ISDCSTRI,4 L A S D ENGINEERISG CHEMISTRY
March, 1925
both are soluble in the solvent used. Several samples of commercial fusible resins were analyzed, and showed a variation in phenolic content from 8.74 to 13.35 per cent. .4sample of fusible resin was tested for free phenol, and several closely agreeing results gave the average figure of 9.33 per cent. Then 0.0735 gram of phenol was put in a tube with 1.0212 grams of this resin, the tube sealed, and solution effected by heat and agitation. This gave a resin with a phenolic content calculated as 15.59 per cent. This mixture was analyzed and the value 15.69 per cent obtained. In the same manner, to a resin with a phenolic content of 2.42 per cent was added phenol to a total of 10.95 per cent. The phenolic content was then determined as 10.48 per cent. Resinoids from Various C o m p o u n d s
The compounds given in the following table were heated with hexamethylenetetramine in the proportion of 1 mol of resin or crystals to one equivalent of CH2 group-that is, 23.3 grams of hexa. In all cases products of true phenol-resinoid characteristic were obtained. The following table shows the source and physical structure of various compounds which hardened to infusible, insoluble resinoids when heated with methylene-furnishing compounds in the proportions of 1 mol of the compound to 1 mol of available CH, group: FORM
COMPOUND
SOURCE
9-Dihydroxydiphenyldimethylmethane Phenoxy-p-hydroxyphenyldimethylmethane 9-Dihydroxydiphenylbutane Phenoxy-9-hydroxyphenylbutane P-Dihydroxytetraphenylmethane
Crystals
Acetone and phenol
Resin Crystals Resin Crystals
Phenoxy-p-hydroxytriphenylmethane
Acetone and phenol N-butaldehyde and phenol .N-butaldehyde and phenol Benzophenonedichloride and phenol
Resin
9-Dihydroxytriphenylmethane
Crystals
Benzophenone d i c h l o r i d e and phenol Benzal chloride and phenol, also benzaldehyde and phenol
Phenoxy-p-hydroxydiphenyl. methane
Resin
0-Dihydroxydiphenylmethane Crystals Phenoxy-p-hydroxyphenylmethane Resin P - Dihydroxydiphenylethane Crystals Phenoxy-9-hydroxyphenylethane Resin
Benzal chloride and phenol, also benzaldehyde and phenol Formaldehyde and phenol Formaldehyde and phenol Acetaldehyde and phenol Acetaldehyde and phenol, also acetylene and phenol
Summary
1-Further evidence has been advanced to indicate the order of reaction in the first stages of the infusible condensation products of phenol and aldehydes designated as phenol resinoids and also known as Bakelite, Resinit, Sipilite, Redmanol, Amberite, Formit, Condensite, Phenoform, Nuloid, Amberdeen, etc., etc. (a) Condensation takes place between the hydroxyl hydrogen of the phenol and the oxygen of the aldehyde or ketone. ( b ) The resulting phenoxy group rearranges to a para-hydroxy compound. ( c ) Condensation takes place between the resulting alcohol and the hydroxyl hydrogen of another phenol molecule. ( d ) This mixed phenoxyphenol compound sometimes rearranges to a diphenol. (e) The rearrangement in ( d ) is immaterial to the success or failure of the resinoid reaction.
2-Further details as to the composition of Novolak resins and phenol resinoids made from various aldehydes have been given. 3-Novolak resins have been made from new starting materials, as from carbon tetrachloride, benzene, and phenol, and from benzal chloride and phenol. 4-Resinoids have been made from these new Xovolak resins by causing them to react with substances containing methylene groups. &Evidence has been advanced to show the importance of the phenoxyphenol rearrangement in the phenol resinoid series.
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6-A theory as to the constitution of the final product of the resinoid reaction has been announced. Bibliography 1-Baekeland, J . Ind. Eng. Chcm., 6, 506 (1913). 2-Manasse, U. S. Patent 526,786 (1894). 3-De Laire, French Patent 350,180 (1905). 4-Aylsworth, U. S. Patent 1,020,593 (1912). 5-Baekeland, U. S. Patent 939,966 (1909). 6-Baeyer, Ber., 6, 25, 280, 1094, 1095 (1872). 7--Kleeberg, A n n . , 263, 283 (1891). 8-Baekeland, J. I n d . Eng. Chem., 4, 737 (1912). 9-Moitessier, Jahresber., 676 (1886). l&Schotten, B e y . , 11, 784 (1878). 11-Piria, A n n . , 48, 7 5 (1843); 66, 37 (1845); 81, 245 (1852); 96, 357 (1855). 12-Ellis, “Synthetic Resins.” p. 99. 13-Baekeland, J. I n d . Eng. Chcm., 6, 507 (1913). 14-De Laire, D . R. P., 189, 262 (1905). 15--Blumer, British Patent 12,880 (1902). l+Baekeland, J. I n d . Eng. Chcm., 1, 545 (1909). 17-Raschig, Z . angcw. Chcm., 26,1945 (1912). 18-Baekeland, J . I n d . Eng, Chem., 1, 149 (1909). Ig-Ibid., 6, 508 (1913). gO-Beatty, French Patent 447,648 (1912). al-Dianin, J . Russ. Phys.-Chem. Ges., 1,488,523,601 (1891). 22-Wohl and Mylo, Ber., 46, 2046 (1912). 23-Glenz, Heleefica C h i n . Acta, 6 , 826 (1923). 24--Baekeland, J . I n d . Eng. Chem., 6 , 511 (1913). 25-Ibid., 6 , 510 (1913). 26-Auwers, A n n . , 366,124 (1907). 39, 1094 (1908). 27-Shorigin, J . Russ.Chcm. SOC., 28--Lunjac, J . Russ. Phys.-Chcm. Gcs., 36, 301 (1905) ; 39,1094 (1908). 29--Buttenberg, J . Chem. SOC.(London), 66, 502A (1894). Ibid., 66, 1188A (1889). 3@-RUSSdnOff, 31-Fabinyi, Ber., 9, 283 (1878). 32-Wagner, J . firakt. Chcm., 66, 313 (1902). 33-Sat0 and Sekine, J. Chcm. I n d . ( J a g a n ) , 24, 321, 332, 580 (1921) 34-Claus and Trainer, Bcr., 19, 3004 (1886). Ber., 9, 286 (1878). 35-Fabinyi, 36-Wenzke and Nieuwland, J . A m . Chcm. SOC.,46, 177 (1924). 37--Lunjac, J . Russ. Phys,-Chem. Gcs., 40, 466 (1909). 38-Mackenzie, J. Chem. SOL.(London), 79, 1209 (1901); 121, 1695 (1922). 39-Gomberg and Jickling, A m . Chem. J., 37,2575 (1915). IC--Claisen, Ann., 237, 270 (1887). 41-Mackenzie, J. Chcm. SOC.(London), 79, 1216T (1901). 42-Gomberg and Buchler, J. A m . Chem. Soc., 42, 2059 (1920). 43-Reychler, Bull. SOC. chim.. 1, 1195 (1907). 44--Ludwig, Claisen, and Eider, Ann., 401, 21 (1913). Ij-Fabre, Ann. chim., 18, 49 (1922) 46-Wenzke and Nieuwland, J . A m . Chem. SOC.,46, 178 (1924). 47-Michael, J . Chcm. SOC.(London), 67, 2338 (1895). 48-Staedel, Ann., 283, 164 (1894). 49-Bentley, Haworth, and Perkin, J . Chcm. SOC.(London). 69, 166T (1896). 5O--Mackenzie, Ibid., 79, 1205T(1901); also Fossi, Comfit. rend., 130, 725, 1194 (1900). 51-Baekeland and Harvey, J . I n d . Eng, Chcm., 13, 153 (1921). 52-Ter Meer, Be?., 7, 1197, 1201 (1874). 53-Baeyer, Ibid.. 6, 280, 1094 (1872). 54-Claisen, Z . angcw. Chem., 36, 478 (1923). 55-Pauly and Schanz, Bcr., 66B,979 (1923). 56-Aylswortl1, U. S. Patent 1,102,630 (1914). 57-Jablonower, J . A m . Chcm. SOC.,36, 811 (1913). 58-Lebedev. Ber., 66B,2349 (1923). 59-Baekeland, J. I n d . Eng. Chcm., 6,950 (1913). 60-Fries and Fickewirth, Ber., 41, 367 (1907). 61-Baeyer, Bn.,6, 25 (1872). 62-Michael, Zbid., 19, 1388 (1886). 63-Herzog, Z . angcw. Chem., 34, 97 (1921); abstracted C. A , , 16, 1969 (1921). 64-Meighan, method soon to be published from the Chemical Engineering Department of Columbia University. G b R e d m a n , Weith, and Brock, J . I n d . Eng. Chcm., 6 , 3 (1914). 6 6 R a s c h i g , Z . anorg. Chcm., 26, 1946 (1912). 67-Gomberg and Snow, J . A m . Chcm. SOC.,47, 199 (1925).
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