CN106588864A - Cyclohexyl dioxolane alcohol methyl methacrylate monomer and application thereof - Google Patents
Cyclohexyl dioxolane alcohol methyl methacrylate monomer and application thereof Download PDFInfo
- Publication number
- CN106588864A CN106588864A CN201610973359.6A CN201610973359A CN106588864A CN 106588864 A CN106588864 A CN 106588864A CN 201610973359 A CN201610973359 A CN 201610973359A CN 106588864 A CN106588864 A CN 106588864A
- Authority
- CN
- China
- Prior art keywords
- methyl methacrylate
- cyclohexyl
- methacrylate monomer
- alcohol methyl
- dioxin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a cyclohexyl dioxolane alcohol methyl methacrylate monomer, which has an ultraviolet curing effect, and an application thereof. The structure formula of the cyclohexyl dioxolane alcohol methyl methacrylate monomer is represented as follow. The cyclohexyl dioxolane alcohol methyl methacrylate monomer is an excellent photo-curing agent, and can be used for ultraviolet curing a modified epoxy acrylic resin oligomer so as to form a cured film.
Description
Technical field
The present invention relates to photocuring technology field, more particularly to cyclohexyl dioxin-pentane alcohol methyl methacrylate photocuring
Agent monomer and application.
Background technology
Photocuring refers to the solidification process of monomer, oligomer or polymer matrix under photoinduction.Light Curing is referred to
Liquid resin becomes the process of solid-state Jing after illumination, and involved photocuring reaction great majority are that light-initiated chain polymerization is anti-
Should.Photocuring technology is the technology of environmental protection, energy-conservation, with very big development prospect.
Since first generation ultraviolet-curing paint being developed from Bayer companies of eighties of last century Germany's sixties, photocuring skill
Art has just obtained fast development.In recent years, due to the demand of environmental protection, photocuring technology constantly improves development, gradually moves to maturity,
To be accepted extensively by people the characteristics of low power consuming, high efficiency, adaptability, the feature of environmental protection, economy, coating, glass, metal,
Widely applied in the fields such as weaving, cement, leather.Photocureable coating is mainly (single by resin (oligomer), reactive diluent
Body), the composition such as crosslinking agent (Polyfunctional monomer) and light trigger or sensitising agent.Reactive diluent (monomer) is used as UV-curing
Change the important component part in coating, it is possible to decrease the viscosity of photocuring system, while also cured film can be formed with oligomer copolymerization.
Light curing agent monomer has to the toxicity and excitant of skin with its functional group and molecular weight (concentration of the carbon-carbon double bond in monomer)
Close.The monomer reaction speed that degree of functionality is higher, molecular weight is less is faster, and viscosity is lower, the solidification cubical contraction of material is higher,
Fragility is bigger, bigger to human toxicity and excitant.Therefore, exploitation there is high-performance, low smell, to skin low irritant, low
The light curing agent monomer of toxicity is into current hot issue.
In general, acrylic ester monomer photocuring post-shrinkage ratio is big, and heat resistance is poor, applies in curing field
Affected by certain.Simultaneously common mono-functional reactive's monomer lower crosslink density, have impact on the film performance after photocuring, hand over
The big polyfunctional group photoactive monomer of connection density easily causes larger volume contraction.Therefore, design and develop new type functional
Esters of acrylic acid photoactive monomer is to expanding it in the application of photo-curing material and preparing high performance photo-curing material tool
There is important meaning.
The content of the invention
Present patent application is synthesis photo-curing monomer --- -- cyclohexyl oxazole alkanol methyl methacrylate.First, with
Glycerine and cyclohexanone are Material synthesis glycerol acetonide cyclohexanone, then synthesize light curing agent monomer using ester-interchange method, finally to solidification
In photocureable coating, (oligomer is modified epoxy acrylic acid tree to agent monomer --- cyclohexyl dioxin-pentane alcohol methyl methacrylate
Fat RJ34713, light trigger be 184) in applied, be prepared into cured film, and hardness, attachment have been carried out to the cured film
The performances such as power are tested.
The structural formula of the cyclohexyl dioxin-pentane alcohol methyl methacrylate monomer is：
Prepare above-mentioned cyclohexyl dioxin-pentane alcohol methyl methacrylate monomer to concretely comprise the following steps：
1) glycerol acetonide cyclohexanone synthesis
By glycerine:Cyclohexanone=1.5:1 ratio, by 13.8135 grams of glycerine, 9.8140 grams of cyclohexanone, consumption is hexamethylene
6% catalyst p-methyl benzenesulfonic acid of ketone quality, 0.5888 gram of water entrainer hexamethylene 10mL is added to equipped with reflux condensing tube, divides
In the 50mL there-necked flasks of hydrophone, react under magnetic agitation in thermostatical oil bath, keep reaction temperature to be 100 DEG C, fully stir
After mixing reaction 2 hours, when the water yield in water knockout drum reaches theoretical water yield, and when no longer changing, stop reaction, use 5% carbonic acid
Sodium solution catalyst neutralisation, in neutrality, adds the moisture that anhydrous sodium sulfate is removed in solution to solution, finally carries out decompression steaming
Evaporate, vacuum is 0.095MPa, collect 156-158 DEG C of cut, as glycerol acetonide cyclohexanone crude product adopts silica gel for suction
Attached dose, eluant, eluent is petroleum ether and dichloromethane, and Jing column chromatographies are purified, you can obtain glycerol acetonide cyclohexanone sterling.
2) cyclohexyl dioxin-pentane alcohol methyl methacrylate synthesis
Above-mentioned steps 1 are added in the there-necked flask of condensing reflux pipe and water knockout drum is equipped with) the middle glycerol production for obtaining
1.7211 grams of contracting cyclohexanone, 4.000 grams of methyl methacrylate, consumption is the fourth of catalyst dibutyltin cinnamic acid two of material total amount 3%
Ji Xi, consumption is the hydroquinone of polymerization retarder of material total amount 0.7%, and with thermostatical oil bath 110 DEG C of temperature is controlled, and is entered under magnetic agitation
Row reaction, using methyl methacrylate and the Methanol product for generating azeotropic mixture is formed, and except the methyl alcohol that dereaction is generated, makes reaction
Carry out to forward direction, react 8 hours, the drop amount for treating water knockout drum no longer changes, stop reaction.Removed using Rotary Evaporators excessive
Methyl methacrylate, product cyclohexyl oxazole alkanol methyl methacrylate is obtained, generally, using ester exchange
Method, the polymerization inhibitor and catalyst in product is typically without removing.
Above-mentioned cyclohexyl dioxin-pentane alcohol methyl methacrylate monomer is applied to photocureable coating, and oligomer is modified ring
Oxypropylene acid resin RJ34713, light trigger is 184, prepares cured film.
Description of the drawings
Fig. 1 is glycerol acetonide cyclohexanone infrared spectrum in the embodiment of the present invention.
Fig. 2 is glycerol acetonide cyclohexanone mass spectrogram.
Specific embodiment
The present invention is further elucidated with reference to specific embodiment, but embodiment is not intended to limit protection scope of the present invention.
Embodiment：
(1) glycerol acetonide cyclohexanone synthesis
By glycerine:Cyclohexanone=1.5:1 ratio, by 13.8135 grams of glycerine, 9.8140 grams of cyclohexanone, consumption is hexamethylene
The catalyst p-methyl benzenesulfonic acid of ketone quality 6%, 0.5888 gram of water entrainer hexamethylene 10mL is added to equipped with reflux condensing tube, divides
In the 50mL there-necked flasks of hydrophone, react under magnetic agitation in thermostatical oil bath, keep reaction temperature to be 100 DEG C, fully stir
After mixing reaction 2 hours, when the water yield in water knockout drum reaches theoretical water yield, and when no longer changing, stop reaction, use 5% carbonic acid
Sodium solution catalyst neutralisation, in neutrality, adds the moisture that anhydrous sodium sulfate is removed in solution to solution, finally carries out decompression steaming
Evaporate, vacuum is 0.095MPa, the cut of 156-158 DEG C of collection, as glycerol acetonide cyclohexanone crude product, take adsorbent to be silicon
Glue, eluant, eluent is petroleum ether and dichloromethane, and the purification of Jing column chromatographies obtains glycerol acetonide cyclohexanone sterling, the gross mass of product
For 12.9083 grams, yield is 75%.Glycerol acetonide cyclohexanone structure, obtains infrared spectrum, mass spectrographic confirmation.
(2) cyclohexyl dioxin-pentane alcohol methyl methacrylate synthesis
The glycerol production obtained in above-mentioned steps (1) is added in the there-necked flask of condensing reflux pipe and water knockout drum is equipped with
1.7211 grams of contracting cyclohexanone, 4.000 grams of methyl methacrylate, consumption is the catalyst dibutyltin cinnamic acid dibutyl of material total amount 3%
Tin, material total amount 0.7% hydroquinone of polymerization retarder, control 110 DEG C of temperature with thermostatical oil bath, carry out under magnetic agitation anti-
Should, azeotropic mixture is formed using methyl methacrylate and the Methanol product for generating, except the methyl alcohol that dereaction is generated, reaction is made to just
To carrying out, react 8 hours, the drop amount for treating water knockout drum no longer changes, stop reaction.Excessive first is removed using Rotary Evaporators
Base methyl acrylate, obtains product cyclohexyl dioxin-pentane alcohol methyl methacrylate.
(3) preparation of photocuring film
Cyclohexyl dioxin-pentane alcohol methyl methacrylate monomer, the light trigger 1- hydroxy cyclohexylphenyls that step (2) is synthesized
Base phenyl ketone, oligomer modified epoxy acrylate resin, are added in beaker by the material proportion of table 1, are stirred until light
Initiator all dissolves, and is made into paint binder.
The paint binder formula of table 1
The paint binder for preparing is smeared on the glass sheet, then sheet glass is put into into 18 volts of ultra violet lamps, lamp away from for
15 centimetres, until cured film reaches surface drying, hardening time is 20 minutes, that is, obtain cured film.Through test, the solidification film hardness
According to GB/T6739-1996 " hardness of paint film pencil determination method " carry out test for 2H, adhesive force according to GB/T9286-1998 standards
It is measured as 2.
Claims (2)
1. a kind of cyclohexyl dioxin-pentane alcohol methyl methacrylate monomer, it is characterised in that described cyclohexyl dioxin-pentane alcohol
The structural formula of methyl methacrylate monomer is：
2. cyclohexyl dioxin-pentane alcohol methyl methacrylate monomer according to claim 1, it is characterised in that described
Cyclohexyl dioxin-pentane alcohol methyl methacrylate monomer is used for ultraviolet light polymerization modified epoxy acrylic acid tree as light curing agent
Fat oligomer, makes epoxy acrylic resin oligomer form cured film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610973359.6A CN106588864A (en) | 2016-11-06 | 2016-11-06 | Cyclohexyl dioxolane alcohol methyl methacrylate monomer and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610973359.6A CN106588864A (en) | 2016-11-06 | 2016-11-06 | Cyclohexyl dioxolane alcohol methyl methacrylate monomer and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106588864A true CN106588864A (en) | 2017-04-26 |
Family
ID=58590795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610973359.6A Pending CN106588864A (en) | 2016-11-06 | 2016-11-06 | Cyclohexyl dioxolane alcohol methyl methacrylate monomer and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106588864A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB852384A (en) * | 1957-07-16 | 1960-10-26 | Rohm & Haas | Process for preparing dihydroxy alkyl acrylates and methacrylates |
| US6146811A (en) * | 1998-08-01 | 2000-11-14 | Korea Advanced Institute Of Science And Technology | Photoresist using dioxaspiro ring-substituted acryl derivatives |
| JP2004059435A (en) * | 2002-07-24 | 2004-02-26 | Osaka Organic Chem Ind Ltd | Method for producing dioxolane compound |
-
2016
- 2016-11-06 CN CN201610973359.6A patent/CN106588864A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB852384A (en) * | 1957-07-16 | 1960-10-26 | Rohm & Haas | Process for preparing dihydroxy alkyl acrylates and methacrylates |
| US6146811A (en) * | 1998-08-01 | 2000-11-14 | Korea Advanced Institute Of Science And Technology | Photoresist using dioxaspiro ring-substituted acryl derivatives |
| JP2004059435A (en) * | 2002-07-24 | 2004-02-26 | Osaka Organic Chem Ind Ltd | Method for producing dioxolane compound |
Non-Patent Citations (1)
| Title |
|---|
| JUI-HSIANG LIU ET AL.: "Preparation and Characterization of Novel Polymers Having Pendent Ketal Moieties for Positive Photoresists", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102141769B1 (en) | Hybrid photosensitive resin and its manufacturing method | |
| CN111138290B (en) | Aromatic ring-containing benzophenone derivative and preparation method and application thereof | |
| JP6483289B2 (en) | Sensitizer for UV-LED photocuring, its production method and use | |
| CN1028433C (en) | Optical solidification compound and preparation method and application thereof | |
| CN111205203B (en) | Benzophenone derivative containing diphenyl carbamate group and preparation and application thereof | |
| CN107501463A (en) | A kind of ultraviolet light self-crosslinking polyacrylates and preparation method thereof | |
| CN107089914A (en) | A kind of cashew nut phenolic group acrylate reactive diluent and its preparation method and application | |
| CN105001088B (en) | Method for preparing all-bio-based photocuring activated monomer and application of all-bio-based photocuring activated monomer | |
| WO2021135222A1 (en) | Multifunctional-epoxy-vegetable-oil-based uv-curable prepolymer, preparation method therefor and use thereof | |
| CN108689853B (en) | Vegetable oil-based multifunctional UV curing active monomer and preparation method and application thereof | |
| CN110724060A (en) | Tri-functionality photoinitiator and preparation method thereof | |
| CN101983959B (en) | Multifunctional acrylic ester monomer for photopolymerization and preparing method thereof | |
| US20230365756A1 (en) | Polyfunctionalized macromolecular photoinitiator containing alpha-aminoketone, and preparation and application thereof | |
| CN106588864A (en) | Cyclohexyl dioxolane alcohol methyl methacrylate monomer and application thereof | |
| CN106588860A (en) | Dimethyl dioxane pentyl alkanol methacrylate monomer and application thereof | |
| CN112300026B (en) | 4-benzo five-membered ring-phenyl ketoxime ester compound and preparation method and application thereof | |
| CN108976180B (en) | Cationic photocuring soybean oil-based oligomer and preparation method and application thereof | |
| CN110305327B (en) | Dendritic eosin B-iodonium salt visible photoinitiator and preparation method and application thereof | |
| JP2005015396A (en) | New alicyclic vinyl ether | |
| CN104830191A (en) | Monovinyl-terminated fluorine-containing prepolymer/epoxy (methyl) acrylate composite UV-cured paint, preparation and applications thereof | |
| Zhao et al. | Synthesis and characterization of tung oil-based UV curable for three-dimensional printing resins | |
| CN111018758B (en) | Sulfur-containing monomer, preparation method and application thereof | |
| CN105001177B (en) | A kind of triarylsulfonium salt containing benzoxazoles skeleton and preparation method thereof | |
| CN103980181A (en) | Triaryl sulfonium salt containing 1-methyl-2-phenyl indole skeleton and preparation method thereof | |
| CN110117335A (en) | A kind of polymerizable type hydroxyl ketone-type photoinitiators and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170426 |
|
| RJ01 | Rejection of invention patent application after publication |