CN102329298B - Optical resin monomer with high refractive index and preparation method thereof - Google Patents
Optical resin monomer with high refractive index and preparation method thereof Download PDFInfo
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Abstract
The invention provides an optical resin monomer with high refractive index. The monomer has the structural formula shown in the specification, wherein in the structural formula, R is hydrogen, alkyl, alcoxyl, halogen and aryl; Ph is a benzene ring; m and n are integers; m is not less than 1 and not more than 6; and n ranges from 0 to (6-m). A preparation method comprises the following steps: taking the following raw materials: aromatic hydrocarbon, NBS (N-bromosuccinimide), BPO (benzoyl peroxide), thiourea, sodium hydroxide, hydrochloric acid, epichlorohydrin and potassium thiocyanate, wherein the mole ratio of aromatic hydrocarbon to NBS to thiourea to sodium hydroxide to hydrochloric acid to epichlorohydrin to potassium thiocyanate is 1:(3-5):0.1:(3-5):(9-12):(6-10):(3-5):(10-15); step 1. carrying out halogenation; step 2. carrying out halogen methylated thiolation: adopting a thiourea hydrocarbylation hydrolysis method or thiocyanate direct substitution method; 3. carrying out epoxidation: using a universal epichlorohydrin preparation method; and 4. preparing cyclic sulfide products: adopting a universal cyclic sulfide preparation method.
Description
Technical field
The present invention relates to class high refractive index optical resin monomer and preparation method thereof, utilize this monomer, can prepare high-performance optics resin material, be used to prepare optics such as resin lens, optical lens.This monomeric outstanding advantage be monomer polymerization thus and optical resin have high specific refractory power and Abbe number.
Background technology
In recent years, optical resin is applied to fields such as eyewear industry, optics and has obtained develop rapidly, to the demand of high-performance optics resin material more and more widely.Such as the optical resin that accounts for main flow on the resin lens market, its refractive index then must improve the refractive index of material in order to make the ultra-thin and low curvature of lens about 1.5.
Introduce element sulphur and be one of effective means that improves refractive index, the advantage of this resin is: the raising degree of refractive index is big, and density and chromatic dispersion increase lessly, and environmental stability is better, toxicological harmless.The main existence form of sulphur is thioether and mercaptan, and common high refractive index optical resin comprises:
(1) polyurethane-type sulfur-bearing optical resin
The refractive index of polyurethane-type thioretinite reaches as high as 1.80, has advantages such as good wear resistance and shock resistance.It mainly contains isocyanate-based and lsothiocyanates type two classes, be by multi-thiol respectively with isocyanic ester and lsothiocyanates prepared in reaction.Table 1 has provided polyurethane-type thioretinite [JP, 05320301,1993 of several high refractive indexes; EP, 351073,1990] monomer structure and resin refractive index.
Table one. the raw material mix of urethane optical resin and refractive index
| Monomer structure | Refractive index (the nd of resin 20) |
| 1.66 | |
| 1.69 | |
| 1.63 | |
| 1.75 | |
| 1.80 |
(2) polyaddition type sulfur-bearing optical resin
Gao Changyou [investigation of materials newspaper, 1999,13:9-16; Journal of Applied Polymer Science, 2000,75:1474-1479] be raw material with mercaptan and methacrylic chloride (MC), successfully synthesize following three kinds of optical resins that contain thioether mercaptan ester structure, the MESDMA over-all properties is better than other two kinds, nd=1.625, ν d=36, glass transition is 150 ℃, and surface hardness is 3 H.The homopolymer of MEPSMA and MMDMA is at room temperature softer, should not prepare the hard glass plastics separately.
(3) epoxy type sulfur-bearing optical resin
Japanese Patent [JP, 10130250,1998.] has synthesized three-functionality-degree sulfur-bearing aliphatic epoxy resin (I), nd=1.63.Japanese Patent [JP, 09316421,1997] has synthesized a kind of diphenyl sulfide type optical bonding level Resins, epoxy (II), and its refractive index (nd=1.698) is the highest in the epoxy monomer of being reported at present.Chinese patent [CN, 1046741,1990] obtains nd=1.66 with (HSCH2CH2SCH2) 4C and Resins, epoxy, the optical resin of vd=33.
(4) hydrogen transfer polymerization type thioretinite
Mercaptan and polyene hydrocarbon can carry out addition reaction under action of evocating, form hydrogen transfer polymerization type resin.With two functionality mercaptan and diene is example, and polymerization process is as follows:
In addition, the polyaddition of the addition reaction of mercaptan and two keys and mercaptan and isocyanic ester combines and then can obtain special hydrogen transfer polymerization type thioretinite [JP, 04264113,1992; BE, 1006040,1994].
(5) epithio class optical resin
Epithio type optical resin is the novel high refractive index optical resin of a class.Mainly by following prepared in one of two ways resin: 1. ion ring-opening polymerization; 2. with isocyanic ester or lsothiocyanates reaction.The epithio type resin refractive index that the ion ring-opening polymerization makes is very high, but resistance to impact shock and thermotolerance are relatively poor.Can effectively avoid such defective by reacting with isocyanic ester or lsothiocyanates, and refractive index is still higher, the over-all properties of resin is better, but reaction conditions is strict.Since nineteen ninety-seven, companies such as the HOYA of Japan, Mitsubishi have applied for the patent about epithio class monomer and optical resin thereof, and table 2 has been listed monomer structure and refractive index [JP, 04264113,1992 of common epithio type high refractive index optical resin; JP, 03084031,1991].
The structure and the refractive index of table two epithio class optical resin monomer
| Monomer structure | Refractive index (nd20) |
| 1.71 | |
| 1.698 | |
| 1.70 |
Lv Changli [Journal of Applied Polymer Science, 2003,89:2426-2430] has prepared two kinds of sulfur-type resin monomer BEPTES and ESDGEBA.The refractive index of copolymer resins and Abbe number increase with the increase of BEPTES monomer mass, nd=1.633 ~ 1.697, ν d=34 ~ 38.In the copolymerization system of BEPTES/TDI, nd=1.652 ~ 1.669, ν d=28.7 ~ 34.6, the good heat resistance of resin, glass transition temp Tg〉130 ℃, surface hardness is 4 H～5 H.Epithio type optical resin is the high refractive index optical resin that the another class behind the polyurethane-type optical resin has development potentiality.
Summary of the invention
Technical problem to be solved:
At the shortcoming of existing epoxies optical material refractive index, the molecular structure of optical resin is redesigned, introduce the modification group, improve refractive index, Vd value and the mechanical property of optical resin.
Technical scheme: a kind of high refractive index optical resin monomer has following general structure:
Wherein: R is hydrogen, alkyl, alcoxyl, halogen, aryl; Ph is a phenyl ring, and m, n are integer, and the span of m is 1≤m≤6, and the value of n is 0～6-m.
The span of described m is: 3≤m≤6.
Prepare a kind of method of high refractive index optical resin monomer, may further comprise the steps:
The first step: carry out halogenating reaction: adopt direct halomethylation, a kind of in the free radical halo mode of utilize NBS " N-bromo-succinimide ", NCS " N-chlorosuccinimide ", halogen;
Second step: the mercaptolation of halomethylation: adopt thiocarbamide hydrocarbylation hydrolysis method or the direct substitution method of sulfur hydrogen salt;
The 3rd step: epoxidation reaction: with general epoxy chloropropane method preparation;
The 4th step: the preparation of epithio product: adopt general episulfide compounds preparation method.
General episulfide compounds preparation method is potassium sulfocyanate catalysis epithioization or thiocarbamide catalysis epithio method in described the 4th step.
Aromatic hydrocarbons in the raw material that extracts can substitute with substituted arene.
Aromatic hydrocarbons in the raw material, substituted arene are respectively phenyl ring, methyl substituted phenyl ring.
Adopting NBS is that halogenating agent prepares the high refractive index optical resin monomer:
Raw material is aromatic hydrocarbons, NBS, BPO, thiocarbamide, sodium hydroxide, hydrochloric acid, epoxy chloropropane, potassium sulfocyanate; Aromatic hydrocarbons: NBS:BPO wherein: thiocarbamide: sodium hydroxide: hydrochloric acid: epoxy chloropropane: the molar percentage of potassium sulfocyanate is 1:3～5:0.2～0.4:3～5:9～12:6～10:3～5:10～15;
The first step: synthetic equal trisbromomethyl benzene: in the single port bottle, add sym-trimethylbenzene 5g successively, NBS25.5g, and make initiator with 0.1gBPO, add CCl then
4Make solvent, magneton stirs, and is warming up to backflow, reaction 24h.Reaction finishes postcooling, and a large amount of white solids are separated out, and cross the filtering solid, revolves to steam to remove to desolvate, and obtains faint yellow slime body, gets white solid with the petroleum ether extraction evaporate to dryness; The nucleus magnetic resonance characterization result is as follows
1H NMR " 400MHz, CDCl3 " δ: 4.452 " s, 6H, methylene radical ", 7.352 " s, 3H, phenyl ring ";
Second step: synthetic equal three thiopurine methyltransferase benzene: add equal trisbromomethyl benzene 4g in the single port bottle, ethanol 100ml is under the room temperature, after dispersed with stirring is even, add thiocarbamide 2.8g, stir 24h, separate out a large amount of white precipitates, behind the filtration drying, pour in the 250ml single port bottle, add water 100ml, stirring and dissolving adds NaOH2.69g again to clarification, reflux 4 ~ 5h, be cooled to room temperature after, use chloroform extraction, the organic phase washing of collecting 3 times, anhydrous sodium sulfate drying revolves steaming and obtains light yellow liquid after the filtration; The nucleus magnetic resonance characterization result is as follows
1H NMR " 400MHz, CDCl
3" δ: 1.771-1.810 " t, 3H, sulfydryl ", 3.687 " s, 6H, methylene radical ", 7.157 " s, 3H, phenyl ring ";
13C NMR " 400MHz, CDCl
3" δ: 28.749,126.559,142.041;
The 3rd step: synthesize 1,3,5-three epoxypropyl sulfydryl benzene: in the 250ml there-necked flask, add equal three thiopurine methyltransferase benzene 3g, epoxy chloropropane 4.23g, methyl alcohol 70ml, ice bath stirs down, drip 10% aqueous sodium hydroxide solution 0.1231g, reacted 20 hours, and then add 40% aqueous sodium hydroxide solution 6.655g, TLC detects to the reaction end, adds 50ml water, boils off methyl alcohol, use chloroform extraction, organic phase washing 3 times, anhydrous sodium sulfate drying, steam after the filtration weak yellow liquid, refractive index 1.60; Nucleus magnetic resonance and mass spectral characteristi result are as follows
1H NMR " 400MHz, CDCl
3" δ: 2.512-2.620 " m, 9H " 2.760-2.782 " t, 3H " oxirane ring methylene radical and coupled methylene radical, 3.065-3.115 " m, 3H, the oxirane ring methyne ", 3.743-3.825 " m, 6H, the methylene radical that phenyl ring links to each other " 7.207 " s, 3H, phenyl ring ";
13C NMR " 400MHz, CDCl
3" δ: 33.313,36.206,46.736,51.850,128.454,138.760; EI-MS [M
+]=407.1;
The 4th step: synthesize 1,3,5-three epithio propyl group sulfydryl benzene: in 250ml single port bottle, add 1,3,5-three epoxypropyl sulfydryl benzene 2g, potassium thiocyanate 6g, water 10ml, ethanol 20ml stirs, and TLC detects until reaction and finishes; Use chloroform extraction again, organic phase washing 3 times, anhydrous sodium sulfate drying, filtration is revolved to steam and is obtained yellow liquid 1.91g, and the chromatographic column separation obtains colourless liquid, refractive index 1.67, Abbe number 44.9; Nucleus magnetic resonance and mass spectral characteristi result are as follows
1H NMR " 400MHz, CDCl
3" δ: 2.156-2.170 " d, 3H ", 2.441-2.514 " m, 6H " oxirane ring methylene radical and methyne, 2.865-2.912,2.962-3.023 " m, 6H, the methylene radical that the epithio ring links to each other "; 3.755-3.832 " m, 6H, the methylene radical that phenyl ring links to each other " 7.213 " s, 3H, phenyl ring ";
13C NMR " 400MHz, CDCl
3" δ: 25.900,33.853,36.515,37.760,128.282,138.956; EI-MS [M
+]=433.0.Show that structure is correct;
The 5th step: with 1,3, after the equal three thiopurine methyltransferase benzene of 5-three epithio propyl group sulfydryl benzene and 5% quality mix, pour mould into, progressively heat up and solidify, obtain colourless at last or the light-coloured transparent resin material; Equal three thiopurine methyltransferase benzene are made solidifying agent;
The structural formula of the high refractive index optical resin monomer by method for preparing is:
Adopt direct halomethylation legal system to be equipped with the high refractive index optical resin monomer:
Raw material is acetum, thiocarbamide, sodium hydroxide, hydrochloric acid, epoxy chloropropane, the potassium sulfocyanate of aromatic hydrocarbons, Paraformaldehyde 96, Glacial acetic acid, hydrogen bromide; Wherein the molar percentage of the acetum of aromatic hydrocarbons, Paraformaldehyde 96, Glacial acetic acid, hydrogen bromide, thiocarbamide, sodium hydroxide, hydrochloric acid, epoxy chloropropane, potassium sulfocyanate is 1:3～4:15～20:12～20:3～5:9～12:6～10:3～5:10～15;
The first step: 1,3,5-trisbromomethyl-2,4,6-trimethylbenzene synthetic: in 250 ml there-necked flasks, add sym-trimethylbenzene 12.00 g " 0.10 mol ", Paraformaldehyde 96 10.00 g " 0.33 mol ", Glacial acetic acid 100 ml, acetum 70 ml of 31% hydrogen bromide are in 120 ℃ of reaction 11 h; In reaction process, Paraformaldehyde 96 dissolves gradually, and system becomes orange clear solution, produces white precipitate afterwards; After reaction stops, reaction solution is poured in the 700 ml distilled water, washed suction filtration, 50 ℃ of dryings in vacuum chamber 3 times; Obtain white powder 30.65 g, productive rate 76.8%; Fusing point: 196～198 ℃;
Second step: 2.3.2 1,3,5-trisbromomethyl-2,4, synthesizing of 6-trimethylbenzene isothiuronium salts: in 500 ml single port flasks, add 1,3,5-trisbromomethyl-2,4,6-trimethylbenzene 20.00 g " 50.12 mmol ", thiocarbamide 11.44 g " 150.00 mmol ", ethanol 220 ml; Under argon shield, reaction 12 h under room temperature; In reaction process, system becomes transparent from muddiness, after occur again muddy; Behind the stopped reaction, filter, 50 ℃ of vacuum-dryings of solid get white powder 29.55 g, productive rate 94.0%;
The 3rd step: 2.3.3 2,4,6-trimethylammonium-1,3,5-benzene three thiomethyl alcohols synthetic: in 500 ml single port flasks
Add 1,3,5-trisbromomethyl-2,4,6-trimethylbenzene thiocarbamide salt 31.44 g " 50.12 mmol ", NaOH solution " massfraction is 6.16% " 220 ml; Under argon shield, 4 h that reflux, ice bath cooling, dripping hydrochloric acid " 6 mol/L "; regulate about pH to 2, a large amount of white solids occur in the system this moment, continues to stir 15 min, pours in the separating funnel; use 150 ml chloroform extractions three times respectively, collect organic phase, anhydrous Na
2SO
4Drying, decompression steams solvent, gets white powder 10.04 g, productive rate 77.5%.Fusing point: 140～143 ℃;
The 4th step: Synthetic 2,4,6-trimethylammonium-1,3,5-three epithio propyl group sulfydryl benzene: in 250ml single port bottle, add 1,3,5-three epoxypropyl sulfydryl benzene 2g, potassium thiocyanate 4.9g, water 10ml, ethanol 20ml stirs, and TLC detects until reaction and finishes.Use chloroform extraction again, organic phase washing 3 times, anhydrous sodium sulfate drying, filtration is revolved to steam and is obtained yellow liquid 2.05g, and the chromatographic column separation obtains colourless liquid, refractive index 1.608, Abbe number 40; The following 1H NMR of nucleus magnetic resonance characterization result " 400MHz; CDCl3 " δ: 2.156-2.170 " d, 3H ", 2.441-2.514 " m, 6H " oxirane ring methylene radical and methyne, 2.865-2.912,2.962-3.023 " methylene radical that m; 6H, epithio ring link to each other ", 3.755-3.832 " m; 6H; the methylene radical that phenyl ring links to each other " 7.213 " s, 3H, phenyl ring "; 13C NMR " 400MHz, CDCl3 " δ: 15.92,25.88,33.00,39.27,46.73,132.37,135.65.Show that structure is correct;
The structural formula of the high refractive index optical resin monomer by method for preparing is:
Beneficial effect: the present invention adopts sym-trimethylbenzene, NBS, thiocarbamide, epoxy chloropropane, potassium thiocyanate etc. to synthesize the optical resin of a kind of refractive index about 1.67 for raw material.Its reaction conditions is easy to reach, and this resin has good thermotolerance, and thermogravimetric analysis shows that its temperature of initial decomposition is 293.65 ℃, far above daily use temperature.
Description of drawings
Fig. 1 is the synthetic route chart of NBS halo method;
Fig. 2 is the synthetic route chart of direct halomethylation;
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of mesitylene;
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of equal three thiopurine methyltransferase benzene;
Fig. 5 is the carbon-13 nmr spectra figure of equal three thiopurine methyltransferase benzene;
Fig. 6 is 1,3,5-three epoxypropyl sulfydryl benzene nucleus mr hydrogen spectrograms;
Fig. 7 is 1,3,5-three epoxypropyl sulfydryl benzene nucleus mr carbon spectrograms;
Fig. 8 is 1,3,5-three epoxypropyl sulfydryl benzene mass spectrums;
Fig. 9 is 1,3,5-three epithio propyl group sulfydryl benzene proton nmr spectras;
Figure 10 is 1,3,5-three epithio propyl group sulfydryl benzene carbon-13 nmr spectras;
Figure 11 is 1,3,5-three epithio propyl group sulfydryl benzene mass spectrums.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is done explanation in further detail.
Designed high refractive index optical resin monomer has following general structure:
Wherein: R is hydrogen, alkyl, alcoxyl, halogen, aryl; Ph is a phenyl ring, and m, n are integer, and the span of m is 1≤m≤6, and preferred m is more than or equal to 3, and promptly the preferable range of m is: 3≤m≤6; The value of n is 0～6-m.
The position of substituting group on phenyl ring can be ortho position, a position and contraposition by raw material and the decision of halo method.
Its synthetic method is expressed as for example:
Raw material is aromatic hydrocarbons, NBS, BPO, thiocarbamide, sodium hydroxide, hydrochloric acid, epoxy chloropropane, potassium sulfocyanate; Aromatic hydrocarbons: NBS wherein: thiocarbamide: sodium hydroxide: hydrochloric acid: epoxy chloropropane: the molar percentage of potassium sulfocyanate is 1:3～5:0.2～0.4:3～5:9～12:6～10:3～5:10～15;
The first step: carry out halogenating reaction: adopt direct halomethylation, a kind of in the free radical halo mode of utilize NBS (N-bromo-succinimide), NCS (N-chlorosuccinimide), halogen; As direct halomethylation, utilize the free radical halo mode of NBS (N-bromo-succinimide), NCS (N-chlorosuccinimide), halogen, aforesaid method has same effect in the present invention.
The raw material that present method adopts is aromatic hydrocarbons, substituted arene; Preferably have phenyl ring or methyl substituted phenyl ring.
Second step: the mercaptolation of halomethylation: adopt thiocarbamide hydrocarbylation hydrolysis method or the direct substitution method of sulfur hydrogen salt;
The 3rd step: epoxidation reaction: with general epoxy chloropropane method preparation;
The 4th step: the preparation of epithio product: adopt general episulfide compounds preparation method, as potassium sulfocyanate catalysis epithioization, thiocarbamide catalysis epithio method.
Following mask body illustrates: it all is raw material with the sym-trimethylbenzene that following institute responds, but is not limited thereto.The scientific research of this area, engineering people
The member adopts similar raw material, the optics that composite structure is similar, performance meets the demands according to ultimate principle of the present invention
Resin monomer is also in protection scope of the present invention.
Embodiment 1: adopting NBS is that halogenating agent prepares the high refractive index optical resin monomer: (n=0, m=3)
Step is as follows: (as shown in Figure 1)
Raw material is aromatic hydrocarbons, NBS, BPO, thiocarbamide, sodium hydroxide, hydrochloric acid, epoxy chloropropane, potassium sulfocyanate; Aromatic hydrocarbons: NBS:BPO wherein: thiocarbamide: sodium hydroxide: hydrochloric acid: epoxy chloropropane: the molar percentage of potassium sulfocyanate is 1:3～5:0.2～0.4:3～5:9～12:6～10:3～5:10～15;
The first step: synthetic equal trisbromomethyl benzene: in the single port bottle, add sym-trimethylbenzene 5g successively, NBS25.5g, and make initiator with 0.1gBPO, add CCl then
4Make solvent, magneton stirs, and is warming up to backflow, reaction 24h.Reaction finishes postcooling, and a large amount of white solids are separated out, and cross the filtering solid, revolves to steam to remove to desolvate, and obtains faint yellow slime body, gets white solid with the petroleum ether extraction evaporate to dryness.Nucleus magnetic resonance characterization result (as shown in Figure 3) is as follows
1H NMR (400MHz, CDCl3) δ: 4.452(s, 6H, methylene radical), 7.352(s, 3H, phenyl ring).Show that structure is correct.
Second step: synthetic equal three thiopurine methyltransferase benzene: add equal trisbromomethyl benzene 4g in the single port bottle, ethanol 100ml is under the room temperature, after dispersed with stirring is even, add thiocarbamide 2.8g, stir 24h, separate out a large amount of white precipitates, behind the filtration drying, pour in the 250ml single port bottle, add water 100ml, stirring and dissolving adds NaOH2.69g again to clarification, reflux 4 ~ 5h, be cooled to room temperature after, use chloroform extraction, the organic phase washing of collecting 3 times, anhydrous sodium sulfate drying revolves steaming and obtains light yellow liquid after the filtration.(as Fig. 4, shown in Figure 5) is as follows for the nucleus magnetic resonance characterization result
1H NMR (400MHz, CDCl
3) δ: 1.771-1.810(t, 3H, sulfydryl), 3.687(s, 6H, methylene radical), 7.157(s, 3H, phenyl ring);
13C NMR(400MHz, CDCl
3) δ: 28.749,126.559,142.041.Show that structure is correct.
The 3rd step: synthesize 1,3,5-three epoxypropyl sulfydryl benzene: in the 250ml there-necked flask, add equal three thiopurine methyltransferase benzene 3g, epoxy chloropropane 4.23g, methyl alcohol 70ml, ice bath stirs down, drip 10% aqueous sodium hydroxide solution 0.1231g, reacted 20 hours, and then add 40% aqueous sodium hydroxide solution 6.655g, TLC detects to the reaction end, adds 50ml water, boils off methyl alcohol, use chloroform extraction, organic phase washing 3 times, anhydrous sodium sulfate drying, steam after the filtration weak yellow liquid, refractive index 1.60.Nucleus magnetic resonance and mass spectral characteristi result (as Fig. 6, Fig. 7, shown in Figure 8) are as follows
1H NMR (400MHz, CDCl
3) δ: 2.512-2.620(m, 9H), 2.760-2.782(t, 3H) oxirane ring methylene radical and coupled methylene radical, 3.065-3.115(m, 3H, the oxirane ring methyne), 3.743-3.825(m, 6H, the methylene radical that phenyl ring links to each other) 7.207(s, 3H, phenyl ring);
13C NMR(400MHz, CDCl
3) δ: 33.313,36.206,46.736,51.850,128.454,138.760; EI-MS [M
+]=407.1.Show that structure is correct.
The 4th step: synthesize 1,3,5-three epithio propyl group sulfydryl benzene: in 250ml single port bottle, add 1,3,5-three epoxypropyl sulfydryl benzene 2g, potassium thiocyanate 6g, water 10ml, ethanol 20ml stirs, and TLC detects until reaction and finishes.Use chloroform extraction again, organic phase washing 3 times, anhydrous sodium sulfate drying, filtration is revolved to steam and is obtained yellow liquid 1.91g, and the chromatographic column separation obtains colourless liquid, refractive index 1.67, Abbe number 44.9.Nucleus magnetic resonance and mass spectral characteristi result (as Fig. 9, Figure 10, shown in Figure 11) are as follows
1H NMR (400MHz, CDCl
3) δ: 2.156-2.170(d, 3H), 2.441-2.514(m, 6H) oxirane ring methylene radical and methyne, 2.865-2.912,2.962-3.023(m, 6H, the methylene radical that the epithio ring links to each other), 3.755-3.832(m, 6H, the methylene radical that phenyl ring links to each other) 7.213(s, 3H, phenyl ring);
13C NMR(400MHz, CDCl
3) δ: 25.900,33.853,36.515,37.760,128.282,138.956; EI-MS [M
+]=433.0.Show that structure is correct.
The 5th step: with 1,3, after the equal three thiopurine methyltransferase benzene (making solidifying agent) of 5-three epithio propyl group sulfydryl benzene and 5% quality mix, pour mould into, progressively heat up and solidify, obtain colourless at last or the light-coloured transparent resin material.
The structural formula of the high refractive index optical resin monomer by method for preparing is:
Embodiment 2: adopt direct halomethylation legal system to be equipped with the high refractive index optical resin monomer: (n=3, m=3)
Step following (as Fig. 2):
Raw material is acetum, thiocarbamide, sodium hydroxide, hydrochloric acid, epoxy chloropropane, the potassium sulfocyanate of aromatic hydrocarbons, Paraformaldehyde 96, Glacial acetic acid, hydrogen bromide; Wherein the molar percentage of the acetum of aromatic hydrocarbons, Paraformaldehyde 96, Glacial acetic acid, hydrogen bromide, thiocarbamide, sodium hydroxide, hydrochloric acid, epoxy chloropropane, potassium sulfocyanate is 1:3～4:15～20:12～20:3～5:9～12:6～10:3～5:10～15.
The first step: 1,3,5-trisbromomethyl-2,4, synthesizing of 6-trimethylbenzene (A1): in 250 ml there-necked flasks, add sym-trimethylbenzene 12.00 g(0.10 mol), Paraformaldehyde 96 10.00 g(0.33 mol), Glacial acetic acid 100 ml, acetum (31%) 70 ml of hydrogen bromide is in 120 ℃ of reaction 11 h.In reaction process, Paraformaldehyde 96 dissolves gradually, and system becomes orange clear solution, produces white precipitate afterwards.After reaction stops, reaction solution is poured in the 700 ml distilled water, washed suction filtration, 50 ℃ of dryings in vacuum chamber 3 times.Obtain white powder 30.65 g, productive rate 76.8%.Fusing point: 196～198 ℃.
Second step: 2.3.2 1,3,5-trisbromomethyl-2,4, synthesizing of 6-trimethylbenzene isothiuronium salts: in 500 ml single port flasks, add 1,3,5-trisbromomethyl-2,4,6-trimethylbenzene 20.00 g(50.12 mmol), thiocarbamide 11.44 g(150.00 mmol), ethanol 220 ml.Under argon shield, reaction 12 h under room temperature.In reaction process, system becomes transparent from muddiness, after occur again muddy.Behind the stopped reaction, filter, 50 ℃ of vacuum-dryings of solid get white powder 29.55 g, productive rate 94.0%.
The 3rd step: 2.3.3 2,4,6-trimethylammonium-1,3,5-benzene three thiomethyl alcohols (A3) synthetic: in 500 ml single port flasks
Add 1,3,5-trisbromomethyl-2,4,6-trimethylbenzene thiocarbamide salt 31.44 g(50.12 mmol), NaOH solution (massfraction is 6.16%) 220 ml.Under argon shield, 4 h that reflux, ice bath cooling, dripping hydrochloric acid (6 mol/L); regulate about pH to 2, a large amount of white solids occur in the system this moment, continues to stir 15 min, pours in the separating funnel; use 150 ml chloroform extractions three times respectively, collect organic phase, anhydrous Na
2SO
4Drying, decompression steams solvent, gets white powder 10.04 g, productive rate 77.5%.Fusing point: 140～143 ℃.
The 4th step: Synthetic 2,4,6-trimethylammonium-1,3,5-three epithio propyl group sulfydryl benzene: in 250ml single port bottle, add 1,3,5-three epoxypropyl sulfydryl benzene 2g, potassium thiocyanate 4.9g, water 10ml, ethanol 20ml stirs, and TLC detects until reaction and finishes.Use chloroform extraction again, organic phase washing 3 times, anhydrous sodium sulfate drying, filtration is revolved to steam and is obtained yellow liquid 2.05g, and the chromatographic column separation obtains colourless liquid, refractive index 1.608, Abbe number 40.The nucleus magnetic resonance characterization result is as follows
1H NMR (400MHz, CDCl
3) δ: 2.156-2.170(d, 3H), 2.441-2.514(m, 6H) oxirane ring methylene radical and methyne, 2.865-2.912,2.962-3.023(m, 6H, the methylene radical that the epithio ring links to each other), 3.755-3.832(m, 6H, the methylene radical that phenyl ring links to each other) 7.213(s, 3H, phenyl ring);
13C NMR(400MHz, CDCl
3) δ: 15.92,25.88,33.00,39.27,46.73,132.37,135.65.Show that structure is correct.
The 5th step: with 1,3, after the equal three thiopurine methyltransferase benzene (making solidifying agent) of 5-three epithio propyl group sulfydryl benzene and 5% mass ratio mix, pour mould into, progressively heat up and solidify, obtain colourless at last or the light-coloured transparent resin material.
The structural formula of the high refractive index optical resin monomer by method for preparing is:
Though the present invention with preferred embodiment openly as above; but they are not to be used for limiting the present invention; anyly be familiar with this skill person; without departing from the spirit and scope of the invention; from when can doing various variations or retouching, so being as the criterion of should being defined with the application's claim protection domain of protection scope of the present invention.
Claims (2)
1. high refractive index optical resin monomer is characterized in that: have following general structure:
Wherein: R is hydrogen or methyl, and m, n are integer, and the span of m is 3≤m≤6, and the value of n is 0～6-m.
2. the preparation method of a kind of high refractive index optical resin monomer according to claim 1 is characterized in that:
Adopting NBS is that halogenating agent prepares the high refractive index optical resin monomer:
The first step: synthetic equal trisbromomethyl benzene: in the single port bottle, add sym-trimethylbenzene 5g successively, NBS25.5g, and make initiator with 0.1gBPO, add CCl then
4Make solvent, magneton stirs, and is warming up to backflow, reaction 24h; Reaction finishes postcooling, and a large amount of white solids are separated out, and cross the filtering solid, revolves to steam to remove to desolvate, and obtains faint yellow slime body, gets white solid with the petroleum ether extraction evaporate to dryness; The nucleus magnetic resonance characterization result is as follows
1H NMR " 400MHz, CDCl3 " δ: 4.452 " s, 6H, methylene radical ", 7.352 " s, 3H, phenyl ring ";
Second step: synthetic equal three thiopurine methyltransferase benzene: add equal trisbromomethyl benzene 4g in the single port bottle, ethanol 100ml is under the room temperature, after dispersed with stirring is even, add thiocarbamide 2.8g, stir 24h, separate out a large amount of white precipitates, behind the filtration drying, pour in the 250ml single port bottle, add water 100ml, stirring and dissolving adds NaOH2.69g again to clarification, reflux 4 ~ 5h, be cooled to room temperature after, use chloroform extraction, the organic phase washing of collecting 3 times, anhydrous sodium sulfate drying revolves steaming and obtains light yellow liquid after the filtration; The nucleus magnetic resonance characterization result is as follows
1H NMR " 400MHz, CDCl
3" δ: 1.771-1.810 " t, 3H, sulfydryl ", 3.687 " s, 6H, methylene radical ", 7.157 " s, 3H, phenyl ring ";
13C NMR " 400MHz, CDCl
3" δ: 28.749,126.559,142.041;
The 3rd step: synthesize 1,3,5-three epoxypropyl thiopurine methyltransferase benzene: in the 250ml there-necked flask, add equal three thiopurine methyltransferase benzene 3g, epoxy chloropropane 4.23g, methyl alcohol 70ml, ice bath stirs down, drip 10% aqueous sodium hydroxide solution 0.1231g, reacted 20 hours, and then add 40% aqueous sodium hydroxide solution 6.655g, TLC detects to the reaction end, adds 50ml water, boils off methyl alcohol, use chloroform extraction, organic phase washing 3 times, anhydrous sodium sulfate drying, steam after the filtration weak yellow liquid, refractive index 1.60; Nucleus magnetic resonance and mass spectral characteristi result are as follows
1H NMR " 400MHz, CDCl
3" δ: 2.512-2.620 " m, 9H " 2.760-2.782 " t, 3H " oxirane ring methylene radical and coupled methylene radical, 3.065-3.115 " m, 3H, the oxirane ring methyne ", 3.743-3.825 " m, 6H, the methylene radical that phenyl ring links to each other " 7.207 " s, 3H, phenyl ring ";
13C NMR " 400MHz, CDCl
3" δ: 33.313,36.206,46.736,51.850,128.454,138.760; EI-MS [M
+]=407.1;
The 4th step: synthesize 1,3,5-three epithio propyl group thiopurine methyltransferase benzene: in 250ml single port bottle, add 1,3,5-three epoxypropyl thiopurine methyltransferase benzene 2g, potassium thiocyanate 6g, water 10ml, ethanol 20ml stirs, and TLC detects until reaction and finishes; Use chloroform extraction again, organic phase washing 3 times, anhydrous sodium sulfate drying, filtration is revolved to steam and is obtained yellow liquid 1.91g, and the chromatographic column separation obtains colourless liquid, refractive index 1.67, Abbe number 44.9;
1H NMR " 400MHz, CDCl
3" δ: 2.156-2.170 " d, 3H ", 2.441-2.514 " m, 6H " epithio ring methylene radical and methyne, 2.865-2.912,2.962-3.023 " m, 6H, the methylene radical that the epithio ring links to each other "; 3.755-3.832 " m, 6H, the methylene radical that phenyl ring links to each other " 7.213 " s, 3H, phenyl ring ";
13C NMR " 400MHz, CDCl
3" δ: 25.900,33.853,36.515,37.760,128.282,138.956; EI-MS [M
+]=433.0;
The structural formula of the high refractive index optical resin monomer by method for preparing is:
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| CN107200846B (en) * | 2016-12-13 | 2020-02-21 | 江苏视科新材料股份有限公司 | Sulfur-containing optical resin material with high transmittance and high refractive index and preparation method thereof |
| CN107200847B (en) * | 2016-12-13 | 2020-03-24 | 江苏视科新材料股份有限公司 | High-refractive-index and high-hardness sulfur-containing optical resin material and preparation method thereof |
| CN107188836B (en) * | 2016-12-13 | 2019-07-12 | 江苏视科新材料股份有限公司 | Tri- thiopurine methyltransferase benzene compound of 1,3,5- and preparation method thereof |
| CN107188882B (en) * | 2016-12-13 | 2020-07-07 | 江苏视科新材料股份有限公司 | 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene compound and preparation method thereof |
| CN106886128B (en) * | 2017-03-28 | 2021-02-19 | 深圳市道尔顿电子材料有限公司 | Negative photoresist |
| CN109111479B (en) * | 2018-10-15 | 2021-04-13 | 江苏俊视光学有限公司 | High-refractive-index optical resin based on natural product eugenol and preparation method thereof |
| CN112480095B (en) * | 2020-11-25 | 2022-06-10 | 益丰新材料股份有限公司 | Preparation method of bis (2, 3-thiocyclopropyl) sulfide |
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