INDUSTRIAL AlVD ENGINEERING CHEMISTRY
316
Vol. 18, No. 3
Organic Rubber Accelerators’ By F r a n c i s B. Leech2 n’ASHIh’GTON
LOANAXD T R U S T BUILDING,WASHINGTON. D.
T
HE widespread interest in the use of rubber products
is manifest. Each year thousands of pounds of the various crude rubbers are utilized in the United States for the manufacture of the divers articles formed therefrom. The automobile industry is probably the largest user of rubber, for each year millions of automobile tires and inner tubes are manufactured. With the tremendous demands for greater production and higher quality in all rubber articles, the step of vulcanization of such articles has been a most important factor. Until a comparatively few years ago, the major portion of manufactured rubber was vulcanized with various inorganic compounds. These compounds were added to shorten the period of time of vulcanization and t o improve the quality of the rubber. At the present time practically all manufactured rubber
-
153,447 226,058 1,081,613 1,081,614
Meyer Gerner Hofmann, ef al. Hofmann, cf ai.
DATE 4/25/74 3/30/80 2/13/13 2/13/13
1,098,609
Aylsworth
6/2/14
1,126,469 1,130,903
Hofmann, et al. Hofmann, et al.
1/26/15 3/9/15
1,149,580 1,157,177 1,182,501 1,184,015 1,229,724 1,242,586 1,242,886 1,249,180 1,249,181 1,249,272 1,271,810
Hofmann, et 01. Peachey Murril Price De Meens Ostromislensky Meyer Ostromislensky Ostromislensky Bow Twiss
8/10/15 10/19/15 5/9/16 5/23/16 6/12/17 10/19/17 10/9/17 12/4/17 12/4/17 12/4/17 7/9/18
1,280,940 1,291,828 1,296,469 1,312,144 1,320,166 1,342,457 1,342,458 1,343,224 1,356,495 1,364,055 1,364,732 1,371,663
Andrews Gibbons Boas Thatcher Ostromislensky Ostromislensky Ostromislensky Malony Scott Boas de Long, el al. Bedford
10/9/18 1/21/19 3/4/19 8/5/19 10/28/19 6/8/20 6/8/20 6/15/20 10/19/20 12/28/20 1/4/21 6/6/22
1,371,664 1,371,665 1,386,153 1,406,717 1,406,718 1,406,7 19 1.41 1,231 1,413,172 1,413,557 1,413,813 1,417,970 1,418,166 1,418,771
Bedford Bedford Bruni Bedford, et al. Bedford, et al. Bedford, et al. Weiss Lorentz Phillips Twiss Caldwell Porrit Bedford
6/6/22 6/6/22 8/2/21 2/14/22 2/14/22 2/14/22 3/28/22 4/18/22 4/18/22 4/25/22 5/30/22 5/30/22 6/6/22
1,418,772
Bedford
6/6/22
1.418,824
Naylor
6/6/22
1,418,825
Naylor
6/6/22
No.
1 2
INVENTOR
Received January 2, 1925. Patent lawyer.
SUBSTANCE USED Paraffin Camphor 6, ?-Dimethylbutadiene Polymerization product of 8 , ydimethylerythrene Halogen derivative of naphthalene Methylene base Piperidine of 8, y-dimethylerythrene Hexamethylenetetramine $-Nitrosodimethylaniline Bone oil Thiocarbanilide Base of aromatic series Halide compounds of rubber Aniline Organic nitro compounds Peroxy compounds Selenium and A-naphthylamine Alkali dissolved in polyhedric alcohol Aminocymene Nitro derivative of anthracene &Naphthylamine Dinitrobenzene Organic dye of nitro group Benzoyl peroxide Nitro benzene Amine bases 0-Tolylthiourea Amines of aromatic aeries Dichloroaniline Nitroso derivative of an aromatic amine Methyleneaniline Hexamethylenetetramine Dithiocarbamic acid $-Nitrosodimethylaniline Thiourea derivatives Substituted thioureas Disubstituted guanidine Tetramethylthiuram disulfide Phenanthrene Alkali metal in phenol Acetaldehyde and aniline Anhydrous sodium phenate Hydrogen sulfide and a nitros0 body Methylene group containing Schiff base Condensation product of fitoluidine and formaldehyde Phenylhydrazine
c.
goods are vulcanized by the addition to the mix of some organic compound. These organic compounds materially decrease the time of vulcanization and give the finished rubber better wearing and aging qualities. Such organic compounds are commonly styled “accelerators” because their presence in the mix hastens or accelerates the vulcanization. Many organic compounds have been utilized for this purpose, as will be apprised from a glance a t the appended list of issued United States patents. This list identifies the various organic substances which have been patented in the United States from their adoption t o November, 1925, for acceleration of vulcanization. It is arranged numerically and chronologically, with the name of the inventor and the organic compound utilized. No. 1,433,093 1,434,909 1,436,894 1,440,176 1,440,961 1,440,962
INv EN ToR Ostromislensky Morton Murril Ricard Caldwell Caldwell
1,440,963
Caldwell
1/2/23
1,440,964 1,444,865
Caldwell Bradley
1/2/23 2/13/23
1,445,621
Caldwell
2/20/23
1.449,493 1,463,794 1,465,743
Caldwell Caldwell Stevens
3/27/23 8/7/23 8/21/23
1,467,197 1,467,984
Russell North
9/4/23 9/11/23
1,473,285
Fisher
11/6/23
1,481,482 1,490,073
Peachy Shepard, el al.
1/22/24 4/8/24
1,496,792
Trumbull
6/10/24
1,503,113
Caldwell
7/29/24
1,503,429 1,503,430 1,507,594
Russell Russell Geer
7/29/24 7/29/24 9/9/24
1,510,652
Caldwell
10/7/24
1,513,122
Nikaido
10/28/24
1,514,571 1,521,720 1,521,739
Sebrell Skellon Weiss
11/4/24 1/6/25 1/6/25
1,522,712 1,526,300
Caldwell Sebrell
1/13/25 2/10/25
1,532,225
Caldwell
4/7/25
1,532,226
Caldwell
4/7/25
1,532,227 1,532,651
Caldwell Brown
4/7/25 4/7/25
8
DATE 10/24/22 11/7/22 11/28/22 12/6/22 1/2/23 1/2/23
SUBSTANCE USED Ozonide of rubber Tertiary amylamine Secondary amines Furfural Zinc ethylxanthogenate Nonnitrogenous carbon o x p u l fide derivative A n amine and a metallic xanthogenate Thiocarbamic acid anhydride Formaldehyde condensation product of an aliphatic amine A thiuram disulfide containing substitute alkyl and aryl groups Dipiperidyl thiuram disulfide Dibenzylamine Diphenylguanidine and tetraphenylmelamine Monobasic fatty acid Condensation product of an aldehyde and an aniline homolog Reaction product of an aliphatic amine and an aliphatic ketone $-Nitroso dimethylaniline Reaction product of carbon disulfide with aniline Condensation product of a l d d with diphenylguanidine Reaction product of ammonia and heptaldehyde Urea Nontoxic urea compound Butylidene p-aminodimethylaniline Thiobenzoic anhydride and an amine Metallic salt of dithiocarbamic acid m-Xylylthiourea Penta-amino zinc Aromatic disubstituted guanidine dibenzyldithiocarbamate Cyclic metallic dithiocarbamate 2-6-Dimercapto, 3.5-diphenyl, 4-oxypentathophene Dibenzylamine and butylthiocarbonic acid disulfide T h i o b e n z o y l disulfideand #toluidine Zinc dithiobenzoate $-Butyl aldehyde
Geer and Bedford, THISJOURNAL, 17, 393 (1925).
INDUSTRISL, A N D ENGINEERING CHEAWISTRY
March, 1926 No.
IWENTOR
1,535,963 1,538,076
Tanner Young
DATE 4 /28/25 5 ’19/25
1,544,687 1,544,688
Sebrell, el 02. Sebrell, et nl.
7/7/25 7/7/25
1,546,713 1,546,876
Bruni Weijs
7/21/25 7 ’21/25
SUBSTANCE US~D Halogenated alkylamine Unsymmetrical ditolyl substituted guanidine Benzothiazole disulfide Lead salt of mercaptobenzothiazole 1-Anilinobenzothiazole Reaction product of diphenylguanidine and dimethyldithiocarbamic acid
317 DATE
NO. 1,546,877
INVENTOR Weiss
7/21/2.5
1,547,554 1,547,553
Bogemann, et al. Bogemann. el al.
7/28/25 7/28/25
1,558,707 Nolony 1,559,196 Stevens 1,559,197 Stevens 1,559,198 Stevens 1,559,393 Whittelsey
10/27/25 10/27/25 10/27/25 10/27/25 10/2;/23
SCBSTANCE USED Disubstituted guanidine and 1mercaptobenzothiazole Dipiperidyl base Di-mer hydrogenated quinoline compounds Tetramethylthiuram disulfide Tetratolytricarbodiimide Tetraxylitricarbodiimide Tetraphenyltricarbodiimide Phenylimidothiosulfurous acid
Chemists’ Club Honors William Henry Nichols HE annual dinner of the Chemists’ Club was held on Wednesday evening, January 27, 1926, and was in honor of William Henry hTichols. This is the first time that one of these annual affairs has had for its main object the honoring of a man who has attained success in the chemical profession. Marston T.Bogert acted as toastmaster. Frank Bailey, chairman of the board of directors of the Prudence Company, Brooklyn, N. Y., an intimate friend of long standing spoke of Dr. Nichols, particularly as a sentimentalist, as a lover of youth, and as a man of great belief and confidence in the future. He pointed out that Dr. Nichols’ gifts are not found listed among those great institutions which are attended by the sons of the wealthy, but rather among those schools 90 per cent of whose attendance is made up of boys who could not pay their expenses to our great institutions. Dr. Nichols not only gives of his money, but follows i t up with his personal attention and devotion to the enterprises in which he is interested. Mr. Bailey attributed much of Dr. Nichols’ success to his being a believer in young men. In his associations with him for many years in the Title Guaranty & Trust Company, Mr. Bailey said: “I never suggested a man for the board from Brooklyn who had not been in his Sunday School class. He believed in that Sunday School class, and there was no man in that Sunday
School class who, in the Doctor’s judgment, was not worthy of being the President of the United States.” Dr. Nichols responded, for the most part, in a facetious vein, %ut before closing his remarks referred to the first meeting of the AMERICANCHEMICALSOCIETY which was attended by thirty-five, of whom he and Dr. Niese are the sole survivors. He said that the chemist has “a great advantage over men of very many other professions. He has a profession to which there is no end,” and “in future the chemist is going to be called upon more and more. The very life of the world and the happenings of the world depend tremendously upon what the chemists do as chemists, but if they want to use their efforts to produce the greatest results they will not only follow out the idea of improving and extending their knowledge as much as they can as they go along, but they will fit themselves so that by their ordinary intelligence, by their citizenship, by their association with their fellowmen, they will not only be shown to be chemists and to know chemistry but to be men who know men and know how to help men.” James F. Norris, president of the AMERICAN CHEMICAL SOCIETY and professor of organic chemistry at Massachusetts Institute of Technology, made the principal address of the evening, which follows.
..............
William H. Nichols By James F. Norris
I
T WAS a happy idea of the past presidents of this club
to give the members an opportunity each year to get together to do honor to the men of achievement in our science. To be selected as the first to be so honored is a distinction in itself. I accepted with keen pleasure an invitation to speak, because I thought highly of the plan, and because I was eager t o do my part in recognizing the work of Dr. Nichols. When I came to think over how the opportunity was to be met, the conclusion was forced upon me that I was not so well qualified to evaluate the services of our honored guest as others who have devoted their energies in the field of applied science. The most distinguished critics of the fine arts have not themselves been experts with the tools of these arts; too close an acquaintance with the details of technic may lead to a point of view so restricted that the broader aspects are not appreciated. It is possible, therefore, that one who has centered his attention largely on pure science may be able to see the significance of the achievements of a man whose place in the scientific world has been won by his ability to apply the results of research to the advancement of civilization. And, further, it takes no knowledge of technical details to recognize true character, high ideals, the spirit of the fellowship of man in world progress, and sane judgment in meeting perplexing prob-
lems.
I want to tell you something of Dr. Nichols’ contributions to the industrial development of America, and I am again in a difficult position. Our inbred sense of propriety makes us feel that we should not praise a man to his face. It is only in the realm of what is called love that one feels free to heap up encomiums: and love is, as you know, a kind of madness-but of a delightful variety. I know all of you will pardon me if I throw away propriety and speak my true convictions, and I hope also that Dr. Nichols will take a more or less detached point of view during the recital of the story of a great individual and at the end perhaps decide whether the hero of the tale utilized to the best the ability given him and the opportunities presented. Many of the things I shall mention are known to you, but i t is good, once in a while, to tell over an inspiring tale. The story opens with a young man eighteen years of age who has just won the degree of bachelor of science a t New York University. He had previously prepared for college a t the Brooklyn Polytechnic Institute, and as a young lad had thought out plans for his life work. After weighing the opportunities in different fields and examining these in the light of his own capabilities, he decided to take up the study of chemistry. He had found in the chemical business that there were few who had been carefully educated for it through exact scientific
