CN106279470B - 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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- CN106279470B CN106279470B CN201610640655.4A CN201610640655A CN106279470B CN 106279470 B CN106279470 B CN 106279470B CN 201610640655 A CN201610640655 A CN 201610640655A CN 106279470 B CN106279470 B CN 106279470B
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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 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- 150000003384 small molecules Chemical class 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 19
- -1 nitro, amino, hydroxyl Chemical group 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 150000003141 primary amines Chemical class 0.000 claims description 5
- 150000003335 secondary amines Chemical class 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 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
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 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
- 239000005864 Sulphur Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000003700 epoxy group Chemical group 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
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 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
- 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
- 239000000047 product 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
- 239000002585 base Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 230000007613 environmental effect Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-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
- 239000012299 nitrogen atmosphere Substances 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
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 2
- 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 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical class C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- 239000012458 free base Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 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
- 238000005286 illumination 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
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 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
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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.Micro-molecular hydrogen abstraction is incorporated on the hyperbranched polyetheramine chain of the amine containing coinitiator using simple method, prepares a kind of new amphipathy macromolecule light trigger.Contain light trigger and coinitiator amine on the light trigger main chain of the present invention, be advantageous to energy transfer between the two, generation free radical spike that can be faster and better improves light-initiated efficiency, has preferably initiation performance.Simultaneously because the introducing of hyperbranched polyetheramine, it all has good compatibility with various solvents, especially there is excellent initiation performance in aqueous so that the amphipathy macromolecule hydrogen-capture-type light initiator of hyperbranched polyetheramine more conforms to the development trend that the aqueous solution of environmentally friendly practicality triggers.Had broad application prospects in coating, ink, photoresist, microelectronics, photoresist, adhesive etc..
Description
Technical field
The present invention relates to a kind of amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and its preparation side
Method, belong to photo chemistry technology field.
Background technology
UV-curing technology has that curing rate is fast, economical and efficient, energy-conserving and environment-protective, it is environment-friendly the features such as, make its
The industrial circles such as coating, ink, photoresist, microelectronics, photoresist, dental material, adhesive, optical media replication have extensively
Application.And light trigger, as the key components in photocuring system, it is low under light illumination that it is related to formula system
Can polymers and diluent fast and effectively be converted into solid-state by liquid, thus the research to light trigger have it is extremely important
Meaning.And traditional small molecule light trigger is readily volatilized and migrates, photopolymerization efficiency of initiation on the one hand can be reduced, separately
On the one hand product is caused smell and toxicity occur so that the application of photocuring system has significant limitation.Small molecule light is drawn
Hair agent is grafted on hyperbranched polyetheramine macromolecular chain, and it is light-initiated to prepare the amphipathy macromolecule based on hyperbranched polyetheramine
Agent, the shortcomings that not only overcoming small molecule xanthochromia easy to migrate, substantially increase initiation performance, also make it that polymerization system is more environmentally-friendly
It is economical.(Chinese patent, CN 1594370A, CN1887913A, CN102432699A)
In recent years, due to the fast development of technology, to the performance requirement more and more higher of light trigger.Do not require nothing more than light-initiated
Agent has superior initiation performance, and requires that it is good with photocuring system compatibility, and small toxicity, environment compatibility is good, stability
The features such as good.With expanding economy, the gradual attention to environmental issue, the water-soluble photoinitiator of practical environmental protection, which is increasingly becoming, to be ground
The focus studied carefully, and turn into light-initiated development trend, there is great development prospect.Peng Huan et al. (Chinese patent, CN
104558630A) develop a kind of thioxanthone and be modified dendriform polyamide-amide water-soluble light trigger, can make in water-based
With having excellent initiation performance.Nie Jun et al. (Chinese patent, CN1887913A) have developed a kind of polymolecularity benzophenone
Light trigger, it can be used in oleaginous system.But there is excellent initiation performance simultaneously in water-based system and oleaginous system, and
And the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine containing coinitiator amine is not reported but.
The content of the invention
It is an object of the invention to the deficiency for currently available technology, there is provided a kind of amphiphilic based on hyperbranched polyetheramine
Property macromolecule hydrogen-capture-type light initiator and preparation method thereof.The initiator efficiency of initiation is high, with water and oil-based solvent compatibility
Good, toxicity is low, and environment compatibility is good, and preparation method is simple, is widely used.
To achieve the above object, small molecule light trigger is grafted to coinitiator by the present invention by simple method
On the chain of the hyperbranched polyetheramine of amine, a kind of new amphipathy macromolecule hydrogen-capture-type light initiator is prepared.Particular technique 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 polyether chain, and Y represents coinitiator amine molecule residue, and P represents photoinitiator molecules residue；Wherein：
The coinitiator amine monomers molecule residues Y has structure shown in formula (3)：
Wherein, R2For C2-C10Straight or branched alkyl, C2-C10Alkoxy, cycloalkyl or the piperazine for being substituted hydrogen by alkyl；R3
For hydrogen, C1-C10Straight or branched alkyl, C1-C10Alkoxy, hydroxyl, carboxyl, ester group, cycloalkyl, phenyl, naphthyl or hetero ring type
Base.
In the present invention, the X has the structure as shown in formula (2)：
Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxy, 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, the photoinitiator molecules residue P is selected from such as one kind of formula (4) institute array structure：
Wherein, R6、R7、R8、R9、R10And R11Separately selected from hydrogen, halogen, C1-C20Straight or branched alkyl, C1-C20
Alkoxy, nitro, amino, hydroxyl, carboxyl, itrile group, sulfonic group, ester group, cycloalkyl, phenyl or naphthyl；R4、R5And R12It is only respectively
The product that on the spot hydrogen atom on aromatic radical or aromatic radical is substituted by any substituent；X1It is former for methylene, oxygen, sulphur 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 a kind of system of the above-mentioned amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine
Preparation Method, comprise the following steps that：
1. it is 0.95 according to mol ratio：1~1:0.95, by the coinitiator containing primary amine and secondary amine and containing diepoxy group
Polyethers mix in organic solvent, under the protection of inert gas, after ice-water bath is stirred 1.5~2.5 days, 75~85 DEG C
At a temperature of react, reaction terminate after, by organic solvent rotate remove, dry, obtain hyperbranched polyetheramine；
2. it is 0.9 according to mol ratio:1~1:0.9, by hyperbranched polyetheramine and the small molecule light trigger with functional group
It is dissolved in organic solvent, is reacted at a temperature of 75~85 DEG C, after reaction terminates, revolving removes organic solvent, is carried out in precipitating reagent
Precipitation, dry, obtain the 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 coinitiator monomer containing primary amine and secondary amine：
Wherein, R2For C2-C10Straight or branched alkyl, C2-C10Alkoxy, cycloalkyl or the piperazine for being substituted hydrogen by alkyl；R3
For hydrogen, C1-C10Straight or branched alkyl, C1-C10Alkoxy, 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 polyethers containing diepoxy group：
Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxy, 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 such as formula (8) of the hyperbranched polyetheramine：
In the present invention, step 2. in, the small molecule light trigger with functional group, shown in structure such as formula (7)：
P-L-R13 (7)
Wherein, P be formula (4) in any initiator residue, L C1-C20Straight or branched alkyl, C1-C20Alkoxy, cycloalkanes
Base or phenyl, R13For epoxide group, carboxyl or ester group.
In the present invention, step 1. and 2. in, the organic solvent is toluene, alcohols, dichloromethane, chloroform, Isosorbide-5-Nitrae-dioxy
Six rings, ketone, dimethyl sulfoxide (DMSO) or DMF.
In the present invention, step 2. in, the precipitating reagent is n-hexane or petroleum ether.
In the present invention, step 2. in, the inert gas is nitrogen or argon gas.
Advantages of the present invention is as follows：The amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine of gained,
Contain hydrogen-capture-type light initiator and coinitiator amine in its molecule, be advantageous to the energy transfer between two, can be faster and more
Generation free radical, improve efficiency of initiation：In addition, as a kind of Polymeric photoinitiators, which overcome traditional small molecule light and draw
It is volatile to send out agent, migration, xanthochromia, stability is poor, there is the defects of residual；Its main chain hyperbranched polyetheramine and water, oiliness are molten simultaneously
Agent and commercial monomer compatibility have good compatibility, the initiation performance not only improved, and light trigger is not easy
Surface is moved to, reduces the toxicity of light trigger, and its Environmental compatibility is good, using environmental protection, draws especially as water-based light
Hair agent meets the development trend that uses of environmental protection, therefore it is in coating, ink, microelectronics, dental material, photoresist, CD
Replicate, photoresist, adhesive, the curing field such as electronic package material has broad application prospects.
The nuclear-magnetism H spectrograms of the present invention are measured by (VarianMercuryPlus400MHz) nmr spectrometer.
The infrared spectrum of the present invention is surveyed by REAL TIME INFRARED THERMAL IMAGE instrument (Thermo IS10 Fourier infrared spectrograph devices)
.
The cure kinetics spectrogram of the present invention is by photic differential calorimeter (Photo-DSC) (DSC6200, Seiko
Instrument Inc) measure.The light source of all cure kinetics experiments of the present invention is the high-pressure mercury with 365nm gratings
Lamp, range of light intensity 50mW/cm2, nitrogen protection is 50ml/min.
Brief description of the drawings
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 its nucleus magnetic hydrogen spectrum spectrogram in chloroformic solution of deuteration.
Fig. 3 is the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine synthesized by embodiment 2
(hPEA101-BP) structure chart and its nucleus magnetic hydrogen spectrum spectrogram in chloroformic solution of deuteration.
Fig. 4 is the hPEA101-TX that embodiment 1 synthesizes, the hPEA211-TX and corresponding small molecule light that embodiment 3 synthesizes
Initiator model compound MGA-TX and small molecule coinitiator triethanolamine (TEOA) and commercial water-soluble photoinitiator
2959 trigger the double bond of water-soluble monomer acrylamide (AM) to be composed under ultraviolet lighting with the cure kinetics of time for exposure the inside
Figure.
The hPEA101-TX that Fig. 5 synthesizes for embodiment 1, the hPEA211-TX that embodiment 3 synthesizes, what embodiment 5 synthesized
HPEA110-TX and corresponding small molecule light trigger model compound MGA-TX and small molecule coinitiator triethanolamine
(TEOA) and commercial oiliness light trigger ITX triggers the double bond of oil-soluble monomer 1,6 hexanediol diacrylate (HDDA)
With the cure kinetics spectrogram of time for exposure inside under ultraviolet lighting.
Embodiment
Below, present invention is further illustrated with embodiment, but protection scope of the present invention is not limited to reality
Apply example.Other changes for being made to those skilled in the art in the case of without departing substantially from spirit and scope of the present invention and
Modification, is included within the scope of the present invention.
Embodiment 1
(1) 17.5g (0.035mol) polyethyleneglycol diglycidylether (PEGDA) and 3.1g (0.035mol) N- ethyl second
Diamines (NEED) is dissolved in ethanol, is added in three-necked flask, is stirred in magneton, and under nitrogen protection, 2 are mixed in ice-water bath
My god, be then changed at 80 DEG C of oil bath and react 24h, solution is rotated surplus 20mL by reaction after terminating, precipitated in n-hexane three times, in
The first hyperbranched polyetheramine (hPEA101) is dried to obtain in 60 DEG C of constant-temperature vacuum baking ovens.
(2) 4.5g (7.7mmol) hPEA101 and 1.96g (6.9mmol) 2- (2,3 glycidoxy) thioxanthone (ETX)
Dissolving in ethanol, is added in three-necked flask, is stirred in magneton, anti-at 80 DEG C of oil bath under the conditions of lucifuge under nitrogen protection
After answering 24h, reaction to terminate, solution is rotated into surplus 10mL, precipitates in n-hexane, is 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 the structure chart and 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 diglycidylethers and 3.1g (0.035mol) NEED are molten
Solution in ethanol, is added in three-necked flask, is stirred in magneton, under nitrogen protection, is mixed 2 days in ice-water bath, is then changed to oil
24h is reacted at 80 DEG C of bath, solution is rotated and remain 20mL, precipitated in n-hexane three times, in 60 DEG C of constant-temperature vacuums by reaction after terminating
The first hyperbranched polyetheramine (hPEA101) is dried to obtain in baking oven.
(2) 3.5g (6.0mmol) hPEA101 and 1.36g (5.4mmol) 2- (2,3 glycidoxy) benzophenone (EBP)
Dissolving in ethanol, is added in three-necked flask, is stirred in magneton, anti-at 80 DEG C of oil bath under the conditions of lucifuge under nitrogen protection
After answering 24h, reaction to terminate, solution is rotated into surplus 10mL, precipitates in n-hexane, is 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 the structure chart and 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 diglycidylether
7.04g (0.08mol) NEED dissolves in ethanol, is added in three-necked flask, is stirred in magneton, nitrogen protection
Under, mixed 2 days in ice-water bath, be then changed at 80 DEG C of oil bath and react 24h, solution is rotated and remains 20mL by reaction after terminating, just
Precipitated in hexane three times, second of hyperbranched polyetheramine (hPEA211) is dried to obtain in 60 DEG C of constant-temperature vacuum baking ovens.
(2) 2.1g (5mmol) hPEA211 and 1.1g (4.5mmol) 2- (2,3 glycidoxy) thioxanthone are dissolved in second
In alcohol, it is added in three-necked flask, is stirred in magneton, under nitrogen protection, reacts 24h at 80 DEG C of oil bath under the conditions of lucifuge, instead
After should terminating, solution is rotated into surplus 10mL, is precipitated in n-hexane, hyperbranched polyether is obtained 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 diglycidylether
7.04g (0.08mol) NEED dissolves in ethanol, is added in three-necked flask, is stirred in magneton, nitrogen protection
Under, mixed 2 days in ice-water bath, be then changed at 80 DEG C of oil bath and react 24h, solution is rotated and remains 20mL by reaction after terminating, just
Precipitated in hexane three times, second of hyperbranched polyetheramine (hPEA211) is dried to obtain in 60 DEG C of constant-temperature vacuum baking ovens.
(2) 4.0g (9.4mmol) hPEA211 and 2.2g (8.5mmol) 2- (2,3 glycidoxy) benzophenone (EBP)
Dissolving in ethanol, is added in three-necked flask, is stirred in magneton, anti-at 80 DEG C of oil bath under the conditions of lucifuge under nitrogen protection
After answering 24h, reaction to terminate, solution is rotated into surplus 10mL, precipitates in n-hexane, is 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 diglycidylethers and the dissolving of 5.37g (0.06mol) NEED
In ethanol, it is added in three-necked flask, is stirred in magneton, under nitrogen protection, is mixed 2 days in ice-water bath, be then changed to oil bath
24h is reacted at 80 DEG C, solution is rotated and remains 20mL by reaction after terminating, and is precipitated in n-hexane three times, is dried in 60 DEG C of constant-temperature vacuums
The third hyperbranched polyetheramine (hPEA110) is dried to obtain in case.
(2) 0.72g (2.5mmol) hPEA110 and the dissolving of 0.63g (2.2mmol) 2- (2,3 glycidoxy) thioxanthone
In ethanol, it is added in three-necked flask, is stirred in magneton, under nitrogen protection, is reacted at 80 DEG C of oil bath under the conditions of lucifuge
24h, after reaction terminates, solution is rotated into surplus 10mL, precipitates in n-hexane, is overspend in 60 DEG C of constant-temperature vacuum oven dryings
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 diglycidylethers and the dissolving of 5.37g (0.06mol) NEED
In ethanol, it is added in three-necked flask, is stirred in magneton, under nitrogen protection, is mixed 2 days in ice-water bath, be then changed to oil bath
24h is reacted at 80 DEG C, solution is rotated and remains 20mL by reaction after terminating, and is precipitated in n-hexane three times, is dried in 60 DEG C of constant-temperature vacuums
The third hyperbranched polyetheramine (hPEA110) is dried to obtain in case.
(2) 2.67g (10mmol) hPEA110 and the dissolving of 2.33g (9.2mmol) 2- (2,3 glycidoxy) benzophenone
In ethanol, it is added in three-necked flask, is stirred in magneton, under nitrogen protection, is reacted at 80 DEG C of oil bath under the conditions of lucifuge
24h, after reaction terminates, solution is rotated into surplus 10mL, precipitates in n-hexane, is overspend in 60 DEG C of constant-temperature vacuum oven dryings
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
Trigger acrylamide or other olefin monomers fast curing-formed, and compared with small molecule light trigger, its hardening time
Shorter, when conversion ratio reaches 100%, the time shortens 140s, and efficiency of initiation is higher, and highest trigger rate improves 0.03s-1.With
Commercial water-soluble photoinitiator 2959 is compared, and embodies obvious advantage, the amphipathy macromolecule of hyperbranched polyetheramine in 40s
Hydrogen-capture-type light initiator is higher than 2959 double bond conversion rate by 50%, illustrates the amphipathy macromolecule hydrogen-abstraction light of hyperbranched polyetheramine
Initiator has excellent efficiency of initiation in aqueous solvent.
Fig. 4 is respectively using the amphipathy macromolecule hydrogen-capture-type light initiator and phase based on hyperbranched polyetheramine of the present invention
Small 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 that embodiment 1 synthesizes, and is implemented
The hPEA211-TX and corresponding small molecule light trigger model compound MGA-TX and small molecule coinitiator TEOA that example 3 synthesizes
And in business water-soluble photoinitiator triggers the double bond of acrylamide as light trigger under ultraviolet lighting under nitrogen atmosphere
With the conversion ratio spectrogram of time for exposure, method of testing is as described below in face：By a certain amount of photo-curing monomer (acrylamide) and light
(hPEA101-TX, hPEA211-TX are total to initiator with corresponding small molecule light trigger model compound MGA-TX and small molecule
Initiator TEOA and business water-soluble photoinitiator 2959) it is dissolved in water according to a certain percentage as sample.Weigh 2mg samples
It is put into aluminum cup, reference substance is empty crucible, sample and reference substance the constant temperature ultraviolet lighting under 50ml/min nitrogen protection,
Curing reaction releasing heat changes over time to be recorded by computer, because curing reaction releases heat with participating in the amount of reaction double bond
It is directly proportional, therefore the heat of curing reaction is obtained by integrating the peak area of exotherm, so as to obtain double bond conversion rate and consolidate
Change reaction rate.The final conversion ratio of double bond represents the degree of polymerisation completion and the efficiency of initiation of light trigger in monomer,
The speed of double bond conversion 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 triggers is much larger than small molecule initiator system and the effect of business aqueous initiator 2959,
When it is 40s to trigger the time, hPEA101-TX, hPEA211-TX conversion ratio reach more than 90%, and small molecule triggers system
For 80% or so, 2959 be 40% or so, and polymeric initiator conversion ratio in 40s reaches and triggers monomer in aqueous
When efficiency of initiation be substantially better than small molecule light trigger and business water-soluble photoinitiator 2959.Main reason is that the base of the present invention
Photoinitiator molecules are grafted on containing coinitiator amine in the amphipathy macromolecule hydrogen-capture-type light initiator of hyperbranched polyetheramine
Hyperbranched polyetheramine chain on both overcome traditional small molecule light trigger easy to migrate, xanthochromia, stability is poor, have residual etc. lack
Fall into, be advantageous to energy transfer between the two again, so as to produce free base spike faster and more, improve light-initiated effect
Rate.It is excellent to illustrate that the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine has in aqueous solvent simultaneously
Trigger 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
Trigger acrylate or other olefin monomers it is fast curing-formed, and with small molecule light trigger and commercial oiliness light
Initiator (ITX) is compared, and the final conversion ratio of monomer double bond improves 10%-25%, i.e. the efficiency of initiation of light trigger improves
10%~25%, it is excellent to illustrate that the amphipathy macromolecule hydrogen-capture-type light initiator of hyperbranched polyetheramine has in oil-based solvent
Efficiency of initiation.
Fig. 5 is respectively using the amphipathy macromolecule hydrogen-capture-type light initiator and phase based on hyperbranched polyetheramine of the present invention
The small molecule light trigger model compound and business oiliness light trigger ITX answered 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
The hPEA101-TX of synthesis, embodiment 3 synthesize hPEA211-TX, embodiment 5 synthesize hPEA110-TX with corresponding small point
Sub-light initiator model compound MGA-TX and small molecule coinitiator TEOA and business oiliness light trigger are as light-initiated
Agent triggers HDDA double bond under nitrogen atmosphere, and the inside is with the conversion ratio spectrogram of time for exposure under ultraviolet lighting, and method of testing is such as
It is lower described：By a certain amount of photo-curing monomer (acrylate) and light trigger (hPEA101-TX, hPEA211-TX,
HPEA110-TX and corresponding small molecule light trigger model compound MGA-TX and small molecule coinitiator TEOA and business
Oiliness light trigger ITX) it is dissolved according to a certain percentage in 1,4- dioxane and is used as sample.Weigh 2mg samples and be put into aluminum
In crucible, reference substance is empty crucible, sample and reference substance constant temperature ultraviolet lighting, curing reaction under 50ml/min nitrogen protection
Releasing heat changes over time to be recorded by computer, because curing reaction releasing heat is directly proportional to the amount for participating in reaction double bond,
Therefore the heat of curing reaction is obtained by integrating the peak area of exotherm, so as to obtain double bond conversion rate and curing reaction speed
Rate.The final conversion ratio of double bond represents the degree of polymerisation completion and the efficiency of initiation of light trigger, double bond conversion in monomer
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 trigger is much larger than small molecule initiator system and business oiliness initiator
ITX effect, final conversion of monomer improve 10%-25% (hPEA110-TX, hPEA211-TX, hPEA101-TX, MGA-
It is 100%, 100%, 87%, 79%, 75% that TX/TEOA, ITX/TEOA, which trigger final conversion of monomer).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 being grafted photoinitiator molecules based on two parent's property hyperbranched polyetheramine macromolecule hydrogen-capture-type light initiators of the present invention
Traditional small molecule light trigger easy to migrate, xanthochromia, stably had both been overcome on the hyperbranched polyetheramine chain containing coinitiator amine
Property it is poor, have the defects of residual, be advantageous to energy transfer between the two again, so as to producing free base spike faster and more,
Improve light-initiated efficiency.Illustrate the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine in oiliness simultaneously
There is excellent initiation performance in solvent.
Claims (9)
- A kind of 1. amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine, it is characterised in that structure such as formula (1) It is shown：Wherein, X represents polyether chain, and Y represents coinitiator amine molecule residue, and P represents photoinitiator molecules residue；It is described to trigger altogether Agent amine is the coinitiator monomer containing primary amine and secondary amine, shown in its structure such as formula (5)：Wherein, R2For C2-C10Straight or branched alkyl；R3For C1-C10Straight or branched alkyl.
- 2. the amphipathy macromolecule hydrogen-capture-type light initiator according to claim 1 based on hyperbranched polyetheramine, its feature It is, the X has the structure as shown in formula (2)：Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxy, 0<n<20.
- 3. the amphipathy macromolecule hydrogen-capture-type light initiator according to claim 1 based on hyperbranched polyetheramine, its feature It is, the photoinitiator molecules residue P is selected from such as one kind 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 The product that hydrogen atom on aromatic radical or aromatic radical is substituted by any substituent；X1For methylene, oxygen, sulphur or nitrogen-atoms； n1,2,3,4,5,6For integer, 0<n1,2,4,5,6<5,0<n3<3。
- 4. the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine according to one of claim 1-3 Preparation method, it is characterised in that comprise the following steps that：1. it is 0.95 according to mol ratio：1~1:0.95 by the coinitiator containing primary amine and secondary amine and 1 part containing diepoxy group Polyethers mixes in organic solvent, under the protection of inert gas, after ice-water bath is stirred 1.5~2.5 days, and 75~85 DEG C of temperature Degree is lower to react, and after reaction terminates, organic solvent is rotated and removed, dried, obtain hyperbranched polyetheramine；2. it is 0.9 according to mol ratio:1~1:0.9 is dissolved in hyperbranched polyetheramine and the small molecule light trigger with functional group In organic solvent, to be reacted at a temperature of 75~85 DEG C, after reaction terminates, revolving removes organic solvent, is precipitated in precipitating reagent, Dry, obtain the amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine；The step 1. in, containing primary amine and Shown in the structure such as formula (5) of the coinitiator monomer of secondary amine：Wherein, R2For C2-C10Straight or branched alkyl；R3For C1-C10Straight or branched alkyl.
- 5. preparation method according to claim 4, it is characterised in that step 1. in, the polyethers containing diepoxy group Structure such as formula (6) shown in：Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxy, 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.
- 6. preparation method according to claim 4, it is characterised in that step 2. in, the small molecule with functional group Light trigger, shown in structure such as formula (7)：P-L-R13 (7)Wherein, P be formula (4) in any initiator residue, L C1-C20Straight or branched alkyl, C1-C20Alkoxy, cycloalkyl or Phenyl, R13For epoxide group, carboxyl or ester group.
- 7. preparation method according to claim 5, it is characterised in that step 1. and 2. in, the organic solvent is toluene, Alcohols, dichloromethane, chloroform, Isosorbide-5-Nitrae-dioxane, ketone, dimethyl sulfoxide (DMSO) or DMF.
- 8. preparation method according to claim 5, it is characterised in that step 2. in, the precipitating reagent is n-hexane or stone Oily ether.
- 9. preparation method according to claim 5, it is characterised in that step 1. in, the inert gas is nitrogen or argon Gas.
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