Document em2p0wZRXzy9rYy848xyB3yk4
Monsanto
L">A1 F. SOBJf'.'.T LHtNCL
TO
A. J. Balek & A. W. Morgan - Galt Labs - 1730 October 26, 1979 POLYSULFIDES
J. H. Orem
CL N. W. Touchette V**" W. T. Vreeland - B3NC R. S. Koehne - B3NC T. C. Mathis G. R. Beck - E2NB
SUMMARY
Scriptset 808,dissolved in polysulfide rubber, improves adhesion and moisture sensitivity. Standard plasticizers, especially Santicizer 261, Santicizer 278 and XA-1112 work well with this system and were somewhat better than chlorinated paraffin. A blend of Scriptset 808/plasticizer, could not be made. The Scriptset must be dissolved in the polysulfide prior to compounding for best results. Standard compounding techniques can be used.
RECOMMENDATION:
1. If patent approval is obtained, distribute the Scriptset 808
data to the field and push for evaluation with XA-1112, Santi
cizer 261 and Santicizer 278.
.
2. Terminate further efforts in polysulfide sealant research ex cept for specific work requests.
DETAILS
Attached
/vw -gls Att.
A. J. Balek A. W. Morgan
DSW 588344 STLCOPCB4093680
Details
Previous work has shown that XA-1112 is a good way of modifying the adhesion characteristics of polysulfide adhesives and sealants. However, the normal use of amine-type accelerators in such polysulfide sealants prevents the effective use of XA-1112 in most commercial applications. As the whole purpose for the XA-1112 development was to achieve cross-linking of the polysulfide, to increase the cohesive energy density, which results in an improvement in water permeability it was then necessary to look for alternate methods of obtaining cross-linking. One of the best methods known in the literature is, of course, phenolic resins or anhydride or polyacid-type resins. In the polysulfide window sealing caulks the use of such resins has a tendency to give infinitely long cure times and this is not advantageous. An amine, ammonium salt, amide, imide, etc. salt of a polyanhydride resin, however, was apparently a previously unevaluated method of obtaining cross-linking. For this reason work was done with Scriptset 808. Figure 1 describes the physical properties and gives a structural formula for Scriptset 808.
Initially, it was attempted to dissolve Scriptset 808 in Santicizer 278 or Santicizer 261. No successful method was found. Attempts to co solvate with tetrahydrofuran, butanol, or with very fine physical dispersions (paint mill, ball mill, etc.) were all unsuccessful. Separation or infinitely long stick lives or poor adhesion was found. This occurred whether the Scriptset 808 was put in on the catalyst (manganese dioxide) side or on the resin (polysulfide) side. Table 1 shows the problems of straight physical blending of Santicizer 278, Scriptset 808, with or without Santicizer 8 in a typical polysulfide screening formulation. It is to be noted that very short stick lives are obtained showing the acceleration possible with Scriptset. Initial adhesion to glass and aluminum strips was quite good, but upon water soaking the adhesion failed badly.
In Table 2, attempts to improve water adhesion were made by incorporating wire and cable modifier (WCM) or phenolic plastics with the Scriptset resin and with benzyl phthalate. In this case, the phenolics prevent the cure and WCM prevents good adhesion even with organo silane ester additive as an adhesion promoter.
In Table 3, the successful method of dispersing Scriptset 808 is first described. The blend of Scriptset 808 with the polysulfide rubber forms a clear homogeneous solution. The blending may occur at any temperature up to the decomposition temperature of the polysulfide rubber. We found 100C with stirring to be convenient although room temperature stirring will also eventually result in a clear solution.
In Table 3, very good stick lives are seen and, it is to be noted, that superior adhesion was found to glass and aluminum even after a 72 hour water soak. It is seen that organo silane ester adhesion promoter is not necessary, a small amount of epoxy resin (Epi Rez 510) is beneficial. Based on this screening data a complete screening series was run. This is shown in Table 4.
DSW 588345
STLCOPCB4093681
Details Continued Page 2.
From this data the wide use of the Scriptset/LP-32 combination may be seen. The control is sample #1. This "State of the art" sample shows relatively rapid loss in the water immersion beads test. It shows good results in the fogging test (Table 5). The use of the LP-32 - Scriptset 808 blend without organo silane promoters in shown in Table 4. Epi-Rez, 510 is used in this system also. Here the good results found in the screening from Table 3 did not show to the extent hoped for, although the water beads test shows a definite improvement over the control.
Sample 3 is exactly the same as 2 except organo silane ester is added. This sample shows very good results particularly in adhesion in the water beads test.
Sample 4 is a state of the art competitive control using chlorinated paraffin. It is seen, as previously reported that this sample is superior to our current "benzyl phthalate" state of the art system. It is also seen that the use of Scriptset 808 with LP-32 and chlorinated paraffin (Sample it!) does also work. Overall evaluation (subjective, least swell) show however that the benzyl phthalates work better than the chlorinated paraffins with Scriptset/LP-32 modification.
Sample 5 shows the substitution of Santicizer 261 for Santicizer 278 in our preferred formulation. Unfortunately, while very good moisture vapor transmission results were found, a fall-off in glass adhesion and a slight fall-off in water immersion is seen. This is still a very good sample, however, and could be of use and might possibly be worthwhile evaluating.
Samples 6 and 8, which use XA-1112 and the Scriptset 808/LP-32 modification were superior. Sample 6 incorporates everything we now know which would give improved performance in a polysulfide system. Overall, based on visual inspection of the water beads sealant test. Sample 6 was rated the best and showed superiority to the chlorinated paraffin control (Sample 7). Sample 8, while quite good, was not quite as good as the sample 6 test which shows an accumulative advantage of organo silane ester adhesion promoter.
It does seem that we have a strong possibility of selling:
A) Scriptset 808 B) XA-1112 or other benzyl phthalate C) A possible reduction of the organo silane ester level to
come close to a Class 1 (Class A) adhesive or sealant.
.
It is hoped that this Scriptset modification will eliminate the problems noted previously with XA-1112 where accelerator interference was seen. It is recommended that this data, as soon as it is cleared with Patent personnel, be taken to the field for evaluation.
DSW 588346
STLCOPCB4093682
FIGURE 1
Scriptset 808
Styrene/Maleic Anhydride Ratio 1:1
Molecular Weight Distribution
Broad
Physical Form
Powder
Sp. Gravity (dried film)
1.27 - 1.29
Soft. Pt. oc
225 - 230C
Acid Number (Ale. KOH.Titration) 290
Viscosity 10% So'n. (cps)
4200 (Brookfield, #1, 25C)
pH 10% Sol'n.
5.7
FORMULA:
-ch2-ch
-CH TI c=o i NH
CHI c=o 09
nh4 *
DSW 588347 STLCOPCB4093683
TABLE ONE
COMPONENTS
123
+5
Scriptset 808 -
10
20
10
10
50
Santicizer 278
90 80 85 80 50
Santicizer 8
'
``--
I.
vt
5 10 >> *t
--
1
Blend #1
25
-
Blend #2
- 25
-
Blend #3
-
25
-
Blend #4 Blend #5
--
25 25
~ Liquid Polysul fide Polymer
50
>
CaCO^ (Atomite)
Hakuenka CC Chemetals Catalyst
1443665 . Stick Life (min.)
30---------------------------------------------------------------------- >
10--------------------------
>
10---------------------------------------------------------------------- >
0 2 15 50
Initial Adhesion Glass Aluminum
Good----------------------------------------------------------------------- > Fair----------------------------------------------------------------------- >
Water Soak Adhesion Giass Aluminum
Fail------------------------------- ----------------------------------------- > Fail------------ ------------------------------------------------------ -->
SW 588348 STLCOPCB4093684
TABLE TWO
COMPONENTS
LP-32 "2ul* *olysulfide Polymer
1 23A 56 50----------------------------------------------------------------- -->
CaCOg (Atomite)
30------------------------------------ ------------------------------------J*
Hakuenka CC
10-------------------'---------------- -----------------------------------^
W.C.M. (Wire & Cable Modifier) AS-2
25
22.5
22.5
20
15
-
Scriptset 808 '
- 2.5 -
2.5 2.5
Phenolic Plastic Bakelite CK-0036
--
2.5 2.5 2.5
Santicizer 278
--
-
- 5 25
A-189 Organo Silane Ester 0.5----------------------------------------- ------------------------- >
Chemetals Catalyst 1443665
10--------------------------------------------------------------------->
Stick Life (min.)
11
co
co
oo 1
20
Initial Adhesion Glass Air
Fail Fail
Fail Fail
Good Good
Water Soak Adhesion
Glass
Fail Fail
--
.--
-- Good
Air
Fail Fail
-
- - Good
DSW 588349 STLCOPCB4093685
TABLE THREE
COMPONENTS
5:l/LP-32:SCRIPTSET 808*
Liquid Polysul fide Polymer Santicizer 278 ' Hakuenka CC CaCO^ (Atomite) A-189 Organo Silane Ester Chemetals Catalyst 1443665 Epi Rez 510 B5-26438 Stick Life (min.)
12 30 30
20
25-----10-----30------
0.5 10--
20
2.5
60 20
3 50
-
20
Initial Adhesion Glass Aluminum
Water Soak (72 hours) Glass Aluminum
Good Good
Good Fail
Good Good
Good Good
Good Poor
Good Good
* Blend prepared 100C with stirring until clear.
\
DSW 588350 STLCOPCB4093686
iL if:
TABLE FOUR
COMPONENTS
1 2 3 45 678
,,,, Liquid Polysul fide Polymer
100 40
40 100
40
40 40 40
5:l/LP-32:SCRIPTSET 808
60 60
60 60 60 60
Sahticizer 278
50 50 50
Santicizer 261
50
HdK.uculcu CC
20
CaCO^ (Atomite) A-189 Organo Silane Ester Epi Rez 510
B5-26438 S-52 Cereclor XA-1112
60 " 1
-
-
-
2.5
-
1 2.5
1
-
-'
-
50
-
1 11-
2.5
-
-
-
50- -
-
" 50
-- 50
Chemetals Catalyst 1443665
Stick Life (min.)
20 ~ 10 10 15 15 45 30 30 10
Adhesion to Glass (all exceed tensile strength of polymer)
-
PSI
- - - 3.1 2.2 2.2 3.2 3
Adhesion to Aluminum
PSI
0.4 - - - - - r- --
(all but sample 2 exceed tensile strength of polymer)
Permeability (Honeywell) g.cm/24 hr.m2.mm Hg
.107
.117
.107
.084
.086
.083
.069
.088
8 Week Water Immersion (Wet U.V.)
CO H
Weeks to Edge Lift
4 weeks plus-
->
Weeks to 5% Loose
4
3
3
Weeks to swelling
1
1
1
Best overall (least swell)-- #6
DSW 588351 STLCOPCB4093687
TABLE FIVE
Started July 12, 1979 3:30pm
0 Hours Total CONTROL
Standard Black
Carrara Glass
Zero Blank in Side
1443695-1 -2 -3 -4 -5 -6 -7 -8,
0 0 0 0 0 0 0 0
0
100 100 100 100 100 100 100 100
100
Not Exposed to
Ultra-Violet Rays
(cold side)
Number Side
Number
with
Side Carrara Glass
85 87 83 87 90 96 85 89 86 91 87 92 92 98 84 87
Exposed to
Ultra-Violet Rays
(Hot Side)
Blank Side
Blank
with
Side Carrara Glass
87 91 77 81
91 97 87 92 88 93 89 94 92 98 85 89
`'
July 26, 1979
45704 Hours on indicator 232 Hours Total August 1. 1979
45771 Hours on indicator 299 Hours Total August 13, 1979
584 Hours Total August 20, 1979
685 Hours Total September 4, 1978
1443695-1 -2 -3 -4 -5 -6 -7 -8
0 0 0 0 0 0 0 0
100 88 100 86 100 90 100 84 100 88 100 84 100 88 100 86
1443695-1 -2 -3 -4 -5 -6 -7 -8
1443695-1 -2 -3 -4 -5 -6 -7 -8
0 0 0 0 0 0 0 n
0 o. 0 0 0 0 0 0
100 100 100 100 100 . 100 100 100
100 100 100 100 100 100 100 100
87 85 92 84 88 84 90 ___ &4_
88 88 90 84 86 84 87 84
1443695-1 -2 -3 -4 -5 -6 -7 -8
0 0 0 0 0 0 0 0
100 87
100 85
100 90 100 84 100 88 100 84 100 87 100 84
1443695-1 -2 -3 -4 -5 -6 -7
... Q
0 0 0 0 0
0 0
o
100 . 100
100 ion 100
100 100
88 85 92 .84 88
84 87 %
O/
92 90 95 88 93 87 93 90 v
92 89 98 88 92 88 95 88________
91 92 96 88 92 87 92 88 '
91 89 96 89 92 87 92 88
92 89 97 87 92
87 92
r> o
89 88 90 88 88 82 88 87
87 88 93 88 88 84 89 86
87 89 91 87 89 82 86 86
87 85 91 88 89 82 86 85
87 86 92 87 88
82 86
or
93 92 96 93 93 84 93 92
91 92 98 92 93 87 94 ; 89
91 94 96 92 94 85 92 90
91 90 96 92 93 85 91 89
92 91 98 91 93
85 ' 91
OA
CM If)
0C0O --
oo if)
V) a
STLCOPCB4093688