CN110117334A - A kind of photothermal integrated initiator and preparation method thereof - Google Patents
A kind of photothermal integrated initiator and preparation method thereof Download PDFInfo
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- CN110117334A CN110117334A CN201810109731.8A CN201810109731A CN110117334A CN 110117334 A CN110117334 A CN 110117334A CN 201810109731 A CN201810109731 A CN 201810109731A CN 110117334 A CN110117334 A CN 110117334A
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- 239000003999 initiator Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 150000002432 hydroperoxides Chemical class 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 17
- 239000012467 final product Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000013067 intermediate product Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- -1 1- phenyl-isopropyl Chemical group 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 125000002619 bicyclic group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical compound CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- RSPISYXLHRIGJD-UHFFFAOYSA-N OOOO Chemical compound OOOO RSPISYXLHRIGJD-UHFFFAOYSA-N 0.000 claims description 4
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 150000003505 terpenes Chemical class 0.000 claims 1
- 235000007586 terpenes Nutrition 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 20
- 238000012719 thermal polymerization Methods 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 abstract 1
- 239000012975 dibutyltin dilaurate Substances 0.000 abstract 1
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 238000005286 illumination Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 4
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 4
- 229930016911 cinnamic acid Natural products 0.000 description 4
- 235000013985 cinnamic acid Nutrition 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 4
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RLAZRBVKESZVAD-UHFFFAOYSA-N C(CCC)[Sn]CCCC.C(C=CC1=CC=CC=C1)(=O)O Chemical compound C(CCC)[Sn]CCCC.C(C=CC1=CC=CC=C1)(=O)O RLAZRBVKESZVAD-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing 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
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of preparation methods of photothermal integrated initiator, and using hydroxyl photoinitiator, diisocyanate and hydroperoxides as raw material, dibutyl tin dilaurate is catalyst, take direct isocyanation esterification that photothermal integrated initiator is made.Solvent is ethyl acetate, acetone, chloroform.The photothermal integrated initiator of the present invention can have preferable compatibility with monomer, the resin in polymerization system, and can cause thermal polymerization by photopolymerization, so that non-light area can also polymerize.
Description
Technical field
The invention belongs to a kind of photothermal integrated initiator and preparation method, belong to a kind of functional initiator MOLECULE DESIGN and
Organic synthesis field.
Background technique
Photopolymerization is a kind of efficient polymerization process, it is by the light-initiated process for making liquid be converted to polymer.Light
Polymerization technique is since the advantages that it is energy saving, environmental-friendly, practical, high-efficient, is widely paid close attention to, and especially China is close
Year is since environmental pollution brings more and more problems, so that the application of environment-friendly material is by favor.Photopolymerization has very much
The field of application, such as high-tech area, photoelectronics, laser imaging, stereolithography and nanotechnology and high-performance coating, oil
The traditional fields such as ink and adhesive.
Although photopolymerization has many advantages, such as low energy cost, high efficiency, photopolymerization one maximum challenge comes
From in intensity gradient, is restricted since deep layer polymerization is absorbed light shield by photoinitiator, limit light and enter penetrating for deep resin
Ability.The ratio absorbed according to langbobier law light by transparent medium is unrelated with the intensity of incident light；It is every on light path
The light of blanket layer Absorption of Medium same ratio value.Therefore photopolymerization is limited primarily to the synthesis of thin material, it is however generally that polymerization thickness
No more than 100 microns.And for thick coating, photopolymerization is difficult to realize.Although photobleaching type photoinitiator or new can be used
The photoinitiator of the high efficiency of initiation of type low concentration can make more light by system to reach hundreds of microns (< 300um)
Thickness solidification.But some polymerization systems are limited by photobleaching type photoinitiator quantity and when free radical polymerization by table
The photoinitiator of the influence low concentration of face oxygen inhibition can prevent material surface from being fully cured, in addition UV-curing technology
It is general to be only used to solidify single material, it is rarely used in the solidification preparation of composite material.Therefore, the application field of photopolymerization by
Great limitation, such as in the dental filling material of deep chamber, the manufacture of 3D object, shadow region or thick-layer pigment sample and
The application in the directions such as functional gradient polymer composites.And Frontal polymerization be then it is a kind of can not only increase curing depth (>
300um) but also the polymerizations of more structural materials can be obtained.
Photopolymerization can cause the temperature of polymerization system to rise to 120 DEG C or higher, and thermal initiator is due to its chemistry knot
Structure is different, thermal decomposition temperature can from 60 to 120 DEG C between be adjusted.It thus completely can be by photoinitiator and thermal initiator
In conjunction with preparing integrated initiator.
A kind of photo-thermal initiator is designed, it had both had the function of ability light-initiated, while that there is heat to cause, worked as illumination
When, photoinitiator decomposition generates free radicals initiation polymerization, once polymerization occurs, since polymerization can generate heat, polymerization system
Temperature increases, and when temperature reaches thermal initiator decomposition temperature, induction thermal initiator decomposition generates free radicals and can further cause
Polymerization, equally can produce polymerization reaction in the thickness that light cannot reach in this way, finally be able to achieve whole polymerizations of system, this
Sample, photopolymerization are not just influenced by polymeric material thickness.
Photothermal integrated initiator has the advantage that the small molecule of system remaining is drawn after solidification compared to photo-thermal initiator compounding
It is few to send out agent；Photoinitiator is connected with thermal initiator, and the heat that photopolymerization generates can be transmitted to rapidly thermal initiator, makes thermal initiator
It can more quickly and effectively decompose.For light-initiated hot Frontal polymerization system, in traditional photoinitiator thermal initiator compound system
Photoinitiator cannot completely consume, and have remaining in polymer network for small molecule photoinitiator and photolysis debris.Remain in
Photoinitiator and photolysis debris in product are easy migration and volatilization, make product aging yellowing, smell and toxicity occur.And photo-thermal
Integrated initiator is the effective way to solve the above problems.This kind of initiator is to contain optical active group and peroxide in molecule simultaneously
Group, stage after the polymerization that is at the front, heat cause in the highest flight, and optical active group can be present in the macromolecular end of the chain, reduce light and draw
Agent is sent out to surface migration.
Summary of the invention
The present invention provides a kind of photothermal integrated initiator and preparation method thereof, the present invention from Molecular Design,
Photoinitiator and thermal initiator are combined together by MOLECULE DESIGN, synthesize photothermal integrated initiator, its structure is seen, both may be used
Light initiation polymerization again can thermal-initiated polymerization.
Photothermal integrated initiator prepared by the present invention, the chemical structural formula of the initiator are as follows:
Wherein R1For methyl or-H, R2For methyl or cyclohexyl, R3ForOr、R4For 1,1-
Dimethyl -4- methyl-1,4- pentylidene, tert-butyl, 1- phenyl-isopropyl, 1-(4- methyl)-cyclohexyl isopropyl, 2,6,6-
Trimethyl bicyclic [3.1.1] heptane base, benzoyl, n=1,2.
The present invention provides a kind of preparation method of photothermal integrated initiator, it is characterised in that:
For Compound I: diisocyanate is added in solvent, hydroxyl photoinitiator A is added after mixing, after
The catalyst dibutyltin dilaurylate (DBTDL) of the 0.1%-3% of reactant gross mass is added in continuous mixing, in 50-100 DEG C of condition
Lower reaction 8-15h, obtains intermediate product.Hydroperoxides are added in reaction unit above again, are reacted under the conditions of 50-70 DEG C
8-15h.Obtained product is rotated by Rotary Evaporators, removes solvent, obtains final product.
For II compound: diisocyanate being added in solvent, hydroperoxides are added after mixing, is continued
The catalyst dibutyltin dilaurylate (DBTDL) of the 0.1%-3% of reactant gross mass is added in mixing, under the conditions of 30-60 DEG C
2-6h is reacted, intermediate product is obtained.Hydroxyl photoinitiator b is added in reaction unit above again, under the conditions of 40-60 DEG C
React 4-6h.Obtained product is rotated by Rotary Evaporators, removes solvent, obtains final product.
The hydroxyl photoinitiator A is alpha-hydroxyalkyl acetophenone (2- hydroxy-2-methyl -1- phenyl -1- acetone (light
Initiator 1173), 1- hydroxycyclohexyl phenyl ketone (photoinitiator 184)), hydroxyl photoinitiator b be 2- hydroxyl -4'-
(2- hydroxy ethoxy) -2- methyl phenyl ketone (photoinitiator 2959).
The diisocyanate is isophorone diisocyanate, toluene di-isocyanate(TDI).
The hydroperoxides be 2,5- dimethyl n-hexane -2,5- diformazan hydroxyl peroxide, cumyl hydroperoxide,
Tert-butyl hydroperoxide, p-menthane hydroperoxide, hydrogen peroxide benzoyl, 2,6,6- trimethyl bicyclic [3.1.1] alkyl hydrogen in heptan mistake
Oxide.
The solvent is ethyl acetate, chloroform, acetone, butyl acetate.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention is carried out further detailed
Description.It should be appreciated that described herein, the specific embodiments are only for explaining the present invention, is not intended to limit the present invention.On the contrary,
The present invention cover any substitution made on the essence and scope of the present invention being defined by the claims, modification, equivalent method with
And scheme.Further, detailed below in datail description of the invention in order to make the public have a better understanding the present invention
Describe some specific detail sections.The description of part can also be complete without these details for a person skilled in the art
Understand the present invention.
Embodiment 1
It is added to 0.03mol(6.6685g) isophorone diisocyanate (IPDI) in 30mL solvent ethyl acetate, mixes
0.015mol(2.6734g is added after uniformly) thermal initiator 2,5- dimethyl n-hexane -2,5- diformazan hydroxyl peroxide, continuation
0.3212g catalyst dibutyltin dilaurylate (DBTDL) is added in mixing, reacts 4h under the conditions of 50 DEG C, obtains intermediate product.
0.03mol(6.7274g) photoinitiator 2959 is added in reaction unit above again, reacts 50h under the conditions of 50 DEG C.It will obtain
Product rotated by Rotary Evaporators, remove solvent ethyl acetate, obtain final product (being denoted as initiator 1).
Embodiment 2
It is added to 0.03mol(6.6691g) isophorone diisocyanate (IPDI) in 30mL solvent chloroform, mixes
0.03mol(6.1280g is added after uniformly) photoinitiator 184, continues to mix two fourth of catalyst dibutyltin cinnamic acid that 0.3303g is added
Ji Xi (DBTDL) reacts 3h under the conditions of 85 DEG C, obtains intermediate product 183-IPDI.0.03mol(4.5656g) heat is drawn again
It sends out agent cumyl hydroperoxide to be added in reaction unit above, reacts 8h under the conditions of 65 DEG C.Obtained product is passed through into rotation
Evaporimeter is rotated, and solvent chloroform is removed, and is obtained final product (being denoted as initiator 2).
Embodiment 3
It is added to 0.03mol(6.6687g) isophorone diisocyanate (IPDI) in 30mL solvent acetone, is uniformly mixed
After 0.03mol(4.9261g is added) photoinitiator 1173, continues to mix be added 0.2823g catalyst dibutyltin cinnamic acid dibutyl
Tin (DBTDL) reacts 12h under the conditions of 75 DEG C, obtains intermediate product 1173-IPDI.0.03mol(2.7337g) heat is drawn again
It sends out agent tert-butyl hydroperoxide to be added in reaction unit above, reacts 8h under the conditions of 65 DEG C.Obtained product is passed through into rotation
Evaporimeter is rotated, and solvent acetone is removed, and is obtained final product (being denoted as initiator 3).
Embodiment 4
It is added to 0.03mol(6.6690g) isophorone diisocyanate (IPDI) in 30mL solvent acetic acid butyl ester, mixes
0.03mol(4.9258g is added after uniformly) photoinitiator 1173, continues to mix the catalyst dibutyltin cinnamic acid two that 0.3252g is added
Butyl tin (DBTDL) reacts 12h under the conditions of 75 DEG C, obtains intermediate product 1173-IPDI.Again by 0.03mol(5.1682g)
Thermal initiator p-menthane hydroperoxide is added in reaction unit above, reacts 8h under the conditions of 65 DEG C.Obtained product is passed through into rotation
Turn evaporimeter to be rotated, remove solvent acetic acid butyl ester, obtains final product (being denoted as initiator 4).
Embodiment 5
It is added to 0.03mol(6.6695g) isophorone diisocyanate (IPDI) in 30mL solvent acetic acid butyl ester, mixes
0.03mol(6.1285g is added after uniformly) photoinitiator 184, continues to mix two fourth of catalyst dibutyltin cinnamic acid that 0.3271g is added
Ji Xi (DBTDL) reacts 13h under the conditions of 85 DEG C, obtains intermediate product 184-IPDI.0.03mol(4.1443g) heat is drawn again
It sends out agent hydrogen peroxide benzoyl to be added in reaction unit above, reacts 8h under the conditions of 65 DEG C.Obtained product is passed through into rotation
Evaporimeter is rotated, and solvent acetic acid butyl ester is removed, and is obtained final product (being denoted as initiator 5).
Embodiment 6
It is added to 0.03mol(6.6688g) isophorone diisocyanate (IPDI) in 30mL solvent ethyl acetate, mixes
0.03mol(5.1094g is added after uniformly) thermal initiator 2,6,6- trimethyl bicyclic [3.1.1] alkyl hydroperoxide in heptan, after
0.3502g catalyst dibutyltin dilaurylate (DBTDL) is added in continuous mixing, reacts 4h under the conditions of 50 DEG C, obtains intermediate production
Object.0.03mol(6.7273g) photoinitiator 2959 is added in reaction unit above again, reacts 50h under the conditions of 50 DEG C.It will
Obtained product is rotated by Rotary Evaporators, removes solvent ethyl acetate, is obtained final product (being denoted as initiator 6)
Embodiment 7
By 0.03mol(5.2243g) toluene di-isocyanate(TDI) (TDI), it is added in 30mL solvent ethyl acetate, after mixing
0.03mol(6.1283g is added) photoinitiator 184, continues to mix the catalyst dibutyltin dilaurylate that 0.2789g is added
(DBTDL), 13h is reacted under the conditions of 85 DEG C, obtains intermediate product 184-TDI.Again by 0.015mol(2.6732g) thermal initiator
2,5- dimethyl n-hexane -2,5- diformazan hydroxyl peroxides are added in reaction unit above, react 8h under the conditions of 65 DEG C.It will
Obtained product is rotated by Rotary Evaporators, removes solvent ethyl acetate, is obtained final product (being denoted as initiator 7).
Embodiment 8
By 0.03mol(5.2246g) toluene di-isocyanate(TDI) (TDI), it is added in 30mL solvent chloroform, after mixing
0.03mol(4.5656g is added) thermal initiator cumyl hydroperoxide, it continuess to mix and 0.3253g catalyst dibutyltin cinnamic acid is added
Dibutyl tin (DBTDL) reacts 4h under the conditions of 50 DEG C, obtains intermediate product.Again by 0.03mol(6.7272g) photoinitiator
2959 are added in reaction unit above, react 50h under the conditions of 50 DEG C.Obtained product is revolved by Rotary Evaporators
It steams, removes solvent chloroform, obtain final product (being denoted as initiator 8).
Embodiment 9
By 0.03mol(5.2247g) toluene di-isocyanate(TDI) (TDI), it is added in 30mL solvent acetone, is added after mixing
0.03mol(4.9257g) photoinitiator 1173 continues to mix the catalyst dibutyltin dilaurylate that 0.2547g is added
(DBTDL), 12h is reacted under the conditions of 75 DEG C, obtains intermediate product 1173-TDI.Again by 0.03mol(2.7338g) thermal initiator
Tert-butyl hydroperoxide is added in reaction unit above, reacts 8h under the conditions of 65 DEG C.Obtained product is passed through into rotary evaporation
Instrument is rotated, and solvent acetone is removed, and is obtained final product (being denoted as initiator 9).
Embodiment 10
By 0.03mol(5.2241g) toluene di-isocyanate(TDI) (TDI), it is added in 30mL solvent acetic acid butyl ester, after mixing
0.03mol(4.9258g is added) photoinitiator 1173, continues to mix the catalyst dibutyltin dilaurylate that 0.3109g is added
(DBTDL), 12h is reacted under the conditions of 75 DEG C, obtains intermediate product 1173-TDI.Again by 0.03mol(5.1679g) thermal initiator
P-menthane hydroperoxide is added in reaction unit above, reacts 8h under the conditions of 65 DEG C.Obtained product is passed through into Rotary Evaporators
It is rotated, removes solvent acetic acid butyl ester, obtained final product (being denoted as initiator 10).
Embodiment 11
By 0.03mol(5.2250g) toluene di-isocyanate(TDI) (TDI), it is added in 30mL solvent acetic acid butyl ester, after mixing
0.03mol(6.1280g is added) photoinitiator 184, continues to mix the catalyst dibutyltin dilaurylate that 0.3154g is added
(DBTDL), 13h is reacted under the conditions of 85 DEG C, obtains intermediate product 184-TDI.Again by 0.03mol(4.1441g) thermal initiator
Hydrogen peroxide benzoyl is added in reaction unit above, reacts 8h under the conditions of 65 DEG C.Obtained product is passed through into rotary evaporation
Instrument is rotated, and solvent acetic acid butyl ester is removed, and is obtained final product (being denoted as initiator 11).
Embodiment 12
By 0.03mol(5.2248g) toluene di-isocyanate(TDI) (TDI), it is added in 30mL solvent ethyl acetate, after mixing
0.03mol(5.1090g is added) thermal initiator 2,6,6- trimethyl bicyclic [3.1.1] alkyl hydroperoxide in heptan continuess to mix
It is added 0.3411g catalyst dibutyltin dilaurylate (DBTDL), reacts 4h under the conditions of 50 DEG C, obtain intermediate product.Again will
0.03mol(6.7270g) photoinitiator 2959 is added in reaction unit above, reacts 50h under the conditions of 50 DEG C.The production that will be obtained
Object is rotated by Rotary Evaporators, removes solvent ethyl acetate, is obtained final product (being denoted as initiator 12).
Above-mentioned photothermal integrated initiator is dissolved in 20g tri (propylene glycol) diacrylate (TPGDA) to (initiator is dense
Degree be 1.5mmol/100gTPGDA(wherein difunctionality photothermal integrated initiator concentration be 0.75mmol/100gTPGDA)), it is molten
Solution completely after be added in the test tube that diameter is 1.8cm, in intensity of illumination be 5mW/cm with mercury lamp2Under conditions of, from test tube top
Portion's illumination.If the different photoinitiators of table 1 are 5mW/cm in intensity of illumination2Under conditions of illumination needed for light-initiated thermal polymerization when
Between and thermal polymerization fltting speed.
The different photoinitiators of table 1 are 5mW/cm in intensity of illumination2Under conditions of light application time and thermal polymerization fltting speed
| Photoinitiator | Light application time s | Thermal polymerization fltting speed cm/min | Photoinitiator | Light application time s | Thermal polymerization fltting speed cm/min |
| 1 | 185 | 1.11 | 7 | 62 | 1.15 |
| 2 | 60 | 1.4 | 8 | 168 | 1.31 |
| 3 | 102 | 0.97 | 9 | 99 | 0.99 |
| 4 | 90 | 1.07 | 10 | 87 | 1.09 |
| 5 | 54 | 1.6 | 11 | 50 | 1.59 |
| 6 | 185 | 1.06 | 12 | 180 | 1.06 |
Claims (7)
1. a kind of photothermal integrated initiator, chemical structural formula are as shown below:
Wherein R1For methyl or-H, R2For methyl or cyclohexyl, R3ForOr、R4For 1,1- bis-
Methyl -4- methyl-1,4- pentylidene, tert-butyl, 1- phenyl-isopropyl, 1-(4- methyl)-cyclohexyl isopropyl, 2,6,6- tri-
Methyl bicyclic [3.1.1] heptane base, benzoyl, n=1,2.
2. leading to a kind of preparation method of photothermal integrated initiator of formula (I) according to patent requirements 1, it is characterised in that:
It is added to diisocyanate in solvent, hydroxyl photoinitiator A is added after mixing, it is anti-to continues to mix addition
The catalyst dibutyltin dilaurylate (DBTDL) for answering the 0.1%-3% of object gross mass, reacts 8-15h under the conditions of 50-100 DEG C,
Obtain intermediate product；Hydroperoxides are added in reaction unit above again, react 8-15h under the conditions of 50-70 DEG C；It will obtain
Product rotated by Rotary Evaporators, remove solvent, obtain final product.
3. leading to a kind of preparation method of photothermal integrated initiator of formula (II) according to patent requirements 1, it is characterised in that:
It is added to diisocyanate in solvent, hydroperoxides are added after mixing, continuess to mix and the total matter of reactant is added
The catalyst dibutyltin dilaurylate (DBTDL) of the 0.1%-3% of amount, reacts 2-6h under the conditions of 30-60 DEG C, obtains intermediate production
Object；Hydroxyl photoinitiator b is added in reaction unit above again, reacts 4-6h under the conditions of 40-60 DEG C；The production that will be obtained
Object is rotated by Rotary Evaporators, removes solvent, obtains final product.
4. a kind of preparation method of photothermal integrated initiator according to claim 2,3, it is characterised in that described hydroxyl
Photoinitiator A be alpha-hydroxyalkyl acetophenone (2- hydroxy-2-methyl -1- phenyl -1- acetone (photoinitiator 1173), 1- hydroxyl
Cyclohexyl phenyl ketone (photoinitiator 184)), hydroxyl photoinitiator b is 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methylbenzene
Acetone (photoinitiator 2959).
5. a kind of preparation method of photothermal integrated initiator according to claim 2,3, it is characterised in that two isocyanide
Acid esters is isophorone diisocyanate, toluene di-isocyanate(TDI).
6. a kind of preparation method of photothermal integrated initiator according to claim 2,3, it is characterised in that the hydrogen peroxide
Compound is 2,5- dimethyl n-hexane -2,5- diformazan hydroxyl peroxide, cumyl hydroperoxide, tert-butyl hydroperoxide, terpene
Alkane hydrogen peroxide, hydrogen peroxide benzoyl, 2,6,6- trimethyl bicyclic [3.1.1] alkyl hydroperoxide in heptan.
7. a kind of preparation method of photothermal integrated initiator according to claim 2,3, it is characterised in that the solvent is
Ethyl acetate, chloroform, acetone, butyl acetate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574350A (en) * | 2020-05-09 | 2020-08-25 | 北京化工大学常州先进材料研究院 | Novel hydroxycyclohexyl acetophenone photoinitiator and preparation method thereof |
-
2018
- 2018-02-05 CN CN201810109731.8A patent/CN110117334A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574350A (en) * | 2020-05-09 | 2020-08-25 | 北京化工大学常州先进材料研究院 | Novel hydroxycyclohexyl acetophenone photoinitiator and preparation method thereof |
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