CN103073659B - Water-soluble organic silicon macromolecular photoinitiator and preparation method thereof - Google Patents
Water-soluble organic silicon macromolecular photoinitiator and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 48
- 239000010703 silicon Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229920001558 organosilicon polymer Polymers 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 20
- 229920000178 Acrylic resin Polymers 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 16
- 150000003384 small molecules Chemical class 0.000 claims description 15
- -1 alkylamino radical acetophenones Chemical class 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 claims description 4
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical class C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 3
- 241000522215 Dipteryx odorata Species 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 1
- 230000001960 triggered effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 229920002521 macromolecule Polymers 0.000 description 8
- 229920002545 silicone oil Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000004103 aminoalkyl group Chemical group 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 0 *N(*)CCCOc(cc1)ccc1C(c1ccccc1)=O Chemical compound *N(*)CCCOc(cc1)ccc1C(c1ccccc1)=O 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a water-soluble organic silicon macromolecular photoinitiator and a preparation method thereof. The water-soluble organic silicon macromolecular photoinitiator and the preparation method have characterized in that an organic silicon polymer is in reaction with a micromolecular photoinitiator to prepare the water-soluble organic silicon macromolecular photoinitiator. The preparation method has the benefits as follows: (1) as the water-soluble organic silicon macromolecular photoinitiator has certain solubility in a water system,the photopolymerization of a water-soluble photopolymerization system is triggered to prepare an environmental-friendly material which is less harmful to the environment and the human body; (2) with outstanding low surface tension and low surface energy, the organic silicon macromolecular photoinitiator is endowed with automatic upfloating capability, so that the organic silicon macromolecular photoinitiator moves toward the surface of the system in the water system spontaneously, and finally the organic silicon macromolecular photoinitiator is distributed at concentration gradient in the water system to trigger the gradient polymerization, so that the a molecular weight gradient polymer is obtained; and (3), the preparation cost is low, the operation is simple, and the yield is high. The water-soluble organic silicon macromolecular photoinitiator overcomes the defects that the traditional micromolecular photoinitiator is easy to volatilize and yellow.
Description
Technical field
The present invention relates to a kind of macromolecular photoinitiator, particularly a kind of water-soluble organic silicon macromolecular photoinitiator, the synthetic method of this macromolecular photoinitiator and the purposes in aqueous systems gradient polymeric thereof.
Background technology
Gradient polymer refers to that the key element (for example, composition or structure) that forms polymkeric substance is the character of continuous gradient variation, material and a kind of type material that function also changes in gradient along a direction by a side direction opposite side.Molecular weight is a fundamental of polymkeric substance, and it all has a great impact the use properties of polymkeric substance and processing characteristics.When the molecular weight of polymkeric substance changes, the performance of polymkeric substance is as in mechanical property (intensity etc.), optical property (specific refractory power etc.), thermal property (second-order transition temperature etc.), electric property (specific conductivity etc.), processing characteristics (rheological etc.) etc., one or more can change thereupon.When the molecular weight of polymkeric substance is changed by a side direction opposite side continuous gradient along a direction, can make the performance of polymkeric substance also occur that continuous gradient changes, the polymkeric substance that this molecular weight is continuous gradient variation along a direction by a side direction opposite side is molecular weight gradient polymer.
Light trigger is one of photopolymerisable important factor of impact, and it can absorb UV-light or visible radiation energy, makes oligopolymer and thinner by liquid state, are transformed into rapidly the compound of solid matter.Traditional small molecules radical photopolymerization initiator and the photolysis debris remaining in system easily move and volatilization, and smell and toxicity, appear in material aging xanthochromia after making to solidify, and restricted the application of photocuring system at aspects such as food and drug packages.In addition, still there are many shortcomings in traditional Photopolymer System, and for example active dilution body has volatility, and environment and human body are had to certain harm etc.Therefore with the water-soluble macromolecule light trigger of active group trigger monomer and oligopolymer polymerization in aqueous systems, become the important development direction in this field.On water-soluble macromolecule light trigger main chain or side chain, be connected to optical active group, after absorbing radiation energy, produce living radical and cause water-based Photopolymer System crosslinking curing.And in photopolymerization, when if water-soluble light trigger is the Gradient distribution of successively decreasing successively in polymerization system from upper layer to deep layer, under photoirradiation, can there is graded in the polymerization degree from the top layer of system to deep layer, after solidifying, the molecular weight distribution gradient of material, realizes gradient polymeric.Meanwhile, upper layer initiator concentration is maximum, can effectively reduce Surface Oxygen inhibition in photopolymerization.For reaching this purpose, need to carry out special molecular designing to water-soluble light trigger.Still there is not the macromolecular photoinitiator that can be applicable to aqueous systems gradient polymeric in this area.
Summary of the invention
The invention provides a kind of water-soluble organic silicon macromolecular photoinitiator for aqueous systems gradient polymeric, its preparation method and in the purposes of aqueous systems gradient polymeric.The inventor, by studying extensively and profoundly, from molecular structure, is incorporated into small molecules light trigger on organo-siloxane chain and generates hydrophilic radical by molecular designing, thus synthesizing water-solubility silicone macromolecule light trigger.The method provides new approaches for realizing the gradient polymeric of water-based system, and safety and environmental protection, simple.
Particularly, the present invention relates to following aspect:
1. the water-soluble organic silicon macromolecular photoinitiator that general formula is (I):
Wherein, q value is 1 or 2, p=3-q;
M is the residue of bitter almond oil camphor class, st-yrax ethers, alkylacetophenone class, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or camphorphorone micromolecular photoinitiator compound, wherein this small molecules photoinitiator compound is selected from hydroxyl, amino, carboxyl, halogen or epoxide group;
A representative:
Wherein the span of n can be 2～50, preferably 2～15, most preferably 2～8; The value of m can be 1～10, preferably 1～5, most preferably 1 or 2; R
7and R
8identical or different, and independently selected from C
1-12alkyl, N, O, the C that S heteroatoms replaces
1-12alkyl, C
1-12alkoxyl group or H;
R
1independently be selected from o,
R
2for C
3-12alkylidene group or the optional C from being replaced by alkyl, aryl and alkoxyl group
1-10alkylidene group, preferably C
3-6alkylidene group, propylidene most preferably;
R
3independently be selected from H, C
1-12alkyl or C
1-12aralkyl;
X
-be selected from halogen anion, preferably halogen anion X
-for Br
-.
2. according to the water-soluble organic silicon macromolecular photoinitiator of item 1, it is characterized in that described M is the residue of the small molecules photoinitiator compound of alkylacetophenone class and benzophenone, this small molecules photoinitiator compound is with being selected from hydroxyl, halogen, the group of amino and carboxyl.
3. according to the water-soluble organic silicon macromolecular photoinitiator of item 1-2 any one, it is characterized in that described R
7and R
8identical, and be C independently
1-12alkyl, preferred C
1-6alkyl, methyl more preferably.
4. according to the water-soluble organic silicon macromolecular photoinitiator of item 1-3 any one, it is characterized in that described R
1for O.
5. according to the water-soluble organic silicon macromolecular photoinitiator of item 1-4 any one, it is characterized in that described R
3for H.
6. according to the water-soluble organic silicon macromolecular photoinitiator of item 2, it is characterized in that this described small molecules photoinitiator compound is with hydroxyl.
7. a method for the water-soluble organic silicon macromolecular photoinitiator of preparation 1-6 any one, is characterized in that making the mixture that comprises following substance A and B to react:
Substance A is that general formula is the organosilicon polymer of (II):
Wherein the span of n ' can be 2～50, preferably 2～15, most preferably 2～8; The value of m ' can be 1～10, preferably 1～5, most preferably 1 or 2;
R
4and R
5identical or different, and independently selected from H, C
1-12alkyl or C
1-12aralkyl;
R
7' and ' R
8' identical or different, and independently selected from C
1-12alkyl, N, O, the C that S heteroatoms replaces
1-12alkyl, C
1-12alkoxyl group or H;
Substance B is that general formula is shown in (III):
X-R
2′-R
1′-M
(III)
Wherein the definition of M is as described in item 1;
R
1' be independently selected from o,
R
2' be C
3-12alkylidene group or the optional C from being replaced by alkyl, aryl and alkoxyl group
1-10alkylidene group, preferably C
3-6alkylidene group, propylidene most preferably;
X is independently selected from halogen atom F, Cl, Br and I, is preferably Cl and Br, more preferably Br.
8. according to the method described in item 7, it is characterized in that described R
7' and R
8' identical, and be C independently
1-12alkyl, preferred C
1-6alkyl, methyl more preferably.
9. according to the method described in item 7-8 any one, it is characterized in that described mixture also comprises the solvent that can dissolve described organosilicon polymer.
10. according to the method described in item 7-9 any one, the mol ratio that it is characterized in that described organosilicon polymer and described substance B compound is 1: (1～4).
11. according to method described in item 7-10 any one, it is characterized in that organosilicon polymer and described substance B temperature of reaction are not particularly limited, and can be any temperature in this area, preferably 40-90 ℃.
The composition of 12. 1 kinds of free redical photocurings, is characterized in that comprising the water-soluble organic silicon macromolecular photoinitiator described in a 1-6 any one.
13. according to the composition of item 12, it is characterized in that the described water-soluble organic silicon macromolecular photoinitiator that said composition comprises 0.2%-3%, photoresponse water soluble resin or the water-soluble monomer of the deionized water of 25%-85% and 14.8%-72%, the gross weight based on said composition.
14. according to the composition of item 13, it is characterized in that described photoresponse water soluble resin is selected from water-base epoxy (methyl) acrylic resin, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, water-based polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of water soluble acrylic acid esterification; Described water-soluble monomer is simple function group, one or more in bifunctional or polyfunctional group (methyl) acrylate monomer, vinylformic acid or acrylamide.
15. according to the method described in item 14, it is characterized in that preferred described water-soluble monomer is acrylamide.
Water-soluble organic silicon macromolecular photoinitiator described in 16. 1-6 any one it is characterized in that causing water soluble resin or water-soluble monomer is prepared the purposes in gradient polymer.
The purposes of 17. 16, is characterized in that described water soluble resin is selected from water-base epoxy (methyl) acrylic resin, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, water-based polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of water soluble acrylic acid esterification; Described hydrophilic monomer is simple function group, one or more in bifunctional or polyfunctional group (methyl) acrylate monomer, vinylformic acid or acrylamide.
Detailed Description Of The Invention
In the description of this invention below, except as otherwise clearly stating, the numerical value in the application all can be considered by word " approximately " to be modified.But the inventor has as far as possible accurately reported the numerical value in embodiment, although these numerical value inevitably comprise certain error.
In this application, unless clearly got rid of, concrete or preferred embodiment of the present invention can combine.In addition, every key element of the embodiment of the present application is the concrete preferred selection of the upper technical characterictic corresponding with it.If described upper technical characterictic can combine with other upper feature, the described key element of embodiment, described concrete preferred selection, also can combine with described other upper feature.These combinations should be regarded as a part for the original record content of the application.
Synthetic method
With preferred specific embodiments, explain synthetic route below, with difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
2-A synthesizes example:
The first step: 4-dihydroxy benaophenonel (HBP) is with excessive 1, and 3-dibromopropane, under the katalysis of sodium ethylate, nucleophilic substitution reaction occurs, synthetic product HBP-Br.
Second step: product HBP-Br and aminoalkyl silicone oil KF-8010 react, synthetic product W-Si-HBP
2-A.
Product W-Si-HBP
2the molecular weight result of-A is as follows:
According to embodiments more of the present invention, the preparation method of water-soluble organic silicon macromolecular photoinitiator is provided, the method comprises: the alkane reaction that (1) contains halogen with small molecules light trigger and the two ends of hydroxyl reaction group, the small molecules light trigger product that generation contains halogen, this reaction is reacted 2～30 hours at 20～80 ℃; (2) the small molecules light trigger that contains halogen reacts with aminoalkyl silicone oil, obtains difunctionality water-soluble organic silicon macromolecular photoinitiator end product, and this reaction is reacted 3～24 hours at 20～90 ℃.
Synthetic water-soluble organic silicon macromolecular photoinitiator not only has excellent light-initiated characteristic, compares with traditional oils dissolubility small molecules light trigger simultaneously, has significantly improved its solubleness in aqueous systems.
Synthesizing water-solubility silicone macromolecule light trigger alkane used in the present invention, with raw materials such as the light trigger of active group, organosilicon polymers, the material that is not limited to enumerate in the present invention, can be also other compound of the same type.
In the present invention, the active group that contains the light trigger of reactive group comprises, but be not limited to, hydroxyl, amino, carboxyl or its mixture, the described light trigger containing reactive group comprises, but be not limited to one or more in bitter almond oil camphor class, st-yrax ethers, alkylacetophenone class, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or camphorphorone micromolecular light trigger.
In the present invention, the catalyzer using can adopt the conventional catalyzer in this area, and there is no particular limitation to them.
The preparation method of the water-soluble organic silicon macromolecular photoinitiator that invention is described has one or more in following beneficial effect: the water-soluble system of (1) energy, thus can be used for preparation to environment and the less material of harm.(2) outstanding low surface tension and the low surface energy of silicone macromolecule light trigger makes it have from the ability that is sent to the migration of diagram of system face, finally in system, forms the Gradient distribution of concentration, and then causes gradient polymeric, obtains molecular weight gradient polymer.(3) preparation cost is low, simple to operate, and productive rate is high.It is volatile that macromolecular photoinitiator has solved traditional small molecules light trigger, decomposes fragment easily migration and disadvantage incompatible with system or that consistency is poor.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.In present specification, unless expressly stated otherwise,, all parts and per-cent are all based on weight.
Raw material sources
Methylene dichloride: Huai’an Chen Hong Chemical Co., Ltd.
Trolamine: Beijing chemical reagents corporation
Sodium Metal 99.5: Nanjing Hai Tong Chemical Co., Ltd.
Ethanol: Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing
4-dihydroxy benaophenonel (HBP): Qingdao abundant Photar Fine Chemical Co., Ltd
1,3-dibromopropane: Li Deshi (Beijing) chemical technology company limited
Aminoalkyl silicone oil (KF-8010, Mn=414): chemical company limited of Shanghai SHIN-ETSU HANTOTAI
Aminoalkyl silicone oil (X-22-161A, Mn=784): chemical company limited of Shanghai SHIN-ETSU HANTOTAI
Aminoalkyl silicone oil (X-22-161B, Mn=1450): chemical company limited of Shanghai SHIN-ETSU HANTOTAI
Acrylamide: Tianjin Fu Chen Chemical Co., Ltd.
Triphenyl phosphorus: Jiang Lai bio tech ltd, Shanghai
Bromine: Beijing blue or green limitless blessing Science and Technology Ltd.
Deionized water: Beijing University of Chemical Technology
Embodiment 1:
Hydrogen-abstraction difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
2-A's is synthetic
The first step: HBP-Br small molecules light trigger synthetic, in agitator, temperature are housed take into account the four-hole boiling flask of prolong, add respectively 0.69g (0.03mol) sodium and 25ml dehydrated alcohol, under room temperature condition, stir, after dissolving completely, sodium adds 5.94g (0.03mol) 4-dihydroxy benaophenonel (HBP), continue to stir 40 minutes, add 6.06g (0.03mol) 1,3-dibromopropane is warming up to 60 ℃ of reactions 4 hours under stirring.Question response finishes rear filtered while hot, revolve to steam and remove after alcohol solvent, by resulting crude product by the Methods For Purification of column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 20, obtain pure white crystal HBP-Br productive rate 86.50%, reaction formula is as follows:
Second step: hydrogen-abstraction difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
2-A's is synthetic, in the four-hole boiling flask that agitator, prolong and thermometer are housed, add respectively 7.38g (0.01mol) aminoalkyl silicone oil KF-8010,6.38g (0.02mol) HBP-Br and 20ml anhydrous acetonitrile, be warming up to 60 ℃ under agitation condition, react 20 hours.After question response finishes, revolve and steam solvent, by resulting crude product by the Methods For Purification of column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 20, obtains hydrogen-abstraction difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
2-A, productive rate 56.80%, reaction formula is as follows:
1H-NMR (the CDCl of the first step end product HBP-Br wherein
3, 600MH
z): δ=6.99-7.86 (9H, phenyl ring), δ=4.20 (2H ,-O-C
h 2), δ=3.65 (2H, Br-C
h 2), δ=2.39 (2H ,-CH
2-C
h 2-CH
2-); Second step end product W-Si-HBP
21H-NMR (the CDCl of-A
3, 600MH
z): 8=6.99-7.80 (18H, phenyl ring), δ=4.22 (4H ,-O-C
h 2-CH
2-CH
2-NH
2-), δ=3.30 (4H ,-O-CH
2-CH
2-C
h 2-NH
2-), δ=3.10 (4H ,-Si-CH
2-C
h 2-NH
2-), δ=2.50 (4H, O-CH
2-C
h 2-CH
2-NH
2-), δ=0.5 (4H, Si-C
h 2-), δ=0.00 (61H, C
h 3-Si-C
h 3).
Embodiment 2:
Cracking type difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-(2959)
2synthetic
The first step: 2959-Br small molecules light trigger synthetic, in round-bottomed flask, add respectively 2.62g (0.01mol) triphenyl phosphorus and 15ml methylene dichloride, under ice-water bath agitation condition, the mixture of 1.6g (0.01mol) bromine and 10ml methylene dichloride is slowly added drop-wise in round-bottomed flask with constant pressure funnel, after 10 minutes, add 2.24g (0.01mol) 2959 small molecules light triggers, continue to stir one hour.After reaction finishes, revolve and steam solvent.By resulting crude product, by the Methods For Purification of column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 8, obtains pure faint yellow product 2959-Br, productive rate 78.65%, and reaction formula is as follows:
Second step: cracking type difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-(2959)
2synthetic, in the four-hole boiling flask that agitator, prolong and thermometer are housed, add respectively 7.38g (0.01mol) aminoalkyl silicone oil KF-8010,5.74g (0.02mol) 2959-Br and 20ml anhydrous acetonitrile, be warming up to 70 ℃ under agitation condition, react 24 hours.Question response finishes, revolve and steam solvent, by resulting crude product, by the Methods For Purification of column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 5, obtains cracking type difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-(2959)
2, productive rate 62.30%, reaction formula is as follows:
Embodiment 3:
Hydrogen-abstraction four functionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
4-A's is synthetic.
The first step: E-Si-HBP
2synthesizing of-A macromolecular photoinitiator, by previously synthetic W-Si-HBP
2-A adds methylene dichloride standing with after the NaOH solution washing of 0.01mol/L three times, after solution layering, discards water layer, revolves and steams methylene chloride, obtains product E-Si-HBP
2-A, reaction formula is as follows:
Second step: hydrogen-abstraction four functionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
4-A's is synthetic, adds 12g (0.01mol) E-Si-HBP in the four-hole boiling flask that agitator, prolong and thermometer are housed
2-A (Mn is about 1200), 6.38g (0.02mol) HBP-Br and 20ml anhydrous acetonitrile, be warming up to 60 ℃ under stirring, react 20 hours.After question response finishes, revolve and steam solvent, by resulting crude product by the Methods For Purification of column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 10, obtains hydrogen-abstraction four functionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
4-A, productive rate 80.75%, reaction formula is as follows:
Embodiment 4:
Composite water dissolubility silicone macromolecule light trigger W-Si-HBP
2-(2959)
2synthetic.
The first step: E-Si-HBP
2synthesizing of-A macromolecular photoinitiator, method is as embodiment 3 the first steps, and reaction formula is as follows:
Second step: composite water dissolubility silicone macromolecule light trigger W-Si-HBP
2-(2959)
2synthetic, in the four-hole boiling flask that agitator, prolong and thermometer are housed, add 12g (0.01mol) E-Si-HBP
2-A (Mn is about 1200), 5.74g (0.02mol) 2959-Br and 20ml anhydrous acetonitrile, be warming up to 70 ℃ under stirring, react 24 hours.After question response finishes, revolve and steam solvent, by resulting crude product by the Methods For Purification of column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 8, obtains composite water dissolubility silicone macromolecule light trigger W-Si-HBP
2-(2959)
2productive rate is 49%, and reaction formula is as follows:
Embodiment 5-6:
Repeat the step of embodiment 1, difference is that the molecular weight of raw material silicone oil used is different, is shown in Table 1:
Embodiment 7
The object of the present embodiment is to illustrate can use the prepared water-soluble organic silicon macromolecular photoinitiator of embodiment 1 in aqueous systems, to cause polymerisation, prepares molecular weight gradient polymer.
Take the water-soluble organic silicon macromolecular photoinitiator W-Si-HBP in 0.01g embodiment 1
2it is 6mm that-A fully mixes rear immigration diameter with water-soluble monomer acrylamide (AM) 0.4g, deionized water 0.6g and trolamine 0.01g, height is in the cylindrical glass bottle of 40mm, standing 60 minutes, then, the cylindrical glass bottle that the mixture of clear is housed is placed under the curing machine of 1000 watts of UV and is exposed, make it that photochemical reaction occur, expose 50 minutes, AM is polymerized to polyacrylamide (PAM) Precipitation in water, its taking-up is inserted to vacuum drying oven and dry.
The present invention is by the right cylinder PAM obtaining before, vertically cut into slices in different heights place from top to bottom, XPS test and molecular weight test have been carried out in the surface of the PAM thin slice that is positioned at different vertical height again section being obtained, and the ratio that Si element accounts for all elements is from top to bottom respectively 14.31%, 12.86%, 11.00% and 8.53%.The PAM thin slice that is positioned at different vertical height that section is obtained is surveyed its molecular weight by gel liquid chromatography, and number-average molecular weight is followed successively by 0.2 * 10 from top to bottom
5, 0.5 * 10
5, 0.8 * 10
5, 1.2 * 10
5.
The invention has the beneficial effects as follows: a few class water-soluble organic silicon macromolecular photoinitiators of synthesized, have kept himself good photosensitivity, and had good water-soluble.Go for the photocuring environment of aqueous systems and prepare molecular weight gradient polymeric material, belonging to environmental friendliness shaped material.Synthetic method is simple, easy handling, the raw material cheapness that is easy to get.
Claims (11)
1. the water-soluble organic silicon macromolecular photoinitiator that general formula is (I):
Wherein, q value is 1 or 2, p=3-q;
M is the residue of bitter almond oil camphor class, st-yrax ethers, alkylacetophenone class, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or camphorphorone micromolecular photoinitiator compound, wherein this small molecules photoinitiator compound is selected from hydroxyl, amino, carboxyl, halogen or epoxide group;
A representative:
Wherein the span of n is 2～50; The value of m is 1～10; R
7and R
8identical or different, and independently selected from C
1-12alkyl, N, O, the C that S heteroatoms replaces
1-12alkyl, C
1-12alkoxyl group or H;
R
1independently be selected from
or
R
2can be C
3-12alkylidene group or the C optionally being replaced by alkyl, aryl and alkoxyl group
1-10alkylidene group;
R
3can independently be selected from H, C
1-12alkyl or C
1-12aralkyl;
X
-be selected from halogen anion.
2. according to the water-soluble organic silicon macromolecular photoinitiator of claim 1, wherein said M is the residue of the small molecules photoinitiator compound of alkylacetophenone class and benzophenone, wherein this small molecules photoinitiator compound is with being selected from hydroxyl, halogen, the group of amino and carboxyl; The span of described n is 2～15; The value of described m is 1～5; Described R
7and R
8identical, and independently selected from C
1-12alkyl; Described R
2for C
3-6alkylidene group; Described X
-for Br
-.
3. according to the water-soluble organic silicon macromolecular photoinitiator of claim 2, be wherein characterised in that described small molecules photoinitiator compound is with hydroxyl; The span of described n is 2～8; The value of described m is 1 or 2; Described R
7and R
8identical and be methyl; Described R
2for propylidene; Described R
1for O; Described R
3for H.
4. a method of preparing the water-soluble organic silicon macromolecular photoinitiator of claim 1, is characterized in that making the mixture that comprises following substance A and B to react:
Substance A is that general formula is the organosilicon polymer of (II):
Wherein the span of n ' is 2～50; The value of m ' is 1～10;
R
4and R
5identical or different, and independently selected from H, C
1-12alkyl or C
1-12aralkyl;
R
7' and R
8' identical or different, and independently selected from C
1-12alkyl, N, O, the C that S heteroatoms replaces
1-12alkyl, C
1-12alkoxyl group or H;
Substance B is that general formula is shown in (III):
X-R
2′-R
1′-M
(III)
Wherein the definition of M as claimed in claim 1;
R
1' be independently selected from
or
R
2' can be C
3-12alkylidene group or the C optionally being replaced by alkyl, aryl and alkoxyl group
1-10alkylidene group;
X is independently selected from halogen atom F, Cl, Br and I.
5. according to the method for the water-soluble organic silicon macromolecular photoinitiator of claim 4, it is characterized in that the span of described n ' is 2～15; The value of m ' is 1～5; Described R
7' and R
8' identical, and be selected from C
1-12alkyl; Described R
2' be C
3-12alkylidene group; Described X is selected from halogen atom Cl or Br.
6. according to the method for the water-soluble organic silicon macromolecular photoinitiator of claim 5, it is characterized in that the span of described n ' is 2～8; The value of described m ' is 1 or 2; Described R
4and R
5identical and be selected from H; Described R
7' and R
8' identical, and be methyl; Described R
1' be selected from O; Described R
2' be propylidene; Described X is selected from halogen atom Br.
7. method according to claim 4, is characterized in that described mixture also comprises the solvent that can dissolve described organosilicon polymer; The mol ratio of described organosilicon polymer and described substance B compound is 1: (1～4); Described organosilicon polymer and described substance B temperature of reaction are 40-90 ℃.
8. a composition for free redical photocuring, is characterized in that comprising water-soluble organic silicon macromolecular photoinitiator claimed in claim 1; The described water-soluble organic silicon macromolecular photoinitiator that described said composition comprises 0.2%-3%, photoresponse water soluble resin or the water-soluble monomer of the deionized water of 25%-85% and 14.8%-72%, the gross weight based on said composition.
9. composition according to claim 8, is characterized in that described photoresponse water soluble resin is selected from water-base epoxy (methyl) acrylic resin, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, water-based polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of water soluble acrylic acid esterification; Described water-soluble monomer is simple function group, one or more in bifunctional or polyfunctional group (methyl) acrylate monomer, vinylformic acid or acrylamide.
10. composition according to claim 9, is characterized in that described water-soluble monomer is acrylamide.
Water-soluble organic silicon macromolecular photoinitiator in 11. claims 1～3 described in any one is prepared the purposes in gradient polymer at initiation water soluble resin or water-soluble monomer, it is characterized in that described water soluble resin is selected from water-base epoxy (methyl) acrylic resin, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, water-based polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of water soluble acrylic acid esterification; Described water-soluble monomer is simple function group, one or more in bifunctional or polyfunctional group (methyl) acrylate monomer, vinylformic acid or acrylamide.
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