ALKYL-SUBSTITUTED THIAPOLYCYCLIC POLYAHLS AND POLYMERS PREPARED THEREFROM

Abstract: The polyahl contains at least one thiapolycyclic moiety, 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.

Description: -1 - ALKYL-SUBSTITUTED THIAPOLYCYCLIC POLYAHLS AND POLYMERS PREPARED THEREFROM 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 mono¬ mers. The character of the monomer unit has a strong effect on the physical and chemical properties of the pol¬ ymer. For example, it is common to incorporate a para- -phenylene group into a monomer to add rigidity to the polymer chain. This can engender desirable properties in the polymer such as: raising the melting point, increas¬ ing the stress strain property ratios and improving the heat distortion performance. -2- The incorporation of aromatic nuclei in poly¬ mer chains, however, has its drawbacks. Polymers contain¬ ing 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 suscep¬ tible to degradation but do not impart the same rigidity. In view of the aforementioned deficiencies of both aliphatic and aromatic polymers, it would be highly desirable to provide a monomer which can form a polymer having rigidity, strength and thermal proper¬ ties characteristic of aromatic polymers and resistance to degradation by light that is characteristic of ali- phatic polymers. In one aspect,__.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. In another aspect this invention is a poly¬ mer of the aforementioned polyahl or an isomeric mixture thereof such as a polyamide, a polyurea, polyether, poly¬ ester or polyurethane. Surprisingly, such polymers hav¬ ing .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 OM?I_ »ϋ " -3- 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) substitueπts and (4) at least one alkyl substituent, all of said substituents being bonded to car¬ bons 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). Illustrative of such active hydrogen moieties are -COOH, -OH, -NH 2 , -NH-, -CONH 2 ,_-SH and -C0NH-. Advantageously, the active hydrogen moieties are bonded to the same or different non-sulfur bridging groups. In addition, 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 pre¬ ferred thiapolycyclic polyahls include those having the formula: -4- wherein A is a residue of an active hydrogen moiety such as -0-, -S-, -NR -, 0 II -CNH- or CO,-; is a thiapolycyclic moiety having at least 6 carbons and a sulfur-containing bridging group and x is 0, 1 or 2; each R 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 ali- phatic alkyl containing 1 to 20 carbon atoms or an inertly- -substituted aliphatic alkyl containing 1 to 20 carbon atoms, with hydrogen being preferred; and n is 0, 1, 2 or 3. By "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. More preferably, in the aforementioned for- 3 mula, AH is an ammo moiety represented by -NR H. Most preferred are the diamines represented by the formulae: -5- wherein each R 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 R3 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 dia- mines 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.l]nonane; 2-endo-6-endo-2,6-diamino-3-endo-7-endo-3,7-dime hyl-9- -thiabicyclo[3.3.l]nonane; 2-endo-6-endo-2,6-diamino-3- -exo-7-exo-3,7-dimethyl-thi__bicyclo[3.3.1]nonane; 2-endo- -6-endo-2,6-diamino-3-endo-7-exo-3,7-dimethyl-9-thiabi- cyclo[3.3.l]nonane; 2-endo-6-endo-2,6-diamino-3-exo-4- -exo-3,4-dimethyl-9-thiabicyclo[3.3.1]nonane; 2-endo-6- -6- -endo-2,6-diamino-3-endo-4-exo-3,4-dimethyl-9-thiabicy- clo[3.3.l]nonane; 2-endo-6-endo-2,6-diamino-3-exo-4-endo- -3, -dimethyl-9-thiabicyclo[3.3.1Jnonane; 2-endo-β-endo- -2,6-diamino-3-endo-4-endo-3,4-dimethyl-9-thiabicyclo- [3.3.1]nonane; 2-endo-5-endo-2,5-diamino-7-endo-8-endo- -7 ,8-dimethyl-9-thiabicyclo[4.2.1] onane; 2-endo-6-endo- -2,6-diamino-7-exo-l,7-dimethyl-9-thiabicyclo[3.3.l]no- nane; 2-endo-6-endo-2,6-diamino-7-endo-l,7-dimethyl-9- -thiabicyclo[3.3.1]nonane; 2-endo-6-endo-2,6-diamino-4- -exo-l,4-dimethyl-9-thiabicyclo[3.3.1]nonane; 2-endo-6- -endo-2,6-diamino-4-endo-l,4-dimethyl-9-thiabicyclo- [3.3.l]nonane; 2-endo-5-endo-2,5-diamino-7-endo-l,7-di- methyl-9-thiabicyclo[3.3.1]nonane; and the N-alkyl deriv¬ atives of such diamines where the N-alkyl can be methyl, ethyl, isopropyl and the like, with the normally liquid mixtures of two or more such isomers being especially preferred. Other isomers which are desirable include 2-endo-5-endo-2,5-diamino-7-exo-8-exo-7,8-dimethyl-9- -thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-diamino-7- -endo-8-exo-7,8-dimethyl-9-thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-diamino-3-exo-4-exo-3,4-dimethyl-9- -thiabicyclo[4.2.l]nonane; 2-endo-5-endo-2,5-diamino-3- -endo-4-endo-3,4-dimethyl-9-thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-di__mino-3-endo-4-exo-3,4-dimethyl-9- -thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-diamino-3- -endo-7-exo-3,7-dimethyl-9-thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-diamino-3-endo-7-endo-3,7-dimethyl-9- -thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-diamino-3- -endo-7-exo-3,7-dimethyl-9-thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-diamino-3-exo-7-endo-3,7-dimethyl-9- -thiabicyclo[4.2.1]nonane; 2-endo-6-endo-2,6-diamino-2- -exo-7-exo-2,7-dimethyl-9-thiabicyclo[3.3.1]nonane; -7- 2-endo-6-endo-2,6-diamino-2-exo-7-endo-2,7-dimethyl-9- -thiabicyclό[3.3.1]nonane; 2-endo-6-endo-2,6-dimethyl-2- -exo-4-exo-2,4-dimethyl-9-thiabicyclo[3.3.1]nonane; 2-endo-6-endo-2,6-diamino-2-exo-4-endo-2,4-dimethyl-9- -thiabicyclo[3.3.1] onane; 2-endo-5-endo-2,5-diamino-2- -exo-4-exo-2,4-dimethyl-9-thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-diamino-2-exo-4-endo-2,4-dimethyl-9- -thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-diamino-2- -exo-7-exo-2,7-dimethyl-9-thiabicyclo[4.2.l]nonane; 2-endo-5-endo-2,5-diamino-2-exo-7- ' endo-2,7-dimethyl-9- -thiabicyclo[4.2.1]nonane; 2-endo-5-endo-2,5-diamino-4- -exo-1,4-dimethyl-9-thiabicyclo[3.3.1]nonane; 2-endo-5- -endo-2,5-diamino-4-endo-l,4-dierathyl-9-thiabicyclo- [3.3.1]nonane; and 2-endo-5-endo-2,5-diamino-7-exo-l,7- -dimethyl-9-thiabicyclo[3.3.l]nonane. Preparation of the most preferred thiabicyclo nonane diamines begins by_reacting C 5 -C a di-unsaturated hydrocarbons such as piperylene or 1,3-pentadiene; 1,3- -hexadiene; 1,3-heptadiene; 5-methyl-l,3-hexadiene or mix- tures of two or more of such aliphatic dienes represented by the formula: via cyclodimerization to form a 1,5-cyclooctadiene hav¬ ing the structure: O PI -8- wherein R 1 and R2 are as defined before. Alternatively, butadiene or isoprene can be cross-dimerized with piperyl- ene 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 cyc¬ lic octadiene. Such cyclodimerization of a diene is known as taught by J. A. Berson et_al., JACS, 98 (19), pp. 5937-68 (1976) (Chem. Abstr. 86:70,955q); and U. M. Dzhemilev et al., Neftekhimiya, 15 (6), pp. 819-24 (1975) (Chem. Abstr. 84:121,245b). These processes yield a mixture of varying amounts of the following isomers: -9- These isomers as well as isomers where one or two R 2 are CH 3 are collectively included as the afore¬ mentioned 1,5-cyclooctadiene used to prepare the most pre¬ ferred thiabicyclononanes. Note that the R 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 groups may be attached only to the 3, 4, 7 and 8 car- bons. When R 2 i»s methyl, that group is attached to a car- 2 bon of the double bond. While the R methyl groups may be attached to the carbons 1, 2, 5 or 6, only two of the 2 R groups can be methyl. The cyclooctadienes may be converted to bicy- clononanes (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. -10- 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, there¬ fore, the reactants should be admixed by slow addition of one to the other, or, preferably, of both to a mutual sol¬ vent. Suitable solvents are any that are substantially inert to sulfur dichloride or other sulfur chloride and cyclooctadiene. Illustrative examples of suitable sol¬ vents include hydrocarbons such as toluene, benzene, hex- ane, cyclohexane, mineral spirits, chlorocarbons such as methylene chloride, carbon tetrachloride, ethylene dichlo¬ ride, trichloroethylene, perchloroethylene, chlorobenzene, ethers such as diethyl ether, or miscellaneous solvents such as carbon disulfide, acetonitrile, thionyl chloride, acetic anhydride, acetyl chloride, nitromethane, nitroben¬ zene, and dimethyl formamide. 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. The reaction is very rapid and generally is complete within a few seconds to a few hours after the reactants are admixed, depending on temperature. There¬ fore, 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. While sulfur dichloride is the preferred reactant, sulfur monochloride may be employed to obtain the dichlorides, however, the use of sulfur monochloride O PI -1 1 - results in a more complex reaction mixture which entails troublesome purification steps. Sulfur tetrachloride may also be used, with resultant formation of some thiabicy- clononane 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 con¬ trolled to ensure a slight molar excess of cyclooctadi- enes. The line is cooled to ensure a maximum reactor temperature of -5°C. Preferably the sulfur dichloride is stabilized according to the method described in US 3,071,441. Such dichlόrides are represented by the formulae: [3.3.1] [4.2.1] wherein the R 1 and R2 groups are as defined before and the R groups are connected to the 3, 4, 7 or 8 ring car¬ bons, but not the carbons directly attached to either the -12- 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 prod¬ uct 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 dichlo- ride with ammonia or a primary amme R 3NH, wherein R3 i.s 'an aliphatic alkyl group containing 1-20 carbon atoms or an inertly-substituted aliphatic alkyl group containing 3 . . 1-20 carbon atoms as R is defined hereinbefore. Examples of aliphatic alkyl groups are methyl, ethyl, n-propyl, isopropyl, dodecyl, etc. Examples of inert substituents are alkyl groups, cycloaliphatic groups, aromatic groups, alkyloxy groups, hydroxy and alkylhydroxy groups. Preferably an excess of NH 3 to chloride is used. Most preferably the excess is at least 17 equiva¬ lents of NH 3 per equivalent of chloro groups. Preferably 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 gener¬ ally called sulfoxides, or sulfones, respectively, and are prepared by the oxidation of the diamine using oxi¬ dizing agents. Illustrative oxidizing agents include hydrogen peroxide, peracetic acid, perbenzoic acid, perphthalic acid or other peroxy organic acids; nitric -13- acid; nitrogen dioxide or tetraoxide; permanganates; chromic acid or dichromates; bromic acid or bromates; hypochlorous acid or hypochlorites; and ozone or molec¬ ular oxygen (preferably using a catalyst such as vana- dium oxide or nitrogen dioxide). The dimethyl thiabicyclononane diamines (DMTBCN) are generally obtained as isomeric mixtures and are therefore liquid at room temperature (normally liquid). This improves the processability of the 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. This is a desirable characteristic for many polymer¬ ization systems which operate with liquid reactants. Thiapolycyclic polyahls other than polyamines are prepared by similar techniques using the dichloride except that other reactants are substituted for the ammo¬ nia or amine. For example, in the preparation of the cor¬ responding diol, 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. In the preparation of the corresponding dithiol, the aforementioned dichloride is first reacted with thio- urea in ethanol and water using conventional procedures. To this reaction mixture is added an aqueous solution of -1 4- 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. In the polymers of the invention derived from the preferred thiabicyclononane polyahls, the polymer has repeating units having the formula: wherein A, R 1, R2 , R3 and x are as defined hereinbefore. The polyamines, more preferably diamines, of the invention may be used to form polyamides, polyureas, polyurethane ureas, and as cross-linkers for epoxy poly¬ mers. Polymers and copolymers which are readily made from the aforementioned diamines include polyamide struc¬ tures which contain monomer units such as: O 0 I! «! ■fZ-C-B-C} wherein Z is the repeating unit, and B is a divalent hydrocarbon radical. Preferably B is an aliphatic -1 5- radical such as C 4 Hg or gH, g . 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 chlo- ride using conventional procedures. Because the DMTBCN diamine is a liquid at room temperature, it is particu¬ larly useful in applications where liquid monomers are normally used. Other polymers which may include the afore- mentioned repeating units also include the polyureas such as: O O fZ-C-N-B-N-C n H H wherein Z, B and n are as defined before. Preferably B i__s_ » C ■ —7H"g,- o « r* » C v *, * i3~H' , -- , ,Q Λ .* 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. Representative of these types are the 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-diisocya¬ nate, hexahydrotolylene diisocyanate (and isomers), naph- thylene-1,5-diisocyanate, l-methoxyphenyl-2,4-diisocya¬ nate, diphenylmethane-4,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, O PI -16- 3,3'-dimethyl-4,4'-biphenyl diisocyanate, and 3,3'-di¬ methyldiphenylmethane-4,4'-diisocyanate; the triisocya- nates such as 4,4' ,4'-triphenylmethane triisocyanate, polymethylene polyphenylisocyanate and tolylene-2,4,6- -triisocyanate; and the tetraisocyanates such as 4,4'- -dimethyldiphenylmethane-2,2' ,5,5*-tetraisocyanate. Also suitable are diisocyanates of thiabicyclononanes. Especially useful due to their availability and proper¬ ties are tolylene diisocyanate, diphenylmethane-4,4'- -diisocyanate and polymethylene polyphenylisocyanate. 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 diisocya- nate obtained by the phosgenation of crude diphenylmethyl- enediamine. The preferred undistilled or crude isocya- nates are disclosed in U§_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 pro¬ cedures 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- 3 . mers. In particular, it is notable that when R is nol hydrogen, this reaction proceeds at a desirable rate. The urethane reaction of polyisocyanate with non-thiacyclic polyahl in the presence of the thiapolycyc¬ lic polyahl chain extender is advantageously practiced in -17- the presence of an amount of urethane catalyst which is effective to catalyze the reaction of the polyahl with the polyisocyanate. Preferably, the amount of urethane catalyst is an amount comparable to that used in conven- tional 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, trieth- ylenediamine, 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 propylenedi- amine, N,N-diethyl-3-diethylaminopropylamine or dimethyl benzylamine. Other 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 propor¬ tions 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 suffi¬ cient 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. More preferably, the amount of thiapolycyclic polyahl chain extending agent is in the range from 0.1 ov?ι sA vv__-o ^ -18- 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. In addition to the foregoing components, it is understood that the 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. Accordingly, other aspects of this invention are such polymers wherein a characterizing amount of repeating units of the above formulae are incorporated and a method for making them. By 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 resis¬ tance resulting from the presence of the monomer. Pref¬ erably, 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. The polymers formed with the above-described monomer units have utility as coatings, films and cast¬ ings. Surprisingly, such polymers may exhibit echani- cal properties superior to those in which aromatic groups have been incorporated into the polymer backbone. The following examples are given to illus¬ trate the invention and should not be construed as limit¬ ing its scope. Unless otherwise indicated all parts and percentages set forth in this application are by weight. -19- Example 1 A. Preparation of Dimethy1-1,5-cyclooctadiene Nickel (II) acetonylacetonate dihydrate was dispersed in toluene and dried by azeotropic removal of the water (which was captured in a Dean-Stark trap). When no further water can be recovered, the dark green toluene solution of nickel (II) acetonylacetonate (Ni (II) acac) was evaporated to dryness, giving anhydrous Ni (II) acac. 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-pro¬ tected 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 (0.0173 mole) of tris(orthophenylphenyl)phosphite. About 40 ml of toluene were removed by distillation to dry the system. The apparatus was allowed to cool, the distilla¬ tion head replaced with a reflux condenser and a nitrogen inlet/outlet (to maintain a nitrogen blanket), and 448.2 g of piperylene concentrate (containing 52 percent piperyl- ene; 3.43 moles of piperylene), which had been distilled away from sodium metal, was added. The heating mantle was replaced with an ice bath, and the contents of the flask were cooled to below 10°C. At this point, 14.30 g of 25 percent w/v triisobutyl aluminum in toluene (0.0179 mole) was slowly added dropwise, causing the green solution to gradually turn yellowish brown. When addition was complete, the ice bath was replaced with a heating mantle and the reaction mixture was allowed to warm to room temperature. Heating was then begun to achieve reflux (color now bright red-orange) for about 60 hours. Gas chromatography of the reaction mixture OMPI -20- showed that conversion was at least 70 percent. The apparatus was then fitted with a 100-cm Vigreux column and the reaction mixture fractionally distilled, the fraction distilling at about 75°C at 60 Torr (8.0 kPa) was collected as product. Yield was approximately 90 percent based on converted piperylene. B. Preparation of Dimethyl Thiabicyclononane The cyclooctadiene of Example 1 was used as the starting material. This example describes a continu- ous process set-up. The reactor used was a static in-line mixer which was jacketed. A 50:5Q 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 re oye products. Dimethyl-l,5-cyclooctadiene (850 ml) (730 g, 5.36 moles DMCOD) containing about 12 percent other piperylene dimers was mixed with 175 ml of methylene chloride. Sulfur dichloride (355 ml) (575 g, 5.58 moles) was dissolved in 3,600 ml of methylene chlo¬ ride. Both reactants were fed to the reactor simul¬ taneously. The DMCOD solution was fed at 45 ml/min. The sulfur dichloride solution was fed at 172 ml/min. The feeds were exhausted in 23 minutes. During the reaction time, the temperature inside the reaction zone rose 11°C. Products were removed from the reaction zone at the same rate that they were added. When the feeds were exhausted -21 - the reaction zone was flushed with methylene chloride. The methylene chloride was evaporated from the product to give a black oil. Distillation of this oil at 85°C- -95°C and 0.05-0.1 mm Hg (7-13 Pa) gave 1,100 g of a very light yellow oil. Infrared and nuclear magnetic resonance spectra were consistent with a mixture of dimethyl TBCN dichloride isomers. C. Preparation of Dimethyl- -Thiabicyclononane Diamines A 2-liter, 316 stainless steel, stirred pres¬ sure vessel was well purged with dry nitrogen and charged with 165 ml of dry heptane and 200 g (0.836 mole) of dis¬ tilled dimethyl-dichloro-9-thiabicyclononanes. The vessel was then sealed and cooled to about -35°C. Gaseous ammo- nia was then introduced to the vessel and allowed to con¬ dense until at least 485 ^ q (28.48 moles) have been col¬ lected. The vessel was then stirred and allowed to warm to about 25°C. After 2 hours at about 25°C, the vessel was vented to release unreacted ammonia. 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 stir¬ ring assembly, a Dean-Stark trap with condenser and nitro¬ gen 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 IN aqueous sodium hydroxide; this was added to the stirred, hot mixture, resulting in the liberation of some NH 3 . The flask was then reheated to achieve reflux, and water removed through the Dean-Stark trap as a result -22- of the heptane-water azeotrope. When all the water had been removed, the mixture was filtered while hot and the filtrate evaporated to give dimethyl-thiabicyclononane diamines as a lightly-colored oil, in quantitative yield (based on the starting dimethyl-dichloro-9-thiabicyclo- nonanes). This oil was distilled in a Kugelrohr distil¬ lation apparatus at 90°C-95°C (air bath temperature) and 0.1-0.2 mm Hg (13-27 Pa), to give a nearly water- -white liquid product. Infrared and nuclear magnetic resonance were consistent with a mixture of dimethyl- -9-thiabicyclononane diamine isomers. A titration of this material in deionized water using 0.520N HC1 gave an equivalent weight between 99.8 and 100.4 (theory 100.2) g/equivalent. When R 3 i.s not hydrogen, the amme may be substituted in the above reaction for the ammonia. The dimethyl thiabicyclononane dialkylamine will form in a similar manner. For example, a bis(isopropylamino)di¬ methyl thiabicyclononane may be made. Examples 2 and 3 and Comparative Run A Into the polyol side tank of a reaction injec¬ tion molding machine were added 5,358 g (1.09 moles) of a glycerin-initiated polyalkylene polyol made from propylene oxide with sufficient ethylene oxide terminal groups (caps) to yield 80 percent of primary hydroxyl based on the total number of hydroxyl and having a weight average molecular weight (M ) between 4800 and 5000 (polyol I), 2,15z3 g (34.7 moles) of ethylene glycol, 375 g (1.87 moles) of a mixture of diamine isomers of dimethyl-9-thiabicyclo- nonane and 12.1 g (0.019 mole) of dibutyltin dilaurate (urethane catalyst). These ingredients were mechanically -23- agitated and heated to 100°F (37.8°C). To the isocyanate tank of the reaction injection molding machine was added 9.47 liters (11.55 kg, 40.11 moles) of diphenylmethane diisocyanate and then agitated and heated to 100°F (37.8°C). Specific gravities of the ingredients in each side tank of the reaction injection molding machine were 1.22 g/ml in the isocyanate tank and 1.04 g/ral in the polyol tank. 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. Upon removal from the mold, 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. For Example 3, a second formulation was pre- pared 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 prop¬ erties and the results are reported in the following Table I. For Comparative Run A, a conventional formu¬ lation was prepared using the foregoing ingredients except that an amine capped propylene oxide polymer represented by the structure CH 3 CH 3 H 2 N{CH-CH 2 0) 5 6 CH 2 CH-NH 2 -24- was substituted for the diamine chain extender of the present invention. This Comparative Run was similarly processed and tested for physical properties and the results are reported in Table I. TABLE I Example Pnm o n r aϊ . a D,_.i.amme Cure Tensile 2 , psi Flexural 3 , psi Heat Sag 5 C »P«- * -_E tenderi Time, (MPa) (MPa) Izod 4 ft-lb/in 6 in 4 i Run Type % Equiv, min. Strength Modulus Strength Modulus (152mm) (102 2 A 6.5 3.74 60 3,340 95,000 4,495 110,000 1.45 0.906 0.1 (23,0) (655) (31.0) (758) (77.4) (23.0) (3. A 3.4 2.07 60 3,960 105,000 4,630 118,000 1.55 0.35 0.0 (27.3) (724) (31.9) (814) (82.7) (8.9) (1. B 6.5 2.10 45 3,310 85,000 4,250 110,000 2.63 1.72 0.3 (22.8) (586) (29.3) (758) (140) (43.7) (9. 1 h - dimethyl-9-thiabicyclononane diamine (a mixture of isomers). B - amine capped propylene oxide polymer as defined hereinbefore. % based on combined weight of polyol I and diamine, equivalent of amine. 2 ASTM D 638 3 ASTM D 790 4 ASTM D 265 5 ASTM D 3769-81 (30 min at 325°F)(163°C) -26- As evidenced by the data shown in Table I, the polyurethanes prepared by the practice of the pres¬ ent invention (Examples 2 and 3) exhibit substantially less heat sag at 6 inches (152 mm) than does the poly- urethane using a conventional polyamine chain extender.

Claims: -27- WHAT IS CLAIMED IS: 1. An alkyl-substituted thiapolycyclic polyahl having at least one thiapolycyclic moiety, which moiety bears at least one alkyl substituent and at least one active hydrogen substituent, provided that the poly¬ ahl has at least two active hydrogen moieties. 2. The polyahl of Claim 1 which is repre¬ sented by the structural formula: wherein A is a residue of an active hydrogen moiety such 3 as -0-, -S-, -NR -, 0 II -CNH- -28- or C0 2 ~ ; is a thiapolycyclic moiety having at least 6 carbons and a sulfur-containing bridging group and x is 0, 1 or 2; each R is independently an alkyl group containing 1 to 3 carbon atoms; each R 2 i.s independently hydrogen or methyl provided that at least two R 2 are hydrogen; y is a number corresponding to available valences for the polycyclic ring; each R 3 i.s 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; and n is 0, 1, 2 or 3. 3. The polyahl of Claim 2 which is repre¬ sented by one of the structural formulae: _2?- 4. The polyahl of Claim 3 wherein each A is I -N- 5. The polyahl of Claim 4 wherein all R" are hydrogen. 6. The polyahl of Claim 5 wherein x is zero. 7. The diamine of Claim 6 wherein each R is methyl. 8. A polyamide, a polyurea, a polyether, a polyester or a polyurethane prepared from the poly¬ ahl of Claim 1. 9. The polymer of Claim 8 having repeating units of the formula: -30- wherem A is a residue of an active hydrogen moiety 3 such as -0-, -S-, -NR -, 0 II •CN- -CO- each R , which may be the same or different, is an alkyl group containing 1 to 3 carbon atoms wherein each R is attached to the 3, 4, 7 or 8 carbon atom and to different carbon atoms in different nonane rings; each R 2, which may be the same or different is hydrogen or methyl, at least two R 2 are hydrogen; each R3 which may be the same or different is hydrogen, an aliphatic alkyl group containing 1 to 20 carbon atoms or an inertly-sub- stituted aliphatic alkyl group containing 1 to 20 carbon atoms; and x is 0, 1 or 2. 10. The polymer of Claim 8 wherein at least 0.5 mole percent of the monomer units are present. \Z ϊi-b

Inventors: HUGHES DAVID W, SUTTON TONJA R, HUGHES, DAVID, W., SUTTON, TONJA, R.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1984
Main classification: C08G18
IPC codes: C07D495, C08G18, C08G63, C08G69