Toughened modified PBT (polybutylene terephthalate) and processing method thereof

Abstract

The invention discloses a processing method of toughened modified PBT (polybutylene terephthalate). The processing method comprises the following steps: S1, performing surface treatment on inorganic nanoparticles to introduce active functional groups; s2, dispersing the modified nano particles in an organic solvent, then adding adamantane diamine and aliphatic triamine, and adding aliphatic diisocyanate under certain reaction conditions for reaction to obtain modified nano particles with core-shell structures; s3, adding the mixture into a mixture consisting of PBT resin, a maleic anhydride derivative, a dispersing agent and an antioxidant, and uniformly stirring and mixing; and S4, carrying out melting, extrusion and granulation to obtain the toughening modified PBT material. The processing method provided by the invention not only improves the toughness and impact resistance of the PBT material, but also optimizes the optical transparency and heat resistance of the material, and can meet the requirements of the fields of automobile lamps, electronic appliances, aerospace and the like on high-performance PBT materials.

Description

Technical Field

[0001] The invention relates to the technical field of PBT materials, and in particular to a toughened modified PBT and a processing method thereof. Background Art

[0002] As an important engineering plastic, polybutylene terephthalate (PBT) is widely used in the automotive, electronics and textile industries due to its excellent mechanical properties, heat resistance, chemical resistance and electrical insulation. However, traditional PBT materials have certain limitations in toughness, optical properties and heat resistance. Especially in high-demand applications such as automotive headlights, the insufficient toughness of PBT materials may lead to cracking during use, poor optical properties will affect the lighting effect, and insufficient heat resistance limits its application in high temperature environments. In addition, the durability of PBT materials during long-term use is also a focus of industry attention. In order to overcome these defects, researchers have been exploring methods to modify PBT by physical or chemical means in order to obtain PBT materials with better comprehensive performance. These modification methods include adding inorganic fillers, using compatibilizers, and adopting different processing technologies, but these methods often fail to take into account the mechanical properties, optical properties and thermal stability of the materials at the same time. Therefore, developing a modification technology that can comprehensively improve the performance of PBT materials has become an important research direction in this field. Summary of the invention

[0003] In view of the above shortcomings of the prior art, the present invention provides a processing method for toughened modified PBT to solve the technical problems of insufficient toughness, poor optical properties, limited heat resistance and insufficient long-term durability of traditional PBT materials. By introducing specific inorganic nanoparticles and performing surface modification on them, and using specific chemical reactions to form modified nanoparticles with a core-shell structure, the present invention not only improves the toughness and impact resistance of the PBT material, but also optimizes its optical transparency and light transmittance, while enhancing the heat resistance and aging resistance of the material. These improvements enable the toughened modified PBT material of the present invention to better meet the stringent requirements for the comprehensive performance of materials in automotive headlights and other high optical performance application fields, such as LED lighting equipment, transparent parts of optical instruments, electronic equipment displays, transparent windows in the aerospace field, and transparent covers in medical devices. These application fields have extremely high requirements for the transparency, heat resistance, chemical resistance and mechanical strength of the material, and the toughened modified PBT material provided by the present invention is an ideal choice for these fields due to its excellent performance.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is: a processing method for toughening and modifying PBT, the processing method comprising the following steps: S1: surface treating inorganic nanoparticles to introduce active functional groups; in step S1, the present invention introduces active functional groups through surface treatment, thereby enhancing the compatibility of inorganic nanoparticles with organic phases and improving their dispersibility in subsequent steps. This surface modification enhances the interfacial bonding force between inorganic nanoparticles and PBT resin and provides active sites for subsequent chemical reactions.

[0005] S2: The inorganic nanoparticles after surface treatment in step S1 are uniformly dispersed in an organic solvent by ultrasonic-assisted stirring, and then adamantane diamine and aliphatic triamine are added, and the stirring and mixing are continued to be uniform, and an organic solution of aliphatic diisocyanate is added under certain reaction conditions, and the reaction is carried out by reduced pressure distillation to obtain modified nanoparticles with a core-shell structure; in step S2 of the present invention, ultrasonic-assisted stirring is used to uniformly disperse the inorganic nanoparticles after surface modification in an organic solvent, and then adamantane diamine and aliphatic triamine are added, and these polyamine compounds react with aliphatic diisocyanate to form modified nanoparticles with a core-shell structure. The introduction of adamantane diamine and aliphatic triamine provides multiple active sites to promote the formation of a core-shell structure, and enhances the toughness and heat resistance of the material due to its special molecular structure. The cross-linking effect of the aliphatic triamine allows it to react with the aliphatic diisocyanate to form a cross-linked network, which improves the mechanical strength and toughness of the material, improves the impact resistance of the material, and thus enables the material to better absorb and disperse energy when impacted by external forces, and reduces the formation and expansion of cracks. The modified nanoparticles with core-shell structure can reduce light scattering and improve the transparency and light transmittance of the material by smoothing the surface of inorganic nanoparticles, which is crucial for applications requiring high optical performance such as automotive lights.

[0006] S3: adding the modified nanoparticles with a core-shell structure obtained in step S2 as a functional additive to a mixture consisting of a PBT resin, a maleic anhydride derivative, a dispersant and an antioxidant, and stirring and mixing the mixture evenly; the introduction of the maleic anhydride derivative of the present invention enhances the interfacial adhesion and toughness of the material, while the addition of the dispersant and the antioxidant improves the processing performance and aging resistance of the material.

[0007] S4: adding the mixed materials in step S3 into a twin-screw extruder for full melt blending, extruding after shearing and mixing, cooling, granulating, drying and packaging to obtain the toughened modified PBT material.

[0008] As a preferred technical solution, the inorganic nanoparticles are silicon dioxide and / or titanium dioxide.

[0009] As a preferred technical solution, the surface treatment method is to disperse the inorganic nanoparticles in an ethanol aqueous solution (volume ratio of 1:1), add terminal amino trimethoxy silane or terminal amino triethoxy silane for hydrolysis reaction, and obtain inorganic nanoparticles with terminal amino groups grafted on the surface.

[0010] As a preferred technical solution, the terminal amino trimethoxysilane is at least one of 3-aminopropyl trimethoxysilane, 4-amino-3,3-dimethylbutyl trimethoxysilane, and N-(beta-aminoethyl)-gama-aminopropyl trimethoxysilane; the terminal amino triethoxysilane is at least one of 3-aminopropyl triethoxysilane, N-(6-aminohexyl)aminomethyl triethoxysilane, 4-aminobutyl triethoxysilane, (2-aminoisopropyl)triethoxysilane, (((2-aminoethyl)amino)methyl)triethoxysilane, and N-aminoethyl-3-aminopropyl triethoxysilane.

[0011] As a preferred technical solution, the adamantane diamine is at least one of 1,3-adamantanediamine, 1,3-adamantanediethylamine, adamantane-1,3-dimethylamine, 1,3-bis(4-aminophenyl)adamantane, and 4,4'-(adamantanedi-2,2-diyl)diphenylamine.

[0012] As a preferred technical solution, the aliphatic triamine is at least one of 1,3,6-triaminohexane, 1,4,7-triaminoheptane, and undecane-1,6,11-triamine.

[0013] As a preferred technical solution, the aliphatic diisocyanate is at least one of methylene diisocyanate, butane-1,4-diisocyanate, 1,6-hexane diisocyanate, and decane-1,10-diisocyanate.

[0014] As a preferred technical solution, the maleic anhydride derivative is at least one of maleic anhydride modified polyethylene, methyl vinyl ether-maleic anhydride copolymer, and polyoxyethylene (2-methyl-2-propenyl) methyl diether-maleic anhydride copolymer.

[0015] As a preferred technical solution, the dispersant is at least one of fatty acids, aliphatic amides, montan wax, silicone, and polyethylene wax; the antioxidant is at least one of antioxidant 168, antioxidant 626, antioxidant 1010, antioxidant 1024, antioxidant 1076, antioxidant 1222, and antioxidant 3114.

[0016] Another aspect of the present invention is to provide a toughened and modified PBT, wherein the PBT is prepared by the processing method of the toughened and modified PBT as described above.

[0017] Beneficial effects of the present invention: The processing method of toughened modified PBT of the present invention not only significantly improves the toughness of the material, but also optimizes the optical properties by innovatively introducing active functional groups on the surface of inorganic nanoparticles and combining adamantane diamine and aliphatic triamine to form modified nanoparticles with a core-shell structure. This design not only enhances the mechanical strength and heat resistance of the material, but also maintains the transparency and light transmittance of the material, which helps to meet the long-term use requirements of high optical performance products such as automotive headlights in various harsh environments.

[0018] In general, the toughened modified PBT of the present invention not only has excellent mechanical properties, thermal stability and optical properties, but also has good processing performance and aging resistance, which can meet the stringent requirements of products with high optical performance requirements such as automotive lamps on material properties, ensuring its long-term durability and stability. DETAILED DESCRIPTION

[0019] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations.

[0020] Example 1, the processing method of toughened modified PBT in this example comprises the following steps: S1: surface treating inorganic nanoparticle silica (D50 is 30 nm) to introduce active functional groups; the surface treatment method is to disperse 30 grams of inorganic nanoparticle silica in 250 milliliters of ethanol aqueous solution (volume ratio is 1:1), add 8 grams of 3-aminopropyltrimethoxysilane, adjust the pH to 9 at 60°C, and perform hydrolysis reaction for 1 hour to obtain inorganic nanoparticles with surface grafted terminal amine groups.

[0021] S2: 15 g of inorganic nanoparticles surface-treated in step S1 were uniformly dispersed in 200 ml of toluene organic solvent by ultrasonic-assisted stirring, and then 7.2 g of 1,3-adamantanediamine and 5.5 g of 1,3,6-triaminohexane were added, and the mixture was stirred and mixed evenly. 15 g of toluene organic solution of methylene diisocyanate was added, and the reaction was carried out by reduced pressure distillation at a temperature of 90° C. and a vacuum degree of 0.05 MPa for 2 hours to obtain modified nanoparticles with a core-shell structure.

[0022] S3: 8 g of the modified nanoparticles with a core-shell structure obtained in step S2 were added as functional additives to a mixture of 150 g of PBT resin, 12 g of maleic anhydride-modified polyethylene, 2 g of polyethylene wax and 0.15 g of antioxidant 168, and stirred to mix well.

[0023] S4: adding the mixed materials in step S3 into a twin-screw extruder for full melt blending, extruding after shearing and mixing, cooling, granulating, drying and packaging to obtain the toughened modified PBT material. The process is carried out at a processing temperature of 220-240° C. and a rotation speed of 150 r / min.

[0024] Example 2, the processing method of toughened modified PBT in this example comprises the following steps: S1: surface treating inorganic nanoparticle titanium dioxide (D50 is 30 nm) to introduce active functional groups; the surface treatment method is to disperse 30 grams of inorganic nanoparticle titanium dioxide in 250 milliliters of ethanol aqueous solution (volume ratio is 1:1), add 9 grams of 4-amino-3,3-dimethylbutyltrimethoxysilane, adjust the pH to 10 at 60°C, and perform hydrolysis reaction for 3 hours to obtain inorganic nanoparticles with surface grafted terminal amino groups.

[0025] S2: 15 g of inorganic nanoparticles surface-treated in step S1 were uniformly dispersed in 200 ml of toluene organic solvent by ultrasonic-assisted stirring, and then 8.5 g of 1,3-adamantane diethylamine and 6.8 g of 1,4,7-triaminoheptane were added, and the mixture was stirred and mixed evenly. 12 g of toluene organic solution of butane-1,4-diisocyanate was added, and the reaction was carried out by reduced pressure distillation at a temperature of 80° C. and a vacuum degree of 0.05 MPa for 2 hours to obtain modified nanoparticles with a core-shell structure.

[0026] S3: 7 g of the modified nanoparticles with a core-shell structure obtained in step S2 were added as a functional additive to a mixture of 160 g of PBT resin, 15 g of methyl vinyl ether-maleic anhydride copolymer, 3 g of montan wax and 0.25 g of antioxidant 168, and the mixture was stirred and mixed evenly.

[0027] S4: adding the mixed materials in step S3 into a twin-screw extruder for full melt blending, extruding after shearing and mixing, cooling, granulating, drying and packaging to obtain the toughened modified PBT material. The process is carried out at a processing temperature of 220-240° C. and a rotation speed of 150 r / min.

[0028] Example 3, the processing method of toughened modified PBT in this example comprises the following steps: S1: surface treating inorganic nanoparticle silica (D50 is 30 nm) to introduce active functional groups; the surface treatment method is to disperse 30 grams of inorganic nanoparticle silica in 250 milliliters of ethanol aqueous solution (volume ratio is 1:1), add 10 grams of 3-aminopropyltriethoxysilane, adjust the pH to 11 at 50°C, and perform hydrolysis reaction for 1 hour to obtain inorganic nanoparticles with surface grafted terminal amine groups.

[0029] S2: 15 g of inorganic nanoparticles surface-treated in step S1 were uniformly dispersed in 200 ml of toluene organic solvent by ultrasonic-assisted stirring, and then 8.8 g of adamantane-1,3-dimethylamine and 5.9 g of undecane-1,6,11-triamine were added, and the mixture was stirred and mixed evenly. 14.2 g of toluene organic solution of 1,6-hexamethylene diisocyanate was added, and the reaction was carried out by reduced pressure distillation at a temperature of 90° C. and a vacuum degree of 0.05 MPa for 2 hours to obtain modified nanoparticles with a core-shell structure.

[0030] S3: 8 g of the modified nanoparticles with a core-shell structure obtained in step S2 are added as a functional additive to a mixture of 160 g of PBT resin, 15 g of polyoxyethylene (2-methyl-2-propenyl) methyl diether-maleic anhydride copolymer, 3 g of silicone and 0.2 g of antioxidant 168, and the mixture is stirred and mixed evenly.

[0031] S4: adding the mixed materials in step S3 into a twin-screw extruder for full melt blending, extruding after shearing and mixing, cooling, granulating, drying and packaging to obtain the toughened modified PBT material. The process is carried out at a processing temperature of 220-240° C. and a rotation speed of 150 r / min.

[0032] Example 4, the processing method of toughened modified PBT in this example comprises the following steps: S1: surface treating inorganic nanoparticle silica (D50 is 30 nm) to introduce active functional groups; the surface treatment method is to disperse 30 grams of inorganic nanoparticle silica in 250 milliliters of ethanol aqueous solution (volume ratio is 1:1), add 8 grams of (2-aminoisopropyl)triethoxysilane, adjust the pH to 11 at 60°C, and perform hydrolysis reaction for 2 hours to obtain inorganic nanoparticles with surface grafted terminal amine groups.

[0033] S2: 15 g of inorganic nanoparticles surface-treated in step S1 were uniformly dispersed in 200 ml of toluene organic solvent by ultrasonic-assisted stirring, and then 7.5 g of 1,3-bis(4-aminophenyl)adamantane and 5.6 g of 1,3,6-triaminohexane were added, and the mixture was stirred and mixed evenly. 14.2 g of toluene organic solution of decane-1,10-diisocyanate was added, and the reaction was carried out by reduced pressure distillation at a temperature of 80° C. and a vacuum degree of 0.05 MPa for 2 hours to obtain modified nanoparticles with a core-shell structure.

[0034] S3: 9 g of the modified nanoparticles with a core-shell structure obtained in step S2 were added as a functional additive to a mixture of 140 g of PBT resin, 10 g of methyl vinyl ether-maleic anhydride copolymer, 2 g of montan wax and 0.15 g of antioxidant 168, and the mixture was stirred and mixed evenly.

[0035] S4: adding the mixed materials in step S3 into a twin-screw extruder for full melt blending, extruding after shearing and mixing, cooling, granulating, drying and packaging to obtain the toughened modified PBT material. The process is carried out at a processing temperature of 220-240° C. and a rotation speed of 150 r / min.

[0036] Example 5, the processing method of toughened modified PBT in this example includes the following steps: S1: surface treating inorganic nanoparticles of titanium dioxide (D50 is 30 nm) to introduce active functional groups; the surface treatment method is to disperse 30 grams of inorganic nanoparticles of titanium dioxide in 250 milliliters of ethanol aqueous solution (volume ratio is 1:1), add 8 grams of N-aminoethyl-3-aminopropyltriethoxysilane, adjust the pH to 9 at 60°C, and perform hydrolysis reaction for 3 hours to obtain inorganic nanoparticles with surface grafted terminal amino groups.

[0037] S2: 15 g of inorganic nanoparticles surface-treated in step S1 were uniformly dispersed in 200 ml of toluene organic solvent by ultrasonic-assisted stirring, and then 8.5 g of 4,4'-(adamantane-2,2-diyl)diphenylamine and 6.5 g of 1,4,7-triaminoheptane were added, and the mixture was stirred and mixed evenly. 15.8 g of toluene organic solution of methylene diisocyanate was added, and the reaction was carried out by reduced pressure distillation at a temperature of 80° C. and a vacuum degree of 0.05 MPa for 2 hours to obtain modified nanoparticles with a core-shell structure.

[0038] S3: 10 g of the modified nanoparticles with a core-shell structure obtained in step S2 were added as functional additives to a mixture of 140 g of PBT resin, 12 g of maleic anhydride-modified polyethylene, 3 g of polyethylene wax and 0.15 g of antioxidant 168, and the mixture was stirred and mixed evenly.

[0039] S4: adding the mixed materials in step S3 into a twin-screw extruder for full melt blending, extruding after shearing and mixing, cooling, granulating, drying and packaging to obtain the toughened modified PBT material. The process is carried out at a processing temperature of 220-240° C. and a rotation speed of 150 r / min.

[0040] Comparative Example 1: The processing method of toughened and modified PBT in this comparative example has the same raw material composition and preparation steps as those in Example 1, except that the modified nanoparticles with a core-shell structure prepared in step S2 are not added in the processing method of this comparative example.

[0041] The toughened modified PBT materials prepared in Examples 1 to 5 and Comparative Example 1 were subjected to performance tests, and the performance results are shown in Table 1:

[0042] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention, and these changes and improvements fall within the scope of the present invention claimed.

Claims

1. A processing method for toughened modified PBT, characterized in that: The processing method comprises the following steps: S1: Inorganic nanoparticles are surface treated to introduce active functional groups; S2: the inorganic nanoparticles surface-treated in step S1 are uniformly dispersed in an organic solvent by ultrasonic-assisted stirring, and then adamantane diamine and aliphatic triamine are added, and the stirring and mixing are continued to be uniform, and an organic solution of aliphatic diisocyanate is added under certain reaction conditions, and the reaction is carried out by reduced pressure distillation to obtain modified nanoparticles with a core-shell structure; S3: adding the modified nanoparticles with a core-shell structure obtained in step S2 as a functional additive to a mixture of PBT resin, maleic anhydride derivative, dispersant and antioxidant, and stirring and mixing uniformly; S4: adding the mixed materials in step S3 into a twin-screw extruder for full melt blending, extruding after shearing and mixing, cooling, granulating, drying and packaging to obtain the toughened modified PBT material.

2. The processing method of toughened modified PBT according to claim 1, characterized in that: The inorganic nanoparticles are silicon dioxide and / or titanium dioxide.

3. The processing method of toughened modified PBT according to claim 1, characterized in that: The surface treatment method comprises dispersing inorganic nanoparticles in an ethanol aqueous solution (volume ratio of 1:1), adding amine-terminated trimethoxysilane or amine-terminated triethoxysilane for hydrolysis reaction, and obtaining inorganic nanoparticles with surface grafted amine groups.

4. The processing method of toughened modified PBT according to claim 1, characterized in that: The terminal amino trimethoxysilane is at least one of 3-aminopropyl trimethoxysilane, 4-amino-3,3-dimethylbutyl trimethoxysilane, and N-(beta-aminoethyl)-gama-aminopropyl trimethoxysilane; the terminal amino triethoxysilane is at least one of 3-aminopropyl triethoxysilane, N-(6-aminohexyl)aminomethyl triethoxysilane, 4-aminobutyl triethoxysilane, (2-aminoisopropyl)triethoxysilane, (((2-aminoethyl)amino)methyl)triethoxysilane, and N-aminoethyl-3-aminopropyl triethoxysilane.

5. The processing method of toughened modified PBT according to claim 1, characterized in that: The adamantane diamine is at least one of 1,3-adamantane diamine, 1,3-adamantane diethylamine, adamantane-1,3-dimethylamine, 1,3-bis(4-aminophenyl)adamantane, and 4,4'-(adamantane-2,2-diyl)diphenylamine.

6. The processing method of toughened modified PBT according to claim 1, characterized in that: The aliphatic triamine is at least one of 1,3,6-triaminohexane, 1,4,7-triaminoheptane and undecane-1,6,11-triamine.

7. The processing method of toughened modified PBT according to claim 1, characterized in that: The aliphatic diisocyanate is at least one of methylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, and decane-1,10-diisocyanate.

8. The processing method of toughened modified PBT according to claim 1, characterized in that: The maleic anhydride derivative is at least one of maleic anhydride modified polyethylene, methyl vinyl ether-maleic anhydride copolymer, and polyoxyethylene (2-methyl-2-propenyl) methyl diether-maleic anhydride copolymer.

9. The processing method of toughened modified PBT according to claim 1, characterized in that: The dispersant is at least one of fatty acids, aliphatic amides, montan wax, silicone, and polyethylene wax; the antioxidant is at least one of antioxidant 168, antioxidant 626, antioxidant 1010, antioxidant 1024, antioxidant 1076, antioxidant 1222, and antioxidant 3114.

10. A toughened modified PBT, characterized in that: The PBT is prepared by the processing method of toughened and modified PBT as claimed in any one of claims 1 to 9.

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