CN110183664A - A kind of preparation method and application of ultraviolet curing type silicone oil containing methacrylate - Google Patents
A kind of preparation method and application of ultraviolet curing type silicone oil containing methacrylate Download PDFInfo
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- CN110183664A CN110183664A CN201910359411.2A CN201910359411A CN110183664A CN 110183664 A CN110183664 A CN 110183664A CN 201910359411 A CN201910359411 A CN 201910359411A CN 110183664 A CN110183664 A CN 110183664A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/001—Release paper
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Abstract
The present invention relates to a kind of preparation method of ultraviolet curing type silicone oil containing methacrylate and applications, firstly, a kind of metacrylic acid ester structure organic matter containing sulfhydryl structure is synthesized, methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester；Secondly, it is reacted with end group polymethyl siloxane containing epoxy, under the catalysis of organic base, sulfydryl efficiently and rapidly carries out the reaction of open loop click chemistry to propylene oxide, side reaction will not be crosslinked, reaction is controllable, and the grafting rate of methacrylate is up to 95% or more, prepares and has excellent performance polymethyl siloxane (PSi-MMA) of the end group containing metacrylic acid ester structure；Using compounding photoinitiator, solidify coated in ultraviolet light on substrate, rapid curing forms a film at room temperature, the characteristics of cleanliness without any pollution, the film prepared has excellent release effect: the remaining Stickiness of standard rubber band is higher than 92%, off-type force is stablized in 15~30 g/in or so, is a solvent-free, non-metal catalyst, the quick organosilicon photocuring system without hot setting.
Description
Technical field
The invention belongs to polymer material science fields, more particularly, to a kind of ultraviolet light (UV) curing type silicone oil material
Preparation method can be applied to the release agent material of photocuring.
Background technique
Polymethyl siloxane, abbreviation silicone oil, backbone structure are connected with silicon oxygen bond, are had fabulous flexibility, are showed simultaneously
High-low temperature resistant out, and used in wider temperature range, with weatherability and resistant of high or low temperature feature, in addition, with routine
Polymer phase ratio, with more excellent barrier property, low-surface-energy and surface tension, corrosion resistance, electric insulating quality, resistance to ozone
The performances such as type, waterproof, anti-flammability, physiological inertia, be widely used in aerospace, separated type material, electric, chemical machinery,
The national economy various industries such as health care, communications and transportation.
Traditional silicone oil carries out curing molding by effective catalyst at high temperature, still, considers from energy conservation and environmental protection angle,
Not only curing rate is slow for conventional curing mode, energy consumption is high, curing efficiency is low in addition solidification process in solvent volatilization and small molecule
Organic matter volatilization pollution environment, and the remaining influence properties of product of metallic catalyst and therefore largely limit using point
The application and popularization of organosilicon.
Ultraviolet light (UV) solidification is a kind of energy-saving and environment-friendly new technology, has curing rate fast, normal temperature cure is uniform, energy saving
Efficiently, curing efficiency will greatly improve, and reduce the advantages that pollution is environmentally friendly, be highly suitable for thermo-responsive substrate or device
It carries out being molded into film on part, has the photoetching feature of ultraviolet locality and semiconductor circuit, therefore, photocuring is that one kind is striven vigorously to advocate greatly
The energy-saving and environment-friendly curing method led.Therefore, by the way that polymethyl siloxane side chain or end to be introduced to the functional group of light sensation, in purple
Outer light irradiation lower the drawbacks of carrying out crosslinking curing, overcoming traditional silicone oil hot setting, embody it is efficient, fast curing-formed,
The many advantages such as clean and environmental protection, energy conservation, and traditional silica-base material have heatproof, weather-proof, electric insulation, low surface tension and
The advantages that low-surface-energy.Conventional light sensation group is usually (methyl) acrylate structural, and photoinitiator is added, small without adding
Molecule volatile monomers, under ultraviolet radiation, photoinitiator excites to form free radical, causes (methyl) free radical acrylate and adds
At polymerization, final crosslinking film forming, system has certain antioxygen polymerizing power, synthetic method and a simple process, preparation cost compared with
Low, the release film streamlined for being specifically for use in different substrate materials (such as paper, PP, PE, PET) quickly manufactures, after solidification not only
The advantage of organosilicon is remained, while having that the film forming of acrylate, colour retention are good, gloss is high, and adhesive property is excellent, is promoted
The application and popularization of organosilicon, such as coating, paint, leather agent, packaging industry.
Currently, there are many method of early stage acrylate polymethyl siloxane of the preparation containing (methyl) acrylate structural, such as
Dichlorosilane and the hydrolysis-condensation reaction of hydroxy-ethyl acrylate (HEA) under base catalysis in polymethyl siloxane are made, but this
Modified polyorganosiloxane contains the Si-O-C key to humidity sensitive, and facile hydrolysis, stability is poor, acrylate structural be easy dissociation and
Inactivation, therefore, it is necessary to the acrylate functional polymethyl siloxane of the high Si-C structure of synthesising stability, primary synthetic methods
To have hydrosilation method, esterification process and dealcoholysis method.The polymethyl siloxane of hydrosilyl group-containing directly with symmetric form double methacrylate into
Row hydrosilylation (Oestreich S, Struck S. Macromol. Symp., 2002,187 (1), 333.),
H2PtO6 6H2Under the catalysis of O, acrylate functional polysiloxanes is just obtained, since double methacrylate has same isoreactivity, is being added
At in reaction process, it may occur that cross-linking reaction between polymer chain is affected, in addition, catalyst costly, limits this
The application of reaction.Using end ring oxygen polymethyl siloxane and acrylic acid under catalyst, esterification process prepares propylene
Esterification polysiloxanes (Carter G R, Watson S L, Pines A N, US 4293678,1981.)；Hold hydroxyalkyl
Esterification occurs for polymethyl siloxane and acrylic acid, obtains acroleic acid esterification polysiloxanes (Hockemeyer F, Preiner
G. US 4554339, 1985.)；He Hua etc. is reacted with Chloropropylpolysiloxanes and hydroxypropyl acrylate, synthesizes acrylate
Base polysiloxanes, as interleaving agent research ultraviolet light curing characteristics and its anti-adhesion performance etc., (He Hua, Tao Yongjie, Li Bing glue
Connect, 2005,26(6), 7.).The activity of esterification limits that esterifying efficiency is lower, and the grafting rate of acrylate influences organosilicon
Application.
With the development of science and technology, demand of the people to polymethyl siloxane rapid cure system is more and more extensive,
It asks also higher and higher, needs to greatly save the time, improve process efficiency, product yield and obtain index with quality and promoted, such as make
Remaining Stickiness for the release film that separated type material, silicon oil solidifying are prepared, standard rubber band is higher than 90%, has to different substrate materials
There is the requirement such as good adhesive force.Therefore, it is solid that the grafting efficiency and reduction preparation cost for promoting acrylate effectively improve UV
The popularization of change type polymethyl siloxane.
Summary of the invention
The object of the present invention is to provide the terminal methyl acrylate functionals of the high grafting rate haveing excellent performance and low cost
Polymethyl siloxane preparation method, firstly, synthesize a kind of metacrylic acid ester structure organic matter containing sulfhydryl structure,
It is secondary, it is reacted with end group polymethyl siloxane containing epoxy, under the catalysis of organic base, sulfydryl efficiently and rapidly carries out propylene oxide
The reaction of open loop click chemistry, prepares polymethyl siloxane (PSi-MMA) of the end group containing metacrylic acid ester structure, solves existing
There is expensive catalyst in technology, is easily crosslinked in synthesis process, acrylic ester grafted low efficiency, solidification process photoinitiator system
The technical problems such as standby cumbersome valuableness.The polymethyl siloxane of gained terminal methyl acrylate functional has preparation simple, is prepared into
This is low, easy to use, and methacrylate grafting rate is high, and activity is high, is a kind of efficiently mild controllable preparation method, ultraviolet light
Solidified forming time is short, and photoinitiator prepares silicon oil modified photoinitiator without cumbersome, selects cheap commercially available compounding
Photoinitiator, organosilicon membrane material after solidification are higher than 92% using the remaining Stickiness of standard rubber band, and off-type force stablizes 15~
30 g/in or so have many advantages, such as high temperature resistant, and weatherability is good, electric insulating quality is good and low surface tension, are widely used in release
The industries such as coating, coating, leather agent and packaging.
The present invention adopts the following technical scheme that are as follows:
The polymethyl siloxane (PSi-MMA) that a kind of ultraviolet light (UV) solidifies terminal methyl acrylate structural has formula [1]
General structure:
[1] chemical structure of PSi-MMA
In formula [1]: n=10-200, molecular weight are 1200~15000；Wherein n is integer.
The PSi-MMA, which passes through the methacrylate compound B prepared containing sulfydryl and the silicone oil of end ring oxide structure, to be had
Carry out epoxy addition click chemistry reaction under machine base catalysis rapidly and efficiently is made, and reactional equation is [2]:
[2] reactional equation of PSi-MMA
The raw material A is epoxy-terminated silicone oil, is made by oneself, and n can be arbitrary integer in structure, may be set to n=10-200,
Molecular weight is 1000~15000.
The raw material B is the methacrylate compound containing sulfydryl, methacrylic acid -3- mercaptopropionyl oxygroup second
Ester.Purity is 98% or more.
In epoxy addition click chemistry (Click Chemistry) reaction process, which is fast
The efficient normal-temperature reaction of speed, belongs to click chemistry (Click Chemistry), and reaction is mild thorough, will not crosslink side reaction,
It is not necessary that excess B is added, the B that identical mole of group is added can be such that reaction carries out thoroughly, and reaction is controllable, and methacrylate connects
Branch rate is up to 95% or more.
Described epoxy addition click chemistry (Click Chemistry) reaction condition is that organic base is usually triethylamine,
Triphenyl phosphorus, triethanolamine, 2,4,6 three (dimethylamino methyl) phenol (DMP-30) etc. carry out under room temperature, and solvent can be selected four
The good solvents such as hydrogen furans, acetone, ethyl acetate, toluene, dimethylbenzene, butanone, reaction time are 3 hours, and post-processing passes through
Vacuum rotary steam, solvent is recyclable to be recycled, and entire process flow is simply controllable.
The preparation of polymethyl siloxane material (PSi-MMA) of the end group containing metacrylic acid ester structure has high
Methacrylate grafting rate, up to 94% or more.In the presence of photoinitiators, ultraviolet light (UV) irradiation is quickly solid under room temperature
Chemical conversion type, or coated in forming a film on film, curing time is 1~5 second, photocuring reaction has rapid curing, solidifies uniform, room
Temperature solidification, energy-efficient, advantages of environment protection, prepare organosilicon membrane material with high temperature resistant, and weatherability is good, electric insulation
Property good and low surface tension the advantages that, be widely used in the industries such as release coating, coating, leather agent and packaging.
The photoinitiator is commercially available normal starter, good with PSi-MMA compatibility, further, passes through Compositional type
Photoinitiator improves space charge force and efficiency, without preparing silicon oil modified photoinitiator complicatedly, greatly simplifies
Preparation method reduces the preparation cost of product, compounds photoinitiator are as follows: 1- hydroxycyclohexyl phenyl ketone (184) and 2- hydroxyl
The similar radical photoinitiator such as base-2- methyl-1-phenyl-1- acetone (1173), is made efficient organosilicon photoinitiator,
He also can be applied in this technology photoinitiator.
Polymethyl siloxane material of the end group containing metacrylic acid ester structure through ultraviolet light film-forming, obtain from
Type film, have excellent low-surface-energy, and excellent release effect: the remaining Stickiness of standard rubber band is higher than 92%, and off-type force is steady
15~30 g/in or so are scheduled on, are a solvent-free, non-metal catalysts, the quick organosilicon photocuring without hot setting
System.
Detailed description of the invention
The high-efficient liquid phase chromatogram of Fig. 1, methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester by purification.
The nuclear magnetic spectrum of Fig. 2, methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester.
Polymethyl siloxane material (the PSi- of Fig. 3, epoxy terminated polymethyl siloxane and terminal methyl acrylate structural
MMA) infrared comparison diagram (A is epoxy terminated polymethyl siloxane, B PSi-MMA01).
The nuclear magnetic spectrogram of Fig. 4, epoxy terminated polymethyl siloxane.
Fig. 5, terminal methyl acrylate structural polymethyl siloxane material (PSi-MMA01) nuclear magnetic spectrogram.
The contact angle test figure of Fig. 6, hot print paper.
Fig. 7, terminal methyl acrylate structural polymethyl siloxane (PSi-MMA01) be coated in it is purple on hot print paper base material
The contact angle test figure of outer photocuring film forming.
Fig. 8, without base stock hot print label figure.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
Methacrylate compound containing sulfydryl, the synthesis of methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester, passes through methyl-prop
Olefin(e) acid hydroxyl ethyl ester reacts to obtain with mercaptopropionic acid esterification, and reactional equation is [3]:
[3] synthesis of methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester
2-hydroxyethyl methacry-late (13.00 g；0.10 mol), 3- mercaptopropionic acid (11.13 g；0.105 mol), to first
Benzene sulfonic acid (1.00 g) is used as polymerization inhibitor, benzene (15.00 mL) conduct as catalyst for esterification reaction, hydroquinone (0.12 g)
Water entrainer is added step-wise in 250 mL three-necked flasks.It is fitted into after water segregator for there-necked flask to be placed in oil bath pan and be slowly heated
To reflux, 8 h of isothermal reaction.It is cooled to product after reaction, 3% dilute solution of sodium bicarbonate is washed 3 times, and water washing is distilled
To neutrality, anhydrous sodium sulfate is dried overnight.Vacuum distillation removal solvent, and after chromatographic silica gel post separation, obtain metering system
Acid -3- mercaptopropionyl oxygroup ethyl ester (MPOEM).Fig. 1 is the height of the methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester by purification
Effect liquid phase chromatogram figure, Cong Tuzhong can analyze to obtain the product purity after chromatographic silica gel post purifies and be up to 98%.Fig. 2 is methyl
Acrylic acid -3- mercaptopropionyl oxygroup ethyl ester1H-NMR spectrum.The proton and nuclear magnetic signal peak of structure correspond, and integrate ratio
It is consistent with proton ratio, is shown to be target product.
Embodiment 2
The synthesis of the polymethyl siloxane material (PSi-MMA) of terminal methyl acrylate structural.
Epoxy terminated polymethoxysiloxanes, structure such as formula [2], self-control, Fig. 4 are epoxy terminated polymethoxysiloxanes
Nuclear magnetic spectrogram, structure and nuclear-magnetism proton peak correspond, and pass through integral calculation, n=14, molecular weight 1300.
Epoxy terminated poly- first is separately added into the 250 mL three-necked flasks with constant pressure bottom liquid funnel and magnetic stir bar
Oxygroup siloxanes (13.00 g, 0.01 mol), triethylamine (0.08 g, 0.0008 mol) and solvent acetone (50 mL).Room temperature
Under stirring, methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester (4.36 g, 0.02 mol) acetone soln (10 mL) is added drop-wise to
In reaction solution, the mass ratio of the material of epoxy terminated polymethoxysiloxanes and methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester
For 1:2, epoxy terminated polymethoxysiloxanes, 10 min are added dropwise, the reaction was continued 1 h, reaction terminates to be concentrated under reduced pressure into 30 mL
Solution, ethanol precipitation, layering remove upper layer ethanol liquid, and continuous purification 3 times removes small molecule, and pure end first is made in drying
The polymethyl siloxane material (PSi-MMA) of base acrylate structural.Fig. 5 is the nuclear magnetic spectrogram of PSi-MMA, passes through nuclear magnetic signal
The structure and nuclear-magnetism proton peak that can analyze out PSi-MMA correspond, and integrate ratio and also coincide, and obtain through nuclear-magnetism integral calculation
The grafting rate of methacrylate is up to 98%, molecular weight 1700.Meanwhile Fig. 3 is epoxy terminated polymethoxysiloxanes and PSi-
MMA INFRARED SPECTRUM comparison diagram, it was found that PSi-MMA contains 1731 cm-1Ester vibration peak, 1406 cm-1Signal be double bond
Vibration peak shows that metacrylic acid ester structure is linked on polymethyl siloxane end group, successfully prepares PSi-MMA, label
PSi-MMA01, grafting rate efficiently quickly prepare target product up to 98%, it is therefore not necessary to the metering system of additional excessive addition
Acid -3- mercaptopropionyl oxygroup ethyl ester does not crosslink equal side reactions in the process, simply mildly efficiently prepares at room temperature epoxy terminated
Polymethoxysiloxanes and PSi-MMA.
Embodiment 3
The synthesis of the polymethyl siloxane material (PSi-MMA) of terminal methyl acrylate structural.
As different from Example 2, the molecular weight of epoxy terminated polymethoxysiloxanes is 2500, n=30.
In the case where not changing the other conditions of embodiment 2, in preparation process epoxy terminated polymethoxysiloxanes and
Methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester quality is respectively as follows: 25.0 g and 4.36 g, and solvent usage is constant, can use tetrahydro
Furans, ethyl acetate, toluene, dimethylbenzene, butanone etc. replace acetone, and operating process is constant, and nuclear magnetic spectrogram and IR Characterization confirm
Successfully prepare PSi-MMA, molecular weight 2900, the grafting rate of methacrylate is up to 97%.Label PSi-MMA02.
Embodiment 4
The synthesis of the polymethyl siloxane material (PSi-MMA) of terminal methyl acrylate structural.
As different from Example 3, catalyst of triethylamine is changed to triphenyl phosphorus.
In the case where not changing the other conditions of embodiment 3, triethylamine becomes triphenyl phosphorus, and solvent usage is constant, can
Acetone is replaced with tetrahydrofuran, ethyl acetate, toluene, dimethylbenzene, butanone etc., operating process is constant, nuclear magnetic spectrogram and infrared table
Sign confirms successfully to prepare PSi-MMA, molecular weight 2900, and the grafting rate of methacrylate is up to 95%.Label PSi-MMA03.
Embodiment 5
The synthesis of the polymethyl siloxane material (PSi-MMA) of terminal methyl acrylate structural.
As different from Example 3, catalyst of triethylamine is changed to triethanolamine.
In the case where not changing the other conditions of embodiment 3, triethylamine becomes triethanolamine, catalysts and solvents dosage
It is constant, acetone can be replaced with tetrahydrofuran, ethyl acetate, toluene, dimethylbenzene, butanone etc., operating process is constant, nuclear magnetic spectrogram and
IR Characterization confirms successfully to prepare PSi-MMA, molecular weight 2900, and the grafting rate of methacrylate is up to 97%.Label PSi-
MMA04。
Embodiment 6
The synthesis of the polymethyl siloxane material (PSi-MMA) of terminal methyl acrylate structural.
As different from Example 3, catalyst of triethylamine is changed to 2,4,6 three (dimethylamino methyl) phenol (DMP-30).
In the case where not changing the other conditions of embodiment 3, triethylamine becomes 2,4,6 three (dimethylamino methyl) phenol
(DMP-30), catalysts and solvents dosage is constant, can replace third with tetrahydrofuran, ethyl acetate, toluene, dimethylbenzene, butanone etc.
Ketone, operating process is constant, and nuclear magnetic spectrogram and IR Characterization confirm successfully to prepare PSi-MMA, molecular weight 2900, metering system
The grafting rate of acid esters is up to 96%.Label PSi-MMA05.
Embodiment 7
The synthesis of polymethyl siloxane material (PSi-MMA) of the side group containing metacrylic acid ester structure.
As different from Example 2, the molecular weight of epoxy terminated polymethoxysiloxanes is 4700, n=60.
In the case where not changing the other conditions of embodiment 2, in preparation process epoxy terminated polymethoxysiloxanes and
Methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester quality is respectively as follows: 23.5 g and 2.18 g, and solvent usage is constant, can use tetrahydro
Furans, ethyl acetate, toluene, dimethylbenzene, butanone etc. replace acetone, and operating process is constant, and nuclear magnetic spectrogram and IR Characterization confirm
Successfully prepare PSi-MMA, molecular weight 5100, the grafting rate of methacrylate is up to 94%.Label PSi-MMA06.
Embodiment 8
The synthesis of polymethyl siloxane material (PSi-MMA) of the side group containing metacrylic acid ester structure.
As different from Example 2, the molecular weight of epoxy terminated polymethoxysiloxanes is 6900, n=90.
In the case where not changing the other conditions of embodiment 2, in preparation process epoxy terminated polymethoxysiloxanes and
Methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester quality is respectively as follows: 34.5 g and 2.18 g, and solvent usage is constant, can use tetrahydro
Furans, ethyl acetate, toluene, dimethylbenzene, butanone etc. replace acetone, and operating process is constant, and nuclear magnetic spectrogram and IR Characterization confirm
Successfully prepare PSi-MMA, molecular weight 7300, the grafting rate of methacrylate is up to 91%.Label PSi-MMA07.
The preparation of the polymer of other different molecular weights can be operated with reference implementation example 2.
Embodiment 9
The ultraviolet light curing reaction of the polymethyl siloxane material (PSi-MMA) of terminal methyl acrylate structural.
Compound photoinitiator: 1- hydroxycyclohexyl phenyl ketone (184) and 2- hydroxy-2-methyl -1- phenyl -1- acetone
(1173), mass ratio 1:1 is mixed.
It is 100:1 by PSi-MMA and above-mentioned compounding photoinitiator quality proportioning, is mixed into homogeneous, selection inert gas,
If high pure nitrogen (99.99%) or argon gas be bubbled except oxygen, in nitrogen atmosphere, by solution roller coating on hot print paper surface,
Serialization carry out ultraviolet light irradiation, 5 seconds, be made PSi-MMA film, Fig. 8 be no base stock hot print label figure, with it is excellent from
Type effect.
The PSi-MMA that will be prepared in embodiment 2~8, film-forming, label are respectively PSi-MMA01~PSi-MMA07.
Release performance test is carried out to cured film, Fig. 6 and Fig. 7 are the polymethyl siloxane of hot print paper and terminal methyl acrylate structural
Contact angle test figure coated in ultraviolet light film-forming on hot print paper base material, hot print paper are 107o, PSi-MMA02 paper is
114o。
The release parameter of 1 PSi-MMA film of table
Table 1 is the release performance of the PSi-MMA film of different structure under the conditions of identical compounding initiator as a result, showing PSi-
The remaining Stickiness highest of MMA02 and PSi-MMA03, up to 95%, while off-type force 21g/in or so, contact angle is from before modified
107oIt is promoted to 114o, the polymer film of other labels also complies with requirement, and PSi-MMA02 and PSi-MMA03 preparation effect is most
Good, molecular weight is that 2900 structures are the most reasonable, and it is optimal anti-that the catalyst for preparing reaction system, which is triethylamine and triphenyl phosphorus,
Answer condition.
By embodiment 2~9 it is found that can effectively cause PSi-MMA, effect using compounding initiator of the present invention
Gap is little, shows that molecular weight influences less remaining Stickiness, molecular weight is bigger, and methylsiloxane content is more, off-type force
It is smaller, the release film of different off-type forces can be prepared, reaction condition is simple, is conducive to promote and apply；PSi-MMA02 and PSi-
MMA03 preparation effect is best, and molecular weight is that 2900 structures are the most reasonable, and embodiment 2 and embodiment 3 are optimal reaction conditions,
Optimum amount based on cost consideration initiator is the 1% of PSi-MMA mass.
The foregoing is merely the preferred embodiment of the invention, are not intended to restrict the invention, to the technology of this field
For personnel, it can still modify to technical solution documented in foregoing embodiments, or to part of skill
Art feature is equivalently replaced.All within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done,
It should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method and application of ultraviolet curing type silicone oil containing methacrylate (PSi-MMA), which is characterized in that
Metacrylic acid ester structure organic matter containing sulfhydryl structure, i.e. methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester (B), with end group
Polymethyl siloxane containing epoxy (A) reaction, under the catalysis of organic base, sulfydryl efficiently and rapidly carries out open loop clickization to epoxy
It learns reaction to be made, for the grafting rate of methacrylate up to 95% or more, reactional equation is [1]:
2. the preparation method of ultraviolet curing type silicone oil containing methacrylate (PSi-MMA) according to claim 1 with
Using, it is characterised in that it is prepared from the following steps:
(1) epoxy terminated polymethoxysiloxanes (A), organic base are added in reaction flask as catalysts and solvents, stirring at normal temperature
Under, methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester solution is added drop-wise in reaction solution, 10 min are added dropwise, after reaction
It is concentrated under reduced pressure into, purification process removes small molecule, the dry polymethyl siloxane that pure terminal methyl acrylate structural is made
Material (PSi-MMA)；
(2) PSi-MMA and above-mentioned compounding photoinitiator are mixed into homogeneously, inert gas is selected be bubbled except oxygen, it will
On paper base material, serialization carries out ultraviolet light irradiation for liquid roller coating, and 1~5 second, PSi-MMA film is made.
3. the preparation method of ultraviolet curing type silicone oil containing methacrylate (PSi-MMA) according to claim 1 to 2
With application, n is arbitrary integer in the structure of the epoxy terminated polymethoxysiloxanes of the raw material, may be set to n=10~200,
Molecular weight is 1000~15000.
4. the preparation method of ultraviolet curing type silicone oil containing methacrylate (PSi-MMA) according to claim 1 to 3
With application, raw material B is methacrylic acid -3- mercaptopropionyl oxygroup ethyl ester, and raw material B dosage is the epoxy terminated poly- of 2 times of moles
Methoxy radical siloxane, organic base are usually triethylamine, triphenyl phosphorus, triethanolamine, 2,4,6 three (dimethylamino methyl) phenol
(DMP-30) etc..
5. the preparation method of ultraviolet curing type silicone oil containing methacrylate (PSi-MMA) described in -4 according to claim 1
With application, reaction temperature is room temperature (25oC), solvent can optional acetone, tetrahydrofuran, ethyl acetate, toluene, dimethylbenzene, fourth
The good solvents such as ketone, reaction time are 1 hour, and solvent is recyclable to be recycled, and entire process flow is simply controllable.
6. the preparation method of ultraviolet curing type silicone oil containing methacrylate (PSi-MMA) described in -5 according to claim 1
With application, the highly efficiency compositional conventional free radical photoinitiator of selection are as follows: 1- hydroxycyclohexyl phenyl ketone (184) and 2- hydroxyl-
The similar radical photoinitiator such as 2- methyl-1-phenyl-1- acetone (1173), mass ratio 1:1 mixing.
7. the preparation method of ultraviolet curing type silicone oil containing methacrylate (PSi-MMA) described in -6 according to claim 1
With application, it is 1% that compounding photoinitiator optimum amount, which is PSi-MMA mass content, is mixed into homogeneous, selection such as high pure nitrogen
(99.99%) or the inert gases such as argon gas are as protective gas, carry out ultraviolet light irradiation 1~5 second, PSi-MMA film is made.
8. the preparation method of ultraviolet curing type silicone oil containing methacrylate (PSi-MMA) described in -7 according to claim 1
With application, the optimal molecular weight of best PSi-MMA is 2900, m=30, and compounding photoinitiator optimum amount is that PSi-MMA mass contains
Amount is 1%, and remaining Stickiness is up to 95% after film forming, 21 g/in of off-type force.
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