CN115368550A - 一种氧杂环丁烷类含氟聚合物及其制备方法 - Google Patents
一种氧杂环丁烷类含氟聚合物及其制备方法 Download PDFInfo
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Abstract
本发明公开一种具有式(I)所示结构的低粘度氧杂环丁烷类含氟聚合物及其制备方法和应用，以及包含其的能量固化组合物，式(I)中R1代表氟代烷基，所述聚合物的重均分子量在300‑4000之间。通过结构设计，所述氧杂环丁烷类含氟聚合物结合了氧杂环丁类基团与含氟低聚物的优点，作为活性稀释剂使用时能够给固化膜带来优异的综合性能。所述氧杂环丁烷类含氟聚合物合成工艺简单，分子量大小可控，成本低且使用方便。
Description
技术领域
本发明属于光电材料领域，具体涉及一种低粘度氧杂环丁烷类含氟聚合物及其制备方法和应用，以及包含其的能量固化组合物。
背景技术
阳离子引发体系具有不受氧阻聚影响、体积收缩率小等优点，应用日益广泛。以往阳离子引发体系中使用的活性稀释剂主要为乙烯基醚和/或环氧类稀释剂，品种较少。然而，活性稀释剂在固化材料中的占比通常达到40％-60％，占据了主导地位，其自身的化学结构对固化膜的性能有很大影响，因此丰富活性稀释剂的品种对促进和推动阳离子引发体系的应用有重要意义。
氧杂环丁烷类是一种低粘度阳离子活性稀释剂，被广泛用于涂料、油墨和感光材料等领域。含氟低聚物具有优异的热稳定性、耐候性、化学稳定性、疏水性及防污等优点。目前，可阳离子固化的氧杂环丁烷类含氟低聚物鲜有报道。
发明内容
本发明的目的在于提供一种低粘度氧杂环丁烷类含氟聚合物及其制备方法和应用，以及包含其的能量固化组合物。通过结构设计，所述氧杂环丁烷类含氟聚合物结合了氧杂环丁类基团与含氟低聚物的优点，作为活性稀释剂使用时能够给固化膜带来优异的综合性能。所述氧杂环丁烷类含氟聚合物合成工艺简单，分子量大小可控，成本低且使用方便。
为了实现上述目的，根据本发明的一个方面，提供具有式(I)所示结构的低粘度氧杂环丁烷类含氟聚合物：
其中，R1代表氟代烷基，且所述聚合物的重均分子量在300-4000之间。
进一步地，式(I)所示聚合物在25℃下的粘度为20-200cps。
作为优选实施方式，R1代表C1-C15的氟代烷基。进一步优选地，R1代表-(CH2)x-(CF2)y-CF3或-(CH2)x-(CF2)y-CF(CF3)-CF3,其中x代表0或1，y代表0、1、2、3、4、5、6、7、8、9或10。
根据本发明的另一方面，提供上述式(I)所示聚合物的制备方法，包括：3-乙基-3-羟甲基氧杂环丁烷与R1取代的环氧乙烷在碱性条件下反应；
反应式如下所示：
上述制备方法中，使用的原料均是现有技术中的已知化合物。非限制性地，所述碱性条件可以是通过在反应体系中加入氢氧化钠、氢氧化钾、碳酸钠、碳酸钾等中的一种或两种以上的组合来实现，这对本领域技术人员而言是容易确定的常规技术。
反应温度优选为80-160℃，反应压力优选为0.01-0.5MPa。
根据本发明的再一方面，提供上述式(I)所示聚合物在能量固化领域中的应用。相应地，本发明还提供一种能量固化组合物，包括上述式(I)所示聚合物。
所述能量固化特别优选是光固化或热固化。适宜地，应用领域包括但不限于涂料、油墨、粘合剂或感光材料等。
本发明的氧杂环丁烷类含氟聚合物结合了氧杂环丁类基团与含氟低聚物的优点，粘度低且分子量大小可控。相较于现有含羟基的氧杂环丁烷单体，式(I)所示氧杂环丁烷类含氟聚合物作为活性稀释剂使用时表现出很好的固化速度，表面固化性能优异，且固化膜硬度有所提高。并且，该含氟聚合物合成工艺简单，反应条件温和，常规设备即可制备，适合工业化生产。
具体实施方式
以下将结合具体实施例对本发明作进一步详细说明，但不应将其理解为对本发明保护范围的限制。
在本发明中，除非另有说明，25℃下粘度通过粘度分析仪(型号：DV1,BROOKFIELD)测定，重均分子量通过凝胶色谱仪(型号：LC-20AD，日本岛津)测定。
制备实施例
实施例1
向250mL四口烧瓶中加入原料1a 11.6g和氢氧化钾0.1g，搅拌加热至120℃，向反应体系通入氮气至压力为0.2MPa，缓慢通入11.2g原料1b，约90min通入完，继续搅拌2h，停止反应，得到聚合物1c。测得粘度为121.25cps(25℃)，重均分子量为389。
实施例2
参照实施例1，其他条件不变，区别在于原料1b通入量为22.4g，得聚合物2c，测得粘度为89.58cps(25℃)，重均分子量为535。
实施例3
参照实施例1，其他条件不变，区别在于原料1b通入量为33.6g，得聚合物3c，测得粘度为45.72cps(25℃)，重均分子量为709。
实施例4
参照实施例1，其他条件不变，区别在于原料1b通入量为44.8g，得聚合物4c，测得粘度为38.48cps(25℃)，重均分子量为819。
实施例5
参照实施例1，其他条件不变，区别在于原料1b通入量为56g，得聚合物5c，测得粘度为36.63cps(25℃)，重均分子量为1004。
实施例6
参照实施例1，其他条件不变，区别在于原料1b通入量为89.6g，得聚合物6c，测得粘度为31.24cps(25℃)，重均分子量为1548。
实施例7
参照实施例1，其他条件不变，区别在于原料1b通入量为112g，反应温度为130℃，得聚合物7c，测得粘度为25.83cps(25℃)，重均分子量为2016。
实施例8
参照实施例1，其他条件不变，区别在于原料1b通入量为33.6g，反应压力为0.3Pa，得聚合物8c，测得粘度为43.42cps(25℃)，重均分子量为709。
实施例9
向250mL四口烧瓶中加入原料1a 11.6g和氢氧化钠0.1g，搅拌加热至125℃，向反应体系通入氮气至压力为0.2MPa，缓慢通入67.8g原料1b’，约150min通入完，继续搅拌2h，停止反应，得到聚合物1c’。测得粘度为33.48cps(25℃)，重均分子量为1245。
实施例10
向250mL四口烧瓶中加入原料1a 11.6g和氢氧化钠0.1g，搅拌加热至125℃，向反应体系通入氮气至压力为0.2MPa，缓慢通入190.4g原料1b”，约180min通入完，继续搅拌2h，停止反应，得到聚合物1c”。测得粘度为20.54cps(25℃)，重均分子量为3448。
性能评价
(一)光固化性能
参照表1中所示固化组合物配方，将上述制得的氧杂环丁烷类含氟聚合物或者用于对比的含羟基氧杂环丁烷单体与环氧类活性单体(6110)混合，然后加入占总量2％的光引发剂PAG202,搅拌均匀备用。
将马口铁片用丙酮和清水清洗，干燥备用。
表1
1、固化速度
将光固化组合物取样于PET基材上，25#线棒涂布得到厚度约为25μm的涂层，将其在履带式曝光机中曝光(曝光机型号RW-UV20101，汞灯)，单次接受30mJ/cm2的辐射能量，记录各配方固化完全所需的最少次数。当固化完在室温下用手指压膜没有任何指纹留下则固化完全。
2、硬度测试
将光固化组合物以25μm的厚度涂于PET膜上，接受200mJ/cm2的辐射能量，使其充分固化。参照GB/T 6739-2006中规定的铅笔硬度评价标准，将铅笔插入试验仪器中并用夹子将其固定，保持水平，铅笔的尖端放在漆膜表面上，以1mm/s的速度朝离开自己的方向推动至少7mm距离，如果未出现划痕，在未测试区域重复实验，更换较高硬度的铅笔直至出现至少3mm长的划痕为止，以没有使涂层出现划痕的最硬的铅笔的硬度表示涂层的硬度。6H代表最硬，6B代表最软。
3、柔韧性
将光固化组合物以25μm的厚度涂于马口铁片上，接受200mJ/cm2的辐射能量，使其充分固化。参照GB/T 1731-1993漆膜柔韧性测试标准，将涂有固化涂层的马口铁板的外侧沿长度方向依次卷绕在15、10、5、4、3、2、1毫米的棒轴上，弯曲2-3s，用放大镜观察，以涂料层破坏的最小的棒轴的直径来表示光固化涂层的柔韧性。
4、附着性
将光固化组合物以25μm的厚度涂于PET膜上，接受200mJ/cm2的辐射能量，使其充分固化。参照GB/T 9286-1998中规定的漆膜划格评价标准，将涂膜切割为百格，刀尖在切割时要划及底材，并且刀尖要锋利，刀尖与涂膜成45度角。用软毛刷刷去漆屑，将3M透明胶带粘在划好的百格上，并施力使胶带牢固的粘在涂膜面及划格部位。在2min内，拿住3M胶带的一端，并呈60度角度，在1秒内平稳地撕离胶带，并按下述标准进行评价。
0级：切割边缘完全平滑无一脱落；
1级：在切口交叉处有少许涂层脱落，但交叉切割面积受影响不能明显大于5％；
2级：在切口交叉处和/或沿切口边缘有涂层脱落，受影响明显大于5％，但不能明显大于15％；
3级：涂层沿切割边缘部分或全部以大碎片脱落，和/或在格子不同部位上部分或全部剥落，受影响的交叉切割面积明显大于15％，但不能明显大于35％；
4级：涂层沿切割边缘大碎片剥落，和/或一些方格部分或全部脱落，受影响的交叉切割面积明显大于35％，但不能明显大于65％；
5级：剥落的程度大于65％。
性能测试结果汇总在表2中。
表2
从表2中可以看到，本发明的氧杂环丁烷含氟聚合物可应用于光固化组合物中，具有与当前广泛使用的含羟基氧杂环丁烷单体相当的性能，部分氧杂环丁烷含氟聚合物的固化膜硬度有所提升。
(二)热固化性能
通过配制具有如表3中所示配方的热固化组合物，对本发明式(I)所示聚合物的热固化应用性能进行评价。
表3
将热固化组合物取样于马口铁上，制得厚度约为25μm的涂层，放入80℃的烘箱2h，观察其固化情况，按以下标准进行热固化性能评价(结果见表4)：
1、油，不固
2、表面油，底层固化
3、表面粘，手触后指纹较重
4、基本表干，手触后略发涩，淡指纹
5、完全固化，表面光滑，手触后无指纹
表4
从表4中可以看到，本发明的氧杂环丁烷类含氟聚合物可应用热固化组合物中，并且固化性能相对优异。
Claims (10)
1.具有式(I)所示结构的低粘度氧杂环丁烷类含氟聚合物：
其中，R1代表氟代烷基，且所述聚合物的重均分子量在300-4000之间。
2.根据权利要求1所述的氧杂环丁烷类含氟聚合物，其特征在于：式(I)所示聚合物在25℃下的粘度为20-200cps。
3.根据权利要求1或2所述的氧杂环丁烷类含氟聚合物，其特征在于：R1代表C1-C15的氟代烷基。
4.根据权利要求1或2所述的氧杂环丁烷类含氟聚合物，其特征在于：R1代表-(CH2)x-(CF2)y-CF3或-(CH2)x-(CF2)y-CF(CF3)-CF3,其中x代表0或1，y代表0、1、2、3、4、5、6、7、8、9或10。
5.权利要求1-4中任一项所述的氧杂环丁烷类含氟聚合物的制备方法，包括：3-乙基-3-羟甲基氧杂环丁烷与R1取代的环氧乙烷在碱性条件下反应；
反应式如下所示：
6.根据权利要求5所述的制备方法，其特征在于：反应温度为80-160℃，反应压力为0.01-0.5MPa。
7.一种能量固化组合物，包括权利要求1-4中任一项所述的氧杂环丁烷类含氟聚合物。
8.权利要求1-4中任一项所述的氧杂环丁烷类含氟聚合物或权利要求7所述的能量固化组合物在能量固化领域中的应用。
9.根据权利要求8所述的应用，其特征在于：所述能量固化是光固化或热固化。
10.根据权利要求8所述的应用，其特征在于：应用领域包括但不限于涂料、油墨、粘合剂或感光材料。
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