Electroplating polyetherimide and preparation method thereof

Abstract

The invention relates to electroplating polyetherimide and a preparation method thereof, and belongs to the technical field of preparation of polyetherimide. The electroplated polyetherimide is prepared from the following raw materials in parts by weight: 75 to 85 parts of polyetherimide, 15 to 25 parts of heat-resistant agent and 0.1 to 1 part of compatilizer, the heat-resistant agent is grafted POSS (Polyhedral Oligomeric Silsesquioxane) and amino silane coupling agent co-modified montmorillonite. According to the invention, grafted POSS and amino silane coupling agent co-modified montmorillonite is used as a heat-resistant agent and is introduced into polyetherimide, a POSS / silane coupling agent organic layer in the co-modified montmorillonite is utilized, so that the heat-resistant agent is uniformly dispersed in the polyetherimide, and the uniformly dispersed heat-resistant agent forms a heat-resistant network with uniform hot spots in the polyetherimide; the heat resistance and the dimensional stability of the electroplated polyetherimide material are improved, and the problem that after a traditional polyetherimide layer is electroplated, the polyetherimide layer is separated from a metal layer is solved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polyetherimide preparation, and particularly relates to electroplated polyetherimide and a preparation method thereof. BACKGROUND

[0002] Polyetherimide, also referred to as PEI, is a new type of thermoplastic polyimide material in which flexible “—O—” groups are introduced into the main molecular chain of traditional polyimide, so that the processability is significantly improved, and the production cost is reduced. Although the flexible “—O—” groups solve the problems of poor processability and high cost of traditional polyimide in some aspects, the heat resistance and the resistance to organic solvent corrosion are lower than the corresponding properties of traditional polyimide due to the flexibility and linear amorphous aggregation of the molecular chain. At the same time, for electroplated polyetherimide, the heat resistance of polyetherimide is strictly required, otherwise, the delamination phenomenon between the polyetherimide layer and the metal layer after electroplating is prone to occur.

[0003] Therefore, the present application provides electroplated polyetherimide and a preparation method thereof. SUMMARY

[0004] In view of the above problems, the present application provides electroplated polyetherimide and a preparation method thereof.

[0005] A first object of the present application is to provide electroplated polyetherimide, which comprises the following raw materials in parts by weight: polyetherimide 75-85 parts, heat-resistant agent 15-25 parts, and compatibilizer 0.1-1 part. The heat-resistant agent is grafted POSS and amino silane coupling agent co-modified montmorillonite.

[0006] In the present application, the co-modified montmorillonite is used as a heat-resistant agent. The interlayer spacing of the montmorillonite is widened by intercalation modification of the montmorillonite with an amino silane coupling agent, and the interlayer spacing of the montmorillonite is further widened by further intercalation modification of the montmorillonite with grafted POSS, thereby forming a micro-nano structure of the superimposed "layered montmorillonite layer + POSS / silane coupling agent organic layer". On the one hand, the dispersion performance of the montmorillonite in the polyetherimide is improved by using the organically modified intercalated montmorillonite, and the processing performance of the montmorillonite and the polyetherimide is improved. Compared with the single modified montmorillonite, the interlayer spacing of the montmorillonite in the present application is larger, and the interfacial performance of the montmorillonite and the polyetherimide is improved. On the other hand, the dispersion performance of the montmorillonite in the polyetherimide is promoted by using the POSS / silane coupling agent organic layer, especially the long alkyl chain (derived from stearic acid) and the silane coupling agent chain grafted in the grafted POSS. Finally, the heat-resistant reinforcing performance of the POSS structure and the montmorillonite is comprehensively utilized. The co-modified montmorillonite is uniformly dispersed in the polyetherimide to form a uniform reinforcing network, thereby improving the heat-resistant performance and dimensional stability of the electroplated polyetherimide material. Moreover, the co-modified montmorillonite also plays a role of rigid reinforcement as a filler, thereby improving the mechanical performance of the obtained polyetherimide electroplating.

[0007] Further, the co-modified montmorillonite is obtained by sequentially performing the first intercalation modification with the amino silane coupling agent and the second intercalation modification with the grafted POSS.

[0008] Further, the co-modification process comprises: The first intercalation modification: the montmorillonite is immersed in a solution containing the amino silane coupling agent, and is ultrasonically treated for 16-24 hours, is centrifuged, the precipitate is taken out, is washed, is freeze-dried, and the above steps are repeated for multiple times, thereby obtaining the first intercalation modified montmorillonite. The second intercalation modification: the first intercalation modified montmorillonite is placed in a solution containing the grafted POSS, and is ultrasonically treated for 10-18 hours, is centrifuged, the precipitate is taken out, is washed, is freeze-dried, and the above steps are repeated for multiple times, thereby obtaining the co-modified montmorillonite.

[0009] Further, in the first intercalation modification process, the mass ratio of the montmorillonite to the amino silane coupling agent is 10:1-3.

[0010] Further, in the second intercalation modification process, the mass ratio of the first intercalation modified montmorillonite to the grafted POSS is 10:2-3.

[0011] Further, the solution containing the amino silane coupling agent is prepared by mixing the amino silane coupling agent and the mixed solvent according to a mass ratio of 1:8-10. Preferably, the mass ratio of the amino silane coupling agent to the first mixed solvent is 1:10.

[0012] Further, the solution containing the grafted POSS is prepared by mixing the grafted POSS and the second mixed solvent in a mass ratio of 1:15-20, preferably, the mass ratio of the grafted POSS and the mixed solvent is 1:16.

[0013] Further, the first mixed solvent and the second mixed solvent are both organic solvents commonly used in the technical field, which are not specifically limited in the present application.

[0014] Further, the grafted POSS is prepared by condensation reaction of octaamino POSS and stearic acid.

[0015] Further, the molar ratio of the octaamino POSS and the stearic acid is 1:1-4.

[0016] Further, the condensation reaction occurs in the presence of a condensation reagent and a reaction solvent.

[0017] Further, the condensation reaction is carried out at a reaction temperature of 60-100℃ for 2-4h.

[0018] The second object of the present application is to provide a preparation method of the electroplated polyetherimide, comprising: After mixing the polyetherimide, the heat-resistant agent and the compatibilizer, melt and pelletize them by a double screw granulator to obtain the electroplated polyetherimide.

[0019] The present application has the following advantages: The electroplated polyetherimide and the preparation method thereof of the present application use the co-modified montmorillonite with grafted POSS and amino silane coupling agent as the heat-resistant agent, which is introduced into the polyetherimide. The organic layer of the co-modified montmorillonite, especially the long alkyl chain and the silane coupling agent chain grafted in the grafted POSS, makes the heat-resistant agent uniformly dispersed in the polyetherimide. The uniformly dispersed heat-resistant agent forms a heat-resistant network with uniform heat-resistant points in the polyetherimide. The heat-resistant points are the micro-nano structure of the superimposed "montmorillonite layer + POSS / silane coupling agent organic layer", which further improves the heat resistance of the obtained electroplated polyetherimide. At the same time, the heat-resistant network with uniform heat-resistant points forms a heat-resistant skeleton of the electroplated polyetherimide during electroplating, which improves the heat resistance and dimensional stability of the electroplated polyetherimide material, and solves the problem of delamination between the polyetherimide layer and the metal layer after electroplating of the traditional polyetherimide layer. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the scope of protection of the present application.

[0021] The size of the montmorillonite in the following embodiments is 20-150 mesh, and the interlayer spacing is 1.27 nm.

[0022] Embodiment 1 Preparation of the co-modified montmorillonite: Preparation of the grafted POSS: After 0.3 mol of stearic acid, 0.1 mol of octaamino POSS and 80 mL of N,N-dimethylacetamide (DMA) are mixed, the mixture is heated to 60°C under stirring, then a condensation reagent (0.33 mol of EDCI and 0.04 mol of HOBt) is added dropwise, stirring is continued for 0.5 h, and the reaction is continued for 1.5 h under heating and stirring, the reaction is stopped, and the product is obtained by rotation, water washing and drying; First intercalation modification: 10 g of montmorillonite is immersed in 100 mL of a solution containing 1 g of amino silane coupling agent (according to a mass ratio of amino silane coupling agent (γ-aminopropyl triethoxysilane) to DMAc of 1:10), and ultrasonic treatment is performed for 24 h, centrifugation is performed, the precipitate is taken out, washed and freeze-dried, and the operation is repeated twice to obtain first intercalation modified montmorillonite (interlayer spacing of 2.41 nm); Second intercalation modification: 10 g of the first intercalation modified montmorillonite is immersed in 100 mL of a solution containing 3 g of grafted POSS (consisting of a mixture of grafted POSS and DMAc according to a mass ratio of 1:16, and a second mixed solvent consisting of a mixture of ethanol and water according to a volume ratio of 3:1), and ultrasonic treatment is performed for 12 h, centrifugation is performed, the precipitate is taken out, washed and freeze-dried, and the operation is repeated twice to obtain co-modified montmorillonite (interlayer spacing of 3.72 nm).

[0023] Embodiment 2 Preparation of the co-modified montmorillonite: Preparation of the grafted POSS: After 0.4 mol of stearic acid, 0.1 mol of octaamino POSS and 80 mL of N,N-dimethylacetamide (DMA) are mixed, the mixture is heated to 60°C under stirring, then a condensation reagent (0.45 mol of EDCI and 0.05 mol of HOBt) is added dropwise, stirring is continued for 0.5 h, and the reaction is continued for 3.5 h under heating and stirring, the reaction is stopped, and the product is obtained by rotation, water washing and drying; Primary intercalation modification: 10 g of montmorillonite was immersed in 100 mL of a solution containing 3 g of amino silane coupling agent (according to the mass ratio of amino silane coupling agent (γ-aminopropyl triethoxysilane) and DMAc 1:10), and ultrasonic was applied for 24 h, centrifuged, and the precipitate was taken, washed, freeze-dried, and repeated twice to obtain the primary intercalation modified montmorillonite (interlayer spacing 2.42 nm); Secondary intercalation modification: 10 g of the primary intercalation modified montmorillonite was immersed in 100 mL of a solution containing 2 g of grafted POSS (consisting of grafted POSS and DMAc mixed according to a mass ratio of 1:16), and ultrasonic was applied for 12 h, centrifuged, and the precipitate was taken, washed, freeze-dried, and repeated twice to obtain the co-modified montmorillonite (interlayer spacing 3.80 nm).

[0024] Comparative Example 1 A single modified montmorillonite was provided, which was the primary intercalation modified montmorillonite obtained in Example 1.

[0025] Comparative Example 2 Preparation of a single modified montmorillonite: Preparation of grafted POSS: After mixing 0.1 mol of stearic acid, 0.1 mol of octaamino POSS, and 80 mL of N,N-dimethylacetamide (DMA), heating was applied to 60°C under stirring, then a condensation reagent (0.11 mol of EDCI and 0.02 mol of HOBt) was added dropwise, stirring was applied for 0.5 h, and the reaction was continued for 1.5 h under heating and stirring, the reaction was stopped, and the product was obtained after rotation, water washing, and drying. Intercalation modification: 10 g of montmorillonite was immersed in 100 mL of a solution containing 3 g of grafted POSS (consisting of grafted POSS and DMAc mixed according to a mass ratio of 1:6), and ultrasonic was applied for 24 h, centrifuged, and the precipitate was taken, washed, freeze-dried, and repeated twice to obtain the co-modified montmorillonite (interlayer spacing 1.56 nm).

[0026] Comparative Example 3 Preparation of a co-modified montmorillonite: Primary intercalation modification: 10 g of montmorillonite was immersed in 100 mL of a solution containing 1 g of amino silane coupling agent (according to the mass ratio of amino silane coupling agent (γ-aminopropyl triethoxysilane) and DMAc 1:10), and ultrasonic was applied for 24 h, centrifuged, and the precipitate was taken, washed, freeze-dried, and repeated twice to obtain the primary intercalation modified montmorillonite (interlayer spacing 2.41 nm); Secondary intercalation modification: 10 g of the primary intercalation modified montmorillonite was immersed in 100 mL of a solution containing 3 g of octaamino POSS (consisting of grafted POSS and DMAc mixed according to a mass ratio of 1:16), and ultrasonic was applied for 12 h, centrifuged, and the precipitate was taken, washed, freeze-dried, and repeated twice to obtain the co-modified montmorillonite (interlayer spacing 3.52 nm).

[0027] Example 3 Preparation of plated polyetherimide: Preparation: including the following raw materials by weight: polyetherimide 85 parts, heat-resistant agent 15 parts (co-modified montmorillonite prepared in Example 1), compatibilizer 0.1 parts (compatibilizer is maleic anhydride grafted to polyethylene); Melt blending extrusion: after mixing the polyetherimide, heat-resistant agent and compatibilizer, melt and pellet through a double screw granulator, to obtain the plated polyetherimide.

[0028] The polyetherimide used in the following examples is PEI base innovative plastics (USA) 9085-1100.

[0029] Example 4 Preparation of plated polyetherimide: Preparation: including the following raw materials by weight: polyetherimide 80 parts, heat-resistant agent 20 parts (co-modified montmorillonite prepared in Example 2), compatibilizer 0.4 parts (compatibilizer is maleic anhydride grafted to polyethylene); Melt blending extrusion: after mixing the polyetherimide, heat-resistant agent and compatibilizer, melt and pellet through a double screw granulator, to obtain the plated polyetherimide.

[0030] Example 5 Preparation of plated polyetherimide: Preparation: including the following raw materials by weight: polyetherimide 75 parts, heat-resistant agent 25 parts (co-modified montmorillonite prepared in Example 1), compatibilizer 1 part (compatibilizer is maleic anhydride grafted to polyethylene); Melt blending extrusion: after mixing the polyetherimide, heat-resistant agent and compatibilizer, melt and pellet through a double screw granulator, to obtain the plated polyetherimide.

[0031] Comparative Example 4 Preparation of plated polyetherimide: compared with Example 3, replace the heat-resistant agent with the same amount of single-modified montmorillonite of Comparative Example 1, and the rest is the same.

[0032] Comparative Example 5 Preparation of plated polyetherimide: compared with Example 3, replace the heat-resistant agent with the same amount of single-modified montmorillonite of Comparative Example 2, and the rest is the same.

[0033] Comparative Example 6 Preparation of plated polyetherimide: compared with Example 3, replace the heat-resistant agent with the same amount of single-modified montmorillonite of Comparative Example 3, and the rest is the same.

[0034] Comparative Example 7 Preparation of polyetherimide: compared with Example 3, delete the heat-resistant agent, and the rest is the same.

[0035] Test: tensile strength: GB / T 1040.1 standard was used; Linear expansion coefficient: GB / T 1036 standard was used; Whether delamination: after electroplating, whether the coating layer had delamination phenomenon was observed within 30 seconds from 20℃ to 90℃, and the results were shown in Table 1.

[0036] Table 1

[0037] From the data in Table 1, it can be seen that the electroplated polyetherimide obtained in Examples 3-5 did not have the problem of metal layer separation after electroplating.

[0038] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as they do not deviate from the invention or exceed the scope defined by the present claims, which shall belong to the protection scope of the present application.

Claims

1. Electroplating polyetherimide, characterized in that, The method comprises the following raw materials in parts by weight: 75-85 parts of polyetherimide, 15-25 parts of heat-resistant agent, and 0.1-1 part of compatibilizer; The heat-resistant agent is montmorillonite co-modified by grafted POSS and aminosilane coupling agent.

2. The electroplated polyetherimide according to claim 1, characterized in that The co-modification process comprises: Primary intercalation modification: immerse the montmorillonite in a solution containing an aminosilane coupling agent, ultrasonicate for 16-24 hours, centrifuge, take the precipitate, freeze-dry, and repeat several times to obtain the primary intercalation modified montmorillonite; Secondary intercalation modification: The primary intercalation modified montmorillonite is placed in a solution containing grafted POSS and ultrasonicated for 10-18 hours, centrifuged, and the precipitate is taken and freeze-dried. This process is repeated several times to obtain the co-modified montmorillonite.

3. The electroplated polyetherimide according to claim 2, characterized in that: In the primary intercalation modification process, the mass ratio of the montmorillonite to the aminosilane coupling agent is 10:1-3; In the secondary intercalation modification process, the mass ratio of the primary intercalation modified montmorillonite to the grafted POSS is 10:2-3.

4. The electroplated polyetherimide according to claim 3, characterized in that The solution containing the aminosilane coupling agent is prepared by mixing the aminosilane coupling agent and the first mixed solvent in a mass ratio of 1:8-10.

5. The electroplated polyetherimide according to claim 3, characterized in that: The solution containing the grafted POSS is prepared by mixing the grafted POSS and a second mixed solvent in a mass ratio of 1:15-20.

6. The electroplated polyetherimide according to claim 1, characterized in that The grafted POSS is prepared by condensation reaction of octaamino POSS and stearic acid.

7. The electroplated polyetherimide according to claim 6, characterized in that: The molar ratio of the octaamino POSS to stearic acid is 1:1-4.

8. The electroplated polyetherimide according to claim 6, characterized in that: The condensation reaction occurs in the presence of a condensation reagent and a reaction solvent.

9. The electroplated polyetherimide according to claim 6, characterized in that: The reaction temperature of the condensation reaction is 60-100° C., and the reaction time is 2-4 hours.

10. The method for preparing electroplated polyetherimide according to any one of claims 1 to 9, characterized in that: include: After polyetherimide, a heat-resistant agent and a compatibilizer are mixed, the mixture is melted and pelletized in a twin-screw pelletizer to obtain electroplated polyetherimide.

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