JPH0133487B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing ketone and sulfone polymers. In the study of organic polymers suitable for use at high temperatures, many repeating units containing various linking bonds between aromatic residues, such as aromatic groups linked by bonds such as imides, ethers, sulfones, and ketones. structure has been proposed. However, as the high temperature performance potential has increased, the suitability of the polymers for conventional techniques of melt molding them has decreased or disappeared. High temperature stability with at least 50% elongation, a property necessary for many polymeric applications (e.g. to allow polymer insulated wire to be twisted around itself without cracking the insulation) Attempts to make synthetic polymers are often accompanied by a similar reduction in melt processability. Aromatic polyketones are known to enjoy relatively good resistance to thermal degradation. In U.S. Pat. No. 3,065,205, Bonner proposed Friedel-Crafts-catalyzed polymerization of specific reactants to obtain polyaryl ketones, and identified ferric chloride and boron trifluoride as typical Friedel-Crafts catalysts. List. The two basic reactions taught by this invention can be summarized as follows: 1 n(HR-O-RH) + n(Cl-A-Cl) → nHCl + H(R-O-R-A) nCl and 2 n (HBH)+n(Cl-A-Cl) →nHCl+Cl(A-B)nH where HBH is a polynuclear aromatic hydrocarbon, such as naphthalene, and HR-O-RH is a diaromatic ether, such as diphenyl ether; and Cl-A-
Cl is diacyl chloride, such as terephthaloyl chloride or phosgene. When phosgene and diphenyl ether react, the resulting polymer contains repeating units of the following structure: From self-condensation of chlorinated diphenyl ether-4-carbonyl, and chlorinated diphenyl ether 4,
The same repeat unit resulting from the reaction of 4'-dicarbonyl and diphenyl ether is described in British Patent No. 971,227. Farnham and Johnson in UK Patent No. 1078234 take a different approach. Here, a polyaryl ether is produced by the reaction of a dihalobenzenoid compound and a dialkali metal salt of a dihydric phenol. Dihydric phenols contain keto groups and it is therefore stated that 4,4'-dihydroxybenzophenones give rise to polyarylether polyarylketones (see, eg claim 15). Another improved method of making polyaryl ketones has been proposed. For example, U.S. Pat .
as Catalysts, etc. Topchiev
et al., Pergamon Press (1959), p. 122; J.Org.
Chem. 26 2401 (1961); I&E Chem. 43 , 746
(1951) has been proposed. Another proposal for an improved method of synthesizing polyaryl ketones is described in GB 1086021. British Patent No. 1086021 discloses that a second compound containing at least two substitutable aromatically bonded hydrogen atoms and a halogen dioxide (preferably the diacid halide and the second compound are in substantially equimolar amounts) Friedel-Crafts condensation polymerization of a single compound containing both a halogenated acid group and at least one replaceable aromatically bonded hydrogen atom. It is further stated that the molecular weight can be adjusted by using non-stoichiometric amounts of the two compounds or by adding a third component that is monofunctional under the conditions of the reaction. Monoacid halides are mentioned as examples of suitable monofunctional molecular weight modifiers. GB 1109842 describes the polymerization reaction of an aryl disulfonyl halide with a compound containing at least two substitutable aromatically bonded hydrogens. As in the embodiment of No. 1086021,
In all examples of this patent, the proposal is either to use equimolar amounts of electrophilic and nucleophilic compounds or to use an excess of electrophilic compound (ie, diacid halide). The patent further states that residual sulfonyl chloride groups on the polymer chain will increase the viscosity of the product upon melting, and states that the post-polymerization addition of bases such as aniline, sodium carbonate or diphenyl ether may result in residual sulfonyl chloride groups being removed. We propose to quench the group. US Pat. No. 3,593,400 proposes the production of polyaryl ketones with an average intrinsic viscosity of 0.8 to about 1.65 (0.1% W/V in sulfonic acid). Reactivity towards acetylation (compared to benzene reactivity in 1)
This intrinsic viscosity and molecular weight can be adjusted through the use of appropriate amounts of selected nucleophiles and reaction conditions in which . In addition to melt instability (due to the presence of excess electrophilicity resulting in residual acid halide polymer chain end groups), the presence of excess acid halide groups (i.e. electrophilic compounds) during polymerization may cause the adjacent has been shown to lead to the formation of branched polymers resulting from ortho-acylation of nucleophilic internal segments (e.g. diphenyl ether moieties) in the polymer chain by the terminal acid halide group of the chain. The use of nucleophiles as molecular weight regulators in this type of polymerization is beneficial. Linear chain formation occurs while many para-positional bands on the nucleophile are still available, but once the concentration at this position is reduced, acylation reactions at the ortho-position, which are usually slower, become more prominent. It seems to be. This problem is addressed in the U.S. patent of Angelo et al.
Discussed in issue 3767620, this is a repeating structure: 9-phenylenexanthhydrol residues through orthoacylation during the preparation of polymers with Describe the formation of Such residues are formed by the reaction of a diphenyl ether with a diacyl halide, with the acyl halide acylating the diphenyl ether at the ortho position to the oxygen atom of each ring (because essentially all para positions are (already blocked by a previous acylation). This orthoacylated moiety has been shown to lead to thermal instability, particularly reduced melt processability. Hydrogenation (reduction) of the polymer with ethanol and hydrochloric acid, formic acid, and preferably triethylsilane in a homogeneous acid medium reduces this degradation and yields a gradually stable 9-
Phenylene xanthene residues can be provided. Reduction by removal of hydroxyl groups and substitution of hydrogen atoms is said to lead to products with brighter color and improved melt stability. Treatment of the aforementioned branched polymers dissolved in dichloroacetic acid with triethylsilane is also recommended by Agolino in US Pat. No. 3,668,057 as a means of stabilizing branched chain residues. Of course, if the polymerization is carried out with an excess of nucleophile and/or as proposed in U.S. Pat. No. 3,593,400,
Alternatively, if the molecular weight adjustment is carried out with a nucleophilic compound, there will be an excess of para positions and the branching reaction will not occur to the same deleterious extent. However, when either or both ends of each polymer chain are phenoxy (or other nucleophilic) residues with a para position available for reaction,
It has been found that the branching reactions known in the art preferably take place in a highly acidic medium such as a hydrogen fluoride/boron trifluoride mixture. This branching is thought to lead to the formation of trisarylcarbonium salts, which combine the carbonyl groups of the polymer itself with the phenoxy (or other nucleophilic) groups (possibly activated, i.e., protonated by the acid medium). ) seems to arise from the reaction. Besides the deleterious effect of branching itself on processability, this salt is very thermally unstable and leads to degradation and coloration of the polymer when melted. As described in U.S. Pat. Thermal stability of polymers produced by Friedel-Crafts condensation polymerization is substantially improved through controlled decomposition of other complexes. However, this post-polymerization treatment does not stop the formation of branched polymer chains by orthoacylation. Furthermore,
This treatment occurs simultaneously with the polymerization reaction itself and can continue as long as the polymer is in a strongly acidic medium and does not inhibit the aforementioned protonated phenoxy group branching reaction catalyzed by strong acids. Polyarylketones and polyaryls by Friedel-Crafts condensation reactions that thus yield linear, unbranched products with reproducible molecular weights, stable and predictable melt viscosities and increased stability in acidic solutions. There remains a need for a process for making sulfones. As used in this application, the term “acylation” refers to an aromatic nucleophile and a moiety ArCO ⁺ or
Refers to the reaction of ArSO ₂ ⁺ in an acidic medium, where Ar represents a protonated monomer or the residue of a polymer chain that continues to undergo polymerization (chain growth) by an acylation reaction. Therefore, acid halides can be partially ArCO ⁺ or
Refers to a reactive compound that forms ArSO ₂ ⁺ . Common examples are Ar―COCl, Ar―COOH and Ar―
Includes COOR and their sulfonyl analogs. The present invention provides: () from about 0.002 to about 0.02 per mole of first monomer when the first monomer is in excess;
0.10 moles of a nucleophilic capping agent: from about 0.002 to about 0.10 moles of an electrophilic capping agent per mole of second monomer if the second monomer is in excess; When the monomer and the second monomer are present in substantially equimolar amounts, approximately
at least one first monomer containing a diacid halide group and at least two substitutable aromatically bonded monomers in the presence of 0.001 to about 0.05 moles of each of an electrophilic and a nucleophilic capping agent. at least one second monomer containing a hydrogen atom, or () from about 0.001 to about 0.001 per mole of monomer;
at least one monomer containing at least one aromatically bonded hydrogen atom displaceable with at least one acid halide group in the presence of 0.05 moles each of a nucleophilic and an electrophilic capping agent; Friedel-Crafts condensation polymerization of either of the following, and when a nucleophilic capping agent is present, the formula:
[Formula] When an electrophilic capping agent is present, the general formula is: Ar″COZ or Ar″SO ₂ Z [In the above formula, -X- is a covalent bond, -O-, -
represents S-, or CR ₂ ; each R, which may be the same or different, is hydrogen, an alkyl or fluoroalkyl group, an unsubstituted phenyl group or a phenyl group substituted with an electron-withdrawing group. Y is
When CN, NO ₂ , [Formula] or [Formula] or -X- represents a covalent bond, it represents hydrogen. Ar'' represents phenyl, naphthyl, biphenyl, terphenyl or phenoxyphenyl which is unsubstituted or substituted with at least one electron-withdrawing group; when Ar'' represents phenoxyphenyl, there is at least one electron on the phenoxy residue; There is an attraction group. Z
represents OH, halogen or OAlk; where
Alk represents an alkyl group. ] A method for producing a polymer is provided. The gist of the invention is to provide at least one acid halide group with at least one substitutable aromatic capping agent in the presence of 0.001 to 0.05 mole of nucleophilic capping agent and electrophilic capping agent, respectively, per mole of monomer. Friedel-Crafts condensation polymerization of at least one monomer containing bonded hydrogen atoms, wherein the nucleophilic capping agent has the general formula: The electrophilic capping agent is represented by the general formula: Ar″COZ or Ar″SO ₂ Z [In the above formula, -X- is a covalent bond, -O-, -
Represents S- or -CR ₂ - (however, each R is
The same or different hydrogen, an alkyl or fluoroalkyl group, an unsubstituted phenyl group or a phenyl group substituted with an electron-withdrawing group. )；Y
represents hydrogen when -CN, -NO ₂ , [Formula] or [Formula] or -X- represents a covalent bond; Ar'' is unsubstituted or substituted with at least one electron-withdrawing group phenyl, naphthyl , represents diphenyl, terphenyl or phenoxyphenyl (however,
When Ar'' represents phenoxyphenyl, there is at least one electron-withdrawing group on the phenoxy residue); Z represents OH, halogen or OAlk (however, Alk is an alkyl group). It consists in a method for producing a characteristic polymer.
That is, the gist of the present invention resides in the condensation polymerization of the above-mentioned type (). By the method of the invention, for example, the formula: [-M-Ar-B-Ar']- (wherein -M- and -B- may be the same or different and each represents -CO- or -SO ₂ - represents,
Ar is [Formula] or [Formula] (where -L- represents -CO-, -SO ₂ -, covalent bond or -T-, where -T- is -O
-, -S-, phenyleneoxy, -O-Ar-O
-- or CR ₂ , each R may be the same or different and is hydrogen, an alkyl or fluoroalkyl group, an unsubstituted phenyl group or a phenyl group substituted with an electron-withdrawing group. ), and Ar′ is represents. ), and has both unterminated groups represented by the formula R′ or R″, where each R′ and R″ is the formula: [Formula] —CO— Ar″ or —SO ₂ —Ar ″ (In the formula, -X- is a covalent bond, -O-, -S-,
or represents CR ₂ . Here R has the same meaning as above; Y
represents hydrogen when CN, NO ₂ , [Formula] or [Formula] or -X- represents a covalent bond; Ar'' is phenyl, naphthyl, biphenyl, unsubstituted or substituted with at least one electron-withdrawing group; , terphenyl or phenoxyphenyl, and when Ar'' represents a phenoxyphenyl group, there is at least one electron-withdrawing group on the phenoxy residue. ) characterized by an inherent viscosity of approximately 0.5 to
2.0 essentially linear polymers are provided. Preferably the alkyl or fluoroalkyl group constituting R contains 1 to 10 carbon atoms. The repeating units in the resulting polymer advantageously consist essentially of repeating units of the formula: [-M-Ar-B-Ar']-, and the polymer is advantageously substantially linear and advantageously is a homopolymer. However, the polymer may also contain units not specified above,
This additional unit is an unrelated structure or unit [-M-Ar-
B-Ar']-, but of trivalent or other higher valence.
The polymer may also contain two or more identical units represented by the general formula: [--M--Ar--B--Ar']--combined with other unrelated repeating units. Preferably, Ar′ is , and when T is -O-Ar-O-, the Ar segment of the T part is [-M-Ar-B-
Ar'] - different from the Ar segment in the unit. The nucleophilic capping agent has the general formula (In the formula, X is a covalent bond, -O-, -S- or -
CR ₂ -, in which each R, which may be the same or different, has the meaning specified above (preferably -
X- represents a covalent bond or -O-) and -Y
is represented by --CN, --NO ₂ , [Formula] [Formula], and when X is a covalent bond, it represents hydrogen). This electrophilic capping agent has the general formula Ar″COZ
or Ar″SO ₂ Z, in which Z represents OH, halogen (preferably chlorine or fluorine) or OAlk, where Alk represents an alkyl group, preferably an alkyl group having up to 10 carbon atoms; and here
Ar'' represents phenyl, naphthyl, biphenyl, terphenyl or phenoxyphenyl having at least one electron-withdrawing group in the phenoxy moiety, preferably having this group in the para position.
The Ar'' group may be separately unsubstituted but is preferably substituted with at least one electron-withdrawing group. Preferred electron-withdrawing groups are halogeno, nitro and cyano. Two or more nucleophilic or electrophilic Mixtures of electrophilic capping agents can be used. In this polymer, all end groups are formed from electrophilic capping agents or nucleophilic capping agents, or some end groups are formed from electrophilic capping agents and some from nucleophilic capping agents. In the preferred case where the polymer is linear, depending on the polymerization reaction used, each chain has both ends formed from electrophilic or nucleophilic capping agents. or having one end group formed from an electrophilic capping agent and the other end group formed from a nucleophilic capping agent. In most cases the polymer chain has two ends. However (i.e. linear), in some situations, for example to produce melt processable polymers with high melt strength, chains with three or more ends, i.e. long chain branching, may be used. It is preferred to provide a polymer having a molecule having a molecule, and in this case the present invention uses the term ``double'' or ``doubly'' to cap all ends of the molecule. Specific examples of suitable diacid halide first monomers include terephthaloyl chloride, isophthaloyl chloride, oxy-bis(4,4-benzoyl chloride). ), diphenylmethane-4,4'-di(carbonyl chloride), phosgene, benzene-
1,4-di(sulfonyl chloride), benzene-1,3-di(sulfonyl chloride), 2-chlorobenzene-1,4-disulfonyl chloride, thiobis(4,4'-benzoyl chloride), oxy-bis (4,4'-benzenesulfonyl chloride), benzophenone-4,4'-di(carbonyl chloride), oxy-bis(3,
3′-benzoyl chloride), thio-bis(3,
3'-benzenesulfonyl chloride), oxy-
bis(3,3'-benzenesulfonyl chloride),
Diphenyl-3,3'-di(carbonyl chloride), benzophenone-3,3'-di(carbonyl chloride), sulfonyl-bis(4,4'-benzoyl chloride), sulfonyl-bis(3,
3'-benzoyl chloride), sulfonyl-bis(3,4'-benzoyl chloride), thio-bis(3,4'-benzoyl chloride), diphenyl-,3,4'-di(carbonyl chloride), oxy-bis [4,4'-(2-chlorobenzoyl chloride)], naphthalene-1,6-di(carbonyl chloride), naphthalene-1,5-di(carbonyl chloride), naphthalene-2,6-di(carbonyl chloride) , naphthalene-1,5-di(sulfonyl chloride), oxy-bis-[7,
7'-naphthalene-2,2'-di(carbonyl chloride)], thiobis-[8,8'-naphthalene-
1,1′-di(carbonyl chloride)], 7,7-
Binaphthyl-2,2'-di(carbonyl chloride), Diphenyl-4,4'-di(carbonyl chloride), Carbonyl-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)], Sulfonyl -bis[6,6'-naphthalene-2,2'-di(carbonyl chloride)] and dibenzofuran-2,7-di(carbonyl chloride), but are not limited thereto. Examples of suitable second monomers containing at least two substitutable aromatically bonded hydrogen atoms are 4,4'-diphenoxybenzophenone, 1,4
- Diphenone benzene, diphenyl sulfide,
p-phenoxyphenol, p-phenylphenol, dibenzofuran, thianthrene, phenoxatin, phenodioxin, 4,4'-diphenoxybiphenyl, 2,2'-diphenoxybiphenyl, 1,2-diphenyl Enoxybenzene, 1,3-diphenoxybenzene, 1-phenoxynaphthalene, 1,2-diphenoxynaphthalene, 1,5-
Diphenoxynaphthalene, diphenylmethane,
Examples include, but are not limited to, 2,2-diphenylhexafluoropropane, triphenylmethane, and 4-nitrophenyldiphenylmethane. Specific examples of suitable monomers containing at least one acid halide group and at least one substitutable aromatically bonded hydrogen atom include p-phenoxybenzoyl chloride, p-(p-phenoxybenzoyl chloride, enoxy)benzoyl chloride, p-phenoxybenzenesulfonyl chloride, p-(phenylthio)benzoyl chloride, m-phenoxybenzoyl chloride, 1-naphthoyl fluoride, 2-naphthoyl chloride, 5-(1
-naphthoxy)-1-naphthoyl chloride, 6
-(2-naphthoxy)-2-naphthoyl chloride, 2-dibenzofurancarbonyl chloride,
2-benzofurancarbonyl chloride, 2-thianthrenecarbonyl chloride, 2-phenoxatine carbonyl chloride, 2-phenodioxycarbonyl chloride, 3-(4'-biphenyloxy)benzoyl fluoride, 4-(4'-biphenyloxy)benzoyl Fluoride, 4-
(2'-biphenyloxy)benzoyl fluoride, 3-(1'-naphthoxy)benzoyl fluoride, 3-(2'-naphthoxy)benzoyl fluoride and 4-(2'-naphthoxy)benzoyl fluoride. but not limited to. The novel multi-capping process of the present invention produces multi-capped polymers that have excellent high temperature stability and are melt-formable, particularly extrudable products suitable for applications such as wire and cable insulation. offer Advantageously, the polymer chain length is from about 5 to about 500,
Preferably it is within the range of about 20 to about 300. Additionally, the polymers of the present invention can be molded by conventional injection molding techniques. Furthermore, these polymers are substantially free of unmodified chain branching; modified chain branching is obtained as described below. The polymers produced by the method of the invention are characterized by a light color and excellent thermal stability. Furthermore, they form stable solutions even in highly acidic media such as hydrogen fluoride/boron trifluoride mixtures.
Furthermore, solutions of the polymers according to the invention in sulfuric acid are light colored, whereas solutions of the corresponding polymers prepared by a method different from the invention are very colored. Furthermore, these polymers are essentially inert for further reaction with either electrophilic or nucleophilic agents, so that they can be dissolved in solution within the reactor (e.g., on the walls of the reactor) after the completion of one polymerization. Residual polymer left behind does not need to be washed before starting another polymerization. The residual polymer must be completely removed from the reactor before the next polymerization is carried out, since in prior art processes its presence results in the production of very high molecular weight fractions in the product of the next polymerization. Additionally, as noted above, polymer solutions prepared by prior art techniques have an undesirable tendency to increase molecular weight on storage. To facilitate a fuller understanding of the invention:
It is appropriate to distinguish between terms that are often and commonly incorrectly used interchangeably in the prior art with respect to Friedel-Crafts catalyzed polymerization. The term "quenching agent" is almost always added in substantial excess to the polymerization reaction mixture after completion of the polymerization reaction in order to react with the polymer endgroup-catalyst complex, so that the polymer molecules are It means a compound, usually a Lewis base (nucleophilic), which makes it substantially less likely to undergo further undesirable reactions. This reaction is effected by chemical attack of the reactive polymer end groups onto adjacent molecules with which the polymer molecules come into contact during subsequent processing or use. In contrast, having a molar excess of either nucleophilic or electrophilic bifunctional reactants during the polymerization and preferably from the initiation of the polymerization or at any time before the completion of the polymerization reaction conditions Molecular weight adjustment is generally carried out by adding nucleophilic or electrophilic reagents which are monofunctional and thus serve as chain terminators. Of course, this chain terminator is also useful when carrying out polymerizations using monomers having both electrophilic and nucleophilic moieties on the same molecule. Of course, it is clear that the quenching agents can be used suitably in combination with molecular weight modifiers. Capping agents, which can be either electrophilic or nucleophilic, function differently than either quenching or molecular weight modifiers. The purpose is to form groups at all (or both, in the case of linear molecules) ends of the polymer molecule and thereby make the end groups of the polymer molecule at least as resistant to chemical attack as the rest of the molecule. The purpose is to make it so that it is. Its main action is not to stop the polymerization; in fact, unlike a quencher, it may be present in the polymerization mixture throughout the polymerization reaction. Compounds that act as capping agents as defined above may, under certain circumstances, perform a molecular weight regulating function or, contrary to the teachings of the present invention,
It should be noted that if added in excess, the reaction can be stopped in some cases. However, under conditions that result in polymer molecules that are reactive, i.e., uncapped at at least one end as defined below, the prior art has consistently used either electrophilic or nucleophilic molecular weight modifiers. There is. for example,
GB 1387303 contains a discussion of the use of so-called capping agents in connection with polymerization reactions similar to those described herein. However, it should be noted that in the context of this patent, the so-called capping agents are actually molecular weight modifiers that act in their own right and are not true capping agents as described herein. In fact, prior art reagents cannot actually achieve the objectives of the present invention when used as described in the aforementioned British patent. In fact, the nature and significance of multiple capping as described and claimed herein was not recognized at the time of the aforementioned British patent. The present invention contemplates the use of capping agents to provide a polymer molecule that is non-reactive and resistant to chemical attack at both ends of the molecule. The use of quenching and/or molecular weight modifiers as defined above in conjunction with capping agents does not provide any useful effect and is in some cases harmful. The distinction between quenching agents and capping agents is to think of the former as reducing the tendency of polymers to attack other molecules, including monomers or oligomers, which are less reactive than polymers, whereas the latter Coalescence can be shown to increase the resistance of the polymer to attack by more reactive species. Since the quencher is only added after the total polymerization is complete, the use of a molecular weight regulator without a capping agent will result in any polymerization reaction mixture in which growth is stopped by the molecular weight regulator, but will nevertheless degrade. This means that there are a significant number of "finished" molecules that are sufficiently unstable to undergo extinction before extinction. Of course, other molecules are still undergoing polymerization, so it is impractical to render these completed molecules inactive by adding a quenching agent. Therefore, when the polymerization reaction is finally quenched, it will contain a significant proportion of molecules whose chain growth was initially completed and subsequently degraded. This problem is particularly evident when highly reactive catalysts such as HF-BF ₃ are used. This is one of the problems unexpectedly solved by the present invention. With this background, the use of the present invention to provide controlled branching can be more easily understood. If the polymerization uses monomers with hydrogens that can be placed with diacid halides, i.e. in type polymerization, molecular weight modifiers with more than two chain initiation sites are used, branching occurs, and capping occurs. The nature and mole percentage of the agent is influenced by the number of starting positions. For example, if the molecular weight modifier is nucleophilic, the end capping agent should be electrophilic and present in a percentage molar ratio equal to the number of initiation positions. Branching also occurs when electrophilic capping agents with polyfunctionality are used, since this caps several growing chains; in combination, molecular weight modifiers are used. If the molecular weight regulator is initiated only on one side and is unreactive on the other side, a single branching position will occur on each molecule, which is suitable. Alternatively, although not preferred, if the molecular weight modifier is polyfunctional and can be initiated on one side but still reactive, more branching will occur and polyfunctional capping agents may be used. If so, it will probably lead to undesirable gelation. In this case, it is advantageous to use both a monofunctional capping agent and a polyfunctional capping agent, with the ratio of the concentration of the monofunctional capping agent to the concentration of the polyfunctional capping agent being equal to the functionality of the former. It is. If the molecular weight modifier is electrophilic, the capping agent should be nucleophilic. If the polymerization is a type polymerization, similar considerations apply, except that both the capping agent and the molecular weight modifier are nucleophilic when the electrophilic monomer is in excess; It may be the other way around. However, although the invention can be used to provide polymers with controlled branching, the preferred products of the invention are essentially linear polymers; an advantage of the process of the invention is that the resulting Includes reproducibility of coalescence and the ability to produce polymerizations of desired chain lengths and thus specific viscosities. The polymer to which this invention is particularly concerned has the structural formula: polyarylketones containing repeating units of, ie, poly(benzophenone ether). Particularly preferred are those having this repeating unit and about 0.8
Homopolymers and copolymers having an average intrinsic viscosity within the range of from about 1.65 to about 1.65 are included. This polymer and its method of preparation are described in British Patent No. 1387303. Second, repeat unit:
Mention may be made of aromatic ketone polymers having the formulas and formulas, and especially homopolymers of p-biphenyloxybenzoyl monomers, and also copolymers thereof blended with small amounts of the corresponding o-comonomers, about 0.5 Particularly preferred are polymers having an average intrinsic viscosity of from about 1.7 to about 1.7. Similar polymers and methods of their preparation are described in U.S. Pat. No. 3,593,400.
listed in the issue. The present invention also relates to sulfonyl analogs of the polyaryl ketones described above, and U.S. Pat.
3442857, 3321449 and other polymers and corresponding processes for their manufacture as described in Goodman UK Patent No. 971227 and Jones No. 1016245; is hereby incorporated by reference to avoid unnecessary enlargement of the present specification. Particularly useful solvents for use in this polymerization include nitrobenzene, o-dichlorobenzene, sym-tetrachloroethane, methylene chloride, mixtures of any of the foregoing, and also anhydrous hydrogen fluoride. Common Friedel-Crafts catalysts are suitably used in the polymerization process, such as aluminum chloride, aluminum bromide, boron trifluoride, hydrogen fluoride, ferric chloride,
Contains stannic chloride, indium chloride and titanium tetrachloride. Aluminum chloride, indium chloride, and ferric chloride are suitable catalysts, and mixtures of hydrogen fluoride and boron trifluoride are particularly suitable. For example, the amount of suitable catalysts such as aluminum chloride and boron trifluoride is usually at least one molar equivalent per carbonyl or sulfonyl group of the monomeric reactant. In the case of ferric chloride or indium, up to 1 molar equivalent is usually used. The polymers to which this invention relates are produced by polycondensation. There are two types of polycondensation used in this invention. In the mold, two monomeric starting materials,
a first monomeric reactant which is an electrophile and is generally a diacid halide; and a second monomeric reactant which contains at least two displaceable aromatically bonded hydrogen atoms and which is a nucleophile. There are two monomeric reactants. [EE] is the molar concentration of the electrophile,
[NN] is the molar concentration of the nucleophile, and
When EE is in excess, the molecular weight of the resulting polymer, MW, is determined by the formula: MW = [EE] + [NN] / [EE] - [NN] x W/2 (where W is the repeat of the polymer). unit (i.e.
is the molecular weight of the EENN residue). Therefore, the use of excess EE provides molecular weight adjustment. Conversely, if NN is in excess to adjust the molecular weight, the molecular weight is equal to [NN] + [EE]/[NN] - [EE] x W/2. When EE is in molar excess, the polymer chains readily react with acid halide ends, which increases the branching of the polymer chains and the instability of the polymer when melted, as is also well known to those skilled in the art. It shows a tendency to have groups. If NN is used in excess to effect molecular weight adjustment and the NN is at least at one end of the polymer chain due to the phenoxy group or excess NN, it contains a group similar to the phenoxy group in its reactivity towards acylation. It was unexpectedly found that reaction of these end groups with ketone catalyst complexes during or after polymerization tends to cause branching, possibly through the formation of trisarylcarbonium ionic salts. . Furthermore, molecular weight adjustment by addition of a monofunctional molecular weight adjustment compound to a stoichiometric mixture of starting materials may further increase the end groups depending on whether the monofunctional reagent is electrophilic or nucleophilic. Each polymer molecule has an electrophilic or nucleophilic group at the end of the polymer molecule away from the molecular weight modifier residues that react and cause chain branching, thus preventing either of the above problems. It turns out it can't be done. The molecular weight of the resulting polymer is determined by the formula: MW = [C] x W/[T], where [C] = [NN] = [EE], and [T] is the molar concentration of the molecular weight modifier used. , and W is the molecular weight of the repeating unit of the polymer). Thus, the use of excess nucleophilic monofunctional molecular weight modifiers to provide molecular weight adjustment to polymers by type reactions does not in any way address or solve the problem of polymer stability that is the object of this invention. That is clear. Another type of polymerization uses a single monomer having both an acid halide group and a substitutable hydrogen bonded to at least one aromatic group. When the molar concentration of the monomer is [EN] and a monofunctional molecular weight modifier is used, the molecular weight of the polymer is according to the formula: MW=[EN]×W/[T], where [T] and W are as defined above). Again, the use of monofunctional reagents for molecular weight adjustment means that at least one end of each polymer molecule is terminated with either a reactive nucleophilic or electrophilic group that serves as a branching initiator. It has the disadvantage of Accordingly, the present invention provides Friedel-Crafts condensation polymers in which the molecule is capped at both ends by groups that do not serve as branching initiators under the polymerization conditions. For type condensation polymerizations, either the electrophilic or nucleophilic agent can be present in excess or in equimolar amounts. In the first and second cases the molecular weight is adjusted by the excess of reactants as described above. In the first case, the nucleophilic capping agent effectively caps both ends of the polymer chain. In the second case, the electrophilic capping agent caps both ends of the polymer molecule. In a type polymerization where equimolar amounts of electrophilic and nucleophilic capping agents are present or in type polymerization, electrophilic and nucleophilic capping agents are added and the polymer chain is capped at one end by a nucleophilic cap. and is capped at the other end by an electrophilic cap. Another advantage of the invention is that in this situation the capping agent serves an additional function of the molecular weight modifier. The electrophilic polymer end cap for polymers made in accordance with the present invention has the structure: Ar"CO-- or Ar" _SO2-- , where Ar" is as previously defined for the electrophilic capping agent. ).The nucleophilic polymer end cap has the structure: (where X and Y are as defined above for nucleophilic capping agents). The preferred ratios of the components according to the invention for type polymerization are as follows: Case a [EE] > [NN] Molar fraction of difunctional electrophile [EE]: 1 Molar fraction of nucleating agent [NN]: 1-a Molar fraction of nucleophilic capping agent: 2a Case b [NN] > [EE] Molar fraction of difunctional electrophile [EE]: 1 Bifunctional Mole fraction of functional nucleophile [NN]: 1 + a Mole fraction of electrophilic capping agent: 2a Case c [NN] = [EE] Mole fraction of bifunctional reagent (EE & NN): 1 Nucleophilic capping Mole fraction of electrophilic capping agent: a Mole fraction of electrophilic capping agent: a The capping agent can be added at any stage of the polymerization, including after the completion of the polymerization in cases a and b; No molecular weight regulator is required. In case c, one of the capping agents also acts as a molecular weight regulator and is therefore preferably added early in the polymerization, optimally at the beginning of the reaction. In contrast, other capping agents can be added at any time. It is preferably electrophilic, but may be nucleophilic. Preferably, in all three cases, the capping agent(s) are added at the beginning or early in the polymerization. As in case c, the object of the invention is achieved by adding approximately equal molar fractions of both electrophilic and nucleophilic capping agents to the type condensation polymerization. Under these circumstances no separate molecular weight regulator is required. The proportions of the components for type condensation are as follows: mole fraction of type monomer: 1 mole fraction of nucleophilic capping agent: a mole fraction of electrophilic capping agent: a actually each capping agent It has been found that extreme precision is not necessary, although it is often difficult to select exactly the same amount of . If it is not possible to provide exactly the same amount of electrophilic and nucleophilic capping agent, it may be desirable to use only a slight excess of nucleophilic agent. For both type and type reactions, the value of a can vary from about 0.001 to about 0.05, preferably from 0.002 to 0.01, based on the value of 1 for the monomers shown above. As mentioned above, the capping agents used in the practice of this invention can be either nucleophilic or electrophilic. Preferred nucleophilic capping agents are biphenyl, 4
- Phenoxybenzophenone, 4-thiophenylbenzophenone, or an equimolar mixture of diphenyl ether and benzoic acid, or in situ 4-phenoxybenzophenone, 4-thiophenylbenzophenone including derivatives thereof that form. Suitable electrophilic capping agents include benzoic acid, benzenesulfonic acid or the corresponding acid halides. The polymers of the present invention preferably have a viscosity ranging from about 0.5 to 2.0 and contain from about 5 to about 300 repeat units. Obviously, both homo and copolymers can be prepared according to the teachings of the present invention by using mixtures of electrophilic and/or nucleophilic difunctional monomers and/or mixtures of monomers of the EN type. can be manufactured. Next, examples will be shown to explain the present invention. In the following Examples, Examples 1, 2, 4 to 8, 11 to
Examples 13, 15, 16(b), 18 and 19 are included in the present invention. “Teflon” and “Waring” are trademarks. All parts are by weight and temperatures are in °C unless otherwise noted. Throughout, the average intrinsic viscosity is the Preparative of Sorensen et al.
Methods of Polymer Chemistry, Interscience (1968) p. 44 [Concentrated sulfuric acid solution 100% at 25°C]
0.1 g of polymer in ml]. 1
The electronic spectra of the polymer solutions were measured on a Perkin-Elmer 450 spectrophotometer using a silica cell with a cm pass distance. 150 by stirring 0.02 to 0.05 g of polymer sample for 15 to 20 minutes.
This sample was dissolved in 5.00 ml of dichloroacetic acid at −160°. Solutions were recorded against a dichloroacetic acid blank. Absorption reading obtained at 495nm in grams per ml
divided by the solution concentration to give the absorbance index value (As), which is a measure of the branching position in the polymer. Example 1 Model Compound Testing Branched with Phenoxy End Groups Interacting with Carbonyl Bonds of the Polymer p-Phenoxybenzoyl Chloride Containing 0.573 mol% Biphenyl and 0.753 mol% Benzoic Acid
A 2.36 g (10 mmol) sample was polymerized using standard methods. Half of the reaction solution was precipitated to obtain a polymer with an intrinsic viscosity of 1.33 and an As value of 10 at 495 nm. This product was compression molded at 400° for 5 minutes to obtain the same intrinsic viscosity.
Obtained 1.33 colorless slabs. To the other half of the polymer solution was added 2.5 g (approximately 10 mmol) of 4-bromodiphenyl ether, which served as a "model" for the reactive end groups formed by prior art polymerization. The mixture was stirred at room temperature for 16 hours and then recovered by precipitation into water. The polymer was washed with acetone to remove excess 4-bromodiphenyl ether, followed by drying to show an intrinsic viscosity of 1.33 and a trisarylcarbonyl structure formed.
A colorless product with As value of 540 at 495 nm was obtained. This product was compression molded at 400° for 5 minutes to obtain a slab of reduced intrinsic viscosity (1.22). Example 2 Suppression of gel formation during polymerization by dicapping A sample of 37.9 parts of p-phenoxybenzoyl chloride containing 0.134 parts (0.50 mol%) of biphenyl was
It was placed in a cold (approximately 0°) pressure vessel lined with FEP polymer and equipped with an agitator, heating and cooling coils, multiple nozzles, and pressure and temperature adjustment and control equipment. Cool the anhydrous hydrogen fluoride to -20° in a separate container,
Approximately 105 parts were then gradually added to the monomer while stirring. The reaction temperature was gradually increased to 20° while maintaining a slow nitrogen purge. The hydrogen chloride generated during this process is released through a condenser (maintained at -10°),
And it was absorbed into the scrub bar. The monomer solution was then cooled to 0° and boron trifluoride was charged to give a system pressure of 2.45 Kg/cm ² and a reaction temperature of 14°. These pressure/temperature conditions were maintained for 4.5 hours. The boron trifluoride feed was then stopped, the contents cooled to +7°, and the scrubber was then vented with boron trifluoride until ambient pressure was established. Transfer the resulting polymer solution to a large container and add hydrogen fluoride and water 13.6
part to give a solids content of 4.5%. This solution was pressurized through a polypropylene cartridge filter (10μ) to a two-fluid spray nozzle for recovery of the solid polymer by spray drying as described in US Pat. No. 3,751,398. During this process,
The filter cartridge became obstructed by the gelatinous polymer material and had to be replaced four times before completing the run. The polymer recovered by spray drying was colorless and had an intrinsic viscosity of 1.38. The gelatinous material removed from the cartridge filter was found to be insoluble in hydrogen fluoride, hydrogen fluoride/boron trifluoride mixtures, or concentrated sulfuric acid. This insoluble material was suspended in hydrogen fluoride and stirred overnight followed by filtration. Wash the filter residue with water and then 110°/
A slightly pink polymer coagulum was obtained by drying at 20 mmHg/16 hours. Compression molding at 400° for 5 minutes resulted in incomplete melting. A dark brown slab was obtained. This molten material was insoluble in concentrated sulfuric acid. Differential scanning calorimetry shows a melting point of 365°, a glass transition temperature of 165°, a recrystallization temperature of 263°, and the corresponding values for the hydrogen fluoride soluble spray-dried polymer are 365°, 165° and 165°, respectively.
It is 210°. 0.0174g coagulum from insoluble residue
Dissolve the sample in 5 ml of dichloroacetic acid at 160° to give a deep red solution, which was diluted 1:20 with dichloroacetic acid.
and analyzed by electronic absorption spectroscopy. A strong band with an absorbance of 0.8 was observed at 495 nm. p-Trisphenoxyphenylcarbinol in dichloroacetic acid
It exhibits strong absorption at 495 nm with an extinction coefficient of 1.1×10 ⁵ . Assuming that the same type of structure is present in the polymer coagulum, calculations suggest about 2 mole percent branching/crosslinking. The above polymer preparation, which is an example of the best available prior art, has been repeated many times, but always results in different degrees of filter blockage. In accordance with the teachings of the present invention
When the polymer preparation was repeated in the presence of 0.50 mol % biphenyl and 0.475 mol % benzoic acid, a polymer with an intrinsic viscosity of 1.35 was obtained, which allowed the batch to be filtered and spray dried without hindrance and virtually free of foreign matter. Many batches could be filtered through the same cartridge before polymeric material build-up necessitated replacement. Example 3 Branching during Polymer Preparation A batch of polymer was prepared using 37.9 parts of p-phenoxybenzoyl chloride in a FEP-lined pressure vessel as described in Example 2, i.e., not according to the invention. did. In two sets of experiments, the residual polymer left in the reactor from the previous run was not removed (A-1, A-2). The next two runs were runs in which the reactor was cleaned of old polymer before charging new monomer and anhydrous hydrogen fluoride (B-1, B-
2). The polymer was recovered by spray drying and the intrinsic viscosity of the powder and compression molded slab was measured. Slab color (classification: 1 = colorless, 10 = dark brown), powder As, and powder extrudability were evaluated using a 3/4 inch Branbeder extruder. The results obtained are shown below. Table 10 During the continuation of the experiment, similar to B-1 and B-2, As was 10 to about 70, despite careful removal of old polymer from the reactor before introducing new monomer The value became . Although this did not have a significant negative effect on extrudability, undesirable color variations were observed in the extrudates. When the polymerization is controlled by dicapping with biphenyl and benzoic acid according to the teachings of the present invention instead of single capping with only biphenyl as taught by the prior art,
As values equal to or less than 25 were consistently observed. Example 4 Shelf life evaluation of mono- versus di-capped polymer solutions p-phenoxybenzoyl chloride containing 0.50 mol% of each capping agent listed in the table below.
2.32 parts of the sample were polymerized at room temperature in 8 parts of anhydrous hydrogen fluoride under a boron trifluoride pressure of 2.1 Kg/cm ² for 4 to 90 hours. The resulting polymer solution was worked up by precipitation into water. Intrinsic viscosity was measured using conventional methods. The results are shown below. Table *These experiments were not in accordance with the present invention.
+ These experiments were in accordance with the present invention.
This experiment shows that multiple capping according to the invention provides a product of consistent viscosity that is not affected by wide variations in reaction time. Example 5 Polymerization in hydrogen fluoride containing sulfur dioxide.
Monocapping vs. dicapping A sample of p-phenoxybenzoyl chloride containing 0.6 mol% biphenyl or a mixture of 0.60 mol% biphenyl and 0.6 mol% benzoyl chloride was prepared at room temperature and 2.1 Kg/ ^cm2 boron trifluoride pressure. Polymerization was carried out at a monomer concentration of 20% in HF with various sulfur dioxide contents for times. The resulting polymer was recovered using standard methods and its intrinsic viscosity was measured. The results are shown below. Table: A portion of the above polymer solution containing only hydrogen fluoride as solvent was diluted with sulfur dioxide after polymerization to a solids content of 5%. The solution was then kept under a boron trifluoride pressure of 2.1 Kg/cm ² for 24 hours. Intrinsic viscosity measurements showed a significant increase for the monocapped polymer while the dicapped polymer showed no change. [Table] * Not in accordance with the present invention + In accordance with the present invention.
Example 6 Post-polymerization of dicapped versus monocapped polymers A 2.3265 g of p-phenoxybenzoyl chloride into a 150 ml polychlorotrifluoroethylene tube
(10.00 mmol), 0.0077 g (0.05 mmol) of biphenyl, 0.057 g (0.05 mmol) of benzoic acid, and a stir bar were charged. To this mixture was gradually added 10 ml of anhydrous hydrogen fluoride. This tube was then connected to a nitrogen purged polychlorotrifluoroethylene vacuum line (Toho Kasei Co., Osaka, Japan). Boron trifluoride gas was introduced and the reaction mixture was maintained at 2.1 Kg/cm ² pressure for 4 hours to obtain a viscous orange solution. After cooling to -78°C, excess boron trifluoride was purged from the reaction system. The polymer solution was diluted with aqueous hydrogen fluoride and then poured into rapidly stirred water. The resulting polymer precipitate was filtered and washed with water, followed by drying at 120°/20 mm Hg to yield a colorless fluff with an intrinsic viscosity of 1.36. B The same process as in section A was used. However, when the polymerization time was increased to 8 hours, the intrinsic viscosity of the product was 1.39. C This polymer was prepared according to the procedure in Section A. After 4 hours of polymerization, excess boron trifluoride was purged from the reaction system and 0.0146 g (0.04 m
mol) was added to the solution. Polymerization continued for 4 hours. The intrinsic viscosity of the product was 1.34. A,
B and C are according to the invention. D 2.3265 g of p-phenoxybenzoyl chloride in a 150 ml polychlorotrifluoroethylene tube
(10.00 mmol), 0.0185 g (0.05 mmol) of 4,4'-diphenoxybenzophenone, and a stir bar were charged. 10 ml of hydrogen fluoride was gradually added to this mixture. This tube was connected to a polychlorotrifluoroethylene vacuum line purged with nitrogen. Add boron trifluoride gas and
The reaction mixture was kept at 2.1 Kg/cm ² for a period of time to obtain a viscous orange solution. After cooling to −78° C., excess boron trifluoride was purged from the reaction system. The polymer solution was diluted with aqueous hydrogen fluoride and then poured into rapidly stirred water. The resulting polymer precipitate was filtered and washed with water, followed by 125°/20
Drying at mmHg gave a colorless fluffy material. The intrinsic viscosity of the product was 1.30. E The same process as in Section D was used, but the polymerization time was increased to 8 hours. The intrinsic viscosity of the product was 1.31. F This polymer was prepared according to the procedure in section D. After 4 hours of polymerization, the reaction system was purged of excess boron trifluoride and 0.0146 g (0.04 m
mol) was added to the solution. Polymerization was then continued for 4 hours. The intrinsic viscosity of the resulting polymer was 4.20. The experiment was repeated to obtain a polymer with an intrinsic viscosity of 4.26. D, E and F are not in accordance with the present invention and indicate that the sensitivity of prior art products to continued polymerization leads to excessively high molecular weights when contacted with excess monomer. Example 7 Molecular weight adjustment by dicapping with biphenyl and benzoic acid 10 mmol of p-phenoxybenzoyl chloride (25% solids concentration) in hydrogen fluoride at room temperature for 4 hours and at a boron trifluoride pressure of 2.1 Kg/cm ² A series of polymerization tests were carried out using The molecular weight was adjusted according to the invention by addition of biphenyl and benzoic acid for an intrinsic viscosity range of 1.0 to 1.6. The results are shown below. Dicapping mole% Biphenyl Benzoic acid Intrinsic viscosity 0.400 0.380 1.58 0.400 0.380 1.62 0.600 0.570 1.23 0.600 0.570 1.27 0.700 0.665 1.15 0.700 0.665 1.15 0 .800 0.764 1.03 0.800 0.764 1.04 0.900 0.855 0.95 0.900 0.855 0.96 Example 8 Apparatus and process of Example 6 using p-phenoxybenzoyl chloride, p-phenoxybenzophenone (0.5 mol%) and benzoic acid (0.50 mol%)
to give a product having essentially the same properties and viscosities as materials A, B and C of the examples when polymerized for a similar time and under similar conditions. Example 9 Using the equipment and process of Example 6, 4,4'-diphenoxybenzophenone (4.95 mmol), terephthaloyl chloride (5.00 mmol) and p-phenoxybenzophenone (0.1 mmol) was polymerized to give a light colored fluffy polymer virtually identical to the polymer of Example 6A, which formed a stable solution with hydrogen fluoride. Example 10 Using the equipment and process of Example 6, 4,4'-diphenoxybenzophenone (5.0 mmol), terephthaloyl chloride (4.95 mmol) and benzoic acid (0.1 mmol) were prepared.
A mixture of mol) was polymerized to yield a material substantially identical to that of Example 9. Example 11 Using the equipment and process of Example 6, p-phenoxybenzoyl chloride, benzoic acid (0.5 mol%) and 0.5 mol% p-cyanodiphenyl ether, p-nitrodif Mixtures of each of enyl ether and p-phenoxydiphenyl sulfone were polymerized to yield polymer products that were extremely stable in hydrogen fluoride solution. Example 12 p-Phenoxybenzoyl chloride, biphenyl (0.5 mol %) and in three experiments 0.5 mol % p-anisic acid, p-phenylbenzoic acid and p-( A polymeric material was prepared from each mixture of 4-chlorophenoxy)benzoic acid, and the material had a stable viscosity in hydrogen fluoride. Example 13 Cooled 150 with PTFE coating agitator
ml Teflon (polytetratrifluoroethylene)
To the flask, add p-phenoxybenzoyl chloride (23.25 parts), biphenyl (0.077 parts, 0.50 mol% nucleophilic capping agent), benzoic acid (0.057 parts, 0.05 parts).
(mol% electrophilic capping agent) and anhydrous hydrogen fluoride (100 parts). 0℃ and 2.1Kg/cm ²
This mixture was stirred with an applied boron fluoride pressure of . The mixture was allowed to warm to room temperature and stirring was continued for 100 hours. The resulting polymer solution was diluted with hydrogen fluoride containing 5% W/V water to about 5% solids content and poured into water in a Waring blender. The granular product was thoroughly washed with water and stored in vacuum (15 mm
Hg). The polymer obtained in quantitative yield had an intrinsic viscosity of 1.4 and an As value of 10 at 495 nm.
This polymer is melt stable and easily extrudable. Example 14 This is an example using the teachings of the prior art. The process of Example 13 was repeated except that the benzoic acid electrophilic capping agent was omitted. The recovered polymer had an intrinsic viscosity of 1.5 and an As value of 400 at 495 nm.
The material was essentially non-extrudable due to excessive decomposition when extrusion was attempted. Example 15 The procedure of Example 13 was followed except that after 4 hours at room temperature the boron fluoride was evacuated and the polymer solution was stirred for an additional 96 hours. The resulting polymer had physical properties identical to those of Example 13, including good extrudability and appearance. Example 16(a) This is an example performed in accordance with the teachings of the prior art. The procedure of Example 15 was followed except that the benzoic acid was omitted. The recovered polymer had an intrinsic viscosity of 1.45 and an As value of 350. Polymers produced in this manner were found to be non-extrudable without undue degradation. If the polymer is recovered immediately after exhausting the boron fluoride (i.e. after 4 hours),
A product is obtained with an intrinsic viscosity of 1.4 and an As value of 35. While the polymer rapidly recovered in this manner has satisfactory extrusion performance, the present example shows that the reaction mixture obtained by the prior art method can be used for a considerable period of time without impairing the processability of the polymer. Indicates that it cannot be stored. This sensitivity makes it very difficult to prepare commercial production of this prior art polymer. In contrast, Example 15 shows that the novel polymers of the present invention have great stability in solution in acidic media, making them very commercially useful. Example 16(b) Following the steps of Example 13, but stirring the reaction mixture at 50° C. for 4 hours after adding boron trifluoride;
It was then processed as in Example 13. The polymer prepared by this method had an intrinsic viscosity of 1.40 and an As value of 20 and could be extruded satisfactorily. Example 17 This is an example performed in accordance with the teachings of the prior art. The process of Example 16(b) was followed except that the benzoic acid was omitted. The polymer produced by this method is
It had an intrinsic viscosity of 1.5 and an As value of 415. This material developed significant crosslinking and discoloration during extrusion. Examples 16(b) and 17 show that polymerizations carried out according to the invention are hardly influenced by polymerization temperature, whereas polymerizations according to the prior art are extremely sensitive to reaction temperature. The polymers of Examples 13-17 contain repeating units of the following structure. Example 18 Polymerization of p-phenoxybenzenesulfonyl chloride Monocapping versus dicapping Sodium p-phenoxybenzenesulfonate 400 g of freshly distilled diphenyl ether ( 2.35 mol) was charged. While stirring, 1200 ml of carbonized methylene chloride was gradually added. A continuous flow of dry N ₂ was passed through the reaction assembly and the flask was cooled to −23° with a dry ice/carbon tetrachloride flash bath. 152 ml (273 g, 2.35 moles) of distilled chlorosulfonic acid was added slowly with stirring from the addition funnel. The reaction mixture was stirred at −23° C. for 12 hours and then at room temperature for 12 hours. Then 3 portions of ice water were added slowly and 3 portions of water was used to transfer the resulting mixture to a separatory funnel. The organic layer was separated and the aqueous phase was extracted with ether (3x800ml). The combined organic layers were extracted with water (2 x 1000 ml), then dried ( _MgSO4 ) and the solvent removed (40-50°/20
mm) yielding 61.37 g (0.36 mol) of diphenyl ether. The combined aqueous extracts were briefly heated to drive off the organic solvent, then solid sodium chloride
1500g was gradually added while stirring. After cooling to room temperature, the crystalline precipitate was left overnight. This was filtered by centrifugation and sodium chloride 10%
Washed with solution. The slightly damp filter cake was recrystallized once more from water. Treatment of the mother liquor gave a second yield. Water was removed from the filter cake by centrifugation at 2500 rpm for 1/2 hour, followed by drying overnight at 110°/0.5 mm to yield a colorless crystalline material.
543.4 g (2.0 mol, approximately 100%, containing some sodium chloride) were obtained. p-Phenoxybenzenesulfonyl chloride Finely divided sodium p-phenoxybenzenesulfonate 610 suspended in 1650 ml of dry dimethylformamide into a dry 3-necked 5 flask equipped with a mechanical stirrer, addition funnel and nitrogen sparge.
g (2.42 mol). The reaction flask was immersed in an ice bath and 195 ml (319 ml) of distilled thionyl chloride
g, 2.68 mol) was gradually added with stirring for 1 hour. The suspension was stirred for 4 hours at room temperature and then poured into a cooled (0°) mixture of ether (1.5) and water (1.5) with vigorous stirring. The aqueous phase was separated and extracted with 300 ml of ether. The combined organic phases were washed with cold water (300 ml), 10% NaOH solution (2 x 300 ml) and water (2 x 150 ml).
The final wash water had a pH of 6.5 to 7. The ether solution was dried (MgSO ₄ ) and the solvent removed [40-50° (bath)/20 mm] to give a pale yellow oil. Add a sample of 5 g of finely dried sodium chloride and use a 15 cm Vigreauz column to
The product suspension was subjected to short-pass distillation at 150-160° (bath)/3 x 10 ^-5 mmHg. The column was covered with heating tape held at approximately 160°. A banana-shaped receiver cooled by running water was used. Colorless distillate 534.9g (1.99
molar, 82%) was obtained. When this distillate was left to stand, it crystallized: mp41-43°. Two recrystallizations from ether/pentane under strictly anhydrous conditions yielded 480 g (1.78 mol, 74%) of colorless crystals: mp43.0-
43.5°. Zone purification and/or vacuum sublimation did not raise the melting point. Ir (KBr): 1181 (s) and 1385 (s) cm ^-1 (sulfonyl chloride), 1255 (s) cm ^-1 (ether):
3080 (w), 1578 (s), 1490 (s) cm ^-1 (aromatic structure). NMR (CDCl ₃ ): δa7.92 (d, 2H, additional fine splitting), δb7.03 (d, 2H, additional fine splitting), Jab9.1Hz, 6.9-7.7 (multiplet, 5H)
ppm. Calculated value for analytical value C ₁₂ H ₉ ClO ₃ S: C,
53.64; H, 3.38; Cl, 13.19; S, 11.93 Actual value: C, 53.77, 53.50, 53.59; H, 3.47,
3.40, 3.42; Cl, 13.06, 13.14, 13.26; S,
11.77, 11.86, 11.96. After conversion with TlC and piperidine, a sulfonamide was generated [SiO ₂ ,
Hexane/ether (1/
1)]: 1 spot. Two purities of p-phenoxybenzenesulfonyl chloride were used for this experiment. One purity melted at 41-43° and the other at 43-43.5°. Samples (10 mmol) of each monomer containing 0.50 mol% biphenyl (monocapped) or 0.50 mol% biphenyl and 0.48 mol% benzoic acid (dicapped) were incubated at room temperature and at 30 psi for 16 hours.
When only biphenyl, a less pure monomer, was used as capping agent, polymerized in 10 ml of anhydrous hydrogen fluoride at ₃ pressures of BF, the resulting viscous solution contained some gelatinous material. All other solutions were gel-free. Standard processing gave colorless polymers and these were measured for intrinsic viscosity before and after compression molding at 400°/5 minutes. The obtained data are shown below. [Table] +: This slab is incompletely dissolved in concentrated sulfuric acid and gelatinized before viscosity measurement.
The carbon-like material was removed by filtration.
Example 19 A sample of 2.32 parts of p-phenoxybenzoyl chloride containing 0.5 mole % diphenyl ether and 1.0 mole % benzoic acid was prepared according to the teachings of the present invention.
Polymerization was carried out in 10 parts of hydrogen fluoride for 4 hours at room temperature under 30 psi of boron trifluoride pressure. This polymer solution was processed as in Example 9 to yield a colorless material with an intrinsic viscosity of 1.46 and an As value of 15. This experiment was repeated but the reaction time was extended to 90 hours.
The obtained polymer had an intrinsic viscosity of 1.51 and an As value of 25. In another series of experiments, the above preparation of the polymer was repeated, but in one experiment only 0.5 mole % benzoic acid was used and in another experiment no benzoic acid was used. After 4 hours of reaction in both experiments, the polymer had an intrinsic viscosity of about 1.45 and low As, but after 90 hours of reaction, the intrinsic viscosity was much higher and the recovered polymer containing gel particles was very expensive
It had an As value. These experiments show a clear effect performed by the molecular weight modifier (diphenyl ether) and the capping agent (benzoic acid).

Claims (1)

[Scope of Claims] 1. At least one acid halide group and at least one substitutable aromatic compound in the presence of 0.001 to 0.05 mole of each nucleophilic capping agent and electrophilic capping agent per mole of monomer. Friedel-Crafts condensation polymerization of at least one monomer containing a hydrogen atom bonded to a nucleophilic capping agent having the general formula: The electrophilic capping agent is represented by the general formula: Ar″COZ or Ar″SO ₂ Z [In the above formula, -X- is a covalent bond, -O-, -S
-, or -CR ₂ - (wherein each R is the same or different and is hydrogen, an alkyl or fluoroalkyl group, an unsubstituted phenyl group, or a phenyl group substituted with an electron-withdrawing group); Y is ―CN，―
When NO ₂ , [Formula] or [Formula] or -X- represents a covalent bond, it represents hydrogen; Ar'' is phenyl unsubstituted or substituted with at least one electron-withdrawing group;
represents naphthyl, biphenyl, terphenyl or phenoxyphenyl (provided that when Ar'' represents phenoxyphenyl there is at least one electron-withdrawing group on the phenoxy residue); Z represents OH, halogen or OAlk; (However, Alk is an alkyl group.) A method for producing a polymer, characterized in that 2. In the reagent containing a substituent Z, Z is
2. A process according to claim 1, wherein Alk is an alkyl group having not more than 10 carbon atoms. 3. Claim 1 or 3, wherein the nucleophilic capping agent is biphenyl, p-phenoxybenzophenone, p-thiophenylbenzophenone, or a mixture of equimolar amounts of diphenyl ether and benzoic acid. The method described in Section 2. 4. The method according to any one of claims 1 to 3, wherein the electrophilic capping agent is benzoic acid or benzenesulfonic acid. 5. The method according to any one of claims 1 to 4, wherein a capping agent is added at the beginning of polymerization. 6. The method according to any one of claims 1 to 5, which is carried out in the presence of a HF/ _BF3 catalyst. 7. A method according to any of claims 1 to 6, wherein the electrophilic and nucleophilic capping agents are present in substantially equimolar amounts. 8 Each of both reagents per mole of monomer
8. A method according to claim 7, wherein said compound is present in an amount of 0.002 to 0.01 mole. 9. The method according to any one of claims 1 to 8, wherein the produced polymer is a homopolymer. 10. The method according to any one of claims 1 to 9, wherein the produced polymer is linear.