WO2005063839A1 - Article et production - Google Patents

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Publication number
WO2005063839A1
WO2005063839A1 PCT/US2004/043111 US2004043111W WO2005063839A1 WO 2005063839 A1 WO2005063839 A1 WO 2005063839A1 US 2004043111 W US2004043111 W US 2004043111W WO 2005063839 A1 WO2005063839 A1 WO 2005063839A1
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WIPO (PCT)
Prior art keywords
molded piece
ring
group
alkylene group
hydrogen
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PCT/US2004/043111
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English (en)
Inventor
Ishida Hatsuo
Abe Hiroshi
Shibayama Koichi
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Sekisui Chemical Co., Ltd.
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Publication of WO2005063839A1 publication Critical patent/WO2005063839A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N

Definitions

  • the present invention relates to a molded piece that is a ring-opened polymer from a bifunctional dihydrobenzoxazine compound and has a low dialect constant and superior mechanical strength and the manufacturing method thereof.
  • thermosetting resins such as phenolic resin, melamine resin, epoxy resin, unsaturated polyester resin, and bismaleimide resin
  • phenolic resin and melamine resin generate volatile by-products at the time of curing
  • epoxy resin and unsaturated polyester resin are inferior in terms of flame resistance
  • bismaleimide resin is very expensive.
  • dihydrobenzoxazine compounds that polymerize without generating volatile components by means of the ring-opening reaction of dihydrobenzoxazine rings have been actively studied.
  • a thermosetting resin(s) characteristically comprising a compound(s) represented by general formula (3) and/or a ring-opened polymer(s) thereof was proposed in Japanese Patent Laid-Open No. 2000-154225 bulletin.
  • R t denotes a substituted or unsubstituted alicyclic hydrocarbon group having five or more and 12 or less carbon atoms, or aromatic hydrocarbon-substituted alkylidene group or straight chain or branched alkylidene group having four or more and 12 or less carbon atoms;
  • R 2 and R 3 are a phenyl group, a phenyl group with a t-butyl group substituted to the ortho position or para position, or an aliphatic group having ten or less carbon atoms.
  • a molded piece obtained by thermosetting the aforementioned dihydrobenzoxazine compound has high flexural strength and flexural modulus, it has low elongation and bending properties and is hard and brittle, and therefore a molded piece, especially a thin molded piece such as film, is hard to fabricate and also unusable; because of this, it has been mixed with phenolic resin, epoxy resin and such for use.
  • the aforementioned dihydrobenzoxazine compound is a compound obtained by bonding benzene rings to each other by means of an alkylene group(s); the only example of a compound obtained by bonding nitrogen atoms of dihydrobenzoxazine rings by means of an alkylene group(s) is a dihydrobenzoxazine compound having the following structural formula(4) listed in USP55435 I6, and the ring-opening polymerization and ring-opened polymer thereof has not been studied at all.
  • the object of the present invention is to provide a molded piece obtained by a ring-opening polymerization reaction of dihydrobenzoxazine compounds that have a low dielectric constant, a low dielectric loss tangent (dielectric loss) and a superior balance of flexural strength, flexural modulus, elongation, and bending properties, as well as a manufacturing method thereof.
  • the molded piece of the present invention is ring-opened polymers from bifunctional dihydrobenzoxazine compounds represented by the following formula (1) that has a dielectric constant of 2.0-3.2 and a dielectric loss tangent of 0.0001-0.006, at 23°C at 100 MHz and 1 GHz.
  • R denotes a straight chain alkylene group having two or more carbon atoms or a branched alkylene group obtained by substituting an alkyl group(s) for hydrogen in the former; hydrogen in the benzene ring may be replaced by an alkyl group or alkoxy group.
  • R in the bifunctional dihydrobenzoxazine compounds represented by the above formula (1) is a straight chain alkylene group having two or more carbon atoms or a branched alkylene group obtained by substituting an alkyl group(s) for hydrogen in the former.
  • the obtained molded piece will have a higher storage modulus (G') and glass transition temperature while a dielectric constant will have higher and elongation and flexibility decrease; on the other hand, if the number of carbon atoms increases, then the obtained molded piece will have higher elongation and flexibility while a dielectric constant will have lower, a dielectric loss tangent (specially, 1GHz) will tend to have a few lower and the storage modulus (G') and glass transition temperature decrease; therefore, the number of carbon atoms is preferably 2-16, more preferably 6-12 and most preferably 6.
  • the obtained molded piece will have a low dielectric constant and a dielectric loss tangent, and will have a preferable storage modulus (G') 5 a Young's modulus (E'), a percent elongation and a glass transition temperature.
  • R may be a branched alkylene group obtained by substituting an alkyl group(s) for hydrogen in the straight chain alkylene group having two or more carbon atoms; however, since the alkyl substitution increases the storage modulus (G') and the glass transition temperature while reducing the elongation and flexibility, there needs to be a balance with the number of carbon atoms in the straight chain alkylene group, which is the main chain. That is, the alkyl substitution is preferable when the number of carbon atoms in the straight chain alkylene group is large; examples of the alkyl group include a methyl group, ethyl group, propyl group, and butyl group.
  • An alkyl group or alkoxy group can be substituted for hydrogen in the benzene ring(s) in the bifunctional dihydrobenzoxazine compound represented by the above formula (1); examples of the alkyl group include a methyl group, ethyl group, propyl group, butyl group, octyl group, and nonyl group and examples of the alkoxy group include a methoxy group, ethoxy group, propoxy group, and butoxy group.
  • the aforementioned bifunctional dihydrobenzoxazine compound is preferably synthesized from univalent phenol, aliphatic diamine represented by the following formula (2), and formaldehydes.
  • R denotes a straight chain alkylene group having two or more carbon atoms or a branched alkylene group obtained by substituting an alkyl group(s) for hydrogen in the former.
  • the aforementioned univalent phenol compound is a compound that has one phenolic hydroxide group and at least one hydrogen at the ortho position; examples include phenol, cresol, xylenol, nonylphenol, p-t-butylphenol, and octylphenol.
  • R in the aliphatic diatnine represented by general formula (2) is the same as R in the bifunctional dihydrobenzoxazine compound represented by formula (1); examples include 1 ,2- diaminoethylene, 1,3-diaminopropane, 1,4-diaminobutane, 1 ,6-diaminohexane, 1 ,8- diaminooctane, and 1,12-diaminododecane.
  • Examples of the aforementioned formaldehydes include formalin, which is an aqueous solution of formaldehyde, and paraformaldehyde, which is polymerized formaldehyde.
  • the aforementioned bifunctional dihydrobenzoxazine compound is synthesized by a reaction between two moles equivalent of univalent phenol, one mole equivalent of the aliphatic diami ⁇ e represented by formula (2), and four moles equivalent of formaldehydes; for the synthetic method, any prior art synthetic method can be used. For example, it can be easily synthesized by mixing two moles of univalent phenol , one mole of the aliphatic diamine represented by formula (2), and four moles of formaldehydes, and stirring the mixture while heating it up to 100-130°C for 10 minutes to one hour.
  • the ingredients can be dissolved in halogenated solvent such as chloroform, dictiloromethane, dichloroethane and trichloroethan; aromatic solvent such as benzene, toluene and xylene; lower alcohols such as methanol, ethanol, propanol and butanol; or in a solvent such as 1,4- dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether before the synthesis.
  • halogenated solvent such as chloroform, dictiloromethane, dichloroethane and trichloroethan
  • aromatic solvent such as benzene, toluene and xylene
  • lower alcohols such as methanol, ethanol, propanol and butanol
  • 1,4- dioxane 1,4- dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
  • a 1 -20 hour-reaction with heating at 50-130°C is sufficient; after completion of the reaction, the solvent is removed; if necessary, unreacted univalent phenol, aliphatic diamine, and formaldehyde can be ' removed by rinsing by alkali solution or alcohols such as methanol, ethanol.
  • the aforementioned molded piece is a ring-opened polymer of the bifunctional dihydrobenzoxazine compound represented by the above formula (1).
  • any conventional prior art of polymerization method can Be used; generally, several hours of heating at 120-260°C is sufficient.
  • the heating temperature is low and/or the heating time is insufficient, then the glass transition temperature does not improve, heat resistance and mechanical strength are insufficient. On the other hand, if the heating temperature is too high and/or the heating time is tpo long, then the glass transition temperature lowers and heat resistance and mechanical strength also decrease. Therefore, it is preferable to conduct the ring-opening polymerization for 0.3-4 hours at 165-195°C.
  • preheating at a lower temperature before the aforementioned ring-opening polymerization is preferable; the preheating is preferably at a temperature of 130°C or higher and lower than 165°C for 0.5-5 hours.
  • a curing accelerator When conducting the ring-opening polymerization of the aforementioned bifunctional dihydrobenzoxazine compound, a curing accelerator can be added.
  • any curing accelerator that is commonly used for ring-opening polymerization of dihydrobenzoxazine compounds can be used; examples include multifunctional phenols such as catechol and bisphenol A, sulfonic acids such as p-toluenesulfonic acid and p- phenolsulfonic acid, carboxylic acids such as benzoic acid, salicylic acid, oxalic acid, and adipic acid, metal complexes such as cobalt (II) acetylacetonate, aluminum (III) acetylacetonate, and zirconium (IV) acetylacetonate, metal oxides such as calcium oxide, cobalt oxide, magnesium oxide, and iron oxide, calcium hydroxide, imidazole and its derivatives, tertiary amines such as diaza
  • the amount of the curing accelerator to be added is not limited in particular; however, since addition of a large amount has an adverse effect on the mechanical properties, it is generally five weight parts or less, preferably three weight parts or less, for 100 weight parts of the aforementioned bifunctional dihydrobenzoxazine compound.
  • the aforementioned molded piece has a dielectric constant of 2.0-3.2 and a dielectric loss tangent of 0.0001-0.006, at 23°C at 100 MHz and 1 GHz.
  • Electronic appliances are now required to satisfy high-density packaging, high-speed signal transmittability and high-frequency applicability, and laminate boards and other electronic materials for them are therefore required to have a reduced dielectric constant.
  • thermosetting resin moldings have a lower dielectric constant as possible.
  • the preferable range of a dielectric constant and a dielectric loss tangent are " different. Therefore, it is not always so but generally it is desirable a dielectric constant of at most 3.5 and a dielectric loss tangent of at most 0.015 at 23°C at 100 MHz and 1 GHz. Therefore, The aforementioned molded piece is preferably used in said use.
  • a 1 mm-thick sheet obtained by the ring-opening polymerization of a bifunctional dihydrobenzoxazine compound was cut to obtain rectangular-shaped sample pieces having a dimension of 15 mm x 15 mm x 1 mm.
  • the obtained sample pieces are set in a dielectric constant meter and analyzed therein at 23°C by the volumetric method, and the date of the dielectric constant and the dielectric loss tangent of the sample at 100 MHz and 1GHz are read. It is desirable that the aforementioned molded piece has a storage modulus (G') of 0.6-5.0 GPa at 23°C.
  • the storage modulus (G') at 23°C is 0.6-5.0 GPa
  • the film is relatively flexible and would not break even if a force strong enough to deform it were applied.
  • the storage modulus (G') at 23°C is preferably 0.8-4.5 GPa.
  • the method for measuring the aforementioned storage modulus (G') in the present invention is as follows.
  • a 1 mm-thick sheet obtained by the ring-opening polymerization of a bifunctional dihydrobenzoxazine compound was cut to obtain rectangular-shaped sample pieces having a dimension of 5 mm x 5 mm x 1 mm.
  • the obtained sample pieces were examined by a dynamic mechanical spectrometer (product name "RMS-800" from Rheometrics, Inc.) and viscoelasticity was measured at 23°C at a frequency of 1 Hz and a strain of 0.05% to obtain the storage modulus (G').
  • the flexural strength at 23°C is preferably 180 MPa or less.
  • the molded piece Since the flexural strength at 23°C is 180 MPa or less, the molded piece is flexible under flexural stress and not easily broken.
  • the method for measuring the aforementioned flexural strength in the present invention is as follows. A 1 mm-thick sheet obtained by the ring-opening polymerization of a bifunctional dihydrobenzoxazine compound was cut into 50 mm x 10 mm pieces and fed into a tensile tester (product name "Tensilon" from ORIENTECH Inc.) and the measurement was conducted according to JIS-K7171.
  • the Young's modulus (E') at 23°C is preferably 1.0-5.5 GPa.
  • the Young's modulus (E') of the aforementioned molded piece is less than 1.0 GPa, the molded piece is not sufficiently self-supporting; if it is more than 5.5 GPa, then the molded piece is harder than necessary and brittle, breaking easily under stress. Therefore it is limited to the range of 1.0-5.5 GPa.
  • A- molded piece having a Young's modulus (E') at 23°C of 1.0-5.5 GPa is flexible even under tensile stress, allows stress relaxation, and does not break or deform due to residual strain.
  • the percent elongation at break at 23°C is preferably 2.0-20%.
  • the molded piece can break under light stress; if it is more than 20%, then the dimension stability of the molded piece becomes insufficient; therefore it is limited to the range of 2.0-20%. Within this range, when the molded piece is a film, it does not break easily due to torsion or tension.
  • the methods for measuring the aforementioned Young's modulus (E') and the percent elongation at break in the present invention are as follows.
  • a sheet-shaped molded piece obtained by the ring-opening polymerization of a bifunctional dihydrobenzoxazine compound was cut into 80 mm x 10 mm pieces and fed into a tensile tester (product name "Tensilon” from ORIENTECH Inc.); tensile testing was conducted at 23°C with a chuck-to-chuck distance of 60 mm and a cross head speed of 5 mm/minute to measure the Young's modulus (E') and the percent elongation at the point of rupture.
  • the glass transition temperature is preferably 100- 200°C.
  • the aforementioned molded piece has a glass transition temperature of 100-200°C, it can be used optimally in environments that require heat resistance such as automobiles and electronic materials.
  • the aforementioned glass transition temperature is measured by the DSC method.
  • the char yield ratio is preferably 2-45%. Since the aforementioned molded piece has a Char generation ratio of 2-45%, it has high flame resistance and can be used in applications that require flame resistance such as electronic materials and automobiles without requiring a large amount of a flame retardant; therefore, a preferable range of the char yield ratio is 2-25%.
  • the method for measuring the aforementioned Char generation ratio in the present invention is as follows.
  • a 1 mm-thick sheet-shaped molded piece obtained by the ring-opening polymerization of a bifunctional dihydrobenzoxazine compound was cut into 50 mm x 25 mm pieces and, according to ASTM E 1354 "Method for testing fiammability of construction materials", they were irradiated and incinerated with a heat ray of 50 kW/m 2 by a cone calorie meter; the char yield was determined by the ratio of the weight after incineration to the weight before incineration.
  • the configuration of the molded piece of the present invention is as described above; it is a molded piece that is a ring-opened polymer of a bifunctional dihydrobenzoxazine compound represented by general formula (1) and has a characteristic of having a dielectric constant of 2.0- 3.2 and a dielectric loss tangent of 0.0001-0.006, at 23°C at 100 MHz and 1 GHz; it is preferable to laminate boards and other electronic materials, required to have a reduced dielectric constant, in particular, for multi-layered substrates for IC packages.
  • the aforementioned molded piece that has a flexural strength of 180 MPa or less at 23°C is flexible under flexural stress and not easily broken by flexural stress.
  • the aforementioned molded piece that has a Young's modulus (E') of 1.0-5.5 GPa at 23°C is flexible even under tensile stress, allows stress relaxation, and does not break or deform due to residual strain and such.
  • the aforementioned molded piece that has a percent elongation at break of 2.0-20% at 23°C does not break easily by torsion or tension when it is in a film form.
  • the aforementioned molded piece that has a glass transition temperature of 100-200°C, can be used optimally in environments that require heat resistance such as automobiles and electronic materials.
  • the aforementioned molded piece that has a char yield ratio of 2-45% has high flame resistance and can be used in applications that require flame resistance such as electronic materials and automobiles without requiring a large amount of a flame retardant.
  • the configuration of the method of manufacturing the molded piece of the present invention is as described above and therefore the obtained molded piece has a homogeneous good external appearance as well ' as a high glass transition temperature, superior heat resistance and mechanical strength.
  • Example 1 1 mole of 1,2-diaminoethane, 2 moles of phenol, 4 moles of paraformaldehyde and 1000 ml of chloroform were mixed and heated up to 60 D with stirring. Under reflux, the reaction was carried out for 2 hours after the start of the reflux. The resulting mixture was rinsed by 1 N sodium hydroxide aqueous solution in the separatory funnel and was thereafter rinsed by ion- exchange water in the separatory funnel.
  • the resulting mixture was evaporated in a rotary-evaporator to obtain a bifunctional dihydrobenzoxazine compound wherein R in formula (1) is an ethylene group.
  • the obtained bifunctional dihydrobenzoxazine compound was fed into a press and was pressed 3 MPa at 140°C for one hour, 160°C for one hour, and finally at 180°C for one hour to carry out ring-opening polymerization and obtain a sheet-shaped molded piece that was 100 mm long, 25 mm wide and 1 mm thick.
  • Example 2 1 mole of 1,4-diaminobutane, 2 moles of phenol, 4 moles of paraformaldehyde and 1000 ml of chloroform were mixed and heated up to 60°C with stirring. Under reflux, the reaction was carried out for 4 hours after the start of the reflux. The resulting mixture was rinsed by 1 N sodium hydroxide aqueous solution in the separatory funnel and was thereafter rinsed by ion- exchange water in the separatory funnel. After drying the chloroform layer by anhydrous sodium sulfate, the resulting mixture was evaporated in a rotary-evaporator to obtain a bifunctional dihydrobenzoxazine compound wherein R in formula (1 ) is an butylene group.
  • the obtained bifunctional dihydrobenzoxazine compound was fed into a press and was pressed 3 MPa at 140°C for one hour, 160°C for one hour, and finally at 180°C for one hour to carry out ring-opening polymerization and obtain a sheet-shaped molded piece that was 100 mm long, 25 mm wide and 1 mm thick.
  • Example 3 1 mole of 1,6-diaminohexane, 2 moles of phenol, 4 moles of paraformaldehyde and 1000 ml of chloroform were mixed and heated up to 60°C with stirring. Under reflux, the reaction was carried out for 8 hours after the start of the reflux.
  • the obtained bifunctional dihydrobenzoxazine compound was fed into a press and was pressed 3 MPa at 140°C for one hour, 160°C for one hour, and finally at 180°C for one hour to carry out ring-opening polymerization and obtain a sheet-shaped molded piece that was 100 mm long, 25 mm wide and 1 mm thick.
  • Example 4 1 mole of 1,8-diaminooctane, 2 moles of phenol, 4 moles of paraformaldehyde and 1000 mlof chloroform were mixed and heated up to 60°C with stirring. Under reflux, the reaction was carried out for 10 hours after the start of the reflux.
  • the obtained bifunctional dihydrobenzoxazine compound was fed into a press and was pressed 3 MPa at 140°C for one hour, 160°C for one hour, and finally at 180°C for one hour to carry out ring-opening polymerization and obtain a sheet-shaped molded piece that was 100 mm long, 25 mm wide and 1 mm thick.
  • Example 5 1 mole of 1 ,12-diaminododecane, 2 moles of phenol, 4 moles of paraformaldehyde and 1000 ml of chloroform were mixed and heated up to 60°C with stirring. Under reflux, the reaction was carried out for 12 hours after the start of the reflux.
  • the obtained bifunctional dihydrobenzoxazine compound was fed into a press and was pressed 3 MPa at 140°C for one hour, 160°C for one hour, and finally at 180°C for one hour to carry out ring-opening polymerization and obtain a sheet-shaped molded piece that was 100 mm long, 25 mm wide and 1 mm thick.
  • the dielectric constant and the dielectric loss tangent of the bifunctional dihydrobenzoxazine compounds obtained in Examples 1-5, were measured by the volumetric method by a dielectric constant measuring device (model number RF impedance material analyzer E4991A from AGILENT) and the results are shown in Table 1.
  • Example 6 1 mole of 1,2-diaminoethane, 2 moles of phenol, and 4 moles of paraformaldehyde were mixed and heated up to 100°C. After the mixture became a homogeneous clear liquid, the temperature was raised to 120°C with stirring and the reaction was carried out for 30 minutes to obtain a bifunctional dihydrobenzoxazine compound wherein R in formula (1) is an ethylene group.
  • the obtained bifunctional dihydrobenzoxazine compound was fed into a 100 mm-long, 25 mm- wide, and 2 mm-deep metal mold and heated at 140°C for one hour, 160°C for one hour, and finally at 180°C for two hours to carry out ring-opening polymerization and obtain a sheet-shaped molded piece that was 100 mm long, 25 mm wide and 1 mm thick.
  • Example 7 1 mole of 1,4-diaminobutane, 2 moles of phenol, and 4 moles of paraformaldehyde were mixed and- heated up to 100°C.
  • Example 8 1 mole of 1,6-diaminohexane, 2 moles of phenol, and 4 moles of paraformaldehyde were mixed and heated up to 10O°C. After the mixture became a homogeneous clear liquid, the temperature was raised to 120°C with stirring and the reaction was carried out for 30 minutes to obtain a bifunctional dihydrobenzoxazine compound wherein R in formula (1) was a hexamethylene group.
  • the obtained bifunctional dihydrobenzoxazine compound was fed into a 100 mm-long, 25 nun- wide, and 2 mm-deep metal mold and heated at 140°C for two hours, 160°C for two hours, and finally at 180°C for two hours to carry out ring-opening polymerization and obtain a sheet-shaped molded piece that was 100 mm long, 25 mm wide and 1 mm thick.
  • Example 9 1 mole of 1,8-diaminooctane, 2 moles of phenol, and 4 moles of paraformaldehyde were mixed and heated up to 10O°C.
  • the obtained sheet-shaped molded piece was cut into 15 mm squares and fed to a dielectric constant measuring device (model number HP4291B from Hewlett Packard) to measure the dielectric constant and dielectric loss tangent at 23°C by the volumetric method.
  • the dielectric constant at 100 MHz was 2.7 and the dielectric loss tangent was 0.0060.
  • the dielectric constant at 1 GHz was 2.7 and the dielectric loss tangent was 0.0051.
  • Example 10 1 mole of 1,12-diaminododecane, 2 moles of phenol, and 4 moles of paraformaldehyde were mixed and heated up to 10O°C.
  • the glass transition temperatures of the bifunctional dihydrobenzoxazine compounds obtained in Examples 6-10 were measured and the results are shown in Table 3. Also, the density, storage modulus (G'), flexural strength, Young's modulus (E'), percent elongation at break, and the char yield ratio of the sheet-shaped molded pieces obtained in Examples 6-10 were measured and the results are shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

L'invention concerne une pièce moulée obtenue par réaction de polymérisation par ouverture de cycle d'un composé de dihydrobenzo oxazine qui possède une faible constante diélectrique, un faible facteur de pertes diélectriques et un équilibre supérieur de résistance à la flexion, de module d'élasticité en flexion, d'élongation, et de propriétés de pliage; l'invention concernant par ailleurs un procédé de fabrication de cette pièce. L'invention concerne en outre une pièce moulée constituée d'un polymère à cycle ouvert d'un composé de dihydrobenzo oxazine bifonctionnel représenté par la formule (I), qui présente une constante diélectrique de 2,0-3,2 et un facteur de pertes diélectriques de 0,0001-0,006, à 23 °C, 100 MHz et 1 GHz. Dans cette formule, R représente un groupe alkylène à chaîne linéaire qui comporte au moins deux atomes de carbone ou un groupe alkylène ramifié obtenu par substitution d'un ou de plusieurs groupes alkyle par l'hydrogène; l'hydrogène dans le cycle benzénique pouvant être remplacé par un groupe alkyle ou un groupe alcoxy.
PCT/US2004/043111 2003-12-23 2004-12-22 Article et production WO2005063839A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169587A (ja) * 2005-11-24 2007-07-05 Sekisui Chem Co Ltd 繊維複合体及びその製造方法
JPWO2007018110A1 (ja) * 2005-08-05 2009-02-19 積水化学工業株式会社 熱硬化性化合物、それを含む組成物、及び成形体
EP2336221A1 (fr) * 2010-12-10 2011-06-22 Henkel AG & Co. KGaA Compositions durcissables
WO2018081394A1 (fr) * 2016-10-31 2018-05-03 3M Innovative Properties Company Composites à perte diélectrique élevée pour des applications d'interférence électromagnétique (emi)

Citations (1)

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US5543516A (en) * 1994-05-18 1996-08-06 Edison Polymer Innovation Corporation Process for preparation of benzoxazine compounds in solventless systems

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US5543516A (en) * 1994-05-18 1996-08-06 Edison Polymer Innovation Corporation Process for preparation of benzoxazine compounds in solventless systems

Non-Patent Citations (1)

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DATABASE CA [online] GRABARNIK ET AL: "Hardening of phenol-formaldehyde and arene-phenol-formaldehyde oligomers without evolution of volatile matter", accession no. STN Database accession no. (111:195985) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2007018110A1 (ja) * 2005-08-05 2009-02-19 積水化学工業株式会社 熱硬化性化合物、それを含む組成物、及び成形体
JP2007169587A (ja) * 2005-11-24 2007-07-05 Sekisui Chem Co Ltd 繊維複合体及びその製造方法
EP2336221A1 (fr) * 2010-12-10 2011-06-22 Henkel AG & Co. KGaA Compositions durcissables
WO2018081394A1 (fr) * 2016-10-31 2018-05-03 3M Innovative Properties Company Composites à perte diélectrique élevée pour des applications d'interférence électromagnétique (emi)
CN109906672A (zh) * 2016-10-31 2019-06-18 3M创新有限公司 用于电磁干扰(emi)应用的高介电损耗复合材料

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