Liquid aromatic bisoxazoline and bisoxazine monomer mixtures and process for crosslinking using phenolics

Compositions having melting points below 100.degree. C. which are useful in the formation of resins by reaction with polyphenolic compounds consisting of a mixture of more than two compounds having the formula ##STR1## wherein A represents a cyclic or acyclic aliphatic or substituted cyclic or acyclic aliphatic moiety having from 1 to 20 carbon atoms or an aromatic mono- or multi-nuclear or aliphatic substituted aryl residue having from 6 to 20 carbon atoms, PA0 R independently represents H, CH.sub.3, CH.sub.2 CH.sub.3 or C.sub.6 H.sub.5, PA0 R.sup.1 independently represents H or CH.sub.3, PA0 R.sup.2 independently represents H or CH.sub.3, and PA0 x represents an integer from 0 to 2 as described.

This invention relates to liquid aromatic bisoxazoline and/or bisoxazine 
monomer mixtures and more particularly pertains to mixtures of these 
monomers combined with aromatic compounds containing both an oxazoline and 
an oxazine ring on the same molecule and to a process for preparing these 
mixtures via blending or preferably by a one-step synthesis procedure. The 
liquid to low melting mixtures (liquid below 100.degree. C.) of 
bisoxzolines and bisoxazines which result from these processes are useful 
as chain extenders and crosslinkers for active hydrogen monomers, 
oligomers and polymers. 
The use of individual bisoxazolines for chain extension and crosslinking of 
polyphenolic compounds has been described in U.S. Pat. No. 4,430,491 and 
the use of bisoxazolines in the crossinking of materials containing 
mercaptan or thiol groups, carboxylic acid groups, and both carboxylic 
acid and phenolic groups is also known. 
The pure forms of the 1,3-phenylene-bisoxazoline, 
1,4-phenylene-bisoxazoline, 1,3-phenylene bisoxazine and/or 
1,4-phenylene-bisoxazine used in the prior art for chain extension and for 
crosslinking purposes individually are relatively high melting, 
crystalline compounds which are not readily mixed at low temperatures with 
the oligomeric or polymeric materials used in the crosslinking reactions. 
It is highly desirable to have bisoxazolines and/or bisoxazines which are 
liquids at ambient conditions or low melting solids, in order to 
facilitate mixing at low temperatures, obviating the need of solvents or 
the use of high temperatures during applications stage. The liquid 
bisoxazolines/bisoxazines mixtures of this invention allow one to have a 
much greater processing window prior to the subsequent curing stage or 
crosslinking/chain extension stage between the bisoxazoline, bisoxazine, 
etc., and the active hydrogen containing monomers, oligomers or polymers. 
Further, in the homopolymerization of bisoxazolines or monomer mixtures 
thereof it is best to have these materials in the liquid state at low 
temperatures, lending flexibility to their use without solvent. 
We have discovered that mixtures of liquid or low melting, aromatic 
bisoxazolines, bisoxazines and combinations thereof may be produced in a 
convenient one-step reaction from a blend of an aromatic dinitrile or 
dinitriles by reaction with a blend of amino alcohols. A two step reaction 
may also be used, starting with mixtures of aromatic dicarboxylic acid 
esters and amino alcohols, followed by subsequent cyclodehydration of the 
produced aromatic diamide diols. However, this procedure is less preferred 
because it is a two-step method. Also, the various aromatic bisoxazolines, 
bisoxazines, etc. compounds may be made independently and subsequently 
blended (mixed) in various ratios to obtain low melting mixtures of 
bisoxazolinesbisoxazines. However, this latter procedure is also less 
preferred since it requires much greater effort to produce a large number 
of compounds for blending and there is no convenient procedure for 
production of aromatic or aliphatic compounds in a pure state with mixed 
oxazoline-oxazine ring systems on the same molecule. We have found that 
the first (one-step reaction) procedure is most convenient (preferred) 
since it requires only a single step and does not require independent 
preparation of a large number of bisoxazolines, bisoxazines, etc., having 
subsequent attempted mixing of these various compounds. 
Oxazolines useful in the mixtures of this invention include more than one 
structurally dissimilar compounds having at least two oxazoline, two 
oxazine, or two tetrahydrooxazepine groups per molecule and/or molecules 
with both an oxazoline and an oxazine, an oxazoline and 
tetrahydrooxazepine or an oxazine and tetrahydrooxazepine residue on the 
same molecule, preferably prepared in a one-step reaction from treatment 
of various amino alcohols mixtures with dinitrile or dinitrile mixtures. 
Bisoxazolines, bisoxazines, and bis-tetrahydrooxazepines compounds or 
compounds with mixed oxazoline, oxazine, and tetrahydrooxazepine moieties 
in the same molecules include mixtures of two or more compounds of the 
following General Formula. 
##STR2## 
wherein A represents a cyclic or acyclic aliphatic or substituted cyclic 
or acyclic aliphatic moiety having from 1 to 20 carbon atoms or an 
aromatic (aryl) mono- or multinuclear or aliphatic substituted aryl 
residue having from 6 to 20 carbon atoms; 
R independently represents H, CH.sub.3, CH.sub.2 --CH.sub.3, or C.sub.6 
H.sub.5, 
R.sup.1 independently represents H or CH.sub.3, 
R.sup.2 independently represents H or CH.sub.3, and 
x represents an integer of from 0 to 2. 
We have discovered a method for producing mixtures of compounds of the 
above General Formula, in one step, which mixtures are useful as chain 
extenders and/or crosslinkers for active hydrogen materials. 
Representative compounds which can be produced in the form of mixtures of 
two or more compounds of the General Formula in this invention include: 
4,4'-tetrahydro-2,2'-bisoxazole, 
5,5',6,6'-tetrahydro-2,2'-bis(4H-1,3-oxazine), 
2,2'-alkanediyl-bis[4,5-dihydrooxazole], and 
2,2'-alkanediyl-bis[5,6-dihydro-4H-1,3-oxazine], e.g., 
2,2'-(1,4-butanediyl)bis[4,5-dihydrooxazole] 
2,2'-(1,4-butanediyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(1-methyl-1,3-propanediyl)bis[4,5-dihydrooxazole] 
2,2'-(1-methyl-1,3-propanediyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(1,3-propanediyl)bis[4,5-dihydrooxazine] 
2,2'-(1,3-propanediyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(1,2-ethanediyl)bis[4,5-dihydrooxazole] 
2,2'-(1,2-ethanediyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(1,8-dodecanediyl)bis[4,5-dihydrooxazole] 
2,2'-(1,8-dodecanediyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(1,6-hexanediyl)bis[4,5-dihydrooxazole] 
2,2'-(1,6-hexanediyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(1,4-cyclohexanediyl)bis[4,5-dihydrooxazole] 
2,2'-(1,4-cyclohexanediyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(arylene)bis[4,5-dihydrooxazole] and 
2,2'-(arylene)bis[5,6-dihydro-4H-1,3-oxazine], e.g., 
2,2'-(1,4-phenylene)bis[4,5-dihydrooxazole] 
2,2'-(1,4-phenylene)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(1,3-phenylene)bis[4,5-dihydrooxazole] 
2,2'-(1,3-phenylene)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(1,5-naphthalenyl)bis[4,5-dihydrooxazole] 
2,2'-(1,5-naphthalenyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(1,8-anthracenyl)bis[4,5-dihydrooxazole] 
2,2'-(1,8-anthracenyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(2,6-naphthalenyl)bis[4,5-dihydrooxazole] 
2,2'-(2,6-naphthalenyl)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'2"-(1,3,5-phenylene)tris[4,5-dihydrooxazole] 
2,2'2"-(1,3,5-phenylene)tris[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(5-t-butyl-1,3-phenylene)bis[4,5-dihydrooxazole] 
2,2'-(5-t-butyl-1,3-phenylene)bis[5,6-dihydro-4H-1,3-oxazine] 
2,2'-(trimethyl-4,5-phenylindanyl)bis[4,5-dihydrooxazole] 
2,2'-(trimethyl-4,5-phenylindanyl)bis[5,6-dihydro-4H-1,3-oxazine] 
A sulfonyl, oxy, thio or alkylene bis-2-(arylene)[4,5-dihydro-oxazole] or 
[5,6-dihydro-4H-1,3-oxazine], e.g., 
sulfonyl bis-1,1'-(phenylene)-4,4'-bis[4,5-dihydrooxazole] 
sulfonyl bis-1,1'-(phenylene)-4,4'-bis[5,6-dihydro-4H-1,3-oxazine] 
oxy bis-1,1'-(phenylene)-4,4'-bis[4,5-dihydrooxazole] 
oxy bis-1,1'-(phenylene)-4,4'-bis[5,6-dihydro-4H-1,3-oxazine] 
thio bis-1,1'-(phenylene)-4,4'-bis[4,5-dihydrooxazole] 
thio bis-1,1'-(phenylene)-4,4'-bis[5,6-dihydro-4H-1,3-oxazine] 
methylene bis-1,1'-(phenylene)-4,4'-bis[4,5-dihydrooxazole] 
methylene bis-1,1'-(phenylene)-4,4'-bis[5,6-dihydro-4H-1,3-oxazine] 
compounds with substituted oxazoline and mixed oxazolineoxazine residues, 
e.g., 
phenylene-1-[2(4,5-dihydrooxazole)]-4-[2(5,6-dihydro-4H-1,3-oxazine)] 
phenylene-1-[2(4,5-dihydrooxazole)]-3-[2(5,6-dihydro-4H-1,3-oxazine)] 
2,2'-(1,3-phenylene)-bis[4-methyl-4,5-dihydrooxazole] 
phenylene-1-[2(4,5-dihydrooxazole)]-3-[2(4-methyl-4,5-dihydrooxazole)] 
phenylene-1-[2(4-methyl-4,5-dihydrooxazole)]-3-[2(5,6-dihydro-4H-1,3-oxazin 
e)] 
2,2'-(1,4-phenylene)-bis[4-methyl-4,5-dihydrooxazole] 
phenylene-1-[2(4,5-dihydrooxazole)]-4-[2(5,6-dihydro-4H-1,3-oxazine)] 
phenylene-1-[2(4-methyl-4,5-dihydrooxazole)]-4-[2(4,5-dihydrooxazole)] 
phenylene-1-[2(4-methyl-4,5-dihydrooxazole)]-4-[2(5,6-dihydro-4H-1,3-oxazin 
e)] 
2,2'-(1,4-phenylene)-bis[4-ethyl-4,5-dihydrooxazole] 
2,2'-(1,3-phenylene)-bis[4-ethyl-4,5-dihydrooxazole] 
phenylene-1-[2(4-ethyl-4,5-dihydrooxazole)]-4-[2(4,5-dihydrooxazole)] 
phenylene-1-[2(4-ethyl-4,5-dihydrooxazole)]-3-[2(4,5-dihydrooxazole)] 
phenylene-1-[2(4-ethyl-4,5-dihydrooxazole)]-4-[2(5,6-dihydro-4H-1,3-oxazine 
)] 
phenylene-1-[2(4-ethyl-4,5-dihydrooxazole)]-3-[2(5,6-dihydro-4H-1,3-oxazine 
)] 
phenylene-1-[2(5-methyl-4,5-dihydrooxazole)]-4-[2(4,5-dihydrooxazole)] 
phenylene-1-[2(5-methyl-4,5-dihydrooxazole)]-4-[2(5,6-dihydro-4H-1,3-oxazin 
e)] 
2,2'-(1,4-phenylene)-bis[5-methyl-4,5-dihydrooxazole] 
phenylene-1-[2(4-ethyl-4,5-dihydrooxazole)]-4-[2(5-methyl-4,5-dihydrooxazol 
e)] 
phenylene-1-[2(5-methyl-4,5-dihydrooxazole)]-3-[2(4,5-dihydrooxazole)] 
phenylene-1-[2(5-methyl-4,5-dihydrooxazole)]-3-[2(5,6-dihydro-4H-1,3-oxazin 
e)] 
2,2'-(1,3-phenylene)-bis[5-methyl-4,5-dihydrooxazole] 
phenylene-1-[2(4-ethyl-4,5-dihydrooxazole)]-3-[2(5-methyl-4,5-dihydrooxazol 
e)] 
2,2'-(1,3-phenylene)-bis[4-phenyl-4,5-dihydrooxazole] 
2,2'-(1,4-phenylene)-bis[4-phenyl-4,5-dihydrooxazole] 
phenylene-1-[2(4-phenyl-4,5-dihydrooxazole)]-4-[2(4,5-dihydrooxazole)] 
phenylene-1-[2(4-phenyl-4,5-dihydrooxazole)]-3-[2(5,6-dihydro-4H-1,3-oxazin 
e)] 
phenylene-1-[2(4-phenyl-4,5-dihydrooxazole)]-4-[2(5,6-dihydro-4H-1,3-oxazin 
e)] 
phenylene-1-[2(4-phenyl-4,5-dihydrooxazole)]-3-[2(4-methyl-4,5-dihydrooxazo 
le)] 
phenylene-1-[2(4-phenyl-4,5-dihydrooxazole)]-4-[2(4-methyl-4,5-dihydrooxazo 
le)] 
phenylene-1-[2(4-phenyl-4,5-dihydrooxazole)]-3-[2(4-ethyl-4,5-dihydrooxazol 
e)] 
phenylene-1-[2(4-phenyl-4,5-dihydrooxazole)]-4-[2(4-ethyl-4,5-dihydrooxazol 
e)] 
phenylene-1-[2(4-phenyl-4,5-dihydrooxazole)]-3-[2(5-methyl-4,5-dihydrooxazo 
le)] 
phenylene-1-[2(4-phenyl-4,5-dihydrooxazole)]-4-[2(5-methyl-4,5-dihydrooxazo 
le)] 
1-[2(5,6-Dihydro-4H-1,3-Oxazinyl)]-4-[2(4,5-dihyrdooxazolyl)]butane 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-4-[2(4,5-dihydrooxazolyl)]butane 
1-[2(4-methyl-4,5-dihydrooxazolyl)]-4-[2(4,5-dihydrooxazolyl)]butane 
1-[2(5-methyl-4,5-dihydrooxazolyl)]-4-[2(4,5-dihydrooxazolyl)]butane 
1-[2(4-phenyl-4,5-dihydrooxazolyl)]-4-[2(4,5-dihydrooxazolyl)]butane 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-4-[2(5,6-dihydro-4H-1,3-oxazinyl)]butane 
1-[2(4-methyl-4,5-dihydrooxazolyl)]-4-[2(5,6-dihydro-4H-1,3-oxazinyl)]butan 
e 
1-[2(5-methyl-4,5-dihydrooxazolyl)]-4-[2(5,6-dihydro-4H-1,3-oxazinyl)]butan 
e 
1-[2(4-phenyl-4,5-dihydrooxazolyl)]-4-[2(5,6-dihydro-4H-1,3-oxazinyl)]butan 
e 
1-[2(4-phenyl-4,5-dihydrooxazolyl)]-4-[2(4-ethyl-4,5-dihydrooxazolyl)]butan 
e 
1-[2(4-phenyl-4,5-dihydrooxazolyl)]-4-[2(4-methyl-4,5-dihydrooxazolyl)]buta 
ne 
1-[2(4-phenyl-4,5-dihydrooxazolyl)]-4-[2(5-methyl-4,5-dihydrooxazolyl)]buta 
ne 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-4-[2(4-methyl-4,5-dihydrooxazolyl)]butan 
e 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-4-[25-methyl-4,5-dihydrooxazolyl)]butane 
2,2'-(1,4-butylene)-bis[4-phenyl-4,5-dihydrooxazole] 
2,2'-(1,4-butylene)-bis[4-ethyl-4,5-dihydrooxazole] 
2,2'-(1,4-butylene)-bis[5-methyl-4,5-dihydrooxazole] 
2,2'-(1,4-butylene)-bis[4-methyl-4,5-dihydrooxazole] 
1-[2(5,6-dihydro-4H-1,3-oxazinlyl)]-3-[2(4,5-dihydrooxazolyl)]-3-methylprop 
ane 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-[2(4,5-dihydrooxazolyl)]-3-methylpropa 
ne 
1-[2(5-methyl-4,5-dihydrooxazolyl)]-3-[2(4,5-dihydrooxazolyl)]-3-methylprop 
ane 
1-[2(4-methyl-4,5-dihydrooxazolyl)]-3-[2(4,5-dihydrooxazolyl)]-3-methylprop 
ane 
1-[2(4-phenyl-4,5-dihydrooxazolyl)]-3-[2(4,5-dihydrooxazolyl)]-3-methylprop 
ane 
2,2'-(3-methyl-1,3-propenyl)-bis[4-phenyl-4,5-dihydrooxazole]2,2'-(3-methy 
l-1,3-propenyl)-bis[4-ethyl-4,5-dihydrooxazole]2,2'-(3-methyl-1,3-propenyl) 
-bis[4-methyl-4,5-dihydrooxazole] 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-[2(4-methyl-4,5-dihydrooxazolyl)]-3-me 
thylpropane 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-[2(5-methyl-4,5-dihydrooxazolyl)]-3-me 
thylpropane 
1-[2(4-methyl-4,5-dihydrooxazolyl)]-3-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-me 
thylpropane 
1-[2(5-methyl-4,5-dihydrooxazolyl)]-3-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-me 
thylpropane 
1-[2(4-methyl-4,5-dihydrooxazolyl)]-3-[2(5-methyl-4,5-dihydrooxazolyl)]-3-m 
ethylpropane 
1-[2(5-methyl-4,5-dihydrooxazolyl)]-3-[2(4-methyl-4,5-dihydrooxazolyl)]-3-m 
ethylpropane 
1-[2(5-phenyl-4,5-dihydrooxazolyl)]-3-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-me 
thylpropane 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-[2(4-phenyl-4,5-dihydrooxazolyl)]-3-me 
thylpropane 
1-[2(4,5-dihydrooxazolyl)]-3-[2(5,6-dihydro-4H-1,3-oxazinyl])]-3-methylprop 
ane 
1-[2(4,5-dihydrooxazolyl)]-3-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-methylpropa 
ne 
1-[2(4,5-dihydrooxazolyl)]-3-[2(5-methyl-4,5-dihydrooxazolyl)]-3-methylprop 
ane 
1-[2(4,5-dihydrooxazolyl)]-3-[2(4-methyl-4,5-dihydrooxazolyl)]-3-methylprop 
ane 
1-[2(4,5-dihydrooxazolyl)]-3-[2(4-phenyl-4,5-dihydrooxazolyl)]-3-methylprop 
ane 
2,2'-(1,3-phenylene)-bis[4,4-dimethyl-4,5-dihydrooxazole] 
2,2'-(1,4-phenylene)-bis[4,4-dimethyl-4,5-dihydrooxazole] 
1-[2(4,5-dihydrooxazolyl)-3-[2(4,4-dimethy-4,5-dihydrooxazolyl)]-3-benzene 
1-[2(4,5-dihydrooxazolyl)-4-[2(4,4-dimethy-4,5-dihydrooxazolyl)]-3-benzene 
1-[2(5,6-dihydro-4H-1,3-oxazinyl)]-3-[2(4,4-dimethyl-4,5-dihydrooxazolyl)]b 
enzene 
1-[2(5,6-dihydro-4H-1,3-oxazinyl)]-4-[2(4,4-dimethyl-4,5-dihydrooxazolyl)]b 
enzene 
2,2'-(1,3-phenylene)-bis[4,5,6,7-tetrahydrooxazepine] 
2,2'-(1,4-phenylene)-bis[4,5,6,7-tetrahydrooxazepine] 
1-[2(4,5,6,7-tetrahydrooxazepinyl)]-4-[2(4,5-dihydrooxazolyl)]benzene 
1-[2(4,5,6,7-tetrahydrooxazepinyl)]-3-[2(4,5-dihydrooxazolyl)]benzene 
1-[2(4,5,6,7-tetrahydrooxazepinyl)]-4-[2(5,6-dihydro-4H-1,3-oxazinyl)]benze 
ne 
1-[2(4,5,6,7-tetrahydrooxazepinyl)]-3-[2(5,6-dihydro-4H-1,3-oxazinyl)]benze 
ne.

EXAMPLE 1 
A statistical mixture of six bisoxazoline, bisoxazine, and substituted 
oxazoline-oxazine compounds, consisting of: 
2,2'-(1,3-phenylene)bis[4,5-dihydrooxazole], 
2,2'-(1,3-phenylene)-bis[5,6-dihydro-4H-1,3-oxazine], 
2,2'-(1,3-phenylene)-bis[5-methyl-4,5-dihydrooxazole], 
1-[2(5,6-dihydro-4H-1,3-oxazinyl)]-3-[2(4,5-dihydrooxazole)]benzene, 
1-[2(5-methyl-4,5-dihydrooxazolyl)]-3-[2(4,5-dihydrooxazolyl)]benzene, 
1-[2(methyl-4,5-dihydrooxazolyl)]-3-[2(5,6-dihydro-4H-1,3-oxazinyl)]benzene 
with several of the latter compounds existing also as D, L, DD, DL and LL 
forms, was prepared as follows: 
A mixture of isophthalonitrile (2.0 mol, 256 g), 2-aminoethanol (1.5 mol, 
92 g), 3-aminopropanol (1.5 mol, 113 g), xylene (1.5 l), and cadmium 
nitrate (20 g) catalyst was heated under nitrogen for 20 hours at 
120.degree. C. The reaction progress was followed by trapping the evolved 
ammonia in an HCl acid trap. The NH.sub.4 Cl collected was dried and 
weighed, obtaining 103 g of NH.sub.4 Cl. This showed approximately 98% 
conversion of nitrile to cyclic imino ether. The mixture was washed with 
water to remove amino alcohols, dried, and the xylene removed under 
reduced pressure, giving 390 g of product. The mixture consisted 
essentially of six compounds, neglecting to count optical isomers, having 
a molecular weight range of 216-244 and an average of 234.5 per various 
weight fraction of monomers. The mixture was found to be a white paste at 
room temperature and a liquid at 50.degree. C., having a viscosity of &lt;100 
cps. 
A sample of the above mixture of bisoxazoline-bisoxazine compounds (24 g) 
was combined with 36 g of Alnovol PN-320 Novolac (American Hoechst, phenol 
free phenolic resin molecular weight 3000-4000), and 0.6 g of diphenyl 
phosphite catalyst. The clear mixture was heated at 175.degree. C., 
showing a gel time of 5 minutes. The neat resin casting, post cured 1 hour 
at 175.degree. C., showed a Tg of 149.degree. C. In a comparative 
experiment in which the same weight ratios of 
2,2'-(1,3-phenylene)-bis[4,5-dihydrooxazole], Alnovol PN 320, and diphenyl 
phosphite was used the gel time was also about 5 minutes, and the Tg of 
the post cured neat resin was 154.degree. C. 
The advantage of the above is that the phenolic resin and oxazoline-oxazine 
mixture may be readily mixed &lt;100.degree. C., in contrast to about the 
150.degree. C. required when using the pure 
2,2'-(1,3-phenylene)-bis[4,5-dihydrooxazole]. Further, in spite of the use 
of five reactive diluents, i.e., additional bisoxazoline, bisoxazine, 
etc., in place of some of the 1,3-phenylene-bisoxazoline, the TG of the 
cured system (neat resin) was not drastically affected. 
EXAMPLE 2 
The procedure of Example 1 was followed using a mixture consisting of 192 g 
(1.5 mol) of isophthalonitrile, 64 g (0.5 mol) of terephthalonitrile, 153 
g (2.5 mol) of 2-aminoethanol, 112.5 (1.5 mol) of 3-aminopropanol, 20 g 
(0.25 mol) of 1-amino-2-propanol, 25 g (0.25 mol) of 2-amino-1-butanol, 20 
g of zinc acetate, and 1.5 l of xylene. The solution was heated under 
nitrogen for 10 hours at 120.degree. C., resulting in 208 g of isolated 
NH.sub.4 Cl (theory, 212 g) and 504 g of mixed monomers. This shows high 
conversion was obtained, i.e., 98% of nitrile groups were converted to 
cyclic imino ethers. The mixture, statistically containing principally 
2,2'-(1,3-phenylene)-bis-[4,5-dihydrooxazole], and 
2,2'-(1,4-phenylene)-bis-[4,5-dihydrooxazole], consisted of twenty 
different bisoxazolines, bisoxazines and molecules with mixed 
oxazoline-oxazine residues. In addition to the various optical isomers, 
the other 18 reactive diluents which were produced in this process are: 
2,2'-[1,3-phenylene)-bis[5,6-dihydro-4H-1,3-oxazine], 
2,2'-(1,4-phenylene)-bis[5,6-dihydro-4H-1,3-oxazine], 
1-[2(4,5-dihydrooxazolyl)]-3-[2(5,6-dihydro-4H-1,3-oxazinyl]benzene, 
1-[2(5,6-dihydro-4H-1,3-oxazinyl]-4-[2(4,5-dihydrooxazolyl)]benzene, 
2,2'-(1,3-phenylene)-bis[5-methyl-4,5-dihydrooxazole], 
2,2'-(1,4-phenylene)-bis[5-methyl-4,5-dihydrooxazole], 
1-[2(5-methyl-4,5-dihydrooxazolyl)]-3-[2(4,5-dihydrooxazolyl)]benzene, 
1-[2(5-methyl-4,5-dihydrooxazolyl)]-4-[2(4,5-dihydrooxazolyl)]benzene, 
1-[2(5-methyl-4,5-dihydrooxazolyl]-3-[2(5,6-dihydro-4H-1,3-oxazinyl)]benzen 
e, 
1-(2[5-methyl-4,5-dihydrooxazolyl]-4-[2(5,6-dihydro-4H-1,3-oxazinyl)]benzen 
e, 
2,2'-(1,3-phenylene)-bis [4-ethyl-5,6-dihydrooxazole], 
2,2'-(1,4-phenylene)-bis [4-ethyl-5,6-dihydrooxazole], 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-[2(4,5-dihydrooxazolyl)]benzene, 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-4-[2(4,5-dihydrooxazolyl)]benzene, 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-[2(5,6-dihydro-4H-1,3-oxazinyl)]benzen 
e, 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-4-[2-(4,5-dihydrooxazolyl)]benzene, 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-3-[2(5-methyl-4,5-dihydrooxazolyl)]benze 
ne, and 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-4-[2(5-methyl-4,5-dihydrooxazolyl)]benze 
ne. 
The mixture was found to be a liquid at room temperature, containing mainly 
2,2'-(1,4-phenylene)-bis[4,5-dihydrooxazole] and 
2,2'-(1,4-phenylene)bis[4,5-dihydrooxazole] mixed with the above-described 
eighteen different reactive diluent compounds. The mixture had a viscosity 
of 700 cps at 25.degree. C. and 200 cps at 45.degree. C. 
Alnovol phenolic resin (American Hoechst Novolac PN 320 molecular weight 
2000-4000), 60% by weight, was combined with the above 
bisoxazoline-bisoxazine mixture, 40% by weight and 1% by weight of 
triphenyl phosphite catalyst at below 100.degree. C. The reactive mixture 
gelled in 9 min. at 175.degree. C. After post curing for 2 hours at 
220.degree. C., the neat resin casting exhibited a TG of 146.degree. C., 
flex strength of 22,800 psi and flex modulus of 704,600 psi. These 
properties are close to those obtained by using a mixture of pure 
2,2'-(1,3-phenylene)-bis[4,5-dihydrooxazole]: Alnovol PN30 in the same 
ratio (40:60) with the same weight percent triphenyl phosphite catalyst, 
i.e., 154.degree. C. Tg, 22,000 psi flex strength, and 780,000 psi flex 
modulus. 
EXAMPLE 3 
The procedure of Example 1 was followed, using 1,4-dicyanobenzene 
(terephthalonitrile) (256 g, 2.0 mol), 125.5 g (2.5 mol) of 
2-aminoethanol, 75 g (1.0 mol) of 2-aminopropanol, 44.5 g (0.5 mol) of 
2-amino-1-butanol, 10 g of zinc acetate, and 1 l of xylene. The product 
mixture, containing six different bisoxazolines and bisoxazines, e.g., 
2,2'-(1,4-phenylene)-bis[4,5-dihydrooxazole], 
2,2'-(1,4-phenylene)-bis[4-ethyl-4,5-dihydrooxazole], 
2,2'-(1,4-phenylene)-bis[4,5-dihydro-4H-1,3-oxazine], 
1-[2(4,5-dihydro-4H-1,3-oxazinyl)]-4-[2(4,5-dihydrooxazolyl)]benzene, 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-4-[2(4,5-dihydrooxazolyl)]benzene, and 
1-[2(4-ethyl-4,5-dihydrooxazolyl)]-4-[2(4,5-dihydrooxazinyl)]benzene, 
and also containing a statistical distribution of D, L, DL, DD, and LL 
optical isomer forms, was obtained in 98% conversion of the dinitrile, as 
evidenced by the 210 g of dry NH.sub.4 Cl collected after reaction for 12 
hours at 120.degree. C. The product was found to be soluble in a variety 
of common solvents such as acetone, and had a melting point of less than 
100.degree. C. In contrast, pure 
2,2'-(1,4-phenylene)-bis[4,5-dihydrooxazole] melts at 254.degree. C. and 
is practically insoluble in common solvents such as acetone, alcohols, 
etc. A cured neat resin sample was prepared in accordance with the 
procedure of Example 1 from 70% by weight of Alnovol PN 320 and 30% by 
weight of the above-described oxazoline-oxazine mixture exhibited a TG of 
134.degree. C. In contrast, a neat resin sample cured under the same 
conditions with 30% pure 2,2'-(1,4-phenylene-bis [4,5-dihydrooxazole] and 
70% Alnovol PN 320 exhibited a Tg of 140.degree. C. In another experiment 
a cured resin sample was prepared from 40% by weight of Alnovol PN 320 and 
60% by weight of the oxazoline-oxazine mixture, of this example with the 
cured sample showing a Tg of 230.degree. C. Such a ratio of reactants as 
is produced by the process of this invention cannot be prepared from pure 
2,2'-(1,4-phenylene)bis[4,5-dihydrooxazole] because the pure oxazoline is 
essentially insoluble in the Alnovol at the foregoing process 
temperatures.