Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
  • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D495/08—Bridged systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3874—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing heterocyclic rings having at least one sulfur atom in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6453—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having sulfur

Definitions

• This invention relates to alkyl-substituted thiapolycyclic polyahls which have utility as monomers in making polyureas, polyamides and other polymers.
• a polymer is a large molecule built up by the repetition of small, simpler chemical units called monomers.
• the character of the monomer unit has a strong effect on the physical and chemical properties of the polymer.
• the incorporation of aromatic nuclei in polymer chains has its drawbacks. Polymers containing aromatic nuclei are susceptible to deterioration. They may stiffen and become brittle, change color, or yellow and weaken. Opaque fillers and light stabilizers and antioxidants are added to alleviate these problems. Aliphatic monomers yield polymers which are less susceptible to degradation but do not impart the same rigidity.
• the present invention is an alkyl-substituted thiapolycyclic polyahl having at least one thiapolycyclic moiety, including the oxide or dioxide forms thereof, which moiety bears at least one alkyl substituent and at least one active hydrogen substituent, provided that the polyahl has at least two active hydrogen moieties.
• this invention is a polymer of the aforementioned polyahl or an isomeric mixture thereof such as a polyamide, a polyurea, polyether, polyester or polyurethane.
• a polymer of the aforementioned polyahl or an isomeric mixture thereof such as a polyamide, a polyurea, polyether, polyester or polyurethane.
• such polymers having the, aforementioned monomer or an isomeric mixture of such monomers having thiabicyclic moieties as the only monomeric components or as a part of a monomeric mixture with monomers which do not contain a thiabicyclic moiety exhibit an increase in rigidity and thermal properties comparable to that resulting from the introduction of an aromatic monomer.
• the polyalkyl thiapolycyclic polyahl of this invention is preferably an aliphatic compound having (1) a bridge system of at least two rings, (2) a sulfur-containing bridging group, (3) at least two active hydrogen (ahl) substituents and (4) at least one alkyl substituent, all of said substituents being bonded to carbons other than bridgehead carbons.
• the active hydrogen moiety suitable for this purpose is a moiety containing a hydrogen atom which, because of its position in the molecule, displays significant activity according to the Zerewitnoff test described by Woller in the Journal of American Chemical Society, Vol. 49, page 3181 (1927).
• active hydrogen moieties are -COOH, -OH, -NH 2 , -NH-, -CONH 2 , -SH and -CONH-.
• the active hydrogen moieties are bonded to the same or different non-sulfur bridging groups.
• at least one and preferably two of the non-sulfur bridging groups bear a pendant lower alkyl moiety such as methyl, ethyl or propyl, preferably methyl.
• Representative preferred thiapolycyclic polyahls include those having the formula:
• A is a residue of an active hydrogen moiety such as -O-, -S-, -NR 3 -,
• each R 1 is independently an alkyl group containing 1 to 3 carbon atoms
• each R 2 is independently hydrogen or methyl provided that at least two R 2 are hydrogen
• y is a number corresponding to available valences for the poly- cyclic ring
• each R 3 is independently hydrogen, an aliphatic alkyl containing 1 to 20 carbon atoms or an inertly-substituted aliphatic alkyl containing 1 to 20 carbon atoms, with hydrogen being preferred
• n is 0, 1, 2 or 3.
• inert it is meant that the substituent group will not react with the araine group or the thiabicyclic moiety, e.g., alkyl or alkoxy are such inert groups.
• AH is an ammo moiety represented by -NR 3 H.
• diamines represented by the formulae:
• each R 1 which may be the same or different, is an alkyl group containing 1 to 3 carbon atoms; each R 2 , which may be the same or different is hydrogen or methyl, at least two R 2 are hydrogen; each R 3 which may be the same or different is hydrogen, an aliphatic alkyl group containing 1 to 20 carbon atoms or an inertly-substituted aliphatic alkyl group containing 1 to 20 carbon atoms; and x is 0, 1 or 2.
• Examples of such preferred thiabicyclic diamines are dialkyl-9-thiabicyclononane diamine isomers and N-alkyl diamine derivatives thereof such as 2-endo-6-endo- -2,6-diamino-4-endo-8-exo-4, 8-dimethyl-9-thiabicyclo [3.3.1]- nonane; 2-endo-6-endo-2, 6-diamino-4-exo-8-exo-4, 8-dimethyl- -9-thiabicyclo[3.3.1]nonane; 2-endo-6-endo-2, 6-diamino-4- -endo-8-endo-4, 8-dimethyl-9-thiabicyclo[3.3.1]nonane; 2-endo-6-endo-2, 6-diamino-3-endo-7-endo-3,7-dimethyl-9- -thiabicyclo [3.3.1]nonane; 2-endo-6-endo-2, 6-diamino-3- -exo-7
• Preparation of the most preferred thiabicyclo nonane diamines begins by reacting C 5 -C 8 di-unsaturated hydrocarbons such as piperylene or 1,3-pentadiene; 1,3- -hexadiene; 1,3-heptadiene; 5-methyl-1,3-hexadiene or mixtures of two or more of such aliphatic dienes represented by the formula: 1
• R 1 and R 2 are as defined before.
• butadiene or isoprene can be cross-dimerized with piperylene or any of the other aforementioned dienes to produce the cyclic octadiene, or any two of said aforementioned dienes can be cross-dimerized to produce the desired cyclic octadiene.
• R 1 groups are as defined above and are not attached to the carbons of the double bond.
• the double bonds are positioned between the 1 and 2 carbons and"between the 5 and 6 carbons.
• the R 1 groups may be attached only to the 3, 4, 7 and 8 carbons.
• R 2 is methyl, that group is attached to a carbon of the double bond.
• R 2 methyl groups may be attached to the carbons 1, 2, 5 or 6, only two of the R 2 groups can be methyl.
• the cyclooctadienes may be converted to bicyclononanes (actually thiabicyclic dichlorides) by the reaction of the cyclooctadiene with sulfur dichloride or other sulfur chloride as disclosed in Weil et al. in J. Org. Chem., 31 (6), pp 1669-1679 (1966); or Corey et al. in J. Org. Chem., 31 (6), pp. 1663-1668 (1966); or Tolstikov et al. in Zh. Org. Khim., 16 (7), pp. 1408- -1418 (1980); or British Patents 1,061,472 and 1,061,473.
• This reaction is most conveniently practiced in the liquid phase, although it can also be accomplished in the vapor phase.
• the reaction is exothermic and, therefore, the reactants should be admixed by slow addition of one to the other, or, preferably, of both to a mutual solvent.
• Suitable solvents are any that are substantially inert to sulfur dichloride or other sulfur chloride and cyclooctadiene.
• suitable solvents include hydrocarbons such as toluene, benzene, hexane, cyclohexane, mineral spirits, chlorocarbons such as methylene chloride, carbon tetrachloride, ethylene dichloride, trichloroethylene, perchloroethylene, chlorobenzene, ethers such as diethyl ether, or miscellaneous solvents such as carbon disulfide, acetonitrile, thionyl chloride, acetic anhydride, acetyl chloride, nitromethane, nitrobenzene, and dimethyl formamide.
• hydrocarbons such as toluene, benzene, hexane, cyclohexane, mineral spirits
• chlorocarbons such as methylene chloride, carbon tetrachloride, ethylene dichloride, trichloroethylene, perchloroethylene, chlorobenzene, ethers such as diethyl ether, or mis
• the reaction temperature is from -40°C to 150°C, however, the preferred range is between -20°C and 100°C. It is particularly convenient to employ reaction temperatures near ambient temperature, and to cool the reaction by water-jacketing the reactor using water, also at ambient temperature.
• reaction is very rapid and generally is complete within a few seconds to a few hours after the reactants are admixed, depending on temperature. Therefore, a catalyst is not necessary. Nonetheless, if desired, the reaction may be catalyzed by addition of Lewis acids (e.g., FeCl 3 ), iodine, light or peroxides.
• Lewis acids e.g., FeCl 3
• sulfur dichloride is the preferred reactant
• sulfur monochloride may be employed to obtain the dichlorides, however, the use of sulfur monochloride results in a more complex reaction mixture which entails troublesome purification steps.
• Sulfur tetrachloride may also be used, with resultant formation of some thiabicyclononane having more than two chlorine atoms per mole.
• a preferred method of making the dichloride is by admitting separate streams of the corresponding cyclooctadiene and sulfur dichloride, each dissolved in an appropriate solvent into a line containing a static mixer. The concentrations of the feed solutions and the ratio in which they are added into the reactor are controlled to ensure a slight molar excess of cyclooctadi- enes. The line is cooled to ensure a maximum reactor temperature of -5°C.
• the sulfur dichloride is stabilized according to the method described in US 3,071,441.
• R 1 and R 2 groups are as defined before and the R 1 groups are connected to the 3, 4, 7 or 8 ring carbons, but not the carbons directly attached to either the sulfur or chlorine atoms (1, 2, 5, 6).
• Either or both of the [3.3.1] and [4.2.1] structures are found in the product as it has been found that the two structures are interconvertible during any reaction, even by merely dissolving in an ionizing solvent.
• the dichloride is converted to the diamine using conventional procedures by contacting the dichloride with ammonia or a primary amme R 3 NH 2 wherein R 3 is an aliphatic alkyl group containing 1-20 carbon atoms or an inertly-substituted aliphatic alkyl group containing 1-20 carbon atoms as R 3 is defined hereinbefore.
• aliphatic alkyl groups are methyl, ethyl, n-propyl, isopropyl, dodecyl, etc.
• inert substituents are alkyl groups, cycloaliphatic groups, aromatic groups, alkyloxy groups, hydroxy and alkylhydroxy groups.
• an excess of NH 3 to chloride is used. Most preferably the excess is at least 17 equivalents of NH 3 per equivalent of chloro groups.
• the temperature of the ammonolysis is kept low to prevent formation of secondary amines. The temperature may be held at 30°C or less and preferably at 20°C or less.
• the 9-oxides or 9,9-dioxides are more generally called sulfoxides, or sulfones, respectively, and are prepared by the oxidation of the diamine using oxidizing agents.
• oxidizing agents include hydrogen peroxide, peracetic acid, perbenzoic acid, perphthalic acid or other peroxy organic acids; nitric acid; nitrogen dioxide or tetraoxide; permanganates; chromic acid or dichromates; bromic acid or bromates; hypochlorous acid or hypochlorites; and ozone or molecular oxygen (preferably using a catalyst such as vanadium oxide or nitrogen dioxide).
• DMTBCN dimethyl thiabicyclononane diamines
• DMTBCN over the unsubstituted thiabicyclononane diamine which melts between 70°C and 71°C.
• This DMTBCN diamine may be pumped in a liquid system at normal room temperature, whereas the unsubstituted diamine must be melted or dissolved to be pumped.
• Thiapolycyclic polyahls other than polyamines are prepared by similar techniques using the dichloride except that other reactants are substituted for the ammonia or amine.
• the aforementioned dichloride is first reacted with potassium acetate and glacial acetic acid to form the corresponding bisacetate which is reacted with sodium methoxide in methanol to form the diol using conventional procedures for converting dichlorides to diols.
• the aforementioned dichloride is first reacted with thiourea in ethanol and water using conventional procedures. To this reaction mixture is added an aqueous solution of sodium hydroxide. The reaction mixture is heated at reflux, cooled and treated with hydrochloric acid and chloroform. The organic phase containing the desired dithiol is separated from the aqueous phase and the dithiol is recovered.
• the polymer has repeating units having the formula:
• polyamines more preferably diamines, of the invention may be used to form polyamides, polyureas, polyurethane ureas, and as cross-linkers for epoxy polymers.
• Polymers and copolymers which are readily made from the aforementioned diamines include polyamide structures which contain monomer units such as:
• B is a divalent hydrocarbon radical.
• B is an aliphatic radical such as C 4 H 8 or C 8 H 16 .
• This polyamide is readily formed by contacting a DMTBCN diamine with a polyacid chloride of a polybasic acid such as adipoyl chloride, terephthaloyl chloride and isophthaloyl chloride using conventional procedures. Because the DMTBCN diamine is a liquid at room temperature, it is particularly useful in applications where liquid monomers are normally used.
• polyureas which may include the aforementioned repeating units also include the polyureas such as:
• B is C 7 H 6 or C 13 H 10 .
• the polyurea is readily formed by contacting the alkyl-substituted thiapolycyclic diamine with an organic polyisocyanate such as aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof.
• organic polyisocyanate such as aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof.
• diisocyanates such as m-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2, 6-diisocyanate, hexamethylene-1, 6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotolylene diisocyanate (and isomers), naphthylene-1, 5-diisocyanate, l-methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,
• diisocyanates of thiabicyclononanes are also suitable.
• diisocyanates of thiabicyclononanes are also suitable.
• diisocyanates of thiabicyclononanes are also suitable due to their availability and properties.
• Crude polyisocyanates may also be used in the practice of the present invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluenediamines or crude diphenylmethylene diisocyanate obtained by the phosgenation of crude diphenylmethyl- enediamine.
• the preferred undistilled or crude isocyanates are disclosed in US 3,215,652.
• Polyurethanes are readily formed by reacting the aforementioned polyisocyanates with alkyl-substituted thiapolycyclic polyals described hereinbefore. Usually such urethane reactions are carried by conventional procedures in the presence of known urethane catalysts. Known techniques may be used. Because the diamines are liquid at room temperature and because the molecule is sterically hindered, reaction with polyisocyanates is sufficiently slowed to allow preparation of such poly- mers. In particular, it is notable that when R 3 is nol hydrogen, this reaction proceeds at a desirable rate.
• the urethane reaction of polyisocyanate with non-thiacyclic polyahl in the presence of the thiapolycyclic polyahl chain extender is advantageously practiced in the presence of an amount of urethane catalyst which is effective to catalyze the reaction of the polyahl with the polyisocyanate.
• the amount of urethane catalyst is an amount comparable to that used in conventional urethane type reactions, e.g., from 0.05 to 5, most preferably from 0.1 to 3, weight percent of the catalyst based on the weight of non-thiacyclic polyahl.
• Any suitable urethane catalyst may be used including tertiary amines such as, for example, triethylenediamine, N-methyl morpholine, N-ethyl morpholine, diethyl ethanolamine, N-coco morpholine, 1-methyl-4-di- methylaminoethyl piperazine, 3-methoxy-N-dimethylpropyl- amine, N,N-dimethyl-N',N'-methyl isopropyl propylenediamine, N,N-diethyl-3-diethylaminopropylamine or dimethyl benzylamine.
• tertiary amines such as, for example, triethylenediamine, N-methyl morpholine, N-ethyl morpholine, diethyl ethanolamine, N-coco morpholine, 1-methyl-4-di- methylaminoethyl piperazine, 3-methoxy-N-dimethylpropyl- amine
• Suitable catalysts are, for example, tin compounds such as stannous chloride, tin salts of carboxylic acids such as dibutyltin di-2-ethyl hexanoate and dibutyltin dilaurate, as well as other organometallic compounds such as are disclosed in US 2,846,408.
• the relative proportions of polyisocyanate to non-thiacyclic polyahl are those conventionally employed in the preparation of polyurethanes, preferably in proportions sufficient to provide isocyanate to active hydrogen equivalent ratios in the range from 0.8:1 to 1.5:1, most preferably from 0.95:1 to 1.1:1.
• the proportion of the thiapolycyclic polyahl employed is that which is sufficient to improve mechanical and/or thermal properties of the polyurethane. Preferably, it is used in an amount sufficient to improve processability of the polyurethane system.
• the amount of thiapolycyclic polyahl chain extending agent is in the range from 0.1 to 50, most preferably from 3 to 25, weight percent of the chain extending agent based on the total weight of the non-thiacyclic polyahl.
• polyurethane formulations of the present invention may also contain suitable amounts of conventional additives such as blowing agents, fillers, surfactants and other additives as such are described in US 4,269,945.
• a characterizing amount it is meant an amount of the aforementioned repeating units are present in the polymer so that the polymer exhibits properties such as rigidity and thermal resistance resulting from the presence of the monomer.
• the polymer has at least 0.5 mole percent of the aforementioned repeating units, more preferably at least 10 mole percent, most preferably at least 40 mole percent up to 100 mole percent.
• polymers formed with the above-described monomer units have utility as coatings, films and castings. Surprisingly, such polymers may exhibit mechanical properties superior to those in which aromatic groups have been incorporated into the polymer backbone.
• a 1000-ml three-necked round-bottom flask was equipped with a heating mantle, a magnetic stirbar and stirrer, a thermometer adaptor and thermometer, a stopcock-protected rubber system, and a distillation head which was connected to give a nitrogen blanket on the system.
• the flask was then charged with 120 ml of toluene, 4.35 g (0.017 mole) of anhydrous Ni (II) acac, and 9.36 g
• the cyclooctadiene of Example 1 was used as the starting material.
• This example describes a continuous process set-up.
• the reactor used was a static in-line mixer which was jacketed.
• a 50:50 by volume mixture of ethylene glycol and water at -30°C was circulated through the jacket. Separate inlets were provided ahead of the reaction zone for cyclooctadiene and sulfur dichloride reactant solutions.
• An outlet valve was provided after the reaction zone to remoye products.
• the dimethyl- -thiabicyclononane diamine dihydrochlorides were obtained as a slurry in heptane; this slurry was transferred to a 5000-ml flask which was equipped with a mechanical stirring assembly, a Dean-Stark trap with condenser and nitrogen inlet/outlet (to provide a nitrogen blanket) and a pressure-compensating addition funnel. To the slurry was added 2 liters of fresh heptane and the mixture was heated to about 95°C. The addition funnel was charged with 1.75 liters of 1N aqueous sodium hydroxide; this was added to the stirred, hot mixture, resulting in the liberation of some NH 3 .
• R 3 is not hydrogen
• the amme may be substituted in the above reaction for the ammonia.
• the dimethyl thiabicyclononane dialkylamine will form in a similar manner.
• a bis(isopropylamino)dimethyl thiabicyclononane may be made.
• the mixing pressure used for impingement was 1500 psi (10.34 MPa) and the ingredients were shot into the mold using approximately a 0.65 lb (0.29 kg) shot size and a 40 lb/min (18 kg/min) throughput.
• the temperature of the mold was 155°F (68.3°C) and the in-mold time for each shot of material was 2 minutes.
• the dimensions of the mold cavity were 254 x 254 x 32 mm.
• the resulting molded article was placed in an oven at 150°C for a post-cure of 30 or 60 minutes as indicated in the following Table I. The molded material was then tested for physical properties.
• Example 3 a second formulation was prepared using 3.4 percent of diamine chain extender based upon the weight of polyol and diamine.
• the resultant molded articles were similarly tested for physical properties and the results are reported in the following Table I.
• the polyurethanes prepared by the practice of the present invention exhibit substantially less heat sag at 6 inches (152 mm) than does the polyurethane using a conventional polyamine chain extender.

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• Polyurethanes Or Polyureas (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1984
  • 1984-06-29 WO PCT/US1984/001033 patent/WO1986000317A1/en not_active Application Discontinuation
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  • 1984-06-29 AU AU31018/84A patent/AU565569B2/en not_active Ceased
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