WO2021068658A1 - 一种活性酯化合物及其制备方法 - Google Patents

一种活性酯化合物及其制备方法 Download PDF

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WO2021068658A1
WO2021068658A1 PCT/CN2020/110973 CN2020110973W WO2021068658A1 WO 2021068658 A1 WO2021068658 A1 WO 2021068658A1 CN 2020110973 W CN2020110973 W CN 2020110973W WO 2021068658 A1 WO2021068658 A1 WO 2021068658A1
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aroyloxy
carboxylic acid
biphenoxy
naphthyloxy
carbon atoms
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PCT/CN2020/110973
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English (en)
French (fr)
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朴龙星
吴涛
夏宇
徐伟红
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苏州巨峰电气绝缘系统股份有限公司
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Publication of WO2021068658A1 publication Critical patent/WO2021068658A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to the field of materials, in particular, to an active ester compound and a preparation method thereof.
  • the circuit substrate prepared by using the active ester compound as a curing agent has excellent heat resistance and flame retardancy, and has a dielectric constant and dielectric loss. It is small and has excellent resistance to deformation at high temperatures.
  • electronic substrates generally refer to copper clad laminates, which are made of reinforced materials (such as glass cloth) impregnated with resin glue, dried, covered with copper foil, and made by high temperature and high pressure in a hot press .
  • Electronic substrates that use epoxy resin as the adhesive in the glue are currently the most widely used glass fiber cloth type (FR-4, FR-5) substrates.
  • Epoxy resin contains more than two epoxy groups in the molecule. Due to the chemical activity of epoxy groups, it can react with a variety of compounds containing active hydrogen to open the ring, and then cure and crosslink to form a network structure.
  • Commonly used thermosetting resin Commonly used thermosetting resin.
  • the industry usually uses phenolic resin as the curing agent for epoxy resin.
  • Phenolic resin has a high-density heat-resistant benzene ring structure, which makes the cured epoxy resin system excellent in heat resistance.
  • the technical staff proposed to modify the phenolic hydroxyl group of the phenolic resin into an active ester as a curing agent for epoxy resin, thereby improving the moisture resistance of the cured product and reducing its water absorption, dielectric constant and dielectric loss value. .
  • one aspect of the present invention provides an active ester compound.
  • the circuit substrate prepared by using the active ester compound as a curing agent has excellent heat resistance and flame retardancy, and has low dielectric constant and dielectric loss. , And excellent resistance to deformation at high temperatures.
  • another aspect of the present invention also provides a method for preparing the above-mentioned active ester compound, which has a simple process, easy operation, good yield, and large-scale production.
  • an active ester compound which is represented by the following chemical formula 1:
  • X may be any one selected from the group consisting of aroyloxynaphthyloxy and aroyloxybiphenoxy;
  • Z or Z' may be the same or different, and are each independently selected from an aryl formyl group containing 1 to 20 carbon atoms or an alkyl formyl group containing 1 to 20 carbon atoms;
  • n can be an integer from 1 to 10.
  • the inventors made specific design modifications to the molecular structure of the active ester curing agent, so that the active ester compound according to the present invention has various excellent properties, so that it can fully improve the final product when curing the epoxy resin.
  • the various physical and electronic properties of the circuit substrate adopts bisphenol A as the main molecular structure, and modifies it on this basis.
  • bisphenol A has a symmetrical structure and has symmetrical phenolic hydroxyl groups at both ends of the molecule, so that the polarity of the phenolic hydroxyl groups can be mutually offset.
  • the condensation of the two phenolic hydroxyl groups of bisphenol A with a specific carboxylic acid can further obtain two units of active ester groups (ie -OZ and -OZ'), both of which can interact with the epoxy groups in the epoxy resin. Reaction to achieve curing.
  • the present invention also introduces aroyloxynaphthyloxy or aroyloxybiphenoxy group into the molecule, which also has an active ester group, which can also play the role of curing epoxy resin, that is, the
  • the active ester curing agent has three active ester groups in each repeating unit, which is three times the curing efficiency of ordinary phenolic active ester compounds containing only one active ester group in the repeating unit.
  • aroyloxynaphthyloxy or aroyloxybiphenoxy also brings aryleneoxy groups to each repeating unit in the molecule, so that the molecule has good flame retardant and heat-resistant effects. , Can impart excellent heat resistance and flame retardancy to the finally produced circuit board.
  • the present invention has so many active ester groups that will be extensively cross-linked with epoxy resin to form a more stable network structure, which further improves the heat resistance of the circuit board and makes it still excellent at high temperatures. The mechanical properties.
  • X may be selected from 1-aroyloxy-2-naphthyloxy, 1-aroyloxy-3-naphthyloxy, 1-aroyloxy- 4-naphthyloxy, 1-aroyloxy-5-naphthyloxy, 1-aroyloxy-6-naphthyloxy, 1-aroyloxy-7-naphthyloxy, 1-aroyloxy Any one of -8-naphthyloxy, 2-aroyloxy-3-naphthyloxy, 2-aroyloxy-6-naphthyloxy and 2-aroyloxy-7-naphthyloxy Species; or 2-aroyloxy-3-biphenoxy, 2-aroyloxy-4-biphenoxy, 2-aroyloxy-5-biphenoxy, 2-aroyloxy Group-6-biphenoxy, 2-aroyloxy-2'-biphenoxy, 2-aroyloxy
  • X may be 1-aroyloxy-4-naphthyloxy, 1-aroyloxy-5-naphthyloxy, 3-aroyloxy-5-biphenoxy or 3-aryloxy
  • the acyloxy-5'-biphenoxy group, wherein the aroyloxy group may preferably be an arylformyl group containing 1 to 12 carbon atoms, and more preferably a benzoyl group.
  • Z or Z' may each independently be an arylformyl group containing 1 to 12 carbon atoms or an alkylformyl group containing 1 to 12 carbon atoms, more preferably a benzoyl group, a naphthoyl group, or a Alkyl formyl group of 1 to 5 carbon atoms.
  • n may be an integer of 1-9, more preferably an integer of 1-7.
  • the active ester compound according to the present invention can better exert the performance of curing epoxy resin, and can improve the heat resistance and flame retardancy of the finally produced circuit board, and reduce the dielectric constant and dielectric constant. The loss is small, and the resistance to deformation at high temperatures is improved.
  • step (2) Add the resultant of step (1) and aroyloxy hydroxynaphthalene or aroyloxy hydroxybiphenyl to an acidic solution, and heat to 70 to 100° C. to react for 4 to 7 hours;
  • step (3) Heating and refluxing the resultant of step (2) and carboxylic acid L or carboxylic acid ester M in the presence of a catalyst for 2 to 10 hours,
  • the carboxylic acid L may be an aryl carboxylic acid containing 1 to 20 carbon atoms or an alkyl carboxylic acid containing 1 to 20 carbon atoms, and
  • the carboxylic acid ester M may be an aryl carboxylic acid ester containing 1 to 20 carbon atoms or an alkyl carboxylic acid ester containing 1 to 20 carbon atoms.
  • the active ester compound according to the present invention can be successfully prepared under relatively mild reaction conditions, the reaction process is simplified, the steps are relatively simple, and the yield is high.
  • the molar ratio of bisphenol A to chloroform may be 1:1 to 1:3, preferably 1:2.
  • the degree of polymerization n of the phosphorus-containing active ester compound prepared by the present invention can be limited to an integer ranging from 1 to 10.
  • the alkaline solution may be an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate with a mass concentration of 10%.
  • the heating temperature in the step (1) may preferably be 70-90°C, and the reaction time may preferably be 4 to 6 hours.
  • step (1) the present invention also includes adding acid to neutralize after the reaction and adding ether to extract the reaction product.
  • step (1) first carries out the Reimer-Tiemann reaction.
  • the alkaline environment can remove the active hydrogen on the phenolic hydroxyl group of bisphenol A, and then the benzene ring resonates with the oxygen atom to make the benzene ring ortho-position
  • the electron cloud density of chloroform increases, and at the same time, chloroform will form dichlorocarbene in an alkaline environment, which is an electrophilic reagent, will undergo an electrophilic addition reaction with the above-mentioned ortho position, and then hydrolyze to remove the chloride ion to form a product .
  • the molar ratio of the resultant from step (1) to aroyloxyhydroxynaphthalene or aroyloxyhydroxybiphenyl may be 0.8:1 to 1.2:1, preferably 1:1.
  • the acidic solution may be an aqueous sulfuric acid solution with a mass concentration of 50% to 70%.
  • the heating temperature in the step (2) may preferably be 80 to 90° C., and the reaction time may preferably be 5 to 6 hours.
  • aroyloxy hydroxy naphthalene namely dihydroxy naphthalene monoaryl carboxylate
  • esterification condensation of aryl carboxylic acid and one of the hydroxyl groups in dihydroxy naphthalene and the ratio of the two is equal. Therefore, the reaction product still retains a hydroxyl group, which can be connected to the aldehyde group of the product obtained in step (1) through a nucleophilic reaction.
  • the oxygen atom of the hydroxyl group has an extra pair of electrons, which will attack the carbon atom of the aldehyde group, thereby causing a nucleophilic reaction.
  • step (2) the present invention also includes removing impurities with methanol after the reaction.
  • the molar ratio of the resultant from step (2) to the carboxylic acid L or the carboxylic acid ester M may be 1:2 to 1:3, preferably 1:2.
  • the carboxylic acid L may be at least one selected from benzoic acid, phenylacetic acid, naphthoic acid and naphthaleneacetic acid; and the carboxylic acid ester M may be selected from alkyl benzoate, alkyl phenylacetate, naphthalene At least one of alkyl formate and alkyl naphthaleneacetate is preferably methyl benzoate, methyl phenylacetate, methyl naphthoate, or methyl naphthaleneacetate.
  • the reaction in the step (3) can use toluene, ethylbenzene or xylene as a solvent, preferably xylene.
  • the heating temperature in the step (3) may preferably be 95 to 105° C., and the reaction time may preferably be 4 to 6 hours.
  • the catalyst in the step (3) may be a Lewis acid catalyst, such as AlCl 3 , TiCl 4 or ZnCl 2 , preferably AlCl 3 .
  • the phenolic hydroxyl group of the step (2) will be condensed with the carbonyloxy group of the carboxylic acid L or the carboxylic acid ester M to form a carboxylic acid ester compound of the phenolic hydroxyl group, and the resulting carboxylic acid ester group It is the so-called "active ester", which can undergo condensation reaction with the epoxy group of the epoxy resin at high temperature, thereby playing the role of curing the epoxy resin.
  • thermosetting resin composition comprising the above-mentioned active ester compound as a curing agent.
  • the present invention also provides a cured product, which is a thermally cured product of the above-mentioned curable resin composition.
  • the present invention also provides a printed circuit board comprising the above-mentioned cured product.
  • the active ester compound according to the present invention contains more active ester groups, so it can more effectively play the role of curing epoxy resin, and also form a more stable network structure with epoxy resin, which improves the final product
  • the heat resistance of the circuit board makes it excellent in resistance to deformation at high temperatures.
  • the symmetric structure of the bisphenol A of the active ester compound can effectively reduce the dielectric constant and the dielectric loss tangent value of the finally produced circuit substrate, making it more suitable for high-frequency circuit environments and effectively reducing energy consumption.
  • the active ester compound of the present invention contains aroyloxynaphthyloxy or aroyloxybiphenoxy to impart excellent heat resistance and flame retardancy to the finally produced circuit board.
  • another aspect of the present invention also provides a method for preparing the above-mentioned active ester compound, which has a simple process, easy operation, good yield, and large-scale production.
  • Figure 1 is a 1 HMNR spectrum of an active ester compound prepared according to Example 1 of the present invention.
  • Figure 2 is a 1 HMNR spectrum of the active ester compound prepared according to Example 2 of the present invention.
  • Figure 3 is a 1 HMNR spectrum of the active ester compound prepared according to Example 3 of the present invention.
  • Figure 4 is a 1 HMNR spectrum of the active ester compound prepared according to Example 4 of the present invention.
  • Bisphenol A Purity 99.8% or more, from CCP Corporation;
  • 1,4-Dihydroxynaphthalene monobenzoate purity over 99%, from Alpha Chemical Company in the United States;
  • 1,5-Dihydroxynaphthalene monobenzoate purity over 99%, from Alpha Chemical Company in the United States;
  • 3,5-Dihydroxybiphenyl monobenzoate purity over 99%, from Alpha Chemical Company in the United States;
  • Methyl benzoate purity over 99.0%, from Alpha Chemical Company in the United States;
  • Epoxy resin Model XD-1000, from Nippon Kayaku Co., Ltd.
  • step (2) Add 0.1 mol of the result of step (1) and 0.1 mol of 1,4-dihydroxynaphthalene monobenzoate to 50 mL of a 50% mass concentration sulfuric acid aqueous solution, and heat at 85° C. for 5 hours. After that, the reaction system was washed with methanol (50 mL ⁇ 3) to remove impurities and excess sulfuric acid, and the reaction solution was vacuum spin-dried.
  • step (3) Dissolve 0.05 mol of the product of step (2) and 0.1 mol of methyl benzoate in 30 mL of xylene, add 0.02 mol of catalyst AlCl 3 , and heat at 100° C. for 5 hours. After that, the reaction system Wash with saturated brine (10 mL ⁇ 3), then with methanol (10 mL ⁇ 3), and spin-dry in vacuum, thereby preparing the active ester compound according to the present invention as shown above.
  • step (2) is 80°C, and the reaction time is 6 hours.
  • the active ester compound according to the present invention as shown above was prepared by the same method as in Example 1.
  • step (2) is 90°C and the reaction time is 6 hours
  • the active ester compound according to the present invention as shown above was prepared in the same method as in Example 1.
  • step (2) is 90°C and the reaction time is 5 hours.
  • the active ester compound according to the present invention as shown above was prepared.
  • the phosphorus-containing active ester compounds prepared in Examples 1 to 4 and the phenolic resin active ester compounds of Comparative Examples 1 to 2 and epoxy resin (model XD-1000) were mixed at an equivalent ratio of 1:1, and 0.3 equivalent of A curing accelerator (DMAP) and 0.3 equivalent of filler (aluminum hydroxide) are added, and a solvent (toluene) is added to the mixture to have a solid content of 60%, and the mixture is evenly stirred to obtain a resin composition glue.
  • DMAP A curing accelerator
  • filler aluminum hydroxide
  • the glass cloth was immersed in the resin composition glue, and then the immersed glass was placed in an oven at 150° C. for 8 minutes to form a prepreg.
  • the 8 prepregs were laminated together, and a layer of electrolytic copper foil was laminated on each of the upper and lower sides, and then pressed in a vacuum hot press to obtain a copper-clad laminate.
  • the pressing conditions were: pressure 2.5MPa, pressing at 240°C 2 hour.
  • the parallel plate method is used to determine the dielectric constant and the dielectric loss tangent at a frequency of 1 GHz.
  • the laminate sample is Before the test, store it for 24 hours in an environment with a temperature of 23°C and a humidity of 50%.
  • test laminate was completely immersed in molten solder at a temperature of 288°C until delamination and blistering appeared on the laminate, and the time for the laminate to appear delamination and blistering was recorded.
  • test laminate into a pressure cooker, add water, cook for 5 hours at 121°C and 105kPa, remove the surface moisture, and calculate the mass percentage added after the laminate is treated, which is the water absorption. After that, the treated laminate was completely immersed in molten solder at a temperature of 288°C until delamination blistering occurred, and the time for the laminate to appear delamination blistering was recorded.
  • the DMA method was used to measure the modulus values (in GPa) at 50°C and 260°C, respectively, where the heating rate was 5°C/min and the frequency was 10Hz.
  • the copper clad laminates prepared by using the active ester compounds prepared according to Examples 1 to 4 of the present invention as the curing agent have higher glass transition temperature, Shows extremely excellent heat resistance; small dielectric constant and dielectric loss tangent value, so that the laminate has low energy consumption, and is suitable for high-frequency circuit environments; excellent flame retardancy at V0 level; excellent immersion tin Heat resistance and PCT tin immersion heat resistance. Smaller PCT water absorption indicates very good resistance to humidity and heat; and can maintain a high modulus at high temperatures, that is, low modulus loss rate at high temperatures , Indicating that high mechanical properties are still maintained at high temperatures.

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Abstract

本发明涉及一种活性酯化合物及其制备方法，采用所述活性酯化合物作为固化剂制得的电路基板耐热性和阻燃性优异，介电常数和介电损耗较小，并且高温下的抗形变能力优良。此外，根据本发明的上述活性酯化合物的制备方法工艺简单，易于操作，收率好，可规模化生产。

Description

一种活性酯化合物及其制备方法
本申请要求了申请日为2019年10月10日，申请号为201910960551.5的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及材料领域，具体地，涉及一种活性酯化合物及其制备方法，采用所述活性酯化合物作为固化剂制得的电路基板耐热性和阻燃性优异，介电常数和介电损耗较小，并且高温下的抗形变能力优良。
背景技术
在电子工业中，电子基板一般是指覆铜层压板，其由增强材料(如玻璃布)浸以树脂胶液，烘干，覆上铜箔，在热压机中经高温高压而制成的。采用环氧树脂作为胶液中的胶黏剂的电子基板是目前最广泛使用的玻璃纤维布基类型(FR-4、FR-5)基板。环氧树脂在分子中含有两个以上的环氧基团，由于环氧基的化学活性，可与多种含有活泼氢的化合物反应而开环，进而固化交联形成网状结构，是一种常用的热固性树脂。在这里，行业通常采用酚醛树脂作为环氧树脂的固化剂，酚醛树脂具有高密度的耐热苯环结构，使得环氧树脂固化后的体系的耐热性优良。
当今电子产品的应用已进入生活和工业的方方面面，这对电子基板产生了更高的要求，特别是电子器件在运行过程中会放出大量的热量，对其耐热性、阻燃性和高温下的机械性能的指标要求也越加苛刻。此外，如今电子产品的信息处理的速度也越来越快，功能也越来越多，因而应用频率也越来越高，除了保持较高的耐热性和阻燃性之外，还要求其介电常数和介电损耗值越低越好。然而，现有的环氧玻璃纤维布层压板(FR-4)已然逐渐不能满足电子产品的耐热、高频的应用需求。
对此，技术人员提出了将酚醛树脂的酚羟基修饰为活性酯，以作为环氧树脂的固化剂，由此改善固化产物的耐湿性，并降低其吸水率、介电常数和介电损耗值。但是，该固化产物在耐热性与介电性能之间很难取得令人满意的平衡，以同时拥有较高的玻璃化转变温度与较低的介电损耗值，并减小其机械性能随温度的变化。
基于上述情况，为了改善环氧玻璃纤维布层压板的性能，本领域技术 人员进行了多种尝试，如添加各种助剂，对环氧树脂、固化剂的分子结构进行修饰等，以求获得基板的各项性能，如耐湿热性、阻燃性、介电常数、介电损耗值、高温机械性能等的均衡改善，但目前效果尚不理想。
发明内容
[技术问题]
为了解决上述问题，本发明的一个方面提供了一种活性酯化合物，采用所述活性酯化合物作为固化剂制得的电路基板耐热性和阻燃性优异，介电常数和介电损耗较小，并且高温下的抗形变能力优良。
此外，本发明的另一个方面还提供了上述活性酯化合物的制备方法，其工艺简单，易于操作，收率好，可规模化生产。
[技术方案]
根据本发明的一个实施方式，提供了一种活性酯化合物，其由以下化学式1表示：
[化学式1]
Figure PCTCN2020110973-appb-000001
其中，X可以为选自芳酰氧基萘氧基和芳酰氧基联苯氧基中的任意一种；
Z或Z’可以相同或不同，且各自独立地为选自含1至20个碳原子的芳基甲酰基或含1至20个碳原子的烷基甲酰基；以及
n可以为1至10的整数。
在本发明中，发明人对活性酯固化剂的分子结构进行了特定的设计修饰，使得根据本发明的活性酯化合物具有各种优良的性能，从而在固化环氧树脂时能够充分改善最终制得的电路基板的各种物理和电子性能。具体 地，本发明采用双酚A作为分子主体结构，并在此基础上加以修饰，首先双酚A具有对称结构，在分子两端具有对称的酚羟基，因而能够相互抵消酚羟基的极性，有效减小最终制得的电路基板的介电常数和介电损耗正切值，使得电路基板更能适应高频电路环境，并有效减少能耗。而且，双酚A的两个酚羟基与特定的羧酸缩合能够进一步获得两个单位的活性酯基团(即-OZ和-OZ’)，均能与环氧树脂中的环氧基团发生反应，实现固化。并且，本发明还在分子中引入了芳酰氧基萘氧基或芳酰氧基联苯氧基，也具备活性酯基团，同样能够起到固化环氧树脂的作用，即根据本发明的活性酯固化剂在各个重复单元中均具有三个活性酯基团，是在重复单元中仅含一个活性酯基团的普通酚醛活性酯化合物的固化效力的三倍。
此外，本发明中，芳酰氧基萘氧基或芳酰氧基联苯氧基还为分子中的各个重复单元带来了亚芳基氧基，使得分子具有良好的阻燃和耐热效力，能够赋予最终制得的电路基板优异的耐热性和阻燃性。特别是，本发明具有如此多的活性酯基团还会与环氧树脂广泛交联形成更稳定的网状结构，更进一步提高了电路基板的耐热性，并使得其在高温下依然保持优良的机械性能。
优选地，在根据本发明的活性酯化合物中，X可以选自1-芳酰氧基-2-萘氧基、1-芳酰氧基-3-萘氧基、1-芳酰氧基-4-萘氧基、1-芳酰氧基-5-萘氧基、1-芳酰氧基-6-萘氧基、1-芳酰氧基-7-萘氧基、1-芳酰氧基-8-萘氧基、2-芳酰氧基-3-萘氧基、2-芳酰氧基-6-萘氧基和2-芳酰氧基-7-萘氧基中的任意一种；或者2-芳酰氧基-3-联苯氧基、2-芳酰氧基-4-联苯氧基、2-芳酰氧基-5-联苯氧基、2-芳酰氧基-6-联苯氧基、2-芳酰氧基-2’-联苯氧基、2-芳酰氧基-3’-联苯氧基、2-芳酰氧基-4’-联苯氧基、2-芳酰氧基-5’-联苯氧基、2-芳酰氧基-6’-联苯氧基、3-芳酰氧基-4-联苯氧基、3-芳酰氧基-5-联苯氧基、3-芳酰氧基-3’-联苯氧基、3-芳酰氧基-4’-联苯氧基、3-芳酰氧基-5’-联苯氧基和4-芳酰氧基-4’-联苯氧基中的任意一种，其中，所述芳酰氧基可以为含1至20个碳原子的芳基甲酰基。更优选地，X可以为1-芳酰氧基-4-萘氧基、1-芳酰氧基-5-萘氧基、3-芳酰氧基-5-联苯氧基或3-芳酰氧基-5’-联苯氧基，其中，所述芳酰氧基可以优选为含1至12个碳原子的芳基甲酰基，更优选为苯甲酰基。
优选地，Z或Z’可以各自独立地为含1至12个碳原子的芳基甲酰基或含1至12个碳原子的烷基甲酰基，更优选为苯甲酰基、萘甲酰基或含1至 5个碳原子的烷基甲酰基。
优选地，n可以为1至9的整数，更优选1至7的整数。
在上述范围内，根据本发明的活性酯化合物能够更好地发挥固化环氧树脂的性能，并能够改善最终制得的电路基板的耐热性和阻燃性，减小介电常数和介电损耗较小，以及提高高温下的抗形变能力。
根据本发明的另一个实施方式，提供了上述活性酯化合物的制备方法，包括以下步骤：
(1)将双酚A和三氯甲烷加入到碱性溶液中，加热至60-100℃反应2至8小时；
(2)将步骤(1)所得物和芳酰氧基羟基萘或芳酰氧基羟基联苯加入到酸性溶液中，加热至70至100℃反应4至7小时；
(3)将步骤(2)所得物和羧酸L或羧酸酯M在催化剂的存在下加热回流2至10小时，
所述羧酸L可以为含1至20个碳原子的芳基羧酸或含1至20个碳原子的烷基羧酸，以及
所述羧酸酯M可以为含1至20个碳原子的芳基羧酸酯或含1至20个碳原子的烷基羧酸酯。
通过上述制备方法，能够以较为温和的反应条件顺利地制得根据本发明的活性酯化合物，反应流程精简，步骤较为简单，收率高。
优选地，在上述步骤(1)中，双酚A与三氯甲烷的摩尔比可以为1∶1至1∶3，优选1∶2。在此范围内，可以将本发明制得的含磷活性酯化合物的聚合度n限定在1至10的整数范围内。
所述碱性溶液可以为质量浓度10％的氢氧化钠、氢氧化钾、碳酸钠或碳酸钾的水溶液。
所述步骤(1)中的加热温度可以优选为70-90℃，反应时间可以优选为4至6小时。
此外，在步骤(1)中，本发明还包括在反应后加酸中和并加入乙醚以萃取反应产物。
在本发明中，步骤(1)首先进行Reimer-Tiemann反应，在该反应中，碱性环境能够脱去双酚A的酚羟基上的活泼氢，之后苯环与氧原子共振使苯环邻位的电子云密度增高，与此同时，三氯甲烷在碱性环境中会形成二氯卡宾，其为亲电子试剂，会与上述邻位发生亲电加成反应，之后水解脱 去氯离子形成产物。在这里，双酚A的两个苯环的对位均被占用，只能生成邻位加成醛基的产物，因此，反应选择性高，产率也较高。之后，邻位加成醛基的双酚A还会在碱性环境下继续发生酚醛缩合反应，生成线性的双酚A酚醛树脂。即一步生成本发明的含磷活性酯化合物的主体骨架。
优选地，在上述步骤(2)中，步骤(1)所得物与芳酰氧基羟基萘或芳酰氧基羟基联苯的摩尔比可以为0.8∶1至1.2∶1，优选1∶1。
所述酸性溶液可以为质量浓度50％至70％的硫酸水溶液。
所述步骤(2)中的加热温度可以优选为80至90℃，反应时间可以优选为5至6小时。
在本发明中，芳酰氧基羟基萘，即二羟基萘单芳基羧酸酯，是由芳基羧酸与二羟基萘中的一个羟基进行酯化缩合而得到的，二者等摩尔比反应，因而反应产物还保留有一个羟基，该羟基即可通过亲核反应连接至步骤(1)所得物的醛基上。在该反应中，所述羟基的氧原子上具有多余的电子对，其会进攻醛基的碳原子，由此发生亲核反应。通过上述反应，不但在双酚A上引入了亚芳基氧基，使得固化剂具备阻燃和耐热效力，还带来了活性酯基团，也能够参与环氧树脂的固化。此外，芳酰氧基羟基联苯，即二羟基联苯单芳基羧酸酯也具有类似情形，在此不做赘述。
此外，在步骤(2)中，本发明还包括在反应后用甲醇除杂。
优选地，在上述步骤(3)中，步骤(2)所得物与羧酸L或羧酸酯M摩尔比可以为1∶2至1∶3，优选1∶2。
所述羧酸L可以为选自苯甲酸、苯乙酸、萘甲酸和萘乙酸中的至少一种；以及所述羧酸酯M可以为选自苯甲酸烷基酯、苯乙酸烷基酯、萘甲酸烷基酯和萘乙酸烷基酯中的至少一种，优选为苯甲酸甲酯、苯乙酸甲酯、萘甲酸甲酯或萘乙酸甲酯。
所述步骤(3)中的反应可以以甲苯、乙苯或二甲苯为溶剂，优选二甲苯。
所述步骤(3)中的加热温度可以优选为95至105℃，反应时间可以优选为4至6小时。
此外，所述步骤(3)中的催化剂可以为路易斯酸催化剂，如AlCl 3、TiCl 4或ZnCl 2，优选AlCl 3。
在本发明中，所述步骤(2)所得物的酚羟基会与羧酸L或羧酸酯M的羰氧基发生缩合，生成酚羟基的羧酸酯化合物，所生成的羧酸酯基团即 为所谓的“活性酯”，其能够在高温下与环氧树脂的环氧基发生缩合反应，从而起到固化环氧树脂的作用。
此外，本发明还提供了一种热固化性树脂组合物，其包含上述活性酯化合物作为固化剂。
本发明还提供了一种固化物，其为上述固化性树脂组合物的热固化产物。
本发明还提供了一种印刷电路基板，其包含上述固化物。
[有益效果]
根据本发明的活性酯化合物包含有更多的活性酯基团，因而能够更有效地发挥固化环氧树脂的作用，并且还会与环氧树脂形成更稳定的网状结构，提高了最终制得的电路基板的耐热性，并使得其在高温下的抗形变能力优良。另外，所述活性酯化合物的双酚A的对称结构能够有效减小最终制得的电路基板的介电常数和介电损耗正切值，使之更能适应高频电路环境并有效减少能耗。此外，本发明的活性酯化合物包含芳酰氧基萘氧基或芳酰氧基联苯氧基，赋予最终制得的电路基板优异的耐热性和阻燃性。
此外，本发明的另一个方面还提供了上述活性酯化合物的制备方法，其工艺简单，易于操作，收率好，可规模化生产。
附图说明
图1为根据本发明的实施例1制得的活性酯化合物的 1HMNR谱图。
图2为根据本发明的实施例2制得的活性酯化合物的 1HMNR谱图。
图3为根据本发明的实施例3制得的活性酯化合物的 1HMNR谱图。
图4为根据本发明的实施例4制得的活性酯化合物的 1HMNR谱图。
具体实施方式
下文中，提供了优选的实施例以便使本领域技术人员更好地理解本发明。然而，这些实施例仅用于说明目的，且并不旨在将本发明限定为这些实施例。
原料试剂
双酚A：纯度99.8％以上，来自CCP株式会社；
1，4-二羟基萘单苯甲酸酯：纯度99％以上，来自美国阿尔法化学公司；
1，5-二羟基萘单苯甲酸酯：纯度99％以上，来自美国阿尔法化学公司；
3，5-二羟基联苯单苯甲酸酯：纯度99％以上，来自美国阿尔法化学公司；
3，5’-二羟基联苯单苯甲酸酯：纯度99％以上，来自美国阿尔法化学公司；
苯甲酸甲酯：纯度99.0％以上，来自美国阿尔法化学公司；
环氧树脂：型号XD-1000，来自日本化药株式会社。
<实施例>
实施例1
Figure PCTCN2020110973-appb-000002
(1)将0.2mol的双酚A和0.4mol的三氯甲烷加入到150mL的10％的氢氧化钠水溶液中，加热至80℃反应5小时。之后，反应体系用稀盐酸中和至pH约等于7，并加入乙醚(70mL×3)萃取，真空旋转干燥有机相。
(2)将0.1mol的步骤(1)所得物和0.1mol的1，4-二羟基萘单苯甲酸酯加入到50mL的质量浓度50％的硫酸水溶液中，在85℃下加热5小时。之后，反应体系用甲醇洗涤(50mL×3)以除去杂质和多余的硫酸，反应液真空旋转干燥。
(3)将0.05mol的步骤(2)所得物和0.1mol的苯甲酸甲酯溶于30mL的二甲苯中，加入0.02mol的催化剂AlCl 3，在100℃下加热5小时，之后，反应体系用饱和食盐水洗涤(10mL×3)，再用甲醇洗涤(10mL×3)，真空旋转干燥，由此制得如上所示的根据本发明的活性酯化合物。
实施例2
Figure PCTCN2020110973-appb-000003
除了采用1，5-二羟基萘单苯甲酸酯来代替1，4-二羟基萘单苯甲酸酯，以及步骤(2)的加热温度为80℃，反应时间为6小时之外，以与实施例1相同的方法制备了如上所示的根据本发明的活性酯化合物。
实施例3
Figure PCTCN2020110973-appb-000004
除了采用3，5-二羟基联苯单苯甲酸酯来代替1，4-二羟基萘单苯甲酸酯，以及步骤(2)的加热温度为90℃，反应时间为6小时之外，以与实施例1相同的方法制备了如上所示的根据本发明的活性酯化合物。
实施例4
Figure PCTCN2020110973-appb-000005
除了采用3，5’-二羟基联苯单苯甲酸酯来代替1，4-二羟基萘单苯甲酸酯，以及步骤(2)的加热温度为90℃，反应时间为5小时之外，以与实施例1相同的方法制备了如上所示的根据本发明的活性酯化合物。
对比实施例1
市售酚醛树脂活性酯化合物(型号HPC-8000，来自DIC株式会社)。
对比实施例2
市售酚醛树脂活性酯化合物(型号SHC-5100，来自韩国信亚株式会社)。
试验实施例
制备电子基板
分别将实施例1至4制得的含磷活性酯化合物以及对比实施例1至2的酚醛树脂活性酯化合物与环氧树脂(型号XD-1000)按当量比1∶1混合，加入0.3当量的固化促进剂(DMAP)和0.3当量的填料(氢氧化铝)，再加入溶剂(甲苯)至混合物固含量为60％，搅拌均匀即制得树脂组合物胶液。
之后，将玻璃布浸渍于该树脂组合物胶液中，然后将经浸渍的玻璃布置于150℃的烘箱中8分钟以形成半固化片。将8张该半固化片层叠在一起，并在其上下侧各叠加一层电解铜箔，之后在真空热压机中压制以获得覆铜层压板，压制条件为：压力2.5MPa，240℃下压制2小时。
性能测试
采用以下测试项目来测定以实施例1至4制得的活性酯化合物以及对 比实施例1至2的酚醛树脂活性酯化合物作为固化剂制得的覆铜层压板的性能。结果如以下表1所示。
(1)玻璃化转变温度(Tg)：
根据IPC-TM-650试验方法手册第2.4.24部分所述的DMA(动态力学分析)方法测定，其中，升温速率为5℃/min，频率为10Hz，温度范围为30-320℃。
(2)介电常数(ε)和介电损耗正切值(tanδ)：
根据IPC-TM-650试验方法手册第2.5.5.9部分所述的DMA方法测定，其中，采用平行板法，测定1GHz频率下的介电常数和介电损耗正切值，其中，层压板试样在测试前在温度23℃，湿度50％的环境下保存24小时。
(3)阻燃性
根据UL94垂直燃烧测试法进行测试。
(4)浸锡耐热性
将测试层压板完全浸入温度为288℃的熔融焊锡中，直至层压板出现分层起泡，记录层压板出现分层起泡的时间。
(5)高压锅蒸煮实验(PCT)的吸水率和浸锡耐热性
将测试层压板放入高压锅中，加水，在121℃、105kPa的条件下蒸煮处理5小时，取出擦干表面水分，计算层压板处理后增加的质量百分比，即为吸水率。之后，将处理过的层压板完全浸入温度为288℃的熔融焊锡中，直至出现分层起泡，记录层压板出现分层起泡的时间。
(6)模量
采用DMA方法分别测定50℃和260℃下的模量值(单位GPa)，其中，升温速率为5℃/min，频率为10Hz。
[表1]
Figure PCTCN2020110973-appb-000006
Figure PCTCN2020110973-appb-000007
参照上述表1，相比于对比实施例1和2，采用根据本发明实施例1至4制得的活性酯化合物作为固化剂制得的覆铜层压板具有：更高的玻璃化转变温度，表明极其优良的耐热性；较小的介电常数和介电损耗正切值，使得层压板耗能低，且适合用于高频电路环境；V0级别的优良的阻燃性；优良的浸锡耐热性和PCT浸锡耐热性，较小的PCT吸水率，表明具有非常优良的耐湿热性能；以及在高温下仍能保持较高的模量，即高温下的模量损失率较低，表明高温下的仍旧保持较高的机械性能。
尽管已用具体实施例来说明和描述了本发明，然而本领域技术人员应当理解的是，在不背离本发明的精神和范围的情况下，可以对前述各实施例所记载的技术方案进行修改，这些修改也应当被认为是在本发明要求保护的技术方案的范围之内。

Claims (10)

  1. 一种活性酯化合物，由以下化学式1表示：
    [化学式1]
    Figure PCTCN2020110973-appb-100001
    其中，X为选自芳酰氧基萘氧基和芳酰氧基联苯氧基中的任意一种；
    Z或Z’相同或不同，且各自独立地为选自含1至20个碳原子的芳基甲酰基或含1至20个碳原子的烷基甲酰基；以及
    n为1至10的整数。
  2. 根据权利要求1所述的活性酯化合物，其中，X选自1-芳酰氧基-2-萘氧基、1-芳酰氧基-3-萘氧基、1-芳酰氧基-4-萘氧基、1-芳酰氧基-5-萘氧基、1-芳酰氧基-6-萘氧基、1-芳酰氧基-7-萘氧基、1-芳酰氧基-8-萘氧基、2-芳酰氧基-3-萘氧基、2-芳酰氧基-6-萘氧基和2-芳酰氧基-7-萘氧基中的任意一种；或者2-芳酰氧基-3-联苯氧基、2-芳酰氧基-4-联苯氧基、2-芳酰氧基-5-联苯氧基、2-芳酰氧基-6-联苯氧基、2-芳酰氧基-2’-联苯氧基、2-芳酰氧基-3’-联苯氧基、2-芳酰氧基-4’-联苯氧基、2-芳酰氧基-5’-联苯氧基、2-芳酰氧基-6’-联苯氧基、3-芳酰氧基-4-联苯氧基、3-芳酰氧基-5-联苯氧基、3-芳酰氧基-3’-联苯氧基、3-芳酰氧基-4’-联苯氧基、3-芳酰氧基-5’-联苯氧基和4-芳酰氧基-4’-联苯氧基中的任意一种，其中，所述芳酰氧基为含1至20个碳原子的芳基甲酰基；
    Z或Z’各自独立地为含1至12个碳原子的芳基甲酰基或含1至12个碳原子的烷基甲酰基；以及n为1至9的整数。
  3. 根据权利要求2所述的活性酯化合物，其中，X为1-芳酰氧基-4-萘氧基、1-芳酰氧基-5-萘氧基、3-芳酰氧基-5-联苯氧基或3-芳酰氧基-5’-联苯氧基，其中，所述芳酰氧基为含1至12个碳原子的芳基甲酰基；Z或Z’各自独立地为苯甲酰基、萘甲酰基或含1至5个碳原子的烷基甲酰基； 以及n为1至7的整数。
  4. 一种权利要求1至3任一项所述的活性酯化合物的制备方法，包括以下步骤：
    (1)将双酚A和三氯甲烷加入到碱性溶液中，加热至60-100℃反应2至8小时；
    (2)将步骤(1)所得物和芳酰氧基羟基萘或芳酰氧基羟基联苯加入到酸性溶液中，加热至70至100℃反应4至7小时；
    (3)将步骤(2)所得物和羧酸L或羧酸酯M在催化剂的存在下加热回流2至10小时，
    所述羧酸L为含1至20个碳原子的芳基羧酸或含1至20个碳原子的烷基羧酸，以及
    所述羧酸酯M为含1至20个碳原子的芳基羧酸酯或含1至20个碳原子的烷基羧酸酯。
  5. 根据权利要求4所述的制备方法，其中，在步骤(1)中，双酚A与三氯甲烷的摩尔比为1∶1至1∶3；所述碱性溶液为质量浓度10％的氢氧化钠、氢氧化钾、碳酸钠或碳酸钾的水溶液；以及所述步骤(1)中的加热温度为70-90℃，反应时间为4至6小时。
  6. 根据权利要求5所述的制备方法，其中，在步骤(1)中，双酚A与三氯甲烷的摩尔比为1∶2。
  7. 根据权利要求4所述的制备方法，其中，在步骤(2)中，步骤(1)所得物与芳酰氧基羟基萘或芳酰氧基羟基联苯的摩尔比为0.8∶1至1.2∶1；所述酸性溶液为质量浓度50％至70％的硫酸水溶液；以及所述步骤(2)中的加热温度为80至90℃，反应时间为5至6小时。
  8. 根据权利要求7所述的制备方法，其中，在步骤(2)中，步骤(1)所得物与芳酰氧基羟基萘或芳酰氧基羟基联苯的摩尔比为1∶1。
  9. 根据权利要求4所述的制备方法，其中，在步骤(3)中，步骤(2)所得物与羧酸L或羧酸酯M摩尔比为1∶2至1∶3；所述羧酸L为选自苯甲酸、苯乙酸、萘甲酸和萘乙酸中的至少一种，所述羧酸酯M为选自苯甲酸烷基酯、苯乙酸烷基酯、萘甲酸烷基酯和萘乙酸烷基酯中的至少一种；所述步骤(3)中的反应以甲苯、乙苯或二甲苯为溶剂；所述步骤(3)中的加热温度为95至105℃，反应时间为4至6小时以及此外，所述步骤(3)中的催化剂为AlCl 3、TiCl 4或ZnCl 2。
  10. 根据权利要求9所述的制备方法，其中，在步骤(3)中，步骤(2)所得物与羧酸L或羧酸酯M摩尔比为1∶2；所述羧酸酯M为苯甲酸甲酯、苯乙酸甲酯、萘甲酸甲酯或萘乙酸甲酯；所述步骤(3)中的反应以二甲苯为溶剂；以及所述步骤(3)中的催化剂为AlCl 3。
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