CN114685790A - Polymer, composition containing same, and polysiloxane-polyimide material - Google Patents
Polymer, composition containing same, and polysiloxane-polyimide material Download PDFInfo
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- CN114685790A CN114685790A CN202110576089.6A CN202110576089A CN114685790A CN 114685790 A CN114685790 A CN 114685790A CN 202110576089 A CN202110576089 A CN 202110576089A CN 114685790 A CN114685790 A CN 114685790A
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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
- C08G73/1057—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
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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
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
A polymer, a composition comprising the same, and a polysiloxane-polyimide material. The polymer comprises a first repeat unit and a second repeat unit. Wherein the first repeating unit has a structure represented by formula (I), and the second repeating unit has a structure represented by formula (II), wherein A1And A3Each independently is a substituted or unsubstituted tetravalent group; a. the2Is a substituted or unsubstituted divalent group; n is more than or equal to 1; m is more than or equal to 1; r1Each independently is hydrogen, C1‑8Alkyl radical, C1‑8Fluoroalkyl radical, C1‑8Alkoxy, or C6‑12An aryl group; r is2Is hydrogen, C1‑8Alkyl radical, C1‑8Fluoroalkyl radical, C1‑8Alkoxy radical, C6‑12Aryl, or reactive functional groups.
Description
Technical Field
The present invention relates to a polymer, a composition comprising the same, and a polysiloxane-polyimide material.
Background
Polyimide has the characteristics of flexibility, sufficient mechanical strength, chemical resistance and the like, and is widely applied to various industries such as plastic industry, electronic industry, aerospace industry and the like.
With the development of display technology, transparent displays have the advantages of being light, thin and transparent, and can combine information on a panel with an entity to provide more information. In recent years, due to the rise of transparent displays, there is an increasing demand for flexible substrates as transparent displays. Polyimide has flexibility and sufficient mechanical strength, and thus is suitable for being used as a substrate of a flexible transparent display. However, some properties of the existing polyimide-based materials still need to be improved to meet the increasingly stringent requirements of display quality.
Disclosure of Invention
The invention provides a polymer. According to an embodiment of the invention, the polymer comprises a first repeat unit and a second repeat unit. The first repeat unit has a structure represented by formula (I), and the second repeat unit has a structure represented by formula (II):
wherein A is1And A3Each independently of the others, is a substituted or unsubstituted tetravalent C6-C25Aryl group, substituted or unsubstituted tetravalent C4-C8Cycloalkyl (cycloalkyl group), substituted or unsubstituted tetravalent C5-C25Heteroaryl (heteroaryl group), substituted or unsubstituted tetravalent C7-C25Alkylaryl (alkylaryl group), alkyl, aryl, or heteroaryl groupSubstituted or unsubstituted tetravalent C7-C25Acylaryl group, substituted or unsubstituted tetravalent C6-C25Aryl ether group, substituted or unsubstituted tetravalent C7-C25Acyloxyaryl (acyloxyaryl group), or substituted or unsubstituted tetravalent C6-C25Sulfonyl aryl (sulfonyl aryl); a. the2Is substituted or unsubstituted C6-C25Arylene group, substituted or unsubstituted C4-C8Cycloalkylene (cycloalkylene group), substituted or unsubstituted C5-C25Heteroarylene (heteroarylene group), substituted or unsubstituted bivalent C7-C25Alkylaryl (alkylaryl group), substituted or unsubstituted divalent C7-C25Acylaryl group, substituted or unsubstituted bivalent C6-C25Aryl ether group, substituted or unsubstituted bivalent C7-C25Acyloxyaryl (acyloxyaryl group), or substituted or unsubstituted divalent C6-C25Sulfonylaryl (sulfoarylaryl); n is more than or equal to 1; m is more than or equal to 1; r1Each independently is hydrogen, C1-8Alkyl radical, C1-8Fluoroalkyl radical, C1-8Alkoxy, or C6-12An aryl group; r2Each independently is hydrogen, C1-8Alkyl radical, C1-8Fluoroalkyl radical, C1-8Alkoxy radical, C6-12Aryl, hydroxy, amino, C2-8Carboxyl (carboxyl group), C2-8Alkenyl, amino, aminoalkyl, C2-8Isocyanate group (isocyanate group), alkylamino group (alkylamino), C3-8Acrylate group (acrylate group), C4-9A methacrylate group (methacrylate group), a glycidyl group (glycidyl group), an oxirane group (oxirane group), an oxetanyl group (oxetanyl group), or a 3,4-epoxycyclohexyl group (3, 4-epoxycyclohexenyl group); and, at least two R2Is hydroxy, amino, C2-8Carboxyl (carboxyl group), C2-8Alkenyl, amino, aminoalkyl(aminoalkyl)、C2-8Isocyanate group (isocyanate group), alkylamino group (alkylamino), C3-8Acrylate group (acrylate group), C4-9Methacrylate group (methacrylate group), glycidyl group (glycidyl group), oxirane group (oxirane group), oxetanyl group (oxetanyl group), or 3,4-epoxycyclohexyl group (3, 4-epoxycyclohexenyl group).
The present invention also provides, according to an embodiment of the present invention, a composition for preparing a polysiloxane-polyimide material. According to an embodiment of the invention, the composition comprises 100 parts by weight of the polymer according to the invention; and 5-40 parts by weight of a crosslinking agent.
According to an embodiment of the present invention, there is also provided a polysiloxane-polyimide material which is a cured product obtained by a crosslinking reaction of the composition of the present invention.
Detailed Description
The polymer, the composition containing the same, and the polysiloxane-polyimide material of the present invention are described in detail below. It is to be understood that the following description provides many different embodiments, or examples, for implementing different aspects of the invention. The specific elements and arrangements described below are merely provided to simplify the description of the invention. These are, of course, merely examples and are not intended to be limiting. In the present invention, the word "about" is used to indicate that the amount specified may increase or decrease in an amount of a size that one of ordinary skill in the art would recognize as being of a general and reasonable size.
Furthermore, the use of ordinal numbers such as "first," "second," "third," etc., in the specification and claims to modify a claim element does not by itself connote any preceding ordinal number of the claimed element, nor is the order in which a claimed element is presented or the order of manufacture of a claimed element, but are used merely to distinguish one claimed element having a certain name from another element having a same name.
The invention provides a polymer, a composition containing the same, and a polysiloxane-polyimide material. By introducing the repeating unit with the polysiloxane group, the polymer provided by the invention has a more rigid chain segment and a softer chain segment at the same time, so that the stress dispersion effect can be achieved. According to the present invention, the polymer can be further matched with a cross-linking agent (or/and an initiator) to prepare the composition of the present invention. It is worth noting that, since the cross-linking agent can react with the polymer of the present invention to form a network cross-linking structure, the rigidity of the structure is enhanced, thereby allowing the stress dispersion between or among molecular chains to be more uniform. Thus, the film layer (i.e., the polysiloxane-polyimide film) prepared from the composition of the present invention has high transparency, good processability, high mechanical properties (high hardness and Young's modulus), and flexibility. According to the embodiment of the present invention, the cured product of the composition of the present invention can be widely applied to the fields of display devices, electro-optical devices, and wearable devices.
According to an embodiment of the invention, the polymer comprises a first repeat unit and a second repeat unit. The first repeat unit has a structure represented by formula (I), and the second repeat unit has a structure represented by formula (II):
wherein A is1And A3Each independently of the others, is a substituted or unsubstituted tetravalent C6-C25Aryl (aryl group), substituted or unsubstituted tetravalent C4-C8Cycloalkyl (cycloalkyl group), substituted or unsubstituted tetravalent C5-C25Heteroaryl (heteroaryl group), substituted or unsubstituted tetravalent C7-C25Alkylaryl (alkylaryl group), substituted or unsubstituted tetravalent C7-C25Acylaryl group, substituted or unsubstituted tetravalent C6-C25Aryl ether group, substituted or unsubstituted tetravalent C7-C25Acyloxyaryl (acyloxyaryl group), or substituted or unsubstituted tetravalent C6-C25Sulfonylaryl (sulfoarylaryl); a. the2C which may be substituted or unsubstituted6-C25Arylene group, substituted or unsubstituted C4-C8Cycloalkylene (cycloalkylene group), substituted or unsubstituted C5-C25Heteroarylene (heteroarylene group), substituted or unsubstituted bivalent C7-C25Alkylaryl (alkylaryl group), substituted or unsubstituted divalent C7-C25Acylaryl group, substituted or unsubstituted bivalent C6-C25Aryl ether group, substituted or unsubstituted bivalent C7-C25Acyloxyaryl (acyloxyaryl group), or substituted or unsubstituted divalent C6-C25Sulfonyl aryl (sulfonyl aryl); n is more than or equal to 1; m is more than or equal to 1; r1Can be each independently hydrogen, C1-8Alkyl radical, C1-8Fluoroalkyl radical, C1-8Alkoxy, or C6-12An aryl group; and R2Can be each independently hydrogen, C1-8Alkyl radical, C1-8Fluoroalkyl radical, C1-8Alkoxy radical, C6-12Aryl, hydroxy, amino, C2-8Carboxyl (carboxyl group), C2-8Alkenyl, amino, aminoalkyl, C2-8Isocyanate group (isocyanate group), alkylamino group (alkylamino), C3-8Acrylate group (acrylate group), C4-9Methacrylate group (methacrylate group), glycidyl group (glycidyl group), oxirane group (oxirane group), oxetanyl group (oxetanyl group), or 3,4-epoxycyclohexyl group (3, 4-epoxycyclohexenyl group). In order to make the polymers of the invention reactive with crosslinking agents to form crosslinked networks, at least two R' s2Can be a reactive functional group, e.g. at least two R2Each independently is hydroxy, amino, C2-8Carboxyl (carboxyl group), C2-8Alkenyl, amino, aminoalkyl, C2-8Isocyanate group (isocyanate group), alkylamino group (alkyl)amino)、C3-8Acrylate group (acrylate group), C4-9Methacrylate group (methacrylate group), glycidyl group (glycidyl group), oxirane group (oxirane group), oxetanyl group (oxetanyl group), or 3,4-epoxycyclohexyl group (3, 4-epoxycyclohexenyl group). According to an embodiment of the present invention, if two R2Being a reactive functional group, the two R2Are bonded to the same Si atom or to different Si atoms, respectively.
According to embodiments of the present invention, the number of the first repeating unit of the polymer may be 2 to 2,000 (e.g., 2 to 1,800, 5 to 1,500, or 10 to 1,200), and the number of the first repeating unit of the polymer may be 2 to 18,000 (e.g., 2 to 16000, 5 to 13,500, or 10 to 11,000). According to an embodiment of the present invention, the first repeating unit and the second repeating unit may be arranged in a random manner or a block manner. According to embodiments of the invention, the weight average molecular weight (Mw) of the polymer may be about 5,000 to 300,000, such as 5,000 to 250,000, 5,000 to 200,000, 5,000 to 180,000, or 5,000 to 150,000. The weight average molecular weight (Mw) of the oligomer or polymer of the present invention can be measured by Gel Permeation Chromatography (GPC) (calibration line is prepared using polystyrene as a standard). According to embodiments of the present invention, the ratio of the number of the first repeating unit to the second repeating unit may be 95:5 to 75:25, such as 90:10, 85:15, or 80: 20. If the ratio of the number of the first repeating unit to the second repeating unit is too high, the resulting polymer has too high a hard segment, resulting in a decrease in ductility and flexibility of a cured product (i.e., a polysiloxane-polyimide film) of the subsequently obtained composition. If the ratio of the number of the first repeating unit to the second repeating unit is too low, the resulting polymer has too high a soft segment, resulting in a decrease in hardness and Young's modulus of a cured product of the subsequently obtained composition.
According to an embodiment of the present invention, in the second repeating unit, there is provided
Radicals of the structure and having
The groups of the structure are arranged in a random manner. According to an embodiment of the invention, 99. gtoreq.n.gtoreq.60, such as 61, 62, 63, 64, 65, 66,67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, or 98; 40 ≧ m ≧ 1, e.g., 2,3,4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, or 39. According to embodiments of the present invention, in order to provide a network-like cross-linked structure formed from the polymer with both high mechanical properties and flexibility, the ratio of n to m may be 3:2 to 99: 1. According to an embodiment of the present invention, in the second repeating unit, there is provided
The molecular weight of the groups of the structure may be 500 to 3,000. If it has
Too high a molecular weight of the structural group leads to a decrease in hardness and Young's modulus of a cured product (i.e., a polysiloxane-polyimide film) of a subsequently obtained composition.
According to an embodiment of the invention, if A1(or/and A)3) In the case of a substituted tetravalent radical, at least one hydrogen of the tetravalent radical (e.g. hydrogen on carbon) may be replaced by fluorine, C1-6Alkyl, or C1-6Fluoroalkyl groups. If A2In the case of a substituted divalent radical, at least one hydrogen of the divalent radical (e.g. a hydrogen on carbon) may be replaced by fluorine, C1-6Alkyl, or C1-6Fluoroalkyl groups.
According to an embodiment of the invention, A1And A3Can each independently be
Wherein A is1And A3The position marked with an asterisk (—) is attached to the carbonyl; z is a single bond, -O-, -SO2-、-C(CH3)2-、-C(CF3)2-、
And, R3Can be hydrogen, fluorine, C1-6Alkyl, or C1-6A fluoroalkyl group.
According to an embodiment of the invention, A2(may be)
Wherein A is2The position indicated by an asterisk (—) is linked to the nitrogen (which may be the nitrogen of the first repeat unit or the second repeat unit); y is a single bond, -O-, -C (CH)3)2-、-C(CF3)2-、
And, R4Can be hydrogen, fluorine, C1-6Alkyl, or C1-6A fluoroalkyl group.
In accordance with the inventionAlternatively, the polymer may have a plurality of first repeat units, and each A1May be the same or different, and each A2May be the same or different. The polymer may have a plurality of second repeating units, and each A3May be the same or different.
According to an embodiment of the present invention, C1-8The alkyl group may be a linear or branched (linear or branched) chain alkyl group. For example, C1-8The alkyl group may be methyl (methyl), ethyl (ethyl), propyl (propyl), butyl (butyl), pentyl (pentyl), hexyl (hexyl), heptyl (heptyl), octyl (octyi), or isomers thereof (isomer). According to an embodiment of the present invention, C1-8Fluoroalkyl refers to an alkyl group in which all or part of the hydrogens on the carbon are replaced with fluorine, and may be straight (linear) or branched (branched), such as fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl, fluorohexyl, or isomers thereof (isomer). Here, the fluoromethyl group according to the present invention may be a monofluoromethyl group, a difluoromethyl group, or a perfluoromethyl group, and the fluoroethyl group may be a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, or a perfluoroethyl group. According to an embodiment of the present invention, the alkylene group of the present invention may be a linear or branched alkylene group. According to an embodiment of the present invention, the alkenyl group of the present invention may be a linear or branched (linear or branched) alkenyl group. According to an embodiment of the present invention, C1-8The alkoxy group may be a linear or branched (linear or branched) alkyl group. For example, C1-8The alkoxy group may be methoxy (methoxy), ethoxy (ethoxy), propoxy (propoxy), butoxy (butoxy), pentoxy (pentoxy), hexoxy (hexoxy), heptoxy (heptoxy), octoxy (octoxy), or isomers thereof.
According to an embodiment of the present invention, the method of preparing the polymer may comprise the following steps. First, a precursor composition is provided, wherein the precursor composition comprises a dianhydride compound, a first diamine, and a second diamine. According to an embodiment of the present invention, the precursor composition may further comprise a solvent such that the dianhydride compound, the first diamine, and the second diamine are uniformly dispersed in the solvent. Then, the precursor composition is imidized to obtain the polymer of the present invention. Methods of imidizing the precursor composition include thermal imidization. The thermal imidization may be carried out at a temperature of 300 to 500 ℃ for 4 to 8 hours, for example, at a temperature of 400 ℃ for 6 hours. According to embodiments of the invention, the ratio of the number of moles of the dianhydride compound to the sum of the number of moles of the first diamine and the second diamine may be about 12:1 to 1: 1.2. According to embodiments of the invention, the molar ratio of the first diamine to the second diamine can be about 95:5 to 75:25 (e.g., 90:10, 85:15, or 80: 20).
According to an embodiment of the present invention, the dianhydride compound may be
Wherein Z is a single bond, -O-, -SO2-、-C(CH3)2-、-C(CF3)2-、
And, R3Is hydrogen, C1-6Alkyl, or C1-6A fluoroalkyl group. According to an embodiment of the present invention, the dianhydride compound may be pyromellitic dianhydride (PMDA), hydrogenated pyromellitic dianhydride (H-PMDA), 4' -2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (4,4' - (hexafluoroisopropanol) -phthalic anhydride, 6FDA), 4' -oxydiphthalic anhydride (4,4' -oxydiphthalic anhydride, ODPA), 1,3-bis (4-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) b)enzene, RODA), 4 '-phthalic acid dianhydride (4,4' -biphthalic dianhydride, BPDA), 4'-bisphenol a dianhydride (4,4' -biphenol a dianhydride, BPADA), p-phenylene bis (trimellitate) dianhydride (p-phenylene bis (trimellitate) dianhydride, TAHQ), hydroquinone bis (phthalic anhydride, hqd), bicyclo [ 2.2.2.2)]Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicyclo [ 2.2.2)]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, B1317), or a mixture thereof.
According to an embodiment of the present invention, the first diamine may be
Y may be a single bond, -O-, -C (CH)3)2-、-C(CF3)2-、
And, R4Can be hydrogen or C1-6Alkyl, or C1-6A fluoroalkyl group. According to an embodiment of the present invention, the first diamine compound may be m-tolidine (m-toluene diamine, m-TB), m-phenylenediamine (m-phenylenediamine, m-PDA), p-phenylenediamine (p-phenylenediamine, p-PDA), 4 '-diaminodiphenyl ether (4,4' -oxydianiline, 4'-ODA),3,4' -diaminodiphenyl ether (3,4'-oxydianiline, 3,4' -ODA), 1,4-bis (4-aminophenoxy) benzene (1,4-bis (4-aminophenoxy) benzene, 1,4-APB), 1,3-bis (4-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene, 1,3-APB), 1,2-bis (4-aminophenoxy) benzene (1,2-bis (4-aminophenoxy) benzene, 1,2-APB), 1,3-bis (3-aminophenoxy) benzene(1,3-bis (3-aminophenoxy) bezene, APB-133), 2,5-bis (4-aminophenoxy) toluene) (2,5-bis (4-aminophenoxy) toluene), bis (4- [ 4-aminophenoxy) toluene]Phenyl) ether (Bis (4- [ 4-aminophenyloxy)]phenyl) ether, BAPE), 4'-bis (4-aminophenoxy) biphenyl (4,4' -bis [ 4-aminophenoxy)]biphenol, BAPB), 2' -bis [4- (4-aminophenoxyphenyl)]Propane (2,2-bis [4- (4-aminophenoxy)]phenyl propane, BAPP), 4' -Bis (4-aminophenoxy) phenylsulfone (Bis- (4- (4-aminophenoxy) phenyl sulfone, BAPS), 2' -Bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2' -Bis (trifluoromethylphenyl) 4,4' -diaminobiphenyi, TFMB), 2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoro-propane, BAHF), or a mixture thereof.
According to an embodiment of the present invention, the second diamine may have the structure
Wherein R is1、R2N, and m are as defined above. According to an embodiment of the present invention, the molecular weight of the second diamine may be 500 to 3,000.
According to the embodiment of the present invention, the solvent is not limited, and may be xylene (xylene), toluene (toluene), tetramethylbenzene, methyl isobutyl ketone, methyl ethyl ketone, ethyl lactate or cyclohexenone, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), Methyl Ethyl Ketone (MEK), N-dimethylacetamide (N, N-dimethylacetamide, DMAc), gamma-butyrolactone (GBL), N-Dimethylformamide (N, N-Dimethylformamide, DMF), dimethyl sulfoxide (DMSO), or a combination thereof.
The present invention also provides, according to an embodiment of the present invention, a composition for preparing a polysiloxane-polyimide material. The composition of the present invention may comprise the above-mentioned polymer and a crosslinking agent. According to embodiments of the invention, the polymer may be present in an amount of 100 parts by weight, and the crosslinking agent may be present in an amount of about 5 to 40 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, or 35 parts by weight. If the content of the crosslinking agent is too low, the degree of crosslinking of the network-like crosslinked structure becomes insufficient, and the hardness and Young's modulus of a cured product of the composition are lowered. If the content of the crosslinking agent is too high, the degree of crosslinking of the network-like crosslinked structure becomes too high, resulting in a decrease in ductility and flexibility of the cured product of the composition.
According to an embodiment of the present invention, the crosslinking agent may be a polyol (e.g., a diol, a triol, or a tetraol), a compound having at least two acrylate groups (acrylate groups) or methacrylate groups (methacrylate groups), or a combination thereof.
According to an embodiment of the present invention, the crosslinking agent may be 1,3-propanediol (1,3-propanediol), 2,3,4-trimethyl-1,3-pentanediol (2,3,4-trimethyl-1,3-pentanediol), 2-butene-1,4-diol (2-butene-1,4-diol), 1,4-butanediol (1, 4-butandiol), 1,3-butanediol (1, 3-butandiol), 1,5-pentanediol (1, 5-pentandiol), 1,6-hexanediol (1,6-hexanediol), 1,2-cyclohexanedimethanol (1,2-cyclohexanedimethanol), 1,2-hexanediol (1,2-hexanediol), 1,3-hexanediol (1,3-hexanediol), 2-methyl-1,3-propanediol (2-methyl-1,3-propanediol), 2,5-hexanediol (2,5-hexanediol), 2-methyl-1,3-pentanediol (2-methyl-1,3-pentanediol), 2-methyl-2,4-pentanediol (2-methyl-2,4-pentanediol), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol), tetraethylene glycol (tetraethylene glycol), polyethylene glycol (polyethylene glycol), propylene glycol (propylene glycol), dipropylene glycol (dipropylene glycol), polypropylene glycol (polypropylene glycol), tripropylene glycol (polypropylene glycol), glycerol (glycerol), polyethylene glycol (glycerol), carbonic acid ester (carbonic acid ester), carbonic acid ester (carbonate), propylene carbonate (1, 2-carbonate), propylene carbonate (carbonate), and propylene carbonate (1, 2-methyl-2, 4-pentanediol).
According to an embodiment of the present invention, the cross-linking agent may be dioxane glycol diacrylate (dioxane glycol diacrylate), 3-hydroxy-2, 2-dimethylpropionic acid 3-hydroxy-2, 2-dimethylpropyl diacrylate (hydroxypropyl methacrylate), 1,6-hexanediol diacrylate (1,6-hexanediol diacrylate), ethoxylated1,6-hexanediol diacrylate (ethoxylated1,6-hexanediol diacrylate), dipropylene glycol diacrylate (dipropylene glycol diacrylate), tripropylene glycol diacrylate (tripropylene glycol diacrylate), tricyclodecane dimethanol diacrylate (tricyclodecane dimethanol diacrylate), polyethylene glycol (200) diacrylate (polyethylene glycol (200) diacrylate), polyethylene glycol (400) diacrylate (polyethylene glycol (400)), polyethylene glycol (600) molecular weight 400 (400)), polyethylene glycol (600) diacrylate (400) molecular weight 400 (400), polyethylene glycol (400) molecular weight 400 (400)), or polyethylene glycol (400) diacrylate (400) molecular weight 400 (400), Polyethylene glycol (200) dimethacrylate (MW 200)), polyethylene glycol (400) dimethacrylate (MW 400), polypropylene glycol diacrylate (polypropylene glycol diacrylate), 2-hydroxyethyl methacrylate phosphate (2-hydroxyethyl methacrylate phosphate), neopentyl glycol diacrylate (vinylic glycol diacrylate), propoxylated neopentyl glycol diacrylate (propoxylated neopentyl glycol diacrylate), ethoxylated bisphenol A diacrylate (ethoxylated bisphenol-A diacrylate), ethoxylated bisphenol A dimethacrylate (ethoxylated bisphenol-A diacrylate), 2-methyl-1,3-propanediol diacrylate (2-methyl-1,3-propanediol diacrylate), 3-propanediol diacrylate), 2-butyl-2-ethyl-1,3-propanediol diacrylate (2-butyl-2-ethyl-1,3-propanediol diacrylate), Ethylene Glycol Dimethacrylate (EGDMA), triethylene glycol dimethacrylate (triethylene glycol dimethacrylate), diethylene glycol dimethacrylate (diethylene glycol dimethacrylate), 1,4-butanediol diacrylate (1,4-butanediol diacrylate), 1,6-hexanediol dimethacrylate (1,6-hexanediol dimethacrylate), allyl cyclohexyl dimethacrylate (allyl cyclohexyl dimethacrylate), diethylene glycol dimethacrylate (diethylene glycol dimethacrylate), triethylene glycol dimethacrylate (2-hydroxyethyl isocyanurate) and triethylene glycol dimethacrylate (2-hydroxyethyl isocyanurate), Pentaerythritol triacrylate (pentaerythrityl triacrylate), ethoxylated trimethylolpropane triacrylate (ethoxylated trimethylolpropane triacrylate), ethoxylated trimethylolpropane trimethacrylate (ethoxylated trimethylolpropane trimethacrylate), propoxylated trimethylolpropane triacrylate (propoxylated trimethylolpropane triacrylate), trimethylolpropane trimethacrylate (trimethopropane trimethacrylate), trimethylolpropane triacrylate (trimethopropylpropionate), pentaerythritol triacrylate (pentaerythrityl triacrylate), ethoxylated pentaerythritol triacrylate (ethoxylated pentaerythritol triacrylate), propoxylated pentaerythritol triacrylate (pentaerythritol tetraacrylate), pentaerythritol tetraacrylate, pentaerythritol (pentaerythritol tetraacrylate), pentaerythritol (pentaerythritol tetraacrylate), pentaerythritol tetraacrylate, pentaerythritol (pentaerythritol tetraacrylate), pentaerythritol (pentaerythritol, pentaerythritol tetraacrylate, pentaerythritol, Dipentaerythritol tetraacrylate (tetramethylethylene tetraacrylate), or combinations of the foregoing.
According to an embodiment of the present invention, the composition of the present invention may further comprise an initiator, such as a photoinitiator, or a thermal initiator. According to an embodiment of the present invention, the content of the initiator is not particularly limited, and may be 0.1 parts by weight to 15 parts by weight. According to an embodiment of the present invention, the photoinitiator may be a benzoin-based compound, an acetophenone-based compound, a thioxanthone-based compound, a ketal (ketal) compound, a benzophenone-based compound, an α -aminoalkylbenzophenone (α -aminoalkylenone) compound, an acylphosphine oxide (acylphosphine oxide) compound, a diazole-based compound, a triazine-based compound, or a combination thereof.
Benzoin-based compounds, such as benzoin (benzoin), benzoin methyl ether (benzoin methyl ether), benzoin dimethyl ether (benzoin dimethyl ether), or other suitable benzoins; acetophenone-based compounds, such as p-dimethylaminoacetophenone (p-dimethylaminoacetophenone), α '-dimethoxyazoxyacetophenone (α, α' -dimethoxyazoxy-acetophenone), 2 '-dimethyl-2-phenylacetophenone (2,2' -dimethyl-2-phenyl-acetophenone), p-methoxyacetophenone (p-methoxy-acetophenone), 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone (2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone), 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone (2-benzyl-2-N, n-dimethylimine-1- (4-morpholinophenyl) -1-butanone); benzophenone-based compounds such as benzophenone, 4,4-bis (dimethylamino) benzophenone (4,4-bis (dimethylamino) benzophenone), 4,4-bis (diethylamino) benzophenone (4,4-bis (dimethylamino) benzophenone), 2,4,6-trimethylaminobenzophenone (2,4,6-trimethylaminobenzophenone), methylphthaloyl (methyl-o-benzophenone), 3-dimethyl-4-methoxybenzophenone (3, 3-dimethyl-4-methylphenophenone), and 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone (3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone); thioxanthone-based compounds such as thioxanthone (thioxanthone), 2, 4-diethylthioxanthone (2, 4-diethyl-thioxanthone), thioxanthone-4-sulfone (thioxanthone-4-sulfone); diimidazole compounds, for example 2,2'-bis (o-chlorophenyl) -4,4', 5,5 '-tetraphenyldiimidazole [2, 2' -bis (o-chlorophenyl) -4,4', 5, 5' -tetraphenyldiimidazole ], 2'-bis (o-fluorophenyl) -4,4', 5,5 '-tetraphenyldiimidazole [2, 2' -bis (o-fluorophenylyl) -4,4', 5, 5' -tetraphenyldiimidazole ], 2'-bis (o-methylphenyl) -4,4', 5,5 '-tetraphenyldiimidazole [2, 2' -bis (o-methylphenyl) -4,4', 5, 5' -tetraphenyldiimidazole ], 2'-bis (o-methoxyphenyl) -4,4', 5,5 '-tetraphenyldiimidazole, 2' -bis (o-methoxyphenyl) -4,4', 5, 5' -tetraphenyldiimidazole [2, 2'-bis (o-methoxyphenyl) -4,4', 5,5 '-tetraphenyldiimidazole ], 2' -bis (o-ethylphenyl) -4,4', 5, 5' -tetraphenyldiimidazole [2, 2'-bis (o-ethylphenyl) -4,4', 5,5 '-tetraphenyldiimidazole ], 2' -bis (p-methoxyphenyl) -4,4', 5, 5' -tetraphenyldiimidazole [2, 2'-bis (p-methoxyphenyl) -4,4', 5,5 '-tetraphenyldiimidazole ], 2' -bis (2,2', 4,4' -tetramethoxyphenyl) -4,4', 5, 5' -tetraphenyldiimidazole [2, 2' -bis (2,2', 4,4' -tetramethylxyphenyl) -4,4', 5,5 ' -tetraphenyldiazole, 2' -bis (2-chlorophenyl) -4,4', 5,5 ' -tetraphenyldiimidazole [2, 2' -bis (2-chlorophenyl) -4,4', 5,5 ' -tetraphenyldiimidazole ], 2' -bis (2,4-dichlorophenyl) -4,4', 5,5 ' -tetraphenyldiimidazole [2, 2' -bis (2,4-dichlorophenyl) -4,4', 5,5 ' -tetraphenyldiimidazole ]; phosphine oxide-based compounds such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (2,4, 6-trimethylbenzoyldiphenylphosphine oxide) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide); the triazine compound is, for example, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid (3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid), ethyl 1,1,1,3,3,3-hexafluoroisopropyl-3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoate (1,1,1,3,3,3-hexafluoroisopropyl-3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoate), ethyl-2- {4- [2,4-bis (trichloromethyl-s-triazin-6-yl ] phenylthio } propanoate, ethyl-2- {4- [2,4-bis (trichloromethyl-s-triazin-6-yl ] phenylthio } propanoic acid methyl acetate Esters (ethyl-2- {4- [2,4-bis (trichloromethyl) -s-triazon-6-yl ] phenylthio } acetate), methyl 2-oxiranyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate (2-epoxyeth-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate), methyl cyclohexyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate (cyclohexexyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate), Benzyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetic acid methyl ester (benzyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate), 3- { chloro-4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid (3- { chloro-4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid), 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanamide (3- {4- [2,4-bis (trichloromethyl) -s-triazon-6-yl ] phenylthio } propionide), 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine (2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine), 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1, 3-butadienyl-s-triazine (2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3, -butadienyl-s-triazine), or 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine (2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine).
According to an embodiment of the present invention, the thermal initiator may be an azo (azo) compound, a cyanovaleric acid-based compound, a peroxide (peroxide), or a combination thereof. The azo compounds include, for example, 2' -azobis (2, 4-dimethyl-N-valeronitrile) (2,2' -azobis (2,4-dimethyl valeronitrile)), dimethyl-2, 2' -azobis (methyl 2-propionate) (dimethyl2, 2' -azobis (2-methyl propionate)), 2-azobis (2-methylisobutyronitrile) (hereinafter, AIBN), 2-azobis (2-methylisobutyronitrile) (2,2-azobis (2-methylisobutyronitrile)), 1 ' -azobis (cyclohexane-1-carbonitrile) (1,1 ' -azobis (cyclohexane-1-carbonitrile)), 2' -azobis [ N-2-propenyl-2-methylpropionamide ] (2,2' -azobis [ N- (2-propylpropionic acid) -2-methylpropionamide ]) (2,2' -azobis [ N- (2-methylisopropyl) -2-propionamide ]), 1- [ (cyano-1-methylethyl) -azo ] carboxamide (1- [ (cyclo-1-methylethyl) azo ] formamide), 2 '-azobis (N-butyl-2-methylpropionamide) (2,2' -azobis (N-butyl-2-methylpropionamide)), 2 '-azobis (N-cyclohexyl-2-methylpropionamide) (2,2' -azobis (N-cyclohexyl-2-methylpropionamide)), or other suitable azo group; such peroxides, for example, benzoyl peroxide (benzoyl peroxide), 1-bis (t-butylperoxy) cyclohexane (1,1-bis (tert-butylperoxy) cyclohexane), 2,5-bis (t-butylperoxy) -2,5-dimethylcyclohexane (2,5-bis (tert-butylperoxy) -2,5-dimethylcyclohexane), 2,5-bis (t-butylperoxy) -2,5-dimethyl-3-cyclohexyne (2,5-bis (tert-butylperoxy) -2,5-dimethyl-3-cyclohexyne), bis (1- (t-butylperoxy) -1-methylethyl) benzene (bis (1- (tert-butylperoxy) -1-methyl-ethyl) benzene), t-butyl hydroperoxide (tert-butyl-hydroxy) benzene, and tert-butyl hydroperoxide (tert-butyl-hydroxy) benzene, T-butyl peroxide (tert-butyl peroxide), t-butyl peroxybenzoate (tert-butyl peroxybenzoate), cumene hydroperoxide (cumene hydroperoxide), cyclohexanone peroxide (cyclohexanone peroxide), dicumyl peroxide (dicumyl peroxide), lauroyl peroxide (lauroyl peroxide), or other suitable peroxides.
According to an embodiment of the present invention, the composition may further comprise a solvent, wherein the polymer, the crosslinking agent, and the initiator are uniformly dispersed in the solvent. The solvent adjusts the viscosity of the composition such that the composition can form a coating on a substrate by a coating process. The solvent can be any inert solvent that can dissolve or disperse the components of the adhesive composition, but does not react with the components. By way of example, solvents that may be used to dissolve or disperse the components of the adhesive composition include, but are not limited to: xylene (xylene), toluene (toluene), tetramethylbenzene, methyl isobutyl ketone, methyl ethyl ketone, ethyl lactate or cyclohexenone, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), Methyl Ethyl Ketone (MEK), N-dimethylacetamide (DMAc), γ -butyrolactone (γ -butyrolactone, GBL), N-Dimethylformamide (N, N-Dimethylformamide, DMF), or dimethyl sulfoxide (DMSO). The respective solvents may be used alone or in any combination. The amount of the solvent used is not particularly limited, and may be in principle any amount that can uniformly dissolve or disperse the components of the resin composition.
According to an embodiment of the present invention, the composition of the present invention may further comprise other components, such as additives known in the art, as necessary, in order to improve the physicochemical properties of the composition and its cured product. Examples of such known additives include, but are not limited to: flame retardants, viscosity modifiers, thixotropic agents (thixotropic agents), defoamers, leveling agents (leveling agents), surface treatment agents, stabilizers, ring-closure promoters, and antioxidants. The additives may be used alone or in combination. The amount of the above additives is not particularly limited, and can be adjusted as required according to the general knowledge of the person skilled in the art after viewing the disclosure of the present invention.
According to an embodiment of the invention, the composition according to the invention does not comprise other organic or inorganic polymers than the polymer according to the invention.
According to an embodiment of the present invention, there is also provided a polysiloxane-polyimide material, wherein the polysiloxane-polyimide material is a cured product obtained by a crosslinking reaction of the above composition. According to an embodiment of the present invention, the method for preparing the polysiloxane-polyimide material may include the following steps. First, a composition according to the present invention is provided. Then, the composition is coated on the substrate by a coating process. Then, the coating is cured to perform a cross-linking reaction to form a film (i.e., a polysiloxane-polyimide film). The temperature of the curing process may be about 80-220 ℃, and the time of the process may be 30 minutes to 4 hours. In addition, before the coating is cured, the coating may be baked to remove the solvent of the resin composition. When the composition is cured, the polysiloxane chain segment of the polymer has a reactive functional group, and can be subjected to crosslinking reaction with the crosslinking agent to form a network crosslinking structure, so that the polysiloxane-polyimide film with high transparency, high rigidity, high hardness and flexibility is obtained. According to an embodiment of the present invention, the composition may be applied by screen printing, spin coating, bar coating, blade coating, roller coating, dip coating, spray coating, or brush coating. The material of the substrate is not limited, and may be, for example, a resin polymer material, a fiber, a silicon substrate, glass, metal, or a transparent film, and any desired film layer may be formed on the substrate.
In addition, although the polysiloxane-polyimide material in the example may be a thin film, the present invention is not limited thereto. The polysiloxane-polyimide material can also be used as coating, fiber, foam plastic, photoresist, orientation aligning agent for liquid crystal display, waveguide material, optical switch material, etc.
In order to make the aforementioned and other objects, features, and advantages of the present invention comprehensible, several embodiments accompanied with figures are described in detail below:
preparation of the composition
Example 1
Mixing 4,4'-2, 2' -bis (3)4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA) (50 parts by mole), bicyclo [2.2.2]]Octyl-7-ene-2, 3,5,6-tetracarboxylic dianhydride (B1317) (50 parts by mol), 2'-bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2'-bis (trifluoromethyl)4,4' -diaminobiphenol, TFMB) (90 parts by mol), and polysiloxane diamine (structure: polysiloxane diamine
n>1；m>1; n is 6: 4; r1is-CH3(ii) a And a R2Being an acrylate group, another R2is-CH3) (molecular weight: about 1280) (10 molar parts), and gamma-Butyrolactone (gamma-Butyrolactone) were added to the reaction flask to obtain a solution (solid content: about 5 wt%). Next, the above solution was reacted at 220 ℃ for 4 hours to obtain a solution having the polymer of the present invention. Next, a crosslinking agent (pentaerythritol triacrylate) (product number ARONIX M-306, available from Toagosei Co., Ltd.) (10 parts by mole) was added to the solution with the polymer described in the present invention to obtain composition (1).
Example 2
Example 2 composition (2) was obtained by proceeding in the same manner as described in example 1, except that TFMB was decreased from 90 molar parts to 80 molar parts and the polysiloxane diamine was increased from 10 molar parts to 20 molar parts.
Example 3
Example 3 composition (3) was obtained by proceeding in the same manner as described in example 2, except that the crosslinking agent was increased from 10 parts by mole to 20 parts by mole.
Example 4
Example 4 was conducted in the same manner as described in example 2 except that the crosslinking agent was increased from 10 parts by mole to 30 parts by mole to obtain composition (4).
Example 5
4,4'-2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA) (50 parts by mole), bicyclo [2.2.2]Octyl-7-ene-2, 3,5,6-tetracarboxylic dianhydride (B1317) (50 parts by mol), 2'-bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2'-bis (trifluoromethyl)4,4' -diaminobiphenol, TFMB) (80 parts by mol), and polysiloxane diamine (structure: polysiloxane diamine
n>1；m>1; n is 6: 4; r is1is-CH3(ii) a And a R2Being an acrylate group, another R2is-CH3) (molecular weight: about 1280) (20 molar parts), and gamma-Butyrolactone (gamma-Butyrolactone) were added to the reaction flask to obtain a solution (solid content: about 5 wt%). Next, the above solution was reacted at 220 ℃ for 4 hours to obtain a solution having the polymer of the present invention. Next, a crosslinking agent (polypropylene glycol diacrylate) (trade name: ARONIX M-225, available from Toagosei Co., Ltd.) (20 parts by mole) was added to the solution with the polymer described in the present invention to obtain composition (5).
Comparative example 1
4,4'-2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA) (50 parts by mole), bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (B1317) (50 parts by mole), 2'-bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2'-bis (trifluoromethyl)4,4' -diaminobiphenol, TFMB) (100 parts by mole), and gamma-Butyrolactone (gamma-Butyrolactone) were added to a reaction flask to obtain a solution (solid content: about 5% by weight). Subsequently, the above solution was reacted at 220 ℃ for 4 hours to obtain composition (6).
Comparative example 2
4,4'-2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA) (50 parts by mole), bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (B1317) (50 parts by mole), 2'-bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2'-bis (trifluoromethyl)4,4' -diaminobiphenol, TFMB) (100 parts by mole), and gamma-Butyrolactone (gamma-Butyrolactone) were added to a reaction flask to obtain a solution (solid content about 5% by weight). Subsequently, after the above solution was reacted at 220 ℃ for 4 hours, a crosslinking agent (pentaerythritol triacrylate) (product number ARONIX M-306, available from Toagosei Co., Ltd.) (30 parts by mol) was added to the resulting solution to obtain composition (7).
Comparative example 3
Comparative example 3 was conducted in the same manner as described in comparative example 2, except that the crosslinking agent was increased from 30 parts by mole to 50 parts by mole to obtain composition (8).
Comparative example 4
Comparative example 4 was conducted in the same manner as described in example 2 except that the crosslinking agent was increased from 10 parts by mole to 50 parts by mole to obtain composition (9).
Comparative example 5
Comparative example 5 was conducted in the same manner as described in example 3 except that TFMB was decreased from 80 to 70 molar parts and polysiloxane diamine was increased from 20 to 30 molar parts to give composition (10).
Comparative example 6
Comparative example 6 was conducted in the same manner as described in example 3 except that TFMB was decreased from 80 parts by mole to 60 parts by mole and polysiloxane diamine was increased from 20 parts by mole to 40 parts by mole to give composition (11).
Next, the compositions (1) to (11) obtained in examples 1 to 5 and comparative examples 1 to 6 were applied to glass by a doctor blade method to form a coating layer (having a thickness of about 20 μm). And then, baking the coating at 80-220 ℃ for 30 minutes to 4 hours to carry out crosslinking reaction and curing on the coating, thereby respectively obtaining film layers. Next, the transmittance, young's modulus, tensile elongation, and hardness of the obtained film were measured, and the flexibility of the film was evaluated, and the results are shown in table 1. The transmittance is measured according to the method specified in ASTM D1746. Young's modulus was determined according to ASTM D882-12 standard test method. Tensile elongation was measured by a method specified in ASTM D412 using a universal tensile machine. Hardness was measured according to the method specified in ASTM D2240. The flexibility evaluation method is to lay the film flat, fold it in half at 180 degrees, repeat the above actions more than ten times, record the film no fracture as O, and record the film fracture as X.
TABLE 1
As can be seen from table 1, when the number ratio of the first repeating unit to the second repeating unit (i.e. the molar ratio of TFMB to polysiloxane diamine) of the polymer of the present invention is between 95:5 and 75:25, the film obtained after crosslinking the composition comprising the same (i.e. the composition described in examples 1-5) can have high transparency, suitable young's modulus, suitable tensile elongation, high hardness, and flexibility. Furthermore, when the polymer had only the first repeating unit (i.e., no polysiloxane diamine added) (comparative examples 2-3), the film layer prepared from the composition was less flexible because the resulting polymer did not contain the second repeating unit described in the present invention. In addition, when no crosslinking agent was added (comparative example 1), the film layer prepared from the composition was inferior in Young's modulus and hardness. When an excessive amount of the crosslinking agent was added (comparative example 4), the film layer prepared from the composition was inferior in tensile elongation and flexibility. Furthermore, when the ratio of the number of the first repeating unit to the number of the second repeating unit (i.e., the molar ratio of TFMB to polysiloxane diamine) is less than 75:25, the mechanical strength of the resulting film after crosslinking of the composition comprising the same (i.e., the composition described in comparative examples 1-5) is significantly reduced.
Example 6
4,4'-2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA) (50 parts by mole), bicyclo [2.2.2]Octyl-7-ene-2, 3,5,6-tetracarboxylic dianhydride (B1317) (50 parts by mol), 2'-bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2'-bis (trifluoromethyl)4,4' -diaminobiphenol, TFMB) (80 parts by mol), and polysiloxane diamine (structure: polysiloxane diamine
n>1；m>1; n is 6: 4; r1is-CH3or-C6H5(ii) a And one R2Is an acrylate group, another R2is-CH3) (molecular weight: about 1520) (20 molar parts), and gamma-Butyrolactone (gamma-Butyrolactone) were charged into a reaction flask to give a solution (solids content: about 5 wt%). Next, the above solution was reacted at 220 ℃ for 4 hours to obtain a solution having the polymer of the present invention. Next, a crosslinking agent (pentaerythritol triacrylate) (product number ARON)IX M-306, available from Toagosei Co., Ltd. (20 parts by mol), was added to the solution with the polymer according to the invention to give composition (12).
Example 7
4,4'-2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA) (50 parts by mole), bicyclo [2.2.2]Octyl-7-ene-2, 3,5,6-tetracarboxylic dianhydride (B1317) (50 parts by mol), 2'-bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2'-bis (trifluoromethyl)4,4' -diaminobiphenol, TFMB) (80 parts by mol), and polysiloxane diamine (structure: polysiloxane diamine
n>1；m>1; n is 6: 4; r1is-CH3or-C6H5(ii) a And a R2Is an alkyl group having an isocyanate substituent, another R2is-CH3) (molecular weight about 2370) (20 molar parts), and gamma-Butyrolactone (gamma-Butyrolactone) were added to the reaction flask to obtain a solution (solid content about 5 wt%). Next, the above solution was reacted at 220 ℃ for 4 hours to obtain a solution having the polymer of the present invention. Subsequently, a crosslinking agent (2-methyl-1,3-propanediol) (20 parts by mole) was added to the solution having the polymer of the present invention to obtain a composition (13).
Comparative example 7
4,4'-2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA) (50 parts by mole), bicyclo [2.2.2]Octyl-7-ene-2, 3,5,6-tetracarboxylic dianhydride (B1317) (50 parts by mol), 2'-bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2'-bis (trifluoromethyl)4,4' -diaminobiphenol, TFMB) (80 parts by mol), and polysiloxane diamine (structure: polysiloxane diamine
n>1；m>1; n is 6: 4; r1is-CH3or-C6H5(ii) a And a R2Is an acrylate group, another R2is-CH3) (molecular weight: about 6300) (20 molar parts), and gamma-Butyrolactone (gamma-Butyrolactone) were added to the reaction flask to obtain a solution (solid content: about 5 wt%). Then, the above solution was reacted at 220 ℃4 hours, a solution with the polymer according to the invention is obtained. Next, a crosslinking agent (pentaerythritol triacrylate) (trade name: ARONIX M-306, available from Toagosei Co., Ltd.) (20 molar parts) was added to the solution with the polymer described in the present invention to give composition (14).
Subsequently, the compositions (12) to (14) obtained in examples 6 to 7 and comparative example 7 were coated on glass by a doctor blade method to form coating layers (having a thickness of about 20 μm). And then, baking the coating at 80-220 ℃ for 30 minutes to 4 hours to carry out crosslinking reaction and curing on the coating, thereby respectively obtaining film layers. Next, the transmittance, young's modulus, tensile elongation, and hardness of the obtained film were measured, and the flexibility of the film was evaluated, and the results are shown in table 2.
TABLE 2
| Transmittance (%) | Young's modulus (Gpa) | Tensile elongation | Hardness of | Flexibility | |
| Example 6 | ～90 | 3.6 | 9.0 | 4B | O |
| Example 7 | ～90 | 3.0 | 8.3 | 5B | O |
| Comparative example 7 | ～90 | 2.9 | 19.3 | ～6B | O |
As can be seen from Table 2, when a polysiloxane diamine having a molecular weight of more than 3000 (i.e., a polysiloxane having a molecular weight of more than 3000 in the second repeat unit of the resulting polymer) is used, the mechanical strength (e.g., hardness) of the resulting film layer obtained after crosslinking the composition (i.e., the composition described in comparative example 7) is significantly reduced.
Example 8
Example 8 was carried out as described in example 6, except that 4,4'-2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA) (50 parts by mole) was reacted with TA-TFMB (structure: TA-TFMB)
) (50 molar parts) to obtain composition (15).
Example 9
Example 9 was conducted in the same manner as described in example 8 except that bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (B1317) (50 parts by mole) was substituted with hydrogenated pyromellitic dianhydride (H-PMDA) (50 parts by mole) to give composition (16).
Next, the compositions (15) and (16) obtained in examples 8 to 9 were each coated on glass by a doctor blade method to form a coating layer (having a thickness of about 20 μm). And then, baking the coating at 80-220 ℃ for 30 minutes to 4 hours to carry out crosslinking reaction and curing on the coating, thereby respectively obtaining film layers. Next, the transmittance, young's modulus, tensile elongation, and hardness of the obtained film were measured, and the flexibility of the film was evaluated, and the results are shown in table 3.
TABLE 3
| Transmittance (%) | Young's modulus (Gpa) | Tensile elongation | Hardness of | Flexibility | |
| Example 8 | ～89 | 5.5 | 7.8 | H | O |
| Example 9 | ～90 | 6.2 | 5.4 | 2H | O |
As can be seen from Table 3, the polymers of the present invention, prepared using different dianhydride compounds, are also suitable for use in the compositions of the present invention.
Although the present invention has been described with reference to several embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (14)
1. A polymer comprising a first repeat unit and a second repeat unit, wherein the first repeat unit has a structure of formula (I) and the second repeat unit has a structure of formula (II):
wherein A is1And A3Each independently of the others, is a substituted or unsubstituted tetravalent C6-C25Aryl, tetravalent C4-C8Cycloalkyl, tetravalent C5-C25Heteroaryl, tetravalent C7-C25Alkylaryl, tetravalent C7-C25Acylaryl, tetravalent C6-C25Aryl ether, tetravalent C7-C25Acyloxyaryl, or tetravalent C6-C25A sulfonyl aryl group; a. the2Is substituted or unsubstituted C6-C25Arylene radical, C4-C8Cycloalkylene radical, C5-C25Heteroarylene, divalent C7-C25Alkylaryl, divalent C7-C25Acylaryl, divalent C6-C25Aryl ether, divalent C7-C25Acyloxyaryl, or divalent C6-C25A sulfonyl aryl group; n is more than or equal to 1; m is more than or equal to 1; r1Each independently is hydrogen, C1-8Alkyl radical, C1-8Fluoroalkyl radical, C1-8Alkoxy, or C6-12An aryl group; r2Each independently is hydrogen, C1-8Alkyl radical, C1-8Fluoroalkyl radical, C1-8Alkoxy radical, C6-12Aryl, hydroxy, amino, C2-8Carboxy, C2-8Alkenyl, amino, aminoalkyl, C2-8Isocyanate group, alkylamino group, C3-8Acrylate group, C4-9A methacrylate group, a glycidyl group, an oxirane group, an oxetane group, or a 3,4-epoxycyclohexyl group; and, at least two R2Is hydroxy, amino, C2-8Carboxy, C2-8Alkenyl, amino, aminoalkyl, C2-8Isocyanate group, alkylamino group, C3-8Acrylate radical, C4-9A methacrylate group, a glycidyl group, an oxirane group, an oxetane group, or a 3,4-epoxycyclohexyl group.
2. The polymer of claim 1, wherein the first repeat unit and the second repeat unit are arranged randomly or in blocks.
3. The polymer of claim 1, wherein a1And A3Each independently is
4. The polymer of claim 1, wherein a2Is composed of
Y is a single bond, -O-, -C (CH)3)2-、-C(CF3)2-、
And, R4Is hydrogen, fluorine, C1-6Alkyl, or C1-6A fluoroalkyl group.
5. The polymer of claim 1, wherein the ratio of the number of the first repeat units to the number of the second repeat units is 95:5 to 75: 25.
6. The polymer of claim 1, wherein in the second repeat unit, there is
A group of the structure and having
The groups of the structure are arranged in a random manner.
7. The polymer of claim 1, wherein in the second repeat unit, there is
The molecular weight of the group of the structure is 500 to 3,000.
8. The polymer of claim 1, wherein the ratio of n to m is from 3:2 to 99: 1.
9. A composition, comprising:
100 parts by weight of a polymer as claimed in any one of claims 1 to 8; and
5-40 parts by weight of a crosslinking agent.
10. The composition of claim 9, wherein the crosslinking agent is a polyol, a compound having at least two acrylate or methacrylate groups, or a combination thereof.
11. The composition of claim 9, wherein the crosslinking agent is 1,3-propanediol, 2,3,4-trimethyl-1,3-pentanediol, 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,2-hexanediol, 1,3-hexanediol, 2-methyl-1,3-propanediol, 2,5-hexanediol, 2-methyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, tripropylene glycol, propylene, Glycerol, polyglycerol, ethylene carbonate, or 1, 2-propanediol carbonate.
12. The composition of claim 9, wherein the cross-linking agent is dioxane diacrylate, 3-hydroxy-2, 2-dimethylpropyl 3-hydroxy-2, 2-dimethylpropionate, 1,6-hexanediol diacrylate, ethoxylated1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate, 2-hydroxyethyl methacrylate phosphate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylate, ethylene glycol (B) acrylate, ethylene glycol (B-2-hexanediol diacrylate, ethylene glycol (B) acrylate, ethylene glycol (B-1-hexanediol diacrylate, ethylene glycol (B) acrylate, ethylene glycol (B-acrylate, ethylene glycol (B) acrylate, ethylene glycol (B-2-hexanediol diacrylate, ethylene glycol (B-hexanediol (B) acrylate, ethylene glycol (B-1-acrylate, ethylene glycol (B) acrylate, ethylene glycol (B-2-acrylate, ethylene glycol (B-propylene glycol (B) acrylate, ethylene glycol (B-ethylene glycol (B) acrylate, ethylene glycol (B-propylene glycol (B) acrylate, and (B-ethylene glycol (B) acrylate, and/or a copolymer (B) acrylate, and/or a copolymer, Ethoxylated bisphenol A dimethacrylate, 2-methyl-1,3-propanediol diacrylate, ethoxylated-2-methyl-1, 3-propanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, Ethylene Glycol Dimethacrylate (EGDMA), triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, allylated cyclohexyl dimethacrylate, diethylene glycol dimethacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated glycerol triacrylate, propoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol tetraacrylate, or combinations of the foregoing.
13. The composition of claim 9, further comprising:
0.1-15 parts by weight of an initiator.
14. A polysiloxane-polyimide material which is a cured product of the composition according to claim 9.
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