CN111349228A - Method for expanding epoxy rotor phase photopolymerization temperature range by using active long-chain monomer and application thereof - Google Patents

Method for expanding epoxy rotor phase photopolymerization temperature range by using active long-chain monomer and application thereof Download PDF

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Publication number
CN111349228A
CN111349228A CN202010186772.4A CN202010186772A CN111349228A CN 111349228 A CN111349228 A CN 111349228A CN 202010186772 A CN202010186772 A CN 202010186772A CN 111349228 A CN111349228 A CN 111349228A
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China
Prior art keywords
photopolymerization
polymerization
real
rotor phase
temperature range
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CN202010186772.4A
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Inventor
何勇
李锋
姚淼
聂俊
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Publication of CN111349228A publication Critical patent/CN111349228A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
    • C08G2650/24—Polymeric initiators

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention belongs to the technical field of photopolymerization, and rotor phase chain type photopolymerization belongs to special solid state polymerization, which has the advantages of small curing shrinkage, insensitivity to oxygen and water vapor and the like which are not possessed by liquid photopolymerization, but has defects. One of the biggest problems limiting the application of photopolymerization is the narrow polymerization temperature range. The invention adopts the doped long-chain alkyl vinyl ether to promote the photopolymerization of the active cationic monomer octadecyl glycidyl ether, widens the temperature range of rotor phase photopolymerization, and provides a certain reference value for researching the rotor phase photopolymerization in the aspect. Can be used in special occasions with lower temperature and strict requirements on the size, such as the fields of precise photoetching, patterning and the like.

Description

Method for expanding epoxy rotor phase photopolymerization temperature range by using active long-chain monomer and application thereof
Technical Field
The invention relates to the field of photocuring, in particular to photopolymerization of an active cation mixed monomer system and influence of the mixed system on widening of a solid photopolymerization reaction temperature range.
Background
Photopolymerization refers to a novel polymerization method for generating a polymer by initiating a monomer or an oligomer to generate a chain reaction under the initiation of visible light or ultraviolet light, and compared with the traditional polymerization, the photopolymerization has incomparable advantages. Since the 20 th century and the 60 th era, photopolymerization technology has been attracting attention and developed rapidly for decades, because of its advantages of low polymerization cost, short polymerization time, no environmental pollution, and polymerization at relatively low temperature.
Because the traditional liquid photopolymerization has serious curing shrinkage and is easy to be inhibited by oxygen and water vapor, the application of the photopolymerization technology is restricted. Therefore, solving these problems is an important prerequisite for the development of photopolymerization technology. And because of the immature knowledge, the solid state polymerization cannot be realized, so that the photopolymerization reaction only focuses on the liquid state polymerization, and the solid state photopolymerization reaction is neglected.
The rotor phase is a special solid state in a special state of aggregation between fully ordered crystals and isotropic liquid. Recent research proves that rotor phase photopolymerization can occur in partial long-chain compounds, and the rotor phase photopolymerization has the advantages of small curing shrinkage, insensitivity to water vapor and the like which are not possessed by liquid photopolymerization, so that the application of solid photopolymerization is greatly expanded.
Previously, solid state photopolymerization using living cationic monomers has been used, and although reaction can occur at the polymerization temperature, the polymerization temperature range is narrow, which greatly limits the application of monomer photopolymerization. In the patent, because the two active monomer end groups are mutually promoted, the temperature range of rotor phase polymerization of the active epoxy cationic monomer can be widened, the application of solid photopolymerization is widened, and the method can be applied to the fields of precision photoetching, patterning and the like.
Disclosure of Invention
The invention aims to broaden the temperature range of solid state polymerization by blending long-chain alkyl glycidyl ether and octadecyl vinyl ether, and can be used in special occasions with lower temperature and strict requirements on size, such as the fields of precision lithography, patterning and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention relates to cationic solid photopolymerization by blending octadecyl glycidyl ether and octadecyl vinyl ether. The cationic photoinitiator is any one of (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, UVI-6976, UVI-6992, Omni550, Omni650 and Omni 440.
The light source employed in the present invention is a mercury lamp.
In order to avoid the change of the crystal structure caused by the light heat release, the invention specially designs a set of circulating water temperature control device, so that water circulates through a test bed for placing samples, and the control of the polymerization temperature is convenient.
The experimental process of the invention is that the molar ratio of octadecyl glycidyl ether to long-chain alkyl vinyl ether is 0.3:0.7-0.8:0.2, and the initiator accounts for 3% of the sum of the weight of octadecyl glycidyl ether and octadecyl alcohol, so that the octadecyl glycidyl ether and the octadecyl alcohol are melted, mixed uniformly and then coated on a carrier. The support was placed on a temperature-controlled table and controlled to the desired temperature by means of a water bath. After the temperature was constant, the polymerization was carried out by irradiation with a mercury lamp light source.
The invention uses real-time infrared to monitor the polymerization process, proves that the temperature interval of the cationic rotor phase photopolymerization of the long-chain epoxy monomer can be enlarged by adding another monomer, and the material phase state of the mixed system is represented by Differential Scanning Calorimetry (DSC).
Drawings
FIG. 1: DSC images of different mixed systems of long-chain alkyl vinyl ether and octadecyl glycidyl ether.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Mixing octadecyl glycidyl ether and octadecyl vinyl ether at a molar ratio of 0.8:0.2, adding 3wt% (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, melting, mixing uniformly, coating on a carrier, and monitoring the polymerization process in real time by using real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 5 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxide conversion of 57%.
Example 2
Mixing octadecyl glycidyl ether and octadecyl vinyl ether at a molar ratio of 0.8:0.2, adding 3wt% (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, melting, mixing uniformly, coating on a carrier, and monitoring the polymerization process in real time by using real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 20 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxy conversion of 74%.
Example 3
Mixing octadecyl glycidyl ether and octadecyl vinyl ether at a molar ratio of 0.5:0.5, adding 3wt% (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, melting, mixing, coating on a carrier, and monitoring the polymerization process in real time by real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 5 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxy conversion of 54%.
Example 4
Mixing octadecyl glycidyl ether and octadecyl vinyl ether at a molar ratio of 0.5:0.5, adding 3wt% (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, melting, mixing, coating on a carrier, and monitoring the polymerization process in real time by real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 20 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxide conversion of 64%.
Example 5
Mixing octadecyl glycidyl ether and octadecyl vinyl ether at a molar ratio of 0.3:0.7, adding 3wt% (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, and melting and mixingThen coating on a carrier, and monitoring the polymerization process in real time by using real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 5 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxy conversion of 58%.
Example 6
Mixing octadecyl glycidyl ether and octadecyl vinyl ether at a molar ratio of 0.3:0.7, adding 3wt% (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, melting, mixing, coating on a carrier, and monitoring the polymerization process in real time by real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 20 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxide conversion of 69%.
Example 7
Octadecyl glycidyl ether and hexadecyl vinyl ether are mixed according to the molar ratio of 0.5:0.5, 3wt% of (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate is added, the mixture is melted and mixed evenly and then coated on a carrier, and the polymerization process is monitored in real time by real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 5 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxy conversion of 60%.
Example 8
Octadecyl glycidyl ether and hexadecyl vinyl ether are mixed according to the molar ratio of 0.5:0.5, 3wt% of (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate is added, the mixture is melted and mixed evenly and then coated on a carrier, and the polymerization process is monitored in real time by real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 20 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxide conversion of 67%.
Example 9
Octadecyl glycidyl ether and tetradecyl vinyl ether are mixed according to the molar ratio of 0.5:0.5, 3wt% of (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate is added, the mixture is melted and mixed uniformly and then coated on a carrier, and the polymerization process is monitored in real time by real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 5 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxide conversion of 64%.
Example 10
Octadecyl glycidyl ether and tetradecyl vinyl ether are mixed according to the molar ratio of 0.5:0.5, 3wt% of (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate is added, the mixture is melted and mixed uniformly and then coated on a carrier, and the polymerization process is monitored in real time by real-time infrared. Experimental conditions for real-time infrared determination of polymerization kinetics: the polymerization temperature is controlled at 20 ℃ by a circulating water system, and a mercury lamp is adopted to obtain light intensity of 10 mW/cm2The polymerization was carried out under light for 15 min. The real-time infrared results show an epoxy conversion of 74%.

Claims (3)

1. A cationic photopolymerizable monomer mixture system, characterized in that octadecyl glycidyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether, and octadecyl vinyl ether are used as the system.
2. The rotor-phase cationic photopolymerization system as claimed in claim 1, wherein the cationic photoinitiator used in the photopolymerization is any one of (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, UVI-6976, UVI-6992, Omni550, Omni650 and Omni 440.
3. The mixed system of claim 1, wherein the initiator accounts for 3% of the sum of the mass of octadecyl glycidyl ether and long chain alkyl vinyl ether.
CN202010186772.4A 2020-03-17 2020-03-17 Method for expanding epoxy rotor phase photopolymerization temperature range by using active long-chain monomer and application thereof Pending CN111349228A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1262492A (en) * 1998-09-30 2000-08-09 凸版资讯股份有限公司 Conductive paste and its solidifying method, information receiver-transmitter and antenna forming method
CN106751349A (en) * 2016-12-12 2017-05-31 中山大简高分子材料有限公司 A kind of radical cation hybrid UV-curing resin and preparation method and application
CN110437369A (en) * 2018-05-03 2019-11-12 北京化工大学 A kind of free radical crystalline monomer mixed system
CN110437352A (en) * 2018-05-03 2019-11-12 北京化工大学 A kind of cationic photopolymerization crystalline monomer mixed system and its application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1262492A (en) * 1998-09-30 2000-08-09 凸版资讯股份有限公司 Conductive paste and its solidifying method, information receiver-transmitter and antenna forming method
CN106751349A (en) * 2016-12-12 2017-05-31 中山大简高分子材料有限公司 A kind of radical cation hybrid UV-curing resin and preparation method and application
CN110437369A (en) * 2018-05-03 2019-11-12 北京化工大学 A kind of free radical crystalline monomer mixed system
CN110437352A (en) * 2018-05-03 2019-11-12 北京化工大学 A kind of cationic photopolymerization crystalline monomer mixed system and its application

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Application publication date: 20200630