CN102391471A - Optical epoxy resin and synthesis method thereof - Google Patents
Optical epoxy resin and synthesis method thereof Download PDFInfo
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- CN102391471A CN102391471A CN2011102788913A CN201110278891A CN102391471A CN 102391471 A CN102391471 A CN 102391471A CN 2011102788913 A CN2011102788913 A CN 2011102788913A CN 201110278891 A CN201110278891 A CN 201110278891A CN 102391471 A CN102391471 A CN 102391471A
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- 230000003287 optical effect Effects 0.000 title claims abstract description 47
- 239000003822 epoxy resin Substances 0.000 title abstract description 9
- 229920000647 polyepoxide Polymers 0.000 title abstract description 9
- 238000001308 synthesis method Methods 0.000 title abstract 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 27
- 239000012044 organic layer Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 21
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 18
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 17
- JGBUSSIEPRTZHI-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)SC1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)SC1=CC=CC=C1 JGBUSSIEPRTZHI-UHFFFAOYSA-N 0.000 claims description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 16
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 7
- -1 YLENE Chemical compound 0.000 claims description 7
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000006840 diphenylmethane group Chemical group 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- NONOKGVFTBWRLD-UHFFFAOYSA-N isocyanatosulfanylimino(oxo)methane Chemical class O=C=NSN=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 24
- 235000011121 sodium hydroxide Nutrition 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- 238000010992 reflux Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000002118 epoxides Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to an optical epoxy resin and a synthesis method thereof. The optical epoxy resin is a thiobisbenzenethio-diphenol diglycidyl ether copolymer. The invention also provides a synthesis method of the optical epoxy resin. The optical epoxy resin and the synthesis method thereof have the advantages of easiness in popularization and application.
Description
Technical field
The present invention relates to a kind of epoxy resin and compound method thereof, especially a kind of optical resin and compound method thereof.
Background technology
Epoxy resin has and solidifies easily, and condition of cure is adjustable and transparent characteristics such as good, therefore use in the optical resin field more, like optics, optical package and optics sizing agent etc.Yet the specific refractory power of common epoxy resin is lower, and its specific refractory power is about about 1.57, can not satisfy the increasingly high requirement of optical material.
Be specific refractory power that improves optical resin and the transmittance that does not reduce material, have the inorganic nano material of employing composite methods to regulate optical resin in the prior art.These inorganic nano materials for example are nano titanium oxide, nano zine oxide, nano-zinc sulfide etc.Yet there are shortcomings such as nanoparticle difficulties in dispersion, consumption be limited in inorganic nano combined method, therefore is difficult to apply.
Summary of the invention
In view of above-mentioned condition, be necessary to provide a kind of optical resin that is easier to apply and compound method thereof.
It is dimercapto diphenyl sulfide-diphenol Racemic glycidol ether copolymer for a kind of optical resin, and its structural formula is:
Wherein, the m value is 0 ~ 10, and the n value is 1 ~ 10; R be to hexichol for propyl, to the hexichol ether, to diphenyl sulfide based, to diphenylmethane group or to phenyl.
A kind of compound method of optical resin, it at first adds 1 part dimercapto diphenyl sulfide, 2.5 ~ 20 parts epoxy chloropropane and 0.01 ~ 2 part 2-glycidyl ethers material or diphenols material in container, and mixes.Then, the catalyzer that in container, adds 0.01 ~ 0.05 part.Then, container is placed in 50 ~ 80 ℃ the temperature, reacted 2 ~ 9 hours.Then, heat this container, and the unreacted epoxy chloropropane distillation of part is reclaimed being lower than under 120 ℃ the condition.Then, container is placed in 60 ~ 85 ℃ the temperature, and in 2 ~ 2.5 hours, in container, adds an amount of alkali.Then, in 60 ~ 85 ℃ temperature, insulation reaction 0.5 ~ 1 hour.Then, in container, add organic solvent.Then, isolate liquid dimercapto diphenyl sulfide-diphenol Racemic glycidol ether copolymer.
The compound method of above-mentioned optical resin can adopt material comparatively commonly used, and carries out through general chemistry synthetic mode, and formed optical resin does not contain inorganic nano material, therefore can be easier to be applicable, and also help and reduce cost.In addition, adopt the compound method institute synthetic optical resin of above-mentioned optical resin and cured product thereof also to have the advantage that specific refractory power is higher, the transparency reaches modest viscosity well.
Description of drawings
Fig. 1 is the ftir analysis figure of dimercapto diphenyl sulfide.
Fig. 2 is the ftir analysis figure of specific embodiment 1 products therefrom.
Fig. 3 is the ftir analysis figure of Bisphenol F glycidyl ether.
Fig. 4 is the ftir analysis figure of specific embodiment 2 products therefroms.
Fig. 5 is the ftir analysis figure of dihydroxyphenyl propane glycidyl ether.
Fig. 6 is the ftir analysis figure of specific embodiment 3 products therefroms.
Embodiment
To combine accompanying drawing and embodiment that the optical resin and the compound method thereof of the embodiment of the invention are done further to specify below.
The optical resin of the embodiment of the invention is dimercapto diphenyl sulfide-diphenol Racemic glycidol ether copolymer, and its structural formula is:
Wherein, the m value is 0 ~ 10, and the n value is 1 ~ 10; R can be to hexichol for propyl, to the hexichol ether, to diphenyl sulfide based, to diphenylmethane group or to phenyl, i.e. optional one of them to following structural formula of the structural formula of R:
,
,
,
and
.
In the compound method of above-mentioned optical resin; Umber is in mole; It at first adds epoxy chloropropane, and the 2-glycidyl ethers material or the diphenols material of 0.01 ~ 2 part (for example 0.01 ~ 2 mole) of the dimercapto diphenyl sulfide of 1 part (for example 1 mole), 2.5 ~ 20 parts (for example 2.5 ~ 20 moles) in container, and mixes.Wherein container for example is the there-necked flask that whipping appts, TM and reflux condensing tube are housed; 2-glycidyl ethers material can be one of bisphenol A diglycidyl ether, Bisphenol F diglycidylether, bis-phenol phenyl ether diglycidylether, bis-phenol diphenyl sulfide diglycidylether and Resorcinol diglycidylether or its compsn; The diphenols material can be one of dihydroxyphenyl propane, Bisphenol F, bis-phenol phenyl ether, bis-phenol diphenyl sulfide and Resorcinol or its compsn.
Then, the catalyzer that in container, adds 0.01 ~ 0.05 part (for example 0.01 ~ 0.05 mole).Wherein, catalyzer can comprise one of alkali, quaternary ammonium salt and triphenyl phosphorus or its compsn.Alkali can be sodium hydroxide, Lithium Hydroxide MonoHydrate or Pottasium Hydroxide; And alkali can alkaline solution form exist, and the concentration of alkaline solution can be 10% ~ saturated.
Then, container is placed in 50 ~ 80 ℃ the temperature, reacted 2 ~ 9 hours.
Then, heating container, and the unreacted epoxy chloropropane distillation of part is reclaimed being lower than under 120 ℃ the condition.
Then, container is placed in 60 ~ 85 ℃ the temperature, and in 2 ~ 2.5 hours, in container, adding an amount of alkali.Wherein, if initial adding is 2-glycidyl ethers material, then the consumption of alkali is 2 ~ 2.5 parts (for example 2 ~ 2.5 moles); If initial adding is the diphenols material, then the consumption of alkali is two times of alkali of adding 2 ~ 2.5 parts (for example 2 ~ 2.5 moles) of the umber of diphenols material.Wherein, alkali can be sodium hydroxide, Lithium Hydroxide MonoHydrate or Pottasium Hydroxide, and the form that alkali can alkaline solution exists, and the concentration of alkaline solution can be 10% ~ saturated.In another embodiment, alkali also can divide with the solid form and joins in the container for 6 ~ 8 times.
Then, in 60 ~ 85 ℃ temperature, insulation reaction 0.5 ~ 1 hour.
Then, in container, add organic solvent.Wherein, organic solvent can be one of toluene, YLENE, benzene, ethylbenzene, diethylbenzene, tetracol phenixin, MIBK, acetone and methylethylketone or its compsn.
At last, isolate liquid optical resin, promptly liquid dimercapto diphenyl sulfide-diphenol Racemic glycidol ether copolymer.In detail, isolate that liquid optical resin adds zero(ppm) water before this in the reaction product that adds organic solvent and vibration makes reaction product be divided into water layer and organic layer; Separatory removes water layer then; Repeat above-mentioned two steps, in organic layer till the no cl ions; Again organic layer is carried out vacuum-drying at ambient temperature,, obtain liquid optical resin to remove organic solvent.
The compound method of above-mentioned optical resin can adopt material comparatively commonly used, and carries out through general chemistry synthetic mode, and formed optical resin does not contain inorganic nano material, therefore can be easier to be applicable, and also help and reduce cost.In addition, adopt the compound method institute synthetic optical resin of above-mentioned optical resin also to have the advantage that specific refractory power is higher, the transparency reaches modest viscosity well.
Through can adding solidifying agent in the obtained optical resin of aforesaid method, thereby form the cured product of optical resin.The solidifying agent that is wherein added can be amine, anhydrides, thio-alcohol, isocyanates or sulphur isocyanates solidifying agent.The gained cured product can have higher specific refractory power.
Have preferable specific refractory power and light transmission for further specifying above-mentioned optical resin and cured product thereof, below will enumerate specific embodiment and further describe.
Embodiment 1 (this example is the contrast reference example)
In the there-necked flask that whipping appts, TM and reflux condensing tube are housed, add 0.25 mole epoxy chloropropane and 0.1 mole dimercapto diphenyl sulfide, in water-bath, carry out stirring and dissolving; The quaternary ammonium salt that adds 0.001 mole is as catalyzer; At bath temperature is 70 ℃, reacts 2 hours; Heat up then, the unreacted epoxy chloropropane distillation of major part is reclaimed being lower than under 120 ℃ the condition; Keeping temperature of reaction afterwards is 70 ℃, and divides in 2 ~ 2.5 hours and add sodium hydrate solid four times, whenever adds once at a distance from 0.5 hour, and the total amount of the sodium hydroxide that wherein adds is 0.2 mole; Under 70 ℃ of temperature, be incubated 0.5 ~ 1 hour, the formation reaction product then.The MIBK that in reaction product, adds 0.2 ~ 2 mole stops to stir discharging then.Material is placed separating funnel, 10 moles of adding distil waters, vibration forms organic layer and water layer, and separatory removes water layer; Repeatedly separatory repeatedly, in organic layer till the no cl ions.The gained organic layer is carried out vacuum-drying at ambient temperature, remove solvent, promptly get dimercapto diphenyl sulfide glycidyl ether.Fig. 1 is the ftir analysis figure of dimercapto diphenyl sulfide.The result through FTIR Spectrometer FTIR (FTIR) analysis of present embodiment 1 products therefrom is as shown in Figure 2,920cm from figure
-1The place can obviously find out the absorption peak of epoxide group.Fig. 2 compares with Fig. 1, can find out obviously that the dimercapto diphenyl sulfide reacts completely basically.
In the there-necked flask that whipping appts, TM and reflux condensing tube are housed, add 0.25 mole epoxy chloropropane, dimercapto diphenyl sulfide and 0.1 mole of Bisphenol F diglycidylether of 0.1 mole, in water-bath, carry out stirring and dissolving; The quaternary ammonium salt that adds 0.001 mole is as catalyzer; At bath temperature is 70 ℃, reacts 2 hours; Heat up then, the unreacted epoxy chloropropane distillation of major part is reclaimed being lower than under 120 ℃ the condition; Keeping temperature of reaction afterwards is 70 ℃, and divides in 2 ~ 2.5 hours and add sodium hydrate solid four times, whenever adds once at a distance from 0.5 hour, and the total amount of the sodium hydroxide that wherein adds is 0.2 mole; Under 70 ℃ of temperature, be incubated 0.5 ~ 1 hour, the formation reaction product then.The MIBK that in reaction product, adds 0.2 ~ 2 mole stops to stir discharging then.Material is placed separating funnel, 10 moles of adding distil waters, vibration forms organic layer and water layer, and separatory removes water layer; Repeatedly separatory repeatedly, in organic layer till the no cl ions.The gained organic layer is carried out vacuum-drying at ambient temperature, remove solvent, promptly get dimercapto diphenyl sulfide-Bisphenol F Racemic glycidol ether copolymer.Fig. 3 is the ftir analysis figure of Bisphenol F glycidyl ether.The result through FTIR Spectrometer FTIR (FTIR) analysis of present embodiment 2 products therefroms is as shown in Figure 4.920cm from figure
-1The place can obviously find out the absorption peak of epoxide group.Fig. 4 compares with Fig. 2 and Fig. 3, can find out obviously that multipolymer and dimercapto diphenyl sulfide glycidyl ether and Bisphenol F glycidyl ether have common peak, explains to have dimercapto diphenyl sulfide glycidyl ether section and Bisphenol F glycidyl ether section in the products therefrom thus.
In the there-necked flask that whipping appts, TM and reflux condensing tube are housed, add 0.25 mole epoxy chloropropane, dimercapto diphenyl sulfide and 0.1 mole of bisphenol A diglycidyl ether of 0.1 mole, in water-bath, carry out stirring and dissolving; The quaternary ammonium salt that adds 0.001 mole is as catalyzer; At bath temperature is 70 ℃, reacts 2 hours; Heat up then, the unreacted epoxy chloropropane distillation of major part is reclaimed being lower than under 120 ℃ the condition; Keeping temperature of reaction afterwards is 70 ℃, and divides in 2 ~ 2.5 hours and add sodium hydrate solid four times, whenever adds once at a distance from 0.5 hour, and the total amount of the sodium hydroxide that wherein adds is 0.2 mole; Under 70 ℃ of temperature, be incubated 0.5 ~ 1 hour, the formation reaction product then.The MIBK that in reaction product, adds 0.2 ~ 2 mole stops to stir discharging then.Material is placed separating funnel, 10 moles of adding distil waters, vibration forms organic layer and water layer, and separatory removes water layer; Repeatedly separatory repeatedly, in organic layer till the no cl ions.The gained organic layer is carried out vacuum-drying at ambient temperature, remove solvent, promptly get dimercapto diphenyl sulfide-dihydroxyphenyl propane Racemic glycidol ether copolymer.Fig. 5 is the ftir analysis figure of dihydroxyphenyl propane glycidyl ether.The result through FTIR Spectrometer FTIR (FTIR) analysis of present embodiment 3 products therefroms is as shown in Figure 6.920cm from figure
-1The place is the absorption peak of epoxide group obviously.Fig. 6 compares with Fig. 2 and Fig. 5, can find out obviously that multipolymer and dimercapto diphenyl sulfide glycidyl ether and dihydroxyphenyl propane glycidyl ether have common peak, explains to have dimercapto diphenyl sulfide glycidyl ether section and dihydroxyphenyl propane glycidyl ether section in the products therefrom thus.
Embodiment 4
In the there-necked flask that whipping appts, TM and reflux condensing tube are housed, add 0.25 mole epoxy chloropropane, dimercapto diphenyl sulfide and 0.2 mole of Bisphenol F diglycidylether of 0.1 mole, in water-bath, carry out stirring and dissolving; The quaternary ammonium salt that adds 0.001 mole is as catalyzer; At bath temperature is 70 ℃, reacts 2 hours; Heat up then, the unreacted epoxy chloropropane distillation of major part is reclaimed being lower than under 120 ℃ the condition; Keeping temperature of reaction afterwards is 70 ℃, and divides in 2 ~ 2.5 hours and add sodium hydrate solid four times, whenever adds once at a distance from 0.5 hour, and the total amount of the sodium hydroxide that wherein adds is 0.2 mole; Under 70 ℃ of temperature, be incubated 0.5 ~ 1 hour, the formation reaction product then.The MIBK that in reaction product, adds 0.2 ~ 2 mole stops to stir discharging then.Material is placed separating funnel, 10 moles of adding distil waters, vibration forms organic layer and water layer, and separatory removes water layer; Repeatedly separatory repeatedly, in organic layer till the no cl ions.The gained organic layer is carried out vacuum-drying at ambient temperature, remove solvent, promptly get dimercapto diphenyl sulfide-Bisphenol F Racemic glycidol ether copolymer.Product type among present embodiment 4 products therefroms and the embodiment 2 seemingly, the result that its FTIR analyzes is similar with Fig. 4.
In the there-necked flask that whipping appts, TM and reflux condensing tube are housed, add 0.25 mole epoxy chloropropane, dimercapto diphenyl sulfide and 0.1 mole of Bisphenol F of 0.1 mole, in water-bath, carry out stirring and dissolving; The quaternary ammonium salt that adds 0.001 mole is as catalyzer; At bath temperature is 70 ℃, reacts 2 hours; Heat up then, the unreacted epoxy chloropropane distillation of major part is reclaimed being lower than under 120 ℃ the condition; Keeping temperature of reaction afterwards is 70 ℃, and divides in 2 ~ 2.5 hours and add sodium hydrate solid four times, whenever adds once at a distance from 0.5 hour, and the total amount of the sodium hydroxide that wherein adds is 0.4 mole; Under 70 ℃ of temperature, be incubated 0.5 ~ 1 hour, the formation reaction product then.The MIBK that in reaction product, adds 0.2 ~ 2 mole stops to stir discharging then.Material is placed separating funnel, 10 moles of adding distil waters, vibration forms organic layer and water layer, and separatory removes water layer; Repeatedly separatory repeatedly, in organic layer till the no cl ions.The gained organic layer is carried out vacuum-drying at ambient temperature, remove solvent, promptly get dimercapto diphenyl sulfide-Bisphenol F Racemic glycidol ether copolymer.Product type among present embodiment 5 products therefroms and the embodiment 2 seemingly, the result that its FTIR analyzes is similar with Fig. 4.
Embodiment 6
In the there-necked flask that whipping appts, TM and reflux condensing tube are housed, add 0.25 mole epoxy chloropropane, dimercapto diphenyl sulfide and 0.1 mole of dihydroxyphenyl propane of 0.1 mole, in water-bath, carry out stirring and dissolving; The quaternary ammonium salt that adds 0.001 mole is as catalyzer; At bath temperature is 70 ℃, reacts 2 hours; Heat up then, the unreacted epoxy chloropropane distillation of major part is reclaimed being lower than under 120 ℃ the condition; Keeping temperature of reaction afterwards is 70 ℃, and divides in 2 ~ 2.5 hours and add sodium hydrate solid four times, whenever adds once at a distance from 0.5 hour, and the total amount of the sodium hydroxide that wherein adds is 0.4 mole; Under 70 ℃ of temperature, be incubated 0.5 ~ 1 hour, the formation reaction product then.The MIBK that in reaction product, adds 0.2 ~ 2 mole stops to stir discharging then.Material is placed separating funnel, 10 moles of adding distil waters, vibration forms organic layer and water layer, and separatory removes water layer; Repeatedly separatory repeatedly, in organic layer till the no cl ions.The gained organic layer is carried out vacuum-drying at ambient temperature, remove solvent, promptly get dimercapto diphenyl sulfide-dihydroxyphenyl propane Racemic glycidol ether copolymer.Product type among present embodiment 6 products therefroms and the embodiment 3 seemingly, the result that its FTIR analyzes is similar with Fig. 6.
Embodiment 7
In the there-necked flask that whipping appts, TM and reflux condensing tube are housed, add 0.25 mole epoxy chloropropane, dimercapto diphenyl sulfide and 0.2 mole of Bisphenol F of 0.1 mole, in water-bath, carry out stirring and dissolving; The quaternary ammonium salt that adds 0.001 mole is as catalyzer; At bath temperature is 70 ℃, reacts 2 hours; Heat up then, the unreacted epoxy chloropropane distillation of major part is reclaimed being lower than under 120 ℃ the condition; Keeping temperature of reaction afterwards is 70 ℃, and divides in 2 ~ 2.5 hours and add sodium hydrate solid four times, whenever adds once at a distance from 0.5 hour, and the total amount of the sodium hydroxide that wherein adds is 0.4 mole; Under 70 ℃ of temperature, be incubated 0.5 ~ 1 hour, the formation reaction product then.The MIBK that in reaction product, adds 0.2 ~ 2 mole stops to stir discharging then.Material is placed separating funnel, 10 moles of adding distil waters, vibration forms organic layer and water layer, and separatory removes water layer; Repeatedly separatory repeatedly, in organic layer till the no cl ions.The gained organic layer is carried out vacuum-drying at ambient temperature, remove solvent, promptly get dimercapto diphenyl sulfide-Bisphenol F Racemic glycidol ether copolymer.Product type among present embodiment 7 products therefroms and the embodiment 2 seemingly, the result that its FTIR analyzes is similar with Fig. 4.
The thioresorcin thioether tetraglycidel ether epoxy resin and the multipolymer thereof of gained in the foregoing description 1 to 7 are carried out specific refractory power, transmittance and viscosimetric analysis respectively; Wherein specific refractory power is to adopt Abbe refractometer and measure specific refractory power with reference to " mensuration (20 ℃) of GB/T 6488-2008 fluid chemical product refractive index "; Transmittance is to measure with reference to " mensuration of GB/T 2410-2008 transparent plastics transmittance and mist degree ", and viscosity adopts rotational viscosimeter to measure with reference to " mensuration of GB/T 2794-1995 tackiness agent viscosity "; Test result is as shown in table 1.
Table 1
As above shown in the table 1, adopt the prepared optical resin of compound method of the optical resin of the embodiment of the invention to have higher specific refractory power and transmittance and lower viscosity.
Through the prepared 3.6 gram synthetic products of the compound method of embodiment of the invention optical resin, add the cured product of different solidifying agent respectively to generate.These cured products are tested, and its result is as shown in table 2.
Table 2
As above shown in the table 2, adopt the optical resin of the embodiment of the invention also to have higher specific refractory power and transmittance.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Though the present invention discloses as above with preferred embodiment; Yet be not in order to limiting the present invention, anyly be familiar with the professional and technical personnel, in not breaking away from technical scheme scope of the present invention; When the technology contents of above-mentioned announcement capable of using is made a little change or is modified to the equivalent embodiment of equivalent variations; In every case be not break away from technical scheme content of the present invention, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (10)
1. optical resin, it is dimercapto diphenyl sulfide-diphenol Racemic glycidol ether copolymer, its structural formula is:
Wherein, the m value is 0 ~ 10, and the n value is 1 ~ 10; R be to hexichol for propyl, to the hexichol ether, to diphenyl sulfide based, to diphenylmethane group or to phenyl.
2. the compound method of an optical resin, umber is in mole, and it may further comprise the steps successively:
In container, add 1 part dimercapto diphenyl sulfide, 2.5 ~ 20 parts epoxy chloropropane and 0.01 ~ 2 part 2-glycidyl ethers material or diphenols material, and mix;
The catalyzer that in this container, adds 0.01 ~ 0.05 part;
This container is placed in 50 ~ 80 ℃ the temperature, reacted 2 ~ 9 hours;
Heat this container, and the unreacted epoxy chloropropane distillation of part is reclaimed being lower than under 120 ℃ the condition;
This container is placed in 60 ~ 85 ℃ the temperature, and in 2 ~ 2.5 hours, in this container, adds an amount of alkali;
In 60 ~ 85 ℃ temperature, insulation reaction 0.5 ~ 1 hour;
In this container, add organic solvent; And
Isolate liquid dimercapto diphenyl sulfide-diphenol Racemic glycidol ether copolymer.
3. the compound method of optical resin as claimed in claim 2, it is characterized in that: this 2-glycidyl ethers material is one of bisphenol A diglycidyl ether, Bisphenol F diglycidylether, bis-phenol phenyl ether diglycidylether, bis-phenol diphenyl sulfide diglycidylether and Resorcinol diglycidylether or its compsn.
4. the compound method of optical resin as claimed in claim 2, it is characterized in that: this diphenols material is one of dihydroxyphenyl propane, Bisphenol F, bis-phenol phenyl ether, bis-phenol diphenyl sulfide and Resorcinol or its compsn.
5. the compound method of optical resin as claimed in claim 2, it is characterized in that: this catalyzer comprises one of alkali, quaternary ammonium salt and triphenyl phosphorus or its compsn.
6. the compound method of optical resin as claimed in claim 2, it is characterized in that: this alkali is one of sodium hydroxide, Lithium Hydroxide MonoHydrate or Pottasium Hydroxide or its compsn; And, when add be 2-glycidyl ethers material the time, the consumption of this alkali is 2 ~ 2.5 parts; When add be the diphenols material time, the consumption of this alkali is that two times of umber of diphenols material are added 2 ~ 2.5 parts.
7. the compound method of optical resin as claimed in claim 6, it is characterized in that: this alkali exists with the form of alkaline solution, and the concentration of this alkaline solution is 10% ~ saturated or alkali solid.
8. the compound method of optical resin as claimed in claim 2, it is characterized in that: this organic solvent is one of toluene, YLENE, benzene, ethylbenzene, diethylbenzene, tetracol phenixin, MIBK, acetone and methylethylketone or its compsn.
9. the compound method of optical resin as claimed in claim 2, it is characterized in that: the method for isolating this liquid state optical resin comprises:
Step 1 adds zero(ppm) water in this reaction product that adds this organic solvent and vibration makes this reaction product be divided into water layer and organic layer;
Step 2, separatory removes water layer;
Step 3, repeating step 1 and step 2 are in this organic layer till the no cl ions; And
Organic layer is carried out vacuum-drying at ambient temperature, to remove this organic solvent.
10. the compound method of optical resin as claimed in claim 2; It is characterized in that: after isolating liquid dimercapto diphenyl sulfide-diphenol Racemic glycidol ether copolymer; Comprise that also curing should liquid state dimercapto diphenyl sulfide-diphenol Racemic glycidol ether copolymer, this solidifying agent is amine, anhydrides, thio-alcohol, isocyanates or sulphur isocyanates solidifying agent.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061753A (en) * | 2015-08-14 | 2015-11-18 | 深圳市三十一科技有限公司 | Preparation method of solar concentrating resin |
| CN105837793A (en) * | 2016-04-08 | 2016-08-10 | 扬州大学 | A preparing method of a sulfur-containing epoxy resin optical lens material with a high refractive index |
| CN111471421A (en) * | 2020-04-15 | 2020-07-31 | 深圳市高仁电子新材料有限公司 | Novel optical cement production process flow |
| CN114525099A (en) * | 2022-03-09 | 2022-05-24 | 上海回天新材料有限公司 | Moisture-heat-resistant low-temperature curing single-component epoxy adhesive |
| CN118341173A (en) * | 2024-06-17 | 2024-07-16 | 江苏奥凯环境技术有限公司 | Filter bag with welding agent material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316421A (en) * | 1996-03-27 | 1997-12-09 | Sumitomo Seika Chem Co Ltd | Adhesive |
| JPH10324858A (en) * | 1997-05-26 | 1998-12-08 | Sumitomo Seika Chem Co Ltd | Adhesive |
| JPH1114802A (en) * | 1997-06-26 | 1999-01-22 | Seiko Epson Corp | Optical resin composition and optical resin |
-
2011
- 2011-09-20 CN CN 201110278891 patent/CN102391471B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316421A (en) * | 1996-03-27 | 1997-12-09 | Sumitomo Seika Chem Co Ltd | Adhesive |
| JPH10324858A (en) * | 1997-05-26 | 1998-12-08 | Sumitomo Seika Chem Co Ltd | Adhesive |
| JPH1114802A (en) * | 1997-06-26 | 1999-01-22 | Seiko Epson Corp | Optical resin composition and optical resin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061753A (en) * | 2015-08-14 | 2015-11-18 | 深圳市三十一科技有限公司 | Preparation method of solar concentrating resin |
| CN105837793A (en) * | 2016-04-08 | 2016-08-10 | 扬州大学 | A preparing method of a sulfur-containing epoxy resin optical lens material with a high refractive index |
| CN111471421A (en) * | 2020-04-15 | 2020-07-31 | 深圳市高仁电子新材料有限公司 | Novel optical cement production process flow |
| CN114525099A (en) * | 2022-03-09 | 2022-05-24 | 上海回天新材料有限公司 | Moisture-heat-resistant low-temperature curing single-component epoxy adhesive |
| CN118341173A (en) * | 2024-06-17 | 2024-07-16 | 江苏奥凯环境技术有限公司 | Filter bag with welding agent material and preparation method thereof |
| CN118341173B (en) * | 2024-06-17 | 2024-10-18 | 江苏奥凯环境技术有限公司 | Filter bag with welding agent material and preparation method thereof |
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