CA1274938A - Polyimide and high-temperature adhesive of polyimide - Google Patents
Polyimide and high-temperature adhesive of polyimideInfo
- Publication number
- CA1274938A CA1274938A CA000528830A CA528830A CA1274938A CA 1274938 A CA1274938 A CA 1274938A CA 000528830 A CA000528830 A CA 000528830A CA 528830 A CA528830 A CA 528830A CA 1274938 A CA1274938 A CA 1274938A
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- Prior art keywords
- radical
- tetracarboxylic dianhydride
- dianhydride
- polyimide
- bis
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/44—Polyamides; Polynitriles
-
- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
POLYIMIDE AND HIGH-TEMPERATURE ADHESIVE OF POLYMIDE
ABSTRACT
This invention relates to a novel polyimide and describes method of its preparation, adhesives of the polyimide and the method for their application.
The polyimide has recurring units of the formula (where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function).
The polyimide can be prepared by reacting 2,6-bis(3-amino-phenoxy)pyridine with tetracarboxylic dianhydride in an organic solvent and imidizing resultant polyamic acid.
Various tetracarboxylic dianhydrides can be used and particularly prefered are pyromellitic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.
ABSTRACT
This invention relates to a novel polyimide and describes method of its preparation, adhesives of the polyimide and the method for their application.
The polyimide has recurring units of the formula (where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function).
The polyimide can be prepared by reacting 2,6-bis(3-amino-phenoxy)pyridine with tetracarboxylic dianhydride in an organic solvent and imidizing resultant polyamic acid.
Various tetracarboxylic dianhydrides can be used and particularly prefered are pyromellitic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.
Description
~3~3 BAClCGRO~lND OF TIIE INVENT[ON
_ _ _ _ _ ~
This invention relates to a novel polyimide~ method Eor preparing the same and high-temperature adhesive of the same. This invention particularly relates to very excellent adhesives having outstanding adhesive strength and high-temperature stability.
Since the polyimide prepared by reacting tetracarboxylic dianhydride with diamine has been traditionally excellent in various physical properties and thermal stability, it is hereafter expected for a wide use in the field where the high-temperature stability is required.
Although many polyimides developed up to this t-lme have exhibited superior characteristics, they have demonstrated such merits and drawbacks on their properties that prominent high-temperature stability was accompanied by poor processability or the resin being prepared Eor improving the processability resulted in an inferior high-temperature stability and solvent resistance.
Therefore the ob~ect of this invention is to provide a novel polyimide having, in addition to its substantially outstanding high-temperature stability, prominent workability and further having excellent bonding strength and durability at high-temperatures for a long period.
S~RY OF TIIE INVENTION
The inventors have examined hard to achieve the above obJect.
~s a result, they have found a novel polyimide and high-temperature adhesives of the same.
The present invention is summarized as follows.
1) Polyimide having recurring units of the formula:
1l 1l _ ~ O ~ O ~ -N/ ~ ~ ~N-.. O O
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons3 cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking functions) wherein polyamic acid precursor oE said polyimide has recurring units of the formula:
' O O
_ ~ O ~ O ~ N~l-C\ /C-N~I- _ HO-IC/ \C-O~I
O O
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g measured at 35-C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent.
$~
'~ ~ 3
_ _ _ _ _ ~
This invention relates to a novel polyimide~ method Eor preparing the same and high-temperature adhesive of the same. This invention particularly relates to very excellent adhesives having outstanding adhesive strength and high-temperature stability.
Since the polyimide prepared by reacting tetracarboxylic dianhydride with diamine has been traditionally excellent in various physical properties and thermal stability, it is hereafter expected for a wide use in the field where the high-temperature stability is required.
Although many polyimides developed up to this t-lme have exhibited superior characteristics, they have demonstrated such merits and drawbacks on their properties that prominent high-temperature stability was accompanied by poor processability or the resin being prepared Eor improving the processability resulted in an inferior high-temperature stability and solvent resistance.
Therefore the ob~ect of this invention is to provide a novel polyimide having, in addition to its substantially outstanding high-temperature stability, prominent workability and further having excellent bonding strength and durability at high-temperatures for a long period.
S~RY OF TIIE INVENTION
The inventors have examined hard to achieve the above obJect.
~s a result, they have found a novel polyimide and high-temperature adhesives of the same.
The present invention is summarized as follows.
1) Polyimide having recurring units of the formula:
1l 1l _ ~ O ~ O ~ -N/ ~ ~ ~N-.. O O
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons3 cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking functions) wherein polyamic acid precursor oE said polyimide has recurring units of the formula:
' O O
_ ~ O ~ O ~ N~l-C\ /C-N~I- _ HO-IC/ \C-O~I
O O
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g measured at 35-C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent.
$~
'~ ~ 3
2) ~ method for preparing polyimide having recurring units of the formula:
1l 1l _ ~ O ~ O ~N~ N--_ O O
(where R is the same as above) which compr~ses thermally or chemically imidizing polyamic acid wherein said polyamic acid has recurring units of the formula:
O O
_ ~O~ O~NH-C~ ~C-NII- _ HO-C~ C-OH
O O ~. .
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g, and is obtained by reacting 2,6-bis(3 aminophenoxy)pyridine with a tetracarboxylic dianhydride represented by the formula:
O O
O~ ~R ~0 Il 11 O O
(where R is the same as above) in an organic solvent.
' i~ i ' ~L2~3B
1l 1l _ ~ O ~ O ~N~ N--_ O O
(where R is the same as above) which compr~ses thermally or chemically imidizing polyamic acid wherein said polyamic acid has recurring units of the formula:
O O
_ ~O~ O~NH-C~ ~C-NII- _ HO-C~ C-OH
O O ~. .
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g, and is obtained by reacting 2,6-bis(3 aminophenoxy)pyridine with a tetracarboxylic dianhydride represented by the formula:
O O
O~ ~R ~0 Il 11 O O
(where R is the same as above) in an organic solvent.
' i~ i ' ~L2~3B
3) A higil-temperat-lre adhesive of polyimlde hav:Lng recurring units of the formula:
, 11 l --~ ~ ~ \C/ ~C/ _ O O
(where R is the same as above) wherein polyamic acid precursor of said polyimide has recurring units of the formula:
O O
C NH _ ~IO_C C-O~I
O O
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g.
, 11 l --~ ~ ~ \C/ ~C/ _ O O
(where R is the same as above) wherein polyamic acid precursor of said polyimide has recurring units of the formula:
O O
C NH _ ~IO_C C-O~I
O O
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g.
4) A method of adhesion which comprises applying polyimide having recurring units of the formula:
1l 1l _ ~--O ~,O~Nt~R ~N--_ O O
(where R is the same as above) wherein polyamic acid precursor of said polyimide has recurring units of the formula:
.. .~ . . ~
,~ ~
S
o o O ~ O ~ N~l-C\ ~C~NI-I- _ ~10-C C-O~I
O O
(where R is the same as above) and an inherent viscosity of O.l to 3.0 dl/g, on a substrate and further overlapping said substrate with another substrate, followed by heating under pressure above the glass transition temperature of said polylmide.
BRIEF DESCRIP~I _ OF THE DR~WING
Figure 1 and 2 illustrate two typical examples of IR absorption spectrum atlas on the polyimides in this invention.
DET~ILED DESCRIPTION OF THE INVENTION
_ .. ..... .
Polyimide of the present invention is characterized in the use of 2,6-bis(3-aminophenoxy)pyr:idine as a diamine component and is obtained by conducting dehydrating ring-closure of polyamic acid which is prepared by polymeri~ing said pyridine derivative with tetracarboxylic dianhydride.
Polyimide of this invention can be derived from diamine having both pyridine ring and arornatic amino radical in a molecule. Polyimide containing the pyridine ring in its polymer chain is a novel one which has not been known up to this time.
:h~ ~ .
r'~ 6 3~
Po:Lyimide o.E this invention has s-lm:llar h:l.gh-temperature stability to that o.E conventional poly:Lmide, and yet has an excel.lent processability and high-temperature adhesion due to the thermoplastic properties o:E said polyimide. Besides polyimide of the present invention has pyridine rings in its polymer chain, and thus metal chelates are formed by doping metal ions to exhibit magnetism or electrical conductivity. In addition, polyimide of this invention can be molded to hollow fibers and thin films which are capable of capturing and separating some kind of cations. Furthermore, polyimide of the present invention is also useEul as a functional polymer which can be employed as a polymer catalyst in polymerization reactions.
Therefore, polyimide of this invention is a very valuable substance which can be applied for a wide variety of fields such as base materials for space and aeronautics, electric and electronic appliances, high-temperature adhesives, medical polymers and separation membranes.
Polyimide of this invention can be prepared by the following methods.
In the first step, polyamic acid is obtained by polymerizing 2,6-bis(3-aminophenoxy)pyridine with tetracarboxylic dianhydride in the organic solvents.
Tetracarboxylic dianhydride for use in the method of this invention has the formula:
O O
Il 11 O\ /R\ /0 Il 11 O O
~L2~
(where R is a tetra-valent radical selected from the group consL~tlng of aliphatic radical having not less than two carbons, cycloaliphat:Lc radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic raclicals are mutually connected with a bond or a crosslinking function).
Tetracarboxylic dianhydride used in the method includes, for example, ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis-(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride and 1,2,7,8-phenanthrene tetracarboxylic dianhydride.
Prefered in particular among these dianhydrides are pyromellitic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.
Tetracarboxylic dianhydride can be used alone or in mixtures of two or more.
3~3 The polyamic ac.Lcl can be normally prepare(l by reactlng ether diamine with tetracarboxylic dlanhydricle in the organic solvents.
The organic solvents used in the reaction include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylaceta~ide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, l,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea and hexamethylphosphoramide.
These solvents can be used alone or in mixtures of two or more.
The reaction temperature is normally 60C or less, preferably 50C or less. The reaction pressure is not restricted in particular and atmospheric pressure ls sufficient for carrying out the reaction, The reaction time depends upon the type of solvents, reaction temperature, and raw materials such as tetracarboxylic dianhydrides, and is normally enough to complete the formation of polyamic acid represented by the undermentioned formula. Reaction for 4 to 24 hours is normally sufficient, Such reaction affords polyamic acid having recurring units of the formula:
O O
_ ~ 0 ~ 0 ~ N~l-C\ /C-NII-IlO-C~ ~C-0~1 O O
(where R is the same as above).
".. ~ ., 93~3 In the present invention, the polyamic aclcl precursor of polyimlde is required to have an inherent viscosity oE 0.1 to 3.0 dl/g, preferably 0.3 to 2.5 dl/g.
In the next step, thermal dehydration of the polyamic acid solution at lO0 to 400C or chemical dehydratlon by treating with common imidi~ing agent such as acetic anhydride afford the corresponding polyimide having recurring units of the formula:
1l l _ ~ 0- ~ 0 ~ N\ /R~ /N- _ O O
(where R is the same as above).
Polyimide of this invention is employed for adhesives by the following method.
The above polyamic acid is thermally or chemically dehydrated to give, for example, a polyimlde film or polyimide powder. The film or powder is inserted between substrates, pressed at 50 to 400C under pressure of 1 to 1000 kg/cm2 and cured at 100 to 400C. The substrates can be strongly bonded.
There is no difficulty at all in containing a part of polyamic acid in polyimide.
In another method, the solution of above polyamic acid dissolved ln the organlc solvent or the reaction mixture as it is, which contains formed polyamic acid in the organic solvent, can be applied as a thin layer on the substrate to be bonded. Then the substrate is preheated for required hours at 180 to 350C, preferably at approximately 220C to 931~1 remove an excess solvent and to convert polyam:Lc acid lnto polylmLde on the surEace of said substrate. The substrate thus obtained is then overlapped with another substrate, pressed at 50 to 400C under pressure of 1 to 1,000 kg/cm2 and cured at 100 to 400C. This method is also a preferable one and a firm adhesion of the substrates can be obtained.
E~MPLES
The present invention will be illustrated with respect to following Synthetic example and Examples.
_ynthetic example A 200 ml flask equipped with a stirrer, nitrogen inlet tube and water separator was charged with 22,4 grams (0.205 mo]) of 3-aminophenol, 12.~ grams (0.22 mol) of 96% potassium hydroxide flake, 100 ml of dimethylsulfoxide and 10 ml of toluene. The mixture was heated with stirring under nitrogen atmosphere. Water generated in the reaction mixture was removed by the water separator under reEluxing of toluene.
After reducing the lnternal temperature below 100C, 14.~ grams (0,10 mol) of 2,6-dichloropyridine was charged, heàted agaln up to the internal temperature of 150 to 160DC and conducted the reaction Eor eight hours. After cooling, the resultant mixture was poured into 500 ml of water.
~L2~L~ 8 The separated brown mass was flltered, washed wi~h water and dried to aEEord 28.2 grams (96.2% y:Leld) oE 2,6-b:Ls(3 amLnophenoxy)-pyridlne. The crude product was recrystallized twlce Erom :Lsopropyl alcohol to obtain pure white crystals having a melting point of 119-120C. Results of elementary analysis and mass spectrum were as follows ElementarY analysis (C17 H15 N3 2~
C ~I N
Calculated (%) 69.61 5.15 14.33 Found (%) 69.86 5.10 14.28 Mass spectrum (M/e) M 293, 185, 157, 92, 65 Example 1 A reaction vessel equipped with a stirrer, reflux condenser and nitrogen inlet tube was charged with 20.53 grams (0.07 mol) of 2,6-bis(3-aminophenoxy)pyridine and 53.09 grams oE N,N-dimethylacetmide.
Under nitrogen atmosphere 14.95 grams (0.067 mol) o pyromellit-lc dianhydride were added by portions at room temperature with care to prevent temperature rise of the solution and stirred for 24 hours at room temperature. Polyamic acid thus obtained had an inherent viscosity of 0.72 dl/g, measured at 35C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent.
3~3 In the next step, a reactlon vessel equipped wlth a stirrer, reflux condenser and nitrogen inlet tube was charged w:Lth 33.3 grams of polyamic acid solution above obtained and 66.7 grams of N,N-dimethylacetamide. IJnder nitrogen atmosphere, 5 55 grams (0.055 mol) of triethylamine and 8.0 grams (0.078 mol) of acetic anhydrlde were added dropwise with stirring at room temperature and stirred for 20 hours. AEter ending the reaction, precipitates were Eiltered, washed with methanol and dried under reduced pressure at 150C for eight hours to afford 9.60 grams (96.0% yield) of yellow polyimide powder.
The polyimide powder had a glass transitlon temperature of 216C
in accordance with DSC measurement, a melting point of 395C and a five percent weight decrease temperature in air of 508C ln accordance with DTA-TG.
~ igure 1 illustrates the IR absorption spectrum atlas of polyimide thus obtalned. In the spectrum atlas, remarkable absorption is found at 1780cm and 1720cm whlch are characterlstlc absorptlon bands of imide ring and 12~0cm whlch ls characterlstlc absorptlon band of ether linkage. The melt viscosity of polyimide powder obtained in thls Example was measured wlth a flow tester CFT-500 from Shlmadzu Seisakusho. Uslng the orlffice of 0.1 cm ln dlameter and 1 cm in length, measurement was perEormed with a preheat time of flve minutes under load of 100 kg at 400C. The polylmlde powder indicated a high flowability and had a melt viscosity of ~2~ poise and a shear rate of 5775 sec . The strand obtained was brown, transparent, very flexible and highly elastic.
~2~
In addition, the poly:Lmide powder was applied between cold rolled steel panels (JIS G3141, spcc/SD, 25mm x 100mm x 1.6mm) whlch were washed with trichloroethylene and preheated at 130C, and pressed at 320C for five minutes under pressure of 20 kg/cm2. The bonded specimen had a lap shear strength of 1~0 kg/cm at room temperature and 82 kg/cm2 at 240C in accordance with JIS-K6848 and K6850.
Example 2 A reaction vessel equipped with a stirrer, reflux condenser and nitrogen inlet tube was charged with 20.5 grams ~0.07 mol) of 2,6-bis(3-amlnophenoxy)pyridine and 131.67 grams of N,N-dimethylacetamide, and added with 21.43 grams (0.067 mol~of 3,3',4,4'-benzophenonetetracarboxylic dianhydride in portions at room temperature under nitrogen atmosphere with care to prevent the temperature rise of the solution. The reaction mixture was further stirred for 24 hours at room temperature.
Po]yamic acid thus obtained had an inherent viscosity of 0,44 dl/g-A part of the polyamic acid solution was casted on a glassplate and heated for one hour each at 100C, 200C and 300C to obtain a light-brown transparent film of polyimide having a thickness of 35 microns. The polyimide film had a glass transition temperature of 204C in accordance with TM~ penetration method and a five percent weight decrease temperature in air of 502C.
Besides the polyimide film had a tensile strength of 12.4 kg/mm2 and an elongation oE 7.5% in accordance with ASTM D-882.
1~
L~
Figure 2 illustrates IR absorption spectrum of the resultant polyimide film. The spectrum atlas shows remarkable absorption at 17SOcm 1 and 1720cm 1 which are characteristic absorption bands oE imlde ring and at 1240cm which is the characteristic absorption band of ether linkage.
Furthermore, the polyimide film was inserted between cold rolled steel panels which were preheated at 130C and pressed for five minutes at 320C with the pressure of 20 kg/cm2 The bonded specimen had a lap shear strength of 330 kg/cm2 at room temperature and 190 kg/cm at 240C.
Example 3 The same reaction vessel as Example 1 was charged with 20.53 grams (0.07 mol) of 2,6-bis(3-aminophenoxy)pyridine and 53.09 grams of N,N-dimethylacetamide and added with 14.95 grams ~0.067 mol) of pyromellitic dianhydride in parts at room temperature under nitrogen atmosphere with care to prevent the temperature rise of the solution.
The reaction mixture was Eurther stirred for 24 hours at room temperature.
Polyamic acid thus obtained had an inherent viscosity of 0.72 dl/g. ~ part of the polyamic acid solution was casted on a glass plate and treated with the same conditions as Example 2 to obtain a light brown opaque film of polyimide hav:Lng a thickness of 35 microns.
The polyimide film had a glass transition temperature of 230C, a melting point of 367C and a five percent weight decrease temperature of 512C The film also had a tensile strength of 7.0 kg/mm2 and an elongation of 5.0~.
93~3 Furthermore, the bonded specimen prepared by ~reating the polyimide film wi~h the same procedure as Examp:Le 2 had a lap shear strength of 120 kg/cm2 at room temperature and 70 kg/cm2 at 2~0C.
Example ~
The procedure of Example 3 was repeated except bis(2-methoxy~
ethyl) ether was used as the solvent in place of N,N-dimethylacetamide.
The polyamic acid thus obtained had an inherent viscosity of 1.10 dl/g.
part of the polyamic acid was treated with the same procedure as Example 2 to obtain a light brown opaque film of polyimide having a thickness of 35 microns. The polyimide film had a glass transition temperature of 228C, a melting point of 362C and a five percent weight decrease temperature in air of 518C. Besides the film had a tensile strength of 7.2 kg/mm and elongation of 4. 8~o ~
Furthermore, the film was inserted between cold rolled steel panels as described in Example 2 and pressed at 320C for five minutes under pressure of 20 kg/cm . The bonded specimen had a lap shear strength of 121 kg/cm at room temperature and 65 kg/cm2 at 240C.
1l 1l _ ~--O ~,O~Nt~R ~N--_ O O
(where R is the same as above) wherein polyamic acid precursor of said polyimide has recurring units of the formula:
.. .~ . . ~
,~ ~
S
o o O ~ O ~ N~l-C\ ~C~NI-I- _ ~10-C C-O~I
O O
(where R is the same as above) and an inherent viscosity of O.l to 3.0 dl/g, on a substrate and further overlapping said substrate with another substrate, followed by heating under pressure above the glass transition temperature of said polylmide.
BRIEF DESCRIP~I _ OF THE DR~WING
Figure 1 and 2 illustrate two typical examples of IR absorption spectrum atlas on the polyimides in this invention.
DET~ILED DESCRIPTION OF THE INVENTION
_ .. ..... .
Polyimide of the present invention is characterized in the use of 2,6-bis(3-aminophenoxy)pyr:idine as a diamine component and is obtained by conducting dehydrating ring-closure of polyamic acid which is prepared by polymeri~ing said pyridine derivative with tetracarboxylic dianhydride.
Polyimide of this invention can be derived from diamine having both pyridine ring and arornatic amino radical in a molecule. Polyimide containing the pyridine ring in its polymer chain is a novel one which has not been known up to this time.
:h~ ~ .
r'~ 6 3~
Po:Lyimide o.E this invention has s-lm:llar h:l.gh-temperature stability to that o.E conventional poly:Lmide, and yet has an excel.lent processability and high-temperature adhesion due to the thermoplastic properties o:E said polyimide. Besides polyimide of the present invention has pyridine rings in its polymer chain, and thus metal chelates are formed by doping metal ions to exhibit magnetism or electrical conductivity. In addition, polyimide of this invention can be molded to hollow fibers and thin films which are capable of capturing and separating some kind of cations. Furthermore, polyimide of the present invention is also useEul as a functional polymer which can be employed as a polymer catalyst in polymerization reactions.
Therefore, polyimide of this invention is a very valuable substance which can be applied for a wide variety of fields such as base materials for space and aeronautics, electric and electronic appliances, high-temperature adhesives, medical polymers and separation membranes.
Polyimide of this invention can be prepared by the following methods.
In the first step, polyamic acid is obtained by polymerizing 2,6-bis(3-aminophenoxy)pyridine with tetracarboxylic dianhydride in the organic solvents.
Tetracarboxylic dianhydride for use in the method of this invention has the formula:
O O
Il 11 O\ /R\ /0 Il 11 O O
~L2~
(where R is a tetra-valent radical selected from the group consL~tlng of aliphatic radical having not less than two carbons, cycloaliphat:Lc radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic raclicals are mutually connected with a bond or a crosslinking function).
Tetracarboxylic dianhydride used in the method includes, for example, ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis-(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride and 1,2,7,8-phenanthrene tetracarboxylic dianhydride.
Prefered in particular among these dianhydrides are pyromellitic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.
Tetracarboxylic dianhydride can be used alone or in mixtures of two or more.
3~3 The polyamic ac.Lcl can be normally prepare(l by reactlng ether diamine with tetracarboxylic dlanhydricle in the organic solvents.
The organic solvents used in the reaction include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylaceta~ide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, l,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea and hexamethylphosphoramide.
These solvents can be used alone or in mixtures of two or more.
The reaction temperature is normally 60C or less, preferably 50C or less. The reaction pressure is not restricted in particular and atmospheric pressure ls sufficient for carrying out the reaction, The reaction time depends upon the type of solvents, reaction temperature, and raw materials such as tetracarboxylic dianhydrides, and is normally enough to complete the formation of polyamic acid represented by the undermentioned formula. Reaction for 4 to 24 hours is normally sufficient, Such reaction affords polyamic acid having recurring units of the formula:
O O
_ ~ 0 ~ 0 ~ N~l-C\ /C-NII-IlO-C~ ~C-0~1 O O
(where R is the same as above).
".. ~ ., 93~3 In the present invention, the polyamic aclcl precursor of polyimlde is required to have an inherent viscosity oE 0.1 to 3.0 dl/g, preferably 0.3 to 2.5 dl/g.
In the next step, thermal dehydration of the polyamic acid solution at lO0 to 400C or chemical dehydratlon by treating with common imidi~ing agent such as acetic anhydride afford the corresponding polyimide having recurring units of the formula:
1l l _ ~ 0- ~ 0 ~ N\ /R~ /N- _ O O
(where R is the same as above).
Polyimide of this invention is employed for adhesives by the following method.
The above polyamic acid is thermally or chemically dehydrated to give, for example, a polyimlde film or polyimide powder. The film or powder is inserted between substrates, pressed at 50 to 400C under pressure of 1 to 1000 kg/cm2 and cured at 100 to 400C. The substrates can be strongly bonded.
There is no difficulty at all in containing a part of polyamic acid in polyimide.
In another method, the solution of above polyamic acid dissolved ln the organlc solvent or the reaction mixture as it is, which contains formed polyamic acid in the organic solvent, can be applied as a thin layer on the substrate to be bonded. Then the substrate is preheated for required hours at 180 to 350C, preferably at approximately 220C to 931~1 remove an excess solvent and to convert polyam:Lc acid lnto polylmLde on the surEace of said substrate. The substrate thus obtained is then overlapped with another substrate, pressed at 50 to 400C under pressure of 1 to 1,000 kg/cm2 and cured at 100 to 400C. This method is also a preferable one and a firm adhesion of the substrates can be obtained.
E~MPLES
The present invention will be illustrated with respect to following Synthetic example and Examples.
_ynthetic example A 200 ml flask equipped with a stirrer, nitrogen inlet tube and water separator was charged with 22,4 grams (0.205 mo]) of 3-aminophenol, 12.~ grams (0.22 mol) of 96% potassium hydroxide flake, 100 ml of dimethylsulfoxide and 10 ml of toluene. The mixture was heated with stirring under nitrogen atmosphere. Water generated in the reaction mixture was removed by the water separator under reEluxing of toluene.
After reducing the lnternal temperature below 100C, 14.~ grams (0,10 mol) of 2,6-dichloropyridine was charged, heàted agaln up to the internal temperature of 150 to 160DC and conducted the reaction Eor eight hours. After cooling, the resultant mixture was poured into 500 ml of water.
~L2~L~ 8 The separated brown mass was flltered, washed wi~h water and dried to aEEord 28.2 grams (96.2% y:Leld) oE 2,6-b:Ls(3 amLnophenoxy)-pyridlne. The crude product was recrystallized twlce Erom :Lsopropyl alcohol to obtain pure white crystals having a melting point of 119-120C. Results of elementary analysis and mass spectrum were as follows ElementarY analysis (C17 H15 N3 2~
C ~I N
Calculated (%) 69.61 5.15 14.33 Found (%) 69.86 5.10 14.28 Mass spectrum (M/e) M 293, 185, 157, 92, 65 Example 1 A reaction vessel equipped with a stirrer, reflux condenser and nitrogen inlet tube was charged with 20.53 grams (0.07 mol) of 2,6-bis(3-aminophenoxy)pyridine and 53.09 grams oE N,N-dimethylacetmide.
Under nitrogen atmosphere 14.95 grams (0.067 mol) o pyromellit-lc dianhydride were added by portions at room temperature with care to prevent temperature rise of the solution and stirred for 24 hours at room temperature. Polyamic acid thus obtained had an inherent viscosity of 0.72 dl/g, measured at 35C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent.
3~3 In the next step, a reactlon vessel equipped wlth a stirrer, reflux condenser and nitrogen inlet tube was charged w:Lth 33.3 grams of polyamic acid solution above obtained and 66.7 grams of N,N-dimethylacetamide. IJnder nitrogen atmosphere, 5 55 grams (0.055 mol) of triethylamine and 8.0 grams (0.078 mol) of acetic anhydrlde were added dropwise with stirring at room temperature and stirred for 20 hours. AEter ending the reaction, precipitates were Eiltered, washed with methanol and dried under reduced pressure at 150C for eight hours to afford 9.60 grams (96.0% yield) of yellow polyimide powder.
The polyimide powder had a glass transitlon temperature of 216C
in accordance with DSC measurement, a melting point of 395C and a five percent weight decrease temperature in air of 508C ln accordance with DTA-TG.
~ igure 1 illustrates the IR absorption spectrum atlas of polyimide thus obtalned. In the spectrum atlas, remarkable absorption is found at 1780cm and 1720cm whlch are characterlstlc absorptlon bands of imide ring and 12~0cm whlch ls characterlstlc absorptlon band of ether linkage. The melt viscosity of polyimide powder obtained in thls Example was measured wlth a flow tester CFT-500 from Shlmadzu Seisakusho. Uslng the orlffice of 0.1 cm ln dlameter and 1 cm in length, measurement was perEormed with a preheat time of flve minutes under load of 100 kg at 400C. The polylmlde powder indicated a high flowability and had a melt viscosity of ~2~ poise and a shear rate of 5775 sec . The strand obtained was brown, transparent, very flexible and highly elastic.
~2~
In addition, the poly:Lmide powder was applied between cold rolled steel panels (JIS G3141, spcc/SD, 25mm x 100mm x 1.6mm) whlch were washed with trichloroethylene and preheated at 130C, and pressed at 320C for five minutes under pressure of 20 kg/cm2. The bonded specimen had a lap shear strength of 1~0 kg/cm at room temperature and 82 kg/cm2 at 240C in accordance with JIS-K6848 and K6850.
Example 2 A reaction vessel equipped with a stirrer, reflux condenser and nitrogen inlet tube was charged with 20.5 grams ~0.07 mol) of 2,6-bis(3-amlnophenoxy)pyridine and 131.67 grams of N,N-dimethylacetamide, and added with 21.43 grams (0.067 mol~of 3,3',4,4'-benzophenonetetracarboxylic dianhydride in portions at room temperature under nitrogen atmosphere with care to prevent the temperature rise of the solution. The reaction mixture was further stirred for 24 hours at room temperature.
Po]yamic acid thus obtained had an inherent viscosity of 0,44 dl/g-A part of the polyamic acid solution was casted on a glassplate and heated for one hour each at 100C, 200C and 300C to obtain a light-brown transparent film of polyimide having a thickness of 35 microns. The polyimide film had a glass transition temperature of 204C in accordance with TM~ penetration method and a five percent weight decrease temperature in air of 502C.
Besides the polyimide film had a tensile strength of 12.4 kg/mm2 and an elongation oE 7.5% in accordance with ASTM D-882.
1~
L~
Figure 2 illustrates IR absorption spectrum of the resultant polyimide film. The spectrum atlas shows remarkable absorption at 17SOcm 1 and 1720cm 1 which are characteristic absorption bands oE imlde ring and at 1240cm which is the characteristic absorption band of ether linkage.
Furthermore, the polyimide film was inserted between cold rolled steel panels which were preheated at 130C and pressed for five minutes at 320C with the pressure of 20 kg/cm2 The bonded specimen had a lap shear strength of 330 kg/cm2 at room temperature and 190 kg/cm at 240C.
Example 3 The same reaction vessel as Example 1 was charged with 20.53 grams (0.07 mol) of 2,6-bis(3-aminophenoxy)pyridine and 53.09 grams of N,N-dimethylacetamide and added with 14.95 grams ~0.067 mol) of pyromellitic dianhydride in parts at room temperature under nitrogen atmosphere with care to prevent the temperature rise of the solution.
The reaction mixture was Eurther stirred for 24 hours at room temperature.
Polyamic acid thus obtained had an inherent viscosity of 0.72 dl/g. ~ part of the polyamic acid solution was casted on a glass plate and treated with the same conditions as Example 2 to obtain a light brown opaque film of polyimide hav:Lng a thickness of 35 microns.
The polyimide film had a glass transition temperature of 230C, a melting point of 367C and a five percent weight decrease temperature of 512C The film also had a tensile strength of 7.0 kg/mm2 and an elongation of 5.0~.
93~3 Furthermore, the bonded specimen prepared by ~reating the polyimide film wi~h the same procedure as Examp:Le 2 had a lap shear strength of 120 kg/cm2 at room temperature and 70 kg/cm2 at 2~0C.
Example ~
The procedure of Example 3 was repeated except bis(2-methoxy~
ethyl) ether was used as the solvent in place of N,N-dimethylacetamide.
The polyamic acid thus obtained had an inherent viscosity of 1.10 dl/g.
part of the polyamic acid was treated with the same procedure as Example 2 to obtain a light brown opaque film of polyimide having a thickness of 35 microns. The polyimide film had a glass transition temperature of 228C, a melting point of 362C and a five percent weight decrease temperature in air of 518C. Besides the film had a tensile strength of 7.2 kg/mm and elongation of 4. 8~o ~
Furthermore, the film was inserted between cold rolled steel panels as described in Example 2 and pressed at 320C for five minutes under pressure of 20 kg/cm . The bonded specimen had a lap shear strength of 121 kg/cm at room temperature and 65 kg/cm2 at 240C.
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1) Polyimide having recurring units of the formula:
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function) and being derived from a polyamic acid precursor which has recurring units of the formula:
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g measured at 35°C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent,
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function) and being derived from a polyamic acid precursor which has recurring units of the formula:
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g measured at 35°C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent,
2) The polyimide as claimed in Claim 1 wherein R is the tetra-valent radical represented by the formula:
or ,
or ,
3) A method for preparing polyimide having recurring units of the formula:
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function) which comprises thermally or chemically imidizing polyamic acid wherein said polyamic acid has recurring units of the formula:
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g measured at 35°C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent, and is obtained by reacting 2,6-bis(3-aminophenoxy)pyridine with a tetracarboxylic dianhydride represented by the formula:
(where R is the same as above) in an organic solvent.
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function) which comprises thermally or chemically imidizing polyamic acid wherein said polyamic acid has recurring units of the formula:
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g measured at 35°C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent, and is obtained by reacting 2,6-bis(3-aminophenoxy)pyridine with a tetracarboxylic dianhydride represented by the formula:
(where R is the same as above) in an organic solvent.
4) The method for preparing polyimide as claimed in Claim 3 wherein R is the tetra-valent radical represented by the formula:
or
or
5) An adhesive which -is stable at a high temperature and consists essentially of a polyimide having recurring units of the formula:
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function) and being derived from a polyamic acid precursor which has recurring units of the formula:
(where R is the same as above) and an inherent viscosity of 0.1 to 3,0 dl/g measured at 35°C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent.
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function) and being derived from a polyamic acid precursor which has recurring units of the formula:
(where R is the same as above) and an inherent viscosity of 0.1 to 3,0 dl/g measured at 35°C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvent.
6) The high-temperature adhasive as claimed in Claim 5 wherein R is the tetra-valent radical represented by the formula:
or
or
7) A method of bonding two substrates, which comprises applying a polyimide having recurring units of the formula:
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function) and being derived from a polyamic acid precursor which has recurring units of the formula:
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g measured at 35°C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvents, to a substrate, overlaying said substrate ontoanother substrate, and then heating under pressure above the glass transition temperature of said polyimide.
(where R is a tetra-valent radical selected from the group consisting of aliphatic radical having not less than two carbons, cyclo-aliphatic radical, monoaromatic radical, condensed polyaromatic radical, and non condensed polyaromatic radical wherein aromatic radicals are mutually connected with a bond or a crosslinking function) and being derived from a polyamic acid precursor which has recurring units of the formula:
(where R is the same as above) and an inherent viscosity of 0.1 to 3.0 dl/g measured at 35°C in a solution of 0.5 gram of said polyamic acid per 100 ml of N,N-dimethylacetamide solvents, to a substrate, overlaying said substrate ontoanother substrate, and then heating under pressure above the glass transition temperature of said polyimide.
8) The method of adhesion as claimed in Claim 7 wherein R is the tetra-valent radical represented by the formula:
or
or
9. The polyimide as claimed in claim 1, wherein R is a tetravalent radical which can be derived rom a tetracarboxylic dianhydride selected from the group consisting of ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis-(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl) methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5-8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride and 1,2,7,8-phenanthrene tetracarboxylic dianhydride.
10. The adhesive as claimed in claim 5, wherein R is a tetravalent radical which can be derived from a tetracarboxylic dianhydride selected from the group consisting of ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis-(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl) methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2/3,4-benzene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride and 1,2,7,8 -phenanthrene tetracarboxylic dianhydride.
11. The adhesive as claimed in claim 5, 6 or 10, wherein the polyimide is used as it is in a film or powder form.
12. The method as claimed in claim 7 or 8, wherein the substrate is made of steel, and the heating is conducted under a pressure of 1 to 1,000 kg/cm2 at a temperature above the glass transition temperature but not higher than 400°C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60193020A JPS6253388A (en) | 1985-09-03 | 1985-09-03 | heat resistant adhesive |
| JP61026936A JPS62185714A (en) | 1985-09-03 | 1986-02-12 | Polyimide and heat-resistant adhesives made of polyimide |
| JP61-026936 | 1986-02-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1274938A true CA1274938A (en) | 1990-10-02 |
Family
ID=40347951
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000528101A Expired - Lifetime CA1274937A (en) | 1985-09-03 | 1987-01-26 | Polyimide for high-temperature adhesive |
| CA000528830A Expired - Lifetime CA1274938A (en) | 1985-09-03 | 1987-02-03 | Polyimide and high-temperature adhesive of polyimide |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000528101A Expired - Lifetime CA1274937A (en) | 1985-09-03 | 1987-01-26 | Polyimide for high-temperature adhesive |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4797466A (en) |
| EP (1) | EP0233069B1 (en) |
| JP (2) | JPS6253388A (en) |
| KR (1) | KR900008963B1 (en) |
| AU (2) | AU579272B2 (en) |
| CA (2) | CA1274937A (en) |
| CH (1) | CH671230A5 (en) |
| DE (1) | DE3788441T2 (en) |
| GB (1) | GB2199586B (en) |
| NL (1) | NL8700005A (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3650656T2 (en) * | 1985-08-27 | 1998-04-30 | Mitsui Toatsu Chemicals | POLYIMIDES AND THESE HEAT-RESISTANT ADHESIVES |
| JPS6250372A (en) * | 1985-08-29 | 1987-03-05 | Mitsui Toatsu Chem Inc | heat resistant adhesive |
| JPS6250375A (en) * | 1985-08-30 | 1987-03-05 | Mitsui Toatsu Chem Inc | heat resistant adhesive |
| JPS6253388A (en) * | 1985-09-03 | 1987-03-09 | Mitsui Toatsu Chem Inc | heat resistant adhesive |
| JP2585552B2 (en) * | 1986-11-19 | 1997-02-26 | 三井東圧化学株式会社 | Polyimide |
| AU591045B2 (en) * | 1987-06-02 | 1989-11-23 | Mitsui Toatsu Chemicals Inc. | Polyimide resin composition |
| JP2672960B2 (en) * | 1988-03-01 | 1997-11-05 | 三井東圧化学株式会社 | Method for producing polyimide having good thermal stability |
| US4937316A (en) * | 1988-02-25 | 1990-06-26 | Amdahl Corporation | Process for preparing polyimides |
| JP2565556B2 (en) * | 1988-12-15 | 1996-12-18 | 三井東圧化学株式会社 | Method for producing polyimide with good moldability |
| CA1317408C (en) * | 1988-03-03 | 1993-05-04 | Barry L. Dickinson | Medical devices made from poly(etherimides) |
| JP2651219B2 (en) * | 1988-11-04 | 1997-09-10 | 日立化成工業株式会社 | Method for producing curable resin containing imide ring |
| JP2563548B2 (en) * | 1988-12-26 | 1996-12-11 | 三井東圧化学株式会社 | Method for producing polyimide with good moldability |
| JP2675110B2 (en) * | 1988-12-28 | 1997-11-12 | 三井東圧化学株式会社 | Method for producing polyimide having good thermal stability |
| DE68921059T2 (en) * | 1988-12-28 | 1995-09-14 | Mitsui Toatsu Chemicals | Polyimide foam. |
| JP2530919B2 (en) * | 1989-11-17 | 1996-09-04 | 三井東圧化学株式会社 | Polyimide |
| US5196506A (en) * | 1989-11-17 | 1993-03-23 | Mitsui Toatsu Chemicals, Inc. | Polymide |
| US5508377A (en) * | 1993-12-21 | 1996-04-16 | Mitsui Toatsu Chemicals, Inc. | Polyimide |
| US6380322B1 (en) | 1998-06-19 | 2002-04-30 | Georgia Tech Research Corporation | Reworkable high temperature adhesives |
| JP4338744B2 (en) | 2007-03-30 | 2009-10-07 | セイコークロック株式会社 | Karakuri Clock |
| US8962890B1 (en) | 2012-04-20 | 2015-02-24 | The United States Of America As Represented By The Secretary Of The Air Force | Multifunctional crosslinkers for shape-memory polyimides, polyamides and poly(amide-imides) and methods of making the same |
| US8791227B1 (en) | 2012-04-20 | 2014-07-29 | The United States Of America As Represented By The Secretary Of The Air Force | Crosslinked aromatic polyimides and methods of making the same |
| US9085661B1 (en) | 2012-10-26 | 2015-07-21 | The United States Of America As Represented By The Secretary Of The Air Force | Photomechanically active copolyimides derived from an azobenzenediamine, a rigid dianhydride, and a flexible dianhydride |
| KR101536398B1 (en) * | 2013-04-24 | 2015-07-13 | 유니마이크론 테크놀로지 코퍼레이션 | Diamine monomer with side group, polyimide with side group and manufacturing method thereof |
| US9139696B1 (en) | 2014-03-28 | 2015-09-22 | The United States Of America, As Represented By The Secretary Of The Air Force | Aromatic diamines containing three ether-linked-benzonitrile moieties, polymers thereof, and methods of making the same |
| US9644071B1 (en) | 2014-09-05 | 2017-05-09 | The United States Of America As Represented By The Secretary Of The Air Force | Bis(azobenzene) diamines and photomechanical polymers made therefrom |
| US10294255B1 (en) | 2015-08-07 | 2019-05-21 | The United States Of America As Represented By The Secretary Of The Air Force | Multifunctional crosslinking agent, crosslinked polymer, and method of making same |
| US10239254B1 (en) | 2015-08-07 | 2019-03-26 | The United States Of America As Represented By The Secretary Of The Air Force | Method of fabricating shape memory films |
| KR102161675B1 (en) * | 2017-05-22 | 2020-10-05 | 주식회사 엘지화학 | Polymer for liquid crystal aligning agent, amd liquid crystal aligning agent comprising the same, and liquid crystal aligning film, liquid crystal display device using the same |
| KR102195313B1 (en) * | 2017-10-20 | 2020-12-24 | 주식회사 엘지화학 | Liquid crystal alignment composition, process for preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
| KR102196880B1 (en) * | 2017-11-03 | 2020-12-30 | 주식회사 엘지화학 | Liquid crystal alignment composition, process for preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
| CN112635769B (en) * | 2020-12-22 | 2022-05-06 | 桂林电器科学研究院有限公司 | Binder for lithium ion battery negative electrode, preparation method thereof, negative electrode containing binder and lithium ion battery |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1934889A1 (en) * | 1969-07-10 | 1971-01-14 | Bayer Ag | Novel pyridine bis (hydroxyarylaether) and process for their preparation |
| GB1317321A (en) * | 1970-04-13 | 1973-05-16 | Int Harvester Co | Polyimides |
| US4111906A (en) * | 1976-07-19 | 1978-09-05 | Trw Inc. | Polyimides prepared from perfluoroisopropylidene diamine |
| US4203922A (en) * | 1976-07-19 | 1980-05-20 | Trw Inc. | Fluorinated aromatic diamine |
| JPS57209607A (en) * | 1981-06-22 | 1982-12-23 | Ube Ind Ltd | Preparation of polyimide separation film |
| JPS58157190A (en) * | 1982-03-12 | 1983-09-19 | 日立化成工業株式会社 | Method of producing substrate for flexible printed circuit |
| JPS5976451A (en) * | 1982-10-26 | 1984-05-01 | Hitachi Ltd | semiconductor equipment |
| US4535101A (en) * | 1984-04-03 | 1985-08-13 | Imi-Tech Corporation | Polyimide of 2,2-bis(4-(4-aminophenoxy)phenyl)-hexafluoropropane and process for the preparation of same |
| JPS6250372A (en) * | 1985-08-29 | 1987-03-05 | Mitsui Toatsu Chem Inc | heat resistant adhesive |
| JPS6250375A (en) * | 1985-08-30 | 1987-03-05 | Mitsui Toatsu Chem Inc | heat resistant adhesive |
| JPS6253388A (en) * | 1985-09-03 | 1987-03-09 | Mitsui Toatsu Chem Inc | heat resistant adhesive |
-
1985
- 1985-09-03 JP JP60193020A patent/JPS6253388A/en active Pending
-
1986
- 1986-02-12 JP JP61026936A patent/JPS62185714A/en active Granted
-
1987
- 1987-01-05 CH CH7/87A patent/CH671230A5/de not_active IP Right Cessation
- 1987-01-06 AU AU67173/87A patent/AU579272B2/en not_active Ceased
- 1987-01-06 NL NL8700005A patent/NL8700005A/en not_active Application Discontinuation
- 1987-01-06 GB GB8700164A patent/GB2199586B/en not_active Expired - Lifetime
- 1987-01-26 CA CA000528101A patent/CA1274937A/en not_active Expired - Lifetime
- 1987-02-03 CA CA000528830A patent/CA1274938A/en not_active Expired - Lifetime
- 1987-02-06 DE DE3788441T patent/DE3788441T2/en not_active Expired - Fee Related
- 1987-02-06 US US07/011,907 patent/US4797466A/en not_active Expired - Fee Related
- 1987-02-06 EP EP19870301063 patent/EP0233069B1/en not_active Expired - Lifetime
- 1987-02-11 AU AU68679/87A patent/AU580468B2/en not_active Ceased
- 1987-02-12 KR KR1019870001164A patent/KR900008963B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0530851B2 (en) | 1993-05-11 |
| NL8700005A (en) | 1988-08-01 |
| AU580468B2 (en) | 1989-01-12 |
| CA1274937A (en) | 1990-10-02 |
| CH671230A5 (en) | 1989-08-15 |
| EP0233069B1 (en) | 1993-12-15 |
| JPS62185714A (en) | 1987-08-14 |
| DE3788441T2 (en) | 1994-05-19 |
| GB2199586A (en) | 1988-07-13 |
| KR870007959A (en) | 1987-09-23 |
| GB8700164D0 (en) | 1987-02-11 |
| DE3788441D1 (en) | 1994-01-27 |
| KR900008963B1 (en) | 1990-12-15 |
| AU579272B2 (en) | 1988-11-17 |
| AU6717387A (en) | 1988-07-07 |
| US4797466A (en) | 1989-01-10 |
| EP0233069A3 (en) | 1988-09-07 |
| GB2199586B (en) | 1990-05-23 |
| AU6867987A (en) | 1987-08-13 |
| JPS6253388A (en) | 1987-03-09 |
| EP0233069A2 (en) | 1987-08-19 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |