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United States Patent Office Patented Dec 3,225,063 United States Patent Office Patented Dec. 21, 1965 2 3,225,063 esters are readily prepared by reacting a poly-carboxylic ORGANIC CYCLC CARBONATES acid anhydride with the alcohol. Typical examples Gaetano F. D'Alelio, South Bend, Ind., assignor to Scott of Such cyclic poly-carboxylic acid anhydrides are Paper Company, Philadelphia, Pa., a corporation of carbon Suboxide, succinic, the alkyl succinic, the halo Pennsylvania Succinic, maleic, phthalic, itaconic, citraconic, the alkyl No Drawing. Filed May 21, 1962, Ser. No. 96,470 mercapto Succinic, hexahydrophthalic, endomethylene 6 Claims. (C. 260-340.2) phthalic, glutaric, 1,2,4,5 benzene tetracarboxylic, This invention is concerned with new foaming systems acetylene dicarboxylic, etc., anhydrides. Representing especially adapted to the production of cellulated or ex the anhydrides by the formula X(CO)2O, the preparation panded polymers. Generally, it deals with the synthesis 0. of the half esters is in accordance with the equation: and use of novel organic compounds, which by the inter CO reaction of functional groups within the compounds, lib x^ erate carbon dioxide. When this carbon dioxide is gen O -- EIO (CH2)CEI-CE - erated within a matrix of a polymer, expanded polymer Yog compositions are obtained. A number of organic car 5 Ye/ bonates, such as ethylene carbonate, propylene carbonate, O glyceryl carbonate, and the like, are known, to liberate EO OC-X-COO CHigh-pH carbon dioxide upon heating. However, the temperature required to liberate the carbon dioxide from such com o o pounds at a useful rate is very high, and if the decomposi 20 C tion is performed in the presence of a resinous polymer, O pyrolysis of the polymer occurs decreasing the values of A Specific illustration of this reaction is the preparation the physical properties of the polymers. As examples, of the hemi-ester of succinic acid and glyceryl carbonate, temperatures in excess of 200 C. are required to liberate thus CO2 from ethylene-, propylene-, and glyceryl-carbonates 25 and compounds of related structure. Even at this tem (Hico perature, the rate of CO2 liberation is too low to be prac | O -- EIOCECH-CH - CEICOOCH-CH-CH tical. It is, therefore, a primary purpose of this inven HCO () () &H,CooH ( ) tion to Synthesize organic compounds of selected struc tures, which liberate CO2 at temperatures below 200 C., 30 Y/ Ye/ preferably at temperatures lower than about 170° C., and for practical utility, above 100° C. This and other ob The esterification reaction using the anhydride may be jectives of the invention will become evident as the de performed simply by melting the two reactants together; scription of the invention proceeds. but preferably to avoid the possibility of decarboxylation, It has been discovered that the objectives of this inven 35 the esterification is performed in an inert solvent such as tion may be achieved, at least in part, by certain deriva heptane, hexane, benzene, toluene, dioxane, tetrahydro tives of the organic 1.2 carbonates, which contain a free furane, etc., and isolating the product or using it dissolved carboxyl group in their structure. These compounds or dispersed in the reaction medium. The monoester will have at least one carboxyl group, -COOH attached thus formed may be used as such or as an intermediate through a divalent organic radical Z, to at least one 1,2 40 for conversion to an alkali or alkali metal salt of the free carbonate moiety, carboxyl group, to -COOM, where M represents an alkali or alkali earth metal, Such as sodium, potassium, – H-H, lithium, calcium, magnesium, etc. () ) These esters may also be prepared directly from the Ye/ 45 polycarboxylic acid in accordance with the general reac O tion: and may be represented by the formula: HOOC-X-COOH -- HO (CH2)CE-CEI - EO OC-2-CHCH / N. O O 50 YNc/ O Hooc-x-cooch)-r-H, - EO O O The nature of the divalent radical, Z, is not critical, Ye/ and, for this reason, the -COOH group may be attached in numerous ways and many forms. One convenient & way of attaching a free carboxyl group is to prepare the by heat alone, or in the presence of a small amount of an hemi-esters of di- or poly-carboxylic acids and the 1,2 acidic esterification catalyst such as Sulfuric, phosphoric, carbonates of alpha, beta, gamma alkane triols, contain toluene sulfonic, etc., and preferably in the presence of an ing three to six carbon atoms in the chain represented by 60 inert azeotroping agent, such as benzene or toluene, to the formula remove the water of esterification continuously. By ad HO(CEI) - H-H, justing the ratio of polycarboxylic acid to the carbonate O alcohol, the amount of any di-ester, if any, is reduced to a N c/ minimum. 65 The -COOM group required in the practice of the O invention may be attached to the where n is an integer having a value of one to four or -CH-CH more. Thus, one class of compounds falling within the scope of this invention are the hemiesters of poly () ) carboxylic acids with the 1,2 carbonates of 1,2,3 propane 70 Yo^ triol; 1,2,4 butane triol; 1,2,5 pentane triol, etc. Such s 3,225,063 3 4. group in a number of other ways as through an ether link or directly through a carbon atom, age. Thus, alpha-chloro-propane carbonate may be re acted with a hydroxy acid, or the alkali derivative of a HSO hydroxy acid, such as (H-HCH.Cl -- KCN --> (H.-E.-CH.CN to o, o o, o 2 5 C C GH-H-CH.C) + Nao( DC OONa. --> O O o, C -o | (H-H-OH.cooh -- NHHSO O O o, C o GH-HOHoc-HicooNa+ Nac O o, / Whereas, the cyclic carbonates, free of carboxyl groups, C such as ethylene carbonate, propylene carbonate, glyceryl O 5 carbonate, chloroethylene carbonate, and alpha-chloro CHCH-CHC -- NaOCEICO OK -) propene carbonate liberate CO at temperatures in excess 7 N o, -o of 200° C., any of the compounds having a C (H-H-() ) O 20 N o^ CEICH-CH2OCH2COOK -- NaCl. 6 o O moiety in combintion with a -COOM group will liberate Y/ CO at temperatures below 170° C. regardless of the 25 nature of the divalent radical -Z- between the two or alternately and inversely, the alcohol may be reacted groups. The di-radical Z may, therefore, be aliphatic, with a haloacid, thus: including cyclo aliphatic and aromatic di-radicals, or a combination of aliphatic and aromatic structures in the di GH-H-CHONa - Cl(CH2)2COONa --> radical, and the structure may be saturated or contain o, lo 30 ethylenic or acetylenic unsaturation, the carbon atoms C of which may be interrupted by hetero-atoms of oxygen, O sulfur and nitrogen. The residual valencies of the car (H-H-0 CHCHCOONa -- NaCl bon atoms in the di-radical -Z- not occupied by the . 35 carbonate o, C o O(H-H- O O N/ With chloroethylene carbonate, the substituent group is attached directly to the ring, thus 40 O and the carboxylate moieties, -COOM, are occupied by GH-HCl -- NaOCH2COONa --> hydrogen and by substituent R groups such as alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, carbalkoxy, acetoxy, o, C o halogeno, nitro, oxy, amino, imino, sulfo, sulfoxy, mer 45 capto, etc. groups usually found as substituents for H in O a hydrocarbon radical. This is so, because the nature of (H-H-0 CH3COONa -- NaCl the di-radical -Z- between the -COOM and o, C o pH-II 50 O o, C -o The substitution may also be through a sulfur atom O or a nitrogen atom, thus: moieties is not critical for the purposes of this invention. (H-HCH.Cl -- SCHCOONa -} Thus, the foaming agents of this invention may be simple o, yo 55 or complex compounds, and those compounds contain C ing olefinic unsaturation may be monomers such as O ch C-H (H-HCH.sch.coot, -- NaCl 60 ".led M 9. o, o o, O C c^ O O and 65 which are disclosed in my copending application Serial (H-HCH.Cl -- NH2(CH2)5COONa --> No. 196,430 filed May 21, 1962 and CHCOO (CH2)CFI-CH o. C o H O OOH Y O (H-HCH-NHCH)-cool -- NaCI which are disclosed in my copending application, Serial o, o No. 196,484 filed May 21, 1962, both applications being C assigned to the same assignee as the present invention, and O to which reference is hereby made. 3,225,063 5 6 These compounds, as such, may be heated to cause method of preparing the compounds suitable for the CO2 generation, or they may be used as polymers or practice of this invention, i.e., compound containing at copolymers, in which cases these monomers assume the least one -COOM group and at least one repeating structures, -CEICE COOH 5 / N -CH-)- O O ÖH,C OO (CH2)CHCH Ye/ / N O O O Ye/ 10 group. This can be achieved also when the monomeric carbonate does not contain the -COOM group by co O polymerizing a second monomer containing a -COOM CO OB group with a monomer containing only -bH-CH- 15 bo O (CH2)CHCH -CECH N 6 NO O s.S. Ne/ Y/ O 20 in the polymers and copolymers. To these units in the groups and no -COOM group. Monomers of this polymers, are attached polymer chains, the nature of kind are disclosed in my copending applications men which depends on the number and the kind of monomers tioned hereinabove, and may be exemplified by the di or comonomers used in preparing the polymerization esters of itaconic and maleic esters of the formulas product.
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