CN102911360A

CN102911360A - Graphene modified polyimide-based composite and preparation method thereof

Info

Publication number: CN102911360A
Application number: CN2012104278407A
Authority: CN
Inventors: 姚正军; 郑文建; 周金堂; 魏东博; 周畅; 姚芮; 陈永鑫
Original assignee: Nanjing University of Aeronautics and Astronautics
Current assignee: Nanjing University of Aeronautics and Astronautics
Priority date: 2012-11-01
Filing date: 2012-11-01
Publication date: 2013-02-06
Anticipated expiration: 2032-11-01
Also published as: CN102911360B

Abstract

The invention discloses a graphene modified polyimide-based composite which is characterized in that the graphene modified polyimide-based composite comprises the following components in parts by weight: 95-105 parts of 4,4'-diaminodiphenyl ether, 110-120 parts of pyromellitic dianhydride and 1-25 parts of graphene. A preparation method comprises the steps of weighing ODA (octyl decyl adipate) and the graphene in proportion, measuring a DMAC (dimethylacetamide) solvent, adding the ODA, the graphene and the DMAC solvent to a reaction vessel, using ultrasonic till the ODA is dissolved sufficiently and the graphene is dispersed completely in the DMAC to obtain a graphene suspension, adding PMDA (pyromellitic dianhydride) in batches under high-speed stirring conditions till weak pole climbing appears, continuing to stir to allow diamine to react with dianhydride completely, and flattening an obtained graphene/PAA (poly acrylic acid) complex to obtain a composite film with uniform thickness so as to obtain a graphene polyimide composite film. The composite is 0.5 g/cm<3>-1.5 g/cm<3> in density and 60-170 KJ/m<2> in tensile strength.

Description

A kind of Graphene modified polyimide based composites and preparation method thereof

Technical field

The invention belongs to superpolymer blending and modifying field, be specifically related to a kind of Graphene modified polyimide based composites and preparation method thereof.

Background technology

The polymer-based dielectric composite material of high-k is widely used in microelectronic, improves its specific inductivity significant for the development of electronic industry.According to seepage theory, in polymeric matrix, add conductive filler material, when filler loading level during near seepage flow value of closing of material, uprushing just can appear in the specific inductivity of matrix material.Graphene has high specific conductivity and very stable chemical property, as simple substance, its speed of at room temperature transmitting electronics is all faster than known conductor, its electronic mobility surpasses only about 10-6 Ω cm of 15000 cm2/Vs resistivity under the normal temperature, lower than copper or silver, be the ideal filler that improves the matrix material specific inductivity.Polyimide (Pl) has unique good characteristic, such as good heat-resisting, winter hardiness, good dielectric properties, outstanding mechanical property and the optimization design that easily realizes molecular structure can be used as the high-performance resin matrix of Graphene/polymer dielectric matrix material to satisfy different performance requriements etc.But the specific inductivity that existing polyimide material exists is not high, stable bad, the shortcomings and deficiencies such as mechanical property is bad of machine-shaping.

Summary of the invention

In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of Graphene modified polyimide based composites and preparation method thereof, the technique simple possible can be prepared high-k and good thermal characteristics and mechanical property Kapton economical and efficient.

The present invention has adopted following technical scheme:

A kind of Graphene modified polyimide based composites is made of by weight following compositions: 95～105 parts of 4,4'-diaminodiphenyl oxides, 110～120 parts of pyromellitic acid acid anhydrides, 1～25 part of Graphene.

4,4'-diaminodiphenyl oxide and the polymerization of pyromellitic acid acid anhydride obtain polyimide, and weight-average molecular weight is between 1～20,000, and the molecular weight distribution mw/mn value is 1.2～2.6, and fusing point is 320 ℃～368 ℃, and degree of crystallinity is 25～55%.

The preparation method of Graphene/Kapton is characterized in that may further comprise the steps:

(1) take by weighing in proportion ODA(4, the 4'-diaminodiphenyl oxide), Graphene, measure solvent DMAC(N,N-DIMETHYLACETAMIDE), all add in the reaction vessel, ultrasonic to ODA fully dissolve, Graphene disperses fully at DMAC, obtains graphene suspension, and is for subsequent use; Graphene needs vacuum-drying in advance; The particle diameter of graphene powder is 10～50nm; Solvent load 40～100ml.

(2) under the high-speed stirring condition, in graphene suspension, add in batches PMDA(pyromellitic acid acid anhydride), along with the increase of PMDA consumption, the viscosity of system constantly increases, until faint rod climbing phenomenon occurs, obtain performed polymer one polyamic acid (PAA) of polyimide this moment; Continue to stir 3～10h, diamines and dianhydride are reacted completely, obtain Graphene/PAA mixture, stirring velocity is 600～1500r/min.

(3) Graphene/PAA mixture is poured on the clean level and smooth flat board, push away flatly, obtain the laminated film of even thickness, with flat board as for convection oven respectively under 80 ℃, 120 ℃, 180 ℃, 240 ℃ and 300 ℃, each dry lh obtains the Graphene polyimide composite film.

The present invention utilizes situ aggregation method that the Graphene particle of non-modified is dispersed in the polyimide matrix, prepares the high dielectric laminated film of Graphene/polyimide of excellent combination property.There are the groups such as hydroxyl, carboxyl on the Graphene surface, can with polyimide on group form hydrogen bond, both consistencies are good, make being dispersed in the polyimide matrix of graphene uniform; In addition, the polyimide matrix Stability Analysis of Structures, good conductivity and mechanical property that Graphene has can be improved mechanical property and the specific inductivity of polyimide, and the composite density that obtains is 0.5 g/cm ³～1.5g/cm ³, specific inductivity 3.1 F/m～9.8 F/m, dielectric loss 0.01～0.02, specific conductivity 0.15S/m～0.8 S/m, tensile strength 60～170KJ/m ², have good mechanical property, processing characteristics.

Embodiment

Below by specific embodiment technical scheme of the present invention is further described; but the present invention is not limited to these embodiment; the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to foregoing, all should belong to the protection domain of the appended claim of the present invention.

Embodiment 1-8 adopts component such as table 1, (unit: weight part)

Table 1

Embodiment	1	2	3	4	5	6	7	8
									4,4'-diaminodiphenyl oxide	95	97	99	101	99	99	103	105
The pyromellitic acid acid anhydride	110	112	114	114	114	114	114	120
									Graphene	1	3	5	10	15	20	20	25

The preparation method:

(1) prescription according to table 1 adds the there-necked flask mixing with abundant dried raw material, adds solvent DMAC 40ml, ultrasonic 30min, and homogeneous reaction obtains graphene suspension, and the particle diameter of graphene powder is 20nm;

(2) under the rotating speed agitation condition of 600r/min, in batches PMDA is added graphene suspension, until faint rod climbing phenomenon occurs, obtain performed polymer one polyamic acid (PAA) of polyimide this moment; Continue to stir 3h, diamines and dianhydride are reacted completely;

(3) Graphene that then reaction is obtained/PAA mixture is poured on the clean level and smooth sheet glass, obtain the laminated film of even thickness, place it in convection oven respectively at the lh that respectively heats up under 80 ℃, 120 ℃, 180 ℃, 240 ℃ and 300 ℃, obtain the Graphene polyimide composite film.

The property indices of embodiment 1-8 gained Graphene polyimide composite film is shown in Table 1, and wherein tensile property is pressed the GB/T1043-1993 standard testing, and each parameter unit is as follows: specific inductivity: (F/m) specific conductivity: S/m resistivity: Ω m.

The performance test results of table 1 embodiment 1-8 resulting materials

?	Specific inductivity	Dielectric loss	Specific conductivity	Resistivity
					Embodiment 1	4.2	0.012	0.17	3.2×10 ⁵
Embodiment 2	4.1	0.014	0.28	2.8×10 ⁵
					Embodiment 3	4.5	0.015	O.34	2.5×10 ⁵
Embodiment 4	6.1	0.013	0.38	2.3×105
					Embodiment 5	9.6	0.017	0.42	2.2×10 ⁵
Embodiment 6	5.6	0.018	0.51	1.8×10 ⁵
					Embodiment 7	4.3	0.2	0.67	1.7×10 ⁵
Embodiment 8	3.3	0.019	0.78	1.6×10 ⁵

Can find out from above-mentioned example, Graphene modified polyimide base blended compound material disclosed by the invention is along with the increase of Graphene add-on, the specific inductivity of matrix material, mechanical property,, crocking resistance, thermomechanical property etc. all obtained good improvement.

Embodiment 9

Component is with embodiment 1, the preparation method except following content with the preparation method of embodiment 1.The particle diameter of the graphene powder that step (1) adopts is 50nm; Step (2) stirring velocity is 1500r/min, obtains performed polymer one polyamic acid (PAA) of polyimide; Continue reaction 10h; Behind step (3) ladder-elevating temperature, at each temperature spot insulation 5h.

Embodiment 10

Component is with embodiment 1, the preparation method except following content with the preparation method of embodiment 1.The particle diameter of the graphene powder that step (1) adopts is 100nm; Step (2) stirring velocity is 800r/min, obtains performed polymer one polyamic acid (PAA) of polyimide; Continue reaction 5h; Behind step (3) ladder-elevating temperature, at each temperature spot insulation 2h.

Claims

1. a Graphene modified polyimide based composites is characterized in that being comprised of by weight following compositions: 95～105 parts of 4,4'-diaminodiphenyl oxides, 110～120 parts of pyromellitic acid acid anhydrides, 1～25 part of Graphene.

2. the preparation method of Graphene/Kapton according to claim 1 is characterized in that the particle diameter of step (1) graphene powder is 20～100nm.

3. based on the preparation method of Graphene/Kapton claimed in claim 1, it is characterized in that may further comprise the steps:

(1) take by weighing in proportion ODA, Graphene, measure solvent DMAC, all add in the reaction vessel, ultrasonic to ODA fully dissolve, Graphene disperses fully at DMAC, obtains graphene suspension, and is for subsequent use;

(2) under the high-speed stirring condition, in graphene suspension, add in batches PMDA, along with the increase of PMDA consumption, the viscosity of system constantly increases, until faint rod climbing phenomenon occurs, obtains performed polymer one polyamic acid of polyimide this moment; Continue to stir 3～10h, diamines and dianhydride are reacted completely, obtain Graphene/PAA mixture; Stirring velocity is 600～1500r/min;

(3) Graphene/PAA mixture is poured on the clean level and smooth flat board, push away flatly, obtain the laminated film of even thickness, flat board is placed under the ladder-elevating temperature to 80 ℃, 120 ℃, 180 ℃, 240 ℃ and 300 ℃, each is incubated l～5h, obtains the Graphene polyimide composite film.

4. the preparation method of Graphene/Kapton according to claim 2 is characterized in that needing vacuum-drying before step (1) Graphene uses.