Substituted ammonium salt of 1,5′-bitetrazole

Information

  • Patent Grant
  • 6300498
  • Patent Number
    6,300,498
  • Date Filed
    Friday, July 23, 1999
    25 years ago
  • Date Issued
    Tuesday, October 9, 2001
    23 years ago
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
US Referenced Citations (3)
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