阅读说明：本技术 一种功能化石墨烯改性聚酰亚胺薄膜的制备方法及制品 (A kind of preparation method and product of functionalization graphene polyimide film ) 是由 王勇 王宇轩 徐伟伟 殷安民 祁晓东 姜新 李静 许培俊 高尚林 于 2019-09-04 设计创作，主要内容包括：本发明公开了一种功能化石墨烯改性聚酰亚胺薄膜的制备方法及制品。首先由二胺与二酐合成聚酰亚胺树脂,然后加入改性石墨烯,经过亚胺化制成。本发明在聚酰亚胺薄膜的制备过程中,加入改性石墨烯,增加了石墨烯在材料中的分散程度,极大的增加了材料的导热性能和力学性能,以满足市场的需要。(The invention discloses the preparation methods and product of a kind of functionalization graphene polyimide film.First by diamines and dianhydride synthesis of polyimides resin, modified graphene is then added, is made by imidization.The present invention is added modified graphene, increases the degree of scatter of graphene in the material, significantly increase the heating conduction and mechanical property of material, to meet the needs in market in the preparation process of Kapton.)

1. a kind of preparation method of functionalization graphene polyimide film, which is characterized in that carry out in accordance with the following steps:

(1) at room temperature, diamines and dianhydride are added to reaction kettle, organic solvent is added under nitrogen protection, after mixing evenly, adds Enter isoquinolin, be warming up to 180-200 DEG C, react 10-14 hours, reaction solution is poured into ethyl alcohol after cooling and is precipitated, polyamides Asia is made Polyimide resin；

(2) polyimide resin of synthesis and the agitated reaction kettle of modified graphene are stirred, mixing speed 1500-2000rpm, Mixing time 1-3h, is made film liquid；

(3) film liquid is pressed into deaeration kettle, sloughs the bubble in film liquid under vacuum conditions；

(4) film liquid after deaeration casting machine is put into be cast to form Kapton in homogeneous thickness；

(5) Kapton is put into imidization furnace and carries out imidization processing, processed by winder and cutting machine, made At finished product.

2. the preparation method of functionalization graphene polyimide film according to claim 1, which is characterized in that described Diamines is m-phenylene diamine (MPD), 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines, diphenyldiamine, hydroquinone di ether diamines, One of two ether diamine of bisphenol-A or more than one.

3. the preparation method of functionalization graphene polyimide film according to claim 1, which is characterized in that described Dianhydride is benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, hydroquinone di ether dianhydride, 5,5 '-(1,1,3,3- tetramethyls-two Siloxanes) carbic anhydride, 1,1,3,3- tetramethyl disiloxane-bis- benzoic acid dianhydride, in two ether dianhydride of resorcinol One or more.

4. the preparation method of functionalization graphene polyimide film according to claim 1, which is characterized in that described Organic solvent is metacresol, cresols, dimethylformamide, one of N-Methyl pyrrolidone or more than one.

5. the preparation method of -4 functionalization graphene polyimide films according to claim 1, which is characterized in that institute State modified graphene the preparation method is as follows:

(1) graphene is dissolved in 25% ethanol water, adds butyramide, be mixed, obtain graphene dispersing solution；

(2) polyethylene glycol dimethacrylate is added in graphene dispersing solution, is warming up to 40-50 DEG C, be mixed；

(3) it is cooled to room temperature, coupling agent and surfactant is added, stirs evenly, is made.

6. the preparation method of functionalization graphene polyimide film according to claim 5, which is characterized in that described Coupling agent is silane resin acceptor kh-550, Silane coupling reagent KH-570, silane coupling agent KH-602, silane coupling agent KH-901, One of silane coupling agent KH-902 or more than one.

7. the preparation method of functionalization graphene polyimide film according to claim 5, which is characterized in that described Surfactant is neopelex, nonylplenyl ether, neopentyl glycol, sodium nitrilo triacetate, triethanolamine, silicic acid Sodium, one of polyphosphate or more than one.

8. the Kapton product that the preparation method of claim 1-7 obtains.

Technical field

The invention belongs to polyimides technical fields, and in particular to a kind of functionalization graphene polyimide film Preparation method and product.

Background technique

Polyimides refers to the quasi polymer for containing imide ring (- CO-NH-CO-) on main chain, wherein to contain phthaloyl The polymer of imine structure is mostly important.Polyimides as a kind of special engineered material, have been widely used Aeronautics and Astronautics, The fields such as microelectronics, nanometer, liquid crystal, seperation film, laser.Polyimide high temperature-resistant is up to 400 DEG C or more, long-term use temperature model - 200~300 DEG C are enclosed, partially without sharp melting point, high insulating property, dielectric loss only 0.004~0.007.

Graphene is a kind of Two-dimensional Carbon nanometer material for forming hexangle type in honeycomb lattice with sp2 hybridized orbit by carbon atom Material.Graphene carbon atom has 4 valence electrons, wherein 3 are electronically generated sp key, i.e., each carbon atom contributes one to be located at pz rail Non- bonding electrons on road, the pz track and plane of neighbour's atom can form pi bond at vertical direction, and the pi bond newly formed is in partly to fill out Full state.Research confirms that the ligancy of carbon atom is 3 in graphene, and the bond distance between every two adjacent carbon atom is 1.42 × 10 Rice, the angle between key and key is 120 °.Other than σ key and other carbon atom chains are connected into the cellular layer structure of hexagonal ring, The pz track perpendicular to layer plane of each carbon atom can form polyatomic big pi bond through holostrome, thus have excellent Conduction and optical property.

Graphene is one of highest material of known strength, while also having good toughness, and can be bent, graphene Theoretical Young's modulus reach 1.0TPa, intrinsic tensile strength be 130GPa.Possessed very by the graphite paper that graphene platelet forms More holes, thus graphite paper seems very crisp, however, obtaining functionalization graphene through oxidation, then is made into stone by functionalization graphene Black paper then can be abnormal firm tough.Graphene has extraordinary heat-conductive characteristic.Pure flawless single-layer graphene is led Hot coefficient is up to 5300W/mK, is the highest carbon material of thermal coefficient so far, receives higher than single-walled carbon nanotube and multi wall carbon Mitron.When it is as carrier, thermal coefficient is also up to 600W/mK.In addition, the trajectory thermal conductivity of graphene can make unit circle The lower limit of the trajectory thermal conductivity of the carbon nanotube of week and length moves down.

Although graphene has good performance, still, be difficult to evenly dispersed, needed to graphene in polyimide material Modification could utilize its excellent properties well.

Summary of the invention

The purpose of the present invention is to provide the preparation methods and its system of a kind of functionalization graphene polyimide film Product.

A kind of preparation method of functionalization graphene polyimide film carries out in accordance with the following steps:

(1) at room temperature, diamines and dianhydride are added to reaction kettle, organic solvent is added under nitrogen protection, stirs evenly Afterwards, isoquinolin is added, is warming up to 180-200 DEG C, reacts 10-14 hours, reaction solution is poured into ethyl alcohol after cooling and is precipitated, is made poly- Imide resin；

(2) polyimide resin of synthesis and the agitated reaction kettle of modified graphene are stirred, mixing speed 1500- 2000rpm, mixing time 1-3h, is made film liquid；

(3) film liquid is pressed into deaeration kettle, sloughs the bubble in film liquid under vacuum conditions；

(4) film liquid after deaeration casting machine is put into be cast to form Kapton in homogeneous thickness；

(5) Kapton is put into imidization furnace and carries out imidization processing, added by winder and cutting machine Finished product is made in work.

The diamines is m-phenylene diamine (MPD), 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines, diphenyldiamine, to benzene Two ether diamine of diphenol, one of two ether diamine of bisphenol-A or more than one.

The dianhydride be benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, hydroquinone di ether dianhydride, 5,5 '-(1,1, 3,3- tetramethyls-disiloxane) carbic anhydride, 1,1,3,3- tetramethyl disiloxane-bis- benzoic acid dianhydride, isophthalic two One of two ether dianhydride of phenol or more than one.

The organic solvent is metacresol, cresols, dimethylformamide, one of N-Methyl pyrrolidone or one kind More than.

The modified graphene the preparation method is as follows:

(1) graphene is dissolved in 25% ethanol water, adds butyramide, be mixed, obtain graphene dispersion Liquid；

(2) polyethylene glycol dimethacrylate is added in graphene dispersing solution, is warming up to 40-50 DEG C, mixing is stirred It mixes；

(3) it is cooled to room temperature, coupling agent and surfactant is added, stirs evenly, is made.

The coupling agent is silane resin acceptor kh-550, Silane coupling reagent KH-570, silane coupling agent KH-602, silane idol Join agent KH-901, one of silane coupling agent KH-902 or more than one.

The surfactant be neopelex, nonylplenyl ether, neopentyl glycol, sodium nitrilo triacetate, Triethanolamine, sodium metasilicate, one of polyphosphate or more than one.

The Kapton product that above-mentioned preparation method obtains.

Beneficial effects of the present invention: modified graphene is added in the preparation process of Kapton in the present invention, increases The degree of scatter of graphene in the material, significantly increases the heating conduction and mechanical property of material, to meet market It needs.

Specific embodiment

The present invention will be further described combined with specific embodiments below.