TWI490251B - Containing unsaturated polyphenylene ether resin and its composition, thermosetting resin composition - Google Patents

Description

Unsaturated polyphenylene ether resin and its composition, thermosetting resin composition

The present invention provides an unsaturated group-containing polyphenylene ether resin and a composition thereof, and a thermosetting resin composition. The unsaturated group-containing polyphenylene ether resin contains one or more allyl functional groups, and may further contain a vinyl functional group. When the number average molecular weight of the unsaturated polyphenylene ether resin is more than 2,500, the solvent solubility is high, the solvent is diversified, and the resin is highly soluble, so that the molecular weight of the polyphenylene ether resin is increased, and the low dielectric constant and low are also achieved. Dielectric loss, high glass transition temperature, easy processing.

The invention provides an unsaturated polyphenylene ether resin and a composition thereof, and a thermosetting resin composition, which can achieve low dielectric constant, low dielectric loss and high glass transition temperature through thermal curing, and can be applied to laminated boards, UV coatings, photoresists, semiconductor packaging materials, coating agents, glass fiber prepregs, printed circuit boards, copper clad laminates, color filters, display seals, etc.

The thermoplastic polyphenylene ether resin has excellent electrical properties and good acid and alkali resistance, but when applied to a printed circuit board substrate, it has high temperature resistance and solvent resistance, low solubility, high crystallinity, and high melt viscosity. The temperature difference between the melting point and the glass transition point is very small, which limits the application of polyphenylene ether resin to electronic materials.

The higher the molecular weight of the traditional polyphenylene ether resin, the better the electrical property, but the worse the solubility, the general toluene is the best solvent, and the common methods for improving the solubility of the polyphenylene ether resin are:

1. Low molecular weight: The number average molecular weight of the polyphenylene ether resin is controlled below 2,500. For example, the Republic of China Patent No. I363770, No. 583221, the low molecular weight polyphenylene ether resin can be completely dissolved in toluene and partially dissolved in methyl ethyl group. ketone.

2. Functionalization: epoxy polyphenylene ether resin, such as the Republic of China patent I227249; acrylate polyphenylene ether resin, such as the Republic of China patent I264440; methylene styrene-based polyphenylene ether resin, such as the Republic of China patent 279418, 250995, 357420, and 342886, although the solubility can be improved, the molecular weight is still limited to the number average molecular weight of 2,500 or less. When the number average molecular weight is above 2,500, the solvent solubility is still not satisfactory, and the industrial demand is not satisfied.

The polyphenylene ether resin of the prior art has a problem in that it cannot meet the requirement of high solubility, diversified solvent selection, and high resin compatibility when the number average molecular weight is more than 2,500, which is still insufficient to meet the actual needs of the industry.

The problem to be solved by the present invention is to provide an unsaturated polyphenylene ether resin containing one or more allyl functional groups, which may further contain a vinyl functional group, and the number average molecular weight of the unsaturated polyphenylene ether-containing resin Above 2500, it has high solvent solubility, diversified solvent selection, high resin compatibility, and when the molecular weight of polyphenylene ether resin increases, it also achieves low dielectric constant, low dielectric loss, high glass transition temperature, and easy Processability

In view of the above problems, the technical means for solving the problem of the present invention provides an unsaturated polyphenylene ether-containing resin having a chemical structure as shown in the formula (I): Wherein R1, R2, R3, and R4 are the same or different and are represented by a hydrocarbon of C1 to C6; and X is selected from the group consisting of: Y is: R5 and R6 are the same or different and are represented by a hydrocarbon of C1 to C4; R7 is a hydrocarbon selected from: C1 to C20, a covalent bond; and A is selected from the group consisting of: m is 2~800 integer; s is 0~30 integer. When n is 0, p is 0, Z is a covalent bond, B is hydrogen; when n is 1~800 integer, p is 0~30 integer, Z For the covalent bond, C1~C20, B is selected from:

The present invention provides an unsaturated polyphenylene ether-containing resin composition comprising at least one unsaturated polyphenylene ether-containing resin; the present invention provides a thermosetting resin composition comprising an unsaturated polyphenylene ether Resin composition and thermal polymerization initiator.

Compared with the efficacy of the prior art, the present invention provides an unsaturated polyphenylene ether resin having a high solvent solubility and a solvent selection diversity when the number average molecular weight is above 2,500. The high resin compatibility property, when the molecular weight of the polyphenylene ether resin is increased, also achieves the purposes of low dielectric constant, low dielectric loss, high glass transition temperature, and easy processability.

The invention provides an unsaturated polyphenylene ether resin and a composition thereof, and a thermosetting resin composition, which can achieve low dielectric constant, low dielectric loss and high glass transition temperature through thermal curing, and can be applied to laminated boards, UV coatings, photoresists, semiconductor packaging materials, coating agents, glass fiber prepregs, printed circuit boards, copper clad laminates, color filters, display seals, etc.

The object of the present invention is to provide an unsaturated polyphenylene ether resin having a chemical structure as shown in the formula (I): Wherein R1, R2, R3, and R4 are the same or different and are represented by a hydrocarbon of C1 to C6; and X is selected from the group consisting of: Y is: R5 and R6 are the same or different and are represented by a hydrocarbon of C1 to C4; R7 is a hydrocarbon selected from: C1 to C20, a covalent bond; and A is selected from the group consisting of: m is 2~800 integer; s is 0~30 integer. When n is 0, p is 0, Z is a covalent bond, B is hydrogen; when n is 1~800 integer, p is 0~30 integer, Z For the covalent bond, C1~C20, B is selected from:

The present invention provides an unsaturated polyphenylene ether resin, wherein the monomer of X can be derived from: dichloromethylbenzene, dichloromethylbiphenyl, dichloromethylphenyl ether, etc.; wherein the monomer of Y is contained Allyl bisphenols can be derived from: diallyl phenol bisphenol A, diallyl phenol bisphenol B, diallyl phenol bisphenol F, diallyl phenol bisphenol M, diallyl Phenol bisphenol Z, methallyl phenol bisphenol A, methallyl phenol bisphenol B, methallyl phenol bisphenol F, methallyl phenol bisphenol M, methallyl Phenol bisphenol Z, butyl allyl phenol bisphenol A, butyl allyl phenol bisphenol B, butyl allyl phenol bisphenol F, butyl allyl phenol bisphenol M, butyl allyl Phenol bisphenol Z, phenyl allyl phenol bisphenol A, phenyl allyl phenol bisphenol B, phenyl allyl phenol bisphenol F, phenyl allyl phenol bisphenol M, phenyl allyl Phenol bisphenol Z or the like; wherein the vinyl monomer in the molecule may be derived from: one or a group of o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene; the invention synthesizes an unsaturated group The allyl monophenols used in the polyphenylene ether resin are o-allyl phenols; Synthesis of an unsaturated group The phenolic polyphenylene ether used in the polyphenylene ether resin preferably has a number average molecular weight of 500 to 7,000, and the number average molecular weight thereof is preferably 2500 to 5000. The present invention synthesizes a phenol group used for an unsaturated polyphenylene ether resin. The polyphenylene ether may be a monophenolic polyphenylene ether or a bisphenol polyphenylene ether; the present invention synthesizes an unsaturated polyphenylene ether resin in a solvent to perform a desalting condensation etherification reaction with a base. The base includes: sodium methoxide, Sodium hydroxide, potassium hydroxide, trimethylamine triethylamine, tributylamine, sodium carbonate, potassium carbonate, sodium ethoxide, etc., preferably having a condensation temperature of 20 ° C to 150 ° C, may be added with a quaternary ammonium salt or a quaternary phosphonium salt The phase transfer agent or the phase transfer agent is not added.

The organic solvent used in the synthesis of an unsaturated polyphenylene ether resin of the present invention comprises at least one selected from the group consisting of: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl- 2 pyrrolidone, dimethyl hydrazine, dimethyl phosphoniumamine, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone, Diisobutyl ketone, tetrahydrofuran, tetramethyl urea, dioxane, γ-butyrolactone, chloroform, dichloromethane, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monopropyl ether, n-butyl acetate, diethylene glycol monobutyl ether acetate, toluene, xylene, and the like.

The present invention provides a thermosetting resin composition comprising an unsaturated polyphenylene ether resin and a thermal polymerization initiator, and the thermal polymerization initiator used therein comprises: azobisisobutyronitrile, azobis ( 2-isopropyl)butyronitrile, azobisisoheptanenitrile, benzammonium peroxide, isobutyl hydrazine peroxide, diethyl hydrazine peroxide, peroxidation (2,4-dichlorobenzidine) , (2-dimethylbenzhydrazide) peroxide, dodecyl peroxide, diisopropyl peroxydicarbonate, bis(3,5,5-trimethylhexyl) peroxide, peroxycyclohexane Ketone, methyl ethyl ketone peroxide, dicyclohexyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tert-butylcyclohexyl peroxydicarbonate), di(2-diethyl peroxydicarbonate) Ethyl) ester, bis(2-phenylethoxy) peroxydicarbonate, dihexadecyl peroxydicarbonate, peroxygen Butyl benzoate, tert-butyl benzoate, peroxyacetic acid, t-butyl peroxypivalate, t-hexyl peroxypivalate, cumene peroxy neodecanoate, benzoyl peroxide Tert-butyl formate, tert-butyl hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, cumene hydroperoxide, para-hydrogen peroxide, peroxide Butyl, dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, peroxide-alkyl metal, oxy-alkyl metal, and the like.

The present invention provides an unsaturated polyphenylene ether-containing resin composition comprising at least one unsaturated polyphenylene ether resin, and further comprising inorganic fiber reinforcing materials including: E glass fiber, NE glass fiber, and 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 a mixture thereof; organic fiber reinforcing material comprises: wholly aromatic polyamide fiber, Polyimide fibers, liquid crystal polyesters, polyester fibers, fluorine-containing fibers, polybenzopyrene fibers, cotton fibers, flax fibers, woven or non-woven fabrics or mixtures thereof.

The present invention provides a composition containing an unsaturated polyphenylene ether resin, which comprises at least one unsaturated polyphenylene ether resin composition, and further comprises an inorganic filler comprising: helium oxygen, fusion helium oxygen, synthetic helium oxygen , globular helium oxygen, hollow helium oxygen, boehmite, hydromagnesite, calcium carbonate, 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.

Example 1 (polyphenylene ether P1)

3,3'5,5'-tetramethyl-4,4'-bisphenol F 12.8 g (0.05 mole), polyphenylene ether 130g (Ssa A made by Asahi) and 300g of toluene were added to a four-reaction reaction flask equipped with mechanical stirring and condensation tube, heated to 80 ° C ~ 90 ° C, 2 g of benzamidine peroxide was added in batches, and washed three times after 24 hours. The toluene and water were removed by pressure distillation to obtain a bifunctional phenolic polyphenylene ether P-1 having a phenolic OH equivalent weight of 1,305 g/mole by FT-IR and a number average molecular weight of 3,735 by GPC.

Example 2 (polyphenylene ether SA120-V)

235.6 g of monofunctional phenolic polyphenylene ether (SA-120/phenolic OH equivalent weight of 2356 g/mole made by GE) and 24.5 g (0.1 mole) of 4,4'-dichloromethylbiphenyl were added to dimethyl group. 300 g of methotrexate was dissolved, and 5.4 g (0.10 mole) of sodium methoxide was added in portions, and the temperature was controlled at 50 ° C to 55 ° C. After 5 hours of reaction, 2,2'-diallyl bisphenol A 30.8 g (0.1) was added. Mole), chloromethylstyrene 15.25g (0.1mole), and then added 11.88g (0.22mole) of sodium methoxide in batches, the temperature is controlled at 45 ° C ~ 50 ° C, after 8 hours of reaction, the reaction solution is dropped into water to obtain a solid Then, it is washed three times with distilled water, and once washed with methanol, the monovinyl polyphenylene ether SA120-V is obtained in a yield of 96%. The average molecular weight measured by GPC is 4217, and the total chlorine content measured by ion chromatography is 70ppm.

Example 3 (polyphenylene ether P1-2V)

Polyphenylene ether P1/261.0g, 4,4'-dichloromethylbiphenyl 24.5g (0.1mole), 2,2'-diallyl bisphenol A 30.8g (0.1mole), added to dimethyl Melamine 350g was dissolved, and then added sodium methoxide 10.8g (0.20mole) in batches, temperature control 50 ° C ~ 55 ° C, after 5 hours of reaction, add chloromethyl styrene 30.5g (0.2mole), and then added in batches Sodium methoxide 11.88g (0.22mole), temperature control 45 ° C ~ 50 ° C, after 8 hours of reaction, the reaction solution was dripped into water to obtain a solid, and then washed three times with distilled water, methanol washed once and dried to obtain a double vinyl Polyphenylene ether PI-2V, yield 95 %, the average molecular weight measured by GPC was 4760, and the total chlorine content by ion chromatography was 80 ppm.

Example 4 (polyphenylene ether P1-VA)

Polyphenylene ether P1/261.0g, 4,4'-dichloromethylbiphenyl 24.5g (0.1mole), 2-allylphenol 13.4g (0.1mole), added to dimethylformamide 350g dissolved Then add 10.8g (0.20mole) of sodium methoxide in batches, control the temperature from 50 °C to 55 °C, and react for 5 hours, add 15.25g (0.1mole) of chloromethylstyrene, and add 5.94g (0.11) of sodium methoxide in batches. Mole), temperature control 45 ° C ~ 50 ° C, after 8 hours of reaction, the reaction solution was dropped into water to obtain a solid, and then washed three times with distilled water, methanol washed once and dried to obtain divinyl polyphenylene ether PI-VA The yield was 96%, the average molecular weight measured by GPC was 4380, and the total chlorine content by ion chromatography was 76 ppm.

Example 5 (polyphenylene ether P1-2A)

Polyphenylene ether P1/261.0g, p-dichloromethylbenzene 35.0g (0.2mole), dissolved in dimethylformamide 450g, and then added sodium methoxide 10.8g (0.20mole) in batches, temperature control 50 ° C After ~5 ° C, 5 hours after the reaction, 2,2'-diallyl bisphenol A 61.6 g (0.2 mole) was added, and then sodium methoxide 10.8 g (0.20 mole) was added in portions, and the temperature was controlled at 50 ° C to 55 ° C. After reacting for 5 hours, 35.0 g (0.2 mole) of p-dichloromethylbenzene was added, and 10.8 g (0.20 mole) of sodium methoxide was added in portions, and the temperature was controlled at 50 ° C to 55 ° C. After reacting for 5 hours, 2-allyl was added. 26.8g (0.2mole) of phenol, adding 15.21g (0.28mole) of sodium methoxide in batches, the temperature is controlled at 45 ° C ~ 50 ° C, after 8 hours of reaction, the reaction solution is dripped into water to obtain a solid, and then washed three times with distilled water. After methanol was washed once and dried, bisallyl polyphenylene ether PI-2A was obtained in a yield of 94%. The average molecular weight measured by GPC was 5590, and the total chlorine content by ion chromatography was 96 ppm.

Example 6~9

Examples 6 to 9 are: 10 g of polyphenylene ether SA120-V, P1-2V, P1-VA, and P1-2A, and 0.01 g of dicumyl peroxide , dissolved in 10 g of toluene at 150 ° C. After baking for 2 hours, the pressure was cast at 150 ° C for 3 hours, and finally cured at 220 ° C for 6 hours to obtain a cured product. The glass transition temperature, dielectric constant and dielectric loss were measured. The data are shown in Table 1. .

Comparative example 1

10 g of commercially available divinyl polyphenylene ether [OPE-St-2200/MGC] was taken, and subjected to degassing molding at 150 ° C for 3 hours, and finally cured at 220 ° C for 6 hours to obtain a cured product, and the glass transition was measured. Temperature, dielectric constant, and dielectric loss are shown in Table 1.

Example 10

10 g of each of polyphenylene ether P1, SA120-V, P1-2V, P1-VA, PI-2A, and OPE-St-2200 were dissolved in 10 g of toluene (TOL) and 10 g of methyl ethyl ketone (MEK). 10 g of propylene glycol methyl ether acetate (PMA) was observed for solubility, and the data are shown in Table 2.

○: a case completely dissolved

△: indicates partial dissolution

×: indicates that it does not dissolve

Example 11~14

Examples 11 to 14 were sequentially obtained: 50 g of polyphenylene ether SA120-V, P1-2V, P1-VA, and P1-2A, and bis(3-ethyl-5-methyl-4-cis-butenylene) Amine phenyl)methane [BMI-5100/Dahe Chemical] 50g , uniformly mixed after grinding, baked at 150 ° C for 2 hours, then degassed at 150 ° C for 3 hours, and finally cured at 220 ° C for 6 hours The cured product was obtained, and its glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 3.

Comparative example 2

100 g of bis(3-ethyl-5-methyl-4-succinimide phenyl)methane [BMI-5100/Dahe Chemical] was uniformly ground and baked at 150 ° C for 2 hours. After degassing at 150 ° C for 3 hours, and finally curing at 220 ° 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 3.

Glass transition temperature (Tg): The dielectric constant (Dk) was measured by DSC manufactured by TA Co., Ltd.: The dielectric loss (Df) was measured at a frequency of 1 GHz using an LCR meter manufactured by Agilent Co., Ltd.: a resonance cavity of Agilent Co., Ltd. was measured at a frequency of 1 GHz.

It can be seen from Table 1 that SA120-V, PI-2V, PI-VA, and PI-2A of Examples 6 to 9 are relatively compared with OPE-St-2200 of Comparative Example 1, and a thermal polymerization initiator is added, which is thermally cured. High glass transition temperature, lower dielectric constant, lower dielectric loss; Table 2 shows that the number average molecular weight of SA120-V, PI-2V, PI-VA, PI-2A is greater than PI, OPE-St- The average molecular weight of 2200, solvent solubility SA120-V, PI-2V, PI-VA, PI-2A is better than PI, OPE-St-2200; It can be seen from Table 3 that the blending of SA120-V, PI-2V, PI-VA, PI-2A and BMI-5100 in Examples 11-14 is relatively solidified with that of Comparative Example 2 alone BMI-5100, showing a lower level. Electrical constant, low dielectric loss characteristics.

The invention provides an unsaturated polyphenylene ether resin and a composition thereof, and a thermosetting resin composition, which can achieve low dielectric constant, low dielectric loss and high glass transition temperature through thermal curing, and can be applied to laminated boards, UV coatings, photoresists, semiconductor packaging materials, coating agents, glass fiber prepregs, printed circuit boards, copper clad laminates, color filters, display seals, 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 (3)

An unsaturated polyphenylene ether resin having a chemical structure as shown in formula (1): Wherein R1, R2, R3, and R4 are the same or different and are represented by a hydrocarbon of C1 to C6; and X is selected from the group consisting of: Y is: R5 and R6 are the same or different and are represented by a hydrocarbon of C1 to C4; R7 is a hydrocarbon selected from: C1 to C20, a covalent bond; and A is selected from the group consisting of: m is 2~800 integer; s is 0~30 integer. When n is 0, p is 0, Z is a covalent bond, B is hydrogen; when n is 1~800 integer, p is 0~30 integer, Z For the covalent bond, C1~C20, B is selected from: An unsaturated polyphenylene ether-containing resin composition comprising at least an unsaturated polyphenylene ether-containing resin as in the first aspect of the patent application. A thermosetting resin composition comprising the unsaturated polyphenylene ether-containing resin composition and the thermal polymerization initiator as claimed in claim 2 of the patent application.