JPH0349905B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention relates to 2-vinyl-4,6-diamino-s-
This paper relates to a method for synthesizing triazine (hereinafter referred to as VT). The compounds obtained by the method of the present invention are useful as comonomers and have diamino-
It is known that when s-triazine is introduced, the softening point and glass transition point of the polymer increase significantly compared to the unintroduced polymer, the specific gravity also increases, and the solubility changes significantly. [For example, Seo, Kakurai: Polymer Papers, 32 , 308 (1975); T.Seo, K.Abe, H.
Honma, T.Kakurai: Polym.Prepn., 20 , 661
(1979)] Prior Art Regarding the synthesis of VT, several methods described below are already known. That is, a method of reacting biguanide with acrylic acid chloride [CG
Overberger et al.: J, ACS, 80, 988 (1958)],
Method for reacting dicyandiamide and β-dimethylamino-propionitrile [Hoechst:
Fr. 1, 563, 255 (1967)], a method of heating 1,2-di{4',6'-diamino-s-triazinyl-(2')}-cyclobutane to 320°C under reduced pressure [Asahi Kasei: Special Publication No. 46-35068], 2-β-methoxyethyl-4,
6-diamino-s-triazine in a nitrogen stream
How to heat to 350℃〔Suddeutsche
Kalkstickstoff Werke AG: Ger.Offen.2,
135, 881 (1973)] etc. Problems to be Solved by the Invention Today, various vinyl compounds are used in the chemical industry, many of which are in liquid form. In consideration of stable storage and stable transportation, polymerization inhibitors are often added to these vinyl compounds. At that time, the polymerization inhibitor is uniformly dissolved in the vinyl compound and exhibits a polymerization inhibiting effect. If necessary, the polymerization inhibitor can be easily removed from the vinyl compound by distillation during use. Therefore, if a liquid vinyl compound can be stored stably, it is easy to transport it stably. On the other hand, solid vinyl compounds cannot be stably stored and transported as easily as liquid vinyl compounds. In particular, if you try to heat and melt VT and then uniformly dissolve and mix the polymerization inhibitor into it,
The problem is that the high melting point raises the temperature, causing thermal polymerization of most of the VT. In addition, VT has very good crystallinity, and even if a polymerization inhibitor is dissolved in a solvent beforehand during recrystallization, it is not uniformly incorporated into the crystal, and there is the problem that VT precipitates independently from the solution. be. For the reasons mentioned above, it is currently almost impossible to uniformly include a polymerization inhibitor in VT. Therefore, VT has the possibility of unexpected polymerization during storage or transportation, which is both dangerous and unsettling. Means for Solving the Problems The inventors of the present invention have conducted extensive research in order to avoid the above-mentioned dangers and concerns, and as a result, have arrived at the present invention. That is, VT is first converted into a salt of 2-β-hydroxyethyl-4,6-diamino-s-triazine (hereinafter referred to as
HT salt) or 2-β-hydroxyethyl-4,6-diamino-s-triazine (hereinafter referred to as
(abbreviated as H.
Since T. salt and HT have the ability to release VT, we have found that the above-mentioned dangers and concerns can be avoided by using HT salt or HT in place of VT when necessary. This can be explained using a reaction formula as follows. In other words, if HT salt or HT is treated with an alkaline aqueous solution, VT will be generated, so HT salt and
HT can be referred to as a VT releasing agent. Therefore, instead of performing certain reactions (e.g. polymerization reactions) in the form of VT, salts or
A similar reaction can be carried out in alkaline solution in the form of HT. The HT salt and the method for synthesizing HT are simple.
In other words, in the case of HT salt, mix VT and HA aqueous solution,
Adjust the pH of the mixed system to 2.0 or higher and heat at 50 to 80°C to make a homogeneous solution. The system is then concentrated under reduced pressure (or without being concentrated under reduced pressure) and then cooled, the precipitated crystals are collected by filtration, the filtered crystals are washed with alcohol, and then dried to obtain the desired HT salt. In the case of HT, mix the HT salt and aqueous alkaline solution, maintain the pH of the system at room temperature in the range of 7.0 to 9.5, and then concentrate the resulting homogeneous solution as it is or under reduced pressure, and collect the precipitated crystals by filtration, wash with water, and dry. You can get HT. When synthesizing HT salt, it is desirable to add a small amount of sodium sulfide (Na ₂ S・9aq) to the system in advance as a polymerization inhibitor. Although various other commercially available polymerization inhibitors (eg, picric acid or hydroquinone) may be used, the use of soda sulfide is the most economical. The purity of the HT salt thus obtained is sufficiently high that it can be used as is for the intended purpose. If further purification is required
The HT salt may be recrystallized with water or alcohol. In the case of HT synthesis, polymerization inhibitors are unnecessary. If further purification is required, HT may be recrystallized with water. The acid used to synthesize the HT salt has a dissociation constant of 6×
Inorganic or organic acids having a molecular weight of 10 ^-4 or more, as shown below. HF, HBr _, HCl, _HNO3 , _H2SO4 ,
_ClCH2COOH ,

【formula】

The alkali used in the present invention is as shown below. i.e. NaOH, KOH, Na ₂ CO ₃ ,
_{K2CO3 , NaHCO3} , _KHCO3 , _NH4OH ,
(NH ₄ ) ₂ CO ₃ , inorganic alkalis such as CaCO ₃ , organic amines such as ethanolamine, methylamine or imidazole. Next, the properties of each object are shown. 1 Hydrochloride of HT mp232℃ (decomposition) (MeOH). Acidic colorless crystals. Soluble in cold water. Hot methanol soluble. Insoluble in hot acetone and hot ethanol. νKBr cm ^-1 : 3170, 3090, 2760, 1665 (first absorption),
1635 (second absorption), 1550 (third absorption), 1485
(3rd absorption), 1405 (5th absorption), 1030 (4th absorption)
absorption), 790 (6th absorption), 735 NMR (D ₂ O): δ4.88, s, 1H (HO-); 4.02,
t, 2H, (α-methylene relative to HO-); 2.92, t, 2H (β-methylene relative to HO-) Mass: (m/e) 155 (M ⁺ -HCl), 138 (155-
HO・） 36 (HCl) 2 Sulfate of HT mp148℃ (decomposition) (W). Acidic colorless crystals. Soluble in hot water. Slightly soluble in cold water. Insoluble in hot alcohol. νKBr cm ^-1 : 3300 (third absorption), 3080 (fourth absorption),
1665 (first absorption), 1635 (second absorption), 1490
(6th absorption), 1135 (5th absorption), 1080 (5th absorption)
absorption), 1030 (fifth absorption), 790 NMR (D ₂ O): δ4.88, s, 1H (HO-); 3.96,
t, 2H, (α-methylene for HO);
2.88, t, 2H (β-methylene relative to HO) Mass: (m/e) 155, 138, 126, 125, 43 3 Nitrate of HT mp180°C (decomposition) (W). Acidic colorless crystals. Easily soluble in hot water, soluble in cold water. Insoluble in hot alcohol. νKBr cm ^-1 : 3420 (4th absorption), 3120 (3rd absorption),
1630 (2nd absorption), 1530 (5th absorption), 1380
(1st absorption), 1110, 1090, 1040, 790 NMR (D ₂ O): δ4.88, s, 1H (HO-); 3.89,
t, 2H, (α-methylene for HO);
2.89, t, 2H (β-methylene relative to HO) Mass: (m/e) 155, 138, 126, 125, 112,
69 (HNO ₃ ), 54, 46, 43, 4 HT bromochloride mp197°C (decomposition) (W). Acidic colorless crystals. Easily soluble in water, insoluble in hot alcohol. νKBr cm ^-1 : 3340 (4th absorption), 3160 (5th absorption),
1680 (first absorption), 1640 (second absorption), 1530
(3rd absorption), 1450 (6th absorption), 1345 (9th absorption)
absorption), 1250, 1200, 1100, (7th absorption),
1040 (8th absorption), 995, 790 (10th absorption) 5 HT monochloroacetate mp147-149°C (W). Acidic colorless crystals. Soluble in cold water. Soluble in hot methanol. νKBr cm ^-1 : 3280 (second absorption), 1715 (third absorption),
1630 (first absorption), 1400 (fourth absorption), 1250
(6th absorption), 1185 (7th absorption), 1050 (5th absorption)
Absorption), 790 (8th absorption), 770 (8th absorption) 6 HT oxalate mp146-147°C (W). Acidic colorless crystals. Easily soluble in cold water. Insoluble in hot alcohol. νKBr cm ^-1 : 3410 (4th absorption), 3300 (5th absorption),
1725 (3rd absorption), 1660 (2nd absorption), 1615
(1st absorption), 1550, 1490, 1250, (6th absorption), 1050, 1010, 790, 720 7 Hydrofluoride salt of HT mp246℃ (decomposition) (MeOH). Acidic colorless crystals. Easily soluble in cold water, soluble in hot methanol. Insoluble in hot ethanol. νKBr cm ^-1 : 3130 (3rd absorption), 1670 (1st absorption),
1540, 1490, 1340, 1190, 1160, 1090,
1040, (5th absorption), 785 (4th absorption), 730
(Second absorption) 8 HT paratoluenesulfonate mp138℃ (decomposition) (MeOH). Acidic colorless crystals. Easily soluble in cold water. Soluble in hot methanol. νKBr cm ^-1 : 3340 (3rd absorption), 3200 (5th absorption),
1680 (first absorption), 1645 (fourth absorption), 1595,
1530, (second absorption), 1450, 1420, 1360,
1200, 1160 (6th absorption), 1120, 1030,
1000, 825, 795, 675 9 HT mp220-222℃ (W). Neutral colorless crystal. Soluble in hot water. Soluble in cold acetic acid and cold DMSO. Slightly soluble in hot alcohol. νKBr cm ^-1 : 3410, 3100 (third absorption), 1650 (second absorption), 1525 (first absorption), 1460 (fourth absorption),
1045 (5th absorption), 1005, 800 (6th absorption) NMR (D ₂ O): δ6.52, s, 4H (-NH ₂ ); 3.72,
t,2H (α-methylene for HO);
3.30, br, s, 1H (-HO); 2.51, t, 2H
(β-methylene relative to HO) Mass: m/e155 (M ⁺ ), 138 (M ⁺ -HO), 69, 43, 28, 18 (W) 10 HT Isocyanurate mp250℃ or higher (water). Acidic colorless crystals. Soluble in hot water. Insoluble in hot methanol and hot ethanol, hot acetone, soluble in cold DMSO. νKBr cm ^-1 : 3560, 3450 (5th absorption), 3340, 3240,
3020, 2800, 1775 (6th absorption), 1720, (1st absorption), 1625 (2nd absorption), 1545 (3rd absorption), 1425 (4th absorption), 1260, 1160, 1070,
1035, 990, 890, 815, 760 This will be specifically explained below using Examples and Reference Examples. Reference example 1 VT0.1 mole (13.7g), water 20ml and
A system consisting of three members of Na ₂ S9aq.0.005 mol (1.2 g)
While maintaining the temperature at 80° C., 100 ml of about 2N HCl was added to the system to adjust the pH of the system to 2.0. The system exhibited a homogeneous aqueous solution.
The aqueous solution was concentrated to 1/3 under reduced pressure and allowed to cool, and then 0.085 mol (16.3 g, yield 85 mol%) of precipitated crystals was collected by filtration. The mp of the crystal was 232°C (decomposition). This product was recrystallized with methanol to obtain 0.08 mol (15.3 g, yield 80 mol%) of an identified sample of HT hydrochloride. Next, add 0.1 mol (19.15 g) of HT hydrochloride to water at room temperature.
Dissolve in 20 ml and add K ₂ CO ₃ aqueous solution to adjust the pH of the system.
8.0, the system was concentrated under reduced pressure, and 0.09 mol (13.9 g, yield 90 mol%) of precipitated crystals was collected by filtration. The mp of this product was 219-220°C. The crystals were recrystallized from water to obtain 0.08 mol (12.4 g, yield 80 mol%) of the purified target product HT. The mp for this one showed 220-222. Reference example 2 VT0.1 mole (13.7g), water 20ml and
A system consisting of three members of Na ₂ S9aq.0.005 mol (1.2 g)
While maintaining the temperature at 70℃, add a dilute sulfuric acid solution to the system.
The pH was set to 2.0. In this way, approximately 40 ml of a homogeneous aqueous solution was obtained. The aqueous solution was concentrated to about 1/2 under reduced pressure, and 0.09 mol (22.8 g, yield 90 mol%) of crystals precipitated by standing to cool was collected by filtration. The mp of the crystal is 148℃ (decomposition)
showed that. This product was recrystallized with water, and 0.075 mol (19.0 g, yield 75 mol%) of HT hydrochloride identification sample was obtained.
I got it. Next, add 0.1 mol (25.3 g) of HT sulfate to water at room temperature.
Dissolve in 40ml and add Na ₂ CO ₃ aqueous solution to adjust the pH of the system.
7.5, and the system was concentrated under reduced pressure to about 1/5 to precipitate.
The mp of this product was 220-221°C. The crystals were recrystallized with water to obtain 0.08 mol (12.4 g,
A yield of 80 mol% was obtained. This thing's mp is 220 ~
221 was shown. Reference example 3 VT0.1 mol (13.7 g), water 20 ml and
A system consisting of three members of Na ₂ S9aq.0.005 mol (1.2 g)
While maintaining the temperature at 80℃, add dilute sulfuric acid aqueous solution to the system.
The pH was set to 2.0. The system thus obtained was allowed to cool, and 0.09 mol (19.6 g, yield 90 mol%) of precipitated crystals was collected by filtration. The mp of the crystal was 174°C (decomposition).
This product was recrystallized with water to obtain 0.07 mol (15.2 g, yield 70 mol%) of HT nitrate. m of this one.
p. indicated 180°C (decomposition). Next, add 0.1 mol (21.8 g) of HT nitrate to water at room temperature.
Dissolve in 40ml and add ammonia water to adjust the pH of the system.
9.5, and 0.09 mol (13.9 g, yield 90 mol%) of precipitated crystals were collected by filtration. The mp of this thing is 218-220℃
showed that. The crystals are recrystallized with water to obtain the purified target H.
0.085 mol (13.2 g, yield 85 mol%) of T.
The mp of this product was 220-222°C. Reference example 4 VT0.1mol (13.7g), water 20ml and
A system consisting of three members of Na ₂ S9aq.0.005 mol (1.2 g)
While maintaining the temperature at 50°C, an aqueous HBr solution was added to the system to adjust the pH of the system to 1.0. In this way, approximately 50 ml of a homogeneous aqueous solution was obtained. The aqueous solution was concentrated under reduced pressure to about 1/5, and 0.085 mol (20.0 g, yield 85 mol %) of crystals precipitated by standing to cool was collected by filtration. The mp of the crystal is 197℃ (decomposition)
showed that. This product was washed with methanol and used as an identification sample. Next, add 0.1 mol (23.5 g) of HT/HBr salt to water at room temperature.
Dissolve in 40ml and add caustic soda aqueous solution to adjust the pH of the system.
was set to 7.4, and 0.095 mol% (14.7 g, yield 95 mol%) of precipitated crystals was collected by filtration. This thing's mp is 217
It showed ~220℃. The crystals were recrystallized from water to obtain 0.08 mol (12.4 g, yield 80 mol%) of the purified target product HT. The mp of this product was 220-222°C. Reference example 5 VT0.1 mol (13.7 g), water 20 ml and picric acid
While maintaining the system consisting of 0.005 mol (1.1 g) of the three components at 80°C, an aqueous monochloroacetic acid solution was added to the system to adjust the pH of the system to 2.0. In this way, a homogeneous aqueous solution was obtained. 0.07 mol of crystals (17.4 g, yield
70 mol%) was collected by filtration. The mp of the crystal is 147-149
℃ was shown. Wash this with methanol and HT
This was used as an identification sample for monochloroacetate. Next, HT monochloroacetate 0.1 mol (24.9 g)
was dissolved in 40 ml of water at room temperature, sodium bicarbonate was added to adjust the pH of the system to 9.0, and the system was concentrated to about 1/5 under reduced pressure to precipitate 0.08 mol (12.4 g, yield 80 mol%) of crystals.
I got it. Reference example 6 VT0.1 mole (13.7g), water 20ml and
A system consisting of three members of Na ₂ S9aq.0.005 mol (1.2 g)
While keeping the temperature at 55℃, add oxalic acid aqueous solution to the system to adjust the pH of the system.
was set to 2.0. Approximately 100 ml of a homogeneous aqueous solution was thus obtained. The aqueous solution was concentrated under reduced pressure to about 1/5, and 0.08 mol (19.6 g, yield 80 mol%) of crystals precipitated by standing to cool was collected by filtration. The mp of the crystal was 145-147°C. This product was washed with methanol to obtain 0.07 mol (17.1 g, yield 70 mol%) of an identified sample of HT oxalate. Next, add 0.1 mol (24.5 g) of HT oxalate to water at room temperature.
Dissolve in 40 ml, add CaCO ₃ to adjust the pH of the system to 7.2, collect the filtrate, concentrate under reduced pressure, and collect 0.08 mol (12.4 g, yield 80 mol%) of precipitated crystals by filtration. The mp of this product is 218 It showed ~221℃. The crystals were recrystallized with water to obtain 0.07 mol (10.8 g, yield 70 mol%) of purified HT. The mp of this product was 220-222°C. Reference example 7 VT0.1 mol (13.7 g), water 20 ml and
A system consisting of three members of Na ₂ S9aq.0.005 mol (1.2 g)
While maintaining the temperature at 50°C, an aqueous p-toluenesulfonic acid solution was added to the system to adjust the pH of the system to 2.0. 0.08 mol (26.2 g, yield 80 mol%) of crystals precipitated by cooling was collected by filtration. The mp of the crystal was 134°C (decomposition). This product was recrystallized from methanol, and 0.07 mol (22.8
g, yield 70 mol%). Next, 0.1 mol (32.7 g) of HTp-toluenesulfonate was dissolved in 60 ml of water at room temperature, and 2-methylimidazole aqueous solution was added to adjust the pH of the system to 7.5.
The system was concentrated under reduced pressure, and 0.09 mol (13.9 g,
A yield of 90 mol% was obtained. This thing's mp is 218 ~
It showed 220℃. The crystals were recrystallized from water to obtain 0.085 mol (13.2 g, yield 85 mol%) of the purified target product HT. of this
mp showed 220-222℃. Reference example 8 VT0.1 mole (13.7g), water 20ml and
A system consisting of three members of Na ₂ S9aq.0.005 mol (1.2 g)
While maintaining the temperature at 80°C, an aqueous solution of hydrofluoric acid was added to the system to adjust the pH of the system to 2.0. 0.075 mol (13.1 g, yield 75 mol%) of crystals precipitated by cooling was collected by filtration. The mp of the crystal was 240°C (decomposition). The crystals were recrystallized from methanol to obtain 0.06 mol (10.5 g, yield 60 mol %) of an identified sample of HT hydrofluoride. Next, dissolve 0.1 mol (17.5 g) of HT hydrofluoride in 60 ml of water at room temperature and add KOH aqueous solution to make the system.
Adjust the pH to 7.0, concentrate the system under reduced pressure, and precipitate crystals.
0.09 mol (13.9 g, yield 90 mol%) was collected by filtration.
The mp of this product was 217-220°C. The crystals were recrystallized with water to obtain 0.07 mol (10.8 g,
A yield of 70 mol% was obtained. This thing's mp is 220 ~
It showed 221℃. Reference example 9 VT0.1 mol (13.7 g), water 40 ml and
A system consisting of three members of Na ₂ S9aq.0.005 mol (1.2 g)
While maintaining the temperature at 70°C, an approximately 5N HCl aqueous solution was added to the system to adjust the pH of the system to 1.0. Then the system (NH ₄ ) ₂ CO ₃
Add an aqueous solution to adjust the pH of the system to 9.5, and precipitate crystals.
0.08 mol (12.4 g, yield 80 mol%) was collected by filtration.
The mp of this product was 216-219°C. The crystals were recrystallized with water to obtain HT0.065 mol (10.0
g, yield 65 mol%). The mp for this is
It showed 220-222℃. Reference example 10 0.1 mol (12.9 g) of isocyanuric acid and 20 ml of water
While maintaining the system consisting of the two components at 80°C, H.
0.1 mole (15.5 g) of T. was added. The homogeneous aqueous solution thus obtained was allowed to cool, yielding 0.071 mol (20.1 g, yield 71 mol%) of precipitated crystals. m of this one.
p. indicated 250℃. The crystals were recrystallized with water to obtain 0.062 mol (17.5 g, yield 62 mol%) of the purified target HT isocyanurate.
I got it. The mp of this product was over 250℃. Reference example 11 A system consisting of 0.1 mol (15.5 g) of HT, 150 ml of water, and 0.2 g of azobis-isobutyronitrile is prepared.
The mixture was heated to reflux for 15 minutes. During this time, the system became a homogeneous solution. After cooling, about 14.0 g of precipitated unreacted HT was collected by filtration. Therefore, it was found that no polymerization reaction occurred. The same system was then heated to reflux and the pH of the system was adjusted with K ₂ CO ₃ .
When it was set to 9.5, insoluble matter was generated. After continuing to reflux for another 15 minutes, filter while hot to remove 14.0g of insoluble matter.
(90 mol% of HT). The insoluble matter was washed with hot water and IR was examined. The results are as follows. νKBr cm ^-1 : 3320 (4th absorption), 3140 (3rd absorption),
1655 (first absorption), 1540 (second absorption), 1450 (fifth absorption), 1340 (sixth absorption), 1260, 1165,
965, 795 (7th absorption) Therefore, the insoluble matter was determined to be a VT polymer. Example 1 Mix 0.1 mol% HT (15.5 g) and 40 ml of water,
Aqueous K ₂ CO ₃ solution was added to bring the pH of the system to 10.0. Then, 13.0 g of insoluble matter in the system was collected by filtration. The insoluble matter collected by filtration showed an mp of 235-239°C. The insoluble matter
Recrystallized with 0.1wt% _Na2S aqueous solution and purified VT0.085
mol (11.6 g, yield 85 mol%). The mp of this product was 239-241°C. Example 2 0.1 mol % (19.2 g) of HT hydrochloride was dissolved in 40 ml of water, and an aqueous KOH solution was added to adjust the pH of the system to 9.6. Then, 12.33 g of insoluble matter in the system was collected by filtration, and the filtered insoluble matter showed an mp of 237 to 239°C. The insoluble matter was recrystallized from a 0.1 wt% Na ₂ S aqueous solution to obtain 0.085 mol (11.6 g, yield 85 mol %) of VT. of this
mp showed 239-241℃.

Claims (1)

[Claims] 1. Structural formula or structural formula [However, in the formula, H is a proton and A is a dissociation constant 6×
2-β-hydroxyethyl ^-4 , which represents the anion of an inorganic acid with a dissociation constant of 6×10 ⁻⁴ or more or the residue (carboxy group) of an organic acid with a dissociation constant of 6×10 −4 or more after removing the hydrogen atom. 6-
2-vinyl-4,6-diamino-s, which is characterized by mixing a diamino-s-triazine compound with an aqueous alkali solution at room temperature and adjusting the pH of the system to 9.5 or higher.
- Method for synthesizing triazine.