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United States Patent (19) 11) Patent Number: 4,605,698 Briden 45) Date of Patent: Aug

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United States Patent (19) 11) Patent Number: 4,605,698 Briden 45) Date of Patent: Aug United States Patent (19) 11) Patent Number: 4,605,698 Briden 45) Date of Patent: Aug. 12, 1986 (54) POLYFUNCTIONAL AZRDINES FOR USE 3,763,132 10/1973 Meiser, Jr. ...................... 525/375 X NCROSSLINKING APPLICATIONS 3,806,498 4/1974 . Wilson et al. ....................... 525/375 3,974,131 8/1976 Puskas et al. ....................... 526/263 75) Inventor: Frank C. Briden, Morristown, N.J. 3,985,920 10/1976 Travis .......... 427/207 A 73 Assignee: Diamond Shamrock Chemicals 4,167,414 9/1979 Morgan ....... ... 96/87 R 4,278,578 7/1981 Carpenter ... ... 524/272 Company, Dallas, Tex. 4,382,135 5/1983 Sinka et al. ......... ... 526/301 21) Appl. No.: 775,430 4,48,164 1/1983 Logullo, Sr. et al. .............. 523/207 22 Filed: Sep. 12, 1985 FOREIGN PATENT DOCUMENTS 26868 2/1983 Japan. Related U.S. Application Data 26869 2/1983 Japan. 62 Division of Ser. No. 513,454, Jul. 13, 1983, Pat, No. 1054635 1/1967 United Kingdom. 4,563,307. Primary Examiner-Theodore E. Pertilla 51) Int. Cl. .............................................. C08L 33/02 Attorney, Agent, or Firm-Neal T. Levin 52) U.S. C. .................................... 524/559; 524/561; 524/591; 524/601; 525/305; 525/375; 525/437; 57 ABSTRACT 525/440 Polyfunctional aziridines useful in crosslinking applica (58) Field of Search ............... 525/375, 305, 437, 440; tions have been developed which are reaction products 524/561, 562, 559, 591, 601 of (1) ethylene imine and (2) acrylates of alkoxylated trimethylol propane, neopentylglycol, pentaerythritol, 56) References Cited bis phenol A, bisphenol F and glycerol, each having a U.S. PATENT DOCUMENTS degree of alkoxylation of from about 2 to about 12. 2,596,200 5/1952 Bestian ............................ 260/239 E Examples are the bis aziridine of the diacrylate of the 3,165,375 1/1965 Tesoro ................................. 8/127.6 adduct of neopentyl glycol and 2 moles of ethylene 3,197,463 7/1965 Tesoro et al. 260/239 R 3,285,798 11/1966 Tesoro .................................. 161/92 oxide and the tris aziridine of the triacrylate of the ad 3,338,885 8/1967 Coker et al..... ... 260/239 E duct of trimethylol propane and 3 moles of ethylene 3,507,837 4/1970 Hidinger, Jr. .. ... 525/375 X oxide. 3,597,146 8/1971 Tesoro ................................. 8/115.7 3,726,862 4/1973 Coker et al. .................... 260/239 E 11 Claims, No Drawings 4,605,698 1. 2 POLYFUNCTIONAL AZRDINES FOR USE IN DESCRIPTION OF THE PREFERRED EMBODIMENTS CROSSLNKING APPLICATIONS Polyfunctional Aziridines This is a division of application Ser. No. 513,454 filed More specifically, the polyfunctional aziridines are July 13, 1983 now U.S. Pat. No. 4,563,307 issued Jan. 7, bis and tris aziridines of di and tri acrylates of alkoxyl 1986. ated polyols selected from the group consisting of neo pentyl glycol, 2,2'-bis(p-hydroxy-phenyl)propane (bis BACKGROUND OF THE INVENTION phenol A), 2,2'-bis(p-hydroxyphenyl)methane (bis 1. Field of the Invention 10 phenol F), glycerol, trimethylolpropane and penta This invention relates to polyfunctional aziridines for erythritol having from about 2 to about 12 moles of one use in crosslinking applications which are the reaction or a mixture of an alkylene oxide selected from the products of ethylene iminie and acrylates of alkoxylated group consisting of ethylene oxide and propylene oxide. trimethyol propane, neopentylglycol, pentaerythritol, 15 Preferably, from about 2 to about 8 moles of one or a bis phenol A, bis phenol F and glycerol. mixture of an alkylene oxide selected from the group 2. Description of the Prior Art consisting of ethylene oxide and propylene oxide can be Polyfunctional aziridines have been shown to be use used. ful as crosslinking agents in various types of coating Examples of polyfunctional aziridines are: the bis aziridine of the diacrylate of the adduct of neo systems such as carboxylated acrylics, vinyl-acetate, 20 pentylglycol and 2 moles of ethylene oxide, carboxylated urethanes and styrene acrylics. Commer the bis aziridine of the diacrylate of the adduct of neo cially available polyfunctional aziridines are trifunc pentylglycol and 2 moles of propylene oxide, tional in character and are reaction products of ethylene the tris aziridine of the triacrylate of the adduct of glyc imine or propylene imine with trimethylol propane 25 erol and 3.8 moles of propylene oxide, triacrylate and ethylene imine with pentaerythritol tri the tris aziridine of the triacrylate of the adduct of tri acrylate. They are effective low temperature crosslink methylol propane and 3 moles of ethylene oxide, ing agents when added to a coat system in amounts of the tris aziridine of the triacrylate of the adduct of tri 0.2 to 5.0% by weight of total formula. methylol propane and 3 moles of propylene oxide, The choice of crosslinking agent used in a coating 30 the tris aziridine of the triacrylate of the adduct of pen system has a significant effect on the preparation of the taerythritol and 4.7 moles of propylene oxide, coating system as well as on the overall properties of the bis aziridine of the diacrylate of the adduct of bis the cured coating. Factors such as water solvency, phenol A and 4 moles of ethylene oxide. viscosity, and functionality will have a bearing on the In other examples, mixed ethylene oxide, propylene ease of preparing the coating. 35 oxide can be used. Regarding the previously mentioned polyfunctional Preparation of Polyfunctional Aziridines aziridines which are used commercially, these materials The polyfunctional aziridines can be prepared as are effective crosslinking agents but tend to be low in shown below, steps A and B being the procedure de water solubility, have negative features in toxicity and scribed in U.S. Pat. No. 4,382,135-Sinka et al, May 3, are poor in corrosion, adhesion and humidity resistance. 1983. The above and other polyfunctional aziridines are, for example, described in the following patents: A. Preparation of Alkoxylated Polyols The specified monomer base is charged to a reaction 2,596,200 Bestian May 13, 1952 45 flask equipped with stirrer, thermometer and gas inlet 3,165,375 Tesoro January 12, 1965 pipes and heated to melt product if necessary. Once 3,197,463 Tesoro et all July 27, 1965 product is uniform, it is heated to 50-140' C. where the 3,285,798 Tesoro November 15, 1966 catalyst, caustic potash, is added. Concentration of cata 3,338,885 Coker et al August 29, 1967 lyst ranges from 0.1-0.3 percent by weight of charge, 3,597,146 Tesoro August 3, 1971 50 depending whether ethoxylation or propoxylation is 3,726,862 Coker et all April 10, 1973 conducted and the type of chain structure. Branched chains and products using propylene oxide usually re Aqueous coating composition containing aziridine quire higher levels of catalyst. To this mixture, ethylene crosslinking agents are described in U.S. Pat. No. oxide, propylene oxide or mixture of both is added 4,278,578-Carpenter, July 14, 1981. 55 slowly until the product obtains final specifications, optionally under an inert atmosphere such as nitrogen. SUMMARY OF THE INVENTION In some instances, the product must be stripped first New polyfunctional aziridines which can be used as under vacuum before alkoxylation to remove any water crosslinking agents in various types of coating systems in base monomer. are provided for. They provide improved physical B. Preparation of Acrylates of Alkoxylated Polyols properties of the crosslinked coating with respect to The alkoxylated monomer of part A is azeotropically moisture resistance, adhesion, ultraviolet light stability, esterified with 20-55 percent by weight of acrylic acid alkali resistance, corrosion resistance and gloss. and 1.5-2.5 percent by weight of p-toluene sulfonic The polyfunctional aziridines of this invention are 65 acid, both based on the weight of the alkoxylated mono aziridine derivatives of particular acrylates of alkoxyl mer in the presence of 20-45 percent by weight of tolu ated polyols having a degree of alkoxylation of from ene based on the weight of the total charge. Concentra about 2 to about 12. tion of ingredients varies depending on degree of esteri 4,605,698 3 4. fication desired (mono, di or tri) and on the particular The crosslinking agents of this invention are present reactivity of the alkoxylated monomer. Inhibitors such in an amount of from about 0.2 percent to about 10.0 as methylene blue, phenothiazine, cuprous oxide, cop percent, preferably from about 0.2% to about 3.0%, by per powder, nitrobenzene and triphenyl phosphite, gen weight of the total. The pH of the coatings is main erally in amounts of from about 0.05% to about 1.0% by 5 tained at greater than 7.0 by use of a volatile amine such weight of the total charge are added during the reaction as triethylamine, ammonia, dimethyl ethanolamine, etc. to inhibit polymerization of product. The reaction is Ancillary ingredients such as pigments, e.g., titanium continued until no further water is isolated. The prod dioxide, red iron oxide and phthalocyanine blue, fillers, uct is then washed and neutralized with sodium carbon e.g., talc, silica, calcium carbonate, pigment dispersing ate. Paramethoxyphenol is added (700 ppm-3500 ppm) 10 agents, defoamers and bactericides can be present. and the toluene distilled off in vacuo (final pressure is The coating systems are prepared as follows. about 28 inches of mercury, final temperature of reac Polymer is weighed into a vessel. A high speed mixer tion is about 100° C). The product is filtered for clarity. such as a Cowles dissolver is placed in the liquid poly mer and agitation is started at a speed of 3000-4000 C.
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