Ternary diblock copolymer, active cationic polymerization initiator composition, diisopropenylbenzene copolymer, terpene polymer, flame-retardant resin composition, flame-retardant resin cured product, and use thereof

Abstract

To provide a ternary diblock copolymer which has characteristics such as high heat resistance, a low relative dielectric constant, a low dielectric loss tangent, flame retardancy and / or film formability and can be applied to uses such as the production of a semiconductor package material in a high-speed and high-frequency field and a high-speed and high-frequency substrate, and to provide a flame-retardant resin composition thereof.SOLUTION: The ternary diblock copolymer is obtained by copolymerizing monomers of (a) diisopropenylbenzene, (b) terpene derived from biomass, and (c) 1, 1-dihydrocarbylalkene, and the chemical structure of the ternary diblock copolymer is poly (diisopropenylbenzene 1, 1-dihydrocarbylalkene) - polyterpene-poly (diisopropenylbenzene 1, 1-dihydrocarbylalkene).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention provides an active cationic polymerization initiator composition; a ternary diblock copolymer, a diisopropenylbenzene copolymer, and a terpene polymer synthesized using the same; a flame-retardant resin composition containing the ternary diblock copolymer, the diisopropenylbenzene copolymer, or the terpene polymer; a cured product of the flame-retardant resin composition; and use of the cured product. [Background technology]

[0002] In 1984, Higashimura and Sawamoto demonstrated activated cationic polymerization by polymerizing alkyl vinyl ethers using a protonic acid as an ion source in combination with a Lewis acid initiator. In activated cationic polymerization, the addition of a Lewis acid to a carbocation generates a weakly equilibrated carbocation, which tends to become dormant. The addition of a weak nucleophile can further reduce the concentration of the less active species. The system activates the dormant state in a reversible and intermittent manner, extending the lifetime of the propagating carbocation. This theory became the focus of subsequent research into activated cationic polymerization. [ka]

[0003] Since the 1950s, researchers have been passionate about cationic polymerization of terpenes, but have only been able to obtain polymers with low glass transition temperatures and low molecular weights. Because of the low molecular weight of terpene polymers, their commercial applications have been limited to adhesives and polymer modifiers. In recent years, the discovery of cyclic polymers (COPs) and cyclic copolymers (COCs) has attracted considerable attention, particularly in the fields of optics and electronics. These resins have low dielectric constants, low moisture absorption, good transparency, and a low refractive index. As the main chain of a molecular skeleton, they can further improve the heat resistance and mechanical properties of polymers.

[0004] Non-Patent Document 1 discloses that known active cationic polymerization regions are broadly classified into the following three types. [ka]

[0005] Cationic polymerization of terpenes is known to use AlCl3 as an initiator and water, hydrochloric acid, sulfuric acid, or alkyl chloride as an ion source. Patent Document 1 (US9790301B2) discloses that AlCl3 is used as an initiator, water as an ion source, and chloromethane as a solvent, with a monomer weight ratio of isobutylene / alloocimene = 10 / 1, and the polymer yield is 86.12%, Mn is 293,000, and Tg is 74°C. Patent Document 2 (US2018 / 0079895A1) discloses that AlCl3 is used as an initiator, trimethylchlorosilane as an ion source, xylene as a solvent, and α-pinene as a monomer, and the polymer softening point is 101.5°C and the yield is 77.3%. Patent Document 3 (US2021 / 0309779A1) discloses that AlCl3 is used as an initiator, sulfuric acid is used as an ion source, and toluene is used as a solvent, the monomer weight ratio is 1,3-cyclohexadiene / α-pinene = 150 / 130, the softening point of the polymer is 148°C, Tg is 85°C, the molecular weight is Mn = 638, Mw = 1,319, and the yield is 79%.

[0006] Patent Document 4 (TWI706963B) discloses a soluble polyfunctional ethylene-based aromatic copolymer, including a polyfunctional ethylene-based aromatic copolymer derived from a divinyl aromatic compound and a monovinyl aromatic compound. The polymerization initiator uses p-toluenesulfonic acid and butyl acetate as initiators and toluene as a solvent, resulting in a copolymer with a molecular weight of Mn=740 / Mw=3,470. The drawbacks of this method are the low molecular weight and high branching of the copolymer, resulting in poor adhesion to fine-line circuit boards and low-roughness copper.

[0007] As can be seen from the above literature, cationic polymerization using aluminum trichloride and p-toluenesulfonic acid as initiators cannot produce terpene polymers and linear divinyl aromatic copolymers with high molecular weights, low polydispersity index (PDI), and high yields, and it is difficult to achieve an ideal active cationic polymerization reaction.

[0008] From the perspective of environmental considerations and sustainability, polymers in which conventional petrochemical monomers are replaced with bio-derived terpenes can reduce CO2 emissions. By precisely controlling the molecular structure of the polymer through the active cationic polymerization reaction of plant-derived terpene monomers and introducing specific groups, the properties of polymers and copolymers can be improved, expanding the range of industrial applications and adding value. [Prior art documents] [Non-patent literature]

[0009] [Non-Patent Document 1] Sadahito Aoshima and Shokyoku, J. Jpn. Soc. color Mater., 82(2),76-88(2009) Summary of the Invention [Problem to be solved by the invention]

[0010] The problem to be solved by the present invention is to overcome the solubility problem of hyperbranched polydivinylbenzene in the prior art by using p-toluenesulfonic acid as an initiator to obtain hyperbranched polydivinylbenzene oligomers. These oligomers suffer from problems of insufficient film-forming ability, adhesion, and heat resistance, and are unable to meet the requirements for thinner wiring, lower copper surface roughness, and thinner films in high-speed and high-frequency substrates. Although hyperbranched polydivinylbenzene has excellent dielectric properties, achieving low dielectric constant, adhesion, and flame retardancy remains a challenge to be overcome in the fields of next-generation semiconductor packaging materials and high-speed and high-frequency substrates. [Means for solving the problem]

[0011] In view of the above-mentioned problems, the present invention discloses an active cationic polymerization initiator composition as a technical means to solve the problems. The composition initiates the polymerization reaction of 1,1-dihydrocarbylalkene monomers via a common complex to produce high-molecular-weight linear polymers with improved film-forming properties, adhesion, and heat resistance. The polymers of the present invention can be precisely controlled to obtain copolymers with specific molecular structures, and these copolymers use bio-derived terpene monomers to enhance the anchoring effect and improve adhesion to copper foil surfaces. The use of 1,1-dihydrocarbylalkene monomers provides stable cationic active chains, promoting chain growth reactions and increasing polymer molecular weight. The use of diisopropenylbenzene monomers provides ethylene-reactive functional groups, improving the heat resistance of cured products. The linear, high-molecular-weight polymers obtained by the novel active cationic polymerization of the present invention have excellent film-forming properties, adhesion, and heat resistance, and can replace conventional hyperbranched, low-molecular-weight polymers. Furthermore, the use of low-dielectric reactive flame retardants can impart flame retardancy to hydrocarbon resins and polyphenylene ether resins. [Effects of the Invention]

[0012] Comparing the effects of conventional techniques, it is known that conventional techniques use p-toluenesulfonic acid as an initiator, acetate as a co-initiator, and divinylbenzene and ethylstyrene as monomers to obtain a hyperbranched polymer with a molecular weight of approximately Mn=3000-4000. Although the polymer has excellent dielectric properties, it has a hyperbranched molecular structure, resulting in poor adhesion to fine-line circuit boards and low-roughness copper foil surfaces, as well as poor film-forming properties. It is known that conventional techniques can only obtain low-molecular-weight polymers by cationic polymerization using aluminum chloride as an initiator and pinene as a monomer.

[0013] The present invention discloses an active cationic polymerization initiator composition. This composition uses aluminum trichloride, triphenylphosphine, and trihydrocarbyl chloromethane to form a common ion complex with a common ion, initiating the polymerization of 1,1-dihydrocarbyl alkene monomers and forming a stable tertiary carbocation to complete the initiation reaction. Copolymerization with diisopropenylbenzene monomer and terpene monomers or other comonomers produces linear, high-molecular-weight polymers with high yields and low PDIs, which can be co-cured with reactive flame retardants. The cured products simultaneously possess properties such as flame retardancy, high heat resistance, low dielectric loss tangent, low dielectric constant, adhesion, and film-forming properties, making them suitable for applications in high-speed and high-frequency substrates, semi-cured films, adhesive sheets, film materials, semiconductor packaging materials, and interlayer insulating films. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention discloses a ternary diblock copolymer obtained by copolymerizing (a) diisopropenylbenzene monomer, (b) biomass-derived terpene monomer, and (c) 1,1-dihydrocarbylalkene monomer. The chemical structure of the ternary diblock copolymer is poly(diisopropenylbenzene 1,1-dihydrocarbylalkene)-polyterpene-poly(diisopropenylbenzene 1,1-dihydrocarbylalkene). Here, diisopropenylbenzene includes m-diisopropenylbenzene, p-diisopropenylbenzene, and o-diisopropenylbenzene. Commercially available diisopropenylbenzene is a mixture of approximately 71% m-diisopropenylbenzene, approximately 27% p-diisopropenylbenzene, and approximately 2% other monomers.

[0015] The present invention relates to a method for producing a terpene monomer derived from biomass, the terpene monomer comprising an isoprene repeating unit (C5H8). nTerpenes containing conjugated dienes but no alicyclic rings include β-myrcene, β-ocimene, alloocimene, farnesene, cosmene, etc. Terpenes containing conjugated dienes and alicyclic rings include α-phellandrene, β-phellandrene, α-terpinene, chamazulene, etc. Terpenes containing conjugated dienes and alicyclic rings include isocitronellene, and terpenes containing no conjugated dienes but no alicyclic rings include isocitronellene. Terpenes contained therein include α-pinene, β-pinene, camphene, β-terpinene, δ-terpinene, limonene, sabinene, humulene, β-caryophyllene, β-bisabolene, α-camphorene, longifolene, isolongifolene, valencene, and the like, and mixtures thereof. Commercially available limonene contains a mixture of 90% limonene and small amounts of β-myrcene, α-pinene, β-pinene, camphene, sabinene, β-phellandrene, carene, ocimene, valencene, farnesene, and cosmene. Commercially available β-pinene contains a mixture of small amounts of α-pinene, camphene, carene, limonene, δ-terpinene, longifolene, and β-caryophyllene. Commercially available α-terpinene contains a small amount of β-terpinene. In the ternary diblock copolymer of the present invention, the biomass-derived terpene monomers are preferably α-terpinene and α-phellandrene, which are terpenes containing a conjugated diene and an alicyclic ring; β-myrcene, which is a terpene containing a conjugated diene but not an alicyclic ring; and camphene, β-pinene, and limonene, which are terpenes containing no conjugated diene but not an alicyclic ring, because they are relatively inexpensive and easily available. Below is a list of some common terpenes suitable for active cationic polymerization. [ka]

[0016] The present invention discloses a ternary diblock copolymer. 1,1-Dihydrocarbylalkene monomers include isobutylene, isoprene, diisoprene, α-methylstyrene, 1,1-diphenylethylene, and 1,1-ditolylethylene. Terpene monomers that produce alicyclic skeletons after polymerization include α-phellandrene, β-phellandrene, α-terpinene, and β-pinene. Terpenes that can produce alicyclic pendent groups after polymerization include limonene, camphene, sabinene, longifolene, α-camphorene, β-caryophyllene, and β-terpinene. Terpenes containing conjugated dienes include β-myrcene, β-ocimene, alloocimene, farnesene, and cosmene. The most preferred 1,1-dihydrocarbyl alkenes are α-methylstyrene, 1,1-diphenylethylene, β-pinene, α-phellandrene, α-terpinene, β-terpinene, limonene, camphene, and β-myrcene.

[0017] The present invention discloses a ternary diblock copolymer. The chemical structure of the ternary diblock copolymer is poly(diisopropenylbenzene 1,1-dihydrocarbylalkene)-polyterpene-poly(diisopropenylbenzene 1,1-dihydrocarbylalkene). Polyterpenes are used as aliphatic chain segments, and α-terpinene, α-phellandrene, β-phellandrene, camphene, β-pinene, sabinene, longifolene, limonene, β-myrcene, ocimene, alloocimene, and farnesene are preferred, with α-terpinene, α-phellandrene, camphene, β-pinene, and β-myrcene being most preferred. When poly(diisopropenylbenzene 1,1-dihydrocarbylalkene) is used as the aromatic or semi-aromatic hard segment, the preferred 1,1-dihydrocarbylalkene monomers are α-methylstyrene, 1,1-diphenylethylene, 1,1-ditolylethylene, camphene, and limonene. The aromatic or semi-aromatic hard segments and aliphatic soft segments of the ternary diblock copolymers are capable of self-assembly, resulting in excellent film-forming properties. Diisopropenylbenzene forms pendant reactive groups on the isopropenylbenzene in poly(diisopropenylbenzene 1,1-dihydrocarbylalkene), giving the ternary diblock copolymer thermosetting properties and imparting high heat resistance to the cured product.

[0018] The present invention discloses a ternary diblock copolymer. The chemical structure of the ternary diblock copolymer is poly(diisopropenylbenzene 1,1-dihydrocarbylalkene)-polyterpene-poly(diisopropenylbenzene 1,1-dihydrocarbylalkene). The ternary diblock copolymer can be obtained by an active cationic polymerization reaction. In an active cationic polymerization reaction, all molecular chains remain active even after the monomers are consumed, and the propagation reaction can continue when new monomers are added. During active cationic polymerization, a mixture of diisopropenylbenzene and 1,1-dihydrocarbylalkene, terpene, and a mixture of diisopropenylbenzene and 1,1-dihydrocarbylalkene are sequentially added in stages to obtain the ternary diblock copolymer.

[0019] Olefin monomers with electron-donating groups can generally undergo cationic polymerization. In terms of monomer structure, the methyl group in methylethylene monomer has weak electron-donating properties and a slow chain growth rate. However, isobutylene has two methyl groups, which increases the electron cloud density of the double bond, resulting in a high affinity for protons and cations, generating a more stable tertiary carbocation and enabling the production of higher molecular weight polymers. Conjugated olefins have better electron-donating properties than methyl, but styrene, α-methylstyrene, butadiene, and isoprene are rarely used industrially as cationic polymerization monomers. The hydrogen atoms of the methylene groups in the growing chain of 1,1-diphenylethylene are protected by phenyl groups and are not easily captured. Stabilizing the carbocation significantly reduces the occurrence of reactions such as isomerization, rearrangement, disproportionation, chain transfer, and termination. However, 1,1-diphenylethylene itself is difficult to homopolymerize due to steric hindrance, but is prone to copolymerization with other monomers. The present inventors have found that diisoallylbenzene itself undergoes rapid homopolymerization and readily forms a hyperbranched structure, leading to gelation. However, copolymerization with an appropriate amount of other 1,1-dihydrocarbylalkene monomers suppresses branching and allows the production of linear polymers while retaining the isoallylbenzene pendant groups. Here, 1,1-diphenylethylene, α-methylstyrene, and diisoallylbenzene can form ideal linear alternating copolymers.

[0020] The present invention discloses an active cationic polymerization initiator composition comprising at least (a) aluminum trichloride, (b) triphenylphosphine, and (c) trihydrocarbyl chloromethane. The active cationic polymerization initiator composition forms a common ion complex with anhydrous aluminum trichloride, triphenylphosphine, and trihydrocarbyl chloromethane to initiate the polymerization reaction of 1,1-dihydrocarbyl alkene monomers. Cationic polymerization is defined as an ionic polymerization reaction in which cations serve as the kinetic-chain carriers. Generally, carbocations are unstable and prone to chain transfer and termination, resulting in the production of low-molecular-weight oily substances. The molecular weight of polymers obtained by cationic polymerization in conventional techniques is relatively low compared to that of polymers obtained by anionic polymerization. Generally, cationic polymerization is faster at low temperatures. When chain transfer and termination are suppressed, the reaction can be called an active cationic polymerization. Active cationic polymerization is a chain-growth polymerization reaction in which a cationic initiator is used to transfer charge to a monomer, rendering it reactive for polymerization and allowing it to undergo recursive reactions with other monomers. This reaction is selective to the monomer, allowing precise control of polymer structure. The active cationic polymerization of the present invention makes it possible to design syndiotactic, alternating, and block polymers.

[0021] Known cationic polymerization initiators include monomers, ion sources, initiators, and coinitiators. In cationic polymerization reactions, the monomers involved in the reaction must have electron-donating substituents. The electron-donating groups increase the electron cloud density of the double bond, and cationic active species attack the double bond of the monomer to form carbocations. The presence of electron-donating groups improves the scarcity of the carbon electron cloud, reduces the energy of the system, and increases the stability of the carbocations. Common electron-donating groups include methyl groups, phenyl groups, olefins, conjugated olefins, ether groups, amine groups, hydrocarbon groups, etc.

[0022] Known ion sources for cationic polymerization reactions include HO, ROH, HCl, and RCOOH, which can release protons, and RCl, RCOCl, and R(CO)2, which can release carbocations. Common initiators include protic acids and Lewis acids. Protic acids include phosphoric acid, sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid, methylsulfonic acid, p-phenylmethylsulfonic acid, perchloric acid, CFCOOH, CClCOOH, and HI. Lewis acids include BF3, AlCl3, AlCl2R, AlClR2, SnCl4, TiCl4, SbCl5, PCl5, ZnCl2, POCl3, CrO2Cl, SOCl2, and VOCl3. Coinitiators are typically nucleophilic Lewis bases such as ethers, esters, dimethyl sulfide, dimethylvinylamine, Bu4NCl, and Bu4PCl. The interaction of an ion source and an initiator generates cationic active species and counterions, which then transfer charge to monomers to generate carbocations, ultimately forming polymers. The intermediate complex formed by the counterion and co-initiator can inhibit the formation of strong and covalent bonds between the counterion and carbocation. Cationic polymerization reactions are highly sensitive to the solvent used, and the dissociation characteristics of the solvent indicate its ability to free ionize. The more free cationic active species there are, the faster the reactivity of the carbocation chains. Therefore, to obtain high-molecular-weight polymers, the solvent, monomer, ion source, initiator, and co-initiator must be compatible with each other.

[0023] Active cationic polymerization is an ideal chain polymerization reaction, suppressing termination and chain transfer reactions. The initiation rate is much faster than the chain growth rate, and the chain growth rate is more stable than in conventional polymerization. Each cation from the ion source generates one cationic active species, and each cationic active species is involved in the polymerization of one molecular chain. Furthermore, the length of each molecular chain is similar, resulting in a narrow molecular weight distribution. Because the synthesis can be carried out in stages, the segments synthesized in different stages can be controlled to contain different monomers and specific functional groups, thereby easily obtaining block copolymers with the desired molecular weight. The basic reactions involved in active cationic polymerization are shown in Equations 1 to 4 below. [ka]

[0024] The present invention discloses an active cationic polymerization initiator composition containing at least (a) aluminum trichloride, (b) triphenylphosphine, and (c) trihydrocarbyl chloromethane. The initiator uses aluminum trichloride, triphenylphosphine, and trihydrocarbyl chloromethane to form a common ion complex and initiate the polymerization reaction of 1,1-dihydrocarbyl alkene monomers. The active cationic polymerization initiator composition effectively suppresses chain transfer and termination reactions, allowing for rapid polymerization at low temperatures of -10°C to 40°C. Compared with conventional active cationic polymerization, it can produce linear polymers with lower PDI (Mw / Mn) and higher yields, achieving an ideal active cationic polymerization reaction. Therefore, the high-molecular-weight linear polymers polymerized using the active cationic polymerization initiator composition employed in the present invention have better film-forming properties and adhesiveness than conventional low-molecular-weight branched polymers. Furthermore, because they possess self-crosslinking curing properties, they can significantly improve heat resistance.

[0025] The present invention discloses an active cationic polymerization initiator composition, including initiation and propagation reactions. Triphenylphosphine is a very weak Lewis base. The polymerization initiation reaction begins with the formation of a quaternary phosphonium salt with triphenylphosphine and trihydrocarbylchloromethane in a non-polar or low-polarity solvent. The phosphorus cation core of the quaternary phosphonium salt is surrounded by three benzenes and a trihydrocarbylmethane. Due to steric hindrance, the phosphorus cation core and the anion Cl are easily separated. - The bond distance between the two is relatively long. Furthermore, by adding aluminum trichloride, AlCl4 - Tertiary carbocation active species and phosphorus cations can be generated by the anion Cl. - and AlCl4 - A stable equilibrium is maintained between the four due to the common ion effect.

[0026] The active cationic polymerization initiator composition of the present invention comprises aluminum trichloride, triphenylphosphine, and trihydrocarbylchloromethane, which form a common ion complex with a common ion. This complex initiates the polymerization reaction of 1,1-dihydrocarbylalkene monomers to form stable tertiary carbocations, completing the initiation reaction. The subsequent propagation reaction involves repeated addition of 1,1-dihydrocarbylalkene monomers to grow a molecular chain. The stable tertiary carbocation chain formed suppresses termination and chain transfer reactions. While conventional active cationic polymerization initiators can only produce liquid low-molecular-weight terpene polymers, the active cationic polymerization initiator composition of the present invention can produce solid high-molecular-weight terpene polymers with higher molecular weights, higher yields, and greater stereoselectivity than conventional active cationic polymerization initiators. The reaction mechanism of the active cationic polymerization initiator composition of the present invention is shown in Equations 5 to 8 below. [ka] where RCl is trihydrocarbylchloromethane, Ph3P is triphenylphosphine, CH2=CX2 is 1,1-dihydrocarbylalkene, and X is an electron donating group.

[0027] The present invention discloses an active cationic polymerization initiator composition. The initiation system comprises aluminum trichloride, triphenylphosphine, and trihydrocarbylchloromethane reacted together to form R + , Cl - , AlCl4 - , PhRP + The common ion effect allows for effective control of the dissociation degree and ion concentration, so that R + , Cl - , AlCl4 - , PhRP + The four ions of can form a common ion complex with loose ion spacing, R + It has the effect of stabilizing carbocation active species. RCl includes primary alkyl chloride, secondary alkyl chloride, benzyl chloride, tertiary alkyl chloride, triphenylmethyl chloride, 2-chloro-2-phenylisopropane, 2-methyl-2-chloropropane, trihydrocarbylchloromethane, etc. The formed R + Tertiary carbocations are the most stable. From the viewpoint of electron-donating group function, triphenyl carbocations are more stable than trialkyl carbocations. The solvent used in the activated cationic polymerization reaction of the present invention is preferably a non-aromatic or lower aromatic solvent, including toluene, xylene, trimethylbenzene, cyclohexane, methylcyclohexane, n-hexane, etc., and mixtures thereof. The common ion effect and the formation of a common ion complex are shown in the following formulas 9 to 13. [ka]

[0028] The present invention discloses an active cationic polymerization initiator composition. 1,1-Dihydrocarbyl alkenes include isobutylene, isoprene, diisoprene, α-methylstyrene, 1,1-diphenylethylene, 1,1-ditolylethylene, o-diisopropylenebenzene, m-diisopropylenebenzene, p-diisopropylenebenzene, limonene, α-terpinene, β-terpinene, camphene, β-pinene, β-myrcene, farnesene, ocimene, alloocimene, β-phellandrene, α-phellandrene, cosmene, β-caryophyllene, α-campholene, longifolene, and valencene. The preferred initiator monomers used as the active cationic polymerization initiator are α-methylstyrene, 1,1-diphenylethylene, 1,1-ditolylethylene, β-pinene, α-terpinene, α-phellandrene, camphene, limonene, and β-myrcene.

[0029] The present invention discloses a diisopropenylbenzene copolymer. The copolymer is obtained by polymerizing an active cationic polymerization initiator composition, and the molar ratio of diisopropenylbenzene monomer to all monomers in the copolymer is 5% to 65%. The monomers in the copolymer must have electron-donating groups that assist in initiation and stabilization of carbocations during chain growth. The comonomer (A) of the diisopropenylbenzene copolymer includes monoolefins such as isobutylene, α-methylstyrene, 1,1-diphenylethylene, and 1,1-ditolylethylene; diolefins such as isoprene and diisoprene; and terpenes such as α-terpinene, α-phellandrene, β-phellandrene, camphene, β-pinene, limonene, sabinene, longifolene, β-myrcene, ocimene, alloocimene, farnesene, cosmene, valencene, α-camphorene, and alkyl vinyl ethers and N-vinylcarbazole. Diisopropenylbenzene copolymers may be alternating, random, block, or graft copolymers. When comonomer A is 1,1-diphenylethylene or 1,1-ditolylethylene, the molar ratio of diisopropenylbenzene (B) to the total monomers is preferably 50%. Due to steric hindrance, homopolymerization of comonomer (A) itself is difficult, so AB-regular alternating copolymers can be formed. The alternating copolymers exhibit high rigidity, and when comonomer (A) is α-methylstyrene, limonene, or camphene, isotactic polymers can be formed in which the isopropenylbenzene pendant groups are on the same side of the main chain. The isotactic polymers exhibit high melting points and rapid crystallization, and the isopropenylbenzene pendant groups in the chain segments significantly improve heat resistance after curing. When diisopropenylbenzene is used as the initiator monomer, carbocations are generated at both ends of the monomer, initiating the reaction.Therefore, the homopolymer of diisopropenylbenzene has a hyperbranched structure and is prone to gelation during the polymerization reaction. However, when the pendant group of isopropenylbenzene has a large adjacent group, steric hindrance can prevent the pendant group of isopropenylbenzene from being attacked by carbocations. Therefore, by appropriately adjusting the ratio of diisopropenylbenzene to comonomer (A), the optimum yield of diisopropenylbenzene copolymer can be achieved.

[0030] The present invention discloses a terpene polymer. The terpene monomer is obtained by polymerizing an active cationic polymerization initiator composition, and the molar ratio of the terpene polymer to all monomers is 5% to 100%. The terpene monomers include α-terpinene, α-phellandrene, β-phellandrene, camphene, β-pinene, limonene, sabinene, longifolene, β-myrcene, ocimene, alloocimene, farnesene, cosmene, valencene, and α-campholene. They are copolymerizable and can form terpenes and terpene copolymers, as well as terpenes and 1,1-dihydrocarbylalkene copolymers. Among the terpene monomers, α-phellandrene, β-phellandrene, β-pinene, β-myrcene, ocimene, alloocimene, farnesene, and cosmen have excellent homopolymerizability, allowing the formation of high-molecular-weight homopolymers or high-molecular-weight block copolymers, which were previously unachievable with conventional technology.

[0031] The present invention also discloses a flame-retardant resin composition comprising at least the following (a) and (b): (a) a hydrocarbon resin comprising at least one selected from the group consisting of a ternary diblock copolymer, a diisopropenylbenzene copolymer, and a terpene polymer; and (b) a reactive flame retardant comprising at least one selected from the group consisting of 1,1-bis(diphenylphosphino)ethylene, 1,1-bis(diphenylphosphine oxide)ethylene, 3,3'-bis(diphenylphosphine oxide)isobutylene. The chemical structure of the reactive flame retardant is shown below. [ka]

[0032] The present invention discloses a flame-retardant resin composition. The reactive flame retardants 1,1-bis(diphenylphosphino)ethylene, 1,1-bis(diphenylphosphine oxide)ethylene, 3,3'-bis(diphenylphosphine)isobutylene, and 3,3'-bis(diphenylphosphine oxide)isobutylene are co-cured with a hydrocarbon resin to form repeating units with symmetric polar groups. As part of the co-cured product, these flame retardants do not impair the inherent dielectric constant and dielectric dissipation factor of the cured hydrocarbon resin, making them ideal for use as flame retardants for hydrocarbon resins and polyphenylene ethers with low dielectric properties. The reactive flame retardants themselves are polar molecules and readily soluble in solvents. After polymerization, the repeating units containing phosphorus structures become symmetric, low-polarity repeating units. The steric hindrance caused by the bulky symmetric groups reduces the amplitude of molecular chain movement, vibration, and rotation, thereby minimizing the impact on the dielectric constant and dielectric dissipation factor of the flame-retardant resin. The present invention has confirmed that the reactive flame retardant has the property of an ultra-low dielectric tangent after polymerization.

[0033] 1,1-bis(diphenylphosphino)ethylene and 3,3'-bis(diphenylphosphine)isobutylene are easily oxidized in air to form 1,1-bis(diphenylphosphine oxide)ethylene and 3,3'-bis(diphenylphosphine oxide)isobutylene. After polymerization, the repeating units of both compounds are also easily oxidized, and they can be used as secondary antioxidants to reduce oxidation of hydrocarbon resins. The addition polymerization and oxidation of 1,1-bis(diphenylphosphino)ethylene is explained as an example. It is shown in Scheme 14 below. [ka]

[0034] The present invention discloses a flame-retardant resin composition. The hydrocarbon resin can be defined as a resin containing only carbon and hydrogen elements, including a styrene-containing aliphatic resin, a styrene-containing alicyclic resin, a styrene-containing aromatic resin, a styrene-containing aliphatic-aromatic copolymer resin, a styrene-containing hydrocarbon compound resin, an α-methylstyrene-containing aliphatic resin, an α-methylstyrene-containing alicyclic resin, an α-methylstyrene-containing aromatic resin, an α-methylstyrene-containing aliphatic-aromatic copolymer resin, an α-methylstyrene-containing hydrocarbon compound resin, an olefin-containing hydrocarbon compound, an olefin-containing hydrocarbon resin, the ternary diblock copolymer of the present invention, the diisopropenylbenzene copolymer of the present invention, and the terpene polymer of the present invention.

[0035] The present invention discloses a flame-retardant resin composition. In addition to a reactive flame retardant, the flame-retardant resin composition may further contain a modified polyphenylene ether. The modified polyphenylene ether includes polyphenylene ethers containing methacrylic acid residues, polyphenylene ethers containing acrylic acid residues, polyphenylene ethers containing styrene groups, polyphenylene ethers containing vinyl groups, and polyphenylene ethers containing allyl groups. The reactive flame retardant provides flame retardancy to the modified polyphenylene ether without impairing the inherent dielectric properties of the modified polyphenylene ether.

[0036] The present invention also discloses a flame-retardant cured resin, the repeating unit of which chemical structure comprises at least one or more repeating units selected from the group consisting of: [ka] The flame-retardant cured resin can be obtained by co-curing a reactive flame retardant with one or more compounds selected from the group consisting of olefin-containing compounds, olefin-containing resins, olefin-containing oligomers, styrene-containing compounds, styrene-containing resins, styrene-containing oligomers, α-methylstyrene-containing compounds, α-methylstyrene-containing resins, α-methylstyrene-containing oligomers, methacrylic acid residue-containing compounds, methacrylic acid residue-containing resins, methacrylic acid residue-containing oligomers, acrylic acid residue-containing compounds, acrylic acid residue-containing resins, and acrylic acid residue-containing oligomers. The phosphorus content of the reactive flame retardants is higher than that of conventional additive-type phosphorus-based flame retardants. The reactive flame retardant can achieve flame retardancy by curing the reactive flame retardant with an ethylene-containing resin to form a flame-retardant resin cured product. Furthermore, the reactive flame retardant used in the flame-retardant resin cured product of the present invention has a high phosphorus content and high reactivity, which allows for a significant reduction in the amount of resin used, making it superior to additive-type flame retardants.

[0037] Polymers used as insulating materials in high-speed, high-frequency circuit boards are required to have properties such as a low dielectric constant (Dk) and a low dielectric loss factor (Df). Among insulating materials, polyphenylene oxide and hydrocarbon resins are already used in the field of high-speed, high-frequency circuit boards, but due to their lack of flame retardancy, a separate flame retardant must be added. Existing additive-type low-dielectric flame retardants are difficult to dissolve in solvents, making them unsuitable for processing into thinner and finer wires.

[0038] The present invention also discloses a cured film comprising the flame-retardant resin composition and the flame-retardant resin. The present invention further discloses a film comprising the ternary diblock copolymer or the terpene polymer. The present invention further discloses the use of a semi-cured film for use in the production of semiconductor packaging materials, IC-mounted substrates, adhesive sheets, adhesive-backed copper foils, high-speed / high-frequency substrates, or printed wiring boards. The present invention further discloses the use of a film for use in the production of semiconductor packaging materials, build-up films, rewiring layers, interlayer insulating films, encapsulants, cover films, or flexible substrates. The present invention also discloses the use of a cured flame-retardant resin for use in the production of semiconductor packaging materials, high-speed / high-frequency substrates, or printed wiring boards.

[0039] The present invention will be described in more detail below with reference to examples. The following examples are provided to illustrate the present invention, and the scope of the present invention includes the scope described in the claims and their substitutions and modifications, and is not limited to the scope of the embodiments.

[0040] Example 1 AD-T synthesis

[0041] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene (abbreviation: TOL) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen, and the mixture was stirred at room temperature to dissolve. 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP) was added, and the mixture was stirred at room temperature for 0.5 hours to produce a red common ion complex. The temperature was controlled at 18°C ​​to 28°C. A mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (abbreviation: A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (abbreviation: D) was slowly added dropwise, and after the addition was completed, the reaction was continued for 0.5 hours, and then 0.1468 mol / 20 g of α-terpinenes (abbreviation: T) was slowly added dropwise, After the dropwise addition was completed, the reaction was continued for 0.5 hours, and then a mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (D) was slowly added dropwise. After the dropwise addition was completed, the temperature was controlled at 20°C to 30°C, and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, washed three times with pure water, and dried in vacuo at 60°C to obtain poly(diisopropenylbenzene 1,1-diphenylethylene)-polyα-terpinene-poly(diisopropenylbenzene 1,1-diphenylethylene) ternary diblock copolymer (AD-T resin). The yield was 67.55%, the measured melting point Tm was 154°C, and the PDI measured by GPC was 35.13. The molar ratio of diisopropenylbenzene monomer to all monomers is 41.5%, and the molar ratio of terpene monomer to all monomers is 16.5%.

[0042] Example 2 AD-C synthesis

[0043] Triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP) 1.79 mmol, triphenylmethyl chloride 3.59 mmol of TPC (Sigma-Aldrich) and 100 g of toluene (TOL) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve the solution. 3.4 g of trichloroaluminum (Sigma-Aldrich) was added and stirred at room temperature for 0.5 hours to form a red common ion complex. The temperature was controlled at 18-28°C, and a mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (D) was slowly added dropwise. After the addition was complete, the reaction was continued for 0.5 hours. 0.1468 mol / 20 g of camphene (C) was then slowly added dropwise. After that, the reaction was continued for 0.5 hours, and then a mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (D) was slowly added dropwise. After the addition was completed, the temperature was controlled at 20°C to 30°C, and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, washed three times with pure water, and dried in vacuo at 60°C to obtain poly(diisopropenylbenzene 1,1-diphenylethylene)-polycamphene-poly(diisopropenylbenzene 1,1-diphenylethylene) ternary diblock copolymer (AD-C resin). The yield was 61.17%, the measured melting point Tm was 153°C, and the PDI measured by GPC was 18.97. The molar ratio of diisopropenylbenzene monomer to all monomers is 41.5%, and the molar ratio of terpene monomer to all monomers is 16.5%.

[0044] Example 3 AD-H synthesis

[0045] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethylchloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene (abbreviation: TOL) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen, and the mixture was stirred at room temperature to dissolve aluminum trichloride (Trichloroaluminum trichloride). Add 3.4 g of (manufactured by Guma-Aldrich) and stir at room temperature for 0.5 hours to produce a red common ion complex. Control the temperature at 18-28°C, and slowly add dropwise a mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (abbreviation: A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (abbreviation: D). After the addition is complete, continue the reaction for 0.5 hours, and then add α-phellandrene. 0.1468 mol / 20 g of α-Phellandrene (abbreviation: H) was slowly added dropwise, and after the addition was completed, the reaction was continued for 0.5 hours. Further, a mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (abbreviation: A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (abbreviation: D) was slowly added dropwise, and after the addition was completed, the temperature was controlled at 20°C to 30°C and the reaction was continued for 3 hours. Next, methanol was added to precipitate the resin. The resin precipitate was washed three times with methanol and three times with pure water, and then vacuum dried at 60°C to obtain poly(diisopropenylbenzene 1,1-diphenylethylene)-polyα-phellandrene-poly(diisopropenylbenzene 1,1-diphenylethylene) ternary diblock copolymer (abbreviated as AD-H resin). The yield was 61.08%, the measured melting point Tm was 139°C, and the PDI measured by GPC was 7.72. The molar ratio of diisopropenylbenzene monomer to all monomers was 41.5%, and the molar ratio of terpene monomer to all monomers was 16.5%.

[0046] Example 4 AD-P synthesis

[0047] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene (abbreviation: TOL) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen, and the mixture was stirred at room temperature to dissolve. 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP) was added, and the mixture was stirred at room temperature for 0.5 hours to produce a red common ion complex. The temperature was controlled at 18 to 28°C. Then, a mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (abbreviation: A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (abbreviation: D) was slowly added dropwise, and after the addition was completed, the reaction was continued for 0.5 hours, and then 0.1468 mol / 20 g of β-pinene (abbreviation: P) was slowly added dropwise, and after the addition was completed, the reaction was continued for 0.5 hours. After completion of the reaction, the reaction was continued for 0.5 hours, and then a mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (D) was slowly added dropwise. After the addition was completed, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, washed three times with pure water, and dried in vacuo at 60°C to obtain poly(diisopropenylbenzene 1,1-diphenylethylene)-polyβ-pinene-poly(diisopropenylbenzene 1,1-diphenylethylene) ternary diblock copolymer (AD-P resin). The yield was 66.30%, the measured melting point Tm was 141°C, and the PDI measured by GPC was 6.95. The molar ratio of diisopropenylbenzene monomer to all monomers is 41.5%, and the molar ratio of terpene monomer to all monomers is 16.5%.

[0048] Example 5 Synthesis of AD-M

[0049] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene (abbreviation: TOL) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve the mixture. 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP) was added, and the mixture was stirred at room temperature for 0.5 hours to produce a red common ion complex. The temperature was controlled at 18 to 28°C. A mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (abbreviation: A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (abbreviation: D) was slowly added dropwise, and after the addition was completed, the reaction was continued for 0.5 hours. Further, 0.1468 mol / 20 g of β-myrcene (abbreviation: M) was slowly added dropwise, and after the addition was completed, the reaction was continued for 0.5 hours. After completion of the reaction, the reaction was continued for 0.5 hours, and then a mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (D) was slowly added dropwise. After the addition was completed, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, washed three times with pure water, and dried in vacuo at 60°C to obtain poly(diisopropenylbenzene 1,1-diphenylethylene)-polyβ-myrcene-poly(diisopropenylbenzene 1,1-diphenylethylene) ternary diblock copolymer (AD-M resin). The yield was 74.65%, the measured melting point Tm was 144°C, and the PDI measured by GPC was 1.36. The molar ratio of diisopropenylbenzene monomer to all monomers is 41.5%, and the molar ratio of terpene monomer to all monomers is 16.5%.

[0050] Example 6 Synthesis of Aa-L

[0051] Triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP) 1.79 mmol, triphenylmethyl chloride 3.59 mmol of TPC (Sigma-Aldrich Co., abbreviation: TPC) and 100 g of TOL (toluene) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve the solution. 3.4 g of trichloroaluminum (Sigma-Aldrich Co., abbreviation: TPC) was added and the mixture was stirred at room temperature for 0.5 hours to form a red common ion complex. The temperature was controlled between 18 and 28°C, and a mixture of 0.1595 mol / 25.3 g of diisopropenylbenzene (A) and 0.3190 mol / 37.7 g of α-methylstyrene (α-Methylstyrene) was slowly added dropwise. After the addition was completed, the reaction was continued for 0.5 hours. 0.1468 mol / 20 g of limonene (Limonene) was added. / abbreviation: L) was slowly added dropwise, and after completion of the addition, the reaction was continued for 0.5 hours. A mixture of 0.1595 mol / 25.3 g of diisopropenylbenzene and 0.3190 mol / 37.7 g of α-methylstyrene was then slowly added dropwise. After completion of the addition, the temperature was controlled at 20 ° C to 30 ° C, and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, washed three times with pure water, and dried in vacuo at 60 ° C to obtain poly(diisopropenylbenzene α-methylstyrene)-polylimonene-poly(diisopropenylbenzene α-methylstyrene) ternary diblock copolymer (abbreviation: Aa-L resin). The yield was 60.17%, the measured melting point Tm was 156 ° C, and the PDI measured by GPC was 11.16. The molar ratio of diisopropenylbenzene monomer to all monomers is 28.9%, and the molar ratio of terpene monomer to all monomers is 13.2%.

[0052] Example 7 AC-P synthesis

[0053] Triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP) 1.79 mmol, triphenylmethyl chloride 3.59 mmol of TPC (Sigma-Aldrich Co., abbreviation: TPC) and 100 g of toluene (TOL) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve the solution. 3.4 g of trichloroaluminum (Sigma-Aldrich Co., abbreviation: TPC) was added and the mixture was stirred at room temperature for 0.5 hours to form a red common ion complex. The temperature was controlled at 18-28°C, and a mixture of 0.1463 mol / 23.15 g of diisopropenylbenzene (A) and 0.2925 mol / 39.85 g of camphene (C) was slowly added dropwise. After the addition was completed, the reaction was continued for 0.5 hours. 0.1468 mol / 20 g of β-pinene (β-pinene) was added. e / abbreviation: P) was slowly added dropwise, and after completion of the addition, the reaction was continued for 0.5 hours. A mixture of 0.1463 mol / 23.15 g of diisopropenylbenzene and 0.2925 mol / 39.85 g of camphene was then slowly added dropwise. After completion of the addition, the temperature was controlled at 20°C to 30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, washed three times with pure water, and dried in vacuo at 60°C to obtain poly(diisopropenylbenzenecamphene)-polyβ-pinene-poly(diisopropenylbenzenecamphene) ternary diblock copolymer (abbreviation: AC-P resin). The yield was 85.10%, the measured melting point Tm was 141°C, and the PDI measured by GPC was 8.96. The molar ratio of diisopropenylbenzene monomer to all monomers is 28.6%, and the molar ratio of terpene monomer to all monomers is 71.4%.

[0054] Example 8 AL-P synthesis

[0055] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene (abbreviation: TOL) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP) was added. The mixture was stirred at room temperature for 0.5 hours to produce a red common ion complex. The temperature was controlled at 18 to 28°C, and diisopropenylbenzene (Diisopropenyl A mixture of 0.1463 mol / 23.15 g of benzene (abbreviation: A) and 0.2925 mol / 39.85 g of limonene (abbreviation: L) was slowly added dropwise, and the reaction was continued for 0.5 hours after the addition was completed. Then, 0.1468 mol / 20 g of β-pinene (abbreviation: P) was slowly added dropwise, and the reaction was continued for 0.5 hours after the addition was completed. Then, 0.1463 mol / 23.15 g of diisopropenylbenzene and 0.2925 mol / 39.85 g of limonene were added dropwise. The mixture was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol and three times with purified water, and then vacuum dried at 60°C to obtain poly(diisopropenylbenzenelimonene)-polyβ-pinene-poly(diisopropenylbenzenelimonene) ternary diblock copolymer (abbreviated as AL-P resin). The yield was 85.60%, the measured melting point Tm was 165°C, and the PDI measured by GPC was 22.90. The molar ratio of diisopropenylbenzene monomer to all monomers was 28.6%, and the molar ratio of terpene monomer to all monomers was 71.4%.

[0056] Example 9 Synthesis of M01

[0057] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene (abbreviation: TOL) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP) was added. The mixture was stirred at room temperature for 0.5 hours to produce a red common ion complex. The temperature was controlled between 18 and 28°C, and the resulting solution was dissolved in 1.0717 mol / l 46g of β-myrcene (abbreviated as M) was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, then three times with purified water, and vacuum dried at 60°C to obtain poly-β-myrcene (abbreviated as M01 resin). The yield was 88.34%, the measured melting point Tm was 143°C, and the PDI measured by GPC was 7.18. The molar ratio of terpene monomer to all monomers was 100%.

[0058] Comparative Example 1 Synthesis of M02

[0059] 100 g of toluene and 9 g of butyl acetate (BAc) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was dissolved by stirring at room temperature, and 3.4 g of aluminum trichloride (Sigma-Aldrich) was added. The mixture was stirred at room temperature for 0.5 hours, the temperature was controlled at 18-28°C, and 1.0717 mol / 146 g of β-myrcene was slowly added dropwise. After the addition was completed, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was added to precipitate the resin. The resin precipitate was washed three times with methanol, then three times with purified water, and dried under vacuum at 60°C to obtain poly-β-myrcene (M02 resin). The yield was 46.57%, the measured melting point (Tm) was 12°C, and the PDI (Protein Dioxide) measured by GPC was 10.28.

[0060] Comparative example 2 ADM-S synthesis

[0061] 3.4 g of 4-methylbenzenesulfonic acid (Sigma-Aldrich, abbreviation: PTS), 100 g of toluene, and 9 g of butyl acetate were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve the mixture. The temperature was controlled at 18°C ​​to 28°C, and a mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (D) was slowly added dropwise. After the addition was complete, the reaction was continued for 0.5 hours. Then, 0.1468 mol / 20 g of β-myrcene (M) was slowly added dropwise. After the addition was complete, the reaction was continued for 0.5 hours. A mixture of 0.1862 mol / 29.4 g of diisopropenylbenzene (abbreviation: A) and 0.1862 mol / 33.6 g of 1,1-diphenylethylene (abbreviation: D) was slowly added dropwise. After the addition was completed, the temperature was controlled at 20°C to 30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, washed three times with pure water, and dried in vacuo at 60°C to obtain poly(diisopropenylbenzene 1,1-diphenylethylene)-polyβ-myrcene-poly(diisopropenylbenzene 1,1-diphenylethylene) ternary diblock copolymer (abbreviation: ADM-S resin). The yield was 41.57%, the measured melting point Tm was 56°C, and the PDI measured by GPC was 3.11.

[0062] [Table 1]

[0063] Example 10 AD synthesis

[0064] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of trichloroaluminum (Sigma-Aldrich Co.) was added and stirred at room temperature for 0.5 hours to form a red common ion complex. The temperature was controlled at 18-28°C, and 0.4313 mol / 68.3 g of diisopropenylbenzene (A) and 1,1-diphenylethyl methyl ... A mixture of 0.4313 mol / 77.7 g of 1,1-diphenylethylene (D) was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol and three times with purified water, and then vacuum dried at 60°C to obtain poly(diisopropenylbenzene-1,1-diphenylethylene) copolymer (AD resin). The yield was 73.23%, the measured melting point Tm was 170°C, and the PDI measured by GPC was 10.34. The molar ratio of diisopropenylbenzene monomer to total monomers was 50.0%.

[0065] Example 11 AH synthesis

[0066] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP), was added, and the mixture was stirred at room temperature for 0.5 hours to form a red common ion complex. The temperature was controlled at 18-28°C, and 0.4958 mol / 78.5 g of diisopropenylbenzene (A), and α-fluorenyl benzene were added. A mixture of 0.4958 mol / 67.5 g of phellandrene (α-Phellandrene, abbreviated as H) was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, then three times with purified water, and vacuum dried at 60°C to obtain poly(diisopropenylbenzene α-phellandrene) copolymer (abbreviated as AH resin). The yield was 74.99%, the measured melting point Tm was 198°C, and the PDI measured by GPC was 12.75. The molar ratio of diisopropenylbenzene monomer to total monomers was 50.0%, and the molar ratio of terpene monomer to total monomers was 50.0%.

[0067] Example 12 AT synthesis

[0068] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP), 0.4958 mol / 78.5 g of diisopropenylbenzene (A), and α were added. The temperature was controlled at 18°C ​​to 28°C. A mixture of 0.4958 mol / 67.5 g of α-terpinenes (abbreviated as T) was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, then three times with purified water, and vacuum dried at 60°C to obtain poly(diisopropenylbenzene α-terpinene) copolymer (abbreviated as AT resin). The yield was 68.69%, the measured melting point Tm was 199°C, and the PDI measured by GPC was 17.17. The molar ratio of diisopropenylbenzene monomer to total monomers was 50.0%, and the molar ratio of terpene monomer to total monomers was 50.0%.

[0069] Example 13 Synthesis of Aa

[0070] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP), 0.3697 mol / 58.5 g of diisopropenylbenzene (A), and α-methylbenzene were added. The temperature was controlled at 18°C ​​to 28°C. A mixture of 0.7404 mol / 87.5 g of diisopropenylstyrene (α-Methylstyrene / abbreviation: a) was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, then three times with pure water, and vacuum dried at 60°C to obtain poly(diisopropenylbenzene α-methylstyrene) copolymer (abbreviation: Aa resin). The yield was 62.30%, the measured melting point Tm was 176°C, and the PDI measured by GPC was 27.35. The molar ratio of diisopropenylbenzene monomer to all monomers was 33.3%.

[0071] Example 14 AC synthesis

[0072] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of trichloroaluminum (Sigma-Aldrich Co., abbreviation: TPP) was added. The mixture was stirred at room temperature for 0.5 hours to produce a red common ion complex. The temperature was controlled at 18 to 28°C, and 0.3697 mmol of diisopropenylbenzene was added. A mixture of 0.7404 mol / 87.5 g of camphene and 58.5 g of 1 / 4 mol was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, then three times with purified water, and vacuum dried at 60°C to obtain poly(diisopropenylbenzenecamphene) copolymer (abbreviated as AC resin). The yield was 69.80%, the measured melting point Tm was 258°C, and the PDI measured by GPC was 41.78. The molar ratio of diisopropenylbenzene monomer to total monomers was 33.3%, and the molar ratio of terpene monomer to total monomers was 66.7%.

[0073] Example 15 AL synthesis

[0074] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of trichloroaluminum (Sigma-Aldrich Co.) was added and stirred at room temperature for 0.5 hours to produce a red common ion complex. The temperature was controlled at 18-28°C, and 0.3697 m of diisopropenylbenzene was added. A mixture of 58.5 g of 0.7404 mol / 87.5 g of limonene and 0.7404 mol / 87.5 g of ...limonene was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was added to precipitate the resin. The resin precipitate was washed three times with methanol and three times with purified water, and then vacuum dried at 60°C to obtain poly(diisopropenylbenzene limonene) copolymer (abbreviated as AL resin). The yield was 89.04%, the measured melting point (Tm) was 201°C, and the PDI measured by GPC was 11.24. The molar ratio of diisopropenylbenzene monomer to total monomers was 33.3%, and the molar ratio of terpene monomer to total monomers was 66.7%.

[0075] Example 16 AM synthesis

[0076] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of trichloroaluminum (Sigma-Aldrich Co.) was added and stirred at room temperature for 0.5 hours to produce a red common ion complex. The temperature was controlled at 18 to 28°C, and 0.0815 mol of diisopropenylbenzene was added. A mixture of 12.9g of diisopropenylbenzene and 0.9770mol of β-myrcene was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, then three times with purified water, and vacuum dried at 60°C to obtain poly(diisopropenylbenzene β-myrcene) copolymer (abbreviated as AM resin). The yield was 66.05%, the measured melting point Tm was 20°C, and the PDI measured by GPC was 7.35. The molar ratio of diisopropenylbenzene monomer to total monomers was 7.7%, and the molar ratio of terpene monomer to total monomers was 92.3%.

[0077] Example 17 AP synthesis

[0078] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve, and 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP) was added. The mixture was stirred at room temperature for 0.5 hours to produce a red common ion complex. The temperature was controlled at 18 to 28°C, and 0.0815 mmol of diisopropenylbenzene was added. A mixture of 12.9g of diisopropenylbenzene and 0.9770mol / 133.1g of β-pinene was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was added to precipitate the resin. The resin precipitate was washed three times with methanol, then three times with purified water, and vacuum dried at 60°C to obtain poly(diisopropenylbenzene β-pinene) copolymer (abbreviated as AP resin). The yield was 95.89%, the measured melting point Tm was 143°C, and the PDI measured by GPC was 5.97. The molar ratio of diisopropenylbenzene monomer to total monomers was 7.7%, and the molar ratio of terpene monomer to total monomers was 92.3%.

[0079] Example 18 MP synthesis

[0080] 1.79 mmol of triphenylphosphine (Sigma-Aldrich Co., abbreviation: TPP), 3.59 mmol of triphenylmethyl chloride (Sigma-Aldrich Co., abbreviation: TPC), and 100 g of toluene (abbreviation: TOL) were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen. The mixture was stirred at room temperature to dissolve the mixture. 3.4 g of aluminum trichloride (Sigma-Aldrich Co., abbreviation: TPP), and the mixture was stirred at room temperature for 0.5 hours to form a red common ion complex. The temperature was controlled at 18-28°C, and 0.2679 mol / 36.5 g of β-myrcene was slowly added dropwise. After the addition was complete, the reaction was continued for 0.5 hours. To the mixture, 0.5358 mol / 73.0 g of β-pinene (abbreviated as P) was slowly added dropwise. After completion of the addition, the reaction was continued for 0.5 hours. Then, 0.2679 mol / 36.5 g of β-myrcene was slowly added dropwise. After completion of the addition, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was added to precipitate the resin. The resin precipitate was washed three times with methanol, then three times with purified water, and vacuum dried at 60°C to obtain polyβ-myrcene-polyβ-pinene-polyβ-myrcene binary diblock copolymer (abbreviated as MP resin). The yield was 73.72%, the measured melting point (Tm) was 86°C, and the PDI (Protein Dioxide Index) measured by GPC was 6.81. The molar ratio of terpene monomer to total monomer was 100.0%.

[0081] Comparative example 3 AD-S synthesis

[0082] 100 g of toluene and 9 g of butyl acetate were added to a four-necked reaction flask equipped with a mechanical stirrer, a drying tube, a distillation receiver, and nitrogen, and the mixture was stirred at room temperature to dissolve. 3.4 g of p-toluenesulfonic acid was then added and the mixture was stirred at room temperature for 0.5 hours. The temperature was controlled at 18°C ​​to 28°C, and 0.4313 mol / 68.3 g of diisopropenylbenzene (A) and 0.4313 mol / 68.3 g of 1,1-diphenylethylene (D) were obtained. A mixture of 77.7g of 1,2-diisopropenylbenzene and 77.7g of 1,2-diphenylethylene was slowly added dropwise. After the addition was complete, the temperature was controlled at 20-30°C and the reaction was continued for 3 hours. Methanol was then added to precipitate the resin. The resin precipitate was washed three times with methanol, then washed three times with pure water, and vacuum dried at 60°C to obtain poly(diisopropenylbenzene-1,1-diphenylethylene) copolymer (abbreviated as AD-S resin). The yield was 67.12%, the measured melting point Tm was 28°C, and the PDI measured by GPC was 12.6.

[0083] [Table 2]

[0084] Examples 19 to 27

[0085] To 100 g of each of the resins AD-T, AD-C, AD-H, AD-P, AD-M, Aa-L, AC-P, AL-P, and MO1 in Examples 1 to 9, 100 g of toluene, 0.2 g of an accelerator, and 0.1 g of an antioxidant were added and mixed uniformly to prepare an adhesive solution. The adhesive solution was applied to a heat-resistant glass plate, dried at 120°C for 2 hours, then at 160°C for 2 hours, then at 180°C for 2 hours, and finally baked at 220°C for 4 hours to obtain a cured product with a film thickness of 1.0 mm. The glass transition temperature, thermal decomposition temperature, dielectric constant (Dk), and dielectric loss tangent (Df) of the cured product were measured. In addition, the adhesive liquid was applied to a heat-resistant glass plate, dried at 120°C for 2 hours, then at 160°C for 2 hours, then at 180°C for 2 hours, and finally baked at 200°C for 4 hours to obtain a cured product with a film thickness of 100 μm. Its solvent resistance and film-forming properties were measured, and the data are shown in Table 3.

[0086] Comparative Examples 4-5

[0087] To 100 g of each of the resins M02 and ADM-S of Comparative Examples 1 and 2, 100 g of toluene, 0.2 g of accelerator, and 0.1 g of antioxidant were added and mixed uniformly to prepare an adhesive solution. The adhesive solution was applied to a heat-resistant glass plate, dried for 2 hours at 120 ° C, 2 hours at 160 ° C, 2 hours at 180 ° C, and finally baked for 4 hours at 220 ° C to obtain a cured product with a film thickness of 1.0 mm. The glass transition temperature, thermal decomposition temperature, relative dielectric constant (Dk), and dielectric loss tangent (Df) were measured. The adhesive solution was also applied to a heat-resistant glass plate, dried for 2 hours at 120 ° C, 2 hours at 160 ° C, 2 hours at 180 ° C, and finally baked for 4 hours at 200 ° C to obtain a cured product with a film thickness of 100 μm. The solvent resistance and film-forming properties were measured, and the data are shown in Table 3.

[0088] [Table 3]

[0089] Examples 28 to 36

[0090] To 100 g of each of the resins Aa, AD, AH, AT, AC, AL, AP, AM, and MP from Examples 10 to 18, 80 g of toluene, 0.2 g of accelerator, and 0.1 g of antioxidant were added and mixed uniformly to prepare an adhesive solution. The adhesive solution was applied to a heat-resistant glass plate, dried at 120 ° C for 2 hours, then at 160 ° C for 2 hours, then at 180 ° C for 2 hours, and finally baked at 220 ° C for 4 hours to obtain a cured product with a film thickness of 1.0 mm. The glass transition temperature, thermal decomposition temperature, dielectric constant (Dk), and dielectric loss tangent (Df) were measured. The adhesive solution was also applied to a heat-resistant glass plate, dried at 120 ° C for 2 hours, then at 160 ° C for 2 hours, then at 180 ° C for 2 hours, and finally baked at 200 ° C for 4 hours to obtain a cured product with a film thickness of 100 μm. The solvent resistance and film-forming properties were measured, and the data are shown in Table 4.

[0091] Comparative Example 6

[0092] In Comparative Example 3, 100 g of resin AD-S was mixed with 100 g of toluene, 0.2 g of accelerator, and 0.1 g of antioxidant to prepare an adhesive solution. The adhesive solution was applied to a heat-resistant glass plate and dried for 2 hours at 120°C, 2 hours at 160°C, 2 hours at 180°C, and finally baked for 4 hours at 220°C to obtain a cured product with a film thickness of 1.0 mm. The glass transition temperature, thermal decomposition temperature, relative dielectric constant (Dk), and dielectric loss tangent (Df) were measured. The adhesive solution was also applied to a heat-resistant glass plate and dried for 2 hours at 120°C, 2 hours at 160°C, 2 hours at 180°C, and finally baked for 4 hours at 200°C to obtain a cured product with a film thickness of 100 μm. The solvent resistance and film-forming ability were measured. The data are shown in Table 4.

[0093] [Table 4]

[0094] Examples 37 to 45

[0095] 50g of each of the resins AD-T, AD-C, AD-H, AD-P, AD-M, Aa-L, AC-P, AL-P, and MO1 from Examples 1 to 9 was added to 50g of PPE resin, 80g of toluene, 18g of flame retardant, 0.2g of accelerator, and 0.1g of antioxidant, and mixed uniformly to prepare adhesive solutions. Each E-glass fiber cloth was impregnated with the adhesive solution and dried at 155°C for 5 minutes to obtain prepreg cloths. Eight individual prepreg cloths were coated with low-roughness copper foil (HVLP2) and cured at 220°C and 3.0MPa to obtain copper-clad substrates. The glass transition temperature (Tg), thermal decomposition temperature (Td3), dielectric constant (Dk), dielectric loss tangent (Df), flame retardancy, and copper foil peel strength were measured, and the data are shown in Table 5.

[0096] Comparative Examples 7-8

[0097] Two 100g PPE samples were mixed with 80g toluene, 0.2g accelerator, and 0.1g antioxidant. One sample (Comparative Example 7) contained 18g of flame retardant, while the other (Comparative Example 8) contained no flame retardant. The mixture was uniformly mixed to prepare adhesive solutions. Each sample was impregnated with E-glass fiber cloth and dried at 155°C for 5 minutes to obtain prepreg cloths. Eight prepreg cloths were coated with low-roughness copper foil (HVLP2) and cured at 220°C and 3.0MPa to obtain copper-clad substrates. The glass transition temperature (Tg), thermal decomposition temperature (Td3), dielectric constant (Dk), dielectric loss tangent (Df), flame retardancy, and copper foil peel strength were measured. The data are shown in Table 6.

[0098] [Table 5]

[0099] Examples 46 to 54

[0100] 50g of each of the resins AD, AH, AT, Aa, AC, AL, AP, AM, and MP from Examples 10 to 18 was added to 50g of PPE resin, 80g of toluene, 18g of flame retardant, 0.2g of accelerator, and 0.1g of antioxidant, and mixed uniformly to prepare adhesive solutions. Each E-glass fiber cloth was impregnated with the adhesive solution and dried at 155°C for 5 minutes to obtain prepreg cloths. Eight individual prepreg cloths were coated with low-roughness copper foil (HVLP2) and cured at 220°C and 3.0MPa to obtain copper-clad substrates. The glass transition temperature (Tg), thermal decomposition temperature (Td3), dielectric constant (Dk), dielectric loss tangent (Df), flame retardancy, and copper foil peel strength were measured, and the data are shown in Table 6.

[0101] Comparative Example 9

[0102] 100g of AD resin was mixed with 80g of toluene, 18g of flame retardant, 0.2g of accelerator, and 0.1g of antioxidant to prepare an adhesive solution. E-glass fiber cloth was impregnated with the adhesive solution and dried at 155°C for 5 minutes to obtain prepreg cloth. Eight prepreg cloths were coated with low-roughness copper foil (HVLP2) and cured at 220°C and 3.0MPa to obtain copper-clad substrates. The glass transition temperature (Tg), thermal decomposition temperature (Td3), dielectric constant (Dk), dielectric loss tangent (Df), flame retardancy, and copper foil peel strength were measured, and the data are shown in Table 6.

[0103] Comparative Example 10

[0104] 50g of PDVB (polydivinylbenzene resin, manufactured by Nippon Steel Corporation) was mixed with 50g of PPE resin, 80g of toluene, 18g of flame retardant, 0.2g of accelerator, and 0.1g of antioxidant to prepare an adhesive solution. E-glass fiber cloth was impregnated with the adhesive solution and dried at 155°C for 5 minutes to obtain prepreg cloth. Eight prepreg cloths were coated with low-roughness copper foil (HVLP2) and cured at 220°C and 3.0MPa to obtain copper-clad substrates. The glass transition temperature (Tg), thermal decomposition temperature (Td3), dielectric constant (Dk), dielectric loss tangent (Df), flame retardancy, and copper foil peel strength were measured, and the data are shown in Table 6.

[0105] [Table 6]

[0106] Diisopropenylbenzene (abbreviation A / purity 99.0% / manufactured by Deltec), α-methylstyrene (abbreviation a / purity 99.0% / manufactured by Thermo Chemical), 1,1-diphenylethylene (abbreviation D / purity 99.0% / manufactured by TCI), α-terpinene (abbreviation T / purity 95.0% / manufactured by Sigma-Aldrich), α-phellandrene (abbreviation H / purity 95.0% / manufactured by Sigma-Aldrich), camphene (abbreviation C / purity 90.0% / manufactured by Sigma-Aldrich), β-pinene (abbreviation P / purity 99.0% / manufactured by Thermo Chemical), limonene (abbreviation L / purity 96.0% / manufactured by Thermo Chemical), β-myrcene (abbreviation M / purity 90.0% / manufactured by Thermo Chemical).

[0107] Flame retardant A: 1,1-bis(diphenylphosphino)ethylene / Sigma-Aldrich, Flame retardant B: 1,1-bis(diphenylphosphine oxide)ethylene / INNOPHARMCHEM, Flame retardant C: 3,3'-bis(diphenylphosphine)isobutylene / Chinyee, Flame retardant D: 3,3'-bis(diphenylphosphine oxide)isobutylene / Chinyee.

[0108] Modified polyphenylene ether (PPE): Styrene-terminated polyphenylene ether / Product name: OPE-2st 2200 / Manufactured by Mitsubishi Gas Chemical Company, Inc.

[0109] Accelerator (trade name: BC-90): 2,3-dimethyl-2,3-diphenylbutane / manufactured by NOF Corporation.

[0110] Antioxidant (trade name: AO-60): pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] / manufactured by ADEKA Corporation.

[0111] Glass transition temperature (Tg): The maximum peak temperature was measured using a dynamic mechanical analyzer (Differential scanning calorimetry, DSC) manufactured by TA Instruments, and the unit is ° C.

[0112] Thermal decomposition temperature (Td3): Measured using a TA Instruments Q500 thermogravimetric analyzer (Thermo Gravimetric Analyzer, TGA), and expressed as the temperature at 3% thermal weight loss / 5% thermal weight loss, in °C.

[0113] Relative permittivity (Dk): Measured at a frequency of 10 GHz using a resonator manufactured by Agilent Technologies.

[0114] Dielectric loss tangent (Df): Measured at a frequency of 10 GHz using an Agilent Technologies resonator.

[0115] Flame retardancy UL-94: Measured according to the UL-94 flame retardancy standard using the vertical burning method. The test piece is 127mm long and 12.5mm wide, and is divided into V-2, V-1, and V-0 grades, with V-0 being the highest flame retardancy grade.

[0116] Film-forming properties: The adhesive liquid was applied to a glass plate, dried and hardened, and then its appearance and smoothness were inspected. ○: Indicates that the surface is very smooth. △: Indicates that the display is slightly uneven. ×: indicates that the film has cracks.

[0117] Solvent resistance: A film was immersed in methyl ethyl ketone (MEK), and the appearance was inspected after 1 hour. ○: indicates no change. △: Shows expansion. ×: Cracks and dissolution are observed.

[0118] Summarizing the above, as shown in Table 1, the melting point of M01 resin (Tm = 143°C) is higher than that of M02 resin (Tm = 12°C), indicating that the crystallinity of M01 resin is higher than that of M02 resin. The melting point of AD-M resin (Tm = 144°C) is higher than that of ADM-S resin (Tm = 56°C), indicating that the crystallinity of AD-M resin is higher than that of ADM-S resin. As shown in Table 2, the melting point of AD resin (Tm = 170°C) is higher than that of AD-S resin (Tm = 28°C), indicating that the crystallinity of AD resin is higher than that of AD-S resin. As can be seen from the above, the polymer synthesized using the active cationic polymerization initiator composition of the present invention has a higher "tacticity" of its molecular chain than polymers synthesized from aluminum trichloride or p-toluenesulfonic acid. It was confirmed that the polymerization reaction using the active cationic polymerization initiator composition employed in the present invention has a high degree of "stereoselectivity" and that the resulting polymer has high physical heat resistance.

[0119] As shown in Table 1, the M01 resin yield of 88.34% was greater than the M02 resin yield of 46.57%, the AD-M resin yield of 74.65% was greater than the ADM-S resin yield of 41.57%, and as shown in Table 2, the AD resin yield of 73.23% was greater than the AD-S resin yield of 67.12%, indicating that the use of the active cationic polymerization initiator composition of the present invention suppresses termination reactions during polymerization. As shown in Table 2, the PDI Mw / Mn of M01 resin (7.18) was smaller than that of M02 resin (10.28). The PDI Mw / Mn of AD-M resin (1.36) was smaller than that of ADM-S resin (3.11). Furthermore, the PDI Mw / Mn of AD resin (10.34) was smaller than that of AD-S resin (12.36). These results demonstrate that chain transfer reactions are suppressed during polymerization when the active cationic polymerization initiator composition of the present invention is used. The polymerization reaction employed in the present invention was confirmed to be an ideal active cationic polymerization reaction. The reaction environment formed by the active cationic polymerization initiator composition of the present invention is superior to that formed by conventional aluminum trichloride or p-toluenesulfonic acid initiators.

[0120] As shown in Table 3, M01 resin Td3=298°C was greater than M02 resin Td3=219°C, M01 resin Tg=149°C was greater than M02 resin Tg=88°C, AD-M resin Td3=285°C was greater than ADM-S resin Td3=272°C, and AD-M resin Tg=93°C was greater than ADM-S resin Tg=54°C. As shown in Table 4, AD resin Td3=306°C was greater than AD-S resin Td3=282°C, and AD resin Tg=127°C was greater than AD-S resin Tg=55°C, demonstrating that the active cationic polymerization initiator composition of the present invention is superior to conventional aluminum trichloride or p-toluenesulfonic acid initiators in terms of chemical heat resistance of the polymer.

[0121] The film-forming properties of AD-T, AD-C, AD-H, AD-P, AD-M, Aa-L, AC-P, and AL-P ternary diblock copolymers and M01 resin were superior to those of M02 and ADM-S, indicating that polymers incorporating the active cationic polymerization initiator composition of the present invention have excellent film-forming properties. The ternary diblock copolymers are capable of self-assembly, which is advantageous for the fabrication of ultrathin films. M01, AD-M, and AD resins also have superior solvent resistance compared to M02, ADM-S, and AD-S, indicating that the active cationic polymerization initiator composition employed in the present invention can maintain more complete olefin groups, resulting in favorable solvent resistance for the cured resins.

[0122] As shown in Table 1, the M01 resin Tm = 143°C is higher than the M02 resin Tm = 12°C, and the molecular weight of the M01 resin is higher than that of the M02 resin. This indicates that the M01 resin obtained using the active cationic polymerization initiator composition of the present invention is a solid terpene homopolymer, while the M02 resin obtained by conventional polymerization reactions is completely different from the liquid terpene homopolymer, and there is a significant difference. Also, as shown in Table 2, the MP resin Tm = 86°C is also a solid terpene and terpene copolymer.

[0123] As shown in Table 5, the cured resins obtained by adding flame retardants to AD-T, AD-C, AD-H, AD-P, AD-M, Aa-L, AC-P, AL-P, and MO1 resins and PPE mixtures can improve their flame retardancy from V-1 to V-0 without compromising their original Df properties. As shown in Table 6, the cured resins obtained by adding flame retardants to AD resins can achieve flame retardancy of V-0 without compromising their original Df properties. As shown in Table 5, the cured products of AD-T, AD-C, AD-H, AD-P, AD-M, Aa-L, AC-P, AL-P, and MO1 resins and PPE blends with flame retardants achieved flame retardancy of V-0, with lower Df than those of PPE blends. These confirm that AD-T, AD-C, AD-H, AD-P, AD-M, Aa-L, AC-P, AL-P, and MO1 resins are novel ultra-low dielectric resins. As shown in Table 6, the cured products of AD, AH, AT, Aa, AC, AL, AM, AP, and MP resins and PPE blends with flame retardants achieved flame retardancy of V-0, with lower Df than those of PPE blends. These confirm that AD, AH, AT, Aa, AC, AL, AM, AP, and MP resins are novel ultra-low dielectric resins. The flame retardants provide low dielectric flame retardancy.

[0124] As shown in Table 5, the cured products of AD-T, AD-C, AD-H, AD-P, AD-M, Aa-L, AC-P, AL-P, and MO1 resins and PPE mixtures to which a flame retardant has been added, and the cured products of AD, AH, AT, Aa, AC, AL, AM, AP, and MP resins and PPE mixtures to which a flame retardant has been added, have copper peel strengths that are superior to those of PDVB (polydivinylbenzene) and PPE mixtures, confirming that the adhesion of the resins of the present invention is superior to that of the prior art PDVB.

[0125] As can be seen from the above, the present invention discloses a cationic polymerization initiator composition that uses aluminum trichloride, triphenylphosphine, and trihydrocarbylchloromethane to form a common ion complex with a common ion, thereby initiating the polymerization of 1,1-dihydrocarbylalkene monomers and forming a stable tertiary carbocation to complete the initiation reaction. Copolymerization of diisopropenylbenzene monomer with terpene monomers or other comonomers can produce linear, high-molecular-weight polymers with high yields and low PDIs, which can also be co-cured with reactive flame retardants. The resulting cured products can possess properties such as flame retardancy, high heat resistance, low dielectric loss tangent, low dielectric constant, adhesion, and / or film-forming properties, making them suitable for applications in high-speed and high-frequency substrates, semi-cured films, adhesive sheets, film materials, semiconductor packaging materials, and interlayer insulating films.

[0126] Although the present invention has been described in conjunction with the above specific embodiments and comparative examples, those skilled in the art to which the present invention pertains can make various modifications based on the above description, and therefore, the scope of patentability of the present invention is not limited thereto. [Industrial Applicability]

[0127] The ternary diblock copolymer, diisopropenylbenzene copolymer, terpene polymer, flame-retardant resin composition, and cured flame-retardant resin of the present invention can be applied to semi-cured films, IC-mounted substrates, adhesive sheets, adhesive-backed copper foils, film materials, interlayer insulating films, encapsulants, cover films, flexible substrates, semiconductor packaging materials, high-speed / high-frequency substrates, and printed wiring boards.

Claims

1. A ternary diblock copolymer, The ternary diblock copolymer is obtained by copolymerizing the monomers of (a) diisopropenylbenzene, (b) biomass-derived terpene, and (c) 1,1-dihydrocarbylalkene, and the chemical structure of the ternary diblock copolymer is poly(diisopropenylbenzene-1,1-dihydrocarbylalkene)-polyterpene-poly(diisopropenylbenzene-1,1-dihydrocarbylalkene). Ternary diblock copolymer.

2. 1. An active cationic polymerization initiator composition comprising: the active cationic polymerization initiator composition comprises (a) aluminum trichloride, (b) triphenylphosphine, and (c) trihydrocarbyl chloromethane, wherein the aluminum trichloride, the triphenylphosphine, and the trihydrocarbyl chloromethane form a common ion complex to initiate the polymerization reaction of 1,1-dihydrocarbyl alkene monomers; Active cationic polymerization initiator composition.

3. The polymerization initiator composition of claim 2 is obtained by polymerizing diisopropenylbenzene monomer with the active cationic polymerization initiator composition of claim 2, and the molar ratio of the diisopropenylbenzene monomer to all monomers is 5% to 65%. Diisopropenyl benzene copolymer.

4. The active cationic polymerization initiator composition according to claim 2 is used to polymerize a terpene monomer, and the molar ratio of the terpene monomer to all monomers is 5% to 100%. Terpene polymers.

5. (a) a hydrocarbon resin comprising at least one selected from the group consisting of the ternary diblock copolymer according to claim 1, the diisopropenyl benzene copolymer according to claim 3, and the terpene polymer according to claim 4; and (b) a reactive flame retardant containing one or more selected from the group consisting of 1,1-bis(diphenylphosphino)ethylene, 1,1-bis(diphenylphosphine oxide)ethylene, 3,3′-bis(diphenylphosphino)isobutylene, and 3,3′-bis(diphenylphosphine oxide)isobutylene; Flame-retardant resin composition.

6. The flame-retardant resin composition according to claim 5 , further comprising a modified polyphenylene ether.

7. A flame-retardant resin cured product formed from the flame-retardant resin composition according to claim 5, wherein the repeating units in the chemical structure of the flame-retardant resin cured product include one or more repeating units selected from the group consisting of: Flame retardant resin cured product. 【Chemistry 1】

8. A flame-retardant resin cured product formed from the flame-retardant resin composition according to claim 6, wherein the repeating units in the chemical structure of the flame-retardant resin cured product include one or more repeating units selected from the group consisting of: Flame retardant resin cured product. 【Chemistry 2】

9. A semi-cured film comprising the flame-retardant resin cured product according to claim 7.

10. A membrane comprising the ternary diblock copolymer according to claim 1 or the terpene polymer according to claim 4.

11. Use of the semi-cured film according to claim 9, Used in the manufacture of semiconductor packaging materials, IC mounting substrates, adhesive sheets, adhesive-backed copper foil, high-speed / high-frequency substrates, or printed wiring boards. use.

12. Use of the membrane according to claim 10, Used in the manufacture of semiconductor packaging materials, build-up films, rewiring layers, interlayer insulating films, encapsulants, cover films, or flexible substrates. use.

13. Use of the flame-retardant resin cured product according to claim 7, Used in the manufacture of semiconductor packaging materials, high-speed and high-frequency substrates, or printed wiring boards, use.

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