摘要:

AbstractInterfacial polycondensation is a rapid, irreversible polymerization at the interface between water containing one difunctional intermediate and an inert immiscible organic solvent containing a complementary difunctional reactant. It is based on the Schotten‐Baumann reaction in which acid chlorides are reacted with compounds containing active hydrogen atoms (OH, NH and SH). A large number of polymers (heat‐sensitive and infusible as well as stable and meltable) can be prepared. The method has been applied to the preparation of polyurethanes, polyamides, polyureas, polysulfonamides, and polyphenyl esters. Interfacial polycondensations are run in simple, open laboratory equipment with or without stirring. With suitable agitation granular or powdered polymers with high molecular weight are prepared at room temperature and isolated within a few minutes. The intermediates need not be absolutely pure or in balance nor is a quantitative yield needed in order to obtain high polymer. The major variables in the interfacial polycondensation process are discussed and the laboratory techniques and principles are contrasted with melt polycon

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013701

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY

摘要:

AbstractIf a solution of a fast‐reacting diacid halide in a water‐immiscible solvent is brought together with an aqueous solution of a diamine without stirring, a thin film of high polymer is formed at once at the interface. Polyurethanes and polyamides in particular form tough films which can be grasped and pulled continuously from the interface as a folded rope of film. This unstirred interfacial polycondensation not only provides a dramatic demonstration of polymer formation but has permitted the observation of polymerization behavior and the study of the effects of many variables upon the process. The polymer‐forming reactions proceed by nucleophilic displacement, and many have rate constants of at least 102–1041. mole−1sec.−1. Polymers derived from diamines were found to form in the organic solvent phase. Therefore the rate of polymer formation is controlled by the transfer of diamine from the aqueous phase. It is believed that the liquid interface does not have any beneficial orienting effect on the reactants but that it provides for the regulated flow of one reactant into an excess of the other. Furthermore, the aqueous phase provides for the removal of the interfering byproduct, hydrogen halide, from the polymerization site. Some of the interrelated variables which have been studied and which are discussed in relation to the physical mechanism are the solvent sensitivity of the polymer, partition coefficients of the reactants, reactant concentration, duration of the polymerization, and the addition of monofunctional reactants, detergents, and salts. The formation of polyphenyl esters is discus

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013702

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY

摘要:

AbstractExperimental details are given for the interfacial polycondensation of thirteen polyamides having widely different structures. The method involves the fast, room‐temperature reaction in a two‐phase system between diamines and diacid chlorides. Aliphatic, alicyclic, and aromatic reactants, primary and secondary diamines, and many reactants containing other functional groups are all operable. The preparations illustrate a variety of procedural modifications and point up the simplicity, rapidity, and broad applicability of the met

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013703

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY

摘要:

AbstractHigh molecular weight polyphthalamides melting above 325°C. were prepared from piperazine, 2‐methylpiperazine, and 2,5‐dimethylpiperazine by interfacial polycondensation. The melt temperatures and decomposition points of the polyphthalamides, polyisophthalamides, and polyterephthalamides of the above diamines were determined. Only low molecular weight polyphthalamides were obtained from primary diamines. Copolymers of high molecular weight were prepared from piperazine and 2,5‐dimethylpiperazine with phthaloyl chloride containing various proportions of terephthaloyl chloride, isophthaloyl chloride, adipoyl chloride, or ethylene bis(chlorofo

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013704

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY

摘要:

AbstractHigh molecular weight polyterephthalamides were synthesized from a homologous series of primary diamines (ethylenediamine to hexamethylenediamine) by the interfacial polycondensation method. These polymers were found to be extremely high‐melting (300–450°C). and difficult to dissolve. Fibers were prepared by dry spinning from solutions in trifluoroacetic acid. A study of the polymer melting points and the fiber modulus as a function of the diamine chain length showed an alternation of properties with the number of carbon atoms, odd or even, in the diamine chain. All the polymers were highly crystalline and gave orientable fibers. As a comparison to the highly intractable polyterephthalimides from the primary diamines, a series of polymers from secondary diamines (N,N′‐dialkyl ethylenediamine toN,N′‐dialkyl hexamethylenediamine) were prepared. In contrast to the polymers from the primary diamines, theseN‐alkylated derivatives were extremely soluble. In fact, some of them were even water‐soluble when prepared as low molecular weight products (ηinh≤ 0.2). TheN‐alkylated polymers melted at least 70°C. lower than the corresponding polyterephthalamides from the primary diamines. TheN‐methylated derivatives were crystalline, while theN‐ethylated ones were amorphous. These results illustrate the importance of hydrogen bonding in determining the melting points and solubility c

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013705

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY

摘要:

AbstractThe preparation of eleven soluble polyamides based on 4,4′‐sulfonyldibenzoic acid by interfacial polycondensation with the use of aliphatic and alicyclic diamines is reported. Polymer melt temperatures of those polyamides prepared from aliphatic diamines decreased with increasing chain length and amount of chain branching in the diamine. The usual odd‐even alternation of melting points was noted. Cyclic secondary diamines gave higher‐melting polyamides than straight‐chain diamines, despite the lack of hydrogen bonding. Solubility decreased with increasing melting point, except for the polyamides based on cyclic diamines, which were both soluble and high‐melting. Fiber properties are reported for those polymers whic

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013706

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY

摘要:

AbstractInterfacial polycondensation of diamines and bischloroformates has been used to prepare a wide variety of high molecular weight polyurethanes, many of which cannot be synthesized by means of the diisocyanate‐glycol addition process. Almost every type of diamine normally used in condensation polymerization, i.e., aliphatic, alicyclic, cyclic secondary, and aromatic diamines, has been found suitable. Aliphatic, alicyclic, and aromatic bischloroformates have been prepared and utilized as coreactants. Of particular interest are the polymers melting above 200°C. which have been obtained from such intermediates as piperazine, ethylenediamine, and the bischloroformates of ethylene glycol, 2,2‐dimethyl‐1,3‐propanediol, hydroquinone, and thecisandtransisomers of 1,4‐cyclohexanediol. The purity of the reactants and the type of organic solvent, acid acceptor, and dispersing agent were found to be important variables which influenced the molecular weight of the pol

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013707

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY

摘要:

AbstractThe application of interfacial polycondensation to the preparation of several polyurethanes and polyamides from AB type monomers is described. The monomers are salts of aminoalkyl chloroformates and aminoacid chlorides, respectively. Differences in method and mechanism from the AA plus BB type interfacial polycondensation are discussed. Several new ring‐containing polymers were synt

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013708

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY

摘要:

AbstractPolysulfonamides may be prepared readily in high molecular weight by interfacial polycondensation. They are formed rapidly at room temperature when a disulfonyl chloride in an organic solvent is emulsified with a diamine in water containing an acid acceptor. The highest polymers have been obtained from aliphatic diamines and aromatic disulfonyl chlorides. Aromatic diamines have given only low molecular weight materials. Reaction conditions for preparing poly(hexamethylene‐1,3‐benzenedisulfonamide) are briefly described. Reactants must be very pure. Dichloromethane and chloroform have been the most useful organic solvents and must be pure and dry. The best concentrations are about 0.1M. The pH and the ionic strength of the aqueous phase exert a power ful effect on the desired partition of diamines between the two phases and the undesired hydrolysis of the sulfonyl chloride. Thus, sodium carbonate works better than sodium hydroxide as an acid acceptor and, in some cases, bicarbonate has been used to avoid imide formation and consequent branch

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013709

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY

摘要:

AbstractThe interfacial polycondensation method has been used for the preparation of polyphenyl esters. Polyphenyl esters can be prepared easily and reproducibly in high molecular weight by mixing in a home blender an aqueous solution of the sodium salt of the bisphenol and a dispersing agent with a solution of the diacid chloride in a water immiscible organic solvent. The organic solvent should be a solvent or swelling agent for the polymer being prepared. Polyphenyl esters with inherent viscosities as high as 2.3 have been prepared by this method. This system is widely applicable to a large number of bisphenols and dibasic acid chlorides, although aromatic acid chlorides, in general, give higher molecular weight polymer than aliphatic acid chlorides. Bisphenols containing negative substituents do not readily give high molecular weight, tough polymers because of the reduced basicity of the phenoxide ion. A series of copolymers of 2,2‐bis(4‐hydroxyphenyl)propane with isophthaloyl and terephthaloyl chlorides has been prepared and the physical properties, such as melting point, glass transition temperature, solubility, and inherent viscosity, have been measured. All of the polymers melt above 225°C. and have glass transition temperatures above 180°C. Polymers with inherent viscosities greater than 0.4 form tough

ISSN:0022-3832    

DOI:10.1002/pol.1959.1204013710

出版商:Interscience Publishers, Inc.    

年代:1959

数据来源: WILEY