Preparation method of modified liquid hydrocarbon polymer, resin composition and application thereof

Abstract

The invention relates to a preparation method of a modified liquid hydrocarbon polymer, a resin composition and application thereof. The carboxylated liquid hydrocarbon polymer and the fluorine-containing alkyl alcohol are subjected to esterification reaction to prepare the modified liquid hydrocarbon polymer, the preparation method not only realizes covalent bond bonding of a fluorine-containing group and the liquid hydrocarbon polymer, but also generates an ester group, so that the compatibility of the hydrocarbon polymer with polyphenyl ether and a polar material interface is improved, and the performance of the liquid hydrocarbon polymer is improved. The dielectric loss is further reduced; by constructing the resin composition with excellent dielectric property, the dielectric property, thermal stability, copper foil adhesion and low thermal expansion coefficient are considered, and the resin composition has great application value in the field of high-frequency and high-speed copper-clad plates.

Description

Technical Field

[0001] The present invention belongs to the field of material science and engineering technology, and in particular relates to a modified liquid hydrocarbon polymer and a preparation method thereof, a resin composition and an application thereof. Background Art

[0002] With the rise of strategic emerging fields such as autonomous driving, 5G+ communications, and artificial intelligence, the electronic information industry has been developing in the direction of high frequency and high speed. As an important carrier for signal reception and data transmission, the dielectric layer resin material of the copper clad laminate plays a decisive role in the overall performance of the copper clad laminate, which places higher demands on dielectric resin manufacturers. Traditional epoxy resins cannot meet the high frequency and high speed requirements of copper clad laminates due to their high dielectric loss. Liquid hydrocarbon polymers have excellent dielectric properties, water resistance, and good processability. Hydrocarbon copper clad laminates have become the most commonly used commercial products in the high frequency and high speed fields. However, because the main chain of liquid hydrocarbon polymers does not contain polar groups, they have poor compatibility with polar materials, resulting in poor filler dispersion, low copper foil peel strength, and easy delamination of composite heat-resistant resins.

[0003] Chinese patent CN115651128A discloses a method for preparing a hydrocarbon resin polymer and a copper-clad laminate containing the same. Styrene, butadiene, and propylene monomers are first added to a reaction device for anionic polymerization to produce a liquid hydrocarbon polymer with a number-average molecular weight of 700 to 2000. The liquid hydrocarbon polymer is used as a dielectric resin material for the copper-clad laminate, relying on its lower molecular weight to improve wettability. However, the liquid hydrocarbon polymer in this solution is a non-polar polymer, has poor compatibility with fillers, insufficient copper foil peel strength, and poor overall stability of the copper-clad laminate. Chinese patent CN104845366A discloses a halogen-free resin composition and its use. A liquid hydrocarbon polymer, an allyl-modified benzoxazine resin, an allyl-modified polyphenylene ether resin, an initiator, an inorganic filler, and a flame retardant are mixed to form a prepreg and a laminate. The prepreg and laminate are co-cured using the carbon-carbon double bonds of each resin component, resulting in good dielectric properties and heat resistance. However, the liquid hydrocarbon polymer has poor compatibility with benzoxazine, polyphenylene ether, and inorganic filler, and the prepared laminate has the risk of delamination and explosion under high-temperature processing. Chinese patent CN111378243A provides a prepreg hydrocarbon composition blended with a multifunctional modified resin, wherein the multifunctional modified resin is a mixture of a hydrocarbon polymer and a modified hydrocarbon polymer, wherein the modified hydrocarbon polymer is a hydrocarbon polymer modified with terminal hydroxyl groups or polyether; the hydrocarbon polymer comprises a liquid hydrocarbon polymer; and by polarizing the hydrocarbon polymer, the filler dispersion, thermal stability, and peel strength of the copper clad laminate are further improved. However, the introduction of polar groups has an adverse effect on dielectric loss. Therefore, the addition amount of the modified hydrocarbon polymer does not exceed 25% of the total resin amount, and the improvement effect on the overall performance of the copper clad laminate is limited. Summary of the Invention

[0004] In response to the deficiencies in the prior art, the present invention provides a method for preparing a modified liquid hydrocarbon polymer, a resin composition, and applications thereof. Chemical bonding of a fluorinated alkyl alcohol and a carboxylated liquid hydrocarbon polymer is achieved through an esterification reaction, and a resin composition with excellent dielectric properties is constructed. Good interfacial interactions with inorganic fillers, copper foil, and resins such as polyphenylene ether are achieved, while taking into account dielectric properties, thermal stability, copper foil adhesion, and a low thermal expansion coefficient, thereby improving the overall performance of copper clad laminates.

[0005] To achieve the above objectives, the present invention provides the following technical solutions: A method for preparing a modified liquid hydrocarbon polymer. The modified liquid hydrocarbon polymer is obtained by esterification reaction of a carboxylated liquid hydrocarbon polymer and a fluorine-containing alkyl alcohol.

[0006] Preferably, the esterification reaction conditions of the carboxylated liquid hydrocarbon polymer and the fluorinated alkyl alcohol are as follows: the carboxylated liquid hydrocarbon polymer is added to toluene and stirred to dissolve; the temperature is controlled at 20-30° C., the fluorinated alkyl alcohol is added and stirred, and after adding the catalyst and reacting for 20-24 hours, the reaction solution is added to ethanol for precipitation, the upper layer solution is poured out, and the precipitate is washed with ethanol and rotary evaporated to obtain the modified liquid hydrocarbon polymer.

[0007] Preferably, the fluorine-containing alkyl alcohol is tridecafluorooctanol or perfluoroalkylethanol, the catalyst is 4-dimethylaminopyridine, and the molar ratio of the catalyst to the fluorine-containing alkyl alcohol is 3 to 5:100.

[0008] Preferably, the carboxylated liquid hydrocarbon polymer is obtained by grafting mercaptocarboxylic acid into a liquid hydrocarbon polymer via a thiol-ene click chemistry reaction chain.

[0009] Preferably, the grafting rate of the carboxylated liquid hydrocarbon polymer is 5-10%; the mercaptocarboxylic acid is one or more of mercaptoacetic acid, mercaptopropionic acid, and mercaptocaproic acid.

[0010] If the grafting rate is too low, the grafting amount of fluorinated alkyl alcohol in the esterification reaction will be reduced, affecting the modification effect and failing to effectively reduce the dielectric loss of the resin composition; if the grafting rate is too high, the carboxyl polar groups will interact with each other to form a physical gel in the solution system, affecting the industrial production process.

[0011] Preferably, the liquid hydrocarbon polymer is a mixture of one or both of liquid polybutadiene and liquid styrene-butadiene copolymer; the number average molecular weight of the liquid hydrocarbon polymer is 4000 to 10000; and the 1,2 structure content is 50 to 90 wt% based on the total content of butadiene structural units.

[0012] A too low molecular weight will result in the introduction of a large amount of butyl lithium initiator during the polymerization process, significantly increasing costs. A too high molecular weight will increase the degree of entanglement in the macromolecular chain, reducing the dispersion of the modified liquid hydrocarbon polymer with polyphenylene ether and fillers. A too low 1,2 structure will reduce the reaction efficiency of mercaptocarboxylic acid in click chemistry. A 1,2 structure above 90% has no significant effect on the grafting rate of mercaptocarboxylic acid in click chemistry, and it is difficult to increase the 1,2 structure above 90% with existing technology.

[0013] Preferably, the method for preparing the carboxylated liquid hydrocarbon polymer comprises the following steps: (1) Preparation of liquid hydrocarbon polymers The liquid hydrocarbon polymer includes liquid polybutadiene and liquid styrene-butadiene copolymer; Preparation of liquid polybutadiene: cyclohexane, butadiene monomer, and polarity regulator are added to a reactor, stirred, and heated. An initiator is added to initiate the polymerization reaction. After termination, the reaction is metal-free and rotary distilled to obtain a liquid hydrocarbon polymer. Preparation of liquid styrene-butadiene copolymer: A three-step addition method is used. Cyclohexane and a certain amount of styrene are added to a reactor, stirred, and heated. An initiator is added to react to obtain a first-stage active product. A polarity regulator and butadiene are added to react to obtain a second-stage active product. A certain amount of styrene is added to terminate the reaction. The liquid styrene-butadiene copolymer is obtained by metal removal and rotary evaporation. (2) Preparation of carboxylated liquid hydrocarbon polymers: Cyclohexane and liquid hydrocarbon polymer are added to the reactor, stirred and dissolved, and then heated to 60-90°C. Mercaptocarboxylic acid and initiator are added, stirred and reacted, and then cooled to room temperature. After precipitation in ethanol, the mixture is washed and rotary evaporated to obtain a carboxylated liquid hydrocarbon polymer. In step (1), the polarity regulator is ditetrahydrofurfuryl propane and the initiator is n-butyl lithium; in step (2), the initiator is benzoyl peroxide.

[0014] The present invention also provides a resin composition comprising the modified liquid hydrocarbon polymer. The raw materials of the resin composition are, in parts by mass: Modified liquid hydrocarbon polymer: 25-50 parts; Vinyl polyphenylene ether: 25-50 parts; Inorganic filler: 30-60 parts; Cross-linking agent: 3-6 parts; Flame retardant: 10-20 parts.

[0015] Preferably, the inorganic filler is one or more of silicon dioxide, titanium dioxide, aluminum oxide, silicon nitride, and hollow glass microspheres; and the crosslinking agent is one or more of dicumyl peroxide, diisopropylbenzene hydroperoxide, di-tert-butyl diisopropylbenzene hydroperoxide, and benzoyl peroxide.

[0016] In addition, the present invention also provides an application of the resin composition, wherein the resin composition is used to prepare a laminate for copper-clad boards.

[0017] Preferably, the laminate is prepared by the following steps: (i) adding a resin composition containing a modified liquid hydrocarbon polymer to toluene and uniformly dispersing the resin composition to obtain a prepreg; wherein the mass ratio of the resin composition to toluene in the prepreg is 66 to 186:100; (ii) impregnating the prepreg with electronic glass fiber cloth and drying to obtain a prepreg for copper clad laminate; the drying temperature is 125 to 135° C., and the drying time is 5 to 15 minutes; (iii) stacking a plurality of prepregs, covering the upper and lower surfaces with copper foil, and laminating at high temperature to obtain the laminate; the high temperature lamination process is performed at a pressure of 2 to 4 MPa, a temperature of 190 to 240° C., and a lamination time of 2 to 5 hours.

[0018] The beneficial effects of the present invention are: The present invention utilizes the carboxyl groups in the carboxylated liquid hydrocarbon polymer and the hydroxyl groups in the fluorinated alkyl alcohol to carry out an esterification reaction. This preparation method not only realizes the covalent bonding of the fluorinated groups and the liquid hydrocarbon polymer, but also generates ester groups. The ester groups and residual carboxyl groups improve the compatibility with vinyl polyphenylene ether, solving the problem of hydrocarbon copper-clad laminates bursting due to composite resin delamination; strengthen the interfacial interaction with inorganic fillers, effectively limit the thermal motion of resin macromolecules, and reduce the thermal expansion coefficient of the copper-clad laminate; form hydrogen bonds with the surface active groups of the copper foil, and improve the peel strength. The fluorinated groups can improve the heat resistance and hydrophobicity of the liquid hydrocarbon polymer, offsetting the higher dielectric loss caused by the ester groups and residual carboxyl groups. By constructing a resin composition with excellent dielectric properties, it takes into account dielectric properties, thermal stability, copper foil adhesion and low thermal expansion coefficient, and has great application value in the field of high-frequency and high-speed copper-clad laminates. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the H-NMR spectrum of the liquid styrene-butadiene copolymer prepared by the present invention; Figure 2 is the H-NMR spectrum of the carboxylated liquid styrene-butadiene copolymer prepared in Example 1 of the present invention; Figure 3 is the H-NMR spectrum of the modified liquid styrene-butadiene copolymer prepared in Example 1 of the present invention; Figure 4 1 is a GPC spectrum of the carboxylated liquid styrene butadiene copolymer and the modified liquid styrene butadiene copolymer prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0020] The technical solutions of the present invention are further specifically described below through examples. These examples are provided for the purpose of illustrating the present invention and are not intended to limit the present invention. All other examples obtained by persons of ordinary skill in the art based on the examples in this application without creative work are intended to fall within the scope of protection of this application.

[0021] The experimental methods described in the examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0022] The mercaptopropionic acid, mercaptohexanoic acid, tridecafluorooctanol, perfluoroalkylethanol, 4-dimethylaminopyridine, and diisopropylbenzene peroxide used in the present invention were all purchased from Beijing Inokai Technology Co., Ltd.; silicon dioxide was purchased from Suzhou Jinyi New Materials Technology Co., Ltd. with a particle size of 5 μm; titanium dioxide was purchased from Shandong Guoci Functional Materials Co., Ltd. with a particle size of 7.5 μm; hollow glass microspheres were purchased from Zhengzhou Shenglait Hollow Microsphere New Materials Co., Ltd. with a particle size of 10 μm; and vinyl polyphenylene ether was purchased from SABIC with a brand name of SA9000 and a molecular weight of 1000.

[0023] Preparation of liquid styrene-butadiene copolymer 5 L of cyclohexane was added to a reactor repeatedly purged with nitrogen, and the temperature was raised to 45°C. 75 g of styrene and 37 ml of n-butyl lithium (2.2 M) were added and the reaction was carried out for 45 min. 8 g of ditetrahydrofurfuryl propane and 350 g of butadiene were added and the reaction was carried out for 60 min. 75 g of styrene was added and the reaction was continued for 45 min before being terminated with saturated carbonic acid. The terminated gel was added to deionized water, stirred thoroughly, and centrifuged to obtain a pure gel from which metals had been removed. After rotary evaporation, a liquid styrene-butadiene copolymer was obtained with a number average molecular weight of 6800. The H NMR spectrum of the prepared liquid styrene-butadiene copolymer is as follows: Figure 1 As shown, the 1,2 structure content is 60% after analysis. The analysis and calculation method is as follows: 1,2 structure content = {A(c) / [A(c)+A(a)]}×100% A(c) represents the peak area of ​​the two H groups on =CH2 in the double bond of the 1,2 structure; A(a) represents the peak area of ​​the two H groups on the -CH=CH- double bond in the 1,4 structure. Example 1

[0024] The preparation method of the modified liquid hydrocarbon polymer is as follows: (1) In a reaction flask equipped with a condenser and nitrogen atmosphere, add 1L of cyclohexane and 100g of liquid styrene-butadiene copolymer, stir and dissolve, then heat to 80°C, continue to add 10g of mercaptopropionic acid and 0.1g of benzoyl peroxide, stir and react for 6 hours, then cool to room temperature, place the resulting product in 3 times ethanol for precipitation, wash, and rotary evaporate to obtain a carboxylated liquid hydrocarbon polymer; the mercaptopropionic acid grafting rate is 8% as calculated by weighing method. The product is shown in the H NMR spectrum. Figure 2 As shown, the peak at chemical shift 2.76 is the displacement peak of H on the methylene -CH2 adjacent to the sulfur atom at d and e, and the peak at chemical shift 2.65 is the displacement peak of H on the methylene -CH2 adjacent to the carbonyl group, indicating that mercaptopropionic acid has been successfully grafted onto the liquid butadiene-styrene copolymer.

[0025] (2) In a reaction flask under nitrogen atmosphere, add 100g of the above carboxylated liquid styrene butadiene copolymer to 1L of toluene, stir thoroughly to dissolve, control the temperature to 25±2℃, add 15g of tridecafluorooctanol, stir thoroughly, add 0.2g of 4-dimethylaminopyridine and react for 22 hours, cool to room temperature, add the reaction solution to 5 times the volume of ethanol for precipitation, pour out the upper solution, wash with ethanol to remove unreacted tridecafluorooctanol and residual catalyst, and obtain the modified liquid styrene butadiene copolymer after rotary evaporation. The grafting rate of tridecafluorooctanol was calculated by weighing method to be 13.4%. The nuclear magnetic hydrogen spectrum of the obtained product is as follows: Figure 3 As shown in the figure, the peak at chemical shift 4.1 is the shift peak of the oxygen atom on the ester group adjacent to the H on the methylene -CH2, indicating that 13-fluorooctanol and the carboxylated liquid styrene-butadiene copolymer have undergone esterification reaction. At the same time, the GPC spectrum of the obtained product is shown in the figure. Figure 4 As shown in the figure, the GPC peak of the modified liquid styrene butadiene copolymer shifted to the left, the elution time shifted from 8.6 min of the carboxylated liquid styrene butadiene copolymer to 8.4 min, and the number average molecular weight increased from 6800 to 7700, which also indicated that esterification reaction occurred between tridecafluorooctanol and the carboxylated liquid styrene butadiene copolymer.

[0026] The resin composition containing a modified liquid hydrocarbon polymer comprises, by weight, 50 parts of modified liquid styrene-butadiene copolymer, 50 parts of vinyl polyphenylene ether, 50 parts of silicon dioxide, 5 parts of dicumyl peroxide crosslinking agent, and 15 parts of decabromodiphenylethane flame retardant. Example 2

[0027] The preparation method of the modified liquid hydrocarbon polymer is as follows: (1) In a reaction flask equipped with a condenser and nitrogen atmosphere, add 1 L of cyclohexane and 100 g of liquid styrene-butadiene copolymer, stir and dissolve, then heat to 80 °C, continue to add 8 g of mercaptopropionic acid and 0.1 g of benzoyl peroxide, stir and react for 6 hours, then cool to room temperature, place the resulting product in 3 times ethanol for precipitation, wash, and rotary evaporate to obtain a carboxylated liquid hydrocarbon polymer; the mercaptopropionic acid grafting rate was calculated by weighing method and was 6%.

[0028] (2) In a reaction flask under a nitrogen atmosphere, 100 g of the above-mentioned carboxylated liquid styrene butadiene copolymer was added to 1 L of toluene and thoroughly stirred to dissolve. The temperature was controlled at 25 ± 2 °C. 13 g of tridecafluorooctanol was added and thoroughly stirred. 0.13 g of 4-dimethylaminopyridine was added and the mixture was reacted for 22 hours. The mixture was cooled to room temperature. The reaction solution was added to 5 volumes of ethanol for precipitation. The upper layer solution was poured out and washed with ethanol to remove unreacted tridecafluorooctanol and residual catalyst. The modified liquid styrene butadiene copolymer was obtained after rotary evaporation. The grafting rate of tridecafluorooctanol was calculated to be 10.7% by weight.

[0029] The resin composition containing a modified liquid hydrocarbon polymer comprises, by weight, 50 parts of modified liquid styrene-butadiene copolymer, 50 parts of vinyl polyphenylene ether, 50 parts of silicon dioxide, 5 parts of dicumyl peroxide crosslinking agent, and 15 parts of decabromodiphenylethane flame retardant. Example 3

[0030] The preparation method of the modified liquid hydrocarbon polymer is as follows: (1) In a reaction flask equipped with a condenser and nitrogen atmosphere, add 1 L of cyclohexane and 100 g of liquid styrene-butadiene copolymer, stir and dissolve, then heat to 80 °C, continue to add 12 g of mercaptopropionic acid and 0.1 g of benzoyl peroxide, stir and react for 6 hours, then cool to room temperature, place the resulting product in 3 times ethanol for precipitation, wash, and rotary evaporate to obtain a carboxylated liquid hydrocarbon polymer; the mercaptopropionic acid grafting rate was calculated by weighing method to be 10%.

[0031] (2) In a reaction flask under a nitrogen atmosphere, 100 g of the above-mentioned carboxylated liquid styrene butadiene copolymer was added to 1 L of toluene and thoroughly stirred to dissolve. The temperature was controlled at 25 ± 2°C. 20 g of tridecafluorooctanol was added and thoroughly stirred. 0.34 g of 4-dimethylaminopyridine was added and reacted for 22 hours. The temperature was cooled to room temperature. The reaction solution was added to 5 times the volume of ethanol for precipitation. After decanting the upper layer, the solution was washed with ethanol to remove unreacted tridecafluorooctanol and residual catalyst. The modified liquid styrene butadiene copolymer was obtained after rotary evaporation. The grafting rate of tridecafluorooctanol was calculated by weight to be 18.5%.

[0032] The resin composition containing a modified liquid hydrocarbon polymer comprises, by weight, 50 parts of modified liquid styrene-butadiene copolymer, 50 parts of vinyl polyphenylene ether, 50 parts of silicon dioxide, 5 parts of dicumyl peroxide crosslinking agent, and 15 parts of decabromodiphenylethane flame retardant. Example 4

[0033] The preparation method of the modified liquid hydrocarbon polymer is as follows: (1) In a reaction flask equipped with a condenser and nitrogen atmosphere, add 1 L of cyclohexane and 100 g of liquid styrene-butadiene copolymer, stir and dissolve, then heat to 80 °C, continue to add 12.5 g of mercaptohexanoic acid and 0.12 g of benzoyl peroxide, stir and react for 6 hours, then cool to room temperature, place the resulting product in 3 times ethanol for precipitation, wash, and rotary evaporate to obtain a carboxylated liquid hydrocarbon polymer; the grafting rate of mercaptohexanoic acid was 10% as calculated by weighing method.

[0034] (2) In a reaction flask under a nitrogen atmosphere, 100 g of the above-mentioned carboxylated liquid styrene butadiene copolymer was added to 1 L of toluene and thoroughly stirred to dissolve. The temperature was controlled at 25 ± 2 °C. 6.5 g of perfluoroalkyl ethanol was added and thoroughly stirred. 0.35 g of 4-dimethylaminopyridine was added and reacted for 22 hours. The temperature was cooled to room temperature. The reaction solution was added to 5 times the volume of ethanol for precipitation. After decanting the upper layer, the solution was washed with ethanol to remove unreacted perfluoroalkyl ethanol and residual catalyst. The modified liquid styrene butadiene copolymer was obtained after rotary evaporation. The grafting rate of perfluoroalkyl ethanol was calculated by weighing method to be 5%.

[0035] The resin composition containing a modified liquid hydrocarbon polymer comprises, by weight, 50 parts of modified liquid styrene-butadiene copolymer, 50 parts of vinyl polyphenylene ether, 50 parts of silicon dioxide, 5 parts of dicumyl peroxide crosslinking agent, and 15 parts of decabromodiphenylethane flame retardant. Example 5

[0036] The difference between Example 5 and Example 1 is that the raw materials of the modified liquid hydrocarbon polymer resin composition, in parts by mass, include: Modified liquid styrene-butadiene copolymer: 50 parts; Vinyl polyphenylene ether: 25 parts; Silicon dioxide: 37 parts; Dicumyl peroxide crosslinking agent: 5 parts; Decabromodiphenylethane flame retardant: 15 parts; The rest are the same as in Example 1. Example 6

[0037] The difference between Example 6 and Example 1 is that the raw materials of the modified liquid hydrocarbon polymer resin composition, in parts by mass, include: Modified liquid styrene-butadiene copolymer: 25 parts; Vinyl polyphenylene ether: 50 parts; Silicon dioxide: 37 parts; Dicumyl peroxide crosslinking agent: 5 parts; Decabromodiphenylethane flame retardant: 15 parts; The rest are the same as in Example 1. Example 7

[0038] The difference between Example 7 and Example 1 is that the raw materials of the modified liquid hydrocarbon polymer resin composition, in parts by mass, include: Modified liquid styrene-butadiene copolymer: 50 parts; Vinyl polyphenylene ether: 50 parts; Hollow glass microspheres: 50 parts; Dicumyl peroxide crosslinking agent: 6 parts; Decabromodiphenylethane flame retardant: 10 parts; The rest are the same as in Example 1. Example 8

[0039] The difference between Example 8 and Example 1 is that the raw materials of the modified liquid hydrocarbon polymer resin composition, in parts by mass, include: Modified liquid styrene-butadiene copolymer: 50 parts; Vinyl polyphenylene ether: 50 parts; Silicon dioxide: 25 parts; Titanium dioxide: 25 parts; Dicumyl peroxide crosslinking agent: 6 parts; Decabromodiphenylethane flame retardant: 10 parts; The rest are the same as in Example 1.

[0040] Comparative Example 1 The liquid hydrocarbon polymer is not carboxylated and modified with a fluorinated alkyl alcohol. The resin composition of the modified liquid hydrocarbon polymer is characterized in that the raw materials include, in parts by mass: Liquid styrene butadiene copolymer: 50 parts; Vinyl polyphenylene ether: 50 parts; Silicon dioxide: 50 parts; Dicumyl peroxide crosslinking agent: 5 parts; Decabromodiphenylethane flame retardant: 15 parts.

[0041] Comparative Example 2 In a reaction flask equipped with a condenser and a nitrogen atmosphere, add 1 L of cyclohexane and 100 g of liquid styrene-butadiene copolymer. After stirring and dissolving, heat to 80°C, continue to add 10 g of mercaptopropionic acid and 0.1 g of benzoyl peroxide, stir and react for 6 hours, then cool to room temperature. The resulting product is placed in 3 times ethanol for precipitation, washed, and rotary evaporated to obtain a carboxylated liquid hydrocarbon polymer; the mercaptopropionic acid grafting rate calculated by weighing method is 8%; no fluorinated alkyl alcohol modification is performed.

[0042] The resin composition of the modified liquid hydrocarbon polymer comprises, in parts by mass, the following raw materials: Carboxylated liquid styrene butadiene copolymer: 50 parts; Vinyl polyphenylene ether: 50 parts; Silicon dioxide: 50 parts; Dicumyl peroxide crosslinking agent: 5 parts; Decabromodiphenylethane flame retardant: 15 parts.

[0043] Application Examples The resin compositions of Examples 1-8 and Comparative Examples 1-2 were used to prepare high-frequency and high-speed copper-clad laminates, respectively. The preparation method was as follows: (1) Add 150 parts of the resin composition to 100 parts of toluene and disperse evenly to obtain a prepreg; (2) impregnating the prepreg with electronic glass fiber cloth (Japan Nittobo NEA2116) and drying at 130°C for 10 minutes to obtain the semi-cured sheet for high-frequency and high-speed copper clad laminate; (3) Stack three layers of semi-cured sheets, cover the upper and lower surfaces with copper foil, and laminate at a pressure of 3 MPa and a temperature of 230°C for 3 hours to obtain a laminated board.

[0044] According to the IPC-TM650 test method, the dielectric constant, dielectric loss, peel strength, thermal delamination time T288, water absorption, and Z-axis thermal expansion coefficient (Z-CTE) of each laminate were tested. The results are shown in Table 1: Table 1

[0045] As can be seen from Table 1, the dielectric loss of the laminates prepared using the resin composition containing the modified liquid hydrocarbon polymer of the present invention in Examples 1 to 8 is less than or equal to 0.002, which can take into account dielectric properties, thermal stability, copper foil peel strength and low thermal expansion coefficient, and the overall performance of the copper clad laminate is excellent; while the liquid styrene butadiene copolymer in Comparative Example 1 is not subjected to chain carboxylation and fluorinated alkyl alcohol modification, the dielectric loss and thermal expansion coefficient are relatively high, and the thermal stability and peel strength are insufficient; the liquid styrene butadiene copolymer in Comparative Example 2 is only subjected to carboxylation modification, and the dielectric loss is relatively high, reaching 0.004. In summary, the modified liquid hydrocarbon polymer and its composition of the present invention have great application value in the field of high-frequency and high-speed copper clad laminates.

[0046] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A method for preparing a modified liquid hydrocarbon polymer, characterized in that: The modified liquid hydrocarbon polymer is obtained by esterification reaction of a carboxylated liquid hydrocarbon polymer and a fluorine-containing alkyl alcohol.

2. The method for preparing the modified liquid hydrocarbon polymer according to claim 1, characterized in that: The esterification reaction conditions of the carboxylated liquid hydrocarbon polymer and the fluorinated alkyl alcohol are as follows: the carboxylated liquid hydrocarbon polymer is added to toluene and stirred to dissolve; the temperature is controlled at 20-30° C., the fluorinated alkyl alcohol is added and stirred, a catalyst is added and reacted for 20-24 hours, the reaction solution is added to ethanol for precipitation, the upper layer solution is poured out, the precipitate is washed with ethanol, and rotary evaporated to obtain the modified liquid hydrocarbon polymer.

3. The method for preparing the modified liquid hydrocarbon polymer according to claim 1 or 2, characterized in that: The carboxylated liquid hydrocarbon polymer is obtained by grafting mercaptocarboxylic acid into a liquid hydrocarbon polymer through a thiol-ene click chemical reaction chain.

4. The method for preparing the modified liquid hydrocarbon polymer according to claim 3, characterized in that: The grafting rate of the carboxylated liquid hydrocarbon polymer is 5-10%; the mercaptocarboxylic acid is one or more of mercaptoacetic acid, mercaptopropionic acid, and mercaptocaproic acid.

5. The method for preparing the modified liquid hydrocarbon polymer according to claim 3, characterized in that: The liquid hydrocarbon polymer is a mixture of one or both of liquid polybutadiene and liquid styrene-butadiene copolymer; the number average molecular weight of the liquid hydrocarbon polymer is 4000-10000; and the 1,2 structure content is 50-90 wt% based on the total content of butadiene structural units.

6. The method for preparing a modified liquid hydrocarbon polymer according to claim 2, characterized in that: The fluorinated alkyl alcohol is tridecafluorooctanol or perfluoroalkyl ethanol, the catalyst is 4-dimethylaminopyridine, and the molar ratio of the catalyst to the fluorinated alkyl alcohol is 3-5:

100.

7. A resin composition, characterized in that The resin composition comprises the modified liquid hydrocarbon polymer according to any one of claims 1 to 6, and the raw materials of the resin composition are, in parts by mass: Modified liquid hydrocarbon polymer: 25-50 parts; Vinyl polyphenylene ether: 25-50 parts; Inorganic filler: 30-60 parts; Cross-linking agent: 3-6 parts; Flame retardant: 10-20 parts.

8. The resin composition according to claim 7, characterized in that The inorganic filler is one or more of silicon dioxide, titanium dioxide, aluminum oxide, silicon nitride, and hollow glass microspheres; the crosslinking agent is one or more of dicumyl peroxide, diisopropylbenzene hydroperoxide, di-tert-butyl diisopropylbenzene hydroperoxide, and benzoyl peroxide.

9. Use of the resin composition according to claim 7, characterized in that: The resin composition is used for preparing a laminate for copper clad plates.

10. Use of the resin composition according to claim 9, characterized in that: The laminate is prepared by the following steps: (i) adding a resin composition containing a modified liquid hydrocarbon polymer to toluene and uniformly dispersing the resin composition to obtain a prepreg; wherein the mass ratio of the resin composition to toluene in the prepreg is 66 to 186:100; (ii) impregnating the prepreg with electronic glass fiber cloth and drying to obtain a prepreg for copper clad laminate; the drying temperature is 125 to 135° C., and the drying time is 5 to 15 minutes; (iii) stacking a plurality of prepregs, covering the upper and lower surfaces with copper foil, and laminating at high temperature to obtain the laminate; the high temperature lamination process is performed at a pressure of 2 to 4 MPa, a temperature of 190 to 240° C., and a lamination time of 2 to 5 hours.

Images