CN101980604A - Storage-stable polymaleimide prepolymer compositions - Google Patents
Storage-stable polymaleimide prepolymer compositions Download PDFInfo
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- CN101980604A CN101980604A CN2009801116500A CN200980111650A CN101980604A CN 101980604 A CN101980604 A CN 101980604A CN 2009801116500 A CN2009801116500 A CN 2009801116500A CN 200980111650 A CN200980111650 A CN 200980111650A CN 101980604 A CN101980604 A CN 101980604A
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- thiazolinyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08G73/12—Unsaturated polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1565—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The present invention relates to a storage-stable advanced polymaleimide prepolymer composition including a polymaleimide prepolymer resulting from the advancement reaction of a polyimide and an alkenylphenol, alkenylphenol ether or mixture thereof in the presence of an amine catalyst; and dioxolane. The storage-stable advanced polymaleimide prepolymer composition may be used in various applications such as prepregs, laminates, printed circuit boards, castings, composites, moulded articles, adhesives and coatings.
Description
The cross reference of related application
The application requires the priority of the Application No. 61/040,956 of submission on March 31st, 2008, is introduced into herein by reference.
Statement about federal funding research or exploitation
Inapplicable.
Technical field
The present invention relates to the lifting poly maleimide prepolymer composite and the product prepared therefrom of stable storing, for example the preimpregnation product.The lifting poly maleimide prepolymer composite of this stable storing comprises: (i) the poly maleimide prepolymer that is obtained by polyimides and thiazolinyl phenol or the lifting reaction (advancement reaction) of thiazolinyl phenolic ether in the presence of amine catalyst and (ii) dioxolanes.
Background technology
BMI can be with acting on the raw material for preparing addition polymerization and polymerizate.For example, U.S. Patent number 3,658,764 disclose the polyaddition products by undersaturated BMI and amine preparation; U.S. Patent number 3,741,942 disclose by BMI and organic disulfide alcohol preparation polyaddition products; U.S. Patent number 4,038,251 and 4,065,433 have described BMI and polyhydric phenols and polyalcohol generate polyaddition products in the presence of catalyzer reaction; U.S. Patent number 4,100,140 have described the polyaddition products by BMI and thiazolinyl phenol or the preparation of thiazolinyl phenolic ether.
Because its heat endurance and favorable mechanical character, the polyaddition products that is prepared by BMI can be used for various preimpregnation application.In this polyaddition products as powder provide a kind of be the product of dimaleoyl imino diphenyl methane and methylene dianiline (MDA).Then this powder polyaddition products is dissolved in and is used for the preimpregnation use in the high boiling solvent (for example N-Methyl pyrrolidone).Yet owing to raise by leaving standstill the precipitation and the viscosity that will take place fast, so the stability of this solution is restricted.Therefore, the preparation of this solution must be carried out before use at once.
At U.S. Patent number 5,189, mentioned improvement in disclosed polyaddition products and the solution in 128 and 5,637,387.U.S. Patent number 5,189,128 disclose by poly maleimide and thiazolinyl phenol or thiazolinyl phenolic ether in the presence of the base catalyst of specific mole and the polyaddition products that the specific reaction time of reaction obtains under specific reaction temperature.Resulting product shows and is precipitating the improved storage stability that generation is confirmed than the improvement solvability in the low boiling point solvent methyl ethyl ketone and by not having.U.S. Patent number 5,637, the another kind of having described storage stability in 387 improves, and wherein adds phenothiasin or quinhydrones after poly maleimide and thiazolinyl phenol or thiazolinyl phenolic ether react.Yet this polyaddition products can continue polymerization along with the time when storing at ambient temperature, the reduction of resin flow in the process that causes using in laminating technology.Exceed particular value in case this resin flow reduces, the bonding strength reduction finally causes layering.Therefore, in order to prevent the reduction of resin flow, need refrigeration usually, this is expensive and always can realize for the prepreg user.
Therefore, the purpose of this invention is to provide the polyaddition products composition of under the situation that can not cause any adverse effect, having eliminated basically the demand of refrigeration of improved stable storing to the heat and the engineering properties of preimpregnation product prepared therefrom.
Summary of the invention
The present invention relates to the lifting poly maleimide prepolymer composite of stable storing, comprise:
The poly maleimide prepolymer that lifting reaction in the presence of amine catalyst obtains by polyimides and thiazolinyl phenol, thiazolinyl phenolic ether or its mixture; With
The dioxolanes of formula (5)
The lifting poly maleimide prepolymer composite of this stable storing can be by following preparation: react in the presence of amine catalyst to generate the poly maleimide prepolymer at polyimides under the rising temperature and thiazolinyl phenol, thiazolinyl phenolic ether or its mixture, remove all amine catalysts basically; Add dioxolanes then.In another embodiment, can prepare prepreg or laminate structures by fabric or the fiber that curing is impregnated with the lifting poly maleimide prepolymer composite of this stable storing of the present invention.
Description of drawings
Fig. 1 has described this lifting polyimide preformed polymer composition in different storage temperatures stability in time with Fig. 2.
Embodiment
The lifting poly maleimide prepolymer composite of this stable storing generally comprises (i) poly maleimide prepolymer that the lifting reaction in the presence of amine catalyst obtains by polyimides and thiazolinyl phenol, thiazolinyl phenolic ether or its mixture; (ii) dioxolanes.Be surprisingly found out that dioxolanes added in this poly maleimide prepolymer and suppressed further lifting, eliminate or greatly reduce further polymerization thus, therefore fully improved the storage stability of this prepolymer composite.The lifting poly maleimide prepolymer composite of stable storing of the present invention can in the time period that prolongs, be stored in room temperature or even be higher than under the temperature of room temperature, and can not cause adverse effect to processing conditions, eliminated the demand that is stored under the low temperature (condition of for example freezing) thus.The about 20 ℃ temperature of " room temperature " expression.In addition, the use of dioxolanes has unexpectedly improved other machining feature of said composition, has for example prolonged effective pot life and has reduced volatile content.
Available polyimides comprises the group of at least two following formulas
R wherein
1Be hydrogen or methyl.
In another embodiment, this polyimides is a poly maleimide, preferably the BMI of following formula
R wherein
1Be hydrogen or methyl, X is that n is 2～20-C
nH
2n-,-CH
2CH
2SCH
2CH
2-, phenylene, naphthylene, dimethylbenzene, cyclopentylene, 1,5,5-trimethyl-1,3-cyclohexylidene, 1,4-cyclohexylidene, 1,4-is two-group of (methylene)-cyclohexylidene or formula (a)
R wherein
2And R
3Be respectively chlorine, bromine, methyl, ethyl or hydrogen, Z is direct key (directbond), methylene, 2, the 2-propylidene ,-CO-,-O-,-S-,-SO-or-SO
2-.Preferably, R
1Be methyl, X is hexa-methylene, tri-methyl hexamethylene, 1,5,5-trimethyl-1, the 3-cyclohexylidene or wherein Z be methylene, 2, the 2-propylidene or-O-and R
2And R
3It is the group of the formula (a) of hydrogen.
The example of polyimides comprises: N, N '-ethylidene-BMI, N, N '-hexa-methylene-BMI, N, N '-m-phenylene-BMI, N, N '-p-phenylene-BMI, N, N '-4,4 '-diphenyl methane-BMI, N, N '-4,4 '-3,3 '-two chloro-diphenyl methane-BMIs, N, N '-4,4 '-(diphenyl ether)-BMI, N, N '-4,4 '-two-phenylsulfone-BMI, N, N '-4,4 '-dicyclohexyl methyl hydride-BMI, N, N '-α, 4,4 '-Dimethylenecyclohexacompound-BMI, N, N '-m-dimethylbenzene-BMI, N, N '-p-dimethylbenzene-BMI, N, N '-4,4 '-diphenyl cyclohexane-BMI, N, N '-m-phenylene-two lemon acid imides (biscitraconimide), N, N '-4,4 '-diphenyl methane-two lemon acid imides, N, N '-4,4 '-2,2-diphenyl propane-BMI, N, N '-α, 1,3-dipropylene-5,5-dimethyl-hydantoins-BMI, N, N '-4,4 '-diphenyl methane-two clothing health acid imides, N, N '-p-phenylene-two clothing health acid imides, N, N '-4,4 '-diphenyl methane-two dimethyl maleimides, N, N '-4,4 '-2,2 '-diphenyl propane-two dimethyl maleimides, N, N '-hexa-methylene-two dimethyl maleimides, N, N '-4,4 '-(diphenyl ether)-two dimethyl maleimides and N, N '-4,4 '-diphenyl sulfone-two dimethyl maleimides.
Available thiazolinyl phenol and thiazolinyl phenolic ether can comprise allyl phenol, methylallyl phenol or its ether.Preferably, this thiazolinyl phenol and thiazolinyl phenolic ether are the compounds of formula (1)～(4):
Wherein R be direct key, methylene, isopropylidene ,-O-,-S-,-SO-or-SO
2-;
R wherein
4, R
5And R
6Independently be hydrogen or C separately
2～C
10Thiazolinyl is preferably pi-allyl or acrylic, as long as R
4, R
5Or R
6In at least one is C
2～C
10Thiazolinyl gets final product;
R wherein
4, R
5, R
6And R
7Independently be hydrogen or C separately
2～C
10Thiazolinyl is preferably pi-allyl or acrylic, as long as R
4, R
5, R
6Or R
7In at least one is C
2～C
10Thiazolinyl gets final product, and R is suc as formula defining in (1); With
R wherein
8, R
9, R
10, R
11, R
12And R
13Independently be hydrogen, C separately
1～C
4Alkyl and C
2～C
10Thiazolinyl is preferably pi-allyl or acrylic, as long as R
8, R
9, R
10, R
11, R
12And R
13In at least one is C
2～C
10Thiazolinyl gets final product, and b is 0～10 integer.Also can use the mixture of the compound of formula (1)～(4).
The example of thiazolinyl phenol and thiazolinyl phenol ether compound comprises: O, O '-diallyl-bisphenol-A, 4,4 '-dihydroxy-3,3 '-diallyl biphenyl, two (4-hydroxyl-3-allyl phenyl) methane, 2, two (the 4-hydroxyls-3 of 2-, 5-diallyl phenyl) propane, O, O '-diformazan is for pi-allyl-bisphenol-A, 4,4 '-dihydroxy-3,3 '-diformazan is for pi-allyl biphenyl, two (4-hydroxyl-3-methylallyl) methane, 2, two (the 4-hydroxyls-3 of 2-, the 5-diformazan is for allyl phenyl)-propane, 4-methylallyl-2-methoxyl group phenol, 2, two (4-methoxyl group-3-allyl phenyl) propane of 2-, 2, two (4-methoxyl group-3-methylallyl phenyl) propane of 2-, 4,4 '-dimethoxy-3,3 '-diallyl biphenyl, 4,4 '-dimethoxy-3,3 '-diformazan is for pi-allyl biphenyl, two (4-methoxyl group-3-allyl phenyl) methane, two (4-methoxyl group-3-methylallyl phenyl) methane, 2, two (the 4-methoxyl groups-3 of 2-, 5-diallyl phenyl) propane, 2, two (4-methoxyl group-3, the 5-diformazan is for the allyl phenyl) propane of 2-, 4-allylveratrol and 4-methylallyl-veratrole.
This thiazolinyl phenol, thiazolinyl phenolic ether or its mixture can use in the scope of about 0.05 mole～2.0 moles/mole polyimides.In another embodiment, this thiazolinyl phenol, thiazolinyl phenolic ether or its mixture can use in the scope of about 0.1 mole～1.0 moles/mole polyimides.
Available amine catalyst comprises uncle, the second month in a season and primary amine or comprises the amine and the quaternary ammonium compound of the amino of several different types.This amine can be monoamine or polyamine, can comprise: diethylamine, tripropyl amine (TPA), tri-n-butylamine, triethylamine, triamylamine, benzene methanamine, tetramethyl-diaminodiphenyl-methane, N, N-diisobutyl aminoacetonitriles, N, N-dibutylamino acetonitrile, heterocyclic bases, for example quinoline, N-crassitude, imidazoles, benzimidazole and homologue and mercaptobenzothiazoler.The example of the quaternary ammonium compound that is fit to that can mention is benzyl trimethyl ammonium hydroxide and benzyl trimethyl ammonium methoxide.Preferred tripropyl amine (TPA).
This amine catalyst can use with about 0.1%～10% amine catalyst weight/this scope that promotes the gross weight of reactant.In another embodiment, this amine catalyst of existence can use with about 0.2%～5% amine catalyst weight/this scope that promotes the gross weight of reactant.
The preparation method of this poly maleimide prepolymer comprises: this polyimides is mixed with this thiazolinyl phenol, thiazolinyl phenolic ether or its mixture, and this mixture is heated to about 25 ℃～150 ℃ temperature until obtaining limpid melt.Can add this amine catalyst then, continue the suitable time in about 100 ℃～140 ℃ thermotonus, so under vacuum, all these amine catalysts are removed.Can monitor the lifting degree at 125 ℃ of melt viscosities of measuring resin by the scale that uses 0～100 pool, be 20～85 pools for this its scope of lifting poly maleimide prepolymer.Also can use gelation time as other parameter, it has reflected that its scope can be 300 seconds～2000 seconds in the time of whole gels formation of about 170 ℃～175 ℃ temperature measuring.
The lifting poly maleimide prepolymer composite of this stable storing comprises the dioxolanes of formula (5) in addition:
This dioxolanes can use with the scope based on about 10wt%～50wt% of the lifting poly maleimide prepolymer composite gross weight of this stable storing.In another embodiment, this dioxolanes can be with the about 17.5wt%～40wt% based on the lifting poly maleimide prepolymer composite gross weight of this stable storing, and preferably the scope of about 20wt%～30wt% is used.
The lifting poly maleimide prepolymer composite of this stable storing can be by following preparation: when promoting reaction and finish dioxolanes is added in the poly maleimide prepolymer.Form high solid and 50 centipoises or lower low viscous composition up to about 80wt% thus, it is stable in room temperature or temperature following a couple of days of being higher than room temperature, precipitation or viscosity can not take place raise.
Except that said components, any stage that the lifting poly maleimide prepolymer composite of this stable storing can be chosen wantonly before curing mixes with one or more stabilizing agents, organic solvent, replenishers, filler, reinforcing agent, pigment, dyestuff, plasticizer, tackifier, rubber, promoter, thinner or its any mixture.
Operable stabilizing agent comprises: phenothiasin self or have 1～3 substituent C-substituted phenothiazine or have 1 substituent N-substituted phenothiazine, for example 3-methyl-phenothiasin, 3-ethyl-phenothiasin, 10-methyl-phenothiasin; 3-phenyl-phenothiasin, 3,7-diphenyl-phenothiasin; 3-chloro phenothiazine, 2-chloro phenothiazine, 3-bromine phenothiasin; 3-nitro phenothiasin, the amino phenothiasin, 3 of 3-, the 7-diaminophenothiazine; 3-sulfonyl-phenothiasin, 3,7-disulfonyl base-phenothiasin, 3,7-two thiocyano phenothiasin; Replace quinine and catechol, copper naphthenate, Methyl disulfide for zinc carbonate; Phosphorus molybdenum acid hydrate and phosphotungstic acid hydrate.This stabilizing agent can be to add in the lifting poly maleimide prepolymer composite of this stable storing based on the amount of the about 0.1%～10wt% that promotes poly maleimide prepolymer composite gross weight.
The organic solvent that can add in the lifting poly maleimide prepolymer composite of this stable storing comprises low boiling point solvent (about at the most 160 ℃ of boiling point, preferably about at the most 100 ℃), for example ketone, glycol ethers and glycol ethers acetic acid esters, hydrocarbon, methoxypropanol, dimethyl formamide and composition thereof.This organic solvent, when existing, can be promoting the about at the most 30wt% of poly maleimide prepolymer composite gross weight based on this, preferably about at the most 25wt%, most preferably the amount of about 20wt% is added in the lifting poly maleimide prepolymer composite of this stable storing at the most.
Operable replenishers, reinforcing agent, filler promoter and pigment for example comprise: coal tar, pitch, glass fibre, boron fibre, carbon fiber, cellulose, polyethylene powders, polypropylene powder, mica, asbestos, quartz powder, gypsum, antimony oxide, bentonite, aerosil (" aerosil "), lithopone, barite, titanium dioxide, eugenol, cumyl peroxide, isoeugenol, carbon black, graphite and iron powder.Can also be with other additive, for example fire-proofing chemical, flow control agent (for example silicone, cellulose acetate-butyrate, butyric acid polyvinyl ester, wax, stearate etc. (its part is also as releasing agent)) add in this lifting poly maleimide prepolymer composite.
The lifting poly maleimide prepolymer composite of above-mentioned stable storing is applicable in the final use of wide region, for example is applicable in laminated product, printed circuit board (PCB), mo(u)lding, compound, mechanograph, binding agent and the coating of prepreg, all thickness.
Can obtain prepreg by lifting poly maleimide prepolymer composite dipping or coating basic material with this stable storing.This basic material comprises all basic materials that are used for laminated product.The example comprises various glass cloth (E glass cloth for example, NE glass cloth and D glass cloth), the natural inorganic fiber fabric, the manufacturing fabric and the non-manufacturing fabric that obtain by liquid crystal fiber (for example aromatic polyamide fibre or aromatic polyester fiber), by synthetic fibers (vinal for example, polyester fiber or acrylic fiber) the manufacturing fabric and the non-manufacturing fabric that obtain, the non-manufacturing fabric of native fiber (bafta for example, sodolin or felt), carbon fibre fabric, native cellulose kind fabric (brown paper for example, cotton paper or paper-glass combination paper) and porous PTFE.
In one embodiment, with lifting poly maleimide prepolymer composite dipping of the present invention or coated polymer basic material.This polymeric base material is not particularly limited, as long as it is the manufacturing fabric that uses polymer separately, non-manufacturing fabric, sheet or porous body.The example comprises liquid crystal polymer, lysotropic liquid crystal polymer for example, be typically aromatic polyamide, polyphenylene benzothiazole, TLCP is typically aromatic polyester, polyesteramide, polyamide, aromatic polyamide resin, polyphenylene ether, polyphenylene sulfides, polyethylene, polypropylene and fluororesin.Suitably select this polymer according to needed expection application or performance.These polymer can be as required separately or be used in combination.The thickness of this basic material is not particularly limited.Usually, it is about 3 μ m～200 μ m.
The preparation method of this prepreg is not particularly limited, as long as it can combine the lifting poly maleimide prepolymer composite of this stable storing to prepare this prepreg with basic material.In one embodiment, provide a kind of method, wherein with above-mentioned lifting poly maleimide prepolymer composite dipping or be applied on this basic material then in drier for example at 80 ℃～200 ℃ said composition heating 1～90 minute is also prepared prepreg thus to the B stage.The resin content scope of this prepreg can be about 30%～90wt%.
By the following laminated product that also can obtain metal coating: a prepreg or at least two prepregs are piled up; Laminated metal foil (for example Copper Foil or aluminium foil) on the upper surface of the prepreg of this accumulation and lower surface or surface; And the heating and the resulting combination of pressurizeing.
The molded condition that is used for the laminated product and the laminated product that multiple-plate ordinary skill can be used for this metal coating of printed circuit board (PCB).For example, usually, at about 100 ℃～300 ℃ temperature and the pressure of about 0.2MPa～10MPa with use about 0.1～5 hour heat time heating time such as multidaylight press, multi-layer vacuum press, continuously moulding, autoclave molding machine etc.In addition, also can combining also by the inner layer circuit board with prepreg of the present invention and independent preparation, the resulting combination of laminated molding prepares multi-layer sheet.
In a particularly embodiment, prepreg or laminate structures comprise the cured article with the basic material of the lifting poly maleimide prepolymer composite dipping of stable storing or coating, and said composition comprises (i) poly maleimide prepolymer that the lifting reaction in the presence of amine catalyst obtains by polyimides and thiazolinyl phenol, thiazolinyl phenolic ether or its mixture; (ii) dioxolanes.
Embodiment
Embodiment 1. these embodiment have described the preparation of the lifting poly maleimide prepolymer composite of stable storing of the present invention.
| Prescription | Parts by weight |
| N, N '-4,4 '-diphenyl methane BMI | 40-45 |
| 4,4 '-(methyl ethylidene) two (2-acrylic) phenol | 30-35 |
| Tripropyl amine (TPA) | 0.1-1.0 |
| 1, the 3-dioxolanes | 20-30 |
| The phosphotungstic acid hydrate | 0.1-1.0 |
With 4,4 '-(methyl ethylidene) two (2-acrylic) phenol adds in the reactor and is placed under the vacuum.With N, N '-4,4 '-diphenyl methane BMI adds in this reactor, and with this 4,4 '-(methyl ethylidene) two (2-acrylic) phenol mixes to form reactant mixture.This reactant mixture is heated to 132 ℃, is placed on then under the vacuum, in a single day become limpid amber solution then, it is cooled to 100 ℃.In this solution, add tripropyl amine (TPA), continuous stirring 30 minutes.Then, the rising temperature also remains on 120 ℃, and this solution was placed 1.5 hours under vacuum.Remove vacuum, add 1 in this solution, the 3-dioxolanes remains on 120 ℃ temperature with temperature, until the viscosity that reach 40～50 pools.Then this solution is cooled to 50 ℃, adds the phosphotungstic acid hydrate thus.To promote the poly maleimide prepolymer composite then and discharge from this reactor, it is at 171 ℃ of gelation times with 963 seconds.
This sample that promotes the poly maleimide prepolymer composite is stored certain hours 4 ℃, room temperature and 50 ℃, measure the gelation time (T=171 ℃) of this sample with particular time interval.The results are shown in the table 1:
Table 1
In addition, each sample is observed precipitation capacity on the identical time interval, the results are shown in table 2:
Table 2
With the storage stability of this liftings prepolymer composite of preparation among the embodiment 1 with according to embodiment 1 but compare with the prepolymer composite that methyl ethyl ketone replacement dioxolanes prepares.The sample of this contrast prepolymer composite is stored certain hour at 4 ℃ and 50 ℃, with the gelation time (171 ℃) of specific measuring space sample.The results are shown in the table 3:
Table 3 (contrast)
| Store fate | The gelation time of 4 ℃ of storage temperatures (second) | The gelation time of 50 ℃ of storage temperatures (second) |
| 0 | 399.6 | 399.6 |
| 7 | 328.5 | 365.0 |
| 14 | 207.1 | 387.5 |
| 21 | 322.6 | 249.5 |
| 28 | 180.0 | 151.6 |
| 35 | 178.7 | 133.2 |
| 41 | 161.3 | 30.1 |
As shown in fig. 1, when being stored in room temperature, according to the gelation time (T=171 ℃) of lifting prepolymer composite of the present invention at least 56 days time greater than 300 seconds.In addition, when being stored in 50 ℃, show in time than the more much longer gelation time of contrast prepolymer composite that is stored in 50 ℃ according to lifting prepolymer composite of the present invention.
Embodiment 2. these embodiment have described the preparation of the lifting poly maleimide prepolymer composite of stable storing of the present invention.
| Prescription | Parts by weight |
| N-N '-4,4 '-diphenyl methane BMI | 25-30 |
| 4,4 '-(methyl ethylidene) two (2-acrylic) phenol | 30-35 |
| Tripropyl amine (TPA) | 0.1-1.0 |
| Phenothiasin | 0.1-1.0 |
| The phosphotungstic acid hydrate | 0.1-1.0 |
| 1, the 3-dioxolanes | 15-25 |
| The methoxy propyl alcohol acetic ester | 15-25 |
With 4,4 '-(methyl ethylidene) two (2-acrylic) phenol adds in the reactor flask and is placed under the vacuum.With N, N '-4,4 '-diphenyl methane BMI adds in this reactor flask, and with this 4,4 '-(methyl ethylidene) two (2-acrylic) phenol mixes to form reactant mixture, is heated 132 ℃.Then this reaction flask is placed under the vacuum,, it is cooled to 100 ℃ in case become limpid amber solution.In this solution, add tripropyl amine (TPA), continue to stir 30 minutes.Then, rising temperature to 120 ℃ is placed this solution 1.5 hours under vacuum.Remove vacuum, add 1, the 3-dioxolanes remains on 120 ℃ temperature with this mixture, until the viscosity that reach 40～45 pools.Then this mixture is cooled to 50 ℃, adds phenothiasin and methoxy propyl alcohol acetic ester thus.After stirring 15 minutes, add the phosphotungstic acid hydrate.Should promote prepolymer composite then discharges from this reactor flask.
The sample that will promote prepolymer composite then stores certain hours 4 ℃, room temperature and 50 ℃, with the gelation time (T=171 ℃) of specific measuring space sample.The results are shown in the table 4:
Table 4
With the storage stability of this liftings prepolymer composite of preparation among the embodiment 2 with according to embodiment 2 but compare with the prepolymer composite that methyl ethyl ketone replacement dioxolanes prepares.The sample of this contrast prepolymer composite is stored certain hour at 4 ℃ and 50 ℃, with the gelation time (T=171 ℃) of specific measuring space sample.The results are shown in the table 5:
Table 5 (contrast)
| Store fate | The gelation time of 4 ℃ of storage temperatures (second) | The gelation time of 50 ℃ of storage temperatures (second) |
| 0 | 402.6 | 402.6 |
| 7 | 323.6 | 361.5 |
| 14 | 320.2 | 340.3 |
| 21 | 290.3 | 305.2 |
| 28 | 249.6 | 210.4 |
| 35 | 259.4 | 156.9 |
| 42 | 256.7 | 120.8 |
| 49 | 270.1 | 114.7 |
| 56 | 262.3 | Gel |
As shown in Figure 2, when being stored in room temperature and 50 ℃, according to the gelation time (T=171 ℃) of lifting poly maleimide prepolymer composite of the present invention at least 56 days time greater than 300 seconds.In addition, when being stored in 50 ℃, show in time than the more much longer gelation time of contrast prepolymer composite that is stored in 50 ℃ according to lifting prepolymer composite of the present invention.
Above disclosed theme be considered to exemplary, and nonrestrictive, appended claim is intended to cover all improvement, enhancing and other embodiment that falls in the true scope of the present invention.Therefore, allow to the full extent that scope of the present invention is determined by the wideest permissible explanation of following claim and equivalent thereof, will not be subjected to preceding detailed description to retrain or limit at law.
Claims (11)
1. the lifting poly maleimide prepolymer composite of stable storing comprises:
(a) the poly maleimide prepolymer that the lifting reaction in the presence of amine catalyst obtains by polyimides and thiazolinyl phenol, thiazolinyl phenolic ether or its mixture; With
(b) dioxolanes of formula (5)
2. the lifting poly maleimide prepolymer composite of the stable storing of claim 1, wherein polyimides is the BMI of following formula
R wherein
1Be hydrogen or methyl, X is n=2-C
nH
2n-,-CH
2CH
2SCH
2CH
2-, phenylene, naphthylene, dimethylbenzene, cyclopentylene, 1,5,5-trimethyl-1,3-cyclohexylidene, 1,4-cyclohexylidene, 1,4-is two-group of (methylene)-cyclohexylidene or formula (a)
R wherein
2And R
3Independent is chlorine, bromine, methyl, ethyl or hydrogen, and Z is direct key, methylene, 2, the 2-propylidene ,-CO-,-O-,-S-,-SO-or-SO
2-.
3. the lifting poly maleimide prepolymer composite of the stable storing of claim 2, wherein R
1Be methyl, X is hexa-methylene, tri-methyl hexamethylene, 1,5,5-trimethyl-1, the 3-cyclohexylidene or wherein Z be methylene, 2, the 2-propylidene or-O-and R
2And R
3It is the group of the formula (a) of hydrogen.
4. the lifting poly maleimide prepolymer composite of the stable storing of claim 2, wherein said BMI is N, N '-4,4 '-diphenyl methane-BMI.
5. the lifting poly maleimide prepolymer composite of the stable storing of claim 1, wherein thiazolinyl phenol or thiazolinyl phenolic ether are the compounds of formula (1)～(4):
Wherein R be direct key, methylene, isopropylidene ,-O-,-S-,-SO-or-SO
2-;
R wherein
4, R
5And R
6Independently be hydrogen or C separately
2～C
10As long as thiazolinyl is R
4, R
5Or R
6In at least one is C
2～C
10Thiazolinyl gets final product;
R wherein
4, R
5, R
6And R
7Independently be hydrogen or C separately
2～C
10As long as thiazolinyl is R
4, R
5, R
6Or R
7In at least one is C
2～C
10Thiazolinyl gets final product, and R is suc as formula defining in (1); With
R wherein
8, R
9, R
10, R
11, R
12And R
13Independently be hydrogen, C separately
1～C
4Alkyl and C
2～C
10As long as thiazolinyl is R
8, R
9, R
10, R
11, R
12And R
13In at least one is C
2～C
10Thiazolinyl gets final product, and b is 0～10 integer.
6. the lifting poly maleimide prepolymer composite of the stable storing of claim 1 comprises the stabilizing agent that is selected from phosphorus molybdenum acid hydrate and phosphotungstic acid hydrate in addition.
7. the lifting poly maleimide prepolymer composite of the stable storing of claim 6 comprises glycol ethers in addition.
8. the preparation method of the lifting poly maleimide prepolymer composite of stable storing may further comprise the steps:
(a) in the presence of amine catalyst, react to generate the poly maleimide prepolymer at polyimides under the rising temperature and thiazolinyl phenol, thiazolinyl phenolic ether or its mixture;
(b) remove all amine catalysts basically; With
(c) in this poly maleimide prepolymer, add dioxolanes, to generate the lifting poly maleimide prepolymer composite of this stable storing.
9. the method for claim 8 is included in step (b) and afterwards stabilizing agent is added to step in this poly maleimide prepolymer.
10. the lifting poly maleimide prepolymer composite of stable storing of preparation according to Claim 8.
11. prepreg or laminate structures comprise lifting poly maleimide prepolymer composite dipping or the fabric that applies or the cured article of fiber with stable storing, the lifting poly maleimide prepolymer composite of described stable storing comprises:
(a) the poly maleimide prepolymer that the lifting reaction in the presence of amine catalyst obtains by polyimides and thiazolinyl phenol, thiazolinyl phenolic ether or its mixture; With
(b) dioxolanes of formula (5)
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| CN201610279867.4A CN105860076A (en) | 2008-03-31 | 2009-03-23 | Storage-stable polymaleimide prepolymer compositions |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4095608P | 2008-03-31 | 2008-03-31 | |
| US61/040,956 | 2008-03-31 | ||
| PCT/US2009/037958 WO2009123876A1 (en) | 2008-03-31 | 2009-03-23 | Storage-stable polymaleimide prepolymer compositions |
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|---|---|
| EP (1) | EP2271215A4 (en) |
| JP (1) | JP5568078B2 (en) |
| KR (1) | KR101591539B1 (en) |
| CN (2) | CN101980604A (en) |
| RU (1) | RU2010144592A (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131008A (en) * | 2013-01-22 | 2013-06-05 | 广东生益科技股份有限公司 | Bismaleimide prepolymer and synthesis method thereof |
| CN103547602A (en) * | 2011-05-17 | 2014-01-29 | 亨斯迈先进材料美国有限责任公司 | Halogen free thermoset resin system for low dielectric loss at high frequency applications |
| CN106009668A (en) * | 2016-06-30 | 2016-10-12 | 高海燕 | Polyimide fiber bismaleimide resin composite and preparation method thereof |
| WO2023241223A1 (en) * | 2022-06-16 | 2023-12-21 | 比亚迪股份有限公司 | Catalyst for synthesizing polyimide and preparation method therefor, and polyimide compound |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2417168B1 (en) * | 2009-03-17 | 2014-11-26 | Huntsman Advanced Materials Americas LLC | Phosphoric acid resistant polymaleimide prepolymer compositions |
| CN114015046B (en) * | 2021-12-07 | 2023-11-10 | 苏州生益科技有限公司 | Modified bismaleimide prepolymer, composition prepared from modified bismaleimide prepolymer, prepreg and laminated board of modified bismaleimide prepolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3764573A (en) * | 1970-10-29 | 1973-10-09 | Gen Electric | Preparation of prepregs |
| US5637387A (en) * | 1991-06-03 | 1997-06-10 | Ciba-Geigy Corporation | Storage-stable advanced polymaleimide compositions |
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|---|---|---|---|---|
| FR1555564A (en) * | 1967-07-13 | 1969-01-31 | ||
| US3741942A (en) * | 1971-07-16 | 1973-06-26 | Gen Electric | Polyimides |
| CH615935A5 (en) * | 1975-06-19 | 1980-02-29 | Ciba Geigy Ag | |
| EP0296112A3 (en) * | 1987-06-18 | 1989-09-06 | Ciba-Geigy Ag | Storage-stable curable compositions |
| EP0348345B1 (en) * | 1988-06-20 | 1996-02-14 | Ciba-Geigy Ag | Solution stable polyimide resin systems |
| JP3250044B2 (en) * | 1991-06-03 | 2002-01-28 | バンティコ アクチエンゲゼルシャフト | Storage stable polyimide prepreg with improved processing properties |
| JPH06128333A (en) * | 1992-10-20 | 1994-05-10 | Toagosei Chem Ind Co Ltd | Production of prepolymer |
| CA2482470C (en) * | 2002-04-19 | 2011-06-07 | Ciba Specialty Chemicals Holding Inc. | Curing of coatings induced by plasma |
| KR101468206B1 (en) * | 2012-02-21 | 2014-12-01 | 한국화학연구원 | Fluoropolymer composition useful for backsheets in photovoltaic modules and method for preparing the backsheets in photovoltaic modules therewith |
-
2009
- 2009-03-23 EP EP09728017.6A patent/EP2271215A4/en not_active Withdrawn
- 2009-03-23 CN CN2009801116500A patent/CN101980604A/en active Pending
- 2009-03-23 WO PCT/US2009/037958 patent/WO2009123876A1/en active Application Filing
- 2009-03-23 RU RU2010144592/04A patent/RU2010144592A/en unknown
- 2009-03-23 JP JP2011501949A patent/JP5568078B2/en active Active
- 2009-03-23 KR KR1020107020211A patent/KR101591539B1/en active IP Right Grant
- 2009-03-23 CN CN201610279867.4A patent/CN105860076A/en active Pending
- 2009-03-31 TW TW098110670A patent/TWI453223B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3764573A (en) * | 1970-10-29 | 1973-10-09 | Gen Electric | Preparation of prepregs |
| US5637387A (en) * | 1991-06-03 | 1997-06-10 | Ciba-Geigy Corporation | Storage-stable advanced polymaleimide compositions |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103547602A (en) * | 2011-05-17 | 2014-01-29 | 亨斯迈先进材料美国有限责任公司 | Halogen free thermoset resin system for low dielectric loss at high frequency applications |
| CN103131008A (en) * | 2013-01-22 | 2013-06-05 | 广东生益科技股份有限公司 | Bismaleimide prepolymer and synthesis method thereof |
| CN103131008B (en) * | 2013-01-22 | 2016-05-25 | 广东生益科技股份有限公司 | A kind of BMI prepolymer and synthetic method thereof |
| CN106009668A (en) * | 2016-06-30 | 2016-10-12 | 高海燕 | Polyimide fiber bismaleimide resin composite and preparation method thereof |
| WO2023241223A1 (en) * | 2022-06-16 | 2023-12-21 | 比亚迪股份有限公司 | Catalyst for synthesizing polyimide and preparation method therefor, and polyimide compound |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI453223B (en) | 2014-09-21 |
| WO2009123876A1 (en) | 2009-10-08 |
| EP2271215A4 (en) | 2013-07-03 |
| EP2271215A1 (en) | 2011-01-12 |
| JP5568078B2 (en) | 2014-08-06 |
| TW200948834A (en) | 2009-12-01 |
| RU2010144592A (en) | 2012-05-10 |
| KR20100125308A (en) | 2010-11-30 |
| CN105860076A (en) | 2016-08-17 |
| JP2011517715A (en) | 2011-06-16 |
| KR101591539B1 (en) | 2016-02-03 |
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