AU565569B2 - Alkyl-substituted thiapolycyclic polyahls and polymers prepared therefrom - Google Patents

Description

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 monomers. The character of the monomer unit has a strong effect on the physical and chemical properties of the polymer. 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, increasing the stress strain property ratios and improving the heat distortion performance. The incorporation of aromatic nuclei in polymer chains, however, 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.

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 properties characteristic of aromatic polymers and resistance to degradation by light that is characteristic of aliphatic 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 polymer of the aforementioned polyahl or an isomeric mixture thereof such as a polyamide, a polyurea, polyether, polyester or polyurethane. Surprisingly, 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).

Illustrative of such active hydrogen moieties are -COOH, -OH, -NH₂, -NH-, -CONH₂, -SH and -CONH-. 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 preferred thiapolycyclic polyahls include those having the formula:

wherein A is a residue of an active hydrogen moiety such as -O-, -S-, -NR³-,

or CO₂-;

is a thiapolycyclic moiety having at least 6 carbons and a sulfur-containing bridging group and x is 0, 1 or 2; each R¹ is independently an alkyl group containing 1 to 3 carbon atoms; each R² is independently hydrogen or methyl provided that at least two R² are hydrogen; y is a number corresponding to available valences for the poly- cyclic ring; each R³ 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; 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 formula, AH is an ammo moiety represented by -NR³H. Most preferred are the diamines represented by the formulae:

wherein each R¹ which may be the same or different, is an alkyl group containing 1 to 3 carbon atoms; each R², which may be the same or different is hydrogen or methyl, at least two R² 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 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-exo-3, 7-dimethyl-thiabicyclo[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- -endo-2, 6-diamino-3-endo-4-exo-3,4-dimethyl-9-thiabicyclo[3.3.1]nonane; 2-endo-6-endo-2, 6-diamino-3-exo-4-endo- -3,4-dimethyl-9-thiabicyclo [3.3.1]nonane; 2-endo-6-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]nonane; 2-endo-6-endo- -2, 6-diamino-7-exo-1, 7-dimethyl-9-thiabicyclo[3.3.1]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-1,4-dimethyl-9-thiabicyclo [3.3.1]nonane; 2-endo-6- -endo-2, 6-diamino-4-endo-l,4-dimethyl-9-thiabicyclo- [3.3.1]nonane; 2-endo-5-endo-2, 5-diamino-7-endo-1, 7-di- methyl-9-thiabicyclo[3.3.1]nonane; and the N-alkyl derivatives 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 [4.2.1]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-diamino-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; 2-endo-6-endo-2, 6-diamino-2-exo-7-endo-2, 7-dimethyl-9- -thiabicyclo [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]nonane; 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 [4.2.1]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-1,4-dierathyl-9-thiabicyclo- [3.3.1]nonane; and 2-endo-5-endo-2,5-diamino-7-exo-1, 7- -dimethyl-9-thiabicyclo[3.3.1]nonane.

Preparation of the most preferred thiabicyclo nonane diamines begins by reacting C₅-C₈ 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

via cyclodimerization to form a 1,5-cyclooctadiene having the structure:

wherein R¹ and R² are as defined before. Alternatively, 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.

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:

These isomers as well as isomers where one or two R² are CH₃ are collectively included as the aforementioned 1,5-cyclooctadiene used to prepare the most preferred thiabicyclononanes. Note that the R¹ 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 R¹ groups may be attached only to the 3, 4, 7 and 8 carbons. When R² is methyl, that group is attached to a carbon of the double bond. While the R² methyl groups may be attached to the carbons 1, 2, 5 or 6, only two of the R² 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. Illustrative examples of 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.

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. Therefore, a catalyst is not necessary. Nonetheless, if desired, the reaction may be catalyzed by addition of Lewis acids (e.g., FeCl₃), 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 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. Preferably the sulfur dichloride is stabilized according to the method described in US 3,071,441.

Such dichlorides are represented by the formulae:

wherein the R¹ and R² groups are as defined before and the R¹ 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 R³NH₂ wherein R³ is an aliphatic alkyl group containing 1-20 carbon atoms or an inertly-substituted aliphatic alkyl group containing 1-20 carbon atoms as R³ 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 NH₃ to chloride is used. Most preferably the excess is at least 17 equivalents of NH₃ 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 generally called sulfoxides, or sulfones, respectively, and are prepared by the oxidation of the diamine using oxidizing agents. Illustrative 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).

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 polymerization 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 ammonia or amine. For example, in the preparation of the corresponding 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 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.

In the polymers of the invention derived from the preferred thiabicyclononane polyahls, the polymer has repeating units having the formula:

wherein A, R¹, 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 polymers. Polymers and copolymers which are readily made from the aforementioned diamines include polyamide structures which contain monomer units such as:

O

'' '' [ ]

wherein Z is the repeating unit, and B is a divalent hydrocarbon radical. Preferably B is an aliphatic radical such as C₄H₈ or C₈H₁₆. 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.

Other polymers which may include the aforementioned repeating units also include the polyureas such as:

wherein Z, B and n are as defined before. Preferably B is C₇H₆ or C₁₃H₁₀.

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-diisocyanate, hexahydrotolylene diisocyanate (and isomers), naphthylene-1, 5-diisocyanate, l-methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; the triisocyanates 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 properties 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 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 R³ 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. Preferably, 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. 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 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. More preferably, 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.

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 resistance resulting from the presence of the monomer. Preferably, 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 castings. Surprisingly, such polymers may exhibit mechanical properties superior to those in which aromatic groups have been incorporated into the polymer backbone.

The following examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated all parts and percentages set forth in this application are by weight. 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-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

(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 distillation 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 piperylene; 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 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 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.

Dimethyl-1,5-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 chloride.

Both reactants were fed to the reactor simultaneously. 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 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 pressure vessel was well purged with dry nitrogen and charged with 165 ml of dry heptane and 200 g (0.836 mole) of distilled dimethyl-dichloro-9-thiabicyclononanes. The vessel was then sealed and cooled to about -35°C. Gaseous ammonia was then introduced to the vessel and allowed to condense until at least 485 g (28.48 moles) have been collected. 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 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 NH₃. The flask was then reheated to achieve reflux, and water removed through the Dean-Stark trap as a result 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 distillation 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 HCl gave an equivalent weight between 99.8 and 100.4 (theory 100.2) g/equivalent.

When R³ 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. For example, a bis(isopropylamino)dimethyl thiabicyclononane may be made.

Examples 2 and 3 and Comparative Run A

Into the polyol side tank of a reaction injection 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 (Mw) between 4800 and 5000 (polyol I), 2,153 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 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/ml 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 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.

For Comparative Run A, a conventional formulation was prepared using the foregoing ingredients except that an amine capped propylene oxide polymer represented by the structure

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.

As evidenced by the data shown in Table I, the polyurethanes prepared by the practice of the present invention (Examples 2 and 3) exhibit substantially less heat sag at 6 inches (152 mm) than does the polyurethane using a conventional polyamine chain extender.

Claims (10)

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 polyahl has at least two active hydrogen moieties.

2. The polyahl of Claim 1 which is represented by the structural formula:

wherein A is a residue of an active hydrogen moiety such as -O-, -S-, -NR³-,

CNH or CO₂- ;

is a thiapolycyclic moiety having at least 6 carbons and a sulfur-containing bridging group and x is 0, 1 or 2; each R¹ is independently an alkyl group containing 1 to 3 carbon atoms; each R² is independently hydrogen or methyl provided that at least two R² are hydrogen; y is a number corresponding to available valences for the polycyclic ring; each R³ 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; and n is 0, 1, 2 or 3.

3. The polyahl of Claim 2 which is represented by one of the structural formulae:

4. The polyahl of Claim 3 wherein each A is

5. The polyahl of Claim 4 wherein all R² are hydrogen.

6. The polyahl of Claim 5 wherein x is zero.

7. The diamine of Claim 6 wherein each R¹ is methyl.

8. A polyamide, a polyurea, a polyether, a polyester or a polyurethane prepared from the polyahl of Claim 1.

9. The polymer of Claim 8 having repeating units of the formula:

wherem A is a residue of an active hydrogen moiety such as -O-, -S-, -NR³-,

;

each R¹, which may be the same or different, is an alkyl group containing 1 to 3 carbon atoms wherein each R¹ is attached to the 3, 4, 7 or 8 carbon atom and to different carbon atoms in different nonane rings; each

R², which may be the same or different is hydrogen or methyl, at least two R² 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.

10. The polymer of Claim 8 wherein at least 0.5 mole percent of the monomer units are present.