CA2480144C - Rtm and ri processable polymide resins - Google Patents
Rtm and ri processable polymide resins Download PDFInfo
- Publication number
- CA2480144C CA2480144C CA002480144A CA2480144A CA2480144C CA 2480144 C CA2480144 C CA 2480144C CA 002480144 A CA002480144 A CA 002480144A CA 2480144 A CA2480144 A CA 2480144A CA 2480144 C CA2480144 C CA 2480144C
- Authority
- CA
- Canada
- Prior art keywords
- resin
- dianhydride
- aromatic
- aminophenoxy
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
-
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- 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]
-
- 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
Abstract
Polyimide resins that are suitable for processing by resin transfer molding (RTM) and resin infusion (RI) methods at reduced processing temperatures are provided. The inventive RTM and RI processable polyimide resins exhibit melting at temperatures of less than about 200 °C and melt viscosities at 200 °C of less than about 3000 centipoise. A process for synthesizing the inventive resins is also provided, as is a fiber-reinforced composite material. The fiber- reinforced composite material employs the inventive polyimide resin as its resin matrix and demonstrates good heat resistance and mechanical properties.
Description
RTM AND RI PROCESSABLE POLYIMIDE RESINS
RELATED APPLICATION
[0001] This application claims priority from U.S. Patent No. US 7,129,318 B2, which issued on October 31, 2006.
TECHNICAL FIELD
RELATED APPLICATION
[0001] This application claims priority from U.S. Patent No. US 7,129,318 B2, which issued on October 31, 2006.
TECHNICAL FIELD
[0002] The present invention relates to polyimide resins having a unique combination of properties rendering them processable by resin transfer molding io (RTM) and resin infusion (RI) methods at reduced processing temperatures, and to fiber-reinforced composite materials obtained therefrom. The present invention also relates to a process for synthesizing the RTM and RI processable polyimide resins.
BACKGROUND ART
BACKGROUND ART
[0003] Fiber-reinforced composite materials, which are made up of reinforcing fibers and matrix resins, are lightweight and have excellent mechanical properties. As such, these composite materials have been widely used in a variety of structural and non-structural applications such as aerospace, 2o automotive, infra-structure repair, marine, military, and sporting goods or other consumer products that must have sufficient toughness and impact resistance to endure many years of harsh service.
[0004] Various methods or techniques such as prepreg, hand lay-up, filament winding, pull-trusion, RTM and RI, have been used to produce fiber-reinforced composite materials. Of these methods or techniques, the RTM
method, in which a preform made up of reinforcing fibers is placed in a mold, a resin poured therein to impregnate the preform, and the impregnated preform cured to produce a molded product, offers the advantage that a large component having a complicated shape can be molded in a short period of time.
method, in which a preform made up of reinforcing fibers is placed in a mold, a resin poured therein to impregnate the preform, and the impregnated preform cured to produce a molded product, offers the advantage that a large component having a complicated shape can be molded in a short period of time.
[0005] Epoxy resins, and to a lesser extent, unsaturated polyester resins, vinyl ester resins, phenol resins, and polyimide resins, have been employed as matrix resins in fiber-reinforced composite materials. The use of composite materials having polyimide resin matrices is increasirig, however, where these materials are now recognized as preferred structural materials in aerospace applications, because of their lightweight and load-bearing characteristics and their oxidative stability at elevated temperatures.
[0006] Fiber-reinforced composite materials that use polyimide resins as the matrix resin are generally prepared using prepreg methods. Current technologies for making prepreg and composites from polyimides utilize solutions from the poly(amide) acids of these resins. Poiy(amide) acid solutions are processed into prepreg with various reinforcing fibers. These poly(amide) acid io solutions are of low solids contents and high viscosity. 'Therefore, the processing of these types of solutions requires overcoming significant problems such as solvent management and good fiber wet out from the high viscosity solutions.
The resultant prepreg typically requires, residual solvent contents of 20 to 25%
by weight (approximately 2-3% water from thermal imidization reaction) for adequate is tack and drape. This residual solvent must then be removed during the composite cure cycle. This material is hand-laid into composites which makes working with this type of material very labor intensive and costly.
The resultant prepreg typically requires, residual solvent contents of 20 to 25%
by weight (approximately 2-3% water from thermal imidization reaction) for adequate is tack and drape. This residual solvent must then be removed during the composite cure cycle. This material is hand-laid into composites which makes working with this type of material very labor intensive and costly.
[0007] The drawbacks inherent in prepreg methods have prompted the development of polyimide resins suitable for processing by RTM and RI methods.
2o The developed resins, however, require relatively high processing and cure temperatures of greater than 250 C, which severely limits their industrial utility due to the need for employing specialized high temperature molding equipment.
2o The developed resins, however, require relatively high processing and cure temperatures of greater than 250 C, which severely limits their industrial utility due to the need for employing specialized high temperature molding equipment.
[0008] For example, Jim M. Criss et a1., Resin Transfer Molding and Resin Infusion Fabrication of High Temperature Composites, Proceedings of the 46th 25 International SAMPE Symposium, Vol. 46 (2001), discloses two phenylethynyi containing imide oligomers that are processable by RTIV1- and RI methods. The two oligomers, which are designated PETI-RTM and RFI, reportedly display low and stable melt viscosities at temperatures of 250 to 290 C. PETI-RTM is defined as BPDA//25 mole% 3,4'-ODA175 mole% APB//PEPA, having a M, = 750 30 g/mole, while PETI-RFI is defined as BPDA//25 mole% 3,4'-ODA/75 mole%
APB//PEPA, having a M, = 1250 g/mole. Composites are prepared by RTM using the PETI-RTM and PETI-RFI oligomers and by Ri using the PETI-RFI oligomer, at processing temperatures of greater than 250 C. The injection temperature used was in the range of 260 to 288 C, while the cure temperature was 371 C.
APB//PEPA, having a M, = 1250 g/mole. Composites are prepared by RTM using the PETI-RTM and PETI-RFI oligomers and by Ri using the PETI-RFI oligomer, at processing temperatures of greater than 250 C. The injection temperature used was in the range of 260 to 288 C, while the cure temperature was 371 C.
[0009] U.S. Patent No. 5,965,687 to Brian J. Jensen discloses mixtures of polymeric materials consisting of branched, star-shaped and linear polyimides, s which are synthesized by using a small yet critical amount of a trifunctional monomer (e.g., a slow-reacting triamine.such as triamino pyrimidine or melamine), along with the conventional difunctional monomers in the polymerization. These mixtures reportedly have lower melt viscosities than linear polymers at the same molecular weight thereby allowing for processing via RTM or RFI, at lower io pressures and temperatures with techniques such as autoclave processing.
See Col. 2, lines 51 to 55, of U.S. Patent No. 5,965,687. Processing temperatures of greater than 250 C are still required, however, thereby limiting the industrial utility of these mixtures.
See Col. 2, lines 51 to 55, of U.S. Patent No. 5,965,687. Processing temperatures of greater than 250 C are still required, however, thereby limiting the industrial utility of these mixtures.
[0010] U.S. Patent No. 6,124,035 to Connell et al. discloses high 15 temperature transfer molding resins prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride (PA) and 4-phenylethynyl phthalic anhydride (PEPA). These resins reportedly have, among other things, relatively low melting temperatures (-182 C), low melt viscosities (< 1 poise at -270 C), and excellent melt stabilities (>2 hours at 250-280 C). As 2o noted above, however, the relatively high temperatures that are required to process these resins severely limit their industrial utility.
[001 i] A need therefore exists for a polyimide resin for use as a matrix resin in a fiber-reinforced composite that possesses properties rendering it suitable for processing by RTM and RI methods at reduced processing 25 temperatures.
[0012] It is therefore a primary object of the present invention to provide such a resin.
[0013] More particularly, it is an object of the present invention to provide polyimide resins that may be processed at reduced processing temperatures, and 30 that exhibit melting at temperatures of less than about 200 C and melt viscosities at 200 C of less than about 3000 centipoise.
[0014] It is another object of the present invention to provide a process for synthesizing such RTM and RI processable polyimide resins.
[0015] it is a further object to provide a fiber-reinforced composite material that employs such a polyimide resin as the matrix resin and that has good heat s resistance and mechanical properties.
SUMMARY OF THE INVENTION
[0016] The present invention therefore provides polyimide resins that are suitable for processing by resin transfer molding and resin infusion methods at io reduced processing temperatures, wherein the resins exhibit melting at temperatures of less than about 200 C and melt viscosities at 200 C of less than about 3000 centipoise.
[0017] The present invention also provides a method for the production of the above-identified polyimide resins, wherein the method comprises:
15 (a) chemically combining:
i. one or more aromatic dianhydrides represented by the following formula (I) o 0 o o MC/
\c il ll or by the following general formula (ll) ~C C\
Z
O O
~ c co '__1 c~ (Il)
[001 i] A need therefore exists for a polyimide resin for use as a matrix resin in a fiber-reinforced composite that possesses properties rendering it suitable for processing by RTM and RI methods at reduced processing 25 temperatures.
[0012] It is therefore a primary object of the present invention to provide such a resin.
[0013] More particularly, it is an object of the present invention to provide polyimide resins that may be processed at reduced processing temperatures, and 30 that exhibit melting at temperatures of less than about 200 C and melt viscosities at 200 C of less than about 3000 centipoise.
[0014] It is another object of the present invention to provide a process for synthesizing such RTM and RI processable polyimide resins.
[0015] it is a further object to provide a fiber-reinforced composite material that employs such a polyimide resin as the matrix resin and that has good heat s resistance and mechanical properties.
SUMMARY OF THE INVENTION
[0016] The present invention therefore provides polyimide resins that are suitable for processing by resin transfer molding and resin infusion methods at io reduced processing temperatures, wherein the resins exhibit melting at temperatures of less than about 200 C and melt viscosities at 200 C of less than about 3000 centipoise.
[0017] The present invention also provides a method for the production of the above-identified polyimide resins, wherein the method comprises:
15 (a) chemically combining:
i. one or more aromatic dianhydrides represented by the following formula (I) o 0 o o MC/
\c il ll or by the following general formula (ll) ~C C\
Z
O O
~ c co '__1 c~ (Il)
11 fl O O
wherein, Z represents -CO-, -0-, -SO2-, or a direct bond, ii. one or more aromatic diamines selected from the group of 3,4'-oxydianiline, m-phenylenediamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 1,3-bis(3-aminophenoxy)benzene, and 1,3-bis(4-aminophenoxy)benzene, wherein, the aromatic diamine(s) may optionally be used in combination with one or more rubber components, and iii. one or more carbocyclic monomeric anhydride end-capping agents selected from the group of nadic anhydride, alkyl derivatives of maleic anhydride, and 2-octen-1-ylsuccinic anhydride, and (b) imidizing the chemical combination.
[0018] The present invention further provides polyimide resins that are produced in accordance with the method described above.
[0019] The present invention also provides a high temperature composite comprising reinforcing fibers embedded in a polyimide resin matrix, wherein the polyimide resin is suitable for processing by resin transfer molding and resin infusion methods at reduced processing temperatures, and wherein the resin exhibits melting at temperatures of less than about 200 C and a melt viscosity at 200 C of less than about 3000 centipoise.
[0020] Other features and advantages of the invention will be apparent to one of ordinary skill from the following detailed description and accompanying drawings.
[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Particular features of the disclosed invention are illustrated by reference to the accompanying drawing labeled FIG. 1, which is a schematic of the method of chemically combining 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) monomers and a citraconic anhydride (CA) end-capping agent, and imidizing the resulting chemical combination to form a BPDA/1BAPP//CA polyimide resin.
BEST MODE FOR CARRYING OUT THE INVENTION
lo [0023] The polyimide resins of the present invention are the reaction products of one or more aromatic dianhydrides, one or more aromatic diamines, and one or more endcapping agents. The inventive polyimide resins' have a unique combination of properties, rendering them suitable for processing by RTM
and RI methods at reduced processing temperatures of less than about 200 C.
The inventive resins exhibit melting at temperatures of less than about 200 C
and melt viscosities at 200 C of less than about 3000 centipose (cps).
[0024] The term "melting point," as used herein, is intended to mean the lowest temperature at which the molten polyimide resins of the present invention start to exhibit a stable melt viscosity. The term "stable" means a melt viscosity fluctuation that does not exceed 100 cps over a period of at least one hour.
Melting points were determined using a TA Instruments, Model AR 1000, rheometer with measurements made in parallel mode (25 millimeter (mm) diameter, 25 mm gap) and a strain of 1.0 %. The temperature was scanned over a predetermined temperature scan rate of 10 C/ minute, with data recordings made every 3 seconds for a period of 37 minutes.
[0025] One aspect of the present invention involves the proper selection of the monomers used to prepare the polyimide resins. Aromatic dianhydrides deemed suitable for use in preparing the inventive RTM and Ri processable polyimide resins are dianhydrides that generally have more than one aromatic ring s in the structure, such as those dianhydrides represented by the following formula (f) c (l) \
II II
or by the foilowing general formula (11) ,c ~ c\
o ~ Z o (II) \c cf where Z represents -CO-, -0-, -SO2-, or a direct bond. The aromatic dianhydride having the structure (1) is 1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic dianhydride or PMDA), while aromatic dianhydrides having the structure (II) include 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 1,1',2,2'-benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (OPDA), and 3,3',4,4'-diphenylsuifone tetracarboxylic diandydride (DSDA).
[0026] One or more dianhydrides are used to prepare the inventive polyimide resins. When two dianhydrides are used, the first dianhydride (e.g., BTDA) is preferably present in an amount ranging from about 5 to about 40 % by wt. (more preferably, from about 10 to about 25 % by wt., and most preferably, from about 20 to about 25 % by wt.), based on the total weight of the dianhydrides, while the second dianhydride (e.g., BPDA) is preferably present in an amount ranging from about 95 to about 60 % by wt. (more preferably, from about 90 to about 75 % by wt., most preferably, from about 80 to about 75 % by wt.), based on the total weight of the dianhydrides.
[0027] Aromatic diamines deemed suitable for use in the present invention are diamines that generally have at least one ether linkage in the structure, such as 3,4'-oxydianiline (3,4'-ODA), m-phenyfenediamine (m-PDA), .2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4-(3-aminophenoxy)phenyl]sulfone (BAPS-M), 1,3-bis(3-aminophenoxy)benzene (APB), and 1,3-bis(4-aminophenoxy)benzene (TPE-R).
[0028] One or more diamines are used to prepare the inventive polyimide resins. When two diamines are used, it is preferred that at least one diamine have one or more oxygen linkages and that this diamine be present in an amount of at io least about 50 % by wt., based on the total weight of the diamines.
[0029] In select embodiments, the aromatic diamine(s) is used in combination with a rubber component. Suitable rubber components include, but are not limited to, amine terminated rubbers. In a preferred embodiment, ari, amine-terminated silicone rubber (SR) is used to prepare the inventive resins.
In this preferred embodiment, the rubber is present in an amount of less than about 30 % by wt., and more preferably in an amount of less than about 20 % by wt., based on the total weight of the aromatic diamine(s) and rubber component.
[0030] End-capping agents, suitable for use in preparing the inventive polyimide resins, are unsaturated carbocyclic monomeric anhydrides that form oligomers that exhibit melting at temperatures of less than about 250 C, and have melt viscosities at 200 C ranging from about 500 to about 3000 cps. Examples of such monomeric anhydrides include nadic anhydride (5-norbornene-2,3-dicarboxylic anhydride), alkyl derivatives of maleic anhydride, namely -methyl maleic anhydride (citraconic anhydride) and dimethyl maleic anhydride, and 2-octen-1-yisuccinic anhydride.
[00311 The polyimide resins of the present invention are synthesized by first preparing an amic acid solution followed by the preparation of an imide powder.
[0032] The preparation of an amic acid solution, in accordance with the teachings of the present invention, basically comprises:
(1) charging at least one dianhydride (e.g., BPDA) and at least one diamine (e.g., BAPP) to separate reaction vessels;
(2) adding quantities of a suitable solvent (e.g., 1-methyl-2-pyrrolidinone (NMP)) to each reaction vessel to form a slurry or solution of dianhydride(s) in one vessel, and a slurry or solution of diamine(s) in the other vessel, (3) heating the slurry or solution contained in each reaction vessel to a temperature ranging from about 50 to about 120 C to dissolve the dianhydride(s) and the diamine(s);
(4) cooling the solutions contained in each reaction vessel to ambient or room temperature;
(5) slowly adding the dianhydride solution to the diamine solution over a period of time ranging from about 10 to about 60 minutes;
(6) adding a solution of end-capping agent (e.g., methyl maleic anhydride or citraconic anhydride (CA) in NMP) to the reaction vessel; and (7) stirring the solution for a period of time ranging from about 15 to about 120 minutes to form an amic acid solution, wherein, the molar ratio of dianhydride(s) to diamine(s) to end-capping agent in the amic acid solution ranges from about 1.0/1.95/2.10 to about 1.0/2.1/2.0 [0033] By way of the present invention, it has been discovered that by slowly adding the dissolved dianhydride reactant to the dissolved diamine reactant, while controlling the reaction temperature, the molecular weight of the resulting resin is reduced causing an advantageous reduction in its melting point and melt viscosity.
[0034] Solvents suitable for use in the present inventive method include amide-based solvents such as NMP, N,N-dimethylacetamide, N,N-demethylformamide and N-methylcaprolactam, among which NMP and N,N-dimethylacetamide are preferred.
[0035] The molar ratio of dianhydride to diamine to end-capping agent is such that stirring the solution forms low molecular weight prepolymers having at least one end cap radical and suitable for chain extension and crosslinking to form polyimides that have a melting point of less than about 200 C, and a melt viscosity at 200 C of less than about 3000 cps. Typically the prepolymers have a weight average molecular weight of less than about 4000 grams per mole (glmol), and generally less than about 3000 g/mol.
[0036] In a preferred embodiment, the molar ratio of dianhydride(s):diamine(s):end-capping agent(s) is 1.0/2.0/2.01, and more preferably the molar ratio is n/n+112.
[0037] The synthesis of an imide powder, in accordance with the teachings of the present invention, involves either chemical or thermal imidization. In a preferred embodiment, the imide powder is prepared via chemical imidization in which a strong acid and an azeotropic agent are used to promote ring closure and io to remove azeotropic water, respectively. In yet a more preferred embodiment, a strong acid such as methane sulfonic acid is employed as a catalyst and azeotropic water removed by use of a tertiary amine co-solvent such as toluene.
More specifically, the imide powder is prepared by:
(1) placing from about 20 to about 40 % by wt. (preferably from ls about 25 to about 35 % by wt.) of the amic acid solution and from about 80 to about 60 % by wt. (preferably from about 75 to about 65 % by wt.) of an azeotropic agent (e.g., toluene) in a reaction vessel;
(2) charging from about 0.05 to about 0.5 % by wt. (preferably 20 from about 0.1 to about 0.2 % by wt.) of a strong acid catalyst (e.g., methane sulfonic acid) to the reaction vessel to form a mixture;
(3) heating the mixture in the reaction vessel to a temperature of from about 100 to about 130 C (preferably, from about 120 to 25 about 125 C) for from about 2 to about 6 hours;
(4) cooling the mixture to ambient or room temperature;
(5) removing the azeotropic agent from 'the reaction vessel; and (6) isolating and recovering the solids or imide powder from the remaining solution contained in the reaction vessel.
30 [0038] By way of the present invention, it has been further discovered that the strong acid and the azeotropic agent, when used in the amounts noted above, serve to effectively controi ring closure temperature. More specifically, the strong acid causes more water to be generated, while the azeotropic agent decreases the reflux point of the system.
[0039] A schematic of the synthesis of one polyimide resin contemplated by the present invention, namely - BPDA//BAPP//CA, is shown in Figure 1.
[0040] The polyimide resins of the present invention exhibit melting at temperatures of less than about 200 C (preferably from about 150 to about 175 C) and low melt viscosities at 200 C of less than about 3000 cps (preferably from about 1000 to about 2000 cps). As such, these resins may be processed at these reduced temperatures. Moreover, the inventive resins have a processing window io (time at minimum melt viscosities) at 200 C of at least about 60 minutes and cure at temperatures ranging from about 325 to about 375 C, preferably from about 330 to about 350 C. The weight average molecular weight of the inventive resins is less than about 4,000, and preferably ranges frorri, about 2000 to about 3000.
[0041] As will be readily appreciated by those skilled in the art, the low is processing temperatures and large processing windows achieved by the inventive resins favorably impact upon process economics allowing for the use of conventional epoxy RTM equipment and avoiding the need for more expensive high temperature injection systems.
[0042] Particularly advantageous polyimide resins are provided when:
20 (a) the resin is prepared by reacting BPDA with a diamine selected from the group of BAPP, BAPP/SR, APB, TPE-R
and 3,4-ODA, and end-capping any remaining amine groups with an unsaturated carbocyclic monomeric anhydride selected from the group of CA, HA and IA. For example, the 25 following resins are contemplated by the present invention:
(i) BPDA//BAPP//CA;
(ii) BPDA//APB//CA;
(iii) BPDA//BAPP/SR//CA;
(iv) BPDA//APB//HA;
30 (v) BPDA//BAPP//HA; and (vi) BPDA//BAPP/IA, (b) the resin is prepared by reacting BTDA with a diamine selected from the group of BAPS-M, BAPP/BAPS-M, m-PDAIBAPS-M, 3,4'-ODA/APB, APB and BAPPISR, and end-capping any remaining amine groups with an unsaturated carbocyclic monomeric anhydride selected from the group of CA, HA and IA. For example, the following resins are contemplated by the present invention:
(i) BTDA//BAPS-M//CA;
(ii) BTDA//BAPP/BAPS-M//CA;
(iii) BTDA//m-PDA/BAPS-M//CA;, (iv) BTDA//3,4'-ODA/APB//CA;
(v) BTDA//APB//CA;
(vi) BTDA//BAPP/SR//CA;
(vii) BTDA//BAPS-M//HA;
(viii) BTDA//APB//HA; and (ix) BTDAUBAPS-M/[A, (c) the resin is prepared by reacting BTDA/BPDA with BAPP, and with CA to form BTDA/BPDA//BAPP//CA, (d) the resin is prepared by reacting PMDA with BAPS-M, and with CA to form PM DA//BAPS-M//CA, (e) the resin is prepared by reacting OPDA with a diamine selected from the group of BAPP and BAPS-M, and with CA
to form OPDA//BAPP//CA and OPDA//BAPS-M//CA, and {f) the resin is prepared by reacting DSDA with a diamine selected from the group of BAPS--M and BAPP, and CA to form DSDA//BAPS-M//CA and DSDA//BAPP//CA.
[0043] The present invention also contemplates the provision of high temperature composites comprising reinforcing fibers embedded in polyimide resin matrices. The inventive composites demonstrate a combination of desirable properties after cure that render them suitable for use in a wide variety of applications such as aerospace, military, and infra-structure repair applications.
More specifically, these high temperature composites exhibit a use temperature of
wherein, Z represents -CO-, -0-, -SO2-, or a direct bond, ii. one or more aromatic diamines selected from the group of 3,4'-oxydianiline, m-phenylenediamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 1,3-bis(3-aminophenoxy)benzene, and 1,3-bis(4-aminophenoxy)benzene, wherein, the aromatic diamine(s) may optionally be used in combination with one or more rubber components, and iii. one or more carbocyclic monomeric anhydride end-capping agents selected from the group of nadic anhydride, alkyl derivatives of maleic anhydride, and 2-octen-1-ylsuccinic anhydride, and (b) imidizing the chemical combination.
[0018] The present invention further provides polyimide resins that are produced in accordance with the method described above.
[0019] The present invention also provides a high temperature composite comprising reinforcing fibers embedded in a polyimide resin matrix, wherein the polyimide resin is suitable for processing by resin transfer molding and resin infusion methods at reduced processing temperatures, and wherein the resin exhibits melting at temperatures of less than about 200 C and a melt viscosity at 200 C of less than about 3000 centipoise.
[0020] Other features and advantages of the invention will be apparent to one of ordinary skill from the following detailed description and accompanying drawings.
[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Particular features of the disclosed invention are illustrated by reference to the accompanying drawing labeled FIG. 1, which is a schematic of the method of chemically combining 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) monomers and a citraconic anhydride (CA) end-capping agent, and imidizing the resulting chemical combination to form a BPDA/1BAPP//CA polyimide resin.
BEST MODE FOR CARRYING OUT THE INVENTION
lo [0023] The polyimide resins of the present invention are the reaction products of one or more aromatic dianhydrides, one or more aromatic diamines, and one or more endcapping agents. The inventive polyimide resins' have a unique combination of properties, rendering them suitable for processing by RTM
and RI methods at reduced processing temperatures of less than about 200 C.
The inventive resins exhibit melting at temperatures of less than about 200 C
and melt viscosities at 200 C of less than about 3000 centipose (cps).
[0024] The term "melting point," as used herein, is intended to mean the lowest temperature at which the molten polyimide resins of the present invention start to exhibit a stable melt viscosity. The term "stable" means a melt viscosity fluctuation that does not exceed 100 cps over a period of at least one hour.
Melting points were determined using a TA Instruments, Model AR 1000, rheometer with measurements made in parallel mode (25 millimeter (mm) diameter, 25 mm gap) and a strain of 1.0 %. The temperature was scanned over a predetermined temperature scan rate of 10 C/ minute, with data recordings made every 3 seconds for a period of 37 minutes.
[0025] One aspect of the present invention involves the proper selection of the monomers used to prepare the polyimide resins. Aromatic dianhydrides deemed suitable for use in preparing the inventive RTM and Ri processable polyimide resins are dianhydrides that generally have more than one aromatic ring s in the structure, such as those dianhydrides represented by the following formula (f) c (l) \
II II
or by the foilowing general formula (11) ,c ~ c\
o ~ Z o (II) \c cf where Z represents -CO-, -0-, -SO2-, or a direct bond. The aromatic dianhydride having the structure (1) is 1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic dianhydride or PMDA), while aromatic dianhydrides having the structure (II) include 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 1,1',2,2'-benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (OPDA), and 3,3',4,4'-diphenylsuifone tetracarboxylic diandydride (DSDA).
[0026] One or more dianhydrides are used to prepare the inventive polyimide resins. When two dianhydrides are used, the first dianhydride (e.g., BTDA) is preferably present in an amount ranging from about 5 to about 40 % by wt. (more preferably, from about 10 to about 25 % by wt., and most preferably, from about 20 to about 25 % by wt.), based on the total weight of the dianhydrides, while the second dianhydride (e.g., BPDA) is preferably present in an amount ranging from about 95 to about 60 % by wt. (more preferably, from about 90 to about 75 % by wt., most preferably, from about 80 to about 75 % by wt.), based on the total weight of the dianhydrides.
[0027] Aromatic diamines deemed suitable for use in the present invention are diamines that generally have at least one ether linkage in the structure, such as 3,4'-oxydianiline (3,4'-ODA), m-phenyfenediamine (m-PDA), .2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4-(3-aminophenoxy)phenyl]sulfone (BAPS-M), 1,3-bis(3-aminophenoxy)benzene (APB), and 1,3-bis(4-aminophenoxy)benzene (TPE-R).
[0028] One or more diamines are used to prepare the inventive polyimide resins. When two diamines are used, it is preferred that at least one diamine have one or more oxygen linkages and that this diamine be present in an amount of at io least about 50 % by wt., based on the total weight of the diamines.
[0029] In select embodiments, the aromatic diamine(s) is used in combination with a rubber component. Suitable rubber components include, but are not limited to, amine terminated rubbers. In a preferred embodiment, ari, amine-terminated silicone rubber (SR) is used to prepare the inventive resins.
In this preferred embodiment, the rubber is present in an amount of less than about 30 % by wt., and more preferably in an amount of less than about 20 % by wt., based on the total weight of the aromatic diamine(s) and rubber component.
[0030] End-capping agents, suitable for use in preparing the inventive polyimide resins, are unsaturated carbocyclic monomeric anhydrides that form oligomers that exhibit melting at temperatures of less than about 250 C, and have melt viscosities at 200 C ranging from about 500 to about 3000 cps. Examples of such monomeric anhydrides include nadic anhydride (5-norbornene-2,3-dicarboxylic anhydride), alkyl derivatives of maleic anhydride, namely -methyl maleic anhydride (citraconic anhydride) and dimethyl maleic anhydride, and 2-octen-1-yisuccinic anhydride.
[00311 The polyimide resins of the present invention are synthesized by first preparing an amic acid solution followed by the preparation of an imide powder.
[0032] The preparation of an amic acid solution, in accordance with the teachings of the present invention, basically comprises:
(1) charging at least one dianhydride (e.g., BPDA) and at least one diamine (e.g., BAPP) to separate reaction vessels;
(2) adding quantities of a suitable solvent (e.g., 1-methyl-2-pyrrolidinone (NMP)) to each reaction vessel to form a slurry or solution of dianhydride(s) in one vessel, and a slurry or solution of diamine(s) in the other vessel, (3) heating the slurry or solution contained in each reaction vessel to a temperature ranging from about 50 to about 120 C to dissolve the dianhydride(s) and the diamine(s);
(4) cooling the solutions contained in each reaction vessel to ambient or room temperature;
(5) slowly adding the dianhydride solution to the diamine solution over a period of time ranging from about 10 to about 60 minutes;
(6) adding a solution of end-capping agent (e.g., methyl maleic anhydride or citraconic anhydride (CA) in NMP) to the reaction vessel; and (7) stirring the solution for a period of time ranging from about 15 to about 120 minutes to form an amic acid solution, wherein, the molar ratio of dianhydride(s) to diamine(s) to end-capping agent in the amic acid solution ranges from about 1.0/1.95/2.10 to about 1.0/2.1/2.0 [0033] By way of the present invention, it has been discovered that by slowly adding the dissolved dianhydride reactant to the dissolved diamine reactant, while controlling the reaction temperature, the molecular weight of the resulting resin is reduced causing an advantageous reduction in its melting point and melt viscosity.
[0034] Solvents suitable for use in the present inventive method include amide-based solvents such as NMP, N,N-dimethylacetamide, N,N-demethylformamide and N-methylcaprolactam, among which NMP and N,N-dimethylacetamide are preferred.
[0035] The molar ratio of dianhydride to diamine to end-capping agent is such that stirring the solution forms low molecular weight prepolymers having at least one end cap radical and suitable for chain extension and crosslinking to form polyimides that have a melting point of less than about 200 C, and a melt viscosity at 200 C of less than about 3000 cps. Typically the prepolymers have a weight average molecular weight of less than about 4000 grams per mole (glmol), and generally less than about 3000 g/mol.
[0036] In a preferred embodiment, the molar ratio of dianhydride(s):diamine(s):end-capping agent(s) is 1.0/2.0/2.01, and more preferably the molar ratio is n/n+112.
[0037] The synthesis of an imide powder, in accordance with the teachings of the present invention, involves either chemical or thermal imidization. In a preferred embodiment, the imide powder is prepared via chemical imidization in which a strong acid and an azeotropic agent are used to promote ring closure and io to remove azeotropic water, respectively. In yet a more preferred embodiment, a strong acid such as methane sulfonic acid is employed as a catalyst and azeotropic water removed by use of a tertiary amine co-solvent such as toluene.
More specifically, the imide powder is prepared by:
(1) placing from about 20 to about 40 % by wt. (preferably from ls about 25 to about 35 % by wt.) of the amic acid solution and from about 80 to about 60 % by wt. (preferably from about 75 to about 65 % by wt.) of an azeotropic agent (e.g., toluene) in a reaction vessel;
(2) charging from about 0.05 to about 0.5 % by wt. (preferably 20 from about 0.1 to about 0.2 % by wt.) of a strong acid catalyst (e.g., methane sulfonic acid) to the reaction vessel to form a mixture;
(3) heating the mixture in the reaction vessel to a temperature of from about 100 to about 130 C (preferably, from about 120 to 25 about 125 C) for from about 2 to about 6 hours;
(4) cooling the mixture to ambient or room temperature;
(5) removing the azeotropic agent from 'the reaction vessel; and (6) isolating and recovering the solids or imide powder from the remaining solution contained in the reaction vessel.
30 [0038] By way of the present invention, it has been further discovered that the strong acid and the azeotropic agent, when used in the amounts noted above, serve to effectively controi ring closure temperature. More specifically, the strong acid causes more water to be generated, while the azeotropic agent decreases the reflux point of the system.
[0039] A schematic of the synthesis of one polyimide resin contemplated by the present invention, namely - BPDA//BAPP//CA, is shown in Figure 1.
[0040] The polyimide resins of the present invention exhibit melting at temperatures of less than about 200 C (preferably from about 150 to about 175 C) and low melt viscosities at 200 C of less than about 3000 cps (preferably from about 1000 to about 2000 cps). As such, these resins may be processed at these reduced temperatures. Moreover, the inventive resins have a processing window io (time at minimum melt viscosities) at 200 C of at least about 60 minutes and cure at temperatures ranging from about 325 to about 375 C, preferably from about 330 to about 350 C. The weight average molecular weight of the inventive resins is less than about 4,000, and preferably ranges frorri, about 2000 to about 3000.
[0041] As will be readily appreciated by those skilled in the art, the low is processing temperatures and large processing windows achieved by the inventive resins favorably impact upon process economics allowing for the use of conventional epoxy RTM equipment and avoiding the need for more expensive high temperature injection systems.
[0042] Particularly advantageous polyimide resins are provided when:
20 (a) the resin is prepared by reacting BPDA with a diamine selected from the group of BAPP, BAPP/SR, APB, TPE-R
and 3,4-ODA, and end-capping any remaining amine groups with an unsaturated carbocyclic monomeric anhydride selected from the group of CA, HA and IA. For example, the 25 following resins are contemplated by the present invention:
(i) BPDA//BAPP//CA;
(ii) BPDA//APB//CA;
(iii) BPDA//BAPP/SR//CA;
(iv) BPDA//APB//HA;
30 (v) BPDA//BAPP//HA; and (vi) BPDA//BAPP/IA, (b) the resin is prepared by reacting BTDA with a diamine selected from the group of BAPS-M, BAPP/BAPS-M, m-PDAIBAPS-M, 3,4'-ODA/APB, APB and BAPPISR, and end-capping any remaining amine groups with an unsaturated carbocyclic monomeric anhydride selected from the group of CA, HA and IA. For example, the following resins are contemplated by the present invention:
(i) BTDA//BAPS-M//CA;
(ii) BTDA//BAPP/BAPS-M//CA;
(iii) BTDA//m-PDA/BAPS-M//CA;, (iv) BTDA//3,4'-ODA/APB//CA;
(v) BTDA//APB//CA;
(vi) BTDA//BAPP/SR//CA;
(vii) BTDA//BAPS-M//HA;
(viii) BTDA//APB//HA; and (ix) BTDAUBAPS-M/[A, (c) the resin is prepared by reacting BTDA/BPDA with BAPP, and with CA to form BTDA/BPDA//BAPP//CA, (d) the resin is prepared by reacting PMDA with BAPS-M, and with CA to form PM DA//BAPS-M//CA, (e) the resin is prepared by reacting OPDA with a diamine selected from the group of BAPP and BAPS-M, and with CA
to form OPDA//BAPP//CA and OPDA//BAPS-M//CA, and {f) the resin is prepared by reacting DSDA with a diamine selected from the group of BAPS--M and BAPP, and CA to form DSDA//BAPS-M//CA and DSDA//BAPP//CA.
[0043] The present invention also contemplates the provision of high temperature composites comprising reinforcing fibers embedded in polyimide resin matrices. The inventive composites demonstrate a combination of desirable properties after cure that render them suitable for use in a wide variety of applications such as aerospace, military, and infra-structure repair applications.
More specifically, these high temperature composites exhibit a use temperature of
12 greater than about 200 C, and further exhibit a T. of greater than about 240 C, toughness, microcrack resistance, solvent and moisture resistance, damage tolerance, and good retention of mechanical properties under hot/wet conditions.
[0044] Reinforcing fibers suitable for use in the inventive composite include carbon fibers, glass fibers, and quartz fibers.
[0045] The subject invention will now be described by reference to the following illustrative examples. The examples are not, however, intended to limit the generally broad scope of the present invention.
WORKING EXAMPLES
[0046] Preparation of RTM and RI Processable Polyimide Resins.
Unless otherwise stated, the procedures, conditions and molar ratios detailed below for the preparation of BPDA//BAPP//CA were also used to prepare the remaining RTM and RI processable polyimide resins in this WORKING EXAMPLES section.
1) BPDA//BAPP//CA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025 mol) was placed in NMP (70g) in a beaker, while BAPP (20.5 g, 0.05 mol) was placed in NMP (70g) in a separate beaker. The beakers were heated to completely dissolve the monomers. The resulting solutioris were cooled to room temperature, and the BAPP solution transferred into a 500 mi three-necked, round-bottom flask equipped with a mechanical stirrer, thermometer and dropping funnel for addirig the BPDA solution. The beakers of BPDA and BAPP solutions were rinsed to remove all reactants by using an additional 5.Og of NMP for each container.
The BPDA solution was then added drop wise into the BAPP solution over a period of three hours. CA (5.6g, 0.05 mol) end-capping agent was then added drop wise to the round-bottom flask over a period of about one hour. The resulting mixture, the temperature of which had increased slightly, was then stirred for one hour to form an amic acid solution having a solids content of 30 % by wt. The addition of the
[0044] Reinforcing fibers suitable for use in the inventive composite include carbon fibers, glass fibers, and quartz fibers.
[0045] The subject invention will now be described by reference to the following illustrative examples. The examples are not, however, intended to limit the generally broad scope of the present invention.
WORKING EXAMPLES
[0046] Preparation of RTM and RI Processable Polyimide Resins.
Unless otherwise stated, the procedures, conditions and molar ratios detailed below for the preparation of BPDA//BAPP//CA were also used to prepare the remaining RTM and RI processable polyimide resins in this WORKING EXAMPLES section.
1) BPDA//BAPP//CA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025 mol) was placed in NMP (70g) in a beaker, while BAPP (20.5 g, 0.05 mol) was placed in NMP (70g) in a separate beaker. The beakers were heated to completely dissolve the monomers. The resulting solutioris were cooled to room temperature, and the BAPP solution transferred into a 500 mi three-necked, round-bottom flask equipped with a mechanical stirrer, thermometer and dropping funnel for addirig the BPDA solution. The beakers of BPDA and BAPP solutions were rinsed to remove all reactants by using an additional 5.Og of NMP for each container.
The BPDA solution was then added drop wise into the BAPP solution over a period of three hours. CA (5.6g, 0.05 mol) end-capping agent was then added drop wise to the round-bottom flask over a period of about one hour. The resulting mixture, the temperature of which had increased slightly, was then stirred for one hour to form an amic acid solution having a solids content of 30 % by wt. The addition of the
13 BPDA solution and CA end-capping agent were performed at room temperature.
Synthesis of Imide Powder.
A quantity of 50g of the amic acid solution and 116g of toluene were placed in a 500m, three-necked, round-bottom flask fitted with a Dean-Stark trap full of toluene and connected to a reflux condenser, nitrogen inlet/outlet, and a temperature sensor connected through a temperature controller. A quantity of 0.3g methane sulfonic acid catalyst was then added to the solution and the resulting mixture heated via an electronic heating mantle to reflux at 120 to 125 C and held for three to four hours. Water generated during this process was collected at the bottom of the Dean-Stark trap. The reaction solution was then allowed to cool to room temperature. The reaction solution was then transferred to an evaporating flask of a rotational evaporator. Toluene was removed from the reaction solution using the rotational evaporator (vacuum -30 mbar, oil heating bath - 120 C). The solution remaining in the evaporating flask of the rotational evaporator was then transferred to a blender containing about one liter of tap water and mixed for five minutes to precipitate the solution. The resulting precipitate was isolated using vacuum filtration, washed twice with tap water and dried in a forced air oven at 105 C overnight to give a quantitative yield (99.5%) of yellow powder.
The calculated number average molecular weight of the prepared polyimide resin was 1266 g/mole.
2) BTDA//BAPS-M//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mol, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), CA (5.60g, 0.05mol).
Synthesis of Imide Powder.
A quantity of 50g of the amic acid solution and 116g of toluene were placed in a 500m, three-necked, round-bottom flask fitted with a Dean-Stark trap full of toluene and connected to a reflux condenser, nitrogen inlet/outlet, and a temperature sensor connected through a temperature controller. A quantity of 0.3g methane sulfonic acid catalyst was then added to the solution and the resulting mixture heated via an electronic heating mantle to reflux at 120 to 125 C and held for three to four hours. Water generated during this process was collected at the bottom of the Dean-Stark trap. The reaction solution was then allowed to cool to room temperature. The reaction solution was then transferred to an evaporating flask of a rotational evaporator. Toluene was removed from the reaction solution using the rotational evaporator (vacuum -30 mbar, oil heating bath - 120 C). The solution remaining in the evaporating flask of the rotational evaporator was then transferred to a blender containing about one liter of tap water and mixed for five minutes to precipitate the solution. The resulting precipitate was isolated using vacuum filtration, washed twice with tap water and dried in a forced air oven at 105 C overnight to give a quantitative yield (99.5%) of yellow powder.
The calculated number average molecular weight of the prepared polyimide resin was 1266 g/mole.
2) BTDA//BAPS-M//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mol, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), CA (5.60g, 0.05mol).
14 3) BTDA//BAPP/BAPS-M//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), BAPP/BAPS-M (5.13g, 0.0125mo!/16.3g, 0.0375mo1, NMP 70g), CA (5.6g, 0.05moi).
s 4) BTDA/BPDA//BAPP//CA
Synthesis of Amic Acid Solution.
BTDA/BPDA (2.0g, 0.006mol/5.5g, 0.019mol, NMP 70g), BAPP (50.5g, 0.05mo1, NMP 70g), CA (5.6g, 0.05mol).
5) BTDA//m-PDA/BAPS-M//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), m-PDA/BAPS-M (1.35g, 0.0125mo1/16.3g, 0.0375moI, NMP 70g), CA (5.6g, 0.05moi) 6) BTDAI/3,4-ODA/APB//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), 3,4-ODA/APB (2.5g, 0.0125mo1/10.95g, 0.0375mo1, NMP 70g), CA (5.6g, 0.05mol).
7) BTDA//APB//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), APB (14.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05mol).
8) BPDA//APB//CA
Syrithesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), APB (14.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05mol).
9) BTDAi/BAPP/SR//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), BAPP/SR (18.45g, 0.05mol/2.05g, NMP 70g), CA (5.6g, 0.05rnoi).
10) BPDA//BAPP/SR//CA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025m1, NMP 70g), BAPP/SR (16.4g, 0.05mol/4.1g, NMP 70g), CA (5.6g, 0.05mol).
11) BPDA/fTPE-R//CA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), TPE-R (14.7g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
s 12) BPDA//3,4-ODA//CA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025moi, NMP 70g), 3,4-ODA (10g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
13) PMDA//BAPS-M//CA
Synthesis of Amic Acid Solution.
PMDA (5.45g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
14) OPDA//BAPP/JCA
Synthesis of Amic Acid Solution.
OPDA (7.75g, 0.025mo1, NMP 70g), BAPP (20.5g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), BAPP/BAPS-M (5.13g, 0.0125mo!/16.3g, 0.0375mo1, NMP 70g), CA (5.6g, 0.05moi).
s 4) BTDA/BPDA//BAPP//CA
Synthesis of Amic Acid Solution.
BTDA/BPDA (2.0g, 0.006mol/5.5g, 0.019mol, NMP 70g), BAPP (50.5g, 0.05mo1, NMP 70g), CA (5.6g, 0.05mol).
5) BTDA//m-PDA/BAPS-M//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), m-PDA/BAPS-M (1.35g, 0.0125mo1/16.3g, 0.0375moI, NMP 70g), CA (5.6g, 0.05moi) 6) BTDAI/3,4-ODA/APB//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), 3,4-ODA/APB (2.5g, 0.0125mo1/10.95g, 0.0375mo1, NMP 70g), CA (5.6g, 0.05mol).
7) BTDA//APB//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), APB (14.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05mol).
8) BPDA//APB//CA
Syrithesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), APB (14.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05mol).
9) BTDAi/BAPP/SR//CA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), BAPP/SR (18.45g, 0.05mol/2.05g, NMP 70g), CA (5.6g, 0.05rnoi).
10) BPDA//BAPP/SR//CA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025m1, NMP 70g), BAPP/SR (16.4g, 0.05mol/4.1g, NMP 70g), CA (5.6g, 0.05mol).
11) BPDA/fTPE-R//CA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), TPE-R (14.7g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
s 12) BPDA//3,4-ODA//CA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025moi, NMP 70g), 3,4-ODA (10g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
13) PMDA//BAPS-M//CA
Synthesis of Amic Acid Solution.
PMDA (5.45g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
14) OPDA//BAPP/JCA
Synthesis of Amic Acid Solution.
OPDA (7.75g, 0.025mo1, NMP 70g), BAPP (20.5g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
15) OPDA//BAPS-M//CA
Synthesis of Amic Acid Solution.
OPDA (7.75g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
Synthesis of Amic Acid Solution.
OPDA (7.75g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05mo1).
16) DSDA//BAPS-M//CA
Synthesis o~ Arnic Acid Solution.
DSDA (8.95g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05moI).
Synthesis o~ Arnic Acid Solution.
DSDA (8.95g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), CA (5.6g, 0.05moI).
17) DSDA//BAPP//CA
Synthesis of Amic Acid Solution.
DSDA (8.95g, 0.025mo1, NMP 70g), BAPP (20.5 g, 0.05mol, NMP 70g), CA (5.6g, 0.05moi).
Synthesis of Amic Acid Solution.
DSDA (8.95g, 0.025mo1, NMP 70g), BAPP (20.5 g, 0.05mol, NMP 70g), CA (5.6g, 0.05moi).
18) BTDA//BAPS-M//HA
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), HA (8.2g, 0.05mo1).
Synthesis of Amic Acid Solution.
BTDA (8.05g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), HA (8.2g, 0.05mo1).
19) BTDA//APB//HA
Synthesis of Amic Acid Solution.
BTDA (8.05g, OA25moi, NMP 70g), APB (14.6g, 0.05mol, NMP 70g), HA (8.2g, 0.05moI).
Synthesis of Amic Acid Solution.
BTDA (8.05g, OA25moi, NMP 70g), APB (14.6g, 0.05mol, NMP 70g), HA (8.2g, 0.05moI).
20) BPDA//APB//HA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), APB (14.6g, 0.05mol, NMP 70g), HA (8.2g, 0.05mo!).
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), APB (14.6g, 0.05mol, NMP 70g), HA (8.2g, 0.05mo!).
21) BPDA//BAPP//HA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), BAPP (20.5g, 0.05mol, NMP 70g), HA (8.2g, 0.05m1).
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), BAPP (20.5g, 0.05mol, NMP 70g), HA (8.2g, 0.05m1).
22) BPDA//BAPP//IA
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), BAPP (20.5g, 0.05mol, NMP 70g), IA (5.6g, 0.05moi).
Synthesis of Amic Acid Solution.
BPDA (7.35g, 0.025mo1, NMP 70g), BAPP (20.5g, 0.05mol, NMP 70g), IA (5.6g, 0.05moi).
23) BTDA//BAPS-M//IA
Synthesis of Amic Acid Solution.
BTDA (7.35g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), IA (5.6g, 0.05mol).
[0047] In Table 1 below, properties of the RTM and RI processable polyimiue resins of the above examples are summarized.
Table I
Properties of RTM and Ri Processable Polyimide Resins Example RTM and Rl Processable Molar Ratio Melting Melt Polyimide Resin Point Viscosity ( C c s 1 BPDA//BAPP/ICA 1:2:2 160/330 1,000 2 BTDA//BAPS-M//CA 1:2:2 160/320 1,000 3 BTDA//BAPP/BAPS-M//CA 1:2 25/75 :2 190/330 1,000 4 BTDA/BPDA//BAPP//CA 125/75:2:2 160/330 1,000 BTDA//m-PDA/BAPS-M//CA 1:2 25/75 :2 175/310 1,000 6 BTDA//3,4ODA/APB//CA 1 :2 25/75 :2 210/305 1,000 7 BTDA//APB//CA 1:2:2 140/335 1,000 8 BPDA//APB/!CA 1:2:2 160/330 1,000 9 BTDA//BAPP/SR//CA 1:2(90/10wt%):2 190/330 950 BPDA//BAPP/SR//CA 1:2 80/20wt% :2 .. 210/345 900 11 BPDA/ITPE-R//CA 1:2:2 280/315 1,100 12 BPDA//3,4ODA//CA 1:2:2 280/310 1,000 13 PM DA//BAPS-M//CA 1:2:2 150/330 1,000 14 OPDA//BAPP/CA 1:2:2 160/330 1,000 OPDA//BAPS-M//CA 1:2:2 160/305 1,000 16 DSDA//BAPS-M//CA 1:2:2 160/320 1,000 17 DSDA//BAPP/ICA 1:2:2 1601330 1,000 18 BTDA//BAPS-M//HA 1:2:2 200/285 1,000 19 BTDA//APB//HA 1:2:2 160/290 1,000 BPDA//APBI/HA 1:2:2 140/305 11,000 21 BPDA//BAPP//HA 1:2:2 200/290 1,000 22 BPDA//BAPP/lA 1:2:2 180/250 1,200 23 BTDA//BAPS-M//IA 1:2:2 190/260 1,000 [0048] Examples I to 5, 7 to 9, 13 to 17, 19, 20, 22 and 23, demonstrate that polyimide resins prepared in accordance with the teachings of the present invention exhibit melting at temperatures of less than about 200 C and melt viscosities at 200 C of less than about 3000 cps, rendering them suitable for io processing by RTM and RI methods at reduced processing temperatures of less than about 200 C. While Examples 6, 10, 18 and 21 exhibited melting at slightly higher temperatures, the melting points of these resins may be reduced by adjusting the weight percents of the diamines in Examples 6, 18 and 21 and by adjusting the weight percents of the diamine and rubber components in Example 15 ' 10. (See, e.g., Examples 9 and 10).
[0049] Preparation and Testing of Carbon Fabric Reinforced Composite.
1) Preparation of BPDA//BAPP//CA Matrix Resin.
Synthesis of Amic Acid Solution.
BPDA (150.52 g, 0.512 mol) was placed in NMP (1200 g) in a beaker, while BAPP (419.84 g, 1.024 mol) was placed in NMP (400 g) in a separate beaker. The beakers vvere heated to completely dissolve the monomers. The resulting solutions were cooled to room temperature, and the BAPP solution trainsferred into a 10,000 mi three-necked, round-bottom flask equipped with a mechanical stirrer, thermometer and dropping funnel for adding the BPDA solution. The beakers of BPDA and BAPP solutions were rinsed to remove all reactants by using an additional 10 g of NMP for each container.
The BPDA solution was then added drop wise into the BAPP solution over a period of three hours. CA (126.15 g, 1.126 mol) end-capping agent was then added drop wise to the round-bottom flask over a period of about one hour. The resulting mixture, the temperature of which had increased slightly, was then stirred for one hour to form an amic acid solution. The addition of the BPDA solution and CA end-capping agent were performed at room temperature.
Synthesis of Imide Powder.
A quantity of 2316.5 g of the amic acid solution and 5,144 g of toluene were placed in a 10 liter, "three-riecked, round-bottom flask fitted with a Dean-Stark trap full of toluene and connected to a reflux condenser, nitrogen inlet/outlet, and a temperature sensor connected through a temperature controller. A quantity of 10 g methane sulfonic acid catalyst was then added to the solution and the resulting mixture heated via an electronic heating mantle to reflux at 120 to 125 C and held for three to four hours. Water generated during this process was collected at the bottom of the Dean-Stark trap. The reaction solution was then allowed to cool to room temperature. The reaction solution was then transferred to an evaporating flask of a rotational evaporator. Toluene was removed from the reaction solution using the rotational evaporator (vacuum -30 mbar, oil heating bath - 120 C). The solution remaining in the evaporating flask of the rotational evaporator was then transferred to a blender containing about 30 liters of tap water and mixed for 5 minutes to precipitate the solution. The resulting precipitate was isolated using vacuum filtration, washed twice with tap water and dried in a forced air oven at 60 C for five hours and then at 105 C
for ten hours to give a quantitative yield (99.5 %) of yellow powder.
The calculated number average molecular weight of the io prepared polyimide resin was 1266 g/mole.
2) Preparation of Carbon Fabric Reinforced Composite.
A resin transfer molding or RTM apparatus was used to prepare a carbon fabric reinforced composite in accordance with the present invention. The RTM apparatus included a mold having at least one surface configured to the shape of the part to be made.
The mold, which measured 25.4 centimeters by 45.7 centimeters, was enclosed and had an upper and a lower part, and a seal for providing an airtight seal between the mold components during use.
The mold further included resin injection and evacuation ports for providing entrance and exit points, respectively, for the matrix resin.
Eight layers of woven carbon fabric obtained from Textile Products, Inc., 2512 Woodland Drive, Anaheim, CA 92801, under the product designation T650135-3k-8hs carbon fabric, were placed one on top of the other in the mold, with warp fibers all running in the same direction. The mold was then sealed and air drawn from the mold to achieve a vacuum -of 70 pascals. The prepared polyimide resin was then melted at 200 C, degassed and pumped into the mold at a pressure of 2.4 megapascals through the resin injection port, which was maintained at a temperature of about 200 C.
After the mold was full, trapped air was removed and the mold isolated using appropriate valving. The mold was then heated to a temperature of from 330 to 340 C and maintained at that temperature for a period of four (4) hours. The mold was then cooled to room temperature, opened, and the cured carbon fabric reinforced composite removed.
The cured composite was then tested for short beam shear s strength, flexural strength and modulus, and compression strength and modulus in accordance with the test methods described in ASTM D2344, ASTM D790, and ASTM D6641, respectively. The test results are shown in Table 2, below.
Table 2 Property Carbon Fabric Reinforced Composite Short Bcam Shear (ASTM D2344) at room temperature, MPa 24.5 at 200'C, MPa 20.6 Flexural Strength (ASTM D790) at room temperature, MPa 420 Flexural Modulus (ASTM D790) at room temperature, GPa 45.7 Compression Strength (ASTM D6641) at room temperature, MPa 360 Compression Modulus (ASTM D6641) at room temperature, GPa 55.7 [0050] As shown above and in Table 2, carbon fabric reinforced composites employing the RTM and RI processable polyimide resins of the present invention may be prepared by RTM methods at reduced processing temperatures, and exhibit good mechanical properties rendering them suitable for use in a variety of structural and non-structural applications.
[0051] While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of the present invention should not be limited by any of the exemplary embodiments.
[0052] Having thus described the invention,
Synthesis of Amic Acid Solution.
BTDA (7.35g, 0.025mo1, NMP 70g), BAPS-M (21.6g, 0.05mol, NMP 70g), IA (5.6g, 0.05mol).
[0047] In Table 1 below, properties of the RTM and RI processable polyimiue resins of the above examples are summarized.
Table I
Properties of RTM and Ri Processable Polyimide Resins Example RTM and Rl Processable Molar Ratio Melting Melt Polyimide Resin Point Viscosity ( C c s 1 BPDA//BAPP/ICA 1:2:2 160/330 1,000 2 BTDA//BAPS-M//CA 1:2:2 160/320 1,000 3 BTDA//BAPP/BAPS-M//CA 1:2 25/75 :2 190/330 1,000 4 BTDA/BPDA//BAPP//CA 125/75:2:2 160/330 1,000 BTDA//m-PDA/BAPS-M//CA 1:2 25/75 :2 175/310 1,000 6 BTDA//3,4ODA/APB//CA 1 :2 25/75 :2 210/305 1,000 7 BTDA//APB//CA 1:2:2 140/335 1,000 8 BPDA//APB/!CA 1:2:2 160/330 1,000 9 BTDA//BAPP/SR//CA 1:2(90/10wt%):2 190/330 950 BPDA//BAPP/SR//CA 1:2 80/20wt% :2 .. 210/345 900 11 BPDA/ITPE-R//CA 1:2:2 280/315 1,100 12 BPDA//3,4ODA//CA 1:2:2 280/310 1,000 13 PM DA//BAPS-M//CA 1:2:2 150/330 1,000 14 OPDA//BAPP/CA 1:2:2 160/330 1,000 OPDA//BAPS-M//CA 1:2:2 160/305 1,000 16 DSDA//BAPS-M//CA 1:2:2 160/320 1,000 17 DSDA//BAPP/ICA 1:2:2 1601330 1,000 18 BTDA//BAPS-M//HA 1:2:2 200/285 1,000 19 BTDA//APB//HA 1:2:2 160/290 1,000 BPDA//APBI/HA 1:2:2 140/305 11,000 21 BPDA//BAPP//HA 1:2:2 200/290 1,000 22 BPDA//BAPP/lA 1:2:2 180/250 1,200 23 BTDA//BAPS-M//IA 1:2:2 190/260 1,000 [0048] Examples I to 5, 7 to 9, 13 to 17, 19, 20, 22 and 23, demonstrate that polyimide resins prepared in accordance with the teachings of the present invention exhibit melting at temperatures of less than about 200 C and melt viscosities at 200 C of less than about 3000 cps, rendering them suitable for io processing by RTM and RI methods at reduced processing temperatures of less than about 200 C. While Examples 6, 10, 18 and 21 exhibited melting at slightly higher temperatures, the melting points of these resins may be reduced by adjusting the weight percents of the diamines in Examples 6, 18 and 21 and by adjusting the weight percents of the diamine and rubber components in Example 15 ' 10. (See, e.g., Examples 9 and 10).
[0049] Preparation and Testing of Carbon Fabric Reinforced Composite.
1) Preparation of BPDA//BAPP//CA Matrix Resin.
Synthesis of Amic Acid Solution.
BPDA (150.52 g, 0.512 mol) was placed in NMP (1200 g) in a beaker, while BAPP (419.84 g, 1.024 mol) was placed in NMP (400 g) in a separate beaker. The beakers vvere heated to completely dissolve the monomers. The resulting solutions were cooled to room temperature, and the BAPP solution trainsferred into a 10,000 mi three-necked, round-bottom flask equipped with a mechanical stirrer, thermometer and dropping funnel for adding the BPDA solution. The beakers of BPDA and BAPP solutions were rinsed to remove all reactants by using an additional 10 g of NMP for each container.
The BPDA solution was then added drop wise into the BAPP solution over a period of three hours. CA (126.15 g, 1.126 mol) end-capping agent was then added drop wise to the round-bottom flask over a period of about one hour. The resulting mixture, the temperature of which had increased slightly, was then stirred for one hour to form an amic acid solution. The addition of the BPDA solution and CA end-capping agent were performed at room temperature.
Synthesis of Imide Powder.
A quantity of 2316.5 g of the amic acid solution and 5,144 g of toluene were placed in a 10 liter, "three-riecked, round-bottom flask fitted with a Dean-Stark trap full of toluene and connected to a reflux condenser, nitrogen inlet/outlet, and a temperature sensor connected through a temperature controller. A quantity of 10 g methane sulfonic acid catalyst was then added to the solution and the resulting mixture heated via an electronic heating mantle to reflux at 120 to 125 C and held for three to four hours. Water generated during this process was collected at the bottom of the Dean-Stark trap. The reaction solution was then allowed to cool to room temperature. The reaction solution was then transferred to an evaporating flask of a rotational evaporator. Toluene was removed from the reaction solution using the rotational evaporator (vacuum -30 mbar, oil heating bath - 120 C). The solution remaining in the evaporating flask of the rotational evaporator was then transferred to a blender containing about 30 liters of tap water and mixed for 5 minutes to precipitate the solution. The resulting precipitate was isolated using vacuum filtration, washed twice with tap water and dried in a forced air oven at 60 C for five hours and then at 105 C
for ten hours to give a quantitative yield (99.5 %) of yellow powder.
The calculated number average molecular weight of the io prepared polyimide resin was 1266 g/mole.
2) Preparation of Carbon Fabric Reinforced Composite.
A resin transfer molding or RTM apparatus was used to prepare a carbon fabric reinforced composite in accordance with the present invention. The RTM apparatus included a mold having at least one surface configured to the shape of the part to be made.
The mold, which measured 25.4 centimeters by 45.7 centimeters, was enclosed and had an upper and a lower part, and a seal for providing an airtight seal between the mold components during use.
The mold further included resin injection and evacuation ports for providing entrance and exit points, respectively, for the matrix resin.
Eight layers of woven carbon fabric obtained from Textile Products, Inc., 2512 Woodland Drive, Anaheim, CA 92801, under the product designation T650135-3k-8hs carbon fabric, were placed one on top of the other in the mold, with warp fibers all running in the same direction. The mold was then sealed and air drawn from the mold to achieve a vacuum -of 70 pascals. The prepared polyimide resin was then melted at 200 C, degassed and pumped into the mold at a pressure of 2.4 megapascals through the resin injection port, which was maintained at a temperature of about 200 C.
After the mold was full, trapped air was removed and the mold isolated using appropriate valving. The mold was then heated to a temperature of from 330 to 340 C and maintained at that temperature for a period of four (4) hours. The mold was then cooled to room temperature, opened, and the cured carbon fabric reinforced composite removed.
The cured composite was then tested for short beam shear s strength, flexural strength and modulus, and compression strength and modulus in accordance with the test methods described in ASTM D2344, ASTM D790, and ASTM D6641, respectively. The test results are shown in Table 2, below.
Table 2 Property Carbon Fabric Reinforced Composite Short Bcam Shear (ASTM D2344) at room temperature, MPa 24.5 at 200'C, MPa 20.6 Flexural Strength (ASTM D790) at room temperature, MPa 420 Flexural Modulus (ASTM D790) at room temperature, GPa 45.7 Compression Strength (ASTM D6641) at room temperature, MPa 360 Compression Modulus (ASTM D6641) at room temperature, GPa 55.7 [0050] As shown above and in Table 2, carbon fabric reinforced composites employing the RTM and RI processable polyimide resins of the present invention may be prepared by RTM methods at reduced processing temperatures, and exhibit good mechanical properties rendering them suitable for use in a variety of structural and non-structural applications.
[0051] While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of the present invention should not be limited by any of the exemplary embodiments.
[0052] Having thus described the invention,
Claims (25)
1. A polyimide resin for processing by one of: i) resin transfer molding and ii) resin infusion methods, wherein the resin is a reaction product of at least one aromatic dianhydride, at least one aromatic diamine, at least one diamine having at least one oxygen linkage in its chemical structure, and at least one endcapping agent, and exhibits melting at temperatures of less than about 200 °C and stable melt viscosities at 200 °C of less than about 3000 centipoise.
2. The polyimide resin of claim 1, wherein the at least one aromatic dianhydride has more than one aromatic ring in its chemical structure.
3. The polyimide resin of claim 2, wherein the at least one aromatic dianhydride is represented by one of the following formulas :
wherein, Z represents -CO-, -O-, -SO2-, or a direct bond.
wherein, Z represents -CO-, -O-, -SO2-, or a direct bond.
4. The polyimide resin of claim 3, wherein the at least one aromatic dianhydride is represented by formula (I) and comprises 1,2,4,5-benzenetetracarboxylic dianhydride.
5. The polyimide resin of claim 3, wherein the at least one aromatic dianhydride is represented by formula (II) and is selected from the group comprising 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,1',2,2'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-diphenyisulfone tetracarboxylic diandydride, and mixtures thereof.
6. The polyimide resin of claim 1, wherein the resin is a reaction product of two aromatic dianhydrides, at least one aromatic diamine, and at least one endcapping agent, wherein a first one of the dianhydrides is present in an amount ranging from about 5 to about 40 % by wt., based on the total weight of the dianhydrides, and wherein a second one of the dianhydrides is present in an amount ranging from about 95 to about 60 % by wt., based on the total weight of the dianhydrides.
7. The polyimide resin of claim 6, wherein the at least one aromatic diamine is selected from the group of 3,4'-oxydianiline, m-phenylenediamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, and mixtures thereof.
8. The polyimide resin of claim 1, wherein the resin is a reaction product of at least one aromatic dianhydride, two aromatic diamines, and at least one endcapping agent, and wherein at least one of the diamines has at least one oxygen linkage in its chemical structure and is present in an amount of at least 50 % by wt., based on the total weight of the diamines.
9. The polyimide resin of claim 1, wherein the at least one end-capping agent is an unsaturated carbocyclic monomeric anhydride that forms oligomers that exhibit melting at temperatures of less than about 250 °C, and that has melt viscosities at 200 °C ranging from about 500 to about centipoise.
10. The polyimide resin of claim 9, wherein the at least one end-capping agent is selected from the group comprising nadic anhydride (5-norbornene-2,3-dicarboxylic anhydride), alkyl derivatives of maleic anhydride, 2-octen-1-ylsuccinic anhydride, and mixtures thereof.
11. A method for producing a polyimide resin for processing by one of: i) resin transfer molding and ii) resin infusion methods, the resin exhibiting melting at temperatures of less than about 200 °C and stable melt viscosities at 200 °C of less than about 3000 centipoise, the method comprising :
(a) chemically combining:
i. at least one aromatic dianhydride represented by one of the following formulas :
wherein, Z represents -CO-, -O-, -SO2-, or a direct bond, ii. at least one aromatic diamine selected from the group of 3,4'-oxydianiline, m-phenylenediamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 1,3-bis(3-aminophenoxy)benzene, and 1,3-bis(4-aminophenoxy)benzene, and iii. at least one carbocyclic monomeric anhydride end-capping agent selected from the group of nadic anhydride, alkyl derivatives of maleic anhydride, and 2-octen-1-ylsuccinic anhydride, and (b) imidizing the resulting combination.
(a) chemically combining:
i. at least one aromatic dianhydride represented by one of the following formulas :
wherein, Z represents -CO-, -O-, -SO2-, or a direct bond, ii. at least one aromatic diamine selected from the group of 3,4'-oxydianiline, m-phenylenediamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 1,3-bis(3-aminophenoxy)benzene, and 1,3-bis(4-aminophenoxy)benzene, and iii. at least one carbocyclic monomeric anhydride end-capping agent selected from the group of nadic anhydride, alkyl derivatives of maleic anhydride, and 2-octen-1-ylsuccinic anhydride, and (b) imidizing the resulting combination.
12. The method of claim 11, wherein the at least one aromatic dianhydride is represented by formula (I) and comprises 1,2,4,5-benzenetetracarboxylic dianhydride.
13. The method of claim 11, wherein the at least one aromatic dianhydride is represented by formula (II) and is selected from the group comprising 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,1',2,2'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic diandydride, and mixtures thereof.
14. A polyimide resin for processing by one of: i) resin transfer molding and ii) resin infusion methods, the resin exhibiting melting at temperatures of less than about 200 °C and stable melt viscosities at 200 °C
of less than about 3000 centipoise, the resin being produced by a method comprising:
(a) chemically combining:
i. at least one aromatic dianhydride represented by one of the following formulas :
wherein, Z represents -CO-, -O-, -SO2-, or a direct bond;
H. at least one aromatic diamine selected from the group of 3,4'-oxydianiline, m-phenylenediamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 1,3-bis(3-aminophenoxy)benzene, and 1,3-bis(4-aminophenoxy)benzene, and iii. at least one carbocyclic monomeric anhydride end-capping agent selected from the group of nadic anhydride, alkyl derivatives of maleic anhydride, and 2-octen-1-ylsuccinic anhydride, and (b) imidizing the resulting combination.
of less than about 3000 centipoise, the resin being produced by a method comprising:
(a) chemically combining:
i. at least one aromatic dianhydride represented by one of the following formulas :
wherein, Z represents -CO-, -O-, -SO2-, or a direct bond;
H. at least one aromatic diamine selected from the group of 3,4'-oxydianiline, m-phenylenediamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 1,3-bis(3-aminophenoxy)benzene, and 1,3-bis(4-aminophenoxy)benzene, and iii. at least one carbocyclic monomeric anhydride end-capping agent selected from the group of nadic anhydride, alkyl derivatives of maleic anhydride, and 2-octen-1-ylsuccinic anhydride, and (b) imidizing the resulting combination.
15. A high temperature composite comprising reinforcing fibers embedded in a polyimide resin matrix prepared using one of: i) resin transfer molding and ii) resin infusion methods, wherein the resin is a reaction product of at least one aromatic dianhydride, at least one aromatic diamine, and at least one endcapping agent, and exhibits melting at temperatures of less than about 200 °C and a stable melt viscosity at 200 °C of less than about 3000 centipoise.
16. The high temperature composite of claim 15, wherein the at least one aromatic dianhydride has more than one aromatic ring in its chemical structure.
17. The high temperature composite of claim 16, wherein the at least one aromatic dianhydride is represented by one of the following formulas:
wherein, Z represents -CO-, -O-, -SO2-, or a direct bond.
wherein, Z represents -CO-, -O-, -SO2-, or a direct bond.
18. The high temperature composite of claim 17, wherein the at least one aromatic dianhydride is represented by formula (I) and comprises 1,2,4,5-benzenetetracarboxylic dianhydride.
19. The high temperature composite of claim 17, wherein the at least one aromatic dianhydride is represented by formula (II) and is selected from the group comprising 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,1',2,2'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic diandydride, and mixtures thereof.
20. The high temperature composite of claim 15, wherein the at least one aromatic diamine has at least one ether linkage in its chemical structure.
21. The high temperature composite of claim 20, wherein the at least one aromatic diamine is selected from the group of 3,4'-oxydianiline, m-phenylenediamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, and mixtures thereof.
22. The high temperature composite of claim 15, wherein the at least one aromatic diamine is used in combination with a rubber component.
23. The high temperature composite of claim 22, wherein the rubber component is an amine terminated rubber.
24. The high temperature composite of claim 15, wherein the at least one end-capping agent is unsaturated carbocyclic monomeric anhydrides that form oligomers that exhibit melting at temperatures of less than about 250 °C, and that have melt viscosities at 200 °C
ranging from about 500 to about 3000 centipose.
ranging from about 500 to about 3000 centipose.
25. The high temperature composite of claim 24, wherein the at least one end-capping agent is selected from the group comprising nadic anhydride (5-norbornene-2,3-dicarboxylic anhydride), alkyl derivatives of maleic anhydride, 2-octen-1-ylsuccinic anhydride, and mixtures thereof.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US49984903P | 2003-09-02 | 2003-09-02 | |
US60/499,849 | 2003-09-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2480144A1 CA2480144A1 (en) | 2005-03-02 |
CA2480144C true CA2480144C (en) | 2009-04-21 |
Family
ID=34135363
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002480144A Active CA2480144C (en) | 2003-09-02 | 2004-09-02 | Rtm and ri processable polymide resins |
Country Status (8)
Country | Link |
---|---|
US (1) | US7129318B2 (en) |
EP (1) | EP1514888B1 (en) |
JP (1) | JP4537158B2 (en) |
CA (1) | CA2480144C (en) |
ES (1) | ES2421646T3 (en) |
MX (1) | MXPA04008505A (en) |
PL (1) | PL1514888T3 (en) |
PT (1) | PT1514888E (en) |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7994274B2 (en) * | 2003-09-02 | 2011-08-09 | I.S.T. (Ma) Corporation | Two-stage cure polyimide oligomers |
US8030433B2 (en) | 2006-05-12 | 2011-10-04 | General Electric Company | RTM and RI processible tailorable polyimide resin systems and composite articles formed therefrom |
US8633284B2 (en) * | 2006-05-12 | 2014-01-21 | General Electric Company | Tailorable polyimide prepolymer blends, crosslinked polymides and articles formed therefrom |
US8030437B2 (en) * | 2006-05-12 | 2011-10-04 | General Electric Company | Methods for forming composite articles from tailorable polyimide resin systems using RTM and RI techniques |
US20070265422A1 (en) * | 2006-05-12 | 2007-11-15 | General Electric Company | Method for making copolymeric polyimide resins |
US20070265417A1 (en) * | 2006-05-12 | 2007-11-15 | General Electric Company | Crosslinked polyimide copolymer material |
US20070265416A1 (en) * | 2006-05-12 | 2007-11-15 | General Electric Company | Polyimide blend with tailorable properties |
US20070265421A1 (en) * | 2006-05-12 | 2007-11-15 | General Electric Company | Method for making a prepolymer polyimide resin blend |
US20070265420A1 (en) * | 2006-05-12 | 2007-11-15 | General Electric Company | fiber reinforced gas turbine engine component |
WO2008004615A1 (en) * | 2006-07-07 | 2008-01-10 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin |
EP2045295B1 (en) * | 2006-07-20 | 2012-12-12 | Mitsubishi Gas Chemical Company, Inc. | Thermocurable polyimide resin composition |
US20080300374A1 (en) * | 2007-05-31 | 2008-12-04 | The Boeing Company | Dinadic phenyl amine reactive endcaps |
US8309663B2 (en) | 2007-05-31 | 2012-11-13 | The Boeing Company | Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication |
US7825211B2 (en) * | 2007-06-22 | 2010-11-02 | The Boeing Company | Single-step-processable polyimides |
US20090112650A1 (en) * | 2007-10-31 | 2009-04-30 | Iwane Donna S | Online method of procuring mortgage loans |
JP2009114415A (en) | 2007-11-09 | 2009-05-28 | Nitto Denko Corp | Resin for optical-semiconductor-element encapsulation containing polyimide and optical semiconductor device obtained with the same |
CN102015834B (en) * | 2008-02-07 | 2013-10-16 | 大和制罐株式会社 | Imide oligomer and polyimide resin obtained by thermal curing thereof |
JP2010006983A (en) * | 2008-06-27 | 2010-01-14 | Hitachi Chem Co Ltd | Sealing filler and semiconductor device |
DE102008038295B4 (en) * | 2008-08-18 | 2013-11-28 | Eads Deutschland Gmbh | Granulation and stabilization of resin systems for use in the manufacture of fiber composite components |
KR101397703B1 (en) | 2011-12-26 | 2014-05-22 | 제일모직주식회사 | Polyamide resin, a method for preparing the same, and an article comprising 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 |
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 |
WO2013181333A1 (en) | 2012-06-01 | 2013-12-05 | E. I. Du Pont De Nemours And Company | An electrochemical cell comprising a nanoweb comprising nanofibers of a cross-linked polyimide |
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 |
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 |
US10174167B2 (en) | 2015-03-19 | 2019-01-08 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin |
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 |
KR101786509B1 (en) | 2016-02-04 | 2017-10-18 | 국방과학연구소 | Resin composition for producing high temperature heat resistingprepreg and method for producing the same |
CN110494477B (en) | 2017-03-30 | 2022-03-29 | 株式会社钟化 | Prepreg, resin composite material, and methods for producing these |
JP6516076B1 (en) * | 2017-08-23 | 2019-05-22 | 宇部興産株式会社 | Electrode mixture paste |
KR102521984B1 (en) * | 2022-05-17 | 2023-04-27 | 주식회사 씨지피머트리얼즈 | Method for manufacturing colorless and transparent polyimide film, and colorless and transparent polyimide film prepared by manufacturing method thereof |
Family Cites Families (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4389504A (en) * | 1981-10-02 | 1983-06-21 | The United States Of America As Represented By The United States National Aeronautics And Space Administration Office Of General Counsel-Code Gp | Elastomer toughened polyimide adhesives |
US4837300A (en) * | 1985-06-20 | 1989-06-06 | The United States Of America As Represented By The Administration Of The National Aeronautics And Space Administration | Copolyimide with a combination of flexibilizing groups |
JPS6454030A (en) | 1987-08-25 | 1989-03-01 | Ube Industries | Terminal-modified imide oligomer and its solution composition |
US5817744A (en) * | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
US4861882A (en) * | 1988-07-14 | 1989-08-29 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Ethynyl terminated imidothioethers and resins therefrom |
US5338827A (en) * | 1990-01-30 | 1994-08-16 | Trw Inc. | Polyimide resins useful at high temperatures |
EP0443352B1 (en) * | 1990-02-20 | 1995-12-06 | National Starch and Chemical Investment Holding Corporation | Polyimides end-capped with diaryl substituted acetylene |
US5145943A (en) * | 1990-12-17 | 1992-09-08 | Ethyl Corporation | Production of particulate amide/imide prepolymers |
DE4232523A1 (en) | 1992-09-29 | 1994-03-31 | Basf Ag | Thermoplastic polyimide-sulphone(s) - from mixts. of oxy-di:phthalic anhydride, di:amino:di:aryl-sulphone(s), other di:anhydride(s) and di:amine(s), and mono:anhydride(s) or -amine(s) |
US5344982A (en) * | 1993-04-02 | 1994-09-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Diamines and polyimides containing pendent ethynyl groups |
GB9310400D0 (en) * | 1993-05-20 | 1993-07-14 | Ici Composites Inc | Curable compositions |
US5412066A (en) * | 1994-03-03 | 1995-05-02 | Ther United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Phenylethynyl terminated imide oligomers |
US5567800A (en) * | 1994-10-28 | 1996-10-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom |
US5606014A (en) * | 1995-08-04 | 1997-02-25 | The United States Of America As Represented By The United States National Aeronautics And Space Administration | Imide oligomers and co-oligomers containing pendent phenylethynyl groups and polymers therefrom |
EP0861280B1 (en) * | 1995-11-13 | 2001-12-12 | Cytec Technology Corp. | Thermosetting polymers for composite and adhesive applications |
US5965687A (en) * | 1996-03-05 | 1999-10-12 | The United States Of America Represented By The Adminstrator Of The National Aeronautics And Space Administration | Method of preparing polymers with low melt viscosity |
JPH10279799A (en) * | 1997-04-04 | 1998-10-20 | Nitto Denko Corp | Thermosetting resin composition |
AU5079299A (en) * | 1998-05-29 | 1999-12-20 | Government of the United States of America as represented by the Administrator of the National Aeronautics and Space Administration (NASA), The | Polyimide precursor solid residuum |
US6133330A (en) * | 1998-05-29 | 2000-10-17 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Aromatic polyimide foam |
DE19828248A1 (en) * | 1998-06-25 | 1999-12-30 | Abb Corporate Research Ltd Bad | Low temperature curing epoxy resin system, useful as an adhesive, matrix resin or casting resin |
US6114494A (en) * | 1998-12-03 | 2000-09-05 | Ranbar Electrical Materials, Inc. | Polyimide material and method of manufacture |
AU2941100A (en) * | 1999-03-11 | 2000-09-28 | Toray Industries, Inc. | Epoxy resin composition, epoxy resin composition for fiber-reinforced composite,and fiber-reinforced composite containing the same |
US6124035A (en) * | 1999-04-13 | 2000-09-26 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | High temperature transfer molding resins |
US6359107B1 (en) * | 2000-05-18 | 2002-03-19 | The United States Of America As Represented By The Administrator, National Aeronautics And Space Administration | Composition of and method for making high performance resins for infusion and transfer molding processes |
WO2000071604A1 (en) * | 1999-05-21 | 2000-11-30 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Hollow polyimide microspheres |
US6514370B1 (en) * | 2000-06-08 | 2003-02-04 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Dry process for manufacturing hybridized boron fiber/carbon fiber thermoplastic composite materials from a solution coated precursor |
US6511789B2 (en) * | 2000-06-26 | 2003-01-28 | Arch Specialty Chemicals, Inc. | Photosensitive polyimide precursor compositions |
US6528145B1 (en) * | 2000-06-29 | 2003-03-04 | International Business Machines Corporation | Polymer and ceramic composite electronic substrates |
JP4461606B2 (en) * | 2000-10-31 | 2010-05-12 | 宇部興産株式会社 | Polyimide powder manufacturing method, polyimide powder, polyimide powder molded body and manufacturing method thereof |
US6444783B1 (en) * | 2000-12-21 | 2002-09-03 | E. I. Du Pont De Nemours And Company | Melt-processible semicrystalline block copolyimides |
US6476182B1 (en) * | 2000-12-21 | 2002-11-05 | E. I. Du Pont De Nemours And Company | Melt-processible, thermoplastic random copolyimides having recoverable crystallinity and associated processes |
JP4133561B2 (en) * | 2003-05-07 | 2008-08-13 | Jsr株式会社 | Polyamic acid oligomers, polyimide oligomers, solution compositions, and fiber reinforced composite materials |
-
2004
- 2004-08-30 US US10/931,070 patent/US7129318B2/en active Active
- 2004-09-01 PL PL04020786T patent/PL1514888T3/en unknown
- 2004-09-01 PT PT40207862T patent/PT1514888E/en unknown
- 2004-09-01 ES ES04020786T patent/ES2421646T3/en active Active
- 2004-09-01 JP JP2004254792A patent/JP4537158B2/en active Active
- 2004-09-01 EP EP20040020786 patent/EP1514888B1/en active Active
- 2004-09-02 CA CA002480144A patent/CA2480144C/en active Active
- 2004-09-02 MX MXPA04008505A patent/MXPA04008505A/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
JP4537158B2 (en) | 2010-09-01 |
MXPA04008505A (en) | 2005-11-17 |
EP1514888B1 (en) | 2013-04-17 |
US20050080229A1 (en) | 2005-04-14 |
PT1514888E (en) | 2013-06-28 |
ES2421646T3 (en) | 2013-09-04 |
US7129318B2 (en) | 2006-10-31 |
CA2480144A1 (en) | 2005-03-02 |
PL1514888T3 (en) | 2013-09-30 |
JP2005076032A (en) | 2005-03-24 |
EP1514888A1 (en) | 2005-03-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2480144C (en) | Rtm and ri processable polymide resins | |
US10125224B2 (en) | Two-stage cure polyimide oligomers | |
PT1516119E (en) | Method for assembling/dismounting components of a wind power plant | |
US5689004A (en) | Diamines containing pendent phenylethynyl groups | |
US5681967A (en) | Phenylethynyl phthalic anhydride | |
US10047246B2 (en) | Varnish including 2-phenyl-4,4′-diaminodiphenyl ether, imide resin composition having excellent moldability, cured resin molded article having excellent breaking elongation, prepreg thereof, imide prepreg thereof, and fiber-reinforced material thereof having high heat resistance and excellent mechanical strength | |
US5091505A (en) | Polymide resins prepared by addition reactions | |
EP2687508B1 (en) | Resin-transfer-moldable terminal-modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether and having excellent moldability, mixture thereof, varnish containing same, and cured resin thereof and fiber-reinforced cured resin thereof made by resin transfer molding and having excellent heat resistance | |
US5328979A (en) | Thermoplastic copolyimides and composites therefrom | |
EP0439916B1 (en) | Polyimide resins prepared by addition reaction | |
EP0540250B1 (en) | Maleimide resin composition, prepreg and fibre-reinforced plastics material | |
WO2019226641A9 (en) | Varnish of polyimide having high heat resistance and excellent mechanical strength | |
US7605223B1 (en) | Low melt viscosity imide oligomers and polyimides therefrom | |
JPH04363360A (en) | Terminal-modified imide oligomer composition | |
JPS63258926A (en) | Imide oligomer composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request |