* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[2] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
[3] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[4] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
2
[ 101-37-1 ]
[ 2916-14-5 ]
[ 6294-79-7 ]
[ 1025-15-6 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[2] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
[3] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[4] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
3
[ 101-37-1 ]
[ 557-40-4 ]
[ 6294-79-7 ]
[ 1025-15-6 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[2] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
[3] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[4] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
4
[ 108-80-5 ]
[ 107-18-6 ]
[ 1025-15-6 ]
Yield
Reaction Conditions
Operation in experiment
98.6%
With triphenylphosphine In 5,5-dimethyl-1,3-cyclohexadiene at 95℃; for 22 h; Inert atmosphere
6.45 g (50 mmol) of isocyanuric acid, 670 mg (2.5 mmol) of triphenylphosphine as an organophosphorus compound and 25.8 g of xylene as a solvent were placed in a reaction vessel, and after purging with nitrogen, a trade name E101 NE / W Manufactured by Evonik Degussa Co., Ltd., palladium-supported activated carbon catalyst supporting a mixture of zero valent metallic palladium and a divalent palladium compound in an amount converted to palladium atoms in terms of palladium atoms) to active charcoal was 266 mg in terms of dry mass , And the mixture was stirred at 95 ° C. for 1 hour. Then, 13.1 g (225 mmol) of allyl alcohol as an alkenyl type alcohol was added dropwise over 1 hour, and the reaction was carried out for 20 hours while returning only the organic layer out of the xylene, allyl alcohol and water azeotropically distilled by Dean Stark into the system. After the reaction, insoluble matter was filtered off. As a result of analyzing the filtrate, 98.6percent of triallyl isocyanurate and 1.4percent of diallyl isocyanurate were formed on the basis of isocyanuric acid, and no monoallyl isocyanurate was produced.
With sodium carbonate; potassium bromide In dimethyl sulfoxide at 65℃; for 1.5 h;
Synthesis Example 3 Isocyanuric acid (135 mg, 1.1 mmol), sodium carbonate (318 mg, 3.0 mmol), potassium bromide (36 mg, 0.3 mmol), and dimethyl sulfoxide (4.1 g) were mixed, and the mixture was heated to 65°C. A mixed solution of 2-propenyl methanesulfonate (409 mg, 3.0 mmol) and dimethyl sulfoxide (409 mg) was added dropwise over 30 minutes. A reaction was carried out for 1 hour. The reaction solution was analyzed by GC, and the yield of 1,3,5-tris-(2-propenyl)-isocyanurate was confirmed to be 68percent.
Reference：
[1] Organic Letters, 2004, vol. 6, # 25, p. 4679 - 4681
[2] Catalysis Communications, 2010, vol. 12, # 3, p. 226 - 230
[3] Journal of Organic Chemistry, 1994, vol. 59, # 17, p. 4931 - 4938
[4] Chemistry - An Asian Journal, 2011, vol. 6, # 6, p. 1520 - 1524
[5] Tetrahedron, 2011, vol. 67, # 8, p. 1530 - 1535
7
[ 108-80-5 ]
[ 107-18-6 ]
[ 6294-79-7 ]
[ 1025-15-6 ]
Yield
Reaction Conditions
Operation in experiment
68.1%
With triphenylphosphine In 5,5-dimethyl-1,3-cyclohexadiene at 95℃; for 8 h; Inert atmosphere
6.45 g (50 mmol) of isocyanuric acid, 670 mg (2.5 mmol) of triphenylphosphine as an organophosphorus compound and 25.8 g of xylene as a solvent were placed in a reaction vessel, and after purging with nitrogen, a trade name E101 NE / W (manufactured by Evonik Degussa Co., Ltd., palladium-supported activated carbon catalyst supporting a mixture of zero valent metallic palladium and divalent palladium compound in terms of palladium atoms in terms of palladium atoms) to 266 mg (125 μmol as the above palladium), and the mixture was stirred at 95 ° C. for 1 hour.Then, 13.1 g (225 mmol) of allyl alcohol as an alkenyl type alcohol was added dropwise over 1 hour, and the reaction was carried out for 6 hours while only the organic layer out of the xylene, allyl alcohol, and water azeotropicaly distilled with Dean Stark was returned to the system.After the reaction, insoluble matter was filtered off.As a result of analyzing the filtrate, 68.1percent of triallyl isocyanurate and 13.0percent of diallyl isocyanurate were formed on the basis of isocyanuric acid, and monoallyl isocyanurate was not produced.
Example 1: The oily material produced in the same manner as defined in Comparative Example 1 was subjected to heating and stirring treatment in a 5percent by weight NaOH aqueous solution at 50°C for 2 hr. Next, the obtained reaction solution was neutralized with hydrochloric acid, and an organic layer was separated therefrom and then subjected to distillative purification to obtain crystals of TAC (yield: 84percent). It was confirmed that neither the organic chloride compounds mixture (A) nor the organic chloride compound of the chemical formula (II) were detected in the thus obtained TAC (less than 10 ppm). Next, the above TAC was subjected to the same procedure subsequent to the rearrangement reaction as defined in Comparative Example 1, thereby obtaining TAIC (yield: 90percent). It was also confirmed that neither the mixture (A) of the organic chloride compounds nor the organic chloride compound of the chemical formula (II) were detected in the thus obtained TAIC (less than 10 ppm).
90%
With copper(II) choride dihydrate In 5,5-dimethyl-1,3-cyclohexadiene at 65 - 75℃; Inert atmosphere
2L separable flask was charged with 407 g of xylene and 7.63 g (0.045 mol) of cupric chloride dihydrate, and a twin star blade and a bar baffle were set and set on a water bath. A reflux condenser (cooling tube) equipped with a dropping funnel, 254 g (1.02 mol) of triallyl cyanurate and 102 g of xylene, attached to a separable flask and equipped with a three-way stopcock for nitrogen sealing in the remaining mouth, and it was fitted with a thermometer. While nitrogen sealing was performed from the top of the condenser, the inside of the separable flask and the inside of the dropping funnel were replaced with nitrogen three times, confirming that the oxygen concentration was 0.3percent by volume or less, and stirring (508 rpm) was started. After raising the temperature of the water bath and confirming that the internal temperature was controlled at 65 °C., half of the raw material of the dropping funnel was charged. After about 90 minutes, heat generation due to heat of reaction was observed, the peak temperature became 100 °C., and when the reaction almost finished and the temperature reached 75 °C. or lower at the end of the reaction, all the remaining raw materials were charged, and after about 120 minutes Heat generation was observed and the peak temperature was 98 °C. After stirring the exotherm, stirring was continued for 20 minutes. Xylene was distilled off from the resulting reaction solution and filtered with a Kiriyama funnel to obtain an oily matter. From analysis by gas chromatography, the purity of triallyl isocyanurate was 99.7percent, and the yield was 90percent.
Reference：
[1] Patent: EP2436677, 2012, A1, . Location in patent: Page/Page column 7
[2] Patent: JP2016/216399, 2016, A, . Location in patent: Paragraph 0040
[3] Patent: US2009/312545, 2009, A1, . Location in patent: Page/Page column 4
9
[ 542-75-6 ]
[ 917-61-3 ]
[ 1025-15-6 ]
Yield
Reaction Conditions
Operation in experiment
91%
With calcium chloride; potassium bromide In N,N-dimethyl-formamide at 120℃;
General procedure: 100 g of sodium cyanate, 14 g of calcium chloride, A solution consisting of 13 g of potassium bromide and 500 g of DMF was kept at 120 °C., and allyl chloride (1,3-dichloropropene: cis form 140 ppm, Containing 140 ppm of trans form) was added dropwise. After reaction ripening, the solvent was distilled off to obtain an oil. Next, this oil was washed with water, The obtained organic layer was distilled under reduced pressure, TAIC was obtained as a viscous liquid (yield 90percent). In this TAIC, the organic chlorine compound of the chemical formula (I) It contained 590 ppm. In Comparative Example 1, as raw material allyl chloride, 1, 3-dichloropropene (allyl chloride containing 0.1 ppm of cis form and 0.1 ppm of trans form was used, TAIC was produced in the same manner as in Comparative Example 1 (yield: 91percent). No organic chlorine compound of general formula (I) was detected in this TAIC (less than 10 ppm).
Reference：
[1] Patent: CN105777659, 2016, A, . Location in patent: Paragraph 0028
12
[ 3047-33-4 ]
[ 106-95-6 ]
[ 1025-15-6 ]
Yield
Reaction Conditions
Operation in experiment
154.6 g
at 120 - 125℃; for 6 h;
Synthesis Example 1 Preparation of Diallylmonoglycidyl Isocyanurate (0207) A reaction vessel was added with 106 g of isocyanuric acid and 420 ml of water of slurry, and then 206 g of 48percent sodium hydroxide solution was dropped into the aforementioned mixture. After the mixture was reacted for 2 hours at 60 to 70° C., water was removed, and the mixture was washed by methanol and then dried to obtain 157.5 g of sodium isocyanurate as white crystal. Then, the reaction vessel equipped with a stirrer and a condenser was added with 400 ml of dimethylformamide as a solvent for reacting 157.5 g of sodium isocyanurate and 290.4 g of 3-bromo-1-propylene for 6 hours at 120 to 125° C., and then an inorganic salt was filtered off. Toluene was extracted out and the reactants were washed with water and dried and the solvent was dried to obtain 154.6 g of triallyl isocyanurate (Mw=249.3) as pale brown oil. 8700 ml of dichloromethane was taken as a solvent, and 154.6 g of triallyl isocyanurate and 267 g of m-chloroperbenzoic acid (not higher than 30° C.) was slowly added into a cooler and stirred and reacted at 25° C. for 4 hours. After completing the reaction, 3000 ml of 10percent sodium bisulfite solution was slowly added at 20° C., and then an insoluble material was filtered off. Chloroform was added for extraction, and the reactants were washed thoroughly with 10percent sodium bisulfite solution and saturated sodium bicarbonate solution. After drying and distilling the solvent, an epoxy compound was obtained. The aforementioned product was purified with silica gel chromatograph to obtain 111.3 g of transparent oil. The obtained epoxy compound was diallylmonoglycidyl isocyanurate (Mw=265).
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[2] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
[3] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[4] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
14
[ 101-37-1 ]
[ 2916-14-5 ]
[ 6294-79-7 ]
[ 1025-15-6 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[2] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
[3] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[4] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
15
[ 101-37-1 ]
[ 557-40-4 ]
[ 6294-79-7 ]
[ 1025-15-6 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[2] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
[3] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[4] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
16
[ 101-37-1 ]
[ 16715-84-7 ]
[ 1025-15-6 ]
[ 118361-38-9 ]
[ 73669-73-5 ]
[ 6291-95-8 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[2] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
[3] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[4] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
[5] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1988, p. 308 - 311[6] Khimiya Geterotsiklicheskikh Soedinenii, 1988, vol. 24, # 3, p. 376 - 379
Then, the reactant was washed using an aqueous solution of 1N sodium hydroxide and brine, dried using MgSO4, and filtered. Solvents were removed using an evaporator to obtain a reaction intermediate. The reaction scheme of the first step in method 2, and the NMR data of the reaction intermediate thus obtained are as follows. The triallyl isocyanurate was synthesized by the process described in the above (1), however may be purchased to use. 1H NMR (400 MHz, CDCl3): delta=2.68-2.70 (m, 2H), 2.83 (t, J=4.8 Hz, 2H), 3.24-3.28 (m, 2H), 4.01 (dd, J=0.8, 4.8 Hz, 1H), 4.04 (dd, J=0.8, 4.8 Hz, 1H), 4.15 (dd, J=2.4, 5.6 Hz, 1H), 4.19 (dd, J=2.4, 5.6 Hz, 1H), 4.50 (dt, J=1.2, 6.0 Hz, 2H), 5.26 (dd, J=1.2, 10.0 Hz, 1H), 5.34 (dd, J=1.2, 17.2 Hz, 1H), 5.83-5.93 (m, 1H).
14
1,3,5-Triallyl-[1,3,5]triazinane-2,4-dione[ No CAS ]
1,3,5-triallyl-6-hydroperoxy-[1,3,5]triazinane-2,4-dione[ No CAS ]
polymer; monomer(s): 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; pentaerythritol tetra(3-mercaptopropionate); hexane-1,6-diol dimethylacrylate[ No CAS ]
With dibenzoyl peroxide; In water; at 65 - 100℃; for 0.5 - 3h;Conversion of starting material;
About 1 g of poly(ethylene terephthalate) (PET) fabric was immersed in 30 mL of distilled water containing a known amount (0.625-15% conc. of two in solution) of ADMH (90-50%) and <strong>[1025-15-6]triallyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione</strong> (10-50%, as co-linker). The solution was heated to a known temperature (65-100 C.). A known amount of benzoyl peroxide (BPO) (0.125-1.5%) dissolved in an organic solvent (acetic acid, or acetone, or ethanol) was then added. Under constant stirring, the solution was kept at that temperature for a certain period of time (30 minutes to 3 hours). After the graft copolymerization, the PET sample was taken out and extracted 3 times with 100 mL of hot acetone at 60 C. for 2 h to remove any un-grafted polymers. The PET sample was then washed with large excess of distilled water, dried at 60 C. for 24 h, and stored in a desiccator for 72 h to reach constant weight. Yields were 2-30%, controllable.
18
[ 893412-17-4 ]
[ 1025-15-6 ]
[ 911415-49-1 ]
Yield
Reaction Conditions
Operation in experiment
With 2,2'-azobis(isobutyronitrile); In tetrahydrofuran; methanol; at 80℃; for 48h;
b) A oven dried 50 mL, round bottom flask was charged with Triallyl-s- triazine-2, 4, 6(1H3 3H, 5H)-trione (0.62 g, 0.25 mmol, 0.75 allyl mmol, Aldrich) and dry THF (2 mL, Aldrich). The flask was flushed with N2 and added ABN (0.016 g, 10 mol%, Aldrich). The reaction mixture from step-(a) was transferred by syringe. The flask was arranged with a refluxing condenser and N2 inlet and heated at 80 C for 2 days. MALDI- TOF MS analysis indicated only mono addition product at 807.521 amu. The mono-addition product was confirmed by MALTI-TOF mass spectrum at 807.521 amu.
copper(II) chloride hydrate; In xylene; at 120℃; for 2h;
Example 1: The oily material produced in the same manner as defined in Comparative Example 1 was subjected to heating and stirring treatment in a 5% by weight NaOH aqueous solution at 50C for 2 hr. Next, the obtained reaction solution was neutralized with hydrochloric acid, and an organic layer was separated therefrom and then subjected to distillative purification to obtain crystals of TAC (yield: 84%). It was confirmed that neither the organic chloride compounds mixture (A) nor the organic chloride compound of the chemical formula (II) were detected in the thus obtained TAC (less than 10 ppm). Next, the above TAC was subjected to the same procedure subsequent to the rearrangement reaction as defined in Comparative Example 1, thereby obtaining TAIC (yield: 90%). It was also confirmed that neither the mixture (A) of the organic chloride compounds nor the organic chloride compound of the chemical formula (II) were detected in the thus obtained TAIC (less than 10 ppm).
90%
With copper(II) choride dihydrate; In 5,5-dimethyl-1,3-cyclohexadiene; at 65 - 75℃;Inert atmosphere;
2L separable flask was charged with 407 g of xylene and 7.63 g (0.045 mol) of cupric chloride dihydrate, and a twin star blade and a bar baffle were set and set on a water bath. A reflux condenser (cooling tube) equipped with a dropping funnel, 254 g (1.02 mol) of triallyl cyanurate and 102 g of xylene, attached to a separable flask and equipped with a three-way stopcock for nitrogen sealing in the remaining mouth, and it was fitted with a thermometer. While nitrogen sealing was performed from the top of the condenser, the inside of the separable flask and the inside of the dropping funnel were replaced with nitrogen three times, confirming that the oxygen concentration was 0.3% by volume or less, and stirring (508 rpm) was started. After raising the temperature of the water bath and confirming that the internal temperature was controlled at 65 C., half of the raw material of the dropping funnel was charged. After about 90 minutes, heat generation due to heat of reaction was observed, the peak temperature became 100 C., and when the reaction almost finished and the temperature reached 75 C. or lower at the end of the reaction, all the remaining raw materials were charged, and after about 120 minutes Heat generation was observed and the peak temperature was 98 C. After stirring the exotherm, stirring was continued for 20 minutes. Xylene was distilled off from the resulting reaction solution and filtered with a Kiriyama funnel to obtain an oily matter. From analysis by gas chromatography, the purity of triallyl isocyanurate was 99.7%, and the yield was 90%.
copper dichloride; In toluene; at 113 - 140℃; under 1.50015 - 2.25023 Torr;Product distribution / selectivity;
EXAMPLE 3; Process according to Example 1, except that, after the onset of the start reaction, a homogeneous, ultrafine-dispersed mixture of 1000 ml of TAC and 0.25 g of anhydrous CuCl2 was metered in. The amount metered in was 10 ml/min; at the same time, 10 ml/min of reaction solution were pumped out. Since the reaction vessel had become low in toluene in the course of time as a result of distilling-off toluene, the operating temperature in the reactor rose continually. In order to prevent polymerization, a vacuum was applied at internal flask temperature 140 C. in order to maintain a constant working temperature through evaporative cooling of the TAIC formed. The vacuum necessary for this purpose was 2.0 to 3.0 hpa. This process afforded TAIC with a purity of 98.5%; the isomerization rate of the TAIC was >99.8%.
platinum vinylsiloxane complex (including 3 wtpercent of platinum); In toluene; xylene; at 105℃; for 4.66h;Inert atmosphere; autoclave;
In an autoclave having a capacity of 2 L, (i) 602 g of toluene and (ii) 626 g of 1,3,5,7-tetramethylcyclotetrasiloxane were poured, and its gas phase section was substituted by nitrogen. Thereafter, this mixture was heated and stirred at a jacket temperature of 105 C. Then, a mixed liquid of (i) 90 g of <strong>[1025-15-6]triallyl isocyanurate</strong>, (ii) 90 g of toluene, and (iii) 0.057 g of xylene solution of platinum vinylsiloxane complex (including 3 wt% of platinum), was dropped into the autoclave for 40 minutes. After 4 hours elapsed since termination of dropping, it was confirmed by NMR measurement that a reaction rate of the allyl group was at least 95 %. Then, the reaction was terminated by cooling the mixture. The non-reacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled under reduced pressure, to obtain a colorless, transparent liquid. The obtained product was NMR measured, and obtained a result that a part of the SiH group in 1,3,5,7-tetramethylcyclotetrasiloxane were ones which reacted with the allyl group of <strong>[1025-15-6]triallyl isocyanurate</strong>, and that the obtained product included 8.6 mmol/g of SiH group. A viscosity of the obtained product was 2Pa·s.
poly[triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione-co-trimethylolpropane tris(3-mercaptopropionate)][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With 2,2-dimethoxy-2-phenylacetophenone; for 0 - 0.0138889h;UV-irradiation;Conversion of starting material;
The purposes of synthesizing oligomeric thiol and ene materials are to optimize both polymer properties and polymerization performance and eliminate odor concerns. Because of the step growth nature of the thiol-ene photopolymerization, it is possible to oligomerize (both synthetic and commercially available) monomers to a significantly higher extent of polymerization prior to formulating the materials and completing the polymerization in the restoration. This technique is expected to have enormous advantages over the low molecular weight embodiments of the present invention studied herein. First, since the overall functional group concentration will be decreased dramatically, the shrinkage will correspondingly be decreased while still maintaining the identical ultimate network structure and material properties. Secondly, with higher molecular weight thiols, it will be more facile to purify the oligomers and remove the trace, low molecular weight compounds responsible for the odor in these systems and to limit further the amount of extractables. By performing the photopolymerization (outside the cavity or body well before the material is needed) with an excess of either the vinyl or thiol functionality, it is possible to form highly functional, reactive non-gelled oligomers that are nearly exclusively one functional group terminated. Polythiol monomer and polyvinyl monomers and DMPA for each oligomerization were added to a 20 mL scintillation vial and stirred magnetically on a coming stirplate using a 0.5 inch by 0.25 inch stirbar throughout the entire polymerization. The specific masses used for each oligomerization are given in Table 1. TABLE 1 Mass amounts of polythiol and polyvinyl monomers and DMPA used for each vinyl or thiol oligomer prepared Thiol Vinyl Mass Mass Mass Monomer Monomer Thiol, g vinyl, g Initiator, g Oligomer Type Trithiol Triallyl 0.47837 1.38395 0.00188 vinyl oliqomer Trithiol Trivinyl 0.25301 0.63064 0.00085 vinyl oliqomer Trithiol triazine 6.19939 0.86898 0.00751 thiol oligomer Triallyl Tetrathiol Triazine 2.3341 0.237 0.00252 thiol oliqomer Triallyl Photoinduced oligomerization was conducted using a 365 nm light source (EFOS Ultracure 100 ss Plus) with an irradiation intensity at the surface of the sample of 80 mW/cm2. Conversion of the thiol and vinyl functional groups was monitored using FTIR (Magna 750, Nicolet Instrument Corp., Madison Wis.) because of its inherent advantage of being able to measure the thiol and vinyl conversions simultaneously and rapidly. The infrared peak at 1643 cm-1 was used to determine the vinyl conversion, and the peak at 2572 cm-1 was used for the thiol group conversion. As a specific example, thiol oligomerization using the monomer functionality ratios mentioned above, results in r values (Equation 1) of 0.15 and 0.23 for the tetrathiol and trithiol oligomers, respectively, and consequently proportionally lowers the vinyl functional group concentration in the polymeric resins. Trithiol/triazine triallyl and tetrathiol/triazine triallyl thiol terminated oligomer conversion for vinyl and thiol functional groups have been superimposed in FIG. 2. These preparations via the photopolymerization method created reactive thiol oligomers, such that the vinyl monomer is almost completely consumed, and the tetrathiol and trithiol react to the expected degree of conversion, as determined by Equation 1. The resulting multifunctional thiol-ene oligomers were used for both kinetic and mechanical evaluation. The prepared thiol-ene oligomers were stored unpurified and away from light sources at ambient conditions.
poly[triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione-co-trimethylolpropane tris(3-mercaptopropionate)][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With 2,2-dimethoxy-2-phenylacetophenone; for 0 - 0.0138889h;UV-irradiation;Conversion of starting material;
The purposes of synthesizing oligomeric thiol and ene materials are to optimize both polymer properties and polymerization performance and eliminate odor concerns. Because of the step growth nature of the thiol-ene photopolymerization, it is possible to oligomerize (both synthetic and commercially available) monomers to a significantly higher extent of polymerization prior to formulating the materials and completing the polymerization in the restoration. This technique is expected to have enormous advantages over the low molecular weight embodiments of the present invention studied herein. First, since the overall functional group concentration will be decreased dramatically, the shrinkage will correspondingly be decreased while still maintaining the identical ultimate network structure and material properties. Secondly, with higher molecular weight thiols, it will be more facile to purify the oligomers and remove the trace, low molecular weight compounds responsible for the odor in these systems and to limit further the amount of extractables. By performing the photopolymerization (outside the cavity or body well before the material is needed) with an excess of either the vinyl or thiol functionality, it is possible to form highly functional, reactive non-gelled oligomers that are nearly exclusively one functional group terminated. Polythiol monomer and polyvinyl monomers and DMPA for each oligomerization were added to a 20 mL scintillation vial and stirred magnetically on a coming stirplate using a 0.5 inch by 0.25 inch stirbar throughout the entire polymerization. The specific masses used for each oligomerization are given in Table 1. TABLE 1 Mass amounts of polythiol and polyvinyl monomers and DMPA used for each vinyl or thiol oligomer prepared Thiol Vinyl Mass Mass Mass Monomer Monomer Thiol, g vinyl, g Initiator, g Oligomer Type Trithiol Triallyl 0.47837 1.38395 0.00188 vinyl oliqomer Trithiol Trivinyl 0.25301 0.63064 0.00085 vinyl oliqomer Trithiol triazine 6.19939 0.86898 0.00751 thiol oligomer Triallyl Tetrathiol Triazine 2.3341 0.237 0.00252 thiol oliqomer Triallyl Photoinduced oligomerization was conducted using a 365 nm light source (EFOS Ultracure 100 ss Plus) with an irradiation intensity at the surface of the sample of 80 mW/cm2. Conversion of the thiol and vinyl functional groups was monitored using FTIR (Magna 750, Nicolet Instrument Corp., Madison Wis.) because of its inherent advantage of being able to measure the thiol and vinyl conversions simultaneously and rapidly. The infrared peak at 1643 cm-1 was used to determine the vinyl conversion, and the peak at 2572 cm-1 was used for the thiol group conversion. As a specific example, thiol oligomerization using the monomer functionality ratios mentioned above, results in r values (Equation 1) of 0.15 and 0.23 for the tetrathiol and trithiol oligomers, respectively, and consequently proportionally lowers the vinyl functional group concentration in the polymeric resins. Trithiol/triazine triallyl and tetrathiol/triazine triallyl thiol terminated oligomer conversion for vinyl and thiol functional groups have been superimposed in FIG. 2. These preparations via the photopolymerization method created reactive thiol oligomers, such that the vinyl monomer is almost completely consumed, and the tetrathiol and trithiol react to the expected degree of conversion, as determined by Equation 1. The resulting multifunctional thiol-ene oligomers were used for both kinetic and mechanical evaluation. The prepared thiol-ene oligomers were stored unpurified and away from light sources at ambient conditions.
With calcium chloride; potassium bromide; In N,N-dimethyl-formamide; at 120℃;
General procedure: 100 g of sodium cyanate, 14 g of calcium chloride, A solution consisting of 13 g of potassium bromide and 500 g of DMF was kept at 120 C., and allyl chloride (1,3-dichloropropene: cis form 140 ppm, Containing 140 ppm of trans form) was added dropwise. After reaction ripening, the solvent was distilled off to obtain an oil. Next, this oil was washed with water, The obtained organic layer was distilled under reduced pressure, TAIC was obtained as a viscous liquid (yield 90%). In this TAIC, the organic chlorine compound of the chemical formula (I) It contained 590 ppm. In Comparative Example 1, as raw material allyl chloride, 1, 3-dichloropropene (allyl chloride containing 0.1 ppm of cis form and 0.1 ppm of trans form was used, TAIC was produced in the same manner as in Comparative Example 1 (yield: 91%). No organic chlorine compound of general formula (I) was detected in this TAIC (less than 10 ppm).
With calcium chloride; potassium bromide; In N,N-dimethyl-formamide; at 120℃;Product distribution / selectivity;
The same procedure as defined in Comparative Example 1 was conducted except that allyl chloride comprising 1,3-dichloropropene (comprising 0.1 ppm of a cis isomer and 0.1 ppm of a trans isomer) was used as the raw material, thereby producing TAC (yield: 91%). As a result, it was confirmed that no organic chloride compound represented by the general formula (I) was detected in the thus obtained TAIC (less than 10 ppm).
Triallylisocyanurate (2) (0.086 ml, 0.40 mmol) was added to silver(I) nitrate (0.2038 g, 1.2 mmol) dissolved in 1 ml water. Slow evaporation of the water over time enabled the isolation of colourless crystals of (6) suitable for single crystal X-ray structure analysis. Yield 0.0568 g, 34%.
Triallylisocyanurate (2) (0.09 ml, 0.40 mmol) was mixed with a solution of silver(I) perchlorate (0.083 g, 0.40 mmol) in acetone. Colourless crystals of (4) were grown overnight by slow evaporation of the solvent supported by ether diffusion into the reaction vial.
With hydrogen sulfide; triethyl phosphite; for 0.333333h;Large scale;
Table III and Table IV summarize certain process conditions and analytical results for the polythiol compositions of Examples 15-21 and Examples 22-29, respectively. The following abbreviations and conventions are used in Tables III-IV: TAIC is 1,3,5-triallylisocyanurate; TMPI is trismercaptopropyl isocyanurate; TEP is triethylphosphite; Irg 500 is Irgacure 500; H2S Molar Ratio equals Moles of H2S / moles of carbon-carbon double bonds of TAIC; and weight and mole percentages of TEP and Irg 500 are based on the amount of TAIC. The % conversion is based on the number of double bonds of TAIC that have reacted. The % mono-S, % DiS, % TMPI, and % Heavies were determined using gas chromatography, where % mono-S equals the amount of compounds having one sulfur; % Di-S equals the amount of compounds having two sulfurs; % TMPI equals the amount of trismercaptopropyl isocyanurate; and % Heavies equals the amount of compounds having at least one sulfide group. Wt. % SH is the total amount of thiol sulfur in the composition, and Wt. % Total S is the total amount of sulfur in the composition. SHEW is the mercaptan equivalent weight (g/eq). The compositions of Examples 15-20 and 22-29 were analyzed prior to WFE and, therefore, contain polythiol molecules having less than three SH groups. Example 21 was a composition prepared after the composition of Example 20 was subjected to WFE. The GC data in Table III does not show all of the heavier compounds of the respective compositions. The Wt. % SH values for Examples 25-27 and 29 listed in Table IV are artificially high due to errors in the analytical testing procedure. FIG. 3 is a plot illustrating the respective amount of material versus the logarithm of molecular weight for TAIC and for the polythiol composition of Example 21 containing TMPI. The largest peak at the lower molecular weight is the reactant, TAIC. The curve for the composition of Example 21 has three definitive peaks to the right of (i.e., at a higher molecular weight than) TAIC. The first and larger peak is TMPI (relative area of 84.4 %). The peaks at the higher molecular weights are indicative of a polythiol molecule having one intermolecular sulfide (relative area of 12.7 %), and a polythiol molecule having two intermolecular sulfides (relative area of 2.3 %), respectively. The structures for these molecules are provided below: o
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane;
(2) Synthesis of Intermediate of Diglycidyl Isocyanurate Having Allyl Group (First Step) 20.0 g of triallyl isocyanurate obtained in the above (1), 39.57 g of 77 wt % m-CPBA (Aldrich), and 200 ml of methylene chloride were put in a 500 ml flask and stirred at room temperature for 1 day. The reactant was worked up using an aqueous solution of saturated sodium thiosulfite and was extracted using ethyl acetate.
34
[ 108-80-5 ]
[ 106-95-6 ]
[ 1025-15-6 ]
Yield
Reaction Conditions
Operation in experiment
With potassium carbonate; In dimethyl sulfoxide; at 20 - 80℃;
(1) Synthesis of triallyl isocyanurate (alkenylation) 30.0 g of isocyanuric acid (Aldrich), 169 g of allyl bromide (Aldrich), 128 g of potassium carbonate, and 773 ml of DMSO were put in a flask and stirred at room temperature for 10 minutes. Then, the temperature increased to 80C and reaction was performed overnight. Subsequently, the temperature of the reactant decreased to room temperature, and worked up after adding 400 ml of ethyl acetate with H2O to remove an inorganic material. MgSO4 was added to an organic layer to remove remaining H2O, and solvents were evaporated to obtain triallyl isocyanurate.
With magnesium sulfate; potassium carbonate; In dimethyl sulfoxide; ethyl acetate;
(1) Synthesis of Triallyl Isocyanurate (Alkenylation) 30.0 g of isocyanuric acid (Aldrich), 169 g of allyl bromide (Aldrich), 128 g of potassium carbonate, and 773 ml of DMSO were put in a flask and stirred at room temperature for 10 minutes. Then, the temperature increased to 80 C. and reaction was performed overnight. Subsequently, the temperature of the reactant decreased to room temperature, and worked up after adding 400 ml of ethyl acetate with H2O to remove an inorganic material. MgSO4 was added to an organic layer to remove remaining H2O, and solvents were evaporated to obtain triallyl isocyanurate.
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 20℃; for 24h;
(2) Synthesis of intermediate of diglycidyl isocyanurate having allyl group (first step) 20.0 g of <strong>[1025-15-6]triallyl isocyanurate</strong> obtained in the above (1), 39.57 g of 77 wt% m-CPBA (Aldrich), and 200 ml of methylene chloride were put in a 500 ml flask and stirred at room temperature for 1 day. The reactant was worked up using an aqueous solution of saturated sodium thiosulfite and was extracted using ethyl acetate. [First step in method 2] [0213] 1H NMR (400MHz, CDCl3): delta=2.68-2.70 (m, 2H), 2.83 (t, J=4.8Hz, 2H), 3.24-3.28 (m, 2H), 4.01 (dd, J=0.8, 4.8Hz, 1H), 4.04 (dd, J=0.8, 4.8Hz, 1H), 4.15 (dd, J=2.4, 5.6Hz, 1H), 4.19 (dd, J=2.4, 5.6Hz, 1H), 4.50 (dt, J=1.2, 6.0Hz, 2H), 5.26 (dd, J=1.2, 10.0Hz, 1H), 5.34 (dd, J=1.2, 17.2Hz, 1H), 5.83-5.93 (m, 1H).
118 g
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 25 - 30℃; for 4h;
Synthesis Example 2 Preparation of Monoallyldiglycidyl Isocyanurate (0208) 8700 ml of dichloromethane was taken as a solvent, and 154.6 g of <strong>[1025-15-6]triallyl isocyanurate</strong> (Mw=154.6) and 535 g of m-chloroperbenzoic acid (not higher than 30 C.) was slowly added into a cooler and stirred and reacted at 25 C. for 4 hours. After completing the reaction, 3000 ml of 10% sodium bisulfite solution was slowly added at 20 C., and then an insoluble material was filtered off. Chloroform was added for extraction, and the reactants were washed thoroughly with 10% sodium bisulfite solution and saturated sodium bicarbonate solution. After drying and distilling the solvent, an epoxy compound was obtained. The aforementioned product was purified with silica gel chromatograph to obtain 118 g of transparent oil. The obtained epoxy compound was monoallyldiglycidyl isocyanurate (Mw=281).
With sodium carbonate; potassium bromide; In dimethyl sulfoxide; at 65℃; for 1.5h;
Synthesis Example 3 Isocyanuric acid (135 mg, 1.1 mmol), sodium carbonate (318 mg, 3.0 mmol), potassium bromide (36 mg, 0.3 mmol), and dimethyl sulfoxide (4.1 g) were mixed, and the mixture was heated to 65C. A mixed solution of 2-propenyl methanesulfonate (409 mg, 3.0 mmol) and dimethyl sulfoxide (409 mg) was added dropwise over 30 minutes. A reaction was carried out for 1 hour. The reaction solution was analyzed by GC, and the yield of 1,3,5-tris-(2-propenyl)-isocyanurate was confirmed to be 68%.
With sodium phosphate dodecahydrate; dihydrogen peroxide; sodium hydrogencarbonate; sodium carbonate; In methanol; water; acetonitrile; at 20℃; for 15h;pH 10.6;
Example 2 1,3,5-tris-(2-propenyl)-isocyanurate (2.2 g, 9.0 mmol), trisodium phosphate dodecahydrate (7.2 g, 18.9 mmol), acetonitrile (10 g, 243.0 mmol), methanol (6 g), and sodium carbonate-sodium hydrogen carbonate buffer solution (pH = 10.6) (10 g) were mixed, the temperature was adjusted to 20C, and an aqueous 35% by mass hydrogen peroxide solution (2.32 mL, 27 mmol) was added dropwise over 1 hour to cause a reaction for 2 hours. Further, the operation of adding dropwise an aqueous 35% by mass hydrogen peroxide solution (2.32 mL, 27 mmol) to cause a reaction for 2 hours was repeated four times, and then the reaction was carried out for additional 4 hours. The reaction solution was analyzed by GC, and the conversion ratio of olefin was 99%. Water was added to the reaction mixture to make it uniform, and methanol and acetonitrile were distilled off under reduced pressure. To the remained aqueous phase, chloroform (50 g) was added, and the mixture was separated into an organic phase and an aqueous phase. An organic phase was obtained by extraction with chloroform (50 g) from the aqueous phase. The organic phase was combined with the obtained organic phase, washed with an aqueous 2% sodium thiosulfate solution (50 g), an aqueous 1 N phosphoric acid solution (50 g), and ion-exchanged water (50 g) twice, and dried under reduced pressure by a vacuum pump. As a result, 1,3,5-tris-(2,3-epoxypropyl)-isocyanurate was obtained in an amount of 0.8 g, a yield of 28%, and a GC area percent purity of 90%.
With 2,2'-azobis(isobutyronitrile); In tetrahydrofuran; at 65℃; for 16.5h;Inert atmosphere;
a) Synthesis of 1,3,5-tris(3-acetylmercaptopropyl)-1,3,5-triazine-2,4,6-trione In a 500-mL three-necked flask, 37.39 g (150 mmol) 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione, 41.10 g (540 mmol) thioacetic acid and 3.69 g (22.5 mmol) 2,2'-azobis(2-methylpropionitrile) were dissolved in 250 mL tetrahydrofuran analogously to U.S. Pat. No. 4,266,055. The reaction solution was rinsed thoroughly with nitrogen for 30 min and then heated under nitrogen atmosphere for 16 hours at 65 C. After cooling of the reaction solution in an ice bath to 0 C., 100 mL of a one molar sodium carbonate solution was added dropwise. After extraction with dichloromethane three times, the combined organic phases were washed with 80 mL of a one molar sodium hydroxide solution as well as saturated sodium chloride solution, dried over magnesium sulphate and freed from the solvent on a rotary evaporator under reduced pressure. The crude product was recrystallized three times from 200 mL methanol in order to obtain 1,3,5-tris(3-acetylmercaptopropyl)-1,3,5-triazine-2,4,6-trione (48.0 g, 100.5 mmol, 67% theoretical) as a colourless and odourless solid. Melting point: 66-67 C.; 1H NMR (300 MHz, CDCl3, delta [ppm]): 3.89 (t, 3JHH=7.1 Hz, 6H, -NCH2-), 2.83 (t, 3JHH=7.1 Hz, 6H, -CH2S-), 2.26 (s, 9H, -CH3), 1.87 (quint., 3JHH=7.1 Hz, 6H, -CH2-); 13C NMR (75 MHz, CDCl3, delta [ppm]): 195.45 (-S(C=O)CH3), 149.03 (-C=O), 42.07 (-NCH2-), 30.68 (-CH3), 28.03 (-CH2-), 26.27 (-CH2S-); FTIR: nu=3024 (w), 2977 (m), 2945 (w), 2923 (w), 1692 (s, nuC=O), 1676 (s, nuC=O), 1508 (w), 1457 (s), 1425 (s), 1373 (m), 1352 (m), 1338 (m), 1327 (m), 1307 (m), 1296 (w), 1283 (w), 1242 (w), 1135 (s), 1107 (s), 1045 (w), 955 (m), 763 (s, nuC-S) cm-; MS (EI) m/z (%): 519 (4) [M+], 477 (16), 476 (32), 444 (12), 434 (14), 402 (26), 400 (12), 390 (11), 360 (24), 358 (22), 348 (42), 326 (12), 314 (12), 306 (50), 272 (40), 184 (16), 130 (23), 96 (10), 87 (19), 56 (15), 55 (17), 43 (100), 41 (10).
With sodium hydrogen sulfate; In dimethyl sulfoxide; at 95℃;
1) Take the appropriate amount of dimethyl sulfoxide, sodium cyanate and sodium bisulfate into the reactor, the reactor internal mixtureHeating and stirring; in the reactor internal temperature reaches 95 C, the reactor inside the addition of chloropropene; to be sodium cyanate and chloropropeneComplete reaction, the reactor into the appropriate amount of internal water, acidic solution and alkaline solution, while the mixture inside the reactor plusHeating and stirring; after the above-mentioned treatment, the reaction mixture in the reaction kettle is taken out and subjected to oil-water separation treatment, and the oil phase liquidNamely triallyl isocyanurate crosslinker crude; 2) the crude triallyl isocyanurate crosslinker obtained in step 1), at a temperature of 110 C, and120 Pa in a vacuum atmosphere, and then subjected to two distillation treatments under the above-mentioned temperature and vacuum environment, respectively.
With dibenzoyl peroxide; In 1,4-dioxane; at 110℃; under 7500.75 Torr; for 12h;Autoclave; Large scale;
In a 5 L autoclave, 3.5 kg of 1,4-dioxane solvent and 0.75 kg of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were charged and heated to 110 C with stirring , Maintaining a pressure of 1 MPa in the autoclave, adding 0.15 kg of <strong>[1025-15-6]triallyl isocyanurate</strong> and 4.5 g of benzoyl peroxide, and stirring the reaction at 110 C for 12 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the reaction solvent 1,4- After cooling, the crude product was poured into 5 kg of ethyl acetate, stirred and washed at 60 C, and then filtered. The solid residue obtained by filtration was dried in an oven at 80 C to obtain the target product DOPO-TAIC, DOPO -TAIC was 88.5%, and the purity of DOPO-TAIC was higher than 95%.
In 5,5-dimethyl-1,3-cyclohexadiene; at 140℃; for 10h;
24.9 g of <strong>[1025-15-6]triallyl isocyanurate</strong> and 129.6 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were placed in a three-necked flask,To the flask was added 250 g of xylene,Heated to 140 C with stirring,After the reactants were completely dissolved and stirred for 10h,After the reaction,Vacuum distillation,Xylene is removed,After cooling, the crude product was added to 3090 g of n-propanol and stirred and washed for 3 h,Maintain 150 C,After standing to cool to room temperature, the product was filtered off,After drying at 200 4h TAIC-DOPO products were obtained.
Synthesis Example 1 Preparation of Diallylmonoglycidyl Isocyanurate (0207) A reaction vessel was added with 106 g of isocyanuric acid and 420 ml of water of slurry, and then 206 g of 48% sodium hydroxide solution was dropped into the aforementioned mixture. After the mixture was reacted for 2 hours at 60 to 70 C., water was removed, and the mixture was washed by methanol and then dried to obtain 157.5 g of sodium isocyanurate as white crystal. Then, the reaction vessel equipped with a stirrer and a condenser was added with 400 ml of dimethylformamide as a solvent for reacting 157.5 g of sodium isocyanurate and 290.4 g of 3-bromo-1-propylene for 6 hours at 120 to 125 C., and then an inorganic salt was filtered off. Toluene was extracted out and the reactants were washed with water and dried and the solvent was dried to obtain 154.6 g of triallyl isocyanurate (Mw=249.3) as pale brown oil. 8700 ml of dichloromethane was taken as a solvent, and 154.6 g of triallyl isocyanurate and 267 g of m-chloroperbenzoic acid (not higher than 30 C.) was slowly added into a cooler and stirred and reacted at 25 C. for 4 hours. After completing the reaction, 3000 ml of 10% sodium bisulfite solution was slowly added at 20 C., and then an insoluble material was filtered off. Chloroform was added for extraction, and the reactants were washed thoroughly with 10% sodium bisulfite solution and saturated sodium bicarbonate solution. After drying and distilling the solvent, an epoxy compound was obtained. The aforementioned product was purified with silica gel chromatograph to obtain 111.3 g of transparent oil. The obtained epoxy compound was diallylmonoglycidyl isocyanurate (Mw=265).
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 25 - 30℃; for 4h;
Synthesis Example 1 Preparation of Diallylmonoglycidyl Isocyanurate (0207) A reaction vessel was added with 106 g of isocyanuric acid and 420 ml of water of slurry, and then 206 g of 48% sodium hydroxide solution was dropped into the aforementioned mixture. After the mixture was reacted for 2 hours at 60 to 70 C., water was removed, and the mixture was washed by methanol and then dried to obtain 157.5 g of sodium isocyanurate as white crystal. Then, the reaction vessel equipped with a stirrer and a condenser was added with 400 ml of dimethylformamide as a solvent for reacting 157.5 g of sodium isocyanurate and 290.4 g of 3-bromo-1-propylene for 6 hours at 120 to 125 C., and then an inorganic salt was filtered off. Toluene was extracted out and the reactants were washed with water and dried and the solvent was dried to obtain 154.6 g of <strong>[1025-15-6]triallyl isocyanurate</strong> (Mw=249.3) as pale brown oil. 8700 ml of dichloromethane was taken as a solvent, and 154.6 g of <strong>[1025-15-6]triallyl isocyanurate</strong> and 267 g of m-chloroperbenzoic acid (not higher than 30 C.) was slowly added into a cooler and stirred and reacted at 25 C. for 4 hours. After completing the reaction, 3000 ml of 10% sodium bisulfite solution was slowly added at 20 C., and then an insoluble material was filtered off. Chloroform was added for extraction, and the reactants were washed thoroughly with 10% sodium bisulfite solution and saturated sodium bicarbonate solution. After drying and distilling the solvent, an epoxy compound was obtained. The aforementioned product was purified with silica gel chromatograph to obtain 111.3 g of transparent oil. The obtained epoxy compound was diallylmonoglycidyl isocyanurate (Mw=265).
1,3,5-tris [3-[[3-(trimethoxysilyl)propyl]thio]propyl]isocyanurate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
100%
With 2,2'-azobis(isobutyronitrile); at 110℃; for 5h;
In a 100 mL flask equipped with a thermometer, 24.9 g (100 mmol) of 1,3,5-<strong>[1025-15-6]triallyl isocyanurate</strong>,And 58.9 g (300 mmol) of (3-mercaptopropyl) trimethoxysilane were placed,After adding 200 mg (1.22 mmol) of azobisisobutyronitrile thereto, the reaction was carried out at 110 C. for 5 hours with stirring. The obtained reaction mixture was cooled to obtain 83.8 g (100% yield) of the title isocyanurate compound as a pale yellow liquid.
With platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex; acetic acid; In toluene; at 53 - 55℃; for 2.5h;
0.2003 mol (24.5 g) of Dynasylan TMOS, 0.1 ml of Catalyst No. 1, a further 40.0 g of toluene as additional solvent/diluent, 0.0665 mol (16.6 g) of TAICROS and 0.4 ml of acetic acid were initially charged in a 0.25 l stirred apparatus with jacketed coil condenser and stirred in an oil bath heated to 53-55 C. for 2.5 hours. This gave 79.9 g of Incompletely converted and colourless bottom product. The volatile components were not removed.
1,3,5-tris[3-(triethoxysilyl)propyl] isocyanurate[ No CAS ]
C24H47N3O9Si2[ No CAS ]
C24H49N3O9Si2[ No CAS ]
C30H63N3O12Si3[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex; acetic acid; In toluene; at 50 - 57℃; for 2.5h;
0.2003 mol (32.9 g) of Dynasylan TEOS-H, 0.1 ml of Catalyst No. 3, a further 40.0 g of toluene as additional solvent/diluent, 0.0665 mol (16.6 g) of TAICROS and 0.4 ml of acetic acid were initially charged in a 0.25 l stirred apparatus with reflux condenser and stirred in an oil bath heated to 50-57 C. for 2.5 hours. This gave 88.2 g of incompletely converted and colourless bottom product. The volatile components were not removed. Result: 86.2% of the allyl groups were converted by hydrosilylation to trimethoxysilylalkyl groups (cf. S1). 12.6% of the allyl groups (A1) have not been converted, and 0.6% propyl groups (P1) and 0.6% isopropyl groups (I1) that contaminate the product have formed. The reaction is incomplete.
With triphenylphosphine; In 5,5-dimethyl-1,3-cyclohexadiene; at 95℃; for 22h;Inert atmosphere;
6.45 g (50 mmol) of isocyanuric acid, 670 mg (2.5 mmol) of triphenylphosphine as an organophosphorus compound and 25.8 g of xylene as a solvent were placed in a reaction vessel, and after purging with nitrogen, a trade name E101 NE / W Manufactured by Evonik Degussa Co., Ltd., palladium-supported activated carbon catalyst supporting a mixture of zero valent metallic palladium and a divalent palladium compound in an amount converted to palladium atoms in terms of palladium atoms) to active charcoal was 266 mg in terms of dry mass , And the mixture was stirred at 95 C. for 1 hour. Then, 13.1 g (225 mmol) of allyl alcohol as an alkenyl type alcohol was added dropwise over 1 hour, and the reaction was carried out for 20 hours while returning only the organic layer out of the xylene, allyl alcohol and water azeotropically distilled by Dean Stark into the system. After the reaction, insoluble matter was filtered off. As a result of analyzing the filtrate, 98.6% of triallyl isocyanurate and 1.4% of diallyl isocyanurate were formed on the basis of isocyanuric acid, and no monoallyl isocyanurate was produced.
With triphenylphosphine; In 5,5-dimethyl-1,3-cyclohexadiene; at 95℃; for 8h;Inert atmosphere;
6.45 g (50 mmol) of isocyanuric acid, 670 mg (2.5 mmol) of triphenylphosphine as an organophosphorus compound and 25.8 g of xylene as a solvent were placed in a reaction vessel, and after purging with nitrogen, a trade name E101 NE / W (manufactured by Evonik Degussa Co., Ltd., palladium-supported activated carbon catalyst supporting a mixture of zero valent metallic palladium and divalent palladium compound in terms of palladium atoms in terms of palladium atoms) to 266 mg (125 mumol as the above palladium), and the mixture was stirred at 95 C. for 1 hour.Then, 13.1 g (225 mmol) of allyl alcohol as an alkenyl type alcohol was added dropwise over 1 hour, and the reaction was carried out for 6 hours while only the organic layer out of the xylene, allyl alcohol, and water azeotropicaly distilled with Dean Stark was returned to the system.After the reaction, insoluble matter was filtered off.As a result of analyzing the filtrate, 68.1% of triallyl isocyanurate and 13.0% of diallyl isocyanurate were formed on the basis of isocyanuric acid, and monoallyl isocyanurate was not produced.
1,3,5-tris[3-(4-mercaptobutylsulfanyl)propyl]isocyanurate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
96%
With 2,2'-azobis(isobutyronitrile); at 70℃; for 4h;
A 100 mL flask equipped with a thermometer was charged with 249 mg (1.0 mmol) of 1,3,5-<strong>[1025-15-6]triallyl isocyanurate</strong>,And 3.7 g (30 mmol) of 1,4-butanedithiol,, And 20 mg of azobisisobutyronitrile(0.12 mmol) was added thereto,The reaction was carried out at 70 C. for 4 hours while stirring.After completion of the reaction,It was concentrated at 100 C.,589 mg of 1,3,5-tris [3- (4-mercaptobutylsulfanyl) propyl] isocyanurate as a clear liquid. Yield 96%.
3. Open the clean water circulation pump of the secondary graphite parallel flow falling absorption tower to a 1000 L glass-lined reactor equipped with a thermometer, a propeller stirrer (rotation number 120 rpm) and a reflux condenser. Add 380 kg of 1,2-dichloroethane, 128 kg of cyanuric acid, 3.1 kg of tetrabutylammonium bromide, 1.3 kg of triethylamine, 1.3 kg of cuprous chloride, and heat to 80 C with stirring. Slowly add 352 kg of bromopropene, about 3.5 hours. After the addition is completed, the reflux reaction is continued at 80 C for 3 hours. The hydrogen bromide gas generated by the reaction is absorbed into the hydrogen by the clean water of the secondary graphite parallel flow falling absorption tower. Bromo acid, after the reaction is over, The compressed air is introduced to drive out the residual hydrogen bromide gas in the reaction system, and then 200 kg of water is added, and the water-soluble impurities in the reaction system are stirred and dissolved. After standing and layering, the organic phase is distilled under reduced pressure to remove the solvent to obtain TAIC. 224.1 kg of product, content 99.4%, yield 93.2% (based on bromopropene).
With platinum catalyst; In toluene; at 119 - 130℃; for 48h;
(1) taking 0.5 g of hydrosilylation catalyst platinum, diluted with 5 mL of toluene, and then added to a 250 mL three-necked flask; (2) 2.49g of 1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (1,3,5-Triallyl-1) , 3,5-triazine-2,4,6(1H,3H,5H)-trione, molecular weight MW=249.27g/mol),diluted with 20mL of toluene and added to a three-necked flask; (3) Take 15.00g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, molecular weight = 333) Diluted with 25 mL of toluene and added to a three-necked flask; (4) Set the oil bath temperature to 130 C, turn on the stirring, and turn on the condensed water. When the temperature in the three-necked flask is 119 C, the reaction mixture starts to reflux; (5) After refluxing for a while, a small amount of the reaction mixture is taken for IR test to determine whether the reaction is complete. (6) After 48 hours, the IR results showed that the carbon-free carbon double bond absorption peak indicates the end of the reaction, and the 1H NMR results showed no vinyl H. At this time, the reaction mixture was transferred to a rotary evaporator to distill off the solvent, and the product cross-linking agent was precipitated.
With monosilane; platinum; In toluene; at 119 - 130℃; for 48h;
(1) Taking 0.5 g for addition catalyst platinum, adding 5 ml toluene dilution, then adding 250 ml three-necked flask in;(2) Taking 2 . 49 g1, - 1, 3, 5 - triazine - 2, 4, 6 3, 5 - triallyl (1 H, 3 H, 5 H) - trione (1, 3, 5 - Triallyl - 1, 3, 5 - triazine - 2, 4, 6 (1 H, 3 H, 5 H) - trione, molecular weight MW=249. 27 g/mol), by adding 20 ml toluene diluted by adding three-necked flask;(3) Taking 8.75 g 1, 2 - double-(dimethyl silyl) benzene (1, 2 - Bis (dimethylsilyl) benzene, molecular weight=194.42), add 25 ml toluene diluted by adding three-necked flask;(4) Set the oil bath temperature 130 C, opening stirring, opening of the condensed water, to the three-necked burning bottle temperature is 119 C when, the reaction mixture began to reflux;(5) Return after a period of time, a small amount of reaction mixture from the IR testing, in order to judge whether the reaction completely.(6) 48 Hours later, the results of the IR display non-carbon-carbon double bond is that the end of the peak absorption of the reaction, 1 H NMR results show that non-vinyl H, at this time the reaction mixture is transferred to the rotary evaporator off the solvent, precipitation product cross-linking agent 4
With platinum hydrosilylation catalyst; In toluene; at 119 - 130℃; for 48h;
(1) taking 0.5 g of hydrosilylation catalyst platinum, diluted with 5 mL of toluene, and then added to a 250 mL three-necked flask;(2) 2.49g of 1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (1,3,5-Triallyl-1) , 3,5-triazine-2,4,6(1H,3H,5H)-trione, molecular weight MW=249.27g/mol),dilutedwith20mL of toluene and added to a three-necked flask; (3) 8.75 g of 1,3-bis(dimethylsilyl)benzene (molecular weight = 194.42), diluted with 25 mL of toluene, and added to a three-necked flask;(4) Set the oil bath temperature to 130 C, turn on the stirring, and turn on the condensed water. When the temperature in the three-necked flask is 119 C, the reactionmixture starts to reflux;(5) After refluxing for a while, a small amount of the reaction mixture is taken for IR test to determine whether the reaction is complete.(6) After 48 hours, the IR results showed that the carbon-free carbon double bond absorption peak indicates the end of the reaction, and the 1H NMR results showed novinyl H. At this time, the reaction mixture was transferred to a rotary evaporator to distill off the solvent, and the product cross-linking agent was precipitated.
50 grams of <strong>[1025-15-6]triallyl isocyanurate</strong> (TAIC, purchased from the Aldrich Chemical) was added to 60 grams of dimethylacetamide (DMAc) solvent. Then, 19.48 grams of furfurylamine (FA, purchased from the Aldrich Chemical) was added to the solution, and then heated to 100 C.160 C. and stirred to react. After completing the reaction, the solution was cooled down to room temperature, and a compound having a structure represented by Formula I-4 was obtained.
With tetraethylammonium bromide; bromine; In dichloromethane; at 60℃; for 20h;
A method for synthesizing a thermally stable TBC flame retardant comprising the following steps:1) 50 g of ?99.0% of <strong>[1025-15-6]triallyl isocyanurate</strong> (TAIC) and 150 g of organic solvent I dichloromethane are added to a 1000 ml reactor according to the ratio.Stir until completely dissolved to prepare an organic solvent reaction system of TAIC;200 g of organic solvent II dichloromethane and quaternary ammonium salt 139 g of tetraethylammonium bromide were added to the 500 ml reactor according to the ratio.Adding 106 g of bromine Br2 dropwise to dissolve all of them to prepare a brominating agent;2) adding the brominating agent prepared in the step 1) to the organic solvent reaction system of TAIC,Raise the temperature to a bromination reaction temperature of 60 C, and keep warm for 20 hours until the reaction is complete;The molar ratio of TAIC in the brominating agent in the organic solvent reaction system of bromine Br2 and TAIC was 3.3:1.3) performing the first water washing step 2) after the reaction solution, after removing the water layer,To the organic layer in the reaction liquid in the step 2), a sodium hydrogen sulfite solution having a mass percentage concentration of 20% is added.Until the reaction system reddish brown disappeared;Add an appropriate amount of lye to adjust the pH of the organic layer to neutral.After a second water washing, 200 ml of water was added to the reaction system, and the organic layer was separated and left to stand;The first water washing step 2) after the reaction solution, the water layer is recovered, and the tetraethylammonium bromide is recovered by washing with water, that is, the quaternary ammonium salt in the solution after the step 2) is recovered.As a raw material for the preparation of a brominating agent, the recovery rate is 90% to 98%.4) 1000 ml of water was added to a 2000 ml solvent separation vessel, and the temperature was raised to 62 C in the solvent separation vessel.Add appropriate amount of high-purity finished TBC finished product with 20g content ?98.5% as seed crystal; under vacuum condition, vacuum degree control -0.9Mpa,The organic layer was slowly added dropwise while stirring, and after the completion of the dropwise addition, the mixture was further stirred for 5 hours to precipitate the product as a powder.After precipitation, the product was filtered off and dried to obtain a thermally stable TBC flame retardant product 144.8 g.Using the principle of azeotrope methylene chloride and water azeotrope but not miscible, supplemented by negative pressure,Achieve crystallization separation of products at lower temperatures,The yield was 99.5%, the bromine content was 65.6%, and the melting point was 107-110 C.5) adding a heat stabilizer 0.5% dibutyltin maleate to the thermally stable TBC flame retardant product prepared in step 4).After mixing, a high thermal stability TBC flame retardant product is obtained.The thermal stability test was performed with a 5% WLT of 280 C
With platinum; In toluene; at 119 - 130℃; for 48h;
1) taking 0.5 g of hydrosilylation catalyst platinum, diluted with 5 mL of toluene, and then added to a 250 mL three-necked flask;(2) Take 2.49g of <strong>[1025-15-6]1,3,5-<strong>[1025-15-6]triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione</strong></strong> (1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, molecular weight MW=249.27g/mol), diluted with 20mL of toluene and added to a three-necked flask;(3) taking 8.75 g of 1,4-Bis (dimethylsilyl)benzene (molecular weight = 194.42), adding 25 mL of toluene and adding to a three-necked flask;(4) setting the oil bath temperature to 130 C, turning on the stirring, turning on the condensed water, and when the temperature in the three-necked flask is 119 C, the reaction mixture starts to reflux;(5) After refluxing for a while, a small amount of the reaction mixture is taken for IR test to determine whether the reaction is complete.(6) After 48 hours, the IR results showed that the carbon-free carbon double bond absorption peak indicates the end of the reaction, and the 1H NMR results showed no vinyl H. At this time, the reaction mixture was transferred to a rotary evaporator to distill off the solvent, and the product cross-linking agent was precipitated. 4
With platinum-containing olefin organic polymer catalyst; at 25℃; for 24h;
Take 1 ml (0.06 mol% Pt) of the catalyst in Example 1,Triethoxysilane 492mg (3mmol)And <strong>[1025-15-6]triallyl isocyanurate</strong> 250 mg (1 mmol)The product was placed in a 5 ml single-necked flask and reacted at 25 C. for 24 hours to isolate the product. The product was detected by GC-MS with an isolation yield of 95%.
With triethylamine; In N,N-dimethyl-formamide; at 20 - 60℃; for 4.17h;Green chemistry;
Weigh 58g of allyl alcohol, 120g of pyridine, and 200g of p-toluenesulfonyl chloride into a 1000mL reaction vessel, stir at 15C for 4 hours, then wash and extract the solvent to obtain 207g of oily product, and then 68.7g of cyanide Sodium sulfate, 2g of triethylamine and 110g of N,N-dimethylformamide were added to the reactor and stirred at room temperature for 10 minutes, then the reactor was heated to 60C, reacted for 4 hours, allowed to stand for cooling, and the precipitate was filtered off The filtrate was analyzed by chromatography to obtain triallyl isocyanurate with a yield of 93%.
With triethylamine In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; Cooling with ice;
Synthesis of Crosslinker-Functionalized Nanosilica.
The surface modification process offunctionalizing SiO2 nanoparticles by grafting the auxiliary crosslinking agent is shown in Figure 1.The mixture solution of 3.92 g MPTMS (0.02 mol), 0.23 g TEA and THF is slowly dropped into thesolution of 4.98 g TAIC (0.02 mol) dissolved in 10 mL THF solvent, stirred under nitrogen protectionin ice-water bath for 5 min, and then naturally warmed to ambient temperature. The liquid product(MTAIC) with 76% yield will be obtained after reacting in thermal insulation for 24 h. By means ofultrasonic dispersion treatment for 30 min, 10 g dried nanosilica was uniformly blended into 100 mLethanol solution (3:1), after which the MTAIC is instilled with the solution being controlled on pH = 4by diluted hydrochloric acid. The obtained suspension is washed and filtered with ethanol for 3 timesand then dried in vacuum at 60 C to finally achieve the functionalized TAIC-s-SiO2 nanomaterial.
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