CN109704989A - A kind of synthetic method of O-phthalic nitrilic type acrylic ester monomer - Google Patents
A kind of synthetic method of O-phthalic nitrilic type acrylic ester monomer Download PDFInfo
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- CN109704989A CN109704989A CN201910069147.9A CN201910069147A CN109704989A CN 109704989 A CN109704989 A CN 109704989A CN 201910069147 A CN201910069147 A CN 201910069147A CN 109704989 A CN109704989 A CN 109704989A
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- acrylic ester
- ester monomer
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Abstract
The present invention provides a kind of synthetic methods of O-phthalic nitrilic type acrylic ester monomer, belong to novel high polymer polymerized monomer preparation technical field.The present invention is prepared for a kind of acrylic ester monomer of phthalonitrile structure by introducing phthalonitrile structure that is cross-linking, being coordinated in the acrylic ester monomer of free redical polymerization.The design feature have the benefit that 1. phthalonitrile structure can by heat cross-linking or and coordinate transition metal salts, formed covalent reversible coordinate bond.Be introduced into polymer molecular structure, under the stimulation such as heating or chemicals, can spontaneous crosslinking or solution crosslinking stimuli responsive material, such as self-healing, intellectual material constituted by the variation of the physical properties such as mechanical property or color.2. the monomer also has broad application prospects in boiomacromolecule field since itrile group and the phthalocyanine structure being cross-linked to form have preferable biocompatibility.
Description
Technical field
The invention belongs to novel high polymer polymerized monomer preparation technical fields, are related to a kind of O-phthalic nitrilic type acrylic acid
The synthetic method of esters monomer.
Background technique
Polyacrylate type resin is a kind of General Linear high molecular material, has excellent processing, mechanics and optical
Can and good chemical stability, be widely used in medical, mechanical, automobile, electronics, intelligence, ship, etc. Material Fields.
Polyacrylate type resin is a kind of by (total) the poly- obtained linear height of the monomer progress containing esters of acrylic acid
Molecularly Imprinted Polymer.Since acrylic acid acrylic monomer is easy to chemical modification, in recent years, it is widely used in intellectual material field.Yang
Et al. synthesized the acrylic ester monomer containing terpyridine structure, presence of the polymer monomer due to terpyridyl, Ke Yiyu
Coordinate transition metal salts obtain reversible crosslinked polymer.Material has good shape-memory properties (AngewandteChemie-
International Edition 2017,59(41),12599-12602.)；Bode et al. is using similar polymer, with chlorination
Cobalt is coordination core, and the cross-linked polymer developed can be used as self-healing material and use (Journal of Materials
Chemistry A 2015,3(44),22145-22153.).Kumpfer et al. use bisbenzimidazole bipyridyl structure for
Body, prepares reversible crosslink polyacrylate resin, and material has good self-healing performance (Journal of the
American Chemical Society 2011,133(32),12866-12874.).But the above-mentioned acrylate containing pyridyl group
Monomer preparation process is complicated, and purification process is cumbersome, it is difficult to commercial applications.Phthalonitrile is a kind of highly polar group, can be with
Form the complexs containing phthalocyanine structure with more than 70 kinds of transition metal salts, thus formed reversible coordination key (high-performance resin matrix
Latest Progress aerospace material technique 2012, (04), 1-6)；It can also be formed in a heated condition with organic diamine permanent
Covalent bond forms cross-linked structure (Journal of Macromolecular Science:Part A-Chemistry:Pure
and Applied Chemistry1982,A18(6),931-937.).Phthalonitrile can also be used to prepare phthalocyanine dye, answer
For electrode material or storage material, conversion ratio and reusability (Journal of Materials with higher
Research 2011,26(18),2369-2372；Advanced Materials 2008,20(9),1766-1771.).
Sastri et al. is crosslinked by o-phthalonitrile resin and diamines and prepares thermostable polymer, applied to space flight, ship etc.
Structural material component (Polymer 1996,17,816-822.).
In order to introduce reversible coordination covalent bond in polyacrylate resin, in line with exploration polyacrylate intellectual material
The phthalonitrile groups of easy crosslinking coordination are introduced into acrylic ester monomer skeleton by thought, the present invention.Such monomer can
Reversible crosslink polyacrylate is prepared through (activity is controllable) free radical polymerization, is all had in intellectual material, boiomacromolecule field
Good application prospect.
Summary of the invention
The present invention provides a kind of synthesis of novel phthalonitrile structural acrylic ester monomer and post-processing approach.
This method is one-step synthesis process, and reaction condition is mild, and last handling process is simple and easy, is easy to be commercialized amplification production；It is adjacent
The complexation reaction of benzene dicarbonitrile is easy to carry out, and transition metal range of choice is wide, and stability is high.The monomer is in self-healing material, intelligence
Energy material and boiomacromolecule field have broad application prospects.
Technical solution of the present invention:
A kind of synthetic method of O-phthalic nitrilic type acrylic ester monomer, steps are as follows:
Acrylic ester monomer, the 4- nitro of hydroxyl structure are sequentially added into the reactor for emptying air by nitrogen
Phthalonitrile, inorganic base and organic solvent, acrylic ester monomer, 4- nitrophthalonitrile and the inorganic base of hydroxyl structure
The molar ratio of three is 1:1~2:0.5~3；Wherein it is preferably in a proportion of acrylic ester monomer, the 4- nitro neighbour's benzene of hydroxyl structure
The molar ratio of dimethoxy nitrile and inorganic base three are 1:1.2:0.7；Consumption of organic solvent is the esters of acrylic acid list of hydroxyl structure
5~20 times (mL) of weight (g).Reaction under nitrogen protection, after (10-25 DEG C) of room temperature is reacted 4~48 hours, stops adding
Heat is poured into product in the NaOH aqueous solution that mass fraction is 5wt.%, after filtering, collects filter cake and is washed till neutrality；Vacuum 50
DEG C after dry 24 hours, using chloroform as eluent, column chromatography collects main component；It is spin-dried for collecting using Rotary Evaporators and produce
Object, and recrystallized with recrystallization solvent, ratio is 1:2~10g/mL.Product is obtained after filtering and after being dried in vacuo.
The acrylic ester monomer of the hydroxyl structure has general structure below:
The inorganic base includes: potassium carbonate, sodium carbonate are its mixture etc..
The organic solvent includes: N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide,
Dimethyl sulfoxide or mixture etc. for two of them or more.
The recrystallization solvent may include the mixing of one or more of methanol, ethyl alcohol, tetrahydrofuran, ethyl acetate etc.
Object.
Beneficial effects of the present invention:
(1) reaction raw materials are easy to get, mild condition, and synthesis and aftertreatment technology are simple to operation, it is easy to accomplish industrial metaplasia
It produces.
(2) it preparing by raw material of the monomer also containing phthalonitrile structure in polymer, complexation reaction is easy to carry out,
Transition metal range of choice is wide, and stability is high.
(3) potential application field of the invention includes self-healing material, intellectual material and boiomacromolecule etc..
Detailed description of the invention
Fig. 1 is the infrared spectrum of typical monomers.
Fig. 2 is the H-NMR spectrum of typical monomers.
Fig. 3 is the C-NMR spectrogram of typical monomers.
Fig. 4 is the DSC spectrogram of typical monomers.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
Embodiment 1
The esters of acrylic acid of hydroxyl structure as shown in Figure 1 is sequentially added into the three-necked flask for emptying air by nitrogen
Monomer HEMA 21.2mL, 4- nitrophthalonitrile NPh 10g, potassium carbonate 20g, DMAC N,N' dimethyl acetamide 200mL.Reaction
Under nitrogen protection, (25 DEG C) of room temperature after reaction 48 hours, stop heating, the NaOH that product is poured into 5% mass fraction is water-soluble
In liquid, after filtering, collects filter cake and be washed till neutrality.After the drying 24 hours of 50 DEG C of vacuum, using chloroform as eluent, column chromatography,
Collect main component.It is spin-dried for collecting product using Rotary Evaporators, and is recrystallized with tetrahydrofuran, ratio 1:10g/mL.It crosses
Product, yield 71% are obtained after filter and after being dried in vacuo.
Embodiment 2
The esters of acrylic acid of hydroxyl structure as shown in Figure 1 is sequentially added into the three-necked flask for emptying air by nitrogen
Monomer HPBA 22.6mL, 4- nitrophthalonitrile NPh 10.3g, potassium carbonate 20g, dimethyl sulfoxide 200mL.Reaction is in nitrogen
Under gas shielded, after 15 DEG C are reacted 24 hours, product is poured into the NaOH aqueous solution of 5% mass fraction, after filtering, collects filter cake
And it is washed till neutrality.After the drying 24 hours of 50 DEG C of vacuum, using chloroform as eluent, column chromatography collects main component.Use rotation
Evaporimeter is spin-dried for collecting product, and with Gossypol recrystallized from chloroform, ratio 1:3g/mL.Product is obtained after filtering and after being dried in vacuo, is received
Rate 64%.
Embodiment 3
The acrylic ester monomer HPBA of hydroxyl structure is sequentially added into the three-necked flask for emptying air by nitrogen
4.0g, 4- nitrophthalonitrile NPh 1.1g, potassium carbonate 2.2g, N-Methyl pyrrolidone 20mL.It reacts under nitrogen protection,
20 DEG C after reaction 36 hours, product are poured into the NaOH aqueous solution of 5% mass fraction, after filtering, filter cake is collected and is washed till
Property.After the drying 24 hours of 50 DEG C of vacuum, using chloroform as eluent, column chromatography collects main component.It is revolved using Rotary Evaporators
It is dry to collect product, and with ethyl alcohol recrystallization, ratio 1:6g/mL.Product, yield 52% are obtained after filtering and after being dried in vacuo.
Embodiment 4
The acrylic ester monomer HPMA of hydroxyl structure is sequentially added into the three-necked flask for emptying air by nitrogen
4.2g, 4- nitrophthalonitrile NPh 1.1g, sodium carbonate 2.2g, DMAC N,N' dimethyl acetamide 20mL.Reaction is in nitrogen protection
Under, after 10 DEG C are reacted 48 hours, product is poured into the NaOH aqueous solution of 5% mass fraction, after filtering, filter cake is collected and is simultaneously washed till
It is neutral.After the drying 24 hours of 50 DEG C of vacuum, using chloroform as eluent, column chromatography collects main component.Use Rotary Evaporators
It is spin-dried for collecting product, and with recrystallizing methanol, ratio 1:1g/mL.Product, yield are obtained after filtering and after being dried in vacuo
78%.
Claims (8)
1. a kind of synthetic method of O-phthalic nitrilic type acrylic ester monomer, which is characterized in that steps are as follows:
Acrylic ester monomer, the 4- nitro neighbour's benzene of hydroxyl structure are sequentially added into the reactor for emptying air by nitrogen
Dimethoxy nitrile, inorganic base and organic solvent, acrylic ester monomer, 4- nitrophthalonitrile and the inorganic base three of hydroxyl structure
Molar ratio be 1:1~2:0.5~3；Consumption of organic solvent mL be hydroxyl structure acrylic ester monomer quality g 5~
20 times；Reaction under nitrogen protection, after reacting 4~48 hours under the conditions of 10-25 DEG C of temperature, stops heating, product is poured into matter
It measures in the NaOH aqueous solution that score is 5wt.%, after filtering, collects filter cake and be washed till neutrality；After the drying 24 hours of 50 DEG C of vacuum,
Using chloroform as eluent, column chromatography collects main component；It is spin-dried for collecting product using Rotary Evaporators, and molten with recrystallizing
Agent recrystallization, ratio are 1:2~10g/mL；Product is obtained after filtering and after being dried in vacuo；
The acrylic ester monomer of the hydroxyl structure has general structure below:
2. synthetic method according to claim 1, which is characterized in that the inorganic base potassium carbonate and/or sodium carbonate.
3. synthetic method according to claim 1 or 2, which is characterized in that the organic solvent is N- crassitude
The mixing of one or more of ketone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide.
4. synthetic method according to claim 1 or 2, which is characterized in that the recrystallization solvent be methanol, ethyl alcohol,
The mixing of one or more of tetrahydrofuran, ethyl acetate.
5. synthetic method according to claim 3, which is characterized in that the recrystallization solvent is methanol, ethyl alcohol, tetrahydro
The mixing of one or more of furans, ethyl acetate.
6. according to claim 1, synthetic method described in 2 or 5, which is characterized in that the esters of acrylic acid of the hydroxyl structure
The molar ratio of monomer, 4- nitrophthalonitrile and inorganic base three is 1:1.2:0.7.
7. synthetic method according to claim 3, which is characterized in that the acrylic ester monomer of the hydroxyl structure,
The molar ratio of 4- nitrophthalonitrile and inorganic base three are 1:1.2:0.7.
8. synthetic method according to claim 4, which is characterized in that the acrylic ester monomer of the hydroxyl structure,
The molar ratio of 4- nitrophthalonitrile and inorganic base three are 1:1.2:0.7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852151A (en) * | 2021-01-11 | 2021-05-28 | 井冈山大学 | Design of multiple self-repairing structure for brittle material with high glass transition temperature |
| CN115073631A (en) * | 2022-08-19 | 2022-09-20 | 河南华佳新材料技术有限公司 | Current collector thin film material for lithium battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006241217A (en) * | 2005-03-01 | 2006-09-14 | Fuji Photo Film Co Ltd | Phthalocyanine compound, coloring image-forming composition, and inkjet recording method using the same |
| JP2007094072A (en) * | 2005-09-29 | 2007-04-12 | Dainippon Printing Co Ltd | Filter for display and display using the same |
| CN103193912A (en) * | 2013-04-19 | 2013-07-10 | 苏州大学 | Copolymer containing zinc-phthalocyanine group on side chain and preparation method thereof |
| CN103342790A (en) * | 2013-06-24 | 2013-10-09 | 苏州大学 | Preparation method for in-situ synthesis of phthalocyanine polymer |
| CN107586469A (en) * | 2016-07-07 | 2018-01-16 | 住友化学株式会社 | Color compositions, coloured composition and cured composition for color |
| JP2018131567A (en) * | 2017-02-16 | 2018-08-23 | キヤノン株式会社 | Dye compound and toner |
-
2019
- 2019-01-24 CN CN201910069147.9A patent/CN109704989A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006241217A (en) * | 2005-03-01 | 2006-09-14 | Fuji Photo Film Co Ltd | Phthalocyanine compound, coloring image-forming composition, and inkjet recording method using the same |
| JP2007094072A (en) * | 2005-09-29 | 2007-04-12 | Dainippon Printing Co Ltd | Filter for display and display using the same |
| CN103193912A (en) * | 2013-04-19 | 2013-07-10 | 苏州大学 | Copolymer containing zinc-phthalocyanine group on side chain and preparation method thereof |
| CN103342790A (en) * | 2013-06-24 | 2013-10-09 | 苏州大学 | Preparation method for in-situ synthesis of phthalocyanine polymer |
| CN107586469A (en) * | 2016-07-07 | 2018-01-16 | 住友化学株式会社 | Color compositions, coloured composition and cured composition for color |
| JP2018131567A (en) * | 2017-02-16 | 2018-08-23 | キヤノン株式会社 | Dye compound and toner |
Non-Patent Citations (5)
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852151A (en) * | 2021-01-11 | 2021-05-28 | 井冈山大学 | Design of multiple self-repairing structure for brittle material with high glass transition temperature |
| CN115073631A (en) * | 2022-08-19 | 2022-09-20 | 河南华佳新材料技术有限公司 | Current collector thin film material for lithium battery |
| CN115073631B (en) * | 2022-08-19 | 2022-11-25 | 河南华佳新材料技术有限公司 | Current collector thin film material for lithium battery |
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