A functional side group-containing polyphenyl ether resin, a preparation method and application thereof

Abstract

The application provides a functional side group-containing polyphenylether resin and a preparation method and application thereof. The polyphenylether side group is modified by using a non-cyclic terpene compound or an olefin with a carbon chain length of 12 carbon atoms or more, so that the melt viscosity is significantly reduced, the processing fluidity and toughness are improved, and the polyphenylether resin is better mixed with a hydrocarbon resin. After crosslinking, a cured product with higher crosslinking degree and more excellent mechanical properties and dimensional stability is obtained. The preparation method of the functional side group-containing polyphenylether polymer is that a halogenated polyphenylether polymer is reacted with alcohol under the action of an activator to realize modification of the functional side chain, so that the use of dangerous reagents is avoided, and the synthesis process is simplified.

Description

Technical Field

[0001] This application belongs to the field of organic polymer compound technology, and particularly relates to a polyphenylene ether resin containing functional side groups, its preparation method and application. Background Technology

[0002] Polyphenylene oxide (PPO) resin is a high-performance thermoplastic engineering plastic with high mechanical strength and heat resistance, good dimensional stability, low moisture absorption, and dielectric constant and dielectric loss that are almost unaffected by temperature, humidity, and frequency. However, thermoplastic PPO has a large molecular weight and high melt viscosity, making it difficult to dissolve in solution processing. To meet the copper clad laminate industry's need for lower molecular weight thermosetting PPO, the molecular weight of PPO can be controlled during polymerization or low molecular weight PPO (LWPPO) can be prepared through a redistribution reaction.

[0003] In existing technologies, the research approach for low molecular weight polyphenylene ethers (PPEs) involves functionalizing the terminal hydroxyl groups to impart new properties, while also increasing their flowability and improving compatibility with other resins; for example, SABIC's SA9000 has methacrylate groups at the molecular chain ends. Chinese patent CN1385454A discloses a method for manufacturing a crosslinkable PPE resin with epoxy groups, which involves redistributing and modifying the PPE resin, followed by functionalization and end-capping with epichlorohydrin. Chinese patent CN102516532A discloses an aminated PPE, which is first copolymerized with two phenols via oxidative coupling to generate a low molecular weight PPE with dihydroxyl groups, and then undergoes nitration and nitro reduction processes to obtain a low molecular weight PPE with diamino groups. Chinese patent CN113248701B discloses a long-chain alkyl PPE with hydroxyl-terminated ends, its preparation method, and its applications, prepared by copolymerizing long-chain alkyldimethylbisphenol and 2,6-dimethylphenol as raw materials. However, since most existing functionalized LWPPOs are dual-ended functional resins with few reactive groups, they cannot form a curing system with high cross-linking density, which greatly affects the mechanical properties, thermal stability, adhesion, and other properties of polyphenylene ether.

[0004] In existing technologies, functional groups are introduced into the side groups of polyphenylene ether molecular chains, such as the allyl polyphenylene ether product from Asahi Kasei Corporation of Japan, which is prepared by reacting polyphenylene ether with n-butyllithium and allyl bromide. Chinese patent CN115160516B discloses a thermosetting polyphenylene ether material containing trifluoromethyl groups, its preparation method, and its application. Trifluoromethyl groups and alkenyl groups containing carbon-carbon double bonds are introduced simultaneously onto the side methyl groups of the polyphenylene ether chain segments. However, the synthesis process of phenolic monomers containing trifluoromethyl groups and alkenyl groups is complex, and there are no commercially available monomers.

[0005] Therefore, existing functionalization of polyphenylene ether molecular chains either involves attaching active groups to both ends of the polyphenylene ether, or the synthetic route is complex, the monomer raw materials are expensive, and the applicability is limited. Summary of the Invention

[0006] This application provides a polyphenylene ether resin containing functional side groups, its preparation method, and its application, to solve the problems existing in related technologies. The technical solution is as follows: In a first aspect, embodiments of this application provide a polyphenylene ether polymer containing functional side groups, having the structure shown in Formula I. ; Wherein, R1 is a noncyclic terpene compound or an olefin with a carbon chain length of 12 or more carbon atoms; n is an integer from 5 to 25.

[0007] In one embodiment, the noncyclic terpene compound is derived from any one of myrcene alcohol, dihydromyrcene alcohol, geraniol, nerol, and citronellol.

[0008] Secondly, embodiments of this application provide a method for preparing a polyphenylene ether polymer containing functional side groups. The halogenated low molecular weight polyphenylene ether with the structure shown in Formula II undergoes a first reaction with a dilute alcohol monomer in a solvent under the action of an activator to obtain the polyphenylene ether polymer containing functional side groups. ; The dilute alcohol monomer is a non-cyclic terpene compound or an enol with a carbon chain length of 12 or more carbon atoms; n is an integer from 5 to 25; In the structure shown in Formula II, X is a halogen atom.

[0009] In one embodiment, the noncyclic terpene compound is any one of myrcene alcohol, dihydromyrcene alcohol, geraniol, nerol, and citronellol; the enol with a carbon chain length of 12 or more carbon atoms is oleyl alcohol.

[0010] In one embodiment, the mixed solvent is a mixture of a first solvent and a co-solvent, wherein the first solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, acetone, or methyl ethyl ketone; and the co-solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, or tert-butanol.

[0011] In one embodiment, the activator is one or a combination of two or more of potassium hydride, sodium hydride, lithium hydride, n-butyllithium, sodium ethoxide, sodium methoxide, or potassium tert-butoxide.

[0012] In one embodiment, the molar ratio of halogen atoms to dilute alcohol monomers in the halogenated low molecular weight polyphenylene ether of Formula II is 1:(0.9-1.2); the mass-volume ratio of the halogenated low molecular weight polyphenylene ether of Formula II to the solvent is 1g:(20-50)mL. The amount of activator added is 20-40% of the mass of the halogenated low molecular weight polyphenylene ether with the structure shown in Formula II; The volume-to-mass ratio of the first solvent to the co-solvent is (50-150) mL: 1 g.

[0013] In one embodiment, the conditions for the first reaction are: reacting at 0-40°C for 0.5-24 hours.

[0014] In one embodiment, a second reaction is carried out in a second solvent with low molecular weight polyphenylene ether, a halogenating agent and an initiator to prepare a halogenated low molecular weight polyphenylene ether with the structure shown in Formula II.

[0015] In one embodiment, the halogenating agent is one or more of N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, dibromodimethylhydantoin, dichlorodimethylhydantoin, trichloroisocyanuric acid, a combination of tetraethylammonium bromide / sodium bromide and an oxidizing agent, benzyltrimethylammonium tribromide, or tetrabutylammonium tribromide.

[0016] In one embodiment, the initiator is one or a combination of two or more of benzoyl peroxide, didecyl peroxide, dioctyl peroxide, dilauryl peroxide, tert-butyl peroxide, cyclohexanone peroxide, or azobisisobutyronitrile.

[0017] In one embodiment, the second solvent is one or more of toluene, xylene, chlorobenzene, ethylbenzene, or trimethylbenzene.

[0018] In one embodiment, the second reaction is carried out at 80-150°C for 0.5-6 hours.

[0019] Thirdly, embodiments of this application provide a cured polyphenylene ether resin containing functional side groups, comprising the following components in parts by weight; The mixture consists of 5-15 parts of a functional side-group polyphenylene ether polymer with the structure shown in Formula I, 50-80 parts of methacrylate-terminated low molecular weight polyphenylene ether, 20-30 parts of a hydrocarbon resin, and 0.3-1 parts of an initiator.

[0020] Fourthly, embodiments of this application provide a method for preparing a cured polyphenylene ether resin containing functional side groups. The functional side-group polyphenylene ether polymer with the structure shown in Formula I, the methacrylate-terminated low molecular weight polyphenylene ether, and the hydrocarbon resin are dissolved in a third solvent, and then an initiator is added to react. After drying and baking, the cured resin is obtained.

[0021] The advantages or beneficial effects of the above technical solutions include at least the following: The functional side-chain polyphenylene ether polymer of this application has reactive groups modified at the side chain positions of low molecular weight polyphenylene ethers—long-chain double-bonded groups. The low polarity and long aliphatic chain structure can not only significantly reduce melt viscosity, improve processing fluidity and toughness, and better mix with hydrocarbon resins, but also obtain cured products with higher cross-linking degree, better mechanical properties and dimensional stability through the reaction of reactive groups.

[0022] The method for preparing polyphenylene ether polymers with functional side groups disclosed in this application involves reacting the halogenated polyphenylene ether polymers with alcohols under the action of an activator to achieve modification of the functional side chains, avoiding the use of hazardous reagents and simplifying the synthesis process.

[0023] The above overview is for illustrative purposes only and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features of this application will become readily apparent from the accompanying drawings and the following detailed description. Attached Figure Description

[0024] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the various drawings denote the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings depict only some embodiments disclosed in this application and should not be construed as limiting the scope of this application.

[0025] Figure 1 These are the 1H NMR spectra of the polyphenylene ether polymers containing functional side groups prepared in the examples and comparative examples; Figure 2 These are the infrared spectra of the polyphenylene ether polymers containing functional side groups prepared in the examples and comparative examples. Detailed Implementation

[0026] In the following description, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments can be modified in various ways without departing from the spirit or scope of this application. Therefore, the drawings and description are considered to be exemplary in nature and not restrictive.

[0027] While polyphenylene ether (PPE) boasts excellent overall performance, its weaknesses include difficult processing and molding, poor solvent resistance, low notched impact strength, and poor weather resistance. Modification of PPE is an effective way to expand its applications. This application provides a PPE resin containing functional side groups, its preparation method, and its applications.

[0028] A polyphenylene ether polymer containing functional side groups has the structure shown in Formula I. ; Wherein, R1 is a noncyclic terpene compound or an olefin with a carbon chain length of 12 or more carbon atoms; n is an integer from 5 to 25.

[0029] This application is based on low molecular weight polyphenylene ether (PPE) with a degree of polymerization of less than 50. As the molecular weight of PPE decreases, its viscosity in the molten state drops sharply, significantly improving its flowability. It also exhibits good solubility in common organic solvents and high compatibility, easily allowing the introduction of active functional groups to upgrade PPE from a physically mixed state to a chemically bonded state, forming homogeneous and stable composite materials with other resins. Therefore, this application introduces an R1 group via an ether bond to the side methyl group of the PPE, introducing a non-cyclic terpene compound or an olefin with a carbon chain length of 12 or more carbon atoms. R1 has a long-chain aliphatic chain and a double bond structure. The long-chain aliphatic chain further modifies the PPE, and the double bonds can polymerize with other resins containing unsaturated bonds to form cross-linked, composite structures. The modified PPE exhibits superior cross-linking degree, mechanical properties, and dimensional stability.

[0030] In one embodiment, the acyclic terpene compound is derived from any one of myrcene alcohol, dihydromyrcene alcohol, geraniol, nerol, and citronellol. Myrcene alcohol, dihydromyrcene alcohol, geraniol, nerol, and citronellol contain terminal hydroxyl groups and double bond structures. The terminal hydroxyl groups can be linked to the methyl groups of low molecular weight polyphenylene ethers, thereby attaching the reactive double bond structure to the polyphenylene ether and modifying the polyphenylene ether.

[0031] This application provides a method for preparing a polyphenylene ether polymer containing functional side groups, wherein a halogenated low molecular weight polyphenylene ether with the structure shown in Formula II undergoes a first reaction with a dilute alcohol monomer in a solvent under the action of an activator to obtain the polyphenylene ether polymer containing functional side groups. ; The dilute alcohol monomer is a non-cyclic terpene compound or an enol with a carbon chain length of 12 or more carbon atoms; n is an integer from 5 to 25; In the structure shown in Formula II, X is a halogen atom; preferably, the halogen is F, Cl or Br.

[0032] This application prepares a polyphenylene ether polymer containing functional side groups. Halogenated low molecular weight polyphenylene ether is used as raw material and reacted with a dilute alcohol monomer containing terminal hydroxyl groups in a first reaction. The first reaction can be carried out in a solvent and in the presence of an activator.

[0033] As one embodiment, the noncyclic terpene compound is any one of myrcene alcohol, dihydromyrcene alcohol, geraniol, nerol, and citronellol; the enol with a carbon chain length of 12 or more carbon atoms is oleyl alcohol.

[0034] In one embodiment, the mixed solvent is a mixture of a first solvent and a co-solvent. The first solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, acetone, or methyl ethyl ketone. The co-solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, or tert-butanol.

[0035] In one embodiment, the activator is one or a combination of two or more of potassium hydride, sodium hydride, lithium hydride, n-butyllithium, sodium ethoxide, sodium methoxide or potassium tert-butoxide.

[0036] In one embodiment, the molar ratio of halogen atoms to dilute alcohol monomers in the halogenated low molecular weight polyphenylene ether of Formula II is 1:(0.9-1.2); the mass-volume ratio of the halogenated low molecular weight polyphenylene ether of Formula II to the solvent is 1g:(20-50)mL. The amount of activator added is 20-40% of the mass of the halogenated low molecular weight polyphenylene ether with the structure shown in Formula II; The volume-to-mass ratio of the first solvent to the co-solvent is (50-150) mL: 1 g.

[0037] As one implementation method, the conditions for the first reaction are: reacting at 0-40°C for 0.5-24 hours.

[0038] As one implementation method, the first reaction end also includes a post-processing step: the product after the first reaction is washed with a fourth solvent, and the solid-liquid separation and drying are performed to obtain the polyphenylene ether polymer containing functional side groups.

[0039] In this embodiment, the fourth solvent is one or a combination of two or more of methanol, ethanol, isopropanol, n-propanol, acetone, butanone, or methyl ethyl ketone. Solid-liquid separation is performed by filtration. The drying conditions are: vacuum drying at 60-85°C for 12-36 hours.

[0040] In one embodiment, a second reaction is carried out in a second solvent with low molecular weight polyphenylene ether, a halogenating agent and an initiator to prepare a halogenated low molecular weight polyphenylene ether with the structure shown in Formula II.

[0041] In one embodiment, the molar ratio of the halogenating agent to the monomer in the low molecular weight polyphenylene ether is (0.8-1):1; the mass-volume ratio of the low molecular weight polyphenylene ether to the second solvent is 1g:(10-30)mL; and the amount of initiator added is 5-10% of the mass of the low molecular weight polyphenylene ether.

[0042] In one embodiment, the halogenating agent is one or more of N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, dibromodimethylhydantoin, dichlorodimethylhydantoin, trichloroisocyanuric acid, a combination of tetraethylammonium bromide / sodium bromide and an oxidizing agent, benzyltrimethylammonium tribromide, or tetrabutylammonium tribromide.

[0043] In one embodiment, the initiator is one or a combination of two or more of benzoyl peroxide, didecyl peroxide, dioctyl peroxide, dilauryl peroxide, tert-butyl peroxide, cyclohexanone peroxide, or azobisisobutyronitrile.

[0044] In one embodiment, the second solvent is one or more of toluene, xylene, chlorobenzene, ethylbenzene, or trimethylbenzene.

[0045] As one implementation method, the conditions for the second reaction are 80-150°C for 0.5-6 hours.

[0046] As one implementation method, the second reaction also includes a post-processing step: the product after the second reaction is washed with a fourth solvent, and the solid-liquid separation and drying are performed to obtain the halogenated low molecular weight polyphenylene ether with the structure shown in Formula II.

[0047] In this embodiment, the fourth solvent is one or a combination of two or more of methanol, ethanol, isopropanol, n-propanol, acetone, butanone, or methyl ethyl ketone. Solid-liquid separation is performed by filtration. The drying conditions are: vacuum drying at 60-85°C for 12-36 hours.

[0048] This application also provides a cured polyphenylene ether resin containing functional side groups, comprising the following components in parts by weight; The mixture consists of 5-15 parts of a functional side-group polyphenylene ether polymer with the structure shown in Formula I, 50-80 parts of methacrylate-terminated low molecular weight polyphenylene ether, 20-30 parts of a hydrocarbon resin, and 0.3-1 parts of an initiator.

[0049] As one embodiment, the methacrylate-terminated low molecular weight polyphenylene ether is preferably NORYL from SABIC. TM SA9000.

[0050] In one embodiment, the olefin-derived structural units of the hydrocarbon resin may be hydrogenated or partially hydrogenated. For dielectric properties, it is preferable that the olefin-derived structural units of the hydrocarbon resin are hydrogenated. The hydrocarbon resin may be a commercially available product, and exemplary examples include, but are not limited to, any one or a combination of at least two of the following: Ricon 153 (butadiene copolymer, Cray Valley), Ricon 100 (butadiene-styrene copolymer, Cray Valley), Ricon 181 (butadiene-styrene copolymer, Cray Valley), Tuftec H1051 (hydrogenated styrene-butadiene copolymer with 42% styrene by mass, Asahi Kasei Chemicals Co., Ltd.), or Tuftec M1913 (hydrogenated styrene-butadiene copolymer with maleic anhydride structural units, with 30% styrene by mass, Asahi Kasei Chemicals Co., Ltd.).

[0051] In one embodiment, the initiator is one or a combination of two or more of the following: benzoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl peroxide, cyclohexanone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyn-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and di-tert-butylperoxyisopropylbenzene.

[0052] This application provides a method for preparing a cured polyphenylene ether resin containing functional side groups. The polyphenylene ether polymer containing functional side groups with the structure shown in Formula I, methacrylate-terminated low molecular weight polyphenylene ether, and hydrocarbon resin are dissolved in a third solvent, and then an initiator is added to react. After drying and baking, the cured resin is obtained.

[0053] In this embodiment, the third solvent is one or a combination of two or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetone, methyl ethyl ketone, toluene, xylene, trimethylbenzene, dimethylformamide, or dimethylacetamide.

[0054] Preferably, after adding the initiator, the mixture is stirred for 0.5-4 hours; then poured into a tray and placed at 20-30°C for 1-24 hours; then vacuum dried in a vacuum oven at 4-100°C for 1-12 hours. The solvent in the resin is removed through the above treatment.

[0055] In this embodiment, baking is carried out in an oven at 60-200°C for 1-15 minutes to obtain a pre-cured resin.

[0056] In this embodiment, the pre-cured resin is pulverized and then the powder is molded by film pressing at 150-240°C for 30-360 minutes to obtain a strip of cured polyphenylene ether resin containing functional side groups.

[0057] The following is a further explanation using specific embodiments.

[0058] Example 1-1 In the reactor, 6.0 g of low molecular weight polyphenylene ether (M... n =1200) was dissolved in 100 mL of chlorobenzene, and 8.9 g of N-bromosuccinimide and 0.5 g of azobisisobutyronitrile were added. The mixture was refluxed at 135 °C for 3 h. Then it was poured into excess ethanol, washed several times, filtered and dried to obtain a powder product, which is the prepared halogenated low molecular weight polyphenylene ether (named BrPPO-5).

[0059] Examples 1-2 In the reactor, 6.0 g of low molecular weight polyphenylene ether (M... n =2300) was dissolved in 100 mL of chlorobenzene, and 11.4 g of dibromodimethylhydantoin and 0.3 g of benzoyl peroxide were added. The mixture was reacted at 150 °C for 0.5 h. Then it was poured into excess methanol, washed several times, filtered and dried to obtain a powder product, which is the prepared brominated low molecular weight polyphenylene ether (named BrPPO-10).

[0060] Examples 1-3 In the reactor, 6.0 g of low molecular weight polyphenylene ether (M... n =6100) was dissolved in 100 mL of xylene, and 3.0 g of N-chlorosuccinimide and 0.6 g of tert-butyl peroxide were added. The mixture was reacted at 80 °C for 6 h. Then it was poured into excess acetone, washed several times, filtered and dried to obtain a powder product, which is the prepared chlorinated low molecular weight polyphenylene ether (named BrPPO-25).

[0061] Example 2-1 In a reactor, 50 mL of anhydrous tetrahydrofuran and 0.46 g of anhydrous ethanol were added, followed by 0.54 g of dihydromyrcenol. The reaction system was cooled to 0°C, and 0.60 g of sodium hydride was added. The reaction system was then heated to 25°C and reacted for 0.5 h. Then, 1.70 g of BrPPO-25 prepared in Example 1 was added, and the reaction was carried out at 25°C for 12 h. After the reaction was completed, the product was washed several times with ethanol and filtered. The filter residue was dried to obtain a powder product, named DIPPO-25.

[0062] Example 2-2 In a reactor, 34 mL of propanol and 0.68 g of anhydrous ethanol were added, followed by 0.93 g of oleyl alcohol. The reaction system was cooled to 0°C, and 0.34 g of sodium ethoxide was added. The reaction system was then heated to 25°C and reacted for 3 h. Then, 1.70 g of BrPPO-25 prepared in Example 1 was added, and the reaction was carried out at 40°C for 0.5 h. After the reaction was completed, the product was washed several times with ethanol and filtered. The filter residue was dried to obtain a powder product, named OAPPO-25.

[0063] Example 2-3 In a reactor, 85 mL of 2-methyltetrahydrofuran and 0.85 g of anhydrous ethanol were added, followed by 0.54 g of citronellol. The reaction system was cooled to 0°C, and 0.68 g of n-butyllithium was added. The reaction system was then heated to 0°C and reacted for 6 h. Then, 1.70 g of ClPPO-25 prepared in Example 1 was added, and the reaction was carried out at 0°C for 24 h. After the reaction was completed, the product was washed several times with ethanol and filtered. The filter residue was dried to obtain a powder product, named CIPPO-25.

[0064] The 1H NMR spectra of DIPPO-25 prepared in Example 2-1, OAPPO-25 prepared in Example 2-2, and CIPPO-25 prepared in Example 2-3 are as follows: Figure 1 As shown, the infrared spectrum is as follows Figure 2 As shown.

[0065] from Figure 2 The infrared spectrum shows that 1105 cm⁻¹ -1 -1106cm -1 The enhanced absorption peak of the ether bond and the chemical shift peak of the hydrogen atom on the carbon-carbon double bond at 5.5 ppm in the 1H NMR spectrum indicate that the alkenyl monomer was successfully bonded to the side group of the polyphenylene ether backbone.

[0066] Example 3-1 In a reactor, 10.0 g of DIPPO-25 prepared in Example 2-1, 65.0 g of methacrylate-terminated low molecular weight polyphenylene ether SA9000, and 25.0 g of hydrocarbon resin Ricon 100 were added to sufficient methyl ethyl ketone and stirred for 2 h. After the resin dissolved, 0.5 g of initiator di-tert-butyl peroxide is added and stirred for another 1 h. The solution was poured into a tray and left at room temperature for 12 h. Then, it was vacuum dried at 60 °C for 6 h in a vacuum oven to remove the solvent methyl ethyl ketone. Finally, it was baked in an oven at 150 °C for 6 min to obtain a pre-cured resin. The pre-cured resin was then pulverized using a high-speed pulverizer. The resulting powder was placed between a steel plate and a release film and molded at 210 °C for 90 min to obtain a strip-shaped cured polyphenylene ether resin containing functional side groups.

[0067] Example 3-2 In a reactor, 10.0 g of OAPPO-25 prepared in Example 2-2, 65.0 g of methacrylate-terminated low molecular weight polyphenylene ether SA9000, and 25.0 g of hydrocarbon resin Ricon 100 were added to sufficient methyl ethyl ketone and stirred for 2 h. After the resin dissolved, 0.5 g of initiator di-tert-butyl peroxide is added and stirred for another 1 h. The solution was poured into a tray and left at room temperature for 12 h. Then, it was vacuum dried at 60 °C for 6 h in a vacuum oven to remove the solvent methyl ethyl ketone. Finally, it was baked in an oven at 150 °C for 6 min to obtain a pre-cured resin. The pre-cured resin was then pulverized using a high-speed pulverizer. The resulting powder was placed between a steel plate and a release film and molded at 210 °C for 90 min to obtain a strip-shaped cured polyphenylene ether resin containing functional side groups.

[0068] Example 3-3 In a reactor, 10.0 g of CIPPO-25 prepared in Examples 2-3, 65.0 g of methacrylate-terminated low molecular weight polyphenylene ether SA9000, and 25.0 g of hydrocarbon resin Ricon 100 were added to sufficient methyl ethyl ketone and stirred for 2 h. After the resin dissolved, 0.5 g of initiator di-tert-butyl peroxide is added and stirred for another 1 h. The solution was poured into a tray and left at room temperature for 12 h. Then, it was vacuum dried at 60 °C for 6 h in a vacuum oven to remove the solvent methyl ethyl ketone. Finally, it was baked in an oven at 150 °C for 6 min to obtain a pre-cured resin. The pre-cured resin was then pulverized using a high-speed pulverizer. The resulting powder was placed between a steel plate and a release film and molded at 210 °C for 90 min to obtain a strip-shaped cured polyphenylene ether resin containing functional side groups.

[0069] Examples 3-4 In a reactor, 5.0 g of DIPPO-25 prepared in Example 2-1, 80.0 g of methacrylate-terminated low molecular weight polyphenylene ether SA9000, and 20.0 g of hydrocarbon resin Ricon 100 were added to a sufficient amount of tetrahydrofuran and stirred for 2 h. After the resin dissolved, 1.0 g of initiator benzoyl peroxide was added and stirred for another 1 h. The solution was poured into a tray and left at room temperature for 12 h. Then, it was vacuum dried at 60 °C for 6 h in a vacuum oven to remove the solvent tetrahydrofuran. Finally, it was baked in an oven at 150 °C for 6 min to obtain a pre-cured resin. The pre-cured resin was then pulverized using a high-speed pulverizer. The resulting powder was placed between a steel plate and a release film and molded at 210 °C for 90 min to obtain a strip-shaped cured polyphenylene ether resin containing functional side groups.

[0070] Examples 3-5 In a reactor, 15.0 g of DIPPO-25 prepared in Example 2-1, 50.0 g of methacrylate-terminated low molecular weight polyphenylene ether SA9000, and 30.0 g of hydrocarbon resin Ricon 100 were added to sufficient acetone and stirred for 2 h. After the resin dissolved, 0.3 g of initiator 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane was added and stirred for another 1 h. The solution was poured into a tray and left at room temperature for 12 h. Then, it was vacuum dried at 60 °C for 6 h in a vacuum oven to remove the solvent acetone. Finally, it was baked in an oven at 150 °C for 6 min to obtain a pre-cured resin. The pre-cured resin was then pulverized using a high-speed pulverizer. The resulting powder was placed between a steel plate and a release film and molded at 210 °C for 90 min to obtain a strip-shaped cured polyphenylene ether resin with functional side groups.

[0071] Comparative Example 1 In a reactor, 75.0 g of methacrylate-terminated low molecular weight polyphenylene ether SA9000 and 25.0 g of hydrocarbon resin Ricon 100 were added to sufficient methyl ethyl ketone and stirred for 2 h. After the resin dissolved, 0.5 g of initiator di-tert-butyl peroxide isopropylbenzene (BIBP) was added and stirred for another 1 h. The solution was poured into a tray and left at room temperature for 12 h. Then, it was vacuum dried at 60 °C for 6 h in a vacuum oven to remove the solvent methyl ethyl ketone. Finally, it was baked in an oven at 150 °C for 6 min to obtain a pre-cured resin. The pre-cured resin was then pulverized using a high-speed pulverizer. The resulting powder was placed between a steel plate and a release film and molded at 210 °C for 90 min to obtain a cured sample.

[0072] Comparative Example 2 In the reactor, 10.0 g of low molecular weight polyphenylene ether (M... n =2300), 65.0g of methacrylate-terminated low molecular weight polyphenylene ether SA9000 and 25.0g of hydrocarbon resin Ricon 100 were added to sufficient methyl ethyl ketone and stirred for 2 hours; after the resin dissolved, 0.5g of initiator di-tert-butyl peroxide isopropylbenzene (BIBP) was added and stirred for another 1 hour; the solution was poured into a tray and left at room temperature for 12 hours, then vacuum dried at 60℃ for 6 hours in a vacuum oven to remove the solvent methyl ethyl ketone; finally, it was baked in an oven at 150℃ for 6 minutes to obtain pre-cured resin, which was then pulverized using a high-speed pulverizer; the resulting powder was placed between a steel plate and a release film and molded at 210℃ for 90 minutes to obtain a cured sample.

[0073] Comparative Example 3 In a reactor, 50 mL of anhydrous tetrahydrofuran and 0.46 g of anhydrous ethanol were added, followed by 0.25 g of crotonol. The reaction system was cooled to 0°C, and 0.60 g of sodium hydride was added. The reaction system was then heated to 25°C and reacted for 0.5 h. 1.70 g of BrPPO-25 prepared in Example 1 was then added, and the reaction was carried out at 25°C for 12 h. After the reaction was complete, the product was washed several times with ethanol and filtered. The filter residue was dried to obtain the product, which was named CAPPO-25. In a reactor, 10.0 g of CAPPO-25, 65.0 g of methacrylate-terminated low molecular weight polyphenylene ether SA9000, and 25.0 g of hydrocarbon resin Ricon 100 were added to sufficient methyl ethyl ketone and stirred for 2 hours. After the resin dissolved, 0.5 g of initiator di-tert-butyl peroxide is added and stirred for another 1 hour. The solution was poured into a tray and left at room temperature for 12 hours. Then, it was vacuum dried at 60°C for 6 hours in a vacuum oven to remove the solvent methyl ethyl ketone. Finally, it was baked in an oven at 150°C for 6 minutes to obtain a pre-cured resin. The pre-cured resin was then pulverized using a high-speed pulverizer. The resulting powder was placed between a steel plate and a release film and molded at 210°C for 90 minutes to obtain a cured sample.

[0074] Performance testing The cured specimens obtained from the above embodiments and comparative examples were subjected to performance tests. Specific test items, methods, and results are as follows: (1) Gel content (GC) was determined by extraction; 2-butanone was used as the extractant, the sample was dried first, and its initial mass was recorded. W a The sample was then placed in the extraction apparatus and extracted for 48 hours. After that, the surface was wiped dry and the sample was dried. The mass at this point was measured. W b The formula for gel content is as follows: .

[0075] (2) Crosslinking density (ν) e The calculation formula for ) is as follows: ; Seeking the middle E r and T These are the rubber plateau areas in the DMA test results ( T g Storage modulus (MPa) and temperature (K) at +30 °C.

[0076] (3) Coefficient of thermal expansion (CTE): The TMA-402F3 thermodynamic analyzer of Netzsch, Germany was used. In compression mode, the sample size was 5mm×5mm×4mm, the compression load was 0.02N, the test temperature range was 30-150℃, and the heating rate was 5℃ / min.

[0077] (4) Tensile properties were tested using the AGX electronic universal testing machine of Shimadzu Corporation of Japan. The test standard was ASTM D63, the sample size was 75mm×5mm×2mm, and the tensile rate was 5mm / min.

[0078] (5) Impact performance test: The Zwick 5113 digital pendulum impact tester was used. The test standard was ASTM D256, the load was 2.75J, the sample size was 80mm×10mm×4mm, and the sample had a V-shaped notch in the middle. The results are shown in Table 1.

[0079] Table 1

[0080] As can be seen from the results in Table 1, Comparative Example 1, which only uses end-modified polyphenylene ether SA9000, showed a significant decrease in all properties compared to Example 3-1. This is because the end-modified polyphenylene ether only crosslinks with the hydrocarbon resin at the end of the polyphenylene ether. In contrast, the double bonds present in the side groups of DIPPO-25 in Example 3-1 can crosslink with SA9000 and hydrocarbon resin. The numerous crosslinking sites in DIPPO-25 crosslink with hydrocarbon resin, SA9000, and between hydrocarbon resin and SA9000, forming a polymer with a higher degree of crosslinking. As a result, the polymer has superior mechanical properties and dimensional stability.

[0081] In Comparative Example 2, low molecular weight polyphenylene ether (M n =2300), mixed with SA9000 and hydrocarbon resin, because low molecular weight polyphenylene ether (M n =2300) does not contain crosslinking sites, so it is merely a physical mixture in the polymer formed by SA9000 and hydrocarbon resin, and the overall performance of the mixture is worse than that of Comparative Example 1.

[0082] The side group of the polyphenylene ether in Comparative Example 3 was crotonol. The performance of the cured resin obtained was significantly lower than that of the cured product of Example 3-1. It was comparable to the performance of the polyphenylene ether SA9000 with only end modification in Comparative Example 1. Therefore, it can be seen that the performance improvement of the cured product formed by crosslinking polyphenylene ether with short chain modification and other resins is not significant.

[0083] In summary, the low molecular weight polyphenylene ether resin containing functional side groups of this application, by introducing reactive functional groups into the polyphenylene ether side groups, gives the polyphenylene ether resin better reactivity; it can be well mixed with hydrocarbon resins, and can obtain cured products with higher crosslinking degree, better mechanical properties and dimensional stability. The preparation process of this application is simple, the reaction process is safe, easy to operate, and conducive to industrial application.

[0084] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of this application. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of those different embodiments or examples.

[0085] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this application, "a plurality of" means two or more, unless otherwise explicitly specified.

[0086] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any person skilled in the art can easily conceive of various variations or substitutions within the technical scope disclosed in this application, and these should all be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A polyphenylene ether polymer containing functional side groups, characterized in that, It has the structure shown in Equation I. ； Wherein, R1 is a noncyclic terpene compound or an olefin with a carbon chain length of 12 or more carbon atoms; n is an integer from 5 to 25.

2. The polyphenylene ether polymer containing functional side groups according to claim 1, characterized in that, The noncyclic terpene compounds are derived from any one of myrcene alcohol, dihydromyrcene alcohol, geraniol, nerol, and citronellol.

3. The method for preparing the polyphenylene ether polymer containing functional side groups according to claim 1 or 2, characterized in that, The halogenated low molecular weight polyphenylene ether with the structure shown in Formula II undergoes a first reaction with a dilute alcohol monomer in a solvent under the action of an activator to obtain the polyphenylene ether polymer containing functional side groups. ； The dilute alcohol monomer is a non-cyclic terpene compound or an enol with a carbon chain length of 12 or more carbon atoms; n is an integer from 5 to 25; In the structure shown in Formula II, X is a halogen atom.

4. The method for preparing the polyphenylene ether polymer containing functional side groups according to claim 3, characterized in that, The noncyclic terpene compounds are any one of myrcene alcohol, dihydromyrcene alcohol, geraniol, nerol, and citronellol; the enols with a carbon chain length of 12 or more carbon atoms are oleyl alcohols. In the mixed solvent, the solvent is a mixture of a first solvent and a co-solvent, wherein the first solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, acetone or methyl ethyl ketone; and the co-solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol. The activator is one or a combination of two or more of potassium hydride, sodium hydride, lithium hydride, n-butyllithium, sodium ethoxide, sodium methoxide or potassium tert-butoxide.

5. The method for preparing the polyphenylene ether polymer containing functional side groups according to claim 3, characterized in that, The molar ratio of halogen atoms to dilute alcohol monomers in the halogenated low molecular weight polyphenylene ether structure shown in Formula II is 1:(0.9-1.2); the mass-volume ratio of the halogenated low molecular weight polyphenylene ether structure shown in Formula II to the solvent is 1g:(20-50)mL. The amount of activator added is 20-40% of the mass of the halogenated low molecular weight polyphenylene ether with the structure shown in Formula II; The volume-to-mass ratio of the first solvent to the co-solvent is (50-150) mL: 1 g.

6. The method for preparing the polyphenylene ether polymer containing functional side groups according to claim 3, characterized in that, The conditions for the first reaction are: reaction at 0-40℃ for 0.5-24 hours.

7. The method for preparing the polyphenylene ether polymer containing functional side groups according to claim 3, characterized in that, A second reaction is carried out in a second solvent with low molecular weight polyphenylene ether, halogenating agent and initiator to prepare halogenated low molecular weight polyphenylene ether with the structure shown in Formula II.

8. The method for preparing the polyphenylene ether polymer containing functional side groups according to claim 7, characterized in that, The halogenating agent is one or more of the following: N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, dibromodimethylhydantoin, dichlorodimethylhydantoin, trichloroisocyanuric acid, a combination of tetraethylammonium bromide / sodium bromide and an oxidizing agent, benzyltrimethylammonium tribromide, or tetrabutylammonium tribromide. The initiator is one or a combination of two or more of the following: benzoyl peroxide, didecyl peroxide, dioctyl peroxide, dilauryl peroxide, tert-butyl peroxide, cyclohexanone peroxide, or azobisisobutyronitrile. The second solvent is one or a combination of two or more of toluene, xylene, chlorobenzene, ethylbenzene or trimethylbenzene; The conditions for the second reaction are 80-150℃ for 0.5-6 hours.

9. A cured product of a functional side group-containing polyphenylene ether resin, characterized by comprising a polyphenylene ether resin and a crosslinking agent. It includes the following components in parts by weight; The mixture consists of 5-15 parts of a functional side-group polyphenylene ether polymer with the structure shown in Formula I, 50-80 parts of methacrylate-terminated low molecular weight polyphenylene ether, 20-30 parts of a hydrocarbon resin, and 0.3-1 parts of an initiator.

10. The method for preparing the cured polyphenylene ether resin containing functional side groups according to claim 9, characterized in that, The functional side-group polyphenylene ether polymer with the structure shown in Formula I, the methacrylate-terminated low molecular weight polyphenylene ether, and the hydrocarbon resin are dissolved in a third solvent, and then an initiator is added to react. After drying and baking, the cured resin is obtained.

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