CN112094490B - Carbon dioxide-cyclohexene oxide copolymer composite material and preparation method thereof - Google Patents
Carbon dioxide-cyclohexene oxide copolymer composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a carbon dioxide-cyclohexene oxide copolymer composite material and a preparation method thereof. The composite material provided by the invention comprises the following components in parts by weight: 100 parts of low molecular weight carbon dioxide-cyclohexene oxide copolymer; 10-30 parts of a high molecular weight carbon dioxide-cyclohexene oxide copolymer; 2-15 parts of nano silicon dioxide; 1-3 parts of wollastonite nano particles with a lamellar structure; 1-3 parts of glass fiber; 0.05-1 part of polymaleic anhydride; 10-20 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer. The carbon dioxide-cyclohexene oxide copolymer is used as a base material, and a proper amount of high molecular weight carbon dioxide-cyclohexene oxide copolymer, silicon dioxide, wollastonite nano particles, glass fiber, polymaleic anhydride and graft copolymer are introduced into the base material, so that the composite material with excellent mechanical strength, heat resistance and light transmittance is obtained.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a carbon dioxide-cyclohexene oxide copolymer composite material and a preparation method thereof.
Background
With the rapid development of productivity, the emission amount of carbon dioxide in industrial production increases year by year, and the direct emission of a large amount of carbon dioxide into the atmosphere environment not only aggravates the greenhouse effect, but also causes waste of carbon resources. Carbon dioxide is one of the main raw materials for synthesizing the carbon dioxide-cyclohexene oxide copolymer, so that the carbon dioxide in the industrial waste gas is used as a carbon source to produce the carbon dioxide-cyclohexene oxide copolymer, thereby realizing the resource utilization of the carbon dioxide waste gas and slowing down the greenhouse effect; but also can reduce the consumption of non-renewable carbon sources such as petrochemical products and the like and relieve the problem of shortage of petrochemical raw materials. In addition, the carbon dioxide-cyclohexene oxide copolymer is also a material which can be completely biodegraded, so that the problem of white pollution can not be generated in the using process, and the carbon dioxide-cyclohexene oxide copolymer has a very wide market prospect.
However, the carbon dioxide-cyclohexene oxide copolymer as an amorphous polymer has a glass transition temperature of only about 100 ℃, low tensile strength, poor heat resistance and poor light transmittance. Therefore, how to improve the mechanical property, heat resistance and light transmittance of the carbon dioxide-cyclohexene oxide copolymer material has become a focus of research in the field of carbon dioxide-cyclohexene oxide copolymer materials.
Disclosure of Invention
In view of this, the invention aims to provide a carbon dioxide-cyclohexene oxide copolymer composite material and a preparation method thereof.
The invention provides a carbon dioxide-cyclohexene oxide copolymer composite material, which comprises the following components in parts by weight:
the weight average molecular weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer is less than or equal to 15 ten thousand;
the weight average molecular weight of the high molecular weight carbon dioxide-cyclohexene oxide copolymer is not less than 25 ten thousand.
Preferably, the weight average molecular weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer is 5-10 ten thousand.
Preferably, the weight average molecular weight of the high molecular weight carbon dioxide-cyclohexene oxide copolymer is 30-50 ten thousand.
Preferably, the particle size of the nano silicon dioxide is 5-100 nm.
Preferably, the lamellar degree of the lamellar wollastonite nanoparticles is 0.5-5 nm.
Preferably, the diameter of the glass fiber is 50-100 nm; the length of the glass fiber is 0.5-1 mm.
Preferably, the molecular weight of the polymaleic anhydride is 500-2000.
Preferably, the grafting degree of the glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer is 0.1-0.5%.
The invention provides a preparation method of a carbon dioxide-cyclohexene oxide copolymer composite material in the technical scheme, which comprises the following steps:
melting and blending the raw materials to obtain a carbon dioxide-cyclohexene oxide copolymer composite material;
the raw materials comprise low molecular weight carbon dioxide-cyclohexene oxide copolymer, high molecular weight carbon dioxide-cyclohexene oxide copolymer, nano silicon dioxide, lamellar wollastonite nano particles, glass fiber, polymaleic anhydride and glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer.
Preferably, the raw materials are dried to the water content of less than or equal to 200ppm before being subjected to melt blending.
Compared with the prior art, the invention provides a carbon dioxide-cyclohexene oxide copolymer composite material and a preparation method thereof. The carbon dioxide-cyclohexene oxide copolymer composite material provided by the invention comprises the following components in parts by weight: 100 parts of low molecular weight carbon dioxide-cyclohexene oxide copolymer; 10-30 parts of a high molecular weight carbon dioxide-cyclohexene oxide copolymer; 2-15 parts of nano silicon dioxide; 1-3 parts of wollastonite nano particles with a lamellar structure; 1-3 parts of glass fiber; 0.05-1 part of polymaleic anhydride; 10-20 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer; the weight average molecular weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer is less than or equal to 15 ten thousand; the weight average molecular weight of the high molecular weight carbon dioxide-cyclohexene oxide copolymer is not less than 25 ten thousand. The carbon dioxide-cyclohexene oxide copolymer is used as a base material, and a proper amount of high molecular weight carbon dioxide-cyclohexene oxide copolymer, nano silicon dioxide, lamellar wollastonite nano particles, glass fibers, polymaleic anhydride and glycidyl methacrylate are introduced into the base material to graft the carbon dioxide-cyclohexene oxide copolymer, so that the composite material with excellent mechanical strength, heat resistance and light transmittance is obtained. Experimental results show that the tensile strength of the carbon dioxide-cyclohexene oxide copolymer composite material provided by the invention is not less than 40MP, the Vicat softening temperature is not less than 105 ℃, and the light transmittance is more than 85%.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a carbon dioxide-cyclohexene oxide copolymer composite material, which comprises the following components in parts by weight:
the weight average molecular weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer is less than or equal to 15 ten thousand;
the weight average molecular weight of the high molecular weight carbon dioxide-cyclohexene oxide copolymer is not less than 25 ten thousand.
The composite material provided by the invention comprises a low molecular weight carbon dioxide-cyclohexene oxide copolymer, a high molecular weight carbon dioxide-cyclohexene oxide copolymer, nano silicon dioxide, lamellar wollastonite nano particles, glass fibers, polymaleic anhydride and glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer. Wherein the weight average molecular weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer is less than or equal to 15 ten thousand, preferably 5 to 10 ten thousand, and specifically can be 5 ten thousand, 5.5 ten thousand, 6 ten thousand, 6.5 ten thousand, 7 ten thousand, 7.5 ten thousand, 8 ten thousand, 8.5 ten thousand, 9 ten thousand, 9.5 ten thousand or 10 ten thousand.
In the composite material provided by the invention, the weight average molecular weight of the high molecular weight carbon dioxide-cyclohexene oxide copolymer is not less than 25 ten thousand, preferably 30 to 50 ten thousand, and specifically may be 30 ten thousand, 31 ten thousand, 32 ten thousand, 33 ten thousand, 34 ten thousand, 35 ten thousand, 36 ten thousand, 37 ten thousand, 38 ten thousand, 39 ten thousand, 40 ten thousand, 41 ten thousand, 42 ten thousand, 43 ten thousand, 44 ten thousand, 45 ten thousand, 46 ten thousand, 47 ten thousand, 48 ten thousand, 49 ten thousand or 50 ten thousand. In the present invention, the content of the high molecular weight carbon dioxide-cyclohexene oxide copolymer in the composite material is 10 to 30 parts by weight, specifically 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, or 30 parts by weight, based on 100 parts by weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer in the composite material.
In the composite material provided by the invention, the particle size of the nano silicon dioxide is preferably 5-100 nm, and specifically can be 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100 nm. In the present invention, the content of the nano-silica in the composite material is 2 to 15 parts by weight, specifically 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight or 15 parts by weight, based on 100 parts by weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer in the composite material.
In the composite material provided by the invention, the lamella degree of the lamellar wollastonite nanoparticles is preferably 0.5-5 nm, and specifically can be 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, 1.1nm, 1.2nm, 1.3nm, 1.4nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm or 5 nm. In the present invention, the content of the lamellar wollastonite nanoparticles in the composite material is 1 to 3 parts by weight, specifically 1 part by weight, 1.1 part by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, or 3 parts by weight, based on 100 parts by weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer in the composite material.
In the composite material provided by the invention, the diameter of the glass fiber is preferably 50-100 nm, and specifically can be 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100 nm; the length of the glass fiber is preferably 0.5-1 mm, and specifically can be 0.5mm, 0.55mm, 0.6mm, 0.65mm, 0.7mm, 0.75mm, 0.8mm, 0.85mm, 0.9mm, 0.95mm or 1 mm. In the present invention, the content of the glass fiber in the composite material is 1 to 3 parts by weight, specifically 1 part by weight, 1.1 part by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, or 3 parts by weight, based on 100 parts by weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer in the composite material.
In the composite material provided by the invention, the molecular weight of the polymaleic anhydride is preferably 500-2000, and specifically can be 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 or 2000. In the present invention, the content of the low molecular weight carbon dioxide-cyclohexene oxide copolymer in the composite material is 0.05 to 1 part by weight, specifically 0.05 part by weight, 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, 0.5 part by weight, 0.55 part by weight, 0.6 part by weight, 0.65 part by weight, 0.7 part by weight, 0.75 part by weight, 0.8 part by weight, 0.85 part by weight, 0.9 part by weight, 0.95 part by weight, or 1 part by weight, based on 100 parts by weight of the content of the low molecular weight carbon dioxide-cyclohexene oxide copolymer in the composite material.
In the composite material provided by the invention, the grafting degree of the glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer is preferably 0.1-0.5%, and specifically can be 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% or 0.5%. In the present invention, the content of the glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer in the composite material is 10 to 20 parts by weight, specifically 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, or 20 parts by weight, based on 100 parts by weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer in the composite material.
The invention also provides a preparation method of the carbon dioxide-cyclohexene oxide copolymer composite material, which comprises the following steps:
melting and blending the raw materials to obtain a carbon dioxide-cyclohexene oxide copolymer composite material;
the raw materials comprise low molecular weight carbon dioxide-cyclohexene oxide copolymer, high molecular weight carbon dioxide-cyclohexene oxide copolymer, nano silicon dioxide, lamellar wollastonite nano particles, glass fiber, polymaleic anhydride and glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer.
In the preparation method provided by the invention, the raw materials are firstly melt blended according to the dosage proportion. Wherein, the raw materials are preferably dried to the water content of less than or equal to 200ppm before being subjected to melt blending; the temperature of the melt blending is preferably 170-190 ℃, and specifically can be 170 ℃, 175 ℃, 180 ℃, 185 ℃ or 190 ℃; the mixing speed of the melt blending is preferably 40-120 r/min, and specifically can be 40 r/min, 50 r/min, 60 r/min, 70 r/min, 80 r/min, 90 r/min, 100 r/min, 110 r/min or 120 r/min; the time for melt blending is preferably 5-10 min, and specifically can be 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min or 10 min; the equipment used for melt blending is preferably a torque rheometer. After the melt blending is finished, cooling the obtained melt to room temperature to obtain the carbon dioxide-cyclohexene oxide copolymer composite material provided by the invention.
In the preparation method provided by the invention, in order to facilitate performance detection, the carbon dioxide-cyclohexene oxide copolymer composite material obtained by cooling is preferably placed on a flat-plate vulcanizing machine for pressing to obtain a film or sheet with the thickness meeting the detection requirement, and then the film or sheet is placed in a cold press for pressure maintaining and cooling to room temperature. Wherein the pressing temperature is preferably 180-230 ℃, and specifically can be 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ or 230 ℃; the pressing pressure is preferably 7-15 MPa, and specifically can be 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa or 15 MPa; the pressure for pressure maintaining and cooling is preferably 1-5 MPa, and specifically may be 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa or 5 MPa.
According to the invention, the carbon dioxide-cyclohexene oxide copolymer is used as a base material, and a proper amount of nano-silica, lamellar wollastonite nano-particles and glass fibers are added as fillers to improve the mechanical strength and heat resistance of the carbon dioxide-cyclohexene oxide copolymer and improve the light transmittance of the material; the melt strength during melt blending is improved by adding a proper amount of high molecular weight carbon dioxide-cyclohexene oxide copolymer into the system, and the dispersion degree of the filler in the matrix resin is improved; the interface bonding strength of matrix resin and filler is improved by adding a proper amount of polymaleic anhydride and glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer as a compatibilizer in a system, and the performance of the composite material is further improved. The carbon dioxide-cyclohexene oxide copolymer composite material provided by the invention has excellent mechanical strength, heat resistance and light transmittance, and the preparation method is simple and has a very wide market popularization prospect. Experimental results show that the tensile strength of the carbon dioxide-cyclohexene oxide copolymer composite material provided by the invention is not less than 40MP, the Vicat softening temperature is not less than 105 ℃, and the light transmittance is more than 85%.
For the sake of clarity, the following examples and comparative examples are given in detail below.
In the following examples and comparative examples of the present invention, the performance evaluation methods according to the present invention were as follows:
1) tensile strength: the film sample is cut into strips with the length of 150mm and the width of 15mm +/-0.1 mm along the direction to be measured, the distance between the clamps is 100mm, and the test speed is 10 mm/min. Test specimens 10 were tested and averaged.
2) Heat resistance: the Vicat softening temperature is tested according to the national standard GB/T1633-2000, a force of 10N is used, and the heating rate is 120 ℃/h.
3) Light transmittance: measured according to the method of the national standard GB/T2410-2008.
In the following examples and comparative examples of the present invention, the glycidyl methacrylate-grafted carbon dioxide-cyclohexene oxide copolymer used was prepared according to the following procedure:
carrying out a grafting reaction on the carbon dioxide-cyclohexene oxide copolymer and glycidyl methacrylate under the action of an initiator to obtain a glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer; wherein the weight average molecular weight of the carbon dioxide-cyclohexene oxide copolymer is consistent with that of the low molecular weight carbon dioxide-cyclohexene oxide copolymer in the corresponding examples and comparative examples, the initiator is dicumyl peroxide, the amount of the initiator is 0.4 wt% of the carbon dioxide-cyclohexene oxide copolymer, the amount of the glycidyl methacrylate is 1.0 wt% of the carbon dioxide-cyclohexene oxide copolymer, and the temperature of the grafting reaction is 170-190 ℃.
Example 1
Preparing a raw material: 100 parts of low-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 10 ten thousand), 15 parts of nano-silica (with the diameter of 5nm), 3 parts of lamellar wollastonite nanoparticles (with the lamellar thickness of 1nm), 3 parts of glass fiber (with the diameter of 50nm and the length of 1mm), 30 parts of high-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 50 ten thousand) and 1 part of polymaleic anhydride (with the molecular weight of 500). 20 parts by weight of a glycidyl methacrylate-grafted carbon dioxide-cyclohexene oxide copolymer (degree of grafting: 0.3%).
Drying the raw materials, placing the dried raw materials in a torque rheometer for melt blending at 190 ℃, wherein the mixing speed is 120 r/min, and the mixing time is 10 min. After the melt blending is finished, the blend is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: tensile strength of 58MPa, Vicat softening temperature of 125 ℃ and light transmittance of 91 percent.
Example 2
Preparing a raw material: 100 parts of low-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 5 ten thousand), 2 parts of nano-silica (with the diameter of 100nm), 1 part of lamellar-structure wollastonite nanoparticles (with the lamellar thickness of 1nm), 1 part of glass fiber (with the diameter of 100nm and the length of 0.5mm), 10 parts of high-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 40 ten thousand), 0.05 part of polymaleic anhydride (with the molecular weight of 2000), and 10 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer (with the grafting degree of 0.3%).
Drying the raw materials, placing in a torque rheometer, and melting and blending at 170 ℃, wherein the mixing speed is 40 r/min, and the mixing time is 5 min. After the melt blending is finished, the blend is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: tensile strength of 40MPa, Vicat softening temperature of 105 ℃ and light transmittance of 88 percent.
Example 3
Preparing a raw material: 100 parts of low molecular weight carbon dioxide-cyclohexene oxide copolymer (with the weight average molecular weight of 8 ten thousand), 10 parts of nano-silica (with the diameter of 20nm), 2 parts of lamellar structure wollastonite nanoparticles (with the lamellar thickness of 1nm), 2 parts of glass fibers (with the diameter of 80nm and the length of 1mm), 20 parts of high molecular weight carbon dioxide-cyclohexene oxide copolymer (with the weight average molecular weight of 50 ten thousand), 0.8 part of polymaleic anhydride (with the molecular weight of 1000), and 16 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer (with the grafting degree of 0.3%).
Drying the raw materials, placing in a torque rheometer, and melting and blending at 180 deg.C with a mixing speed of 100 r/min and a mixing time of 8 min. After the melt blending is finished, the blend is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: the tensile strength is 55MPa, the Vicat softening temperature is 120 ℃, and the light transmittance is 90%.
Example 4
Preparing a raw material: 100 parts of low-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 8 ten thousand), 10 parts of nano-silica (with the diameter of 12nm), 2 parts of lamellar-structure wollastonite nanoparticles (with the lamellar thickness of 1nm), 2 parts of glass fibers (with the diameter of 80nm and the length of 1mm), 20 parts of high-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 50 ten thousand), 0.8 part of polymaleic anhydride (with the molecular weight of 1000), and 16 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer (with the grafting degree of 0.3%).
Drying the raw materials, placing in a torque rheometer, and melting and blending at 180 deg.C with a mixing speed of 100 r/min and a mixing time of 8 min. After the melt blending is finished, the blend is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: the tensile strength is 56MPa, the Vicat softening temperature is 122 ℃, and the light transmittance is 90%.
Comparative example 1
Drying low molecular weight carbon dioxide-cyclohexene oxide copolymer (weight average molecular weight is 8 ten thousand), placing in a torque rheometer, and melting and stirring at 180 deg.C with stirring speed of 100 r/min and stirring time of 8 min. After the melting and stirring are finished, the melt is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer material is detected, and the result is as follows: tensile strength of 33MPa, Vicat softening temperature of 98 ℃ and light transmittance of 83 percent.
Comparative example 2
Preparing a raw material: 100 parts of low molecular weight carbon dioxide-cyclohexene oxide copolymer (with the weight average molecular weight of 8 ten thousand), 10 parts of nano silicon dioxide (with the diameter of 12nm), 2 parts of lamellar structure wollastonite nano particles (with the lamellar thickness of 1nm), 2 parts of glass fibers (with the diameter of 80nm and the length of 1mm), 0.8 part of polymaleic anhydride (with the molecular weight of 1000) and 16 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer (with the grafting degree of 0.3%).
Drying the raw materials, placing in a torque rheometer, and melting and blending at 180 deg.C with a mixing speed of 100 r/min and a mixing time of 8 min. After the melt blending is finished, the blend is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: the tensile strength is 45MPa, the Vicat softening temperature is 115 ℃, and the light transmittance is 86%.
Comparative example 3
Preparing a raw material: 100 parts of low molecular weight carbon dioxide-cyclohexene oxide copolymer (with the weight average molecular weight of 8 ten thousand), 10 parts of nano silicon dioxide (with the diameter of 12nm), 20 parts of high molecular weight carbon dioxide-cyclohexene oxide copolymer (with the weight average molecular weight of 50 ten thousand), 0.8 part of polymaleic anhydride (with the molecular weight of 1000), and 16 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer (with the grafting degree of 0.3%).
Drying the raw materials, placing in a torque rheometer, and melting and blending at 180 deg.C with a mixing speed of 100 r/min and a mixing time of 8 min. After the melt blending is finished, the blend is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: tensile strength 43MPa, Vicat softening temperature 110 ℃ and light transmittance 88 percent.
Comparative example 4
Preparing a raw material: 100 parts of low-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 8 ten thousand), 10 parts of nano-silica (with the diameter of 12nm), 2 parts of lamellar-structure wollastonite nanoparticles (with the lamellar thickness of 1nm), 20 parts of high-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 50 ten thousand), 0.8 part of polymaleic anhydride (with the molecular weight of 1000), and 16 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer (with the grafting degree of 0.3%).
Drying the raw materials, placing the raw materials in a torque rheometer for melt blending at 180 ℃, wherein the mixing speed is 100 r/min, the mixing time is 8min, after the melt blending is finished, directly cooling the blend in the room-temperature air state, cutting the blend into small blocks, pressing the small blocks into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ and 10MPa for testing, and then quickly placing the films or sheets in a cold press for pressure maintaining and cooling to room temperature at the pressure of 2MPa to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: tensile strength of 44MPa, Vicat softening temperature of 117 ℃ and light transmittance of 89%.
Comparative example 5
Preparing a raw material: 100 parts of low-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 8 ten thousand), 10 parts of nano-silica (with the diameter of 12nm), 2 parts of glass fiber (with the diameter of 80nm and the length of 1mm), 20 parts of high-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 50 ten thousand), 0.8 part of polymaleic anhydride (with the molecular weight of 1000) and 16 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer (with the grafting degree of 0.3%).
Drying the raw materials, placing in a torque rheometer, and melting and blending at 180 deg.C with a mixing speed of 100 r/min and a mixing time of 8 min. After the melt blending is finished, the blend is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: the tensile strength is 43MPa, the Vicat softening temperature is 115 ℃, and the light transmittance is 88%.
Comparative example 6
Preparing a raw material: 100 parts of low molecular weight carbon dioxide-cyclohexene oxide copolymer (with the weight average molecular weight of 8 ten thousand), 10 parts of nano-silica (with the diameter of 12nm), 2 parts of lamellar structure wollastonite nanoparticles (with the lamellar thickness of 1nm), 2 parts of glass fiber (with the diameter of 80nm and the length of 1mm), and 20 parts of high molecular weight carbon dioxide-cyclohexene oxide copolymer (with the weight average molecular weight of 50 ten thousand).
Drying the raw materials, placing in a torque rheometer, and melting and blending at 180 deg.C with a mixing speed of 100 r/min and a mixing time of 8 min. After the melt blending is finished, the blend is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: the tensile strength is 30MPa, the Vicat softening temperature is 105 ℃, and the light transmittance is 84%.
Comparative example 7
Preparing a raw material: 100 parts of low molecular weight carbon dioxide-cyclohexene oxide copolymer (with the weight average molecular weight of 8 ten thousand), 10 parts of nano-silica (with the diameter of 12nm), 2 parts of lamellar structure wollastonite nanoparticles (with the lamellar thickness of 1nm), 2 parts of glass fiber (with the diameter of 80nm and the length of 1mm), 20 parts of high molecular weight carbon dioxide-cyclohexene oxide copolymer (with the weight average molecular weight of 50 ten thousand) and 0.8 part of polymaleic anhydride (with the molecular weight of 1000).
Drying the raw materials, placing the raw materials in a torque rheometer for melt blending at 180 ℃, wherein the mixing speed is 100 r/min, the mixing time is 8min, after the melt blending is finished, directly cooling the blend in the room-temperature air state, cutting the blend into small blocks, pressing the small blocks into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ and 10MPa for testing, and then quickly placing the films or sheets in a cold press for pressure maintaining and cooling to room temperature at the pressure of 2MPa to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: the tensile strength is 48MPa, the Vicat softening temperature is 115 ℃, and the light transmittance is 89%.
Comparative example 8
Preparing a raw material: 100 parts of low-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 8 ten thousand), 10 parts of nano-silica (with the diameter of 12nm), 2 parts of lamellar-structure wollastonite nanoparticles (with the lamellar thickness of 1nm), 2 parts of glass fiber (with the diameter of 80nm and the length of 1mm), 20 parts of high-molecular-weight carbon dioxide-cyclohexene oxide copolymer (with the weight-average molecular weight of 50 ten thousand) and 16 parts of glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer (with the grafting degree of 0.3%).
Drying the raw materials, placing in a torque rheometer, and melting and blending at 180 deg.C with a mixing speed of 100 r/min and a mixing time of 8 min. After the melt blending is finished, the blend is directly cooled in the air state at room temperature, cut into small blocks, pressed into films or sheets with different thicknesses on a flat vulcanizing machine at 200 ℃ under the pressure of 10MPa for testing, and then quickly placed into a cold press to be cooled to room temperature under the pressure of 2MPa, so as to obtain the carbon dioxide-cyclohexene oxide copolymer composite material.
The performance of the prepared carbon dioxide-cyclohexene oxide copolymer composite material is detected, and the result is as follows: tensile strength of 46MPa, Vicat softening temperature of 113 ℃ and light transmittance of 85 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A carbon dioxide-cyclohexene oxide copolymer composite material comprises the following components in parts by weight:
the weight average molecular weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer is less than or equal to 15 ten thousand;
the weight average molecular weight of the high molecular weight carbon dioxide-cyclohexene oxide copolymer is not less than 25 ten thousand;
the particle size of the nano silicon dioxide is 5-100 nm;
the lamella degree of the wollastonite nanoparticles with the lamellar structure is 0.5-5 nm;
the diameter of the glass fiber is 50-100 nm, and the length of the glass fiber is 0.5-1 mm.
2. The carbon dioxide-cyclohexene oxide copolymer composite material according to claim 1, wherein the low-molecular-weight carbon dioxide-cyclohexene oxide copolymer has a weight average molecular weight of 5 to 10 ten thousand.
3. The carbon dioxide-cyclohexene oxide copolymer composite material of claim 1, wherein the high molecular weight carbon dioxide-cyclohexene oxide copolymer has a weight average molecular weight of 30 to 50 ten thousand.
4. The carbon dioxide-cyclohexene oxide copolymer composite material of claim 1, wherein the polymaleic anhydride has a molecular weight of 500 to 2000.
5. The carbon dioxide-cyclohexene oxide copolymer composite material according to claim 1, wherein the glycidyl methacrylate-grafted carbon dioxide-cyclohexene oxide copolymer has a grafting degree of 0.1 to 0.5%.
6. A method for preparing the carbon dioxide-cyclohexene oxide copolymer composite material as claimed in any one of claims 1 to 5, comprising the following steps:
melting and blending the raw materials to obtain a carbon dioxide-cyclohexene oxide copolymer composite material;
the raw materials comprise low molecular weight carbon dioxide-cyclohexene oxide copolymer, high molecular weight carbon dioxide-cyclohexene oxide copolymer, nano silicon dioxide, lamellar wollastonite nano particles, glass fiber, polymaleic anhydride and glycidyl methacrylate grafted carbon dioxide-cyclohexene oxide copolymer.
7. The method according to claim 6, wherein the raw materials are dried to a water content of 200ppm or less before melt blending.
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