WO2019019482A1 - Low polarity resin, and preparation method therefor and use thereof - Google Patents

Low polarity resin, and preparation method therefor and use thereof Download PDF

Info

Publication number
WO2019019482A1
WO2019019482A1 PCT/CN2017/110810 CN2017110810W WO2019019482A1 WO 2019019482 A1 WO2019019482 A1 WO 2019019482A1 CN 2017110810 W CN2017110810 W CN 2017110810W WO 2019019482 A1 WO2019019482 A1 WO 2019019482A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
chloride
reaction
phenolic
combination
Prior art date
Application number
PCT/CN2017/110810
Other languages
French (fr)
Chinese (zh)
Inventor
苏民社
Original Assignee
广东生益科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Publication of WO2019019482A1 publication Critical patent/WO2019019482A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J125/00—Adhesives based on 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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Definitions

  • the invention belongs to the technical field of thermosetting resins, and relates to a low polarity resin and a preparation method and application thereof.
  • thermosetting resins are widely used in aerospace, rail transit, power insulation, microelectronic packaging due to their excellent heat resistance, flame retardancy, weather resistance, electrical insulation, good mechanical properties and dimensional stability. Resin matrix, high temperature insulation materials and adhesives for composite materials in other fields. Commonly used high-performance thermosetting resins are epoxy resin, phenolic resin, bismaleimide resin, etc., but the above-mentioned resin has brittleness, resulting in insufficient impact resistance of the material, and the resin has a high molecular structure polarity, resulting in high dielectric constant and loss. Weaknesses have limited its promotion and application in certain fields. Research on thermosetting resin modification has always been a research topic of concern for material workers.
  • thermosetting resins typified by bismaleimide resins have been used in aerospace radar radomes, rail transit circuit insulation materials and microelectronic circuit boards.
  • the ordinary high temperature resistant thermosetting resin has high dielectric constant and loss, and its transmission insulation performance cannot be improved.
  • CN104311756A discloses a silicon-containing bismaleimide resin with the introduction of a silicon-containing group which reduces the dielectric constant to below 3.0.
  • CN104479130A discloses a novel double horse monomer having a fluorine-containing structure, which significantly reduces the dielectric constant and loss of the bismale resin.
  • the above-mentioned novel structure double horse monomer synthesis process is complicated, high in cost, and difficult Batch preparation and application.
  • copolymerization modification by other resins is one of the important methods to improve the insulation properties of thermosetting resins.
  • CN101338032A discloses the preparation of a prepreg using a cyanate-modified bismale resin, and the dielectric constant and loss of the composite material are significantly reduced.
  • this method has certain effects on improving the dielectric properties of the resin, but the degree is limited, and there is still a certain gap in the distance application.
  • the resin of the present invention does not contain a polar group (for example, a hydroxyl group), has low molecular polarity, high reactivity, lowers the dielectric constant and loss of the cured product, and overcomes the high frequency dielectric constant caused by the polarity of the general thermosetting resin. And the defect with high loss, at the same time, the resin has a highly active unsaturated group, and the high temperature resistance is remarkably improved by the crosslinking curing reaction with other resins.
  • a polar group for example, a hydroxyl group
  • the present invention adopts the following technical solutions:
  • the invention provides a low polarity resin having the structure of Formula I below:
  • R is a linear or branched alkyl group, -O-, X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two; A is a group containing an unsaturated double bond, and n is 1-20. Integer.
  • the low polarity means that it does not contain a polar group, especially does not contain a hydroxyl group, so that the resin has a lower polarity, overcoming the polarity of the universal thermosetting resin.
  • Large-scale high-frequency dielectric constant and high-loss defects, and cross-linking curing can be achieved by structures such as allyl groups and other unsaturated double-bond groups in the structure, which significantly improves high-temperature resistance and ensures curing. Mechanical strength.
  • said R is a C1-C6 (eg C1, C2, C3, C4, C5 or C6) linear alkyl group or a C3-C6 (eg C3, C4, C5 or C6) branched alkyl group, in particular Can be -CH 2 -, Wait.
  • C1-C6 eg C1, C2, C3, C4, C5 or C6
  • C3-C6 eg C3, C4, C5 or C6 branched alkyl group
  • R is -CH 2 -, -O-, -CH 2 -O-, n is an integer of 1-20, and X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two, and A is a group containing an unsaturated double bond. group.
  • n is an integer of 1-20, for example, n may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 , 18, 19 or 20.
  • R' is a linear alkyl group of C1-C6 (eg C1, C2, C3, C4, C5 or C6) or a C3-C6 (eg C3, C4, C5 or C6) branched alkyl group, for example -CH 2 -, -CH 2 CH 2 -, Wait.
  • C1-C6 eg C1, C2, C3, C4, C5 or C6
  • C3-C6 eg C3, C4, C5 or C6 branched alkyl group
  • X and Y are independently C1-C21 (eg, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, a linear alkyl group of C19, C20 or C21) or C3-C21 (eg C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19) , C20 or C21) branched alkyl.
  • C1-C21 eg, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19
  • the low polarity resin is any one or a combination of at least two of the compounds having the structure represented by the following formula A-form D:
  • n is an integer from 1-20.
  • the present invention provides a method of preparing a low polarity resin as described above, the method comprising the steps of:
  • R 1 is a linear or branched alkyl group, -O-
  • R 2 is a linear or branched alkyl group, -O-
  • R 3 is a linear or branched alkyl group, -O-
  • R is a linear or branched alkyl group, -O-
  • X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two
  • A is a group containing an unsaturated double bond
  • n is 1-20. Integer.
  • step (2) when R 2 is In the case where the allyl ether group therein is rearranged, resulting in the intermediate unit R 3 of the allylated phenolic resin of the formula IV containing an allyl group due to rearrangement, and further in the product formula I
  • the R unit of the low-polarity resin shown includes allyl groups due to rearrangement, and the simple expression in the present invention does not directly represent the allyl group to the corresponding structures of R 3 and R, but only by X.
  • X contains allyl groups due to rearrangement
  • the benzene ring carries other substituents X, after the rearrangement reaction of step (2), then the structure of R 3
  • the middle X may represent a combination of allyl groups produced by rearrangement and other substituents before the reaction.
  • R 2 is also included.
  • R 2 unit allyl ether group rearrangement reaction does not occur at this time, the reaction product of R 3 and R before the reaction of X in the allyl ether of formula III in the resin of R 2 X
  • the groups are the same.
  • the phenolic compound or the phenolic resin in the step (1) is a phenol, a dihydric phenol, a polyhydric phenol or a derivative thereof, preferably phenol, o-cresol, bisphenol A, bisphenol F, tetramethyl Any one or a combination of at least two of bisphenol A, a phenol resin, an o-cresol novolac resin, or a cyclopentadiene phenol resin.
  • the allylation reagent is any one or a combination of at least two of allyl silanol, allyl chloride, allyl bromide, allyl iodide or allylamine.
  • the molar ratio of the phenolic hydroxyl group to the allyl group in the phenolic resin is 1: (0.3 to 1.2), for example, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1 or 1:1.2.
  • the reaction of the step (1) is carried out in the presence of a basic substance, preferably any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate or a combination of at least two.
  • a basic substance preferably any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate or a combination of at least two.
  • the molar ratio of the basic substance to the phenolic hydroxyl group contained in the phenolic compound or the phenolic resin in the step (1) is (0.3 to 1.4):1, for example, 0.3:1, 0.4:1, 0.5: 1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1 or 1.4:1.
  • step (1) is carried out in the presence of a phase transfer catalyst.
  • the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioxane Any one or a combination of at least two of methylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride.
  • the phase transfer catalyst is added in an amount of 0.1-5%, such as 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, of the mass of the phenolic compound or the phenolic resin in the step (1). 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5%.
  • the solvent of the reaction in the step (1) is any one of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent or a combination of at least two, preferably ethanol, propanol, butanol, toluene or xylene Any one or a combination of at least two.
  • the solvent is added in an amount of the phenolic compound or the phenolic resin of the step (1). 2-5 times, for example 2, 2.3, 2.5, 2.8, 3, 3.3, 3.5, 3.8, 4, 4.3, 4.5, 4.8 or 5 times.
  • the temperature of the reaction in the step (1) is 60-90 ° C, such as 60 ° C, 63 ° C, 65 ° C, 68 ° C, 70 ° C, 75 ° C, 78 ° C, 80 ° C, 85 ° C, 88 ° C or 90 °C.
  • the reaction time of the step (1) is 4-6 hours, such as 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
  • the protective gas in step (2) is nitrogen or argon.
  • the heating in step (2) is heating to 180-220 ° C, such as 180 ° C, 185 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C, 215 ° C or 220 ° C.
  • the reaction time in the step (2) is 4-6 hours, such as 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
  • the hydroxyl-terminated reagent containing an unsaturated double bond group in the step (3) is a halogenated compound, an acid anhydride or an acid chloride containing an unsaturated double bond group which can be etherified and esterified with a phenolic hydroxyl group.
  • a halogenated compound an acid anhydride or an acid chloride containing an unsaturated double bond group which can be etherified and esterified with a phenolic hydroxyl group.
  • the molar ratio of the phenolic hydroxyl group in the allylated phenolic resin represented by the formula III in the step (3) to the terminal group in the hydroxyl-terminated reagent containing an unsaturated double bond group is 1: (1) 1.2), for example 1:1, 1:1.05, 1:1.1, 1:1.15 or 1:1.2.
  • the phenolic hydroxyl group in the molecular structure of the resin obtained by the reaction is completely blocked by a terminal group containing an unsaturated double bond group, so that the resin has no polar hydroxyl group.
  • the reaction of the step (3) is carried out in the presence of a basic substance.
  • the basic substance is an inorganic base or an organic base, preferably any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.
  • the molar ratio of the basic substance to the phenolic hydroxyl group in the allylated phenolic resin represented by Formula III is (1 to 1.4): 1, for example, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1 or 1.4:1.
  • step (3) is carried out in the presence of a phase transfer catalyst.
  • the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioxane Any one or a combination of at least two of methylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride.
  • the phase transfer catalyst is added in an amount of 0.1-5%, such as 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, of the mass of the allylated phenolic resin of the step (3). 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5%.
  • the solvent of the reaction in the step (3) is any one of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent or a combination of at least two, preferably ethanol, propanol, butanol, toluene or xylene Any one or a combination of at least two.
  • the solvent is added in an amount of 2-5 times, for example, 2 times, 2.3 times, 2.5 times, 2.8 times, 3 times, 3.3 times, 3.5, of the mass of the allylated phenolic resin in the step (3). Times, 3.8, 4, 4.3, 4.5, 4.8 or 5 times.
  • the temperature of the reaction in the step (3) is 40-90 ° C, for example 40 ° C, 45 ° C, 48 ° C, 50 ° C, 55 ° C, 58 ° C, 60 ° C, 63 ° C, 65 ° C, 68 ° C, 70 °C, 75°C, 78°C, 80°C, 85°C, 88°C or 90°C.
  • the hydroxyl-terminated reagent containing an unsaturated double bond group used in the step (3) is vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl bromide, m-vinylbenzyl chloride.
  • the temperature of the reaction in the step (3) is 60-90 ° C;
  • the hydroxy-terminated reagent containing the unsaturated double bond group used in the step (3) is acryloyl chloride, acrylic anhydride, methacrylic anhydride
  • the temperature of the reaction described in the step (3) is 40 to 90 °C.
  • the reaction time in the step (3) is 4-6 hours, such as 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
  • the resin prepared by the method of the invention does not contain polar hydroxyl groups, has stable molecular structure, has low molecular polarity and high reactivity, and does not generate polar hydroxyl groups in the processing process thereof, avoiding The effect of the resulting secondary hydroxyl groups on the properties of their products.
  • the preparation method of the present invention can significantly improve the softening point of the resin by rearranging the combination of the hydroxyl group-capping reagent containing the unsaturated double bond group to the phenolic hydroxyl group, thereby being more suitable for the preparation and improvement of the solid prepreg. Resin molding process performance.
  • the softening point of a typical allyl phenolic resin can be increased from 20 ° C to 90 ° C.
  • the present invention provides the use of a low polarity resin as described above in the preparation of a resin composite.
  • the low-polarity resin of the present invention can be used for one of the components of the matrix resin in the resin composite material, and can be co-crosslinked and cured with other thermosetting resins such as bismaleimide, and the dielectric constant and dielectric loss of the resin are remarkably lowered.
  • the resin composite material may be an aerospace wave-transparent composite material, a power insulating material, a resin composite material for electronic packaging, and a resin composite material for a copper-clad laminate.
  • the invention provides the use of a low polarity resin as described above in the preparation of electronic packaging materials.
  • the low-polarity resin of the invention has the characteristics of low molecular polarity and high reactivity, and can also be applied to preparation of materials such as electronic packaging adhesives and potting resins.
  • the present invention provides the use of a low polarity resin as described above in the preparation of a metal foil laminate.
  • the low polarity resin of the present invention can be used for one of the components of the matrix resin in the resin composite material, It can be co-crosslinked and cured with other thermosetting resins such as bismaleimide, which significantly reduces the dielectric constant and dielectric loss of the resin. It is used in the preparation of metal foil-clad laminates to reduce the dielectric of metal foil-clad laminates. The constant and dielectric loss make the metal foil laminate have good overall performance.
  • the present invention has the following beneficial effects:
  • the resin of the invention does not contain a polar hydroxyl group, has a stable molecular structure, has the characteristics of low molecular polarity and high reactivity, and does not generate polar hydroxyl groups in the processing process of the application, thereby avoiding secondary generation.
  • the effect of hydroxyl on the properties of the product, improving the dielectric properties, the resin with highly reactive unsaturated groups, significantly improving the high temperature resistance by crosslinking curing reaction with other resins, significantly lowering the dielectric constant and dielectric of the resin Loss, which is used in the preparation of metal foil-clad laminates, is advantageous for reducing the dielectric constant and dielectric loss of the metal foil-clad laminate, and significantly improving the high temperature resistance, so that the metal foil-clad laminate has good comprehensive performance.
  • Example 1 is an infrared spectrum diagram of a low polarity resin prepared in Example 1.
  • a low polarity resin is prepared by the following method, including the following steps:
  • a low polarity resin is prepared by the following method, including the following steps:
  • a low polarity resin is prepared by the following method, including the following steps:
  • a low polarity resin is prepared by the following method, including the following steps:
  • Example 5 The only difference from Example 5 was that the 2-allylphenyl(3-vinyl)benzyl ether obtained in Example 1 was replaced with the methacrylated allyl phenolic resin prepared in Example 2.
  • Example 5 The only difference from Example 5 is that the 2-allylphenyl(3-vinyl)benzyl ether prepared in Example 1 is replaced by the acrylated allylcyclopentadiene phenolic prepared in Example 4. Resin.
  • the low polarity resin prepared by the invention can make the copper clad plate have lower dielectric constant and dielectric loss, and has better high temperature resistance, flame retardant performance and good process formability.
  • the present invention describes the low-polarity resin of the present invention and its preparation method and application by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented by relying on the above embodiments. . It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the materials selected for the present invention, and the addition of the auxiliary ingredients, the selection of the specific means, etc., are all within the scope of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

The present invention provides a low polarity resin, and a preparation method therefor and the use thereof. The low polarity resin has a structure as shown in formula I and is based on a phenolic compound or resin, and prepared by a three-step reaction of allyl etherification, rearrangement and terminating phenolic hydroxyl groups with a hydroxyl-terminated reagent containing an unsaturated double bond group. The resin does not contain polar hydroxyl groups in the molecular formula thereof, has a stable molecular structure, low polarity and high reactivity, and does not generate polar hydroxyl groups during application and processing, thereby avoiding the influence of secondary hydroxyl groups on the performance of products thereof, and improving the dielectric performance. The resin bears highly active unsaturated groups, and significantly improves the resistance to high temperature by a cross-linking and curing reaction with other resins, and significantly reduces the dielectric constant and dielectric loss of the resin. The use of the resin in the preparation of a metal foil clad laminate facilitates reducing the dielectric constant and dielectric loss of the metal foil clad laminate, and results in higher resistance to high temperature, such that the metal foil clad laminate has good comprehensive properties.

Description

一种低极性树脂及其制备方法和应用Low polarity resin and preparation method and application thereof 技术领域Technical field
本发明属于热固性树脂技术领域，涉及一种低极性树脂及其制备方法和应用。The invention belongs to the technical field of thermosetting resins, and relates to a low polarity resin and a preparation method and application thereof.
背景技术Background technique
高性能热固性树脂以其优异的耐热性、阻燃性、耐候性、电绝缘性，良好的力学性能和尺寸稳定性等特点，被广泛应用于航空航天、轨道交通、电力绝缘、微电子封装等领域复合材料的树脂基体、耐高温绝缘材料和胶粘剂等。常用的高性能热固性树脂有环氧树脂、酚醛树脂、双马来酰亚胺树脂等，但上述树脂存在着脆性导致材料抗冲击能力不足，树脂分子结构极性大导致介电常数和损耗偏高等弱点，从而限制了其在某些领域的推广应用，对热固性树脂改性研究一直是材料工作者关注的研究课题。High performance thermosetting resins are widely used in aerospace, rail transit, power insulation, microelectronic packaging due to their excellent heat resistance, flame retardancy, weather resistance, electrical insulation, good mechanical properties and dimensional stability. Resin matrix, high temperature insulation materials and adhesives for composite materials in other fields. Commonly used high-performance thermosetting resins are epoxy resin, phenolic resin, bismaleimide resin, etc., but the above-mentioned resin has brittleness, resulting in insufficient impact resistance of the material, and the resin has a high molecular structure polarity, resulting in high dielectric constant and loss. Weaknesses have limited its promotion and application in certain fields. Research on thermosetting resin modification has always been a research topic of concern for material workers.
近年来，以双马来酰亚胺树脂为代表的耐高温热固性树脂，越来越多的用于航空航天雷达天线罩，轨道交通电路绝缘材料和微电子电路板等领域。随着上述产业的迅猛发展，电磁发射功率和频率不断增大，对材料的透波、绝缘性能要求日益提高，普通耐高温热固性树脂由于介电常数和损耗偏高，其透波绝缘性能已经不能满足雷达、绝缘材料和微电子电路板的设计要求。因此，如何降低树脂极性，进而降低介电常数和损耗一直是研究人员关注的技术瓶颈问题。In recent years, high temperature thermosetting resins typified by bismaleimide resins have been used in aerospace radar radomes, rail transit circuit insulation materials and microelectronic circuit boards. With the rapid development of the above-mentioned industries, the electromagnetic emission power and frequency are increasing, and the requirements for the wave transmission and insulation properties of materials are increasing. The ordinary high temperature resistant thermosetting resin has high dielectric constant and loss, and its transmission insulation performance cannot be improved. Meet the design requirements of radar, insulation and microelectronic circuit boards. Therefore, how to reduce the polarity of the resin, and thus reduce the dielectric constant and loss, has always been a technical bottleneck concern of researchers.
合成新结构单体或树脂是降低介电常数和损耗的可行方法。CN104311756A公开了一种含硅双马来酰亚胺树脂，含硅基团的引入可将介电常数降低至3.0以下。CN104479130A公开了一种含氟结构的新型双马单体，显著降低双马树脂的介电常数和损耗。但是，上述新型结构双马单体合成工艺复杂、成本高，难以 批量制备及应用。此外，通过其他树脂共聚改性是改善热固性树脂绝缘性能的重要方法之一。CN101338032A公开了采用氰酸酯改性双马树脂，制备预浸料，复合材料介电常数和损耗显著降低。然而，该方法对于改善树脂介电性能虽有一定效果，但程度有限，距离应用尚有一定差距。Synthesizing new structural monomers or resins is a viable way to reduce dielectric constant and loss. CN104311756A discloses a silicon-containing bismaleimide resin with the introduction of a silicon-containing group which reduces the dielectric constant to below 3.0. CN104479130A discloses a novel double horse monomer having a fluorine-containing structure, which significantly reduces the dielectric constant and loss of the bismale resin. However, the above-mentioned novel structure double horse monomer synthesis process is complicated, high in cost, and difficult Batch preparation and application. In addition, copolymerization modification by other resins is one of the important methods to improve the insulation properties of thermosetting resins. CN101338032A discloses the preparation of a prepreg using a cyanate-modified bismale resin, and the dielectric constant and loss of the composite material are significantly reduced. However, this method has certain effects on improving the dielectric properties of the resin, but the degree is limited, and there is still a certain gap in the distance application.
因此，在本领域中，期望得到一种低极性的树脂材料以降低其固化物的介电常数和损耗，同时保持覆铜板的其他方面的优良性能。Therefore, in the art, it is desirable to obtain a low polarity resin material to lower the dielectric constant and loss of its cured product while maintaining excellent properties of other aspects of the copper clad laminate.
发明内容Summary of the invention
针对现有技术的不足，本发明的目的在于提供一种低极性树脂及其制备方法和应用。本发明的树脂不含有极性基团(例如羟基)、分子极性低、反应活性高，降低其固化物的介电常数和损耗，克服了通用热固性树脂极性大导致的高频介电常数和损耗高的缺陷，同时，该树脂带有高活性的不饱和基团，通过与其他树脂的交联固化反应显著改善耐高温性能。In view of the deficiencies of the prior art, it is an object of the present invention to provide a low polarity resin and a preparation method and application thereof. The resin of the present invention does not contain a polar group (for example, a hydroxyl group), has low molecular polarity, high reactivity, lowers the dielectric constant and loss of the cured product, and overcomes the high frequency dielectric constant caused by the polarity of the general thermosetting resin. And the defect with high loss, at the same time, the resin has a highly active unsaturated group, and the high temperature resistance is remarkably improved by the crosslinking curing reaction with other resins.
为达到此发明目的，本发明采用以下技术方案：To achieve the object of the present invention, the present invention adopts the following technical solutions:
一方面，本发明提供一种低极性树脂，所述低极性树脂具有如下式I所示的结构：In one aspect, the invention provides a low polarity resin having the structure of Formula I below:
Figure PCTCN2017110810-appb-000001
Figure PCTCN2017110810-appb-000001
其中，R为直链或支链烷基，
Figure PCTCN2017110810-appb-000002
-O-、
Figure PCTCN2017110810-appb-000003
Figure PCTCN2017110810-appb-000004
X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合；A为含有不饱和双键的基团，n为1-20的整数。Wherein R is a linear or branched alkyl group,
Figure PCTCN2017110810-appb-000002
-O-,
Figure PCTCN2017110810-appb-000003
Figure PCTCN2017110810-appb-000004
X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two; A is a group containing an unsaturated double bond, and n is 1-20. Integer.
在本发明所述的低极性树脂中，所述低极性是指不含有极性基团，尤其是不含有羟基基团，使得树脂具有较低的极性，克服了通用热固性树脂极性大导致的高频介电常数和损耗高的缺陷，同时可通过该结构中的烯丙基以及其他不饱和双键基团等结构实现交联固化，显著改善耐高温性能，并保证固化后的力学强度。In the low-polarity resin of the present invention, the low polarity means that it does not contain a polar group, especially does not contain a hydroxyl group, so that the resin has a lower polarity, overcoming the polarity of the universal thermosetting resin. Large-scale high-frequency dielectric constant and high-loss defects, and cross-linking curing can be achieved by structures such as allyl groups and other unsaturated double-bond groups in the structure, which significantly improves high-temperature resistance and ensures curing. Mechanical strength.
优选地，所述R为C1-C6(例如C1、C2、C3、C4、C5或C6)的直链烷基或C3-C6(例如C3、C4、C5或C6)支链烷基，具体地可以为-CH2-、
Figure PCTCN2017110810-appb-000005
Figure PCTCN2017110810-appb-000006
等。Preferably, said R is a C1-C6 (eg C1, C2, C3, C4, C5 or C6) linear alkyl group or a C3-C6 (eg C3, C4, C5 or C6) branched alkyl group, in particular Can be -CH 2 -,
Figure PCTCN2017110810-appb-000005
Figure PCTCN2017110810-appb-000006
Wait.
优选地，R为-CH2-、
Figure PCTCN2017110810-appb-000007
-O-、-CH2-O-、
Figure PCTCN2017110810-appb-000008
n为1-20的整数，X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合，A为含有不饱和双键的基团。Preferably, R is -CH 2 -,
Figure PCTCN2017110810-appb-000007
-O-, -CH 2 -O-,
Figure PCTCN2017110810-appb-000008
n is an integer of 1-20, and X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two, and A is a group containing an unsaturated double bond. group.
在本发明中，n为1-20的整数，例如n可以为1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20。In the present invention, n is an integer of 1-20, for example, n may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 , 18, 19 or 20.
优选地，R′为C1-C6(例如C1、C2、C3、C4、C5或C6)的直链烷基或 C3-C6(例如C3、C4、C5或C6)支链烷基，例如可以为-CH2-、-CH2CH2-、
Figure PCTCN2017110810-appb-000009
Figure PCTCN2017110810-appb-000010
等。Preferably, R' is a linear alkyl group of C1-C6 (eg C1, C2, C3, C4, C5 or C6) or a C3-C6 (eg C3, C4, C5 or C6) branched alkyl group, for example -CH 2 -, -CH 2 CH 2 -,
Figure PCTCN2017110810-appb-000009
Figure PCTCN2017110810-appb-000010
Wait.
优选地，X和Y独立地为C1-C21(例如C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20或C21)的直链烷基或C3-C21(例如C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20或C21)支链烷基。Preferably, X and Y are independently C1-C21 (eg, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, a linear alkyl group of C19, C20 or C21) or C3-C21 (eg C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19) , C20 or C21) branched alkyl.
优选地，A为-CH2(C6H6)CH＝CH2、
Figure PCTCN2017110810-appb-000011
Preferably, A is -CH 2 (C 6 H 6 )CH=CH 2 ,
Figure PCTCN2017110810-appb-000011
优选地，所述低极性树脂为具有如下式A-式D所示结构的化合物中的任意一种或至少两种的组合：Preferably, the low polarity resin is any one or a combination of at least two of the compounds having the structure represented by the following formula A-form D:
Figure PCTCN2017110810-appb-000012
Figure PCTCN2017110810-appb-000012
Figure PCTCN2017110810-appb-000013
Figure PCTCN2017110810-appb-000013
其中n为1-20的整数。Wherein n is an integer from 1-20.
另一方面，本发明提供了如上所述的低极性树脂的制备方法，所述方法包括以下步骤：In another aspect, the present invention provides a method of preparing a low polarity resin as described above, the method comprising the steps of:
(1)式II所示酚类化合物或酚类树脂与烯丙基化试剂反应得到式III所示烯丙基醚化树脂，反应式如下：(1) The phenolic compound or phenolic resin represented by the formula II is reacted with an allylation reagent to obtain an allyl etherified resin of the formula III, and the reaction formula is as follows:
Figure PCTCN2017110810-appb-000014
Figure PCTCN2017110810-appb-000014
(2)在保护性气体保护下，将式III所示烯丙基醚化树脂加热，发生分子内重排反应得到式IV所示烯丙基化酚类树脂；(2) heating the allyl etherified resin of formula III under protective gas protection, and undergoing intramolecular rearrangement reaction to obtain an allylated phenolic resin of formula IV;
Figure PCTCN2017110810-appb-000015
Figure PCTCN2017110810-appb-000015
(3)式III所示烯丙基化酚类树脂与含有不饱和双键基团的羟基封端试剂发生反应，得到式I所示低极性树脂； (3) an allylated phenolic resin of the formula III is reacted with a hydroxyl-terminated reagent containing an unsaturated double bond group to obtain a low-polarity resin of the formula I;
Figure PCTCN2017110810-appb-000016
Figure PCTCN2017110810-appb-000016
其中，R1为直链或支链烷基，
Figure PCTCN2017110810-appb-000017
-O-、
Figure PCTCN2017110810-appb-000018
Figure PCTCN2017110810-appb-000019
R2为直链或支链烷基，
Figure PCTCN2017110810-appb-000020
-O-、
Figure PCTCN2017110810-appb-000021
R3为直链或支链烷基，
Figure PCTCN2017110810-appb-000022
-O-、
Figure PCTCN2017110810-appb-000023
R为直链或支链烷基，
Figure PCTCN2017110810-appb-000024
-O-、
Figure PCTCN2017110810-appb-000025
Figure PCTCN2017110810-appb-000026
X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合；A为含有不饱和双键的基团，n为1-20的整数。Wherein R 1 is a linear or branched alkyl group,
Figure PCTCN2017110810-appb-000017
-O-,
Figure PCTCN2017110810-appb-000018
Figure PCTCN2017110810-appb-000019
R 2 is a linear or branched alkyl group,
Figure PCTCN2017110810-appb-000020
-O-,
Figure PCTCN2017110810-appb-000021
R 3 is a linear or branched alkyl group,
Figure PCTCN2017110810-appb-000022
-O-,
Figure PCTCN2017110810-appb-000023
R is a linear or branched alkyl group,
Figure PCTCN2017110810-appb-000024
-O-,
Figure PCTCN2017110810-appb-000025
Figure PCTCN2017110810-appb-000026
X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two; A is a group containing an unsaturated double bond, and n is 1-20. Integer.
在本发明中，步骤(2)的重排步骤中，当R2为
Figure PCTCN2017110810-appb-000027
Figure PCTCN2017110810-appb-000028
时，包括其中的烯丙醚基会发生重排的情况，导致在式IV所示烯丙基化酚类树脂的中间单元R3中含有由于重排而产生烯丙基，进而在产物式I所示低极性树脂的R单元中包括由于重排而产生的烯丙基，本发明中为了表述的简单未将该烯丙基直接表示至R3和R的相应结构中，而仅仅由X来代表了苯环上所有的取代基，然而在此明确此处X包含由于重排而产生的烯丙基，如果在重排反应前R2为
Figure PCTCN2017110810-appb-000029
Figure PCTCN2017110810-appb-000030
苯环上带有其他取代基X，在步骤(2)的重排反应后，则在R3的结构
Figure PCTCN2017110810-appb-000031
中X可以表示重排产生的烯丙基和反应前的其他取代基的组合。当然在步骤(2)的重排步骤中，也包括R2为
Figure PCTCN2017110810-appb-000032
时，R2单元中烯丙醚基不发生重排反应的情况，此时，反应后R3以及产物R中的X与反应前式III所示烯丙基醚化树脂中R2中的X基团相同。In the present invention, in the rearrangement step of step (2), when R 2 is
Figure PCTCN2017110810-appb-000027
Figure PCTCN2017110810-appb-000028
In the case where the allyl ether group therein is rearranged, resulting in the intermediate unit R 3 of the allylated phenolic resin of the formula IV containing an allyl group due to rearrangement, and further in the product formula I The R unit of the low-polarity resin shown includes allyl groups due to rearrangement, and the simple expression in the present invention does not directly represent the allyl group to the corresponding structures of R 3 and R, but only by X. To represent all of the substituents on the phenyl ring, however it is hereby expressly that X contains allyl groups due to rearrangement, if R 2 is before the rearrangement reaction
Figure PCTCN2017110810-appb-000029
Figure PCTCN2017110810-appb-000030
The benzene ring carries other substituents X, after the rearrangement reaction of step (2), then the structure of R 3
Figure PCTCN2017110810-appb-000031
The middle X may represent a combination of allyl groups produced by rearrangement and other substituents before the reaction. Of course, in the rearrangement step of step (2), R 2 is also included.
Figure PCTCN2017110810-appb-000032
When, R 2 unit allyl ether group rearrangement reaction does not occur at this time, the reaction product of R 3 and R before the reaction of X in the allyl ether of formula III in the resin of R 2 X The groups are the same.
优选地，步骤(1)所述酚类化合物或酚类树脂为酚、二元酚、多元酚或它们的衍生树脂，优选为苯酚、邻甲酚、双酚A、双酚F、四甲基双酚A、酚醛树脂、邻甲酚酚醛树脂或环戊二烯酚醛树脂中的任意一种或至少两种的组合。 Preferably, the phenolic compound or the phenolic resin in the step (1) is a phenol, a dihydric phenol, a polyhydric phenol or a derivative thereof, preferably phenol, o-cresol, bisphenol A, bisphenol F, tetramethyl Any one or a combination of at least two of bisphenol A, a phenol resin, an o-cresol novolac resin, or a cyclopentadiene phenol resin.
优选地，所述烯丙基化试剂为烯丙基硅醇、烯丙基氯、烯丙基溴、烯丙基碘或烯丙基胺中的任意一种或至少两种的组合。Preferably, the allylation reagent is any one or a combination of at least two of allyl silanol, allyl chloride, allyl bromide, allyl iodide or allylamine.
优选地，所述酚类化合物或酚类树脂中酚羟基与烯丙基化试剂中烯丙基的摩尔比为1∶(0.3～1.2)，例如1∶0.3、1∶0.4、1∶0.5、1∶0.6、1∶0.7、1∶0.8、1∶0.9、1∶1、1∶1.1或1∶1.2。Preferably, the molar ratio of the phenolic hydroxyl group to the allyl group in the phenolic resin is 1: (0.3 to 1.2), for example, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1 or 1:1.2.
优选地，步骤(1)所述反应在碱性物质存在下进行，所述碱性物质优选氢氧化钠、氢氧化钾、碳酸钠或碳酸钾中的任意一种或至少两种的组合。Preferably, the reaction of the step (1) is carried out in the presence of a basic substance, preferably any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate or a combination of at least two.
优选地，所述碱性物质与步骤(1)所述酚类化合物或酚类树脂中所含酚羟基的摩尔比为(0.3～1.4)∶1，例如0.3∶1、0.4∶1、0.5∶1、0.6∶1、0.7∶1、0.8∶1、0.9∶1、1∶1、1.1∶1、1.2∶1、1.3∶1或1.4∶1。Preferably, the molar ratio of the basic substance to the phenolic hydroxyl group contained in the phenolic compound or the phenolic resin in the step (1) is (0.3 to 1.4):1, for example, 0.3:1, 0.4:1, 0.5: 1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1 or 1.4:1.
优选地，步骤(1)所述反应在相转移催化剂存在下进行。Preferably, the reaction of step (1) is carried out in the presence of a phase transfer catalyst.
优选地，所述相转移催化剂为季铵盐类相转移催化剂，优选四丁基氯化铵、四丁基溴化铵、苄基三乙基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵或十四烷基溴三甲基氯化铵中的任意一种或至少两种的组合。Preferably, the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioxane Any one or a combination of at least two of methylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride.
优选地，所述相转移催化剂的加入量为步骤(1)所述酚类化合物或酚类树脂质量的0.1-5％，例如0.1％、0.3％、0.5％、0.8％、1％、1.3％、1.5％、1.8％、2％、2.3％、2.5％、2.8％、3％、3.3％、3.5％、3.8％、4％、4.3％、4.5％、4.8％或5％。Preferably, the phase transfer catalyst is added in an amount of 0.1-5%, such as 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, of the mass of the phenolic compound or the phenolic resin in the step (1). 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5%.
优选地，步骤(1)所述反应的溶剂为醇类溶剂、芳香烃溶剂或酮类溶剂中的任意一种或至少两种的组合，优选为乙醇、丙醇、丁醇、甲苯或二甲苯中的任意一种或至少两种的组合。Preferably, the solvent of the reaction in the step (1) is any one of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent or a combination of at least two, preferably ethanol, propanol, butanol, toluene or xylene Any one or a combination of at least two.
优选地，所述溶剂的加入量为步骤(1)所述酚类化合物或酚类树脂质量的 2-5倍，例如2倍、2.3倍、2.5倍、2.8倍、3倍、3.3倍、3.5倍、3.8倍、4倍、4.3倍、4.5倍、4.8倍或5倍。Preferably, the solvent is added in an amount of the phenolic compound or the phenolic resin of the step (1). 2-5 times, for example 2, 2.3, 2.5, 2.8, 3, 3.3, 3.5, 3.8, 4, 4.3, 4.5, 4.8 or 5 times.
优选地，步骤(1)所述反应的温度为60-90℃，例如60℃、63℃、65℃、68℃、70℃、75℃、78℃、80℃、85℃、88℃或90℃。Preferably, the temperature of the reaction in the step (1) is 60-90 ° C, such as 60 ° C, 63 ° C, 65 ° C, 68 ° C, 70 ° C, 75 ° C, 78 ° C, 80 ° C, 85 ° C, 88 ° C or 90 °C.
优选地，步骤(1)所述反应的时间为4-6小时，例如4小时、4.3小时、4.5小时、4.8小时、5小时、5.2小时、5.5小时、5.8小时或6小时。Preferably, the reaction time of the step (1) is 4-6 hours, such as 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
优选地，步骤(2)所述保护性气体为氮气或氩气。Preferably, the protective gas in step (2) is nitrogen or argon.
优选地，步骤(2)所述加热为加热至180-220℃，例如180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃或220℃。Preferably, the heating in step (2) is heating to 180-220 ° C, such as 180 ° C, 185 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C, 215 ° C or 220 ° C.
优选地，步骤(2)所述反应的时间为4-6小时，例如4小时、4.3小时、4.5小时、4.8小时、5小时、5.2小时、5.5小时、5.8小时或6小时。Preferably, the reaction time in the step (2) is 4-6 hours, such as 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
优选地，步骤(3)所述含有不饱和双键基团的羟基封端试剂为可与酚羟基发生醚化、酯化反应的含有不饱和双键基团的卤代化合物、酸酐或酰氯，优选乙烯基苄基氯、问乙烯基苄基氯、对乙烯基苄基溴、间乙烯基苄基溴、丙烯酰氯、丙烯酸酐、甲基丙烯酰氯或甲基丙烯酸酐中的任意一种或至少两种的组合。Preferably, the hydroxyl-terminated reagent containing an unsaturated double bond group in the step (3) is a halogenated compound, an acid anhydride or an acid chloride containing an unsaturated double bond group which can be etherified and esterified with a phenolic hydroxyl group. Preference is given to any one or at least one of vinylbenzyl chloride, vinylidene chloride chloride, p-vinylbenzyl bromide, m-vinylbenzyl bromide, acryloyl chloride, acrylic anhydride, methacryloyl chloride or methacrylic anhydride. A combination of the two.
优选地，步骤(3)所述式III所示烯丙基化酚类树脂中酚羟基与含有不饱和双键基团的羟基封端试剂中封端基团的摩尔比为1∶(1～1.2)，例如1∶1、1∶1.05、1∶1.1、1∶1.15或1∶1.2。使得反应得到的树脂分子结构中酚羟基被含有不饱和双键基团的封端基完全封端，从而使树脂中无极性羟基基团。Preferably, the molar ratio of the phenolic hydroxyl group in the allylated phenolic resin represented by the formula III in the step (3) to the terminal group in the hydroxyl-terminated reagent containing an unsaturated double bond group is 1: (1) 1.2), for example 1:1, 1:1.05, 1:1.1, 1:1.15 or 1:1.2. The phenolic hydroxyl group in the molecular structure of the resin obtained by the reaction is completely blocked by a terminal group containing an unsaturated double bond group, so that the resin has no polar hydroxyl group.
优选地，步骤(3)所述反应在碱性物质存在下进行。Preferably, the reaction of the step (3) is carried out in the presence of a basic substance.
优选地，所述碱性物质为无机碱或有机碱，优选氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、三乙胺或吡啶中的任意一种或至少两种的组合。Preferably, the basic substance is an inorganic base or an organic base, preferably any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.
优选地，所述碱性物质与式III所示烯丙基化酚类树脂中酚羟基的摩尔比为 (1～1.4)∶1，例如1∶1、1.05∶1、1.1∶1、1.15∶1、1.2∶1、1.25∶1、1.3∶1、1.35∶1或1.4∶1。Preferably, the molar ratio of the basic substance to the phenolic hydroxyl group in the allylated phenolic resin represented by Formula III is (1 to 1.4): 1, for example, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1 or 1.4:1.
优选地，步骤(3)所述反应在相转移催化剂存在下进行。Preferably, the reaction of step (3) is carried out in the presence of a phase transfer catalyst.
优选地，所述相转移催化剂为季铵盐类相转移催化剂，优选四丁基氯化铵、四丁基溴化铵、苄基三乙基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵或十四烷基溴三甲基氯化铵中的任意一种或至少两种的组合。Preferably, the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioxane Any one or a combination of at least two of methylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride.
优选地，所述相转移催化剂的加入量为步骤(3)所述烯丙基化酚类树脂质量的0.1-5％，例如0.1％、0.3％、0.5％、0.8％、1％、1.3％、1.5％、1.8％、2％、2.3％、2.5％、2.8％、3％、3.3％、3.5％、3.8％、4％、4.3％、4.5％、4.8％或5％。Preferably, the phase transfer catalyst is added in an amount of 0.1-5%, such as 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, of the mass of the allylated phenolic resin of the step (3). 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5%.
优选地，步骤(3)所述反应的溶剂为醇类溶剂、芳香烃溶剂或酮类溶剂中的任意一种或至少两种的组合，优选为乙醇、丙醇、丁醇、甲苯或二甲苯中的任意一种或至少两种的组合。Preferably, the solvent of the reaction in the step (3) is any one of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent or a combination of at least two, preferably ethanol, propanol, butanol, toluene or xylene Any one or a combination of at least two.
优选地，所述溶剂的加入量为步骤(3)所述烯丙基化酚类树脂质量的2-5倍，例如2倍、2.3倍、2.5倍、2.8倍、3倍、3.3倍、3.5倍、3.8倍、4倍、4.3倍、4.5倍、4.8倍或5倍。Preferably, the solvent is added in an amount of 2-5 times, for example, 2 times, 2.3 times, 2.5 times, 2.8 times, 3 times, 3.3 times, 3.5, of the mass of the allylated phenolic resin in the step (3). Times, 3.8, 4, 4.3, 4.5, 4.8 or 5 times.
优选地，步骤(3)所述反应的温度为40-90℃，例如40℃、45℃、48℃、50℃、55℃、58℃、60℃、63℃、65℃、68℃、70℃、75℃、78℃、80℃、85℃、88℃或90℃。Preferably, the temperature of the reaction in the step (3) is 40-90 ° C, for example 40 ° C, 45 ° C, 48 ° C, 50 ° C, 55 ° C, 58 ° C, 60 ° C, 63 ° C, 65 ° C, 68 ° C, 70 °C, 75°C, 78°C, 80°C, 85°C, 88°C or 90°C.
在本发明中，当步骤(3)中使用的含有不饱和双键基团的羟基封端试剂为乙烯基苄基氯、间乙烯基苄基氯、对乙烯基苄基溴、间乙烯基苄基溴时，步骤(3)所述反应的温度为60-90℃；当步骤(3)中使用的含有不饱和双键基团的羟基封端试剂为丙烯酰氯、丙烯酸酐、甲基丙烯酸酐、甲基丙烯酰氯时，步骤(3)所述反应的温度为40-90℃。 In the present invention, the hydroxyl-terminated reagent containing an unsaturated double bond group used in the step (3) is vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl bromide, m-vinylbenzyl chloride. In the case of phenyl bromide, the temperature of the reaction in the step (3) is 60-90 ° C; the hydroxy-terminated reagent containing the unsaturated double bond group used in the step (3) is acryloyl chloride, acrylic anhydride, methacrylic anhydride In the case of methacryloyl chloride, the temperature of the reaction described in the step (3) is 40 to 90 °C.
优选地，步骤(3)所述反应的时间为4-6小时，例如4小时、4.3小时、4.5小时、4.8小时、5小时、5.2小时、5.5小时、5.8小时或6小时。Preferably, the reaction time in the step (3) is 4-6 hours, such as 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
通过本发明的方法制备得到的树脂中不含有极性的羟基、并且分子结构稳定，具有分子极性低、反应活性高的特点，在其应用的加工过程中也不会产生极性羟基，避免了产生的二次羟基对于其产物的性能的影响。The resin prepared by the method of the invention does not contain polar hydroxyl groups, has stable molecular structure, has low molecular polarity and high reactivity, and does not generate polar hydroxyl groups in the processing process thereof, avoiding The effect of the resulting secondary hydroxyl groups on the properties of their products.
本发明的制备方法通过重排、含有不饱和双键基团的羟基封端试剂对酚羟基进行封端反应的组合，能够显著提高树脂软化点，从而更适用于固态预浸料的制备，改善树脂成型工艺性能。典型烯丙基酚醛树脂软化点可从20℃提高至90℃。The preparation method of the present invention can significantly improve the softening point of the resin by rearranging the combination of the hydroxyl group-capping reagent containing the unsaturated double bond group to the phenolic hydroxyl group, thereby being more suitable for the preparation and improvement of the solid prepreg. Resin molding process performance. The softening point of a typical allyl phenolic resin can be increased from 20 ° C to 90 ° C.
另一方面，本发明提供了如上所述的低极性树脂在树脂复合材料制备中的应用。In another aspect, the present invention provides the use of a low polarity resin as described above in the preparation of a resin composite.
本发明的低极性树脂可用于树脂复合材料中基体树脂的组分之一，能够与双马来酰亚胺等其他热固性树脂共交联固化，显著降低树脂介电常数和介电损耗。The low-polarity resin of the present invention can be used for one of the components of the matrix resin in the resin composite material, and can be co-crosslinked and cured with other thermosetting resins such as bismaleimide, and the dielectric constant and dielectric loss of the resin are remarkably lowered.
在本发明中，所述树脂复合材料可以为航空航天透波复合材料、电力绝缘材料、电子封装用树脂复合材料以及覆铜板用树脂复合材料等。In the present invention, the resin composite material may be an aerospace wave-transparent composite material, a power insulating material, a resin composite material for electronic packaging, and a resin composite material for a copper-clad laminate.
另一方面，本发明提供了如上所述的低极性树脂在电子封装材料制备中的应用。In another aspect, the invention provides the use of a low polarity resin as described above in the preparation of electronic packaging materials.
本发明的低极性树脂由于具有分子极性低、反应活性高的特点，还可以应用于电子封装胶黏剂、灌封树脂等材料的制备。The low-polarity resin of the invention has the characteristics of low molecular polarity and high reactivity, and can also be applied to preparation of materials such as electronic packaging adhesives and potting resins.
另一方面，本发明提供了如上所述的低极性树脂在覆金属箔层压板制备中的应用。In another aspect, the present invention provides the use of a low polarity resin as described above in the preparation of a metal foil laminate.
本发明所述的低极性树脂可用于树脂复合材料中基体树脂的组分之一，能 够与双马来酰亚胺等其他热固性树脂共交联固化，显著降低树脂介电常数和介电损耗，将其用于覆金属箔层压板制备中有利于降低覆金属箔层压板的介电常数和介电损耗，使得覆金属箔层压板具有良好的综合性能。The low polarity resin of the present invention can be used for one of the components of the matrix resin in the resin composite material, It can be co-crosslinked and cured with other thermosetting resins such as bismaleimide, which significantly reduces the dielectric constant and dielectric loss of the resin. It is used in the preparation of metal foil-clad laminates to reduce the dielectric of metal foil-clad laminates. The constant and dielectric loss make the metal foil laminate have good overall performance.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明的树脂中不含有极性的羟基、并且分子结构稳定，具有分子极性低、反应活性高的特点，在其应用的加工过程中也不会产生极性羟基，避免了产生的二次羟基对于其产物的性能的影响，提高介电性能，该树脂带有高活性的不饱和基团，通过与其他树脂的交联固化反应显著改善耐高温性能，显著降低树脂介电常数和介电损耗，将其用于覆金属箔层压板制备中有利于降低覆金属箔层压板的介电常数和介电损耗，显著改善耐高温性能，使得覆金属箔层压板具有良好的综合性能。The resin of the invention does not contain a polar hydroxyl group, has a stable molecular structure, has the characteristics of low molecular polarity and high reactivity, and does not generate polar hydroxyl groups in the processing process of the application, thereby avoiding secondary generation. The effect of hydroxyl on the properties of the product, improving the dielectric properties, the resin with highly reactive unsaturated groups, significantly improving the high temperature resistance by crosslinking curing reaction with other resins, significantly lowering the dielectric constant and dielectric of the resin Loss, which is used in the preparation of metal foil-clad laminates, is advantageous for reducing the dielectric constant and dielectric loss of the metal foil-clad laminate, and significantly improving the high temperature resistance, so that the metal foil-clad laminate has good comprehensive performance.
附图说明DRAWINGS
图1为实施例1制备得到的低极性树脂的红外光谱图。1 is an infrared spectrum diagram of a low polarity resin prepared in Example 1.
具体实施方式Detailed ways
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。The technical solution of the present invention will be further described below by way of specific embodiments. It should be understood by those skilled in the art that the present invention is not to be construed as limited.
实施例1Example 1
在本实施例中，通过以下方法制备低极性树脂，包括以下步骤：In this embodiment, a low polarity resin is prepared by the following method, including the following steps:
(1)三口反应瓶中加入188g丙酮，将228g双酚A加入反应瓶中，搅拌溶解后，加入106g碳酸钠。缓慢滴加153g氯丙烯溶液，然后升温反应4小时后停止反应。过滤，除去大部分溶剂，洗涤，再除去残留的溶剂和水，即得到双酚A二烯丙基醚。(1) 188 g of acetone was added to a three-necked reaction flask, and 228 g of bisphenol A was added to the reaction flask, and after stirring and dissolved, 106 g of sodium carbonate was added. 153 g of a chloropropene solution was slowly added dropwise, and then the reaction was stopped after raising the temperature for 4 hours. Filtration, removal of most of the solvent, washing, and removal of residual solvent and water gave bisphenol A diallyl ether.
(2)将步骤(1)制备的134g双酚A二烯丙基醚放入反应瓶中，加热进行 重排反应，降温出料，得到棕色粘稠液体即二烯丙基双酚A。(2) 134 g of bisphenol A diallyl ether prepared in the step (1) was placed in a reaction flask and heated. The reaction was rearranged, and the temperature was discharged to obtain a brown viscous liquid, that is, diallyl bisphenol A.
(3)反应瓶中加入402g正丁醇，将步骤(2)制备的154g二烯丙基双酚A放入反应瓶中，搅拌溶解后，加入138g碳酸钾。缓慢滴加152.5g间乙烯基苄基溴溶液，然后升温反应6小时后停止反应。过滤，除去大部分溶剂，洗涤，再除去残留的溶剂和水，即得到2-烯丙基苯基(3-乙烯基)苄基醚，其结构如下所示：(3) 402 g of n-butanol was added to the reaction flask, and 154 g of diallyl bisphenol A prepared in the step (2) was placed in a reaction flask, and after stirring and dissolved, 138 g of potassium carbonate was added. 152.5 g of a solution of m-vinylbenzyl bromide was slowly added dropwise, and then the reaction was stopped after raising the temperature for 6 hours. Filtration, removal of most of the solvent, washing, and removal of residual solvent and water gave 2-allylphenyl(3-vinyl)benzyl ether, the structure of which is shown below:
Figure PCTCN2017110810-appb-000033
Figure PCTCN2017110810-appb-000033
该实施例制备得到的2-烯丙基苯基(3-乙烯基)苄基醚的红外光谱图如图1所示，可以看出，3300-3500cm-1处的羟基结构已经消失，不含有极性的羟基基团，使分子极性显著降低。The infrared spectrum of 2-allylphenyl(3-vinyl)benzyl ether prepared in this example is shown in Fig. 1. It can be seen that the hydroxyl structure at 3300-3500 cm -1 has disappeared and does not contain Polar hydroxyl groups significantly reduce the polarity of the molecule.
实施例2Example 2
在本实施例中，通过以下方法制备低极性树脂，包括以下步骤：In this embodiment, a low polarity resin is prepared by the following method, including the following steps:
(1)三口反应瓶中加入300g正丁醇，将114g线型酚醛树脂加入反应瓶中，搅拌溶解后，加入56g氢氧化钾。缓慢滴加153g溴丙烯溶液，然后升温反应4小时后停止反应。过滤，洗涤，再除去残留的溶剂和水，即得到烯丙基醚化酚醛树脂。(1) 300 g of n-butanol was added to a three-neck reaction flask, and 114 g of a novolak type phenol resin was added to the reaction flask, and after stirring and dissolved, 56 g of potassium hydroxide was added. 153 g of a bromopropene solution was slowly added dropwise, and then the reaction was stopped after raising the temperature for 4 hours. Filtration, washing, and removal of residual solvent and water gave an allyl etherified phenolic resin.
(2)将步骤(1)制备的141g烯丙基醚化酚醛树脂放入反应瓶中，加热进行重排反应，降温出料，得到棕色粘稠液体即烯丙基酚醛树脂。(2) 141 g of the allyl etherified phenolic resin prepared in the step (1) was placed in a reaction flask, heated to carry out a rearrangement reaction, and the temperature was discharged to obtain a brown viscous liquid, that is, an allyl phenol resin.
(3)反应瓶中加入402g正丁醇，将步骤(2)制备的141g烯丙基酚醛树脂放入反应瓶中，搅拌溶解后，加入102g三乙胺。缓慢滴加80g甲基丙烯酸酐 溶液，然后升温反应6小时后停止反应，洗涤，再除去溶剂和水，即得到甲基丙烯酸酯化烯丙基酚醛树脂，其Mn为1250，其结构如下所示：(3) 402 g of n-butanol was added to the reaction flask, and 141 g of the allyl phenol resin prepared in the step (2) was placed in a reaction flask, stirred and dissolved, and then 102 g of triethylamine was added. Slowly add 80g of methacrylic anhydride After the solution was heated for 6 hours, the reaction was stopped, washed, and the solvent and water were removed to obtain a methacrylated allyl phenolic resin having an Mn of 1250. The structure is as follows:
Figure PCTCN2017110810-appb-000034
Figure PCTCN2017110810-appb-000034
实施例3Example 3
在本实施例中，通过以下方法制备低极性树脂，包括以下步骤：In this embodiment, a low polarity resin is prepared by the following method, including the following steps:
(1)三口反应瓶中加入250g甲苯，将118g邻甲酚酚醛树脂加入反应瓶中，搅拌溶解后，加入100g氢氧化钠水溶液(浓度40％)，再加入1g四丁基溴化铵。缓慢滴加153g氯丙烯溶液，然后升温反应4小时后停止反应，洗涤，再除去溶剂，即得到烯丙基醚化邻甲酚酚醛树脂。(1) To a three-necked reaction flask, 250 g of toluene was added, and 118 g of o-cresol novolac resin was added to the reaction flask, and after stirring and dissolved, 100 g of an aqueous sodium hydroxide solution (concentration: 40%) was added, and 1 g of tetrabutylammonium bromide was further added. 153 g of a chloropropene solution was slowly added dropwise, and then the reaction was allowed to proceed for 4 hours after the temperature was raised, washed, and the solvent was removed to obtain an allyl etherified o-cresol novolac resin.
(2)将步骤(1)制备的159g烯丙基醚化邻甲酚酚醛树脂放入反应瓶中，加热进行重排反应4小时，降温出料，得到深棕色半固体为烯丙基邻甲酚酚醛树脂。(2) 159 g of allyl etherified o-cresol novolac resin prepared in the step (1) was placed in a reaction flask, and subjected to a rearrangement reaction by heating for 4 hours, and the temperature was discharged to obtain a dark brown semi-solid as an allyl ortho Phenolic phenolic resin.
(3)反应瓶中加入300g甲苯，将步骤(2)制备的159g烯丙基邻甲酚酚醛树脂放入反应瓶中，搅拌溶解后，加入100g吡啶。缓慢滴加104.5g丙烯酰氯，然后升温反应6小时后停止反应，洗涤，再除去溶剂和水，即得到丙烯酸酯化烯丙基邻甲酚酚醛树脂，其Mn为1380，其结构如下所示： (3) 300 g of toluene was added to the reaction flask, and 159 g of the allyl o-cresol novolac resin prepared in the step (2) was placed in a reaction flask, stirred and dissolved, and then 100 g of pyridine was added. 104.5 g of acryloyl chloride was slowly added dropwise, and then the reaction was stopped after heating for 6 hours. The reaction was washed, and the solvent and water were removed to obtain an acrylated allyl o-cresol novolac resin having an Mn of 1380. The structure is as follows:
Figure PCTCN2017110810-appb-000035
Figure PCTCN2017110810-appb-000035
实施例4Example 4
在本实施例中，通过以下方法制备低极性树脂，包括以下步骤：In this embodiment, a low polarity resin is prepared by the following method, including the following steps:
(1)三口反应瓶中加入250g二甲苯，将131g环戊二烯酚醛树脂加入反应瓶中，搅拌溶解后，加入100g氢氧化钠水溶液(浓度40％)，再加入1g四丁基溴化铵。缓慢滴加153g烯丙基硅醇溶液，然后升温反应4小时后停止反应，洗涤，再除去二甲苯，即得到烯丙基醚化环戊二烯酚醛树脂。(1) Add 250 g of xylene to a three-neck reaction flask, add 131 g of cyclopentadiene phenolic resin to the reaction flask, stir and dissolve, add 100 g of sodium hydroxide aqueous solution (concentration: 40%), and add 1 g of tetrabutylammonium bromide. . 153 g of the allyl silanol solution was slowly added dropwise, and then the reaction was allowed to proceed for 4 hours after the temperature was raised, washed, and then xylene was removed to obtain an allyl etherified cyclopentadiene phenol resin.
(2)将步骤(1)制备的147g烯丙基醚化环戊二烯树脂放入反应瓶中，加热进行重排反应4小时，降温出料，得到深棕色半固体为烯丙基环戊二烯酚醛树脂。(2) 147 g of the allyl etherified cyclopentadiene resin prepared in the step (1) was placed in a reaction flask, and subjected to a rearrangement reaction by heating for 4 hours, and the temperature was discharged to obtain a dark brown semi-solid as an allyl cyclopentane. Diene phenolic resin.
(3)反应瓶中加入300g二甲苯，将步骤(2)制备的147g烯丙基环戊二烯酚醛树脂放入反应瓶中，搅拌溶解后，加入100g吡啶。缓慢滴加123g丙烯酸酐，然后升温反应6小时后停止反应，洗涤，再除去溶剂和水，即得到丙烯酸酯化烯丙基环戊二烯酚醛树脂，其Mn为1420，其结构如下所示：(3) 300 g of xylene was added to the reaction flask, and 147 g of allylcyclopentadiene phenol resin prepared in the step (2) was placed in a reaction flask, stirred and dissolved, and then 100 g of pyridine was added. 123 g of acrylic anhydride was slowly added dropwise, and then the reaction was stopped after heating for 6 hours, and the solvent and water were removed to obtain an acrylated allylcyclopentadiene phenol resin having an Mn of 1420. The structure is as follows:
Figure PCTCN2017110810-appb-000036
Figure PCTCN2017110810-appb-000036
实施例5Example 5
将80重量份的液体丁苯树脂Ricon100，20重量份的实施例1制备的2-烯丙基苯基(3-乙烯基)苄基醚，85重量份的二氧化硅(525)，6.5重量份的引发剂DCP混合，用溶剂甲苯调至合适的粘度，搅拌混合均匀，使填料均一的分散在树脂中，制得胶液。用1080玻璃纤维布浸渍以上胶液，然后烘干去掉溶剂后制得半固化片。将八张已制成的半固化片相叠合，在其两侧压覆loz(盎司)厚度的铜箔，在压机中进行2小时固化，固化压力为50Kg/cm2，固化温度为190℃，得到覆铜板。80 parts by weight of liquid styrene-butadiene resin Ricon 100, 20 parts by weight of 2-allylphenyl (3-vinyl) benzyl ether prepared in Example 1, 85 parts by weight of silica (525), 6.5 weight The initiator DCP is mixed, adjusted to a suitable viscosity with a solvent toluene, stirred and uniformly mixed, and the filler is uniformly dispersed in the resin to obtain a glue liquid. The above glue was impregnated with a 1080 glass fiber cloth, and then the solvent was removed by drying to obtain a prepreg. Eight pre-cured sheets were laminated, and a copper foil of a thickness of loz (ounces) was pressed on both sides thereof, and solidified in a press for 2 hours at a curing pressure of 50 kg/cm 2 and a curing temperature of 190 ° C. A copper clad laminate is obtained.
实施例6Example 6
与实施例5的区别仅在于将实施例1制备得到的2-烯丙基苯基(3-乙烯基)苄基醚替换为实施例2制备得到的甲基丙烯酸酯化烯丙基酚醛树脂。The only difference from Example 5 was that the 2-allylphenyl(3-vinyl)benzyl ether obtained in Example 1 was replaced with the methacrylated allyl phenolic resin prepared in Example 2.
实施例7Example 7
与实施例5的区别仅在于将实施例1制备得到的2-烯丙基苯基(3-乙烯基)苄基醚替换为实施例3制备得到的丙烯酸酯化烯丙基邻甲酚酚醛树脂。The only difference from the embodiment 5 is that the 2-allylphenyl(3-vinyl)benzyl ether obtained in the first embodiment is replaced with the acrylated allyl o-cresol novolac resin prepared in the third embodiment. .
实施例8Example 8
与实施例5的区别仅在于将实施例1制备得到的2-烯丙基苯基(3-乙烯基)苄基醚替换为实施例4制备得到的丙烯酸酯化烯丙基环戊二烯酚醛树脂。The only difference from Example 5 is that the 2-allylphenyl(3-vinyl)benzyl ether prepared in Example 1 is replaced by the acrylated allylcyclopentadiene phenolic prepared in Example 4. Resin.
比较例1Comparative example 1
将80重量份的液体丁苯树脂Ricon100，85重量份的二氧化硅(525)，5.8重量份的引发剂DCP混合，用溶剂甲苯调至合适的粘度，搅拌混合均匀，使填料均一的分散在树脂中，制得胶液。用1080玻璃纤维布浸渍以上胶液，然后烘干去掉溶剂后制得半固化片。将八张已制成的半固化片相叠合，在其两侧压覆loz(盎司)厚度的铜箔，在压机中进行2小时固化，固化压力为50Kg/cm2，固化 温度为190℃，得到覆铜板。80 parts by weight of liquid styrene- butadiene resin Ricon 100, 85 parts by weight of silica (525), 5.8 parts by weight of initiator DCP were mixed, adjusted to a suitable viscosity with a solvent of toluene, stirred and uniformly mixed, and the filler was uniformly dispersed. In the resin, a glue is obtained. The above glue was impregnated with a 1080 glass fiber cloth, and then the solvent was removed by drying to obtain a prepreg. Eight pre-cured sheets were laminated, and a copper foil of a thickness of loz (ounces) was pressed on both sides thereof, and solidified in a press for 2 hours at a curing pressure of 50 kg/cm 2 and a curing temperature of 190 ° C. A copper clad laminate is obtained.
实施例6-10以及对比例1所应用到的原料来源如表1所示，制备得到的覆铜板的物性数据如表2所示。The raw material sources to which the examples 6-10 and the comparative example 1 were applied are shown in Table 1, and the physical property data of the prepared copper clad laminates are shown in Table 2.
表1Table 1
Figure PCTCN2017110810-appb-000037
Figure PCTCN2017110810-appb-000037
表2Table 2
Figure PCTCN2017110810-appb-000038
Figure PCTCN2017110810-appb-000038
由表2可知，本发明制备得到的低极性树脂可以使得覆铜板具有较低的介电常数和介电损耗，具有较好的耐高温性能以及阻燃性能、良好的工艺成型性。It can be seen from Table 2 that the low polarity resin prepared by the invention can make the copper clad plate have lower dielectric constant and dielectric loss, and has better high temperature resistance, flame retardant performance and good process formability.
申请人声明，本发明通过上述实施例来说明本发明的低极性树脂及其制备方法和应用，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。 The Applicant declares that the present invention describes the low-polarity resin of the present invention and its preparation method and application by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented by relying on the above embodiments. . It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the materials selected for the present invention, and the addition of the auxiliary ingredients, the selection of the specific means, etc., are all within the scope of the present invention.

Claims (10)

  1. 一种低极性树脂，其特征在于，所述低极性树脂具有如下式I所示的结构：A low polarity resin characterized in that the low polarity resin has a structure represented by the following formula I:
    Figure PCTCN2017110810-appb-100001
    Figure PCTCN2017110810-appb-100001
    其中，R为直链或支链烷基，
    Figure PCTCN2017110810-appb-100002
    Figure PCTCN2017110810-appb-100003
    X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合；A为含有不饱和双键的基团，n为1-20的整数。    Wherein R is a linear or branched alkyl group,
    Figure PCTCN2017110810-appb-100002
    Figure PCTCN2017110810-appb-100003
    X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two; A is a group containing an unsaturated double bond, and n is 1-20. Integer.
  2. 根据权利要求1所述的低极性树脂，其特征在于，R为-CH2-、
    Figure PCTCN2017110810-appb-100004
    Figure PCTCN2017110810-appb-100005
    n为1-20的整数，X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合，A为含有不饱和双键的基团；    The low polarity resin according to claim 1, wherein R is -CH 2 -,
    Figure PCTCN2017110810-appb-100004
    Figure PCTCN2017110810-appb-100005
    n is an integer of 1-20, and X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two, and A is a group containing an unsaturated double bond. group;
    优选地，A为-CH2(C6H6)CH＝CH2、
    Figure PCTCN2017110810-appb-100006
    Preferably, A is -CH 2 (C 6 H 6 )CH=CH 2 ,
    Figure PCTCN2017110810-appb-100006
    优选地，所述低极性树脂为具有如下式A-式D所示结构的化合物中的任意一种或至少两种的组合： Preferably, the low polarity resin is any one or a combination of at least two of the compounds having the structure represented by the following formula A-form D:
    Figure PCTCN2017110810-appb-100007
    Figure PCTCN2017110810-appb-100007
    其中n为1-20的整数。Wherein n is an integer from 1-20.
  3. 根据权利要求1或2所述的低极性树脂的制备方法，其特征在于，所述方法包括以下步骤：The method for producing a low-polarity resin according to claim 1 or 2, wherein the method comprises the steps of:
    (1)式II所示酚类化合物或酚类树脂与烯丙基化试剂反应得到式III所示烯丙基醚化树脂，反应式如下： (1) The phenolic compound or phenolic resin represented by the formula II is reacted with an allylation reagent to obtain an allyl etherified resin of the formula III, and the reaction formula is as follows:
    Figure PCTCN2017110810-appb-100008
    Figure PCTCN2017110810-appb-100008
    (2)在保护性气体保护下，将式III所示烯丙基醚化树脂加热，发生分子内重排反应得到式IV所示烯丙基化酚类树脂；(2) heating the allyl etherified resin of formula III under protective gas protection, and undergoing intramolecular rearrangement reaction to obtain an allylated phenolic resin of formula IV;
    Figure PCTCN2017110810-appb-100009
    Figure PCTCN2017110810-appb-100009
    (3)式III所示烯丙基化酚类树脂与含有不饱和双键基团的羟基封端试剂发生反应，得到式I所示低极性树脂；(3) an allylated phenolic resin of the formula III is reacted with a hydroxyl-terminated reagent containing an unsaturated double bond group to obtain a low-polarity resin of the formula I;
    Figure PCTCN2017110810-appb-100010
    Figure PCTCN2017110810-appb-100010
    其中，R1为直链或支链烷基，
    Figure PCTCN2017110810-appb-100011
    Figure PCTCN2017110810-appb-100012
    R2为直链或支链烷基，
    Figure PCTCN2017110810-appb-100013
    Figure PCTCN2017110810-appb-100014
    R3为直链或支链烷基，
    Figure PCTCN2017110810-appb-100015
    R 为直链或支链烷基，
    Figure PCTCN2017110810-appb-100016
    Figure PCTCN2017110810-appb-100017
    X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合；A为含有不饱和双键的基团，n为1-20的整数。    Wherein R 1 is a linear or branched alkyl group,
    Figure PCTCN2017110810-appb-100011
    Figure PCTCN2017110810-appb-100012
    R 2 is a linear or branched alkyl group,
    Figure PCTCN2017110810-appb-100013
    Figure PCTCN2017110810-appb-100014
    R 3 is a linear or branched alkyl group,
    Figure PCTCN2017110810-appb-100015
    R is a linear or branched alkyl group,
    Figure PCTCN2017110810-appb-100016
    Figure PCTCN2017110810-appb-100017
    X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two; A is a group containing an unsaturated double bond, and n is 1-20. Integer.
  4. 根据权利要求3所述的制备方法，其特征在于，步骤(1)所述酚类化合物或酚类树脂为酚、二元酚、多元酚或它们的衍生树脂，优选为苯酚、邻甲酚、双酚A、双酚F、四甲基双酚A、酚醛树脂、邻甲酚酚醛树脂或环戊二烯酚醛树脂中的任意一种或至少两种的组合；The preparation method according to claim 3, wherein the phenolic compound or the phenolic resin in the step (1) is a phenol, a dihydric phenol, a polyhydric phenol or a derivative thereof, preferably phenol or o-cresol. Any one or a combination of at least two of bisphenol A, bisphenol F, tetramethyl bisphenol A, phenolic resin, o-cresol novolac resin or cyclopentadiene phenolic resin;
    优选地，所述烯丙基化试剂为烯丙基硅醇、烯丙基氯、烯丙基溴、烯丙基碘或烯丙基胺中的任意一种或至少两种的组合；Preferably, the allylation reagent is any one or a combination of at least two of allyl silanol, allyl chloride, allyl bromide, allyl iodide or allylamine;
    优选地，所述酚类化合物或酚类树脂中酚羟基与烯丙基化试剂中烯丙基的摩尔比为1∶(0.3～1.2)；Preferably, the molar ratio of the phenolic hydroxyl group in the phenolic compound or the phenolic resin to the allyl group in the allylation reagent is 1: (0.3 to 1.2);
    优选地，步骤(1)所述反应在碱性物质存在下进行，所述碱性物质优选氢氧化钠、氢氧化钾、碳酸钠或碳酸钾中的任意一种或至少两种的组合；Preferably, the reaction in the step (1) is carried out in the presence of a basic substance, preferably any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate or a combination of at least two;
    优选地，所述碱性物质与步骤(1)所述酚类化合物或酚类树脂中所含酚羟基的摩尔比为(0.3～1.4)∶1。Preferably, the molar ratio of the basic substance to the phenolic hydroxyl group contained in the phenolic compound or the phenolic resin in the step (1) is (0.3 to 1.4):1.
  5. 根据权利要求3或4所述的制备方法，其特征在于，步骤(1)所述反应在相转移催化剂存在下进行；The preparation method according to claim 3 or 4, wherein the reaction in the step (1) is carried out in the presence of a phase transfer catalyst;
    优选地，所述相转移催化剂为季铵盐类相转移催化剂，优选四丁基氯化铵、四丁基溴化铵、苄基三乙基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵、十 二烷基三甲基氯化铵或十四烷基溴三甲基氯化铵中的任意一种或至少两种的组合；Preferably, the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioxane Methyl ammonium chloride, ten Any one or a combination of at least two of dialkyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride;
    优选地，所述相转移催化剂的加入量为步骤(1)所述酚类化合物或酚类树脂质量的0.1-5％；Preferably, the phase transfer catalyst is added in an amount of 0.1 to 5% by mass of the phenolic compound or the phenolic resin of the step (1);
    优选地，步骤(1)所述反应的溶剂为醇类溶剂、芳香烃溶剂或酮类溶剂中的任意一种或至少两种的组合，优选为乙醇、丙醇、丁醇、甲苯或二甲苯中的任意一种或至少两种的组合；Preferably, the solvent of the reaction in the step (1) is any one of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent or a combination of at least two, preferably ethanol, propanol, butanol, toluene or xylene Any one or a combination of at least two;
    优选地，所述溶剂的加入量为步骤(1)所述酚类化合物或酚类树脂质量的2-5倍；Preferably, the solvent is added in an amount of 2-5 times the mass of the phenolic compound or the phenolic resin in the step (1);
    优选地，步骤(1)所述反应的温度为60-90℃；Preferably, the temperature of the reaction in the step (1) is 60-90 ° C;
    优选地，步骤(1)所述反应的时间为4-6小时。Preferably, the reaction time in the step (1) is 4-6 hours.
  6. 根据权利要求3-5中任一项所述的制备方法，其特征在于，步骤(2)所述保护性气体为氮气或氩气。The preparation method according to any one of claims 3 to 5, wherein the protective gas in the step (2) is nitrogen or argon.
    优选地，步骤(2)所述加热为加热至180-220℃；Preferably, the heating in step (2) is heating to 180-220 ° C;
    优选地，步骤(2)所述反应的时间为4-6小时。Preferably, the reaction time in the step (2) is 4-6 hours.
  7. 根据权利要求3-6中任一项所述的制备方法，其特征在于，步骤(3)所述含有不饱和双键基团的羟基封端试剂为可与酚羟基发生醚化、酯化反应的含有不饱和双键基团的卤代化合物、酸酐或酰氯，优选乙烯基苄基氯、间乙烯基苄基氯、对乙烯基苄基溴、间乙烯基苄基溴、丙烯酰氯、丙烯酸酐、甲基丙烯酰氯或甲基丙烯酸酐中的任意一种或至少两种的组合；The preparation method according to any one of claims 3 to 6, wherein the hydroxyl group-terminated reagent containing an unsaturated double bond group in step (3) is etherified and esterified with a phenolic hydroxyl group. Halogenated compound, acid anhydride or acid chloride containing an unsaturated double bond group, preferably vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl bromide, m-vinylbenzyl bromide, acryloyl chloride, acrylic acid anhydride Any one or a combination of at least two of methacryloyl chloride or methacrylic anhydride;
    优选地，步骤(3)所述式III所示烯丙基化酚类树脂中酚羟基与含有不饱和双键基团的羟基封端试剂中封端基团的摩尔比为1∶(1～1.2)；Preferably, the molar ratio of the phenolic hydroxyl group in the allylated phenolic resin represented by the formula III in the step (3) to the terminal group in the hydroxyl-terminated reagent containing an unsaturated double bond group is 1: (1) 1.2);
    优选地，步骤(3)所述反应在碱性物质存在下进行； Preferably, the reaction in the step (3) is carried out in the presence of a basic substance;
    优选地，所述碱性物质为无机碱或有机碱，优选氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、三乙胺或吡啶中的任意一种或至少两种的组合；Preferably, the basic substance is an inorganic base or an organic base, preferably any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine;
    优选地，所述碱性物质与式III所示烯丙基化酚类树脂中酚羟基的摩尔比为(1～1.4)∶1；Preferably, the molar ratio of the basic substance to the phenolic hydroxyl group in the allylated phenolic resin of formula III is (1 to 1.4):1;
    优选地，步骤(3)所述反应在相转移催化剂存在下进行；Preferably, the reaction in the step (3) is carried out in the presence of a phase transfer catalyst;
    优选地，所述相转移催化剂为季铵盐类相转移催化剂，优选四丁基氯化铵、四丁基溴化铵、苄基三乙基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵或十四烷基溴三甲基氯化铵中的任意一种或至少两种的组合；Preferably, the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioxane Any one or a combination of at least two of methylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride;
    优选地，所述相转移催化剂的加入量为步骤(3)所述烯丙基化酚类树脂质量的0.1-5％；Preferably, the phase transfer catalyst is added in an amount of 0.1 to 5% by mass of the allylated phenolic resin of the step (3);
    优选地，步骤(3)所述反应的溶剂为醇类溶剂、芳香烃溶剂或酮类溶剂中的任意一种或至少两种的组合，优选为乙醇、丙醇、丁醇、甲苯或二甲苯中的任意一种或至少两种的组合；Preferably, the solvent of the reaction in the step (3) is any one of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent or a combination of at least two, preferably ethanol, propanol, butanol, toluene or xylene Any one or a combination of at least two;
    优选地，所述溶剂的加入量为步骤(3)所述烯丙基化酚类树脂质量的2-5倍；Preferably, the solvent is added in an amount of 2-5 times the mass of the allylated phenolic resin of the step (3);
    优选地，步骤(3)所述反应的温度为40-90℃；Preferably, the temperature of the reaction in the step (3) is 40-90 ° C;
    优选地，步骤(3)所述反应的时间为4-6小时。Preferably, the reaction time in the step (3) is 4-6 hours.
  8. 根据权利要求1或2所述的低极性树脂在树脂复合材料制备中的应用。Use of the low polarity resin according to claim 1 or 2 in the preparation of a resin composite.
  9. 根据权利要求1或2所述的低极性树脂在电子封装材料制备中的应用。Use of the low polarity resin according to claim 1 or 2 in the preparation of an electronic packaging material.
  10. 根据权利要求1或2所述的低极性树脂在覆金属箔层压板制备中的应用。 Use of the low polarity resin according to claim 1 or 2 in the preparation of a metal foil-clad laminate.
PCT/CN2017/110810 2017-07-26 2017-11-14 Low polarity resin, and preparation method therefor and use thereof WO2019019482A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710618307.1 2017-07-26
CN201710618307.1A CN109305896B (en) 2017-07-26 2017-07-26 Low-polarity resin and preparation method and application thereof

Publications (1)

Publication Number Publication Date
WO2019019482A1 true WO2019019482A1 (en) 2019-01-31

Family

ID=65039357

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/110810 WO2019019482A1 (en) 2017-07-26 2017-11-14 Low polarity resin, and preparation method therefor and use thereof

Country Status (3)

Country Link
CN (1) CN109305896B (en)
TW (1) TWI662051B (en)
WO (1) WO2019019482A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220165275A (en) * 2020-05-28 2022-12-14 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 Multifunctional vinyl resin and its manufacturing method
WO2024004618A1 (en) * 2022-06-30 2024-01-04 日鉄ケミカル＆マテリアル株式会社 Polyfunctional vinyl resin and method for producing same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100140A (en) * 1975-06-19 1978-07-11 Ciba-Geigy Corporation Process for the manufacture of crosslinked polymers which contain imide groups
US4835232A (en) * 1987-01-23 1989-05-30 Basf Aktiengesellschaft Heat-curable molding compositions
US5138000A (en) * 1989-02-28 1992-08-11 Ciba-Geigy Corporation Curable compositions based on aromatic bismaleimides
CN103709718A (en) * 2013-12-19 2014-04-09 华为技术有限公司 Thermosetting resin composition and applications thereof
CN103756315A (en) * 2013-12-19 2014-04-30 华为技术有限公司 Thermosetting resin composition and applications thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3071155D1 (en) * 1979-12-22 1985-11-07 Ciba Geigy Ag Compositions containing acrylate and their polymerisation
US4387204A (en) * 1980-04-11 1983-06-07 Ciba-Geigy Corporation Self-crosslinkable monomer composition containing alkenylphenyl substituted acrylates or methacrylates
JPH04282336A (en) * 1991-03-08 1992-10-07 Fuji Photo Film Co Ltd Polyallylic compound
US5919602A (en) * 1997-06-19 1999-07-06 Macdermid Acumen, Inc. Photocurable composition based on acid functional primary resinous mercaptans
US6620905B1 (en) * 2002-02-23 2003-09-16 National Starch And Chemical Investment Holding Corporation Curable compositions containing benzoxazine
US20060223937A1 (en) * 2005-04-04 2006-10-05 Herr Donald E Radiation curable cycloaliphatic barrier sealants
US7495047B2 (en) * 2005-10-06 2009-02-24 At&T Intellectual Property, I, L.P. Poly(arylene ether) composition, method, and article
CN104629341B (en) * 2013-11-08 2017-01-04 中山台光电子材料有限公司 Low dielectric resin composition, applies its semi-solid preparation film, copper clad foil substrate, circuit board
CN107074794B (en) * 2014-11-12 2019-09-24 昭和电工株式会社 The manufacturing method of multivalence glycidyl compound
WO2016093383A1 (en) * 2014-12-09 2016-06-16 한국생산기술연구원 Thermosetting alkoxysilyl compound having two or more alkoxysilyl groups, composition and cured product comprising same, use thereof, and method for preparing alkoxysilyl compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100140A (en) * 1975-06-19 1978-07-11 Ciba-Geigy Corporation Process for the manufacture of crosslinked polymers which contain imide groups
US4835232A (en) * 1987-01-23 1989-05-30 Basf Aktiengesellschaft Heat-curable molding compositions
US5138000A (en) * 1989-02-28 1992-08-11 Ciba-Geigy Corporation Curable compositions based on aromatic bismaleimides
CN103709718A (en) * 2013-12-19 2014-04-09 华为技术有限公司 Thermosetting resin composition and applications thereof
CN103756315A (en) * 2013-12-19 2014-04-30 华为技术有限公司 Thermosetting resin composition and applications thereof

Also Published As

Publication number Publication date
CN109305896A (en) 2019-02-05
CN109305896B (en) 2022-07-19
TW201910360A (en) 2019-03-16
TWI662051B (en) 2019-06-11

Similar Documents

Publication Publication Date Title
WO2018120564A1 (en) Phosphorus-containing active ester, halogen-free composition and copper-clad foil substrate thereof
CN111363308B (en) Epoxy modified low-dielectric fluorine-containing polyphenyl ether coating and high-frequency high-speed copper-clad plate prepared from same
WO2019019482A1 (en) Low polarity resin, and preparation method therefor and use thereof
US11377551B2 (en) Thermosetting resin composition, prepreg made therefrom, laminate clad with metal foil, and high-frequency circuit board
US11319397B2 (en) Thermosetting resin composition, prepreg made therefrom, laminate clad with metal foil, and high-frequency circuit board
WO2019019481A1 (en) Low polarity resin, and preparation method therefor and use thereof
CN116041911B (en) High heat-resistant toughened epoxy resin for copper-clad plate and preparation method thereof
CN114536892B (en) Ultra-low dielectric loss high-frequency high-speed copper-clad plate and preparation method thereof
WO2019019483A1 (en) Intrinsic flame-retardant resin with low polarity, and preparation method therefor and use thereof
TWI658046B (en) Thermosetting resin composition, prepreg made therefrom, metal foil-clad laminate and high-frequency circuit board
CN114573426B (en) Benzocyclobutene derivative and application thereof
WO2019127389A1 (en) Epoxy resin composition, prepreg, laminate and printed circuit board
WO2021068658A1 (en) Active ester compound and preparation method therefor
WO2021068304A1 (en) Phosphorus-containing active ester compound and preparation method therefor
CN117487155A (en) Preparation method of modified low-molecular-weight difunctional polyphenyl ether oligomer with vinyl-terminated polyphenyl ether
TW201041930A (en) Thermosetting resin composition and application
CN115028967A (en) Resin composition and manufacturing method of high-frequency high-speed copper-clad plate
CN117024681A (en) Synthesis method of active ester curing agent
JP2024516247A (en) Capped bisphenol polyether oligomers and compositions, methods of manufacture, and articles made therefrom
CN111793348A (en) High-performance halogen-free resin composition for high-frequency high-speed circuit substrate
JPH0355238A (en) Resin composition for laminated sheet
JPS6119639A (en) Preparation of laminate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17919296

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17919296

Country of ref document: EP

Kind code of ref document: A1