CN1171924C - Method for preparing optical plastic of polythiocarbamic acid ether - Google Patents
Method for preparing optical plastic of polythiocarbamic acid ether Download PDFInfo
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- CN1171924C CN1171924C CNB021451303A CN02145130A CN1171924C CN 1171924 C CN1171924 C CN 1171924C CN B021451303 A CNB021451303 A CN B021451303A CN 02145130 A CN02145130 A CN 02145130A CN 1171924 C CN1171924 C CN 1171924C
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Abstract
The present invention discloses a method for preparing polythiocarbamic acid ether type optical plastics. The present invention is characterized in that thiol containing thioether bonds and a plurality of sulfhydryls are synthesized, and the mixture of the self-made polynary thiol and polyisocyanate is directly injected into a mould to react in an in-situ polymerization mode so as to obtain the polythiocarbamic acid ether type optical plastics having the advantages of favorable transparency, high refractive index and high impact strength. The method has the advantages of simple synthesis technology, high monomer purity, favorable product combination property, low cost, favorable controllability and favorable repeatability of the reaction process, and mild reaction condition. The polythiocarbamic acid ether type optical plastics can be used in various fields. The polythiocarbamic acid ether type optical plastics are suitable for manufacturing various transparent devices, and are especially suitable for manufacturing devices with high requirements on the refractive index, for example, prisms, lenses, ultrathin resin lenses, etc.
Description
Technical field
The present invention relates to a kind of method for preparing optical plastics, is with multi-thiol and polyisocyanate compound in-situ polymerization in mould specifically, the method for the poly-thiocarbamate optical plastics of preparation.
Background technology
Polymer optical resin (optical plastics) has obtained widespread use in recent years with advantages such as its impact resistance is good, density is low, cheap, easy machine-shapings in industrial or agricultural, communication, aerospace and daily life.As the lens on the wind shelves on plastic optical fiber, the aircraft, glasses, visual telescope, magnifying glass, the photographic camera and other industry and civilian installation.Till settled the present, polystyrene, polycarbonate, polymethylmethacrylate, poly-diallyl diglycol carbonates as the traditional optical plastics still in occupation of the dominant position in optical plastics market.Yet along with the continuous development of modern economy and new and high technology, the different application occasion requires difference increasing to the optical plastics specific performance, and the application in a lot of fields of traditional optical plastics is restricted.Typical situation such as optical lens (comprising the most frequently used ophthalmic lens) general requirement have higher refractive index and lower chromatic dispersion.For obtaining identical refracting power, the lens of being processed by the high-index material making are thinner, weight is lighter, therefore can obtain ultra-thin lens.Because the thickness of lens descends, the material that then requires to make lens has better mechanical strength to guarantee the intensity and the use properties of device.In view of its important use is worth and demand, high refractive index type resin is the main direction in the present optical plastics research.
For improving the refractive index of polymkeric substance, people have carried out concluding summary to all kinds of functional groups, and think that following group has obvious effect to improving specific refractory power: (1) haloid element (defluorination), (2) heavy metal ion, (3) phenyl ring and condensed ring, (4) sulphur, phosphorus atom.Cl is less to improving the specific refractory power effect in the haloid element, and the introducing of I is difficulty comparatively, and cost is also high, thus the most frequently used to be Br.But the over-all properties of this halogen-containing resin is often relatively poor, as easy coloring and variable color, matter is crisp, proportion is bigger, and really have practical value resin (generally being copolymerization) refractive index difficulty be improved largely.Though contain the flint P series glass of heavy metal element such as Pb, La is the highest kind of refractive index in the opticglass, these elements is introduced in the organic polymer realized in the hope of the optical plastics that makes high refractive index equally is difficult.With introduce in the opticglass differently with the form of metal oxide, heavy metal ion is incorporated in the monomer with the form of organometallics or organic unsaturated hydrochlorate substantially.Although the molar refraction of metal ion is higher, the molar refraction of coordinate organic group is lower with it, so the total molar refraction of monomer is difficult to improve.In addition, these monomers can not homopolymerization prepare optical plastics mostly, and will take to carry out copolymerization with lower existing monomer such as the vinylbenzene of other molar refraction.The refractive index of gained resin can not be very high like this, and proportion is bigger.The optical plastics that contains phenyl ring generally has higher relatively specific refractory power, as polystyrene and polycarbonate, in the preparation also than being easier to.With halogen-containing different with optical plastics heavy metal element, the raising of phenyl ring refractive index mainly is its easy polarizability.Like this, the chromatic dispersion that contains the phenyl ring resin must become big.In addition, the raising of phenyl ring refractive index is limited, must and other group in conjunction with just obtaining the more resin of high refractive index.The research of sulfur-bearing monomer and resin is the most important direction of current high refractive index optical plastics.This resinoid not only refractive index is higher, and is easy to prepare, and chromatic dispersion is less, and proportion is lighter.For further improving refractive index, often introduce phenyl ring in the monomer simultaneously.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of synthesis technique, prepares the method for the poly-thiocarbamate optical plastics of high refractive index high strength with multi-thiol and polyisocyanates in-situ polymerization.
Method of the present invention may further comprise the steps:
1) syndeme multi-thiol at first, be 2,2 respectively '-dimercapto ethyl-sulfide, 2,2 '-dimercapto ethylenebis dithiocarbamate ethane, 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and 1,2,3-tri-thiol ethylenebis dithiocarbamate propane;
2) be 0.8～1.4 to mix a kind of or its mixture in the above-mentioned mercaptan and polyisocyanates or its mixture by sulfydryl and isocyanate groups mol ratio, add the inner pattern releasing agent applicable phosphoric acid ester of gross weight 0.1～2%;
3) with step 2) the gained mixture was in 50～80 ℃ of following pre-polymerizations 10～60 minutes, and the vacuum removal bubble is injected in the mould simultaneously;
4) mould that will contain prepolymer was placed 2～12 hours down in 40～50 ℃, rose to 80～100 ℃ with 5 ℃/30 minutes clock rate then, continued to place 2～5 hours, and the last cool to room temperature demoulding promptly gets and gathers the thiocarbamate optical plastics.
Among the present invention, said multi-thiol: 2,2 '-dimercapto ethyl-sulfide, 2,2 '-dimercapto ethylenebis dithiocarbamate ethane, 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and 1,2,3-tri-thiol ethylenebis dithiocarbamate propane can adopt following method synthetic, but are not limited to following method:
1. 2,2 '-the dimercapto ethyl-sulfide is synthetic:
1) be 1: 2～3: 2～5 to join in the reaction vessel that is equipped with stirring rod, thermometer and reflux condensate device in molar ratio with dihydroxyethylsulfide, thiocarbamide and concentration 36% hydrochloric acid;
2) step 1) gained mixture was refluxed 1～10 hour in 100～110 ℃;
3) with step 2) products therefrom is chilled to below 70 ℃, logical nitrogen, drip or 2～6 times of moles of disposable adding in the sodium hydroxide (being mixed with solution uses) of dihydroxyethylsulfide.Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
4) with behind the hcl acidifying, divide oil-yielding stratum, to neutral, anhydrous sodium sulfate drying gets colourless to faint yellow crude product with distilled water wash;
5) with the underpressure distillation of step 4) gained crude product, water white transparency liquid, be 2,2 '-the dimercapto ethyl-sulfide.
2. 2,2 '-dimercapto ethylenebis dithiocarbamate ethane is synthetic:
1) is to join in the reaction vessel that be equipped with stirring rod, thermometer and reflux condensate device at 2～3: 1 in molar ratio with mercaptoethanol and ethylene dichloride, mixes logical nitrogen protection;
2) with step 1) gained mixture in being heated to 50～70 ℃, drip 1～3 times of mole in the sodium hydroxide of mercaptoethanol (being mixed with solution uses).Can be observed red-purple in the reaction process occurs.When reactant is become when colourless or faint yellow by red-purple, illustrate that the reaction of mercaptoethanol and ethylene dichloride is finished;
3) with step 2) products therefrom with hcl acidifying after, colorless oil liquid, be condensed into white solid after the cooling.Obtain intermediate 2,2 '-dihydroxy ethyl sulfo-ethane;
4) with 2,2 '-dihydroxy ethyl sulfo-ethane, thiocarbamide and concentration 36% hydrochloric acid are 1: 2～3: 2～5 to join in the reaction vessel that is equipped with stirring rod, thermometer and reflux condensate device in molar ratio;
5) step 4) gained mixture was refluxed 1～10 hour in 100～110 ℃;
6) the step 5) products therefrom is chilled to below 70 ℃, logical nitrogen, drip or 2～6 times of moles of disposable adding in 2,2 '-sodium hydroxide (being mixed with solution uses) of dihydroxy ethyl sulfo-ethane.Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
7) with behind the hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes water and small molecules such as ethanol wherein, final white solid thing, be 2,2 '-dimercapto ethylenebis dithiocarbamate ethane.
3. 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan is synthetic, and two kinds of schemes are arranged.
Scheme 1:
1) with mercaptoethanol and 2, the 3-dibromo-propanol is to join in the reaction vessel that be equipped with stirring rod, thermometer and reflux condensate device at 2～3: 1 in molar ratio, mixes, logical N
2Protection;
2), drip the sodium hydroxide (be mixed with solution use) of 1～3 times of mole in mercaptoethanol with step 1) gained mixture heating up to 50～70 ℃.Can be observed red-purple in the reaction process occurs.When reactant is become when colourless or faint yellow by red-purple, mercaptoethanol and 2 are described, the reaction of 3-dibromo-propanol is finished;
3) above-mentioned reaction mixture need not to separate and purifying, directly add 1.5～2.5 times of moles in the thiocarbamide of mercaptoethanol and 1.5～4 times of moles in concentration 36% hydrochloric acid of mercaptoethanol;
4) step 3) gained mixture was refluxed 1～10 hour in 100～110 ℃;
5) the step 4) products therefrom is chilled to below 70 ℃, logical nitrogen, dropping or 1.5～5 times of moles of disposable adding are in the sodium hydroxide (being mixed with solution uses) of mercaptoethanol.Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
6) with behind the hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes water and small molecules such as ethanol wherein, and final colourless or light yellow oil is 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan.
Scheme 2:
1) is 1: 0.05～1 to join in the reaction vessel that is equipped with stirring rod, thermometer and reflux condensate device in molar ratio with the sodium hydroxide solution of mercaptoethanol and 20～30%, mixes logical N
2Protection;
2) with step 1) gained mixture heating up to 50～70 ℃, drip 0.3～1.5 times of mole in the epoxy chloropropane of mercaptoethanol, drip the sodium hydroxide solution (total mole number of sodium hydroxide be 1～3 times of mercaptoethanol) of 0.5～2 times of mole then in mercaptoethanol.Can be observed red-purple in the reaction process occurs.When reactant is become when colourless or faint yellow by red-purple, illustrate that the reaction of mercaptoethanol and epoxy chloropropane is finished;
3) above-mentioned reaction mixture need not to separate and purifying, directly add 1.5～2.5 times of moles in the thiocarbamide of mercaptoethanol and 1.5～4 times of moles in concentration 36% hydrochloric acid of mercaptoethanol;
4) step 3) gained mixture was refluxed 1～10 hour in 100～110 ℃;
5) the step 4) products therefrom is chilled to below 70 ℃, logical nitrogen, dropping or 1.5～5 times of moles of disposable adding are in the sodium hydroxide (being mixed with solution uses) of mercaptoethanol.Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
6) with behind the hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes water and small molecules such as ethanol wherein, and final colourless or light yellow oil is 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan.
4. 1,2,3-tri-thiol ethylenebis dithiocarbamate propane is synthetic:
1) is to join in the reaction vessel that be equipped with stirring rod, thermometer and reflux condensate device at 3～5: 1 in molar ratio with mercaptoethanol and trichloropropane, mixes logical nitrogen protection;
2) with step 1) gained mixture heating up to 60～100 ℃, drip 1～3 times of mole in the potassium hydroxide solution of mercaptoethanol.Can be observed red-purple in the reaction process occurs.When reactant is become when colourless or faint yellow by red-purple, illustrate that the reaction of mercaptoethanol and trichloropropane is finished;
3) with above-mentioned mixed solution suction strainer, remove Repone K after, in separating funnel, leave standstill separatory.Intermediate product 1,2,3-trihydroxy-ethylenebis dithiocarbamate propane removes small molecules in 70 ℃ of decompressions;
4) with 1,2,3-trihydroxy-ethylenebis dithiocarbamate propane, 1～1.5 times of mole join in the reaction vessel that is equipped with stirring rod, thermometer and reflux condensate device in concentration 36% hydrochloric acid of mercaptoethanol in thiocarbamide and 1～2.5 times of mole of mercaptoethanol, mix, logical nitrogen protection;
5) step 4) gained mixture was refluxed 1～10 hour in 100～110 ℃;
6) the step 5) products therefrom is chilled to below 70 ℃, logical nitrogen, dropping or 1～3 times of mole of disposable adding are in the sodium hydroxide (being mixed with solution uses) of mercaptoethanol.Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
7) with behind the hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes water and small molecules such as ethanol wherein, and final colourless or light yellow oil is 1,2,3-tri-thiol ethylenebis dithiocarbamate propane.
Among the present invention, said polyisocyanates compounds, (compound NCO) is as tolylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate tripolymer, Xylene Diisocyanate, isophorone diisocyanate, isophorone diisocyanate trimer, phenylene diisocyanate, cyclohexyl diisocyanate, '-diphenylmethane diisocyanate etc. or its mixture to be meant the isocyanate groups that contains in the molecular structure more than two or two.
The inventive method synthesis technique is simple, monomer purity is high, the product excellent combination property, and cost is lower; The controllability of reaction process and good reproducibility, the reaction conditions gentleness.The present invention at first designs and has synthesized 4 kinds of thioether type mercaptan that sulphur content is very high, and reactant used during it is synthetic is simple in structure, and raw material sources are rich and easy to get; The reaction conditions gentleness, controlled easy repetition.The quality of gained mercaptan is good, of light color, homopolymerization and copolymerization are functional.And then carry out polyaddition by a plurality of sulfydryls in the mercaptan and a plurality of isocyanate groups in the isocyanic ester, thereby in-situ polymerization obtains the poly-thiocarbamate optical plastics that the transparency is good, refractive index is high, shock strength is high in mould.Because of containing the reactive group more than 3 or 3 in mercaptan or the isocyanic ester, therefore the polymkeric substance that obtains is highly cross-linked.By in polymer architecture, introducing the strong thiocarbamate polar group of hydrogen bond action power and forming highly cross-linked network, the polymer materials cohesive energy density(CED) that obtains is improved, structure is tight, has higher physical strength.The highly cross-linked network limits that forms in the polymerization process crystallization of high density thiocarbamate group, guarantee that the polymer materials obtain has the properties of transparency of height.The optical plastics that therefore, can synthesize high refractive index, excellent combination property by the present invention of these technology.
Gained of the present invention gathers thiocarbamate type optical plastics, and the transparency is good, refractive index is high, impact strength is high, excellent combination property.This polymkeric substance optical plastics can be applicable to multiple field, is suitable for making various transparent devices, is particularly useful for device that refractive index is had relatively high expectations, as prism, lens and ultra-thin resin lens etc.
Embodiment
Following example further specifies the present invention, but these examples are not used for limiting the present invention.
Example 1
Employing scheme 1 Synthetic 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan:
In four-hole boiling flask, add 118.6g (0.5443 mole) 2 in turn, 3-dibromo-propanol and 85g (1.0885 moles) mercaptoethanol, heating in water bath to 60 ℃ under the nitrogen protection.Dripped 1.1974 mole of 20% sodium hydroxide solution in 1 hour, controlled temperature is about 60 ℃.Sodium hydroxide solution is bordering on when adding, and solution is become colorless to faint yellow by lavender.Above-mentioned reaction mixture need not to separate and purifying, directly adds 130.5g (1.7145 moles) thiocarbamide and 150mL (1.7962 moles) concentration 36% hydrochloric acid.105 ℃ of backflows were chilled to below 70 ℃ after 6 hours, logical nitrogen, disposable adding 78.2g (1.8778 moles) sodium hydroxide (purity 96% is mixed with 20% solution and uses).Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70 ℃ of reactions 0.5～1 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear.Behind hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes wherein water and small molecules such as ethanol about 70 ℃, and is final colourless or be with yellow liquid slightly, is 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan.Total recovery: 79%, refractive index (n
d 20)=1.643, Abb (ν
d)=33.4.Proton nmr spectra (
1HNMR) :-SH (1.773ppm, t) ,-C-H (2.7-3.0, m); Carbon-13 nmr spectra (
13CNMR): 25.74,25.96,29.54,35.92,36.69,37.42,49.10ppm; Fourier-transform infrared (FTIR): SH (2552cm
-1), OH absorbs disappearance.
With above-mentioned gained 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and tolylene diisocyanate are 1.05 to mix by sulfydryl and isocyanate groups (SH/NCO) mol ratio, add the inner pattern releasing agent applicable phosphoric acid ester of gross weight 0.2%; Then with mixture in 60 ℃ of following pre-polymerizations 40 minutes, simultaneously the vacuum removal bubble is injected in the mould; The mould that will contain prepolymer was again placed 12 hours down in 50 ℃, was warming up to 80 ℃ with 5 ℃/30 minutes clock rate then and placed 2 hours, placed 2 hours for 100 ℃, and the last cool to room temperature demoulding promptly gets and gathers the thiocarbamate optical plastics.The refractive index of gained optical plastics is 1.6795, and Abb is 26, has good light transmittance energy and mechanical property, sees Table 1.
Table 1
| Isocyanic ester | Refractive index | Abb | Density g/cm 3 | Water-intake rate % | Shock strength kJ.m -2 | Surface hardness | Transmittance %, 550nm | Y | Second-order transition temperature ℃ |
| Tolylene diisocyanate | 1.6795 | 26 | 1.3795 | 0.08 | 12～15 | 2H | 85.6 | 0.067 | 101 |
| '-diphenylmethane diisocyanate | 1.6863 | 24.2 | 1.334 | 0.12 | 16.5 | 2H | 86.3 | 0.066 | 115 |
| Isophorone diisocyanate | 1.5937 | 40 | 1.2346 | 0.11 | 2H | 88.2 | 0.042 | 98 | |
| The hexamethylene diisocyanate tripolymer | 1.5822 | 41.7 | 1.2687 | 0.2 | 33.8 | HB | 85.7 | 0.03 | 70 |
In the table 1, shock strength is that non-notch simply supported beam method is measured; Value when transmittance is wavelength 550nm; Y is proportional to yellowness index, is defined as (1-T
450/ T
650), T
450And T
650Be respectively the transmittance of wavelength 450nm and 650nm.
Example 2
Tolylene diisocyanate in the example 1 is replaced with '-diphenylmethane diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate tripolymer respectively.Keeping sulfydryl and isocyanate groups (SH/NCO) mol ratio is 1.05, and other condition is constant.The optical plastics performance that obtains after the curing is listed in table 1.
Example 3
Utilize synthetic 2 in the example 1,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and hexamethylene diisocyanate tripolymer by changing sulfydryl and isocyanate groups (SH/NCO) molar ratio, keep other condition constant, obtain the different optical plastics of performance after the curing.Sulfydryl and isocyanate groups (SH/NCO) mol ratio is to 2, and the poly-thiocarbamate optical plastics Effect on Performance that 3-dimercapto ethylenebis dithiocarbamate propylmercaptan/hexamethylene diisocyanate tripolymer polymerization obtains is listed in table 2.
Table 2
| SH/ NCO | Refractive index | Abb | Density g/cm 3 | Water-intake rate % | Shock strength kJ.m -2 | Surface hardness | Transmittance %, 550nm | Y | Second-order transition temperature ℃ |
| 1.33 | 1.5892 | 39.8 | 1.2806 | 0.2 | 29 | HB | 87.8 | 0.041 | 64 |
| 1.19 | 1.5886 | 41.3 | 1.2793 | 0.2 | 43.2 | HB | 87.2 | 0.037 | 73 |
| 1.05 | 1.5822 | 41.7 | 1.2687 | 0.2 | 33.8 | HB | 85.7 | 0.03 | 70 |
| 0.95 | 1.5775 | 42.7 | 1.2644 | 0.24 | 42.4 | HB | 87.3 | 0.028 | 64 |
Example 4
Utilize synthetic 2 in the example 1,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and tolylene diisocyanate and hexamethylene diisocyanate tripolymer carry out copolymerization, and keeping sulfydryl and isocyanate groups (SH/NCO) mol ratio is 1.05, and other condition is constant.The optical plastics performance that obtains after the curing is listed in table 3.
Table 3
| Hexamethylene diisocyanate tripolymer weight % | Refractive index | Abb | Density g/cm 3 | Water-intake rate % | Shock strength kJ.m -2 | Surface hardness | Transmittance %, 550nm | Y |
| 0 | 1.6795 | 26 | 1.3795 | 0.08 | 12～15 | 2H | 85.6 | 0.067 |
| 30 | 1.6519 | 28.2 | 1.3471 | 0.12 | 13 | 2H | 82.4 | 0.051 |
| 56.5 | 1.6298 | 31 | 1.3277 | 0.16 | 20 | 1H | 85.5 | 0.043 |
| 75.3 | 1.6107 | 34.8 | 1.3087 | 0.17 | 15 | 1H | 85.2 | 0.044 |
| 89.1 | 1.5935 | 38.3 | 1.2877 | 0.19 | 28 | HB | 84.7 | 0.073 |
| 100 | 1.5822 | 41.7 | 1.2687 | 0.2 | 33.8 | HB | 85.7 | 0.03 |
Example 5
Utilize synthetic 2 in the example 1,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and tolylene diisocyanate and isophorone diisocyanate carry out copolymerization, and keeping sulfydryl and isocyanate groups (SH/NCO) mol ratio is 1.05, and other condition is constant.The optical plastics performance that obtains after the curing is listed in table 4.
Table 4
| Isophorone diisocyanate weight % | Refractive index | Abb | Density g/cm 3 | Water-intake rate % | Shock strength kJ.m -2 | Surface hardness | Transmittance %, 550nm | Y |
| 0 | 1.6795 | 26 | 1.3795 | 0.08 | 12～15 | 2H | 85.6 | 0.067 |
| 12.3 | 1.6695 | 27.2 | 1.3586 | 0.15 | 7.8 | 2H | 79.1 | 0.143 |
| 33.3 | 1.6520 | 29.3 | 1.3308 | 0.14 | 6.7 | 2H | 83.5 | 0.074 |
| 51.6 | 1.6355 | 31.1 | 1.3035 | 0.16 | 12.3 | 2H | 78 | 0.139 |
| 69.2 | 1.6198 | 34.3 | 1.2736 | 0.16 | 3.5 | 1H | 87.4 | 0.048 |
| 85.3 | 1.6033 | 36.5 | 1.2501 | 0.2 | 1.3 | 1H | 84.8 | 0.031 |
| 100 | 1.5937 | 40 | 1.2346 | 0.11 | 2H | 88.2 | 0.042 |
Example 6
Utilize synthetic 2 in the example 1,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and '-diphenylmethane diisocyanate and hexamethylene diisocyanate tripolymer carry out copolymerization, and keeping sulfydryl and isocyanate groups (SH/NCO) mol ratio is 1.05, and other condition is constant.The optical plastics performance that obtains after the curing is listed in table 5.
Table 5
| Hexamethylene diisocyanate tripolymer weight % | Refractive index | Abb | Density g/cm 3 | Water-intake rate % | Shock strength kJ.m -2 | Surface hardness | Transmittance %, 550nm | Y | Second-order transition temperature ℃ |
| 0 | 1.6863 | 24.2 | 1.334 | 0.12 | 16.5 | 2H | 86.3 | 0.066 | 115 |
| 27.4 | 1.664 | 26.6 | 1.3179 | 0.12 | 45.8 | 2H | 86.4 | 0.044 | 108 |
| 42.9 | 1.6482 | 27.9 | 1.3147 | 0.13 | 8.3 | 2H | 86.2 | 0.037 | |
| 50 | 1.6431 | 28.8 | 1.3071 | 0.11 | 17.7 | 1H | 87.8 | 0.042 | 92 |
| 76.5 | 1.6179 | 33.4 | 1.2908 | 0.14 | 27.8 | 1H | 84.9 | 0.041 | 80 |
| 100 | 1.5880 | 41.3 | 1.2757 | 0.2 | 43 | HB | 87.3 | 0.043 | 73 |
Example 7
Utilize synthetic 2 in the example 1,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and '-diphenylmethane diisocyanate and isophorone diisocyanate carry out copolymerization, and keeping sulfydryl and isocyanate groups (SH/NCO) mol ratio is 1.05, and other condition is constant.The optical plastics performance that obtains after the curing is listed in table 6.
Table 6
| Isophorone diisocyanate weight % | Refractive index | Abb | Density g/cm 3 | Water-intake rate % | Shock strength kJ.m -2 | Surface hardness | Transmittance %, 550nm | Y | Second-order transition temperature ℃ |
| 0 | 1.6863 | 24.2 | 1.334 | 0.12 | 16.5 | 2H | 86.3 | 0.066 | 115 |
| 22.1 | 1.6655 | 26.2 | 1.3086 | 0.11 | 18 | 2H | 87.1 | 0.059 | 108 |
| 39.2 | 1.65 | 28.2 | 1.2884 | 0.13 | 21.6 | 2H | 81 | 0.103 | 90 |
| 50 | 1.639 | 29.8 | 1.2777 | 0.24 | 10.2 | 2H | 81.1 | 0.098 | 86 |
| 72.6 | 1.6226 | 34.2 | 1.2294 | 0.26 | 1.6 | 2H | 83.1 | 0.07 | 86 |
| 100 | 1.5937 | 40 | 1.2346 | 0.11 | 2H | 88.2 | 0.042 | 98 |
Example 8
Employing scheme 2 Synthetic 2s, 3-dimercapto ethylenebis dithiocarbamate propylmercaptan:
In four-hole boiling flask, add 100g (1.28 moles) mercaptoethanol and 10mL30% sodium hydroxide solution in turn, heating in water bath to 70 ℃ under the nitrogen protection.Dropwise 5 9.2g in 1 hour (0.64 mole) epoxy chloropropane dripped 65mL 30% sodium hydroxide solution (the sodium hydroxide total mole number is 0.768) then in 0.5 hour, controlled temperature is at 70～75 ℃.Sodium hydroxide solution is bordering on when adding, and solution is become colorless to faint yellow by lavender.Above-mentioned reaction mixture need not to separate and purifying, directly adds 160.8g (2.112 moles) thiocarbamide and 192mL (2.304 moles) concentration 36% hydrochloric acid.108 ℃ of backflows were chilled to below 70 ℃ after 6 hours, logical nitrogen, disposable adding 250mL30% (2.496 moles) sodium hydroxide solution.Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70 ℃ of reactions 0.5～1 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear.Behind hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes wherein water and small molecules such as ethanol about 70 ℃, and is final colourless or be with yellow liquid slightly, is 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan.Total recovery: 74.8%, refractive index (n
d 20)=1.634, chromatic dispersion (ν
d)=34.4.Proton nmr spectra (
1HNMR) :-SH (1.83ppm, t) ,-C-H (2.83-3.0, m); Fourier transform infrared spectroscopy (FTIR): SH (2550cm
-1), OH absorbs disappearance.
With above-mentioned gained 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and '-diphenylmethane diisocyanate are 1.05 to mix by sulfydryl and isocyanate groups (SH/NCO) mol ratio, add the inner pattern releasing agent applicable phosphoric acid ester of gross weight 0.2%; Then with mixture in 60 ℃ of following pre-polymerizations 40 minutes, simultaneously the vacuum removal bubble is injected in the mould; The mould that will contain prepolymer was again placed 12 hours down in 50 ℃, was warming up to 80 ℃ with 5 ℃/30 minutes clock rate then and placed 2 hours, placed 2 hours for 100 ℃, and the last cool to room temperature demoulding promptly gets and gathers the thiocarbamate optical plastics.The refractive index of gained optical plastics is 1.6865, and Abb is 24.2, has good light transmittance energy and mechanical property, sees Table 7.
Table 7
| Hexamethylene diisocyanate weight % | Refractive index | Abb | Density g/cm 3 | Shock strength kJ.m -2 | Transmittance %, 550nm | Y | Second-order transition temperature ℃ |
| 0 | 1.6863 | 24.2 | 1.3326 | 7.6 | 85.2 | 0.02 | 118 |
| 25 | 1.6685 | 26.2 | 1.3243 | 1.8 | 80.3 | 0.084 | 97.3 |
| 50 | 1.6487 | 29 | 1.3091 | 15.3 | 83.4 | 0.065 | 79.3 |
| 75 | 1.6285 | 33.4 | 1.3008 | 34.7 | 85.2 | 0.037 | 61.1 |
| 100 | 1.609 | 37.7 | 1.2865 | 71.6 | 88.2 | 0.018 | 44.7 |
Example 9
Utilize synthetic 2 in the example 8,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and '-diphenylmethane diisocyanate and hexamethylene diisocyanate carry out copolymerization, and keeping sulfydryl and isocyanate groups (SH/NCO) mol ratio is 1.05, and other condition is constant.The optical plastics performance that obtains after the curing is listed in table 7.
Example 10
Utilize synthetic 2 in the example 8,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and Xylene Diisocyanate are 1.05 to mix by sulfydryl and isocyanate groups (SH/NCO) mol ratio, add the inner pattern releasing agent applicable phosphoric acid ester of gross weight 0.2%wt; Then with said mixture in 60 ℃ of following pre-polymerizations 40 minutes, simultaneously the vacuum removal bubble is injected in the mould; The mould that will contain prepolymer was again placed 12 hours down in 50 ℃, was warming up to 80 ℃ with 5 ℃/30 minutes clock rate then and placed 2 hours, placed 2 hours for 100 ℃, and the last cool to room temperature demoulding promptly gets and gathers the thiocarbamate optical plastics.The refractive index 1.659 of gained optical plastics, Abb 31, density 1.2243g.cm
-3, water-intake rate 0.13%, non-notch shock strength 20～30kJ.m
-2, 550nm transmittance 87.5%, uv-absorbing cutoff wavelength 340nm.
Example 11
Synthesize 1,2,3-tri-thiol ethylenebis dithiocarbamate propane:
In four-hole boiling flask, add 76g (0.5153 mole) trichloropropane in turn, purify through underpressure distillation), 121g (1.55 moles) mercaptoethanol, logical nitrogen, heating in water bath to 85～90 ℃ slowly drip 1.5768 moles of hydrogen potassium oxides (50% solution).Visible red-purple occurs in the dropping process, and potassium hydroxide is when dripping off, and it is colourless that solution gradually becomes, and the residual hydrogen potassium oxide is added fast, moments later carefully is acidified to neutrality with concentration 36% hydrochloric acid.This step needs 1.5 hours approximately.With above-mentioned mixed solution suction strainer, remove Repone K after, in separating funnel, leave standstill separatory.Intermediate product 1,2,3-trihydroxy-ethylenebis dithiocarbamate propane removes small molecules in 70 ℃ of decompressions.Directly add 123.6g (1.6232 moles) thiocarbamide and 141.7mL (1.7 moles) concentration 36% hydrochloric acid.108 ℃ of backflows were chilled to below 70 ℃ after 6 hours, logical nitrogen, disposable adding 74.1g (1.778 moles) sodium hydroxide (purity 96% is mixed with 20% solution and uses).Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70 ℃ of reactions 0.5～1 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear.Behind hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes wherein water and small molecules such as ethanol about 70 ℃, and is final colourless or be with yellow liquid slightly, is 1,2,3-tri-thiol ethylenebis dithiocarbamate propane.Yield: 70%, refractive index (n
d 20)=1.6395, chromatic dispersion (ν
d)=34.5.Proton nmr spectra (
1HNMR) :-SH (1.75ppm, t) ,-C-H (2.7-3.0ppm, m); Fourier transform infrared spectroscopy (FTIR): SH (2546cm
-1), OH absorbs disappearance.
With above-mentioned gained 1,2,3-tri-thiol ethylenebis dithiocarbamate propane and tolylene diisocyanate or '-diphenylmethane diisocyanate are 1.05 to mix by sulfydryl and isocyanate groups (SH/NCO) mol ratio, add the inner pattern releasing agent applicable phosphoric acid ester of gross weight 0.2%; Then with mixture in 60 ℃ of following pre-polymerizations 40 minutes, simultaneously the vacuum removal bubble is injected in the mould; The mould that will contain prepolymer was placed 12 hours down in 50 ℃, being warming up to 80 ℃ with 5 ℃/30 minutes clock rate again placed 2 hours, placed 2 hours for 100 ℃, the last cool to room temperature demoulding promptly gets and gathers the thiocarbamate optical plastics, have high refractive index, good light transmittance energy and mechanical property, see Table 8.
Table 8
| Isocyanic ester | Refractive index | Abb | Density g/cm 3 | Shock strength kJ.m -2 | Second-order transition temperature ℃ |
| Tolylene diisocyanate | 1.6741 | 26.7 | 1.3641 | 5.7 | 72 |
| '-diphenylmethane diisocyanate | 1.68 | 25.4 | 1.3296 | 5 | 75 |
Example 12
Synthetic 2,2 '-the dimercapto ethyl-sulfide:
In the 1000ml four-hole boiling flask, add 111g (0.91 mole) dihydroxyethylsulfide in turn, 146g (1.92 moles) thiocarbamide, 167ml (2 moles) concentration 36% hydrochloric acid.102～108 ℃ of backflows were chilled to below 70 ℃ after 6 hours, logical nitrogen, disposable adding 87g (2.088 moles) sodium hydroxide (being mixed with 20% solution uses).Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70 ℃ of reactions 0.5～1 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear.Behind hcl acidifying, divide oil-yielding stratum, to neutral, anhydrous sodium sulfate drying gets colourless extremely faint yellow crude product, yield: 90% with distilled water wash.Crude product is through underpressure distillation, and collecting boiling range is 120～121 ℃/5mmHg cut, water white transparency liquid, be 2,2 '-the dimercapto ethyl-sulfide.Total recovery 82.5%.Refractive index (n
d 20)=1.5900, chromatic dispersion (ν
d)=36.5.Proton nmr spectra (
1HNMR) :-SH (1.73ppm, t) ,-C-H (2.6-2.8ppm, m); Fourier transform infrared spectroscopy (FTIR): SH (2546cm
-1), OH absorbs disappearance.
With above-mentioned gained 2,2 '-dimercapto ethyl-sulfide and hexamethylene diisocyanate tripolymer are 1.05 to mix by sulfydryl and isocyanate groups (SH/NCO) mol ratio, add the inner pattern releasing agent applicable phosphoric acid ester of gross weight 0.2%; Then with mixture in 60 ℃ of following pre-polymerizations 40 minutes, simultaneously the vacuum removal bubble is injected in the mould; The mould that will contain prepolymer was again placed 12 hours down in 50 ℃, was warming up to 80 ℃ with 5 ℃/30 minutes clock rate then and placed 2 hours, placed 2 hours for 100 ℃, and the last cool to room temperature demoulding promptly gets and gathers the thiocarbamate optical plastics.The refractive index 1.5786 of gained optical plastics, Abb 42.4, density 1.255g.cm
-3, water-intake rate 0.28%, non-notch shock strength 55kJ.m
-2, surface hardness HB, 550nm transmittance 87.3%, uv-absorbing cutoff wavelength 285nm, 56 ℃ of second-order transition temperatures.
Example 13
Synthetic 2,2 '-dimercapto ethylenebis dithiocarbamate ethane:
In the 1000ml four-hole boiling flask, add 2 moles of mercaptoethanols and 1 mole of ethylene dichloride, mix, logical N
2Protection.50～60 ℃ of water-baths drip 2.2 mole of 30% sodium hydroxide solution, keep constant temperature by exothermic heat of reaction, have red-purple to occur in the reaction process.Add an about half at sodium hydroxide, system temperature obviously descends, after being heated to 70 ℃, continue to drip remaining sodium hydroxide, during near terminal point, red-purple fades away, become colourless or pale yellow oily liquid floats on the water layer, behind hcl acidifying, get colorless oil liquid, be condensed into white solid after the cooling.Obtain intermediate 2,2 '-dihydroxy ethyl sulfo-ethane, 64 ℃ of fusing points.With 2,2 '-dihydroxy ethyl sulfo-ethane direct and 160g (2.1 moles) thiocarbamide and 183.3mL (2.2 moles) concentration 36% mixed in hydrochloric acid, in 108 ℃ refluxed 6 hours after, be chilled to below 70 ℃, logical nitrogen, disposable adding 95.8g (2.3 moles) sodium hydroxide (purity 96% is mixed with 20% solution and uses).Be that adularescent precipitation produces, keep temperature≤70 ℃.Slowly be heated to 70 ℃ of reactions 0.5～1 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear.Behind hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes wherein water and small molecules such as ethanol about 70 ℃, final white solid thing, be 2,2 '-dimercapto ethylenebis dithiocarbamate ethane.Total recovery 90%, 32 ℃ of fusing points, refractive index (n
d 30)=1.61, chromatic dispersion (ν
d)=33.8.Proton nmr spectra (
1HNMR) :-SH (1.75ppm, t) ,-C-H (2.7-2.9ppm, m); Fourier transform infrared spectroscopy (FTIR): SH (2520cm
-1), OH absorbs disappearance.
With 2,2 '-dimercapto ethylenebis dithiocarbamate ethane and example 1 synthetic 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan, example 12 synthetic 2,2 '-dimercapto ethyl-sulfide three mixes by a certain percentage, keeping total sulfydryl and isocyanate groups (SH/NCO) mol ratio is 1.05, and mixes with tolylene diisocyanate or '-diphenylmethane diisocyanate, adds the inner pattern releasing agent applicable phosphoric acid ester of gross weight 0.2%; Then with mixture in 60 ℃ of following pre-polymerizations 40 minutes, simultaneously the vacuum removal bubble is injected in the mould; The mould that will contain prepolymer was again placed 12 hours down in 50 ℃, being warming up to 80 ℃ with 5 ℃/30 minutes clock rate then placed 2 hours, placed 2 hours for 100 ℃, the last cool to room temperature demoulding promptly gets and gathers the thiocarbamate optical plastics, and the performance of the poly-thiocarbamate optical plastics that is obtained by the multi-thiol copolymerization sees Table 9.
Table 9
| 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan | 2,2 '-dimercapto ethyl-sulfide | 2,2 '-dimercapto ethylenebis dithiocarbamate ethane | Isocyanic ester | Refractive index | Abb | Shock strength kJ.m -2 | Transmittance %, 550nm | Y |
| The SH% mole | ||||||||
| 15 | 90 | 0 | Tolylene diisocyanate | 1.6697 | 25.5 | 80 | 0.025 | |
| 75 | 30 | 0 | Tolylene diisocyanate | 1.678 | 25.8 | 85 | 0.046 | |
| 75 | 30 | 0 | '-diphenylmethane diisocyanate | 1.6844 | 24.2 | 40 | 85 | 0.057 |
| 15 | 45 | 45 | Tolylene diisocyanate | 1.6733 | 26.7 | 2.6～3 | 82.5 | 0.083 |
| 75 | 0 | 30 | Tolylene diisocyanate | 1.6782 | 25.8 | 13 | Translucent | |
| 75 | 0 | 30 | '-diphenylmethane diisocyanate | 1.6872 | 24.3 | 27.7 | Muddy | |
In the table 9, the mole number of the sulfydryl (SH) of every kind of mercaptan contribution of " SH% mole " representative.
Claims (8)
1. one kind prepares the method for gathering the thiocarbamate optical plastics, it is characterized in that may further comprise the steps:
1) syndeme multi-thiol at first, be 2,2 respectively '-dimercapto ethyl-sulfide, 2,2 '-dimercapto ethylenebis dithiocarbamate ethane, 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan and 1,2,3-tri-thiol ethylenebis dithiocarbamate propane;
2) be 0.8～1.4 to mix a kind of or its mixture in the above-mentioned mercaptan and polyisocyanates or its mixture by sulfydryl and isocyanate groups mol ratio, add the inner pattern releasing agent applicable phosphoric acid ester of gross weight 0.1～2%;
3) with step 2) the gained mixture was in 50～80 ℃ of following pre-polymerizations 10～60 minutes, and the vacuum removal bubble is injected in the mould simultaneously;
4) mould that will contain prepolymer was placed 2～12 hours down in 40～50 ℃, rose to 80～100 ℃ with 5 ℃/30 minutes clock rate then, continued to place 2～5 hours, and the last cool to room temperature demoulding promptly gets and gathers the thiocarbamate optical plastics.
2. by the method for the poly-thiocarbamate optical plastics of the described preparation of claim 1, it is characterized in that said multi-thiol 2,2 '-the dimercapto ethyl-sulfide is synthetic with the following method:
1) be 1: 2～3: 2～5 to join in the reaction vessel that is equipped with stirring rod, thermometer and reflux condensate device in molar ratio with dihydroxyethylsulfide, thiocarbamide and concentrated hydrochloric acid;
2) step 1) gained mixture was refluxed 1～10 hour in 100～110 ℃;
3) with step 2) products therefrom is chilled to below 70 ℃, logical nitrogen, drip or 2～6 times of moles of disposable adding in the sodium hydroxide of dihydroxyethylsulfide, promptly the adularescent precipitation produces, and keeps temperature≤70 ℃.Slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
4) with behind the hcl acidifying, divide oil-yielding stratum, to neutral, anhydrous sodium sulfate drying gets colourless to faint yellow crude product with distilled water wash;
5) with the underpressure distillation of step 4) gained crude product, water white transparency liquid, be 2,2 '-the dimercapto ethyl-sulfide.
3. by the method for the poly-thiocarbamate optical plastics of the described preparation of claim 1, it is characterized in that said 2,2 '-dimercapto ethylenebis dithiocarbamate ethane is synthetic with the following method:
1) is to join in the reaction vessel that be equipped with stirring rod, thermometer and reflux condensate device at 2～3: 1 in molar ratio with mercaptoethanol and ethylene dichloride, mixes logical nitrogen protection;
2) with step 1) gained mixture in being heated to 50～70 ℃, drip 1～3 times of mole in the sodium hydroxide of mercaptoethanol, can be observed red-purple in the reaction process and occur,, illustrate that the reaction of mercaptoethanol and ethylene dichloride is finished when reactant is become when colourless or faint yellow by red-purple;
3) with step 2) products therefrom with hcl acidifying after, colorless oil liquid, be condensed into white solid after the cooling, obtain intermediate 2,2 '-dihydroxy ethyl sulfo-ethane;
4) with 2,2 '-dihydroxy ethyl sulfo-ethane, thiocarbamide and concentrated hydrochloric acid are 1: 2～3: 2～5 to join in the reaction vessel that is equipped with stirring rod, thermometer and reflux condensate device in molar ratio;
5) step 4) gained mixture was refluxed 1～10 hour in 100～110 ℃;
6) the step 5) products therefrom is chilled to below 70 ℃, logical nitrogen, dropping or 2～6 times of moles of disposable adding are in 2,2 '-sodium hydroxide of dihydroxy ethyl sulfo-ethane, be that adularescent precipitation produces, keep temperature≤70 ℃, slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
7) with behind the hcl acidifying, divide oil-yielding stratum, to neutral, end product is with the absolute ethanol washing after-filtration with distilled water wash, and decompression removes water and small molecules such as ethanol wherein, final white solid thing, be 2,2 '-dimercapto ethylenebis dithiocarbamate ethane.
4. by the method for the poly-thiocarbamate optical plastics of the described preparation of claim 1, it is characterized in that saidly 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan is synthetic with the following method:
1) with mercaptoethanol and 2, the 3-dibromo-propanol is to join in the reaction vessel that be equipped with stirring rod, thermometer and reflux condensate device at 2～3: 1 in molar ratio, mixes, logical nitrogen protection;
2) with step 1) gained mixture heating up to 50～70 ℃, drip 1～3 times of mole in the sodium hydroxide of mercaptoethanol, can be observed red-purple in the reaction process and occur, when reactant is become when colourless or faint yellow by red-purple, mercaptoethanol and 2 are described, the reaction of 3-dibromo-propanol is finished;
3) above-mentioned reaction mixture directly add 1.5～2.5 times of moles in 1.5～4 times of moles of thiocarbamide of mercaptoethanol in the concentrated hydrochloric acid of mercaptoethanol;
4) step 3) gained mixture was refluxed 1～10 hour in 100～110 ℃;
5) the step 4) products therefrom is chilled to below 70 ℃, logical nitrogen, dropping or 1.5～5 times of moles of disposable adding are in the sodium hydroxide of mercaptoethanol, be that the adularescent precipitation produces, keep temperature≤70 ℃, slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
6) with behind the hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes water and small molecules such as ethanol wherein, and final colourless or light yellow oil is 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan.
5. by the method for the poly-thiocarbamate optical plastics of the described preparation of claim 1, it is characterized in that saidly 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan is synthetic with the following method:
1) is 1: 0.05～1 to join in the reaction vessel that is equipped with stirring rod, thermometer and reflux condensate device in molar ratio with the sodium hydroxide solution of mercaptoethanol and 20～30%, mixes logical nitrogen protection;
2) with step 1) gained mixture heating up to 50～70 ℃, drip 0.3～1.5 times of mole in the epoxy chloropropane of mercaptoethanol, drip 0.5～2 times of mole then in the sodium hydroxide solution of mercaptoethanol, can be observed red-purple in the reaction process occurs, when reactant is become when colourless or faint yellow by red-purple, illustrate that the reaction of mercaptoethanol and epoxy chloropropane is finished;
3) above-mentioned reaction mixture directly add 1.5～2.5 times of moles in the thiocarbamide of mercaptoethanol and 1.5～4 times of moles in the concentrated hydrochloric acid of mercaptoethanol;
4) step 3) gained mixture was refluxed 1～10 hour in 100～110 ℃;
5) the step 4) products therefrom is chilled to below 70 ℃, logical nitrogen, dropping or 1.5～5 times of moles of disposable adding are in the sodium hydroxide of mercaptoethanol, be that the adularescent precipitation produces, keep temperature≤70 ℃, slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
6) with behind the hcl acidifying, divide oil-yielding stratum, to neutral, end product is with the absolute ethanol washing after-filtration with distilled water wash, and decompression removes water and small molecules such as ethanol wherein, and final colourless or light yellow oil is 2,3-dimercapto ethylenebis dithiocarbamate propylmercaptan.
6. by the method for the poly-thiocarbamate optical plastics of the described preparation of claim 1, it is characterized in that saidly 1,2,3-tri-thiol ethylenebis dithiocarbamate propane is synthetic with the following method:
1) is to join in the reaction vessel that be equipped with stirring rod, thermometer and reflux condensate device at 3～5: 1 in molar ratio with mercaptoethanol and trichloropropane, mixes logical nitrogen protection;
2) with step 1) gained mixture heating up to 60～100 ℃, drip 1～3 times of mole in the potassium hydroxide solution of mercaptoethanol, can be observed red-purple in the reaction process and occur,, illustrate that the reaction of mercaptoethanol and trichloropropane is finished when reactant is become when colourless or faint yellow by red-purple;
3) with above-mentioned mixed solution suction strainer, after removing, in separating funnel, leave standstill separatory, intermediate product 1,2,3-trihydroxyethyl sulfo-propane removes small molecules in 70 ℃ of decompressions;
4) with intermediate product 1,2,3-trihydroxyethyl sulfo-propane, 1～1.5 times of mole join in the reaction vessel that is equipped with stirring rod, thermometer and reflux condensate device in the concentrated hydrochloric acid of mercaptoethanol in thiocarbamide and 1～2.5 times of mole of mercaptoethanol, mix, logical nitrogen protection;
5) step 4) gained mixture was refluxed 1～10 hour in 100～110 ℃;
6) the step 5) products therefrom is chilled to below 70 ℃, logical nitrogen, dropping or 1～3 times of mole of disposable adding are in the sodium hydroxide of mercaptoethanol, be that the adularescent precipitation produces, keep temperature≤70 ℃, slowly be heated to 70～90 ℃ of reactions 0.5～3 hour then, this moment, the white solid thing disappeared, and oil reservoir, water layer separate clear;
7) with behind the hcl acidifying, divide oil-yielding stratum, extremely neutral with distilled water wash.End product is with the absolute ethanol washing after-filtration, and decompression removes water and small molecules such as ethanol wherein, and final colourless or light yellow oil is 1,2,3-tri-thiol ethylenebis dithiocarbamate propane.
7. by the method for the poly-thiocarbamate optical plastics of the described preparation of claim 1, it is characterized in that said polyisocyanates compounds, be meant the compound that contains the isocyanate groups more than two or two in the molecular structure.
8. by the method for the poly-thiocarbamate optical plastics of the described preparation of claim 7, it is characterized in that said polyisocyanates compounds is tolylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate tripolymer, Xylene Diisocyanate, isophorone diisocyanate, isophorone diisocyanate trimer, phenylene diisocyanate, cyclohexyl diisocyanate, '-diphenylmethane diisocyanate or its mixture.
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| CN107986999A (en) * | 2017-11-29 | 2018-05-04 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of thio two sweet mercaptan |
| JP7296755B2 (en) * | 2019-03-28 | 2023-06-23 | ホヤ レンズ タイランド リミテッド | Resin composition for optical member, optical member, and spectacle lens |
| CN112500549B (en) * | 2019-09-16 | 2021-12-28 | 西安交通大学 | Synthesis and recycling reprocessing method of recyclable shape memory thermosetting resin |
| CN110724077A (en) * | 2019-11-19 | 2020-01-24 | 山东益丰生化环保股份有限公司 | Preparation method of 1,2, 3-trithio-ethyl-thiopropane |
| CN115232421A (en) * | 2022-06-30 | 2022-10-25 | 江苏可奥熙光学材料科技有限公司 | 1.67 high-refractive-index resin lens monomer based on sulfur-containing polyurethane modification and preparation method thereof |
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2002
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