CN112029016A - 一种脂溶性柱（杯）芳烃作为光引发剂的应用 - Google Patents

一种脂溶性柱（杯）芳烃作为光引发剂的应用 Download PDF

Info

Publication number
CN112029016A
CN112029016A CN202010917699.3A CN202010917699A CN112029016A CN 112029016 A CN112029016 A CN 112029016A CN 202010917699 A CN202010917699 A CN 202010917699A CN 112029016 A CN112029016 A CN 112029016A
Authority
CN
China
Prior art keywords
photoinitiator
column
photopolymerization
arene
cup
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.)
Granted
Application number
CN202010917699.3A
Other languages
English (en)
Other versions
CN112029016B (zh
Inventor
常银成
裴迪
聂俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN202010917699.3A priority Critical patent/CN112029016B/zh
Publication of CN112029016A publication Critical patent/CN112029016A/zh
Application granted granted Critical
Publication of CN112029016B publication Critical patent/CN112029016B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F122/00—Homopolymers 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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/10—Esters
    • C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

本发明涉及光引发剂技术领域，提供了一种脂溶性柱(杯)芳烃作为光聚合引发剂的应用。脂溶性柱(杯)芳烃具有大环结构。是一种新型的光引发剂。在光辐射条件下，柱(杯)芳烃环状分子断裂形成双自由基的直链寡聚物，可以高效引发单体的光聚合反应。与传统商业光引发剂相比，本发明提供的光引发剂本身安全无毒，不需要任何其他助剂，光辐照断裂后形成直链寡聚物，并在引发光聚合反应后被固定到聚合物中，无小分子碎片生成，可以极大的降低光引发剂的迁移，从而避免光聚合固化产物的毒性、气味等问题。

Description

一种脂溶性柱(杯)芳烃作为光引发剂的应用
技术领域：
本发明属于光聚合和光固化领域，具体涉及一种脂溶性柱(杯)芳烃作为光引发剂的应用。
背景技术：
光聚合在印刷油墨、涂层、牙疗、光刻、激光成像等领域发挥着重要作用，受到越来越多的关注。作为影响光聚合效率的关键因素，人们在光引发剂的研究和开发方面投入了大量的精力。目前已开发出多种I型裂解和II型夺氢自由基光聚合引发剂。其中I型光引发剂在光辐照下，裂解成两个自由基片段，引发光聚合。II型光引发剂需要供氢化合物作为助引发剂，产生自由基引发聚合反应。但I型和II型引发剂面临着如毒性、气味强、光解后有害物质的浸出等问题，，限制了其进一步的应用，特别是在食品包装或生物医学方面的应用。
针对这些问题，本发明提出利用柱(杯)芳烃作为光引发剂。在光辐射条件下，柱(杯)芳烃环状分子断裂形成双自由基的直链寡聚物，可以高效引发单体的光聚合反应。与传统商业光引发剂相比，柱(杯)芳烃本身安全无毒，不需要其他助剂，在光辐照断裂后形成双自由基直链寡聚物，并在引发光聚合后被固定到聚合物中，无小分子碎片生成，可以极大的降低光引发剂的迁移，从而避免光聚合固化产物的毒性、气味等问题。另外制备成本低，容易进行工业化生产，具有很强的市场化潜力。
发明内容
本发明目的在于提供一种新型脂溶性柱(杯)芳烃类光引发剂，该引发剂具有较低的迁移率，可避免光聚合固化产物的毒性、气味等问题，是一种新型的光引发剂。
一种脂溶性柱(杯)芳烃类光引发剂，其特征在于具有亚甲基桥连苯单元形成的大环结构，并且具有脂溶性。具有通式I所示结构：
通式I中：R1，R2，R3可以是羟基、烷氧基、烷基、芳香基、杂环芳香基、烯基、炔基，以及含有卤素取代基、带氧取代基、带氮取代基、带硫取代基的烷基、芳香基、杂环芳香基、烯基、烷氧基、炔基。其中n＝2-10。*为与芳香环的键合点。
在光辐射条件下，柱(杯)芳烃环状分子断裂形成双自由基的直链寡聚物，可以高效引发单体的光聚合反应。柱(杯)芳烃安全无毒，迁移率低，从而避免光聚合固化产物的毒性、气味等问题。
本发明涉及的脂溶性柱(杯)芳烃按照已发表的的文献合成：
Tomoki Ogoshi,Suguru Kanai,Shuhei Fujinami,Tada-aki Yamagishi,andYoshiaki Nakamoto，para-Bridged Symmetrical Pillar[5]arenes:Their Lewis AcidCatalyzed Synthesis and Host–Guest Property.J.Am.Chem.Soc.2008,130,5022-5023.
Xiao-Bo Hu,Zhenxia Chen,Lei Chen,Ling Zhang,Jun-Li Hou and Zhan-TingLi,Pillar[n]arenes(n＝8–10)with two cavities:synthesis,structures andcomplexing properties.Chem.Commun.,2012,48,10999-11001.
附图说明：
图1为脂溶性柱(杯)芳烃的化学结构通式。
图2为两端带有乙氧基的柱[6]芳烃(P6OC2H5)作为光引发剂的示意图和不同单体的化学结构式。
图3是P6OC2H5作为光引发剂引发不同单体的光聚合动力学曲线。
图4是光引发剂TPO、1173、P6OC2H5的迁移率。
下面结合实施例对本发明提供的方案进行详细的说明。但是不能把它们理解为对本发明保护范围的限定。
实施例1
优选的，如图2，我们选择两端带有乙氧基的柱[6]芳烃(P6OC2H5)作为引发剂，选择带有一个双键的HEA，带有两个双键的PEGDA，带有三个双键的TMPTA作为单体。称取10mgP6OC2H5,分别溶于1g HEA、TPGDA、TMPTA单体中，配置质量分数为1％的引发剂-单体混合体系。然后在20mW/cm2汞灯辐照下，用实时红外测定其光聚合动力学曲线。
实验结果如图3所示，在光辐照下，HEA、TPGDA、TMPTA三种单体的双键发生快速的转化，且最终的转化率较高。说明P6OC2H5作为光引发剂，可以高效的引发HEA、TPGDA、TMPTA三种单体的光聚合。其中TMPTA由于粘度较大，双键转化率略有下降，属于正常情况。
取10.68mg P6OC2H5，溶于1mL PEG200DA单体中，用汞灯辐照固化成为0.1mm厚度薄膜。取0.1g薄膜浸泡在10mL乙腈中，2h、4h、8h、10h测定乙腈溶液的紫外吸收，从而计算其迁移率。对于商用引发剂TPO和1173，采用同样的步骤测定迁移率。
实验结果如图4所示，与商用的引发剂TPO和1173相比，P6OC2H5作为光引发剂具有更低的迁移率。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (2)

1.一种脂溶性柱(杯)芳烃类光引发剂，其特征在于具有亚甲基桥连苯单元形成的大环结构，并且具有脂溶性，具有通式I所示结构：
Figure FDA0002665606310000011
通式I中：R1，R2，R3可以是羟基、烷氧基、烷基、芳香基、杂环芳香基、烯基、炔基，以及含有卤素取代基、带氧取代基、带氮取代基、带硫取代基的烷基、芳香基、杂环芳香基、烯基、烷氧基、炔基，其中n＝2-10，*为与芳香环的键合点。
2.根据权利要求1所述的脂溶性柱(杯)芳烃类光引发剂，其特征在于，所述脂溶性柱(杯)芳烃类光引发剂在光辐照下，可以高效的引发单体光聚合反应，并且柱(杯)芳烃安全无毒，迁移率低，从而避免光聚合固化产物的毒性、气味等问题。
CN202010917699.3A 2020-09-03 2020-09-03 一种脂溶性柱（杯）芳烃作为光引发剂的应用 Active CN112029016B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010917699.3A CN112029016B (zh) 2020-09-03 2020-09-03 一种脂溶性柱（杯）芳烃作为光引发剂的应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010917699.3A CN112029016B (zh) 2020-09-03 2020-09-03 一种脂溶性柱（杯）芳烃作为光引发剂的应用

Publications (2)

Publication Number Publication Date
CN112029016A true CN112029016A (zh) 2020-12-04
CN112029016B CN112029016B (zh) 2022-09-13

Family

ID=73591987

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010917699.3A Active CN112029016B (zh) 2020-09-03 2020-09-03 一种脂溶性柱（杯）芳烃作为光引发剂的应用

Country Status (1)

Country Link
CN (1) CN112029016B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004170A (zh) * 2021-03-05 2021-06-22 天津孚信阳光科技有限公司 一种基于柱[5]芳烃的共价大环聚合物及其制备与应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0334955A (ja) * 1989-06-30 1991-02-14 Ricoh Co Ltd カリックスアレーン誘導体
CN101337865A (zh) * 2008-08-11 2009-01-07 同济大学 一种制备含羟基杯[4]芳烃衍生物的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0334955A (ja) * 1989-06-30 1991-02-14 Ricoh Co Ltd カリックスアレーン誘導体
CN101337865A (zh) * 2008-08-11 2009-01-07 同济大学 一种制备含羟基杯[4]芳烃衍生物的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TOMOKI OGOSH ET AL.,: "para-Bridged Symmetrical Pillar[5]arenes: Their Lewis Acid Catalyzed Synthesis and Host–Guest Property", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 》 *
XIAO-BO HU ET AL.,: "Pillar[n]arenes (n = 8–10) with two cavities: synthesis, structures and complexing properties", 《CHEMICAL COMMUNICATIONS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004170A (zh) * 2021-03-05 2021-06-22 天津孚信阳光科技有限公司 一种基于柱[5]芳烃的共价大环聚合物及其制备与应用

Also Published As

Publication number Publication date
CN112029016B (zh) 2022-09-13

Similar Documents

Publication Publication Date Title
Jian et al. Thiol–epoxy/thiol–acrylate hybrid materials synthesized by photopolymerization
Wu et al. Thioxanthone based one-component polymerizable visible light photoinitiator for free radical polymerization
Sautrot-Ba et al. Quinizarin derivatives as photoinitiators for free-radical and cationic photopolymerizations in the visible spectral range
Temel et al. Polymeric side chain thioxanthone photoinitiator for free radical polymerization
CN111925462B (zh) 一种水溶性柱（杯）芳烃作为光引发剂的应用
Gencoglu et al. A Water Soluble, Low Migration, and Visible Light Photoinitiator by Thioxanthone‐Functionalization of Poly (ethylene glycol)‐Containing Poly (β‐amino ester)
CN112029016B (zh) 一种脂溶性柱（杯）芳烃作为光引发剂的应用
Karaca et al. Thioxanthonation of fluorenone: Visible photoinitiator for radical polymerization
Wang et al. Novel polymeric photoinitiators comprising of side-chain benzophenone and coinitiator amine: Photochemical and photopolymerization behaviors
Wang et al. Novel polymeric photoinitiators with side-chain benzophenone: Facile synthesis and photopolymerization properties without coinitiator
Guo et al. A novel thioxanthone-hydroxyalkylphenone bifunctional photoinitiator: Synthesis, characterization and mechanism of photopolymerization
Xue et al. A bis-acrylate functionalized enone as photoinitiator and crosslinker in photopolymerization
Liao et al. Strategies to develop α-aminoketone derivatives photoinitiators with low migration ability for UV–vis LED photopolymerization
Lai et al. N-Aryl glycines as versatile initiators for various polymerizations
Yang et al. High efficiency photoinitiators with extremely low concentration based on furans derivative
Poly et al. Polymers synthesized by RAFT as versatile macrophotoinitiators
Degirmenci et al. Synthesis and characterization of cyclohexene oxide functional poly (ε‐caprolactone) macromonomers and their use in photoinitiated cationic homo‐and copolymerization
Balaban et al. Cyclopolymerizable and cyclopolymeric photoinitiators from diallyl amine and α-hydroxy ketones
Wang et al. Benzophenone-1, 3-dioxane as a free radial initiator for photopolymerization
Macarie et al. The influence of temperature and photoinitiator concentration on photoinitiated polymerization of diacrylate monomer
Ohar et al. Synthesis and application of macrophotoinitiators obtained via benzoin tethering with copolymers of maleic anhydride
CN114591452A (zh) 一种含有α-氨基酮多官能化大分子光引发剂及其制造方法和应用
Wang et al. 6-Benzoyl-1, 3-benzodioxolane as a photoinitiator for free radical polymerization
Jin et al. Low migration and high performance thioxanthone based photoinitiators
Yusubov et al. HYPERVALENT IODINE COMPOUNDS AS POLYMERIZATION INITIATORS

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
GR01 Patent grant
GR01 Patent grant