Патент USA US3028374код для вставки
United States Patent 0 "ice 3,028,364 Patented Apr. 3, 1962 2 1 of the present invention will appear from the following description and claims. It has now been found that if diphenols and dicar boxylic acids are condensed in a two-phase mixture of liquids, the acid chloride of the dicarboxylic acid being dissolved in organic liquid which is a solvent for the reaction product formed, and the bis-phenol being dis solved in another liquid which is immiscible with the former, it is possible to carry out the condensation reac 3,028,364 PRODUCTION OF LINEAR AROMATIC POLYESTERS André Jan Conix, Hove-Antwerp, and Urbain Leopold Laridon, Mortsel-Antwerp, Belgium, assignors to Gevaert Photo-Producten N.V., Mortsel, Belgium, 2! company of Belgium No Drawing. Filed Apr. 1, 1958, Ser. No. 725,498 Claims priority, application Great Britain Apr. 2, 1957 3 Claims. (Cl. 260-47) 10 tion at room temperature and to obtain high molecular weight products which dissolve in low-boiling solvents. This invention relates to the production of polymeric It has further been found that this condensation method materials and particularly of linear aromatic polyesters. can be applied for obtained polyesters of high molecular It is known to prepare aromatic polyesters by causing Weight, starting from a wide variety of bis-phenols and terephthalic acid and derivatives to react with glycols having 2 to 12 carbon atoms. The most valuable rep 15 dicarboxylic acids. According to the present invention, a process for the resentative of the series of polyesters thus obtained is polyethylene terephthalate. production of linear aromatic polyesters comprises react ing phenolate of a diphenol of the general formula It has also been proposed to produce aromatic poly esters by substituting diphenols for glycols in reactions with dicarboxylic acids but it Was found di?icult or im 20 possible to obtain polyesters having su?iciently high mo lecular weights. Accordingly for the production of poly with a diacid chloride of an aromatic dicarboxylic acid _ esters of this type recourse has been had to the reaction between the free diphenol and the dihalide, usually the dichloride of the dicarboxyl acid, the reaction being car 25 of the general formula ' 1100c 00011 ried out in the presence of a base for instance sodium j hydroxide. It is very di?icult, however, to obtain ac— in which formulae the hydroxyl groups and the carboxyl cording to this method really high-molecular polyesters groups may be in the para- or meta-position and wherein which can be formed in ?laments and ?lms; moreover the reaction is not smooth and the reaction mass tends 30 each of the R and R’ represents a single bond or an alkyl-, aryl- or halogen substituted methylene group or a carbon to become pasty, the end product frequently being yellow atom which forms part of the cycloaliphatic ring, or to brown. one represents such a group or form parts of such a ring Products of high-molecular weight can be obtained, or such a carbon atom, and the other represents an oxy however, according to British patent speci?cation No. 621,102, by condensing the dicarboxylic acid with the 35 gen atom or a carbonyl- or sulphonyl group, or a satu rated hydrocarbon radical such as a methylene- or ethyl diacetate of the diphenol or by reacting the dicarboxylic ene group, the said reaction being carried out by dissolv acid with the diphenol in the presence of acetic anhydride. ing the aromatic dicarboxylic acid chloride in a solvent In the copending US. patent application Serial No. 702,252, a process is described for the production of 40 for the reaction product and adding thereto the diphe nolate dissolved in a solvent which is immiscible with linear ‘aromatic polyesters by polycondensation of diphe the solvent in which the acid chloride is dissolved while nols with aromatic dicarboxylic acids accordingv to which maintaining the temperature at substantially room tem high molecular linear aromatic polyesters are obtained perature and precipitating the reaction product, e.g. by which dissolve in low boiling solvents by selecting as the diphenols those of the general ‘formula 45 pouring the reaction mixture into boiling water. ‘The following are examples of such radicals: or chemically equivalent derivatives thereof, such as di acetates and other diesters, and as dicarboxylic acids those 50 of the ‘general formula HO O C C OOH @WQ 55 or chemically equivalent derivatives thereof, such as and esters or anhydrides, wherein each of the R and R’ rep resents an alkyl- or aryl-substituted methylene group or forms part of a cycloaliphatic ring, or one represents such a group or forms part of such a ring, and the other 60 represents an oxygen atom or a methylene- or carbonyl group. The polycondensation is carried out according to the above-mentioned copending application by heating the a. on3 l (0112):: (($111) n1 Ha wherein n and n’ each represents a positive number from dicarboxylic acid and the diphenol, preferably in the form 65 1 to 7, of the diacetate e.g. to a temperature of 305° C. It is therefore an object of the present invention to provide new linear aromatic polyesters which dissolve quite well in low-boiling solvents and show high soften ing temperature. A further object of the present inven 70 tion is to provide a suitable method for the production of such linear aromatic polyesters. Still further objects 3,028,364 wherein R and R’ represent radicals as de?ned above. The following examples illustrate the invention with out limiting, however, the scope thereof. The softening points are obtained on ?lms prepared from the polyesters. Especially high-molecular weights are obtained if the reaction is carried out in the presence of a suitable cat alyst, such as a quaternary ammonium compound. Ex 10 The elongation of strips of ?lms subjected to a load of 0.17 kg/mm.2 is measured in function of the tempera ture. The temperature where a large rise in elongation is observed is taken as the softening temperature. It is to be emphasized that these temperatures have only a amples of- such catalysts are trimethylbenzyl ammonium chloride, triethyl benzyl ammonium hydroxide, and tri ethyl benzyl ammonium chloride. It is an important advantage of the present invention that the reaction may be carried out at room temperature 15 comparative value and are not to be confounded with consisting of non-miscible solvents which separately keep melting temperatures. In fact they correspond more or less with glass transition temperature. in dissolution the sodium diphenolate and the acid chlo Example 1 and at atmospheric pressure in a liquid reaction medium ride together with the polyester formed. ' We use Water as the solvent for the diphenolates and 20 methylene chloride as common solvent for the acid chlo A ?ltered solution of 3.15 g. of di-p-carboxy-phenyl 2,2-propane di-acid chloride in 20 cm.3 of methylene chlo ride is brought into a vessel, ?tted with a stirrer and a dropping funnel. To this solution is added 0.05 g. of rides and the polyester formed during the reaction. Other water immiscible organic solvents can be used in associ triethylbenzyl ammonium chloride. Under stirring and ation with water, such as dichloroethane, tetrachloro 25 during 30 minutes, a solution of 2.3 g. of di-p-‘iydroxy ethane, benzene and toluene. phenyl-2,2-propane and 0.8 g. of sodium hydroxide in 20 The diphenolates can be formed by dissolving the di cm.3 of water is dropwise added. The reaction tempera— phenols in water in the presence of equivalent quantities ture is held by cooling to approximately 25° C. The of metal hydroxides such as sodium- or potassium hy solution is subsequently stirred for 75 minutes. After droxides. The dichlorides can be obtained a.o. by re— this period, the reaction mixture became extremely vis 30 action of the respective dicarboxylic acids with thionyl cous. The viscous mixture is brought into boiling water chloride. whereupon the polymer precipitates. The polymer is The following are examples of aromatic dicarboxylic isolated by ?ltration and dried. The intrinsic viscosity acids the dihalide of which can be used for preparing the of the polymer determined in dichloroethane solution at polyesters according to the present invention: 35 25° C. is 1.9. The polymer dissolved in methylene chlo 4,4’-dicarboxy-diphenyl, 4,4'-dicarboxy-diphenyl ether, 4,4’-dicarboxy-diphenyl sulphone, 4,4’-dicarhoxy-diphenyl methane, 1,2- and 1,1-(4,4'-dicarboxy-diphenyl)ethane, 4,4'-dicarboxy-benzophenone, 4,4’~dicarboxy-diphenyl dichloromethane, 2,2-(4,4'-dicarboxy-diphenyl)propane, 2,2-(3,3'-dicarboxy-diphenyl)propane, 2,2-(4,4'-dicarboxy-diphenyl) 1,1-dimethylpropane, 3,3-(4,4'-dicarboxy-diphenyl)heptane, 3,3-(3,3'-dicarboxy-diphenyl)heptane, 1,1-(4,4’-dicarboxy-diphenyl)propane, 1,1-(3,3'-dicarboxyediphenyl)propane, ride can be cast to tough, transparent, colorless ?lms which are characterized by a low water-absorption and a high softening point (225° C.). This ?lm material is particularly useful as base for photographic materials. 40 29.5 g. of the di-acid chloride of di-(p-carboxy-phenyl) ether and 0.5 g. of triethylbenzyl ammonium chloride is brought into a vessel, ?tted with a stirrer and a dropping funnel. To this solution is dropwise added under vigor ous stirring and during 35 minutes a solution of 22.8 g. di-(p-hydroxy—phenyl)-2,2’-propane and 8 g. of sodium hydroxide in 200 cm.3 of Water. The reaction mixture 50 is subseduently stirred for 3 hours at a temperature of approximately 25° C. The viscous solution is brought 1,1 or 2,2-(4,4'-dicarboxy-diphenyl)butane, 1,1 or 2,2-(4,4'-dicarboxy-diphenyl)pentane. into boiling water, whereupon the polymer precipitates, The following are bis-phenols the metal phenolates of which can be used for preparing the polyesters according to the present invention: and can be isolated by ?ltration. The polymer has an intrinsic viscosity of 0.76 measured in a dichloroethane 55 solution at 25° C. which are characterized by a low water-absorption and a l-phenyl- 1 , 1- (4,4’-dihydroxy-diphenyl) methane, high softening point (200° (1.). Similarly, the polymer l-phenyl- 1 , 1- ( 4,4’-dihydroxy-diphenyl) ethane, 2,2- (4,4’-dihydroxy-3 ,3 '-dimethyl-diphenyl ) propane, can be moulded into transparent objects showing a high '60 impact 1,1,1-trichloro-2,2-(4,4'-dihdroxy-diphenyl) ethane, a particularly high-distortion ' Example 3 2,2-(4,4'-dihydroxy-diphenyl) 1,1-vdimethylpropane, 1, 1-(4,4'-dihydroxy-diphenyl) propane, 1,1 or 2,2-(4,4'-dihydroxy-diphenyl) butane, 1,1-, 2,2- or 3,3- ( 4,4'-dihydroxy-diphenyl ) pentane. strength and temperature. 2,2- ( 4,4'-dihydroxy-diphenyl ) propane, 3 ,3- (4,4'-dihydroxy-diphenyl ) heptane, The polymer can be cast from a solution in methylene chloride to tough, transparent ?lms 1,1-(4,4'-dihydroxy-diphenyl)-cyclohexane, > 4,4'-dihydroxy-diphenyl-sulphone, Example 2 A solution consisting of 100 cm.3 of methylene chloride, A polyester is prepared by proceeding as in Example 2 65 but using 1 mol of the di-acid chloride of 2,2-(4,4'-di carboxy-diphenyl)propane and -1 mol of the di~sodium salt of 4,4'-dioxy-diphenyl~phenyl methane of the formula The invention includes polyesters obtained by reacting a mixture of two or more of the speci?ed diphenolates 70 With one or more of the speci?ed aromatic dicarboxylic acid chlorides or mixtures of two or more of these acid chlorides with one or more of the said diphenolates. In this way, polyesters are obtained containirsY the re curring structural units according to the general formula: 75 A'polyester, soluble in low-boiling chlorinated hydro 8,028,364 6 carbons such as methylene chloride, is obtained. The softening point of the ?lms cast from solution, is 218° C. rated by ?ltration. The polymer is soluble in tetrachloro ethane. From this solvent the polymer can be cast into but using as starting materials the di-acid chloride of solution amounts to 0.95. colorless, transparent ?lms showing good ?exibility and Example 4 a high softening point (220-250° C.). The intrinsic A polymer is prepared by proceeding as in Example 3 5 viscosity of the polymer, determined in tetrachloroethane 2,2-(4,4’-dicarboxy-diphenyl)propane and 4,4'-dioxy-di~ phenyl-l,l-cyclohexane of the formula Example 7 CH3 [ OYHIB | _l ~000Q000C>OC0~ l- . ([1113 Y_ J 15 H2O CH2 solution was added over a period of 20 minutes to a A polyester soluble in methylene chloride and showing l. CH3 1 3 (I: 000 4,4'_dicarbony1_ch10ride in 50 cm’s of 1,1,Ltrich1oro ethane. Example 5 OH 5.127 g. (0.02 mol) of 2,2-(4,4'-dihydroxy-3,3'-di~ methyl-diphenyl)propane and 150 mg. of triethylbenzyl 20 vigorously stirred suspension of 5.583 g. of diphenyl a softening Point of about 170° C’ is obtamai l , I ammonium chloride were dissolved in 40.4 cm.3 of NaOH N. At a temperature not exceeding 23° C. this CH’ —o (‘1113 Stirring was continued for an additional 4 hours, subsequently the upper layer was decanted and replaced s02 l oo— v ..l 4.566 g. (0.02 mol) of 2,2-(4,4'-dihydroxydiphenyl)pro- 30 by 100 cm.3 of distilled Water. The mixture was again pane and 150 mg. of triethylbenzylammonium chloride stirred for 30 minutes. Subsequently the aqueous layer were dissolved in 40.4 cm.3 of NaOH N and 20 cm..3 was decanted and removed. Upon pouring the organic of 1,1,2-trichloroethane were added. At a temperature layer into an excess of ethanol, a ?brous white polymer not exceeding 19° C., a solution of 6.864 g. of sulphone precipitated which could be isolated by ?ltration. The 4,4'-dibenzoylchloride in 60 cm.3 of 1,1,2-trichloroethane 35 polymer is soluble in methylene Chloride, 1,2-dich10r0 was added over a period of 15 minutes to the vigorously ethane, 1,1,2-trichloroethane, tetrachloroethane and di stirred mixture. Stirring was continued for an additional oxane; from these Solvents the Polymer can be cast into 150 minutes. Subsequently the upper aqueous layer was colorless, transparent ?lms Showing good ?exibility and decanted and replaced by 50 cm.3 of distilled water; a_ high Softenlhg P0111t (230—2_50° the mixture was again Stirred for 30 minutes_ The intrinsic This pl.o_ 40 vlscosity of the polymer, determined in tetrachloroethane cedure was repeated once more. The polymer was precipitated into an excess of ethanol and is found to ‘be solut1on amounts to 1'45‘ Example 8 2111: 5.128 g. (0.02 mol) of 3,3-(4,4'-dihydroxy-diphen soluble in methylene chloride, 1.,2-dichloroethane, 50 yl)pentane and 100 mg. of triethylbenzylammonium 1,1,2-trichloroethane and tetrachloroethane. From these solvents the polymer can be cast into colorless, trans chloride Were dissolved in 40.4 cm.3 of NaOH N. pafeht ?h'hs Showing gohd heX'ibili'ty ?hd a high Softening temperature not exceeding 20° C., this solution was At a Polht (200° C)’ The mtrlnslc VISCQSIW of the Polymer’ added over a period of 15 minutes to a vigorously stirred determined in tetrachloroethane solut1on amounts to 0.64. 55 mixture of 5583 g‘ of diphenyl_4,4I_dicmbonyl chloride Example 6 in 60 cm.3 of 1,1,2-trichloroethane. Stirring was con tinued for an additional 2 hours. Subsequently 40 cm.3 5.006 g. (0.02 mol) of 4,4’-dihydroxydiphenylsulphone and 200 mg. of triethylbenzylammonium chloride were of l,1,2~trichloroethane and 100 cm.P of water were dissolved in 40.0 cm.3 of NaOH N and 20 cm.3 of added to the viscous mixture and stirring continued for l,l,2-trichloroethane were added. At a temperature not 65 30 minutes. Subsequently the upper aqueous layer was exceeding 20° C. a solution of 6.424 g. of 4,4'-(2,2-pro- decanted and replaced by 100 6111-3 0f W?tef- The miX~ pylene)dibenzoylchloride in 40 cm.3 of l,l,2-trichloroethane was added over a period of 20 minutes to the . ture was again Stirred for 1 hour. Subsequently the Polymer Was Precipitated into an eXCeSS of ethanol- The vigorously stirred mixture. Stirring was continued for ?brous white polymer is soluble in methylene chloride, an additional 4 hours, subsequently the upper layer was 70 1,2-dichloroethane, 1,1,2-trichloroethane and tetrachloro decanted and replaced by 100 cm.3 of distilled Water. ethane; from these solvents the polymer can be cast into The mixture was again stirred for 30 minutes. Subsecolorless, transparent ?lms showing good ?exibility and quently the upper layer was decanted and removed. Upon a high softening point (260-290“ C.). The intrinsic pouring the organic layer into an excess of ethanol, a viscosity of the polymer, determined in tetrachloroethane ?brous white polymer precipitated which could be sepa- 75 solution amounts to 2.25. 3,028,364 ‘Z Example 9 5.808 g. (0.02 mol) of 1,l-(4,4'-dihydroxy-diphenyl ture. Stirring was continued for an additional 3 hours. phenyl) ethane and 150 mg. of triethylbenzylamrnonium 10 The upper aqueous layer was decanted, and the residue chloride were mixed with 40.4 cm.3 of NaGH N and washed with 20 crn.3 Water by stirring during 15 minutes. 10 crn.3 of 1,1,2-trichloroethane at a temperature not exceeding 10° C. Over a period of 20 minutes a mixture The aqueous layer was decanted and the residue was poured into ethanol. A ?brous white polymer was of 5.583 g. of diphenyl-4,4’-dicarbonyl chloride and obtained, with an intrinsic viscosity determined in tetra 50 crrr.3 of 1,1,2-trichloroethane was added at a tem 15 chloroethane of 0.92 and a softening point of 180° C. perature not exceeding 28° C. Meanwhile the reaction it is soluble in methylene chloride, 1,1,2-trichloroethane, mass was vigorously stirred. Stirring Was continued for l,2—dichloroethane, tetrachloroethane, dioxane and tetra hydrofurane. an additional 3 hours, subsequently the aqueous layer was decanted and replaced by 100 cm.3 of distilled water; Example 12 CCls the mixture was again stirred for 30 minutes. Subse quently the aqueous layer was decanted and the polymer precipitated into an excess of ethanol. 9.525 g. (0.03 mol) of 1,1,1-trichloro-2,2-(4,4’-dihy droxy-diphenyl)ethane was mixed with 45.5 cm.3 of The ?brous white NaOH 1.5 N at a temperature not exceeding -—-l0° C. and a solution of 150 mg. of triethylbenzylammonium chloride in 50 (1111.3 of methylene chloride was added. At a temperature not exceeding —5° C. a solution of polymer is soluble in methylene chloride, 1,2-dichle-ro ethane, 1,1,2-trichloroethane, tetrachloroethane and di oxane; from these solvents the polymer can be cast into colorless, transparent ?lms showing good flexibility and a high softening point (280-309° C.). The intrinsic viscosity of the polymer, determined in tetrachloroethane solution amounts to 1.95. .85 g. of diphenylether 4,4’~dicarbonylchloride and 150 mg. of triethylbenzylarnmonium chloride in 50 cm.3 of methylenechloride was added over a period of 10 minutes 35 Example 10 to the vigorously stirred. mixture. Stirring was continued for an additional 5 hours at a temperature not exceeding 1 CH3 1 4.566 g. (0.02 mol) of 2,2-(4,4'-dihydroxy-diphen 0° C. Subsequently the upper aqueous layer was decanted and replaced by 100 cm.3 of distilled water. The mixture was again stirred for 1 hour. Subsequently the aqueous layer was decanted and the organic layer was poured yl)propane and 150 mg. of triethylbenzylarnmoniurn chloride were dissolved in 40.4 cm.3 of NaOI-l N and 20 cm.3 of 1,1,2-trichloroethane were added. At a ten - perature not exceeding 5° C., a. solution of 7.242 g. into boiling water; a ?brous White polymer could easily be separated. The polymer is soluble in methylene 30 cm.3 of 1,1,2-trichloroethane was added over a. period chloride, 1,2-dichloroethane, 1,1,2-tricldoroet one, tetra— of 25 minutes while the mixture was vigorously stirred. chioroethane, dioxane and tetrahydrofurane. From these Stirring was continued for an additional 3 hours at a 50 solvents the polymer can be cast into colorless, transparent temperature slowly rising to 20° C. Subsequently the showing good ?ex'bility and a high. softening point upper aqueous laye was decanted and replaced by 101'.) (‘180° C). The intrinsic viscosity of the polymer, deter of 4,4’-benzophenone dichloride dicarbonyl chloride in 0111.3 of distilled water. for 30 minutes. decanted The mixture was again stirred mined in tetrachloroethane solution amounts to 1.3. We claim: Subsequently the aqueous layer was removed. Upon pouring the organic layer 55 into an excess of ethanol, at ?brous white polymer pre 1. A process for preparing highly polymeric linear polyesters, having an intrinsic viscosity of at least 0.4 cipitated which could be isolated by ?ltration. The poly when measured in a solution of a chlorinated hydrocar mer is soluble in methylene chloride, 1,2-dichloroethanc, bon, which comprises condensing a diacid halide of an 1,1,2-trichloroethane, tetrachloroethane and dioxane; from aromatic dicarboxylic acid, dissolved in an alkyl halide these solvents the polymer can be cast into colorless, 60 which is a solvent for the polyester formed, with an transparent films showing good ?exibility and a high alkali metal salt of a bis-phenol dissolved in water, the softening point (HO-260° C.). The intrinsic viscosity aromatic dicarboxylic acid is a member of the group consisting of of the polymer, determined in tetrachlorocthane solution amounts to 0.90. Example 11 65 1.535 g. of 1,2-diphenylethane 4,4’-dicarbonylchloride 70 and 0.025 g. of triethylbenzyiammonium chloride were dissolved into 15 crn.3 of 1,1.2-trichloroethane. A solu tion of 1.14 g. of 4,4’-dihydroxy-diphenyl-2,2-propane HO——CO—Ar'—R’—-—Ar’--CO—OH and the bisphenol is a member of the group consisting of I-IO-—Ar—Ar-—OH and HO-—Ar-—R—A1‘~—OH in which formulae each of the links Ar and Ar’ represents and 10.2 cm.3 of NaOH 1.0077 N was added over a period of 10 minutes to the stirred solution at room tempera“ 75 a bivalent aromatic radical selected from the group con 3,028,364 9 sisting of an unsubstituted para-phenylene radical, a metaphenylene radical, a methyl substituted paraphenyl ene radical and R and R’ each represents a bivalent radi cal selected from the group consisting of an ether radical, a carbonyl radical, a sulphonyl radical, a saturated lower 10 2. A process according to claim 1, wherein the con densation is carried out in the presence of a catalyst selected from the group consisting of the quaternary am monium compounds. 3. A process according to claim 1 wherein su?icien-t water is added to the reaction mixture to precipitate the hydrocarbon radical, and a carbon atom which forms part polymer formed. of a cycloaliphatic ring, at least one of the radicals R and R’ is a bivalent saturated lower hydrocarbon radical References Cited in the ?le of this patent selected from the group consisting of a lower alkyl-sub 10 UNITED STATES PATENTS stituted methylene group, an aryl substituted methylene group, a lower alkyl- and aryl substituted methylene 2,595,343 Drewitt ______________ __ May 6, 1952 group, a halo-methyl substituted methylene group, a halogen-substituted methylene group and a carbon atom which forms part of a cycloaliphatic ring, whereby the polyester is dissolved in the alkyl halide as it is formed, 15 permitting the formation of highly polymeric linear poly esters. 2,600,376 Caldwell _____________ __ June 17, 1952 2,808,394 2,839,508 Speck ________________ __ Oct. 1, 1957 Williams _____________ __ June 17, 1958 OTHER REFERENCES Conix: Ind. Eng. Chem., 52, 147-150 (1959).