Information
-
Patent Grant
-
6300498
-
Patent Number
6,300,498
-
Date Filed
Friday, July 23, 199925 years ago
-
Date Issued
Tuesday, October 9, 200123 years ago
-
Inventors
-
Original Assignees
-
Examiners
Agents
-
CPC
-
US Classifications
Field of Search
US
- 149 36
- 544 185
- 544 196
- 544 336
- 544 358
- 544 410
- 548 251
-
International Classifications
- C07D40304
- C07D25706
- C06B2300
-
Abstract
The 1,5′-bitetrazole of the invention comprises 1,5′-bitetrazole, and ammonia or an amine. The 1,5′-bitetrazole of the invention decomposes sharply and generates a nontoxic gas.
Description
BACKGROUND OF THE INVENTION
The present invention relates to novel 1,5′-bitetrazole compounds and processes for their production.
The present invention also relates to gas generating agents containing the 1,5′-bitetazole compounds.
The present invention further relates to foaming agents for precision molding of resins, foaming agents for reducing weight of molded articles, smoking agents for effectively diffusing chemicals such as agricultural chemicals or insecticides, and air bag gas generating agents.
It is difficult td mold crystalline resins into the shape defined by a mold, since they crystallize and shrink upon cooling after molding. Conventionally, for precision molding of crystalline resins, apparent shrinkage is empirically inhibited by using specially devised molds, which, however, cannot accomplish complete precision molding. Accordingly, additional techniques for further reducing shrinkage of molded articles are employed, which include physical blowing of gas into the core portion of molded articles (Japanese Examined Patent Publications Nos. 41264/1973 and 14968/1982), and addition of chemical foaming agents (Japanese Unexamined Patent Publications Nos. 129563/1975, 12864/1978 and 61435/1981, and U.S. Pat. No. 4,871,861). In conventional techniques, azodicarbonamide (ADCA) has been used widely for a long period of time, mainly for foam molding of resins.
ADCA, although utilized widely as a gas generating agent, is not wholly satisfactory for use in precision molding or high-foam molding for weight reduction, because it has too broad a decomposition temperature range relative to the molding temperature and causes air bubbles on the surface of molded articles, which impair the appearance. Moreover, decomposition gases and residues of ADCA contain toxic substances such as ammonia, biurea or isocyanuric acid, and thus are harmful to humans and animals and the environment. Further, the decomposition residue contaminates molds, decreasing the molding efficiency and yield of molded articles.
To solve the above problems, use of tetrazoles as gas generating agents was proposed. Tetrazoles, which decompose completely, are free from the above problems. However, since high decomposability means low stability, tetrazoles are highly sensitive to friction or other physical factors, lacking handling safety.
Further, although air bag gas generating agents and smoking agents are required to be harmless to humans and animals, safe, and odorless, conventional air bag gas generating agents and smoking agents do not fully satisfy these requirements.
SUMMARY OF THE INVENTION
An object of the invention is to provide a novel 1,5′-bitetrazole compound which is highly sensitive only to temperature and which decomposes sharply, i.e., decomposes in a narrow temperature range, and generates a nontoxic gas.
Another object of the invention is to provide a gas generating agent which is highly sensitive only to temperature and which decomposes sharply and generates a nontoxic gas.
The present inventors did extensive research to achieve the above objects and directed their attention to 1,5′-bitetrazole which leaves substantially no residue upon decomposition. They found that ammonia or amine can be used to reduce the physical sensitivities of 1,5′-bitetrazole. The present invention has been accomplished based on this novel finding.
The present invention provides the following 1,5′-bitetrazole, processes for their production, and gas generating agents containing the.
1. A 1,5′-bitetrazole represented by the formula (1):
wherein Tz
31
represents
R
1
, R
2
and R
3
are the same or different and each represent a hydrogen atom; C
1-10
alkyl which may be substituted by amino, di(C
1-4
alkyl)amino, C
1-8
alkoxy, hydroxy or phenyl; C
3-20
alkenyl; phenyl; —C(═NH)NH
2
; —C(═NH)NHNH
2
; —C(═NH)NHCN; triazolyl; amino; carbamoyl; triazinyl which may be substituted by amino and methyl; —NHCS;
or —R
4
—NH
3
+
Tz
−
wherein Tz
−
is as defined above, R
4
represents a single bond, C
2-6
alkylene, phenylene, —CO— or
when R
1
is a hydrogen atom, R
2
and R
3
may be taken together with the nitrogen atom to which they are attached to form a 5- to 7-membered saturated heterocycle; when R
1
is a hydrogen atom, R
2
and R
3
may be taken together to form
and R
1
, R
2
and R
3
may be taken together to form
2. A process for producing a 1,5′-bitetrazole amine salt according to Item 1 comprising the step of reacting 1,5′-bitetrazole or its alkali salt with ammonia or an or its carbonate or halide, the amine being represented by the formula:
R
5
R
6
R
7
N (2)
wherein R
5
, R
6
and R
7
are the same or different and each represent a hydrogen atom; C
1-10
alkyl which may be substituted by amino, di(C
1-4
alkyl)amino, C
1-8
alkoxy, hydroxy or phenyl; C
3-20
alkenyl; phenyl; —C(═NH)NH
2
; —C(═NH)NHNH
2
; —C(═NH)NHCN; triazolyl; amino; carbamoyl; triazinyl which may be substituted by amino and methyl; —NHCS;
or —R
8
—NH
2
wherein R
8
represents a single bond, C
2-6
alkylene, phenylene, —CO— or
when R
5
is a hydrogen atom, R
6
and R
7
may be taken together with the nitrogen atom to which they are attached to form a 5- to 7-membered saturated heterocycle; when R
5
is a hydrogen atom, R
6
and R
7
may be taken together to form
and R
5
, R
6
and R
7
may be taken together to form
3. A gas generating agent containing a 1,5′-bitetrazole according to Item 1.
4. A foaming agent for molding resins, which contains a 1,5′-bitetrazole according to Item 1.
5. An air bag gas generating agent containing a 1,5′-bitetrazole according to Item 1.
6. A smoking agent for diffusing chemicals, which contains a 1,5′-bitetrazole according to Item 1.
The 1,5′-bitetrazole amine salt of the invention comprises 1,5′-bitetrazole, and ammonia or an amine.
Useful amines include monomethylamine, monoethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, t-butylamine, n-hexylamine, n-octylamine, 2-ethylhexylamine, oleylamine, allylamine, 3-dimethylaminopropylamine, 3-dibutylaminopropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 2-ethylhexyloxypropylamine, methyliminobispropylamine, cyclohexylamine, aniline, benzylamine, phenethylamine, dicyandiamide, guanidine, aminoguanidine, aminotriazole, monoethanolamine and like primary monoamines; ethylenediamine, hexamethylenediamine, phenylenediamine, xylenediamine, xylylenediamine, acetoguanamine, hydrazine, urea, carbohydazide, thiocarbohydrazide, N-acetyl-m-phenylenediamine, 2,4-diamino-6-methyl-symtriazine, 1,4-bis(3-aminopropyl)piperazine and like primary diamines; melamine and like primary triamines; dimethylamine, diethylamine, dicyclohexylamine, di-2-ethylhexylamine, diethanolamine, piperazine, piperidine, diphenylamine and like secondary monoamines or secondary diamines; and trimethylamine, triethylamine, N,N,N′,N′-tetramethylethylenediamine, hexamethylenetetramine, pyridine, N,N-dimethylaniline, N,N-dimethylcyclohexyl-amine, triethanolamine and like tertiary amines.
The process for producing the novel 1,5′-bitetrazole of the invention comprises the steps of dissolving 1,5′-bitetrazole or its alkali metal salt in water, an alcohol (preferably a C
1-3
alcohol) or dimethylformamide (DMF), and adding ammonia or the above amine or its carbonate or halide in an equivalent amount relative to the 1,5′-bitetrazole or its alkali metal salt, followed by stirring. When an alkali metal salt of 1,5′-bitetrazole and an amine halide are used, it is preferable to select such a combination that the alkali metal halide produced as a byproduct is soluble in water, alcohol or DMF, so that 1,5′-bitetrazole can be easily obtained by collecting crystals by filtration.
The reaction is carried out at preferably 0 to 100° C., more preferably 20 to 60° C., for a period of preferably 0.5 to 10 hours, more preferably 1 to 3 hours.
The 1,5′-bitetrazole is a novel substance which has low detonability and high stability against physical shocks, i.e., low sensitivity to impact or friction. Unlike ADCA, the 1,5′-bitetrazole is free from the problems of toxic decomposition gas or residue, since it decomposes completely and generates a nontoxic gas. Therefore, it is usable as an air bag gas generating agent or a smoking agent. Moreover, since the compound decomposes sharply, its use as a foaming agent, for example in injection molding, enables formation of a smooth skin layer which cannot be obtained by use of ADCA or like substance, and achieves precision molding free from sinkmarks or warpage.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1
shows the result of differential thermal analysis of 1,5′-bitetrazole guanidine salt as an embodiment of the invention.
FIG. 2
shows the infrared absorption spectrum of 1,5′-bitetrazole guanidine salt as an embodiment of the invention.
FIG. 3
shows the result of NMR analysis of 1.5′-bitetrazole guanidine salt as an embodiment of the invention.
BEST MODE FOR CARRYING OUT THE INVENTION
The following examples are intended to illustrate the present invention in further detail.
EXAMPLE 1
A 500-ml, four-necked flask equipped with a stirrer and thermometer was set in an oil bath and charged with 50 g (0.362 moles) of 1,5′-bitetrazole (molecular weight: 138.09), followed by addition of 300 ml of water. The mixture was heated to 40° C., and 15.6 g (0.181 moles) of piperazine (molecular weight: 86.14) was added with stirring. Simultaneously with addition of the piperazine, crystals formed and the reaction mixture became pale yellow. The reaction mixture was cooled to room temperature with stirring, and subjected to suction filtration using a No. 2 filter paper, whereby 1,5′-bitetrazole piperazine salt (molecular weight: 362.32) was obtained in a yield of 85%.
EXAMPLE 2
2 g of 1,5′-bitetrazole was measured out into a 50-ml beaker, and dissolved by addition of 50 ml of methanol. 0.87 g of saturated aqueous ammonia was added, followed by thorough stirring. The methanol was allowed to evaporate to collect crystals, which were then washed with acetone and analyzed.
EXAMPLE 3
2 g of 1,5′-bitetrazole was measured out into a 50-ml beaker, and dissolved by addition of 50 ml of methanol. 10 ml of water and 1.37 g of benzylamine were added in this order. Crystals formed were collected and washed in the same manner as in Example 2, dried and analyzed.
EXAMPLE 4
1,5′-bitetrazole were obtained using amines other than those used in Examples 1, 2 and 3 and following the procedure of Example 1, 2 or 3.
EXAMPLE 5
The 1,5′-bitetrazole obtained in Examples 1 to 4 were subjected to determination of melting point and decomposition temperature, elementary analysis, infrared absorption analysis, and NMR analysis. The results are shown in Tables 1 to 8.
In the column of “decomposition” in Tables 1 and 2, “sharp” indicates that the decomposition occurred in a narrow temperature range, while “broad” indicates that the decomposition occurred over a broad temperature range.
TABLE 1
|
|
Melting Point and Decomposition Temperature
|
Primary Amine Salt
|
De-
|
comp.
Boiling Point/
|
M.P.
Temp.
Sublimation Temp.
Decom-
|
Amine salt
(° C.)
(° C.)
(° C.)
position
|
|
1,5-BHT.H
2
O
—
148
sharp
|
Ammonium
—
185
sharp
|
Monomethylamine
159
170
sharp
|
Ethylamine
123
176
broad
|
n-Propylamine
—
206
sharp
|
Isopropylamine
—
218
258
broad
|
sec-Butylamine
168
197
broad
|
t-Butylamine
145
187
broad
|
n-Hexylamine
—
181
sharp
|
n-Octylamine
93
185
broad
|
2-Ethylhexylamine
85
185
broad
|
Oleylamine
91
188
broad
|
Allylamine
—
209
sharp
|
Cyclohexylamine
159
189
broad
|
Monoethanolamine
125
169
sharp
|
Aniline
132
206
broad
|
Benzylamine
135
185
broad
|
Phenethylamine
155
186
broad
|
Guanidine
187
189
sharp
|
Aminoguanidine
174
177
sharp
|
Dicyandiamide
—
201
sharp
|
3-Amino-1H-
—
167
sharp
|
1,2,4-triazole
|
Ethylenediamine
—
185
sharp
|
Hexamethylenediamine
141
172
sharp
|
m-Phenylenediamine
—
201
233
broad
|
m-Xylylenediamine
166
186
broad
|
Hydrazine
144
178
broad
|
1-Urea
131
149
217
broad
|
2-Urea
119
151
215
broad
|
Thiocarbohydrazide
141
194
sharp
|
Melamine 1/3
190
255
311
broad
|
Melamine 2/3
189
251
305
broad
|
Melamine 1/1
—
256
326
broad
|
|
Notes:
|
(1) In Tables 1 and 2, “—” indicates that no clear melting point was found by the determination.
|
(2) “1,5-BHT” indicates 1,5′-bitetrazole. The same applies hereinafter.
|
TABLE 2
|
|
Melting Point and Decomposition Temperature
|
Secondary and Tertiary Amine Salts
|
De-
|
comp.
Boiling Point/
|
M.P.
Temp.
Sublimation Temp.
Decom-
|
Amine salt
(° C.)
(° C.)
(° C.)
position
|
|
Dimethylamine
134
152
broad
|
Piperazine
—
205
sharp
|
Piperidine
—
183
broad
|
Diphenylamine
140
157
broad
|
Trimethylamine
—
204
sharp
|
Hexamethylene-
148
178
broad
|
tetramine
|
|
TABLE 3
|
|
Elementary Analysis
|
Primary Amine Salt
|
C
H
N
|
Cal-
Cal-
Cal-
|
Amine Salt
cd.
Found
cd.
Found
cd.
Found
|
|
1,5-BHT.H
2
O
15.39
15.42
2.58
2.52
71.78
71.25
|
t-Butylamine
34.12
35.57
6.20
6.24
59.68
58.63
|
n-Hexylamine
44.16
33.21
7.16
5.89
52.68
59.86
|
n-Octylamine
44.93
43.53
7.92
7.74
47.15
49.84
|
2-Ethylhexylamine
44.93
44.59
7.92
8.07
47.15
47.50
|
Oleylamine
59.23
58.88
9.69
10.12
31.08
30.64
|
Allylamine
30.77
29.53
4.65
4.59
64.58
63.66
|
Cyclohexylamine
40.50
40.81
6.37
6.48
53.13
52.39
|
Monoethanolamine
24.12
24.60
4.55
4.60
63.29
62.00
|
Aniline
41.56
41.80
3.92
4.01
54.52
54.29
|
Benzylamine
44.08
44.92
4.52
4.51
51.40
51.81
|
Phenethylamine
46.33
46.38
5.05
5.20
48.62
48.00
|
Guanidine
18.28
19.07
3.58
3.43
78.15
78.63
|
Arninoguanidine
16.98
16.75
3.80
4.11
79.22
79.77
|
Dicyandiamide
21.62
21.58
2.72
3.00
75.65
74.21
|
3-Amino-1H-
23.08
22.80
2.91
2.88
74.01
74.23
|
1,2,4-triazole
|
Ethylenediamine
21.43
20.90
3.60
4.05
74.96
75.02
|
Hexamethylene-
37.79
36.21
7.13
7.08
55.08
55.32
|
diamine
|
m-Phenylenediamine
39.02
38.68
4.09
3.81
56.88
57.01
|
m-Xylylenediamine
34.95
34.56
3.91
4.05
61.14
59.48
|
Hydrazine
15.59
15.39
2.62
2.43
81.80
82.56
|
1-Urea
18.19
17.85
3.05
2.93
70.69
70.76
|
2-Urea
18.61
18.78
3.90
3.87
65.10
66.17
|
Thiocarbohydrazide
15.71
15.38
2.64
3.09
73.27
71.68
|
Melamine 1/3
20.00
20.00
2.44
2.50
77.76
78.00
|
Melamine 2/3
20.90
20.17
2.51
2.60
76.60
75.80
|
Melamine 1/1
22.73
22.61
3.05
2.98
74.22
73.99
|
|
TABLE 4
|
|
Elementary Analysis
|
Secondary and Tertiary Amine Salts
|
C
H
N
|
Cal-
Cal-
Cal-
|
Amine Salt
cd.
Found
cd.
Found
cd.
Found
|
|
Dimethylamine
26.23
25.37
4.95
4.50
68.82
69.07
|
Piperazine
26.52
26.51
3.89
4.11
69.58
68.27
|
Piperidine
37.66
37.43
5.87
5.97
56.47
55.97
|
Diphenylamine
54.72
55.85
4.26
4.11
41.02
41.57
|
Trimethylamine
30.45
30.17
5.62
5.49
63.92
63.15
|
Hexamethylene-
34.53
34.14
5.07
5.11
54.83
59.01
|
tetramine
|
|
TABLE 5
|
|
Infrared Spectroscopic Analysis
|
Primary Amine Salt
|
Amine Salt
Characteristic Absorption (cm
−1
)
|
|
Ammonium
νNH2856.5
|
Monomethyl-
(N—CH3) νasCH 2879.5, νaCH 2758.0
|
amine
(N—CH3) δasCH 1461.9. δsCH 1380.0
|
(—NH3+) δasNH 1544.9. δsNH 1494.7
|
Ethylamine
(—CH3) νasCH 2999.1. (CH2) νasCH2 2912.3,
|
νsCH2 2912.3
|
(—CH3) δasCH 1463.9, δsCH 1377.5
|
(—NH3+) δasNH 1571.9, δsNH 1491.6
|
n-Propylamine
(—CH3) νasCH 2977.9, (CH2) νasCH2 2906.7,
|
νsCH2 2846.9
|
(—CH3) δasCH 1460.0, δsCH 1380.6
|
(—NH3+) δasNH 1606.6, δsNH 1514.4
|
Isopropylamine
(—CH3) νasCH 2977.9, (CH2) νasCH2 2906.7,
|
νsCH2 2846.9
|
(—CH3) δasCH 1460.0, δsCH 1380.6
|
(—NH3+) δasNH 1589.2, δsNH 1514.4
|
sec-Butylamine
(—CH3) νasCH 2977.9, (—CH3) δasCH 1460.0,
|
δsCH 1387.6
|
(—CH—(CH3) 2) skeleton 1187.6
|
(—NH3+) δasNH 1589.2, δsNH 1514.4
|
t-Butylamine
(—CH3) νasCH 2970.2. νsCH 2883.4
|
(—C—(CH3) 3) skeleton 1262.0, 1218.9, 964.1
|
n-Hexylamine
(—CH3) νasCH 3002.4, (GH2) νasCH2 2979.8,
|
νsCH2 2860.2
|
(—CH3) δasCH 1458.1, δsCH 1370.8,
|
—CH2—rocking 708.1
|
(—NH3+) δasNH 1610.0, δsNH 1513.2
|
n-Octylamine
(—CH3) νasCH 2954:5, νsCH2 2856.4,
|
(CH2) νasCH2 2918.1
|
νasCH2 2823.6, (—CH3) δasCH 1461.9, δsCH 1376.8
|
(—NH3+) δasNH 1604.7, δsNH 1500.5
|
2-Ethylhexyl-
(—CH3) νasCH2962.5, νsCH2 2871.8,
|
(CH2) νasCH2 2931.6
|
amine
νasCH2 2856.4, (—CH3) δasCH 1461.9, δsCH 1373.2
|
(—NH3+) δasNH 1618.4, δsNH 1508.2
|
Oleylamine
(—CH3) νasCH 2952. 2, (CH2) νasCH2 2918. l,
|
νsCH2 2850. 6
|
(CH3) δasCH 1463.9, δsCH 1372.1,
|
—CH2—C═C—1435.4
|
(—NH3+) δasNH 1606.6, δsNH 1506.3
|
Allylamine
(—C═CH) νCH 3023.9, (CH2) νasCH2 2919.8,
|
νsCH2 2837.3
|
(—C═C—) νC═C 16.07.7, δ in plane
|
CH 1441.4, δ out of plane CH 863.6
|
Cyclohexyl-
(CH2) νasCH2 2935.5, νsCH2 2862.2
|
amine
(—CH2) δCH scissors 1454.2
|
(—NH3+) δasNH 1591.2, δsNH 1488.0
|
Monoethanol-
(CH2) νasCH2 2933.5, νsCH2 2879.5
|
amine
(—CH2) δCH, scissors 1479.3
|
(—NH3+) δasNH 156.4, δsNH 1502.4
|
Aniline
νCH 3047.8˜2574.8, δ out of plane
|
CH 1967.7, 1831.3, 1751.0 1647.1
|
(—NH3+) δasNH 1596.8, δsNH 1498.6
|
Benzylamine
(—CH2—) δ scissors CH 1456.2
|
(—NH3+) δasNH 1575.0, δsNH 1495.2
|
(—CH2—) νasCH 2929.7, νout of plane
|
CH 1955.7, 18380.4, 1750.0
|
Phenethyl-
(—CH2—) δ scissors CH 1460.0
|
amine
(—NH3+) δasNH 1583.7, δsNH 1496.7
|
Guanidine
νNH 3435.0˜3361.7
|
νC═N 1654.8
|
Aminoguanidine
νNH 3448.5˜3260.7
|
νC═N 1674.1, (—NH3+) δasNH 1544.9,
|
δsNH 1453.3
|
Dicyandiamide
νNH 3438.8—3260.7, νC═N 2193.8, 2167.5
|
νC═N 1689.5, 1641.3
|
3-Amino-1H-
νNH 3369.4˜3265.3, νC═N 1679.9, 1647.1
|
1,2,4-triazole
(—NH3+) δasNH 1556.4, δsNH 1505.9
|
Ethylenediamine
νNH 3456.2˜3074.3.(—NH3+) δasNH 1624.4
|
(—NH2—) νasCH 2943.4, νsCH 2883.4,
|
scissors CH 1455.7
|
Hexamethylene-
νNH 3433.0˜3026.3, (—NH3+) δasNH
|
1556.4, δsNH 15U5.9
|
diamine
(—CH2—) νasCH 2935.4, νsCH 2868.0,
|
δ scissors CH 1463.9
|
m-Phenylene-
νNH 3476.1˜3080.1, (—NH3+) δasNH
|
diamine
1596.8.δsNH 1498.6
|
νCH 3047.8˜2574.8, δ out of plane
|
CH 1967.7, 1831.3, 1751.0, 1647.1
|
m-Xylylene-
νCH 3448.5˜3023.9, (—NH3+) δasNH
|
diamine
1595.7, δsNH 1504.4
|
(overlapped with Ph nucleus) δCH out of plane 1649.0
|
(—CH2—) νasCH 2918.9, νCH 2894.7,
|
δ scissors CH 1479.3
|
Hydrazine
νNH 3325.0˜3055.0
|
(—NH3+) δasNH 1610.5, δsNH 1519.8
|
Urea
νNH 3419.6˜3095.5, (—NH3+) δasNH
|
1593.1, δsNH 1505.9
|
νC═O non—association 1697.2,
|
νC═O association 1652.9
|
Thiocarbo-
νNH 3211.3, (—N3+) δasNH 1527.5,
|
δsNH 15U5.9
|
hydrazide
νC═O non—association 1625.9
|
δC═S 1527.5, 1279.9, 1120.6, 931.6, 767.9
|
Melamine 1/3
νNH 3461.7˜3328.9, (—NH2)
|
δ in-plane scissors NH 1668.3, 1552.6
|
(—NH3+) δasNH 1614.3, δsNH 1504.4
|
(—NH2) δ out-of-plane scissors NH 1094.5, 812.2
|
Melamine 2/3
νNH 3461.7˜3334.7, (—NH2) δ in-plane
|
scissors NH 1670.2, 1554.5
|
(—NH3+) δasNH 1612.4, δsNH 1506.3 (—NH2)
|
δ out-of-plane scissors NH
|
1095.5, 812.2
|
Melamine 1/3
νNH 3469.7˜3332.8, (—NH2) δ in-plane
|
scissors NH 1664.5, 1552.6
|
(—NH3+) δasNH 1614.3, δsNH 1500.0
|
(—NH2) δ out-of-plane scissors NH 1022.7, 813.9
|
|
TABLE 6
|
|
Infrared Spectroscopic Analysis
|
Secondary and Tertiary Amine Salts
|
Amine Salt
Characteristic absorption (cm
−1
)
|
|
Dimethylamine
(—CH3) νasCH 2976.0, νsCH 2759.9, δasCH 1460.0,
|
δsCH 1382.8
|
νCH 3406.7˜3026.1, (—NH3+) δasNH 1544.9,
|
δsNH 1494.7
|
Piperazine
(—CH2) νasCH2 2950.9, νsCH2 2862.2,
|
δsNH scissors 1460.0
|
NH 3236.8, 2758.0, δNH1608.9
|
Piperidine
(—CH2) νasCH2 2950.9, νsCH2 2862.2,
|
δCH scissors 1428.2
|
νNH 2753.6, 2526.3, 1607.7
|
Diphenylamine
νNH 3419.6, (—NH3+) δasNH
|
1610.5, δsNH 1519.R
|
νCH 3091.7, δ out of plane
|
CH 1697.2, 1652.9, Ph nucleus 1593.1
|
Trimethylamine
(—CH2) νasCH 3004.9, νsCH2 2756.1,
|
δasNH 1460.0,
|
δsCH 1384.0
|
νNH 3398.3˜3246.8, (—NH+)
|
δasNH 1544.9, δsNH 1494.7
|
Hexamethylene-
νC—N 1238.1, δCH2 rocking 1008.7, 817.8, 657.7
|
tetramine
|
|
TABLE 7
|
|
NMR Analysis
|
Primary Amine Salt
|
Amine Salt
(ppm)
Solvent
|
|
Ammonium
δ9.95 (s, 1H)
D
2
O
|
Monomethylamine
δ9.7 (s, 1H), δ2.75 (S, 3H)
D
2
O
|
Ethylamine
δ9.7 (s, 1H), δ3.35-2.95 (q, 2H),
D
2
O
|
δ1.5-1.25 (t, 3H)
|
n-Propylamine
δ9.0 (s, 1H) δ2.5-2.1 (t, 2H)
D
2
O
|
δ1.4-0.8 (2H), δ0.6-0.3(t, 3H)
|
Isopropylamine
δ9.1 (s, 1H), δ1.0 (d, 6H).6 3.5-3.0 (1H)
D
2
O
|
n-Butylamine
δ9.9 (s, 1H), δ3.3 (9H)
DMSO
|
sec-Butylamine
δ9.9 (s, 1H), δ1.5(t, 2H), δ1.1(d, 6H),
DMSO
|
δ3.3 (1H)
|
t-Butylamine
δ9.7 (s, 1H), δ1.4 (s, 9H)
D
2
O
|
n-Hexylamine
δ9.9(s, 1H), δ1.5 (13H)
DMSO
|
n-Octylamine
δ9.7 (s, 1H), δ2.0-2.1 (n, 14H),
D
2
O
|
δ0.8 (s, 3H)
|
2-Ethylhexyl-
δ9.7 (s, 1H), δ2.9-3.1 (d, 2H)
D
2
O
|
amine
δ1.5-1.0 (m, 6H), δ0.8-1.0(m, 6H)
|
Oleylamine
δ9.7 (s, 1H), δ5.2 (s, 2H), 1.0 (s, 28H).
DMSO
|
δ0.7 (s, 3H)
|
Allylamine
δ9.9 (s, 1H), δ5.3 (t, 2H), δ5.8(1H),
DMSO
|
δ3.4 (d, 2H)
|
Cyclohexylamine
δ9.7 (s, 1H), δ3.4-3.0 (1H),
D
2
O
|
δ2.2-1.0 (10H)
|
Monoethanol-
δ9.0 (s, 1H), δ3.3-3.0 (t, 2H),
D
2
O
|
amine
δ2.7-2.4 (t, 12H)
|
Aniline
δ9.2 (s, 1H), δ6.9 (s, 5H)
D
2
O
|
Benzylamine
δ9.9 (s, 1H), δ7.4 (ph, 5H), δ4.1 (s, 2H)
DMSO
|
Phenethylamine
δ9.65 (s, 1H), δ7.25 (s, 5H),
D
2
O
|
δ3.5-2.8 (dd, 4H)
|
Guanidine
δ9.9 (s, 1H), δ6.9 (s, 1H),
D
2
O
|
δ3.35 (s, 2H)
|
Aminoguanidine
Hydrogen in amine cannot be
DMSO
|
independently determined
|
Dicyandiamide
δ9.9 (s, 1H)
DMSO
|
3-Amino-1H-
δ8.1 (s, 1H)
D
2
O
|
1,2,4-triazole
|
Ethylenediamine
δ9.7 (s, 2H), δ3.6 (s, 4H)
D
2
O
|
Hexamethylene-
δ9.7 (s, 2H), δ3.3-2.8 (4H),
D
2
O
|
diamine
δ2.1-1.3 (4H)
|
m-Phenylene-
δ9.7 (s, 2H), δ7.6-7.2 (4H)
D
2
O
|
diamine
|
m-Xylylenediamine
δ9.9 (s, 2H), δ7.5 (ph, 4H), δ4.1 (s, 4H)
DMSO
|
Hydrazine
δ9.7 (s, 2H),
D
2
O
|
1-Urea
δ10.1 (s, 1H), δ7.5 (s, 5H)
DMSO
|
2-Urea
δ10.2 (s, 1H), δ8.2 (s, 6H)
DMSO
|
Thiocarbohydrazide
δ9.8 (s, 2H)
D
2
O
|
Melamine 1/3
δ9.8 (s, 3H), δ6.5 (s, 10H)
DMSO
|
Melamine 2/3
δ7.3 (s, 2H), δ4.6 (s, 8H)
DMSO
|
Melamine 1/1
δ8.0 (s, 1H), δ3.4 (s, 4H)
DMSO
|
|
TABLE 8
|
|
NMR Analysis
|
Secondary and Tertiary Amine Salts
|
Amine Salt
(ppm)
Solvent
|
|
Dimethylamine
δ9.7 (S, 1H), δ2.4 (s, 6H)
D
2
O
|
Piperazine
δ9.7 (s, 1H), δ3.85 (s, 8H)
D
2
O
|
Piperidine
δ9.7 (s, 1H), δ3.4-3.0 (t, 4H),
D
2
O
|
δ2.0-1.6 (s, 6H)
|
Diphenylamine
δ10.0 (s, 1H), δ7.2 (t, 4H)
DMSO
|
δ7.1 (d, 4H), δ6.8 (t, 2H)
|
Trimethylamine
δ9.9 (s, 1H), δ2.8 (s, 9H)
DMSO
|
Hexamethylene-
δ9.7 (s, 1H), δ4.7 (s, 12H)
D
2
O
|
tetramine
|
|
The above results reveal that the 1,5′-bitetrazole of the invention is a novel substance.
EXAMPLE 6
The crystals of 1,5′-bitetrazole piperazine salt obtained in Example 1 were finely ground in a mortar, added to a low-density polyethylene (melting point: 90° C.) in a proportion of 5 wt. % relative to the polyethylene, and extrusion-molded using an extruder at a resin temperature of 140° C., giving master chips having a diameter of about 3 mm and a length of about 3 mm.
EXAMPLE 7
The crystals of 1,5′-bitetrazole guanidine salt obtained in Example 4 were finely ground in a mortar, added to an acrylonitrile-styrene resin (AS resin; Vicat softening point: 104° C.) in a proportion of 5 wt. % relative to the resin, and extrusion-molded using an extruder at a resin temperature of 140° C., giving master chips having a diameter of about 3 mm and a length of about 3 mm.
EXAMPLE 8
The master chips obtained in Example 6 were added to a polypropylene resin to be molded, in a proportion of 2 wt. % relative to the resin, and injection-molded at 220° C. using a test mold measuring 3 mm thick, 100 mm wide and 100 mm long and having ribs with three different widths of 4 mm, 5 mm and 6 mm. The obtained molded article was compared with a blank molded article containing no foaming agent. The blank article had sinkmarks on the surface opposite to the ribbed surface and was commercially unacceptable, whereas the molded article containing the foaming agent of the present invention was completely free from sinkmarks.
EXAMPLE 9
The master chips obtained in Example 7 were added to a polyacetal resin to be molded, in a proportion of 2 wt. % relative to the resin, and injection-molded at 210° C. using a test mold measuring 3 mm thick, 100 mm wide and 100 mm long and having ribs with three different widths of 4 mm, 5 mm and 6 mm. The obtained molded article was compared with a blank molded article containing no foaming agent. The blank article had sinkmarks on the surface opposite to the ribbed surface and was commercially unacceptable, whereas the molded article containing the foaming agent of the present invention was completely free from sinkmarks and had a smooth skin layer.
COMPARATIVE EXAMPLE 1
Master chips were prepared in the same manner as in Example 6 except for using 20 wt. % of ADCA in place of the crystals of 1,5′-bitetrazole piperazine salt, and added to a polypropylene resin to be molded, in a proportion of 2 wt. % relative to the resin. The mixture was injection-molded at 220° C. using a test mold measuring 3 mm thick, 100 mm wide and 100 mm long and having ribs with three different widths of 4 mm, 5 mm and 6 mm. The obtained molded article was compared with a blank molded article containing no foaming agent and with the molded article of Example 8. The molded article obtained in this comparative example was satisfactorily foamed but had so-called “silver blisters”, i.e., air bubbles on the surface. Also, the mold was severely contaminated when repeated test molding was carried out.
COMPARATIVE EXAMPLE 2
Master chips were prepared in the same manner as in Example 7 except for using 20 wt. % of ADCA in place of the crystals of 1,5′-bitetrazole guanidine salt, and added to a polyacetal resin to be molded, in a proportion of 2 wt. % relative to the resin. The mixture was injection-molded in the same manner as in Comparative Example 1. The obtained molded article was compared with a blank molded article and with the molded article of Example 9. The molded article obtained in this comparative example was satisfactorily foamed but had so-called “silver blisters”, i.e., air bubbles on the surface, and did not have clearly defined edges. Also, the mold was severely contaminated when repeated test molding was carried out.
Claims
- 1. A substituted ammonium salt of 1,5′-bitetrazole represented by formula (1): wherein Tz− represents R1, R2, and R3 are the same or different and each represent a hydrogen atom; C1-10 alkyl which may be substituted by amino, di(C1-4 alkyl) amino, C1-8 alkoxy, hydroxy or phenyl; C3-20 alkenyl; phenyl; —C(═NH)NH2; —C(═NH)NHNH2; —C(═NH)NHCN; triazolyl; amino; carbamoyl; triazinyl which may be substituted by amino and methyl; —NHCS; or —R4—NH3+ Tz− wherein Tz− is as defined above, R4 represents a single bond, C2-6 alkylene, phenylene, —CO— or when R1 is a hydrogen atom, R2 and R3 may be taken together with the nitrogen atom to which they are attached to form a 5— to 7—membered saturated heterocycle; when R1 is a hydrogen atom, R2 and R3 may be taken together to form and R1, R2 and R3 may be taken together to form
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Number |
Name |
Date |
Kind |
5439251 |
Onishi et al. |
Aug 1995 |
|
5682014 |
Highsmith et al. |
Oct 1997 |
|
5872329 |
Burns et al. |
Feb 1999 |
|
Foreign Referenced Citations (1)
Number |
Date |
Country |
10-298168 |
Nov 1998 |
JP |