TWI851772B - Silane-modified polyphenylene ether resin and preparation method thereof - Google Patents
Silane-modified polyphenylene ether resin and preparation method thereof Download PDFInfo
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- TWI851772B TWI851772B TW109125181A TW109125181A TWI851772B TW I851772 B TWI851772 B TW I851772B TW 109125181 A TW109125181 A TW 109125181A TW 109125181 A TW109125181 A TW 109125181A TW I851772 B TWI851772 B TW I851772B
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- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 70
- 229920005989 resin Polymers 0.000 title claims abstract description 70
- 239000011347 resin Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 28
- 125000000524 functional group Chemical group 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 229920002554 vinyl polymer Chemical group 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- -1 acryl Chemical group 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000077 silane Inorganic materials 0.000 abstract description 10
- 229920013638 modified polyphenyl ether Polymers 0.000 abstract 1
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 229920004482 WACKER® Polymers 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCFOLUKWAIAKFB-UHFFFAOYSA-N CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br Chemical compound CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br KCFOLUKWAIAKFB-UHFFFAOYSA-N 0.000 description 2
- 239000004727 Noryl Substances 0.000 description 2
- 229920001207 Noryl Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 2
- JQIUXGUNXKKBQX-UHFFFAOYSA-N 2-dimethoxysilylethyl 2-methylprop-2-enoate Chemical compound CO[SiH](CCOC(=O)C(C)=C)OC JQIUXGUNXKKBQX-UHFFFAOYSA-N 0.000 description 1
- JNJGROHZMWDCCM-UHFFFAOYSA-N C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)O Chemical compound C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)O JNJGROHZMWDCCM-UHFFFAOYSA-N 0.000 description 1
- GBYIPEFQQCCCJP-UHFFFAOYSA-N Cl.C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound Cl.C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 GBYIPEFQQCCCJP-UHFFFAOYSA-N 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- JYNMIXFGWAQWLU-UHFFFAOYSA-N [I-].CCC1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [I-].CCC1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 JYNMIXFGWAQWLU-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WQTNGCZMPUCIEX-UHFFFAOYSA-N dimethoxy-methyl-prop-2-enylsilane Chemical compound CO[Si](C)(OC)CC=C WQTNGCZMPUCIEX-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Polyethers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本發明是有關於一種改質聚苯醚樹脂及其製備方法，且特別是有關於一種矽烷改質聚苯醚樹脂及其製備方法。The present invention relates to a modified polyphenylene ether resin and a preparation method thereof, and in particular to a silane-modified polyphenylene ether resin and a preparation method thereof.
近年來，隨著半導體技術發展、電子元件尺寸縮小，電路板中的金屬導線線寬越來越細，導線之間的線距也越來越小，而金屬導線配線之間容易引起訊號干擾，金屬導線與介電層也容易引起訊號傳遞延遲，因此，介電層的電氣性質在電路板中扮演重要角色。介電層的介電常數（Dk）與介電損失（Df）越小，有助於減少印刷電路板材料的訊號損失與提升傳遞速度。In recent years, with the development of semiconductor technology and the reduction in the size of electronic components, the width of metal wires in circuit boards has become thinner and the line spacing between wires has become smaller. Metal wires are prone to signal interference, and metal wires and dielectric layers are also prone to signal transmission delay. Therefore, the electrical properties of the dielectric layer play an important role in circuit boards. The smaller the dielectric constant (Dk) and dielectric loss (Df) of the dielectric layer, the more it helps to reduce the signal loss of printed circuit board materials and improve the transmission speed.
習知常應用於高頻高速印刷電路板的低Dk/Df材料包括聚苯醚，由於聚苯醚具有較高的玻璃化轉移溫度、較低的Dk/Df及較低的吸水性，因此，成為目前研究高頻高速電子領域中受到矚目的材料。目前市售的聚苯醚包括端羥基型樹脂，羥基反應活性低，反應基團少，無法形成高交聯密度的固化體系，導致熱穩定性能、機械性能及黏結力等性能都受到較大影響，且因羥基極性大容易吸水，因此，導致端羥基聚苯醚樹脂的Dk/Df較大而不符合需求。基於上述，對聚苯醚樹脂進行改質以獲得更好的性能，為本領域技術人員亟欲發展的目標。It is known that low Dk/Df materials commonly used in high-frequency and high-speed printed circuit boards include polyphenylene ether. Since polyphenylene ether has a higher glass transition temperature, a lower Dk/Df and a lower water absorption, it has become a material that has received attention in the current research of high-frequency and high-speed electronics. Currently available polyphenylene ethers include hydroxyl-terminated resins. The hydroxyl group has low reactivity and few reactive groups, and cannot form a high crosslinking density solidification system, resulting in a significant impact on thermal stability, mechanical properties, and adhesion. In addition, due to the high polarity of the hydroxyl group, it is easy to absorb water, so the Dk/Df of the hydroxyl-terminated polyphenylene ether resin is large and does not meet the requirements. Based on the above, modifying polyphenylene ether resin to obtain better performance is a goal that technical personnel in this field are eager to develop.
本發明提供一種矽烷改質聚苯醚樹脂及其製備方法，透過本發明的製備方法獲得雙端帶有可反應乙烯基的矽烷改質聚苯醚樹脂，以獲得更好的性能。The present invention provides a silane-modified polyphenylene ether resin and a preparation method thereof. The silane-modified polyphenylene ether resin with reactive vinyl groups at both ends is obtained by the preparation method of the present invention to obtain better performance.
本發明的矽烷改質聚苯醚樹脂，其結構由式（1）表示： 式（1） 在式（1）中，R1、R2、R3及R4各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R5、R6、R7及R8各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R9為直鏈或支鏈的C1至C6烷基或芳基，R10為氫或C1至C6烷基，R11為帶有可交聯雙鍵的官能基，Y為直鏈、支鏈或環狀的C1至C10烷基，a及b各自獨立地為0至50的整數，n及m各自獨立地為1至4的整數。The silane-modified polyphenylene ether resin of the present invention has a structure represented by formula (1): Formula (1) In formula (1), R1, R2, R3 and R4 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R5, R6, R7 and R8 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R9 is a linear or branched C1 to C6 alkyl group or an aryl group, R10 is hydrogen or a C1 to C6 alkyl group, R11 is a functional group with a crosslinkable double bond, Y is a linear, branched or cyclic C1 to C10 alkyl group, a and b are each independently integers from 0 to 50, and n and m are each independently integers from 1 to 4.
在本發明的一實施例中，帶有可交聯雙鍵的官能基包括丙烯基（allyl）、乙烯基（vinyl）、丙烯酸基（acrylate）或甲基丙烯酸基（methacrylate）。In one embodiment of the present invention, the functional group having a cross-linkable double bond includes allyl, vinyl, acrylate or methacrylate.
在本發明的一實施例中，帶有可交聯雙鍵的官能基包括C1至C4烷基丙烯酸基（alkylacrylate）、C1至C4烷基乙烯基或C1至C3甲基丙烯醯氧烷基。In one embodiment of the present invention, the functional group having a crosslinkable double bond includes a C1 to C4 alkylacrylate, a C1 to C4 alkylvinyl or a C1 to C3 methacryloxyalkyl.
本發明的矽烷改質聚苯醚樹脂，其結構由式（2）表示： 式（2） 在式（2）中，R1、R2、R3及R4各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R5、R6、R7及R8各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R9為直鏈或支鏈的C1至C6烷基或芳基，R11為帶有可交聯雙鍵的官能基，Y為直鏈、支鏈或環狀的C1至C10烷基，a及b各自獨立地為0至50的整數，W為1至4的整數。The silane-modified polyphenylene ether resin of the present invention has a structure represented by formula (2): Formula (2) In formula (2), R1, R2, R3 and R4 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R5, R6, R7 and R8 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R9 is a linear or branched C1 to C6 alkyl group or an aryl group, R11 is a functional group with a crosslinkable double bond, Y is a linear, branched or cyclic C1 to C10 alkyl group, a and b are each independently an integer from 0 to 50, and W is an integer from 1 to 4.
在本發明的一實施例中，帶有可交聯雙鍵的官能基包括丙烯基、乙烯基、丙烯酸基或甲基丙烯酸基。In one embodiment of the present invention, the functional group having a crosslinkable double bond includes an acrylic group, a vinyl group, an acrylic group or a methacrylic group.
在本發明的一實施例中，帶有可交聯雙鍵的官能基包括C1至C4烷基丙烯酸基、C1至C4烷基乙烯基或C1至C3甲基丙烯醯氧烷基。In one embodiment of the present invention, the functional group having a crosslinkable double bond includes a C1 to C4 alkyl acrylate group, a C1 to C4 alkyl vinyl group or a C1 to C3 methacryloxyalkyl group.
本發明的矽烷改質聚苯醚樹脂的製備方法，用以製備上述矽烷改質聚苯醚樹脂，其合成反應式由反應式（1）表示： 反應式（1） 在反應式（1）中，R1、R2、R3及R4各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R5、R6、R7及R8各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R9為直鏈或支鏈的C1至C6烷基或芳基，R10為氫或C1至C6烷基，R11為帶有可交聯雙鍵的官能基，Y為直鏈、支鏈或環狀的C1至C10烷基，W為1至4的整數，a及b各自獨立地為0至50的整數，n及m各自獨立地為1至4的整數。The method for preparing the silane-modified polyphenylene ether resin of the present invention is used to prepare the above-mentioned silane-modified polyphenylene ether resin, and its synthesis reaction formula is represented by reaction formula (1): Reaction formula (1) In reaction formula (1), R1, R2, R3 and R4 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R5, R6, R7 and R8 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R9 is a linear or branched C1 to C6 alkyl group or an aryl group, R10 is hydrogen or a C1 to C6 alkyl group, R11 is a functional group with a crosslinkable double bond, Y is a linear, branched or cyclic C1 to C10 alkyl group, W is an integer from 1 to 4, a and b are each independently integers from 0 to 50, and n and m are each independently integers from 1 to 4.
在本發明的一實施例中，帶有可交聯雙鍵的官能基包括丙烯基、乙烯基、丙烯酸基或甲基丙烯酸基。In one embodiment of the present invention, the functional group having a crosslinkable double bond includes an acrylic group, a vinyl group, an acrylic group or a methacrylic group.
在本發明的一實施例中，帶有可交聯雙鍵的官能基包括C1至C4烷基丙烯酸基、C1至C4烷基乙烯基或C1至C3甲基丙烯醯氧烷基。In one embodiment of the present invention, the functional group having a crosslinkable double bond includes a C1 to C4 alkyl acrylate group, a C1 to C4 alkyl vinyl group or a C1 to C3 methacryloxyalkyl group.
在本發明的一實施例中，反應式（1）的反應溫度為100℃至160℃，反應時間為6小時至20小時。In one embodiment of the present invention, the reaction temperature of reaction formula (1) is 100°C to 160°C, and the reaction time is 6 hours to 20 hours.
基於上述，本發明利用雙端具有羥基的聚苯醚樹脂與端基帶有至少一個烷氧基及至少一個乙烯基的矽烷進行反應，以得到端基帶有可反應乙烯基的矽烷改質聚苯醚樹脂。所獲得的矽烷改質聚苯醚樹脂除了具備聚苯醚優良的介電性能、耐熱性、尺寸穩定性、低吸水率及低限性膨脹係數之外，更因導入低極性的矽烷，提高聚苯醚樹脂本身的流動性、熱穩定性，更可藉由結構上的乙烯基在過氧化物作用下進行交聯反應，進而提高整體交聯密度，形成高交聯密度的固化樹脂，提升玻璃化轉移溫度（Tg）。Based on the above, the present invention uses a polyphenylene ether resin with hydroxyl groups at both ends to react with a silane with at least one alkoxy group and at least one vinyl group at the end to obtain a silane-modified polyphenylene ether resin with a reactive vinyl group at the end. The obtained silane-modified polyphenylene ether resin not only has the excellent dielectric properties, heat resistance, dimensional stability, low water absorption rate and low limiting expansion coefficient of polyphenylene ether, but also improves the fluidity and thermal stability of the polyphenylene ether resin itself due to the introduction of low-polarity silane. The vinyl groups on the structure can undergo cross-linking reaction under the action of peroxide, thereby increasing the overall cross-linking density, forming a cured resin with a high cross-linking density, and raising the glass transition temperature (Tg).
以下，將詳細描述本發明的實施例。然而，這些實施例為例示性，且本發明揭露不限於此。Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are exemplary, and the present invention is not limited thereto.
在本文中，由「一數值至另一數值」表示的範圍，是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此，某一特定數值範圍的記載，涵蓋該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍，如同在說明書中說明文寫出該任意數值和該較小數值範圍一樣。In this article, the range expressed by "a value to another value" is a summary expression method to avoid listing all the values in the range one by one in the specification. Therefore, the description of a specific numerical range covers any numerical value in the numerical range and the smaller numerical range defined by any numerical value in the numerical range, just as the arbitrary numerical value and the smaller numerical range are written in the description text in the specification.
本發明提出一種矽烷改質聚苯醚樹脂，其結構由式（1）表示： 式（1） 在式（1）中，R1、R2、R3及R4各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R5、R6、R7及R8各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R9為直鏈或支鏈的C1至C6烷基或芳基，R10為氫或C1至C6烷基，R11為帶有可交聯雙鍵的官能基，Y為直鏈、支鏈或環狀的C1至C10烷基，a及b各自獨立地為0至50的整數，n及m各自獨立地為1至4的整數。The present invention provides a silane-modified polyphenylene ether resin, the structure of which is represented by formula (1): Formula (1) In formula (1), R1, R2, R3 and R4 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R5, R6, R7 and R8 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R9 is a linear or branched C1 to C6 alkyl group or an aryl group, R10 is hydrogen or a C1 to C6 alkyl group, R11 is a functional group with a crosslinkable double bond, Y is a linear, branched or cyclic C1 to C10 alkyl group, a and b are each independently integers from 0 to 50, and n and m are each independently integers from 1 to 4.
更詳細而言，在式（1）中，R11為帶有可交聯雙鍵的官能基，帶有可交聯雙鍵的官能基可包括丙烯基（allyl）、乙烯基（vinyl）、丙烯酸基（acrylate）或甲基丙烯酸基（methacrylate），或者，帶有可交聯雙鍵的官能基也可包括C1至C4烷基丙烯酸基（alkylacrylate）、C1至C4烷基乙烯基或C1至C3甲基丙烯醯氧烷基，但本發明並不以此為限。More specifically, in formula (1), R11 is a functional group having a cross-linkable double bond, and the functional group having a cross-linkable double bond may include allyl, vinyl, acrylate or methacrylate, or the functional group having a cross-linkable double bond may include C1 to C4 alkylacrylate, C1 to C4 alkylvinyl or C1 to C3 methacryloxyalkyl, but the present invention is not limited thereto.
除了以上由式（1）表示的矽烷改質聚苯醚樹脂之外，本發明也提出另一種矽烷改質聚苯醚樹脂，其結構由式（2）表示： 式（2） 在式（2）中，R1、R2、R3及R4各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R5、R6、R7及R8各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R9為直鏈或支鏈的C1至C6烷基或芳基，R11為帶有可交聯雙鍵的官能基，Y為直鏈、支鏈或環狀的C1至C10烷基，a及b各自獨立地為0至50的整數，W為1至4的整數。In addition to the silane-modified polyphenylene ether resin represented by formula (1) above, the present invention also proposes another silane-modified polyphenylene ether resin, whose structure is represented by formula (2): Formula (2) In formula (2), R1, R2, R3 and R4 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R5, R6, R7 and R8 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R9 is a linear or branched C1 to C6 alkyl group or an aryl group, R11 is a functional group with a crosslinkable double bond, Y is a linear, branched or cyclic C1 to C10 alkyl group, a and b are each independently an integer from 0 to 50, and W is an integer from 1 to 4.
更詳細而言，在式（2）中，R11為帶有可交聯雙鍵的官能基，帶有可交聯雙鍵的官能基可包括丙烯基（allyl）、乙烯基（vinyl）、丙烯酸基（acrylate）或甲基丙烯酸基（methacrylate），或者，帶有可交聯雙鍵的官能基也可包括C1至C4烷基丙烯酸基（alkylacrylate）、C1至C4烷基乙烯基或C1至C3甲基丙烯醯氧烷基，但本發明並不以此為限。More specifically, in formula (2), R11 is a functional group having a cross-linkable double bond, and the functional group having a cross-linkable double bond may include allyl, vinyl, acrylate, or methacrylate, or the functional group having a cross-linkable double bond may include C1 to C4 alkylacrylate, C1 to C4 alkylvinyl, or C1 to C3 methacryloxyalkyl, but the present invention is not limited thereto.
同時，本發明也提出一種矽烷改質聚苯醚樹脂的製備方法，用以製備上述由式（1）及式（2）表示的矽烷改質聚苯醚樹脂，其合成反應式由反應式（1）表示： 反應式（1） 在反應式（1）中，R1、R2、R3及R4各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R5、R6、R7及R8各自獨立地為氫、直鏈或支鏈的C1至C6烷基，R9為直鏈或支鏈的C1至C6烷基或芳基，R10為氫或C1至C6烷基，R11為帶有可交聯雙鍵的官能基，Y為直鏈、支鏈或環狀的C1至C10烷基，W為1至4的整數，a及b各自獨立地為0至50的整數，n及m各自獨立地為1至4的整數。At the same time, the present invention also provides a method for preparing a silane-modified polyphenylene ether resin, which is used to prepare the silane-modified polyphenylene ether resin represented by formula (1) and formula (2). The synthesis reaction formula is represented by reaction formula (1): Reaction formula (1) In reaction formula (1), R1, R2, R3 and R4 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R5, R6, R7 and R8 are each independently hydrogen, a linear or branched C1 to C6 alkyl group, R9 is a linear or branched C1 to C6 alkyl group or an aryl group, R10 is hydrogen or a C1 to C6 alkyl group, R11 is a functional group with a crosslinkable double bond, Y is a linear, branched or cyclic C1 to C10 alkyl group, W is an integer from 1 to 4, a and b are each independently integers from 0 to 50, and n and m are each independently integers from 1 to 4.
更詳細而言，在反應式（1）中，R11為帶有可交聯雙鍵的官能基，帶有可交聯雙鍵的官能基可包括丙烯基（allyl）、乙烯基（vinyl）、丙烯酸基（acrylate）或甲基丙烯酸基（methacrylate），或者，帶有可交聯雙鍵的官能基也可包括C1至C4烷基丙烯酸基（alkylacrylate）、C1至C4烷基乙烯基或C1至C3甲基丙烯醯氧烷基，但本發明並不以此為限。More specifically, in reaction formula (1), R11 is a functional group having a cross-linkable double bond, and the functional group having a cross-linkable double bond may include allyl, vinyl, acrylate or methacrylate, or the functional group having a cross-linkable double bond may include C1 to C4 alkylacrylate, C1 to C4 alkylvinyl or C1 to C3 methacryloxyalkyl, but the present invention is not limited thereto.
如上方反應式（1）所示，本發明主要是利用雙端具有羥基的聚苯醚樹脂與端基帶有至少一個烷氧基及至少一個乙烯基的矽烷，在催化劑的作用下進行反應，以得到端基帶有乙烯基的矽烷改質聚苯醚樹脂（即，由式（1）及式（2）表示的矽烷改質聚苯醚樹脂）。反應式（1）的反應溫度例如是100℃至160℃，較佳例如是130℃至150℃，反應時間例如是6小時至20小時，較佳例如是10小時至20小時，反應式（1）在氮氣環境下進行反應。在本實施例中，以聚苯醚樹脂的羥基及含乙烯基的二烷氧基矽烷的烷氧基莫耳比計算，聚苯醚樹脂與含乙烯基的二烷氧基矽烷的比例例如是1：0.5至1：4.0。As shown in the above reaction formula (1), the present invention mainly utilizes a polyphenylene ether resin having hydroxyl groups at both ends and a silane having at least one alkoxy group and at least one vinyl group at the end to react under the action of a catalyst to obtain a silane-modified polyphenylene ether resin having a vinyl group at the end (i.e., a silane-modified polyphenylene ether resin represented by formula (1) and formula (2)). The reaction temperature of reaction formula (1) is, for example, 100°C to 160°C, preferably, 130°C to 150°C, and the reaction time is, for example, 6 hours to 20 hours, preferably, 10 hours to 20 hours. Reaction formula (1) is carried out in a nitrogen environment. In this embodiment, the ratio of the polyphenylene ether resin to the vinyl-containing dialkoxysilane is, for example, 1:0.5 to 1:4.0, calculated based on the molar ratio of the hydroxyl group of the polyphenylene ether resin to the alkoxy group of the vinyl-containing dialkoxysilane.
在本實施例中，催化劑的用量例如是對聚苯醚樹脂重量的300 ppm至3000 ppm，催化劑的種類可包括但不限於酸催化劑、鹼催化劑、金屬化合物催化劑、酯類催化劑或其組合，較佳例如是乙基三苯基氯化膦（ETPPCl）、乙基三苯基溴化膦（ETPPBr）、乙基三苯基碘化膦（ETPPI）、乙基三苯基醋酸膦（ETPPAAc）、四丁基溴化銨（TBAB）、三苯基膦（TPP）或四正丁基乙酸銨（TBAAc），但本發明並不以此為限。In the present embodiment, the amount of the catalyst used is, for example, 300 ppm to 3000 ppm based on the weight of the polyphenylene ether resin. The type of the catalyst may include but is not limited to an acid catalyst, an alkali catalyst, a metal compound catalyst, an ester catalyst or a combination thereof, preferably ethyltriphenylphosphine chloride (ETPPCl), ethyltriphenylphosphine bromide (ETPPBr), ethyltriphenylphosphine iodide (ETPPI), ethyltriphenylphosphine acetate (ETPPAAc), tetrabutylammonium bromide (TBAB), triphenylphosphine (TPP) or tetra-n-butylammonium acetate (TBAAc), but the present invention is not limited thereto.
在反應式（1）中，本發明所使用的含乙烯基的烷氧基矽烷由式（A）表示：式（A） 如同上文所述，在式（A）中，R9為直鏈或支鏈的C1至C6烷基或芳基，R10為氫或C1至C6烷基，R11為帶有可交聯雙鍵的官能基，帶有可交聯雙鍵的官能基可包括丙烯基（allyl）、乙烯基（vinyl）、丙烯酸基（acrylate）或甲基丙烯酸基（methacrylate），或者，帶有可交聯雙鍵的官能基也可包括C1至C4烷基丙烯酸基（alkylacrylate）、C1至C4烷基乙烯基或C1至C3甲基丙烯醯氧烷基，但本發明並不以此為限。在本實施例中，式（A）的具體例可包括甲基乙烯基二甲氧基矽烷、甲基乙烯基二乙氧基矽烷、1-(甲基丙烯醯氧甲基)甲基二甲氧基矽烷、3-(甲基丙烯醯氧丙基)甲基二甲氧基矽烷、3-(甲基丙烯醯氧丙基)甲基二乙氧基矽烷、烯丙基甲基二甲氧基矽烷、1-烯丙基-2,2-二甲氧基-1,2-氮雜矽環戊烷或其組合，但本發明並不以此為限。具體案例的化學結構式如下所示：甲基乙烯基二甲氧基矽烷甲基乙烯基二乙氧基矽烷 1-(甲基丙烯醯氧甲基)甲基二甲氧基矽烷 3-(甲基丙烯醯氧丙基)甲基二甲氧基矽烷 3-(甲基丙烯醯氧丙基)甲基二乙氧基矽烷 1-烯丙基-2,2-二甲氧基-1,2-氮雜矽環戊烷In reaction formula (1), the vinyl-containing alkoxysilane used in the present invention is represented by formula (A): Formula (A) As described above, in formula (A), R9 is a linear or branched C1 to C6 alkyl or aryl group, R10 is hydrogen or a C1 to C6 alkyl group, and R11 is a functional group having a cross-linkable double bond. The functional group having a cross-linkable double bond may include allyl, vinyl, acrylate or methacrylate, or the functional group having a cross-linkable double bond may also include C1 to C4 alkylacrylate, C1 to C4 alkylvinyl or C1 to C3 methacryloxyalkyl, but the present invention is not limited thereto. In this embodiment, specific examples of formula (A) may include methylvinyldimethoxysilane, methylvinyldiethoxysilane, 1-(methacryloxymethyl)methyldimethoxysilane, 3-(methacryloxypropyl)methyldimethoxysilane, 3-(methacryloxypropyl)methyldiethoxysilane, allylmethyldimethoxysilane, 1-allyl-2,2-dimethoxy-1,2-azasilacyclopentane or a combination thereof, but the present invention is not limited thereto. The chemical structure of the specific case is shown below: Methylvinyl dimethoxysilane Methylvinyldiethoxysilane 1-(Methacryloyloxymethyl)methyldimethoxysilane 3-(Methacryloyloxypropyl)methyldimethoxysilane 3-(Methacryloyloxypropyl)methyldiethoxysilane 1-Allyl-2,2-dimethoxy-1,2-azidosilycyclopentane
在本實施例中，式（A）可由以下式（A-1）表示：式（A-1） 在式（A-1）中，Z為C1至C4的伸烷基。 式（A）也可由以下式（A-2）表示：式（A-2） 在式（A-2）中，P為C1至C3的伸烷基。In this embodiment, formula (A) can be represented by the following formula (A-1): Formula (A-1) In formula (A-1), Z is a C1 to C4 alkylene group. Formula (A) can also be represented by the following formula (A-2): Formula (A-2) In formula (A-2), P is a C1 to C3 alkylene group.
以下，藉由實驗例來詳細說明上述本發明所提出的矽烷改質聚苯醚樹脂。然而，下述實驗例並非用以限制本發明。實驗例 The following experimental examples are used to explain in detail the silane-modified polyphenylene ether resin proposed in the present invention. However, the following experimental examples are not intended to limit the present invention.
為了證明本發明所提出的製備方法可獲得矽烷改質聚苯醚樹脂，以下特別作此實驗例。In order to prove that the preparation method proposed in the present invention can obtain silane-modified polyphenylene ether resin, the following experimental example is specially made.
在實驗例中，可使用例如SABIC生產的NORYL SA90作為聚苯醚樹脂，GPC資料分析（以二甲基乙醯胺（DMAc）為移動相，聚苯乙烯為標準品）可發現SA90的數目平均分子量（Mn）和重量平均分子量（Mw）分別為1912克/莫耳和2999克/莫耳。然而，本發明並不以此為限，除了SABIC生產的NORYL SA90之外，也可使用其他帶有端羥基的聚苯醚樹脂。實例 1 In the experimental example, NORYL SA90 produced by SABIC can be used as the polyphenylene ether resin. GPC data analysis (using dimethylacetamide (DMAc) as the mobile phase and polystyrene as the standard) can find that the number average molecular weight (Mn) and weight average molecular weight (Mw) of SA90 are 1912 g/mol and 2999 g/mol, respectively. However, the present invention is not limited thereto. In addition to NORYL SA90 produced by SABIC, other polyphenylene ether resins with terminal hydroxyl groups can also be used. Example 1
將聚苯醚樹脂（SA90，SABIC）60.0g與二甲苯（xylene）60.0 g放入帶攪拌、熱電偶、回流冷凝管、油水分離器的250 mL三口燒瓶中，在溫度80℃下溶解攪拌均勻，加入甲基乙烯基二甲氧基矽烷（XL12，德國Wacker）16.997 g均勻攪拌，再加入乙基三苯基溴化膦（ETPPBr）0.06 g，提高內溫到145℃，等待三口燒瓶中開始有溶液回流，計時反應13小時。降溫到80℃收料，得到一含乙烯基的矽烷改質聚苯醚樹脂A1，將樹脂A1取樣進行GPC檢測（以二甲基乙醯胺（DMAc）為移動相，聚苯乙烯為標準品），得到數目平均分子量（Mn）/重量平均分子量（Mw）：2251/4479。圖1是實例1的矽烷改質聚苯醚樹脂與聚苯醚樹脂進行比較的凝膠滲透層析法（Gel Permeation Chromatography，GPC）圖。實例 2 Put 60.0 g of polyphenylene ether resin (SA90, SABIC) and 60.0 g of xylene into a 250 mL three-necked flask equipped with a stirrer, a thermocouple, a reflux condenser, and an oil-water separator, dissolve and stir evenly at 80°C, add 16.997 g of methylvinyldimethoxysilane (XL12, Wacker, Germany) and stir evenly, then add 0.06 g of ethyltriphenylphosphine bromide (ETPPBr), raise the internal temperature to 145°C, wait for the solution to begin to reflux in the three-necked flask, and time the reaction for 13 hours. The temperature was lowered to 80°C and the material was collected to obtain a vinyl-containing silane-modified polyphenylene ether resin A1. The resin A1 was sampled for GPC detection (using dimethylacetamide (DMAc) as the mobile phase and polystyrene as the standard), and the number average molecular weight (Mn)/weight average molecular weight (Mw) was obtained: 2251/4479. Figure 1 is a gel permeation chromatography (GPC) diagram of the silane-modified polyphenylene ether resin of Example 1 compared with the polyphenylene ether resin. Example 2
將聚苯醚樹脂（SA90，SABIC）60.0 g與二甲苯（xylene）40.0 g放入三口燒瓶中，在溫度80℃下溶解攪拌均勻，加入甲基乙烯基二甲氧基矽烷（XL12，德國Wacker）11.80 g均勻攪拌，提高內溫到100℃，再加入乙基三苯基溴化膦（ETPPBr）0.06 g，提高內溫到145℃，等待三口燒瓶中開始有溶液回流，計時反應10小時。降溫到80℃收料，得到一含乙烯基的矽烷改質聚苯醚樹脂A2，將樹脂A2取樣進行GPC檢測，得到Mn/ Mw：2116/3915。實例 3 Put 60.0 g of polyphenylene ether resin (SA90, SABIC) and 40.0 g of xylene into a three-necked flask, dissolve and stir evenly at 80°C, add 11.80 g of methylvinyl dimethoxysilane (XL12, Wacker, Germany) and stir evenly, raise the internal temperature to 100°C, then add 0.06 g of ethyltriphenylphosphonium bromide (ETPPBr), raise the internal temperature to 145°C, wait for the solution in the three-necked flask to reflux, and react for 10 hours. Cool down to 80°C to collect the material, and obtain a vinyl-containing silane-modified polyphenylene ether resin A2. Take a sample of resin A2 for GPC detection, and obtain Mn/Mw: 2116/3915. Example 3
將聚苯醚樹脂（SA90，SABIC）60.0 g與二甲苯（xylene）60.0 g放入三口燒瓶中，在溫度80℃下溶解攪拌均勻，加入甲基乙烯基二甲氧基矽烷（XL12，德國Wacker）16.99 g均勻攪拌，提高內溫到100℃，再加入四丁基溴化銨（TBAB）0.06 g，提高內溫到135℃，等待三口燒瓶中開始有溶液回流，計時反應10小時。降溫到80℃收料，得到一含乙烯基的矽烷改質聚苯醚樹脂A3，將樹脂A3取樣進行GPC檢測，得到Mn/ Mw：2027/3369。實例 4 Put 60.0 g of polyphenylene ether resin (SA90, SABIC) and 60.0 g of xylene into a three-necked flask, dissolve and stir evenly at 80°C, add 16.99 g of methylvinyl dimethoxysilane (XL12, Wacker, Germany) and stir evenly, raise the internal temperature to 100°C, then add 0.06 g of tetrabutylammonium bromide (TBAB), raise the internal temperature to 135°C, wait for the solution to reflux in the three-necked flask, and react for 10 hours. Cool down to 80°C to collect the material, and obtain a vinyl-containing silane-modified polyphenylene ether resin A3. Take a sample of resin A3 for GPC detection, and obtain Mn/Mw: 2027/3369. Example 4
將聚苯醚樹脂（SA90，SABIC）60.0 g與二甲苯（xylene）60.0 g放入三口燒瓶中，在溫度80℃下溶解攪拌均勻，加入甲基乙烯基二甲氧基矽烷（XL12，德國Wacker）16.99 g均勻攪拌，提高內溫到100℃，再加入三苯基膦（TPP）0.06 g，提高內溫到145℃，等待三口燒瓶中開始有溶液回流，計時反應10小時。降溫到80℃收料，得到一含乙烯基的矽烷改質聚苯醚樹脂A4，將樹脂A4取樣進行GPC檢測，得到Mn/ Mw：2120/3686。實例 5 Put 60.0 g of polyphenylene ether resin (SA90, SABIC) and 60.0 g of xylene into a three-necked flask, dissolve and stir evenly at 80°C, add 16.99 g of methylvinyl dimethoxysilane (XL12, Wacker, Germany) and stir evenly, raise the internal temperature to 100°C, then add 0.06 g of triphenylphosphine (TPP), raise the internal temperature to 145°C, wait for the solution to reflux in the three-necked flask, and react for 10 hours. Cool down to 80°C to collect the material, and obtain a vinyl-containing silane-modified polyphenylene ether resin A4. Take a sample of resin A4 for GPC detection, and obtain Mn/Mw: 2120/3686. Example 5
將聚苯醚樹脂（SA90，SABIC）84.0 g與二甲苯（xylene）45.23 g放入三口燒瓶中，在溫度80℃下溶解攪拌均勻，加入甲基乙烯基二甲氧基矽烷（XL12，德國Wacker）6.608 g均勻攪拌，提高內溫到100℃，再加入乙基三苯基溴化膦（ETPPBr）0.042 g，提高內溫到155℃，等待三口燒瓶中開始有溶液回流，計時反應13小時。降溫到80℃收料，得到一含乙烯基的矽烷改質聚苯醚樹脂A5，將樹脂A5取樣進行GPC檢測，得到Mn/ Mw：2295/4050。圖2是實例5的矽烷改質聚苯醚樹脂與聚苯醚樹脂進行比較的凝膠滲透層析法圖。實例 6 84.0 g of polyphenylene ether resin (SA90, SABIC) and 45.23 g of xylene were placed in a three-necked flask, dissolved and stirred evenly at 80°C, 6.608 g of methylvinyl dimethoxysilane (XL12, Wacker, Germany) was added and stirred evenly, the internal temperature was raised to 100°C, and 0.042 g of ethyltriphenylphosphonium bromide (ETPPBr) was added, the internal temperature was raised to 155°C, and the solution in the three-necked flask began to reflux, and the reaction time was 13 hours. The temperature was lowered to 80°C to collect the material, and a vinyl-containing silane-modified polyphenylene ether resin A5 was obtained. The resin A5 was sampled for GPC detection, and Mn/Mw: 2295/4050 was obtained. FIG2 is a gel permeation chromatography diagram of the silane-modified polyphenylene ether resin of Example 5 compared with the polyphenylene ether resin. Example 6
將聚苯醚樹脂（SA90，SABIC）60.0 g與二甲苯（xylene）60.0 g放入三口燒瓶中，在溫度80℃下溶解攪拌均勻，加入甲基乙烯基二甲氧基矽烷（XL12，德國Wacker）16.99g均勻攪拌，提高內溫到100℃，再加入四丁基溴化銨（TBAB）0.18 g，提高內溫到130℃，等待三口燒瓶中開始有溶液回流，計時反應15小時。降溫到80℃收料，得到一含乙烯基的矽烷改質聚苯醚樹脂A6，將樹脂A6取樣進行GPC檢測，得到Mn/ Mw：2137/3606。60.0 g of polyphenylene ether resin (SA90, SABIC) and 60.0 g of xylene were placed in a three-necked flask, dissolved and stirred evenly at 80°C, 16.99 g of methylvinyl dimethoxysilane (XL12, Wacker, Germany) was added and stirred evenly, the internal temperature was raised to 100°C, and 0.18 g of tetrabutylammonium bromide (TBAB) was added, the internal temperature was raised to 130°C, and the solution in the three-necked flask began to reflux, and the reaction time was 15 hours. The temperature was lowered to 80°C to collect the material, and a vinyl-containing silane-modified polyphenylene ether resin A6 was obtained. The resin A6 was sampled for GPC detection, and Mn/Mw: 2137/3606 was obtained.
實例1至實例6的配比與原料SA90的GPC檢測結果整理於以下表1：
綜上所述，本發明的發明目的為克服端羥基聚苯醚化合物的缺陷，以改善聚苯醚化合物本身因熔點高、加工性能不佳，端基所帶羥基反應活性低，無法形成高交聯密度的固化體系，機械性能、熱穩定性能、黏結力等性能不佳。本發明利用雙端具有羥基的聚苯醚樹脂與端基帶有至少一個烷氧基及至少一個乙烯基的矽烷進行脫醇反應，以得到端基帶有乙烯基的矽烷改質聚苯醚樹脂，反應過程產生的副產物為醇類，可透過加熱過程蒸發排除，不會有腐蝕PCB的風險。In summary, the purpose of the invention is to overcome the defects of terminal hydroxyl polyphenylene ether compounds, so as to improve the poor mechanical properties, thermal stability, adhesion and other properties of the polyphenylene ether compounds themselves due to high melting point, poor processing performance, low reactivity of the hydroxyl groups carried by the terminal groups, and inability to form a high crosslinking density solidification system. The present invention utilizes a polyphenylene ether resin with hydroxyl groups at both ends and a silane with at least one alkoxy group and at least one vinyl group at the terminal group to carry out a dealcoholization reaction to obtain a silane-modified polyphenylene ether resin with a vinyl group at the terminal group. The byproducts produced in the reaction process are alcohols, which can be evaporated and removed through a heating process, and there is no risk of corroding PCBs.
此外，本發明所使用的矽烷為端基帶有兩個烷氧基的烷基乙烯基矽烷，並非帶三個烷氧基的矽烷（tri-alkoxy），帶三個烷氧基的矽烷（tri-alkoxy）傾向於自行縮聚成矽樹脂。本發明所使用的端基帶有兩個烷氧基的烷基乙烯基矽烷與聚苯醚端基的羥基進行脫醇縮合反應後，易生成呈現線性的矽烷-聚苯醚結構。然而，使用端基帶有三個烷氧基的矽烷與聚苯醚端基的羥基進行脫醇縮合反應，即使有少數的烷氧基成功與聚苯醚端基的羥基接上，也無法避免剩餘的烷氧基進一步產生縮聚形成三維交聯的矽氧烷（矽油），進而導致分子量變大、黏度上升、操作性不佳、相容性變差。本發明所使用的矽烷帶有至少一個乙烯基，可藉由過氧化物作用進行交聯反應，進一步提高交聯密度，形成高交聯密度的固化樹脂。In addition, the silane used in the present invention is an alkyl vinyl silane with two alkoxy groups at the end, not a silane with three alkoxy groups (tri-alkoxy). The silane with three alkoxy groups (tri-alkoxy) tends to condense by itself into a silicone resin. The alkyl vinyl silane with two alkoxy groups at the end used in the present invention is easy to generate a linear silane-polyphenylene ether structure after a dealcoholization condensation reaction with the hydroxyl group at the end of the polyphenylene ether. However, when a silane with three alkoxy groups at the end is used to carry out a dealcoholization condensation reaction with the hydroxyl group at the end of polyphenylene ether, even if a small number of alkoxy groups are successfully connected to the hydroxyl group at the end of polyphenylene ether, it is impossible to avoid the remaining alkoxy groups from further condensing to form a three-dimensional cross-linked siloxane (silicone oil), which in turn leads to an increase in molecular weight, increased viscosity, poor operability, and poor compatibility. The silane used in the present invention has at least one vinyl group, which can be cross-linked by the action of peroxide to further increase the cross-linking density and form a cured resin with a high cross-linking density.
無without
圖1是實例1的矽烷改質聚苯醚樹脂與聚苯醚樹脂進行比較的凝膠滲透層析法（Gel Permeation Chromatography，GPC）圖。 圖2是實例5的矽烷改質聚苯醚樹脂與聚苯醚樹脂進行比較的凝膠滲透層析法圖。Figure 1 is a Gel Permeation Chromatography (GPC) graph of the silane-modified polyphenylene ether resin in Example 1 for comparison with the polyphenylene ether resin. Figure 2 is a Gel Permeation Chromatography graph of the silane-modified polyphenylene ether resin in Example 5 for comparison with the polyphenylene ether resin.
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