invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the invention, and that elements of the embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of the invention to adapt particular situations or materials to the teachings of the invention. Therefore, this invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention, but rather is intended to encompass all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated otherwise, any use of the terms first, second, etc., does not indicate any order or importance, but is used to distinguish one element from another.

Claims

1. A wood grain TPU composite material, characterized in that, The raw materials of the wood grain TPU composite material include the following components measured by weight: 20-30 parts modified plant fiber, 60-70 parts TPU particles, 3-6 parts silane coupling agent, 1-3 parts lubricant, 1 part titanium dioxide, and 0.5-1 parts antioxidant; wherein, the preparation method of the modified plant fiber includes: placing reed fiber in a cellulase aqueous solution at a temperature of 55℃ and a pH of 4.8 and stirring thoroughly for 3-4 hours, removing the cellulose component that provides mechanical strength while retaining the basic morphology; the cellulase includes endoglucanase, exoglucanase, and β-glucosidase; the TPU particles are selected from polyester-type polyurethane particles; the length of the reed fiber is 1-5 cm and the diameter is 0.1-1 mm.

2. The wood grain TPU composite material according to claim 1, characterized in that: The silane coupling agent includes Dow Corning Silane Coupling Agent 6011.

3. The wood grain TPU composite material according to claim 1, characterized in that: The lubricant includes zinc stearate and / or calcium stearate.

4. The wood grain TPU composite material according to claim 1, characterized in that: The antioxidants include liquid hindered phenolic antioxidant 1135 or liquid hindered amine antioxidant 5057.

5. A method for preparing a wood grain TPU composite material, characterized in that, include: Modified plant fiber is prepared by placing reed fiber in a cellulase aqueous solution at 55℃ and pH 4.8 and stirring thoroughly for 3-4 hours. The basic morphology is retained while the cellulose component that provides mechanical strength is removed. The cellulase includes endoglucanase, exoglucanase and β-glucosidase. The length of the reed fiber is 1-5 cm and the diameter is 0.1-1 mm. The wood grain TPU composite material is prepared by mixing 20-30 parts by weight of modified plant fiber, 60-70 parts by weight of TPU particles, 3-6 parts by weight of silane coupling agent, 1-3 parts by weight of lubricant, 1 part by weight of titanium dioxide and 0.5-1 parts by weight of antioxidant evenly, and then extruding at a temperature of 170℃-210℃ and a speed of 20-80r / min.

6. The use of the wood grain TPU composite material according to any one of claims 1-4 in the preparation of elastic protective shells or other elastomeric decorative parts.

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