CN116574477A - High-temperature-resistant polyimide adhesive based on dynamic boron-oxygen bond and preparation method thereof - Google Patents
High-temperature-resistant polyimide adhesive based on dynamic boron-oxygen bond and preparation method thereof Download PDFInfo
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- CN116574477A CN116574477A CN202310363260.4A CN202310363260A CN116574477A CN 116574477 A CN116574477 A CN 116574477A CN 202310363260 A CN202310363260 A CN 202310363260A CN 116574477 A CN116574477 A CN 116574477A
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- polyimide
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 71
- 239000000853 adhesive Substances 0.000 title claims abstract description 70
- 229920001721 polyimide Polymers 0.000 title claims abstract description 56
- 239000004642 Polyimide Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 125000005619 boric acid group Chemical group 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- -1 boric acid compound Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- CZLJVZVIMFMGCH-UHFFFAOYSA-N (2-aminophenoxy)boronic acid Chemical compound NC1=CC=CC=C1OB(O)O CZLJVZVIMFMGCH-UHFFFAOYSA-N 0.000 claims description 2
- CMHUCBWVERRLNW-UHFFFAOYSA-N (2-carbamoylphenoxy)boronic acid Chemical compound NC(=O)C1=CC=CC=C1OB(O)O CMHUCBWVERRLNW-UHFFFAOYSA-N 0.000 claims description 2
- UTHULKKJYXJZLV-UHFFFAOYSA-N (3-aminophenoxy)boronic acid Chemical compound NC1=CC=CC(OB(O)O)=C1 UTHULKKJYXJZLV-UHFFFAOYSA-N 0.000 claims description 2
- RXLCGZAYEQCDNG-UHFFFAOYSA-N (4-carbamoylphenoxy)boronic acid Chemical compound NC(=O)C1=CC=C(OB(O)O)C=C1 RXLCGZAYEQCDNG-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- FPWCQFXFVGRFLP-UHFFFAOYSA-N NC(=O)C1=CC=CC(OB(O)O)=C1 Chemical compound NC(=O)C1=CC=CC(OB(O)O)=C1 FPWCQFXFVGRFLP-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 5
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical group B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 2
- 239000010935 stainless steel Substances 0.000 abstract description 2
- 229920005575 poly(amic acid) Polymers 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 4
- JMZFEHDNIAQMNB-UHFFFAOYSA-N m-aminophenylboronic acid Chemical compound NC1=CC=CC(B(O)O)=C1 JMZFEHDNIAQMNB-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XIPRTRJDLZVSHO-UHFFFAOYSA-N aminooxy(phenoxy)borinic acid Chemical compound NOB(O)OC1=CC=CC=C1 XIPRTRJDLZVSHO-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a high-temperature resistant polyimide adhesive based on dynamic boron-oxygen bonds and a preparation method thereof. The invention firstly synthesizes linear polyamic acid with a boric acid group at the molecular end, and then forms polyimide crosslinked by boron-oxygen hexacyclic ring through high-temperature dehydration. The formation of the boroxine ring as a cross-linking point further improves the thermal and chemical stability of the polyimide adhesive. Meanwhile, the adhesive can be de-crosslinked under an acidic condition based on hydrolysis reaction of the boron-oxygen hexaring, and has the characteristics of de-adhesion and repeated processing. The cross-linked polyimide can be used as a reversible adhesive, and has excellent adhesive strength, high-temperature heat stability, chemical stability and de-adhesion weight plasticity for metals such as stainless steel.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a high-temperature resistant polyimide adhesive based on dynamic boron-oxygen bonds and a preparation method thereof.
Background
On-demand debonding adhesives constitute a class of rapidly evolving materials that need to exhibit high holding power during use to achieve reliable bonding, while at the end of application having simple and clean removability. The on-demand debonding adhesives are widely used, including selective removal of adhered parts and repair of complex structures in automated manufacturing processes, wafer level packaging in the microelectronics industry, and recovery and regeneration of high value materials after the end of the useful life of automobiles or smart products (notebook, cell phones, etc.), among others. Conventional adhesives are not suitable for high temperature processes such as assembly and sealing of thermal protection systems, connection and repair of brake and engine system components, and wafer thinning processes. Abrasion or impact under high temperature conditions can easily lead to bond failure. It is well known that the extreme temperatures of most polymeric binders are typically below 400 ℃, which greatly limits their use in high temperature environments. Most commercial temporary adhesives are also low melting point heat sensitive polymers. Therefore, development of an advanced temporary adhesive having high adhesive strength and excellent heat resistance has become urgent.
Polyimide is the preferred substrate for adhesives in the high temperature bonding field due to its high heat resistance, excellent mechanical properties and good chemical stability. In general, polymer structures with intra-chain covalent bonds and inter-chain entangled networks are critical to achieving high bond strength. However, wholly aromatic polyimide has characteristics of high molecular weight and strong inter-chain interaction, which results in high polymer viscosity, high crystallinity and low solubility. These properties reduce their ability to penetrate the substrate, resulting in shrinkage defects that are likely to occur after curing, resulting in poor adhesion and failure to meet the demand for on-demand debonding. In order to reduce the cohesive energy of polyimide, flexible segments (-O-, -c=o-and-Si-O-), aliphatic units (-CH) are usually introduced 3 and-CH 2 (-) or asymmetric structure, thereby reducing the rigidity of the polymer backbone, inhibiting close packing of the chains and reducing inter-chain interactions. In addition, the molecular weight can be controlled to reduce the viscosity. However, the above strategies tend to lead to a drastic decrease in thermal, adhesive and chemical stability. Thus, preparing polyimide adhesives with high heat resistance, high adhesion and chemical stability, which can be debonded on demand, still faces a great challenge.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide a novel high-temperature-resistant polyimide adhesive based on dynamic boron-oxygen bonds and a preparation method thereof.
The invention provides a dynamic cross-linked polyimide adhesive, which is characterized in that diamine, dianhydride monomer and boric acid monomer are used as raw materials to synthesize PI-b with boric acid groups at the molecular terminals; and then, the PI-b is subjected to dehydration condensation to synthesize the boron-oxygen bond crosslinked polyimide. As a crosslinking point, the formation of the boroxine ring further improves the thermal and chemical stability of the polyimide adhesive. Meanwhile, the adhesive can be de-crosslinked under an acidic condition based on hydrolysis reaction of the boron-oxygen hexaring, and has the characteristics of de-adhesion and repeated processing. The cross-linked polyimide can be used as a reversible adhesive, and has excellent adhesive strength, high-temperature heat stability, chemical stability and de-adhesion weight plasticity for metals such as stainless steel.
The invention also provides a synthesis method of the high-temperature resistant polyimide adhesive based on dynamic boron-oxygen bond,
the method comprises the following steps:
(1) Synthesizing a macromolecule PI-b with a boric acid group at the molecular end: under the protection of nitrogen, adding diamine monomer into a solvent, adding excessive dianhydride monomer in batches after dissolution to generate polyimide prepolymer with anhydride at the molecular end, then adding amino-containing boric acid compound, and linking phenylboronic acid at the molecular chain end of the prepolymer through the reaction of amino and anhydride to obtain PI-b with boric acid group at the molecular end;
(2) Synthesizing a high-temperature resistant polyimide adhesive based on dynamic boron-oxygen bonds: and (3) solidifying the PI-b obtained in the step (1) under the heating condition, and dehydrating at high temperature to obtain the high-temperature-resistant polyimide adhesive based on the dynamic boron-oxygen bond.
Preferably, in step (1), the diamine monomer used is selected from at least one of 4,4' -diaminodiphenyl ether, 4-diaminodiphenyl sulfide, 2-bis [4- (4-aminophenoxy) phenyl ] propane, p-phenylenediamine, 4' -dichlorodiphenylmethane, 4' -diaminodiphenyl sulfone;
the mass fraction of the diamine monomer in the solvent is 10-15%.
Preferably, in step (1), the dianhydride monomer used is selected from at least one of pyromellitic anhydride, 4-oxydiphthalic anhydride, 3, 4-oxydiphthalic anhydride, 4-hexafluoroisopropyl phthalic anhydride, 2,3',3,4' -biphenyl tetracarboxylic dianhydride;
the molar ratio of the dianhydride monomer to the diamine monomer is 1.03-1.2.
Preferably, in step (1), the amino-containing boric acid compound used is selected from at least one of 3-aminophenylboric acid, 2-aminophenylboric acid, 4-aminophenylborate, 3-aminophenylborate, 2-aminophenylborate, 4-carbamoylphenylboric acid, 3-carbamoylphenylboric acid, 2-carbamoylphenylboric acid;
the addition proportion of the boric acid compound containing amino is 6-40% of the molar quantity of diamine monomer.
Preferably, in the step (1), the solvent is at least one selected from the group consisting of N, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
Preferably, in the step (2), the curing step is: curing according to a stepwise procedure of 80 ℃/3h,120 ℃/1h,150 ℃/1h,180 ℃/1h,250 ℃/1h and 300 ℃/1 h;
or pre-cured for 4 hours at 80-200℃followed by curing for 1 hour at 300 ℃.
The high-temperature resistant polyimide adhesive based on dynamic boron-oxygen bonds, which is prepared by the invention, has the following characteristics: the boron-oxygen bond crosslinking polyimide agent has the characteristics of reversible cyclic conversion and repeatable processing. Specifically, the adhesive realizes de-crosslinking and de-bonding under acidic conditions through hydrolysis reaction and is repeatedly used; the hydrolysis reaction comprises the following steps: the adhesive is soaked in a mixed solvent containing acid to be debonded.
Preferably, the acid is selected from at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, perchloric acid, hydrobromic acid.
Preferably, the solvent is at least one selected from the group consisting of N, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, acetone, diethyl ether, chloroform, and dichloromethane.
The invention further researches the mechanism and the characteristics of the boron-oxygen bond crosslinked polyimide adhesive. The linear polyimide prepolymer with the boric acid group at the molecular chain end is synthesized by the invention, and the boric acid group at the molecular chain end is used for carrying out trimerization reaction to form the boron-oxygen hexacyclic ring to obtain the boron-oxygen bond crosslinked polyimide. Through the dynamic reversible reaction of the boroxine, the crosslinked polyimide polymer network structure can be transformed and recombined, and further has the characteristics of debonding and repeatable processing as required. In addition, the boroxine ring further improves the high-temperature heat stability, the bonding strength and the chemical stability of the polyimide adhesive.
Compared with the prior art, the invention has the following advantages:
(1) The boron-oxygen bond crosslinked polyimide adhesive prepared by the invention has excellent high-temperature heat stability, bonding strength and chemical stability. Meanwhile, the dynamic cross-linked polyimide adhesive can be de-bonded, recycled and reused under an acidic condition, so that reversible bonding is realized, and the dynamic cross-linked polyimide adhesive has positive significance for development of high-temperature-resistant reversible adhesives.
(2) The synthesis method of the boron-oxygen bond cross-linked polyimide adhesive provided by the invention has the advantages of easiness in operation, low-cost and easily available raw materials, flexible and various formulas and products and the like.
Drawings
FIG. 1 is a synthetic route of a polyimide adhesive prepared by the invention, wherein A is diamine monomer, B is dianhydride monomer, C is aminophenylboric acid, D is polyimide prepolymer PI-B with anhydride at the end, and E is boron-oxygen bond crosslinked polyimide.
FIG. 2 is an external view of a boron oxygen bonded crosslinked polyimide film prepared in example 1.
FIG. 3 is an infrared spectrum of a boron-oxygen bond crosslinked polyimide film prepared in example 1.
Fig. 4 shows the adhesive strength of the crosslinked polyimide adhesive prepared in example 2.
FIG. 5 is a graph showing the thermal weight loss of the boron-oxygen bonded crosslinked polyimide film prepared in example 3.
FIG. 6 is a graph showing the adhesive strength of the boron oxygen bonded crosslinked polyimide adhesive prepared in example 3 at various temperatures.
FIG. 7 shows the debonding of the boron oxygen bonded crosslinked polyimide adhesive prepared in example 3 in various solvents.
FIG. 8 is the adhesive strength of the boron oxygen bonded crosslinked polyimide adhesive prepared in example 3 in different solvents.
FIG. 9 is a schematic illustration of the debonding of the boron oxygen bonded crosslinked polyimide adhesive prepared in example 4 in a NMP/DCM/HCl mixed solvent.
Fig. 10 shows the adhesive strength of the boron oxygen bonded cross-linked polyimide adhesive prepared in example 4 for 4 dissolution-bonding.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
Weighing 4.1g (10 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, dissolving in 34.3-g N-methylpyrrolidone, adding 3.42g (11 mmol) of 4, 4-oxydiphthalic anhydride in batches after dissolving, stirring at normal temperature for 6h under the protection of nitrogen, and uniformly stirring to obtain a transparent viscous solution with 18% of solid content; 0.274g (2 mmol) of 3-aminophenylboronic acid was added and stirring was continued for 4h to give a pale yellow solution. And then coating the solution on a glass plate, and curing the solution into a film according to a step program of 80 ℃/3h,120 ℃/1h,150 ℃/1h,180 ℃/1h,250 ℃/1h and 300 ℃/1h to obtain the boron-oxygen bond crosslinked polyimide sample 1.
The appearance of sample 1 is shown in fig. 2, and it can be seen from fig. 2 that the boron-oxygen bond crosslinked polyimide film has good transparency.
The infrared spectrum of sample 1 is shown in FIG. 3, and it can be seen from FIG. 3 that the infrared spectrum is at 719cm -1 Characteristic peaks of B-O are shown, confirming the formation of boroxine crosslinks.
Example 2
8.2g (20 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane is weighed and dissolved in 67.9-g N-methylpyrrolidone, 6.7g (21.6 mmol) of 4, 4-oxydiphthalic anhydride is added in batches after dissolution, and the mixture is stirred for 6 hours at normal temperature under the protection of nitrogen, and a transparent viscous solution with 18% of solid content is obtained after uniform stirring; 0.44g (3.2 mmol) of 3-aminophenylboronic acid was added thereto and stirring was continued for 4 hours to obtain a pale yellow solution. The pale yellow solution was coated on the polished steel sheet with a coating area of 20X 12.5mm and a coating thickness of 0.2mm, pre-cured at 250℃for 4 hours, and then the steel sheet was adhesively fixed and cured at 300℃for 1 hour to obtain an adhesive member adhered by the crosslinked polyimide sample 2. The adhesive was subjected to shear adhesion strength test using a tensile tester, and the results are shown in fig. 4. Sample 2 has a higher adhesive strength than a linear polyimide adhesive cured according to the same procedure with the same diamine and dianhydride ratio (no added phenylboronic acid).
Example 3
Weighing 4.1g (10 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, dissolving in 33.5-g N-methylpyrrolidone, adding 3.26g (10.5 mmol) of 4, 4-oxydiphthalic anhydride in batches after dissolving, stirring for 6 hours at normal temperature under the protection of nitrogen, and uniformly stirring to obtain a transparent viscous solution with the solid content of 18%; 0.14g (1 mmol) of 3-aminophenylboronic acid was added thereto and stirring was continued for 4 hours to obtain a pale yellow solution. And then cured under the elevated temperature conditions described in example 1 to give sample 3 of the boron oxygen bonded crosslinked polyimide.
As shown in FIG. 5, the thermal weight loss curve of sample 3 has excellent heat resistance, wherein the 5% decomposition temperature is above 500 ℃; the increase in decomposition temperature after crosslinking was 23 ℃, indicating that the boroxine ring further increased thermal stability.
The steel sheets bonded in sample 3 were subjected to shear adhesion strength test using a tensile tester at different temperatures, and the results are shown in fig. 6. As can be seen from fig. 6, sample 3 has an initial adhesive strength of 26MPa and exhibits excellent adhesive properties at high temperatures. Below 300 ℃, the adhesion strength is hardly affected. After heat treatment for 1h at 350 ℃, the lap shear strength still reaches more than 20 MPa.
The steel sheet bonded with sample 3 was immersed in a different single solvent for 1 hour, then the weight was hung again, and finally a tensile tester was used for shear strength test, and the results are shown in fig. 7 and 8. After solvent treatment, the adhesive piece can still bear the weight of 2.5kg in the solvent, the adhesive strength is still maintained above 22MPa, and the adhesive piece has excellent chemical stability.
Example 4
8.2g (20 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane is weighed and dissolved in 67.1-g N-methylpyrrolidone, 6.52g (21 mmol) of 4, 4-oxydiphthalic anhydride is added in batches after diamine is dissolved, and the mixture is stirred for 6 hours at normal temperature under the protection of nitrogen, and a transparent viscous solution with 18% of solid content is obtained after uniform stirring; 0.28 (2 mmol) of 3-aminophenylboronic acid was added and stirring was continued for 4h to give a pale yellow solution. And heating and curing in the above stage to obtain an initial cross-linked polyimide adhesive sample 4.
The steel sheet bonded with sample 4 was immersed in a mixed solvent of NMP/DCM/HCl to remove the bond, and a tensile tester was used to test the shear adhesion strength, and the immersion time and the change of the adhesion strength are shown in FIG. 9. As the soaking time is increased, the bonding strength of the boron-oxygen bond crosslinked polyimide adhesive is gradually reduced, and the adhesive can realize the purpose of debonding according to the requirement.
And (3) soaking the sample 4 in a mixed solvent of NMP/DCM/HCl for dissolution, then recoating on a clean steel sheet for resolidification and adhesion, and repeating the steps to obtain the boron-oxygen bond crosslinked polyimide adhesive which is recovered for a plurality of times.
The adhesive-bonded steel sheets of the above different recovery times were subjected to shear adhesion strength test using a tensile tester, and the results are shown in fig. 10. The adhesive maintained an adhesive strength of 25MPa during the 4 cycles of dissolution-bonding, indicating good recyclability and reusability of sample 4.
Claims (10)
1. The synthesis method of the high-temperature-resistant polyimide adhesive based on the dynamic boron-oxygen bond is characterized by comprising the following steps of:
(1) Synthesizing PI-b with boric acid groups at the molecular terminals: under the protection of nitrogen, adding diamine monomer into a solvent, adding excessive dianhydride monomer in batches after dissolution to generate polyimide prepolymer with anhydride at the molecular end, then adding amino-containing boric acid compound, and linking phenylboronic acid at the molecular chain end of the prepolymer through the reaction of amino and anhydride to obtain PI-b with boric acid group at the molecular end;
(2) Synthesizing a high-temperature resistant polyimide adhesive based on dynamic boron-oxygen bonds: and (3) solidifying the PI-b obtained in the step (1) under the heating condition, and dehydrating at high temperature to obtain the high-temperature-resistant polyimide adhesive based on the dynamic boron-oxygen bond.
2. The synthetic method according to claim 1, wherein in the step (1), the diamine monomer used is at least one selected from the group consisting of 4,4' -diaminodiphenyl ether, 4-diaminodiphenyl sulfide, 2-bis [4- (4-aminophenoxy) phenyl ] propane, p-phenylenediamine, 4' -dichlorodiphenyl methane, and 4,4' -diaminodiphenyl sulfone;
the mass fraction of the diamine monomer in the solvent is 10-15%.
3. The synthetic method according to claim 1, wherein in the step (1), the dianhydride monomer used is at least one selected from the group consisting of pyromellitic anhydride, 4-oxydiphthalic anhydride, 3, 4-oxydiphthalic anhydride, 4-hexafluoroisopropyl phthalic anhydride, 2,3',3,4' -biphenyl tetracarboxylic dianhydride;
the molar ratio of the dianhydride monomer to the diamine monomer is 1.03-1.2.
4. The synthetic method according to claim 1, wherein in the step (1), the amino-containing boric acid compound used is at least one selected from the group consisting of 3-aminophenylboric acid, 2-aminophenylboric acid, 4-aminophenylborate, 3-aminophenylborate, 2-aminophenylborate, 4-carbamoylphenylboric acid, 3-carbamoylphenylboric acid, 2-carbamoylphenylboric acid;
the addition proportion of the boric acid compound containing amino is 6-40% of the molar quantity of diamine monomer.
5. The synthetic method according to claim 1, wherein in the step (1), the solvent is at least one selected from the group consisting of N, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
6. The method of synthesis according to claim 1, wherein in step (2), the curing step is: curing according to a stepwise procedure of 80 ℃/3h,120 ℃/1h,150 ℃/1h,180 ℃/1h,250 ℃/1h and 300 ℃/1 h;
or pre-cured for 4 hours at 80-200℃followed by curing for 1 hour at 300 ℃.
7. A high temperature resistant polyimide adhesive based on dynamic boron oxygen bonds prepared by the synthetic method of any one of claims 1 to 6.
8. The adhesive according to claim 7, wherein the adhesive is de-crosslinked and de-bonded under acidic conditions by hydrolysis and is reused; the hydrolysis reaction comprises the following steps: the adhesive is soaked in a mixed solvent containing acid to be debonded.
9. The adhesive of claim 8, wherein the acid is selected from at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, perchloric acid, hydrobromic acid.
10. The adhesive of claim 8, wherein the solvent is selected from at least one of N, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, acetone, diethyl ether, chloroform, and dichloromethane.
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| CN116769434A (en) * | 2023-08-25 | 2023-09-19 | 广东远东高分子科技有限公司 | Air chain riveting glue and processing technology thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116769434A (en) * | 2023-08-25 | 2023-09-19 | 广东远东高分子科技有限公司 | Air chain riveting glue and processing technology thereof |
| CN116769434B (en) * | 2023-08-25 | 2023-10-31 | 广东远东高分子科技有限公司 | Air chain riveting glue and processing technology thereof |
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