Composition and method for producing fuel resistant liquid polythioether polymers with good low temperature flexibility
5 claims: 1 independent, 4 dependent
- 1PATENTKRAV 1. En polytioeter som innefattar en struktur med formeln I —R 1 - [S—(CH2)2—O- [-R 2 —O-] m- (CH 2 ) 2 —S—R 1- ] n - I i vilken R 1 anger en C 2 _ 6 n-alkylen-, C 3 _ 6 grenad alkylen-, en C 6 -s cykloalkyl- eller en C 6 -io alkylcykloalkylgrupp, - [ (-CH 2 -) p -X-] q - (CH 2 -) r - eller- [ (-CH 2 -) P -X-J q - (CH 2 -) r -, i vilka åtminstone en enhet -CH 2 - är substituerad med en metylgrupp, R 2 anger en C 2 _ 6 n-alkylen-, en C 2 _ 6 grenad alkylen-, en C 6 -g cykloalkylen- eller en C 6 -io alkylcykloalkylengrupp eller - [ (-CH 2 -) P -X-1 q - (CH 2 -) r - , X anger en, som utväljes från den grupp som består av O, S och -NR 6 -, R 6 anger H eller metyl, varvid sagda polytioeter är flytande vid rumstemperatur och rumstryck.
- 2Polytioeter enligt krav 1, vilken har en glasövergångstemperatur T g som inte är högre än -50 °C.
- 3Polytioeter enligt krav 1, vilken då den härdats har en procentuell volymökning som inte är större än 25 % efter nedsänkning under en vecka i JRF typ vid 60 °C och atmosfärstryck.
- 4Polytioeter enligt krav 1, vilken har en aritmetisk medelmolekylvikt mellan ca 500 och 20000.
- 5Polytioeter enligt krav 1 med formeln II 520 698 \\CURRENT\SYS\PUBLIC\DOC\P\3062045.doc II A- (- [R 3 ] y—R 4 ] 2 i vilken Y R 3 R 4 s R 5 anger en struktur med formeln I, är 0 eller 1, anger en enda bindning då y = 0 och -S-(CH 2 ) 2 - [-0—R 2 -] m -0- då y = 1, anger -SH eller -S-(CH 2 -) 2+s -0—R 5 då och -CH 2 = CH 2 eller -(CH 2 -) 2 -S—R 5 då y = 1, är ett heltal från 0 till 10, anger en Ci- 6 n-alkyl som är ej substituerad eller substituerad med åtminstone en OH- eller R 7 HN-grupp, och anger H eller en Cx-6 n-alkylgrupp R 7 i vilken enligt krav 1 med formeln III anger en struktur med formeln I, III 520 698 \\CURRENT\SYS\PUBLIC\DOC\P\3062045.doc Υ är 0 eller 1, R 3 anger en enkelbindning då y=0 och -S-(CH 2 ) 2 -(O—R 2 -] m _ 0- då y=l R 4 anger -SH eller -S-(CH2-) 2+5-O—R 5 då y=0 och -CH2 = CH 2 eller -(CH 2 -) 2 -S—R 5 då y = 1, s är ett heltal från 0 till 10, R 5 anger en Ci_ 6 n-alkyl som är ej substituerad eller substituerad med åtminstone en -OH- eller R 7 HN-grupp, R 7 anger H eller en Οχ_6 n-alkylgrupp, Z är ett heltal från 3 till 6, och B anger en z-valent rest hos ett polyfunktionaliseringsmedel. -S- (CH 2 -) 2+s -C^-R 5 . - (CH 2 -) 2 -S—R 5 . 24. En metod för framställning av polytioetern enligt krav 7, vilken innefattar steget att låta (n+1) moler av en förening med formeln IV HS—R 1 —SH IV eller en blandning av åtminstone två olika föreningar med formeln IV reagera med (n) moler av en förening med formeln V -] ra -CH=CH 2 520 698 \\CURRENT\SYS\PUBLIC\DOOP\3062045.doc eller en blandning av åtminstone två olika föreningar med formeln V i närvaro av en katalysator som utväljes från den grupp som består av katalysatorer, vilka alstrar fria radikaler, joniska katalysatorer samt ultraviolett ljus. 25. Metod enligt krav 24, i vilken sagda katalysator är en katalysator som alstrar fria radikaler. 26. Metod enligt krav 24, i vilken (i) då m=l och R 2 =n-butyl, R 1 är ej etyl eller n-propyl samt (ii) då m=l, p=2, q=2, r=2 samt R 2 =etyl, X är ej O. 27. En metod för framställning av polytioetern enligt krav 9, vilken innefattar steget att låta (n+1) moler av en förening med formeln IV HS—R 1 —SHIV eller en blandning av åtminstone två olika föreningar med formeln IV reagera med (n) moler av en förening med formeln IV CH 2 =CH—O- [R 2 —O-] m -CH=CH 2 V eller en blandning av åtminstone två olika föreningar med formeln V samt ca 0,05 till ca 2 moler av en förening med formeln VI CH 2 =CH- (CH 2 ) s -0—R 5 VI eller en blandning av två olika föreningar med formeln VI reagera i närvaro av en katalysator som utväljes från den grupp som består av katalysator, vilka alstrar fria radikaler, joniska katalysatorer samt ultraviolett ljus. 28. En mstod föi? 3.11 framställa polytioetern enligt krav 12, vilken innefattar steget att låta (n) moler av en förening med formeln IV 520 698 WCURRENT\SYS\PUBLIC\DOC\P\3062045.doc HS—R 1 —SH IV eller en blandning av åtminstone två olika föreningar med formeln IV reagera med (n+1) moler av en förening med formeln V CH 2 = CH—O- [R 2 —O-] m -CH=CH 2 V eller en blandning av två olika föreningar med formeln V reagera i närvaro av en katalysator som utväljes från den grupp som består av katalysator, vilka alstrar fria radikaler, joniska katalysatorer samt ultraviolett ljus. 29. En metod för framställning av polytioetern enligt krav 13, vilken innefattar steget att låga (n) moler av en förening med formeln IV HS—R 1 —SHIV eller en blandning av åtminstone två olika föreningar med formeln IV reagera med (n+1) moler av en förening med formeln V CH 2 =CH—O- [R 2 —O-] m -CH=CH 2 V eller en blandning av åtminstone två olika föreningar med formeln V samt ca 0,05 till ca 2 moler av en förening med formeln VII HS—R 5 VII eller en blandning av två olika föreningar med formeln VII reagera i närvaro av en katalysator som utväljes från den grupp som består av katalysator, vilka alstrar fria radikaler, joniska katalysatorer samt ultraviolett ljus. WCURRENTSYS\PUBLIC\DOC\P\3062045.doc 520 698 Γ ivr;' ... 45 ........'‘L.-.c; Ζ·· ·,- ,L 3 V :ί ί. 30. En metod för framställning av polytioetern enligt krav 19, vilken innefattar stegen (ii) att blanda (a) (n+1) moler av en förening med formeln IV HS—R 1 —SH IV eller en blandning av åtminstone två olika föreningar med formeln IV, (b) (n) moler av en förening med formeln V CH 2 =CH—O- [R 2 -O-] m -CH=CH 2 V eller en blandning av åtminstone två olika föreningar med formeln V, samt (c) ett z-valent polyfunktionaliseringsmedel, i vilket z är ett heltal från 3 till 6, för bildning av en reaktionsblandning, och (iii) att låta sagda reaktionsblandning reagera i närvaro av en katalysator som utväljes från den grupp som består av katalysatorer, vilka alstrar fria radikaler, joniska katalysatorer samt ultraviolett ljus. 31. Metod enligt krav 30, i vilken sagda katalysator är en katalysator som alstrar fria radikaler. 32. Metod enligt krav 30, i vilken sagda z-valenta polyfunktionaliseringsmedel är ett trifunktionaliseringsmedel. 33. Metod enligt krav 32, i vilken sagda trifunktionaliseringst.iedel utväljes från den grupp som består av triallylcyanurat, trimetylpropan-trivinyleter samt 1,2,3propantritiol. 34. En metod för framställning av polytioetern enligt krav 20, vilken innefattar stegen (i) att blanda (a) (n+1) moler av en förening med formeln IV 520 698 WCURRENT\SYS\PUBLlC\DOC\P\3062045.doc Λ ( HS—R 1 —SH IV eller en blandning av åtminstone två olika föreningar med formeln IV, (b) (n) moler av en förening med formeln V CH 2 =CH—0- [R 2 —O-] m -CH=CH 2 V eller en blandning av åtminstone två olika föreningar med formeln V, (c) ca 0,05 till ca (z) moler av en förening med formeln VI CH 2 =CH- (CH 2 ) s -0—R 5 VI eller en blandning av två olika föreningar med formeln V, samt (d) ett (z)-valent polyfunktionaliseringsmedel, i vilket z är ett heltal från 3 till 6, för bildning av en reaktionsblandning, och (ii) att låta sagda reaktionsblandning reagera i närvaro av en katalysator som utväljes från den grupp som består av katalysatorer, vilka alstrar fria radikaler, joniska katalysatorer samt ultraviolett ljus. 35. En metod för framställning av polytioetern enligt krav 22, vilken innefattar stegen (i) att blanda (a) (n) moler av en förening med formeln IV HS—R 1 —SH IV eller en blandning av åtminstone två olika föreningar med formeln IV (b) (n+1) moler av en förening med formeln V 520 698 WCURRENT\SYS\PUBLIC\DOC\P\3062045.doc CH 2 =CH—O- [R 2 —O-] m -CH=CH 2 V eller en blandning av åtminstone två olika föreningar med formeln V, samt (c) ett z-valent polyfunktionaliseringsmedel, i vilken z är ett heltal från 3 till 6, för bildning av en reaktionsblandning, och (ii) att låta sagda reaktionsblandning reagerar i närvaro av en katalysator som utväljes från den grupp som består av katalysatorer, vilka alstrar fria radikaler, joniska katalysatorer samt ultraviolett ljus. 36. En metod för framställning av polytioetern enligt krav 23, vilken innefattar stegen (i) att blanda (a) (n) moler av en förening med formeln IV HS—R 1 —SH IV eller en blandning av åtminstone två olika föreningar med formeln IV (b) (n+1) moler av en förening med formeln V CH 2 =CH—O- [ -R 2 —O- ] m -CH=CH 2 V eller en blandning av åtminstone två olika föreningar med formeln V (c) ca 0,05 till ca (z) moler av en förening med formeln VII HS—R 5 VII eller en blandning av två olika föreningar med formeln VII, OCh 520 698 WCURRENT\SYS\PUBLIC\DOC\P\3062045.doc ingöverket i-i- ί 2 (d) ett z-valent polyfunktionaliseringsmedel, i vilket z är ett heltal från 3 till 6, för bildning av en reaktionsblandning, och (ii) att låta sagda reaktionsblandning reagera i närvaro av en katalysator som utväljes från den grupp som består av katalysatorer, vilka alstrar fria radikaler, joniska katalysatorer samt ultraviolett ljus. 37. En polymeriserbar komposition som innefattar (i) ca 30 till ca 90 vikt% av åtminstone en polytioeter enligt krav 1, varvid sagda åtminstone ena polytioeter har en glasövergångstemperatur som inte är högre än -55 °C, (ii) en härdare i en mängd från ca 90 till ca 150 % på stökiometrisk basis av mängden sagda åtminstone ena polytioeter, samt (iii) ca 5 till ca 60 vikt% av ett fyllmedel, varvid samtliga viktprocent är baserade på totalvikten av ej flyktiga komponenter i kompositionen, varvid sagda komposition är härdbar vid en lägsta temperatur om 0 °C. 38. Polymeriserbar komposition enligt krav 37, vilken har en glasövergångstemperatur T g som inte är högre än -60 °C. 39. Polymeriserbar komposition enligt krav 37, vilken då den härdats har en procentuell volymökning som inte är större än 25 % efter nedsänkning i JRF typ 1 under en vecka vid 60 °C och atmosfärstryck. 40. Polymeriserbar komposition enligt krav 37, vilken ytterligare innefattar en tillsats som utväljes från den grupp som består av ett pigment i en mängd från ca 0,1 till ca 10 vikt%, ett tixotropimedel i en mängd från ca 0,1 till ca 5 vikt%, en accelerator i en mängd från ca 0,1 till ca 5 ett f ördrOj nliiyöiiiedel i en mängd från ca 0,1 till ca 5 vikt%, en vidhäftningsbefrämjare i en mängd från ca 0,1 520 698 WCURRENT\SYS\PUBLIC\DOC\P\3062045.doc till ca 5 vikt% samt ett maskeringsmedel i en mängd från ca 0,1 till ca 1 vikt%. 41. Polymeriserbar komposition enligt krav 37, vilken omfattar en blandning av åtminstone två olika polytioetrar (i) · 42. En polymeriserbar komposition som innefattar (i) ca 30 till ca 90 vikt% av åtminstone en polytioeter enligt krav 1, varvid sagda åtminstone ena polytioeter har en glasövergångstemperatur som inte är större än -50 °C, (ii) en härdare i en mängd från ca 90 till ca 150 % av en stökiometriskt baserad mängd av sagda åtminstone ena polytioeter, (iii) en mjukgörare i mängd från ca 1 till ca 40 vikt%, samt (iv) ca 5 till ca 60 vikt% av ett fyllmedel, med samtliga viktprocent baserade på totalvikten av ej flyktiga komponenter i kompositionen, varvid sagda komposition är härdbar vid en lägsta temperatur om 0 °C. 43. Polymeriserbar komposition enligt krav 42, vilken har en glasövergångstemperatur T g som inte är större än -55 °C. 44. Polymeriserbar komposition enligt krav 42, vilken då den härdats har en procentuell volymökning som inte är större än 25 % efter nedsänkning i en vecka vid rumstemperatur och rumstryck. 45. Polymeriserbar komposition enligt krav 42, i vilken sagda mjukgörare utväljes från den grupp som består av ftalatestrar, klorerade paraffiner samt hydrerade terfenyler. 46. Polymeriserbar komposition enligt krav 42, vilken ytterligare innefattar en tillsats som utväljes från den grupp som består av ett pigment i en mängd från ca 0,1 till ca 10 vikt%, ett tixotropimedel i en mängd från ca 0,1 till 520 698 WCURRENT\SYS\PUBLlC\DOC\P\3062045.doc ca 5 vikt%, en accelerator i en mängd från ca 0,1 till ca 5 vikt%, ett fördröjningsmedel i en mängd från ca 0,1 till ca 5 vikt%, en vidhäftningsbefrämjare i en mängd från ca 0,1 till ca 5 vikt% samt ett maskeringsmedel i en mängd från ca 5 0,1 till ca 1 vikt%. 47. Polymeriserbar komposition enligt krav 42, vilken innefattar en blandning av åtminstone två olika polytioetrar (i) . 520 698 -r.ngsve,· ket ·;.· , J n, , ) 1... v . i z. Extruderingshastighet (E)
Independent claims5
453 paragraphs in 5 sections, as filed
(54) (56) (57)
Assignee
INVENTOR
PRC-Desoto International Inc, Glendale CA US
5430 San Fernando Road
Jonathan Zook, Santa Clarita CA US, Suzanna DeMoss, Los
Angeles CA US, David Jordan, Northridge CA US, Chandra B Rao, Valencia CA US
OMBUD Ström & Gulliksson Intellectual Property Consulting AB
NAME Composition and method for preparing fuel-resistant liquid polytioether polymers with good, low temperature flexibility
CALLED PUBLICATIONS:
EP Al 005 5531 (C08G 75/12)
SUMMARY:
A polytioether includes a structure of formula I: -R<sup>1</sup>- (S— (CH 2) 2 - O - [-R<sup>2</sup>-O-] .- (CH2) -S-in which R<sup>1</sup> denotes a C 2 -s n-alkylene, C 3 -s branched alkylene, a C 5a -cycloalkyl or a C 6 -10 alkylcycloalkyl group, - [(- CH 2 -) X-] q- (CH 2 -) r- or - [(-CH2-) pX-] q- (CH2-) r-, in which at least one moiety -CH2- is substituted by a methyl group, R<sup>2</sup> indicates a C2_<sub>6</sub> n-alkylene-, and C<sub>2</sub>.<sub>s</sub> branched alkylene, and C<sub>s</sub>_<sub>8</sub> cycloalkylene or a C<sub>o</sub>.<sub>lo </sub>alkylcycloalkylene group or - [(-CH<sub>2</sub>-) <sub>p</sub>-X-], - (CH<sub>2</sub>-) <sub>r</sub>-, X denotes one, which is selected from the group consisting of O, S and -NR<sup>6</sup>-, R<sup>6</sup> 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 6 10. The polytioether is liquid at room temperature and room pressure.
The numbers in brackets indicate international identification code, INID code. Letters in clamps indicate international document code.
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SAMMAMDRAG
A polytioether includes a structure of formula I: -R<sup>1</sup>- [S— (CH 2) 2 - O - [-R<sup>2</sup>-O-] m- (CH<sub>2</sub>) —S – R<sup>1</sup>-] n-, in which R<sup>1</sup> indicates a C2.<sub>6</sub> n-alkylene-, C<sub>3</sub>_<sub>6</sub> branched alkylene, and C<sub>6</sub>.<sub>8</sub> cycloalkyl or a C<sub>6</sub>.<sub>10</sub> alkylcycloalkyl group, - [(- CH<sub>2</sub>-)<sub>p</sub>X]<sub>q</sub>- (CH<sub>2</sub>-)<sub>r</sub>- or- [(-CH<sub>2</sub>-) <sub>p</sub>-X-] <sub>q</sub>- (CH<sub>2</sub>-)<sub>r</sub>-, in which at least one unit -CH<sub>2</sub>- is substituted by a methyl group, R<sup>2</sup> denotes a C<sub>2</sub>.<sub>6</sub> n-alkylene-, and C<sub>2</sub>_<sub>6</sub> branched alkylene, and C<sub>6</sub>.<sub>8</sub> cycloalkylene or a C<sub>6</sub>.<sub>10</sub> alkylcycloalkylene group or - [(-CH<sub>2</sub>-) <sub>p</sub>-XJ <sub>q</sub>- (CH<sub>2</sub>-) <sub>r</sub>-, X denotes one, which is selected from the group consisting of O, S and -NR<sup>6</sup>-, R<sup>6</sup> 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 6 10. The polytioether is liquid at room temperature and room pressure.
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This is a continuation application of U.S. Patent Application Serial No. 08 / 802,130, filed February 19, 1997, the disclosure of which is incorporated herein by reference in its entirety.
Field of invention
The present invention relates to liquid polytioether polymers which have good low temperature flexibility and fuel resistance when cured. The invention is also directed to methods for manufacturing the polymers by reacting polytiols with oxygenated dienes (divinyl ethers), which essentially eliminates smelly, condensed cyclic by-products.
Background of the invention
Sulfur-containing polymers with a thiol at the end are known to be well suited for use in space seals, which depend on their fuel-resistant property in cross-linking. Among the commercially available polymeric materials which have sufficient sulfur content to exert this desirable property are the polyformed polysulfide polymers disclosed, for example, in US2,466,963, and the alkyl side chain-containing polytioether polyether polymers disclosed, for example, in US4,366,307. Materials useful in this context also have the desirable properties of low temperature flexibility (low glass transition temperature T<sub>g</sub>) and flowability at room temperature.
A further desirable combination of properties for space seals, which is much more difficult to achieve, is the combination of long use time (i.e., the time during which the seal remains useful) ha_L dnliiy S t id (the time required to achieve a predetermined most power) . Singh et al., U.S. Patent No. 4,366,307, disclose
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1999 -10 'in 2 such materials. Singh et al. refers to acid-catalyzed condensation of thioethers with hydroxyl function. The hydroxyl groups are in favor of increased condensation reactivity in the β position with respect to a sulfur atom. The patent of Singh et al. also relates to the use of hydroxyl function thioethers having pendant methyl groups to obtain polymers of good flexibility and flowability. However, the condensation reaction shown has a maximum yield of the desired condensation product of about 75%. In addition, the acid-catalyzed reaction of β-hydroxysulfide monomers yields significant amounts (typically not less than about 25%) of an aqueous solution of thermally stable and highly odorous cyclic by-products, such as 1-thia4-oxa-cyclohexane. This results in the commercial viability of the polymers shown being limited.
Another desirable property of polymers suitable for use in space seals is high temperature resistance. Including covalently bonded sulfur atoms in organic polymers has been shown to increase performance at high temperature. In the polyform polysulfide polymers disclosed in U.S. Patent No. 2,466,963, the multiple -SS couplings in the polymer's basic structure result in compromised thermal resistance. In the polymers of Singh et al., U.S. Patent No. 4,366,307, increased thermal stability is achieved by replacing the polysulfide couplings with polytioether couplings (-S-). In practice, however, the materials shown have compromised thermal resistance, which is due to traces of residual catalyst from the acidic condensate ion.
Morris et al., U.S. Patent No. 4,609,762, describe the reaction of dithiols with secondary or tertiary alcohols to yield liquid polytioethers without any oxygen in the polymeric basic structure. However, cured polymeric materials formed from these polymers have the disadvantage of reduced fuel resistance due to the large
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The Registry number of pending methyl groups that exist. Furthermore, residual catalyst from the process shown does not produce desirable aqueous acidic waste.
Cameron, U.S. Patent No. 5,225,472, discloses the production of polytioether polymers by the acid-catalyzing condensation of dithiols with active carbonyl compounds such as HCOOH. Again, this process does not produce desirable aqueous acidic waste.
Addition polymerization of aliphatic dithiols with diene monomers has been described in the literature. See, for example, Klemm, E. et al., J. Macromol. Sci. - Chem., A28 (9), pp. 875-883 (1991); Nuyken, O. et al., Macromol.
Chem., Rapid Commun. 11, 365-373 (1990). Neither Klemm et al. or Nuyken, however, suggests selection of particular starting materials, especially divinyl ethers and dithiols, to form a polymer which is liquid at room temperature and, upon curing, has excellent low temperature flexibility (low T<sub>g</sub>) and high resistance to fuels, ie liquid hydrocarbons. Nor does Klemm et al. production of a polymer which is additionally curable at room temperature or lower. Those of Klemm et al. The reactions shown also produce undesirable cyclic by-products.
Summary of preferred embodiments
In accordance with one aspect of the present invention, a polytioether of formula I -R is provided<sup>1</sup>- [-S- (CH2) 2 -O- [-R<sup>2</sup>-O-] m- (CH<sub>2</sub>)<sub>2</sub>-S-R<sup>1</sup>-]<sup>11</sup>- In which
R<sup>1</sup> denotes a C<sub>2</sub>.<sub>6</sub> n-alkylene-, C<sub>3</sub>_<sub>6</sub> branched alkylene, and C<sub>6</sub>_<sub>8</sub> cycloalkyl or a C<sub>6</sub>_<sub>10</sub> alkylcycloalkyl group, 1 (-CII<sub>2</sub>-) pX - j g- (CH<sub>2</sub>-) <sub>r</sub>- or - [(-CH<sub>2</sub>-) <sub>p</sub>-X-] <sub>q</sub>- (CH<sub>2</sub>-) <sub>r</sub>-, in which at least one unit -CH<sub>2</sub>- is substituted by a methyl group,
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19S3 'i 2
R<sup>2</sup> denotes a C<sub>2</sub>-s n-alkylene-, and C<sub>2</sub>_<sub>6</sub> branched alkylene, en
C<sub>6</sub>-8 cycloalkylene- or a C<sub>6</sub>_in<sub>0</sub> alkylcycloalkylene group or - [(-CH<sub>2</sub>-) <sub>P</sub>-XJ <sub>q</sub>- (CH<sub>2</sub>-) <sub>r</sub>- ,
X indicates one, which is selected from the group consisting of
O, S and -NR<sup>6</sup>-,
R<sup>6</sup> denotes H or methyl,
<td>m</td><td>is</td><td>one</td><td colspan="3">rational number</td><td>from</td><td> ; 0</td><td>to</td>
<td>n</td><td>is</td><td>one</td><td>integer</td><td>from</td><td> 1</td><td>to</td><td> 60,</td><td></td>
<td>P</td><td>is</td><td>one</td><td>integer</td><td>from</td><td> 2</td><td>to</td><td> 6,</td><td></td>
<td>q</td><td>is</td><td>one</td><td>integer</td><td>from</td><td> 1</td><td>to</td><td> 5,</td><td>and</td>
<td>r</td><td>is</td><td>one</td><td>integer</td><td>from</td><td> 2</td><td>to</td><td> 10,</td><td></td>
wherein the polytioether is liquid at room temperature and room pressure.
Preferably, the polytioether has an average molecular weight between about 500 and about 20,000.
In a first preferred embodiment, the polytioether has formula II
A- (- [R<sup>3</sup>]dizzy<sup>4</sup>) 2 II in which
A denotes a structure of formula I,
Y is 0 or 1,
R<sup>3</sup> denotes a single bond when y = 0 and -S- (CH 2) 2- [-O-R<sup>2</sup>-] mO- where y = 1,
R<sup>4</sup> denotes -SH or -S- (CH 2 -) 2 + s-O-R<sup>5</sup> where Y = 0 and -CH 2 = CH<sub>2</sub> or - (CH<sub>2</sub>-)<sub>2</sub>-S-R<sup>5</sup> where y = 1, s is an integer from 0 to 10,
R<sup>5</sup> indicates a C<sub>6</sub> n-alkyl which is not substituted or substituted by at least one OH- or -R<sup>7</sup>HN group, and
R<sup>7</sup> denotes H or a C 1-6 n-alkyl group. Polytioethers in which R<sup>4</sup> are -SH, are not topped, ie, include unreacted terminal thiol groups.
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Polytioethers of the invention also include topped polytioethers, i.e. polytioethers comprising terminal groups other than unreacted thiol groups. These terminal groups may be groups such as -OH or -NH<sub>2</sub>, or groups such as alkyl groups or terminal, ethically unsaturated groups.
In a more particularly preferred embodiment, y = 0 in formulas II and R denotes<sup>4</sup> -SH. That is, the polytioether is a non-topped polytioether with structure
HS-R<sup>1</sup>- [-S- (CH2) 2 -O- [-R<sup>2</sup>-O-] m- (CH<sub>2</sub>)<sub>2</sub>-S-R-n-SH.
In another more particularly preferred embodiment, the inventive polytioether is a topped polytioether in which in the formula II y = 0 and R<sup>4</sup> denotes -S- (CH<sub>2</sub>-) <sub>2 + s</sub>-0-R<sup>5</sup>. Particularly preferred is R<sup>5</sup> an unsubstituted or substituted n-alkyl group such as ethyl, 4-hydroxybutyl or 3-aminopropyl.
In yet another particular, preferred embodiment, the formula II is y = 1 and R<sup>4</sup> denotes -CH = CH<sub>2</sub>. That is, the polytioether is a non-topped polytioether with terminal vinyl groups.
In yet another more particular, preferred embodiment, the inventive polytioether is a topped polytioether in which in formula II y = 1 and R<sup>4</sup> indicates - (CH<sub>2</sub>-)<sub>2</sub>-S-R<sup>5</sup>- .
In a second preferred embodiment, the polytioether has formula III
B- (A- [R<sup>3</sup>]dizzy<sup>4</sup>) z III in which
A denotes a structure of formula I,
Y is 0 or 1,
R<sup>3</sup> denotes a single bond when y = 0 and -S- (CH<sub>2</sub>)<sub>2</sub>- (O-R<sup>2</sup>-]<sub>m</sub>-O- where y = 1
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CogiSb ... f the government in 2
R<sup>4</sup> denotes -SH or -S- (CH<sub>2</sub>-) <sub>2+</sub>p-0-R<sup>5</sup> where y = 0 and -CH<sub>2</sub> = CH<sub>2</sub> or - (CH<sub>2</sub>-)<sub>2</sub>-S-R<sup>5</sup> where y = 1, s is an integer from 0 to 10, R<sup>5</sup> denotes a C 1-6 n-alkyl which is not substituted or substituted by at least one -OH- or R<sup>7</sup>HN group, R<sup>7</sup> denotes H or a Οχ ^<sub>6</sub> n-alkyl group, z is an integer from 3 to 6, and
B denotes a z-valent residue of a polyfunctionalizer.
That is, polyfunctionalized embodiments comprise three or more structures of formula I bonded to the rest of a suitable polyfunctionalizer.
In a more specific embodiment, z = 3 and the polyfunctional agent is thus a trifunctionalizer. In another more specific embodiment, the average functionality of the polytioether ranges from about 2.05 to about 3.00.
In accordance with another aspect of the present invention, methods are provided for preparing the above-mentioned polytioethers.
In a first preferred embodiment, a polytioether of the invention is prepared by allowing (n + 1) moles of a compound of formula IV
HS - R<sup>1</sup> - SH IV or a mixture of at least two different compounds of formula IV react with (n) moles of a compound of formula V
CH<sub>2</sub> = CH - O - [- R<sup>2</sup> — 0 -]<sub>m</sub> - CH = CH<sub>2</sub> V or a mixture of at least two different compounds of formula V and, optionally, about 0.05 to about 2 moles of a compound of formula VI
CH<sub>2</sub> = CH - (CH<sub>2</sub>)<sub>s</sub>- O - R<sup>5</sup>
WE
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F iöQisti sningssverket
Υ'υ'ώ -. 2 - 1 2 or a mixture of two different compounds of formula VI in the presence of a catalyst. The catalyst is selected from the group consisting of catalysts generating free radicals, ionic catalysts and ultraviolet light. Preferably, the catalyst is a catalyst generating free radicals, such as an azo compound.
In a second preferred embodiment, a polytioether of the invention is prepared by reacting (n) moles of a compound of formula IV, or a mixture of at least two different compounds of formula IV, with (n + 1) moles of a compound of formula V or a mixture of at least two different compounds of formula V, optionally, together with 0.05 to about 2 moles of a compound of formula VII
HS - R<sup>5</sup> VII or a mixture of two different compounds of formula VII in the presence of a catalyst as described above.
Similar methods for preparing polyfunctional polytioethers using the above-mentioned reactants together with suitable polyfunctionalizing agents are also provided.
Polytioethers are also provided which are prepared by the above methods.
In accordance with yet another aspect of the present invention, there is provided a polymerizable composition comprising (i) about 30 to about 90% by weight of at least one polytioether as defined herein, wherein said at least one polytioether has a glass transition temperature not greater than - (Ii) a curing agent in an amount of from about 90 to about 150% of a stoichiometric based amount of said at least one polytioether, and (iii) about 5 to about 60% by weight of a filler; whereby all weight percent is based on no
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WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc total weight of volatile components in the composition. The inventive composition is curable at a temperature of 0 ° C or higher, preferably at a temperature of -20 ° C or higher.
In accordance with a further aspect of the present invention, there is provided a polymerizable composition comprising (i) about 30 to about 90% by weight of at least one polytioether as defined herein, said at least one polytioether having a glass transition temperature not greater than -50 ° C, (ii) a hardener in an amount of from about 90 to about 150% of a stoichiometric based amount of said at least one polytioether, (iii) a plasticizer in an amount of from about 1 to about 40% by weight, and (iv) a filler in an amount of from about 5 to about 60% by weight, all weight percentages being based on the total weight of non-volatile components in the composition. The composition is curable at a temperature of 0 ° C or higher, preferably at a temperature of -20 ° C or higher.
Cured polymeric materials prepared by polymerizing the above compositions are also provided.
Other objects, features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description. It should be understood, however, that the detailed description and specific examples, while specifying preferred embodiments of the present invention, are provided for illustrative and non-limiting purposes. Many changes and modifications within the scope of the present invention can be made without departing from its spirit of the invention, and the invention includes all such modifications.
Brief description of the drawings
The invention can be more readily understood with reference to the accompanying drawings, in which
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Rogisti 'circuitry ί ·. χ. c * - - i 2
Figure 1 shows linear scale curves of the extrusion rate (E) versus time (T) of sealing compositions of the invention in comparison with extrusion rate curves of known types of sealing compositions, and
Fig. 2 is a semi-logarithmic scale graph of the extrusion rate of a polytioether according to the invention (♦) and a prior art polysulfide ().
Detailed description of preferred embodiments
Surprisingly, it has been discovered that the combination of certain polytiols with oxygenated dienes of the present invention results in polytioether polymers which are liquids at room temperature and room pressure and which have desirable physical and rheological properties, and which are furthermore substantially free of malodorous cyclic by-products. The inventive materials are also substantially free of harmful catalyst residues and thus have excellent thermal insulation properties.
According to the present invention, polytioethers are provided which are liquid at room temperature and room pressure and have excellent low temperature flexibility (low T<sub>g</sub>) and fuel resistance. As used herein, the term room temperature and room pressure indicates about 77 ° F (25 ° C) and 1 atmosphere.
In the most general aspect, the inventive polytioethers include a structure of formula I-R<sup>1</sup>- [-S- (CH2) 2 -O- [-R<sup>2</sup>^ -] m- (CH2) 2<sup>—</sup>S-R<sup>1</sup>-] <sup>n</sup>- In which
R<sup>1</sup> denotes a C<sub>2</sub>-6 n-alkylene-, C<sub>3</sub>_<sub>6</sub> branched alkylene, and C<sub>5</sub>_<sub>8 </sub>cycloalkyl or a C<sub>6</sub>-10 alkylcycloalkyl group,
520 698 \\ CURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc • eghl. nngGverkst
<img file="SE520698C2_D0004.tif" />
- [(-CH<sub>2</sub>-)<sub>p</sub>-X-]<sub>q</sub>- (CH<sub>2</sub>-)<sub>r</sub>- or - [(-CH<sub>2</sub>-) <sub>P</sub>-X-] <sub>q</sub>- (CH<sub>2</sub>-) <sub>r</sub>-, in which at least one unit -CH<sub>2</sub>- is substituted by a methyl group,
R<sup>2</sup> denotes a C<sub>2</sub>_<sub>6</sub> n-alkylene-, and C<sub>2</sub>_<sub>6</sub> branched alkylene, and C<sub>6</sub>_<sub>8</sub> cycloalkylene or a C<sub>6</sub>-io alkylcycloalkylene group or - [(-CH<sub>2</sub>-) <sub>P</sub>-X-] <sub>q</sub>- (CH<sub>2</sub>-) <sub>r</sub>-,
X denotes one selected from the group consisting of 0, S and -NR<sup>6</sup>-,
R<sup>6</sup> denotes H or methyl,
<td>m</td><td>is</td><td>one</td><td colspan="2">rational i</td><td>speech</td><td>. from</td><td>. 0 to 10,</td>
<td>n</td><td>is</td><td>one</td><td>integer</td><td>from</td><td> 1</td><td>to</td><td> 60,</td>
<td>P</td><td>is</td><td>one</td><td>integer</td><td>from</td><td> 2</td><td>to</td><td> 6,</td>
<td>q</td><td>is</td><td>one</td><td>integer</td><td>from</td><td> 1</td><td>to</td><td>5, also</td>
<td>r</td><td>is</td><td>one</td><td>integer</td><td>from</td><td> 2</td><td>to</td><td> 10 .</td>
<td></td><td colspan="3">Preferably</td><td>have <</td><td>than</td><td colspan="2">polytioeterpolyme</td>
the invention a glass transition temperature T<sub>g</sub> which is not higher than -50 ° C. More preferred is the inventive polymer T<sub>g</sub> not higher than -55 ° C. Very preferred is the inventive polymer T<sub>g</sub> not higher than -60 ° C. Low T<sub>g</sub> indicates good flexibility at low temperature, which can be determined by known methods, for example with the methods described in AMS (Aerospace Material Specification) 3267 §4.5.4.7, MIL-S (Military Specification) -8802E §3.3.12 and MIL -S-29574, and with methods similar to those described in ASTM (American Society for Testing and Materials) D522-88.
The polytioethers of the invention exert highly desirable fuel resistance properties when cured. One measure of the fuel resistance of the inventive polymers is their percentage swelling in volume after prolonged exposure to a hydrocarbon fuel, which can be quantitatively determined using methods similar to those described in ASTM D792 or AMS 3269. they hardened, a percentage
In a • X. t. OCN
Ragisti arlngöverket
1999 -'3- i 2
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WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc volume swelling not greater than 25% after immersion in jet reference fluid (JRF) type 1 for one week at 140 ° F (60 ° C) and atmospheric pressure. Very preferably, the percentage swelling of the cured polymers in volume is not greater than 20%.
JRF type 1, as used herein to determine fuel resistance, has the following composition (see AMS
2629, issued July 1, 1989) section 3 paragraph 3.1.1 onwards, available from the SAE (Society of
Automotive Engineers, Warrendale, PA):
toluene
Cyclohexane (technical)
isooctane
Tertiary dibutyl disulfide (doctor sweet)
Tertiary butyl mercaptan
It is desirable that ± 1 vol% ± 1 vol% ± 1 vol% ± 0.005 vol%
0.015 ± 0.0015% by weight of the other four components of the inventive polytioethers have average molecular weights ranging from about 500 to 20,000, preferably about 1,000 to
000, most preferably 2,000 to 5,000.
Liquid polytioether polymers within the scope of the present invention may be bifunctional, i.e. linear polymers with two end groups, or polyfunctional, i.e. branched polymers having three or more end groups. Depending on the relative amounts of dithiol (s) and divinyl ether (ethers) used to prepare the polymers, the polymers may have terminal thiol groups (-SH) or terminal vinly groups (-CH = CH<sub>2</sub>). Furthermore, the polymers may be non-topped, ie, include terminal thiols or vinyl groups which do not react further, or topped, i.e., include thiol or vinyl groups which react further with other components. The topping of polytioethers of the invention makes it possible to introduce additional terminal functions, for example hydroxyl 520 698<sub>p</sub> -:. .Xnt- oca
r.sgisti tnngsverket <sup>12</sup> fetté - '. 3- 12
WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc or amine groups, to the inventive polymers, or alternatively to introduce end groups which counteract further reaction, such as terminal alkyl groups.
A first preferred embodiment of the inventive polytioethers is of formula II
A- (- [R<sup>3</sup>]dizzy<sup>4</sup>) 2 II in which
A denotes a structure of formula I,
Y is 0 or 1,
R<sup>3</sup> denotes a single bond when y = 0 and -S- (CH<sub>2</sub>) <sub>2</sub>- [- 0-R<sup>2</sup>-]<sub>m</sub>-O- where y = 1,
R<sup>4</sup> denotes -SH or -S- (CH<sub>2</sub>-) <sub>2 + s</sub>-0-R<sup>5</sup> THEN Y = 0 and -CH<sub>2</sub> = CH<sub>2</sub> or - (CH<sub>2</sub>-)<sub>2</sub>-S-R<sup>5</sup> where y = 1, s is an integer from 0 to 10,
R<sup>5</sup> indicates a Ci-<sub>6</sub> n-alkyl which is not substituted or substituted by at least one OH- or -R<sup>7</sup>HN group, and
R<sup>7</sup> denotes H or a C<sub>6</sub>.
Thus, the polytioethers of Form II are linear, bifunctional polymers, which may not be topped or topped. When y = 0, the polymer comprises terminal thiol groups or topped derivatives thereof. When y = 1, the polymer comprises terminal vinly groups or topped derivatives thereof.
In a preferred embodiment, the inventive polytioether is a bifunctional thiol at the end (not topped). That is, in form II y - 0 and R are<sup>4</sup> is -SH. Thus, the polytioether has the following structure:
HS-R<sup>1</sup>- [-S- (CH2) 2 -O- [-R<sup>2</sup>-O-] m- (CH<sub>2</sub>)<sub>2</sub>-S-R-n-SH
The above-mentioned polymers were prepared, for example, by a divinyl ether or a mixture of such sheep
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<img file="SE520698C2_D0005.tif" />
react with an excess of a dithiol or a mixture of such as discussed in detail below.
In a more particularly preferred embodiment of the above-mentioned polytioether, then m = 1 and R are<sup>2</sup> = n-butylene of formula II, R<sup>1</sup> not ethylene or n-propylene. Also preferred is when m = 1, p = 2, q = 2, r = 2 and R<sup>2</sup> = ethylene, X not 0.
In another preferred embodiment, the inventive polytioether is a topped polymer in which the above-mentioned terminal SH groups are replaced by -S - (- CH<sub>2</sub>-) 2 + sO - R<sup>5</sup>Such peaks are accomplished by reacting the terminal thiol group with an alkyl ωalkenyl ether such as a monovinyl ether, for example by including in the reaction mixture a topping agent or a mixture thereof, as discussed in detail below.
Above R indicates<sup>5</sup> an unsubstituted or substituted alkyl group, preferably an n-alkyl group which is unsubstituted or substituted by at least one OH or NHR<sup>7</sup>group, wherein R<sup>7</sup> denotes H or C<sub>6</sub> n-alkyl. Examples of useful R<sup>s</sup>groups include alkyl groups such as ethyl, propyl and butyl; hydroxyl-substituted groups such as 4hydroxybutyl; amine-substituted groups such as 3aminopropyl; etc.
Polytioethers of the invention also include bifunctional polytioethers with vinyl groups at the end (not topped). That is, in form II, y = 1 and R<sup>4 </sup>is -CH = CH<sub>2</sub>. These polymers are prepared, for example, by reacting a dithiol or a mixture thereof with an excess of a divinyl ether or a mixture thereof, as discussed in detail below. Analogs topped with polytioethers include at the end - (CH<sub>2</sub>-)<sub>2</sub>-S-R<sup>5</sup>.
The above-mentioned polytioethers are linear polymers with a functionality of two (taking into account alkyl and other non-reactive peaks within this whole). Polytioethers with higher functionality also fall within the scope of the present invention. Such polymers are prepared, such as<sub>r</sub>; ·· '·. - · '-% - OC .-' i
Fegisti Lfingeverket
/. <sup>Λ</sup> - O iiz'v v; '520 698 \\ CURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc is discussed in detail below, using a polyfunctional agent. The term polyfunctional agent, as used herein, denotes a compound having more than two groups reactive with the end groups -SH and / or -CH = CH<sub>2</sub>.
The polyfunctionalizer preferably comprises from 3 to 6 such groups, and is thus designated as a cool polyfunctionalizer, where z is the number (preferably from 3 to 6) of such groups included in the agent, and thus the number of separate branches comprising the polyfunctional polytioether. The polyfunctionalizer may be represented by the formula
B- (R<sup>8</sup>) <sub>z</sub> where R<sup>8</sup> denotes a group reactive with -SH or -CH = CH<sub>2 </sub>at the end and which may be the same or different, and B is the zvalent residue of the polyfunctional agent, i.e. the portion of the agent other than the reactive groups R<sup>7</sup>.
Thus, polyfunctional polytioethers of the present invention preferably have formula III
BAR<sup>3</sup>]dizzy<sup>4</sup>) z III in which
A denotes a structure of formula I,
Y is 0 or 1,
R<sup>3</sup> denotes a single bond when y = 0 and -S- (CH<sub>2</sub>) <sub>2</sub>- [-0 — R<sup>2</sup>-]<sub>m</sub>-O- where y = 1,
R<sup>4</sup> denotes -SH or -S - (- CH<sub>2</sub>-) <sub>2 + s</sub>-0-R<sup>5</sup> where y = 0 and -CH<sub>2</sub>= CH<sub>2</sub> or - (CH<sub>2</sub>-)<sub>2</sub>-S-R<sup>5</sup> when y = 1,
R<sup>5</sup> anger Ci_<sub>6</sub> n-alkyl which is unsubstituted or substituted by at least one OH or NHR<sup>7</sup>-group,
R<sup>7</sup> denotes H or a 0χ_<sub>6</sub> n-alkyl group, z is an integer from 3 to 6, and
B denotes a z-valent residue of a polyfunctionalizer
WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc
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As with previous bifunctional embodiments, the polyfunctional polytioethers of the present invention may include terminal SH or CH = CH<sub>2</sub>groups or they may be topped and thus include
S - (- CH<sub>2</sub>-) 2 + sO - R<sup>5</sup>- or (CH<sub>2</sub>-)<sub>2</sub>-S-R<sup>5</sup>groups. Partially topped polyfunctional polymers, i.e., polymers in which some but not all branches are topped, also fall within the scope of the present invention.
Specific polyfunctionalizers include trifunctionalizers, i.e., compounds of z = 3. Preferred trifunctionalizers include triallylcyanurate (TAC), which is reactive with compounds of formula II (R<sup>8</sup> = allyl), and 1,2,3-propanethritiol, which is reactive with compounds of formula III (R<sup>8</sup> = -SH). Mixed functionality agents, i.e. agents comprising groups (typically separate groups) that react with both thiol and vinyl groups, may also be used.
Other useful polyfunctionalizers include trimethylpropane trivinyl ether, and the polytiols disclosed in patents US-4,366,307, US-4,609,762, and US-5,225,472, each of which is incorporated herein in its entirety as reference. Mixtures of polyfunctionalizers can also be used.
Polyfunctional agents having more than three reactive groups (ie, z> 3) give polytioethers and hyperbranched star type polytioethers. For example, two moles of TAC can be reacted with one mole of dithiol to give a material having an average functionality of 4. This material can then be reacted with a divinyl ether or a dithiol to give a polymer, which in turn can be mixed with a trifunctional agent to provide a polymer blend having an average functionality between 3 and 4.
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The above-described polytioethers have a large average range of functionality. For example, trifunctional agents provide average functionalities from about 2.05 to 3.0, preferably about 2.1 to 2.6. Larger average functional ranges can be achieved by using tetrafunctional or higher polyfunctional agents. The functionality can also be influenced by factors such as stoichiometry, as is known to those skilled in the art.
Methods for manufacturing the polyfunctional polytioethers above are discussed in detail below.
Polytioethers within the scope of the present invention are prepared by a number of methods. In a first preferred method, (n + 1) moles of a compound of formula IV are obtained
HS-R<sup>1</sup>-SH
IV or a mixture of at least two different compounds of formula IV react with n moles of a compound of formula V
<img file="SE520698C2_D0006.tif" />
or a mixture of at least two different compounds of formula V, in the presence of a catalyst. In formulas IV and V above, R is<sup>1</sup>, R<sup>2</sup> and all symbols as defined in Formula I. This method yields a non-peaked, thiol-terminated difunctional polytioether.
The compounds of formula IV are dithiol compounds. Preferred dithiols include those compounds in which R<sup>1</sup> is a C<sub>2</sub>-6-n-alkylene group, ie 1,2-ethanedithiol, 1,3 propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol or 1,6hexanedithiol.
Further preferred dithiols include those compounds in which R<sup>1</sup> is a C<sub>3</sub>_<sub>6</sub> branched alkylene group having one or more pendant groups which may, for example
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WCURRENT \ SYSVPUBLIC \ DOC \ P \ 3062045.doc be methyl or ethyl groups. Preferred compounds having branched alkylene-R<sup>1</sup> includes 1,2-propanedithiol, 1,3butanedithiol, 2,3-butanedithiol, 1.3 pentanedithiol, and 1,3dithio-3-methylbutane. Other useful dithiols include those in which R<sup>1</sup> is a C<sub>6</sub>-8 ~ cycloaclylene- or a C<sub>6</sub>-ioalkylcycloalkylene group, for example dipentane dimercaptan and ethylcyclohexyldithiol (ECHDT).
Further preferred dithiols include one or more heteroatom substituents in the carbon chain, i.e. dithiols in which X is a heteroatom such as O, S or other bivalent heteroatom radical; a secondary or tertiary amine group, i.e. -NR<sup>6</sup>-, where R<sup>6</sup> is hydrogen or methyl; or another substituted trivalent heteroatom. X is in a preferred embodiment 0 or S, and thus R is<sup>1</sup> - [(CH<sub>2</sub>-)<sub>p</sub>-0-L<sub>q</sub>- (CH<sub>2</sub>-)<sub>r</sub>- or - [(CH<sub>2</sub>-)<sub>p</sub>-SL<sub>q</sub>- (- CH<sub>2</sub>-)<sub>r</sub>-. Preferably, the symbols p and r are the same, and most preferably they have both value 2. Particularly preferred examples of dithiols of this type include dimercaptodiethyl sulfide (DMDS) (p, r = 2, q = 1, X = S); dimercaptodioxoctane (DMDO) (p, g, r = 2, X = O); and 1,5dithia-3-oxapentane. It is also possible to use dithiols which include both heteroatom substituents in the carbon chain as well as pendant alkyl groups, in particular methyl groups. Such compounds include methyl-substituted DMDS, such as HS-CH<sub>2</sub>CH (CH<sub>3</sub>) -S-CH<sub>2</sub>CH<sub>2</sub>-SH, HS-CH (CH<sub>3</sub>) CH<sub>2</sub>-SCH<sub>2</sub>CH<sub>2</sub>-SH and dimethyl substituted DMDS such as HSCH<sub>2</sub>CH (CH<sub>3</sub>) -S-CH (CH<sub>3</sub>) CH<sub>2</sub>-SH and HS-CH (CH<sub>3</sub>) CH<sub>2</sub>-S-CH<sub>2</sub>CH (CH<sub>3</sub>) -SH.
Two or more different dithiols of formula IV may also be used if desired in the preparation of polytioethers of the invention.
The compounds of formula V are divinyl ethers. Divinyl ether per se (m = 0) can be used. Preferred divinyl ethers include those compounds having at least one oxyalkylene group, more preferably from 1 to 4 oxyalkylene groups (i.e., those compounds in which m is an integer from 1 to 4). Very preferred is that m is an integer from 2
520 698
WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc i 'J to 4. It is also possible to use commercially available divinyl ether mixtures in the preparation of polytioethers of the invention. Such mixtures are characterized by a non-integer mean of the number of alkoxy groups per molecule. Thus, in formula V, m can also obtain rational values which are not integers between 0 and 10, preferably between 1 and 10, very much preferred between 1 and 4, especially between 2 and 4.
Examples of divinyl ethers include those compounds in which R<sup>2</sup> is C<sub>2</sub>-6 n-alkylene or C<sub>2</sub>-6 branched alkylene. Preferred divinyl ethers of this type include ethylene glycol divinyl ether (EG-DVE) (R<sup>2</sup>= ethylene, m = 1); butanediol divinyl ether (BD-DVE) (R<sup>2</sup>= butylene, m = 1); hexanediol divinyl ether (HD-DVE) (R<sup>2</sup>= hexylene, m = 1); diethylene glycol divinyl ether (DEG-DVE) (R<sup>2</sup>= ethylene, m = 2); triethylene glycol divinyl ether (R<sup>2</sup>= ethylene, m = 3); and tetraethylene glycol divinyl ether (R<sup>2</sup>= ethylene, m = 4). Useful divinyl ether mixtures include divinyl ether mixtures of type PLURIOL®, such as PLURIOL® E-200 (commercially available from BASF), for which R<sup>2</sup>= ethyl and m = 3.8, as well as DPE polymer blends such as DPE-2 and DPE-3 (commercially available from International Specialty Products, Wayne, New Jersey). Of these, DEG-DVE and PLURIOL® E-200 are particularly preferred.
Useful divinyl ethers in which R<sup>2</sup> is C2-6 branched alkylene, can be prepared by reacting a polyhydroxyl compound with acetylene. Examples of compounds of this type include compounds in which R<sup>2</sup> is an alkyl-substituted methylene group such as -CH (CH 3) ~ or an alkyl-substituted ethylene such as -CH<sub>2</sub>CH (CH<sub>3</sub>) - .
Other useful divinyl ethers include compounds in which R<sup>2</sup> is polytetrahydrofuryl (poly-THF) or
<img file="SE520698C2_D0007.tif" />
monomer units.
preferably with an average value of about 3
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<img file="SE520698C2_D0009.tif" />
<img file="SE520698C2_D0010.tif" />
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Two or more compounds of formula V can be used in the above method. Thus, in preferred embodiments of the invention, two compounds of formula IV and one compound of formula V, one compound of formula IV and two compounds of formula V, two compounds of formula IV and of formula V, and more than two compounds of one or both formulas may be used to prepare a number of polytioethers of the invention, and all such combinations of compounds are intended to fall within the scope of the invention.
Although compounds of formulas IV and V, with pendant alkyl groups, for example pendant methyl groups, are useful according to the invention as stated above, it has been surprisingly discovered that compounds of formulas IV and V which are free of pendant methyl groups or other alkyl groups, also provides polytioethers, which are liquid at room temperature and room pressure.
The reaction of the compounds of formulas IV and V is preferably catalyzed by a catalyst which produces free radicals. Preferred catalysts which generate free radicals include azo compounds, for example azobisnitril compounds, such as azo (bis) isobutyronitrile (AIBN); organic peroxides such as benzoyl peroxide and t-butyl peroxide; and similar generators of free radicals. The reaction can also be carried out by irradiation with ultraviolet light, either with or without a cationic photoinitiation group. Ionic catalysis methods, using either inorganic or organic bases, for example triethylamine, also provide materials useful in connection with this invention.
Topped analogs to the above polytioethers can be prepared by allowing (n + 1) moles of a compound of formula IV or a mixture of at least two different compounds of formula IV, (n) moles of a compound of formula V or a mixture of at least two various
520 698 .. . <sub>c</sub> , <sub>2</sub> 0 F.? Gurnqsverke
WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc compounds of formula V and about 0.05 to about 2 moles of a compound of formula VI
CH<sub>2</sub>= CH- (CH<sub>2</sub>) so — R<sup>5</sup> VI or a mixture of two different compounds of formula VI react in the presence of a suitable catalyst.
Compounds of formula VI are alkyl-ro-alkenyl ethers (ethers with an ethylenically unsaturated group at the end) which react with thiol groups at the end to top polytioether polymers.
In formula VI, s is an integer from 0 to 10, preferably 0 to 6, more preferably 0 to 4. Specific, preferred compounds of formula VI are monovinyl ethers (s = 0), comprising amino and hydroxyalkylvinyl ethers such as 3-aminopropyl -vinyl ether and 4-hydroxybutyl-vinyl ether (butanediol-monovinyl ether) as well as unsubstituted alkyl vinyl ethers, such as ethyl vinyl ether. Further preferred compounds of formula VI include allyl ethers (s = 1) such as 4-aminobutyl allyether, 3-hydroxypropyl allyl ether, etc. Although compounds can be used in which s is greater than 6, the resulting polymers may have poorer fuel resistance than those in which s is 6 or less.
Use of two moles of the compounds of formula VI yields fully topped polymers, while the use of smaller amounts results in partially topped polymers.
In another preferred method, (n) moles of a compound of formula IV, or a mixture of at least two different compounds of formula IV, react with (n + 1) moles of a compound of formula V, or a mixture of at least two various compounds of formula V, again in the presence of a suitable catalyst. This method yields a non-topped bifunctional polytioether with vinyl at the end.
Topped analogs to the above polytioethers with vinyl at the end can be prepared by allowing (n + 1) moles of a
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<img file="SE520698C2_D0011.tif" />
<img file="SE520698C2_D0012.tif" />
in compound of formula V or a mixture of at least two different compounds of formula V, (n) moles of a compound of formula IV or a mixture of at least two different compounds of formula IV and about 0.05 to about 2 moles of a compound of formula VII
HS-R<sup>5</sup> VII or a mixture of two different compounds of formula VII react in the presence of a suitable catalyst.
Compounds of formula VII are monothiols which may be unsubstituted or substituted by, for example, hydroxyl or amino groups. Examples of peak compounds of formula VII include mercapto alcohols, such as 3-mercaptopropanol, and mercaptoamines such as 4 mercaptobutylamine.
Polyfunctional analogs of the above bifunctional polytioethers are similarly prepared by mixing one or more compounds of formula IV and one or more compounds of formula V in appropriate amounts with a polyfunctionalizer, as described above, and allowing the mixture to react. Thus, according to a method of manufacturing polyfunctional polytioethers of the present invention, (n + 1) moles of a compound or compounds of formula IV, (n) moles of a compound or compounds of formula V, and a z-valent polyfunctionalizer to form a reaction mixture. The mixture is then allowed to react in the presence of a suitable catalyst, as described above, to yield polyfunctional polythioethers with thiol at the end. Topped analogs of the above polytioethers are prepared by including in the starting reaction mixture about 0.05 to about (z) moles of one or more suitable topped compounds VI. Use of (z) mols gives fully topped polyfunctional polymers, while the use of smaller amounts again gives partially topped polymers.
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<img file="SE520698C2_D0013.tif" />
Similarly, (n) moles of a compound or compounds of formula IV, (n + 1) moles of a compound or compounds of formula V and a z-valent polyfunctionalizer are formed to form a reaction mixture which is allowed to react as above. to provide polyfunctional polytioethers with vinyl at the end. Topped analogs of the above polytioethers are prepared by including in the starting reaction mixture one or more suitable topping compounds VII.
The inventive polytioethers are preferably prepared by mixing at least one compound of formula IV and at least one compound of formula V, optionally with one or more topical compounds VI and / or VII, as appropriate, and / or a polyfunctional agent followed by addition of a suitable catalyst and to carry out the reaction at a temperature of from about 30 to about 120 ° C for a period of from about 2 to about 24 hours. Preferably, the reaction is carried out at a temperature of from about 70 to about 90 ° C for a period of from about 2 to about 6 hours.
Since the inventive reaction is an addition reaction rather than a condensation reaction, the reaction typically proceeds substantially to its end, i.e., the inventive polytioethers are prepared in yields of about 100%. No or substantially no unwanted by-products are formed. In particular, the reaction does not produce appreciable amounts of smelly, cyclic by-products, such as those characteristic of known methods for preparing polytioethers. In addition, the polytioethers prepared according to the invention are substantially free of harmful residual catalyst. This results in no free catalyst being available for further reaction with the polytioether, especially in the presence of water at room temperature, to degrade polymers and to produce smelly cyclic compounds. The inventive
WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc
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1J tv '-' Thus, in the polytioethers, both thermal stability and low odor are characterized.
Polytioethers of the invention are useful in applications such as coating and sealing compositions and are preferably prepared as polymerizable sealing compositions in applications where low temperature flexibility and fuel resistance are important. Such sealing compositions are useful, for example, as space seals and coatings for fuel tanks. Thus, a first preferred polymerizable composition comprises at least one polytioether as described herein; a hardener or combination of hardeners; and a filler.
The polytioether or combination of polytioethers is preferably present in the polymerizable composition in an amount of from about 30% to about 90% by weight, more preferably about 40 to about 80% by weight, most preferably about 45 to about 75% by weight, where calculated weight percent is based on the weight of all non-volatile components in the composition. Preferably, T is<sub>g</sub> of the polytioether (or polytioethers) used in the polymerizable composition not higher than -55 ° C, more preferably no higher than -60 ° C.
Polymerizable compositions of the invention useful as curing agents include epoxy resins, for example hydantoin dipoxide, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, Novolak epoxides and any epoxidized, unsaturated and phenolic resins. Other useful additives include such unsaturated compounds as acrylic and methacrylic esters of commercially available polyols, unsaturated synthetic and naturally occurring resin compounds, TACs and derivatives of the compounds of the present invention with end-of-life olefin. In addition, useful cures can be obtained by oxidative coupling of
520 698
WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc thiol groups using organic and inorganic peroxides (for example, MnO<sub>2</sub>), which is known to those skilled in the art. The choice of a special hardener can affect T<sub>g</sub> of the cured composition. For example, hardeners having a T<sub>g</sub> which is considerably lower than the polytioether T<sub>g</sub>, reduce the cured composition T<sub>g</sub>.
Depending on the polytioethers used in the composition, the composition will contain about 90% to about 150%, preferably about 95% to about 125% of the stoichiometric amount of selected hardener.
Useful fillers in the polymerizable compositions of the invention include those commonly used in the art, such as carbon black and calcium carbonate (CaCO<sub>3</sub>). Preferably, the compositions comprise about 5 to about 60% by weight of the selected filler or combination of filler, more preferably about 10 to 50% by weight.
Polytioethers, hardeners and fillers used in polymerizable compositions of the invention as well as optional additives, as described above, should be selected so as to be compatible with each other. Selection of compatible ingredients for the inventive compositions can be readily performed by one of ordinary skill in the art without resorting to unnecessary experimental activities.
The above polymerizable compositions are preferably curable at a minimum temperature of about 0 ° C (i.e., at a temperature of about 0 ° C or higher), more preferably about -10 ° C, most preferably about -20 ° C, cured a T<sub>g</sub> which is not higher than about -55 ° C, more preferably not higher than -60 ° C, much preferably not higher than -65 ° C. When cured, the polymerizable compositions preferably have a percentage increase in volume not greater than 25%, more preferably not greater than, and atmospheric pressure in jet fuel reference fluid (JRF) type 1.
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In addition to the above ingredients, polymerizable compositions of the invention may optionally comprise one or more of the following: pigments; thixotropic agents; accelerators; delay means; adhesion promoters; and masking agents.
Useful pigments include those conventionally used in the art, such as carbon black and metal oxides. The pigments are preferably present in an amount of from about 0.1% to about 10% by weight.
Thixotropic agents, for example quartz, are preferably used in an amount of from about 0.1 to about 5% by weight.
Accelerators known in the art, such as amines, are preferably present in an amount of from about 0.1 to about 5% by weight. Two such useful accelerators are 1,4-diazabicyclo [2.2.2] octane (DABCO, commercially available from Air Products, Chemical Additives Division, Allentown, Pennsylvania) and DMP-30 (an accelerator composition comprising 2,4,6-tri ( dimethylaminomethyl) phenol, commercially available from Rohm and Haas, Philadelphia, Pennsylvania).
Retardants such as stearic acid are also preferably used in an amount of from about 0.1 to about 5% by weight. Adhesive promoters, which may, for example, be conventional phenolic compounds or silanes, occur if they are preferably used in an amount of from about 0.1 to about 5% by weight. Masking agents, such as pine scent or other scents, which are useful for concealing any low odor level of the composition, are preferably present in an amount of from about 0.1 to about 1% by weight.
A further advantage of the sealing compositions of the invention is their improved curing properties. The extent of curing of the sealing composition as a function of time is usually difficult to measure directly, but can be estimated by determining the extrusion rate of the composition as a function of time. Extruder 520 698 \ CURRENT \ SYS \ P UBLIC \ D0C \ P \ 3062045.doc in the sgiSu fuselage plant fai. The velocity is the rate at which a mixed sealing composition, i.e., a sealing composition together with an accelerator system, extrudes from an application device. As the sealing composition is mixed with the accelerator system, the curing and extrusion rate begin to change over time. The rate of extrusion is thus inversely related to the extent of curing. That is, when the extent of curing is small, the viscosity of the mixed sealant composition is low and thus the extrusion rate is high. As the reaction is nearing its end, the viscosity becomes very high and thus the extrusion rate becomes low.
Referring to Fig. 1, the viscosity of certain known types of sealing compositions remains low for an extended period of time because the compositions cure slowly. Such compositions have extrusion curves which are qualitatively similar to curve A. Other known types of sealing compositions cure very rapidly and their viscosity thus increases rapidly. This causes the rate of extrusion to decrease rapidly, as shown in curve B. It is desirable that a mixed sealant composition should have a low viscosity and thus a high extrusion rate for a period of time sufficient to permit uniform application of the sealant composition to the surface to be sealed, but it should then cure rapidly after application, i.e. its extrusion rate. should decrease rapidly. The sealing composition of the present invention is characterized by this desirable extrusion curve, as illustrated qualitatively in curve C.
The sealing composition of the present invention, depending on the particular formulation, may have as high initial extrusion rates as 500 g / min or higher along with low extrusion rates of the order of about 5 to 10 g / min or less after curing times of the order of 1 hour.
520 698 \ 'CURRENT \ SYS \ PUBLIC \ DOC \ P'3062045.doc
<img file="SE520698C2_D0014.tif" />
As shown in Fig. 2, the initial extrusion rate of a polymer of the present invention (Example 1 below, cured with an epoxy hardener as described below) is about 550 g / min, after which it rapidly drops to about 20 g / min after 70 min. my. By comparison, a known polysulfide (cured with MnO)<sub>2</sub>) an initial extrusion rate of about 90 g / min, which slowly decreases to about 20 g / min after 70 min.
A second preferred polymerizable composition integrates one or more plasticizers with the polytioether (s), hardener (s) and filler (s) described above. Use of a plasticizer allows the polymerizable composition to comprise polyethers having higher T<sub>g</sub> than could normally be used in a space seal. That is, the use of a plasticizer effectively reduces the T of the composition<sub>g</sub> and thus, the flexibility of the cured polymerizable composition at low temperature increases below that which would be expected on the basis of the polytioether T<sub>g</sub> solely.
Plasticizers useful in polymerizable compositions of the invention include phthalate esters, chlorinated paraffins, hydrogenated terphenyls, etc. The plasticizer or combination of plasticizers preferably comprises 1 to about 40% by weight, more preferably 1 to about 10% by weight of the composition.
Depending on the nature and amount of plasticizer (s) used and the composition (s) used in the composition, polytioethers of the invention can be used which have Tg values of up to about -50 ° C, preferably up to about -55 ° C.
The above polymerizable compositions are also preferably curable at a lowest temperature of about 0 ° C, more preferably about -10 ° C, most preferably about -20 ° C.
The present invention will be illustrated in more detail with reference to non-limiting examples.
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<img file="SE520698C2_D0015.tif" />
<img file="SE520698C2_D0016.tif" />
In Examples 1-8, liquid polytioethers are prepared by mixing, with stirring, one or more dithiols with one or more divinyl esters and a trifunctional agent. The reaction mixture was then heated and a catalyst added, which produces free radicals. All reactions proceeded mainly to their end (about 100% yield).
Example 1
In a 2 liter flask, 524.8 g (3.32 mole) of diethylene glycol divinyl ether (DEG-DVE) and 706.7 g (3.87 mole) of dimercaptodioxooctane (DMDO) were mixed and heated to 77 ° C with 19.7 g (0.08 mol) of triallyl cyanurate (TAC). To the heated reaction mixture was added 4.6 g (0.024 mol) of azobisnitril, a catalyst which produces free radicals (VAZO® 67 [2,2'-azobis (2-methylbutyronitrile), commercially available from DuPont). The reaction proceeded substantially to its end after 2 hours to give 1,250 g (0.39 mol, 100% yield) of a liquid polytioether resin with a T<sub>g</sub> about -68 ° C and a viscosity of 65 pois. The resin was slightly yellow and had low odor.
Example 2
In a 1 liter flask, 404.4 g (1.60 mole) of divinyl ether PLURIOL®E-200 and 355.88 g (1.94 mole) of DMDO were mixed with 12.1 g (0.049 mole) of TAC and allowed to react as in Example 1. The reaction proceeded essentially to its end after 5 hours to give 772 g (0.024 mol, 100% yield) of a resin with a T<sub>g</sub> about -66 ° C and a viscosity of 48 pois. The resin was yellow and had a low odor.
Example 3
In a 100 ml flask, 3.2 g (0.21 mole) of DEG-DVE and 26.48 g (0.244 mole) of 1.2propanedithiol were mixed and heated to 71 ° C with 0.75 g (0.003 mole) of TAC. To the heated (pre-reaction mixture) was added 0.15 g (0.8 mmol) of VAZO 67. The reaction proceeded essentially to its end after 7 hours to give 60 g (0.03 mol, 100% yield) of a resin
520 698
WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc * —Q.ou -tngS '/ ar <2- 1 2 with one T<sub>g</sub> about -61 ° C and a viscosity of 22 pois. The resin had a noticeable PDT odor.
Example 4
In a 100 ml flask, 33.3 g (0.136 mole) of tripropylene glycol divinyl ether (DPE-3) and 27.0 g (0.170 mole) of dimercaptodiethyl sulfide (DMDS) were mixed and heated to 77 ° C with 0.69 g (0.003 mole) ) TAC. To the heated reaction mixture was added 0.15 g (0.8 mmol) of VAZO®67. The reaction proceeded substantially to its end after 6 hours to give 61 g (0.028 mol, 100% yield) of a resin with a T<sub>g</sub> about -63 ° C and a viscosity of 26 pois.
Example 5
In a 250 ml flask, 113.01 g (0.447 mole) of divinyl ether PLURIOL®E-200 and 91.43 g (0.498 mole) of DMDO were mixed with 1.83 g (0.013 mole) of 1,2,3-propanetriol (PTT). and allowed to react exothermically for 72 hours. The mixture was then heated to 80 ° C. To the heated reaction mixture was added 0.2 g (1 mmol) of VAZO®67. The reaction mixture was maintained at 80 ° C and the reaction proceeded substantially to its end after 3 hours to give 200 g (0.06 mol, 100% yield) of a resin with a T<sub>g</sub> about -66 ° C and a viscosity of 55 pois.
Example 6
In a small jar, 14.0 g (0.055 mole) of divinyl ether PLURIOL® E-200, 6.16 g (0.336 mole) DMDO and 5.38 g (0.336 mole) DMDS were mixed and heated to 82 ° C with 0.42 g (0.017 mol) TAC (which is briefly heated to melt the same). To the heated reaction mixture was added 0.2 g (0.001 mol) of VAZO®67. The reaction proceeded substantially to its end after 18 hours to give 26 g (8.4 mmol, 100% yield) of a resin with a T<sub>g</sub> about -63 ° C and a viscosity of 80 pois.
Example 7
In a small jar, 13.55 g (0.054 mol) of divinyl ether PLURIOL®E-200, 10.44 g (0.57 mol) of DMDO and 1.44 g (8.1 mmol) of ethyl cyclohexanedithiol were mixed and heated to 82 ° C.
520 698
WCURRENT \ SYS \ PUBLIC \ DOC \ P \ 3062045.doc (ECHDT) with 0.40 g (1.6 mmol) of TAC (which is briefly heated to melt it). To the heated reaction mixture was added 0.2 g (0.001 mol) of VAZO®67. The reaction proceeded substantially to its end after 5 hours to give 26 g (8.1 mmol, 100% yield) of a resin with a T<sub>g</sub> of 66 ° C and a viscosity of 58 pois.
Example 8
In a small glass jar, 9.11 g (0.036 mol) of divinyl ether PLURIOL®E-200, 5.71 g (0.031 mol) of DMDO, 1.52 g (7.8 mmol) of ECHDT, 5, was mixed and heated to 82 ° C. 08 g (0.031 mole) of DMDS and 4.11 g (0.024 mole) of hexanediol-divinyl ether (HD-DVE) with 0.39 g (1.6 mmol) of TAC (which was briefly heated to dissolve it). To the heated reaction mixture was added 0.6 g (3.1 mmol) of VAZO 67. The reaction proceeded substantially to its end after about 45 hours to give 26 g (7.8 mmol, 100% yield) of a resin with a T<sub>g</sub> about -66 ° C and a viscosity of 304 pois. The resin had a cloudy appearance.
Each of the resins above was evaluated for odor. The following scale was used:
3: strong, unpleasant odor; 2: moderate odor; 1: weak odor; 0: essentially without odor.
The polymer described in Example 3 of U.S. Patent No. 4,366,307 was used as a control. This polymer (the control polymer) had an odor of 3.
The results were as follows:
<td>Polymer</td><td>Odor</td><td>Polymer</td><td>Odor</td>
<td> 1</td><td> 1</td><td> 5</td><td> 1</td>
<td> 2</td><td> 1</td><td> 6</td><td> 1</td>
<td> 3</td><td> 3</td><td> 7</td><td> 1</td>
<td> 4</td><td> 1</td><td> 8</td><td> 2</td>
All liquid polytioethers thus had weak or moderate odor, except polymer 3, which had a strong odor.
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They are then prepared in Examples 1-8. The curing was carried out on those resins with a hardener and one had the following composition: epoxynovolac (eq. Weight 175.5) epoxy hydantoin (eq. Weight 132) calcium carbonate carbon black adhesion promoter (silane) resins cured non-compounded accelerator DABCO. Hardener weight% weight% weight% weight% weight%
The cured resins were evaluated for odor according to the procedure shown above. For each of the cured resins, T was also measured<sub>g</sub> and the percentage weight gain after immersion in JRF type 1 for one week at room temperature and room pressure. The percentage increase in volume and weight was determined for each of the cured materials as follows:
Wi = initial weight in air w<sub>2</sub> = initial weight in H<sub>2</sub>O w<sub>3</sub> = final weight in air w<sub>4</sub> = final weight in H<sub>2</sub>0% volume increase = 100x [(w2 + w3) - (wl + w4)] / (wl-w2)% weight increase = 100x (w3-wl) / wl
The results are given in Table 1:
<td colspan="9">TABLE 1</td>
<td>Cured resin</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td>
<td>Odor</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>
<td>Tg (° C)</td><td> -59</td><td> -61</td><td> -61</td><td> -63</td><td> -62</td><td> -56</td><td> -59</td><td> -58</td>
<td>% volume increase in fuel</td><td> 19</td><td> 22</td><td></td><td></td><td> 23</td><td> 19</td><td> 24</td><td> 2 7</td>
<td>% weight gain</td><td> 14</td><td> 15</td><td> 15</td><td> 23</td><td> 15</td><td> 15</td><td> 19</td><td> 20</td>
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<img file="SE520698C2_D0018.tif" />
By comparison, the control polymer had an odor of 1-2 when cured.
Example 9
Polytioethers having an arithmetic mean molecular weight about
2100 and an average functionality F of 2.1 is prepared by mixing a divinyl ether with a dithiol, as shown in Table 2, and reacting the materials as described herein. The uncompounded polytioethers were then cured using 15 g of the curing agent described above and
0.30 g of DABCO. For each of the polytioethers thus prepared, the following quantities were measured: viscosity (uncured material, powder p); Shore Hardness A (Cured Material, Value with Rex Durometer); % weight gain (cured material) after one week at 140 ° F (60 ° C) and atmospheric pressure in JRF type 1; and T<sub>g</sub> (uncured material, ° C). The results were as follows:
<img file="SE520698C2_D0019.tif" />
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<td colspan="5">Table 2</td>
<td>dithiol divinyl</td><td>ECHDT</td><td>DMDS</td><td>DMDO</td><td>HDT<sup>d</sup></td>
<td>DEG-DVE</td><td>145p</td><td>(solid)</td><td>27 p</td><td>24 p</td>
<td></td><td>44 Rex</td><td>94 Rex</td><td>2 5 Rex</td><td>2 5 Rex</td>
<td></td><td> 27 %</td><td> 3 %</td><td> 14 %</td><td> 29 %</td>
<td></td><td> -53</td><td> -63</td><td> -69</td><td> -77</td>
<td>PLURIOL®<sup>A</sup></td><td>77 p</td><td>41 p</td><td>59 p</td><td>25 p</td>
<td></td><td>43 Rex</td><td>4 7 Rex</td><td>2 7 Rex</td><td>23 Rex</td>
<td></td><td> 27 %</td><td> 11 %</td><td> 18 %</td><td> 30 %</td>
<td></td><td> -57</td><td> -61</td><td> -67</td><td> -76</td>
<td>BD-DVE<sup>b</sup></td><td>185 p</td><td>(solid)</td><td>(solid)</td><td>(solid)</td>
<td></td><td>42 Rex</td><td></td><td>2 0 Rex</td><td>22 Rex</td>
<td></td><td> 44 %</td><td></td><td> 21 %</td><td> 44 %</td>
<td></td><td> -59</td><td></td><td> -79</td><td> -85</td>
<td>HD DVE</td><td>155 p</td><td>(solid)</td><td>(solid)</td><td>(soft, firm)</td>
<td></td><td>5 0 Rex</td><td></td><td>14 Rex</td><td>2 9 Rex</td>
<td></td><td> 57 %</td><td></td><td> 27 %</td><td> 68 %</td>
<td></td><td> -60</td><td> -63</td><td> -78</td><td> -86</td>
<td>Poly-THF<sup>C</sup></td><td>91 p</td><td>(solid)</td><td>27 p</td><td></td>
<td></td><td>3 0 Rex</td><td>75 Rex</td><td>17 Rex</td><td></td>
<td></td><td> 64 %</td><td> 29 %</td><td> 37 %</td><td></td>
<td></td><td> -69</td><td> -79</td><td> -79</td><td></td>
<sup>A</sup>PLURIOL® E-200 divinyl ether <sup>b</sup>Butanediol divinyl ether <sup>c</sup>Polytetrahydrofuran divinyl ether <sup>d</sup>hexanedithiol
From the table above it is evident that the following combinations of divinyl ether and dithiol provide liquid polytioethers with unexpectedly superior fuel resistance and low temperature flexibility when cured: PLURIOL® E200 / DMDO; and DEG-DVE / DMDO. Other potentially useful combinations include: DEG-DVE / ECHDT; DEG-DVE / HDT;
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PLURIOL® E-200 / ECHDT; PLURIOL® E-200 / HDT; as well as poly-THF / DMDO. PLURIOL® E-200 / DMDS also has excellent fuel resistance and low temperature flexibility when cured, but the non-compounded material does not remain in a liquid state for an extended period of time.
Example 10
Addition of DMDS to Polymers PLURIOL® / DMDO Four liquid polytiols are prepared as described herein. The polymers had the following compositions (the values given are molar equivalents):
<td></td><td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td>PLURIOL® E-200</td><td> 6,6</td><td> 6,6</td><td> 6,6</td><td> 6,6</td>
<td>DMDO</td><td> 8</td><td> 6</td><td> 4,5</td><td> 4</td>
<td>DMDS</td><td> 0</td><td> 2</td><td> 3,5</td><td> 4</td>
Each uncompounded polymer was cured as in Example 9 (15 g of the curing composition and 0.30 g
DABCO) with the addition of 0.2 molar equivalents of TAC to give polymers with an average arithmetic molecular weight of about 3000 and a functionality F of 2.2. For each polymer, the following properties were measured: T<sub>g</sub> (resin, ° C); T<sub>g</sub> (cured, ° C); viscosity (p); % swelling in JRF type 1; % weight gain in JRF type 1; and% weight gain in water. The results are given in Table 3.
<td colspan="5">TABLE 3</td>
<td></td><td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td>T<sub>g</sub> (resin)</td><td> -67</td><td> -66</td><td> -64</td><td> -63</td>
<td>(hardened)</td><td> -59</td><td> -58</td><td> -56</td><td> -56</td>
<td>JRF % swelling</td><td> 24</td><td> 21</td><td> 21</td><td> 20</td>
<td>o,], + _ -! Ό V -L JVUkJJX.llJLliy</td><td>Ί r »± O</td><td> 15</td><td> 16</td><td> 16</td>
<td>hrs<sub>2</sub>O % weight gain</td><td> 11,8</td><td> 11,5</td><td> 7,4</td><td> 7,5</td>
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All of the above polymers showed excellent fuel resistance. In particular, polymers 1 and 2 also exhibited excellent low temperature flexibility.
Example 11
Addition of ECHDT to polymers PLURIOL® / DMDO
Four liquid polytiols were prepared as described herein. The polymers had the following compositions (the values given are molar equivalents):
<td></td><td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td>PLURIOL® E-200</td><td> 6,6</td><td> 6,6</td><td> 6,6</td><td> 6,6</td>
<td>DMDO</td><td> 8</td><td> 7</td><td> 6</td><td> 5</td>
<td>ECHDT</td><td> 0</td><td> 1</td><td> 2</td><td> 3</td>
Each uncompounded polymer was cured as in Example 10 to provide the polymer with an average arithmetic molecular weight of about 3000 and a functionality F of 2.2. For each polymer, the following properties were measured: Tg (resin, ° C); Tg (cured, ° C); viscosity (p); % swelling in JRF type 1; % weight gain in JRF type 1; and% weight gain in water. The results are given in Table 4.
<td colspan="5">TABLE 4</td>
<td></td><td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td>Tg (resin)</td><td> -67</td><td> -66</td><td> -65</td><td> -64</td>
<td>(hardened)</td><td> -59</td><td> -59</td><td> -58</td><td> -56</td>
<td>Viscosity</td><td> 59</td><td> 36</td><td> 44</td><td> 50</td>
<td>JRF type 1% swelling</td><td> 24</td><td> 25</td><td> 28</td><td> 29</td>
<td>% weight gain</td><td> 18</td><td> 18</td><td> 19</td><td> 19</td>
<td>hrs<sub>2</sub>O % weight gain</td><td> 11,8</td><td> 10,8</td><td> 8,3</td><td> 7,8</td>
All of the above polymers showed good fuel resistance and low temperature flexibility.
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Example 12
In a 250 ml three-neck flask equipped with a stirrer, thermometer and cooler, 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 (ca. 170 ° F). To the mixture is added 0.8 g (4.2 mmol) of catalyst VAZO®67. The reaction mixture is allowed to react at 82 ° C (about 180 ° F) for about 6 hours to give 200 g (0.06 mol, 100% yield) of a low viscosity liquid polytioether resin having a thiol equivalent of 1625 and a functionality F of 2.0.
Example 13
In a 250 ml three-neck flask equipped with a stirrer, thermometer and cooler, 26.7 g (0.107 mole) of TAC, 56.4 g (0.357 mole) of DEG-DVE and 117.0 g (0.642 mole) are mixed. DMDO and heated to 77 ° C (about 170 ° F). To the mixture is added 0.8 g (4.2 mmol) of catalyst VAZO®67. The reaction mixture is allowed to react at 82 ° C (about 180 ° F) for about 6 hours to give 200 g (0.07 mol, 100% yield) of a high viscous liquid polytioether resin having an equivalent of 800 and a functionality F of about 3 5.
Example 14
sealing composition
A sealing composition comprising the polythioether polymer DMDO / DEG-DVE of Example 1 was compounded as follows (the amounts in parts by weight):
Polytioether DMDO / DEG-DVE 100 Calcium Carbonate 60 Magnesium Oxide 1 Phenolic Resin 1 DMP-30 1 Isopropyl Alcohol 3
The compounded polymer was intimately mixed with the epoxy resin hardener of Examples 9-11 above in a 10: 1 weight ratio and cured at ambient temperature
520 698
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<img file="SE520698C2_D0020.tif" />
and humidity. Following the cured composition
Cured hardness at 25 ° C
Tensile strength
Fractional elongation Tear strength Flexibility at low temp (AMS 3267 §4.5.4.7) physical property obtained for
Shore A
550 psi
600 %
100 p / i was good enough
Example 15
sealing composition
A sealing composition comprising the polytioether polymer ECHDT / DEG-DVE of Example 9 was compounded as follows (amounts by weight):
Polytioether ECHDT / DEG-DVE 100 Calcium Carbonate 54 Hydrated Alumina 20 Magnesium Oxide 1 Phenolic Resin 1 Hydrogenated Terphenyl Softener 6 DMP-30 1 Isopropyl Alcohol 3
The compounded polymer was intimately mixed with the 10: 1 weight ratio epoxy resin and cured at ambient temperature and humidity. The following physical properties were obtained for the cured composition:
Cured hardness at 25 ° C
Shore A
Tensile strength
Elongation at break
Tear
550 psi acr \ 2tt V Ό p / i
520 698 hy, t. Cth ϊ .agist; tringsverket
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<img file="SE520698C2_D0021.tif" />
Flexibility at low temp was good enough
Example 16
Topped polytioether with -OH at the end
In a 500 ml flask, 275.9 g (1.09 mol) of divinyl ether PLURIOL® E-200, 174.7 g (0.95 mol) of DMDO, 28.7 g (0.30 mol) of 3-mercaptopropanol and 1.83 g (7.3 mmol) of TAC. The mixture was heated to 70 ° C and 2.3 g (12 mmol) of VAZO®67 was added slowly. The reaction mixture was stirred and heated at 85-90 ° C for 4 hours to give 480 g (0.15 mol, 100% yield) of a polymer having an equivalent weight of 1670 (arithmetic mean molecular weight = 3200, functionality F = 2.05).
Example 17
Topped polytioether with -OH at the end
In a 250 ml flask, 104.72 g (0.57 mol) of DMDO, 80.73 (0.51 mol) of DEG-DVE and 75.7 ° C were mixed and heated to 75 ° C.
14.96 g (0.13 mol) of butanediol monovinyl ether. To the heated mixture was slowly added 0.60 g (3 mmol) of VAZO 67. The reaction mixture was stirred and heated at 7585 ° C for 6 hours to give 200 g (0.064 mol, 100% yield) of a clear, almost colorless polymer with very low odor and a viscosity of 79 pois at 20 ° C. The equivalent weight was 1570 (arithmetic mean molecular weight = 3200, functionality F = 2.00).
Example 18
Polytioether with vinyl at the end
In a 250-ml flask, 97.63 g (0.53 mole) of DMDO, 97.66 g (0.62 mole) of DEG-DVE and 5.31 g (0.21 mole) of TAC were mixed and heated to 70 ° C. . 0.80 g (4 mmol) of VAZO®67 was slowly added to the heated mixture. The reaction mixture was stirred and heated at 85-90 ° C for 4 hours to give 200 g (0.11 mol, 100% yield) of a low odor polymer having a T<sub>g</sub> about -68 ° C and a viscosity of 25
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Example 19
Polytioether with ethyl vinyl ether at the end
In a 100 ml flask, mix and heat to 80 ° C
43.05 g (0.24 mole) of DMDO, 34.22 g (0.22 mole) of DEG-DVE as well
2.84 g (0.04 mole) of ethyl vinyl ether. 0.28 g (1.5 mmol) of VAZO®67 was slowly added to the heated mixture.
The reaction mixture was stirred and heated at 85 ° C for 6 hours to give 80 g (0.02 mol, 100% yield) of a polymer with a T<sub>g</sub> about -67 ° C and a viscosity of 64 pois at 20 ° C (arithmetic mean molecular weight = 4100, functionality F = 2.0).
520 69rf.
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Contents5
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| Document | Office | Kind | Date |
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| 80213097 | United States of America | A | |
| 80213097 | United States of America | A | |
| 92897297 | United States of America | A | |
| 92897297 | United States of America | A | |
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| 802130 | – | – | – |
| 928972 | – | – | – |
| PCTUS9803223 | – | – | – |
| US19970802130 | – | – | – |
| US19970928972 | – | – | – |
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Numbers
- Publication, DOCDB
- 520698
- Publication, EPODOC
- SE520698
- Application
- 9902713
- Application, DOCDB
- 9902713
- Application, EPODOC
- SE19990002713
Titles2
- English
- Composition and Method for Preparing Fuel Resistant Liquid Polytioether Polymers with Good, Low Temperature Flexibility
- Swedish
- Komposition och metod för framställning av bränslebeständiga, flytande polytioeterpolymerer med god, låg temperaturflexibilitet
Classification
- CPC, 4
- C08G75/045
- C08G75/12
- C08L61/06
- C08L81/02
- IPC, 7
- C09K3 10
- C08G75 04
- C08G75 12
- C08K3 00
- C08K3 013
- C08L61 06
- C08L81 02
