Complex, preparation method and use thereof, composition, prepreg and laminated board

Abstract

To provide a complex that can improve the flame retardant property of a polyphenylene ether polymer, and has small impact on the dielectric property thereof, and a preparation method of the complex, and also to provide a polyphenylene ether composition using the complex, a prepreg resulting from thermally curing the composition, and a laminated board resulting from curing the prepreg, which has high flame retardant property as well as low dielectric constant and dielectric loss.SOLUTION: The invention discloses a complex, represented by [Ln2(DPPA)3], where Ln is a rare earth ion, and DPPA is a phenylphosphinic acid having a structure represented by formula (I).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a complex, a method for preparing the same, and use thereof, and further relates to a polyphenylene ether composition, a prepreg, and a laminate.

Background Art

[0002] With the rapid development of electronic technology, there is a demand for higher frequencies and faster digitalization of information processing in electronic products in fields such as mobile communication and autonomous driving. Currently, the main development direction of high-frequency high-speed substrates is the development of low-dielectric resin materials. Commonly used low-dielectric resin materials include polytetrafluoroethylene, modified epoxy, polyphenylene ether-based resins, hydrocarbon resins, and the like. Polytetrafluoroethylene resin is too costly, modified epoxy resin has a high dielectric constant, and hydrocarbon resin has poor flame retardancy performance. Polyphenylene ether-based resins have good mechanical properties, low dielectric constant and dielectric loss, and have certain flame retardancy performance by themselves, so they are gradually becoming preferred high-frequency low-dielectric printed wiring board materials.

[0003] Polyphenylene ether-based materials still cannot meet the needs of the printed wiring board industry in terms of flame retardancy performance, and it is necessary to add a flame retardant to the polyphenylene ether-based materials when in use. For example, CN116003987A discloses a resin composition containing a modified polyphenylene ether resin, a bismaleimide resin, a flame retardant, a crosslinking agent, a toughening agent, an initiator, a filler, and a solvent. The flame retardant contains a cyclic phosphazene compound containing a biphenyl structure. CN115991931A discloses a low dielectric flame retardant performance polyphenylene ether composition composed of a polyphenylene ether resin, a chlorinated polyethylene resin, antimony trioxide, a polyphosphate ester-based flame retardant, modified hollow glass beads, polyphenylene ether graft maleic anhydride, a hindered amine light stabilizer, and a benzotriazole-based ultraviolet absorber. The polyphosphate ester-based flame retardant has a phosphaphenanthrene ring and a biphenyl ring structure in its molecular structure. These flame retardants reduce the heat resistance and dielectric properties of polyphenylene ether-based materials.

Summary of the Invention

[0004] In view of this, one object of the present invention is to provide a complex that can improve the flame retardant performance of polyphenylene ether-based polymers and has a small impact on their dielectric properties. Furthermore, the complex can endow the polyphenylene ether-based polymer with good heat resistance. Another object of the present invention is to provide a method for preparing the complex. Another object of the present invention is to provide the use of the complex. Another object of the present invention is to provide a polyphenylene ether composition. Another object of the present invention is to provide a prepreg. Another object of the present invention is to provide a laminate having high flame retardant performance and low dielectric constant and dielectric loss.

[0005] The above object is achieved by the following configuration.

[0006] In one aspect, the present invention is [Ln2(DPPA)3], wherein Ln is a rare earth ion, DPPA provides a complex having the structure shown in formula (I). TIFF2025113957000002.tif47170(In formula (I), R1 to R8 are each independently selected from H and C1-C6 alkyl groups.)

[0007] According to the complex of the present invention, preferably, Ln is one or more selected from lanthanum ions, cerium ions, and samarium ions.

[0008] The structure of the DPPA is as follows. TIFF2025113957000003.tif26170In another aspect, the present invention provides a method for preparing the complex, which includes reacting a water-soluble rare earth inorganic salt with a compound represented by formula (A) to obtain a complex.

[0009] TIFF2025113957000004.tif48170(In formula (A), R1 to R8 are each independently selected from H and C1-C6 alkyl groups.) According to the preparation method of the present invention, preferably, the molar ratio of the rare earth element contained in the water-soluble rare earth inorganic salt to the compound represented by formula (A) is (2-2.5):3.

[0010] According to the preparation method of the present invention, preferably, the water-soluble rare earth inorganic salt and the compound represented by formula (A) are subjected to a hydrothermal reaction at 150-220°C to obtain a complex.

[0011] According to the preparation method of the present invention, preferably, the water-soluble rare earth inorganic salt and the compound represented by formula (A) are reacted under the condition of pH 5-6 to obtain a complex.

[0012] In another aspect, the present invention provides the use of the complex in improving the flame retardancy performance and / or heat resistance of polyphenylene ether-based polymers.

[0013] In another aspect, the present invention provides a polyphenylene ether composition containing a polyphenylene ether-based polymer and the complex.

[0014] In another aspect, the present invention provides a prepreg comprising a glass cloth and a semi-cured product supported on the glass cloth, wherein the semi-cured product is obtained by heat-curing the polyphenylene ether composition.

[0015] In another aspect, the present invention provides a laminate comprising two layers of metal foil and a cured resin sandwiched between the two layers of metal foil, wherein the cured resin is obtained by curing the prepreg.

[0016] The complex according to the present invention can improve the flame retardancy performance of the polyphenylene ether-based polymer and has little influence on its dielectric properties. Furthermore, the complex can endow the polyphenylene ether-based polymer with good heat resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0017]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

[0018] Hereinafter, the present invention will be further described with reference to specific embodiments, but the protection scope of the present invention is not limited thereto.

[0019] <Complex> The complex according to the present invention is [Ln2(DPPA)3].

[0020] Ln is a rare earth ion. Ln is one or more selected from lanthanum ion, cerium ion, praseodymium ion, neodymium ion, promethionium ion, samarium ion, europium ion, gadolinium ion, terbium ion, dysprosium ion, holmium ion, erbium ion, thulium ion, ytterbium ion, lutetium ion, scandium ion, yttrium ion. In some embodiments, Ln is one or more selected from lanthanum ion, cerium ion, samarium ion. According to one embodiment of the present invention, Ln is a lanthanum ion. According to another embodiment of the present invention, Ln is a cerium ion.

[0021] DPPA has a structure represented by formula (I).

[0022] TIFF2025113957000005.tif47170The substitution positions of R1, R2 and R3 may each independently be selected from the ortho, para or meta positions of the benzene ring. In some embodiments, in R1, R2 and R3, one substituent is located at the para position of the benzene ring, and the other two substituents are located at the ortho positions of the benzene ring. In some embodiments, in R1, R2 and R3, one substituent is located at the para position of the benzene ring, and the other two substituents are located at the meta positions of the benzene ring. In some embodiments, R1, R2, R3 are located at the ortho, para, meta positions of the benzene ring respectively.

[0023] The substitution positions of R4, R5, and R6 may each independently be selected from the ortho, para, or meta positions of the benzene ring. In some embodiments, for R4, R5, and R6, one substituent is located at the para position of the benzene ring, and the other two substituents are located at the ortho positions of the benzene ring. In some embodiments, for R4, R5, and R6, one substituent is located at the para position of the benzene ring, and the other two substituents are located at the meta positions of the benzene ring. In some embodiments, R4, R5, and R6 are located at the ortho, para, and meta positions of the benzene ring, respectively.

[0024] R1 to R8 are each independently selected from H and C1-C6 alkyl groups. Preferably, R1 to R8 are each independently selected from H and C1-C3 alkyl groups. More preferably, all of R1 to R8 are H.

[0025] Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, propyl group, isopropyl group, butyl group, methylpropyl group, pentyl group, methylbutyl group, dimethylpropyl group, ethylpropyl group, hexyl group, methylpentyl group, dimethylbutyl group, ethylbutyl group, cyclopropyl group, cyclopentyl group.

[0026] According to an embodiment of the present invention, the structure of DPPA is as follows.

[0027] TIFF2025113957000006.tif26170

[0028] <Method for preparing complex> The method for preparing the complex according to the present invention includes a step of reacting a water-soluble rare earth inorganic salt with a compound represented by formula (A) to obtain a complex.

[0029] TIFF2025113957000007.tif48170 (In formula (A), R1 to R8 are each independently selected from H and C1-C6 alkyl groups. R1 to R8 are as described above and are not repeated here.) According to one embodiment of the present invention, the compound of formula (A) is as follows.

[0030] TIFF2025113957000008.tif19170 The water-soluble rare earth inorganic salt may be one or more selected from rare earth chlorides, rare earth nitrates, and rare earth acetates. The water-soluble rare earth inorganic salt may be used in a form having water of crystallization.

[0031] The molar ratio of the rare earth element contained in the water-soluble rare earth inorganic salt to the compound represented by formula (A) is (2 to 2.5):3, preferably (2 to 2.3):3, and more preferably (2 to 2.1):3.

[0032] In some embodiments, the water-soluble rare earth inorganic salt and the compound represented by formula (A) are subjected to a hydrothermal reaction to obtain a complex. The hydrothermal reaction may be carried out in a hydrothermal reaction kettle. Specifically, there is a tetrafluoroethylene tank in the hydrothermal reaction kettle.

[0033] The hydrothermal reaction temperature may be 150°C to 220°C, preferably 170°C to 200°C, and more preferably 180°C to 190°C.

[0034] The hydrothermal reaction time may be 2 to 13 h (hours), preferably 4 to 10 h, and more preferably 5 to 8 h.

[0035] Specifically, a mixture containing the water-soluble rare earth inorganic salt and water is added to a dispersion containing the compound represented by formula (A) and water, and then stirred to form a reactant. The reactant is subjected to a hydrothermal reaction. The stirring time may be 1 to 10 h, preferably 3 to 5 h.

[0036] In the dispersion, the mass ratio of the compound represented by formula (A) to water may be 11.6:(500 to 900), preferably 11.6:(600 to 800), and more preferably 11.6:(700 to 750).

[0037] In the mixture, the mass ratio of the water-soluble rare earth inorganic salt to water is (7 - 9):(30 - 200). In some embodiments, the mass ratio of the water-soluble rare earth inorganic salt to water is (7 - 9):(50 - 150).

[0038] In some embodiments, the water-soluble rare earth inorganic salt and the compound represented by formula (A) are reacted under the conditions of pH 5 - 6 to obtain a complex.

[0039] The reaction temperature may be 40°C - 80°C, preferably 45°C - 60°C.

[0040] The reaction time may be 1 - 10 h, preferably 2 - 8 h, more preferably 3 - 5 h.

[0041] Specifically, a mixed solution is formed from the compound represented by formula (A) and a basic aqueous solution. The pH of the mixed solution is adjusted to 5 - 6 with a pH adjuster, and then it is mixed with a mixture containing the water-soluble rare earth inorganic salt and water to form a reaction product.

[0042] The basic aqueous solution may be ammonia water. The concentration of ammonia water may be 5 - 10 wt%, preferably 5 - 8 wt%.

[0043] The mass-to-volume ratio of the compound represented by formula (A) to the basic aqueous solution may be 11.6:(70 - 200) g / mL, preferably 11.6:(80 - 150) g / mL.

[0044] The pH adjuster may be hydrochloric acid. The concentration of hydrochloric acid may be 0.5 - 5 wt%, preferably 1 - 3 wt%.

[0045] In the mixture, the mass ratio of the water-soluble rare earth inorganic salt to water is (7 - 9):(30 - 200). In some embodiments, the mass ratio of the water-soluble rare earth inorganic salt to water is (7 - 9):(50 - 150).

[0046] In some embodiments, the method further includes filtering the reaction product obtained by the reaction and optionally washing it to obtain a solid product. The solid product is dried to obtain the complex. The drying temperature may be 70 to 150 °C, preferably 80 to 120 °C.

[0047] <Use of the complex> The complex according to the present invention can effectively improve the flame retardancy and heat resistance of the polyphenylene ether-based polymer, and has little influence on its electrical properties. Therefore, the present invention provides the use of the complex in improving the flame retardancy and / or heat resistance of the polyphenylene ether-based polymer.

[0048] <Polyphenylene ether composition> The polyphenylene ether composition according to the present invention is prepared from raw materials including a polyphenylene ether-based polymer and a complex. In some embodiments, the polyphenylene ether composition further contains one or more of an organic phosphorus flame retardant, an inorganic filler, an initiator, a crosslinking agent, a polyolefin-based substance, and a solvent.

[0049] The polyphenylene ether-based polymer may be a polyphenylene ether-based polymer containing an unsaturated double bond. The polyphenylene ether-based polymer is one or more selected from allylated polyphenylene ether and vinylated polyphenylene ether. Examples of the polyphenylene ether-based polymer include, but are not limited to, methacrylate polyphenylene ether and vinylbenzyl polyphenylene ether.

[0050] The amount of the polyphenylene ether-based polymer used may be 50 to 100 parts by weight, preferably 60 to 90 parts by weight, more preferably 70 to 80 parts by weight.

[0051] Details of the complex are as described above and will not be repeated here. The amount of the complex used may be 40 to 90 parts by weight, preferably 50 to 80 parts by weight, more preferably 60 to 70 parts by weight.

[0052] The organic phosphorus flame retardant may be any one or a mixture of at least two selected from 2-(diphenylphosphono)-1,4-benzenediol, tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, a phosphate ester, a polyphosphate ester, a polyphosphonic acid ester, or a phosphonate ester-carbonate ester copolymer.

[0053] The amount of the organic phosphorus flame retardant used may be 15 to 50 parts by weight, preferably 20 to 40 parts by weight, and more preferably 30 to 35 parts by weight.

[0054] The crosslinking agent may be any one or a plurality of selected from trialkenyl isocyanurate compounds, polyfunctional acrylate compounds, polyfunctional methacrylate compounds, polyfunctional vinyl compounds, and divinylbenzene compounds. Preferably, the crosslinking agent is one or more selected from 1,2,4-trivinylcyclohexane, divinylbenzene, triallyl isocyanurate, divinylphenyl ether isocyanate, polyphenylene ether resin, maleimide, polyamide, polyimide, styrene maleic anhydride copolymer, styrene-butadiene copolymer, styrene-butadiene-divinylbenzene terpolymer, polyester, olefin polymer, anhydride curing agent, tricyclodecane dimethanol diacrylate, polybutadiene, and triethylene cyclohexane. In some embodiments, the crosslinking agent is a composition of 1,2,4-trivinylcyclohexane and tricyclodecane dimethanol diacrylate. The mass ratio of 1,2,4-trivinylcyclohexane to tricyclodecane dimethanol diacrylate may be 1:(0.5 to 3), preferably 1:(0.8 to 2).

[0055] The usage amount of the crosslinking agent may be 3 to 45 parts by weight, preferably 10 to 30 parts by weight, and more preferably 15 to 25 parts by weight.

[0056] The polyolefin-based substance contains at least one unsaturated bond. The polyolefin-based substance may be one selected from polybutadiene, polypentadiene, and polyhexadiene.

[0057] The usage amount of the polyolefin-based substance may be 3 to 30 parts by weight, preferably 5 to 20 parts by weight, and more preferably 10 to 15 parts by weight.

[0058] The initiator may be one or more selected from dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumyl hydroperoxide, and azobisisobutyronitrile. Preferably, the initiator is 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne.

[0059] The usage amount of the initiator may be 0.3 to 3 parts by weight, preferably 0.5 to 2 parts by weight, and more preferably 1 to 1.5 parts by weight.

[0060] The inorganic filler may be one or more selected from silica, aluminum oxide, titanium oxide, mica, aluminum hydroxide, magnesium hydroxide, talc, aluminum borate, barium sulfate, and calcium carbonate. Preferably, the inorganic filler is spherical silica.

[0061] The usage amount of the inorganic filler may be 50 to 100 parts by weight, preferably 60 to 90 parts by weight, and more preferably 70 to 80 parts by weight.

[0062] The solvent may be one or more selected from toluene, butanone, acetone, dimethylamide, methyl ethyl ketone, and propylene glycol methyl ether. In some embodiments, the solvent is a mixture of toluene and butanone. The mass ratio of toluene to butanone is 100:(10 - 50), preferably 100:(20 - 40).

[0063] The amount of the solvent used may be 70 - 180 parts by weight, preferably 100 - 160 parts by weight, and more preferably 120 - 140 parts by weight.

[0064] <Prepreg> The prepreg according to the present invention includes a glass cloth and a semi-cured product supported on the glass cloth. The semi-cured product is obtained by heat-curing the polyphenylene ether composition. The heat-curing temperature may be 100 - 200°C, preferably 150 - 180°C. The heat-curing time may be 2 - 10 min (minutes), preferably 4 - 7 min.

[0065] <Laminated board> The laminated board according to the present invention includes two layers of metal foil and a cured resin sandwiched between the two layers of metal foil. The cured resin is obtained by curing the prepreg. The metal foil may be a copper foil.

[0066] Specifically, two metal foils are stacked on the upper and lower surfaces of the prepreg respectively, and the metal foil and the prepreg are laminated to obtain a laminated board. As specific lamination conditions, the lamination is carried out under vacuum (pressure less than 10 -2 Pa), with a heating rate of 1.1 - 2.5°C / min. When the prepreg temperature reaches 90 - 120°C, a maximum pressure of 350 - 450 psi is applied to the metal foil and the prepreg. During curing, the prepreg temperature is controlled at 195 - 210°C and kept warm for 90 - 140 min.

[0067] Hereinafter, the raw materials will be introduced.

[0068] The chemical structural formula of (1,4-phenylenedimethylene) bis(phenylphosphonic acid) is as follows.

[0069] TIFF2025113957000009.tif19170(1,4-phenylenedimethylene) bis(phenylphosphonic acid) is prepared by the following method.

[0070] 2.2 g of p-dibenzyl chloride was charged into a three-necked flask equipped with a thermometer, a condenser tube, and a flap rubber plug, replaced with N2, 10 g of chlorobenzene was injected with a syringe, magnetically stirred, heated to 80 °C in an oil bath to dissolve p-dibenzyl chloride, then 5 g of diethyl phenyl phosphate was injected with a syringe, the temperature was continuously raised to 132 °C, slightly boiled, and reacted while refluxing for 5 hours. After cooling to about 90 °C, distillation under reduced pressure was carried out to distill off chlorobenzene to obtain 5.85 g of intermediate product A.

[0071] As can be seen from Figure 4, the molecular weight of intermediate product A was consistent with the molecular weight of diethyl (1,4-phenylbis(methylene)) bis(phenylphosphonate). As can be seen from Figure 6, the infrared spectrum of intermediate product A had a -CH2 stretching vibration absorption peak at 2890 - 2980 cm -1 and had an absorption peak of P=O and P-O ester bonds at 1217 - 1100 cm -1 and had a benzene ring carbon skeleton C-H out-of-plane bending vibration absorption peak at 900 - 650 cm -1 As can be seen from Figure 8, the results of nuclear magnetic property evaluation were almost consistent with those of diethyl (1,4-phenylbis(methylene)) bis(phenylphosphonate). Thus, it was confirmed that intermediate product A was diethyl (1,4-phenylbis(methylene)) bis(phenylphosphonate).

[0072] Take 2 g of intermediate product A, add 8 mL of methanol, heat and dissolve it at 60 °C, then raise the temperature to 80 °C, add 2 g of a NaOH solution with a concentration of 50 wt%, and after a white, relatively sticky solid floats on the liquid surface, add water to the reaction system. When water drips, a white solid is generated. After stirring, the system becomes clear. As water is dripped, the generation of the white solid ceases. Stop adding water, and the amount of water added is approximately 25 mL. After reacting for 4 hours, cool down to about 70 °C, perform distillation under reduced pressure, distill off the alcohol, then cool down to room temperature, neutralize this system to pH 5 - 6 with dilute hydrochloric acid. During the neutralization process, a white solid gradually forms and finally precipitates in large amounts. Filter it, wash the cake several times with water, and dry the cake at 65 °C to obtain the final product, (1,4-phenylenedimethylene)bis(phenylphosphonic acid).

[0073] As can be seen from Figure 5, the molecular weight of the final product was consistent with the molecular weight of (1,4-phenylenedimethylene)bis(phenylphosphonic acid). As can be seen from Figure 7, the infrared spectrum of the final product had an -OH absorption peak at 3443 cm -1 and had absorption peaks of P=O and P - O ester bonds at 1217 - 1100 cm -1 and had an out - of - plane bending vibration absorption peak of the benzene ring carbon skeleton C - H at 900 - 650 cm -1 As can be seen from Figure 9, the results of the nuclear magnetic property evaluation were almost consistent with those of (1,4-phenylenedimethylene)bis(phenylphosphonic acid). Thus, it was confirmed that the final product was (1,4-phenylenedimethylene)bis(phenylphosphonic acid).

[0074] Vinylbenzyl polyphenylene ether: The product name is OPE - 2St, and it was purchased from Mitsubishi Gas Chemical Company, Inc.

[0075] 2-(Diphenylphosphono)-1,4 - benzenediol was purchased from Qingdao Fusilin Chemical Technology Co., Ltd.

[0076] Tricyclodecane dimethanol diacrylate: The product name is Sartomer SR833s, purchased from Shanghai Kayin Chemical Co., Ltd.

[0077] Polybutadiene: The product name is Ricon142, purchased from Shanghai Kayin Chemical Co., Ltd.

[0078] 1,2,4-Trivinylcyclohexane was purchased from Evonik Industries group.

[0079] 2,5-Di(tert-butylperoxy)-2,5-dimethyl-3-hexyne was purchased from Sigma-Aldrich.

[0080] Spherical silica: The product name is SC-2050, purchased from Admatechs.

[0081] The glass cloth is NAN YA 2116 glass cloth.

[0082] Example 1 (1,4-Phenylenedimethylene)bis(phenylphosphonic acid) 11.6 g and water 704 g were placed in the tetrafluoroethylene tank of the hydrothermal reactor to form a dispersion. A mixture consisting of 7.5 g of cerium chloride heptahydrate and 50 g of water was added to the dispersion, and the mixture was stirred for 3 h to form a reaction product. The reaction product was reacted in the hydrothermal reactor at 180 °C for 8 h to obtain a reaction product. After the reaction product was cooled, it was filtered and washed to obtain a solid product. The solid product was dried at 100 °C to obtain a complex. The yield was 95%.

[0083] Example 2 (1,4-Phenylenedimethylene)bis(phenylphosphinic acid) (11.6 g) and 15 mL of 8 wt% aqueous ammonia were mixed to form a mixture. The mixture was adjusted to pH 5 - 6 with 2 wt% hydrochloric acid, and then a mixture consisting of 7.58 g of cerium(III) chloride heptahydrate and 100 g of water was added. The reaction was carried out at 60 °C for 3 h to obtain a reaction product. The reaction product was filtered to obtain a solid product. The solid product was dried at 100 °C to obtain a complex.

[0084] Example 3 (1,4-Phenylenedimethylene)bis(phenylphosphinic acid) (11.6 g) and 710 g of water were placed in a tetrafluoroethylene tank of a hydrothermal reactor to form a dispersion. A mixture consisting of 8.7 g of cerium(III) nitrate hexahydrate and 50 g of water was added to the dispersion, and the mixture was stirred for 3 h to form a reaction mixture. The reaction mixture was reacted in the hydrothermal reactor at 180 °C for 5 h to obtain a reaction product. After the reaction product was cooled, it was filtered and washed to obtain a solid product. The solid product was dried at 100 °C to obtain a complex. The yield was 97%.

[0085] Example 4 (1,4-Phenylenedimethylene)bis(phenylphosphinic acid) (11.6 g) and 710 g of water were placed in a tetrafluoroethylene tank of a hydrothermal reactor to form a dispersion. A mixture consisting of 8.6 g of lanthanum(III) nitrate hexahydrate and 50 g of water was added to the dispersion, and the mixture was stirred for 3 h to form a reaction mixture. The reaction mixture was reacted in the hydrothermal reactor at 180 °C for 8 h to obtain a reaction product. After the reaction product was cooled, it was filtered and washed to obtain a solid product. The solid product was dried at 100 °C to obtain a complex.

[0086] Example 5 (1,4-Phenylenedimethylene)bis(phenylphosphinic acid) (11.6 g) and 100 mL of 8 wt% aqueous ammonia were mixed to form a mixture. The mixture was adjusted to pH 5 - 6 with 2 wt% hydrochloric acid, and then a mixture consisting of 8.6 g of lanthanum(III) nitrate hexahydrate and 100 g of water was added. The reaction was carried out at 60 °C for 3 h to obtain a reaction product. The reaction product was filtered to obtain a solid product. The solid product was dried at 100 °C to obtain a complex.

[0087] Examples 6 - 10 70 parts by weight of vinylbenzyl polyphenylene ether, 65 parts by weight of complex, 30 parts by weight of 2-(diphenylphosphono)-1,4-benzenediol, 10 parts by weight of tricyclodecane dimethanol diacrylate, 10 parts by weight of polybutadiene, 10 parts by weight of 1,2,4-trivinylcyclohexane, 1 part by weight of 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne, 70 parts by weight of spherical silica, 100 parts by weight of toluene and 30 parts by weight of acetone were stirred to form a polyphenylene ether composition.

[0088] A glass cloth was impregnated with the polyphenylene ether composition and baked at 160 °C for 5 min to obtain a prepreg.

[0089] The specific complex types were shown in Table 1.

[0090] TIFF2025113957000010.tif22170 Comparative Example 1 The polyphenylene ether composition did not contain a complex, and except that the amount of 2-(diphenylphosphono)-1,4-benzenediol used was 95 parts by weight, the others were the same as in Example 6.

[0091] Examples 11 - 15 and Comparative Example 2 Two metal foils were respectively stacked on both the upper and lower surfaces of the prepreg, and the copper foil and the prepreg were laminated to obtain a laminate. As specific lamination conditions, the lamination was carried out under vacuum (pressure less than 10 -2 Pa), the heating rate was 2 °C / min, when the prepreg temperature reached 120 °C, a maximum pressure of 400 psi was applied to the metal foil and the prepreg, when curing, the prepreg temperature was controlled at 200 °C and kept warm for 120 min.

[0092] The specific prepreg types were shown in Table 2.

[0093] TIFF2025113957000011.tif28170 Test Example 1. The infrared spectrum was obtained by the following method, that is, it was tableted using KBr and measured with a Nicolet Nexus 470 Fourier transform infrared spectrometer.

[0094] The XRD spectrum was obtained by the following method, that is, it was measured by the powder tablet method using a PAN X / pert Pro X-ray diffractometer. The scanning range was 3 to 80°.

[0095] Figure 7 is the infrared spectrum of (1,4-phenylenedimethylene)bis(phenylphosphonic acid). Figure 1 is the infrared spectrum of the complex obtained in Example 1. Figure 2 is the infrared spectrum of the complex obtained in Example 2. In Figures 1 to 2 and 7, the main adsorption peaks are the stretching vibration absorption peaks of P=O and C-P in the range of 1300 cm -1 ~900 cm -1 and the absorption peaks of the benzene ring in the range of 860 cm -1 ~680 cm -1 . The complexes of Example 1 and Example 2 have stronger stretching vibration absorption peaks of P=O and C-P in the range of 1300 cm -1 ~900 cm -1 .

[0096] Figure 3 is the XRD diagram of (1,4-phenylenedimethylene)bis(phenylphosphonic acid) of the complexes obtained in Example 1 and Example 2. As can be seen from Figure 3, since the diffraction peaks of the complex obtained in Example 1 are sharper than those in Example 2, it is indicated that the complex obtained in Example 1 has higher crystallinity and a higher content of the crystalline phase than the complex of Example 2. The complexes obtained in Example 1 and Example 2 hardly contain the diffraction peaks of the raw material (1,4-phenylenedimethylene)bis(phenylphosphonic acid), indicating that a new substance was formed by the reaction.

[0097] 2. Laminated board performance measurement: Glass transition temperature: Measure in accordance with the DSC method specified in IPC-TM-650 Test Method 3.4.25.

[0098] Z-axis coefficient of thermal expansion: Measure the coefficient of expansion of the Z-axis (z-CTE) when the temperature is raised from 50°C to 250°C in accordance with the TMA method specified in IPC-TM-650 Test Method 2.4.24.

[0099] Heat resistance: Follow the method specified in IPC-TM-650 Test Method 2.4.24.1. Before measurement, bake the sample at 105 ± 2°C for 2 hours and then cool it to room temperature in a desiccator. Raise the temperature from room temperature to 288°C at a heating rate of 10°C / min, then keep it at a constant temperature and record the time when the sample undergoes delamination.

[0100] Dielectric constant and dielectric loss factor: Use the network analyzer N5247A from Keysight Technology to measure the relative dielectric constant and dielectric tangent in the in-plane direction at a frequency of 10 GHz by the split dielectric resonator method (SPDR method). Calculate the dielectric loss factor from the measured relative dielectric constant and dielectric tangent.

[0101] Flame retardant performance: Conduct a vertical burning method test in accordance with the UL-94 standard.

[0102] The results obtained are shown in Table 3.

[0103] TIFF2025113957000012.tif46170The present invention is not limited to the above embodiments, and all possible deformations, improvements, substitutions, etc. that can be conceived by those skilled in the art within the scope not departing from the spirit of the present invention are included in the scope of the present invention.

Claims

1. [Ln ２ (DPPA) ３ , and Ln is a rare earth ion, DPPA has a structure represented by formula (I), and is a complex. (In formula (I), R １ ~R ８ are each independently selected from H and C1-C6 alkyl groups.)

2. Ln is one or more selected from lanthanum ions, cerium ions and samarium ions, The structure of the DPPA is as follows, and the complex according to claim 1.

3. The method for preparing the complex according to claim 1, characterized by including the step of reacting a water-soluble rare earth inorganic salt with a compound represented by formula (A) to obtain a complex. (In formula (A), R １ ~R ８ are each independently selected from H and C1-C6 alkyl groups.)

4. The preparation method according to claim 3, wherein the molar ratio of the rare earth element contained in the water-soluble rare earth inorganic salt to the compound represented by formula (A) is (2 to 2.5):

3.

5. The preparation method according to claim 3, wherein the water-soluble rare earth inorganic salt and the compound represented by formula (A) are subjected to a hydrothermal reaction at 150 to 220 °C to obtain a complex.

6. The preparation method according to claim 3, wherein the water-soluble rare earth inorganic salt and the compound represented by formula (A) are reacted under the condition of pH 5 to 6 to obtain a complex.

7. Use of the complex according to claim 1 in improving the flame retardancy and / or heat resistance of a polyphenylene ether-based polymer.

8. A polyphenylene ether composition, characterized by including a polyphenylene ether-based polymer and the complex according to claim 1.

9. A prepreg, including a glass cloth and a semi-cured product supported on the glass cloth, wherein the semi-cured product is obtained by heat-curing the polyphenylene ether composition according to claim 8.

10. A laminate, including two layers of metal foil and a cured resin sandwiched between the two layers of metal foil, wherein the cured resin is obtained by curing the prepreg according to claim 9.

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