CN104520376A - Polymerizable composition for epoxy acrylic optical material, and method for preparing epoxy acrylic optical material - Google Patents
Polymerizable composition for epoxy acrylic optical material, and method for preparing epoxy acrylic optical material Download PDFInfo
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- CN104520376A CN104520376A CN201380042260.9A CN201380042260A CN104520376A CN 104520376 A CN104520376 A CN 104520376A CN 201380042260 A CN201380042260 A CN 201380042260A CN 104520376 A CN104520376 A CN 104520376A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
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Abstract
The present invention relates to a polymerizable composition for an epoxy acrylic optical material, and a method for preparing an epoxy acrylic optical material, and particularly, to: a polymerizable composition for an epoxy acrylic optical material which maintains suitable viscosity and reaction velocity, and thereby facilitates preparation of an optical material; and a method for preparing an optical material. The present invention provides a polymerizable composition for an epoxy acrylic optical material, comprising an epoxy acrylate-based compound and a dibenzyl malate product containing 10-25 wt% of monobenzyl malate. The present invention can provide a polymerizable composition for an epoxy acrylic optical material which uses a dibenzyl malate product containing 10-25 wt% of monobenzyl malate together with a monomer component, thereby having a suitable handling property and reactivity to facilitate the preparation of an optical material. It is possible to prepare, in a high yield, a high quality epoxy acrylic optical material having a high refractive index, a high Abbe's number and remarkable optical properties such as transparency, lightweightness, heat resistance and the like by template polymerizing the polymerizable composition of the present invention.
Description
Technical field
The present invention relates to the preparation method of propylene oxide acids polymerizable composition for optical material and propylene oxide acids optical material, especially, relate to and maintain suitable viscosity and speed of response and be easily prepared into the propylene oxide acids polymerizable composition for optical material of optical material and the preparation method of optical material.
Background technology
Plastic optical lens introduction is solve as the high specific gravity of glass lens problem and the substitute of low impact.Representational have polyoxyethylene glycol diene propyl carbonate (polyethylene glycol bis (allyl carbonate)), polymethylmethacrylate (polymethyl methacrylate), Phthalic acid, diallyl ester (diallyl phthalate) etc.But, the optical lens prepared by the polymkeric substance in them is outstanding in the physical property such as template, dyeability, hard coat film compactness, shock-resistance, but there is the problem making lens thickening because specific refractory power drops to 1.50 (nD) and 1.55 (nD) left and right.Therefore, in order to reduce the thickness of lens, attempt to develop the high optical material of various specific refractory power.
Disclose different from this thioxanthamide class lens in Korea S login special permission 10-0496911,10-0498896 etc., there is high specific refractory power, the optical characteristics such as Abbe number is high, transparent, light weight, thermotolerance are outstanding, and the cheap propylene oxide acids composition for optical material of material.With regard to this propylene oxide acids optical material, in the area of high temperature and humidity, also without the need to additional management moisture in air, and lens can be produced, and also the center of lens will be deformed because of the moisture in air when preserving lens.But, when polymeric epoxy acrylate compounds prepares lens, need the reactive diluent of Adjustable viscosity and speed of response.As this reactive diluent, in the past, employ vinylbenzene (styrene), Vinylstyrene (divinylbenzene), alpha-methyl styrene (α-methyl styrene), α-methylstyrenedimer (α-methyl styrene dimer), benzyl methacrylate (benzyl methacrylate), chloro-styrene (chlorostyrene), bromstyrol (bromostyrene), methoxy styrene (methoxy styrene), a kind of in dibenzyl maleate (dibenzyl maleate) etc. or the two or more mixture in them.Wherein, dibenzyl maleate has the advantage of economy, replaces other monomer components, thus has the effect of the usage quantity of other monomer components that can reduce high price, therefore, also together uses with other reaction diluents in the past.But because dibenzyl maleate is solid phase, be thus difficult to the viscosity and the speed of response that regulate Polymerizable composition, make the treatability in the process of blend compositions poor, and maintain suitable speed of response aspect existing problems afterwards.Reduce the main concern that production cost becomes nearest lens art, the lower rationality in preparation process causes the preparation section being difficult to carry out optical material, thus becomes the factor reducing productivity.And, when suitable speed of response cannot be maintained, that is, speed of response is slow at the beginning, when but rising along with temperature and accelerate suddenly, the quality producing the lens such as arteries and veins reason likely reduces, on the contrary, when the post-polymerization of mixing carries out too fast, imperfect owing to being polymerized, the various optical characteristics such as specific refractory power, intensity, the transparency likely reduce, and thus maintaining suitable speed of response becomes important factor to lens quality.
Prior art document
Patent documentation
Patent documentation 1: Korea S logs in Application Publication 10-0496911
Patent documentation 2: Korea S logs in Application Publication 10-0498896
Summary of the invention
Technical problem
The present inventor has unexpectedly found following situation: if use the dibenzyl maleate for reactive diluent not carry out the dibenzyl of 100% in the preparation of propylene oxide acids optical material in preparation process, but prepare with the state of the toxilic acid list benzyl ester (monobenzyl maleate) comprising 10 ~ 25 weight percentage ranges, then there is suitable mobility, and improve with the treatability of the Polymerizable composition of the epoxy acrylate compound as monomer, and suitable speed of response can be maintained.The present invention confirms foregoing and completes, the object of the invention is to, there is provided and utilize the dibenzyl maleate prepared product of the toxilic acid list benzyl ester containing constant basis to improve to make treatability, and suitably can maintain the propylene oxide acids polymerizable composition for optical material of speed of response.Further, the object of the invention is to, by aforesaid method, improve the productivity of lens, and prepare the optical material of the outstanding high-quality of optical characteristics with high lens yield.
Technical scheme
In this specification sheets, " dibenzyl maleate prepared product " refers to, as the final product that the preparation section by dibenzyl maleate obtains, except as except the dibenzyl maleate of desired substance, what together comprised by the by product of the toxilic acid list benzyl ester produced in preparation process etc. prepares product, or using dibenzyl maleate as principal constituent, comprise the composition of a part of toxilic acid list benzyl ester or dibenzyl fumarate (dibenzyl fumarate) as required.
The invention provides the propylene oxide acids polymerizable composition for optical material of the dibenzyl maleate prepared product comprising compound that (a) represented by following chemical formula 1 and (b) toxilic acid list benzyl ester containing 10 ~ 25 weight percents.Propylene oxide acids polymerizable composition for optical material of the present invention also can comprise the compound represented by following chemical formula 2.
Chemical formula 1:
(wherein n=0 ~ 15, R
1for H or CH
3, R
2for H or Br.)
Chemical formula 2:
(wherein, R is H or CH
3, m=0 ~ 5, n=0 ~ 5, m with n be 0 time different, m+n=1 ~ 10.)
And, the invention provides the preparation method of propylene oxide acids optical material, the preparation method of above-mentioned propylene oxide acids optical material comprises the steps: when the Polymerizable composition comprising the compound represented by above-mentioned chemical formula 1 is carried out template polymerization, and the dibenzyl maleate prepared product being 10 ~ 25 weight percents by the content of toxilic acid list benzyl ester makes an addition to above-mentioned Polymerizable composition and carries out template polymerization after mixing.
Further, the invention provides and above-mentioned Polymerizable composition is carried out the optical material that template polymerization obtains and the optical lens formed by above-mentioned optical material.Above-mentioned optical lens especially comprises ophthalmic lens or polarized lenses.
Useful effect
In the present invention, be that dibenzyl maleate prepared product and the monomer component of 10 ~ 25 weight percents together uses by the content of toxilic acid list benzyl ester, can provide and easily be prepared into there is suitable treatability and reactive propylene oxide acids polymerizable composition for optical material and utilizing its optical material of optical material.The treatability of Polymerizable composition of the present invention is outstanding, the productivity of lens can be improved, and suitably can maintain speed of response, thus optical characteristics can be obtained with high yield, that is, there is the propylene oxide acids optical material of the outstanding high-quality of the optical characteristics such as high refractive index, high Abbe number, the transparency, light weight, thermotolerance.
Embodiment
Propylene oxide acids polymerizable composition for optical material of the present invention comprises the dibenzyl maleate prepared product that (a) is 10 ~ 25 weight percents containing the acrylic ester compound of compound represented by following chemical formula 1 and the content of (b) toxilic acid list benzyl ester.Polymerizable composition of the present invention also can comprise the compound represented by following chemical formula 2.
Chemical formula 1:
Wherein n be 0 ~ 15, R
1for H or CH
3, R
2for H or Br.N is preferably 0 ~ 10, is more preferably 0 ~ 5.
Chemical formula 2:
(wherein, R is H or CH
3, m=0 ~ 5, n=0 ~ 5, m with n are 0 time different, m+n=1 ~ 10.)
As above-mentioned dibenzyl maleate prepared product, preferably, dibenzyl completely can be used in preparation process, but be in the material of the state of the toxilic acid list benzyl ester remained about 10 ~ 25 weight percents.In dibenzyl maleate prepared product, when the content of toxilic acid list benzyl ester is less than 10 weight percent, become solid phase on the whole, make poor fluidity, this can reduce the treatability of Polymerizable composition, also produces bad impact to reactivity.Further, when the content of toxilic acid list benzyl ester is greater than 25 weight percent, be difficult to the suitable speed of response maintaining Polymerizable composition, cause likely producing arteries and veins reason when preparing lens, and make the specific refractory power step-down of lens.
And, when preparing the dibenzyl maleate as cis body, as the trans-isomer(ide) of geometrical isomer, namely, the dibenzyl fumarate of constant basis can be mixed into, but reaffirmed that the mobility of incorporation rate to dibenzyl maleate prepared product as the dibenzyl fumarate of trans-isomer(ide) has an impact in the present invention, and this has an impact to the viscosity of Polymerizable composition and speed of response.Preferably, in dibenzyl maleate prepared product, the content of dibenzyl fumarate is less than 40 weight percents.When the content of dibenzyl fumarate is greater than 40 weight percent, the state of dibenzyl maleate prepared product becomes solid phase, and poor fluidity, this can reduce the treatability of Polymerizable composition, and produces bad impact to the suitable speed of response of maintenance.More preferably, in dibenzyl maleate prepared product, the content of dibenzyl fumarate is 5 to 25 weight percents.
Dibenzyl maleate prepared product of the present invention, except toxilic acid list benzyl ester and/or dibenzyl fumarate, also can comprise other by products generated unintentionally in preparation process.As other by products, especially can comprise mono-benzyl fumarate, preferably, in dibenzyl maleate prepared product, the content of mono-benzyl fumarate is a small amount of, preferably, is no more than the maximum half of the content of toxilic acid list benzyl ester.
The content comprising toxilic acid list benzyl ester is in the epoxy acrylic Type of Collective composition of the present invention of the dibenzyl maleate prepared product of 10 ~ 25 weight percents, preferably, liquid phase viscosity is 20 ~ 600cp, liquid phase specific refractory power (nE at 25 DEG C of temperature, 20) be 1.50 ~ 1.58, solid phase specific refractory power (nE, 20) is 1.54 ~ 1.63.If the viscosity of liquid phase is less than 20cps, when then injecting liquid phase resin combination to the glass mold assembled by synthetic resin gasket and carry out shaping, there is the problem that composition flows out outside mould, if the viscosity of liquid phase is greater than 500cps, then exists and be difficult to problem composition being flow into mould.Viscosity is more preferably 30 ~ 600cps.
Polymerizable composition of the present invention, except above-mentioned dibenzyl maleate prepared product, also can comprise other reactive diluents.As other reactive diluents, such as, Polymerizable composition of the present invention can comprise and is selected from by vinylbenzene, Vinylstyrene, alpha-methyl styrene, α-methylstyrenedimer, benzyl methacrylate, chloro-styrene, bromstyrol, methoxy styrene, mono-benzyl fumarate (monobenzyl fumarate), dibenzyl fumarate, methyl-benzyl maleic acid ester (methyl benzyl maleate), dimethyl maleate (dimethyl maleate), ethyl maleate (diethyl maleate), dibutyl maleinate (dibutyl maleate), dibutyl fumarate (dibutylfumarate), butyl maleate (monobutyl maleate), toxilic acid list pentyl ester (monopentyl maleate), dipentyl maleate (dipentyl maleate), fumaric acid list pentyl ester (monopentyl fumarate), one or more compound in the group that fumaric acid diamyl ester (dipentyl fumarate) and diethylene glycol bis-aryl carbonates (diethylene glycol bis-aryl carbonate) form.
Preferably, the ratio comprising the global reactivity thinner of dibenzyl maleate prepared product relative to 100 weight parts the compound represented by above-mentioned chemical formula 1 or be mixed with the acrylic ester compound of the compound represented by above-mentioned chemical formula 1 and the compound represented by chemical formula 2, about using 30 ~ 300 weight parts.When use is less than the reactive diluent of 30 weight parts, reduce the workability injecting mould because viscosity is high.Further, using in the reactive diluent situation being greater than 300 weight parts, because viscosity is too low, when flowing into the glass mold assembled by pad, Polymerizable composition likely flows out outside mould.
In addition, Polymerizable composition of the present invention also can comprise inner parting agent, thermo-stabilizer, UV light absorber, organic dye, mineral dye, painted preventing agent, antioxidant, photostabilizer, catalyzer etc. according to the preparation method of common optical lens.
As inner parting agent, can use in phosphate compound, silicon class tensio-active agent, fluorine class tensio-active agent etc. one or more.Preferably, as inner parting agent, phosphate compound can be used.Preferably, in Polymerizable composition, the inside parting agent of 0.001 ~ 10 weight percent can be comprised.Phosphate compound for inner parting agent such as (can add 5 weight percents of the oxyethane of 5 moles for being selected from by polyoxyethylene nonylphenol ether phosphate (polyoxyethylene nonyl phenolether phosphate), add 80 weight percents of the oxyethane of 4 moles, add 10 weight percents of the oxyethane of 3 moles, add 5 weight percents of the oxyethane of 1 mole), polyoxyethylene nonylphenol ether phosphate (adds 5 weight percents of the oxyethane of 9 moles, add 80 weight percents of the oxyethane of 8 moles, add 10 weight percents of the oxyethane of 7 moles, add 5 weight percents of the oxyethane of less than 6 moles), polyoxyethylene nonylphenol ether phosphate (adds 3 weight percents of the oxyethane of 11 moles, add 80 weight percents of the oxyethane of 8 moles, add 5 weight percents of the oxyethane of 9 moles, add 6 weight percents of the oxyethane of 7 moles, add 6 weight percents of the oxyethane of 6 moles), polyoxyethylene nonylphenol ether phosphate (adds 3 weight percents of the oxyethane of 13 moles, add 80 weight percents of the oxyethane of 12 moles, add 8 weight percents of the oxyethane of 11 moles, add 3 weight percents of the oxyethane of 9 moles, add 6 weight percents of the oxyethane of 4 moles), polyoxyethylene nonylphenol ether phosphate (adds 3 weight percents of the oxyethane of 17 moles, add 79 weight percents of the oxyethane of 16 moles, add 10 weight percents of the oxyethane of 15 moles, add 4 weight percents of the oxyethane of 14 moles, add 4 weight percents of the oxyethane of 13 moles), polyoxyethylene nonylphenol ether phosphate (adds 5 weight percents of the oxyethane of 21 moles, add 78 weight percents of the oxyethane of 20 moles, add 7 weight percents of the oxyethane of 19 moles, add 6 weight percents of the oxyethane of 18 moles, add 4 weight percents of the oxyethane of 17 moles), two sad phosphoric acid ester (dioctyl acid phosphate) and Zelec UN
tMone or more compound in the group of composition.
Preferably, in composition, the thermo-stabilizer of 0.01 ~ 5 weight percent can be comprised.When use is less than the thermo-stabilizer of 0.01 weight percent, thermal stability result is low, when use is greater than the thermo-stabilizer of 5 weight percents, is polymerized fraction defective high when there is solidification, and the problem that the thermostability of cured article is low on the contrary.As thermo-stabilizer, such as, can use one or more the compound be selected from as in the compound of the calcium stearate, barium stearate, Zinic stearas, cadmium stearate, lead stearate, Magnesium Stearate, aluminum stearate, potassium stearate, zinc octoate etc. of fatty acid metal salt.Further, the triphenyl phosphite (triphenylphosphite) be selected from as Phosphorus can be used, phenylbenzene decyl phosphorous acid ester (diphenyl decyl phosphite), phenyl didecyl phosphite (phenyl didecyl phosphite), phenylbenzene dodecyl phosphorous acid ester (diphenyl dodecyl phosphite), trinonylphengl phosphite (trinonylphenyl phosphite), phenylbenzene iso-octyl phosphorous acid ester (diphenyl isooctyl phosphite), tributyl phosphate (tributyl phosphate), tripropyl phosphite (tripropyl phosphite), triethyl-phosphite (triethyl phosphite), trimethyl phosphite (trimethyl phosphite), three (single decyl phosphorous acid esters) (tris (monodecyl phosphite)), one or more compound in three (single phenyl phosphites) (tris (monophenyl phosphite)).Further, the 3PbO.PbSO4.4H be selected from as plumbous class can also be used
2o, 2PbO.Pb (C
8h
4o
4), 3PbO.Pb (C
4h
2o
4) .H
2one or more in the compound of O etc., also the dibutyl tin laurate (dibutyltin dilaurate) be selected from as organic tin can be used, dibutyitin maleate (dibutyltin maleate), two (the different monooctyl ester of toxilic acid) (dibutyltin bis (the isooctyl maleate)) of dibutyl tin, dioctyl maleate (dioctyl maleate), two (monomethyl maleate) (dibutyltin bis (the monomethyl maleate)) of dibutyl tin, two (lauryl mercaptan) (dibutyltin bis (the lauryl mercaptan)) of dibutyl tin, two (different oxygen base mercaptoacetate) (dibutyl bis (the isooxyl mercapto acetate)) of dibutyl, Monobutyltin three (isooctyl mercaptoacetate) (monobutyltin tris (isooctyl mercapto acetate)), two (isooctyl mercaptoacetate) (dimethyltin bis (the isooctyl mercapto acetate)) of tin methide, three (isooctyl mercaptoacetates) (tris (isooctyl mercapto acetate)), two (isooctyl mercaptoacetate) (dioctyltin bis (the isooctyl mercapto acetate)) of dioctyl tin, two (2 mercapto ethanol salt) (dibutyltin bis (2-mercaptoethylate)) of dibutyl tin, Monobutyltin three (2 mercapto ethanol salt) (monobutyltin tris (2-mercapto ethylate)), two (2 mercapto ethanol salt) (dimethyltin bis (the 2-mercapto ethylate)) of tin methide, one or more in the compound of monomethyl tin three (2 mercapto ethanol salt) (monomethyltin tris (2-mercapto ethylate)) etc.Further, also can mix the two or more thermo-stabilizer of different series in above-mentioned illustrative thermo-stabilizer and use.Most preferably, using Phosphorus thermo-stabilizer, be not only the priming color of shaping lens, also when not reducing the optical characteristics such as the transparency, shock strength, thermotolerance and polymerization yield, greatly improving the thermostability of optical lens.
In the preparation method of propylene oxide acids optical material of the present invention, when the Polymerizable composition comprising the compound represented by above-mentioned chemical formula 1 is carried out template polymerization, the content adding toxilic acid list benzyl ester to above-mentioned Polymerizable composition is the dibenzyl maleate prepared product of 10 ~ 25 weight percents and carries out template polymerization after mixing.Now, according to preferred embodiment, above-mentioned Polymerizable composition also can comprise the compound represented by above-mentioned chemical formula 2.According to preferred embodiment, after hybrid epoxidized acrylic compound and reactive diluent, add catalysts and carry out vacuum deaerator after stirring, thus injecting Polymerizable composition to mould.The mould being injected with Polymerizable composition is put into forced cyclic type baking oven, and is slowly heating and curing after 100 DEG C from 30 DEG C, be cooled to about 70 ~ 10 DEG C, thus mounting or dismounting mould obtains lens.
Embodiment
Below, the present invention is illustrated in greater detail by specific embodiment.But these embodiments are only for further illustrating the present invention, and scope of the present invention should not be limited to these embodiments.
dibenzyl maleate prepared product
Synthesis example 1
Four-hole boiling flask to 2L puts into the dimethyl maleate of 144g (1.0 moles) and the phenylcarbinol of 216g (2.0 moles), the Dibutyltin oxide (dibutyltin oxide) adding 0.2g stirs as after catalyzer, heats up (outside heat medium temperature is set as 160 DEG C) when internal temperature is 140 DEG C.From the moment that internal temperature reaches 140 DEG C after about 1 hour, start to produce methyl alcohol, after producing the methyl alcohol of about 30g, speed of response is slack-off.Afterwards, utilize vacuum pump to carry out underpressure distillation, thus add the methyl alcohol reclaiming about 21g, and carry out cooling with the mode gas clean-up making contents temperature become less than 105 DEG C, reclaim residual benzyl alcohol, and the content being condensed into the phenylcarbinol in entire content is less than 1%.Afterwards, be cooled to less than 60 DEG C, and after removing decompression, GC analysis carried out to resultant.When each GC area sum of the toxilic acid analyzed through GC list benzyl ester, dibenzyl maleate, dibenzyl fumarate is set to 100%, obtain the dibenzyl maleate prepared product that generated toxilic acid list benzyl ester is 15.6%, dibenzyl maleate is 79.2%, dibenzyl fumarate is the 280g of 5.2%.Liquid phase specific refractory power is 1.5482, places after 24 hours at 15 ~ 24 DEG C of temperature, and property is liquid phase mutually and processes without any problem.
physical property experiment method
Measure physical property by following physical property measurement method, and have recorded its result in lower list 1.
1) specific refractory power and Abbe number: the Abbe refractometer being used as love to open up the DR-M4 model of (Atago) company measures.
2) vapor-phase chromatography (GC, Gas Chromatography) analyze: be used as the GC equipment of the 7890A model of Agilent (Agilent) company to measure, according to measurement result, temperature range is 60 DEG C ~ 260 DEG C, and heating condition is 20 DEG C/min.Using HP-5 (L:30, I.D.:0.320, film (Film): 0.25mm) as post, inject the nitrogen of 20mL/min, solvent employs acetone.
Synthesis example 2 ~ synthesis example 7
Use the raw material identical with synthesis example 1, carry out with identical operation, and change each reaction conditions a little to the mutually different dibenzyl maleate prepared product of the degree that is mixed into obtaining dibenzyl degree and trans-isomer(ide).The characteristic of each dibenzyl maleate prepared product obtained is shown in lower list 1.
Relatively synthesis example 1 ~ compare synthesis example 3
Use the raw material identical with synthesis example 1, carry out with identical operation, and change each reaction conditions to the mutually different dibenzyl maleate prepared product of the degree that is mixed into obtaining dibenzyl degree and trans-isomer(ide).The characteristic of each dibenzyl maleate prepared product obtained is shown in lower list 1.
Table 1
* each GC area of toxilic acid list benzyl ester, dibenzyl maleate, dibenzyl fumarate is set to 100%.
epoxy Acrylates compound
1) synthesis of composition (I) compound
Composition (I) compound is represented at chemical formula 3, be add vinylformic acid in the YD-128 epoxy resin of the national capital chemistry of 187 and carry out acroleic acid esterification (react at 105 DEG C of temperature and prepare for 20 hours) to have prepared the compound that equivalent is 259 to equivalent, to be molecular-weight average be 518 mixture.
Chemical formula 3:
(n＝0～15)
2) composition (II) compound
Composition (II) compound is represented at chemical formula 4, be add vinylformic acid in the epoxy resin of 201 and carry out acroleic acid esterification (react at 105 DEG C of temperature and prepare for 20 hours) to have prepared the compound that equivalent is 273 to equivalent, to be molecular-weight average be 546 mixture.
Chemical formula 4:
(n＝0～15)
3) composition (III) compound
Composition (III) compound is represented at chemical formula 5, be add vinylformic acid in the YDB-400 epoxy resin of the national capital chemistry of 400 and carry out acroleic acid esterification (react at 105 DEG C of temperature and prepare for 20 hours) to have prepared the compound that equivalent is 472 to equivalent, to be molecular-weight average be 944 mixture.Be equivalent be 472, molecular-weight average is the mixture of 944.
Chemical formula 5:
(n＝0～15)
4) composition (IV) compound
Composition (IV) compound is represented at chemical formula 6, be add vinylformic acid in the epoxy resin of 414 and carry out acroleic acid esterification (react at 105 DEG C of temperature and prepare for 20 hours) to have prepared the compound that equivalent is 486 to equivalent, to be molecular-weight average be 972 mixture.
Chemical formula 6:
(n＝0～15)
5) composition (V) compound
Be be added with in the ethanol of oxyethane in the dihydroxyphenyl propane of 175 to add vinylformic acid and carry out acroleic acid esterification (react at 105 DEG C of temperature and prepare for 20 hours) to have prepared the compound that equivalent is 229 to equivalent.To be molecular-weight average be 458 mixture, structural formula is as following chemical formula 7.
Chemical formula 7:
(m=0 ~ 5, n=0 ~ 5 are 0, m+n=1 ~ 10 when m with n is different.)
6) composition (VI) compound
Be be added with in the ethanol of oxyethane in the dihydroxyphenyl propane of 175 to add methacrylic acid (methacrylicacid) and carry out acroleic acid esterification (react at 105 DEG C of temperature and prepare for 20 hours) to have prepared the compound that equivalent is 243 to equivalent.To be molecular-weight average be 486 mixture, structural formula is as following chemical formula 8.
Chemical formula 8:
(m=0 ~ 5, n=0 ~ 5 are 0, m+n=1 ~ 10 when m with n is different.)
Embodiment 1
Vinylbenzene, the alpha-methyl styrene of 5g, the methyl styrene dimer thing of 2g, the tributyl phosphate (TBP of 2g of 35g is added in the composition (III) of the composition (I) of the 20g in the Epoxy Acrylates compound obtained in the above-described manner, 15g and the composition (V) of 15g, and the dibenzyl maleate prepared product of the synthesis example 1 of 8g, and stir about 30 minutes tributylphosphite).Afterwards, utilize the filter paper of less than 0.45 μm to filter, and the 3-M adding V65,0.13g of 0.05g is wherein as catalyzer, utilizes inner parting agent to mix the ZelecUN of 0.2g
tM, thus prepared ophthalmic lens resin combination.After the ophthalmic lens resin combination so prepared is stirred 1 hour, vacuum deaerator 10 minutes also filters, and afterwards, flows into the glass mold assembled by polyester adhesive tape.The glass mold being injected with ophthalmic lens resin combination is put into forced cyclic type baking oven, was heating and curing after to 110 DEG C from 35 DEG C through 20 hours, is cooled to 70 DEG C, and install and remove glass mold to obtain ophthalmic lens.It is after 72mm that the lens obtained are processed to diameter, in alkali aqueous rinsing liquid, carry out ultrasonic cleaning, afterwards, and anneal 2 hours at 120 DEG C of temperature.Measure physical property in the following manner, and the results are shown in table 2.
physical property experiment method
Measure the physical property of the optical lens prepared by following physical property experiment method, and by its outcome record in lower list 2.
1) specific refractory power and Abbe number: the Abbe refractometer being used as love to open up the DR-M4 model of (Atago) company measures.
2) proportion: utilize analytical balance and measured by method of substitution in water.
3) be polymerized unbalanced: observe by naked eyes and as the mercuryarc lamp (Mercury Arc Lamp) of USH10USH-102D 100 lens obtained in operation, if there is the optical distortion of less than 1, then be expressed as " ◎ ", if there are 2 ~ 3 optical distortions, then be expressed as "○", be greater than the optical distortion of 3 if occur, be then expressed as " X ".
Embodiment 2 ~ embodiment 7
Prepare composition and optical lens respectively according to moiety described in table 2 in the same manner as in Example 1, physical property is tested, and the results are shown in table 2.
Comparative example 1
Add the dibenzyl maleate prepared product of the comparison synthesis example 1 of the vinylbenzene of 35g, the alpha-methyl styrene of 5g, the methyl styrene dimer thing of 2g, the tributyl phosphate of 2g and 8g in the composition (III) of the composition (I) of the 20g in Epoxy Acrylates compound, 15g and the composition (V) of 15g after, stir about 30 minutes.Afterwards, utilize the filter paper of less than 0.45 μm to filter, and the 3-M adding V65,0.13g of 0.05g is wherein as catalyzer, utilizes inner parting agent to mix the Zelec UN of 0.2g
tM, thus prepared optical lens resin combination in the same manner as in Example 1.Prepare optical lens by above-mentioned composition, measure the physical property of lens, and the results are shown in table 2.
Comparative example 2 ~ comparative example 3
Prepare composition and optical lens with the method identical with comparative example 1 respectively according to moiety described in table 2, physical property is tested, and the results are shown in table 2.
Table 2
Be called for short
inner parting agent
Zelec UN
tM: the phosphate compound standby by Si Taipan (Stapan) Inc., commodity are called Zelec UN
DOP: two sad phosphoric acid ester (dioctyl acid phosphate)
8-PENPP: polyoxyethylene nonylphenol ether phosphate (5 weight percents adding 5 weight percents of the oxyethane of 9 moles, add 80 weight percents of the oxyethane of 8 moles, add 10 weight percents of the oxyethane of 7 moles, add the oxyethane of less than 6 moles)
thermally-stabilised
TPP: triphenyl phosphite (triphenylphosphite)
TBP: tributyl phosphate (tributylphosphite)
DPP: phosphorous acid hexichol isodecyl ester (diphenylisodecylphosphite)
polymerization starter
V65:2, two (2,4-methyl pentane nitrile) (2,2 '-azobis (2, the 4-dimethylvaleronitrile) of 2 '-azo
3-M:1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane (1,1-bis (t-butylperoxy)-3,3,5-trimethyl cyclohexane)
Utilizability in industry
According to the present invention, can easily prepare propylene oxide acids optical material of fine qualities with low preparation expense.Propylene oxide acids optical material prepared in accordance with the present invention replaces existing thioxanthamide class optical material, extensively can be used in the multiple optical material field comprising ophthalmic lens or camera lens etc.Especially, plastic spectacle lens can be utilized as, the 3D polarized lenses etc. of light polarizing film is installed at ophthalmic lens, in addition, can be used in and be used in the recording medium substrate of prism, fiber optics, CD etc. or the multiple optical articles of painted strainer and ultraviolet radiation absorption strainer.
Claims (17)
1. a propylene oxide acids polymerizable composition for optical material, is characterized in that,
Comprise:
A compound that () is represented by following chemical formula 1, and
The dibenzyl maleate prepared product of (b) toxilic acid list benzyl ester containing 10 ~ 25 weight percents,
Chemical formula 1:
(wherein, n=0 ~ 15, R
1for H or CH
3, R
2for H or Br).
2. propylene oxide acids polymerizable composition for optical material according to claim 1, is characterized in that, also comprises the compound represented by following chemical formula 2,
Chemical formula 2:
(wherein, R is H or CH
3, m=0 ~ 5, n=0 ~ 5 are 0, m+n=1 ~ 10 when m with n is different).
3. propylene oxide acids polymerizable composition for optical material according to claim 1 and 2, it is characterized in that, above-mentioned dibenzyl maleate prepared product contains the dibenzyl fumarate of below 40 weight percents.
4. propylene oxide acids polymerizable composition for optical material according to claim 1 and 2, it is characterized in that, in above-mentioned propylene oxide acids polymerizable composition for optical material, liquid phase viscosity is 20 ~ 600cps at 25 DEG C of temperature, liquid phase specific refractory power (nE, 20 DEG C) be 1.50 ~ 1.58, solid phase specific refractory power (nE, 20 DEG C) is 1.54 ~ 1.63.
5. propylene oxide acids polymerizable composition for optical material according to claim 1 and 2, it is characterized in that, reactive diluent also comprises and is selected from by vinylbenzene, Vinylstyrene, alpha-methyl styrene, α-methylstyrenedimer, benzyl methacrylate, chloro-styrene, bromstyrol, methoxy styrene, mono-benzyl fumarate, dibenzyl fumarate, methyl-benzyl maleic acid ester, dimethyl maleate, ethyl maleate, dibutyl maleinate, dibutyl fumarate, butyl maleate, toxilic acid list pentyl ester, dipentyl maleate, fumaric acid list pentyl ester, one or more compound in the group of fumaric acid diamyl ester and diethylene glycol bis-aryl carbonates composition.
6. propylene oxide acids polymerizable composition for optical material according to claim 5, it is characterized in that, relative to 100 weight parts the compound represented by above-mentioned chemical formula 1 or be mixed with the acrylic ester compound of the compound represented by above-mentioned chemical formula 1 and the compound represented by chemical formula 2, comprise the global reactivity thinner containing dibenzyl maleate prepared product of 30 ~ 300 weight parts.
7. propylene oxide acids polymerizable composition for optical material according to claim 1 and 2, is characterized in that, also comprises phosphate compound as inner parting agent.
8. propylene oxide acids polymerizable composition for optical material according to claim 7, is characterized in that, above-mentioned phosphate compound (adds 5 weight percents of the oxyethane of 5 moles for being selected from by polyoxyethylene nonylphenol ether phosphate, add 80 weight percents of the oxyethane of 4 moles, add 10 weight percents of the oxyethane of 3 moles, add 5 weight percents of the oxyethane of 1 mole), polyoxyethylene nonylphenol ether phosphate (adds 5 weight percents of the oxyethane of 9 moles, add 80 weight percents of the oxyethane of 8 moles, add 10 weight percents of the oxyethane of 7 moles, add 5 weight percents of the oxyethane of less than 6 moles), polyoxyethylene nonylphenol ether phosphate (adds 3 weight percents of the oxyethane of 11 moles, add 80 weight percents of the oxyethane of 8 moles, add 5 weight percents of the oxyethane of 9 moles, add 6 weight percents of the oxyethane of 7 moles, add 6 weight percents of the oxyethane of 6 moles), polyoxyethylene nonylphenol ether phosphate (adds 3 weight percents of the oxyethane of 13 moles, add 80 weight percents of the oxyethane of 12 moles, add 8 weight percents of the oxyethane of 11 moles, add 3 weight percents of the oxyethane of 9 moles, add 6 weight percents of the oxyethane of 4 moles), polyoxyethylene nonylphenol ether phosphate (adds 3 weight percents of the oxyethane of 17 moles, add 79 weight percents of the oxyethane of 16 moles, add 10 weight percents of the oxyethane of 15 moles, add 4 weight percents of the oxyethane of 14 moles, add 4 weight percents of the oxyethane of 13 moles), polyoxyethylene nonylphenol ether phosphate (adds 5 weight percents of the oxyethane of 21 moles, add 78 weight percents of the oxyethane of 20 moles, add 7 weight percents of the oxyethane of 19 moles, add 6 weight percents of the oxyethane of 18 moles, add 4 weight percents of the oxyethane of 17 moles), two sad phosphoric acid ester and Zelec UN
tMone or more compound in the group of composition.
9. propylene oxide acids polymerizable composition for optical material according to claim 1 and 2, is characterized in that, in total composition, comprises the thermo-stabilizer of 0.01 ~ 5 weight percent.
10. the preparation method of a propylene oxide acids optical material, it is characterized in that, comprise the steps: when the propylene oxide acids polymerizable composition for optical material comprising the compound represented by following chemical formula 1 is carried out template polymerization, the dibenzyl maleate prepared product being 10 ~ 25 weight percents by the content of toxilic acid list benzyl ester makes an addition to above-mentioned propylene oxide acids polymerizable composition for optical material and carries out template polymerization after mixing
Chemical formula 1:
(wherein, n=0 ~ 15, R
1for H or CH
3, R
2for H or Br).
The preparation method of 11. propylene oxide acids optical materials according to claim 10, it is characterized in that, above-mentioned Polymerizable composition also comprises the compound represented by following chemical formula 2,
Chemical formula 2:
(wherein, R is H or CH
3, m=0 ~ 5, n=0 ~ 5, m with n are 0 time different, m+n=1 ~ 10).
The preparation method of 12. propylene oxide acids optical materials according to claim 10 or 11, it is characterized in that, above-mentioned dibenzyl maleate prepared product contains the dibenzyl fumarate of below 40 weight percents.
The preparation method of 13. propylene oxide acids optical materials according to claim 10 or 11, it is characterized in that, comprise the steps: except above-mentioned dibenzyl maleate prepared product, as reactive diluent, also will be selected from by vinylbenzene, Vinylstyrene, alpha-methyl styrene, α-methylstyrenedimer, benzyl methacrylate, chloro-styrene, bromstyrol, methoxy styrene, mono-benzyl fumarate, dibenzyl fumarate, methyl-benzyl maleic acid ester, dimethyl maleate, ethyl maleate, dibutyl maleinate, dibutyl fumarate, butyl maleate, toxilic acid list pentyl ester, dipentyl maleate, fumaric acid list pentyl ester, one or more compound in the group of fumaric acid diamyl ester and diethylene glycol bis-aryl carbonates composition makes an addition to above-mentioned propylene oxide acids polymerizable composition for optical material and carries out template polymerization after mixing.
The preparation method of 14. propylene oxide acids optical materials according to claim 12, it is characterized in that, relative to 100 weight parts the compound represented by above-mentioned chemical formula 1 or be mixed with the acrylic ester compound of the compound represented by above-mentioned chemical formula 1 and the compound represented by chemical formula 2, add the global reactivity thinner comprising dibenzyl maleate prepared product of 30 ~ 300 weight parts and mix.
15. 1 kinds of propylene oxide acids optical materials, is characterized in that, the propylene oxide acids polymerizable composition for optical material described in claim 1 or 2 is carried out template polymerization and obtains.
16. 1 kinds of optical lenses, is characterized in that, are formed by optical material according to claim 15.
17. optical lenses according to claim 16, is characterized in that, above-mentioned optical lens is ophthalmic lens or polarized lenses.
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| CN104583252A (en) * | 2012-08-28 | 2015-04-29 | 可奥熙搜路司有限公司 | Polymerization composition for epoxy acrylic optical material and method for manufacturing epoxy acrylic optical material |
| CN110256640A (en) * | 2019-06-12 | 2019-09-20 | 江苏韩创新材料有限公司 | A kind of optical mirror slip and manufacturing method |
| CN115304723A (en) * | 2022-07-18 | 2022-11-08 | 江苏可奥熙光学材料科技有限公司 | Antifouling and mildew-proof resin monomer composition and preparation process thereof |
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Also Published As
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| WO2014027849A1 (en) | 2014-02-20 |
| KR20140022737A (en) | 2014-02-25 |
| CN104520376B (en) | 2016-10-05 |
| KR101979033B1 (en) | 2019-05-17 |
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