CN101717508A

CN101717508A - Method for preparing nano-silica-containing polyimide hybrid material

Info

Publication number: CN101717508A
Application number: CN200910040285A
Authority: CN
Inventors: 周显宏; 武秀文; 兰善红; 李纠; 蒋欣; 刘煜平
Original assignee: Dongguan University of Technology
Current assignee: Dongguan University of Technology
Priority date: 2009-06-16
Filing date: 2009-06-16
Publication date: 2010-06-02

Abstract

The invention provides a method for preparing nano-silica-containing polyimide hybrid material. The preparation method comprises the following steps: ultrasonically mixing nano-silica, coupling agents and toluene in a reaction kettle filled with nitrogen; stirring the mixture at a certain temperature to cool the mixture to room temperature; adding paraformaldehyde and the phenol to the sol so as to obtain transparent modified silica sol; adding diamine monomer PAPB and ODA to N,N-dimethylacetamide under nitrogen protection and stirring to completely dissolve the obtained product; adding an equimolar amount of pyromellitic dianhydride equally divided to the solution in two steps so as to obtain polyamide acid solution; adding the obtained modified silica sol to the obtained polyamide acid solution so as to obtain mixed glue solution; and placing the obtained glue solution at a certain temperature for vacuum drying so as to obtain the nano-silica-containing polyimide hybrid material. Compared with non-hybrid polyimide, the composite material synthesized by the method has better mechanical properties, thermal stability and lower coefficient of thermal expansion.

Description

A kind of preparation method of polyimide hybrid material of nano-silica-containing

Technical field

The present invention relates to the preparation method of a kind of polyimide hybrid material of nano-silica-containing in the chemical field

Background technology

Fragrant polyimide (PI) has superior dielectric properties, mechanical property, thermal stability, oxidation-stabilized performance, chemical resistance and radiation resistance, and range of application is very extensive.

In recent years, electronic product develops to high-performance and miniaturization, thereby requires electronic component and their substrate of installation also to develop to high-performance and densification direction.

Universal polyimide is its performed polymer-polyamic acid of preparation earlier, and film forming becomes polyimide through the high-temperature sub amination then.This film has certain snappiness, powerful performance and the thermostability learned, and has very wide application prospect in electron trade.

But this film is in preparation process, because the thermal expansivity (CTE) of polyimide and Copper Foil is different, in the heating and cooling process, substrate is easy to generate curling, and has bigger residual stress, has bigger dimensional change behind the etching Copper Foil; The downstream client uses in the course of processing, also has the multistage heating process, and the difference of CTE also can cause dimensional change, and then causes problems such as fine rule road bad connection.

Equally, in downstream client's manufacturing procedure, the liquid medicine that also has multistage soaks and bake process.The water absorbability of polyimide is very strong, and bigger expansion can take place volume after its moisture absorption, and the wet swelling of Copper Foil is almost nil.Therefore, not only can influence dimensional stability, make easily also that substrate produce to curl, warpage or distortion, influence the quality and the use of substrate.

Summary of the invention

Studies show that in recent years, middle some functional groups or the inorganic nano material introduced in polyimide can improve thermostability and dimensional stability keeping reducing the specific inductivity of polyimide film material under the flexible prerequisite of polyimide.

Purpose of the present invention is exactly by introducing benzoxazine structure in nano silicon, improve the consistency of nano silicon and polyimide resin, synthesize a kind of more hybrid polyimide material of high thermal stability, mechanical property that has, can be used for specific technical field such as flexibility coat copper plate or other universal polyimide are carried out modification.

Preparation method of the present invention is as follows:

In being filled with the reactor of nitrogen, with the 1-10% nano silicon, 1-10% coupling agent KH550 mixed 30-60 minute with 80-98% toluene is ultrasonic, stirred 8-15 hour under 120-140 ℃ of temperature condition; Be cooled to the normal temperature state, again 0.1-1% Paraformaldehyde 96 and 0.2-2% phenol added in the above-mentioned colloidal sol, stir and be warming up to 85-100 ℃, reacted 5-7 hour, obtain transparent modified silicon dioxide gel;

Under nitrogen protection, temperature of reaction is 0 ℃, and 3-6% diamine monomer PAPB (1, two (4-amino-benzene oxygen) benzene of 3-), ODA (diaminodiphenyl oxide) are added in the N,N-dimethylacetamide, stirs more than 2 minutes it to be dissolved fully; To divide equally secondary with the pyromellitic acid anhydride of equimolar amount 3-7% again and add in the above-mentioned solution, each timed interval 20-40 minute; Be warming up to normal temperature again, stir and made polyamic acid solution in 5-10 hour; Again the modified silicon dioxide sol that makes is added in the polyamic acid solution that makes, stir and made mixed glue solution in 10-20 hour; At last, the glue that makes is placed under the 80-120 ℃ of temperature vacuum-drying 2-4 hour, under 150-200 ℃ of temperature, vacuum-drying 2-4 hour, under 270-300 ℃ of temperature, dry 1-3 hour, obtain containing the polyimide/nano silicon dioxide hybridization material of the nano silicon of 1-10%.

Because nano silicon be at present known to one of the material of thermal expansivity minimum, be introduced in the polyimide, can reduce the thermal expansivity of hybrid material, improve thermostability.Yet because inorganic silicon-dioxide is mutual exclusive with organic polyimide, the present invention adopts the nano silicon that can carry out the band benzoxazine structure of organic reaction with it to increase the effect of it and polyimide, avoids even eliminate its uncompatibility.Therefore with synthetic matrix material of the present invention more not the polyimide of hydridization have better mechanical property, thermostability and lower thermal expansivity.

Embodiment

The present invention will be further described now to lift an example.

Embodiment

In being filled with the reactor of nitrogen, with 3% nano silicon, 1% coupling agent KH550 mixed 30-60 minute with 98% toluene is ultrasonic, stirred 8 hours under 140 ℃ of temperature condition; Be cooled to the normal temperature state, again 0.26% Paraformaldehyde 96 and 0.51% dihydroxyphenyl propane added in the above-mentioned colloidal sol, stir and be warming up to 85 ℃, reacted 5-7 hour,, obtain transparent modified silicon dioxide gel; Under nitrogen protection, 5% diamine monomer PAPB, ODA are added in the N,N-dimethylacetamide, stirring dissolves it more than 2 minutes fully; To divide equally secondary with the pyromellitic acid anhydride of equimolar amount 5.5% again and add in the above-mentioned solution, and in each 20 minutes timed intervals, stir and made polyamic acid solution in 5 hours; Again the modified silicon dioxide sol that makes is added in the polyamic acid solution that makes, stir and made mixed glue solution in 15 hours; At last, the glue that makes is placed under 80 ℃ of temperature, vacuum-drying 4 hours, under 150 ℃ of temperature, vacuum-drying 2 hours under 270 ℃ of temperature, dry 3 hours, obtains containing the polyimide hybrid material of the nano-silica-containing of 5% nano silicon.

Claims

1. method with bonded leather to manufacture high-simulation leather, it is characterized in that: this invention preparation method is as follows: in being filled with the reactor of nitrogen, with the 1-10% nano silicon, 1-10% coupling agent KH550 mixed 30-60 minute with 80-98% toluene is ultrasonic, stirred 8-15 hour under 120-140 ℃ of temperature condition; Be cooled to the normal temperature state, again 0.1-1% Paraformaldehyde 96 and 0.2-2% phenol added in the above-mentioned colloidal sol, stir and be warming up to 85-100 ℃, reacted 5-7 hour, obtain transparent modified silicon dioxide gel; Under nitrogen protection, temperature of reaction is 0 ℃, and 3-6% diamine monomer PAPB (1, two (4-amino-benzene oxygen) benzene of 3-), ODA (diaminodiphenyl oxide) are added N, and in N one N,N-DIMETHYLACETAMIDE, stirring dissolves it more than 2 minutes fully; To divide equally secondary with the pyromellitic acid anhydride of equimolar amount 3-7% again and add in the above-mentioned solution, each timed interval 20-40 minute; Be warming up to normal temperature again, stir and made polyamic acid solution in 5-10 hour; Again the modified silicon dioxide sol that makes is added in the polyamic acid solution that makes, stir and made mixed glue solution in 10-20 hour; At last, the glue that makes is placed under 80 1 120 ℃ of temperature vacuum-drying 2-4 hour, under 150 1 200 ℃ of temperature, vacuum-drying 2-4 hour, under 270-300 ℃ of temperature, dry 1-3 hour, obtain containing the polyimide/nano silicon dioxide hybridization material of the nano silicon of 1-10%.