CN106279470A - Amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and preparation method thereof - Google Patents
Amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and preparation method thereof Download PDFInfo
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- CN106279470A CN106279470A CN201610640655.4A CN201610640655A CN106279470A CN 106279470 A CN106279470 A CN 106279470A CN 201610640655 A CN201610640655 A CN 201610640655A CN 106279470 A CN106279470 A CN 106279470A
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- hydrogen
- capture
- hyperbranched polyetheramine
- amphipathy macromolecule
- type light
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- 239000003999 initiator Substances 0.000 title claims abstract description 54
- 229920002521 macromolecule Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- -1 C2-C10Alkoxyl Chemical group 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 11
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052756 noble gas Inorganic materials 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 150000003335 secondary amines Chemical class 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 abstract description 19
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000013558 reference substance Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000005548 dental material Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
- C08G83/006—After treatment of hyperbranched macromolecules
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a kind of amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and preparation method thereof.Use simple method micro-molecular hydrogen abstraction to be incorporated on the hyperbranched polyetheramine chain containing coinitiator amine, prepare a kind of novel amphipathy macromolecule light trigger.Containing light trigger and coinitiator amine on the light trigger main chain of the present invention, be conducive to energy transfer between the two, it is possible to faster and better generation free radical spike, improve light-initiated efficiency, have and preferably cause performance.Simultaneously because the introducing of hyperbranched polyetheramine, it all has the good compatibility with various solvents, there is the initiation performance of excellence the most in aqueous so that the amphipathy macromolecule hydrogen-capture-type light initiator of hyperbranched polyetheramine more conforms to the development trend that the practical aqueous solution of environmental protection causes.Have broad application prospects at aspects such as coating, ink, photoresist, microelectronics, photoresist, binding agents.
Description
Technical field
The present invention relates to a kind of amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and preparation side thereof
Method, belongs to photo chemistry technology field.
Background technology
The features such as it is fast that UV-curing technology has curing rate, economical and efficient, energy-conserving and environment-protective, environmental friendliness so that it is
Coating, ink, photoresist, microelectronics, photoresist, dental material, binding agent, the industrial circle such as optical media replication has extensively
Application.And light trigger is as the key components in photocuring system, it is the lowest that it is related to formula system
Can polymers and diluent be converted into solid-state by liquid fast and effectively, and therefore the research to light trigger has extremely important
Meaning.And traditional little molecule light trigger is readily volatilized and migrates, on the one hand photopolymerization efficiency of initiation can be reduced, separately
On the one hand cause product that abnormal smells from the patient and toxicity occur so that the application of photocuring system has significant limitation.Little molecule light is drawn
Send out agent to be grafted on hyperbranched polyetheramine macromolecular chain, prepare amphipathy macromolecule based on hyperbranched polyetheramine light-initiated
Agent, not only overcomes little molecule and easily migrates the shortcoming of xanthochromia and substantially increase initiation performance, also make polymerization system more environmentally-friendly
Economical.(Chinese patent, CN 1594370A, CN1887913A, CN102432699A)
In recent years, due to the fast development of technology, more and more higher to the performance requirement of light trigger.Do not require nothing more than light-initiated
Agent has superior initiation performance, and requires that it is good with the photocuring system compatibility, and toxicity is little, and environment compatibility is good, stability
The feature such as good.Along with expanding economy, the gradually attention to environmental issue, the water-soluble photoinitiator of practical environmental protection is increasingly becoming and grinds
The focus studied carefully, and become light-initiated development trend, there is great development prospect.Peng Huan et al. (Chinese patent, CN
104558630A) develop a kind of thioxanthone modification dendriform polyamide-amide water-soluble light trigger, can make in water-based
With, there is the initiation performance of excellence.Nie Jun et al. (Chinese patent, CN1887913A) have developed a kind of polymolecularity benzophenone
Light trigger, can use in oleaginous system.But there is in water-based system and oleaginous system the excellent performance that causes simultaneously, and
And the most do not report containing the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine of coinitiator amine.
Summary of the invention
Present invention aims to the deficiency of currently available technology, it is provided that a kind of amphiphilic based on hyperbranched polyetheramine
Property macromolecule hydrogen-capture-type light initiator and preparation method thereof.This initiator efficiency of initiation is high, with water and the oil-based solvent compatibility
Good, toxicity is low, and environment compatibility is good, and preparation method is simple, is widely used.
For achieving the above object, little molecule light trigger is grafted to have coinitiator by simple method by the present invention
On the chain of the hyperbranched polyetheramine of amine, prepare a kind of novel amphipathy macromolecule hydrogen-capture-type light initiator.Concrete technical side
Case is described below.
The present invention provides a kind of amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine, structure such as formula
(1) shown in:
Wherein, X represents that polyether chain, Y represent coinitiator amine molecule residue, and P represents photoinitiator molecules residue；Wherein:
Described coinitiator amine monomers molecule residues Y has a structure shown in formula (3):
Wherein, R2For C2-C10Straight or branched alkyl, C2-C10Alkoxyl, cycloalkyl or the piperazine by alkyl replacement hydrogen；R3
For hydrogen, C1-C10Straight or branched alkyl, C1-C10Alkoxyl, hydroxyl, carboxyl, ester group, cycloalkyl, phenyl, naphthyl or hetero ring type
Base.
In the present invention, described X has a structure as shown in formula (2):
Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxyl, cycloalkyl, phenyl, naphthyl, hetero ring type base or
The product that these group hydrogen atoms are substituted with a substituent, 0 < n < 20；
In the present invention, described photoinitiator molecules residue P is selected from such as the one of formula (4) institute array structure:
Wherein, R6、R7、R8、R9、R10And R11Separately selected from hydrogen, halogen, C1-C20Straight or branched alkyl, C1-C20
Alkoxyl, nitro, amino, hydroxyl, carboxyl, itrile group, sulfonic group, ester group, cycloalkyl, phenyl or naphthyl；R4、R5And R12The most solely
On the spot the hydrogen atom on aromatic radical or aromatic radical is optionally substituted the substituted product of base；X1Former for methylene, oxygen, sulfur or nitrogen
Son；n1,2,3,4,5,6For integer, 0 < n1,2,,4,5,6< 5,0 < n3<3；
The present invention also provides for the system of a kind of above-mentioned amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine
Preparation Method, specifically comprises the following steps that
1. it is 0.95:1～1:0.95 according to mol ratio, by the coinitiator containing primary amine and secondary amine with containing diepoxy group
Polyethers mix in organic solvent, under the protection of noble gas, ice-water bath stirring mixing 1.5～2.5 days after, 75～85 DEG C
At a temperature of react, reaction terminate after, by organic solvent rotation be evaporated off, be dried, obtain hyperbranched polyetheramine；
2. it is 0.9:1～1:0.9 according to mol ratio, by hyperbranched polyetheramine and the little molecule light trigger with functional group
Being dissolved in organic solvent, react at a temperature of 75～85 DEG C, after reaction terminates, rotation is evaporated off organic solvent, carries out in precipitant
Precipitation, is dried, obtains amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine；Wherein:
Step 1. in, shown in the structure such as formula (5) of the described coinitiator monomer containing primary amine and secondary amine:
Wherein, R2For C2-C10Straight or branched alkyl, C2-C10Alkoxyl, cycloalkyl or the piperazine by alkyl replacement hydrogen；R3
For hydrogen, C1-C10Straight or branched alkyl, C1-C10Alkoxyl, hydroxyl, carboxyl, ester group, cycloalkyl, phenyl, naphthyl or hetero ring type
Base；
In the present invention, step 1. in, shown in the structure such as formula (6) of the described polyethers containing diepoxy group:
Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxyl, cycloalkyl, phenyl, naphthyl, hetero ring type base or
The product that these group hydrogen atoms are substituted with a substituent, 0 < n < 20.
In the present invention, step 1. and 2. in, shown in the structure of described hyperbranched polyetheramine such as formula (8):
In the present invention, step 2. in, the described little molecule light trigger with functional group, shown in structure such as formula (7):
P-L-R13 (7)
Wherein, P is arbitrary initiator residue in formula (4), and L is C1-C20Straight or branched alkyl, C1-C20Alkoxyl, cycloalkanes
Base or phenyl, R13For epoxide group, carboxyl or ester group.
In the present invention, step 1. and 2. in, described organic solvent is toluene, alcohols, dichloromethane, chloroform, Isosorbide-5-Nitrae-dioxy
Six rings, ketone, dimethyl sulfoxide or DMF.
In the present invention, step 2. in, described precipitant is normal hexane or petroleum ether.
In the present invention, step 2. in, described noble gas is nitrogen or argon.
Advantages of the present invention is as follows: the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine of gained,
Energy transfer containing hydrogen-capture-type light initiator and coinitiator amine in its molecule, between beneficially two, it is possible to faster and more
Generation free radical, improve efficiency of initiation: it addition, as a kind of Polymeric photoinitiators, which overcome traditional little molecule light and draw
Send out agent volatile, migrate, xanthochromia, poor stability, have the defects such as residual；Its main chain hyperbranched polyetheramine and water simultaneously, oiliness is molten
Agent and commerciality monomer compatibility have the good compatibility, the initiation performance not only improved, and light trigger is difficult to
Move to surface, reduce the toxicity of light trigger, and its Environmental compatibility is good, use environmental protection, draw especially as aqueous light
Sending out agent and meet the development trend that environmental protection uses, therefore it is at coating, ink, microelectronics, dental material, photoresist, CD
Replicating, photoresist, binding agent, the curing field such as electronic package material has broad application prospects.
The nuclear-magnetism H spectrogram of the present invention is recorded by (VarianMercuryPlus400MHz) nmr spectrometer.
The infrared spectrum of the present invention is to be surveyed by REAL TIME INFRARED THERMAL IMAGE instrument (Thermo IS10 Fourier infrared spectrograph device)
?.
The cure kinetics spectrogram of the present invention is by photic differential calorimeter (Photo-DSC) (DSC6200, Seiko
Instrument Inc) record.The light source of the present invention all cure kinetics experiment is the high-pressure mercury with 365nm grating
Lamp, range of light intensity 50mW/cm2, nitrogen protection is 50ml/min.
Accompanying drawing explanation
Fig. 1 is the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine synthesized by case study on implementation 1
(hPEA101-TX) infrared spectrum.
Fig. 2 is the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine synthesized by embodiment 1
(hPEA101-TX) structure chart and the nucleus magnetic hydrogen spectrum spectrogram in chloroformic solution of deuteration thereof.
Fig. 3 is the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine synthesized by embodiment 2
(hPEA101-BP) structure chart and the nucleus magnetic hydrogen spectrum spectrogram in chloroformic solution of deuteration thereof.
Fig. 4 is the hPEA101-TX of embodiment 1 synthesis, the hPEA211-TX of embodiment 3 synthesis and corresponding little molecule light
Initiator model compound MGA-TX and little molecule coinitiator triethanolamine (TEOA) and commerciality water-soluble photoinitiator
2959 cause the double bond of water-soluble monomer acrylamide (AM) the inside under ultraviolet lighting to compose with the cure kinetics of time of exposure
Figure.
Fig. 5 is the hPEA101-TX of embodiment 1 synthesis, the hPEA211-TX of embodiment 3 synthesis, embodiment 5 synthesis
HPEA110-TX and corresponding little molecule light trigger model compound MGA-TX and little molecule coinitiator triethanolamine
(TEOA) and commerciality oiliness light trigger ITX cause oil-soluble monomer 1,6 hexanediol diacrylate (HDDA) double bond
Under ultraviolet lighting, the inside is with the cure kinetics spectrogram of time of exposure.
Detailed description of the invention
Below, further illustrate present invention by embodiment, but protection scope of the present invention is not limited to reality
Execute example.Other the change that those skilled in the art is made in the case of without departing substantially from spirit and scope of the present invention and
Amendment, within being included in scope.
Embodiment 1
(1) 17.5g (0.035mol) polyethyleneglycol diglycidylether (PEGDA) and 3.1g (0.035mol) N-ethyl second
Diamidogen (NEED) dissolves in ethanol, joins in there-necked flask, stirs at magneton, under nitrogen protection, mixes 2 in ice-water bath
My god, then it being changed at oil bath 80 DEG C react 24h, solution rotation is steamed surplus 20mL after terminating by reaction, precipitates three times in normal hexane, in
60 DEG C of constant-temperature vacuum baking ovens are dried to obtain the first hyperbranched polyetheramine (hPEA101).
(2) 4.5g (7.7mmol) hPEA101 and 1.96g (6.9mmol) 2-(2,3 glycidoxy) thioxanthone (ETX)
Dissolve in ethanol, join in there-necked flask, stir at magneton, under nitrogen protection, anti-at oil bath 80 DEG C under the conditions of lucifuge
Answer 24h, after reaction terminates, surplus 10mL is steamed in solution rotation, precipitates in normal hexane, surpassed in 60 DEG C of constant-temperature vacuum oven dryings
The amphipathic thioxanthone photo initiator (hPEA101-TX) of branch polyether amine.
Fig. 1 is structure chart and the nucleus magnetic hydrogen spectrum of target product, and Fig. 2 is the infrared spectrum of target product.1HNMR
(CDCl3400MHz): 8.66-7.29 (aromatic radical), 4.42-3.39 (-OCH ,-OCH2), 2.66 (-NH2), 0.96-1.30 (-
CH3).FT-IR (KBr): 3448cm-1(O-H),2876cm-1(C-H),1646cm-1(C=O), 1465cm-1(C-N)。
Embodiment 2
(1) 17.5g (0.035mol) polyethyleneglycol diglycidylether and 3.1g (0.035mol) NEED are molten
Solution in ethanol, joins in there-necked flask, stirs at magneton, under nitrogen protection, mixes 2 days, be then changed to oil in ice-water bath
Reacting 24h at bathing 80 DEG C, solution rotation is steamed surplus 20mL after terminating by reaction, precipitates three times, in 60 DEG C of constant-temperature vacuums in normal hexane
Baking oven is dried to obtain the first hyperbranched polyetheramine (hPEA101).
(2) 3.5g (6.0mmol) hPEA101 and 1.36g (5.4mmol) 2-(2,3 glycidoxy) benzophenone (EBP)
Dissolve in ethanol, join in there-necked flask, stir at magneton, under nitrogen protection, anti-at oil bath 80 DEG C under the conditions of lucifuge
Answer 24h, after reaction terminates, surplus 10mL is steamed in solution rotation, precipitates in normal hexane, surpassed in 60 DEG C of constant-temperature vacuum oven dryings
The amphipathic diphenyl ketone photo initiator (hPEA101-BP) of branch polyether amine.
Fig. 1 is structure chart and the nucleus magnetic hydrogen spectrum of target product.1HNMR(CDCl3400MHz): 7.85-6.96 (aromatic radical),
4.20-3.38(-OCH,-OCH2),2.65(-NH2), 0.98-1.89 (-CH3).FT-IR (KBr): 3486cm-1(O-H),
2847cm-1(C-H), 1646cm-1(C=O), 1455cm-1(C-N)。
Embodiment 3
(1) 20g (0.04mol) polyethyleneglycol diglycidylether, 6.96g (0.04mol) Ethylene glycol diglycidyl ether
7.04g (0.08mol) NEED dissolves in ethanol, joins in there-necked flask, stirs at magneton, and nitrogen is protected
Under, ice-water bath mixing 2 days, is then changed at oil bath 80 DEG C react 24h, solution rotation is steamed surplus 20mL, just after terminating by reaction
Hexane precipitates three times, in 60 DEG C of constant-temperature vacuum baking ovens, is dried to obtain the second hyperbranched polyetheramine (hPEA211).
(2) 2.1g (5mmol) hPEA211 and 1.1g (4.5mmol) 2-(2,3 glycidoxy) thioxanthone is dissolved in second
In alcohol, join in there-necked flask, stir at magneton, under nitrogen protection, under the conditions of lucifuge, at oil bath 80 DEG C, react 24h, instead
After should terminating, surplus 10mL is steamed in solution rotation, precipitates in normal hexane, obtain hyperbranched polyether in 60 DEG C of constant-temperature vacuum oven dryings
The amphipathic thioxanthone photo initiator (hPEA211-TX) of amine.
1HNMR(CDCl3400MHz): 8.68-7.28 (aromatic radical), 4.20-3.42 (-OCH ,-OCH2), 2.64 (-
NH2),0.82-1.29(-CH3).FT-IR (KBr): 3439cm-1(O-H), 2876cm-1(C-H), 1646cm-1(C=O),
1465cm-1(C-N)。
Embodiment 4
(1) 20g (0.04mol) polyethyleneglycol diglycidylether, 6.96g (0.04mol) Ethylene glycol diglycidyl ether
7.04g (0.08mol) NEED dissolves in ethanol, joins in there-necked flask, stirs at magneton, and nitrogen is protected
Under, ice-water bath mixing 2 days, is then changed at oil bath 80 DEG C react 24h, solution rotation is steamed surplus 20mL, just after terminating by reaction
Hexane precipitates three times, in 60 DEG C of constant-temperature vacuum baking ovens, is dried to obtain the second hyperbranched polyetheramine (hPEA211).
(2) 4.0g (9.4mmol) hPEA211 and 2.2g (8.5mmol) 2-(2,3 glycidoxy) benzophenone (EBP)
Dissolve in ethanol, join in there-necked flask, stir at magneton, under nitrogen protection, anti-at oil bath 80 DEG C under the conditions of lucifuge
Answer 24h, after reaction terminates, surplus 10mL is steamed in solution rotation, precipitates in normal hexane, surpassed in 60 DEG C of constant-temperature vacuum oven dryings
The amphipathic diphenyl ketone photo initiator (hPEA211-BP) of branch polyether amine.
1HNMR(CDCl3400MHz): 6.92-7.86 (aromatic radical), 4.29-3.31 (-OCH ,-OCH2), 2.64 (-
NH2), 0.84-1.29 (-CH3).FT-IR (KBr): 3448cm-1(O-H), 2857cm-1(C-H), 1656cm-1(C=O),
1455cm-1(C-N)。
Embodiment 5
(1) 10.63g (0.06mol) Ethylene glycol diglycidyl ether and 5.37g (0.06mol) NEED dissolve
In ethanol, join in there-necked flask, stir at magneton, under nitrogen protection, ice-water bath mixes 2 days, is then changed to oil bath
Reacting 24h at 80 DEG C, solution rotation is steamed surplus 20mL after terminating by reaction, precipitates three times, dry in 60 DEG C of constant-temperature vacuums in normal hexane
Case is dried to obtain the third hyperbranched polyetheramine (hPEA110).
(2) 0.72g (2.5mmol) hPEA110 and 0.63g (2.2mmol) 2-(2,3 glycidoxy) thioxanthone dissolves
In ethanol, join in there-necked flask, stir at magneton, under nitrogen protection, react at oil bath 80 DEG C under the conditions of lucifuge
24h, after reaction terminates, steams surplus 10mL by solution rotation, precipitates, overspend in 60 DEG C of constant-temperature vacuum oven dryings in normal hexane
Change the amphipathic thioxanthone photo initiator (hPEA110-TX) of polyetheramine.
1HNMR(CDCl3400MHz): 8.69-7.28 (aromatic radical), 4.40-3.39 (-OCH ,-OCH2), 2.69 (-
NH2),0.82-1.31(-CH3).FT-IR (KBr): 3458cm-1(O-H), 2838cm-1(C-H), 1646cm-1(C=O),
1465cm-1(C-N)。
Embodiment 6
(1) 10.63g (0.06mol) Ethylene glycol diglycidyl ether and 5.37g (0.06mol) NEED dissolve
In ethanol, join in there-necked flask, stir at magneton, under nitrogen protection, ice-water bath mixes 2 days, is then changed to oil bath
Reacting 24h at 80 DEG C, solution rotation is steamed surplus 20mL after terminating by reaction, precipitates three times, dry in 60 DEG C of constant-temperature vacuums in normal hexane
Case is dried to obtain the third hyperbranched polyetheramine (hPEA110).
(2) 2.67g (10mmol) hPEA110 and 2.33g (9.2mmol) 2-(2,3 glycidoxy) benzophenone dissolves
In ethanol, join in there-necked flask, stir at magneton, under nitrogen protection, react at oil bath 80 DEG C under the conditions of lucifuge
24h, after reaction terminates, steams surplus 10mL by solution rotation, precipitates, overspend in 60 DEG C of constant-temperature vacuum oven dryings in normal hexane
Change the amphipathic diphenyl ketone photo initiator (hPEA110-BP) of polyetheramine.
1HNMR(CDCl3400MHz): 7.88-6.95 (aromatic radical), 4.32-3.41 (-OCH ,-OCH2), 2.69 (-
NH2), 0.81-1.29 (-CH3).FT-IR (KBr): 3467cm-1(O-H), 2847cm-1(C-H), 1646cm-1(C=O),
1455cm-1(C-N)。
Application case 1
The amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine of the present invention can be quick by ultraviolet light
Acrylamide triggered or other olefin monomers are fast curing-formed, and compared with little molecule light trigger, its hardening time
Shorter, when conversion ratio reaches 100%, the time shortens 140s, and efficiency of initiation is higher, and the highest trigger rate improves 0.03s-1.With
Commerciality water-soluble photoinitiator 2959 is compared, and embodies obvious advantage, the amphipathy macromolecule of hyperbranched polyetheramine when 40s
The hydrogen-capture-type light initiator double bond conversion rate than 2959 is high by 50%, and the amphipathy macromolecule hydrogen-abstraction light of hyperbranched polyetheramine is described
Initiator has the efficiency of initiation of excellence in aqueous solvent.
Fig. 4 is amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and the phase using the present invention respectively
Little molecule light trigger model compound and business water-soluble photoinitiator 2959 is answered to draw under nitrogen atmosphere as light trigger
Send out the cure kinetics spectrogram of water-soluble monomer acrylamide.Specifically, Fig. 4 is the hPEA101-TX of embodiment 1 synthesis, implements
HPEA211-TX and the corresponding little molecule light trigger model compound MGA-TX and little molecule coinitiator TEOA of example 3 synthesis
And business water-soluble photoinitiator as the most acrylamide triggered double bond of light trigger under ultraviolet lighting in
Face is with the conversion ratio spectrogram of time of exposure, and method of testing is as described below: by a certain amount of photo-curing monomer (acrylamide) and light
(hPEA101-TX, hPEA211-TX are total to initiator with corresponding little molecule light trigger model compound MGA-TX and little molecule
Initiator TEOA and business water-soluble photoinitiator 2959) it is dissolved in water according to a certain percentage as sample.Weigh 2mg sample
Putting in aluminum cup, reference substance is empty crucible, sample and reference substance constant temperature ultraviolet lighting under the nitrogen of 50ml/min is protected,
Curing reaction is released heat and is changed over by computer recording, owing to curing reaction releases heat and participates in the amount of reaction double bond
It is directly proportional, therefore is obtained the heat of curing reaction by the peak area of integration exotherm, thus obtain double bond conversion rate and consolidate
Change reaction rate.In monomer, the final conversion ratio of double bond represents degree and the efficiency of initiation of light trigger that polyreaction completes,
The speed that double bond converts represents the speed of light trigger initiated polymerization.
Figure 4, it is seen that the amphipathy macromolecule hydrogen-capture-type light initiator hPEA101-TX of hyperbranched polyetheramine,
The double bond conversion rate that hPEA211-TX causes is much larger than little initiator molecule system and the effect of business aqueous initiator 2959,
When the initiation time is 40s, the conversion ratio of hPEA101-TX, hPEA211-TX reaches more than 90%, and little molecule initiator system
Being about 80%, 2959 is about 40%, and polymeric initiator conversion ratio when 40s reaches trigger monomer in aqueous
Time efficiency of initiation be substantially better than little molecule light trigger and business water-soluble photoinitiator 2959.Main reason is that the base of the present invention
Photoinitiator molecules is grafted on containing coinitiator amine by the amphipathy macromolecule hydrogen-capture-type light initiator in hyperbranched polyetheramine
Hyperbranched polyetheramine chain on both overcome traditional little molecule light trigger and easily migrate, xanthochromia, poor stability, have residual etc. to lack
Fall into, be conducive to again energy transfer between the two, thus be produced from faster and more by base spike, improve light-initiated effect
Rate.Illustrate that amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine has excellence in aqueous solvent simultaneously
Cause performance.
Application case 2
The amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine of the present invention can be quick by ultraviolet light
Initiating methacrylates or other olefin monomers are fast curing-formed, and with little molecule light trigger and commerciality oiliness light
Initiator (ITX) is compared, and the final conversion ratio of monomer double bond improves the efficiency of initiation of 10%-25%, i.e. light trigger and improves
10%～25%, illustrate that the amphipathy macromolecule hydrogen-capture-type light initiator of hyperbranched polyetheramine has excellence in oil-based solvent
Efficiency of initiation.
Fig. 5 is amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and the phase using the present invention respectively
The little molecule light trigger model compound and the business oiliness light trigger ITX that answer draw under nitrogen atmosphere as light trigger
The cure kinetics spectrogram of hair oil soluble monomers 1,6 hexanediol diacrylate (HDDA).Specifically, Fig. 5 is embodiment 1
Synthesis hPEA101-TX, embodiment 3 synthesis hPEA211-TX, embodiment 5 synthesis hPEA110-TX with corresponding little point
Sub-light trigger model compound MGA-TX and little molecule coinitiator TEOA and business oiliness light trigger are as light-initiated
Agent causes the double bond of HDDA under nitrogen atmosphere, and under ultraviolet lighting, the inside is with the conversion ratio spectrogram of time of exposure, and method of testing is such as
Lower described: by a certain amount of photo-curing monomer (acrylate) and light trigger (hPEA101-TX, hPEA211-TX,
HPEA110-TX and corresponding little molecule light trigger model compound MGA-TX and little molecule coinitiator TEOA and business
Oiliness light trigger ITX) it is dissolved according to a certain percentage in 1,4-dioxane as sample.Weigh 2mg sample and put into aluminum
In crucible, reference substance is empty crucible, sample and reference substance constant temperature ultraviolet lighting, curing reaction under the nitrogen of 50ml/min is protected
Release heat to change over by computer recording, release heat due to curing reaction and be directly proportional to the amount participating in reaction double bond,
Therefore obtained the heat of curing reaction by the peak area of integration exotherm, thus obtain double bond conversion rate and curing reaction speed
Rate.In monomer, the final conversion ratio of double bond represents degree and the efficiency of initiation of light trigger that polyreaction completes, and double bond converts
Speed represent the speed of light trigger initiated polymerization.
From figure 5 it can be seen that the amphipathy macromolecule hydrogen-capture-type light initiator hPEA101-TX of hyperbranched polyetheramine,
The double bond conversion rate that hPEA211-TX, hPEA110-TX cause is much larger than little initiator molecule system and business oiliness initiator
The effect of ITX, final conversion of monomer improves 10%-25% (hPEA110-TX, hPEA211-TX, hPEA101-TX, MGA-
The final conversion ratio of TX/TEOA, ITX/TEOA trigger monomer is 100%, 100%, 87%, 79%, 75%).This explanation is based on super
The amphipathy macromolecule hydrogen-capture-type light initiator of branch polyether amine efficiency of initiation in oil-based solvent is high, and trigger rate is fast.Mainly
Reason is photoinitiator molecules being grafted based on two parent's property hyperbranched polyetheramine macromolecule hydrogen-capture-type light initiators of the present invention
Hyperbranched polyetheramine chain containing coinitiator amine had both overcome traditional little molecule light trigger easily migrate, xanthochromia, stable
Property poor, have the defects such as residual, be conducive to again energy transfer the most between the two, thus be produced from by base spike faster and more,
Improve light-initiated efficiency.Illustrate that amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine is in oiliness simultaneously
Solvent has the initiation performance of excellence.
Claims (9)
1. an amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine, it is characterised in that structure such as formula (1)
Shown in:
Wherein, X represents that polyether chain, Y represent coinitiator amine molecule residue, and P represents photoinitiator molecules residue；Wherein,
Described coinitiator amine monomers molecule residues Y has a structure shown in formula (3):
Wherein, R2For C2-C10Straight or branched alkyl, C2-C10Alkoxyl, cycloalkyl or the piperazine by alkyl replacement hydrogen；R3For
Hydrogen, C1-C10Straight or branched alkyl, C1-C10Alkoxyl, hydroxyl, carboxyl, ester group, cycloalkyl, phenyl, naphthyl or hetero ring type base.
Amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine the most according to claim 1, its feature
Being, described X has a structure as shown in formula (2):
Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxyl, cycloalkyl, phenyl, naphthyl, hetero ring type base or these bases
The product that group's hydrogen atom is substituted with a substituent, 0 < n < 20.
Amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine the most according to claim 1, its feature
Being, described photoinitiator molecules residue P is selected from such as the one of formula (4) institute array structure:
Wherein, R6、R7、R8、R9、R10And R11Separately selected from hydrogen, halogen, C1-C20Straight or branched alkyl, C1-C20Alcoxyl
Base, nitro, amino, hydroxyl, carboxyl, itrile group, sulfonic group, ester group, cycloalkyl, phenyl or naphthyl；R4、R5And R12Separately
Hydrogen atom on aromatic radical or aromatic radical is optionally substituted the substituted product of base；X1For methylene, oxygen, sulfur or nitrogen-atoms；
n1,2,3,4,5,6For integer, 0 < n1,2,,4,5,6< 5,0 < n3<3。
4. according to the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine one of claim 1-3 Suo Shu
Preparation method, it is characterised in that specifically comprise the following steps that
1. it is 0.95:1～1:0.95 by the coinitiator containing primary amine and secondary amine and 1 part containing diepoxy group according to mol ratio
Polyethers mixes in organic solvent, under the protection of noble gas, after ice-water bath stirring mixes 1.5～2.5 days, and 75～85 DEG C of temperature
The lower reaction of degree, after reaction terminates, is evaporated off organic solvent rotation, is dried, obtains hyperbranched polyetheramine；
2. it is that hyperbranched polyetheramine is dissolved in by 0.9:1～1:0.9 with the little molecule light trigger with functional group according to mol ratio
In organic solvent, reacting at a temperature of 75～85 DEG C, after reaction terminates, rotation is evaporated off organic solvent, precipitates in precipitant,
It is dried, obtains amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine；Wherein:
Described step 1. in, shown in the structure such as formula (5) of the coinitiator monomer containing primary amine and secondary amine:
Wherein, R2For C2-C10Straight or branched alkyl, C2-C10Alkoxyl, cycloalkyl or the piperazine by alkyl replacement hydrogen；R3For
Hydrogen, C1-C10Straight or branched alkyl, C1-C10Alkoxyl, hydroxyl, carboxyl, ester group, cycloalkyl, phenyl, naphthyl or hetero ring type base.
Preparation method the most according to claim 4, it is characterised in that step 1. in, the described polyethers containing diepoxy group
Structure such as formula (6) shown in:
Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxyl, cycloalkyl, phenyl, naphthyl, hetero ring type base or these bases
The product that group's hydrogen atom is substituted with a substituent, 0 < n < 20.
Preparation method the most according to claim 4, it is characterised in that step 2. in, the described little molecule with functional group
Light trigger, shown in structure such as formula (7):
P-L-R13 (7)
Wherein, P is arbitrary initiator residue in formula (4), and L is C1-C20Straight or branched alkyl, C1-C20Alkoxyl, cycloalkyl or
Phenyl, R13For epoxide group, carboxyl or ester group.
Preparation method the most according to claim 5, it is characterised in that step 1. and 2. in, described organic solvent is toluene,
Alcohols, dichloromethane, chloroform, Isosorbide-5-Nitrae-dioxane, ketone, dimethyl sulfoxide or DMF.
Preparation method the most according to claim 5, it is characterised in that step 2. in, described precipitant is normal hexane or stone
Oil ether.
Preparation method the most according to claim 5, it is characterised in that step 2. in, described noble gas is nitrogen or argon
Gas.
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| CN111363135A (en) * | 2020-03-14 | 2020-07-03 | 浙江恒丰新材料有限公司 | Preparation method and application of melamine-ethylene oxide/propylene oxide copolymer polyether polyol |
| WO2023123747A1 (en) * | 2021-12-29 | 2023-07-06 | 广州鹿山光电材料有限公司 | Hydrogen abstraction photoinitiator, preparation method therefor, and use thereof |
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