Патент USA US3038881код для вставки
United States Patent O??ce 3,038,871 Patented June '12, 1962 2 1 3,038,871 FLAME RESESTANT POLY(DIPHENYL)-TYPE COOSITIONS James D. Doedens, Midland, Mich, assignor to The Dow C17H3 ghgrnical Company, Midland, Mich, a corporation of fatty amide condensates, exempli?ed by e aware cnHaacoN (C2H4OH) 2 No Drawing. Filed Oct. 5, 1959, Ser. No. 844,200 6 Claims. (Cl. 260-37) . This invention concerns composite structures contain CH3 ) CgHéSO 3N3. and the cationic quaternary ammonias, exempli?ed by 10 C12H25(C5H5CH2)——N(CH3)2C1. ing inert inorganic ?llers compounded with resinous poly (diphenyl)-type binders, i.e., poly(diphenyl), poly(di phenylmethane), poly(o-phenylphenol) and poly(p phenylphenol). It also concerns their method of manu facture. In accordance with this invention, novel structural mate rials having desirable physical properties are prepared MiXtuI'CS Such as ?lat of sorbitan mono-oleate, polyoxyethylene esters of mixed fatty and resin acids and alkylamine aryl sulfonates are particularly advantageous as emulsifying agents for the HMDP’s. The HMDP’s are prepared by reaction of a holo methylating agent, such as methyl chloromethyl ether, methyl bromomethyl ether, bis-(chloromethyl)ether, bis (bromomethyl) ether or a mixture of formaldehyde and HCl or l-lBr with a diphenyl type compound, as speci?ed, in the presence of a Friedel-Crafts type catalyst for the glass mats, ?brous glass cloth, silica, alumina, magnesia, 20 reaction, such as Zinc chloride, aluminum chloride, ferric etc. with a halomethylated diphenyl type monomer as chloride, boron tri?uoride, etc. Procedures for carrying such or in solution or emulsion form, and heating the out halomethylation reactions are well-known in the art, mass to liberate hydrogen halide and form a condensed and can be applied in halomethylating diphenyl type com resinous binder ?lled with inorganic ?ller. pounds such as those mentioned above, to obtain HMDP’s Suitable binders for the practice of this invention in useful as starting materials in the practice of this inven clude the condensation products resulting from the reac tion. See, for example, US. Patent, 2,911,380, ?led tion of a Friedel-Crafts catalyst and a halomethyl~, i.e., August 26, 1955, and Organic Reactions, vol. 1, pages chlorornethyl- or ‘bromomethyl-diphenyl, diphenylmeth 63-90 (1942). Mono< or poly-HMDP’s or mixtures there ane, o-phenylphenol and p-phenylphenol, ringing from of can be obtained thereby, depending upon the propor their monohalomethyl to their tetrahalomethyl substitu 30 tions of halomethylating agent used, the extent of the tion products, and including their commercial mixtures halomethylation reaction and whether steps are taken to which contain small amounts of non-halornethylated di separate and purify individual HMDP’s. Residual cata by a process which comprises combining various inert inorganic ?llers, such as mica, glass rovings, ?brous phenyl type compounds. Hereafter diphenyl, diphenyl methane, o-phenylphenol and p-phenylphenol will be re ferred to as diphenyl type compounds. When the monomers indicated are compound with the indicated ?llers and heat polymerized, hydrogen halide lyst need not be removed. In fact, it promotes subsequent polymerization. When it is desired to accelerate the poly meriz-ation rate, additional amounts of catalyst are added to the monomer, advantageously to give from a trace up to about 2 weight percent total, monomer basis. It is is evolved and solid or foamed condensation products are not necessary that the HMDP’s be separated or puri?ed. obtained depending on the halomethyl content of the On the contrary, mixtures of unseparated and unpuri?ed monomer, the content of Friedel~Crafts catalyst, the tem HMDP’s containing up to 50 weight percent of one or perature and the thickness of the monomer layer. Mon more unreacted diphenyl type compounds vare commer omers having up to one halomethyl group per molecule cially attractive. Such mixtures contain HMDP’s of vary on a statistical basis give solid products when polymer ing halornethyl content up to the tetrahalomethylated ized. Other monomers having more than one halomethyl product, in addition to unreacted diphenyl type com group per molecule give foams when polymerized at cur 45 pound. Unreacted diphenyl type compounds enter into ing temperatures, e.g., between 90° and 400° C., prefer ably between 100° and 150° C. The monomers can be used individually or in admixture with one another. A mixture of mono- and di(halomethyl)diphenyl type com pounds is particularly advantageous. The halornethyl diphenyl type compounds, hereafter abbreviated as HMDP’s, are used as such or in solution or emulsion form, advantageously containing between 5 the condensation reaction via the Friedel-Crafts method. The following examples are in illustration of the inven tion and are not intended to be limitative thereof. EXAMPLE 1 Chloromethyl o-Phenylphenol This material was dissolved in acetone to give a 35 per cent solids concentration. The following mixtures there and 75 weight percent of monomer when a solution is 55 with were prepared. used; or between 5 and 25 weight percent when an emul (A) 50 g. Johns Manville No. 7 asbestos and 25 g. sion is used, the balance being about 75 to 60 weight parts solution. ‘of Water and about 5 to 14 weight parts of an oil'in-water (B) 25 g. perlite-plaster aggregate (perlite is an 'ex emulsifying agent. The ?llers are compounded with the panded volcanic glass) and 50 g. solution. monomers or their solutions or emulsions, generally to (C) 75 g. magnesium oxide and 25 g. solution. provide a resin uptake between 5 and 15 percent, by mix 60 The chlorine content of the monomer was 15.1 per ing, dipping, spraying and ‘the like, draining, and heating cent. Its analysis indicated 20~25 percent o-phenyl phenol, 45—50 percent chloromethyl-, 20—25 percent di chloromethyl-, 1—2 percent trichloromethyl- and 0-1 per time sufficient to liberate hydrogen halide and give a con cent tetrachloromethyl o-phenylphenol. densation resin. Solutions containing about 5 to 75 weight 65 at a polymerzing temperature ranging between about 90° and 400° C., preferably between 100° and 150° C., for a percent monomer in aromatic hydrocarbon or halohydro carbon solvents boiling between about 40° and 110° C. are advantageously used in the practice of this invention. Suitable emulsifying agents include the following well EXAMPLE 2 Chloromethylated Diplzenylmethane This material was dissolved in methylene chloride to give a 40 percent solids concentration. The following known types: alkylaryl sulfonates, exempli?ed by 70 mixtures therewith were prepared: C12H25—C6H4—$O3Na; fatty alkyl sulfates, exempli?ed (A) 25 g. perlite-plaster aggregate and 25 g. solution by C12H25OSO3Na; nonionic esters, exempli?ed by 3,038,871 3 4 (B) 75 g. MgO and 25 g. solution (C) 50 g. asbestos and 25 g. solution 4.5" X 4.5" X 2 mm. and saturated with 30 g. chloro— methylated diphenyl (15.2 percent chlorine) containing 0.3 g. ZnCl2. The chlorine content of the monomer was 16.65 per cent. Its analysis indicated 15-20 percent diphenyl methane, 40-45 percent chloromethyl-, 25-30 percent dichloromethyl-, 1-3 percent trichloromethyl and 0-1 for 15 min. at 150° C. It was then oven cured The sample was then subjected to ASTM test D-757-44T. Average burning rate for ?ve samples was 0.1430 inch per minute. percent tetrachloromethyl-diphenylmethane. Chloromethylated EXAMPLE Diphenyl 3 _ “ The press was closed and the composition cured at 160° C. for 15 min. EXAMPLE 5 10 This material was dissolved in methylene chloride to give a 40 percent solution. Mixtures of the following Chlorometlzylated Diphenylmethane were prepared: The procedure of Example 4 was repeated with the following: (A) 25 g. perlite-plaster aggregate and 25 g. solution 15 (a) A quantity of 35 g. chlorornethylated diphenyl (B) 75 g. MgO and 25 g. solution methane (16.65 percent chlorine). (C) 50 g. asbestos and 25 g. solution (b) The composition was cured in the press and did The chlorine content of the monomer ‘was 15.2 per not need further curing in the oven. ASTM Test D-757-44T results on ?ve samples showed 50 percent chloromethyl-, 20-25 percent dichlorometh 20 an average burning rate of 0.1741 inch per minute. yl-, 1-2 percent trichloromethyl- and 0-1 percent tetra~ What is claimed is: chloromethyl diphenyl. l. The combination of an inert inorganic ?ller and a cent. Its analysis indicated 20-25 percent diphenyl, 45 The mixtures of Examples l-3 were made by thor oughly stirring the dry inorganic materials in the solutions polymeric Friedel-Crafts condensation product of the group of halomethylated diphenyl, diphenylmethane, o until each particle was coated. The mixtures were then 25 phenylphenol and p-phenylphenol and mixtures thereof allowed to stand at room temperature 16 hours to evapo— having from 1 to 4 halomethyl groups per molecule and rate the solvent. Individually the mixtures were put in wherein halomethyl is a member of the group consisting a 2" X 4” X 5/s" mold, placed in a Carver press and of chloromethyl and bromomethyl. cured for 15 min. at 150° C. and 625 p.s.i. In all cases 2. The composition of claim 1, wherein the ?ller is an extremely hard molded material was recovered from 30 ?brous glass. the press having the following dimensions: 2" X 4” X 1A". 3. The composition of claim 1, wherein the ?ller is Each of these articles had the strength and appearance perlite-plaster aggregate. of transite. All of the binders adhered well and were insoluble in organic solvents and resistant to bases and 4. The composition of claim 1, wherein the ?ller is acids. 35 exploded mica. Rate of burning was determined by allowing a 1/2” x 5. The composition of claim 1, wherein the ?ller is 4" X 1A" piece of the molded material to touch an magnesia. electrically heated bar which was cherry red (bar sup— 6. Method for making a composite structure of an plied by 350 watts power) for 3 minutes and measuring inert inorganic ?ller and .a polymeric diphenyl binder by the amount of resin burned 01f, sample blackening, etc. 40 condensing at a temperature ranging between 90° and during this time period. Masonite, transite, and white 400° C. in the presence of a Friedel-Crafts catalyst, a pine were run in this test also to give comparable results. Results are summarized in the following table. monomer of the group of halomethylated diphenyl, di phenylmethane, o-phenylphenol, p-phenylphenol and FLAME RESISTANT BINDERS FOR INORGANIC MATERIALS ASTM D-757-44’l‘ Sample Binder 3 N 0. Inorganic material Percent binder in ?nal product Flame during burning test Inches] min. resin burn o? Inches/ min. blacken ing of General Description of Molded Article product CMOPP 15.1% Cl ____ __ asbestos _______ -_ 15 MgO __________ __ 10. 8 No ____ __ 0.00 0.145 0. 031 O. 125 gray color, hard, lookslike transits, much the same 5 ___________ _-__do _________________ __ MgO __________ __ 11.8 0. 031 0. 083 properties as phenolic bonded asbestos. light yellow color, hard, good bonding. gray color, hard, looks and acts like transite, much the same as phenolic white color,properties hard on surface, softerbonded inside. asbestos. _____d0 _______________ __ perlite-plaster___ OMD 15.2% 01... ___ asbestos _______ __ 16.7 l6. 7 0.062 0. 00 O. 145 0. 104 light gray color, hard, good bonding. looks like transite, hard, strong, difficult to saw. _ perlite-plaster... asbestos... _.__ d ._._ MgO __________ __ perlite-plaster_._ l5 16. 7 11.8 16. 7 0. 041 0. 00 0.031 0. 145 0. 104 0. 150 0.062 0. 145 0.250 0.00 0.250 0. 333 0. 166 0. 292 white color, hard on surfaces, softer bonding inside. white color, hard on surface, softer bond on inside. light tan in color, hard, good bonding. 1Flamed throughout whole 3 min. of test. 2 Flame went out after 2.5 min. of test. 3 CM OPP = Ohloromethylated o-phenylphenol; OMDPM = chlorome thylated diphenylmethane; OMD =chloromcthylated diphenyl. When a chloromethylated p-phenylphenol containing 16.8 percent Cl was substituted for the monomer of EX ample 1, similar advantageous results were obtained. EXAMPLE 4 Chlaromethylated Diphenyl Four thicknesses of glass cloth were placed in a mold mixtures thereof having from 1 to 4 halomethyl groups per molecule and wherein halomethyl is a member of the group consisting of chloromethyl and bromomethyl 70 in admixture with an inert inorganic ?ller in proportions at least su?icient to bind said inorganic ?ller. No references cited.