CN110407719A - A kind of polymerizable mono-stripped hydrogen light initiating agent and preparation method thereof - Google Patents
A kind of polymerizable mono-stripped hydrogen light initiating agent and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 17
- 239000001257 hydrogen Substances 0.000 title claims abstract description 17
- 230000000977 initiatory effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 carboxyl compound Chemical class 0.000 claims abstract description 19
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 11
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 11
- 239000012965 benzophenone Substances 0.000 claims abstract description 10
- 150000003384 small molecules Chemical class 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 7
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical class [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000002459 sustained effect Effects 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 10
- 230000001988 toxicity Effects 0.000 abstract description 8
- 231100000419 toxicity Toxicity 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 239000003999 initiator Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKUSWAGOKUGEDX-UHFFFAOYSA-N C(CCC)Br(CCCC)(CCCC)CCCC Chemical compound C(CCC)Br(CCCC)(CCCC)CCCC OKUSWAGOKUGEDX-UHFFFAOYSA-N 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to field of light-sensitive high molecular materials.The present invention provides a kind of preparation methods of polymerizable mono-stripped hydrogen light initiating agent, carboxyl compound containing double bonds is synthesized by dihydromethyl propionic acid and the reaction of isocyanates ethyl acrylate, the problems such as epoxy on benzophenone and thioxanthone containing epoxy group synthesizes polymerizable mono-stripped hydrogen light initiating agent, greatly reduces toxicity caused by the migration of small molecule photoinitiator and niff is opened with the carboxyl again later.The present invention provides the preparation methods of this polymerizable mono-stripped hydrogen light initiating agent, and reaction condition is mildly simple, post-process simple easy purification.
Description
Technical field
The invention belongs to field of light-sensitive high molecular materials, a kind of polymerizable mono-stripped hydrogen light initiating agent and its preparation side
Method.
Background technique
Photocuring is a kind of economic, environmental-friendly technology, since itself VOC discharges, it is energy saving, quick the advantages that and obtain
To extensive use, in the application such as coating, ink, adhesive of traditional field；High-tech area application as photoelectricity, laser at
Picture, stereolithography.Photoinitiator plays a crucial role in UV curing system, and specific wavelength can be absorbed in they
Light, generate free radicals or ion activity kind cause system polymerization.Micro-molecular hydrogen abstraction, which needs to add amine and helps, draws
Agent is sent out, the small molecule photolysis debris generated when its decomposition of smell, the various problems such as xanthochromia, and photoinitiator is easily caused and is easy
It is migrated in system, or even moves to system surface and generate toxicity.Researcher is thus in order to improve or solve these
Problem and develop and have developed polymeric initiator and polymerizable photoinitiator etc., wherein polymerizable photoinitiator can be by poly-
Conjunction is reacted into polymer backbone, the fragment less residue of photoinitiator after solidification, and photoinitiator polymerize addition system can be big
Its migration is reduced greatly, therefore can substantially reduce its toxicity, and small molecule amine access initiator molecule can also be improved into smell
Problem.
Summary of the invention
The technical problem to be solved by the present invention is light-initiated in order to solve traditional small molecule benzophenone and thioxanthones
Agent photodissociation generates the problems such as niff that small molecules fragments bring toxicity and small molecule active amine generate, by can
The double bond and amine component of polymerization introduce photoinitiator, so that reaching reduces initiator photolysis debris migration bring toxicity, unpleasant
Smell the problems such as.
The present invention solves the technological means that technical problem uses: a kind of polymerizable mono-stripped hydrogen light initiating agent,
Structure are as follows:
The preparation reaction equation of novel polymerizable mono-stripped hydrogen light initiating agent are as follows:
The trigger for optical solidification preparation method, includes the following steps:
Dihydromethyl propionic acid is put into 250ml three-necked flask by step 1), and butanone is added and makees solvent, and three two laurels of drop are added dropwise
Sour dibutyl tin makees catalyst, and a small amount of p-hydroxyanisole is added and makees polymerization inhibitor, and isocyanates propylene is added in dropping funel
Acetoacetic ester is warming up to 40 degree, stirs lower beginning and isocyanates ethyl acrylate is slowly added dropwise, be added dropwise within two hours, drip
At rear sustained response for a period of time with di-n-butylamine titration drop reaction terminal, it is spare to steam solvent；
The small molecules such as the benzophenone containing epoxy group or thioxanthone are put into first step products therefrom by step 2)
In toluene system, tetrabutylammonium bromide is added and makees catalyst, is warming up to 90 degree of reactions；
Step 3) product retains organic phase, steams solvent to wash, and with ice ethyl alcohol recrystallization.
Specifically, the R group can be different hydrogen-abstraction small molecule photoinitiators；
Specifically, the ratio between amount of isocyanates ethyl acrylate and dihydromethyl propionic acid substance is 2:1 in the step 1)；
Specifically, the benzophenone containing epoxy group or thioxanthone and dihydromethyl propionic acid substance in the step 2)
The ratio between amount be 1:1；
Specifically, duration of the reaction is 0.5~2 hour in the step 2).
Polymerizable photoinitiator is formed the beneficial effects of the present invention are: double bond is introduced into photoinitiator system, simultaneously
Active amine component is introduced into initiator molecule, polymerizable mono-stripped hydrogen light initiating agent is synthesized, this photoinitiator is in body
It is small compared to micro-molecular hydrogen abstraction small toxicity, smell when being used in system, it greatly reduces to the bad of human and environment
It influences.
The present invention provides the preparation methods of this polymerizable mono-stripped hydrogen light initiating agent, and reaction process is simple, real
Mild condition is tested, post-processing and purifying are simple easy to operate.
Specific embodiment
The present invention will be described in detail for the following example, but does not limit the scope of the invention.
Embodiment 1:
The structural formula of compound 1
Dihydromethyl propionic acid is put into 250ml three-necked flask, butanone is added and makees solvent, three drop two fourths of tin dilaurate are added dropwise
Ji Xi makees catalyst, and a small amount of p-hydroxyanisole is added and makees polymerization inhibitor, and isocyanates ethyl acrylate is added in dropping funel,
40 degree are warming up to, lower beginning is stirred and isocyanates ethyl acrylate is slowly added dropwise, be added dropwise within two hours, continue after being added dropwise to complete
Reaction a period of time, it is spare to steam solvent with di-n-butylamine titration drop reaction terminal；By the 4- (2,3- containing epoxy group
Glycidoxy) benzophenone small molecule investment first step products therefrom toluene system in, be added tetrabutylammonium bromide urge
Agent is warming up to 90 degree of reactions, and product retains organic phase, steam solvent to wash, and is obtained with ice ethyl alcohol recrystallization white solid
Body.
It is disappeared by epoxy characteristic peak in infrared detection product, illustrates that carboxyl is successfully carried out with epoxy reaction.
Embodiment 2
The structural formula of compound 2 are as follows:
Dihydromethyl propionic acid is put into 250ml three-necked flask, butanone is added and makees solvent, three drop two fourths of tin dilaurate are added dropwise
Ji Xi makees catalyst, and a small amount of p-hydroxyanisole is added and makees polymerization inhibitor, and isocyanates ethyl acrylate is added in dropping funel,
40 degree are warming up to, lower beginning is stirred and isocyanates ethyl acrylate is slowly added dropwise, be added dropwise within two hours, continue after being added dropwise to complete
Reaction a period of time, it is spare to steam solvent with di-n-butylamine titration drop reaction terminal；By the 4- (2- containing epoxy group
(epoxy methoxyl group) ethyoxyl) benzophenone small molecule investment first step products therefrom toluene system in, be added tetrabutyl bromine
Change ammonium and make catalyst, be warming up to 90 degree of reactions, product retains organic phase, steam solvent, and obtained with ice ethyl alcohol recrystallization to wash
White solid.
It is disappeared by epoxy characteristic peak in infrared detection product, illustrates that carboxyl is successfully carried out with epoxy reaction.
Embodiment 3
The structural formula of compound 3 are as follows:
Dihydromethyl propionic acid is put into 250ml three-necked flask, butanone is added and makees solvent, three drop two fourths of tin dilaurate are added dropwise
Ji Xi makees catalyst, and a small amount of p-hydroxyanisole is added and makees polymerization inhibitor, and isocyanates ethyl acrylate is added in dropping funel,
40 degree are warming up to, lower beginning is stirred and isocyanates ethyl acrylate is slowly added dropwise, be added dropwise within two hours, continue after being added dropwise to complete
Reaction a period of time, it is spare to steam solvent with di-n-butylamine titration drop reaction terminal；By 4 containing epoxy group, 4 '-
(2,3- glycidoxy) benzophenone small molecule is put into the toluene system of first step products therefrom, and tetrabutylammonium bromide is added
Make catalyst, be warming up to 90 degree of reactions, product retains organic phase, steam solvent to wash, and is obtained with ice ethyl alcohol recrystallization white
Solid.
It is disappeared by epoxy characteristic peak in infrared detection product, illustrates that carboxyl is successfully carried out with epoxy reaction.
Embodiment 4
The structural formula of compound 4 are as follows:
Dihydromethyl propionic acid is put into 250ml three-necked flask, butanone is added and makees solvent, three drop two fourths of tin dilaurate are added dropwise
Ji Xi makees catalyst, and a small amount of p-hydroxyanisole is added and makees polymerization inhibitor, and isocyanates ethyl acrylate is added in dropping funel,
40 degree are warming up to, lower beginning is stirred and isocyanates ethyl acrylate is slowly added dropwise, be added dropwise within two hours, continue after being added dropwise to complete
Reaction a period of time, it is spare to steam solvent with di-n-butylamine titration drop reaction terminal；By the 4- (2,3- containing epoxy group
Glycidoxy) thioxanthone small molecule investment first step products therefrom toluene system in, be added tetrabutylammonium bromide urge
Agent is warming up to 90 degree of reactions, and product retains organic phase, steam solvent to wash, and is obtained with ice ethyl alcohol recrystallization white solid
Body.
It is disappeared by epoxy characteristic peak in infrared detection product, illustrates that carboxyl is successfully carried out with epoxy reaction.
Comparative example 5
1, photosensitive polymer combination is prepared
According to the specific formula in following ratio and table 1, Photosensitve resin composition is prepared
A: acrylate copolymer (100 mass parts)
B: photoinitiator (5 mass parts)
Table 1-1
Table 1-2
| Embodiment 4 | Comparative example 2 | |
| A | 100 | 100 |
| B4 (product 4) | 5 | |
| B”(ITX) | 5 |
2, filming performance is tested
Above-mentioned composition is protected from light after being uniformly mixed, feeding, using bar film, forms film thickness in PET template
Then about 10 μm of film uses mercury lamp light source (light intensity 240mJ/cm2) film is exposed, time for exposure 120s observes it
Whether being capable of film-forming.
Test result is as shown in table 2:
Table 2
3, migration is tested
Above-mentioned formula is prepared respectively, they are injected separately into 30mm × 4mm × 1mm silicagel pad mold, is solidified in UV
Solidify 3min, light intensity 30mW/cm in case2.Then batten is crushed, respectively takes 0.1g, extract 4 at room temperature with 10ml acetonitrile
It.Finally, same amount of extract liquor is taken to carry out UV absorption test.Product 1,2,3 can be obtained relative to BP by formula (1) and (2), 4
Relative mobility relative to ITX.
C=A/ (ε × b) formula (1)
R=CProduct/CBP/ITX× 100% formula (2)
Wherein C is the concentration (molL of initiator in extract liquor-1)；A is absorbance；ε is molar extinction coefficient (L
mol-1·cm-1)；B is sample cell thickness (cm)；C product is the concentration of product in extract liquor；CBP/ITXFor BP in extract liquor or
The concentration of ITX；R is the relative mobility of macromole evocating agent.
It is indicated in test result such as table 3:
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| Mobility | 12 | 15 | 9 | 13 | 100 | 100 |
Under equal conditions, the mobility of synthetic is only the 9-15% of comparative example, greatly reduces the toxicity of cured film,
This illustrates that polymerizable mono-stripped hydrogen light initiating agent prepared by the present invention can effectively reduce the migration of initiator, reduces
The problems such as its bring toxicity smell xanthochromia.
Claims (5)
1. a kind of preparation method of polymerizable mono-stripped hydrogen light initiating agent, it is characterised in that include the following steps:
Dihydromethyl propionic acid is put into 250ml three-necked flask by step 1), and butanone is added and makees solvent, and three drop tin dilaurates two are added dropwise
Butyl tin makees catalyst, and a small amount of p-hydroxyanisole is added and makees polymerization inhibitor, and isocyanates acrylic acid second is added in dropping funel
Ester is warming up to 40 degree, stirs lower beginning and isocyanates ethyl acrylate is slowly added dropwise, be added dropwise within two hours, after being added dropwise to complete
With di-n-butylamine titration drop reaction terminal, it is spare to steam solvent for a period of time for sustained response；
The small molecules such as the benzophenone containing epoxy group or thioxanthone are put into the toluene of first step products therefrom by step 2)
In system, tetrabutylammonium bromide is added and makees catalyst, is warming up to 90 degree of reactions；
Step 3) product retains organic phase, steams solvent to wash, and with ice ethyl alcohol recrystallization.
The polymerizable mono-stripped hydrogen light initiating agent structural formula is
2. a kind of preparation method of polymerizable mono-stripped hydrogen light initiating agent as described in claim 1, it is characterised in that: institute
Stating the small molecule containing epoxy group can be benzophenone or thioxanthones.
3. a kind of preparation method of polymerizable mono-stripped hydrogen light initiating agent as described in claim 1, it is characterised in that: institute
Stating the ratio between amount of isocyanates ethyl acrylate and dihydromethyl propionic acid substance in step 1) is 2:1.
4. a kind of preparation method of polymerizable mono-stripped hydrogen light initiating agent as described in claim 1, it is characterised in that: institute
The ratio between amount of benzophenone or thioxanthone and dihydromethyl propionic acid substance in step 2) containing epoxy group is stated as 1:1.
5. a kind of preparation method of polymerizable mono-stripped hydrogen light initiating agent as described in claim 1, it is characterised in that: institute
Stating step 2) duration of the reaction is 0.5~2 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022040292A (en) * | 2019-12-13 | 2022-03-10 | Ｋｊケミカルズ株式会社 | Photopolymerization initiator |
| CN115572229A (en) * | 2022-11-10 | 2023-01-06 | 江苏三木化工股份有限公司 | Preparation method of polymerizable photoinitiator based on alpha-hydroxyketone |
| 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 |
-
2018
- 2018-04-27 CN CN201810393448.2A patent/CN110407719A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022040292A (en) * | 2019-12-13 | 2022-03-10 | Ｋｊケミカルズ株式会社 | Photopolymerization initiator |
| JP7262722B2 (en) | 2019-12-13 | 2023-04-24 | Ｋｊケミカルズ株式会社 | Photoinitiator |
| 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 |
| CN115572229A (en) * | 2022-11-10 | 2023-01-06 | 江苏三木化工股份有限公司 | Preparation method of polymerizable photoinitiator based on alpha-hydroxyketone |
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