1,3-BISISOCYANATOMETHYLCYCLOHEXANE COMPOSITION AND OPTICAL RESIN PREPARED THEREFROM

Abstract

Disclosed is a 1,3-bisisocyanatomethylcyclohexane composition and an optical resin prepared therefrom. The composition comprises, based on the weight of 1,3-bisisocyanatomethylcyclohexane, a) 65%-95 wt % of trans-1,3-bisisocyanatomethylcyclohexane; b) greater than 0 and less than or equal to 0.5 wt %, preferably 0.02-0.5 wt % of 1,4-bisisocyanatomethylcyclohexane. Preferably, the 1,3-bisisocyanatomethylcyclohexane composition contains greater than 0 and less than or equal to 600 ppm of 1-isocyanatomethyl-3-methylcyclohexane, based on the weight of 1,3-bisisocyanatomethylcyclohexane. The 1,3-bisisocyanatomethylcyclohexane composition is used for preparing an optical resin, which can be applied to produce an optical lens with a better performance in preventing opacification and optical distortion.

Claims

1. A 1,3-bis(isocyanatomethyl)cyclohexane composition, comprising: based on a weight of 1,3-bis(isocyanatomethyl)cyclohexane, a) 65 wt % to 95 wt % of trans-1,3-bis(isocyanatomethyl)cyclohexane; and b) greater than 0 and less than or equal to 0.5 wt % of 1,4-bis(isocyanatomethyl)cyclohexane; wherein the 1,3-bis(isocyanatomethyl)cyclohexane comprises cis-1,3-bis(isocyanatomethyl)cyclohexane and trans-1,3-bis(isocyanatomethyl)cyclohexane.

2. The 1,3-bis(isocyanatomethyl)cyclohexane composition according to claim 1, wherein the 1,3-bis(isocyanatomethyl)cyclohexane composition comprises more than 0 and less than or equal to 600 ppm of 1-isocyanatomethyl-3-methylcyclohexane, based on the weight of 1,3-bis(isocyanatomethyl)cyclohexane.

3. The 1,3-bis(isocyanatomethyl)cyclohexane composition according to claim 1, wherein a preparation method of the composition comprises the following steps: (1) a salt-forming process, mixing a 1,3-cyclohexyldimethylamine raw material with hydrogen chloride to prepare 1,3-cyclohexyldimethylamine hydrochloride; (2) an isocyanate-forming process, subjecting the 1,3-cyclohexyldimethylamine hydrochloride and phosgene to an isocyanate-forming reaction, of which a product includes 1,3-bis(isocyanatomethyl)cyclohexane and 1-isocyanatomethyl-3-methylcyclohexane; and (3) a purification process, performing purification on the product of step (2) to prepare the 1,3-bis(isocyanatomethyl)cyclohexane composition.

4. The 1,3-bis(isocyanatomethyl)cyclohexane composition according to claim 3, wherein in the 1,3-cyclohexyldimethylamine raw material, trans-1,3-cyclohexyldimethylamine has a content of 50 wt % to 95 wt %, and cis-1,3-cyclohexyldimethylamine has a content of 5 wt % to 50 wt %, based on the weight of 1,3-cyclohexyldimethylamine raw material.

5. The 1,3-bis(isocyanatomethyl)cyclohexane composition according to claim 3, wherein a preparation method of the 1,3-cyclohexyldimethylamine raw material comprises the following step: subjecting 1,3-cyclohexyldimethylamine (trans-1,3-cyclohexyldimethylamine cis-1,3-cyclohexyldimethylamine=50:50) to a isomerization reaction for 1 h to 4 h, with a ruthenium/alumina catalyst, a hydrogen absolute pressure of 4 MPa to 6 MPa, and a temperature of 200° C. to 220° C.

6. An optical resin, which is prepared by polymerizing the 1,3-bis(isocyanatomethyl)cyclohexane composition according to claim 1 and a polythiol compound raw material.

7. The optical resin according to claim 6, wherein the polythiol compound comprises one or more of aliphatic polythiol, aromatic polythiol, polythiol containing a heterocycle, aliphatic polythiol containing a sulfur atom in addition to mercapto, aromatic polythiol containing a sulfur atom in addition to mercapto, and polythiol containing a sulfur atom in addition to a heterocycle and mercapto.

8. The optical resin according to claim 7, wherein the polythiol compound comprises one or more of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercapto methylthio)propane and 2-mercaptoethanol.

9. A lens, which is prepared from the optical resin according to claim 6.

10. The 1,3-bis(isocyanatomethyl)cyclohexane composition according to claim 1, comprising: based on a weight of 1,3-bis(isocyanatomethyl)cyclohexane, a) 65 wt % to 95 wt % of trans-1,3-bis(isocyanatomethyl)cyclohexane; and b) 0.02 wt % to 0.5 wt % of 1,4-bis(isocyanatomethyl)cyclohexane.

11. The 1,3-bis(isocyanatomethyl)cyclohexane composition according to claim 2, wherein the 1,3-bis(isocyanatomethyl)cyclohexane composition comprises 0.1 ppm to 600 ppm of 1-isocyanatomethyl-3-methylcyclohexane, based on the weight of 1,3-bis(isocyanatomethyl)cyclohexane.

12. The 1,3-bis(isocyanatomethyl)cyclohexane composition according to claim 4, wherein in the 1,3-cyclohexyldimethylamine raw material, trans-1,3-cyclohexyldimethylamine has a content of 65 wt % to 95 wt %, and cis-1,3-cyclohexyldimethylamine has a content of 5 wt % to 35 wt %, based on the weight of 1,3-cyclohexyldimethylamine raw material.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0031] FIG. 1 is a .sup.1H NMR spectrum of 1-isocyanatomethyl-3-methyl cyclohexane;

[0032] FIG. 2 is a .sup.13C NMR spectrum of 1-isocyanatomethyl-3-methylcyclohexane.

DETAILED DESCRIPTION

[0033] Although the method provided by the present disclosure is further illustrated below through embodiments, the present disclosure is not limited to the listed embodiments, and further comprises any other common modifications within the scope of the claims of the present disclosure.

[0034] The isomer content and micro-impurities of the present disclosure were determined by Agilent 7890 Gas Chromatography. Gas chromatography analysis parameters are as follows: (1) column DB-5 (30 m×0.25 mm×0.25 μm); (2) injection volume: 0.5 μL; (3) split ratio: 1/30; (4) injection port temperature: 260° C.; (5) flow rate in the column: 1.5 mL/min; (6) programed temperature: holding 100° C. for 1 min, warming up to 280° C. at 10° C./min and holding for 20 min; (7) FID detector temperature: 280° C.; (8) hydrogen flow rate: 40 mL/min, and air flow rate: 400 ml/min.

[0035] The viscosity test of the present disclosure was performed on a Brookfield rotor viscometer.

[0036] The nuclear magnetic analysis of the present disclosure was performed on Bruker 400 MHz.

[0037] Incidence rate of optical distortion: optical distortion refers to a phenomenon that the local refractive index is different from the surrounding normal refractive index, one reason of which is the different resin compositions. Under a high-pressure mercury lamp, 100 lenses were visually observed, and the lens confirmed to show striation was judged as a lens with optical distortion, and the incidence rate of optical distortion was calculated.

[0038] Incidence rate of white turbidity: under a high-pressure mercury lamp, 100 lenses were visually observed, and the lens confirmed to be turbid was judged as a lens with white turbidity, and the incidence rate of white turbidity was calculated.

[0039] Polymerization rate: the time when the polymerizability composition was prepared was regarded as 0 hour, and the viscosity after 5 hours was regarded as an index to evaluate.

[0040] Isomerization of 1,3-cyclohexyldimethylamine

[0041] To a stainless steel reactor equipped with a stirrer, thermometer and gas-feeding tube, 1000 g of 1,3-cyclohexyldimethylamine (Tokyo Chemical, trans-1,3-cyclohexyldimethylamine:cis-1,3-cyclohexyldimethylamine=50:50), 16 g ruthenium/alumina catalyst (Sigma Aldrich) and 1000 g heptane were added, and the reactor was displaced with hydrogen three times. With stirring of 500 rpm, temperature of 210° C. and hydrogen absolute pressure of 5 MPa, the mixture reacted for 1 h to 4 h, and cooled to the room temperature after the reaction was finished, and subjected to filtration to remove the catalyst. The solvent was removed, and by rectification separation the 1,3-cyclohexyldimethylamine raw material was obtained. According to the different reaction time, the following 1,3-cyclohexyldimethylamine raw materials were obtained respectively.

TABLE-US-00001 TABLE 1 Condition and result of the isomerization of 1,3-cyclohexyldimethylamine 1,3-cyclohexyldimethylamine Reaction Content of trans-1,3- raw material time/h cyclohexyldimethylamine/% (A) 1 65 (B) 1.5 75 (C) 2 80 (D) 2.5 85 (E) 3 90 (F) 3.5 95

[0042] Structure Determination of 1-isocyanatomethyl-3-methylcyclohexane

[0043] In a stainless steel reactor, 1420 g of 1,3-cyclohexyldimethylamine raw material (B) was dissolved in 12240 g of o-dichlorobenzene, and hydrogen chloride gas was introduced at a rate of 800 L/h. The salt-forming reaction was performed, controlling the temperature to less than 30° C. After the salt-forming was finished, a milk-white viscous substance was obtained. The temperature was raised to 150° C., and phosgene was introduced at a rate of 500 L/h to perform the phosgenation reaction, and the unreacted phosgene was collected through condensation and then introduced to the alkaline cleaning system for elimination. When the reaction liquid became clarified, the phosgenation reaction was completed, and nitrogen was introduced to drive out the unreacted phosgene, and after subsequent solvent removal, the crude product of 1,3-HXDI was obtained.

[0044] 500 g of 1,3-HXDI crude product was subjected to heat treatment at 190° C. for 2 h, and the obtained sample was to be rectification separated. Then the substance was fed from the middle of rectification column. The operating pressure in top of the column was 100 pa, and the temperature of the reboiler at bottom of the column was 140° C. At this time, the temperature in top of the column was 110° C., and the reflux ratio was controlled at 20:1. After reaching a steady state, 25 g of light component was collected from the top of the column Through gas chromatography analysis, the light component contained 99.0% impurity of 1-isocyanatomethyl-3-methylcyclohexane, and the NMR data is: .sup.1H NMR (400 MHz, DMSO) δ 3.40-3.36 (m, 1H), 3.19-3.15 (m, 1H), 1.61-1.40 (m, 7H), 1.27-1.24 (m, 3H), 0.95-0.97 (d, 3H); .sup.13C NMR (100 MHz, DMSO): δ 122.7, 53.6, 39.1, 34.4, 31.8, 31.5, 31.2, 21.0, 20.6.

Example 1

[0045] In a stainless steel reactor, 1420 g of 1,3-cyclohexyldimethylamine raw material (B) was dissolved in 12240 g of o-dichlorobenzene, and hydrogen chloride gas was introduced at a rate of 800 L/h. The salt-forming reaction was performed, controlling the temperature to less than 30° C. After the salt-forming was finished, a milk-white viscous substance was obtained. The temperature was raised to 150° C., and phosgene was introduced at a rate of 500 L/h to perform the phosgenation reaction, and the unreacted phosgene was collected through condensation and then introduced to the alkaline cleaning system for elimination. When the reaction liquid became clarified, the phosgenation reaction was completed, and nitrogen was introduced to drive out the unreacted phosgene, and after subsequent solvent removal, the crude product of 1,3-HXDI was obtained.

[0046] Then, a glass rectification column, which had an inner diameter of 20 mm and a length of 1500 mm and was filled with structured packing, was used to performed rectification on the obtained crude 1,3-HXDI. The crude 1,3-HXDI was preheated to 120° C. with a preheater, and then fed from the middle of the rectification column. The operating pressure in the top of the column is 100 pa, and the temperature of the reboiler at bottom of the column was 145° C. At this time, the temperature in top of the column was 115° C., and the reflux ratio was controlled at 30:1. After reaching a steady state, 1,3-HXDI composition was collected from the top of the column. Through gas chromatography analysis, 1,4-HXDI had a content of 0.1 wt % in the composition, and 1-isocyanatomethyl-3-methylcyclohexane had a content of 10 ppm, which were calculated based on the weight of 1,3-HXDI in the composition; and the trans isomer accounted for 75% in 1,3-HXDI.

[0047] At 25° C., 53.7 g of the 1,3-HXDI composition prepared above, 0.075 g of dibutyltin dichloride as a catalyst, 0.10 g of acid-form phosphate (Stepan company, trade name Zelec UN), 0.05 g of ultraviolet absorber (Kyodo Co., Ltd., trade name BioSorb 583) were mixed and dissolved. Moreover, 48 g of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane (Chambroad Chemical. Co., Ltd.) was added and mixed to form a mixed uniform liquid (polymerizable composition). The time when the mixed uniform liquid was prepared was regarded as 0 hours, and the viscosity after 5 hours was measured.

[0048] At 25° C., 53.7 g of 1,3-HXDI composition, 0.075 part (namely 0.075 g) of dibutyltin dichloride as catalyst, 0.10 part (namely 0.10 g) of acid-form phosphate (Stepan company, trade name Zelec UN), 0.05 part (namely 0.05 g) of ultraviolet absorber (Kyodo Co., Ltd., trade name BioSorb 583) were mixed and dissolved. Moreover, 48 g (namely 48 g) of 1,2-bis[(2-mercapto ethyl)thio]-3-mercaptopropane (Chambroad Chemical. Co., Ltd.) was added and mixed to form a mixed uniform liquid (polymerizable composition). After defoamed under 600 Pa for 1 hour, the mixed uniform liquid was filtrated by a 1μ PTFE (polytetrafluoroethylene) filter. Then, the liquid was injected into an injection mold for lens, which was consisted of a 4D glass mold with a diameter of 75 mm and adhesive tapes. The injection mold was placed in an oven, and kept at 40° C. for 2 hours, heated to 50° C. in 4 hours and kept for 2 hours, and heated to 60° C. in 3 hours and kept for 2 hours. Then, the mold was further heated to 70° C. in 3 hours and kept for 2 hours, and heated to 100° C. in 3 hours, and further heated to 130° C. in 1 hour and kept for 2 hours. After the polymerization is completed, the injection mold was taken out from the oven and demolded to obtain a lens. The obtained lens was then annealed at 120° C. for 3 hours. According to the same method, 100 lenses were produced, and the incidence of glass wave (namely incidence rate of optical deformation) and the incidence of white turbidity were calculated. The results are shown in Table 2.

Examples 2-6 and Comparative Examples 1-5

[0049] By changing the 1,3-cyclohexyldimethylamine raw material and regulating different reflux ratios, the samples with different indexes were obtained, as shown below in Table 2.

TABLE-US-00002 TABLE 2 Condition and result of Examples 1-6 and Comparative Examples 1-5 1-isocyanatomethyl- Incidence Incidence 1,3-cyclohexyl- trans-1,3- 1,4- 3-methylcyclo- Viscosity rate of rate of dimethylamine reflux HXDI HXDI hexane after optical white No. raw material ratio content/% content/% content/ppm 5 h/cp distortion turbidity Example 1 (B) 30:1 75 0.1 10 280 0 0 2 (C) 20:1 80 0.2 50 300 0 1 3 (D) 10:1 85 0.3 150 350 1 0 4 (E)  8:1 90 0.4 400 360 0 1 5 (F)  5:1 95 0.5 600 380 1 1 6 (A) 40:1 65 0.02 0.1 270 0 0 Comparative 1 (F) 50:1 96 0.2 50 470 4 2 example 2 (B)  8:1 75 0.6 10 450 5 3 3 (B)  1:1 75 0.1 700 200 6 4 4 (A) 10:1 60 0.1 10 210 3 5 5 (B) 50:1 75 0.1 0 450 5 4

[0050] “Trans-1,3-HXDI content/%” in Table 2 refers to the content of trans-1,3-HXDI based on the weight of 1,3-HXDI.

[0051] “1,4-HXDI content/%” refers to the content of 1,4-HXDI based on the weight of 1,3-HXDI.

[0052] “1-isocyanatomethyl-3-methylcyclohexane content/ppm” refers to the content of 1-isocyanatomethyl-3-methylcyclohexane based on the weight of 1,3-HXDI.