CA1216300A - Alkyl-substituted thiapolycyclic polyahls and polymers prepared therefrom - Google Patents

Abstract

ABSTRACT
This invention is directed to alkyl-substi-tuted thiapolycyclic polyahls and to polymers prepared therefrom. The polyahl is represented by the structural formula:

wherein A is a residue of an active hydrogen moiety, 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; and n is 0, 1, 2 or 3.

Description

~2~63C~

ALKYL- SUB ST I TUTED
THIAPOLYCYCL I C POLYAHLS
AND POLYMER~; PREP~RED l~IEREFROM

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 proper~ies in the polymer such as: raising the melting point, increas-ing the stress strain propexty ratios and improving the heat distortion performance.

29,434B-F -1-...
d 3C~) The incorporation o aromatic nuclei in poly-mer chains, however, has its drawbacks. Polymers contain-ing aromatic nuclei are susceptible to deterioration.
They may s-tiffen and become brittle, change color, or S 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 a~orementioned 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 isan alkyl-substituted thiapolycyclic polyahl ha~ing 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 mi~ture thereof such as a polyamide, a polyurea, polyether, poly~
ester or polyurethane. Surprisin~ly, 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 29,434B-F -2~

g~

exhibit an increase in rigidity and thermal properties comparable to that resulting ~rom the introduction of an aromatic monomer.

The alkyl-substituted thiapolycyclic polyahl of this invention is represented by the structural formula:

1~2 ~R1~2 ~A--_ 2 --El ( )y_4 (R )y_4 n wherein A is a residue of an active hydrogen moiety;

is a thiapolycyclic moiety ha~ing at least 6 carbons and a sulfur-containing bridging group and x is 0, 1 or 2;
each Rl is independently ~n alkyl group con~aining 1 to 3 carbon atoms; each R2 is independently hydrogen or methyl provided that at least two R2 are hydrogen; y is i5 a number corresponding to available valences for the polycyclic ring; and n is 0, 1, 2 or 3. The active hydrogen moiety suitable for this purpose is a moiety containing a hydrogen atom which, because of its posi-tion in the molecule, displays significant activity according to the Zerewitnoff test described by Woller in the Journal of American Chemical Societ~, Vol. 49, page 3181 (1927). Illustratiye of such active hydrogen 29,434B-F -3-~Z3L63~

moieties are -COOH, -OH, -NH2, -NH-, -CONH2, -SH and -CONH-. Advantageously, the active hydrogen moieties are bonded to the same or different non-sulfur bridg-ing 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.

More preferably, in the aforementioned for-mula, A is represented by -NR3-, R3 is 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. By "inert'~
it is meant that the substituent group will no-t react with the amine group or the thiabicyclic moiety, e.gOS
alkyl or alkoxy are such inert groups. Most preferred are the diamines represented by the formulae:

29,434B-F -4-~2~63~

(R1~2 (R1~2 R3HlN ~R2 R~o,~R2 ~ ~ _NHlR3 R3HlN ~ ~ NHlR3 R2 R2 R2 ~-- R2 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 th~
same or different is hydrogen, an aliphatic alkyl group containing 1 to 20 carbon atoms or an inertly-substituked 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-dime~hyl--9-thiabicyclo~3.3.13nonane; 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-thi~bicyclo[3.3.13nonane; 2-e _ --6-endo-2,6-diamino-3-endo-7-exo-3,7-dimethyl-9-thiabi-cyclo~3.3.1]nonane; 2-endo-6-endo-2,6-diamino-3-exo-4--exo-3,4 dimethyI-9-thiabicyclo[3.3.1]nonane; 2~endo-6-29,434B-F -5--6 ~63~0 -endo-2,6-diamino-3-endo-4-exo-3,4-dimethyl-9-thiabicy-clo[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-1,7-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--èndo-2,6-diamino-4-endo-1,4-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 deriv-atives of such diamines where the N-alkyl can be methyl, ethyl, isopropyl and the like, with the normally liquid mi~tures 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.l]nonane; 2-endo-5-endo-2,5-diamino-7--endo-8-exo-7,8-dimethyl-9-thiabicyclo[4.2.1]nonane;
2-e _ -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 e _ -5-endo-2,5-diamino-3-endo-4-exo-3,4-dimethyl-9--thiabicyclol4.2.1]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;

29,434B-F -6-2-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[3.3.13nonane; 2-endo-5--endo-2,5-diamino-4-endo-1,4-diemthyl-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 pre~erred 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 mix-tures o~ two or more of such aliphatic dienes representedby the formula:

CH2=CH-C=CHR

via cyclodimerization to ~orm a 1,5-cyclooctadiene hav-ing the structure:

29,434B-F ~7-~2~63~b~

1~6 R~ R2 wherein Rl and R2 are as defined before. Alternatively, butadie~e 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:

29,434B-F -8-9~ .i3~0 R2 ~ 2 These isomers as well as isomers where one or two R are CH3 are collectively included as the afore-mentioned 1,5-cyclooctadiene used to prepare the most pre-ferred 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 R groups may be attached only to the 3, 4, 7 and 8 car-bons. When R is methyl, that group is attached to a car-bon of the double bond. While the R2 methyl groups maybe attached to the carbons 1, 2, 5 or 6, only two of the R groups can be methyl.

The cyclooctadienes may be converted to bicy-clononanPs (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. Or~. Khim., 16 (7), pp. 1408--1418 (1980); or British Patents 1,061,472 and 1,061,473.

29,434B-F -9--10- 12163~(~

This reaction is most conveniently pxacticed 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 asmethylene 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 t mperature is from -40C to 150C, however, the preferred range is between -20C
and 100C. 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 cataly~t is not necessary. Nonetheless, if desired, the reaction may be catalyzed by addition of Lewis acids (e.g., FeC13), 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 29,434B-F -10-results in a more complex reac-tion mixture which entails troublesome purification steps. Sul~ur tetrachloride may also be used, with resultant ~ormation 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 -5C. Preferably the sulfur dichloride is stabilized according to the method described in US
3,071,441.

Such dichlorides are represented by the formulae:

(I )2 (I )2 Cl ~ R2 ~ ~ R2 Cl Cl ~ Cl [3.3.1] [4.2.1]

wherein the R1 and R2 groups are as defined before and the R1 groups are connected to the 3, 4, 7 or 8 ring car-bons, but not the carbons directly attached to either the 29,434B-F -11--12~ ~Z~63~

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 amine 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 hereinbe~ore.

Examples of aliphatic alkyl groups are methyl, ethyl, n-propyl, isopropyl, dodecyl, etc.
Examples of inert substituents are al~yl groups, cycloaliphatic groups, aromatic groups, alkyloxy groups, hydroxy and alkylhydroxy groups.

Pre~erably an excess of NH3 to chloride is used. Most preferably the excess is at least 17 equiva-lents of NH3 per equivalent of chloro groups. Preferably the temperature of the ammonolysis is kept low to pxevent fonmation of secondary amines. The temperature may be held at 30C or less and preferably at 20C 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 29,434B-F -12-~Zl~i3~() 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 70C and 71C. 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 technigues 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 29,434B-F -13- .

-14- ~2~6;~'0 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:

or wherein A, R , R , R 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 O
,. ,. .
~Z-C-B-C~

wherein Z is the repeating unit, and B is a di~alent hydrocarbon radical. Preferably B is an aliphatic 29,434B-F -14-~2163~0 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 chloxide, terephthaloyl chloride and isophthaloyl chlo-ride using conventional procedures. Recause the DMTBCNdiamine 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 wherein Z, B and n are as defined before. Preferably B
is C7H6 or Cl3Hl0 The polyurea is readily ~ormed 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, 1-methoxyphenyl-2,4-diisocya-nate, diphenylmethane-4,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 29,434B-F -15-~Z1631[~0 3,3'-dimethyl-4,4'-biphenyl diisocyanate, and 3,3'-di-me-thyldiphenylme-thane-4,4'-diisocyanate; the triisocya-nates such as 4,4',4'-triphenylmethane triisocyanate, polymethylene polyphenylisocyanate and tolylene-2,g,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 US 3,215,652.

Polyurethanes are readily ~ormed by reacting the aforementioned polyisocyanates with al~yl-substituted - 20 thiapolycyclic polyals described hereinbefore. Usually such urethane reactions are carriecl by conventional pro-cedures in the presence of known urethane catalysts.
Known techni~ues 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 not hydrogen, this reaction proceeds at a desirable rate.

The urethane reaction of polyisocyanate with non-thiacyclic polyahl in the pr~sence of the thiapolycyc-lic polyahl chain extender is advantageously practiced in 29,434B-F -16-:`

-17- ~ 2 16 3U'~

the presence o~ an amount of urethane catalyst which is effective to cataly~e the reaction of the polyahl with the polyisocyanate. Preferably, the amount of uret.hane 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 sui-table 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, l-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 a~_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 ran~e from 0.8:1 to 1.5:1, most preferably from 0.~5:1 to l.l:l. The proportion of the thiapolycyclic polyahl employed is that which is suffi-cient to improve mechanical and/or therma~ 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 29,434B-F -17--18- 121~3~0 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 arnount, it is meant an amount of the aforementioned repeating units are present in the pol~ner so that the polymer exhibits properties such as rigidity and thermal resis-tance resulting from the presence of the monomer. Pref-erably, the polyrner 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 form~d with the above-described monomer units have utility as coatings, films and cast-ings. Surprisingly, such polymers may exhibit mechani-cal properties superior to those in which aromatic groupshave been incorporated into the polymer backbone.

The following ex~nples 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.

29,434B-F -18-:.

3(~0 Example 1 A. Preparation of Dimethyl-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 dr~ness, 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 (O.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 lo~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 29,434B-F -19--20- ~Z~63~

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 75C 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 50:50 by volume mixture of ethylene glycol and water at -30C 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~ove products.

Dimethyl-1,5-cyclooctadiene (850 ml) (730 g, 5.36 moles DMCOD) containing a~out 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 11C.
Products were removed from the reaction zone at the same rate that they were added. When the feeds were e~hausted 29,434B-F -20-lZ~63~

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 85C--95C 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 -35C. Gaseous ammo-nia was then introduced to the vessel and allowed to con-dense until at least 48_ g (28.48 moles) have been col-lected. The vessel was then stirred and allowed to warm to about 25C. After 2 hours at about 25C, 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 95C. The addition funnel was charged with 1.75 liters of lN aqueous sodium hydroxide; this was added to the stirred, hot mixture, resulting in the liberation of some NH3. The flask was then reheated to a~hieve reflux, and water removed through the Dean-Stark trap as a result 29,434B-F -21--22- ~Z1~3~

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 90C-95C (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 amine 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 (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 29,434B-F -22-, -23- ~2~63~

agitated and heated to 100F (37.8C). 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 100F
(37.8C). Specific gravities of the ingredients in each side tank of the reac-tion 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 155F ~68.3C) 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 150C 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 follQwing Ta~le I.

For Comparative Run A, a conventional formu-lation was prepared using the ~oregoing ingredients except that an amine capped propylene oxide polymer represented by the structure H2N~CH-CH2O)5.6C~2CH NH2 29,434B-F-23-3(~0 was substituted for the diamine chain extender of the present invention. This Comparat:ive Run was similarly processed and tested for physical properties and the results are reported in Table I.

29,434B-F -24--25-~Zl1~3~0 oo _ _ ~t O ~
~rl N ~1 ~ O . ~ .

d' ~1 o _ o-- o _ ~ ~ ~--O ~ E3 O O Lt) C5~ N r`
m ~,, N ~ ~ ~
Lll ' ~ ' ~0 ' ~9 ~1 O ~ O-- ~1 _ _ ~, ,1 ~ ~
3 Lt') d' ~ l` ~ O
Or4 ~ ~ ~
N
~I t~~I CON _ ~rl _ _ . ~
ta o o o~ ~ o .,1 . 0-- 0-- o~ _ ~q ,1 o ~ o ~ o 1 ca o ::~ ~ h o ~ o _ O , ~o ~ ~ ~ 1 0 t~ ~ ~:
_ ~ Ll~ O O ~ O
~ ~ ~ . ~ . ~ .~ a~
X ~ e~ N ~n O
a~
-- d~
S~
U~
~1 ul O o O ,X (I) O~ O~ O~~~ ~ rl ~1 -1 o In o d~ O ~ ' .. : ~n U~
_ O ~5~-- O `_ ~ _ ` fd ~
_ _ _ ~ ~ _ ~ `_ ~ O O O ~ O OD ~ ~ O
~1 ~ ~ ~
~A ~~') ~~ r`~7 N rt O O ~0 F~ ~ ` N` ~ ` N
a~ s~
E~ ~ a~ ~ o u~
~ ~1 0 O O O
)~ ~ o o u~
~o ~ ~ O

:~ d' t` O ~ 3 ~
-~ ~ 1` 'i ~ h ~ ~ ~ N ~ ~ C:~
rl ~ ~ ~ rl ~ ~ l u~ ~ u) I al ,~
~ ~ S~ . . . ~ R ~ '~
~
~ ~ ~ m ~ ~ a~ o Ln ~
~ ~ ~ o ~ a~
E-~ a) s~ ` N
~ rl ~
a) Ll ,~ ~ ~ a a I I
1:1 0 ~ N t`') ~ U~

29, 434B-F -25-~Z~ 3~0 As evidenced by the data shown in Table I, the polyurethanes prepared by the practice o~ 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.

29,434B-F -26-

Claims (9)

IN THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An alkyl-substituted thiapolycyclic polyahl represented by the structural formula:

wherein A is a residue of an active hydrogen moiety;

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; and n is 0, 1, 2 or 3.

2. The polyahl of Claim 1 which is repre-sented by one of the structural formulae:

wherein R1, R2 and A are as defined in Claim 1.

3. The polyahl of Claim 2 wherein each A is R3 is hydrogen, an aliphatic alkyl containing 1 to 20 carbon atoms or an inertly-substituted aliphatic alkyl containing 1 to 20 carbon atoms.

4. The polyahl of Claim 3 wherein all R2 are hydrogen.

5. The polyahl of Claim 4 wherein x is zero.

6. The polyahl of Claim 5 wherein each R1 is methyl.

7. The polymer having repeating units of the formula:

or wherein A is a residue of an active hydrogen moiety;
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; and x is 0, 1 or 2.

8. The polymer of Claim 7 wherein at least 0.5 mole percent of the monomer units are present.

9. The polymer of Claim 7 wherein each A is , each R3, which may be the same or different, is hydro-gen, an aliphatic alkyl group containing 1 to 20 carbon atoms or an inertly-substituted aliphatic alkyl group containing 1 to 20 carbon atoms.