阅读说明：本技术 一种玄武岩鳞片纤维改性的聚酰亚胺薄膜及其制备方法 (A kind of Kapton and preparation method thereof of basalt scale fibre modification ) 是由 苏桂明 姜海健 方雪 陈明月 崔向红 张晓臣 马宇良 宫禹 刘晓东 李天智 宋美 于 2019-09-06 设计创作，主要内容包括：一种玄武岩鳞片纤维改性的聚酰亚胺薄膜及其制备方法,比未改性的同种薄膜具有更低吸水率、更高的强度和更好的耐热性。本发明为了解决玄武岩鳞片纤维的层间作用力使其在聚合物基体中极易产生团聚,不易分散的技术问题,使用端氨基硅烷偶联剂对玄武岩鳞片纤维进行表面改性,通过微波液相辅助法改变玄武岩鳞片纤维的表面粗糙度,可以使端氨基硅烷偶联剂浸润改性的效果得到提升,提高氨基官能团的接枝率,再通过原位聚合使改性后玄武岩鳞片纤维表面的氨基与单体二酐键合,将无机物纤维以化学键合的方式均匀稳定的分散于聚酰亚胺体系中,避免了鳞片纤维团聚,本方法适用于各种以二胺及二酐为单体的原位聚合反应。本发明属于改性聚酰亚胺薄膜领域。(A kind of Kapton and preparation method thereof of basalt scale fibre modification has more low water absorption, higher intensity and better heat resistance than unmodified identical films.The present invention makes it easily generate reunion in a polymer matrix to solve the interlaminar action power of basalt scale fiber, it is not easy the technical issues of dispersing, it is modified that surface is carried out to basalt scale fiber using Amino End Group silane coupling agent, change the surface roughness of basalt scale fiber by microwave liquid phase auxiliary law, the effect that the infiltration of Amino End Group silane coupling agent can be made modified gets a promotion, improve the grafting rate of amido functional group, it is bonded the amino of modified basalt scale fiber surface with monomer dianhydride by in-situ polymerization again, it is scattered in inorganic matter fiber is uniform and stable in a manner of being chemically bonded in polyimides system, avoid the reunion of scale fiber, this method is suitable for various using diamines and dianhydride as the home position polymerization reaction of monomer.The invention belongs to polyimide film fields.)

1. a kind of Kapton of basalt scale fibre modification, it is characterized in that: including matter in the Kapton Measure the basalt scale fiber modified through Amino End Group coupling agent surface that score is 1~5%.

2. a kind of Kapton of basalt scale fibre modification described in claim 1, it is characterised in that the film Preparation method is as follows

One, basalt scale fiber is added to absolute ethanol, ultrasonic disperse, cleaning, is obtained by pretreated basalt squama Piece fiber；

Two, Amino End Group silane coupling agent is added in ethyl alcohol, is configured to immersion fluid, be added and pass through pretreated basalt scale Fiber stirs at low speed 1h under ultrasound condition, dries at being rinsed 3 times, 80 DEG C after taking-up with soaked in absolute ethyl alcohol, obtains coupling agent Treated basalt scale fiber；

Three, at 0 DEG C~5 DEG C, first molfraction is added for the basalt scale fiber after 1 part of diamine monomer and coupling agent treatment Enter into solvent, solvent adding amount is 15% calculating according to product solid content mass fraction, is stirred to after being completely dissolved, and then will The dianhydride monomer that molfraction is 1.1 is added portionwise, and carries out home position polymerization reaction, after addition, sustained response 1-12h is obtained To polyamic acid solution；

Four, 200 mesh copper mesh of polyamic acid solution are filtered, carries out film on a glass using automatic film applicator, applies film thickness Degree be 0.5mm, in clean room drying at room temperature for 24 hours after, be put into air dry oven echelon heating carry out hot imidization, obtain the Black Warrior Rock scale fibre modification Kapton.

3. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Amino End Group siloxanes described in rapid two is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- β (ammonia second Base)-aminopropyl trimethoxysilane, N- β (aminoethyl)-aminopropyltriethoxy dimethoxysilane, N- β (aminoethyl)-aminopropyl Triethoxysilane or N- β (aminoethyl)-aminopropyltriethoxy diethoxy silane are other even containing Amino End Group functional silanes Join one of agent.

4. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Coupling agent mass fraction is 5%~10% in the ethyl alcohol immersion fluid prepared in rapid two, and surface modifying method is microwave in step 2 Liquid phase auxiliary law.

5. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Modified basalt scale fiber additional amount is put into monomer gross mass 1%~5% in rapid three.

6. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Diamines described in rapid three is diaminodiphenyl ether, p-phenylenediamine, benzidine or benzophenone tetracid dianhydride；

Dianhydride described in step 3 is benzophenone tetracid dianhydride, pyromellitic dianhydride or diphenyl ether tetracid dianhydride.

7. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Diamines described in rapid three is fluorinated diamine or alicyclic diamine monomer.

8. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Dianhydride described in rapid three is fluorine-containing dianhydride or alicyclic dianhydride monomer.

9. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Rapid three organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone and tetrahydrofuran One or more of a mixture of arbitrary proportions.

10. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Hot imidization technique in rapid four are as follows: 120 DEG C of constant temperature 1.5h, 180 DEG C of constant temperature 1h, 240 DEG C of constant temperature 1h, 280 DEG C of constant temperature 1h.

Technical field

The invention patent relates to a kind of Kaptons and preparation method thereof of basalt scale fibre modification.

Background technique

Basalt scale is a kind of novel scale material, transparent or bottle green laminated structure is presented, thickness is generally on 3 μm of left sides The right side, size is generally in 25 μm~3mm or so.Since ferriferous oxide, titanium dioxide, aluminium oxide, calcium oxide contain in basalt scale Amount is high and wherein basic anhydride content is less, therefore can not only generate screen effect, and in acid and alkali-resistance and corrosion resistance Aspect also has unique advantage.This characteristic makes it have extensive industrial application prospect in waterproof Waterproof corrosion erosion field, but Basalt scale fiber belongs to lamella fiber type, and interlaminar action power makes its easily generate reunion in a polymer matrix, is not easy point It dissipates.

Summary of the invention

The purpose of the present invention is to solve the interlaminar action power of basalt scale fiber to make fiber in a polymer matrix Easily generate and reunite, be not easy the technical issues of dispersing, provide a kind of basalt scale fibre modification Kapton and Preparation method, the method are suitable for the various home position polymerization reactions that PI is prepared using diamines as monomer.

A kind of Kapton of basalt scale fibre modification is comprising mass fraction in the Kapton 1~5% basalt scale fiber modified through Amino End Group coupling agent surface.

The preparation method of basalt scale fibre modification Kapton follows the steps below:

One, basalt scale fiber is added to absolute ethanol, ultrasonic disperse, cleaning are obtained by the pretreated Black Warrior Rock scale fiber；

Two, Amino End Group silane coupling agent is added in ethyl alcohol, is configured to immersion fluid, be added and pass through pretreated basalt Scale fiber stirs at low speed 1h under ultrasound condition, dries at being rinsed 3 times, 80 DEG C after taking-up with soaked in absolute ethyl alcohol, obtains idol Join agent treated basalt scale fiber；

Three, first that molfraction is fine for the basalt scale after 1 part of diamine monomer and coupling agent treatment at 0 DEG C~5 DEG C Dimension is added in solvent, and solvent adding amount is 15% calculating according to product solid content mass fraction, is stirred to after being completely dissolved, so The dianhydride monomer that molfraction is 1.1 is added portionwise afterwards, home position polymerization reaction is carried out and (notices that each inventory excessive not made It is sudden and violent poly- that generation can not be dissolved at local monomer), after addition, sustained response 1-12h obtains polyamic acid solution；

Four, 200 mesh copper mesh of polyamic acid solution are filtered, carries out film on a glass using automatic film applicator, applied Film thickness is 0.5mm, in clean room drying at room temperature for 24 hours after, be put into air dry oven echelon heating carry out hot imidization, obtain Basalt scale fibre modification Kapton.

Amino End Group siloxanes described in step 2 is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy silicon Alkane, N- β (aminoethyl)-aminopropyl trimethoxysilane, N- β (aminoethyl)-aminopropyltriethoxy dimethoxysilane, N- β (ammonia second Base)-aminopropyl triethoxysilane or N- β (aminoethyl)-aminopropyltriethoxy diethoxy silane or other contain Amino End Group official One of silane coupling agent can be rolled into a ball.

Coupling agent mass fraction is 5%~10% in the ethyl alcohol immersion fluid prepared in step 2, and surface is modified in step 2 Method is microwave liquid phase auxiliary law.

Modified basalt scale fiber additional amount is put into monomer gross mass 1%~5% in step 3.

Diamines described in step 3 is diaminodiphenyl ether, p-phenylenediamine, benzidine or benzophenone tetracid dianhydride；

Dianhydride described in step 3 is benzophenone tetracid dianhydride, pyromellitic dianhydride or diphenyl ether tetracid dianhydride.

Diamines described in step 3 is fluorinated diamine or alicyclic diamine monomer.

Dianhydride described in step 3 is fluorine-containing dianhydride or alicyclic dianhydride monomer.

Organic solvent described in step 3 is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone And one or more of tetrahydrofuran a mixture of arbitrary proportions.

The purpose of the invention is to prepare a kind of basalt scale fibre modification PI film, modified caudacoria has better The basalt scale of surface attachment amido functional group is added in heat resistance and lower water absorption rate, the present invention in polyimides system Fiber, amido functional group are chemically reacted with anhydride monomers, are dispersed in polyimides system in the form of chemical bond.It improves The dispersibility of basalt scale in a polymer matrix needs to be surface modified basalt scale, and it is compatible to improve interface Property, it is chemically bonded.Surface grafting has the basalt scale fiber of amino group can be with the acid anhydrides in polyimide monomers It is chemically reacted, is dispersed in polyimides system.It, can be bright since basalt scale is fibroplastic " labyrinth effect " The osmotic-pressure-tolerant and corrosion resistance of aobvious enhancing polymeric matrix, so as to improve the water resistance, impervious with enhancing Kapton Permeability, corrosion resistance and mechanical property.

The present invention changes the surface roughness of basalt scale fiber by microwave liquid phase auxiliary law, can make Amino End Group silicon The modified effect of alkane coupling agent infiltration gets a promotion, and improves the grafting rate of amido functional group, then the method for using in-situ polymerization, makes Basalt scale fiber is uniform and stable in a manner of being chemically bonded to be scattered in polyimides system, and scale coma is avoided It is poly- to be negatively affected caused by polymer performance.

Detailed description of the invention

Fig. 1 be in experiment one before modified after basalt fibre infrared spectrum analysis figure；

Fig. 2 is modified PI membrane forces section basalt fibre distribution stereoscan photograph in experiment two；

Fig. 3 is modified polyimide film TG test chart in experiment two.

Specific embodiment

The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment Any combination.