CN111500247A - Adhesive and application thereof in electrochromic field - Google Patents

Adhesive and application thereof in electrochromic field Download PDF

Info

Publication number
CN111500247A
CN111500247A CN201910088374.6A CN201910088374A CN111500247A CN 111500247 A CN111500247 A CN 111500247A CN 201910088374 A CN201910088374 A CN 201910088374A CN 111500247 A CN111500247 A CN 111500247A
Authority
CN
China
Prior art keywords
composite adhesive
group
cyanate ester
siloxane resin
polyimide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910088374.6A
Other languages
Chinese (zh)
Other versions
CN111500247B (en
Inventor
曹贞虎
胡珊珊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Ninuo Electronic Technology Co ltd
Original Assignee
Ningbo Ninuo Electronic Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Ninuo Electronic Technology Co ltd filed Critical Ningbo Ninuo Electronic Technology Co ltd
Priority to CN201910088374.6A priority Critical patent/CN111500247B/en
Publication of CN111500247A publication Critical patent/CN111500247A/en
Application granted granted Critical
Publication of CN111500247B publication Critical patent/CN111500247B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/161—Gaskets; Spacers; Sealing of cells; Filling or closing of cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a composite adhesive, which comprises a polyimide-siloxane resin containing a cyanate ester group and a cyanate ester resin. Wherein the content of the cyanate ester group-containing polyimide-siloxane resin is 5-15 wt%, and the content of polysiloxane in the cyanate ester group-containing polyimide-siloxane resin is 10-40 wt%. The composite adhesive provided by the invention forms a rigid highly-crosslinked structure after being cured, and the polysiloxane chain segment in the composite adhesive can play a role in improving the toughness and hydrophobicity of the composite adhesive and shows excellent humidity and heat resistance stability. The composite adhesive provided by the invention can be used for packaging a solution type electrochromic device.

Description

Adhesive and application thereof in electrochromic field
Technical Field
The invention relates to an adhesive, in particular to an adhesive for packaging a solution type electrochromic device.
Background
Electrochromism is an electrically driven color changing technology, and is a process that the color of a material is changed by getting and losing electrons under the action of an external voltage. The material has great application value in electrochromic windows, automobile rearview mirrors, electrochromic glasses, high-resolution photoelectric camera equipment, photoelectric chemical energy conversion/storage devices, military camouflage, decorative materials and the like.
The basic structure of the electrochromic device is similar to a sandwich, and the electrochromic material is arranged between two substrates plated with conductive materials. Electrochromic devices can be classified into solution type electrochromic devices, semi-solution type electrochromic devices and all-solid state electrochromic devices according to the physical state of electrochromic materials. In the solution type electrochromic device, the electrochromic material is always dissolved in the electrolyte. In a semi-solution type electrochromic device, when the device is in a transparent state, an electrochromic material is dissolved in an electrolyte; when the device is in a coloring state, the electrochromic material can be enriched on the surface of the electrode and cover the surface of the electrode to form a layer of thin film. In all-solid-state electrochromic devices, the electrochromic material is always in the solid state.
The solution type electrochromic device has the characteristics of low cost, simple structure, simple and convenient preparation process, short response time and the like, so the solution type electrochromic device is always a hotspot of the research of the electrochromic device and is widely applied. The cross-sectional view of the basic solution-type electrochromic device is shown in fig. 1: 1 and 2 are substrates; 3 and 4 are transparent conductive materials plated on a substrate; 5 is an adhesive; and 6 is a cavity filled with electrochromic solution. In order to meet the requirements of specific functions and performances, the surface of the substrate can be plated with functional materials such as reflecting materials, anti-reflecting materials, hydrophilic materials, ultraviolet light blocking materials and the like (such as US4902108, US5202787, US5790298, US5940201 and the like).
The adhesive is used as one of the components of the solution type electrochromic device, and has the functions of separating conducting layers on the front substrate and the rear substrate, preventing the electrochromic solution from leaking, blocking the influence of oxygen, water vapor and other harmful steam on the electrochromic solution and the like. Therefore, the quality of the sealing effect of the adhesive plays a key role in the service life, safety, performance and the like of the electrochromic device. As indicated in patent US5336448, the aging resistance of the electrochromic device at high temperature at zero potential is an important stability evaluation parameter, and the test temperature is preferably 120 ℃. A more extreme method for detecting the sealing effect of the adhesive is to test the electrochromic device for 168 hours under saturated high-pressure steam at the temperature of 121 ℃ and at the pressure of 14-16 psi, and detect whether the electrochromic device and the function of the electrochromic device are intact after the test.
For example, US6714334 discloses an adhesive for sealing an electrochromic device composed of an epoxy resin (including bisphenol a epoxy resin, bisphenol F epoxy resin, and novolac epoxy resin) and a curing agent (including bis (aminocyclohexyl) methane, alicyclic amine, and bis (alicyclic) amine) in order to increase the reflection area of the electrochromic device, US5790298 uses a sealant having a light transmittance of more than 50% between two glass plates constituting the electrochromic device, selected from resins having acrylate, epoxy, and polyisobutadiene structures, and a filler such as fumed silica or cured particles of the above-mentioned resins may be added to the sealant.
However, epoxy resin has poor stability against humidity and heat, and is easily corroded by electrochromic materials at high temperature, so that the adhesive performance is ineffective, and electrolyte leakage is caused, and thus the requirement of long-term use in harsh environments is difficult to meet.
Disclosure of Invention
The invention aims to provide an adhesive which has the advantages of good heat resistance, high bonding strength, good hydrophobic effect and good organic solvent resistance after crosslinking and curing, and can meet the application requirements of a solution type electrochromic device.
The adhesive provided by the invention is a composite adhesive, which comprises a cyanate ester group-containing polyimide-siloxane resin and a cyanate ester resin.
In the composite adhesive, the content of cyanate ester resin is 85-95 wt%, the content of cyanate ester group-containing polyimide-siloxane resin is 5-15 wt%, and the content of polysiloxane in the cyanate ester group-containing polyimide-siloxane resin is 10-40 wt%.
The cyanate resin contains two or more cyanate functional groups, and the cyanate functional groups are subjected to a tricyclohexyl reaction under the action of heat or a catalyst to generate a triazine ring-containing macromolecule with high crosslinking density, and the triazine ring-containing macromolecule has the properties of low water absorption, high temperature resistance and high strength. Moreover, the polar group on the cyanate resin can form a chemical bond with a polar group such as a hydroxyl group on the surface of metal or glass, etc., and even form a complex with a metal ion, so that it has excellent adhesion. However, the high crosslinking density and the large amount of aromatic structures of cyanate ester resins also cause poor toughness, and limit the use of cyanate ester resins. The polysiloxane chain segment has good flexibility, and can improve the impact resistance and brittleness of the cyanate ester resin. Although the polysiloxane can also be chemically reacted to attach a cyanate group, the formed new chemical bond is insufficient in heat resistance and solvent resistance and is liable to become a degradation point.
The polyimide has good heat resistance, aging resistance, mechanical property and electrical insulation property, and the coefficient of thermal expansion is small, so that the polyimide is earlier used for structural engineering materials, and the polyimide can be used for high-temperature adhesives due to abundant polar groups on the structure. The polyimide and the polysiloxane can be connected through an imide ring with good stability to form the polyimide-siloxane resin. The cyanate ester group-containing polyimide-siloxane resin is compounded with the cyanate ester resin, the compatibility of the polyimide-siloxane resin and the cyanate ester resin can be improved due to the existence of the polyimide chain segment, the cyanate ester group introduced into the polyimide chain segment participates in the crosslinking reaction of the cyanate ester resin, and the polyimide-siloxane resin is organically combined with the cyanate ester resin, so that the influence of the introduction of the polyimide-siloxane resin on the heat resistance of the cyanate ester resin can be avoided. The polysiloxane has good flexibility and diffusivity, and can improve the impact resistance and reduce the brittleness of the polyimide-siloxane resin and cyanate ester resin composite adhesive containing cyanate ester groups. In addition, the polysiloxane chain segment has low surface energy and is easy to concentrate on the surface, and a large amount of hydrophobic groups in the structure are combined, so that the water absorption of the cyanate ester resin is further reduced, and the weather resistance is improved.
The cyanate ester group-containing polyimide-siloxane resin is formed by the following structural units (1), (2), (3) and (4) together:
Figure 176301DEST_PATH_IMAGE001
wherein, the group Ar is selected from one or more of the following groups:
Figure 162974DEST_PATH_IMAGE002
,
Figure 550093DEST_PATH_IMAGE003
,
Figure 44528DEST_PATH_IMAGE004
，
Figure 935123DEST_PATH_IMAGE005
，，
Figure 13118DEST_PATH_IMAGE007
，
Figure 186610DEST_PATH_IMAGE008
，
Figure 275920DEST_PATH_IMAGE009
，
Figure 243876DEST_PATH_IMAGE010
，
Figure 340008DEST_PATH_IMAGE011
，
Figure 677711DEST_PATH_IMAGE012
，
Figure 542899DEST_PATH_IMAGE013
。
said group Ar1One or more selected from the following groups:
Figure 681756DEST_PATH_IMAGE014
，
Figure 389818DEST_PATH_IMAGE015
，
Figure 639534DEST_PATH_IMAGE016
，
Figure 624807DEST_PATH_IMAGE017
，，，，，，
Figure 969780DEST_PATH_IMAGE023
，
Figure 905506DEST_PATH_IMAGE024
，
Figure 599793DEST_PATH_IMAGE025
，
Figure 251354DEST_PATH_IMAGE026
,
Figure 421304DEST_PATH_IMAGE027
,
Figure 816513DEST_PATH_IMAGE028
,
Figure 365306DEST_PATH_IMAGE029
,
Figure 125452DEST_PATH_IMAGE030
,
Figure 392485DEST_PATH_IMAGE031
,
Figure 591385DEST_PATH_IMAGE032
,
Figure 909251DEST_PATH_IMAGE033
,
Figure 168194DEST_PATH_IMAGE034
,
Figure 922523DEST_PATH_IMAGE035
。
said group Ar2One or two selected from the following groups:
Figure 331639DEST_PATH_IMAGE036
，
Figure 855024DEST_PATH_IMAGE037
。
in the structural unit (3), a group R is selected from methyl, phenyl or trifluoropropyl; n is an integer of 10 to 50.
Preferably, the group Ar is selected from
Figure 284869DEST_PATH_IMAGE006
And the group Ar1Is selected from
Figure 339543DEST_PATH_IMAGE018
，
Figure 880246DEST_PATH_IMAGE019
，
Figure 523717DEST_PATH_IMAGE020
，
Figure 484982DEST_PATH_IMAGE021
，
Figure 213904DEST_PATH_IMAGE022
One kind of (1). The ketone carbonyl group on the benzophenone structure in the combination can be crosslinked with the methyl group on the benzene ring under the irradiation of ultraviolet light, the mechanism is shown in the following formula (5), the ketone carbonyl group is excited by UV to deprive active hydrogen on the methyl group, 2 free radicals are generated simultaneously, and the 2 free radicals are combined to form a crosslinking structure. The introduction of the photosensitive group enables the polyimide-siloxane resin containing cyanate ester groups and the cyanate ester resin composite adhesive to be appropriately crosslinked in a short time after being irradiated by ultraviolet light when being applied to a part to be bonded, thereby avoiding the adhesive from flowing and deforming during subsequent heating crosslinking curing and shortening the curing time.
Figure 292718DEST_PATH_IMAGE038
（5）
As a advancePreferably, the group Ar1Is selected from
Figure 462799DEST_PATH_IMAGE022
The thioether bond can improve the hydrogen donating ability, thereby improving the photosensitivity.
Cyanate resin is mostly solid or semi-solid substance at normal temperature, the melting point and the melt viscosity are low, and the cyanate resin is usually generated by reacting dihydric phenol or polyhydric phenol with cyanide halide in the presence of tertiary amine, so different dihydric phenol or polyhydric phenol can be adopted to synthesize cyanate with different structures, such as tetramethyl bisphenol F type cyanate, bisphenol A type cyanate, bisphenol E type cyanate, dicyclopentadiene type cyanate and resorcinol cyanate. Preferably, the cyanate ester structure is
Figure 968867DEST_PATH_IMAGE039
The methyl in the structure can generate light cross-linking reaction with the ketone carbonyl on the benzophenone structure.
The invention also provides a preparation method of the cyanate ester group-containing polyimide-siloxane resin, which comprises the following steps:
(1) dissolving aromatic dianhydride in a mixed solvent of a polar solvent and a non-polar solvent, adding amino-terminated polysiloxane, stirring at room temperature for 1-10 hours, and then decompressing and extracting the non-polar solvent, so that the amino-terminated polysiloxane and the aromatic dianhydride are combined;
(2) adding aromatic diamine and hydroxyl-containing aromatic diamine into the solution obtained in the step (1), and stirring at room temperature for 1-10 hours, so that the aromatic diamine, the hydroxyl-containing aromatic diamine, the amino-terminated polysiloxane and the aromatic dianhydride are subjected to polycondensation; then adding aniline, and stirring at room temperature for 1-10 hours, thereby capping the obtained polymer with aniline; then adding a water-carrying agent, and reacting at 140-200 ℃ for 5-20 hours to complete the imidization process;
(3) under the ice water bath, cyanogen chloride or cyanogen bromide and equivalent or excessive triethylamine are added into the solution obtained in the step (2), and the reaction is carried out for 0.5-2 hours at room temperature;
(4) and (4) adding the solution obtained in the step (3) into acetone, separating out a precipitate, washing the precipitate for a plurality of times by using acetone, and drying to obtain the cyanate ester group-containing polyimide-siloxane resin.
The aromatic dianhydride is selected from, but not limited to, 1,2,4, 5-benzenetetracarboxylic dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic anhydride, 2,3,3 ', 4' -biphenyltetracarboxylic anhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic anhydride, 2 ', 3, 3' -diphenylethertetracarboxylic anhydride, 2,3,3 ', 4' -diphenylethertetracarboxylic anhydride, 3,3 ', 4, 4' -diphenylethertetracarboxylic anhydride, 2 ', 3, 3' -diphenylsulfide tetracarboxylic anhydride, 2,3,3 ', 4' -diphenylsulfide tetracarboxylic anhydride, 3,3 ', 4, 4' -diphenylsulfide tetracarboxylic anhydride, 2 ', 3, 3' -benzophenonetetracarboxylic anhydride, 2,3,3 ', 4' -benzophenonetetracarboxylic anhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic anhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl ether dianhydride.
The amino-terminated polysiloxane is one or more selected from amino-terminated phenyl polydimethylsiloxane, amino-terminated phenyl polymethylphenylsiloxane or amino-terminated phenyl polymethyltrifluoropropylsiloxane, and a structural unit-Si (CH) in the structure3)2-O-、-Si(CH3)(C6H5) -O-or-Si (CH)3)(CH2CH2CF3) The amount of-O-is 10 to 50.
The aromatic diamine is selected from, but not limited to, 1, 3-phenylenediamine, 4 '-diaminodiphenylmethane, 3' -diaminodiphenyl ether, 4 '-diaminodiphenyl ether, 3' -dimethyl-4, 4 '-diaminodiphenyl ether, 3', 5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane, 3 '-dimethyl-4, 4' -diaminodiphenyl sulfide, 3 ', 5, 5' -tetramethyl-4, 4 '-diaminodiphenyl sulfide, 3' -diethylthio-4, 4 '-diaminodiphenyl sulfide, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl ketone, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, and mixtures thereof, 4,4 ' -diaminobenzophenone, 2 ' -bis (trifluoromethyl) diaminobiphenyl, 2 ' -bis (trifluoromethyl) -4,4 ' -diaminodiphenyl ether, 2 ' -bis (trifluoromethyl) -4,4 ' -diaminodiphenyl sulfide, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-aminophenyl) hexafluoropropane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4 ' -bis (3-aminophenoxy) diphenylsulfone, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane.
The aromatic diamine containing hydroxyl is selected from one of bis (4-aminophenyl) -4-hydroxyphenyl methane or 3, 5-bis (4-aminophenoxy) phenol.
The ratio of the sum of the molar amounts of the aromatic diamine, the hydroxyl-containing aromatic diamine and the amino-terminated polysiloxane to the molar amount of the aromatic dianhydride is 9/10-9.8/10; the molar ratio of aniline to aromatic dianhydride is 0.4/10 to 2/10.
In the preparation process, the added mass of the amino-terminated polysiloxane accounts for 10-40 wt% of the total mass of the aromatic dianhydride, the aromatic diamine, the hydroxyl-containing aromatic diamine and the amino-terminated polysiloxane.
The molar ratio of the aromatic diamine to the hydroxyl-containing aromatic diamine is 1/5-5/1.
The aromatic dianhydride, the aromatic diamine and the hydroxyl-containing aromatic diamine are easily dissolved in a polar solvent; the amino-terminated polysiloxane is readily soluble in a nonpolar solvent, and its solubility in a polar solvent decreases with an increase in molecular weight, so that it is necessary to add a nonpolar solvent. Furthermore, as the molecular weight of the amino-terminated polysiloxane increases, the proportion of the nonpolar solvent needs to be increased.
The polar solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
The nonpolar solvent is selected from one or more of 2-methyltetrahydrofuran, cyclopentyl methyl ether or tetrahydrofuran.
The volume ratio of the nonpolar solvent to the polar solvent is 1/3-3/1.
The water-carrying agent is selected from one of toluene, xylene or ortho-dichlorobenzene.
The invention also provides a curing process of the composite adhesive formed by the cyanate ester group-containing polyimide-siloxane resin and the cyanate ester resin, and the curing process is carried out by gradually heating up and crosslinking at the melting temperature of-350 ℃.
Preferably, the curing process is as follows: gradually heating up, crosslinking and curing at the melting temperature of 300 ℃ under the catalysis of a catalyst, wherein the catalyst is one of transition metal salt/phenols or organic tin. The catalyst is added when the polyimide-siloxane resin containing the cyanate ester group is compounded with the cyanate ester resin.
When the cyanate group-containing polyimide-siloxane resin contains
Figure 185085DEST_PATH_IMAGE006
Structure, and contain
Figure 146219DEST_PATH_IMAGE018
，
Figure 498703DEST_PATH_IMAGE019
，
Figure 441251DEST_PATH_IMAGE020
，
Figure 551289DEST_PATH_IMAGE021
，
Figure 971906DEST_PATH_IMAGE022
In one of the structures, the preferred curing process is: firstly, irradiating the composite adhesive containing transition metal salt/phenols or organic tin catalysts at the melting temperature under ultraviolet light; and after moderate crosslinking, heating to 200-300 ℃ for crosslinking and curing. After sizing, properly crosslinking the polyimide-siloxane resin containing the cyanide group at a lower temperature, so that the viscosity of the composite adhesive is improved, and the composite adhesive is prevented from flowing and deforming in the heating and curing process; and after the viscosity is improved through photocatalytic crosslinking, the temperature can be directly raised to a higher temperature for thermal curing, so that the curing time is shortened, and the efficiency is improved.
The invention also provides application of the composite adhesive formed by the cyanate ester group-containing polyimide-siloxane resin and the cyanate ester resin, and particularly relates to application of the composite adhesive in bonding of front and rear substrates of a solution type electrochromic device.
When the composite adhesive is applied to bonding the front and rear substrates of an electrochromic device, preferably, spherical insoluble particles such as glass, plastics or clay with the volume fraction of 1/10000-1/1000 are added into the composite adhesive, and the diameter of the spherical insoluble particles is consistent with the interval between the front and rear substrates of the electrochromic device, so that the front and rear substrates of the electrochromic device are kept parallel and the interval between the front and rear substrates is kept consistent.
Compared with the prior art, the invention has the beneficial effects that:
the adhesive provided by the invention is a compound of the cyanate ester group-containing polyimide-siloxane resin and the cyanate ester resin, and the cyanate ester resin forms a rigid highly-crosslinked structure after being cured, so that the adhesive has excellent humidity and heat resistance stability. The addition of the cyanate ester group-containing polyimide-siloxane resin, wherein the polyimide chain segment can participate in the crosslinking and curing of the cyanate ester resin through the cyanate ester group introduced into the structure of the polyimide chain segment, the polysiloxane chain segment plays a role in improving the toughness of the cyanate ester resin, and the polysiloxane chain segment can also improve the hydrophobicity of the cyanate ester resin. The structures of the polyimide-siloxane resin containing the cyanate ester group and the cyanate ester resin are rich in polar groups, so that the bonding strength of the polyimide-siloxane resin containing the cyanate ester group and the cyanate ester resin to substrates such as metal or glass is guaranteed. In addition, the invention also provides the photocurable cyanate ester group-containing polyimide-siloxane resin, so that after sizing, moderate crosslinking can be performed at a lower temperature, flowing of a composite adhesive in a heating curing process is avoided, and the curing time can be shortened.
Drawings
Fig. 1 is a cross-sectional view of an electrochromic device according to application examples 4,5 and 6 of the present invention; wherein 1 and 2 represent glass substrates; 3 and 4 are represented by aluminum-doped zinc oxide conductive layers; 5 is represented as an adhesive; and 6 is denoted as filled electrochromic solution.
Detailed Description
The present invention is described in further detail with reference to specific examples, which should be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
Performance detection
Flexural strength was tested according to GB/T2570-;
water absorption test: boiling in water for 1 hour under normal pressure, wiping off surface moisture, and testing the mass difference before and after the test by using an analytical balance;
glass transition temperature: the test instrument is a Mettler Toledo DMA dynamic thermal mechanical analyzer of the Switzerland Mettler Toledo company;
and (3) viscosity testing: the testing instrument is Austria Physica MCR 301 rheometer;
and (3) testing the solubility: placing in a 100 ℃ solvent for 24 hours;
and (3) testing the bonding strength: according to the GB/T7124 and 2008 standard, a gasket is used for ensuring that acting force is in an adhesive surface, and before testing, damp and heat treatment is carried out for 24 hours in an environment with the temperature of 70 ℃ and the relative humidity of 95%.
Example 1:
preparation of a cyanate ester group-containing polyimide-siloxane resin:
(1) dissolving 3,3 ', 4, 4' -diphenyl sulfide tetracarboxylic anhydride (20 mmol) in a mixed solvent of N, N-dimethylacetamide and tetrahydrofuran (volume 150m L, volume ratio 1/1), adding aminophenylpolydimethylsiloxane (2 mmol) with the molecular weight of 1995g/mol, stirring at room temperature for 3 hours, and then extracting the tetrahydrofuran under reduced pressure;
(2) adding 4, 4' -diaminodiphenyl ether (8.5 mmol) and 3, 5-bis (4-aminophenoxy) phenol (8.5 mmol) into the solution obtained in the step (1), stirring at room temperature for 5 hours, then adding aniline (2 mmol), stirring at room temperature for 5 hours, then adding water-carrying agent xylene (30 m L), and reacting at 180 ℃ for 10 hours;
(3) under the ice water bath, cyanogen chloride (8.5 mmol) and triethylamine (10 mmol) are added into the solution obtained in the step (2), and the reaction is carried out for 1 hour at room temperature;
(4) and (4) adding the solution obtained in the step (3) into acetone, separating out a precipitate, washing the precipitate for a plurality of times by using acetone, and drying to obtain the cyanide group-containing polyimide-siloxane resin.
Heating and stirring the polyimide-siloxane resin containing the cyanate ester group (5.0 g) and the bisphenol A cyanate ester (50 g) at 100 ℃, dissolving, stopping stirring, degassing under a vacuum condition for half an hour, and then curing by processes of 1 hour at each of 130 ℃, 150 ℃, 180 ℃, 200 ℃, 250 ℃ and 300 ℃. And (3) measuring: the bending strength is 126.7 MPa; impact strength 11.2KJ/m2(ii) a Water absorption of 1.4 wt%; the glass transition temperature is 265 ℃; the tensile shear strength measured at normal temperature by taking an aluminum plate as a substrate is 23MPa, and the damage occurs to the adhesive body; the compound is insoluble and non-swellable in solvents such as N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, butyrolactone, propylene carbonate, dimethyl sulfoxide, o-dichlorobenzene and xylene.
Comparative example 1
And curing the bisphenol A cyanate ester at the temperature of 130 ℃, 150 ℃, 180 ℃, 200 ℃, 250 ℃ and 300 ℃ for 1 hour respectively. And (3) measuring: the bending strength is 98.2 MPa; impact strength of 6.3KJ/m2(ii) a The water absorption rate is 2.5 wt%; a glass transition temperature of 268 ℃; the tensile shear strength measured at normal temperature by taking an aluminum plate as a substrate is 14MPa, and the damage occurs at the interface between the adhesive and the aluminum plate; the compound is insoluble and non-swellable in solvents such as N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, butyrolactone, propylene carbonate, dimethyl sulfoxide, o-dichlorobenzene and xylene.
Example 2
Preparation of a cyanate ester group-containing polyimide-siloxane resin:
(1) dissolving 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride (20 mmol) in a mixed solvent (150 m L, volume ratio 2/1) of N, N-dimethylformamide and tetrahydrofuran, adding aminophenyl polymethyltrifluoropropylsiloxane (3 mmol) having a molecular weight of 2100g/mol, stirring at room temperature for 5 hours, and then removing tetrahydrofuran under reduced pressure;
(2) adding 4, 4' -diaminodiphenyl ether (4 mmol) and 3, 5-bis (4-aminophenoxy) phenol (12 mmol) into the solution obtained in the step (1), stirring at room temperature for 5 hours, then adding aniline (2 mmol), stirring at room temperature for 5 hours, then adding water-carrying agent o-dichlorobenzene (40 m L), and reacting at 200 ℃ for 5 hours;
(3) under the ice water bath, cyanogen chloride (12 mmol) and triethylamine (15 mmol) are added into the solution obtained in the step (2), and the reaction is carried out for 1 hour at room temperature;
(4) and (4) adding the solution obtained in the step (3) into acetone, separating out a precipitate, washing the precipitate for a plurality of times by using acetone, and drying to obtain the cyanide group-containing polyimide-siloxane resin.
The preparation method comprises the steps of dissolving the polyimide-siloxane resin containing the cyanate ester groups (5.0 g) and phenolic cyanate ester (35.0 g) with the viscosity of 150mPa ∙ S in N, N-dimethylformamide, then gradually heating up to remove a solvent and defoaming between 50-100 ℃ under a vacuum condition, and then curing by processes of respectively 1 hour at 120 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃ and 320 ℃. And (3) measuring: the bending strength is 134.1 MPa; impact strength 13.6 KJ/m2(ii) a Water absorption of 0.8 wt%; the glass transition temperature is 358 ℃; the tensile shear strength measured at normal temperature by taking a glass plate as a substrate is 18MPa, and the damage occurs to an adhesive body; the compound is insoluble and non-swellable in solvents such as N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, butyrolactone, propylene carbonate, dimethyl sulfoxide, o-dichlorobenzene and xylene.
Comparative example 2
And curing the phenolic cyanate with the viscosity of 150mPa ∙ S according to the processes of 120 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃ and 320 ℃ for 1 hour respectively. And (3) measuring: the bending strength is 82.7 MPa; impact strength 7.3KJ/m2(ii) a The water absorption rate is 2.3 wt%; the glass transition temperature is 356 ℃ below zero; the tensile shear strength measured at normal temperature by taking a glass plate as a substrate is 9MPa, and the damage occurs at the interface between the adhesive and the glass plate; the compound is insoluble and non-swellable in solvents such as N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, butyrolactone, propylene carbonate, dimethyl sulfoxide, o-dichlorobenzene and xylene.
Example 3
Preparation of a cyanate ester group-containing polyimide-siloxane resin:
(1) dissolving 3,3 ', 4, 4' -benzophenone tetracarboxylic anhydride (20 mmol) in a mixed solvent (150 m L, volume ratio 2/1) of N-methylpyrrolidone and tetrahydrofuran, adding amino-terminated phenyl polymethyltrifluoropropylsiloxane (3 mmol) with molecular weight of 2100g/mol, stirring at room temperature for 5 hours, and then extracting the tetrahydrofuran under reduced pressure;
(2) adding 3,3 ', 5,5 ' -tetramethyl-4, 4 ' -diaminodiphenyl sulfide (8 mmol) and 3, 5-bis (4-aminophenoxy) phenol (8 mmol) into the solution obtained in the step (1), stirring at room temperature for 5 hours, then adding aniline (2 mmol), stirring at room temperature for 5 hours, then adding water-carrying agent xylene (30 m L), and reacting at 180 ℃ for 10 hours;
(3) under the ice water bath, cyanogen chloride (8 mmol) and triethylamine (10 mmol) are added into the solution obtained in the step (2), and the reaction is carried out for 1 hour at room temperature;
(4) and (4) adding the solution obtained in the step (3) into acetone, separating out a precipitate, washing the precipitate for a plurality of times by using acetone, and drying to obtain the cyanide group-containing polyimide-siloxane resin.
The preparation method comprises the following steps of uniformly mixing the polyimide-siloxane resin (5.0 g) containing the cyanate ester group, the bisphenol E type cyanate ester resin (45 g) and 1% of dibutyltin dilaurate in N, N-dimethylformamide, and then removing a solvent and bubbles under a vacuum condition at 50 ℃ to obtain the composite adhesive. The composite adhesive is irradiated for 10min at 50 ℃ under ultraviolet light with the wavelength of 405 nm and the power of 600W, and then cured at 200 ℃ and 250 ℃ for 1 hour respectively.
And (3) measuring: before ultraviolet irradiation, the viscosity at 50 ℃ is 87mPa & s; after being irradiated by ultraviolet light for 10min, the viscosity is 1045 mPa.s at 50 ℃; after the curing is completed, the bending strength is 121.1 MPa; impact strength 11.3 KJ/m2(ii) a Water absorption rate is 1.2 wt%; the glass transition temperature is-258 ℃; the tensile shear strength measured at normal temperature by taking a glass plate as a substrate is 21MPa, and the damage occurs to an adhesive body; the compound is insoluble and non-swellable in solvents such as N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, butyrolactone, propylene carbonate, dimethyl sulfoxide, o-dichlorobenzene and xylene.
Example 4
To form ZnO + Al2O3The sintered ceramics is used as a target material (the target material is doped with Al)2O3Ceramic target formed by sintering ZnO powder of powder at high temperature, wherein Al in the ZnO powder2O32%) on the first and second glass substrates by means of radio frequency magnetron sputtering (working pressure 1Pa, power 140W, time 40 min during sputtering) to deposit a conductive layer of aluminum-doped zinc oxide with a thickness of 150 nm on the first and second glass substrates.
To the composite adhesive formed by the cyanate ester group-containing polyimide-siloxane resin obtained in example 1 and the bisphenol a type cyanate ester resin, 0.05% by volume of spherical glass particles with a diameter of 0.1mm were added and applied to the edge of the first glass substrate. Then, the first glass substrate and the second glass substrate are placed in parallel (one side containing the transparent conducting layer is arranged in an opposite mode) and are pressed tightly, only one electrochromic solution injection port is reserved around the sealing to form a cavity, and then the curing is carried out according to the processes of 1 hour each of 130 ℃, 150 ℃, 180 ℃, 200 ℃, 250 ℃ and 300 ℃.
Dissolving 1,1 '-dihexyl-4, 4' -bipyridyl bis (trifluoromethanesulfonate) and 5, 10-dihydro-5, 10-dimethylphenazine in butyrolactone (the concentrations are both 50 mmol/L), pouring the mixture into a cavity of the electrochromic device, and sealing the cavity with glue to obtain the device with the electrochromic function, wherein the transmittance of light with the wavelength of 500nm is 89% when the device is measured under the condition of no external voltage, the transmittance of light with the wavelength of 500nm is 5.6% when the device is electrified, and the discoloration response time is 0.9 s.
The solution type electrochromic device is placed under saturated high-pressure steam at the temperature of 121 ℃ and at the pressure of 14-18 psi, after 168 hours, the device is still intact, the electrochromic solution is not leaked, and the color change depth and the color change speed of the electrochromic solution are not changed.
Example 5
Adding 0.1% by volume of spherical glass particles with the diameter of 0.1mm into the composite adhesive obtained in the embodiment 2, applying the spherical glass particles to the edge of the first glass substrate obtained in the embodiment 4, then placing the first glass substrate and the second glass substrate in parallel (with the side containing the transparent conductive layer facing each other) and pressing, only leaving an electrochromic solution injection port around the seal to form a cavity, and then curing according to the processes of 1 hour each at 120 degrees, 150 degrees, 200 degrees, 250 degrees, 300 degrees and 320 degrees.
Reference example 4 an electrochromic solution of 1,1 '-dihexyl-4, 4' -bipyridine bis (trifluoromethanesulfonate) and 5, 10-dihydro-5, 10-dimethylphenazine (both at a concentration of 50 mmol/L) in propylene carbonate was injected and sealed, and the electrochromic solution had a light transmittance of 86% at a wavelength of 500nm as measured in the absence of an applied voltage, a light transmittance of 5.3% at a wavelength of 500nm as measured after energization, and a discoloration response time of 0.8 sec.
The solution type electrochromic device is placed under saturated high-pressure steam at the temperature of 121 ℃ and at the pressure of 14-18 psi, after 168 hours, the device is still intact, the electrochromic solution is not leaked, and the color change depth and the color change speed of the electrochromic solution are not changed.
Example 6
Adding 0.1% by volume of spherical glass particles with the diameter of 0.1mm into the composite adhesive obtained in the embodiment 3, applying the spherical glass particles to the edge of the first glass substrate obtained in the embodiment 4, then placing the first glass substrate and the second glass substrate in parallel (with one side containing the transparent conductive layer facing each other) and pressing, only leaving an electrochromic solution injection port around the seal to form a cavity, then irradiating for 10min at 50 ℃ under ultraviolet light with the wavelength of 405 nm and the power of 600W, and curing at 200 ℃ and 250 ℃ for 1 hour respectively.
Reference example 4 an electrochromic solution of 1,1 '-dihexyl-4, 4' -bipyridine bis (trifluoromethanesulfonate) and 5, 10-dihydro-5, 10-dimethylphenazine (both at a concentration of 50 mmol/L) in propylene carbonate was injected and sealed, and the electrochromic solution had a light transmittance of 86% at a wavelength of 500nm as measured in the absence of an applied voltage, a light transmittance of 5.4% at a wavelength of 500nm as measured after energization, and a discoloration response time of 0.8 sec.
The solution type electrochromic device is placed under saturated high-pressure steam at the temperature of 121 ℃ and at the pressure of 14-18 psi, after 168 hours, the device is still intact, the electrochromic solution is not leaked, and the color change depth and the color change speed of the electrochromic solution are not changed.

Claims (10)

1. The composite adhesive is characterized by comprising the following components: cyanate ester group-containing polyimide-siloxane resins and cyanate ester resins.
2. The composite adhesive according to claim 1, wherein the content of the cyanate ester group-containing polyimide-siloxane resin is 5 to 15 wt%, and the content of the polysiloxane in the cyanate ester group-containing polyimide-siloxane resin is 10 to 40 wt%.
3. The composite adhesive according to claim 1 or 2, wherein the cyanate ester group-containing polyimide-siloxane resin is composed of the structural units (1), (2), (3) and (4):
Figure 661864DEST_PATH_IMAGE001
wherein, the group Ar is selected from one or more of the following groups:
Figure DEST_PATH_IMAGE002
,
Figure 28123DEST_PATH_IMAGE003
,
Figure DEST_PATH_IMAGE004
，
Figure 929345DEST_PATH_IMAGE005
，
Figure DEST_PATH_IMAGE006
，
Figure 572816DEST_PATH_IMAGE007
，
Figure DEST_PATH_IMAGE008
，
Figure 32616DEST_PATH_IMAGE009
，
Figure DEST_PATH_IMAGE010
，
Figure 387636DEST_PATH_IMAGE011
，
Figure DEST_PATH_IMAGE012
，
Figure 591085DEST_PATH_IMAGE013
；
said group Ar1One or more selected from the following groups:
Figure DEST_PATH_IMAGE014
，
Figure 551098DEST_PATH_IMAGE015
，
Figure DEST_PATH_IMAGE016
，
Figure 322745DEST_PATH_IMAGE017
，
Figure DEST_PATH_IMAGE018
，
Figure 398017DEST_PATH_IMAGE019
，
Figure DEST_PATH_IMAGE020
，
Figure 641042DEST_PATH_IMAGE021
，
Figure DEST_PATH_IMAGE022
，
Figure 383739DEST_PATH_IMAGE023
，
Figure DEST_PATH_IMAGE024
，
Figure 952386DEST_PATH_IMAGE025
，
Figure DEST_PATH_IMAGE026
,
Figure 390321DEST_PATH_IMAGE027
,
Figure DEST_PATH_IMAGE028
,
Figure 935571DEST_PATH_IMAGE029
,
Figure DEST_PATH_IMAGE030
,
Figure 34240DEST_PATH_IMAGE031
,
Figure DEST_PATH_IMAGE032
,
Figure 147689DEST_PATH_IMAGE033
,
Figure DEST_PATH_IMAGE034
,
Figure 931974DEST_PATH_IMAGE035
；
said group Ar2Is selected from the followingOne or two of the following groups:
Figure DEST_PATH_IMAGE036
，
Figure 47960DEST_PATH_IMAGE037
；
in the structural unit (3), a group R is selected from methyl, phenyl or trifluoropropyl; n is an integer between 10 and 50.
4. The composite adhesive of claim 3, wherein the group Ar is selected from
Figure 109457DEST_PATH_IMAGE006
(ii) a Said group Ar1Is selected from
Figure 393808DEST_PATH_IMAGE018
，
Figure 930969DEST_PATH_IMAGE019
，
Figure 958967DEST_PATH_IMAGE020
，
Figure 140550DEST_PATH_IMAGE021
，
Figure 690742DEST_PATH_IMAGE022
One kind of (1).
5. The composite adhesive of claim 3 or 4, wherein the group Ar is selected from
Figure 590565DEST_PATH_IMAGE006
(ii) a Said group Ar1Is selected from
Figure 156676DEST_PATH_IMAGE022
。
6. The composite adhesive of claim 3, wherein the cyanate ester group-containing polyimide-siloxane resin is prepared by condensation polymerization and imidization of aromatic dianhydride, aromatic diamine, hydroxyl group-containing aromatic diamine and terminated amino polysiloxane, and then reaction of hydroxyl group with cyanogen bromide or cyanogen chloride.
7. The composite adhesive according to any one of claims 1 to 5, wherein the curing is performed by: the composite adhesive is gradually heated and crosslinked and cured at the melting temperature of 350 ℃, or gradually heated and crosslinked and cured at the melting temperature of 300 ℃ under the catalysis of a transition metal salt/phenol or organic tin catalyst.
8. The composite adhesive according to any one of claims 4 or 5, wherein the curing is carried out by: the composite adhesive is firstly compounded with a transition metal salt/phenol or organic tin catalyst, then is appropriately crosslinked by ultraviolet irradiation in a molten state, and is heated and crosslinked and cured at 200-300 ℃.
9. Use of the composite adhesive according to any one of claims 1 to 5 in a solution type electrochromic device.
10. The use of the composite adhesive according to claim 9 in a solution type electrochromic device, wherein the composite adhesive is used for bonding front and rear substrates of the solution type electrochromic device.
CN201910088374.6A 2019-01-30 2019-01-30 Adhesive and application thereof in electrochromic field Active CN111500247B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910088374.6A CN111500247B (en) 2019-01-30 2019-01-30 Adhesive and application thereof in electrochromic field

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910088374.6A CN111500247B (en) 2019-01-30 2019-01-30 Adhesive and application thereof in electrochromic field

Publications (2)

Publication Number Publication Date
CN111500247A true CN111500247A (en) 2020-08-07
CN111500247B CN111500247B (en) 2022-04-19

Family

ID=71868812

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910088374.6A Active CN111500247B (en) 2019-01-30 2019-01-30 Adhesive and application thereof in electrochromic field

Country Status (1)

Country Link
CN (1) CN111500247B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992004395A1 (en) * 1990-09-07 1992-03-19 Ciba-Geigy Ag Thermosetting compositions based on cyanate ester compounds and polyimide compounds having diorganopolysiloxane grouping(s)
CN1464898A (en) * 2001-07-09 2003-12-31 钟渊化学工业株式会社 Resin composition
CN106926781A (en) * 2015-12-29 2017-07-07 宁波祢若电子科技有限公司 The electrochromism air locking that a kind of high pressure resistant water vapour corrodes
CN108641665A (en) * 2018-05-14 2018-10-12 中国科学院化学研究所 A kind of polyimides adhesive and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992004395A1 (en) * 1990-09-07 1992-03-19 Ciba-Geigy Ag Thermosetting compositions based on cyanate ester compounds and polyimide compounds having diorganopolysiloxane grouping(s)
CN1464898A (en) * 2001-07-09 2003-12-31 钟渊化学工业株式会社 Resin composition
CN106926781A (en) * 2015-12-29 2017-07-07 宁波祢若电子科技有限公司 The electrochromism air locking that a kind of high pressure resistant water vapour corrodes
CN108641665A (en) * 2018-05-14 2018-10-12 中国科学院化学研究所 A kind of polyimides adhesive and preparation method thereof

Also Published As

Publication number Publication date
CN111500247B (en) 2022-04-19

Similar Documents

Publication Publication Date Title
CN112194792B (en) High-strength low-thermal-expansion transparent polyimide and preparation method thereof
US7820742B2 (en) Adhesive exhibiting maximum melt viscosity of 10,000 Pa s at 40 to 80 degrees C
CN112194790B (en) Low-thermal-expansion transparent polyimide film and preparation method thereof
KR101351736B1 (en) Liquid crystal aligning agent and liquid crystal display device
CN101681104A (en) Photosensitive adhesive composition, film-like adhesive, adhesive sheet, method for forming adhesive pattern, semiconductor wafer with adhesive layer, semiconductor device and method for manufacturing
CN102137906A (en) Double-faced adhesive film and electronic component module using same
JPS61500997A (en) Solar panels and their manufacturing method
JP2010513592A (en) Polyimide resin, liquid crystal alignment film and polyimide film using the same
Rabilloud High-Performance Polymer...
CN101238188A (en) Adhesive film and semiconductor device using same
CN101111368B (en) Method for joining members, composite film and use thereof
KR20210091231A (en) multilayer polymer film
KR100266548B1 (en) Adhesive tape for electronic parts and liquid adhesive
EP1508584B1 (en) Adhesive resin and film adhesives made by using the same
KR20160037847A (en) Resin composition for display substrate, thin resin film for display substrate, and process for producing thin resin film for display substrate
KR102663141B1 (en) Film forming composition, cured film, liquid crystal alignment film and retardation film
CN111500247B (en) Adhesive and application thereof in electrochromic field
CN112574411B (en) Polyimide precursor, polyimide film, preparation method of polyimide film and display device
US20220213267A1 (en) Extreme high temperature stable adhesives and coatings
CN109722212B (en) Imide epoxy organic silica gel and preparation method thereof
CN113861481B (en) High-transmittance hydrophobic optical polyimide composite film material and preparation method thereof
JPH0967560A (en) Adhesive tape for electronic part and liquid adhesive
KR100435528B1 (en) Polyamic acid and polyimide dielectrics having alkoxy silane groups
CN115537166B (en) Adhesive composition with high bonding and high moisture permeability characteristics and application thereof
JPS61226732A (en) Liquid crystal display element

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant