TW201425289A - Allyl compound and composition thereof, co-oligomer and thermosetting resin composition - Google Patents

Abstract

The present invention provides an allyl compound, a composition of the allyl compound, a co-oligomer and a thermosetting resin composition, which can modify and toughen bismaleimide resin, can achieve low dielectric constant, low dielectric loss and high glass transition temperature, and can be applied to multiple uses such as a glass fiber prepreg, a printed circuit board, a copper clad laminate, a casting resin, an insulating material, a structural material, an abrasion-resistant material, a composite material, an aeronautical material, etc.

Description

Allyl compound and composition thereof, copolymerized oligomer, thermosetting resin composition

The allyl compound of the invention and the composition thereof can be modified and toughened with the bimarininimide resin, and achieve low dielectric constant, low dielectric loss, high glass transition temperature, and can be applied to various applications such as glass fiber. Prepregs, printed circuit boards, copper clad laminates, casting resins, insulating materials, structural materials, wear resistant materials, composite materials, aerospace materials, etc.

Diallyl bisphenol A is an allyl compound toughened and modified double-maleimide resin, which is the most widely used, but contains phenolic hydroxyl groups in the molecule, which easily absorbs water and causes dielectric constant (Dielectric Constant/ Dk) and Dissipation Factor (Df) cannot be effectively reduced, making the application of diallyl bisphenol A modified double maleimide resin in the electronics industry limited.

In addition to emphasizing lightness, thinness, shortness, and smallness, the new generation of electronic products emphasizes additional functions and speed. High-density wiring and high-frequency transmission of printed circuit boards are effective solutions. In order to improve transmission speed and maintain signal integrity, it is necessary. By reducing the dielectric constant (Dielectric Constant/Dk) and the Dissipation Factor (Df) of the printed circuit board substrate, the signal transmission speed and the signal transmission loss are improved.

The prepolymer or mixture of the bismaleimide compound and the cyanate resin is not only a BT resin (Mitsubishi Gas brand name), but BT resin is widely used in high-function printed circuit boards and semiconductor packaging materials in recent years; using a traditional double horse The quinone imine compound is made into a BT resin and exhibits excellent properties in heat resistance, chemical resistance, and electrical properties. However, the conventional bismaleimide compound is not easily dissolved in a solvent, and the BT resin solution is precipitated by crystallization over a long period of time, which causes a problem that the cured product has low moisture absorption heat resistance and metal adhesion and insufficient peeling strength of the cured product.

Japanese Patent JP-A-7-53864, Republic of China Patent TW200621852, in order to improve the solvent solubility of the bismaleimide compound, to increase the alkyl group on the benzene nucleus, is disadvantageous in that the peel strength of the BT resin cured product is still insufficient.

The Republic of China patent TW200942578A1 is used to improve the electrical and toughness of BT resin, and uses divinyl polyphenylene ether. The disadvantage is that the peel strength of the cured product of BT resin is still insufficient.

There is a known problem with diallyl bisphenol A, a well-known technique, in that diallyl bisphenol A is used as a toughened modified bismaleimide resin, although it can improve the curing of bismaleimide resin. The brittleness of the material, but the residual phenolic hydroxyl group easily absorbs water, resulting in the dielectric constant (Dielectric Constant/Dk) and the loss factor (Dissipation Factor/Df) cannot be effectively reduced; the traditional practice is in the bismaleimide resin and The addition of an epoxy resin to diallyl bisphenol A allows the epoxy resin to react with the phenolic hydroxyl group to enhance the toughening effect, but the epoxy group reacts with the phenolic hydroxyl group to form a more water-absorbing alcohol after ring opening. The hydroxyl group makes the dielectric constant and dielectric loss not effectively reduced, and it is still insufficient for the increasingly demanding mobile communication products.

The problem to be solved by the present invention is to provide an allyl compound having a molecule containing two or more allyl groups, having no hydroxyl group in the molecule, and not absorbing water, causing a dielectric constant and a dielectric loss factor. It can not be effectively reduced, and a biphenyl structure can be introduced into the molecular chain to improve the crystallinity of the molecule, thereby improving molecular water absorption, shrinkage of the cured product, and increasing the glass transition temperature to meet the requirements of low dielectric constant and low dielectric loss. .

In view of the above problems, the technical means for solving the problem of the present invention provides an allyl compound whose chemical structure is as shown in the formula (I): Formula (I) Where Y is: Where X is selected from: One or more of the group consisting of; wherein R1, R2, R3, and R4 are the same or different, and are represented by hydrogen, a hydrocarbon of C1 to C6; and R5 and R6 are the same or different, and are represented by hydrogen, C1~ a hydrocarbon of C6; A is selected from the group consisting of: a covalent bond, a hydrocarbon of C1 to C20; and n is an integer selected from 0 to 50.

The present invention provides a composition of an allyl compound, the composition comprising at least: (a) an allyl compound; (b) a marlinimine resin comprising: a bismaleimine compound, a double marlin One or more of the group consisting of a quinone imine oligomer, a compound containing one to five marlinimine functional groups, and a copolymerized oligomer containing one to five marlinimine functional groups.

The present invention provides a copolymerized oligomer comprising at least an allyl compound monomer; the present invention provides a thermosetting resin composition comprising at least: (a) a copolymerized oligomer; (b) an organic filler , including: polyphenylene ether, polytetrafluoroethylene One or more of the groups consisting of alkene and polyetheretherketone.

The bismaleimide resin has good mechanical properties and heat resistance, but the unmodified bismaleimide resin has disadvantages such as high melting point, poor solubility, high molding temperature, and high brittleness of the cured product; The compound toughened and modified double-maleimide resin is the most effective method. The prepolymer of allyl compound and bismaleimide resin has good storage stability, easy dissolution, good adhesion, toughness and toughness of cured product. High temperature and high humidity, and has good mechanical and electrical properties.

The allyl compound, the composition of the allyl compound, the copolymerized oligomer, and the thermosetting resin composition of the present invention can be modified and toughened with the double-maleimine resin to achieve a low dielectric constant and a low dielectric constant. Loss, high glass transfer temperature, can be applied to a variety of applications such as glass fiber prepreg, printed circuit boards, copper clad laminates, casting resins, insulating materials, structural materials, wear-resistant materials, composite materials, aerospace materials.

The object of the present invention is to provide an allyl compound having a chemical structure as shown in the formula (I): Where Y is: Where X is selected from: One or more of the group consisting of; wherein R1, R2, R3, and R4 are the same or different, and are represented by hydrogen, a hydrocarbon of C1 to C6; and R5 and R6 are the same or different, and are represented by hydrogen, C1~ a hydrocarbon of C6; A is selected from the group consisting of: a covalent bond, a hydrocarbon of C1 to C20; and n is an integer selected from 0 to 50.

The present invention provides a composition of an allyl compound, the composition comprising at least: (a) an allyl compound; (b) a marlinimine resin comprising: a bismaleimine compound, a double marlin One or more of the group consisting of a quinone imine oligomer, a compound containing one to five marlinimine functional groups, and a copolymerized oligomer containing one to five marlinimine functional groups.

The present invention provides a copolymerized oligomer comprising at least an allyl compound monomer; the present invention provides a thermosetting resin composition comprising at least: (a) a copolymerized oligomer; (b) an organic filler And comprising: one or more of the group consisting of polyphenylene ether, polytetrafluoroethylene, and polyetheretherketone.

The present invention provides an allyl compound, which can be used in the synthesis of solvents including: toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., dichloromethyl The base aromatic compound and the allyl phenol may further comprise a desalting condensation etherification reaction of the bisphenol in a solvent with a base, the base comprising: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium ethoxide, etc. The preferred condensation temperature is from 20 ° C to 150 ° C, and a phase transfer agent of a quaternary ammonium salt or a quaternary phosphonium salt may be added or not. Add phase transfer agent.

The present invention provides an allyl compound, wherein the dichloromethyl aromatic monomer used in X may be selected from the group consisting of: dichloromethylbenzene, dichloromethylbiphenyl, dichloromethylphenyl ether; wherein Y The bisphenol monomer used may be selected from the group consisting of: bisphenol A, bisphenol B, bisphenol F, bisphenol M, bisphenol Z, diallyl bisphenol A, diallyl bisphenol F, two Allyl bisphenol M, diallyl bisphenol B, diallyl bisphenol Z, diallyl biphenyl, bis(2,6 dimethyl phenol), bis (2,6 dimethyl phenol) Methane, bis(2-phenylphenol)methane, bis(2-allylphenol)methane, bis(2,6-dimethylphenol)propane, bis(2,6-dimethylphenol) 4,4'-di Methylbiphenyl, bis(2,6 dimethylphenol) 4,4'-dimethyldiphenyl ether, bis(2,6 dimethylphenol) 1,4-dimethylbenzene, two (2, 6 dimethylphenol) 4,4'-dioxymethylbiphenyl, bis(2,6-dimethylphenol) 4,4'-dioxymethyldiphenyl ether, bis(2,6-dimethylphenol) 1,4-Dimethoxymethylbenzene, bis(2,6-diethylphenol), bis(2,6-diethylphenol)methane, bis(2,6-diethylphenol)propane, di(2, 6 diethyl phenol) 4,4'-dimethylbiphenyl, bis(2,6-diethylphenol) 4,4'-dimethyldiphenyl ether, two (2,6 di-B) Phenol) 1,4-dimethylbenzene, bis(2,6-diethylphenol) 4,4'-dioxymethylbiphenyl, bis(2,6-diethylphenol) 4,4'-di Oxygen T methyl diphenyl ether, bis(2,6 diethyl phenol) 1,4-dimethoxymethyl benzene (2,6 dipropyl phenol), bis (2,6 dipropyl phenol) methane, Di(2,6-dipropylphenol)propane, bis(2,6-dipropylphenol) 4,4'-dimethylbiphenyl, di(2,6-dipropylphenol) 4,4'-dimethyl Diphenyl ether, bis(2,6 dipropyl phenol) 1,4-dimethylbenzene, bis(2,6 dipropyl phenol) 4,4'-dioxymethylbiphenyl, two (2, 6 dipropyl phenol) 4,4'-dioxymethyl diphenyl ether, bis (2,6 dipropyl phenol) 1,4-dimethoxymethyl benzene other diphenols and the like. Wherein the allyl phenols may be selected from the group consisting of: 2-allyl phenol, 2-allyl 6-methyl phenol, 2-allyl 6-ethyl phenol, 2-allyl 6-propyl phenol 2-allyl 6-ene Propyl phenol, 2-allyl 6-phenylphenol, etc.

The present invention provides a composition of an allyl compound, the composition comprising at least: (a) an allyl compound; (b) a marlinimine resin comprising: a bismaleimine compound, a double marlin One or more of the group consisting of a quinone imine oligomer, a compound containing one to five marlinimine functional groups, and a copolymerized oligomer containing one to five marlinimine functional groups.

The present invention provides a composition of an allyl compound, and the marlinimine monomer used in the marlinimine resin comprises: bis(cis-butenylene phenyl) ether, bis(cis-butenylene) Iminophenyl)methane, bis(cis-butenylene phenyl) sulfone, bis(cis-butenylene phenyl) fluorene, bis(3-ethyl-5-methyl-4-cis-butane Indole phenyl)methane, bis(3-methyl-5-methyl-4-cis-butylimine phenyl)methane, bis(3-ethyl-5-ethyl-4-cis-butane醯iminophenyl)methane, bis(n-butenenimine)m-benzene, bis(succinimide)-p-benzene, bis(cis-s-imine)-o-benzene, bis(cis-butenylene) Imine) toluene, bis(succinimide)biphenyl, bis(n-butenenimine)methane, bis(cis-succinimide)ethane, bis(succinimide) Alkane, bis(n-butenenimine)hexane, bis(cis-butenyleneimine)methane, bis(cis-succinimide)octane, bis(cis-butenyleneimine)decane, two (cis-butenylene imine) dodecane, cis-butenylene phenyl, cis-butenylene phenol group, a compound having one to five marlinimine functional groups, and the like.

The composition of the allyl compound of the present invention may contain various additives, such as inorganic fiber reinforcing materials, organic fiber reinforcing materials, inorganic fillers, organic fillers, resins, etc., which may be used in combination as needed; The agent includes: polyvinyl acetal, polyimide, phenoxy resin, acrylic resin, bismuth resin, Alkyd resin, polyurethane resin, polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber , fluorine-containing rubber, styrene-isoprene diene rubber, epoxidized butadiene, etc.; and addition of polyene compounds such as divinylbenzene, dipropylene benzene, dipropylene bisphenol, isocyanurate, Dipropylene phthalate, vinyl pyrrolidone, polyether ether ketone, polyether ketone, polyether ketone ketone, polytetrafluoroethylene, etc.; inorganic fiber reinforced materials include: E glass fiber, NE glass fiber, D glass Fiber, S glass fiber, T glass fiber, xenon glass fiber, carbon fiber, aluminum fiber, tantalum carbide fiber, asbestos, rock wool fabric or non-woven fabric or mixture thereof; organic fiber reinforcing material includes: wholly aromatic polyamide fiber , polyimine fiber, liquid crystal polyester, polyester fiber, fluorine-containing fiber, polybenzopyrene fiber, cotton fiber, linen fiber, woven or non-woven fabric or mixture thereof; inorganic filler includes: 矽 oxygen, fusion 矽Oxygen, synthetic helium oxygen, globular helium oxygen, hollow helium oxygen, bo Stone, talc, calcined talc, kaolin, strontium ore, aluminum hydroxide, non-alkaline glass, molten glass tantalum carbide, alumina, aluminum nitride, yttrium aluminum oxide, boron nitride, titanium dioxide, mica, synthetic mica, gypsum, Calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, and the like.

The present invention provides a copolymerized oligomer comprising at least an allyl compound monomer of the formula (I), and the monomer copolymerized with the allyl compound monomer may include: a bismaleimide resin, a vinyl group Polyphenylene ether, allyl polyphenylene ether, unsaturated polyester resin, acrylate compound, thermosetting quinone imine resin, allyl compound, propylene compound, vinyl compound, double bond-containing compound, etc., preferably The polymerization temperature is from 50 ° C to 200 ° C, and a polymerization initiator may be added or no polymerization initiator may be added.

The present invention provides a thermosetting resin composition, which can be used as a thermal polymerization initiator: azobisisobutyronitrile, azobis(2-isopropyl)butyronitrile, azobisisoheptanenitrile, peroxide II Benzoyl hydrazine, acetoamidine isobutyl hydrazine, diethyl hydrazine peroxide, peroxidation (2,4-dichlorobenzhydrazide), peroxy (2-dimethylbenzhydrazide), ruthenium peroxide , diisopropyl peroxydicarbonate, bis(3,5,5-trimethylhexanyl peroxide), cyclohexanone peroxide, methyl ethyl ketone peroxide, dicyclohexyl peroxydicarbonate, peroxide Dicyclohexyl carbonate, di(4-tert-butylcyclohexyl)dicarbonate, di(2-ethylhexyl)peroxydicarbonate, bis(2-phenylethoxy)peroxydicarbonate Ester, dihexadecyl peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxybenzoate, peroxyacetic acid, t-butyl peroxypivalate, tert-butyl peroxypivalate , peroxyphenyl neodecanoate, tert-butyl peroxybenzoate, t-butyl hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, cumene Hydrogen peroxide Hydrogen peroxide, di-tert-butyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, peroxide-alkyl metal, oxy-alkyl metal, etc. .

The allyl compound, the composition of the allyl compound, the copolymerized oligomer, and the thermosetting resin composition of the present invention can be modified and toughened with the double-maleimine resin to achieve a low dielectric constant and a low dielectric constant. Loss, high glass transfer temperature, can be applied to a variety of applications such as glass fiber prepreg, printed circuit boards, copper clad laminates, casting resins, insulating materials, structural materials, wear-resistant materials, composite materials, aerospace materials.

Example 1 (allyl compound A-1)

44.5g (0.1mole) of 4,4'-dichloromethylbiphenyl, 26.8g (0.2mole) of 2-allylphenol and 100g of dimethylformamide were added to the four ports equipped with mechanical stirring and condensation tube. In the reaction flask, heat to 40 ° C ~ 50 ° C, stir well, then add 37.8 g (0.21 mole / concentration 30% by weight) of methanolic sodium methoxide solution to the reaction flask in small portions, and maintain the reaction temperature at 50 ° C for 3 hours. Then, the reaction solution was dropped into water to obtain a solid, which was washed three times with distilled water, and once washed with methanol, and dried to obtain an allyl compound A-1, the yield was 95.3%, and the purity was analyzed to be 99.6% (HPLC). The chlorine content is 80 ppm (ion chromatograph).

Example 2 (allyl compound A-2)

35 g (0.2 mole), 3,3'-5,5'-tetramethyl-4,4'-5 biphenyl diphenol (2,0 g (0.1 mole)), 2-allyl phenol 26.8g (0.2mole), 100g of dimethylformamide was added to a four-reaction reaction flask equipped with mechanical stirring and condensation tube, heated to 40 ° C ~ 50 ° C, and stirred, the sodium methoxide methanol solution 75.6g (0.42) A mole/concentration of 30% by weight) was added to the reaction flask in small portions, and the reaction temperature was maintained at 50 ° C for 3 hours. Then, the reaction solution was dropped into water to obtain a solid, which was washed three times with distilled water, and washed with methanol once and dried. The allyl compound A-2 was obtained in a yield of 96.1%, and its purity was analyzed to be 99.2% (HPLC), and the total chlorine content was 95 ppm (ion chromatograph).

Example 3 (allyl compound A-3)

4,4'-dichloromethylbiphenyl 49g (0.2mole), 2,2'-diallyl bisphenol A 30.8g (0.1mole), 2-allyl phenol 26.8g (0.2mole), 100g of dimethylformamide is added to a four-reaction reaction flask equipped with a mechanical stirring and condensing tube, and heated to 40 ° C ~ 50 After stirring at °C, 75.6 g (0.42 mole/concentration: 30% by weight) of sodium methoxide in methanol was added to the reaction flask in small portions, and the reaction temperature was maintained at 50 ° C for 3 hours, after which the reaction solution was dropped into water to obtain a solid. Then, it was washed three times with distilled water, and once washed with methanol, the allyl compound A-3 was obtained in a yield of 96.3%, and its purity was 99.3% (HPLC), and the total chlorine content was 90 ppm (ion chromatograph).

Example 4 (alkenyl compound A-4)

4,4'-dichloromethylphenyl ether 267g (0.4mole), bis(2,6-dimethylphenol)methane 76.8g (0.3mole), 2-allylphenol 26.8g (0.2mole), two 200 g of methylformamide was added to a four-neck reaction flask equipped with a mechanical stirring and a condenser, heated to 40 ° C to 50 ° C, and stirred uniformly, and the methanol solution of sodium methoxide was 113.4 g (0.63 mole / concentration 30% by weight). The amount was added to the reaction flask in portions, and the reaction temperature was maintained at 50 ° C for 3 hours. Then, the reaction solution was dropped into water to obtain a solid, which was washed three times with distilled water, and once washed with methanol, dried to obtain an allyl compound A-4. The yield was 97.1%, and the purity was analyzed to be 99.5% (HPLC), and the total chlorine content was 99 ppm (ion chromatography).

Comparative example 1

50% of diallyl bisphenol A (abbreviation: DABPA) and bis(3-ethyl-5-methyl-4-cis-butenylene phenyl)methane (abbreviation: BMI-5100/Daiwa Chemical) 50g was uniformly mixed, degassed at 150 ° C for 3 hours, then cured at 180 ° C for 3 hours, and finally cured at 210 ° C for 6 hours to obtain a cured product, which was measured for glass transition temperature, dielectric constant, dielectric loss. The data is shown in Table 1.

Example 5

Bis(3-ethyl-5-methyl-4-cis-buteneniminephenyl)methane (abbreviation: 50 g of BMI-5100/Daiwa Chemical Co., Ltd. 50 g of dimethylacetamide was added to a four-neck reaction flask equipped with a mechanical stirring and a condenser, heated to 160 ° C, and the reaction temperature was 4 hours to obtain di(3-ethyl- Oligomer of 5-methyl-4-succinimide phenyl)methane (abbreviation: BO-5100), then added with allyl compound A-1/50g, uniformly mixed, and degassed at 150 ° C After forming for 3 hours, curing at 180 ° C for 3 hours, and finally curing at 210 ° C for 6 hours, a cured product was obtained, and the glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 1.

Example 6

The allyl compound A-2/50g is uniformly mixed with 50g of bis(3-ethyl-5-methyl-4-cis-butenylene phenyl)methane (abbreviation: BMI-5100/Daiwa Chemical). Degassing at 150 ° C for 3 hours, curing at 180 ° C for 3 hours, and finally curing at 210 ° C for 6 hours to obtain a cured product, measuring its glass transition temperature, dielectric constant, dielectric loss, such as data Table 1 shows.

Example 7

50 g of phenylmethane maleimide (abbreviation: BMI-2300 / manufactured by Daiwa Chemical Co., Ltd.) and 50 g of dimethylacetamide were placed in a four-neck reaction flask equipped with a mechanical stirring and a condenser, and heated to 160 ° C. The reaction temperature is four hours to obtain an oligomer of bis(3-ethyl-5-methyl-4-cis-buteneniminephenyl)methane (abbreviation: BO-2300); Compound A-3/50g was uniformly mixed, degassed at 150 ° C for 3 hours, then cured at 180 ° C for 3 hours, and finally cured at 210 ° C for 6 hours to obtain a cured product. The glass transition temperature and dielectric were measured. Constant, dielectric loss, the data is shown in Table 1.

Example 8

The allyl compound A-4/50g was uniformly mixed with 50 g of phenylmethane maleimide (abbreviation: BMI-2300/manufactured by Daiwa Chemical Co., Ltd.), and cast at a temperature of 150 ° C for 3 hours, and then at 180 ° C. After curing for 3 hours, and finally curing at 210 ° C for 6 hours, a cured product was obtained, and the glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 1.

Example 9

33 g of bis(3-ethyl-5-methyl-4-cis-butenenimine phenyl)methane (abbreviation: BMI-5100/manufactured by Daiwa Chemical Co., Ltd.) and 50 g of dimethylacetamide were added to the machine with mechanical stirring. In a four-neck reaction flask of a condenser, the mixture was heated to 160 ° C and the reaction temperature was 4 hours to obtain an oligomer of bis(3-ethyl-5-methyl-4-cis-buteneniminephenyl)methane ( Abbreviation: BO-5100), then the allyl compound A-1/67g is degassed at 150 ° C for 3 hours, then cured at 180 ° C for 3 hours, and finally cured at 210 ° C for 6 hours to obtain curing. The material was measured for its glass transition temperature, dielectric constant, and dielectric loss. The data is shown in Table 1.

Glass transition temperature: determined by DSC manufactured by TA

Dielectric constant: measured at 1 GHz using an LCR Meter manufactured by Agilent

Dielectric loss: measured at 1 GHz using a cavity made by Agilent

Example 10

Allyl compound A-1/50g, vinyl polyphenylene ether (OPE-1000/Mitsubishi Gas) methane 50g, and toluene 50g were added to a four-reaction reaction flask equipped with mechanical stirring and condensation tube, and heated to 180 °C. The reaction temperature was 6 hours to obtain a copolymerized oligomer of allyl compound A-1 and vinyl polyphenylene ether, which was baked at 160 ° C for 1 hour, then cured at 180 ° C for 2 hours, and finally cured at 220 ° C. After hours, a cured product was obtained, and its glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 2.

Example 11

Allyl compound A-2/33g, bis(3-ethyl-5-methyl-4-cis-butenenimine phenyl)methane (abbreviation: BMI-5100/Daiwa Chemical) 67g, dimethyl Ethylamine 50g was added to a four-neck reaction flask equipped with a mechanical stirring and condensing tube, heated to 160 ° C, and the reaction temperature was 6 hours to obtain a copolymerized oligomer of allyl compound A-2 and BMI-5100, which was baked at 160 ° C. After an hour, it was cured at 180 ° C for 2 hours, and finally cured at 220 ° C for 3 hours to obtain a cured product. The glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 2.

Comparative example 2

Add DABPA/33g, BMI-5100/67g, and dimethylacetamide 50g to a four-neck reaction flask equipped with a mechanical stirring and condensation tube, heat to 160 ° C, and react for 6 hours to obtain DABPA and BMI-5100. The copolymerized oligomer was baked at 160 ° C for 1 hour, then cured at 180 ° C for 2 hours, and finally cured at 220 ° C for 3 hours to obtain a cured product, and the glass transition temperature, dielectric constant, dielectric loss thereof were measured. The data is shown in Table 2.

Example 12

A-1/40g, BMI-5100/50g, and 100g of dimethylacetamide were added to a four-neck reaction flask equipped with a mechanical stirring and a condenser, heated to 160 ° C, and the reaction temperature was 6 hours. A copolymerized oligomer of A-1 and BMI-5100 was obtained, 0.01 g of dicumyl peroxide and 0.05 g of zinc octoate were added, and 15 g of polyphenylene ether was dispersed therein to prepare a varnish solution, and 0.1 mm of plain woven E glass was obtained. The fabric was immersed in a varnish solution and dried at 160 ° C for 6 minutes to obtain a B-stage prepreg. Six prepregs were stacked, and 18 μm copper foil was placed on the upper and lower surfaces of the stack, respectively, at a pressure of 200 ° C / 3 MPa. After pressing for 120 minutes, a copper-clad laminate of 0.6 mm was obtained, and the glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 3.

Example 13

A-3/40g, BMI-5100/50g, dimethylacetamide 100g was added to a four-neck reaction flask equipped with a mechanical stirring and a condenser, heated to 160 ° C, and the reaction temperature was 6 hours to obtain A-3 and BMI-5100 copolymer oligomer, 0.01 g of dicumyl peroxide, 0.05 g of zinc octoate, and 15 g of polyetheretherketone were dispersed therein to prepare a varnish solution, and a 0.1 mm plain woven E glass fabric was immersed in the varnish. The solution was dried at 160 ° C for 6 minutes to obtain a B-stage prepreg. Six prepregs were stacked, and 18 μm copper foil was placed on the upper and lower surfaces of the stack, and hot pressed at 200 ° C / 3 MPa for 120 minutes. A copper-clad laminate of 0.6 mm was obtained, and the glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 3.

Example 14

A-4/40g, BMI-5100/50g, and 100g of dimethylacetamide were added to a four-reaction reaction flask equipped with a mechanical stirring and a condenser, heated to 160 ° C, and the reaction temperature was 6 hours to obtain A-4 and BMI-5100 copolymer oligomer, 0.01 g of dicumyl peroxide, 0.05 g of zinc octoate, and 15 g of polytetrafluoroethylene were dispersed therein to prepare a varnish solution. A 0.1 mm plain weave E glass fabric was immersed in a varnish solution and dried at 160 ° C for 6 minutes to obtain a B-stage prepreg. Six prepregs were stacked and placed on the upper and lower surfaces of the stack with 18 μm copper foil. 200 ° C / 3 MPa pressure hot pressing for 120 minutes, a 0.6 mm copper clad laminate was obtained, and its glass transition temperature, dielectric constant, and dielectric loss were measured. The data are shown in Table 3.

Comparative example 3

DABPA/40g, BMI-5100/50g, BPA-CE/10g, 0.01 g of dicumyl peroxide, and 0.05 g of zinc octoate were dissolved in 100 g of dimethylacetamide to prepare a varnish solution, 0.1 mm. The plain weave E glass fabric was immersed in the varnish solution and dried at 160 ° C for 6 minutes to obtain a B-stage prepreg. Six prepregs were stacked, and 18 μm copper foil was placed on the upper and lower surfaces of the stack at 200 ° C. /3MPa pressure hot pressing for 120 minutes, a 0.6 mm copper clad laminate was obtained, and the glass transition temperature, dielectric constant, and dielectric loss were measured. The data are shown in Table 3.

It can be seen from Table 1 that Examples 5-9 and Comparative Example 1 show that allyl compounds A-1, A-2, A-3, and A-4 perform better than DABPA, and have a higher glass transition temperature and lower mediation. Electrical constant and dielectric loss; Table 2 shows that the copolymerized oligomers of Examples 10-11 allyl compounds A-1 and A-2 and the copolymerized oligomer of Comparative Example 2 DABPA exhibited higher glass transfer. Temperature, lower dielectric constant and dielectric loss; Tables 3 to 14 (comonomers of allyl compounds A-1, A-3, A-4 and organic fillers) are relative to Comparative Example 3 (BT resin and DABPA) exhibited a higher glass transition temperature, lower dielectric constant and dielectric loss.

The object of the present invention is to provide an allyl compound and a composition thereof, a copolymerization oligomer, and a thermosetting resin composition, which have low dielectric constant, low dielectric loss, high glass transition temperature after curing, and can be applied to glass fiber. Prepregs, printed circuit boards, copper clad laminates, casting resins, insulating materials, structural materials, wear resistant materials, composite materials, aerospace materials, etc.

The present invention has been described in connection with the foregoing specific embodiments and comparative examples, and those skilled in the art can make various changes based on the above description, and do not limit the scope of the patent application of the present invention.

Claims (4)

An allyl compound having a chemical structure as shown in formula (I): Where Y is: Where X is selected from: One or more of the group consisting of; wherein R1, R2, R3, and R4 are the same or different, and are represented by hydrogen, a hydrocarbon of C1 to C6; and R5 and R6 are the same or different, and are represented by hydrogen, C1~ a hydrocarbon of C6; A is selected from the group consisting of: a covalent bond, a hydrocarbon of C1 to C20; and n is an integer selected from 0 to 50. A composition of an allyl compound, the composition comprising at least: (a) an allyl compound as claimed in claim 1; (b) a marlinimine resin comprising: bismaleimide One of a group consisting of a compound, a bismaleimine oligomer, a compound containing one to five marlinimine functional groups, and an oligomer containing one to five marlinimine functional groups or A variety. A copolymerized oligomer comprising at least an allyl compound monomer as in claim 1 of the patent application. A thermosetting resin composition comprising: (a) a copolymer oligomer according to item 3 of the patent application; (b) an organic filler comprising: polyphenylene ether, polytetrafluoroethylene, polyether One or more of the groups consisting of ether ketones.