Bio-based high-flowability mineral reinforced PC / PET alloy material and preparation method thereof

Abstract

The invention relates to the technical field of materials, and discloses a bio-based high-flowability mineral reinforced PC / PET alloy material and a preparation method thereof.The alloy material is prepared from bio-based polycarbonate resin, PET, a modified mineral reinforced material and the like, the modified mineral reinforced material is prepared by modifying the surface of hydrotalcite with a macromolecular substance connected through an ester bond, and the modified mineral reinforced material is prepared through a high-temperature heat treatment technology. As benzene rings in a macromolecular substance structure can generate conjugation with benzene rings in PC and PET structures, the affinity between the talcum powder and PC and PET can be greatly improved, molecular chains among the macromolecular substance, PC and PET can generate interaction in a melt extrusion process, a cross-linked network with the talcum powder as a core is further formed, and the cross-linked network is formed. In addition, silicon-oxygen bonds with high bond energy in the macromolecular substance structure can also be beneficial to enhancing the thermal stability of the alloy material.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and particularly relates to a bio-based high-flow mineral-reinforced PC / PET alloy material and a preparation method thereof. Background Art

[0002] Polycarbonate (PC) is a high molecular polymer containing carbonate groups in its molecular chain, which is mainly divided into aliphatic, aromatic, and aliphatic-aromatic. Among them, aromatic polycarbonate has achieved industrial production due to its excellent heat resistance, transparency, and dimensional stability, etc., and has become the fastest-growing general engineering plastic among the five major engineering plastics, and is widely used in the fields of automobiles, construction, electronics, medical treatment, etc. Bio-based polycarbonate can be made from green raw materials such as dimethyl carbonate, which is more in line with the development concept of green environmental protection. Moreover, bio-based polycarbonate not only maintains the transparency and impact resistance of traditional polycarbonate, but also improves scratch resistance and wear resistance. Therefore, it has been widely studied in recent years. However, bio-based polycarbonate also has the defect of being sensitive to notches, which makes it difficult to meet the rapidly developing material requirements.

[0003] Mixing bio-based polycarbonate with other types of high molecular materials, such as polyethylene terephthalate (PET), etc., to make PC / PET alloy materials can utilize the advantages of each other and produce a complementary effect, so that the prepared alloy materials have good comprehensive properties. However, the difference in crystallinity between polycarbonate and polyethylene terephthalate leads to poor compatibility between the two, resulting in poor mechanical strength of the made alloy, and it will also exacerbate deterioration in the later stage of the use of the alloy material. Therefore, how to prepare PC / PET alloy materials with high strength has gradually become the research focus. Summary of the Invention

[0004] (I) Technical Problems to be Solved Aiming at the deficiencies of the prior art, the present invention provides a bio-based high-flow mineral-reinforced PC / PET alloy material and a preparation method thereof.

[0005] (II) Technical Solutions A preparation method of a bio-based high-flow mineral-reinforced PC / PET alloy material, wherein the alloy material is made from the following raw materials in parts by weight: 70-78 parts of bio-based polycarbonate resin, 25-35 parts of PET, 2-5.5 parts of modified mineral reinforcing material, 5-10 parts of compatibilizer, 0.5-1.5 parts of antioxidant, 0.2-0.5 parts of transesterification inhibitor, 0.5-1 part of lubricant; The preparation method includes the following steps: Step 1: According to the weight parts, add the bio-based polycarbonate resin and PET into a high-speed mixer, stir and mix evenly. Then, add the modified mineral reinforcing agent, compatibilizer, antioxidant, transesterification inhibitor, and lubricant into the high-speed mixer, and stir and blend to form a uniform material. Step 2: Put the material into a twin-screw extruder for melt extrusion granulation, and that's it.

[0006] Further preferably, the modified mineral reinforcing agent is prepared by the following method: Step 1: Disperse talcum powder in an ethanol aqueous solution medium with a volume fraction of 70%. Then, add an epoxy-substituted silane coupling agent. After adding, raise the temperature to 60 - 70 °C, keep warm and stir for 4 - 8 h, and centrifuge out the solid material to obtain organically modified talcum powder. Step 2: Add the organically modified talcum powder into a toluene medium, disperse it evenly by ultrasonic wave. Then, add a benzene diacetic acid substance and a catalyst. After adding, raise the temperature to 70 - 80 °C, keep warm and stir for 2 - 6 h. Then, continue to add a silane derivative. After adding, further raise the temperature to 85 - 95 °C, continuously keep warm and stir for 12 - 24 h, then stop heating. Wait until it cools to room temperature, centrifuge out the solid, and after washing and vacuum drying treatment, obtain the modified mineral reinforcing agent.

[0007] Further preferably, the epoxy-substituted silane coupling agent is 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane.

[0008] Further preferably, the benzene diacetic acid substance is 1,4-benzenediacetic acid or 1,3-benzenediacetic acid.

[0009] Further preferably, the silane derivative is prepared by the following method: Add dichlorotetramethyldisilane and glycidol into a tetrahydrofuran medium, introduce dry nitrogen for protection, start stirring. After forming a uniform reaction solution, continue to add triethylamine to the reaction solution. After adding, raise the temperature to 60 °C, stir for 8 h, then rotary evaporate to remove the solvent, and through a purification process, the silane derivative can be obtained.

[0010] Further preferably, the molar ratio of dichlorotetramethyldisilane to glycidol is 1:2.

[0011] Further preferably, the catalyst is any one of tetramethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate, or N,N-dimethylbenzylamine.

[0012] Further preferably, the mass ratio of the benzene diacetic acid substance, the silane derivative, and the organically modified talcum powder is 1.8 - 3:2.4 - 3.6:1.

[0013] In the above technical solution, first, the surface of talcum powder is modified with an epoxy-substituted silane coupling agent to modify epoxy substituents on the surface of talcum powder, and organically modified talcum powder is obtained. Then, a phthalic acid substance is used as a bridging linker. First, under the action of a catalyst, the active carboxyl substituent at one end of its structure undergoes ring-opening esterification with the epoxy group of the organically modified talcum powder, and the other end undergoes ring-opening esterification with the epoxy group in the structure of the silane derivative. The excessive phthalic acid substance and silane derivative in the system can undergo a continuous ring-opening reaction, thereby modifying the surface of the hydrotalcite with macromolecular substances connected by ester bonds to obtain a modified mineral reinforcing material.

[0014] Among them, the silane derivative is prepared by using dichlorotetramethyldisilane and glycidol as reactants, and the silicon-chlorine substituent and hydroxyl substituent in their respective structures undergo a substitution reaction under the catalytic action of triethylamine.

[0015] Further preferably, the compatibilizer is a mixture of maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer and glycidyl methacrylate grafted POE, with a mass ratio of 1:1; the antioxidant is at least one of antioxidant 1010, antioxidant 168, or antioxidant 1073; the transesterification inhibitor is diisooctyl phosphate or triphenyl phosphite; the lubricant is montan wax or polyethylene wax.

[0016] A bio-based high-flow mineral-reinforced PC / PET alloy material is prepared by the above preparation method.

[0017] (III) Beneficial technical effects By selecting a mixture of maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer and glycidyl methacrylate grafted POE as the compatibilizer, the present invention combines the advantages of reactive compatibilizers and elastomers, can effectively improve the compatibility between PC and PET, and is beneficial to improving the processing fluidity of the alloy material.

[0018] By modifying the surface of the hydrotalcite with macromolecular substances connected by ester bonds to obtain a modified mineral reinforcing material, the present invention can greatly improve the affinity between talcum powder and PC and PET because the benzene ring in the macromolecular substance structure can produce a conjugated effect with the benzene rings in the PC and PET structures. During the melt extrusion process, the molecular chains among the macromolecular substance, PC, and PET will interact with each other, and then form a crosslinked network with talcum powder as the core, thereby being able to utilize the reinforcing advantage of talcum powder to achieve the overall strengthening of the alloy material. In addition, the high bond energy silicon-oxygen bonds in the macromolecular substance structure can also be beneficial to enhancing the thermal stability of the alloy material. Specific embodiments

[0019] In order to facilitate the understanding of the present invention, the present invention will be described more fully below. Preferred embodiments of the present invention are given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0020] Example 1 A bio-based high-flow mineral-reinforced PC / PET alloy material is made from the following raw materials in parts by weight: 70 parts of bio-based polycarbonate resin, 25 parts of PET, 2 parts of modified mineral reinforcement, 5 parts of compatibilizer, 0.5 parts of antioxidant 168, 0.2 parts of diisooctyl phosphate, and 0.5 parts of montan wax; The preparation method of the alloy material comprises the following steps: The first step is to add the bio-based polycarbonate resin and PET into a high-speed mixer according to the weight ratio, stir and mix, then add the modified mineral reinforcement, the compatibilizer, the antioxidant 168, the diisooctyl phosphate and the montan wax into the high-speed mixer, stir and blend to form a uniform material; The second step is to put the material into a twin-screw extruder, control the temperature of the feed section to 200°C, the temperature of the plasticizing section to 250°C, the temperature of the homogenizing section to 270°C, and the screw speed to 400rpm, and perform melt extrusion granulation.

[0021] The bio-based polycarbonate resin was purchased from Dongguan Nabaichuan Plastics Co., Ltd. with the product number D5380R; the compatibilizer was a mixture of maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer and glycidyl methacrylate grafted POE with a mass ratio of 1:1, and the following were the same.

[0022] Example 2 A bio-based high-flow mineral-reinforced PC / PET alloy material is made from the following raw materials in parts by weight: 72 parts of bio-based polycarbonate resin, 30 parts of PET, 5 parts of modified mineral reinforcement, 6 parts of compatibilizer, 1 part of antioxidant 1010, 0.3 parts of triphenyl phosphite, 1 part of polyethylene wax; The preparation method of the alloy material comprises the following steps: The first step is to add the bio-based polycarbonate resin and PET into a high-speed mixer according to the weight ratio, stir and mix, then add the modified mineral reinforcement, the compatibilizer, the antioxidant 1010, the triphenyl phosphite and the polyethylene wax into the high-speed mixer, stir and blend to form a uniform material; Step 2: Put the materials into a twin-screw extruder, control the temperature of the feeding section at 200°C, the plasticizing section at 250°C, the homogenizing section at 270°C, and the screw speed at 400 rpm, and carry out melt extrusion granulation, then it's done.

[0023] Example 3 A bio-based high-flow mineral-reinforced PC / PET alloy material is made from the following raw materials by weight: 78 parts of bio-based polycarbonate resin, 35 parts of PET, 5.5 parts of modified mineral reinforcement, 10 parts of compatibilizer, 1.5 parts of antioxidant 1010, 0.5 part of triphenyl phosphite, 1 part of polyethylene wax; The preparation method of the alloy material includes the following steps: Step 1: According to the weight parts, add the bio-based polycarbonate resin and PET into a high-speed mixer, stir and mix evenly, then add the modified mineral reinforcement, compatibilizer, antioxidant 1010, triphenyl phosphite, and polyethylene wax into the high-speed mixer, and stir and blend to form a uniform material; Step 2: Put the materials into a twin-screw extruder, control the temperature of the feeding section at 200°C, the plasticizing section at 250°C, the homogenizing section at 270°C, and the screw speed at 400 rpm, and carry out melt extrusion granulation, then it's done.

[0024] The modified mineral reinforcement in the above examples is prepared by the following method: Step 1: Disperse 2.4 g of talc powder in an ethanol aqueous solution medium with a volume fraction of 70%, then add 1 g of 3-glycidoxypropyltriethoxysilane. After adding, raise the temperature to 70°C, keep stirring for 6 h, and centrifuge to obtain the solid material to prepare the organically modified talc powder; Step 2: Add 1.8 g of the organically modified talc powder into the toluene medium, ultrasonically disperse it evenly, then add 4 g of 1,4-benzenediacetic acid and 0.2 g of tetrabutylammonium bromide. After adding, raise the temperature to 80°C, keep stirring for 4 h, then continue to add 5.5 g of silane derivative. After adding, further raise the temperature to 90°C, keep stirring for 18 h, then stop heating. Wait until it cools to room temperature, centrifuge to obtain the solid, and after washing and vacuum drying, the modified mineral reinforcement is prepared.

[0025] The silane derivative is prepared by the following method: Add 0.8 g of dichlorotetramethyldisilane and 0.6 g of glycidol into the tetrahydrofuran medium, introduce dry nitrogen for protection, start stirring. After forming a uniform reaction solution, continue to add 0.1 g of triethylamine to the reaction solution. After adding, raise the temperature to 60°C, stir for 8 h, then rotary evaporate to remove the solvent, and through the purification process, the silane derivative can be prepared.

[0026] Comparative Example 1 A bio-based high-flow mineral-reinforced PC / PET alloy material is made from the following raw materials by weight: 72 parts of bio-based polycarbonate resin, 30 parts of PET, 5 parts of talc powder, 6 parts of compatibilizer, 1 part of antioxidant 1010, 0.3 parts of triphenyl phosphite, 1 part of polyethylene wax; The preparation method of the alloy material includes the following steps: First step, according to the weight parts, add the bio-based polycarbonate resin and PET into a high-speed mixer, stir and mix evenly, and then add the talc powder, compatibilizer, antioxidant 1010, triphenyl phosphite, and polyethylene wax into the high-speed mixer, and stir and blend to form a uniform material; Second step, put the material into a twin-screw extruder, control the temperature of the feeding section at 200 °C, the temperature of the plasticizing section at 250 °C, the temperature of the homogenizing section at 270 °C, and the screw speed at 400 rpm, and carry out melt extrusion granulation to obtain the product.

[0027] Comparative Example 2 A PC / PET alloy material is made from the following raw materials by weight: 72 parts of bio-based polycarbonate resin, 30 parts of PET, 6 parts of compatibilizer, 1 part of antioxidant 1010, 0.3 parts of triphenyl phosphite, 1 part of polyethylene wax; The preparation method of the alloy material includes the following steps: First step, according to the weight parts, add the bio-based polycarbonate resin and PET into a high-speed mixer, stir and mix evenly, and then add the compatibilizer, antioxidant 1010, triphenyl phosphite, and polyethylene wax into the high-speed mixer, and stir and blend to form a uniform material; Second step, put the material into a twin-screw extruder, control the temperature of the feeding section at 200 °C, the temperature of the plasticizing section at 250 °C, the temperature of the homogenizing section at 270 °C, and the screw speed at 400 rpm, and carry out melt extrusion granulation to obtain the product.

[0028] Test Example The alloy materials in the examples and comparative examples are made into test specimens and corresponding tests are carried out. The results are recorded in the following table:

[0029] Among them, the tensile strength is tested according to the standard ISO 527-2-2012, and the tensile rate is set at 50 mm / min; the notched impact strength is tested according to the standard ISO 179-1-2010; the heat distortion temperature is tested according to the standard ISO75-2-2013.

[0030] Analysis shows that although using unmodified talc powder as an additive can enhance the alloy material to a certain extent, due to the problem of interfacial incompatibility, it is difficult to be uniformly dispersed in the alloy material matrix, and it cannot effectively exert its own advantages, resulting in poor enhancement effect.

[0031] In the description of this specification, the description referring to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0032] Based on the inspiration of the ideal embodiments of the present invention, through the above description, relevant personnel can completely make various changes and modifications without departing from the technical idea of this invention. The technical scope of this invention is not limited to the content in the specification, and the technical scope must be determined according to the scope of the claims.

Claims

1. A preparation method of a bio-based high-flow mineral-reinforced PC / PET alloy material, characterized in that, The alloy material is made of the following raw materials by weight parts: 70 - 78 parts of bio - based polycarbonate resin, 25 - 35 parts of PET, 2 - 5.5 parts of modified mineral reinforcing agent, 5 - 10 parts of compatibilizer, 0.5 - 1.5 parts of antioxidant, 0.2 - 0.5 parts of transesterification inhibitor, 0.5 - 1 part of lubricant; The preparation method includes the following steps: First step, according to the weight parts, add the bio - based polycarbonate resin and PET into a high - speed mixer, stir and mix evenly. Then add the modified mineral reinforcing agent, compatibilizer, antioxidant, transesterification inhibitor, and lubricant into the high - speed mixer and stir - blend to form a uniform material; Second step, put the material into a twin - screw extruder for melt extrusion granulation, and that's it; The modified mineral reinforcing agent is prepared by the following method: Step one, in an ethanol - aqueous solution medium, use an epoxy - substituted silane coupling agent to carry out organic modification on talcum powder to obtain organically modified talcum powder; Step two, using toluene as the medium, using a benzene - diacetic acid - type substance as a bridging linker, and a silane derivative as a ring - opening polymerization monomer, carry out in - situ ring - opening polymerization on the surface of the organically modified talcum powder under the action of a catalyst to obtain the modified mineral reinforcing agent.

2. The preparation method of a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 1, characterized in that The epoxy - substituted silane coupling agent is 3 - glycidoxypropyltrimethoxysilane or 3 - glycidoxypropyltriethoxysilane.

3. The preparation method of a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 1, characterized in that, The benzene - diacetic acid - type substance is 1,4 - benzene - diacetic acid or 1,3 - benzene - diacetic acid.

4. The preparation method of a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 1, characterized in that The silane derivative is prepared by the following method: In a tetrahydrofuran medium, using dichlorotetramethyldisilane and glycidol as raw materials, react under the action of triethylamine to obtain the silane derivative.

5. The preparation method of a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 4, characterized in that, The molar ratio of dichlorotetramethyldisilane to glycidol is 1:

2.

6. The preparation method of a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 1, wherein, The catalyst is any one of tetramethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate, or N,N - dimethylbenzylamine.

7. The preparation method of a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 1, characterized in that, The mass ratio of the benzene - diacetic acid - type substance, silane derivative, and organically modified talcum powder is 1.8 - 3:2.4 - 3.6:

1.

8. The preparation method of a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 1, characterized in that, The compatibilizer is a mixture of maleic anhydride - grafted styrene - ethylene - butadiene - styrene copolymer and glycidyl methacrylate - grafted POE, with a mass ratio of 1:1; the antioxidant is at least one of antioxidant 1010, antioxidant 168, or antioxidant 1073; the transesterification inhibitor is di - isooctyl phosphate or triphenyl phosphite; the lubricant is montan wax or polyethylene wax.

9. A bio-based high-flow mineral-reinforced PC / PET alloy material, characterized in that, Prepared by the preparation method according to any one of claims 1 - 8.

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