A bio-based high-flow mineral-reinforced PC / PET alloy material and its preparation method

Abstract

The present invention relates to the field of material technology and discloses a bio-based high-flow mineral-reinforced PC / PET alloy material and a preparation method thereof. The alloy material uses bio-based polycarbonate resin, PET, modified mineral reinforcement and the like as raw materials, wherein the modified mineral reinforcement is prepared by modifying the surface of hydrotalcite with a macromolecular substance connected by ester bonds. Since the benzene rings in the structure of the macromolecular substance can produce a conjugated effect with the benzene rings in the structures of PC and PET, the affinity between talc powder and PC and PET can be greatly improved. During the melt extrusion process, the molecular chains of the macromolecular substance, PC and PET interact with each other to form a cross-linked network with talc powder as the core, thereby achieving overall reinforcement of the alloy material. In addition, the high-energy silicon-oxygen bonds in the structure of the macromolecular substance can also help enhance the thermal stability of the alloy material.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and in particular 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-weight polymer containing carbonate groups in its molecular chain, primarily classified as aliphatic, aromatic, and aliphatic-aromatic. Aromatic polycarbonate, due to its excellent heat resistance, transparency, and dimensional stability, has achieved industrialized production, becoming the fastest-growing general-purpose engineering plastic among the five major engineering plastics, with widespread applications in the automotive, construction, electronics, and medical sectors. Bio-based polycarbonate, on the other hand, can be produced from environmentally friendly raw materials such as dimethyl carbonate, making it more aligned with the concept of green and environmentally friendly development. Furthermore, bio-based polycarbonate not only maintains the transparency and impact resistance of traditional polycarbonate but also improves its scratch and wear resistance, leading to extensive research in recent years. However, bio-based polycarbonate also suffers from notch sensitivity, making it difficult to meet rapidly developing material demands.

[0003] Mixing bio-based polycarbonate with other polymer materials, such as polyethylene terephthalate (PET), to create PC / PET alloys can leverage their respective strengths, creating a complementary effect and resulting in alloys with excellent overall performance. However, differences in the crystallinity of polycarbonate and polyethylene terephthalate result in poor compatibility between the two, leading to poor mechanical strength of the resulting alloys, which can even deteriorate over time. Therefore, the development of high-strength PC / PET alloys has become a research priority. Summary of the Invention

[0004] (1) Technical problems solved

[0005] In view of 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.

[0006] (2) Technical solution

[0007] A method for preparing a bio-based high-flow mineral-reinforced PC / PET alloy material, wherein the alloy material is prepared from the following raw materials in parts by weight:

[0008] 70-78 parts of bio-based polycarbonate resin, 25-35 parts of PET, 2-5.5 parts of modified mineral reinforcement, 5-10 parts of compatibilizer, 0.5-1.5 parts of antioxidant, 0.2-0.5 parts of transesterification inhibitor, 0.5-1 parts of lubricant;

[0009] The preparation method comprises the following steps:

[0010] The first step is to add the bio-based polycarbonate resin and PET into a high-speed blender according to parts by weight and stir to mix. Then, the modified mineral reinforcement, compatibilizer, antioxidant, transesterification inhibitor, and lubricant are added into the high-speed blender and stirred to form a uniform material.

[0011] The second step is to put the material into a twin-screw extruder for melt extrusion and granulation.

[0012] Further preferably, the modified mineral reinforcement is prepared by the following method:

[0013] Step 1: Disperse talc powder in a 70% by volume ethanol aqueous solution medium, then add an epoxy-substituted silane coupling agent, raise the temperature to 60-70°C after addition, keep stirring for 4-8 hours, and centrifuge the solid material to obtain an organically modified talc powder;

[0014] Step 2: Add the organic modified talc powder to the toluene medium and disperse it evenly by ultrasonication. Then, add the phenylenediacetic acid substance and the catalyst. After the addition is completed, heat it to 70-80 ° C, keep it warm and stir for 2-6 hours, and then continue to add the silane derivative. After the addition is completed, the temperature is further increased to 85-95 ° C, and the mixture is kept warm and stirred for 12-24 hours. Then, heating is stopped, and the mixture is cooled to room temperature. The solid matter is centrifuged, washed, and vacuum dried to obtain a modified mineral reinforcement.

[0015] More preferably, the epoxy-substituted silane coupling agent is 3-glycidyloxypropyltrimethoxysilane or 3-glycidyloxypropyltriethoxysilane.

[0016] More preferably, the benzenediacetic acid substance is 1,4-benzenediacetic acid or 1,3-benzenediacetic acid.

[0017] Further preferably, the silane derivative is prepared by the following method:

[0018] Dichlorotetramethyldisilane and glycidol are added to a tetrahydrofuran medium, dry nitrogen is introduced for protection, stirring is started, and after a uniform reaction liquid is formed, triethylamine is added to the reaction liquid. After the addition is completed, the temperature is raised to 60°C, and after stirring for 8 hours, the solvent is removed by rotary evaporation. After purification, a silane derivative can be obtained.

[0019] More preferably, the molar ratio of dichlorotetramethyldisilane to glycidol is 1:2.

[0020] More preferably, the catalyst is any one of tetramethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate or N,N-dimethylbenzylamine.

[0021] Further preferably, the mass ratio of the phenylenediacetic acid substance, the silane derivative and the organically modified talc is 1.8-3:2.4-3.6:1.

[0022] In the above technical solution, talc is first surface-modified using an epoxy-substituted silane coupling agent, and epoxy substituents are modified on the surface of the talc to obtain an organically modified talc. Next, a phenylenedicarboxylic acid-based substance is used as a bridge connector. 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 talc, and the other end undergoes ring-opening esterification with the epoxy group in the silane derivative structure. The excess phenylenedicarboxylic acid-based substance and silane derivative in the system can undergo continuous and uninterrupted ring-opening reaction, thereby modifying the surface of the hydrotalcite with macromolecular substances connected by ester bonds to obtain a modified mineral reinforcement.

[0023] The silane derivative is prepared by using dichlorotetramethyldisilane and glycidol as reactants, and the silicon-chloride substituent and the hydroxyl substituent in each other's structure undergo a substitution reaction under the catalysis of triethylamine.

[0024] 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 ester exchange inhibitor is diisooctyl phosphate or triphenyl phosphite; and the lubricant is montan wax or polyethylene wax.

[0025] A bio-based high-flow mineral-reinforced PC / PET alloy material is prepared by the above-mentioned preparation method.

[0026] (3) Beneficial technical effects

[0027] The present invention selects a mixture of maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer and glycidyl methacrylate grafted POE as a compatibilizer, combines the advantages of a reactive compatibilizer and an elastomer, can effectively improve the compatibility between PC and PET, and is conducive to improving the processing fluidity of the alloy material.

[0028] The present invention prepares a modified mineral reinforcement material by modifying the surface of hydrotalcite with a macromolecular substance connected by ester bonds. Since the benzene ring in the structure of the macromolecular substance can produce a conjugated effect with the benzene ring in the structure of PC and PET, the affinity between talc powder and PC and PET can be greatly improved. During the melt extrusion process, the molecular chains of the macromolecular substance, PC and PET will interact with each other to form a cross-linked network with talc powder as the core, thereby utilizing the reinforcing advantage of talc powder to achieve overall reinforcement of the alloy material. In addition, the high bond energy silicon-oxygen bonds in the structure of the macromolecular substance can also help enhance the thermal stability of the alloy material. DETAILED DESCRIPTION

[0029] To facilitate understanding of the present invention, the present invention will be described in more detail below. Preferred embodiments of the present invention are provided below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0030] Example 1

[0031] A bio-based high-flow mineral-reinforced PC / PET alloy material is made from the following raw materials in parts by weight:

[0032] 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 dioctyl phosphate, and 0.5 parts of montan wax;

[0033] The preparation method of the alloy material comprises the following steps:

[0034] The first step is to add the bio-based polycarbonate resin and PET into a high-speed blender according to parts by weight and stir to mix. Then, the modified mineral reinforcement, compatibilizer, antioxidant 168, dioctyl phosphate, and montan wax are added into the high-speed blender and stirred to form a uniform material.

[0035] The second step is to put the material into a twin-screw extruder, control the temperature of the feeding 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.

[0036] 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.

[0037] Example 2

[0038] A bio-based high-flow mineral-reinforced PC / PET alloy material is made from the following raw materials in parts by weight:

[0039] 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, and 1 part of polyethylene wax;

[0040] The preparation method of the alloy material comprises the following steps:

[0041] The first step is to add the bio-based polycarbonate resin and PET into a high-speed blender according to parts by weight and stir to mix. Then, the modified mineral reinforcement, compatibilizer, antioxidant 1010, triphenyl phosphite, and polyethylene wax are added into the high-speed blender and stirred to form a uniform material.

[0042] The second step is to put the material into a twin-screw extruder, control the temperature of the feeding 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.

[0043] Example 3

[0044] A bio-based high-flow mineral-reinforced PC / PET alloy material is made from the following raw materials in parts by weight:

[0045] 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 parts of triphenyl phosphite, and 1 part of polyethylene wax;

[0046] The preparation method of the alloy material comprises the following steps:

[0047] The first step is to add the bio-based polycarbonate resin and PET into a high-speed blender according to parts by weight and stir to mix. Then, the modified mineral reinforcement, compatibilizer, antioxidant 1010, triphenyl phosphite, and polyethylene wax are added into the high-speed blender and stirred to form a uniform material.

[0048] The second step is to put the material into a twin-screw extruder, control the temperature of the feeding 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.

[0049] The modified mineral reinforcement in the above examples is prepared by the following method:

[0050] Step 1: Disperse 2.4 g of talc in a 70% by volume ethanol aqueous solution, then add 1 g of 3-glycidyloxypropyltriethoxysilane. After the addition, raise the temperature to 70°C, keep stirring for 6 hours, and centrifuge the solid material to obtain an organically modified talc.

[0051] Step 2: Add 1.8 g of organically modified talc to a toluene medium and disperse it evenly by ultrasonication. Then, add 4 g of 1,4-benzenedioic acid and 0.2 g of tetrabutylammonium bromide. After the addition is completed, heat to 80 ° C., keep stirring for 4 hours, and then add 5.5 g of silane derivative. After the addition is completed, the temperature is further increased to 90 ° C. After continuous stirring for 18 hours, stop heating, cool to room temperature, centrifuge the solid, wash and vacuum dry to obtain a modified mineral reinforcement.

[0052] The silane derivatives are prepared by the following method:

[0053] 0.8 g of dichlorotetramethyldisilane and 0.6 g of glycidol were added to a tetrahydrofuran medium, and dry nitrogen was introduced for protection. Stirring was started, and after a uniform reaction liquid was formed, 0.1 g of triethylamine was added to the reaction liquid. After the addition was completed, the temperature was raised to 60°C, and after stirring for 8 hours, the solvent was removed by rotary evaporation. After purification, a silane derivative was obtained.

[0054] Comparative Example 1

[0055] A bio-based high-flow mineral-reinforced PC / PET alloy material is made from the following raw materials in parts by weight:

[0056] 72 parts of bio-based polycarbonate resin, 30 parts of PET, 5 parts of talc, 6 parts of compatibilizer, 1 part of antioxidant 1010, 0.3 parts of triphenyl phosphite, 1 part of polyethylene wax;

[0057] The preparation method of the alloy material comprises the following steps:

[0058] The first step is to add the bio-based polycarbonate resin and PET into a high-speed blender according to parts by weight and stir to mix. Then, talc, a compatibilizer, antioxidant 1010, triphenyl phosphite, and polyethylene wax are added into the high-speed blender and stirred to form a uniform material.

[0059] The second step is to put the material into a twin-screw extruder, control the temperature of the feeding 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.

[0060] Comparative Example 2

[0061] A PC / PET alloy material is made from the following raw materials in parts by weight:

[0062] 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, and 1 part of polyethylene wax;

[0063] The preparation method of the alloy material comprises the following steps:

[0064] The first step is to add the bio-based polycarbonate resin and PET into a high-speed blender according to parts by weight and stir to mix. Then, the compatibilizer, antioxidant 1010, triphenyl phosphite, and polyethylene wax are added into the high-speed blender and stirred to form a uniform material.

[0065] The second step is to put the material into a twin-screw extruder, control the temperature of the feeding 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.

[0066] Test Case

[0067] The alloy materials in the examples and comparative examples were made into test specimens and tested accordingly. The results are recorded in the following table:

[0068]

[0069] The tensile strength was tested according to ISO 527-2-2012 with a tensile rate of 50 mm / min; the notched impact strength was tested according to ISO 179-1-2010; and the heat deflection temperature was tested according to ISO 75-2-2013.

[0070] Analysis shows that although unmodified talc powder as an additive can play a certain degree of reinforcing role on the alloy material, due to the problem of interface incompatibility, it is difficult to be evenly dispersed in the alloy material matrix and cannot effectively exert its own advantages, resulting in poor reinforcement effect.

[0071] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction 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 any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0072] Based on the ideal embodiments of the present invention, and with reference to the above description, relevant personnel can make various changes and modifications without departing from the technical scope of the present invention. The technical scope of the present invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A method for preparing a bio-based high-flow mineral-reinforced PC / PET alloy material, characterized in that: The alloy material is made of 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 reinforcement, 5-10 parts of compatibilizer, 0.5-1.5 parts of antioxidant, 0.2-0.5 parts of transesterification inhibitor, 0.5-1 parts of lubricant; The preparation method comprises the following steps: The first step is to add the bio-based polycarbonate resin and PET into a high-speed blender according to parts by weight and stir to mix. Then, the modified mineral reinforcement, compatibilizer, antioxidant, transesterification inhibitor, and lubricant are added into the high-speed blender and stirred to form a uniform material. The second step is to put the material into a twin-screw extruder for melt extrusion and granulation; The modified mineral reinforcement is prepared by the following method: Step 1: In an ethanol aqueous solution medium, talc is organically modified using an epoxy-substituted silane coupling agent to obtain organically modified talc; Step 2: Using toluene as a medium, using phenylenediacetic acid as a bridge connector, and using a silane derivative as a ring-opening polymerization monomer, in the presence of a catalyst, an in-situ ring-opening polymerization is carried out on the surface of the organically modified talc to obtain a modified mineral reinforcement; The silane derivatives are prepared by the following method: In tetrahydrofuran medium, dichlorotetramethyldisilane and glycidol are used as raw materials and reacted under the action of triethylamine to produce silane derivatives.

2. The method for preparing 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-glycidyloxypropyltrimethoxysilane or 3-glycidyloxypropyltriethoxysilane.

3. The method for preparing a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 1, characterized in that: The phenylenediacetic acid substance is 1,4-phenylenediacetic acid or 1,3-phenylenediacetic acid.

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

2.

5. The method for preparing a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 1, characterized in that: The catalyst is any one of tetramethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate or N,N-dimethylbenzylamine.

6. The method for preparing a bio-based high-flow mineral-reinforced PC / PET alloy material according to claim 1, characterized in that: The mass ratio of the phenylenediacetic acid substance, the silane derivative and the organic modified talc is 1.8-3:2.4-3.6:

1.

7. The method for preparing 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 ester exchange inhibitor is diisooctyl phosphate or triphenyl phosphite; and the lubricant is montan wax or polyethylene wax.

8. A bio-based high-flow mineral reinforced PC / PET alloy material, characterized in that: The method is as described in any one of claims 1 to 7.

Images