USOO6509418B1

(12) United States Patent (10) Patent No.: US 6,509,418 B1

Z00k et al. (45) Date of Patent: *Jan. 21, 2003

(54) SEALANTS AND POTTING FORMULATIONS (56) References Cited

INCLUDING MERCAPTO-TERMINATED
POLYMERS PRODUCED BY THE U.S. PATENT DOCUMENTS
REACTION OF A POLYTHOLAND 3,506,626 A 4/1970 Warner et al.
POLY WINYL ETHER MONOMER 3,697.402 A 10/1972 Kehr et al.
3,725,229 A 4/1973 Kehr et al.
(75) Inventors: Jonathan D. Zook, Santa Clarita, CA 3,734.968 A 5/1973 Hickner
(US); Susan E. DeMoss, Van Nuys, CA 4,366,307 A 12/1982 Singh et al.
(US); David W. Jordan, Northridge, 4,609.762 A 9/1986 Morris et al.
CA (US); Chandra B. Rao, Valencia, 5,225,472 A 7/1993 Cameron et al.
CA (US); Hakam Singh, Bradbury, CA 5,516,455 A 5/1996 Jacobine et al.
(US); Ahmed Sharaby, Canyon 5,912,319 A 6/1999 Zook et al.
6,172,179 B1 1/2001 Zook et al.
Country, CA (US) 6,372,849 B2 * 4/2002 DeMoss et al. ............. 525/212
(73) Assignee: PRC-DeSoto International, Inc., FOREIGN PATENT DOCUMENTS
Glendale, CA (US) EP O 552 SSO A2 7/1993
(*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS
patent is extended or adjusted under 35
U.S.C. 154(b) by 82 days. Klemm, E. et al., 1991, J. Macromol. Sci-Chem, A28(9),
875-883.
This patent is Subject to a terminal dis Nuyken, O. et al., 1990, Makromol, Chem., Rapid Commun.
claimer. 11, 365-373.
Ameduri, B. et al., 1991, Polymer Bulletin 26, 377–382.
(21) Appl. No.: 09/756,573 Klemm, E. et al., 1985, Chemical Abstracts 103:197058Z.
(22) Filed: Jan. 8, 2001 Yamaguchi, K. et al., 1973, Polymer, 14:87–90.
Related U.S. Application Data (List continued on next page.)
(63) Continuation-in-part of application No. 08/928.972, filed on Primary Examiner Duc Truong
Sep. 12, 1997, now Pat. No. 6,172,179, which is a continu (74) Attorney, Agent, or Firm-Finnegan, Henderson,
ation-in-part of application No. 08/802,130, filed on Feb. 19, Farabow, Garrett & Dunner, L.L.P.
1997, now Pat. No. 5,912,319, application No. 09/756,573,
which is a continuation-in-part of application No. 09/318, (57) ABSTRACT
500, filed on May 25, 1999, now Pat. No. 6.232,401, which
is a division of application No. 08/802,130, filed on Feb. 19, Sealant and potting formulations are provided which are
1997, now Pat. No. 5,912,319, application No. 09/756,573 prepared from components including ungelled mercapto
(60) Provisional application No. 60/215,548, filed on Jun. 30, terminated polymer(s) prepared by reacting reactants com
2000, and provisional application No. 60/182,396, filed on
Feb. 14, 2000. prising polyvinyl ether monomer(s) and polythiol material
(S); curing agent(s) reactive with a mercapto group of the
(51) --- ------ ----- C08L 41/00; CO8G 75/00 mercapto-terminated polymer; and additive(s) selected from
(52) O ---- --- -- -------- 525/212; 525/328.5; 525/328.9;
the group consisting of fillers, adhesion promoters, plasti
528/376; 528/373 cizers and catalysts.
(58) Field of Search .............................. 525/212,328.5,
525/328.9; 528/376, 373 21 Claims, 2 Drawing Sheets

Title)
 US 6,509,418 B1
Page 2

OTHER PUBLICATIONS Klemm, E. et al., 1992, Polymer Bulletin 28, 653–656.

Nuyken, O. et al., 1984, Polymer Bulletin 11, 165–170.
Marvel, C. et al., J. Pol. Sci., 6(6):711–716. Organic Sulfur Chemistry: Structure & Mechanism,
Marvel, C. et al., J. Pol. Sci., 8(3):313–320. 408-410 and 418.
Cai, G. et al., Synthesis of Polythioether Ethers from Diallyl Klemm, E. et al., 1990, Makromol. Chem. 191, 2403–2411.
Ether. Nuyken, O. et al., “Dimercapto Telechelics by Polyaddition
Nuyken, O. et al., 1991, Makromol. Chem. 192, 1959–1968. of Diothiols onto Diolefines”, 197-198.
Nuyken, O. et al., 1981, Polymer Bulletin 4, 61-65. Musorin, G.K. et al., 1991, “A simple Synthesis of
Chemical Abstracts Selects: 1992, Novel Polymers from 2-Methyl-1,4-Dithiacycloheptane from diallyl Sulfide and
Patents, Issue 7, 116:107048n; 1970, Warner et al., Organic Hydrogen Sulfide,” Plenum Publishing Corporation, 2423.
Sulfur Polymers, 112186X. Haucourt, Nancy H., 1994, Macromolecules, 27:1329-1333.
Abstract of U.S. Patent No. 2,664.414, Dec. 29, 1953.
Klemm, E. et al., 1987, Chem., 27Jg, 4:145-146. * cited by examiner
U.S. Patent Jan. 21, 2003 Sheet 1 of 2 US 6,509,418 B1

Fig. 1

A.

f
Y

a
O

i B C

Tirne (T)
U.S. Patent Jan. 21, 2003 Sheet 2 of 2 US 6,509,418 B1

(uru/f) eye uropslaxa

 US 6,509,418 B1
1 2
SEALANTS AND POTTING FORMULATIONS have multiple -S-S-linkages in the polymer backbones
INCLUDING MERCAPTO-TERMINATED which result in compromised thermal resistance. In the
POLYMERS PRODUCED BY THE polymers of Singh et al., U.S. Pat. No. 4,366,307, enhanced
REACTION OF A POLYTHOLAND thermal Stability is achieved through replacement of poly Sul
POLY WINYL ETHER MONOMER fide linkages with polythioether (-S-) linkages. However,
the thermal resistance of these polythioetherS is limited as a
CROSS-REFERENCE TO RELATED result of residual acid condensation catalyst.
APPLICATIONS Morris et al., U.S. Pat. No. 4,609,762, describes reacting
This application is a continuation-in-part of U.S. patent dithiols with secondary or tertiary alcohols to afford liquid
application Ser. No. 08/928,972 filed Sep. 12, 1997 now polythioethers having no oxygen in the polymeric backbone.
U.S. Pat. No. 6,172,179, which is a continuation-in-part of Cured polymeric materials formed from these polymers
Ser. No. 08/802/130, filed Feb. 19, 1997 now U.S. Pat. No. have the disadvantage, however, of reduced fuel resistance
5,912,319. Also, this application is a continuation-in-part of due to the large number of pendant methyl groups that are
U.S. patent application Ser. No. 09/318,500 filed May 25, present. In addition, the disclosed process generates unde
1999 now U.S. Pat. No. 6,232,401 which is a division of Ser.
15 Sirable aqueous acidic waste.
No. 08/802,130, filed Feb. 19, 1997 now U.S. Pat. No. Cameron, U.S. Pat. No. 5,225,472, discloses production
5,912,319. This application also claims the benefit of U.S. of polythioether polymers by the acid-catalyzed condensa
provisional application No. 60/182,396 filed Feb. 14, 2000 tion of dithiols with active carbonyl compounds Such as
and U.S. provisional application No. 60/215.548 filed Jun. HCOOH. Again, this process generates undesirable aqueous
30, 2000. acidic waste.
The addition polymerization of aromatic or aliphatic
FIELD OF THE INVENTION dithiols with diene monomers has been described in the
The present invention relates to a Sealant or potting literature. See, e.g., Klemm, E. et al., J. Macromol. Sci.-
formulation prepared from a mercapto-terminated polymer 25
Chem., A28(9), pp. 875–883 (1991); Nuyken, O. et al.,
produced by the reaction of polythiol(s) and polyvinyl ether Makromol. Chem., Rapid Commun. 11, 365-373 (1990).
However, neither Klemm et al. nor Nuyken Suggest Selection
monomer(s), the formulation having good low temperature of particular starting materials to form a polymer that is
flexibility and fuel resistance. liquid at room temperature and, upon curing, has excellent
BACKGROUND OF THE INVENTION low-temperature flexibility (low T) and high resistance to
fuels, i.e., hydrocarbon fluids. Nor do Klemm et al. Suggest
Commercially available polymeric materials which have production of a polymer that also is curable at room or lower
sufficient sulfur content to exhibit desirable sealing and fuel temperatures. Moreover, the reactions disclosed by Klemm
resistance properties for aerospace Sealants and electrical et al. also generate undesirable cyclic byproducts.
potting compounds are the polysulfide polyformal polymers 35 There exists a need in the art for Sealant, coating and
described, e.g., in U.S. Pat. No. 2,466,963, and the alkyl side electrical potting formulations or compositions that can
chain containing polythioether polyether polymers provide good pot life as well as good performance
described, e.g., in U.S. Pat. No. 4,366,307 to Singh et al. properties, Such as fuel resistance, flexural Strength, thermal
Materials useful in this context also have the desirable resistance and longevity in use.
properties of low temperature flexibility characterized by a 40 SUMMARY OF THE INVENTION
low glass transition temperature (T) and liquidity at room
temperature. The present invention provides a Sealant or potting for
An additional desirable combination of properties for mulation prepared from components comprising (a) at least
aerospace Sealants which is much more difficult to obtain is one ungelled mercapto-terminated polymer prepared by
the combination of long application time (i.e., the time 45 reacting reactants comprising at least one polyvinyl ether
during which the Sealant remains usable) and short curing monomer and at least one polythiol material; (b) at least one
time (the time required to reach a predetermined Strength). curing agent reactive with a mercapto group of the
Singh et al., U.S. Pat. No. 4,366,307, disclose such materi mercapto-terminated polymer; and (c) at least one additive
als. Singh et al. teach the acid-catalyzed condensation of Selected from the group consisting of fillers, adhesion
hydroxyl-functional thioethers. The hydroxyl groups are in 50
promoters, plasticizers and catalysts.
the B-position with respect to a Sulfur atom for increased Another aspect of the present invention is a Sealant or
condensation reactivity. The Singh et al. patent also teaches potting formulation prepared from components comprising:
the use of such hydroxyl-functional thioethers with pendant (a) at least one ungelled mercapto-terminated polymer pre
methyl groups to afford polymers having good flexibility pared from reactants comprising diethylene glycol divinyl
and liquidity. However, the disclosed condensation reaction 55 ether and dimercapto dioxaoctane; (b) at least one curing
has a maximum yield of about 75% of the desired conden agent reactive with a mercapto group of the mercapto
sation product. Furthermore, the acid-catalyzed reaction of terminated polymer; and (c) at least one additive Selected
B-hydroxySulfide monomers yields significant quantities of from the group consisting of fillers, adhesion promoters,
an aqueous Solution of thermally stable and highly malodor plasticizers and catalysts.
ous cyclic byproducts, Such as 1-thia-4-Oxa-cyclohexane 60 The above sealant formulations are useful in a variety of
which limits the Suitable application of the disclosed poly applications, Such as for example aerospace applications or
CS. as electrical potting compounds.
Another desirable feature in polymerS Suitable for use in Other than in the operating examples, or where otherwise
aerospace Sealants is high temperature resistance. While indicated, all numbers expressing quantities of ingredients,
incorporating Sulfur to carbon bonds into a polymer gener 65 reaction conditions, and So forth used in the Specification
ally enhances high temperature performance, the poly Sulfide and claims are to be understood as being qualified in all
polyformal polymers disclosed in U.S. Pat. No. 2,466,963 instances by the term “about'. Also, as used herein, the term
 US 6,509,418 B1
3 4
"polymer is meant to refer to oligomers, homopolymers An advantage of the formulations of the present invention
and copolymers. is that they exhibit very desirable fuel resistance character
BRIEF DESCRIPTION OF THE DRAWINGS
istics when cured, due at least in part to the use of the
mercapto-terminated polymers discussed herein. The fuel
The invention may be more readily understood by refer resistance of a cured Sealant can be determined by percent
ring to the accompanying drawings in which: Volume Swell after prolonged exposure of the cured Sealant
FIG. 1 depicts linear graphs of extrusion rate (E) versus to a hydrocarbon fuel, which can be quantitatively deter
time (T) for Sealant compositions of the invention in com mined using methods similar to those described in ASTM
parison to extrusion rate curves for known types of Sealant D792 or AMS 3269, which are incorporated herein by
composition, and 1O reference. For fuel resistance testing, the cured Sealant can
FIG. 2 is a Semi-log graph of the extrusion rate curve of be prepared from 100 parts by weight of mercapto
a polythioether sealant composition of the invention (0) and terminated polymer, 50 parts by weight of precipitated
a prior art polysulfide Sealant composition (). calcium carbonate and an epoxy curing agent in a 1:1
equivalent ratio of mercapto groups to epoxy groups. The
DETAILED DESCRIPTION OF THE 15 epoxy curing agent is prepared from a 60:40 weight ratio of
PREFERRED EMBODIMENTS EPON 828 bisphenol A diglycidyl ether (available from
The Sealant and potting formulations of the present inven Shell Chemical) to DEN 431 bisphenol A novolac resin
tion comprise one or more ungelled mercapto-terminated (available from Dow Chemical).
polymers or polythioethers. It has Surprisingly been discov In a preferred embodiment, the cured Sealants of the
ered that polythioethers prepared from the combination of present invention have a percent Volume Swell not greater
polythiol(s) with polyvinyl ether monomer(s) according to than 40%, and preferably not greater than 25% after immer
the present invention result in ungelled mercapto-terminated sion for one week at 140° F (60° C.) and ambient pressure
polymers that are liquid at room temperature and pressure in jet reference fluid (JRF) type 1. More preferably, the
and that have desirable physical and rheological properties, percent Volume Swell of the cured polymerS is not greater
and that furthermore are substantially free of malodorous
25 than 20%, and more preferably ranges from Zero to 20%. Jet
cyclic by-products. The inventive materials also are Sub reference fluid JRF type 1, as employed herein for determi
Stantially free of deleterious catalyst residues, and have nation of fuel resistance, has the following composition (see
Superior thermal resistance properties. AMS 2629, issued Jul. 1, 1989), S3.1.1 et seq., available
The mercapto-terminated polymers useful in the Sealant from SAE (Society of Automotive Engineers, Warrendale,
and potting formulations of the present invention are pref Pa.) (that is incorporated herein by reference):
erably liquid at room temperature and preSSure and cured
Sealants including Such polymers have excellent low tem
perature flexibility and fuel resistance. AS used herein, the Toluene 28 + 1% by volume
term "room temperature and preSSure' denotes conditions of 35 Cyclohexane (technical) 34 + 1% by volume
approximately 77 F. (25 C.) and 1 atmosphere (760 mm Isooctane 38 + 1% by volume
Hg) pressure. Tertiary dibutyl disulfide 1 + 0.005% by volume
(doctor Sweet)
The mercapto-terminated polymer is ungelled or Substan Tertiary butyl mercaptain 0.015% + 0.0015 by weight of the other
tially free of crosslinking. By “ungelled' is meant that the four components
mercapto-terminated polymer is Substantially free of 40
crosslinking and has an intrinsic Viscosity when dissolved in Preferably, the ungelled mercapto-terminated polymers
a Suitable Solvent, as determined, for example, in accordance have a number average molecular weight ranging from
with ASTM-D1795 or ASTM-D4243. The intrinsic viscosity about 500 to about 20,000 grams per mole, more preferably
of the mercapto-terminated polymer is an indication of its from about 1,000 to about 10,000, and most preferably from
finite molecular weight. A gelled reaction product, on the 45 about 2,000 to about 5,000, the molecular weight being
other hand, Since it is of essentially infinitely high molecular determined by gel-permeation chromatography using a
weight, will have an intrinsic Viscosity too high to measure. polystyrene Standard.
Preferably, the mercapto-terminated polymer has a glass Liquid mercapto-terminated polymers within the Scope of
transition temperature (T,) that is not higher than -50° C., the present invention can be difunctional, that is, linear
more preferably not higher than -55 C. and most preferably 50 polymers having two end groups, or polyfunctional, that is,
not higher than -60 C. Generally, it is preferred that the branched polymers having three or more end groups.
glass transition temperature of the mercapto-terminated The mercapto-terminated polymers are prepared by react
polymer ranges from -85. C. to -50 C., and more prefer ing reactants comprising one or more polyvinyl ether mono
ably -70° C. to -50 C., as determined by differential merS and one or more polythiol materials. Useful polyvinyl
Scanning calorimetry (DSC). 55
ether monomers include divinyl ethers having the formula
Low temperature flexibility can be determined by known (V):
methods, for example, by the methods described in AMS
(Aerospace Material Specification) 3267 S4.5.4.7, MIL-S
(Military Specification) -8802E $3.3.12 and MIL-S-29574, where R is C. n-alkylene, Ce branched alkylene, Cas
and by methods similar to those described in ASTM 60 cycloalkylene or Co alkylcycloalkylene group or
(American Society for Testing and Materials) D522-88, (CH-)-O-)-(-CH-)- and m is a rational
which are incorporated herein by reference. Cured formu number ranging from 0 to 10, p is an independently Selected
lations having good low temperature flexibility are desirable integer ranging from 2 to 6, q is an independently Selected
in aerospace applications because the formulations are Sub integer ranging from 1 to 5 and r is an independently
jected to wide variations in environmental conditions, Such 65 Selected integer ranging from 2 to 10.
as temperature and preSSure, and physical conditions Such as The materials of formula V are divinyl ethers. Such
joint contraction and expansion and vibration. divinyl ether monomers as described herein can provide
 US 6,509,418 B1
S 6
polymers having Superior fuel resistance and low tempera where R' can be a C-: n-alkylene group; C. branched
ture performance as compared to prior art polymers prepared alkylene group, having one or more pendant groups which
from alkenyl ether and conjugated dienes Such as 1,3 buta can be, for example, hydroxyl groups, alkyl groupS Such as
diene copolymerized with a dithiol such as DMDS. Divinyl methyl or ethyl groups, alkoxy groups, Cos cycloalkylene;
ether (m=0) is operative herein. Preferred divinyl ethers Cio alkylcycloalkylene group; -(-CH-)-X)-(–
include those compounds having at least one oxyalkylene CH-)-; or -(-CH-)-X)-(-CH-)- in which at
group, more preferably from 1 to 4 oxyalkylene groupS. Such least one -CH2- unit is Substituted with a methyl group
as those compounds in which m is an integer from 1 to 4. and in which p is an independently Selected integer ranging
More preferably, m is an integer from 2 to 4. It is also from 2 to 6, q is an independently Selected integer ranging
possible to employ commercially available divinyl ether from 1 to 5 and r is an independently Selected integer
mixtures in producing mercapto-terminated polymers ranging from 2 to 10.
according to the invention. Such mixtures are characterized Further preferred dithiols include one or more heteroatom
by a non-integral average value for the number of alkoxy Substituents in the carbon backbone, that is, dithiols in which
units per molecule. Thus, m in formula V can also take on X includes a heteroatom Such as O, S or another bivalent
rational number values between 0 and 10.0; preferably 15 heteroatom radical; a Secondary or tertiary amine group, i.e.,
between 1.0 and 10.0; very preferably between 1.0 and 4.0, -NR-, where R is hydrogen or methyl; or another
particularly between 2.0 and 4.0. substituted trivalent heteroatom. In a preferred embodiment,
Suitable polyvinyl ether monomers include divinyl ether X is O or S, and thus R is - (-CH-)-O-)-(-
monomers, Such as divinyl ether, ethylene glycol divinyl CH ), O ( CH )e S la ( CH ),
ether (EG-DVE) (R-ethylene, m=1), butanediol divinyl Preferably, p and rare equal, and most preferably both have
ether (BD-DVE) (R-butylene, m=1), hexanediol divinyl the value of 2.
ether (HD-DVE) (R-hexylene, m=1), diethylene glycol Useful polythiols include but are not limited to dithiols
divinyl ether (DEG-DVE) (R-ethylene, m=2) (preferred), Such as 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-
triethylene glycol divinyl ether (R =ethylene, m=3), tetra propanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-
ethylene glycol divinyl ether (R =ethylene, m=4), cyclohex 25 butanedithiol, 1,3-pentanedithiol, 1,5-pentanedithiol, 1,6-
anedimethanol divinyl ether, polytetrahydrofuryl divinyl he Xane dithiol, 1,3-dimercapto-3-methylbutane,
ether, trivinyl ether monomerS Such as trimethylolpropane dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT),
trivinyl ether, tetrafunctional monomerS Such as pentaeryth dimer cap to diethylsulfide, methyl-substituted
ritol tetravinyl ether and mixtures thereof. The polyvinyl dimer cap to diethylsulfide, dimethyl-substituted
ether material can have one or more pendant groups Selected dimercaptodiethylsulfide, dimercaptodioxaoctane, 1,5-
from alkyl groups, hydroxyl groups, alkoxy groupS and dimercapto-3-oxapentane and mixtures thereof. The poly
amine groups. thiol material can have one or more pendant groups Selected
Useful divinyl ethers in which R is Ce branched alky from lower alkyl groups, lower alkoxy groups and hydroxyl
lene can be prepared by reacting a polyhydroxy compound groupS. Suitable alkyl pendant groups include C-C linear
with acetylene. Exemplary compounds of this type include 35 alkyl, C-C branched alkyl, cyclopentyl, and cyclohexyl.
compounds in which R is an alkyl-substituted methylene Preferred dithiols include dimercaptodiethylsulfide
group such as -CH(CH)- (for example “PLURIOLE” (DMDS) (p=2, r=2, q=1, X=S); dimercaptodioxaoctane
blends such as PLURIOLORE-200 divinyl ether (BASF (DMDO) (p=2, q=2, r=2, X=0); and 1,5-dimercapto-3-
Corp. of Parsippany, N.J.), for which R=ethylene and oxapentane (p=2, r=2, q=1, X=O). It is also possible to use
m=3.8) or an alkyl-substituted ethylene (for example 40 dithiols that include both heteroatom Substituents in the
-CHCH(CH) - such as “DPE" polymeric blends includ carbon backbone and pendant alkyl groups, Such as methyl
ing DPE-2 and DPE-3 (International Specialty Products of groups. Such compounds include methyl-Substituted
Wayne, N.J.)). DMDS, such as HS-CHCH(CH)–S-CHCH-SH,
Other useful divinyl ethers include fluorinated com HS-CH(CH)CH-S-CHCH-SH and dimethyl sub
pounds or compounds in which R is polytetrahydrofuryl 45 stituted DMDS such as HS-CHCH(CH)–S-CH(CH)
(poly-THF) or polyoxyalkylene, preferably having an aver CH-SH and HS-CH(CH)CH-S-CH-CH(CH)–
age of about 3 monomer units. SH.
Two or more polyvinyl ether monomers of the formula V Two or more different polythiols can be used if desired to
can be used in the foregoing method. Thus in preferred prepare useful polythioethers.
embodiments of the invention, two polythiols of formula IV 50 Preferably, the polythiol material has a number average
(discussed below) and one polyvinyl ether monomer of molecular weight ranging from 90 to 1000 grams per mole,
formula V, one polythiol of formula IV and two polyvinyl and more preferably 90 to 500 grams per mole.
ether monomers of formula V, two polythiols of formula IV Relative amounts of dithiol and divinyl ether materials
and two polyvinyl ether monomers of formula V, and more used to prepare the polymers are chosen to yield terminal
than two compounds of one or both formulas, can be used 55 mercapto groups (-SH). These mercaptan-terminated poly
to produce a variety of polymers according to the invention, mers can include thiol terminal groups that are not further
and all Such combinations of compounds are contemplated reacted ("uncapped'), or include one or more thiol groups
as being within the Scope of the invention. that are further reacted with other materials to provide
Generally, the polyvinyl ether monomer comprises 20 to reactive or non-reactive terminal or pendant groups
less than 50 mole percent of the reactants used to prepare the 60 (“capped’). Capping the polymers of the present invention
mercapto-terminated polymer, and preferably 30 to less than enables introduction of additional terminal functionalities,
50 mole percent. for example, hydroxyl or amine groups, to the polymers, or
Suitable polythiol materials for preparing the mercapto in the alternative, introduction of end groups that resist
terminated polymer include compounds, monomers or poly further reaction, Such as terminal alkyl groups. Preferably,
merS having at least two thiol groups. Useful polythiols 65 the stoichiometric ratio of polythiol to divinyl ether mate
include dithiols having the formula (IV): rials is less than one equivalent of polyvinyl ether to one
HS-R'-SH (IV) equivalent of polythiol, resulting in mercapto-terminated
 US 6,509,418 B1
7 8
polymers. More preferably, the Stoichiometric ratio is In formula VI, S is an integer from 0 to 10, preferably 0
Selected to fully terminate the polymer with mercapto to 6, more preferably 0 to 4 and R is an unsubstituted or
groupS. Substituted alkyl group, preferably a C. n-alkyl group
Hydroxyl- or amino-functional terminal polymers can be which can be substituted with at least one -OH or -NHR'.
produced, for example, by reacting a vinyl terminated mate group, with R" denoting H or C. alkyl. Exemplary useful
rial with mercaptoalcohols Such as 3-mercaptopropanol or R groups include alkyl groups, such as ethyl, propyl and
mercaptoamines Such as 4-mercaptobutylamine, butyl, hydroxyl-Substituted groupS Such as 4-hydroxybutyl,
respectively, or by reacting a mercaptain terminated material amine Substituted groups Such as 3-aminopropyl, etc.
with a vinyl terminated material having hydroxyl function Specific preferred materials of the formula VI are
ality Such as butane diol monovinyl ether or amine func monovinyl ethers (S=0), including amino- and hydroxyalkyl
tionality Such as aminopropyl vinyl ether. Vinyl ethers, Such as 3-aminopropyl Vinyl ether and
Preferably, the mercapto-terminated polymer comprises 4-hydroxybutyl vinyl ether (butanediol monovinyl ether), as
30 to 90 weight percent of the sealant formulation on a basis well as unsubstituted alkyl vinyl ethers such as ethyl vinyl
of total weight of the Sealant formulation, and more prefer ether. Additional preferred materials of the formula VI
ably 30 to 60 weight percent. 15 include allyl ethers (S=1), Such as 4-aminobutyl allyl ether,
The reactants from which the mercapto-terminated poly 3-hydroxypropyl allyl ether, etc. Although materials in
mers are prepared can further comprise one or more free which S is greater than 6 can be used, the resulting polymers
radical catalysts. Preferred free radical catalysts include azo may have less fuel resistance than those in which S is 6 or
compounds, for example azobis-nitrile compounds Such as leSS.
aZO(bis)isobutyronitrile (AIBN); organic peroxides Such as Use of equivalent amounts of materials of the formula VI
benzoyl peroxide and t-butyl peroxide, inorganic peroxides relative to thiol groups present in formula IV provides fully
and Similar free-radical generators. The reaction can also be capped mercapto polymers, while use of lesser amounts
effected by irradiation with ultraviolet light either with or results in partially capped polymers.
without a cationic photoinitiating moiety. Ionic catalysis Preferably, an equivalent of polyvinyl ether is reacted
methods, using either inorganic or organic bases, e.g., 25 with dithiol or a mixture of polythiols.
triethylamine, also yield materials useful in the context of A preferred linear Structured mercapto-terminated poly
this invention. mer useful in the Sealant and potting formulations of the
Mercapto-terminated polymers within the Scope of the present invention has the structure of formula (I):
present invention can be prepared by a number of methods.
According to a first preferred method, (n+1) moles of a (I)
material having the formula IV:
wherein
HS-R'-SH (IV) R" denotes a Co n-alkylene, Ce branched alkylene,
or a mixture of at least two different compounds having the Cos cycloalkylene or Co alkylcycloalkylene group,
formula IV, are reacted with n moles of a material having the 35 heterocyclic, -(-CH-)-X)-(-CH-)-; or
formula V: (-CH-)-X)-(-CH-)- in which at least one
-CH2- unit is Substituted with a methyl group;
R° denotes a Con-alkylene, Ce branched alkylene,
or a mixture of at least two different compounds having the Cos cycloalkylene or C-1 alkylcycloalkylene group,
40
formula V, in the presence of a catalyst. This method heterocyclic, -(-CH-)-X-(-CH2);
provides an uncapped, mercapto-terminated difunctional X denotes one Selected from the group consisting of O, S
polymer. and -NR-;
Although, as indicated above, compounds of the formulas R" denotes H or methyl;
IV and V which have pendant alkyl groups, for example 45 m is an independently Selected rational number from 1 to
pendant methyl groups, are useful according to the 50; and
invention, it has Surprisingly been discovered that com n is an independently Selected integer from 1 to 60;
pounds of the formulas IV and V which are free of pendant p is an independently Selected integer ranging from 2 to
methyl or other alkyl groups also afford mercapto 6;
terminated polymers that are ungelled at room temperature 50 q is an independently Selected integer ranging from 1 to
and preSSure. 5; and
Capped analogs to the foregoing mercapto-terminated
polymers can be prepared by reacting a material having the r is an independently Selected integer from 2 to 10.
formula IV or a mixture of at least two different compounds In a more preferred embodiment of the foregoing
having the formula IV and a material having the formula V 55
polymer, R' is C-C alkyl and R is C-C alkyl.
or a mixture of at least two different compounds having the In a preferred embodiment, the polythioether has the
formula V in a Stoichiometric ratio of less than one equiva formula (II):
lent of dithiol per vinyl equivalent of formula V, with about A-(-R-R), (II)
0.05 to about 2 moles of a material having the formula VI
60
wherein
CH=CH-(CH2)-O-R (VI) A denotes a structure having the formula I,
or a mixture of two different materials having the formula y is 0 or 1,
VI, in the presence of an appropriate catalyst. R denotes a single bond when y=0 and -S-(CH)-
Materials of the formula VI are alkyl ()-alkenyl ethers -O-R-I-O- when y=1,
having a terminal ethylenically unsaturated group which 65 R" denotes -SH or -S-(-CH-)-O-R when
react with terminal thiol groups to cap the polythioether y=0 and -CH=CH or -(CH-)-S-R when
polymer. y=1,
 US 6,509,418 B1
9 10
S is an integer from 0 to 10, Z-Valent residue of the polyfunctionalizing agent, i.e., the
R denotes C, alkyl group which is unsubstituted or portion of the agent other than the reactive moieties R.
substituted with at least one -OH or -NHR" group, Polyfunctional mercapto-terminated polymers according
and to the present invention thus preferably have the formula:
R" denotes H or a C., n-alkyl group.
Thus, polythioethers of the formula II are linear, difunc
tional polymers which can be uncapped or capped. When
y=0, the polymer includes terminal thiol groups or capped O
derivatives thereof. In an alternative embodiment, when y=1
(not preferred), the polymer includes terminal vinyl groups CH-S
or capped derivatives thereof.
According to a preferred embodiment, the inventive poly
thioether is a difunctional thiol-terminated (uncapped) poly wherein
thioether. That is, in formula II, y=0 and R' is -SH. Thus, B denotes a Z-Valent residue of a polyfunctionalizing
the polythioether has the following structure: HS-R'-- 15 agent,
S-(CH2)-O--R-O-)-(CH2)2-S-R'-) R", R., n and m denote structures and values discussed
SH
In a preferred embodiment, R'=-(-CH-)-X)-(- above with reference to Formula I,
CH), , where p=2, X=O, q=2 and r=2, R is ethylene R denotes a moiety which is reactive with a terminal
group, m=2 and n is about 9. Vinyl group or mercapto group, and
The foregoing polymers are produced, for example, by Z is an integer from 3 to 6.
reacting a divinyl ether or mixture thereof with an excess of Polyfunctional polythioethers according to the present
a dithiol or mixture thereof, as discussed in detail below. invention can preferably have the formula (III):
In an alternative embodiment of the foregoing
polythioether, when m=1 and R=n-butylene in formula II, B-(A-Ry-R). (III)
R" is not ethylene or n-propylene. Also preferably, when 25
m=1, p=2, q=2, r=2 and R=ethylene, X is not O. wherein
Although not preferred, polythioethers according to the
invention can also include difunctional vinyl-terminated A denotes a structure having the formula I,
polythioethers. That is, in formula II, y=1 and R' is -CH= Y is 0 or 1,
CH. These polymers are produced, for example, by reacting R denotes a single bond when y=0 and -S-(CH)-
a dithiol or mixture thereof with an excess of a divinyl ether -O-R-I-O- when y=1,
or mixture thereof, as discussed in detail below. Analogous R" denotes -SH or -S-(-CH-)-O-R when
capped polythioethers include terminal -(CH2-)-S- y=O and -CH=CH or -(CH-)-S-R when
R y=1,
Preferably, the mercapto-terminated polymers are essen 35
R denotes C, alkyl that is unsubstituted or substituted
tially free of Sulfone, ester or disulfide linkages, and more with at least one -OH or -NHR7 group,
preferably free of Such linkages. The absence of these R" denotes H or a C- n-alkyl group,
linkages can provide good fuel and temperature resistance
and good hydrolytic Stability. AS used herein, "essentially S is an integer from 0 to 10,
free of Sulfone, ester or disulfide linkages' means that leSS 40 Z is an integer from 3 to 6, and
than 2 mole percent of the linkages in the mercapto B denotes a Z-Valent residue of a polyfunctionalizing
terminated polymer are Sulfone, ester or disulfide linkages. agent.
Disulfide linkages are particularly Susceptible to thermal AS with the preceding difunctional embodiments, the
degradation, Sulfone linkages are particularly Susceptible to foregoing polyfunctional polythioethers of the present
hydrolytic degradation. 45 invention optionally include terminal -SH or -CH=CH
Mercapto-terminated polymers useful in the formulations groups, or are capped and thus include terminal -S-(-
of the present invention have a mercapto functionality of at CH-)-O-R or -(CH-)-S-R groups. Par
least 2. Polyfunctional analogs of the foregoing difunctional tially capped polyfunctional polymers, i.e., polymers in
mercapto-terminated polymers can be prepared by reacting which Some but not all of the branches are capped, are also
one or more compounds of formula IV and one or more 50 within the Scope of the present invention.
compounds of formula V, in appropriate amounts, with one Specific polyfunctionalizing agents include trifunctional
or more polyfunctionalizing agents. izing agents, that is, compounds with Z=3. Preferred trifunc
The term “polyfunctionalizing agent' as employed herein tionalizing agents include triallylcyanurate (TAC), which is
denotes a compound having more than two moieties that are reactive with dithiol, and 1,2,3-propanetrithiol, which is
reactive with -SH and/or -CH=CH groups. The poly 55 reactive with polyvinyl ether. Agents having mixed
functionalizing agent preferably includes from 3 to 6 Such functionality, i.e., agents that include moieties which are
moieties, and thus is denoted a “Z-Valent” polyfunctionaliz typically Separate moieties that react with both thiol and
ing agent, where Z is the number (preferably from 3 to 6) of Vinyl groups, can also be employed.
Such moieties included in the agent, and hence the number Other useful polyfunctionalizing agents include trimethy
of Separate branches which the polyfunctional mercapto 60 lolpropane trivinyl ether, and the polythiols described in
terminated polymer comprises. U.S. Pat. Nos. 4,366,307; 4,609,762 and 5,225,472, the
The polyfunctionalizing agent can be represented by the disclosures of each of which are incorporated in their
formula entireties herein by reference. Mixtures of polyfunctional
izing agents can also be used.
65 Polyfunctionalizing agents having more than three reac
where R denotes a moiety or several moieties that are tive moieties (i.e., Z>3) afford “star” polymers and hyper
reactive with -SH or -CH=CH groups, and B is the branched polymers. For example, two moles of TAC can be
 US 6,509,418 B1
11 12
reacted with one mole of a dithiol to afford a material having The mercapto-terminated polymer or combination of
an average functionality of 4. This material can then be mercapto-terminated polymers as detailed herein preferably
reacted with a diene and a dithiol to yield a polymer, which is present in the polymerizable Sealant composition in an
can in turn be mixed with a trifunctionalizing agent to afford amount from about 30 wt % to about 90 wt %, more
a polymer blend having an average functionality between 3 preferably about 40 to about 80 wt %, very preferably about
and 4. 45 to about 75 wt %, with the wt % being calculated based
Inventive polymers as described above have a wide range on the weight of total Solids of the composition.
of average functionality. For example, trifunctionalizing The Sealant or potting formulations of the present inven
agents afford average functionalities from about 2.05 to 3.0, tion further comprise one or more curing agents, Such as
preferably about 2.1 to 2.6. Wider ranges of average func polyolefins, polyacrylates, metal oxides, polyepoxides and
tionality can be achieved by using tetrafunctional or higher mixtures thereof as appropriate. Curing agents useful in
polyfunctionalizing agents. Functionality will also be polymerizable Sealant compositions of the invention include
polyepoxides or epoxy functional resins, for example,
affected by factorS Such as Stoichiometry, as is known to hydantoin diepoxide, bisphenol-A epoxides, bisphenol-F
those skilled in the art. epoxides, novolac type epoxides, aliphatic polyepoxides,
It is contemplated that other functional groups may be 15 and any of the epoxidized unsaturated and phenolic resins.
employed as a Substitute for the thiol groups discussed Other useful curing agents include unsaturated compounds
herein to react with the curing agent in order to form the Such as acrylic and methacrylic esters of commercially
polyfunctional material of the present invention. These available polyols, unsaturated Synthetic or naturally occur
functional groups include, for example, hydroxyl functional ring resin compounds, TAC, and olefinic terminated deriva
groupS and amine groups. These thiol Substitutes may be tives of the compounds of the present invention. In addition,
employed in the reaction chemistry by one of ordinary skill useful cures can be obtained through oxidative coupling of
in the art of Sealant formation based upon the examples and the thiol groups using organic and inorganic peroxides (e.g.,
methodology discussed herein. MnO) known to those skilled in the art. Selection of the
Thus, according to one method for making polyfunctional particular curing agent may affect the T of the cured
polymers of the present invention, (n+1) moles of a com 25 composition. For example, curing agents that have a T.
pound or compounds having the formula IV, (n) moles of a significantly lower than the T of the polythioether may
compound or compounds having the formula V, and a lower the T of the cured composition.
Z-Valent polyfunctionalizing agent in an amount Sufficient to Depending on the nature of the mercapto-terminated
obtain a predetermined molecular weight and functionality, polymer(s) used in the composition, the composition can
are combined to form a reaction mixture. The mixture is then comprise about 90% to about 150% of the stoichiometric
reacted in the presence of a Suitable catalyst as described amount of the Selected curing agent(s) based upon -SH
above to afford mercapto-terminated polyfunctional poly equivalents, preferably about 95 to about 125%.
merS. Capped analogs of the foregoing mercapto-terminated Fillers useful in the polymerizable compositions of the
polyfunctional polymers are prepared by inclusion in the invention for aerospace application include those commonly
starting reaction mixture of about 0.05 to about (Z) moles 35 used in the art, Such as carbon black and calcium carbonate
one or more appropriate capping compounds VI. Use of (Z) (CaCO). Potting compound fillers illustratively include
moles affords fully capped polyfunctional polymers, while high band gap materials. Such as Zinc Sulfide and inorganic
use of lesser amounts again yields partially capped poly barium compounds. Preferably, the compositions include
CS. about 10 to about 70 wt % of the selected filler or combi
The inventive polymers preferably are prepared by com 40 nation of fillers, more preferably about 10 to 50 wt % based
bining at least one compound of formula IV and at least one upon the total weight of the composition.
compound of formula V, optionally together with one or The Sealant and potting compositions of the present
more capping compounds VI and/or VII as appropriate, invention can comprise one or more adhesion promoters.
and/or a polyfunctionalizing agent, followed by addition of Suitable adhesion promoters include phenolics Such as
an appropriate catalyst, and carrying out the reaction at a 45 METHYLON phenolic resin available from Occidental
temperature from about 50 to about 120° C. for a time from Chemicals, organosilanes Such as epoxy, mercapto or amino
about 2 to about 24 hours. Preferably, the reaction is carried functional silanes Such as A-187 and A-1100 available from
out at a temperature from about 70 to about 90° C. for a time OSi Specialities. Preferably, an adhesion promoter is
from about 2 to about 6 hours. employed in an amount from 0.1 to 15 wt % based upon total
Since the inventive reaction is an addition reaction, rather 50 weight of the formulation.
than a condensation reaction, the reaction typically proceeds Common Substrates to which the Sealant compositions of
Substantially to completion, i.e., the inventive mercapto the present invention are applied can include titanium,
terminated polymers are produced in yields of approxi Stainless Steel, aluminum, anodized, primed, organic coated
mately 100%. No or substantially no undesirable and chromate coated forms thereof, epoxy, urethane,
by-products are produced. In particular, the reaction does not 55 graphite, fiberglass composite, KEVLARE), acrylics and
produce appreciable amounts of malodorous cyclic polycarbonates.
by-products Such as are characteristic of Several known Preferably, a plasticizer is present in the Sealant formu
methods for producing polythioethers. Moreover, the poly lation in an amount ranging from 1 to 8 weight percent based
merS prepared according to the invention are Substantially upon total weight of the formulation. Plasticizers that are
free of residual catalyst. 60 useful in polymerizable compositions of the invention
Methods of making the foregoing polyfunctional inven include phthalate esters, chlorinated paraffins, hydrogenated
tive polymers are discussed in detail below. terphenyls, etc.
Preferably, the mercapto-terminated polymer has a vis The formulation can further comprise one or more organic
cosity of less than about 500 poise at a temperature of about Solvents, Such as isopropyl alcohol, in an amount ranging
25 C. and a pressure of about 760 mm Hg determined 65 from 0 to 15 percent by weight on a basis of total weight of
according to ASTM D-2849 S79-90 using a Brookfield the formulation, preferably less than 15 weight percent and
Viscometer. more preferably less than 10 weight percent.
 US 6,509,418 B1
13 14
A typical Sealant formulation is provided in Example 18. low extrusion rates on the order of about 5 to 10 g/min or
Polymerizable Sealant composition cure time is reduced less after curing times on the order of one hour.
considerably by using an organic amine catalyst having a As shown in FIG. 2, the initial extrusion rate of a sealant
pKb of 10 or above. Preferred organic amine catalysts are containing a polymer of the present invention (Example 1,
organic tertiary amines. Specific catalysts which are useful below, cured with an epoxy curing agent as described below)
in the present invention are triethylene diamine, diazabicy is about 550 g/min, then falls rapidly to about 20 g/min after
clo (2.2.2) octane (DABCO) (preferred), diazabicycloun 70 minutes. In comparison, a known polysulfide polymer
decene (DBU), 2,4,6-tri(dimethylamino methyl) phenol based Sealant (cured with MnO2) has an initial extrusion rate
(DMP-30) and tetramethyl guanidine (TMG). The reaction of about 90 g/min, which slowly falls to about 20 g/min after
time when utilizing the organic amine catalysts, and par 70 minutes.
ticularly the organic tertiary amine catalysts, is in general Another preferred curable Sealant formulation combines
between about one hour to about 20 hours which is a one or more plasticizers with the mercapto-terminated
considerable difference compared to using no amine cata polymer(s), curing agent(s) and filler(s) described above.
lyst. Use of a plasticizer allows the polymerizable formulation to
Generally the amount of catalyst ranges from 0.05 wt % 15 include mercapto-terminated polymers which have higher
to 3 wt %, based on the total weight of the Starting reactants. T. than would ordinarily be useful in an aerospace sealant or
The foregoing Sealant or potting formulations preferably potting compound, i.e., use of a plasticizer effectively
are cured at ambient temperature and pressure, however the reduces the T of the formulation, and thus increases the
formulations generally can be cured at a temperature ranging low-temperature flexibility of the cured polymerizable for
from about 0° C. to about 100° C. mulation beyond that which would be expected on the basis
In addition to the foregoing ingredients, polymerizable of the T of the mercapto-terminated polymers alone.
Sealant compositions of the invention can optionally include The present invention is illustrated in more detail by
one or more of the following: pigments; thixotropes, retar means of the following non-limiting examples which are
dants, and masking agents. presently representative of preferred embodiments. These
Useful pigments include those conventional in the art, 25 examples are exemplary and are not intended as a limitation
Such as carbon black and metal oxides. Pigments preferably on the Scope of the invention as detailed in the appended
are present in an amount from about 0.1 to about 10 wt % claims.
based upon total weight of the formulation.
Thixotropes, for example fumed Silica or carbon black, EXAMPLES
are preferably used in an amount from about 0.1 to about 5 In Examples 1-8, liquid polythioethers were prepared by
wt % based upon total weight of the formulation. Stirring together one or more dithiols with one or more
An additional advantage of Sealant formulations accord divinyl ethers and a trifunctionalizing agent. The reaction
ing to the invention is their improved curing behavior. The mixture was then heated and a free radical catalyst was
extent of cure of a Sealant formulation as a function of time
is often difficult to measure directly, but can be estimated by 35
added. All reactions proceeded Substantially to completion
determining the extrusion rate of the composition as a (approximately 100% yield).
function of time. The extrusion rate is the rate at which a Example 1
mixed Sealant formulation, i.e., a Sealant formulation
together with an accelerator System, is extruded from an In a 2 L flask, 524.8 g (3.32 mol) of diethylene glycol
applicator device. AS the Sealant formulation is mixed with 40 divinyl ether (DEG-DVE) and 706.7 g (3.87 mol) of dimer
the accelerator System, curing begins, and the extrusion rate captodioxaoctane (DMDO) were mixed with 19.7 g (0.08
changes with time. The extrusion rate thus is inversely mol) of triallylcyanurate (TAC) and heated to 77° C. To the
related to the extent of cure. When the extent of cure is low, heated reaction mixture was added 4.6 g (0.024 mol) of an
the Viscosity of the mixed ungelled Sealant formulation is azobisnitrile free radical catalyst (VAZO(R) 67 2,2-azobis
low and thus the extrusion rate is high. When the reaction 45 (2-methylbutyronitrile), commercially available from
approaches completion, the Viscosity becomes very high, DuPont). The reaction proceeded substantially to comple
and the extrusion rate thus becomes low. The extrusion rate tion after 2 hours to afford 1250 g (0.39 mol, yield 100%) of
can be measured according to AMS Method 3276 (section a liquid polythioether resin having a T of -68 C. and a
4.5.10), which is incorporated herein by reference. Viscosity of 65 poise and a number average molecular
With reference to FIG. 1, the viscosity of some known 50 weight of about 3165 grams per mole and a thiol function
types of Sealant formulations remains low for an extended ality of 2.2. The polymer was faintly yellow and had low
time, because the compositions are Slow to cure. Such odor.
formulations have extrusion curves qualitatively similar to
curve A. Other known types of Sealant formulations cure Example 2
very quickly, and thus their Viscosity rapidly increases. 55
Consequently, the extrusion rate rapidly decreases, as shown In a 1 L flask, 404.4 g (1.60 mol) of PLURIOLOR E-200
in curve B. Desirably, a mixed sealant formulation should divinyl ether and 355.88 g (1.94 mol) of DMDO were mixed
have a low Viscosity, and thus a high extrusion rate, for a with 12.1 g (0.049 mol) of TAC and reacted as in Example
length of time Sufficient to allow even application of the 1. The reaction proceeded Substantially to completion after
Sealant formulation to the area requiring Sealing, but then 60 5 hours to afford 772 g (0.024 mol, yield 100%) of a resin
should cure rapidly after application, i.e., their extrusion rate having a T of -66° C. and a viscosity of 48 poise. The
should quickly decrease. Sealant formulations according to polymer was yellow and had low Odor.
the present invention are characterized by this desirable Example 3
extrusion curve, as illustrated qualitatively in curve C.
Sealant formulations according to the present invention 65 In a 100 mL flask, 33.2 g (0.21 mol) of DEG-DVE and
can have, depending on the particular formulation, initial 26.48 g (0.244 mol) of 1,2-propanedithiol were mixed with
extrusion rates as high as 500 g/min or higher, together with 0.75 g (0.003 mol) of TAC and heated to 71° C. To the
 US 6,509,418 B1
15 16
heated reaction mixture was added 0.15 g (0.8 mmol) of The polymer described in Example 3 of U.S. Pat. No.
VAZO(R 67. The reaction proceeded substantially to 4,366,307 was used as a control. This polymer (the “control
completion after 7 hours to afford 60 g (0.03 mol, yield polymer”) had an odor of 3.
100%) of a resin having a T of -61° C. and a viscosity of Results were as follows:
22 poise. The polymer had a noticeable PDT (propane
dithiol) odor.
Example 4 Polymer Odor
In a 100 mL flask, 33.3 g (0.136 mol) of tripropylene
glycol divinyl ether (DPE-3) and 27.0 g (0.170 mol) of
dimercaptodiethylsulfide (DMDS) were mixed with 0.69g
(0.003 mol) of TAC and heated to 77° C. To the heated
reaction mixture was added 0.15 g (0.8 mmol) of VAZO(R)
67. The reaction proceeded substantially to completion after
6 hours to afford 61 g (0.028 mol, yield 100%) of a polymer 15
having a T of -63 C. and a viscosity of 26 poise.
Example 5 All of the liquid polythioethers thus had little or moderate
In a 250 mL flask, 113.01 g (0.447 mol) of PLURIOLOR odor except polymer 3, which had a strong odor.
E-200 divinyl ether and 91.43 g (0.498 mol) of DMDO were The polymers prepared in Examples 1-8 were then cured.
mixed with 1.83 g (0.013 mol) of 1,2,3-propanetrithiol Curing was carried out using the uncompounded resins with
(PTT) and allowed to react exothermically for 72 hours. The a curing agent and DABCO accelerator. The curing agent
mixture was then heated to 80 C. To the heated reaction had the following composition:
mixture was added 0.2 g (1 mmol) of VAZO(E) 67. The
reaction mixture was maintained at 80 C., and the reaction 25
proceeded substantially to completion after 3 hours to afford epoxy novolac" (equivalent weight 175.5) 22 wt %
200 g (0.06 mol, yield 100%) of a polymer having a T of hydantoin epoxy (equivalent weight 132) 34 wt %
-66 C. and a viscosity of 55 poise. calcium carbonate 34 wt %
carbon black 5 wt %
Example 6 silane adhesive promoter 5 wt %
In a small jar, 14.0 g (0.055 mol) of PLURIOLO(RE-200 "DEN-431 epoxy novolac available from Dow Chemical of Midland,
divinyl ether, 6.16 g (0.0336 mol) of DMDO and 5.38 g Michigan.
*ARACASTXU A4238 hydantoin epoxy available from Ciba-Geigy.
(0.0336 mol) of DMDS were mixed with 0.42 g (0.017 mol)
of TAC (briefly heated to melt the TAC) and heated to 82° The cured resins were evaluated for odor according to the
C. To the heated reaction mixture was added 0.2 g (0.001 35
procedure set forth above. The T and the percent weight
mol) of VAZO(R) 67. The reaction proceeded substantially to gain after immersion in JRF type 1 for one week at room
completion after 18 hours to afford 26 g (8.4 mmol, yield temperature and preSSure were also measured for each of the
100%) of a polymer having a T of -63 C. and a viscosity cured resins. The Volume Swell and weight gain percentages
of 80 poise. were determined for each cured material as follows:
40
Example 7 w=initial weight in air
In a small jar, 13.55 g (0.054 mol) of PLURIOL.(R) E-200 w=initial weight in H2O
divinyl ether, 10.44 g (0.057 mol) of DMDO and 1.44 g (8.1 w=final weight in air
mmol) of ethylcyclohexanedithiol (ECHDT) were mixed w=final weight in HO
with 0.40 g (1.6 mmol) of TAC (heated briefly to melt the 45
% volume Swell=100x(w-w)-(w+W)/(w-w)
TAC) and heated to 82°C. To the heated reaction mixture % weight gain=100x(w-w)/w
was added 0.2 g (0.001 mol) of VAZO(E) 67. The reaction The results are given in Table 1:
proceeded substantially to completion after 5 hours to afford
26 g (8.1 mmol, yield 100%) of a polymer having a T of TABLE 1.
-66 C. and a viscosity of 58 poise. 50

Example 8 Cured Resin

Odor
1.
O
2
O
3
O
4
O
5
O
6
O
7
O
8
O
In a small glass jar, 9.11 g (0.036 mol) of PLURIOLOR T., ( C.)
% fuel Swell
-59
19
-61
22
-61 -63 -62
23
-56
19
-59
24
-58
27
E-200 divinyl ether, 5.71 g (0.031 mol) of DMDO, 1.52g % wt. Gain 14 15 15 23 15 15 19 2O
(7.8 mmol) of ECHDT, 5.08 g (0.031 mol) of DMDS and 55
4.11 g (0.024 mol) of hexanediol divinyl ether (HD-DVE)
were mixed with 0.39 g (1.6 mmol) of TAC (heated briefly In comparison, the control polymer had an odor of 1-2 when
to dissolve the TAC) and heated to 82° C. To the heated cured.
reaction mixture was added 0.6 g (3.1 mmol) of VAZO(R 67. Example 9
The reaction proceeded Substantially to completion after 60
about 45 hours to afford 2.6 g (7.8 mmol, yield 100%) of a Polythioethers having a number average molecular
polymer having a T of -66° C. and a viscosity of 304 poise. weight of 2100 and an average SH functionality F of 2.1
The polymer had a cloudy appearance. were prepared by combining a divinyl ether with a dithiol as
Each of the foregoing polymers was evaluated for odor. shown in Table 2 and reacting the materials as previously
The following Scale was employed: 3: Strong, offensive 65 described herein. The uncompounded polythioethers were
odor; 2: moderate odor; 1: Slight odor; 0: Substantially then cured using 15 g of the curing agent described above
odorless. and 0.30 g of DABCO. For each polythioether so prepared,
 US 6,509,418 B1
17
the following quantities were measured: Viscosity (uncured
material, poise p); Shore A hardness (cured material, Rex TABLE 3
durometer value); % weight gain (cured material) after one 1. 2 3 4
week at 140° F (60° C) and atmospheric pressure in JRF
type 1; and T (cured material, C.). Results were as follows: 5 T (resin) -67 -66 -64 -63
(cured) -59 -58 -56 -56
TABLE 2 Viscosity 59 53 62 8O
JRF
Dithiol
Divinyl % Swell 24 21 21 2O
Ether ECHDT DMDS DMDO HDT 1O % Wt Gain 18 15 16 16
HO 11.8 11.5 7.4 7.5
DEG-DVE 145 p (solid) 27 24 p % Wt Gain
44 Rex 94 Rex 25 Rex 25 Rex
27% 3% 14% 29%
-53 -63 -69 -77 All of the foregoing polymers displayed excellent fuel
PLURIOL(R) 77 p. 41 p. 59 25 p 15 resistance. PolymerS 1 and 2 in particular also displayed
43 Rex 47 Rex 27 Rex 23 Rex excellent low temperature flexibility when tested according
27% 11% 18% 30%
-57 -6 -67 -76
to AMS 3267 S 4.5.4.7.
BD-DVEP 185 p (solid) (solid) (solid) Example 11
42 Rex 2O Rex 22 Rex
44% 21% 44% Addition of ECHDT to PLURIOLOR/DMDO Polymers
-59 -79 -85 Four liquid polythiol ether polymers were prepared as
HD-DVE 155 p (solid) (solid) (soft solid) previously described herein. The polymers had the follow
50 Rex
57%
14 Rex
27%
29 Rex
68%
ing compositions (listed values are molar equivalents):
-60 -63 -78 -86
Poly-THF 91 p. (solid) 27 25
30 Rex 75 Rex 17 Rex
64% 29% 37% 1. 2 3 4
-69 -79 -79
PLUROL (R) E-2OO 6.6 6.6 6.6 6.6
DMDO 8 7 6 5
PLURIOL(R) E200 divinyl ether ECHDT O 1. 2 3
Butanediol divinyl ether
polytetrahydrofuran divinyl ether
Hexanedithiol
Each of these polymers had a number average molecular
From the foregoing table it is apparent that the following weight of about 3000 and a SH functionality F of 2.2. Each
combinations of divinyl ether and dithiol afford liquid resultant uncompounded polymer was cured as in Example
polythioethers having good fuel resistance and low tempera 35
10. For each polymer, the following properties were mea
ture flexibility when cured: PLURIOLOR E-200/DMDO; and sured: T. (resin, C.); T (cured, °C.); viscosity (p); % swell
DEG-DVE/DMDO. Other potentially useful combinations in JRF type 1; % weight gain in JRF type 1; and % weight
include DEG-DVE/ECHDT; DEG-DVE/HDT; PLURIOLOR gain in water. Results are given in Table 4.
E-200/ECHDT; PLURIOLOR E-200/HDT; and poly-THF/ TABLE 4
DMDO. PLURIOLOR) E-2OO/DMDS also has excellent fuel 40
resistance and low temperature flexibility when cured, but 1. 2 3 4
the uncompounded material does not remain in a liquid State T (resin) -67 -66 -65 -64
for an extended period of time. (cured) -59 -59 -58 -56
Viscosity 59 36 44 50
Example 10 45 JRF type 1
Addition of DMDS to PLURIOLOR/DMDO Polymers % Swell 24 21 28 29
Four liquid polythiol ether polymers were prepared as % Wt Gain 18 18 19 19
HO 11.8 10.8 8.3 7.8
previously described herein. The polymers had the follow % Wt Gain
ing compositions (listed values are molar equivalents): 50

All of the foregoing polymers displayed good fuel resis

tance and low temperature flexibility.
1. 2 3 4
Example 12
PLUROL (R) E-2OO 6.6 6.6 6.6 6.6 55
DMDO 8 6 4.5 4 In a 250 mL 3-neck flask equipped with a stirrer, ther
DMDS O 2 3.5 4 mometer and condenser, 87.7 g (0.554 mol) of DEG-DVE
and 112.3 g (0.616 mol) of DMDO are mixed and heated to
77° C. (about 170 F). To the mixture is added 0.8 g. (4.2
To each of these polymers was added 0.2 molar equiva mmol) of VAZO(R) 67 catalyst. The reaction mixture is
lents of TAC to afford a number average molecular weight 60
reacted at 82° C. (about 180°F) for about 6 hours to afford
of about 3000 and a SH functionality F of 2.2. Each resultant 200 g (0.06 mol, yield 100%) of a low viscosity liquid
uncompounded polymer was cured as in Example 9 (15g of polythioether resin having a thiol equivalent weight of 1625
the curing agent composition and 0.30 g of DABCO). For and a SH functionality F of 2.0.
each polymer, the following properties were measured: T. Example 13
(resin, C.); T (cured, °C.); viscosity (p); % Swell in JRF 65
type 1; % weight gain in JRF type 1; and % weight gain in In a 250 mL 3-neck flask equipped with a stirrer, ther
water. Results are given in Table 3. mometer and condenser, 26.7 g (0.107 mol) of TAC, 56.4g
 US 6,509,418 B1
19
(0.357 mol) of DEG-DVE and 117.0 g (0.642 mol) of
DMDO are mixed and heated to 77° C. (about 1700°F). To -continued
the mixture is added 0.8 g. (4.2 mmol) of VAZO 67 catalyst. Elongation at break 450%
The reaction mixture is reacted at 82°C. (about 180°F) for Notched tear strength 85 p?i
about 6 hours to afford 200 g (0.07 mol, yield 100%) of a 5 Low-temperature flexibility Passed
high Viscosity liquid polythioether resin having an equiva
lent weight of 800 and a SH functionality F of about 3.5.
Example 14 Example 16
Sealant Composition OH-Terminated Capped Polythioether
A sealant composition including the DMDO/DEG-DVE In a 500 ml flask, 275.9 g (1.09 mol) PLURIOL(R) E-200
polythioether polymer of Example 1 was compounded as
follows (amounts in parts by weight): divinyl ether, 174.7 g (0.95 mol) DMDO, 28.7 g (0.30 mol)
3-mercaptopropanol and 1.83 g (7.3 mmol) TAC were
15 mixed. The mixture was heated to 70° C., and 2.3 g (12
mmol) VAZO(R) 67 were added slowly. The reaction mixture
DMDO/DEG-DVE Polythioether 1OO was stirred and heated at 85-90° C. for 4 hours to afford 480
Calcium carbonate 60
Magnesium oxide 1. g (0.15 mol, yield 100%) of a polymer having an OH
Phenolic resin 1. equivalent weight of 1670 (number average molecular
DMP-30 1. weight=3200, OH functionality F=2.05).
Isopropyl alcohol 3
Example 17
The compounded polymer was mixed intimately with the OH-Terminated Capped Polythioether
epoxy resin curing agent of Examples 9-11 above, in the
weight ratio of 10:1 and cured at ambient temperature and 25 In a 250 ml flask, 104.72 g (0.57 mol) DMDO, 80.73 g
humidity. Tensile Strength and elongation were evaluated (0.51 mol) DEG-DVE and 14.96 g (0.13 mol) butanediol
according to ASTM 3269 and AMS 3276. The die used to monovinyl ether were mixed and heated to 75 C. To the
prepare the test samples is described in ASTM D 412. The heated mixture 0.60 g (3 mmol) VAZO(R) 67 were added
die used to prepare test Samples for tear Strength testing is Slowly. The reaction mixture was Stirred and heated at
described in ASTM D1004. The following physical proper 75-85° C. for 6 hours to afford 200 g (0.064 mol, yield
ties were obtained for the cured composition: 100%) of a clear, nearly colorless polymer with very low
odor and a viscosity of 79 poise at 20°C. The OH equivalent
weight was 1570 (number average molecular weight=3200,
Cure hardness at 25 C. 60 Shore A
OH functionality F=2.00).
35
Tensile strength at break 550 psi
Elongation at break 600% Example 18
Notched tear strength 100 p?i
Low-temperature flexibility Passed Sealant Composition
(AMS 3267 $4.5.4.7) A sealant composition including the DMDO/DEG-DVE
40 polythioether polymer of Example 1 was compounded as
follows (amounts in weight percent):
Example 15 Base Composition
Sealant Composition
A sealant composition including the ECHDT/DEG-DVE
polythioether polymer of Example 9 was compounded as 45
Wt. 2% Component
follows (amounts in parts by weight):
O.277 Tung oil
1.053 triethylene diamine, diazabicyclo (2.2.2) Octane'
55.466 Polythioether polymer of Example 1
ECHDT/DEG-DVE Polythioether 1OO 50
O.831 Phenolic resin adhesion promoter
Calcium carbonate 54 O.554 Phenolic/polysulfide adhesion promoter
Hydrated aluminum oxide 2O O.277 Titanate"
Magnesium oxide 1. 1.108 Amino functional silane
Phenolic resin of Example 14 O.222 Fumed silica
Hydrogenated terphenyl plasticizer O.554 Titanium dioxide
DMP-30 O.831 Amorphous silica
Isopropyl alcohol 55 8.32O Aluminum hydroxide
30.506 precipitated calcium carbonate
The compounded polymer was mixed intimately with an DABCO triethyl amine, diazabicyclo (2.2.2) octane available from Air
Products & Chemicals.
epoxy resin curing agent of Examples 9-12 above in the METHYLON 75108 phenolic resin available from Occidental Chemical.
weight ratio of 10:1 and cured at ambient temperature and 60 The phenolic/polysulfide adhesion promoter was prepared by reacting
humidity. The following physical properties were obtained about 31% VARCUM 29202 phenolic resin, 66%. Thiokol LP-3 polysulfide
for the cured composition: and 3% of a polymer prepared according to Example 4 of U.S. Pat. No.
4,623,711 (at a ratio of 1 mole dithiol to 1 mole polysulfide) (incorporated
by reference herein) at a temperature of about 150 F (65 C.) for 45
mins, then heated to 230 F. (110° C.) over a 45-60 minute period, then
65 heated at 230° F (110° C) for 165 mins.
Cure hardness at 25 C. 72 Shore A "TYZORTBT titanate available from E.I. duPont de Nemours Company.
Tensile strength at break 550 psi A-1100 amino functional silane available from OSi Specialities, Inc.
 US 6,509,418 B1
21 22
Accelerator the group consisting of alkyl groups, hydroxyl groups,
alkoxy groups and mixtures thereof.
12. The Sealant formulation of claim 1, wherein said
Wt. 2% Component
polythiol material is a dithiol.
5 13. The Sealant formulation of claim 12, wherein said
26.525 Bisphenol A digiycidyl ether dithiol material is Selected from the group consisting of
17.684 Epoxy novolac' 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol,
10.699 Plasticizer' 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,3-
42.440 Calcium carbonate
O.221 Carbon black pentanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,3-
O.088 Carbamate salt"? dimercapto-3-methylbutane, dipentenedimercaptain,
2.247 Epoxy functional silane" ethylcyclohexyldithiol, dimercaptodiethylsulfide, methyl
O.O85
O.O11
Deionized water
Diphenylguanidine
substituted dimercaptodiethylsulfide, dimethyl-substituted
dimercaptodiethylsulfide, dimercaptodioxaoctane, 1,5-
EPON 828 bisphenol A diglycidyl ether available from Shell Chemical. dimercapto-3-oxapentane and mixtures thereof.
'DEN 431 epoxy novolac available from Dow Chemical. 15 14. The Sealant formulation of claim 1, wherein said
'HB-40 plasticizer available from Monsanto Co. polythiol material has a pendant group Selected from the
Ferbam 76% WDG carbamate salt available from Cabot Corp. group consisting of alkyl groups, hydroxyl groups, and
"A-187 epoxy functional silane available from OSi Specialities, Inc. alkoxy groups.
Therefore, we claim: 15. The Sealant formulation of claim 1, wherein said
1. A Sealant formulation prepared from components com polythiol material has a number average molecular weight
prising: ranging from 200 to 5000.
(a) at least one ungelled mercapto-terminated polymer 16. The Sealant formulation of claim 1, wherein said
prepared by reacting reactants comprising at least one polythiol material comprises from 40 to 80 mole percent of
polyvinyl ether monomer and at least one polythiol the reactants used to prepare the mercapto-terminated poly
material; 25 C.
(b) at least one curing agent reactive with a mercapto 17. The Sealant formulation of claim 1, wherein said
group of the mercapto-terminated polymer; and reactants from which said mercapto-terminated polymer are
(c) at least one additive Selected from the group consisting prepared further comprise a catalyst.
of fillers, adhesion promoters, plasticizers and cata 18. The Sealant formulation of claim 1, wherein said
lysts. curing agent is Selected from a group consisting of
2. The Sealant formulation of claim 1, wherein said polyolefins, polyacrylates, metal oxides, polyepoxides and
mercapto-terminated polymer has a glass transition tempera mixtures thereof.
ture of less than -50 C. 19. A Sealant formulation prepared from components
3. The Sealant formulation of claim 1, wherein said comprising:
mercapto-terminated polymer has a Viscosity of less than 35 (a) at least one ungelled mercapto-terminated polymer
about 500 poise at a temperature of about 25 C. and a prepared from reactants comprising diethylene glycol
pressure of about 760 mm Hg. divinyl ether and dimercapto dioxaoctane;
4. The Sealant formulation of claim 1, wherein said (b) at least one curing agent reactive with a mercapto
mercapto-terminated polymer has a number average group of the mercapto-terminated polymer; and
molecular weight of between 500 and 20,000. 40
(c) at least one additive selected from the group consisting
5. The Sealant formulation of claim 4, wherein said of fillers, adhesion promoters, plasticizers and cata
mercapto-terminated polymer has a number average lysts.
molecular weight of between 2000 and 5000. 20. An aerospace Sealant formulation prepared from com
6. The Sealant formulation of claim 1, wherein said ponents comprising:
mercapto-terminated polymer comprises 30 to 90 weight 45
(a) at least one ungelled mercapto-terminated polymer
percent of the Sealant formulation based upon total weight of prepared by reacting reactants comprising at least one
the components used to prepare the Sealant formulation. polyvinyl ether monomer and at least one polythiol
7. The Sealant formulation of claim 1, wherein said material;
polyvinyl ether monomer is a divinyl ether monomer. (b) at least one curing agent reactive with a mercapto
8. The Sealant formulation of claim 7, wherein said 50
group of the mercapto-terminated polymer; and
divinyl ether monomer is Selected from the group consisting
of divinyl ether, ethylene glycol divinyl ether, butanediol (c) at least one additive selected from the group consisting
divinyl ether, hexanediol divinyl ether, diethylene glycol of fillers, adhesion promoters, plasticizers and cata
divinyl ether, triethylene glycol divinyl ether, trimethylol lysts.
propane trivinyl ether, tetraethylene glycol divinyl ether, 55 21. An electrical potting formulation prepared from com
cyclohexanedimethanol divinyl ether, polytetrahydrofuryl ponents comprising:
divinyl ether and mixtures thereof. (a) at least one ungelled mercapto-terminated polymer
9. The Sealant formulation of claim 1, wherein said prepared by reacting reactants comprising at least one
polyvinyl ether monomer is a mixture of components com polyvinyl ether monomer and at least one polythiol
prising divinyl ether and polyvinyl ether having at least three 60 material;
Vinyl groups. (b) at least one curing agent reactive with a mercapto
10. The Sealant formulation of claim 1, wherein said group of the mercapto-terminated polymer; and
polyvinyl ether monomer comprises 20 to 60 mole percent (c) at least one additive selected from the group consisting
of the reactants used to prepare the mercapto-terminated of fillers, adhesion promoters, plasticizers and cata
polymer. 65 lysts.
11. The Sealant formulation of claim 1, wherein said
polyvinyl ether monomer has a pendant group Selected from