CN103275249A - Free radical photoinitiator containing single vinyl ether group or single propenyl ether group, and preparation method thereof - Google Patents
Free radical photoinitiator containing single vinyl ether group or single propenyl ether group, and preparation method thereof Download PDFInfo
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- CN103275249A CN103275249A CN2013101974586A CN201310197458A CN103275249A CN 103275249 A CN103275249 A CN 103275249A CN 2013101974586 A CN2013101974586 A CN 2013101974586A CN 201310197458 A CN201310197458 A CN 201310197458A CN 103275249 A CN103275249 A CN 103275249A
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- free radical
- vinyl ether
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- ZKJNETINGMOHJG-GGWOSOGESA-N (e)-1-[(e)-prop-1-enoxy]prop-1-ene Chemical group C\C=C\O\C=C\C ZKJNETINGMOHJG-GGWOSOGESA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 63
- 239000012949 free radical photoinitiator Substances 0.000 title abstract 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 141
- 150000003254 radicals Chemical class 0.000 claims abstract description 89
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 36
- 238000005886 esterification reaction Methods 0.000 claims abstract description 36
- -1 hydroxyl radicals Chemical class 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 44
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 35
- 230000032050 esterification Effects 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 28
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 25
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 25
- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical compound C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 claims description 14
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 8
- FSDGGBSMJHFROK-UHFFFAOYSA-N 2-prop-1-enoxyethanol Chemical compound CC=COCCO FSDGGBSMJHFROK-UHFFFAOYSA-N 0.000 claims description 8
- GNYPMQZTSVRUEZ-UHFFFAOYSA-N 3-prop-1-enoxypropan-1-ol Chemical compound CC=COCCCO GNYPMQZTSVRUEZ-UHFFFAOYSA-N 0.000 claims description 8
- UFRCCJVCWZAEBT-UHFFFAOYSA-N 4-prop-1-enoxybutan-1-ol Chemical compound CC=COCCCCO UFRCCJVCWZAEBT-UHFFFAOYSA-N 0.000 claims description 8
- XRDCVFNQMZXGND-UHFFFAOYSA-N 6-prop-1-enoxyhexan-1-ol Chemical compound CC=COCCCCCCO XRDCVFNQMZXGND-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- IEZWOVIWXFLQTP-UHFFFAOYSA-N hydroperoxyethene Chemical compound OOC=C IEZWOVIWXFLQTP-UHFFFAOYSA-N 0.000 claims description 8
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 claims description 7
- ANHLDZMOXDYFMQ-UHFFFAOYSA-N 2-hydroxythioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(O)=CC=C3SC2=C1 ANHLDZMOXDYFMQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 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 7
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 claims description 3
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 239000003814 drug Substances 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
- 239000000463 material Substances 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 102
- 238000010521 absorption reaction Methods 0.000 description 15
- 230000006837 decompression Effects 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 239000013067 intermediate product Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a free radical photoinitiator containing a single vinyl ether group or a single propenyl ether group, and a preparation method thereof. The method comprises the following steps of: firstly adding diisocyanate, hydroxyl single vinyl ether or hydroxyl single propenyl ether into a reaction container and performing an ammonia esterification reaction; after reacting, adding a small-molecular free radical photoinitiator containing hydroxyl radicals, a solvent, a polymerization inhibitor and a catalyst into the reaction container and continuously performing the ammonia esterification reaction; and removing the solvent after reacting, thereby obtaining the free radical photoinitiator product containing the single vinyl ether group or the single propenyl ether group. Based on the vinyl ether group or the propenyl ether group, the free radical photoinitiator can be used for overcoming the defect of other polymerizable photoinitiators which are easy to polymerize automatically and poor in photostability, and has the good storage stability. When the free radical photoinitiator is used for a free radical photo-curing system, the free radical photoinitiator also has the advantages of low mobility and high stability. The free radical photoinitiator which is reliable and safe can be applied to UV (ultraviolet)-cured adhesives, coating materials and printing inks. Thus, the free radical photoinitiator has the great significance for the application and the popularization of photo-curing products in food packaging and medicine packaging.
Description
Technical field
The invention belongs to the light trigger technical field, particularly relate to a kind of free radical photo-initiation that contains mono vinyl ether or single propenyl ether group and preparation method thereof.
Background technology
Photocuring is to utilize UV-light or visible light to cause to have chemically active material rapid polymerization, and instantaneous solidification becomes the process of solid-state material.Photocuring technology is compared with other curing technologies, have energy consumption low, pollute less, at room temperature just can quick and complete curing and plurality of advantages such as wide adaptability, be a kind of novel green technology.Follow the difference according to initiated polymerization mechanism, photocuring can be divided into radical photoinitiator curing, cation photocuring, free radical-cationic hybrid photocuring.Wherein, free radical-cationic hybrid photocuring is learnt from other's strong points to offset one's weaknesses because combining the advantage of radical photoinitiator curing and cation photocuring, uses more and more widely at industrial circles such as photo-cured coating, light-curable ink and Photocurable adhesives.
In photocuring system, light trigger is one of principal element of decision system photocuring speed, is the important component part of photocuring system.But small molecules light trigger toxicity commonly used is general bigger, and the small molecules light trigger and the photolysis debris that remain in the photocuring product are easy to overflow, and this has seriously limited the application of photocuring product in packings such as food and medicine.At present, the effective ways of head it off are to introduce polymerizable groups to make the polymerizable light trigger in the small molecules light trigger, in the photocuring system solidification process, polymerizable groups participates in polymerization, light trigger just is connected to formed polymkeric substance and has suffered, thereby greatly reduces light trigger to external migration.Free radical photo-initiation is often introduced the group that can participate in radical polymerization, disclose a kind of polymerizable free radical photo-initiation that contains ethylenic unsaturation class amide group as CN102329399A, ethylenic unsaturation class amide group can participate in radical polymerization in the illumination process; And for example US 2001007880A1 has synthesized 2-hydroxyl-1-phenyl-2-methyl-5-vinyl-1-ketone, 2-methyl isophthalic acid-phenyl-2-methacryloxy-1-acetone etc. and has contained the vinyl that can participate in radical polymerization or the free radical photo-initiation of acryloxy; CN 101481450A is keyed to light-initiated group on the acrylate-based performed polymer, and same along with acrylate-based radical polymerization, light-initiated group also is keyed to formed polymkeric substance and has suffered.And cation light initiator is often introduced the group that can participate in cationoid polymerisation, has announced that as US 6558871B1 intramolecularly contains salt compounded of iodine and the sulfosalt of epoxy group(ing) or vinyl ether group.
Yet the polymerizable groups of these polymerizable light triggers is also easily caused by self and from coagel, though solved the migration problem of light trigger, is inconvenient to store, and uses not extensive.And along with free radical-cationic hybrid photocuring product application is more and more wider, the light trigger that is used for free radical-cationic hybrid photocuring product also more and more is required.Vinyl ether responds active high, and toxicity is low, and is good with the oligopolymer consistency, the high advantage of transformation efficiency in free radical-cationic hybrid photocuring system; And the two keys in vinyl ether or the propenyl ether group are the two keys of electron rich, are difficult for being caused and homopolymerization by free radical, and especially mono vinyl ether or single propenyl ether product are even also be difficult for polymerization under the strong UV illumination of short period of time.Thereby, invent the free radical photo-initiation that contains mono vinyl ether or single propenyl ether group in a kind of molecule, join in free radical-cationic hybrid photocuring system with the polymerizable cationic light trigger, vinyl ether or propenyl ether group not only can participate in the migration that polymerization reduces light trigger in the solidifying product, and in storage process, this free radical photo-initiation that contains mono vinyl ether or single propenyl ether group is difficult for being caused autohemagglutination by self, overcome the difficult problem of other polymerizable light trigger poor storage stability, for light-curable ink, application and the popularization of products such as curable adhesive in packings such as food and medicine has very big meaning, is an innovative works with actual application value.
Summary of the invention
The technical problem to be solved in the present invention provides and contains mono vinyl ether or single propenyl ether group can cause response type light trigger of radical photopolymerization and preparation method thereof, and a kind of free radical photo-initiation that contains mono vinyl ether or single propenyl ether group and preparation method thereof namely is provided.The present invention adopt vulcabond respectively with the small molecules free radical photo-initiation proceed step by step reaction of hydroxyl mono vinyl ether or hydroxyl list propenyl ether, hydroxyl, prepare and not only contain mono vinyl ether or single propenyl ether group, but also contain the light trigger of a photosensitive group, namely prepare the free radical photo-initiation that product of the present invention contains mono vinyl ether or single propenyl ether group.
In order to address the above problem, the technical solution used in the present invention is:
The invention provides a kind of free radical photo-initiation that contains mono vinyl ether or single propenyl ether group, the described general structure that contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group is:
Described R
1Be Toluene-2,4-diisocyanate, the 4-vulcabond is except the part the-NCO, or isophorone diisocyanate is except the part the-NCO, or 2,4 '-diphenylmethanediisocyanate is except the part the-NCO, or Methylcyclohexyl diisocyanate is except the part the-NCO, or 4-MDPM-3,4 '-vulcabond is except the part the-NCO, or 2, and 4 '-diphenyl sulfide vulcabond is except the part the-NCO;
R
1The concrete structure formula as follows:
(Toluene-2,4-diisocyanate, the 4-vulcabond is except the part the-NCO),
(isophorone diisocyanate is except the part the-NCO),
(2,4 '-diphenylmethanediisocyanate is except the part the-NCO),
(Methylcyclohexyl diisocyanate is except the part the-NCO),
(4-MDPM-3,4 '-vulcabond is except the part the-NCO),
(2,4 '-diphenyl sulfide vulcabond is except the part the-NCO);
Described R
2For the 4-hydroxy butyl vinyl ether except the part the-OH, or the Diethylene Glycol mono vinyl ether is except the part the-OH, or 2-hydroxyethyl propenyl ether is except the part the-OH, or 3-hydroxypropyl propenyl ether is except the part the-OH, or 4-hydroxybutyl propenyl ether is except the part the-OH, or 6-hydroxyl hexyl propenyl ether is except the part the-OH;
R
2The concrete structure formula as follows:
(the 4-hydroxy butyl vinyl ether is except the part the-OH),
(the Diethylene Glycol mono vinyl ether is except the part the-OH),
(be 2-hydroxyethyl propenyl ether during n=2 except the part the-OH, be 3-hydroxypropyl propenyl ether during n=3 except the part the-OH, being 4-hydroxybutyl propenyl ether during n=4 except the part the-OH, is 6-hydroxyl hexyl propenyl ether during n=6 except the part the-OH);
Described R
3For light trigger 2959 is that 2-hydroxy-2-methyl-to hydroxyethyl ether phenyl-acetone-1 is except linking to each other with ethyl-part the OH, or light trigger 1173 is 2-hydroxy-2-methyl-phenyl-acetone-1 except the part the-OH, or the 4-dihydroxy benaophenonel is except the part the-OH, or 2-hydroxyl-thioxanthone is except the part the-OH, or the 7-hydroxy-4-methylcoumarin is except the part the-OH.
R
3The concrete structure formula as follows:
(light trigger 2959 except link to each other with ethyl-part the OH),
(light trigger 1173 is except the part the-OH),
(the 4-dihydroxy benaophenonel is except the part the-OH),
(2-hydroxyl thioxanthone is except the part the-OH),
(the 7-hydroxy-4-methylcoumarin is except the part the-OH).
A kind of above-mentioned preparation method who contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group, described preparation method may further comprise the steps:
A, at first in reaction vessel, add vulcabond, hydroxyl mono vinyl ether or hydroxyl list propenyl ether and carry out the ammonia esterification, temperature of reaction system is 30～45 ℃, with in the reaction system after testing-the NCO mass content be down to certain value and invariable serve as the foundation of judging reaction end; Described vulcabond-NCO and hydroxyl mono vinyl ether or hydroxyl list propenyl ether-mol ratio of OH between the two is 2:1;
After b, step a reaction finishes, the small molecules free radical photo-initiation, solvent, stopper and the catalyzer that then add hydroxyl in its reaction vessel, make the small molecules free radical photo-initiation of hydroxyl of adding and product that step a generates under heating condition, proceed the ammonia esterification, temperature of reaction system is 45～60 ℃, react under the lucifuge, with in the reaction system after testing-to be lower than 0.1% be the foundation of judging reaction end for the mass content of NCO; Reaction finishes back underpressure distillation desolventizing, obtains the free radical photo-initiation that product contains mono vinyl ether or single propenyl ether group after the desolventizing;
Generate among the described step a product-the small molecules free radical photo-initiation of NCO and hydroxyl-mol ratio between the OH is 1:1～1.05, the consumption of described solvent accounts for 30～50% of reaction raw materials total mass, the consumption of described stopper accounts for 0.1～0.2% of reaction raw materials total mass, and described catalyst consumption accounts for 0.05～0.10% of reaction raw materials total mass; Described raw material total mass is the quality sum of three kinds of raw materials of small molecules free radical photo-initiation of vulcabond, hydroxyl mono vinyl ether or hydroxyl list propenyl ether and the hydroxyl of adding in the reaction.
Preparation method according to the above-mentioned free radical photo-initiation that contains mono vinyl ether or single propenyl ether group, vulcabond described in the step a is Toluene-2,4-diisocyanate, 4-vulcabond, or isophorone diisocyanate, or 2,4 '-diphenylmethanediisocyanate, or Methylcyclohexyl diisocyanate, or 4-MDPM-3,4 '-vulcabond, or 2,4 '-diphenyl sulfide vulcabond.
According to the preparation method of the above-mentioned free radical photo-initiation that contains mono vinyl ether or single propenyl ether group, the mono vinyl ether of hydroxyl described in the step a is 4-hydroxy butyl vinyl ether or Diethylene Glycol mono vinyl ether; Described hydroxyl list propenyl ether is 2-hydroxyethyl propenyl ether, or 3-hydroxypropyl propenyl ether, or 4-hydroxybutyl propenyl ether, or 6-hydroxyl hexyl propenyl ether.
Preparation method according to the above-mentioned free radical photo-initiation that contains mono vinyl ether or single propenyl ether group, the small molecules free radical photo-initiation of hydroxyl described in the step b is that light trigger 2959 is 2-hydroxy-2-methyl-to hydroxyethyl ether phenyl-acetone-1, or light trigger 1173 is 2-hydroxy-2-methyl-phenyl-acetone-1, or 4-dihydroxy benaophenonel, or 2-hydroxyl-thioxanthone, or 7-hydroxy-4-methylcoumarin.
According to the preparation method of the above-mentioned free radical photo-initiation that contains mono vinyl ether or single propenyl ether group, solvent described in the step b is butanone, or pimelinketone, or toluene, or dimethylbenzene.
According to the preparation method of the above-mentioned free radical photo-initiation that contains mono vinyl ether or single propenyl ether group, stopper described in the step b is para benzoquinone, or tertiary butyl para benzoquinone.
According to the preparation method of the above-mentioned free radical photo-initiation that contains mono vinyl ether or single propenyl ether group, catalyzer described in the step b is dibutyl tin laurate, or N, the N-dimethylcyclohexylamine, or five methyl diethylentriamine, or diethyl cyclohexylamine, or triethylenediamine.
The raw material " 2; 4 '-diphenylmethanediisocyanate; Methylcyclohexyl diisocyanate; 4-MDPM-3; 4 '-vulcabond and 2,4 '-diphenyl sulfide vulcabond " that the present invention adopts comes from " Liu Yijun, urethane raw and auxiliary agent handbook [M]; Beijing: Chemical Industry Press, 2005 ".Wherein 2,4 '-diphenylmethanediisocyanate (CAS number: 5873-54-1) come from the 9th page; Methylcyclohexyl diisocyanate comes from the 40th page; 4-MDPM-3, and 4 '-vulcabond (CAS number: 75790-84-0) with 2,4 '-diphenyl sulfide vulcabond (CAS number: 75790-87-3) come from the 41st page.
The raw material " 2-hydroxyethyl propenyl ether; 3-hydroxypropyl propenyl ether; 4-hydroxybutyl propenyl ether and 6-hydroxyl hexyl propenyl ether " that the present invention adopts comes from the patent of invention of the patent No. 201110254823.3, and the patent of invention name is called a kind of light-cured polyurethane acrylate vinyl/propenyl ether hydridization prepolymer and preparation method thereof.Perhaps please refer to: Li Shujuan, the synthetic and photopolymerization dynamics research of acrylate-propenyl ether hybrid monomers, master thesis, Beijing University of Chemical Technology.
Positive beneficial effect of the present invention:
1, technical solution of the present invention employing hydroxyl mono vinyl ether or hydroxyl list propenyl ether are one of main raw material, its toxicity is low, and the reactive behavior height with isocyanic ester, desired reaction temperature is low in the preparation process, significantly reduced the energy consumption that heat-processed causes thus, thereby reduced cost, had remarkable economic efficiency and social benefit; In addition, whole process of preparation all utilizes-reaction of NCO and-OH, preparation technology is simple,-NCO and mol ratios such as-OH is basically, approach absolutely conversion, thereby prevented residual side effects such as polyisocyanates effectively, belong to the friendly process of energy-conserving and environment-protective.
2, the prepared product of the present invention contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group in storage process, because double bond containing mono vinyl ether or single propenyl ether group are difficult for being initiated and autohemagglutination, thereby stability in storage is good, has solved the relatively poor difficult problem of other polymerizable light trigger stability in storagies in the prior art.
3, the prepared product of the present invention free radical photo-initiation and the polymerizable cationic light trigger one that contain mono vinyl ether or single propenyl ether group is used from free radical-cationic hybrid photocuring system, the mono-vinyl ether group of itself or the participation polymerization of single propenyl ether group and transformation efficiency are higher, make the part relic of light trigger and decomposition be connected in the formed polymkeric substance with chemical bond-linking, thereby the transfer ability of light trigger and relic in the reduction solidifying product can be used in the photocuring product of packing such as food and medicine.
4, product of the present invention contain the polymerizable free radical photo-initiation of mono-vinyl ether group or single propenyl ether group by mono-vinyl ether compound or single propenyl ether compound, the vulcabond of hydroxyl, have the compound of light-initiated activity to synthesize according to fixing mole proportioning reaction.This polymerizable free radical photo-initiation that contains mono-vinyl ether group or single propenyl ether group is suitable for free radical-cationic hybrid photocuring system, and salt is had sensibilization, improves the light-initiated efficient of photoinitiator system and to the capacity usage ratio of light; The vinyl ether group of self or propenyl ether group participate in cationoid polymerisation, speed of reaction is fast, the transformation efficiency height, and not only the migration amount is low in the photocuring product, and having overcome the shortcoming of other polymerizable light triggers easy autohemagglutinations, light stability difference, stability in storage is good; In addition, be used for the advantage that the radical photoinitiator curing system has low migration and high stability equally.Can be used in sizing agent that UV solidifies, coating, the printing ink, safe and reliable, application and the popularization in food and drug packaging has very big meaning for the photocuring product.
Four, description of drawings:
Fig. 1: the product of the embodiment of the invention 1 preparation contains the free radical photo-initiation H-T-2959 of mono-vinyl ether group and the uv absorption spectra of small molecules free radical photo-initiation 2959; The ultraviolet maximum absorption wavelength λ of product H-T-2959 of the present invention
MaxAt the 275nm place, in molar absorptivity ε=1.608 * 10 of this wavelength
4L/molcm, uv-absorbing intensity is suitable with industrial small molecules free radical photo-initiation 2959 commonly used, illustrates that product H-T-2959 of the present invention also is a kind of light trigger very strong to ultraviolet absorption ability.
Fig. 2: the product of the embodiment of the invention 1 preparation contains free radical photo-initiation H-T-2959 infrared absorption spectrum (KBr, the cm of mono-vinyl ether group
-1): 1662 cm
-1Be C=O stretching vibration absorption peak in the aryl ketones, 1710 cm
-1Be C=O stretching vibration absorption peak in the amido linkage, 1617cm
-1Be C=C stretching vibration absorption peak, 1222 cm
-1, 1059 cm
-1For among=the C-O-C near the C-O stretching vibration absorption peak of two keys with apart from two key C-O stretching vibration absorption peaks far away, 2872 cm
-1Be the stretching vibration absorption peak of C-H in the symmetrical methyl, verified the molecular structure of H-T-2959.
Fig. 3: the product of the embodiment of the invention 1 preparation contains the free radical photo-initiation H-T-2959 of mono-vinyl ether group
1The H-NMR nmr spectrum (
1H-NMR, 300MHz, CDCl
3, δ ppm): 3.9857 ~ 4.0071(d 1H) is CH
2Terminal 1 H of=CH-O-, 4.1982 ~ 4.2600(d 1H) is CH
2Terminal 2 H of=CH-O-, 6.4455 ~ 6.4984(m 1H) is=H of CH-O-that 2.1896(s 3H) is-CH on the phenyl ring
3H, 6.9723 ~ 6.9945(d, 2H) be near on the phenyl ring-the substituent Ar-H of O-, 8.0614 ~ 8.0835(d 2H) be-the substituent Ar-H of C=O that 1.6350(s 6H) is symmetry-CH on the close phenyl ring
3H, further verified the H-T-2959 molecular structure.
Fig. 4: the product of the embodiment of the invention 2 preparations contains the free radical photo-initiation H-T-1173 of mono-vinyl ether group and the uv absorption spectra of small molecules free radical photo-initiation 1173; H-T-1173 is in molar absorptivity ε=0.915 * 10 at 244nm place
4L/mol.cm, uv-absorbing intensity is almost suitable with industrial small molecules free radical photo-initiation 1173 commonly used, illustrates that product H-T-1173 of the present invention also is a kind of light trigger stronger to ultraviolet absorption ability.
Fig. 5: the product of the embodiment of the invention 2 preparations contains free radical photo-initiation H-T-1173 infrared absorption spectrum (KBr, the cm of mono-vinyl ether group
-1): 3341cm
-1Be N-H stretching vibration absorption peak, 1739 cm
-1Be C=O stretching vibration absorption peak, 1617cm
-1Be C=C stretching vibration absorption peak, 1228 cm
-1Be C-O stretching vibration absorption peak, 2872 cm
-1Be the stretching vibration absorption peak of C-H in the symmetrical methyl, 1390 cm
-1, 1365 cm
-1For C-H flexural vibration absorption peak in the symmetrical methyl that connects tertiary carbon atom, verified the H-T-1173 molecular structure.
Five, embodiment:
Following examples only in order to further specify the present invention, do not limit content of the present invention.
Embodiment 1:
A kind of free radical photo-initiation H-T-2959 that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product H-T-2959 of the present invention is with 4-hydroxy butyl vinyl ether, Toluene-2,4-diisocyanate, and 4-vulcabond and light trigger 2959 are prepared from for basic raw material.
Embodiment 2: the preparation method of the embodiment of the invention 1 product H-T-2959
A kind of preparation method who contains the free radical photo-initiation H-T-2959 of mono-vinyl ether group of the embodiment of the invention 1 described product, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, then under 45 ± 2 ℃ of constant temperatures, carry out the ammonia esterification, when the mass content of measurement-NCO reaches 14.5 ± 0.5% and almost no longer be reduced to reaction end, the structural formula of reaction back gained intermediate product is:
After b, step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 200mL butanone gradually, in 30 ± 1min, add; Add 0.60g para benzoquinone and 0.30g dibutyl tin laurate again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, it is reaction end when the mass content of measurement-NCO is lower than 0.1%, reaction finishes the back decompression and steams butanone, obtain 342.3g light yellow viscous liquid shape product, be and have a kind of free radical photo-initiation product---H-T-2959 that contains the mono-vinyl ether group of the products obtained therefrom of the present invention of structural formula among the embodiment 1, productive rate is 66.6%.
Embodiment 3:
A kind of free radical photo-initiation H-T-1173 that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product H-T-1173 of the present invention is with 4-hydroxy butyl vinyl ether, Toluene-2,4-diisocyanate, and 4-vulcabond and light trigger 1173 are prepared from for basic raw material.
Embodiment 4: the preparation method of the embodiment of the invention 3 product H-T-1173
A kind of preparation method who contains the free radical photo-initiation H-T-1173 of mono-vinyl ether group of the embodiment of the invention 3 described products, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, then under 45 ± 2 ℃ of constant temperatures, carry out the ammonia esterification, when the mass content of measurement-NCO reaches 14.5 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 172.4g (1.05mol) light trigger 1173 and 200mL toluene gradually, in 30 ± 1min, add, add 0.60g para benzoquinone and 0.30g dibutyl tin laurate again, carry out the ammonia esterification under 60 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams toluene, obtain 308.7g white solid powdery product, be and have free radical photo-initiation product---the H-T-1173 that the product another kind of the present invention of structural formula among the embodiment 3 contains the mono-vinyl ether group, productive rate 68.0%.
Embodiment 5:
A kind of free radical photo-initiation H-T-BP that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with 4-hydroxy butyl vinyl ether, Toluene-2,4-diisocyanate, and 4-vulcabond and 4-dihydroxy benaophenonel are that basic raw material is prepared from.
Embodiment 6:
A kind of preparation method who contains the free radical photo-initiation H-T-BP of mono-vinyl ether group of the embodiment of the invention 5 described products, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, the control temperature is 30 ± 2 ℃, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, then under 45 ± 2 ℃ of constant temperatures, carry out the ammonia esterification, when the mass content of measurement-NCO reaches 14.5 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 208.1g (1.05mol) 4-dihydroxy benaophenonel and 200mL pimelinketone gradually, in 30 ± 1min, add, add 0.60g para benzoquinone and 0.40g dibutyl tin laurate again, carry out the ammonia esterification under 60 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams pimelinketone, obtain 313.3g faint yellow solid powdery product, a kind of free radical photo-initiation product---the H-T-BP that contains the mono-vinyl ether group that namely has the embodiment of the invention 5 described product structure formulas, productive rate 64.1%.
Embodiment 7:
A kind of free radical photo-initiation H-T-TX that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with 4-hydroxy butyl vinyl ether, Toluene-2,4-diisocyanate, and 4-vulcabond and 2-hydroxyl-thioxanthone are that basic raw material is prepared from.
Embodiment 8:
A kind of preparation method who contains the free radical photo-initiation H-T-TX of mono-vinyl ether group of the embodiment of the invention 7 described products, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 14.5 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 239.4g (1.05mol) 2-hydroxyl-thioxanthone and 200mL pimelinketone gradually, in 30 ± 1min, add, add 0.60g para benzoquinone and 0.40g dibutyl tin laurate again, carry out the ammonia esterification under 60 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams pimelinketone, obtain 321.2g faint yellow solid powdery product, be a kind of free radical photo-initiation product---the H-T-TX that contains the mono-vinyl ether group with the embodiment of the invention 7 described product structure formulas, productive rate 62.0%.
Embodiment 9:
A kind of free radical photo-initiation H-T-MC that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with 4-hydroxy butyl vinyl ether, Toluene-2,4-diisocyanate, and 4-vulcabond and 7-hydroxy-4-methylcoumarin are that basic raw material is prepared from.
Embodiment 10:
A kind of preparation method who contains the free radical photo-initiation H-T-MC of mono-vinyl ether group of the embodiment of the invention 9 products, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 14.5 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 184.9g (1.05mol) 7-hydroxy-4-methylcoumarin and 200mL pimelinketone gradually, in 30 ± 1min, add, add 0.60g para benzoquinone and 0.40g dibutyl tin laurate again, carry out the ammonia esterification under 60 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams pimelinketone, obtain 301.5g faint yellow solid powdery product, the another kind that namely has the embodiment of the invention 9 described product structure formulas contains free radical photo-initiation product---the H-T-MC of mono-vinyl ether group, productive rate 64.7%.
Embodiment 11:
A kind of free radical photo-initiation H-I-2959 that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is to be that basic raw material is prepared from 4-hydroxy butyl vinyl ether, isophorone diisocyanate and light trigger 2959.
Embodiment 12:
A kind of preparation method who contains the free radical photo-initiation H-I-2959 of mono-vinyl ether group of the embodiment of the invention 11 products, this preparation method's detailed step is as follows:
A, at first 222g (1mol) isophorone diisocyanate is joined be equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 12.4 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 200mL dimethylbenzene gradually, in 30 ± 1min, add, add 0.70g para benzoquinone and 0.40g dibutyl tin laurate again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams dimethylbenzene, obtain 345.6g light yellow viscous liquid shape product, the another kind that namely has the embodiment of the invention 11 described product structure formulas contains free radical photo-initiation product---the H-I-2959 of mono-vinyl ether group, productive rate 61.5%.
Embodiment 13:
A kind of free radical photo-initiation H-M-2959 that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with 4-hydroxy butyl vinyl ether, 2, and 4 '-diphenylmethanediisocyanate and light trigger 2959 are prepared from for basic raw material.
Embodiment 14:
A kind of preparation method who contains the free radical photo-initiation H-M-2959 of mono-vinyl ether group of the embodiment of the invention 13 products, this preparation method's detailed step is as follows:
A, at first with 250g (1mol) 2,4 '-diphenylmethanediisocyanate joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 11.5 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 250mL butanone gradually, in 30 ± 1min, add, add 0.70g tertiary butyl para benzoquinone and 0.40g dibutyl tin laurate again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams butanone, obtain 364.1g light yellow viscous liquid shape product, be the another kind with the embodiment of the invention 13 described product structures and contain free radical photo-initiation product---the H-M-2959 of mono-vinyl ether group, productive rate 61.7%.
Embodiment 15:
A kind of free radical photo-initiation H-HT-2959 that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is to be that basic raw material is prepared from 4-hydroxy butyl vinyl ether, Methylcyclohexyl diisocyanate and light trigger 2959.
Embodiment 16:
A kind of preparation method who contains the free radical photo-initiation H-HT-2959 of mono-vinyl ether group of the embodiment of the invention 15 described products, this preparation method's detailed step is as follows:
A, at first 180g (1mol) Methylcyclohexyl diisocyanate is joined be equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 14.2 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 200mL butanone gradually, in 30 ± 1min, add, add 0.60g para benzoquinone and 0.30g N again, the N-dimethylcyclohexylamine, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams butanone, obtain 367.1g light yellow viscous liquid shape product, be free radical photo-initiation product---the H-HT-2959 that the another kind with the embodiment of the invention 15 described product structures contains the mono-vinyl ether group, productive rate 70.6%.
Embodiment 17:
A kind of free radical photo-initiation H-MD-2959 that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with 4-hydroxy butyl vinyl ether, 4-MDPM-3, and 4 '-vulcabond and light trigger 2959 are prepared from for basic raw material.
Embodiment 18:
A kind of preparation method who contains the free radical photo-initiation H-MD-2959 of mono-vinyl ether group of the embodiment of the invention 17 described products, this preparation method's detailed step is as follows:
A, at first with 264g (1mol) 4-MDPM-3,4 '-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 11.1 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 250mL butanone gradually, in 30 ± 1min, add, add 0.70g para benzoquinone and 0.40g five methyl diethylentriamine again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams butanone, obtain 380.5g light yellow viscous liquid shape product, be the another kind with the embodiment of the invention 17 described product structures and contain free radical photo-initiation product---the H-MD-2959 of mono-vinyl ether group, productive rate 63.0%.
Embodiment 19:
A kind of free radical photo-initiation H-DS-2959 that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with 4-hydroxy butyl vinyl ether, 2, and 4 '-diphenyl sulfide vulcabond and light trigger 2959 are prepared from for basic raw material.
Embodiment 20:
A kind of preparation method who contains the free radical photo-initiation H-DS-2959 of mono-vinyl ether group of the embodiment of the invention 19 described products, this preparation method's detailed step is as follows:
A, at first with 268g (1mol) 2,4 '-diphenyl sulfide vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 4-hydroxy butyl vinyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 10.9 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 250mL butanone gradually, in 30 ± 1min, add, add 0.70g para benzoquinone and 0.40g diethyl cyclohexylamine again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams butanone, obtain 392.3g light yellow viscous liquid shape product, be the another kind with the embodiment of the invention 19 described product structures and contain free radical photo-initiation product---the H-DS-2959 of mono-vinyl ether group, productive rate 64.5%.
Embodiment 21:
A kind of free radical photo-initiation D-T-2959 that contains the mono-vinyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with Diethylene Glycol mono vinyl ether, Toluene-2,4-diisocyanate, and 4-vulcabond and light trigger 2959 are prepared from for basic raw material.
Embodiment 22:
A kind of preparation method who contains the free radical photo-initiation D-T-2959 of mono-vinyl ether group of the embodiment of the invention 21 described products, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 132g (1mol) Diethylene Glycol mono vinyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 13.7 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 200mL butanone gradually, in 30 ± 1min, add, add 0.60g para benzoquinone and 0.30g triethylenediamine again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams butanone, obtain 357.2g light yellow viscous liquid shape product, the another kind that is the embodiment of the invention 21 described product structures contains free radical photo-initiation product---the D-T-2959 of mono-vinyl ether group, productive rate 67.4%.
Embodiment 23:
A kind of free radical photo-initiation EA-T-2959 that contains single propenyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with 2-hydroxyethyl propenyl ether, Toluene-2,4-diisocyanate, and 4-vulcabond and light trigger 2959 are prepared from for basic raw material.
Embodiment 24:
A kind of preparation method who contains the free radical photo-initiation EA-T-2959 of single propenyl ether group of the embodiment of the invention 23 described products, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 102g (1mol) 2-hydroxyethyl propenyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 15.2 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 200mL butanone gradually, in 30 ± 1min, add, add 0.60g para benzoquinone and 0.30g dibutyl tin laurate again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams butanone, obtain 362.5g light yellow viscous liquid shape product, be a kind of free radical photo-initiation product---the EA-T-2959 that contains single propenyl ether group with the embodiment of the invention 23 described product structures, productive rate 72.5%.
Embodiment 25:
A kind of free radical photo-initiation PA-T-2959 that contains single propenyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with 3-hydroxypropyl propenyl ether, Toluene-2,4-diisocyanate, and 4-vulcabond and light trigger 2959 are prepared from for basic raw material.
Embodiment 26:
A kind of preparation method who contains the free radical photo-initiation PA-T-2959 of single propenyl ether group of the embodiment of the invention 25 described products, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 116g (1mol) 3-hydroxypropyl propenyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 14.5 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 200mL butanone gradually, in 30 ± 1min, add, add 0.60g para benzoquinone and 0.30g dibutyl tin laurate again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams butanone, obtain 362.8g light yellow viscous liquid shape product, be the another kind with the embodiment of the invention 25 described product structures and contain free radical photo-initiation product---the PA-T-2959 of single propenyl ether group, productive rate 70.6%.
Embodiment 27:
A kind of free radical photo-initiation BA-T-2959 that contains single propenyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is with 4-hydroxybutyl propenyl ether, Toluene-2,4-diisocyanate, and 4-vulcabond and light trigger 2959 are prepared from for basic raw material.
Embodiment 28:
A kind of preparation method who contains the free radical photo-initiation BA-T-2959 of single propenyl ether group of the embodiment of the invention 27 described products, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 130g (1mol) 4-hydroxybutyl propenyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 13.8 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 200mL butanone gradually, in 30 ± 1min, add, add 0.60g para benzoquinone and 0.30g dibutyl tin laurate again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams butanone, obtain 362.8g light yellow viscous liquid shape product, be the another kind with the embodiment of the invention 27 described product structures and contain free radical photo-initiation product---the BA-T-2959 of single propenyl ether group, productive rate 68.7%.
Embodiment 29:
A kind of free radical photo-initiation HA-T-2959 that contains single propenyl ether group of product of the present invention, its concrete structure formula is:
Product of the present invention is that 4-vulcabond and light trigger 2959 are prepared from for basic raw material with 6-hydroxyl hexyl propenyl ether, Toluene-2,4-diisocyanate.
Embodiment 30:
A kind of preparation method who contains the free radical photo-initiation HA-T-2959 of single propenyl ether group of the embodiment of the invention 29 described products, this preparation method's detailed step is as follows:
A, at first with 174g (1mol) Toluene-2,4-diisocyanate, the 4-vulcabond joins and is equipped with in the reaction vessel that connects drying tube on thermometer, agitator, dropping funnel and the condenser, stir, 30 ± 2 ℃ of control temperature, add 158g (1mol) 6-hydroxyl hexyl propenyl ether gradually, in 30 ± 1min, add, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperatures, when the mass content of measurement-NCO reaches 12.7 ± 0.5% and almost no longer be reduced to reaction end, the concrete structure formula of reaction back gained intermediate product is:
B, after step a reaction finishes, in 45 ± 2 ℃ temperature downhill reaction container, add 235g (1.05mol) light trigger 2959 and 200mL butanone gradually, in 30 ± 1min, add, add 0.65g para benzoquinone and 0.35g dibutyl tin laurate again, carry out the ammonia esterification under 45 ± 2 ℃ of constant temperature lucifuge conditions, when the mass content of measurement-NCO is lower than 0.1%, be reaction end, reaction finishes the back decompression and steams butanone, obtain 366.0g light yellow viscous liquid shape product, be the another kind with the embodiment of the invention 29 described product structures and contain free radical photo-initiation product---the HA-T-2959 of single propenyl ether group, productive rate 65.8%.
Claims (8)
1. a free radical photo-initiation that contains mono vinyl ether or single propenyl ether group is characterized in that, the described general structure that contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group is:
Described R
1Be Toluene-2,4-diisocyanate, the 4-vulcabond is except the part the-NCO, or isophorone diisocyanate is except the part the-NCO, or 2,4 '-diphenylmethanediisocyanate is except the part the-NCO, or Methylcyclohexyl diisocyanate is except the part the-NCO, or 4-MDPM-3,4 '-vulcabond is except the part the-NCO, or 2, and 4 '-diphenyl sulfide vulcabond is except the part the-NCO;
Described R
2For the 4-hydroxy butyl vinyl ether except the part the-OH, or the Diethylene Glycol mono vinyl ether is except the part the-OH, or 2-hydroxyethyl propenyl ether is except the part the-OH, or 3-hydroxypropyl propenyl ether is except the part the-OH, or 4-hydroxybutyl propenyl ether is except the part the-OH, or 6-hydroxyl hexyl propenyl ether is except the part the-OH;
Described R
3For light trigger 2959 is that 2-hydroxy-2-methyl-to hydroxyethyl ether phenyl-acetone-1 is except linking to each other with ethyl-part the OH, or light trigger 1173 is 2-hydroxy-2-methyl-phenyl-acetone-1 except the part the-OH, or the 4-dihydroxy benaophenonel is except the part the-OH, or 2-hydroxyl-thioxanthone is except the part the-OH, or the 7-hydroxy-4-methylcoumarin is except the part the-OH.
2. described preparation method who contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group of claim 1 is characterized in that described preparation method may further comprise the steps:
A, at first in reaction vessel, add vulcabond, hydroxyl mono vinyl ether or hydroxyl list propenyl ether and carry out the ammonia esterification, temperature of reaction system is 30～45 ℃, with in the reaction system after testing-the NCO mass content be down to certain value and invariable serve as the foundation of judging reaction end; Described vulcabond-NCO and hydroxyl mono vinyl ether or hydroxyl list propenyl ether-mol ratio of OH between the two is 2:1;
After b, step a reaction finishes, the small molecules free radical photo-initiation, solvent, stopper and the catalyzer that then add hydroxyl in its reaction vessel, make the small molecules free radical photo-initiation of hydroxyl of adding and product that step a generates under heating condition, proceed the ammonia esterification, temperature of reaction system is 45～60 ℃, react under the lucifuge, with in the reaction system after testing-to be lower than 0.1% be the foundation of judging reaction end for the mass content of NCO; Reaction finishes back underpressure distillation desolventizing, obtains the free radical photo-initiation that product contains mono vinyl ether or single propenyl ether group after the desolventizing;
Generate among the described step a product-the small molecules free radical photo-initiation of NCO and hydroxyl-mol ratio between the OH is 1:1～1.05, the consumption of described solvent accounts for 30～50% of reaction raw materials total mass, the consumption of described stopper accounts for 0.1～0.2% of reaction raw materials total mass, and described catalyst consumption accounts for 0.05～0.10% of reaction raw materials total mass; Described raw material total mass is the quality sum of three kinds of raw materials of small molecules free radical photo-initiation of vulcabond, hydroxyl mono vinyl ether or hydroxyl list propenyl ether and the hydroxyl of adding in the reaction.
3. the preparation method who contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group according to claim 2, it is characterized in that: vulcabond described in the step a is Toluene-2,4-diisocyanate, 4-vulcabond, or isophorone diisocyanate, or 2,4 '-diphenylmethanediisocyanate, or Methylcyclohexyl diisocyanate, or 4-MDPM-3,4 '-vulcabond, or 2,4 '-diphenyl sulfide vulcabond.
4. the preparation method who contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group according to claim 2, it is characterized in that: the mono vinyl ether of hydroxyl described in the step a is 4-hydroxy butyl vinyl ether or Diethylene Glycol mono vinyl ether; Described hydroxyl list propenyl ether is 2-hydroxyethyl propenyl ether, or 3-hydroxypropyl propenyl ether, or 4-hydroxybutyl propenyl ether, or 6-hydroxyl hexyl propenyl ether.
5. the preparation method who contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group according to claim 2, it is characterized in that: the small molecules free radical photo-initiation of hydroxyl described in the step b is that light trigger 2959 is 2-hydroxy-2-methyl-to hydroxyethyl ether phenyl-acetone-1, or light trigger 1173 is 2-hydroxy-2-methyl-phenyl-acetone-1, or 4-dihydroxy benaophenonel, or 2-hydroxyl-thioxanthone, or 7-hydroxy-4-methylcoumarin.
6. the preparation method who contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group according to claim 2, it is characterized in that: solvent described in the step b is butanone, or pimelinketone, or toluene, or dimethylbenzene.
7. the preparation method who contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group according to claim 2, it is characterized in that: stopper described in the step b is para benzoquinone or tertiary butyl para benzoquinone.
8. the preparation method who contains the free radical photo-initiation of mono vinyl ether or single propenyl ether group according to claim 2, it is characterized in that: catalyzer described in the step b is dibutyl tin laurate, or N, the N-dimethylcyclohexylamine, or five methyl diethylentriamine, or diethyl cyclohexylamine, or triethylenediamine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106749689A (en) * | 2016-11-14 | 2017-05-31 | 嘉宝莉化工集团股份有限公司 | Whisker modified difunctional light trigger of nano-cellulose and preparation method thereof |
| CN115745844A (en) * | 2022-11-30 | 2023-03-07 | 厦门琪星新材料有限公司 | Photoinitiator, adhesive using photoinitiator and preparation methods of photoinitiator and adhesive |
| CN117025122A (en) * | 2023-10-08 | 2023-11-10 | 汕头市恒顺包装材料有限公司 | Lens cold-stamping film and preparation method thereof |
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| WO2001068602A1 (en) * | 2000-03-13 | 2001-09-20 | Perstorp Flooring Ab | A new oligomer compound and a use thereof |
| CN102584631A (en) * | 2011-06-16 | 2012-07-18 | 湖北固润科技股份有限公司 | Urethane polymeric monomer with end groups including vinyl ether and allyl ether and synthetic method thereof |
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| CN1102825A (en) * | 1993-07-02 | 1995-05-24 | 希巴-盖吉股份公司 | Functionalized photoinitiators, macromers thereof, and the use thereof |
| WO2001068602A1 (en) * | 2000-03-13 | 2001-09-20 | Perstorp Flooring Ab | A new oligomer compound and a use thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749689A (en) * | 2016-11-14 | 2017-05-31 | 嘉宝莉化工集团股份有限公司 | Whisker modified difunctional light trigger of nano-cellulose and preparation method thereof |
| CN106749689B (en) * | 2016-11-14 | 2019-04-09 | 嘉宝莉化工集团股份有限公司 | The whisker modified difunctional photoinitiator and preparation method thereof of nano-cellulose |
| CN115745844A (en) * | 2022-11-30 | 2023-03-07 | 厦门琪星新材料有限公司 | Photoinitiator, adhesive using photoinitiator and preparation methods of photoinitiator and adhesive |
| CN115745844B (en) * | 2022-11-30 | 2024-04-16 | 厦门琪星新材料有限公司 | Photoinitiator, adhesive using same and preparation methods of photoinitiator and adhesive |
| CN117025122A (en) * | 2023-10-08 | 2023-11-10 | 汕头市恒顺包装材料有限公司 | Lens cold-stamping film and preparation method thereof |
| CN117025122B (en) * | 2023-10-08 | 2024-02-06 | 汕头市恒顺包装材料有限公司 | Lens cold-stamping film and preparation method thereof |
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