CN114163550A - Multifunctional macromolecular photoinitiator and preparation method thereof - Google Patents
Multifunctional macromolecular photoinitiator and preparation method thereof Download PDFInfo
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- CN114163550A CN114163550A CN202111530251.7A CN202111530251A CN114163550A CN 114163550 A CN114163550 A CN 114163550A CN 202111530251 A CN202111530251 A CN 202111530251A CN 114163550 A CN114163550 A CN 114163550A
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- photoinitiator
- maleic anhydride
- styrene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 28
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 17
- 150000003384 small molecules Chemical class 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000007127 saponification reaction Methods 0.000 claims description 10
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical group C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims description 9
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 7
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical group CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- -1 ammonium ions Chemical class 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000003999 initiator Substances 0.000 abstract description 7
- 150000008064 anhydrides Chemical class 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a multifunctional macromolecular photoinitiator and a preparation method thereof. The invention belongs to the field of macroinitiator, and the invention utilizes esterification reaction of anhydride and hydroxyl to graft a photoinitiator containing hydroxyl into a styrene/maleic anhydride copolymer with certain molecular weight to prepare the macroinitiator with controllable molecular weight and branching degree. The prepared multifunctional macromolecular photoinitiator has high activity, low toxicity, weak mobility and simple process steps, can be prepared into lipophilic, hydrophilic or amphiphilic initiators according to different requirements, is suitable for initiating and preparing polymer products with different types and different branching degrees, and can be used for practical application in the fields of printing ink, water treatment, papermaking, coating, adhesives and the like.
Description
Technical Field
The invention relates to the technical field of macroinitiators, in particular to a polyfunctionality macrophotoinitiator and a preparation method thereof.
Background
The ultraviolet radiation initiated polymerization has the characteristics of high efficiency and controllability, and is widely applied in the industries of printing ink, coating and the like. The essence is that the photoinitiator is rapidly cracked under the irradiation of ultraviolet light to generate active free radicals, so that monomers in a system are initiated to be polymerized. Generally, the photoinitiator mostly refers to small molecular photoinitiators such as benzophenone, Darocure1173, and arylformyl phosphine oxide, and the photoinitiators have strong migration capability, are free in the whole system, and are uniformly initiated.
However, the strong migration ability of small molecule photoinitiators also causes the limited application of small molecule photoinitiators in the fields of medicine, food, health and the like, because the small molecules often have certain toxicity, and when the small molecules are left in the system, the small molecule photoinitiators are exposed once being touched with hot water or solvents, so that the small molecule photoinitiators are harmful to human bodies, the environment or products. Secondly, the small molecular photoinitiator is easy to generate oxygen inhibition phenomenon, so that the reaction is insufficient, the problem is solved by increasing the using amount of the initiator or increasing an oxygen removal working section in the industry, but new problems of initiator residue, cost increase and the like are brought. In addition, the use of small molecule photoinitiators generally produces or produces only linear polymers, and branched, lightly crosslinked, or crosslinked products are clearly more advantageous for the abrasion resistant coating or water treatment industry.
Aiming at the problems, two main solutions for preparing a copolymerization type photoinitiator and a macromolecular photoinitiator are provided at present. For a copolymerization type photoinitiator, such as a vinyl-containing photoinitiator prepared by reacting methacryloyl chloride with 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, although the problems are effectively solved, unsaturated double bonds and the photoinitiator exist in the system at the same time, so that the storage and transportation of the photoinitiator are possibly at a greater risk; for macromolecular photoinitiator, the advantages of higher molecular weight, enrichment of initiation points and the like well solve the problems of migration, oxygen inhibition and the like. Meanwhile, one molecular chain contains a plurality of initiation points, so that the preparation method is more suitable for preparing branched or crosslinked products. However, at present, commercial macrophotoinitiators are still few, and even the reported macrophotoinitiators still have partial defects: 1. The initiation points are few, and the branching degree is low; 2. the carbon chain is taken as a main chain, and the oil solubility is taken as a main chain, so that the carbon chain has certain limitation; 3. the preparation process is complex, and the controllable number of initiator points is difficult to realize.
Disclosure of Invention
The invention aims to solve the technical pain of the conventional macromolecular photoinitiator and provides a novel multifunctional macromolecular photoinitiator and a preparation method thereof.
The invention provides a multifunctional macromolecular photoinitiator which is characterized in that the chemical structure of the macromolecular photoinitiator is shown as the following formula (1):
wherein R is1Is a small molecule photoinitiator residue, R2The photoinitiator is hydrogen group, metal ion or alkyl, the weight average molecular weight of the macromolecular photoinitiator is 5000-25000, and the functionality is 3-40.
Preferably or alternatively, the small molecule photoinitiator residue is selected from benzoin residue, 4-hydroxybenzophenone residue, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone residue, and the chemical structures thereof are shown as the following formulas (2), (3), (4):
preferably or alternatively, the metal ions may be sodium ions, potassium ions or ammonium ions;
preferably or alternatively, the alkyl group may be a C1-C12 alkyl group.
Preferably or alternatively, the photoinitiator is one or more of hydrophilic, lipophilic or amphiphilic.
The invention provides a preparation method of a multifunctional macromolecular photoinitiator, which comprises the following steps:
step 1, taking tetrahydrofuran as a solvent to prepare a linear styrene-maleic anhydride copolymer;
step 2, adding a small molecular photoinitiator, and carrying out esterification reaction with the styrene-maleic anhydride copolymer;
step 3, directly carrying out reduced pressure distillation; or adding alkyl alcohol and weak base aqueous solution for esterification and saponification, and then distilling under reduced pressure to obtain the macromolecular photoinitiator or the aqueous solution thereof.
Preferably or alternatively, when the styrene-maleic anhydride copolymer is prepared in the step 1, the molar ratio of the styrene to the maleic anhydride is 1.00: 1.00-1.00: 1.05.
Preferably or optionally, a small-molecule photoinitiator and a weak base are also added when the styrene-maleic anhydride copolymer is prepared; the molar ratio of the micromolecular photoinitiator to the maleic anhydride is 0.04: 1.00-0.40: 1.00; the molar ratio of the weak base to the maleic anhydride is 0: 1.00-1.85: 1.00.
Preferably or optionally, when the styrene-maleic anhydride copolymer is prepared in the step 1, the reaction temperature is 60-80 ℃,
preferably or optionally, in the step 2 and the step 3, the temperature of the esterification reaction is 60-80 ℃, and the temperature of the saponification reaction is 20-30 ℃.
The invention has the following beneficial effects:
(1) the invention utilizes the esterification reaction of anhydride and alcohol to graft and fix the micromolecule photoinitiator on the styrene-maleic anhydride copolymer to prepare the novel multifunctional macromolecule photoinitiator, can obviously reduce the migration capability of the micromolecule photoinitiator, and has the advantage of simple process. The invention can obtain the macromolecular photoinitiator with medium molecular weight by controlling the molar ratio of two monomers of the main chain monomer, so that the macromolecular photoinitiator has both reactivity and solubility.
The invention can control the molecular weight of the copolymer and the molar ratio of the copolymer to the micromolecular photoinitiator, and can adjust the functionality of the product in an expected way so as to prepare the product with different branching degrees and crosslinking degrees.
(2) The small molecular photoinitiator used in the invention is selected from benzoin, 4-hydroxybenzophenone and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, and the hydroxyl-containing photoinitiator has the advantage of low steric hindrance, reduces the difficulty of esterification reaction and reduces the production cost to a certain extent.
(3) R of the invention2The group may be a hydrogen radical, a metal ion or an alkyl alcohol residue: the metal ions and the hydrogen radical can improve the polarity of the macromolecular photoinitiator, so that the hydrophilicity and the water solubility of the product are obviously improved.
(4) The alkyl alcohol can also react with residual acid anhydride, so that the macromolecular photoinitiator can be effectively prevented from being hydrolyzed when meeting water, and the compatibility of the macromolecular photoinitiator with other high polymer materials is improved.
(5) The invention can also select the HLB value of the micromolecule photoinitiator participating in the esterification reaction, and further adjust the hydrophilicity and lipophilicity of the macromolecule photoinitiator, so that the photoinitiator is suitable for different occasions.
(6) The invention takes the copolymer of styrene and maleic anhydride as a macromolecular skeleton, and the side chain of the linear polymer is a small group, so that the problems that the polymer with a branched structure has large steric hindrance, and the structure and the reaction site can not be controlled and the like can be solved.
(7) The invention can obtain the macromolecular photoinitiator with medium molecular weight by controlling the proportion of two monomers in the styrene-maleic anhydride copolymer, so that the macromolecular photoinitiator has reaction activity and dissolvability.
(8) The invention can control the molecular weight of the copolymer and the molar ratio of the copolymer to the micromolecular photoinitiator, and can adjust the functionality of the product in an expected way so as to prepare the product with different branching degrees and crosslinking degrees.
(9) When the styrene-maleic anhydride copolymer is prepared, the molar ratio of styrene to maleic anhydride is 1.00: 1.00-1.00: 1.05; the molar ratio of the micromolecule photoinitiator to the maleic anhydride is 0.04: 1.00-0.40: 1.00; the molar ratio of the alkyl alcohol or weak base to the maleic anhydride is 0: 1.00-1.85: 1.00; the copolymerization reaction temperature of styrene-maleic anhydride is 60-80 ℃, the esterification reaction temperature is 60-80 ℃, and the saponification reaction temperature is 20-30 ℃. Wherein, when styrene-maleic anhydride is copolymerized, the monomer concentration is controlled to be 12.5-17.5% so as to obtain linear macromolecules with narrow molecular weight distribution, AIBN is used as an initiator, and the reaction time is 3-8 h. The esterification reaction time is controlled to be 2-8 h, the reaction is rapid and thorough because the content of the anhydride is far greater than that of the micromolecular photoinitiator, and pyridine or 4-dimethylaminopyridine is selected as a catalyst. During saponification, the weak base is added in a manner of dropwise adding the aqueous solution of the weak base, so that the phenomenon that local temperature is too high and initiating groups in a macromolecular photoinitiator are hydrolyzed and fall off is avoided, and the reaction lasts for 15-24 hours.
(10) The invention can prepare macromolecular photoinitiators with different HLB values according to different requirements by direct reduced pressure distillation or by adding weak base aqueous solution for esterification and saponification reaction and then reduced pressure distillation.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
The technical scheme for realizing the aim of the invention is a multifunctional macromolecular photoinitiator and a preparation method thereof, and is characterized in that the chemical structure of the macromolecular photoinitiator is shown as the following formula (1):
wherein R is1Is a small molecule photoinitiator residue, R2The photoinitiator is H, metal ions or alkyl alcohol residues, the weight average molecular weight of the macromolecular photoinitiator is 5000-25000, and the functionality is 3-40. The molecular weight of the macromolecular photoinitiatorIt is not desirable to be too high or too low, which may affect activity, solubility or may not function to reduce migration; particularly, the linear chain styrene-maleic anhydride polymer is taken as a framework, so that the problems of large steric hindrance, uncontrollable structure and the like caused by a branched structure are avoided; the functionality is controlled by the molecular weight of the styrene-maleic anhydride copolymer and the addition amount of the micromolecular photoinitiator, a small amount of micromolecular photoinitiator is added when the molecular weight is low, the low-functionality macromolecular initiator is prepared, the use amount of the micromolecular photoinitiator is increased when the molecular weight is high, and the high-functionality macromolecular photoinitiator is prepared.
The residue of the small molecular photoinitiator is selected from benzoin residue, 4-hydroxybenzophenone residue, and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone residue, and the chemical structures are shown as (2), (3) and (4):
the small molecular photoinitiator is selected from photoinitiators with hydroxyl and lower steric hindrance, so that the photoinitiator can be better grafted to a styrene-maleic anhydride skeleton.
The metal ions include sodium ions, potassium ions or ammonium ions. The metal ions are generated by the reaction of weak bases such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and ammonia water with residual acid anhydride in the macromolecular photoinitiator, and are used for improving the water solubility of the product.
The alkyl alcohol residue comprises the residue of C1-C12 monohydric or polyhydric alcohol after 1 active hydrogen is removed. The alkyl alcohol can react with residual anhydride in the macromolecular photoinitiator, so that the macromolecular photoinitiator can be prevented from being hydrolyzed in water, and lipophilicity and compatibility with other high polymer materials are improved.
The macromolecular photoinitiator is one of hydrophilic, lipophilic or amphiphilic. The macromolecular photoinitiator has different hydrophilic, lipophilic and amphiphilic properties, so that the macromolecular photoinitiator is suitable for various occasions.
The preparation method of the multifunctional macromolecular photoinitiator comprises the following steps:
1) taking tetrahydrofuran as a solvent to prepare a linear styrene-maleic anhydride copolymer;
2) adding a micromolecular photoinitiator, and carrying out esterification reaction with the styrene-maleic anhydride copolymer;
3) directly carrying out reduced pressure distillation; or adding alkyl alcohol and weak base aqueous solution for esterification and saponification, and then distilling under reduced pressure to obtain the macromolecular photoinitiator or the aqueous solution thereof.
Further, when the styrene-maleic anhydride copolymer is prepared, the molar ratio of the styrene to the maleic anhydride is 1.00: 1.00-1.00: 1.05; the molar ratio of the micromolecule photoinitiator to the maleic anhydride is 0.04: 1.00-0.40: 1.00; the molar ratio of the weak base to the maleic anhydride is 0: 1.00-1.85: 1.00; the copolymerization reaction temperature of styrene-maleic anhydride is 60-80 ℃, the esterification reaction temperature is 60-80 ℃, and the saponification reaction temperature is 20-30 ℃. Wherein, when styrene-maleic anhydride is copolymerized, the monomer concentration is controlled to be 12.5-17.5% so as to obtain linear macromolecules with narrow molecular weight distribution, azodiisobutyronitrile is used as an initiator, and the reaction time is 3-8 h. The esterification reaction time is controlled to be 2-8 h, the reaction is rapid and thorough because the content of the anhydride is far greater than that of the micromolecular photoinitiator, and pyridine or 4-dimethylaminopyridine is selected as a catalyst. During saponification, the weak base is added in a manner of dropwise adding the aqueous solution of the weak base, so that the phenomenon that local temperature is too high and initiating groups in a macromolecular photoinitiator are hydrolyzed and fall off is avoided, and the reaction lasts for 15-24 hours.
Example 1
(1) Weighing 150mL of tetrahydrofuran, pouring into a 500mL three-neck flask, weighing 13.7g of maleic anhydride, 14.6g of styrene and 0.28g of AIBN respectively, pouring into the three-neck flask, fully stirring, introducing nitrogen for 20min after uniform dissolution, controlling the temperature to 68 ℃ by using a constant-temperature water bath kettle, and reacting for 8h to obtain the tetrahydrofuran solution of the styrene-maleic anhydride copolymer.
(2) And (2) adding 130mL of tetrahydrofuran, 1.13g of 4-dimethylaminopyridine and 2.75g of 4-hydroxybenzophenone into the solution obtained in the step (1), controlling the temperature to 72 ℃ in a water bath, and continuing to react for 4 hours to obtain the tetrahydrofuran solution of the multifunctional macromolecular photoinitiator.
(3) Distilling the solution obtained in the step (2) at 35 ℃ under reduced pressure to obtain a solid polyfunctional macromolecular photoinitiator, wherein the number average molecular weight of the photoinitiator is 1.6 ten thousand and the molecular weight dispersity is 1.36 measured by GPC; 1730cm on infrared spectrum-1Adding an absorption peak of C ═ O in the newly added ester group; residual anhydride was hydrolyzed sufficiently with base and, after titration with hydrochloric acid, an average of about 8 active sites per styrene-maleic anhydride copolymer molecule was calculated, i.e., an average functionality of about 8.
Example 2
(1) The macromolecular photoinitiator solution obtained in step (2) of example 1 was transferred to a 1L single-neck flask, 372g of a 6 wt% sodium bicarbonate solution was added dropwise while maintaining stirring, and stirring was continued for 15 hours after the addition.
(2) And (2) distilling the mixed solution obtained in the step (1) at 35 ℃ under reduced pressure to obtain the aqueous solution of the macromolecular photoinitiator corresponding to the embodiment 1.
Example 3
(1) Weighing 180mL of tetrahydrofuran, pouring the tetrahydrofuran into a 500mL three-neck flask, weighing 14.7g of maleic anhydride, 16.4g of styrene and 0.3g of AIBN respectively, pouring the mixture into the three-neck flask, fully stirring, introducing nitrogen for 20min after uniform dissolution, then controlling the temperature to 70 ℃ by using a constant-temperature water bath kettle, and reacting for 6h to obtain the tetrahydrofuran solution of the styrene-maleic anhydride copolymer.
(2) Adding 215mL of tetrahydrofuran, 1.24g of pyridine and 6.21g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone into the solution obtained in the step (1), controlling the temperature to 70 ℃ in a water bath, and continuing to react for 4 hours to obtain the tetrahydrofuran solution of the multifunctional macromolecular photoinitiator.
(3) And (3) distilling the solution obtained in the step (2) at 35 ℃ under reduced pressure to obtain the solid multi-functionality macromolecular photoinitiator, wherein the number average molecular weight of the solid multi-functionality macromolecular photoinitiator is 1.9 ten thousand, the molecular weight dispersity of the solid multi-functionality macromolecular photoinitiator is 1.48, and the average functionality of the solid multi-functionality macromolecular photoinitiator is about 17.
Example 4
(1) Adding 12.43g of ethanol into the macromolecular photoinitiator solution obtained in the step (2) in the embodiment 3, controlling the temperature in a water bath at 70 ℃, and reacting for 4 hours to obtain the tetrahydrofuran solution of the oil-soluble multifunctional macromolecular photoinitiator.
(2) And (2) distilling the mixed solution obtained in the step (1) at 35 ℃ under reduced pressure to obtain the oil-soluble solid macromolecular photoinitiator corresponding to the embodiment 3.
Example 5
(1) Weighing 200mL of tetrahydrofuran, pouring the tetrahydrofuran into a 1000mL three-neck flask, weighing 16.7g of maleic anhydride, 18.6g of styrene and 0.26g of AIBN respectively, pouring the mixture into the three-neck flask, fully stirring, introducing nitrogen for 20min after uniform dissolution, then controlling the temperature to 70 ℃ by using a constant-temperature water bath kettle, and reacting for 8h to obtain the tetrahydrofuran solution of the styrene-maleic anhydride copolymer.
(2) And (2) adding 237mL of tetrahydrofuran, 1.41g of pyridine and 7.07g of 4-hydroxybenzophenone into the solution obtained in the step (1), controlling the temperature to 70 ℃ in a water bath, and continuing to react for 5 hours to obtain a tetrahydrofuran solution of the multifunctional macromolecular photoinitiator.
(3) And (3) distilling the solution obtained in the step (2) at 35 ℃ under reduced pressure to obtain the solid multi-functionality macromolecular photoinitiator, wherein the number average molecular weight of the solid multi-functionality macromolecular photoinitiator is 2.3 ten thousand, the molecular weight dispersity is 1.52, and the average functionality is about 28.
Example 6
(1) And (3) adding 10.4g of n-butanol into the macromolecular photoinitiator solution obtained in the step (2) in the embodiment 5, controlling the temperature to 70 ℃ in a water bath, and continuously reacting for 6 hours to obtain a partially esterified macromolecular photoinitiator tetrahydrofuran solution.
(2) 279g of 1 wt% ammonia water is added into the mixed solution in the step (1) dropwise, stirring is kept during the dropwise adding process, and stirring is continued for 24 hours after the dropwise adding is finished.
(3) And (3) distilling the mixed solution obtained in the step (2) at 35 ℃ under reduced pressure to obtain the amphiphilic waterborne macromolecule photoinitiator aqueous solution corresponding to the embodiment 5.
Example 7
(1) Weighing 200mL of tetrahydrofuran, pouring into a 500mL three-neck flask, weighing 14.2g of maleic anhydride, 15.8g of styrene and 0.5g of AIBN respectively, pouring into the three-neck flask, fully stirring, introducing nitrogen for 20min after uniform dissolution, controlling the temperature to 68 ℃ by using a constant-temperature water bath kettle, and reacting for 6h to obtain the tetrahydrofuran solution of the styrene-maleic anhydride copolymer.
(2) And (2) adding 171mL of tetrahydrofuran, 1.20g of pyridine and 3.04g of benzoin into the solution obtained in the step (1), controlling the temperature to 70 ℃ in a water bath, and continuing to react for 4 hours to obtain the tetrahydrofuran solution of the multifunctional macromolecular photoinitiator.
(3) And (3) distilling the solution obtained in the step (2) at 35 ℃ under reduced pressure to obtain the solid multi-functionality macromolecular photoinitiator, wherein the number average molecular weight of the solid multi-functionality macromolecular photoinitiator is 0.96 ten thousand, the molecular weight dispersity is 1.97, and the average functionality is about 4.
Example 8
(1) 9.9g of ethylene glycol was added to the macromolecular photoinitiator solution obtained in step (2) of example 7, the temperature was controlled to 70 ℃ in a water bath, and the reaction was continued for 4.5 hours to obtain a partially esterified macromolecular photoinitiator tetrahydrofuran solution.
(2) And (2) dropwise adding 212g of 5 wt% potassium bicarbonate aqueous solution into the mixed solution in the step (1), keeping stirring in the dropwise adding process, and continuously stirring for 20 hours after the dropwise adding is finished.
(3) And (3) distilling the mixed solution obtained in the step (2) at 35 ℃ under reduced pressure to obtain the amphiphilic meta-oily macromolecular photoinitiator aqueous solution corresponding to the embodiment 7.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (10)
1. A multifunctional macromolecular photoinitiator, which is characterized in that the chemical structure of the macromolecular photoinitiator is shown as the following formula (1):
wherein R is1Is a small molecule photoinitiator residue, R2The photoinitiator is hydrogen group, metal ion or alkyl, the weight average molecular weight of the macromolecular photoinitiator is 5000-25000, and the functionality is 3-40.
2. The multifunctional macromolecular photoinitiator according to claim 1, wherein said small molecule photoinitiator residue is selected from the group consisting of benzoin residue, 4-hydroxybenzophenone residue, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone residue, and the chemical structures thereof are represented by the following formulae (2), (3), (4):
3. the multifunctional macrophotoinitiator according to claim 1, wherein the metal ions are selected from the group consisting of sodium ions, potassium ions and ammonium ions.
4. The multifunctional macrophotoinitiator according to claim 1, wherein the alkyl group is selected from the group consisting of C1-C12 alkyl groups.
5. The multifunctional macrophotoinitiator according to claim 1, wherein the photoinitiator is one or more of hydrophilic, lipophilic or amphiphilic.
6. A preparation method of a multifunctional macromolecular photoinitiator comprises the following steps:
step 1, taking tetrahydrofuran as a solvent to prepare a linear styrene-maleic anhydride copolymer;
step 2, adding a small molecular photoinitiator, and carrying out esterification reaction with the styrene-maleic anhydride copolymer;
step 3, directly carrying out reduced pressure distillation; or adding alkyl alcohol and weak base aqueous solution for esterification and saponification, and then distilling under reduced pressure to obtain the macromolecular photoinitiator or the aqueous solution thereof.
7. The method according to claim 6, wherein the styrene-maleic anhydride copolymer prepared in step 1 has a molar ratio of styrene to maleic anhydride of 1.00:1.00 to 1.00: 1.05.
8. The preparation method according to claim 7, wherein a small molecule photoinitiator and a weak base are further added when the styrene-maleic anhydride copolymer is prepared; the molar ratio of the micromolecular photoinitiator to the maleic anhydride is 0.04: 1.00-0.40: 1.00; the molar ratio of the weak base to the maleic anhydride is 0: 1.00-1.85: 1.00.
9. The preparation method according to claim 6, wherein the reaction temperature is 60 to 80 ℃ when the styrene-maleic anhydride copolymer is prepared in the step 1.
10. The method according to claim 6, wherein the esterification temperature in the step 2 and the step 3 is 60 to 80 ℃ and the saponification temperature is 20 to 30 ℃.
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| US5576145A (en) * | 1995-02-10 | 1996-11-19 | Morton International, Inc. | Esterified styrene/maleic anhydride polymer and polymer-containing photoimageable composition having improved alkaline process resistance |
| CN102898549A (en) * | 2012-10-09 | 2013-01-30 | 长沙新宇高分子科技有限公司 | Highly branched macro-molecule photoinitiator and preparation method thereof |
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| CN103342764A (en) * | 2013-06-09 | 2013-10-09 | 中山大学 | Photoinitiator and preparation method thereof |
| CN110606902A (en) * | 2019-07-29 | 2019-12-24 | 长兴电子（苏州）有限公司 | Novel macromolecular photoinitiator and synthesis method thereof |
| CN110724060A (en) * | 2019-11-11 | 2020-01-24 | 南昌航空大学 | Tri-functionality photoinitiator and preparation method thereof |
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| FR2304941A1 (en) * | 1975-03-21 | 1976-10-15 | Minnesota Mining & Mfg | Negative photoresist amidised styrene maleic anhydride compsn. - contg. photopolymerisable monomer and photoinitiator |
| US5576145A (en) * | 1995-02-10 | 1996-11-19 | Morton International, Inc. | Esterified styrene/maleic anhydride polymer and polymer-containing photoimageable composition having improved alkaline process resistance |
| CN103131315A (en) * | 2006-07-25 | 2013-06-05 | 科洛普拉斯特公司 | Coating composition |
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