CN115490852A - Modified polyimide, preparation method thereof and polyimide film - Google Patents
Modified polyimide, preparation method thereof and polyimide film Download PDFInfo
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- CN115490852A CN115490852A CN202210703818.4A CN202210703818A CN115490852A CN 115490852 A CN115490852 A CN 115490852A CN 202210703818 A CN202210703818 A CN 202210703818A CN 115490852 A CN115490852 A CN 115490852A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 154
- 239000004642 Polyimide Substances 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 20
- 125000004185 ester group Chemical group 0.000 claims abstract description 19
- 230000001629 suppression Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 28
- 150000004985 diamines Chemical class 0.000 claims description 16
- 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 14
- 230000002401 inhibitory effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- -1 fluoro secondary propyl group Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 claims description 2
- VXTJVMWIVSZHNI-UHFFFAOYSA-N 2-amino-4-propylphenol Chemical compound CCCC1=CC=C(O)C(N)=C1 VXTJVMWIVSZHNI-UHFFFAOYSA-N 0.000 claims description 2
- MESFSCWCECYZNL-UHFFFAOYSA-N 2-amino-5-[3-(4-amino-3-hydroxyphenoxy)phenoxy]phenol Chemical compound C1=C(O)C(N)=CC=C1OC1=CC=CC(OC=2C=C(O)C(N)=CC=2)=C1 MESFSCWCECYZNL-UHFFFAOYSA-N 0.000 claims description 2
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 claims description 2
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 claims description 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 2
- SSCWKGFVVGEADK-UHFFFAOYSA-N cyclopentene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)=C(C(O)=O)C1C(O)=O SSCWKGFVVGEADK-UHFFFAOYSA-N 0.000 claims description 2
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 150000003949 imides Chemical group 0.000 claims 1
- 125000005462 imide group Chemical group 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 31
- 238000003786 synthesis reaction Methods 0.000 description 31
- 239000012190 activator Substances 0.000 description 21
- 229920001225 polyester resin Polymers 0.000 description 21
- 239000004645 polyester resin Substances 0.000 description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000002872 contrast media Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- WVOLTBSCXRRQFR-DLBZAZTESA-M cannabidiolate Chemical compound OC1=C(C([O-])=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012803 optimization experiment Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
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- 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
- C08G73/1057—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
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- 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
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- C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention provides a modified polyimide, which is prepared by reacting a polyimide precursor with a curing agent, wherein the polyimide precursor comprises a main chain and a branch chain, the main chain comprises an imide ring and a color suppression group, the branch chain comprises an epoxy group, the curing agent comprises an active ester group, and the branch chain with the epoxy group and the curing agent with the active ester group react to prepare the modified polyimide. The modified polyimide has good mechanical property, low dielectric constant and hardness ≧ 4H, and transparency >88% (550 nm) is maintained. In addition, the application also provides a preparation method of the modified polyimide and a polyimide film.
Description
Technical Field
The invention relates to modified polyimide, a preparation method thereof and a polyimide film.
Background
Generally, polyimide is brown and yellow due to high aromatic ring density, the light transmittance in a visible light region is low, most of the polyimide is synthesized by using alicyclic structures, diamines and acid anhydrides containing bulky groups-CF 3 or connecting groups such as-O-, SO 2-and the like, and the molecular structure design can achieve the transmittance of more than 88%, but the mechanical properties of the film are reduced and the dielectric properties are improved, SO that the polyimide can be applied to a touch panel of a display.
Disclosure of Invention
In view of the above, it is desirable to provide a modified polyimide having excellent transmittance, mechanical properties and dielectric properties.
The modified polyimide is prepared by reacting a polyimide precursor with a curing agent, wherein the polyimide precursor comprises a main chain and a branch chain, the main chain comprises an imide ring and a color suppression group, the branch chain comprises an epoxy group, the curing agent comprises an active ester group, and the branch chain with the epoxy group and the curing agent with the active ester group are reacted to prepare the modified polyimide.
Further, the color-suppressing group includes any one of a polar group, an asymmetric group, and a bulky group.
Further, the polar groups include-O-, -SO 2 -and-CO-.
Further, the asymmetric group comprises
At least one of (1).
Further, the bulky group comprises
And
at least one of (a).
Further, the chemical formula of the curing agent is shown in the specification
Wherein n is a natural number of 7 to 12. X is at least one of hydrogen (H.), an alkyl group (-R-) having 1 to 3 carbon atoms or an alkoxy group (-RO-). Y is an ether group (-O-), a sulfonyl group (-S (= O) 2-), a methylene group (-CH 2-), or one of a secondary propyl group (-C (CH 3) 2-), and a fluoro-secondary propyl group (-C (CF 3) 2-). Z is at least one of hydrogen (H), an alkyl group (-R-) having 1 to 3 carbon atoms, or an alkoxy group (-RO-).
A preparation method of modified polyimide comprises the following steps: a transparent polyimide precursor is provided that includes an amide backbone that includes a color suppressing group. And bonding at least one epoxy group on the amide main chain to obtain the transparent polyimide. And mixing the transparent polyimide and a curing agent, wherein the curing agent comprises an active ester group, and the modified polyimide is obtained after the epoxy group reacts with the active ester group.
Further, the molar equivalent ratio of the epoxy group to the active ester group is 1:1.0 to 1.5.
Further, the method for preparing the transparent polyimide precursor comprises the steps of: diamine monomers and dianhydride monomers are provided, wherein the diamine monomers and/or the dianhydride monomers comprise color inhibiting groups. Mixing the diamine monomer and the dianhydride monomer to polymerize them to produce the transparent polyimide precursor.
Further, the diamine monomer includes one of bis (3-amine-4-hydroxyphenyl) hexafluoropropane, 4, 6-diaminoresorcinol, 2-bis (4-hydroxy-3-aminophenyl) propane, 1, 3-bis (3-hydroxy-4-aminophenoxy) benzene, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
Further, the dianhydride monomer includes one of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 1,2,3, 4-cyclopentene tetracarboxylic dianhydride, and 1,2,4, 5-cyclohexanetetracarboxylic dianhydride.
A polyimide film is prepared by heating the modified polyimide, and is prepared by reacting transparent polyimide with a curing agent. The transparent polyimide comprises a color suppression group and an epoxy group, and the curing agent comprises an active ester group which reacts with the epoxy group to bond the transparent polyimide and the curing agent.
The modified polyimide has transparency of more than 88% (550 nm) by bonding the color inhibiting group on the main chain, and has good mechanical property, low dielectric constant and hardness of not less than 4H by bonding the curing agent on the branch chain.
Drawings
FIG. 1 shows a process for preparing a modified polyimide according to a preferred embodiment of the present invention.
FIG. 2 is a schematic diagram of a process for preparing a polyimide film according to a preferred embodiment of the present invention.
Description of the main elements
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The application provides modified polyimide, which is prepared by reacting a polyimide precursor with a curing agent. The polyimide precursor comprises a main chain and a branch chain, wherein the main chain comprises an imide ring (-CO-N-CO-) and a color inhibiting group, and the branch chain comprises an epoxy group (-CH (O) CH-). The curing agent includes an active ester group (-COOR). The modified polyimide is prepared by reacting the polyimide precursor having an epoxy group with a curing agent having an active ester group.
In this embodiment, the polyimide precursor is transparent polyimide, and the color-suppressing group includes at least one of a polar group, an asymmetric group, and a bulky group. Wherein the polar group includes at least one of an ether group (-O-), a sulfonyl group (- = O) 2-) and a carbonyl group (-CO-). The asymmetric group comprises
At least one of (1). The bulky group comprises
At least one of (1). The color inhibiting group has the following action principle: the color inhibiting groups destroy or reduce the intermolecular and intramolecular charge transfer degree of the polyimide, so that the light passing through the polyimide is less absorbed, the light transmittance is improved, and finally the polyimide is changed into transparent polyimide.
In this embodiment, the curing agent includes a polyester resin activator, and the chemical formula of the polyester resin activator is:
Referring to fig. 1, the present application further provides a method for preparing a modified polyimide, including the steps of:
s1, providing a polyimide precursor, wherein the polyimide precursor comprises a main chain, the main chain comprises an imide ring (-CO-N-CO-) and a color inhibiting group, and the color inhibiting group comprises at least one of a polar group, an asymmetric group and a large-volume group.
In this embodiment, the preparation method of the polyimide precursor includes the steps of:
s10, providing a diamine monomer and a diacid anhydride monomer, wherein the diamine monomer and/or the diacid anhydride monomer comprise a color suppression group;
and S11, mixing the diamine monomer and the dianhydride monomer to polymerize the diamine monomer and the dianhydride monomer to produce the polyimide precursor.
Wherein A comprises:
b comprises the following steps:
and S2, bonding at least one epoxy group on the main chain to obtain an intermediate.
In this embodiment, step S2 includes:
and S21, mixing the polyimide precursor and epoxy chloropropane to bond an epoxy group on the main chain.
And S3, mixing the intermediate and a curing agent, wherein the curing agent comprises an active ester group, and the modified polyimide is obtained after the epoxy group reacts with the active ester group.
In this embodiment, the equivalent ratio of the epoxy group of the intermediate to the active ester group of the curing agent is 1 to 1.5.
The invention also provides a polyimide film, which is formed by coating the modified polyimide on the surface of a base material and then cyclizing at high temperature. The substrate can be a substrate which is conventionally applied to the preparation of polyimide films, such as a steel plate, a release film, a metal foil, resin and the like. Specifically, referring to fig. 2, the process of forming the polyimide film includes: firstly, preparing a substrate 10; then coating a modified polyimide dispersion 21 (prepared from a modified polyimide and a solvent) on one side of the substrate 10; then heating the substrate 10 coated with the modified polyimide dispersion 21 to cause cyclization of the modified polyimide to form a polyimide film 20 while evaporating the solvent; then, the substrate 10 is removed, and a polyimide film 20 is obtained.
The modified polyimide of the present invention will be further described with reference to specific examples.
The first step is as follows: the synthesis of polyimide precursor, wherein the intermediate can be carried out as in synthesis examples 1 to 4 below.
Synthesis example 1
Referring to table 1 and table 2, 3.3' -DABS (0.1 mol, 28.03 g) and 1, 4-butyrolactone/N-methylpyrrolidone (1/1, 142.92 g) as a solvent are sequentially added to a 500 ml reaction flask, after stirring until dissolution, CBDA (0.1 mol, 19.61 g) and solid (solidcontent) are added, stirring is performed for 12 hours, then 80 ℃ is performed, and stirring is performed for 4 hours, xylene (28.58 g) is added during the reaction, then 180 ℃ is increased and a reflux pipe is erected, xylene is added to the reflux pipe, stirring is continuously performed for 16-18 hours at constant temperature of 180 ℃ to obtain transparent polyimide, then 80 ℃ is decreased, epichlorohydrin (0.2 mol, 18.5 g) is added to react for 24 hours, and polyimide precursor a is synthesized.
Synthesis example 2
Referring to table 1 and table 2, 6FAP (0.1 mol, 36.63 g) and 1, 4-butyrolactone/N-methylpyrrolidone (1/1, 168.71 g) as a solvent are sequentially added into a 500 ml reaction bottle, after stirring until dissolution, CBDA (0.1 mol, 19.61 g) and 20-25% of solid are added, stirring is performed for 12 hours, then 80 ℃ is heated, stirring and dissolution reaction is performed for 4 hours, xylene (33.74 g) is added during the reaction, then 180 ℃ is heated and a reflux pipe is erected, xylene is added into the reflux pipe, stirring is continuously performed for 16-18 hours at constant temperature of 180 ℃ to obtain transparent polyimide, then epichlorohydrin (0.2 mol, 18.5 g) is added to the reaction bottle after cooling to 80 ℃ to react for 24 hours, and a polyimide precursor b is synthesized.
Synthesis example 3
Referring to tables 1 and 2, 3.3' -DABS (0.1 mol, 28.03 g) and 1, 4-butyrolactone/N-methyl pyrrolidone (1/1, 217.36 g) as a solvent were sequentially added to a 500 ml reaction flask, after stirring until the solvents were dissolved, 6FDA (0.1 mol, 44.42 g) was added and the solid content was 20 to 25%, stirring was carried out for 12 hours and then 80 ℃ was added and the reaction was carried out for 4 hours, xylene (43.47 g) was added to the reaction, then 180 ℃ was heated and a reflux tube was erected, and then toluene was added to the reflux tube, and the mixture was kept stirred at 180 ℃ for 16 to 18 hours to obtain a transparent polyimide, and then epichlorohydrin (0.2 mol, 18.5 g) was added to the reaction flask at 80 ℃ to react for 24 hours to synthesize a polyimide precursor c.
Synthesis example 4
Referring to tables 1 and 2, 6FAP (0.1 mol, 36.63 g) and 1, 4-butyrolactone/N-methylpyrrolidone (1/1, 243.15 g) as a solvent are sequentially added into a 500 ml reaction bottle, after stirring until dissolution, 6FDA (0.1 mol, 44.42 g) and 20 to 25% of solid are added, stirring is performed for 12 hours, then 80 ℃ is added, stirring and dissolution reaction is performed for 4 hours, xylene (48.63 g) is added during the reaction, then 180 ℃ is heated, a reflux pipe is erected, xylene is added into the reflux pipe, stirring is continuously performed for 16 to 18 hours at constant temperature of 180 ℃ to obtain transparent polyimide, then epichlorohydrin (0.2 mol, 18.5 g) is added after cooling to 80 ℃ to react for 24 hours, and a polyimide precursor d is synthesized.
Synthesis example 5
Adding 4.4' -DDS (0.1 mol, 24.83 g) and a solvent 1, 4-butyrolactone/N-methyl pyrrolidone (1/1, 207.76 g) into a 500 ml reaction bottle in sequence, stirring until the mixture is dissolved, then adding 6FDA (0.1 mol, 44.42 g) and 20-25% of solid, stirring for 12 hours, heating to 80 ℃, stirring for dissolving for reaction for 4 hours, adding dimethylbenzene (41.55 g) into the reaction, heating to 180 ℃, erecting a return pipe, adding dimethylbenzene into the return pipe, and continuously stirring for 16-18 hours at constant temperature of 180 ℃ to obtain the polyimide contrast.
Table one: name, abbreviation and CAS number of acid anhydride in Synthesis examples 1-4.
Table two: names, abbreviations and CAS numbers of diamines in Synthesis examples 1-4.
And secondly, respectively carrying out penetration test, pencil hardness test, tensile strength test, elongation test and dielectric constant test on the polyimide precursors a-d. The test results are shown in table three. Wherein, the penetration test is to carry out light transmittance test on the polyimide precursors a-d by adopting electromagnetic waves with the wavelength of 550nm (the same below). The pencil hardness was tested for polyimide precursors a-d using standard IPC-TM-650 (the same applies below). The tensile strength and elongation were tested using the standard ASTM D638 for tensile strength and elongation of polyimide precursors a-D. The dielectric constant was measured using the polyimide precursors a-D using the standard ASTM-D150 (the same applies below).
Table three: synthetic feeding and performance test results of polyimide precursors a-d
By analyzing the properties of the polyimide precursors a to d, it can be found that: the polyimide precursor has excellent light transmittance and 91-93 percent of penetration, wherein the intermediate is obtained by the reaction of diamine monomer and dianhydride monomer, and the diamine monomer comprises alicyclic structure and bulky group-CF 3 Or with-O-, SO 2 And (c) a color-inhibiting group of the type (a) or (b), the dianhydride monomer comprising an alicyclic structure, a bulky group-containing-CF 3 Or with-O-, SO 2 -and the like.
The third step: synthesis of modified polyimide, which can be carried out from intermediates a to d and a polyester resin activator, according to the following Synthesis examples 6 to 13.
Synthesis example 6
10 g of polyimide precursor a and 8.87 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide a can be obtained.
Synthesis example 7
10 g of polyimide precursor b and 7.60 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide b can be obtained.
Synthesis example 8
10 g of polyimide precursor c and 5.91 g of polyester resin activator are added into a 100 ml reaction bottle, and the mixture is stirred for 6 hours to obtain modified polyimide c.
Synthesis example 9
10 g of polyimide precursor d and 5.32 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide d can be obtained.
Synthesis example 10
10 g of polyimide precursor a and 13.31 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide e can be obtained.
Synthesis example 11
10 g of polyimide precursor b and 11.40 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide f can be obtained.
Synthesis example 12
10 g of polyimide precursor c and 8.87 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, g of modified polyimide is obtained.
Synthesis example 13
10 g of polyimide precursor d and 7.98 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide h can be obtained.
Table two: modified polyimide a-h synthesis feeding and performance test results
By analyzing the properties of the modified polyimides a to h, it can be found that: the polyimide precursor has excellent light transmittance, the penetration degree is 88-91%, and the hardness of the polyimide precursor reaches 4H.
The fourth step: the modified polyimide synthesis conditions were optimized, wherein the optimization experiment was carried out by designing the following synthesis examples 14 to 22:
synthesis example 14
10 g of a polyimide control and 2.0 g of a polyester resin activator were put in a 100 ml reaction flask and stirred for 6 hours to obtain a polyimide control.
Synthesis example 15
10 g of polyimide precursor a and 4.44 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide i can be obtained.
Synthesis example 16
10 g of polyimide precursor b and 3.80 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, the modified polyimide j can be obtained.
Synthesis example 17
10 g of polyimide precursor c and 2.96 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide k can be obtained.
Synthesis example 18
10 g of polyimide precursor d and 2.66 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide l can be obtained.
Synthesis example 19
10 g of polyimide precursor a and 17.74 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide m can be obtained.
Synthesis example 20
10 g of polyimide precursor b and 15.20 g of polyester resin activator are added into a 100 ml reaction bottle, and the mixture is stirred for 6 hours to obtain modified polyimide n.
Synthesis example 21
10 g of polyimide precursor c and 11.83 g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, the modified polyimide o can be obtained.
Synthesis example 22
10 g of polyimide precursor d and 10.64g of polyester resin activator are added into a 100 ml reaction bottle, and after stirring for 6 hours, modified polyimide p can be obtained.
By analyzing the feeding conditions of the modified polyimides a-h and i-p, it can be found that:
it is known that, when the amount of epoxy equivalents of the modified polyimide precursor: the molar equivalent of the polyester resin activator is 1.0 to 1.5, the synthesized modified polyimide has good mechanical properties, a low dielectric constant and a hardness of 4H or more, and the transparency of the polyimide is maintained at more than 88% (550 nm).
The polyimide contrast agent has no epoxy functional group, so that the polyimide contrast agent cannot perform a crosslinking reaction with active ester (-COOR), and has no chemical bonding, so that the polyimide contrast agent and the active ester (-COOR) have a phase separation phenomenon, and the mechanical property is reduced.
In addition, it is obvious to those skilled in the art that other various changes and modifications can be made according to the technical idea of the present invention, and all such changes and modifications should fall within the protection scope of the claims of the present invention.
Claims (12)
1. The utility model provides a modified polyimide, is made by polyimide precursor and curing agent reaction, its characterized in that, the polyimide precursor includes main chain and branch chain, the main chain includes imide ring and presses down the colour group, the branch chain includes the epoxy, the curing agent includes active ester group, has epoxy branch chain and the curing agent reaction that has active ester group prepare modified polyimide.
2. The modified polyimide according to claim 1, wherein the color-suppressing group comprises any one of a polar group, an asymmetric group, and a bulky group.
3. The modified polyimide of claim 2, wherein the polar groups comprise-O-, -SO 2 -and-CO-.
4. The modified polyimide of claim 2, wherein the asymmetric group comprises
At least one of (1).
5. The modified polyimide of claim 2, wherein the bulky group comprises
And
at least one of (1).
6. The modified polyimide of claim 1, wherein the curing agent has the formula
Wherein n is a natural number of 7 to 12;
x is at least one of hydrogen, alkyl or alkoxy with 1-3 carbon atoms;
y is one of ether group, sulfonyl group, methylene group, secondary propyl group and fluoro secondary propyl group;
z is at least one of hydrogen, alkyl with 1-3 carbon atoms or alkoxy.
7. A preparation method of modified polyimide is characterized by comprising the following steps:
providing a transparent polyimide precursor, wherein the transparent polyimide precursor comprises an amide main chain, and the amide main chain comprises a color inhibiting group;
bonding at least one epoxy group on the amide main chain to obtain transparent polyimide;
and mixing the transparent polyimide and a curing agent, wherein the curing agent comprises an active ester group, and the modified polyimide is obtained after the epoxy group reacts with the active ester group.
8. The method according to claim 7, wherein the molar equivalent ratio of the epoxy group to the active ester group is 1.0 to 1.5.
9. The method of preparing according to claim 7, wherein the method of preparing the transparent polyimide precursor comprises the steps of:
providing a diamine monomer and a dianhydride monomer, wherein the diamine monomer and/or the dianhydride monomer comprises a color inhibiting group;
mixing the diamine monomer and the dianhydride monomer to polymerize them to produce the transparent polyimide precursor.
10. The method of claim 9, wherein the diamine monomer comprises one of bis (3-amine-4-hydroxyphenyl) hexafluoropropane, 4, 6-diaminoresorcinol, 2-bis (4-hydroxy-3-aminophenyl) propane, 1, 3-bis (3-hydroxy-4-aminophenoxy) benzene, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
11. The method of claim 9, wherein the dianhydride monomer comprises one of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 1,2,3, 4-cyclopentenetetracarboxylic dianhydride, and 1,2,4, 5-cyclohexanetetracarboxylic dianhydride.
12. A polyimide film obtained by heating the modified polyimide according to any one of claims 1 to 6, wherein the polyimide film is obtained by reacting a transparent polyimide with a curing agent,
the transparent polyimide comprises a color suppression group and an epoxy group, and the curing agent comprises an active ester group which reacts with the epoxy group to bond the transparent polyimide and the curing agent.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009086311A (en) * | 2007-09-28 | 2009-04-23 | Fujifilm Corp | Photosensitive resin composition, pattern manufacturing method using the composition, and electronic device |
| CN103502312A (en) * | 2011-03-07 | 2014-01-08 | 日产化学工业株式会社 | Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN109694555A (en) * | 2018-12-29 | 2019-04-30 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, laminate and high-frequency circuit board comprising it |
| CN110515269A (en) * | 2018-05-22 | 2019-11-29 | 臻鼎科技股份有限公司 | Photosensitve resin composition and preparation method thereof, polymeric membrane and copper-clad plate |
| CN112194792A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | High-strength low-thermal-expansion transparent polyimide and preparation method thereof |
| CN113174231A (en) * | 2020-10-15 | 2021-07-27 | 荒川化学工业株式会社 | Polyimide resin composition, adhesive composition, and related articles |
| CN113403021A (en) * | 2021-07-13 | 2021-09-17 | 宜昌奥马电子材料有限公司 | Composition slurry, preparation method thereof and film |
| TWI749914B (en) * | 2020-11-27 | 2021-12-11 | 臻鼎科技股份有限公司 | Transparent polyimide solution, method for manufacturing the transparent polyimide solution, transparent polyimide film and its application |
-
2022
- 2022-06-21 CN CN202210703818.4A patent/CN115490852A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009086311A (en) * | 2007-09-28 | 2009-04-23 | Fujifilm Corp | Photosensitive resin composition, pattern manufacturing method using the composition, and electronic device |
| CN103502312A (en) * | 2011-03-07 | 2014-01-08 | 日产化学工业株式会社 | Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN110515269A (en) * | 2018-05-22 | 2019-11-29 | 臻鼎科技股份有限公司 | Photosensitve resin composition and preparation method thereof, polymeric membrane and copper-clad plate |
| CN109694555A (en) * | 2018-12-29 | 2019-04-30 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, laminate and high-frequency circuit board comprising it |
| CN112194792A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | High-strength low-thermal-expansion transparent polyimide and preparation method thereof |
| CN113174231A (en) * | 2020-10-15 | 2021-07-27 | 荒川化学工业株式会社 | Polyimide resin composition, adhesive composition, and related articles |
| TWI749914B (en) * | 2020-11-27 | 2021-12-11 | 臻鼎科技股份有限公司 | Transparent polyimide solution, method for manufacturing the transparent polyimide solution, transparent polyimide film and its application |
| CN113403021A (en) * | 2021-07-13 | 2021-09-17 | 宜昌奥马电子材料有限公司 | Composition slurry, preparation method thereof and film |
Non-Patent Citations (2)
| Title |
|---|
| AYUMI KOBAYASHI等: "Preparation of polyimide with pendant glycidyl groups for cationic electrodeposition coatings and evaluation of their properties", 《JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY》 * |
| HAN SUNG YU等: "Synthesis and Chemically Amplified Photo-Cross-Linking Reaction of a Polyimide Containing an Epoxy Group", 《MACROMOLECULES》 * |
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