CN108929203A - 一种芳香族乙烯基醚及其合成方法和应用 - Google Patents
一种芳香族乙烯基醚及其合成方法和应用 Download PDFInfo
- Publication number
- CN108929203A CN108929203A CN201810922442.XA CN201810922442A CN108929203A CN 108929203 A CN108929203 A CN 108929203A CN 201810922442 A CN201810922442 A CN 201810922442A CN 108929203 A CN108929203 A CN 108929203A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- aromatic
- added
- alkali
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- MGNZXYYWBUKAII-UHFFFAOYSA-N C1C=CC=CC1 Chemical compound C1C=CC=CC1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
- C07C41/08—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only to carbon-to-carbon triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
- C07C43/1787—Unsaturated ethers containing hydroxy or O-metal groups containing six-membered aromatic rings and having unsaturation outside the aromatic rings
-
- 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
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/24—Trifluorochloroethene
- C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
- C08F214/247—Trifluorochloroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
- C08F214/267—Tetrafluoroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
- C08F214/285—Hexyfluoropropene with non-fluorinated comonomers
- C08F214/287—Hexyfluoropropene with non-fluorinated comonomers with non-fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
-
- 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
- C09J127/00—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 a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
- C09J127/00—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 a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/18—Homopolymers or copolymers of tetrafluoroethene
-
- 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
- C09J127/00—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 a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/20—Homopolymers or copolymers of hexafluoropropene
-
- 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
- C09J129/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/10—Homopolymers or copolymers of unsaturated ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于化工技术领域,具体涉及一种芳香族乙烯基醚及其合成方法和应用。本发明的合成方法一是含酚的芳香醇通过加入碱、二溴乙烷,醇钾消除得到芳香族乙烯基醚;方法二是芳香族烷基醇与碱、乙炔反应生成芳香族乙烯基醚。本发明的芳香族乙烯基醚用作高频低介电常数覆铜板粘合剂树脂改性的共聚单体,其与含氟烯烃的共聚物耐高温、绝缘性能好。
Description
技术领域
本发明属于化工技术领域,具体涉及一种芳香族乙烯基醚及其合成方法和应用。
背景技术
随着现代科技的快速发展,高分子材料已是材料科学中最具代表性的、最具发展前途的一类材料。
随着4G通信技术向5G通信技术的发展,以及高频的通信技术(6G到10G)将是未来的发展趋势,相应的电子设备信号传输高频化和高速数字化,对电子设备中承载电子元件的基板材料的各种性能的要求越来越高:传输信号的损耗和功率损耗小;在基板的介质中,信号传输过程会发生信号损耗和功率损耗,其损耗的大小随着传输信号的频率增加而增大,介质中介电常数(εr)1/2和损耗正切角tanδ的增大而增加。由于信号的介质损耗转变为热能而引起基板温升,基板温升又引起更大的信号介质损耗,使信号传输变差。因此,对于高频信号和高速数字信号的传输用基板必须选择低介电常数和低介电损耗的材料。材料本身还应满足低吸水率、高耐热性、力学性能以及优异的加工性能等。
一般常见的环氧树脂、聚四氟乙烯(PTFE)、聚酰亚胺(PI)、聚苯醚(PPE)、液晶聚合物(LCP)介电常数分别为3.9、2.1、3.3、2.5、2.9。含氟聚合物在高频条件下具有良好的低介电性能,但纯聚四氟乙烯(PTFE)加工性能较差,需要在其表面进行处理增加与铜箔的粘结性,才能进行下一步的应用。目前普通的PCB基材是不能满足高速信号传输要求的,这将成为电子工业发展中的技术“瓶颈”,因此,开发易加工、高性能的含氟树脂低介电材料是相当必要的,能与含氟烯烃共聚的单体的开发是获得高性能树脂的关键。我们开发出的芳香族乙烯基醚将满足此功能要求。
发明内容
有鉴于此,本发明的目的在于提供一种芳香族乙烯基醚的合成方法和应用。本发明合成的芳香族乙烯基醚与含氟烯烃共聚的聚合物耐高温、绝缘性能好,在电子材料工业中具有很大的应用前景,尤其用于高频低介电常数覆铜板粘合剂树脂改性的共聚单体。
为实现上述目的,本发明的技术方案为:
一种芳香族乙烯基醚,其结构如下式Ⅰ或Ⅱ所示:
其中,m,n为1至8的整数,m,n可以相等,也可以不相等;取代基可以是邻、间、对位取代,也可以是直链、支链取代。
本发明的目的之二在于提供一种芳香族乙烯基醚的合成方法,式Ⅰ化合物是含酚的芳香醇通过加入碱、二溴乙烷,醇钾溶液发生反应,得到芳香族乙烯基醚;式Ⅱ化合物是芳香族烷基醇与碱、乙炔反应生成芳香族乙烯基醚。
乙炔与含酚的芳香醇不能直接通过加成反应制备芳香族乙烯基醚,原因是乙炔与含酚的芳香醇最初形成的乙烯基醚,高温下发生重排,易聚合。间接采用溴代烷基芳香族烷基醇消去反应合成芳香族乙烯基醚,合成工艺不复杂,产品不发生重排。芳香族烷基醇分子结构不含酚,类似脂肪族醇,与乙炔直接反应可得芳香族乙烯基醚。
作为一种优选,所述的碱为含碱金属元素的碱,包括KOH、NaOH。优选KOH。
进一步,以式Ⅲ化合物为原料,加入碱、二溴乙烷、醇钾溶液发生反应,即得式Ⅰ化合物;
其中,式Ⅲ化合物为酚羟基与醇羟基取代的芳烃,n为1至8的整数;取代基可以是邻、间、对位取代,也可以是直链、支链取代。
作为一种优选,所述醇钾液为甲醇钾或乙醇钾溶液。
进一步,碱与式Ⅲ化合物、二溴乙烷的摩尔比为1.0-1.2:1.0-3.0;醇钾液与式Ⅲ化合物生成的中间体溴乙基芳香族醇的摩尔比为1.0-2.0:1。
由于二溴乙烷过量有助于生成一溴代烷基芳基醇,减少副产物,碱量应将酚转化为酚盐,碱过量将会增加副产物,因此碱与式Ⅲ化合物、二溴乙烷的摩尔比为1.0~1.2:1.0:1.0~3.0;醇钾液必须与溴代烷基芳基醇摩尔量相当,略微过量有助于提高产品的收率,醇钾液过量成本较高,废物增加,因此醇钾液与式Ⅲ化合物的摩尔比为1.0~2.0:1。
作为一种优选,碱与式Ⅲ化合物、二溴乙烷的摩尔比为1.0-1.2:1.0:2.0。
作为一种优选,碱与式Ⅲ化合物、二溴乙烷的摩尔比为1.05:1.0:2.0。
作为一种优选,碱与式Ⅲ化合物、二溴乙烷的摩尔比为1.05:1.0:1.5。
作为一种优选,醇钾溶液与溴乙基芳香族醇的摩尔比为1.5:1,更优选为1.2:1。
进一步,式Ⅰ化合物的合成方法包括以下步骤:
1)将式Ⅲ化合物加入到碱液中,充分溶解,得溶液A;
2)在反应釜中加入二溴乙烷,滴入溶液A反应,反应温度为30-80℃,2-8h后,油水分离,油层为溴乙基芳香族醇B;
3)将油层加入反应釜加热脱水后,加入醇钾液,40-80℃反应4-6小时,过滤,滤液蒸馏后剩余物为芳香族乙烯基醚C,重结晶得产品。
作为一种优选,步骤2)中反应温度为50~70℃,反应时间为4~6h。
作为一种优选,将步骤3)得到的芳香族乙烯基醚经过减压精馏或结晶提纯得到式Ⅰ的芳香族乙烯基醚产品。
进一步,以式Ⅳ化合物为原料,加入碱、乙炔反应,即得式Ⅱ化合物;
其中,式Ⅳ化合物为醇羟基取代的芳烃,m,n为1至8的整数,m,n可以相等,也可以不相等。碱可以氢氧化钠、氢氧化钾、氢氧化钙等,优选为氢氧化钾。
进一步,碱与式Ⅳ化合物、乙炔的摩尔比为0.05-0.5:1:0.2-1.0。
作为一种优选,碱与式Ⅳ化合物、与乙炔的摩尔比为0.1-0.3:1:0.3-0.8。
作为一种优选,碱与式Ⅳ化合物、乙炔的摩尔比为0.2-0.3:1:0.4-0.6。
进一步,式Ⅱ化合物的合成方法包括以下步骤:
1)将式Ⅳ化合物加入反应釜后,加入碱,加热至100-160℃减压脱水,得醇碱液B;
2)反应釜氮气置换后,在100-180℃中通入乙炔气,反应4-10h后,停止反应,反应液蒸馏出半成品,半成品经过高真空精馏得产品。
作为一种优选,高真空精馏的真空度为-0.090~-0.0995MPa。
进一步,步骤1)中真空度维持在-0.5~-0.98MPa,反应时间为2~8h。
作为一种优选,步骤1)中反应温度为140~150℃;反应时间为4~6h。
作为一种优选,步骤2)中反应温度为120-180℃,反应时间为4~12h;优选反应温度为140~160℃,反应时间为6~10h。
本发明的目的之三在于提供一种上述的芳香族乙烯基醚在制备化工试剂、耐高温的粘结材料及电子材料中的应用,所述应用包括在作为共聚单体在制备高频低介电常数覆铜板粘合剂中的应用;所述应用包括芳香族烯乙基醚与含氟烯烃共聚的聚合物在绝缘、耐高温的电子材料中的应用。
所述含氟烯烃优选为三氟氯乙烯、四氟乙烯、六氟丙烯,最优选为四氟乙烯。本发明的芳香族乙烯基醚与含氟烯烃的共聚物耐高温、绝缘性能好。
本发明的目的还在于提供一种含氟高分子材料的用途。式Ⅰ或式Ⅱ的化合物与含氟烯烃聚合,得到的树脂用于满足5G及以上通信技术所需高频低介电常数材料的需求。所述的树脂可以通过以下技术方案来实现:
式Ⅰ或式Ⅱ的化合物与三氟氯乙烯、四氟乙烯、六氟丙烯等氟烯烃聚合。优选四氟乙烯、六氟丙烯,最优选四氟乙烯。本发明所述的共聚物由下列结构单元构成:(a)氟烯烃;(b)式Ⅰ或式Ⅱ的化合物。各结构单元的含量分别为:(a)大于20mol%,小于80mol%,(b)大于20mol%,小于80mol%。结构如下所示:
其中R为Cl或F或CF3。
本发明的有益效果在于:
1)本发明提供的芳香族乙烯基醚在热稳定性、绝缘性等方面具有优势,同时在聚合反应过程中活性较高,广泛地应用于合成特殊性能的高分子材料,具有很大的应用前景。
2)本发明提供的芳香族乙烯基醚与含氟烯烃聚合,得到的树脂用于满足5G及以上通信技术所需高频低介电材料的需求。
具体实施方式
以下将对本发明的优选实施例进行详细描述。优选实施例中未注明具体条件的实验方法,通常按照常规条件,所举实施例是为了更好地对本发明的内容进行说明,但并不是本发明的内容仅限于所举实施例。所以熟悉本领域的技术人员根据上述发明内容对实施方案进行非本质的改进和调整,仍属于本发明的保护范围。
实施例1
50克对羟基苯甲醇(0.40mol)加入到20%氢氧化钾液500mL烧杯中,得A液,在1L的三颈瓶中加入二溴乙烷94.0g(0.50mol),在60℃下滴加A液,反应3小时,油水分离,油层减压蒸馏得剩余物B液,B液滴加入甲醇钾液,反应温度维持60℃约4小时,过滤约,滤液蒸馏后的剩余物C,剩余物C加入少量丙酮重结晶,得淡黄色粉末产品4-乙烯氧基苯甲醇28.0g,GC分析99.2%。
实施例2
1000ml的三口烧瓶中加入300克对二苯甲醇(0.82mol),加热至融化,再入30g氢氧化钾,搅拌溶解,在140-160℃减压脱出水分,至无任何馏出物。将制得含对二苯甲醇的催化剂加入2L高压釜中,通入氮气置换,置换后在120-160℃反应约6小时,反应结束后,加热蒸馏得半成品,半成品经过高真空精馏得产品乙烯氧基甲基苯甲醇60g,GC分析含量99.3%。
对比实施例1
50克对羟基苯甲醇(0.40mol)加入到20%氢氧化钾液500mL烧杯中,得A液,在1L的三颈瓶中加入二溴乙烷g(0.3mol),在60℃下滴加A液,反应3小时,油水分离,油层减压蒸馏得剩余物B液,B液滴加入甲醇钾液,反应温度维持60℃约4小时,过滤约,滤液蒸馏后的剩余物C,剩余物C加入少量丙酮重结晶,得淡黄色粉末产品4-乙烯氧基苯甲醇12.0g,GC分析含量97.6%。
对比实施例2
1000ml的三口烧瓶中加入300克对二苯甲醇(0.82mol),加热至融化,再加入5g氢氧化钾,搅拌溶解,在140-160℃减压脱出水分,至无任何馏出物。将制得含对二苯甲醇的催化剂加入2L高压釜中,通入氮气置换,置换后在120-160℃反应约6小时,反应结束后,加热蒸馏得半成品,半成品经过高真空精馏得产品乙烯氧基甲基苯甲醇10.2g,GC分析含量99.1%。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (10)
1.一种芳香族乙烯基醚,其特征在于,其结构如下式Ⅰ或Ⅱ所示:
其中,m、n为1至8的整数,m、n可以相等,也可以不相等;取代基可以是邻、间、对位取代,也可以是直链、支链取代。
2.权利要求1中芳香族乙烯基醚的合成方法,其特征在于,式Ⅰ化合物是含酚的芳香醇通过加入碱、二溴乙烷,醇钾溶液发生反应,得到芳香族乙烯基醚;式Ⅱ化合物是芳香族烷基醇与碱、乙炔反应生成芳香族乙烯基醚。
3.根据权利要求2所述的合成方法,其特征在于,以式Ⅲ化合物为原料,加入碱、二溴乙烷、醇钾溶液发生反应,即得式Ⅰ化合物;
其中,式Ⅲ化合物为酚羟基与醇羟基取代的芳烃,n为1至8的整数;
取代基可以是邻、间、对位取代,也可以是直链、支链取代。
4.根据权利要求3所述的合成方法,其特征在于,碱与式Ⅲ化合物、二溴乙烷的摩尔比为1.0-1.2:1.0:1.0-3.0;醇钾液与式Ⅲ化合物生成的中间体溴乙基芳香族醇的摩尔比为1.0-2.0:1。
5.根据权利要求3或权利要求4任一项所述的合成方法,其特征在于,式Ⅰ化合物的合成方法包括以下步骤:
1)将式Ⅲ化合物加入到碱液中,充分溶解,得溶液A;
2)在反应釜中加入二溴乙烷,滴入溶液A反应,反应温度为30-80℃,2-8h后,油水分离,油层为溴乙基芳香族醇;
3)将油层加入反应釜加热脱水后,加入醇钾液,40-80℃反应4-6小时,过滤,滤液蒸馏后剩余物为芳香族乙烯基醚,重结晶得产品。
6.根据权利要求2所述的合成方法,其特征在于,以式Ⅳ化合物为原料,加入碱、乙炔反应,即得式Ⅱ化合物;
其中,式Ⅳ化合物为醇羟基取代的芳烃,m,n为1至8的整数,m,n可以相等,也可以不相等。
7.根据权利要求6所述的合成方法,其特征在于,碱与式Ⅳ化合物、乙炔的摩尔比为0.05-0.5:1:0.5-1.5。
8.根据权利要求6或权利要求7任一项所述的合成方法,其特征在于,式Ⅱ化合物的合成方法包括以下步骤:
1)将式Ⅳ化合物加入反应釜后,加入碱,加热至100-160℃减压脱水,得醇碱液B;
2)反应釜氮气置换后,在100-180℃中通入乙炔气,反应4-10h后,停止反应,反应液蒸馏出半成品,半成品经过高真空精馏得产品。
9.根据权利要求8所述的合成方法,其特征在于,步骤1)中真空度维持在-0.5~-0.98MPa,反应时间为2~8h。
10.根据权利要求1所述的芳香族乙烯基醚应用在化工试剂制备、耐高温的粘结材料及电子材料中,其特征在于,所述应用包括在作为共聚单体在制备高频低介电常数覆铜板粘合剂中的应用;所述应用包括芳香族烯乙基醚与含氟烯烃共聚的聚合物在绝缘、耐高温的电子材料中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810922442.XA CN108929203A (zh) | 2018-08-14 | 2018-08-14 | 一种芳香族乙烯基醚及其合成方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810922442.XA CN108929203A (zh) | 2018-08-14 | 2018-08-14 | 一种芳香族乙烯基醚及其合成方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108929203A true CN108929203A (zh) | 2018-12-04 |
Family
ID=64445290
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810922442.XA Pending CN108929203A (zh) | 2018-08-14 | 2018-08-14 | 一种芳香族乙烯基醚及其合成方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108929203A (zh) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101006053A (zh) * | 2004-06-18 | 2007-07-25 | 比奥里波克斯公司 | 用于治疗炎症的吲哚 |
US20080070916A1 (en) * | 2002-08-27 | 2008-03-20 | Schreiber Stuart L | Dihydropyrancarboxamides and uses thereof |
CN103235484A (zh) * | 2013-04-25 | 2013-08-07 | 京东方科技集团股份有限公司 | 光阻组合物及其制备方法和显示装置 |
KR20160061143A (ko) * | 2014-11-21 | 2016-05-31 | 주식회사 엘지화학 | 올레핀 공중합체의 제조방법 및 이로부터 제조된 올레핀 공중합체 |
JP2018115152A (ja) * | 2017-01-19 | 2018-07-26 | 住友化学株式会社 | 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
-
2018
- 2018-08-14 CN CN201810922442.XA patent/CN108929203A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080070916A1 (en) * | 2002-08-27 | 2008-03-20 | Schreiber Stuart L | Dihydropyrancarboxamides and uses thereof |
CN101006053A (zh) * | 2004-06-18 | 2007-07-25 | 比奥里波克斯公司 | 用于治疗炎症的吲哚 |
CN103235484A (zh) * | 2013-04-25 | 2013-08-07 | 京东方科技集团股份有限公司 | 光阻组合物及其制备方法和显示装置 |
KR20160061143A (ko) * | 2014-11-21 | 2016-05-31 | 주식회사 엘지화학 | 올레핀 공중합체의 제조방법 및 이로부터 제조된 올레핀 공중합체 |
JP2018115152A (ja) * | 2017-01-19 | 2018-07-26 | 住友化学株式会社 | 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10544254B2 (en) | Preparation and application of dicyclopentadiene-phenol and 2,6-dimethyl phenol copolymer epoxy resin | |
US20220002485A1 (en) | Method for synthesizing dihydroxyl-terminated polyphenylene oxide oligomer | |
JP2018184578A (ja) | ジシクロペンタジエンフェノールと2,6−ジメチルフェノールの共重合体のエポキシ樹脂の調製及び用途 | |
JP2004123742A (ja) | ベンゾオキサジン化合物の製造方法 | |
Su et al. | Preparation, characterization and curing properties of epoxy-terminated poly (alkyl-phenylene oxide) s | |
WO2002014334A1 (fr) | Composes phenoles, compositions de resine et produits polymerises obtenus a partir de ces compositions de resine | |
EP3921356A1 (en) | Recyclable and reworkable epoxy resins | |
CN108929203A (zh) | 一种芳香族乙烯基醚及其合成方法和应用 | |
JP4591946B2 (ja) | ポリ(ビニルベンジル)エーテル化合物およびその製造方法 | |
WO2021172319A1 (ja) | 硬化性樹脂、硬化性樹脂組成物、硬化物、電子デバイス、積層板材料、電子部品封止材および硬化性樹脂の製造方法 | |
JP6183918B2 (ja) | ポリヒドロキシポリエーテル樹脂、ポリヒドロキシポリエーテル樹脂の製造方法、そのポリヒドロキシポリエーテル樹脂を含有する樹脂組成物、及びそれから得られる硬化物 | |
CA1280540C (en) | Thermoset polymers of styrene terminated tetrakis phenols | |
CA2300973A1 (en) | Polyhydric phenol compounds, epoxy resins, epoxy resin compositions and cured products thereof | |
CN103467707A (zh) | 一种酚醛环氧树脂的合成方法 | |
CN106661208B (zh) | 聚苯并噁嗪前体及其制备方法 | |
TW201902977A (zh) | 順丁烯二醯亞胺樹脂組成物、預浸體及其硬化物 | |
CN110407674A (zh) | 4-烯丙氧基苯甲醇、合成方法及应用 | |
JP2015513585A (ja) | シクロドデカンポリフェノールのエポキシ樹脂の調製法および使用法 | |
US8431656B2 (en) | Curable cyclic phosphazene compound and method of preparing the same | |
US11629216B2 (en) | Polyhydric phenol resin, glycidyl ether of polyhydric phenol resin, and uses thereof | |
WO2024071047A1 (ja) | 多官能ビニル樹脂、その製造方法、組成物及び硬化物 | |
CN109415506A (zh) | 苯并噁嗪类混合物及其用途 | |
JP7464474B2 (ja) | マレイミド樹脂、硬化性樹脂組成物およびその硬化物 | |
CN111454466B (zh) | 双酚酸基环氧树脂乳化剂及其水性乳液与制备方法 | |
TWI600674B (zh) | 二環戊二烯-酚樹脂與2,6二甲基苯酚共聚物環氧樹脂製造與應用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181204 |