CN117500849A - 可自由基聚合的共聚物、包含其的可自由基聚合的组合物、以及来自其的聚合反应产物 - Google Patents
可自由基聚合的共聚物、包含其的可自由基聚合的组合物、以及来自其的聚合反应产物 Download PDFInfo
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- CN117500849A CN117500849A CN202280041133.6A CN202280041133A CN117500849A CN 117500849 A CN117500849 A CN 117500849A CN 202280041133 A CN202280041133 A CN 202280041133A CN 117500849 A CN117500849 A CN 117500849A
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- radically polymerizable
- free radically
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- copolymer
- acrylate
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 150000001450 anions Chemical class 0.000 claims abstract description 7
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了可自由基聚合的共聚物,该共聚物包含二价单体单元:a);b);和任选的c)。每个R1独立地表示具有1至8个碳原子的烷基基团。R2表示H或甲基基团。Z表示具有2至12个碳原子的烷亚基基团。X‑表示非干扰性阴离子。还公开了含有它们的可自由基聚合的组合物以及相应的聚合组合物。a)b)c)
Description
技术领域
本公开广泛地涉及具有异丁烯和(甲基)丙烯酰氧基官能化苯乙烯单体单元的可自由基聚合的共聚物和包含它们的可固化组合物。
背景技术
聚异丁烯就其低介电常数(在2.5GHz下为Dk 2.2)、低耗散因子(在2.5GHz下为Df0.0005)、阻隔性能以及抗湿性和耐化学性方面而言是用于第五代技术标准(5G)电信设备的表现最好的商品聚合物之一,但它是树胶。为了在许多5G应用(例如,粘合剂和膜应用)中有用,它必须交联至一定程度。
发明内容
有利地,本公开提供用(甲基)丙烯酸酯侧基官能化的可自由基聚合的异丁烯共聚物、包含它们的组合物、以及它们的交联反应产物。在自由基聚合后,它们形成交联的聚合物网络。未聚合的共聚物和聚合的组合物通常非常适合用于5G应用。
在第一方面,本公开提供了可自由基聚合的共聚物,该共聚物包含二价单体单元:
和任选的
其中:
每个R1独立地表示具有1至8个碳原子的烷基基团,
R2表示H或甲基基团,
Z表示具有2至12个碳原子的烷亚基基团;并且
X-表示非干扰性阴离子。
在另一方面,本公开提供了可自由基聚合的组合物,该组合物包含:
i)至少一种根据本公开的可自由基聚合的共聚物;
ii)至少一种可自由基聚合的单体;和
iii)任选的自由基引发剂。
在又一方面,本公开提供一种根据本公开的可自由基聚合的组合物的聚合反应产物。
如本文所用,
术语“(甲基)丙烯酰基”指丙烯酰基和/或甲基丙烯酰基;和
术语“非干扰性阴离子”是指不会不利地影响自由基聚合的任何阴离子(有机或无机)。
在考虑具体实施方式以及所附权利要求书时,将进一步理解本公开的特征和优点。
具体实施方式
可用的可自由基聚合的共聚物包含二价单体单元:
和任选的
每个R1独立地表示具有1至8个碳原子,优选地1至4个碳原子,更优选地1或2个碳原子的烷基基团。示例包括甲基、乙基、丙基、丁基、戊基、己基、庚基和辛基。
R2表示H或甲基基团。
Z表示具有2至12个碳原子,优选地2至8个碳原子,更优选地2至6个碳原子,更优选地2至4个碳原子的烷亚基基团。
X-表示如上文所定义的非干扰性阴离子。合适的非干扰性阴离子的示例可包括(取决于其它组分)氟离子、氯离子、溴离子、络合金属卤化物(例如六氟磷酸根、六氟锑酸根、五氟羟基锑酸根、四氯锡酸根、氢氧根、磺酸根(例如三氟甲磺酸根、甲磺酸根、对甲苯磺酸根)、四氟硼酸根、硝酸根、硫酸根、碳酸根、碳酸氢根、磷酸根或膦酸根、高氯酸根;硝酸根;碳酸根;硫酸根;和碳酸氢根。
前述聚合物可例如由对甲基苯乙烯和异丁烯的相应共聚物通过以下步骤合成:例如一些或所有苄基甲基基团的自由基溴化和随后用叔氨基烷基(甲基)丙烯酸酯诸如下式表示的叔氨基烷基(甲基)丙烯酸酯进行亲核反应:
其中R1、R2和Z如先前所定义。通常,溴化共聚物(或其它合适的前体)发生足够的官能化,使得所得的可自由基聚合的共聚物包含至少2个、至少3个或甚至至少4个-(甲基)丙烯酰氧基,尽管一些单官能共聚物在一些情况下可能是有用的。
其中溴原子与苄基碳原子键合的异戊二烯和对甲基苯乙烯的溴化共聚物可以商品名EXXPRO从德克萨斯州休斯顿的埃克森美孚公司(ExxonMobil,Houston,Texas)商购获得(例如,以等级EXXPRO 3563、EXXPRO 3035、EXXPRO 3745和EXXPRO 3433)。
合适的此类叔胺的示例包括:N,N-二甲基氨基乙基(甲基)丙烯酸酯、N,N-二乙基氨基乙基(甲基)丙烯酸酯、N-乙基-N-甲基氨基乙基(甲基)丙烯酸酯、N,N-二甲基氨基-丙基(甲基)丙烯酸酯、N,N-二乙基氨基丙基(甲基)丙烯酸酯、N,N-二甲基氨基丁基(甲基)丙烯酸酯、N,N-二乙基氨基丁基(甲基)丙烯酸酯、N,N-二甲基氨基己基(甲基)丙烯酸酯、N,N-二乙基氨基己基(甲基)丙烯酸酯、N,N-二甲基氨基辛基(甲基)丙烯酸酯、N,N-二乙基氨基辛基(甲基)丙烯酸酯、N,N-二丙基氨基乙基(甲基)丙烯酸酯、N,N-二丁基氨基乙基(甲基)丙烯酸酯、N,N-二戊基氨基乙基(甲基)丙烯酸酯、N,N-二己基氨基乙基(甲基)丙烯酸酯、和N,N-二辛基氨基乙基(甲基)丙烯酸酯。这些叔胺可从商业供应商获得和/或通过已知方法合成。
虽然上述过程产生溴化物盐,但其它盐可容易地制备,例如通过熟知的离子交换方法(例如使用阴离子交换柱)。
单体单元a)、b)和任选的c)的比率可以是任何比率。通常,期望具有大部分单体单元a),因为它对于5G通信应用而言具有最期望的性质。在一些实施方案中,组分a)与组合的组分b)和任选的c)的摩尔比为至少80:20、至少85:15、至少90:10、至少95:5、至少97:3、至少98:2或甚至至少99:1。
单体单元b)与单体单元c)(如果存在的话)的比率可以是任何摩尔比。示例包括99:1至1:99、99:1至95:5、99:1至90:10、以及99:1至80:20,但也可使用其它比率。
至少一种根据本公开的可自由基聚合的共聚物可与至少一种可自由基聚合的单体和任选的自由基光引发剂组合。
示例性的合适的可自由基聚合的单体包括单官能和多官能(即,具有至少两个(甲基)丙烯酰基基团)(甲基)丙烯酸单体。可使用任何比率的可自由基聚合的共聚物和可自由基聚合的单体。在一些实施方案中,可自由基聚合的共聚物与可自由基聚合的单体的重量比为5:95至50:50,优选为10:90至25:75。
可自由基聚合的(甲基)丙烯酸单体的示例包括:例如单、二或聚(甲基)丙烯酸类(例如,丙烯酸酯和甲基丙烯酸酯),诸如(甲基)丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸异丙酯、丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸异冰片酯、丙烯酸十八酯、丙烯酸烯丙酯、甘油三丙烯酸酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、三环癸烷二甲醇二甲基丙烯酸酯、1,10-癸二醇二甲基丙烯酸酯、1,3-丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三丙烯酸酯、1,2,4-丁三醇三甲基丙烯酸酯、1,4-环己二醇二丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、山梨醇六丙烯酸酯、(甲基)丙烯酸四氢糠酯、双[1-(2-丙烯酰氧基)]-对乙氧基苯基二甲基甲烷、双[1-(3-丙烯酰氧基-2-羟基)]-对丙氧基苯基二甲基甲烷、乙氧基化双酚A二(甲基)丙烯酸酯和异氰脲酸三甲基丙烯酸三羟乙酯;(甲基)丙烯酰胺(即丙烯酰胺和甲基丙烯酰胺)诸如(甲基)丙烯酰胺、甲亚基双(甲基)丙烯酰胺和乙酰丙酮(甲基)丙烯酰胺;脲烷(甲基)丙烯酸酯;聚乙二醇类的双(甲基)丙烯酸酯(通常分子量为200至500);丙烯酸酯化单体的可共聚混合物,诸如美国专利4,652,274号(Boettcher等人)中的那些;丙烯酸酯化低聚物,诸如美国专利4,642,126号(Zador等人)中的那些;以及乙烯基化合物,诸如苯乙烯、邻苯二甲酸二烯丙基酯、琥珀酸二乙烯酯、己二酸二乙烯酯和邻苯二甲酸二乙烯酯。其它合适的附加的可自由基聚合的单体包括如(例如)公开于PCT专利公布号WO 00/38619(Guggenberger等人)、WO 01/92271(Weinmann等人)、WO 01/07444(Guggenberger等人)、WO 00/42092(Guggenberger等人)中的硅氧烷官能化(甲基)丙烯酸酯,和如(例如)公开于美国专利号5,076,844(Fock等人)、美国专利号4,356,296(Griffith等人)和欧洲专利申请号0 373 384(Wagenknecht等人)、0 201 031(Reiners等人)和0 201778(Reiners等人)中的含氟聚合物官能化的(甲基)丙烯酸酯。
附加的可自由基聚合的单体的其它示例包括诸如以下的材料:(甲基)丙烯酸羟烷基酯,诸如(甲基)丙烯酸2-羟乙酯和(甲基)丙烯酸2-羟丙酯;单(甲基)丙烯酸甘油酯或二(甲基)丙烯酸甘油酯;三羟甲基丙烷单(甲基)丙烯酸酯或三羟甲基丙烷二(甲基)丙烯酸酯;季戊四醇单(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯和季戊四醇三(甲基)丙烯酸酯;山梨醇单(甲基)丙烯酸酯、山梨醇二(甲基)丙烯酸酯、山梨醇三(甲基)丙烯酸酯、山梨醇四(甲基)丙烯酸酯或山梨醇五(甲基)丙烯酸酯;和2,2-双[4-(2-羟基-3-甲基丙烯酰氧基丙氧基)苯基]丙烷。
一种示例性的可用的可自由基聚合的化合物以基于脂族疏水主链的CN309丙烯酸酯得自宾夕法尼亚州埃克斯顿的沙多玛公司(SartomerCo.,Exton,Pennsylvania)。
示例性的合适的可自由基聚合的单体还包括具有一个或多个碳-碳双键且具有1至18个碳原子的烯烃(例如,乙烯、丙烯、丁烯、丁二烯、异戊二烯、己烯、环己烯、辛烯、癸烯、十六碳烯或十八碳烯)。同时可以包括其它可自由基聚合的单体。
在一些实施方案中,合适的可自由基聚合的单体不含N、P和/或S原子。在一些实施方案中,合适的可自由基聚合的单体不含N、O、P和/或S原子。
如本文所用,术语“自由基光引发剂”是指当暴露于光化辐射(例如,紫外线和/或可见光)时可引起自由基聚合或共聚的任何化合物或化合物的组合。自由基引发剂的选择、量和聚合条件在本领域普通技术人员的能力范围内。
通常包含至少有效量的自由基光引发剂。所谓的术语“有效量”意指这样的量,该量至少足以引起可自由基聚合的组合物在聚合条件下自由基聚合。通常,基于可自由基聚合的组合物的总重量,自由基引发剂的总量以0.0001重量%至20重量%(优选地0.001重量%至5重量%)范围内的量使用,但这不是必需的。
自由基光引发剂的示例包括:2-苄基-2-(二甲基氨基)-4'-吗啉代-丁酰苯;1-羟基环己基-苯基酮;2-甲基-1-[4-(甲硫基)苯基]-2-吗啉-丙-1-酮;4-甲基二苯甲酮;4-苯基二苯甲酮;2-羟基-2-甲基-1-苯基丙酮;1-[4-(2-羟基乙氧基)-苯基]-2-羟基-2-甲基丙酮;2,2-二甲氧基-2-苯基苯乙酮;4-(4-甲基苯硫基)二苯甲酮;二苯甲酮;2,4-二乙基噻吨酮;4,4'-双(二乙基氨基)二苯甲酮;2-异丙基噻吨酮;酰基膦氧化物衍生物、酰基次膦酸酯衍生物和酰基膦衍生物(例如,苯基双(2,4,6-三甲基苯甲酰基)膦氧化物(可以OMNIRAD819购自伊利诺斯州圣查尔斯的IGM树脂公司(IGM Resins,St.Charles,Illinois))、苯基双(2,4,6-三甲基苯甲酰基)膦(例如,可以OMNIRAD 2100购自IGM树脂公司(IGM Resins))、双(2,4,6-三甲基苯甲酰基)苯基膦氧化物、2,4,6-三甲基苯甲酰基二苯基膦氧化物(例如,可以OMNIRAD 8953X购自IGM树脂公司(IGM Resins))、异丙氧基苯基-2,4,6-三甲基苯甲酰基膦氧化物、二甲基新戊酰基膦酸酯)、乙基(2,4,6-三甲基苯甲酰基)苯基次膦酸酯(例如,可以OMNIRAD TPO-L购自IGM树脂公司(IGM Resins));双(环戊二烯基)双[2,6-二氟-3-(1-吡咯基)苯基]钛(例如,以商品名OMNIRAD 784购自IGM树脂公司(IGM Resins));以及它们的组合。
合适的光化辐射源包括例如激光器、弧形灯(例如,中压汞弧灯)、LED灯、氙闪光灯、微波驱动灯(例如,配备有H型灯泡或D型灯泡)。合适的曝光条件的选择将在本领域技术人员的能力范围内。
基于膜前体组合物的总重量,自由基光引发剂的量通常在0.01重量%至5重量%的范围内。该量可为至少0.01重量%、至少0.05重量%、至少0.1重量%、至少0.5重量%、至少1重量%,以及至多5重量%、至多4重量%、至多3重量%、至多2重量%、或至多1重量%;然而,也可使用更高的量。
可使可自由基聚合的组合物聚合以提供相应的聚合反应产物,其可用作例如间隙填料、粘合剂和/或密封剂,尤其是在5G启用的电信设备(例如,蜂窝电话)、膝上型计算机和平板计算机中。
通过以下非限制性实施例,进一步示出了本公开的目的和优点,但在这些实施例中引用的具体材料及其量以及其他条件和细节不应视为对本公开的不当限制。
实施例
除非另有说明,否则实施例及本说明书其余部分中的所有份数、百分比、比等均以重量计。
下表1报告了实施例中所用材料的名称、描述和来源。
表1
测试方法
核磁共振(NMR)光谱
使用配备有CPBBO梯度冷冻探针、Bruker B-ACS 60自动取样机和Bruker Topspin3.04软件的Bruker AVANCE III 500MHz NMR光谱仪进行NMR光谱分析。用15°1H激发脉冲和4秒的采集时间记录质子NMR光谱。还收集二维(2D)1H-13C NMR光谱,并且以HSQC(异核单量子相干)绝热材料扫描宽度模式记录。使用先进化学开发(Advanced ChemistryDevelopment)软件(多伦多,加拿大(Toronto,Canada))分析光谱。
介电测量
通过将10mL的制剂溶液(25重量%,在甲苯中)倒入Teflon衬里的玻璃皮氏培养皿中并在室温下干燥24小时来制备样品。将所得的盘从Teflon上剥离,并表征在10.1GHz下的介电常数和耗散因子。
在10.1GHz下固体的分离柱介电谐振器测量
根据标准IEC 61189-2-721:2015“用于介电材料、印制板以及其它互联结构和组件的测试方法-部分2-721:用于互联结构的材料的测试方法-使用分离柱介电谐振器测量铜包覆层合体在微波频率下的相对介电常数和损耗切线(Test Methods For ElectricalMaterials,Printed Boards And Other Interconnection Structures And Assemblies-Part 2-721:Test Methods For Materials For Interconnection Structures-Measurement Of Relative Permittivity And Loss Tangent For Copper CladLaminate At Microwave Frequency Using A Split Post Dielectric Resonator)”在10.1GHz频率下进行分离柱介电谐振器测量。将每个薄材料或膜***两个固定的介电谐振器之间。试样对柱的共振频率和质量因子的影响使得能够直接计算复介电常数(介电常数和电介质损失)。该10.1GHz谐振器以仅具有方位角电场分量的TE01d模式操作,使得电场在电介质界面上保持连续。分离柱介电谐振器测量在样本的平面中的介电常数分量。在这些介电谐振器测量中的每个介电谐振器测量中使用环耦合(临界耦合)。该10.1GHz分离柱谐振器测量***与Keysight VNA(型号为PNA 8364C的矢量网络分析仪,10MHz-50GHz)结合。执行计算以确定每个试样在10.1GHz下的复介电常数。
通过DSC表征
通过称量材料并将其装载到特拉华州纽卡斯尔TA仪器公司(TA Instruments(NewCastle,Delaware))的DSC铝制样品盘中来制备用于热分析的DSC样品。使用TAInstruments Discovery差示扫描量热仪(DSC-SN DSC1-0091),利用热-冷-热方法在标准模式(以10℃/min从-155℃至约50℃)下分析样本。在收集数据之后,使用TA UniversalAnalysis通用分析程序分析热转变。使用标准热流(HF)曲线中的阶跃变化评估玻璃化转变温度。报告第二次热转变的中点(半高)温度。
聚合物1的制备
在70℃下在搅拌下将EXXPRO 3745(9.22g)溶于甲苯(60mL)中。添加甲基丙烯酸2-二乙基-氨基乙酯(0.34g)。在70℃下搅拌混合物3小时,添加15mL的甲氧基丙醇,并且将混合物在70℃下再搅拌48小时。将产物沉淀到乙腈(50mL)中并用乙腈(2×20mL)洗涤两次,在溶剂烘箱(130℃,2小时)中干燥,并以白色树胶获得。通过相对于起始共聚物的2D1H-13CHSQC NMR(CDCl3)表征产物显示在4.5ppm(1H)/33ppm(13C)处PhCH2Br甲亚基信号的损失,并且在4.0ppm(1H)/66ppm(13C)处出现期望的PhCH2NR3 +Br-甲亚基信号。
EXXPRO 3745和聚合物1的介电常数、耗散因子和玻璃化转变温度记录在下表2中。
表2
实施例 | 介电常数,20℃,10.1GHz下 | TANδ,20℃,10.1GHz下 | Tg,℃ |
EXXPRO 3745 | 2.31 | 0.0025 | -62 |
聚合物1 | 2.33 | 0.0053 | -62 |
实施例E-1至E-15以及比较例CE-1和CE-2
通过在甲苯中加热直至均匀来制备表3中报告的制剂的溶液(25重量%固体)。通过经由移液管将0.25mL的制剂溶液沉积到玻璃显微镜载玻片上,并将载玻片放置在热板(150℃,2分钟)上来制备样品。通过以下方式来将样品暴露于UV固化条件下:添加2重量%的TPO-L,经由移液管将0.25mL的制剂沉积到玻璃显微镜载玻片上,用RF02N衬垫(韩国首尔的SKC Haas(SKC Haas,Seoul,South Korea);2密耳;51微米)覆盖,以及使用ClearstoneCF1000 UV LED***(明尼苏达州霍普金斯的Clearstone科技公司(ClearstoneTechnologies Inc.,Hopkins,Minnesota),395nm,100%强度,在距样品表面1cm的距离处固化两分钟)进行固化。
表3
实施例 | EXXPRO 3745 | DEAEM | 聚合物1 | CN309 | DCP | DDMA |
CE-1 | 100 | |||||
CE-2 | 100 | |||||
EX-3 | 100 | |||||
EX-4 | 90 | 10 | ||||
EX-5 | 75 | 25 | ||||
EX-6 | 50 | 50 | ||||
EX-7 | 25 | 75 | ||||
EX-8 | 90 | 10 | ||||
EX-9 | 75 | 25 | ||||
EX-10 | 50 | 50 | ||||
EX-11 | 25 | 75 | ||||
EX-12 | 90 | 10 | ||||
EX-13 | 75 | 25 | ||||
EX-14 | 50 | 50 | ||||
EX-15 | 25 | 75 |
表3中的制剂对固化条件的响应和UV固化的展示报告于表4(下文)和表5中。
表4
表5(下文)报道了聚合物1与市售(甲基)丙烯酸酯的UV固化制剂的产物。
表5
实施例 | 透明度? | 产品 |
EX-4 | 是 | 粘性固体 |
EX-5 | 是 | 粘性固体 |
EX-6 | 是 | 软固体 |
EX-7 | 是 | 膜 |
EX-8 | 是 | 粘性固体 |
EX-9 | 是 | 粘性固体 |
EX-10 | 是 | 软固体 |
EX-11 | 是 | 膜 |
EX-12 | 是 | 粘性固体 |
EX-13 | 是 | 粘性固体 |
EX-14 | 是 | 硬固体 |
EX-15 | 是 | 膜 |
表5中报告的结果表明,聚合物1适用于具有普通低介电常数(甲基)丙烯酸酯单体(CN309、DCP和DDMA)的制剂,并且在一系列组合物中获得透明材料(例如,光学透明粘合剂)。取决于聚合物1与单体的比率,可以获得从粘性固体到硬固体膜范围的固化材料。
为了使本领域的普通技术人员能够实践受权利要求书保护的本公开而给出的前述说明不应理解为是对本公开范围的限制,本公开的范围由权利要求书及其所有等同形式限定。
Claims (15)
1.一种可自由基聚合的共聚物,所述共聚物包含二价单体单元:
a)
b)和任选的
c)
其中:
每个R1独立地表示具有1至8个碳原子的烷基基团,
R2表示H或甲基基团,
Z表示具有2至12个碳原子的烷亚基基团;并且
X-表示非干扰性阴离子。
2.根据权利要求1所述的可自由基聚合的共聚物,其中存在单体单元c)。
3.根据权利要求1或2所述的可自由基聚合的共聚物,其中单体单元b)的摩尔数小于或等于单体单元a)、b)和c)的总摩尔数的5%。
4.根据权利要求1或2所述的可自由基聚合的共聚物,其中单体单元b)的摩尔数小于或等于单体单元a)、b)和c)的总摩尔数的1%。
5.根据权利要求1至4中的任一项所述的可自由基聚合的共聚物,其中每个R1独立地为甲基或乙基基团。
6.根据权利要求1至5中的任一项所述的可自由基聚合的共聚物,其中Z表示具有2至8个碳原子的烷亚基基团。
7.根据权利要求1至5中的任一项所述的可自由基聚合的共聚物,其中Z表示具有2至4个碳原子的烷亚基基团。
8.根据权利要求1至7中的任一项所述的可自由基聚合的共聚物,其中Z表示乙亚基基团。
9.根据权利要求1至8中的任一项所述的可自由基聚合的共聚物,其中X-表示氯离子、溴离子、六氟磷酸根、六氟锑酸根、五氟羟基锑酸根或氢氧根。
10.一种可自由基聚合的组合物,所述组合物包含以下组分:
i)至少一种根据权利要求1至9中的任一项所述的可自由基聚合的共聚物;
ii)至少一种可自由基聚合的单体;和
iii)任选的自由基引发剂。
11.根据权利要求10所述的可自由基聚合的组合物,其中组分ii)包含可自由基聚合的单体,所述可自由基聚合的单体包含至少两个(甲基丙烯酰基)基团。
12.根据权利要求10或11所述的可自由基聚合的组合物,其中组分iii)存在并包含光引发剂。
13.一种根据权利要求10所述的可自由基聚合的组合物的聚合反应产物。
14.一种根据权利要求11所述的可自由基聚合的组合物的聚合反应产物。
15.一种根据权利要求12所述的可自由基聚合的组合物的聚合反应产物。
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US274A (en) | 1837-07-17 | Improvement in the mode of constructing locks for fire-arms | ||
US4652A (en) | 1846-07-20 | Machinery foe steering vessels | ||
US4356296A (en) | 1981-02-25 | 1982-10-26 | The United States Of America As Represented By The Secretary Of The Navy | Fluorinated diacrylic esters and polymers therefrom |
US4642126A (en) | 1985-02-11 | 1987-02-10 | Norton Company | Coated abrasives with rapidly curable adhesives and controllable curvature |
DE3516257A1 (de) | 1985-05-07 | 1986-11-13 | Bayer Ag, 5090 Leverkusen | (meth)-acrylsaeureester und ihre verwendung |
DE3516256A1 (de) | 1985-05-07 | 1986-11-13 | Bayer Ag, 5090 Leverkusen | (meth)-acrylsaeureester und ihre verwendung |
DE3844619A1 (de) | 1988-12-10 | 1990-07-12 | Goldschmidt Ag Th | Verwendung von perfluoroalkylgruppen aufweisenden (meth-)acrylsaeureestern in der dentaltechnik |
US5076844A (en) | 1988-12-10 | 1991-12-31 | Goldschmidt AG & GDF Gesellschaft fur Dentale Forschung u. Innovationen GmbH | Perfluoroalkyl group-containing (meth-)acrylate esters, their synthesis and use in dental technology |
DE19860361A1 (de) | 1998-12-24 | 2000-06-29 | Espe Dental Ag | Vernetzbare Monomere auf Cyclosiloxanbasis, deren Herstellung und deren Verwendung in polymerisierbaren Massen |
DE19860364C2 (de) | 1998-12-24 | 2001-12-13 | 3M Espe Ag | Polymerisierbare Dentalmassen auf der Basis von zur Aushärtung befähigten Siloxanverbindungen, deren Verwendung und Herstellung |
DE19934407A1 (de) | 1999-07-22 | 2001-01-25 | Espe Dental Ag | Hydrolysierbare und polymerisierbare Silane mit geringer Viskosität und deren Verwendung |
DE10026432A1 (de) | 2000-05-29 | 2002-02-14 | 3M Espe Ag | Präpolymere (Meth)acrylate mit polycyclischen oder aromatischen Segmenten |
WO2002100935A1 (en) * | 2001-06-08 | 2002-12-19 | Exxonmobil Chemical Patents Inc. | Low permeability nanocomposites |
JP5824489B2 (ja) * | 2013-09-02 | 2015-11-25 | エクソンモービル ケミカル パテンツ インコーポレーテッド | バリア用のトリエチルアミン官能化エラストマー |
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2022
- 2022-06-10 CN CN202280041133.6A patent/CN117500849A/zh active Pending
- 2022-06-10 EP EP22743557.5A patent/EP4355794A1/en active Pending
- 2022-06-10 WO PCT/IB2022/055424 patent/WO2022263987A1/en active Application Filing
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EP4355794A1 (en) | 2024-04-24 |
WO2022263987A1 (en) | 2022-12-22 |
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