WO2022182198A1 - Procédé de préparation d'un composé à base de vinyle - Google Patents

Procédé de préparation d'un composé à base de vinyle Download PDF

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Publication number
WO2022182198A1
WO2022182198A1 PCT/KR2022/002789 KR2022002789W WO2022182198A1 WO 2022182198 A1 WO2022182198 A1 WO 2022182198A1 KR 2022002789 W KR2022002789 W KR 2022002789W WO 2022182198 A1 WO2022182198 A1 WO 2022182198A1
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Prior art keywords
vinyl
monomer
group
based compound
compound
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PCT/KR2022/002789
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English (en)
Korean (ko)
Inventor
이은용
이지애
홍성호
정용수
황재석
이귀항
백미정
정원호
강성연
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주식회사 신아티앤씨
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Publication of WO2022182198A1 publication Critical patent/WO2022182198A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers

Definitions

  • the present invention relates to a method for producing a vinyl-based compound, and more particularly, to a method for producing a polymer compound including a substituent having a vinyl group.
  • the transmission loss of an electric signal may increase, which is a problem for this, and it is required for a material used as an insulating layer to have a low dielectric loss tangent.
  • a material used as an insulating layer to have a low dielectric loss tangent.
  • Silicon oxide which has been commonly used as a semiconductor insulating material, has a dielectric constant value of about 3.9 to 4.2, and an epoxy resin has a dielectric constant between 3.5 and 4.5 and a dielectric loss tangent of 10 -2 . Research on improving the dielectric properties of resins through blending with low-k resins has been conducted.
  • polyimide, benzoxyxlobutene, polynorbornene, etc. are used as materials with low dielectric properties to utilize physical properties such as excellent thermal stability, low absorption, and electrical and optical isotropy. Research is in progress, and research on a thermoplastic PPE resin with low dielectric properties is being conducted.
  • thermoplastic PPE resin In the case of thermoplastic PPE resin, it has excellent physical properties such as mechanical properties, heat resistance, electrical properties and dimensional stability, but due to its high glass transition temperature (Tg), overall fluidity and processability are not good, so there are limitations in commercialization. Research for developing a material having a low glass transition temperature and dielectric constant while improving solubility in organic solvents and adhesion to metals is further demanded.
  • Tg glass transition temperature
  • One aspect of the present invention is an invention devised to solve the problems of the prior art, which provides a polymer for manufacturing a 5G communication (5G) substrate having excellent heat resistance, low viscosity, high fluidity, and low dielectric properties. it has its purpose
  • One aspect of the present invention is
  • a method for producing a vinyl-based compound comprising:
  • the repeating number n of structure A is an integer satisfying 0 ⁇ n ⁇ 10, and A is an alkyl group, a cycloalkyl group, an aromatic compound, or a polymer thereof)
  • the first monomer is a compound containing a functional group, and preferably a compound containing at least two or more functional groups.
  • the step S2 is preferably a step of adding 30 to 60 parts by weight of the first monomer based on 100 parts by weight of the copolymer.
  • the ratio of the moles of the first monomer to the number of moles of the copolymer is preferably 0.3 to 1.0.
  • the S1 step is preferably performed using a phase transfer catalyst
  • the S2 step is preferably performed under a basic condition, and it is preferable to include a step of checking the progress of the reaction by tracking the amount of the halide remaining in the S2 step .
  • the second monomer is preferably a vinyl aromatic compound containing two or less vinyl groups
  • the second monomer is preferably a styrene monomer or divinylbenzene.
  • the method for producing a vinyl-based compound according to an aspect of the present invention includes phenol and dicyclopentadiene as monomers, and by modifying a styrene monomer in a vinyl-based compound, has excellent heat resistance, low viscosity, dielectric constant and dielectric loss. It has the advantage of being suitable for use in semiconductor substrates or printed circuit boards (PCB) because of its low low, and it is a manufacturing method capable of manufacturing a vinyl-based compound used as a substrate material having low dielectric properties for 5G use.
  • PCB printed circuit boards
  • the vinyl-based compound prepared according to the present invention satisfies the physical properties required for the use of copper clad laminates or electronic components used in printed circuit boards, so that sealing materials, molding materials, casting materials, adhesives, materials for electrical insulation paints, etc. It has the advantage of including a low dielectric characteristic while being able to have the use of.
  • the term comprise, comprises, comprising is meant to include the stated object, step or group of objects, and steps, and any other object. It is not used in the sense of excluding a step or a group of objects or groups of steps.
  • the first aspect of the present invention is a vinyl-based compound, wherein the vinyl-based compound is a compound in which a compound containing a vinyl group at the terminal is bonded to a phenol resin modified with an unsaturated cyclic hydrocarbon compound. dielectric properties can be realized.
  • the vinyl-based compound according to an aspect of the present invention is a compound including a structure represented by the following Chemical Formula 1.
  • structure A in Formula 1 is a polymer that is repeated n times, where n is an integer greater than or equal to 0 and less than or equal to 10.
  • n is preferably an integer of 1 or more and 10 or less
  • A may be a cycloalkyl group, an aryl group, or a polymer thereof, and a substituted or unsubstituted alkylaryl ether group Alternatively, it may be an atomic group including an ether group, such as an alkylphenyl ether group, and preferably has a structure represented by the following formula (2).
  • the cycloalkane structure included in Formula 1 is a structure in which double bond electrons react in cyclopentadiene to form two single bonds, and may be referred to as a dicyclopentadiene derivative, and is bonded to other compounds in the structure of the dicyclopentadiene derivative
  • the position and bonding direction of the single bond to be formed is not significantly limited.
  • the vinyl-based compound includes a benzene ring and oxygen bonded to the benzene ring at both ends, and the term phenol derivative is used below, including a benzene ring, oxygen bonded to the benzene ring, and a substituent bonded to oxygen.
  • the vinyl-based compound includes a phenol derivative at both ends, and a phenol derivative including R1 and a phenol derivative including R3 are included in the vinyl - based compound.
  • the vinyl-based compound may include a cyclic hydrocarbon structure having 10 carbon atoms derived from dicyclopentadiene (DCPD) as a part of A of Formula 1, and hereinafter, the cyclic hydrocarbon structure is dicyclopentadiene. It is referred to by the term diene derivative.
  • DCPD dicyclopentadiene
  • the vinyl-based compound may include a dicyclopentadiene derivative in the structure A of Formula 1.
  • R 1 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylalkyl group, or an allyl group.
  • substituted or unsubstituted alkyl group examples include methyl, ethyl, n-butyl, sec-butyl, tert-butyl, isopropyl, and pentyl groups.
  • the arylalkyl group refers to an alkyl group in which an aryl group including an aromatic ring is substituted, and is used to include alkylaryl, wherein the aryl group includes an aromatic ring and a substituted derivative thereof. , a phenyl group, a benzyl group, a naphthyl group, and the like.
  • a substituted or unsubstituted aryl group means an aryl group and a structure in which a part of the aryl group includes a substituent, for example, tolyl, vinylphenyl, and allylphenyl groups, etc. have.
  • the arylalkyl group means a substituent including both an aryl group and an alkyl group, and includes, for example, benzyl, vinylbenzyl, and alkylbenzyl, preferably vinylbenzyl or alkylbenzyl.
  • R 1 is preferably a carbon number greater than that of R 3 , specifically, a hydrocarbon having 9 to 25 carbon atoms, for example, an unsaturated alkyl group having 9 to 25 carbon atoms, an allyl group or an arylalkyl group, and the following formula It is good to have a structure of 3.
  • R 1 may have 17 to 25 carbon atoms, and a preferred embodiment of the present invention includes R 1 having 17 carbon atoms.
  • R 1 is a dimer in which two or more sp3 hybridized carbon and sp3 hybridized carbon bonded to oxygen in the phenol derivative structure of the vinyl compound and sp3 hybridized carbon are bonded to a benzene ring and contained as a substituent or two or more styrene monomers are polymerized ( It may include an oligomeric polymer structure such as a dimer) structure and a trimer structure.
  • R 1 is oxygen and methylene contained in the terminal phenol derivative of Formula 1 in which one aromatic ring in a structure including a styrene monomer having a structure including a substituent on an aromatic ring or a dimer or trimer polymer of a styrene monomer It is preferable to have a structure bonded to a group (-CH2-).
  • R 1 By including a styrene monomer, dimer or trimer structure, it may have an effect of lowering the dielectric constant during curing of the resin composition including the vinyl-based polymer, which is an aspect of the present invention.
  • R 2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylalkyl group, or an allyl group.
  • R 2 may not be included in the vinyl-based compound depending on the value of n in Formula 1, but the value of n in Formula 1 is preferably 1 or more, and R 2 is preferably included.
  • n in Formula 1 is preferably 1 or more
  • R 2 is preferably included.
  • a phenol derivative and a dicyclopentadiene derivative appear alternately, and a phenol derivative-dicyclopentadiene derivative may constitute a skeleton.
  • a skeleton composed of a phenol derivative - a dicyclopentadiene derivative shows a phenol derivative at both ends, and each phenol derivative includes a substituent in oxygen.
  • the molar ratio (dicyclopentadiene derivative/phenol derivative) of the dicyclopentadiene derivative and the phenol derivative contained in the vinyl-based compound is preferably less than 1.0, preferably 0.5 to 1.0.
  • the molar ratio of the dicyclopentadiene derivative and the phenol derivative is less than the corresponding range, the number of vinyl ends of the prepared vinyl compound is too small, the heat resistance is lowered, and there may be a problem in that the dielectric properties are deteriorated. If it is large, other monomers may be included instead of the phenol derivative of the entire compound, which may cause a problem in that dielectric properties are deteriorated.
  • R 2 may include a vinyl group at the terminal.
  • the vinyl-based compound includes two or more R 2 , and in this case, at least one of two or more R 2 may include a vinyl group.
  • R 2 does not contain a vinyl group
  • the number of vinyl groups in the total vinyl-based compound is too low, and the concentration of functional groups (vinyl groups) is lowered, so that the reactivity with other molecules is low, and the curing rate is slow or curing is not performed well. There may be, and the dielectric properties and dielectric loss may not be good even after curing.
  • R 2 is preferably an unsaturated hydrocarbon having 2 to 10 carbon atoms, preferably 3 to 9 carbon atoms.
  • R 2 is preferably a vinyl compound containing both sp3 hybridized carbon and sp2 hybridized carbon, and in particular, 2 or less sp3 hybridized carbons, preferably 1 or less.
  • the flexibility of R 2 increases, so there may be a problem in that the reactivity becomes too large or a reaction with other functional groups occurs in the molecule.
  • R 2 is more specifically, for example, an allyl group (Allyl), 1,3-pentadienyl group, vinylbenzyl group, cyclopentadienyl group or a piperylenyl group such as an isoprene group, preferably a piperylenyl group, more preferably It is preferable to include a structure of the following formula (4).
  • the -CH 2 - group which is an sp3 hybridized carbon, is bonded to the oxygen of the phenolic body, and due to the inclusion of a vinylbenzene or allyl group containing sp2 hybridized carbon, rotation is possible by an O-C single bond in R 2 . Because the three-dimensional structure of the compound can be flexibly changed, the orientation of the vinyl group included at the terminal is free, so that the reactivity can be improved, and due to the rigid double bond or unsaturated hydrocarbon structure containing the sp2 carbon contained therein It can effectively prevent polymerization or cyclization from proceeding between adjacent vinyl groups or vinyl groups in a molecule.
  • a preferred embodiment of the present invention includes a vinylbenzyl group as R 2 .
  • the vinylbenzene group of this embodiment is a structure obtained by the reaction of a -OH functional group of a phenol group with a vinylbenzene halide, and has the same structure as a methylene group (CH 2 ) is substituted with a styrene monomer to form a carbon-oxygen bond.
  • the position where the vinyl group is bonded to benzene is not limited, but it is preferable that it is an ortho- or para- position with respect to the benzyl carbon bonded to the phenol derivative by stabilization by resonance, etc., and steric hindrance, etc. Considering the para position is more preferable.
  • R 2 when a vinylbenzyl group is utilized as R 2 , since the styrene structure exposed at the terminal includes a vinyl group, the number of vinyl groups smaller than or equal to n, which is the repeating number of structure A, may be included in the vinyl-based compound, specifically, the vinyl-based compound.
  • R 2 of the vinylbenzyl group included in the compound may be 1 to 10.
  • n preferably satisfies the range of 0 to 10, and preferably n satisfies the range of 1 to 5.
  • n a vinyl-based compound having no structure A may be used, and when n is 10, a vinyl-based compound including 10 R 2 groups is used.
  • the concentration of the total vinyl groups included in the vinyl-based compound may vary depending on the number of vinyl groups included in R 2 included in the repeated structure A, and the concentration of the vinyl groups included in the vinyl-based compound is 1.0 ⁇ 10 -3 to 5.0 ⁇ 10 -3 mol/g, preferably 2.0 ⁇ 10 -3 to 4.0 ⁇ 10 -3 mol/g.
  • concentration of the vinyl group is less than the corresponding range, solvent compatibility and dielectric constant may be deteriorated, and if the concentration of the vinyl group is larger than the corresponding range, storage stability and curing speed control problems may occur.
  • R 3 is a substituent provided in the terminal phenol derivative of the vinyl-based compound, and may be a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylalkyl group, or an allyl group, preferably a hydrocarbon group including a vinyl group bonded to an aromatic ring. it's good
  • R 3 included in the vinyl-based compound of the present invention is an unsaturated hydrocarbon containing a vinyl group at the terminal and having 2 to 10 carbon atoms, preferably 3 to 9 carbon atoms, for example, it is preferable that the structure of the above formula (4) is It is also possible to include a structure in which divinylbenzene is polymerized to a vinylbenzyl group or a vinylbenzyl group.
  • R 3 is preferably a vinyl-based compound containing both sp3 hybridized carbon and sp2 hybridized carbon, and in particular, 4 or less sp3 hybridized carbons, preferably 1 or less.
  • the sum of the average number of carbon atoms of R 2 and the number of carbon atoms of R 3 is larger than the number of carbon atoms of R 1 .
  • the total molecular weight of the vinyl-based compound may be 200 to 2,000, preferably 400 to 1,000.
  • the vinyl-based compound according to an aspect of the present invention includes at least one vinyl group at the terminal, and in this case, R 1 to R 3 preferably include a vinyl group at the terminal, more preferably at least one R 2 and It is preferable that R 3 includes a vinyl group at the terminal.
  • R 1 includes a styrene polymer structure
  • the styrene monomer provided at the terminal does not include a vinyl group
  • R 1 having a structure not including a vinyl group is obtained at the end of the polymerization reaction.
  • R 1 at the terminal does not contain a vinyl group, there is an advantageous effect of preventing intramolecular polymerization or cyclization in the interior of the vinyl-based compound, and the length of the compound increases through the bond between the ends of the vinyl-based compound, resulting in a surface area
  • the effect of improving dielectric properties and dielectric loss after curing by forming a network structure of the vinyl-based compound by preventing the increase and forming a bond through the vinyl group contained therein can form a branch or cross-link.
  • R 1 and R 2 do not include a vinyl group
  • the concentration of the vinyl group included in the entire vinyl-based compound may be too low to reduce the dielectric effect, and since it becomes difficult for the vinyl-based compound to form a network structure, R It is preferable that at least one of 1 or R 2 , preferably R 2 has a structure having a vinyl group.
  • R 2 all have the same structure, and when R 2 all contain a vinyl group, when mixed with other polyfunctional polymers to form a resin composition, the dielectric constant and dielectric loss may be lowered, and the substrate for 5G A substrate having low dielectric constant and low dielectric loss characteristics can be manufactured during the manufacturing process.
  • R 3 does not contain a vinyl group or has a structure in which a styrene monomer is bonded to a vinyl group
  • the curing rate can be adjusted during peroxide curing, and the overall average molecular weight increases, thereby improving cracking during substrate manufacturing there is
  • a second aspect of the present invention is a method for producing the above-described vinyl-based compound.
  • the method for producing a vinyl-based compound includes several steps of reaction, a step of preparing a copolymer having a structure of the following formula (6) (S1), a first intermediate by bonding a first monomer including a vinyl group to the copolymer preparing a (S2), preparing a second intermediate by binding a second monomer to the first intermediate (S3), and coupling a third monomer to the second intermediate to prepare a vinyl compound (S4) include
  • n is an integer satisfying 0 ⁇ n ⁇ 10
  • A may be a cycloalkyl group, an aryl group, or a polymer thereof, and may be an atomic group including a substituted or unsubstituted alkylaryl ether or alkylphenyl ether group, , preferably having a structure of the following formula (2).
  • the dicyclopentadiene (or dicyclopentadiene) derivatives each independently have a random directionality, and may be oriented and bonded in the opposite direction to the direction shown in Formula 6,
  • the compound represented by the structure of Chemical Formula 6 includes all compounds having different directions of dicyclopentadiene derivatives.
  • the step of preparing the copolymer (S1) is a step of preparing a copolymer having the structure of Formula 5 and including a phenol derivative and a dicyclopentadiene (CPD) derivative, and phenol and dicyclopentadiene as shown in Formula 6
  • a polymerized copolymer obtained by polymerizing the may be prepared.
  • the first monomer is a compound containing a functional group, preferably a compound containing at least two or more functional groups, and preferably an aromatic compound containing at least one vinyl group as a functional group.
  • a chemical containing a vinyl group and an aromatic ring is the first monomer, and a vinyl benzyl halide compound may be used.
  • the vinylbenzyl halide preferably has a structure including a benzyl carbon in the styrene monomer including a vinyl group bonded to an aromatic benzene ring, and the position of the benzyl carbon is preferably an ortho- or para-position. .
  • the content of the polymer and the first monomer included in the reactant may be 30 to 60 parts by weight, preferably 40 to 50 parts by weight, of the first monomer based on 100 parts by weight of the copolymer, and the number of moles of the first monomer relative to the number of moles of the copolymer
  • the ratio is preferably 0.3 to 1.0, preferably 0.4 to 0.7.
  • the ratio of the first monomer to the copolymer is greater than the corresponding range, the first intermediate formed by polymerization is polymerized, resulting in increased viscosity and poor solvent compatibility. If it is smaller than the corresponding range, the first monomer is not sufficiently bound to the copolymer, so the physical properties are poor, and there may be a problem in that a by-product is formed during the subsequent reaction, thereby reducing the yield.
  • the catalyst is not limited as long as it is a catalyst that promotes the reaction of the polymer and the monomer, and any catalyst may be used as long as it is a catalyst within a range that can be employed by those skilled in the art, but preferably crown ether, quaternary ammonium salt, phospho It is preferable to use a phase transfer catalyst such as a phonium salt or DMSO.
  • An embodiment of the present invention promotes the reaction by using DMSO as a phase transfer catalyst.
  • a process of increasing the temperature in the range of 50 to 70° C. or performing stirring may be further included.
  • the organic solvent is not particularly limited as long as it is a solvent in which the reactant is well soluble, and a conventional organic solvent such as toluene, xylene, THF, dichloroethane, chloroform, methyl isobutyl ketone may be used.
  • the step (S2) of preparing a first intermediate by binding a first monomer including a vinyl group to the copolymer is a step of reacting the copolymer and the first monomer under catalytic conditions.
  • the step (S2) of preparing a first intermediate by binding a first monomer containing a vinyl group to the copolymer occurs under the conditions of a base such as sodium hydroxide, and the number of moles of an aqueous solution of sodium hydroxide, etc. calculated to optimize the reaction conditions
  • a base such as sodium hydroxide, and the number of moles of an aqueous solution of sodium hydroxide, etc. calculated to optimize the reaction conditions
  • a basic reagent may be added.
  • step S2 can be confirmed by tracing the amount of halide such as chloride remaining.
  • halide such as chloride remaining.
  • the phenolic compound contained in the copolymer reacts with the first monomer, vinylbenzene chloride, and XRF analysis By measuring the remaining chloride content through
  • Such a reaction may be advantageously carried out at both ends of the copolymer resin, and it is preferable that the reaction occurs only at either end of both ends, and it is also possible for the reaction to occur at both ends.
  • the first intermediate may be recovered by repeatedly performing separation processes such as washing with water, washing, and removing the layer after adjusting the pH by adding an organic solvent to the reaction vessel. If the number of repetitions is not limited, the yield of the first intermediate may increase as the number of repetitions increases.
  • the step (S3) of preparing the second intermediate by binding the second monomer to the first intermediate is a step of adding a new reactant, a second monomer, and a catalyst to further react the first intermediate.
  • the first intermediate and the second monomer may be dissolved in an organic solvent, and the same solvent as the solvent used in step S1 may be used, but it is also possible to use a different solvent.
  • the second monomer is a compound containing a functional group, preferably a vinyl aromatic compound containing a vinyl group as a functional group, and the number of functional groups is not limited, but preferably includes two or less functional groups. It is preferable to use a monofunctional unsaturated aromatic compound containing one vinyl group, such as styrene, or a bifunctional compound such as divinylbenzene having a divinyl group, and a mixture thereof as the second monomer.
  • a process of raising the temperature in the range of 40 to 70° C. or performing agitation may be further included.
  • the contents of the first intermediate and the second monomer included in the mixture of the first intermediate and the second monomer 10 to 30 parts by weight of the second monomer, preferably 20 to 25 parts by weight based on 100 parts by weight of the first intermediate. and the ratio of moles of the first intermediate to the number of moles of the second monomer is preferably 0.1 to 1.5, preferably 0.8 to 1.2.
  • the ratio of the second monomer to the first intermediate is greater than the corresponding range, the molecular weight of the reactant increases during the reaction, so the solvent compatibility is lowered and a precipitation problem may occur.
  • the step (S3) of preparing the second intermediate by binding the second monomer to the first intermediate is a step of causing a reaction by adding a catalyst to the mixture of the first intermediate and the second monomer.
  • the catalyst used is not limited, but three It is preferable that boron fluoride (BF 3 ) or an ether complex of boron trifluoride, for example, diethyl ether or the like is used.
  • the reaction is preferably carried out for 1 to 10 hours at a temperature range of 50 to 100 °C, preferably for 4 to 6 hours at a temperature condition of 70 °C.
  • the neutralizing agent is not limited, but preferably a weak acid or weakly basic aqueous solution such as an aqueous sodium hydrogen carbonate solution, and the separation and purification of the second product can be accomplished by repeatedly performing methods such as washing with water, washing, and recovery under reduced pressure.
  • the step (S4) of preparing a vinyl compound by binding the third monomer to the second intermediate is a step of mixing and dissolving the third monomer capable of reacting with the second intermediate.
  • the second intermediate, the catalyst, and the third monomer are added to the organic solvent and then dissolved.
  • the organic solvent used is not limited, but the same organic solvent as the solvent used in the previous step may be used, and other organic solvents may be used do.
  • a process of raising the temperature to a range of 50 to 70° C. or performing stirring may be further included for uniform mixing of the reactants.
  • the third monomer is a compound containing a functional group, preferably a compound containing at least two or more functional groups, and preferably a divinyl aromatic compound containing a vinyl group as a functional group.
  • the third monomer may be a monomer having a structure different from that of the second monomer, and an embodiment of the present invention discloses a method for preparing a copolymer in which the third monomer and the first monomer are the same compound.
  • the catalyst used in the vinyl-based compound preparation step (S4) is preferably a phase transfer catalyst, and it is also possible to use the same catalyst as the catalyst used in the first intermediate preparation step.
  • the second intermediate and the third monomer included in the reactant 15 to 35 parts by weight of the third monomer, preferably 20 to 30 parts by weight, based on 100 parts by weight of the second intermediate, and the amount of the third monomer
  • the mole ratio of the second intermediate to the number of moles is preferably 0.1 to 1.5, preferably 0.8 to 1.2.
  • the solvent compatibility during the reaction may cause a precipitation problem. have.
  • the vinyl-based compound preparation step (S4) may proceed in substantially the same manner as the first intermediate preparation step (S2), and when the same compound as the first monomer is used as the third monomer, the reaction of the same or similar mechanism may proceed. have.
  • the first intermediate and the third intermediate include a vinyl group
  • the concentration of the vinyl group of the third intermediate is preferably higher than or equal to the concentration of the vinyl group of the first intermediate, and the ratio is 1 to 11 times.
  • the first intermediate includes one vinyl group regardless of the value of n in the structure of Formula 6, and the third intermediate includes a vinyl group bonded to R 3 and a vinyl group bonded to n R 2 , so in the third intermediate
  • the total number of vinyl groups included is n+1, and since the range of n is 0 or more and 10 or less, the ratio of the first intermediate to the third intermediate is 1 to 11 times.
  • the vinyl group concentration of the second intermediate is lower than or equal to the vinyl group concentration of the first intermediate and the third intermediate, preferably lower than the vinyl group concentration of the first intermediate.
  • the low-k resin composition comprises a vinyl-based compound having the above-described characteristics or a vinyl-based compound prepared by the above-described manufacturing method.
  • the vinyl-based compound is preferably a copolymer having the above-described structure or a copolymer prepared by the above-described manufacturing method, and the contents of the vinyl-based compound are omitted within the overlapping range with the above-mentioned contents.
  • the low-k resin composition may include an unsaturated compound including a reactive unsaturated group.
  • the unsaturated compound is not limited, but physical properties and dielectric properties of the resin composition may vary depending on the composition and number of unsaturated groups, for example, bismaleimide-based compounds, diallyl phthalate, diallyl terephthalate, diallyl male Eate, diallyl fumarate, diallyl itaconate, diallyl adipate, diallyl ether, triallyl cyanurate, triallyl isocyanurate, ethylene glycol divinyl ether, n-butanediol divinyl ether, octadecane divinyl ether, vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol diacrylate, At least one compound of triethylene glycol diacrylate, poly
  • each unsaturated compound containing a reactive unsaturated group may be included, and each unsaturated compound may be included in an amount of 5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the vinyl-based compound, More preferably, it is included in an amount of 15 to 20 parts by weight.
  • the total of the unsaturated compound may be 5 to 50 parts by weight based on 100 parts by weight of the vinyl-based compound, preferably 20 to 40 parts by weight, and more preferably 30 to 35 parts by weight.
  • the blending amount of the unsaturated compound is less than the corresponding range, the degree of bonding within the molecule may be lowered and the dielectric constant and heat resistance of the composition may deteriorate. The outgasing phenomenon in which the compounds not included in the system are lost may occur and the heat resistance may decrease.
  • the ratio of the blending weight of the first unsaturated compound included in a relatively equal or greater weight among the blended unsaturated compounds to the blending weight of the second unsaturated compound included in a relatively small amount is 1.0 to 2.0, preferably 1.0 to 1.2.
  • the dielectric constant and heat resistance may deteriorate during curing, and even if it is out of the corresponding range, similarly, the dielectric constant or heat resistance may be deteriorated.
  • the low-k resin composition includes an initiator for polymerization.
  • the initiator is included to proceed the polymerization reaction of the unsaturated compound, the type of the initiator is not limited, and a thermal polymerization initiator or photoinitiator capable of supplying free radicals may be used, for example, organic peroxide, hydroperoxide, oxidation -Reducing agents, azo compounds, organometallic reagents, etc.
  • dialkyl peroxide preferably dialkyl peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, 2,3-dichlorobenzoyl peroxide, lauroyl peroxide, dicumyl Peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (1-hydroxycyclohexyl peroxide), cumene hydroperoxide, t-butyl hydroperoxide, dibenzyl peroxide, diso
  • a peroxide such as propyl peroxycarbonate or an azo compound such as azobisisobutylonitrile is used.
  • the resin composition may be reacted with a curing agent to form a cured resin product.
  • a curing agent a conventionally known curing agent may be used, and the curing agent is not particularly limited, and examples thereof include an amine-based compound, an anhydride-based compound, an amide-based compound, a compound having a phenolic structure, and an imidazole-based compound.
  • the resin composition is cured to obtain a cured product, and the obtained cured product may provide a cured resin with low dielectric constant and low dielectric loss having a low dielectric constant.
  • a vinyl-based compound was synthesized and obtained in the same manner as in Example 1, except that a mixture of a styrene monomer and divinylbenzene was used instead of a styrene monomer in Example 1.
  • Reaction and separation were performed in the same manner as in Example 1, except that a polymer in which cresol and naphthalene are alternately polymerized was used instead of a polymer in which phenol and dicyclopentadiene were alternately polymerized to obtain a vinyl compound as a final product. obtained.
  • the dielectric constant (D k ) and the dielectric loss (D f ) of the sample were measured as JIS-C-6481 using an Agilent E4991A RF Impedence/Material analyzer. It was measured at a frequency of 1 GHz, and T g (glass transition temperature, T d (decomposition temperature), SP (softening point) was measured using a differential thermal analyzer (DSC).
  • DSC differential thermal analyzer
  • the decomposition temperature was recorded by measuring the temperature when the weight of the sample decreased by 1%, 3%, or 5%, and when there was no glass transition, it was expressed as TgL.
  • Example 4 Example 5 Example 6 Comparative Example 3 Comparative Example 4 D k 2.70 2.75 2.80 2.78 2.80 D f 0.0022 0.0035 0.0067 0.0075 0.0043 T d (-1/-3/-5) 390/410/418 388/407/420 380/398/410 377/391/399 380/400/408 T g (DSC) TgL TgL TgL TgL S.P. 60 °C 50 °C 90 °C 50 °C 100 °C
  • Example 5 the softening point of the resin composition fell, and rather good heat resistance was obtained.
  • the resin composition of Example 4 showed a lower D k value of 2.70 than the resin compositions of Comparative Examples 3 and 4, and a D f value of 0.0022, Comparative Examples 3 and 4 of 50% or less, indicating that the Df value was low during curing of the resin composition including the vinyl-based compound of Example 1, indicating that the low dielectric properties were excellent.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Un aspect de la présente invention concerne un procédé de préparation d'un composé à base de vinyle comprenant une étape de préparation d'un copolymère ayant la structure de formule chimique 1 (S1) ; une étape de préparation d'un premier intermédiaire par addition d'un premier monomère contenant un groupe vinyle au copolymère (S2) ; une étape de préparation d'un second intermédiaire par addition d'un deuxième monomère au premier intermédiaire (S3) ; et une étape de préparation d'un composé vinylique par addition, au second intermédiaire (S4), d'un troisième monomère contenant un noyau aromatique et un groupe vinyle lié au noyau aromatique.
PCT/KR2022/002789 2021-02-25 2022-02-25 Procédé de préparation d'un composé à base de vinyle WO2022182198A1 (fr)

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KR20190090020A (ko) * 2016-12-16 2019-07-31 노보셋, 엘엘씨 수지 조성물
KR20200021079A (ko) * 2017-07-26 2020-02-27 셍기 테크놀로지 코. 엘티디. 열경화성 수지 조성물, 이로 제조된 프리프레그, 금속박 적층판 및 고주파 회로기판
WO2020059625A1 (fr) * 2018-09-18 2020-03-26 Dic株式会社 Composé phénolique, résine d'ester actif, procédé de production de résine d'ester actif, composition de résine thermodurcissable, et produit durci de composition de résine thermodurcissable
US20200263031A1 (en) * 2019-02-20 2020-08-20 A.C.R. Tech Co., Ltd. Resin, copper clad laminate made of resin, and printed circuit board

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KR101059778B1 (ko) 2004-10-21 2011-08-26 재단법인서울대학교산학협력재단 유기 용매에 대한 용해도가 우수한 저유전성 노보넨계공중합체

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KR20190090020A (ko) * 2016-12-16 2019-07-31 노보셋, 엘엘씨 수지 조성물
KR20200021079A (ko) * 2017-07-26 2020-02-27 셍기 테크놀로지 코. 엘티디. 열경화성 수지 조성물, 이로 제조된 프리프레그, 금속박 적층판 및 고주파 회로기판
WO2020059625A1 (fr) * 2018-09-18 2020-03-26 Dic株式会社 Composé phénolique, résine d'ester actif, procédé de production de résine d'ester actif, composition de résine thermodurcissable, et produit durci de composition de résine thermodurcissable
US20200263031A1 (en) * 2019-02-20 2020-08-20 A.C.R. Tech Co., Ltd. Resin, copper clad laminate made of resin, and printed circuit board

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