A PTT composite material and its preparation method

Abstract

This invention relates to the field of polymer materials, and more particularly to a PTT composite material and its preparation method. The material comprises, by weight, 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1-5 parts artificial quartz waste, and 1-5 parts pine cone activated carbon / Mexen multilayer composite. This invention significantly improves the impact strength when artificial quartz waste is used alone by introducing the pine cone activated carbon / Mexen multilayer composite into PPT and artificial quartz waste. Compared to traditional fillers, using artificial quartz waste can reduce raw material costs and improve the economics of the composite material.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, and more particularly to a PTT composite material and its preparation method. Background Technology

[0002] Polypropylene terephthalate (PTT) is synthesized from terephthalic acid (PTA) and 1,3-propanediol (1,3-1,3-propanediol) as monomers. PTT fiber is a high-performance polyester fiber developed by Shell Chemical Company in the United States. It combines the softness of nylon, the bulkiness of acrylic, the stain resistance of polyester, and its own inherent elasticity. It can also be dyed at room temperature, showing great market potential in both woven and nonwoven fields. Bio-based PTT fiber is made from glycerol, glucose, or starch as raw materials, using 1,3-1,3-propanediol and PTA produced by microbial fermentation as monomers. It is produced as PTT filaments or staple fibers using a melt spinning process similar to PET, and has excellent mechanical and chemical properties.

[0003] Artificial engineered stone is a material made primarily from natural engineered stone, using purified terephthalic acid (PTA), diethylene glycol (DEG), styrene (St), and maleic anhydride (MA) as crosslinking agents. It is produced through processes such as vacuum mixing, vibration molding, and room temperature curing. In recent years, it has gradually become an important interior decoration material due to its aesthetic appeal, design flexibility, ease of mass production, and low price. However, the cutting and polishing processes generate a large amount of artificial engineered stone waste (AMWs). These wastes are coated with approximately 7% thermosetting unsaturated polyester, which is difficult to reprocess or degrade, resulting not only in resource waste but also significant environmental pressure and water pollution.

[0004] Existing technologies use PTT and artificial quartz waste to form a composite, but its performance needs further improvement. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a PTT composite material and its preparation method.

[0006] This invention is achieved through the following technical solution:

[0007] A PTT composite material, comprising, by weight, 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1-5 parts artificial quartz waste, and 1-5 parts pine cone activated carbon / MXene multilayer material composite.

[0008] Furthermore, the mass fraction of the artificial quartz waste is 5 parts, and the mass fraction of the pine cone activated carbon / MXene multilayer material composite is 4 parts.

[0009] Furthermore, it also includes antioxidants and epoxy resins.

[0010] Furthermore, the antioxidant is selected from antioxidant 1010, and the weight is 1 part; the epoxy resin is 1 part by weight.

[0011] Furthermore, the preparation method of the pine cone activated carbon / MXene multilayer material composite includes the following steps: dispersing MXene multilayer material and pine cone activated carbon in 70% (v / v) ethanol water at a mass ratio of 1:1, then ultrasonically dispersing for 45 min, then magnetically stirring for 45 min, and finally ultrasonically dispersing for 30 min, and then vacuum drying at 80°C to obtain the pine cone activated carbon / MXene multilayer material composite.

[0012] Further, the preparation method of the pine cone activated carbon is as follows: 5g of pine cone powder is soaked in 50mL of 20% (w / w) phosphoric acid solution, heated to 70℃, and then maintained at 70℃ for 24h or until the water is completely evaporated; then dried overnight in an oven, and the product is ground into powder; then carbonized at 500℃ for 3h under a nitrogen atmosphere with a nitrogen flow rate of 100 cubic centimeters / minute and a heating rate of 10℃ / minute; after natural cooling, it is washed with distilled water and dried overnight in an oven at 80℃; the dried product and n-heptadecane are dispersed in anhydrous ethanol, stirred for 4 hours, and then dried in an oven at 60℃ for 48 hours to obtain pine cone activated carbon.

[0013] Furthermore, the dried product and n-heptadecane are in a mass ratio of 1:9.

[0014] Further, the preparation method of the MXene multilayer material is as follows: Ti3AlC2 is added to a plastic container containing HF, then stirred with a magnetic stirrer, heated to 45°C, and maintained at 45°C for 24 hours; then centrifuged, and the precipitate is washed with deionized water until the pH is neutral; then vacuum dried at 80°C to obtain the MXene multilayer material.

[0015] This invention also provides a method for preparing a PTT composite material, comprising the following steps:

[0016] Step S1: First, mix dimethyl terephthalate and 1,3-propanediol, slowly add tetrabutyl titanate as an additive, vacuum, stir and heat, and after the solution becomes clear, add antioxidant, epoxy resin and pine cone activated carbon / MXene multilayer material composite.

[0017] Step S2: Then heat up, maintain the temperature and stir the reaction for 10 minutes, and then cool naturally to room temperature to obtain the PTT composite material.

[0018] Furthermore, the heating temperature in step S1 is 200°C, and the temperature in step S2 is raised to 250°C.

[0019] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0020] This invention significantly improves the impact strength of artificial quartz waste when used alone by introducing a pine cone activated carbon / MXene multilayer material composite into PPT and artificial quartz waste. Compared with traditional fillers, using artificial quartz waste can reduce raw material costs and improve the economics of the composite material. Attached Figure Description

[0021] The accompanying drawings, which are included to provide a further understanding of the embodiments of the present invention and form part of this application, do not constitute a limitation on the embodiments of the present invention.

[0022] Figure 1 This is a SEM image of the pine cone activated carbon / MXene multilayer material composite in Example 1 of the present invention;

[0023] Figure 2 These are impact test data for various embodiments and comparative examples in this invention. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments and accompanying drawings. The illustrative embodiments and descriptions of the present invention are only used to explain the present invention and are not intended to limit the present invention.

[0025] In this invention, all artificial quartz waste (AMWs) is pulverized and passed through a 1000-mesh sieve for later use. Pine cones are also pulverized and passed through a 1000-mesh sieve for later use. Dimethyl terephthalate (DMT), 1,3-propanediol (PDO), and tetrabutyl titanate (TBT) in this invention are all purchased from commercially available products and have not undergone further processing. The HF acid concentration is 40%. In this invention, all artificial quartz waste (AMWs) is pulverized and passed through a 1000-mesh sieve for later use. Pine cones are also pulverized and passed through a 1000-mesh sieve for later use.

[0026] Example 1

[0027] A PTT composite material, by weight, comprises 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, 5 parts artificial quartz waste, and 1 part pine cone activated carbon / MXene multilayer material composite.

[0028] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant, epoxy resin, and pine cone activated carbon / MXene multilayer material composite are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0029] The preparation method of pine cone activated carbon / MXene multilayer material composite includes the following steps: MXene multilayer material and pine cone activated carbon are dispersed in 70% (v / v) ethanol water at a mass ratio of 1:1, then ultrasonically dispersed for 45 min, magnetically stirred for 45 min, and finally ultrasonically dispersed for 30 min. Then, the pine cone activated carbon / MXene multilayer material composite is obtained by vacuum drying at 80℃. Figure 1 TEM image of pine cone activated carbon / MXene multilayer material composite.

[0030] The preparation method of pine cone activated carbon is as follows: 5g of pine cone powder is soaked in 50mL of 20% (w / w) phosphoric acid solution, heated to 70℃, and then maintained at 70℃ for 24h or until the water is completely evaporated; then dried in an oven overnight, and the product is ground into powder; then carbonized at 500℃ for 3h under a nitrogen atmosphere with a nitrogen flow rate of 100 cubic centimeters / minute and a heating rate of 10℃ / minute; after natural cooling, it is washed with distilled water and dried in an oven at 80℃ overnight; the dried product and n-heptadecane are dispersed in anhydrous ethanol at a mass ratio of 1:9, stirred for 4 hours, and then dried in an oven at 60℃ for 48 hours to obtain pine cone activated carbon.

[0031] The preparation method of MXene multilayer material is as follows: 2g of Ti3AlC2 is added to a plastic container containing 40mL of HF, and then stirred with a magnetic stirrer at 300r / min. The mixture is heated to 45℃ and maintained at 45℃ for 24h. Then, the mixture is centrifuged and the precipitate is washed with deionized water until the pH is neutral. Finally, the mixture is vacuum dried at 80℃ to obtain MXene multilayer material.

[0032] Example 2

[0033] A PTT composite material, by weight, comprises 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, 5 parts artificial quartz waste, and 2 parts pine cone activated carbon / MXene multilayer material composite.

[0034] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant, epoxy resin, and pine cone activated carbon / MXene multilayer material composite are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0035] The preparation method of the pine cone activated carbon / MXene multilayer material composite is the same as in Example 1.

[0036] Example 3

[0037] A PTT composite material, by weight, comprises 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, 5 parts artificial quartz waste, and 3 parts pine cone activated carbon / MXene multilayer material composite.

[0038] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant, epoxy resin, and pine cone activated carbon / MXene multilayer material composite are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0039] The preparation method of the pine cone activated carbon / MXene multilayer material composite is the same as in Example 1.

[0040] Example 4

[0041] A PTT composite material, by weight, comprises 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, 5 parts artificial quartz waste, and 4 parts pine cone activated carbon / MXene multilayer material composite.

[0042] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant, epoxy resin, and pine cone activated carbon / MXene multilayer material composite are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0043] The preparation method of the pine cone activated carbon / MXene multilayer material composite is the same as in Example 1.

[0044] Example 5

[0045] A PTT composite material, by weight, comprises 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, 5 parts artificial quartz waste, and 5 parts pine cone activated carbon / MXene multilayer material composite.

[0046] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant, epoxy resin, and pine cone activated carbon / MXene multilayer material composite are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0047] The preparation method of the pine cone activated carbon / MXene multilayer material composite is the same as in Example 1.

[0048] Comparative Example 1

[0049] A PTT composite material comprises, by weight, 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, and 5 parts artificial quartz waste.

[0050] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant and epoxy resin are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0051] Comparative Example 2

[0052] A PTT composite material comprises, by weight, 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, 5 parts artificial quartz waste, and 4 parts pine cone activated carbon.

[0053] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant, epoxy resin, and pine cone activated carbon / MXene multilayer material composite are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0054] The preparation method of pine cone activated carbon is as follows: 5g of pine cone powder is soaked in 50mL of 20% (w / w) phosphoric acid solution, heated to 70℃, and then maintained at 70℃ for 24h or until the water is completely evaporated; then dried in an oven overnight, and the product is ground into powder; then carbonized at 500℃ for 3h under a nitrogen atmosphere with a nitrogen flow rate of 100 cubic centimeters / minute and a heating rate of 10℃ / minute; after natural cooling, it is washed with distilled water and dried in an oven at 80℃ overnight; the dried product and n-heptadecane are dispersed in anhydrous ethanol at a mass ratio of 1:9, stirred for 4 hours, and then dried in an oven at 60℃ for 48 hours to obtain pine cone activated carbon.

[0055] Comparative Example 3

[0056] A PTT composite material, by weight, comprises 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, 5 parts artificial quartz waste, and MXene multilayer material.

[0057] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant, epoxy resin, and pine cone activated carbon / MXene multilayer material composite are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0058] The preparation method of MXene multilayer material is as follows: 2g of Ti3AlC2 is added to a plastic container containing 40mL of HF, and then stirred with a magnetic stirrer at 300r / min. The mixture is heated to 45℃ and maintained at 45℃ for 24h. Then, the mixture is centrifuged and the precipitate is washed with deionized water until the pH is neutral. Finally, the mixture is vacuum dried at 80℃ to obtain MXene multilayer material.

[0059] Comparative Example 4

[0060] In this comparative example, the pine cone activated carbon was not modified with n-heptadecane.

[0061] A PTT composite material, by weight, comprises 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, 5 parts artificial quartz waste, and 4 parts unmodified pine cone activated carbon / MXene multilayer material composite.

[0062] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant, epoxy resin, and unmodified pine cone activated carbon / MXene multilayer material composite are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0063] The preparation method of unmodified pine cone activated carbon / MXene multilayer material composite includes the following steps: MXene multilayer material and pine cone activated carbon are dispersed in 70% (v / v) ethanol water at a mass ratio of 1:1, then ultrasonically dispersed for 45 min, magnetically stirred for 45 min, ultrasonically dispersed for 30 min, and then vacuum dried at 80℃ to obtain pine cone activated carbon / MXene multilayer material composite.

[0064] The preparation method of pine cone activated carbon is as follows: 5g of pine cone powder is soaked in 50mL of 20% (w / w) phosphoric acid solution, heated to 70℃, and then maintained at 70℃ for 24h or until the water is completely evaporated; then dried in an oven overnight, and the product is ground into powder; then carbonized at 500℃ for 3h under a nitrogen atmosphere with a nitrogen flow rate of 100 cubic centimeters / minute and a heating rate of 10℃ / minute; after natural cooling, it is washed with distilled water and dried overnight in an oven at 80℃ to obtain unmodified pine cone activated carbon.

[0065] The preparation method of MXene multilayer material is as follows: 2g of Ti3AlC2 is added to a plastic container containing 40mL of HF, and then stirred with a magnetic stirrer at 300r / min. The mixture is heated to 45℃ and maintained at 45℃ for 24h. Then, the mixture is centrifuged and the precipitate is washed with deionized water until the pH is neutral. Finally, the mixture is vacuum dried at 80℃ to obtain MXene multilayer material.

[0066] Comparative Example 5

[0067] A PTT composite material comprises, by weight, 116 parts dimethyl terephthalate, 100 parts 1,3-propanediol, 1 part tetrabutyl titanate, 1 part antioxidant, 1 part epoxy resin, 5 parts artificial quartz waste, and 4 parts pine cone powder.

[0068] A method for preparing a PTT composite material: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate is slowly added dropwise as an additive. The mixture is then vacuumed, stirred, and heated to 200°C. After the solution becomes transparent, an antioxidant, epoxy resin, and pine cone powder are added. The temperature is then raised to 250°C, and the mixture is stirred and reacted for 10 minutes. After naturally cooling to room temperature, the PTT composite material is obtained.

[0069] Test Example 1

[0070] The PTT composite materials used in the various examples and comparative examples were pulverized and injection molded into 80 mm × 10 mm × 4 mm specimens for impact strength testing. The impact strength was determined according to ISO 180 standard, with a pendulum energy of 5.5 J. The test results were obtained from... Figure 2 As shown. From Figure 1 As can be seen, adding artificial quartz waste to the PPT matrix and then adding pine cone activated carbon / MXene multilayer material composite can toughen the matrix, thereby improving the impact strength.

[0071] Test Example 2

[0072] DSC non-isothermal melting crystallization test: 9–10 mg of sample was weighed and pressed into a crucible in an aluminum crucible. Under a high-purity nitrogen atmosphere, the temperature was increased from room temperature to 280 °C at a rate of 40 °C / min and held for 1 min. The temperature was then decreased to 0 °C at a rate of 10 °C / min and held for 1 min to complete the crystallization process. The temperature was then increased to 280 °C at a rate of 10 °C / min to complete the melting process. The cooling and heating curves at 10 °C / min were recorded, and the results are shown in Table 1.

[0073] Table 1. Non-isothermal DSC parameters

[0074]

[0075] As can be seen from Table 1, the initial crystallization temperature (T0) and crystallization peak temperature (T) of Examples 1-5 compared to Comparative Examples 1-5 are significantly different. c peak The melting peak temperature (T) showed a significant increase, while the melting peak temperature (T) was significantly higher. m The impact is relatively small, and there is essentially no difference in the integrity of crystals among the various embodiments and comparative examples.

[0076] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A PTT composite material, characterized in that, The contents include 116 parts by weight of dimethyl terephthalate, 100 parts of 1,3-propanediol, 1 part of tetrabutyl titanate, 1-5 parts of artificial quartz stone waste, and 1-5 parts of pine cone activated carbon / MXene multilayer material composite. The preparation method of the pine cone activated carbon / MXene multilayer material composite includes the following steps: dispersing MXene multilayer material and pine cone activated carbon in 70% ethanol water at a mass ratio of 1:1, then ultrasonically dispersing for 45 min, then magnetically stirring for 45 min, and finally ultrasonically dispersing for 30 min, and then vacuum drying at 80℃ to obtain the pine cone activated carbon / MXene multilayer material composite. The preparation method of the pine cone activated carbon is as follows: 5g of pine cone powder is soaked in 50mL of 20% phosphoric acid solution, heated to 70℃, and then maintained at 70℃ for 24h or until the water is completely evaporated; then dried overnight in an oven, and the product is ground into powder; then carbonized at 500℃ for 3h under a nitrogen atmosphere with a nitrogen flow rate of 100 cubic centimeters / minute and a heating rate of 10℃ / minute; after natural cooling, it is washed with distilled water and dried overnight in an oven at 80℃; the dried product and n-heptadecane are dispersed in anhydrous ethanol, stirred for 4 hours, and then dried in an oven at 60℃ for 48 hours to obtain pine cone activated carbon.

2. The PTT composite material according to claim 1, characterized in that, The artificial quartz waste residue has a mass fraction of 5 parts, and the pine cone activated carbon / MXene multilayer material composite has a mass fraction of 4 parts.

3. The PTT composite material according to claim 2, characterized in that, It also includes antioxidants and epoxy resins.

4. The PTT composite material according to claim 3, characterized in that, The antioxidant is selected from antioxidant 1010, and the weight is 1 part; the epoxy resin is 1 part by weight.

5. The PTT composite material according to claim 1, characterized in that, The dried product and n-heptadecane are in a mass ratio of 1:

9.

6. The PTT composite material according to claim 5, characterized in that, The preparation method of the MXene multilayer material is as follows: Ti3AlC2 is added to a plastic container containing HF, then stirred with a magnetic stirrer, heated to 45°C, and maintained at 45°C for 24 hours. Then, the precipitate was centrifuged and washed with deionized water until the pH was neutral; then, it was vacuum dried at 80°C to obtain MXene multilayer material.

7. The method for preparing the composite material according to any one of claims 1 to 6, characterized in that, Includes the following steps: Step S1: First, dimethyl terephthalate and 1,3-propanediol are mixed, and tetrabutyl titanate catalyst is slowly added dropwise. Vacuum is drawn, the mixture is stirred and heated. After the solution becomes clear, antioxidant, epoxy resin and pine cone activated carbon / MXene multilayer material composite are added. Step S2: Then the temperature is raised and the reaction is maintained by stirring for 10 minutes. After naturally cooling to room temperature, PTT composite material is obtained.

8. The method for preparing the composite material according to claim 7, characterized in that, In step S1, the heating temperature is 200°C, and in step S2, the temperature is raised to 250°C.

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