Composition and method for producing fuel resistant liquid...

Details Composition and method for producing fuel resistant liquid... Composition and method for producing fuel resistant liquid...

1997-09-12

2001-01-09

Truong, Duc (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From sulfur-containing reactant

C528S374000, C528S378000, C525S212000, C568S029000

Reexamination Certificate

active

06172179

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to liquid polythioether polymers that have good low temperature flexibility and fuel resistance when cured. The invention is also directed to methods for making the polymers by reacting polythiols with oxygenated dienes (divinyl ethers) which substantially eliminate malodorous condensed cyclic by-products.
BACKGROUND OF THE INVENTION
Thiol-terminated sulfur-containing polymers are known to be well-suited for use in aerospace sealants due to their fuel resistant nature upon cross-linking. Among the commercially available polymeric materials which have sufficient sulfur content to exhibit this desirable property are the polysulfide polyformal polymers described, e.g., in U.S. Pat. No. 2,466,963, and the alkyl side chain containing polythioether polyether polymers described, e.g., in U.S. Pat. No. 4,366,307 to Singh et al. Materials useful in this context also have the desirable properties of low temperature flexibility (low glass transition temperature T
g
) and liquidity at room temperature.
An additional desirable combination of properties for aerospace sealants which is much more difficult to obtain is the combination of long application time (i.e., the time during which the sealant remains usable) and short curing time (the time required to reach a predetermined strength). Singh et al., U.S. Pat. No. 4,366,307, disclose such materials. Singh et al. teach the acid-catalyzed condensation of hydroxyl-functional thioethers. The hydroxyl groups are in the &bgr;-position with respect to a sulfur atom for increased condensation reactivity. The Singh et al. patent also teaches the use of hydroxyl-functional thioethers with pendent methyl groups to afford polymers having good flexibility and liquidity. However, the disclosed condensation reaction has a maximum yield of about 75% of the desired condensation product. Furthermore, the acid-catalyzed reaction of &bgr;-hydroxysulfide monomers yields significant quantities (typically not less than about 25%) of an aqueous solution of thermally stable and highly malodorous cyclic byproducts, such as 1-thia-4-oxa-cyclohexane. As a result, the commercial viability of the disclosed polymers is limited.
Another desirable feature in polymers suitable for use in aerospace sealants is high temperature resistance. Inclusion of covalently bonded sulfur atoms in organic polymers has been shown to enhance high temperature performance. However, in the polysulfide polyformal polymers disclosed in U.S. Pat. No. 2,466,963, the multiple —S—S— linkages in the polymer backbones result in compromised thermal resistance. In the polymers of Singh et al., U.S. Pat. No. 4,366,307, enhanced thermal stability is achieved through replacement of polysulfide linkages with polythioether (—S—) linkages. In practice, however, the disclosed materials also have compromised thermal resistance due to traces of the residual acid condensation catalyst.
Morris et al., U.S. Pat. No. 4,609,762, describes reacting dithiols with secondary or tertiary alcohols to afford liquid polythioethers having no oxygen in the polymeric backbone. Cured polymeric materials formed from these polymers have the disadvantage, however, of reduced fuel resistance due to the large number of pendent methyl groups that are present. In addition, residual catalyst from the disclosed process generates undesirable aqueous acidic waste.
Cameron, U.S. Pat. No. 5,225,472, discloses production of polythioether polymers by the acid-catalyzed condensation of dithiols with active carbonyl compounds such as HCOOH. Again, this process generates undesirable aqueous acidic waste.
The addition polymerization of aliphatic dithiols with diene monomers has been described in the literature. See, e.g., Klemm, E. et al., J. Macromol. Sci.—Chem., A28(9), pp. 875-883 (1991); Nuyken, O. et al., Makromol. Chem., Rapid Commun. 11, 365-373 (1990). However, neither Klemm et al. nor Nuyken suggest selection of particular starting materials, specifically divinyl ethers and dithiols, such that a polymer is formed that is liquid at room temperature and, upon curing, has excellent low-temperature flexibility (low T
g
) and high resistance to fuels, i.e., hydrocarbon fluids. Nor do Klemm et al. suggest production of a polymer that in addition is curable at room or lower temperatures. Moreover, the reactions disclosed by Klemm et al. also generate undesirable cyclic byproducts.
SUMMARY OF THE PREFERRED EMBODIMENTS
In accordance with one aspect of the present invention, there is provided a polythioether having the formula I
—R
1
—[—S—(CH
2
)
2
—O—[—R
2
—O—]
m
—(CH
2
)
2
—S—R
1
]
n
—  I
wherein
R
1
denotes a C
2-6
n-alkylene, C
3-6
branched alkylene, C
6-8
cycloalkyl or C
6-10
alkylcycloalkyl group, —[(—CH
2
—)
p
—X—]
q
—(—CH
2
—)
r
—, or —[(—CH
2
—)
p
—X—]
q
—(—CH
2
—)
r
— in which at least one —CH
2
— unit is substituted with a methyl group,
R
2
denotes methylene C
2-6
n-alkylene, C
2-6
branched alkylene, C
6-8
cycloalkylene or C
6-10
alkylcycloalkylene group, or —[(—CH
2
—)
p
—X—]
q
—(—CH
2
—)
r
—,
X denotes one selected from the group consisting of O, S and —NR
6
—,
R
6
denotes H or methyl,
m is a rational number from 0 to 10,
n is an integer from 1 to 60,
p is an integer from 2 to 6,
q is an integer from 1 to 5, and
r is an integer from 2 to 10,
the polythioether being a liquid at room temperature and pressure and alkylene has the same structure as divalent alkyl.
Preferably the polythioether has a number average molecular weight between about 500 and about 20,000.
In a first preferred embodiment, the polythioether has the formula II
A—(—[R
3
]
y
—R
4
)
2
  II
wherein
A denotes a structure having the formula I,
y is 0 or 1,
R
3
denotes a single bond when y=0 and —S—(CH
2
)
2
—[—O—R
2
—]
m
—O— when y=1,
R
4
denotes —SH or —S—(—CH
2
—)
2+s
—O—R
5
when y=0 and —CH
2
=CH
2
or —(CH
2
—)
2
—S—R
5
when y=1,
s is an integer from 0 to 10,
R
5
denotes C
1-6
n-alkyl which is unsubstituted or substituted with at least one —OH or —NHR
7
group, and
R
7
denotes H or a C
1-6
n-alkyl group.
Polythioethers in which R
4
is —SH are “uncapped,” that is, include unreacted terminal thiol groups. Polythioethers according to the invention also include “capped” polythioethers, that is, polythioethers including terminal groups other than unreacted thiol groups. These terminal groups can be groups such as —OH or —NH
2
, or groups such as alkyl or terminal ethylenically unsaturated groups.
In a more particular preferred embodiment, y=0 in formula II and R
4
denotes —SH. That is, the polythioether is an uncapped polythioether having the structure
HS—R
1
—[—S—(CH
2
)
2
—O—[—R
2
—O—]
m
—(CH
2
)
2
—S—R
1
]
n
—SH.
In another more particular preferred embodiment, the inventive polythioether is a capped polythioether in which y=0 in formula II and R
4
denotes —S—(—CH
2
—)
2+s
—O—R
5
. Particularly preferably, R
5
is an unsubstituted or substituted n-alkyl group such as ethyl, 4-hydroxybutyl or 3-aminopropyl.
In still another particular preferred embodiment, y=1 in formula II and R
4
denotes —CH═CH
2
. That is, the polythioether is an uncapped polythioether having terminal vinyl groups.
In yet another more particular preferred embodiment, the inventive polythioether is a capped polythioether in which y=1 in formula II and R
4
denotes —(CH
2
—)
2
—S—R
5
.
In a second preferred embodiment, the polythioether has the formula III
 B—(A—[R
3
]
y
—R
4
)
z
  III
wherein
A denotes a structure having the formula I,
y is 0 or 1,
R
3
denotes a single bond when y=0 and —S—(CH
2
)
2
—[—O—R
2
—]
m
—O— when y=1,
R
4
denotes —SH or —S—(—CH
2
—)
2+s
—O—R
5
when y=0 and —CH
2
=CH
2
or —(CH
2
—)
2
—S—R
5
when y=1,
s is an integer from 0 to 10,
R
5
denotes C
1-6
n-alkyl which is unsubstituted or substituted with at least one —OH or —NHR
7
group,
R

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