CA2190751A1

CA2190751A1 - Oximino silane terminated polymers and elastomers formed therefrom

Info

Publication number: CA2190751A1
Application number: CA002190751A
Authority: CA
Inventors: Dale Russell Flackett; Edward Thanaraj Asirvatham; Chempolil Thomas Mathew
Original assignee: Individual
Current assignee: Honeywell International Inc
Priority date: 1994-06-07
Filing date: 1995-05-03
Publication date: 1995-12-14
Also published as: HU9603384D0; EP0764179A1; CZ358896A3; MX9605594A; AU2372995A; BR9507837A; NZ285011A; KR970703377A; JPH10502392A; CN1149880A; WO1995033784A1; HUT75496A

Abstract

Oximinosilane terminated polymers which are cured at room temperature to become stable elastomers. The polymers have hydrolyzable ketoximino silyl group at each end of each molecule and are prepared by reacting a hydroxyl-terminated liquid polymer with an organic diisocyanate to produce an isocyanate terminated prepolymer. The resulting prepolymer is then converted into a mercaptan terminated polymer either by reacting with a mercapto alcohol or by reacting with an olefinic alkylene alcohol or amine to give an olefin-terminated polymer which is then reacted with a dimercaptan. When the mercaptan terminated polymer is reacted with a vinyl oximino silane or a vinylalkoxyoximino silane, a silane terminated liquid polymer is obtained. Such polymers have improved elongation, moisture resistance tensile and tear strength properties in adhesive, coating and sealant formulations.

Description

~ W0 95l33784 2 ~ 9 0 7 5 1 r~ C4~3 OXIMINO SII;AN_ TRRMTNATRn POLY~LRRS
AND ELASTOMRRS FOR~D ~_R_FROM
5 BACRGROUND OF TFR I NV~ UN
Field of the Invention:
The invention relates to nl-lm;nn6;1~n_ terminated polymers which are cured at room temperature to become stable elastomers. They have improved physical lO properties such as elongation, moisture resistance, variahle cure rate, tensile and tear strength in various f 1~tions. Such polymers have use as adhesives, ~^n~3 t; n j^. and sealants .
15 Description of the Prior Art It is k-nown in the art that the curing of isocyanate and mercaptan t^rm; nAt-d lic~uid polymers requires amines to form urea/urethanes or peroxides forming disulfides.
Both urethane and mercapto type polymers are commonly 20 used in two sealant systems where the mixing of the main polymer component with a curing catalyst or reactive - ^-lt i8 ^A~_nt;~l prior to use.
Incorpor~t;nj n~r;m~ n^A in these licLuid polymers has the advantage of moisture cure wlr~;7~t;on due to the 25 extreme reactivity of oximesilanes with moisture. Room temperature moisture cure of oximesilane t^rm;n~t^d polymers _1 ;m;n~t-^ the need for h~nfl1 ;nj toxic isocyanates and peroxides. In the silicone sealant industry, polysiloxane having hydrolyzable silicon-end 30 groups are o~ten used in single-~ sealant f, 1 ~ t inn^~ . Upon exposure to the atmosphere, the polymer undergoes rapid v~ n;~t;nn with ~ "'^ric moisture. Due to the high cost of polysiloxane polymers, it is desirable to use low- cost organic polymers such as 35 polyethers, polyesters and polysulfides as the polymer b~^khnn^ .

W095133784 2 1 ~ 0 75 1 ~ 473 ~
.

Among the commercially available liquid polymers, silane tPrm; nAted polymers are the most ~tP13i rAhl e due to the ea~e of curing with atmospheric moisture and their low 5 odor and toxicity. However, these silane tPrm;
polymers are in limited use because of their poor physical properties such as low tensile and tear strengths. Therefore it is desirable to produce organic liquid polymers which cure to become elastomeric 10 materials with faster cure rates, hydrolytic stability, good elnnr~ ~A~t i nn, high tensile and tear strength characteristics. U.S. Patent 3,317,461 discloses oximesilane tPrmtnAtPrl polysulfides made by reacting a mercaptan tPrm;nAtPd polysulfide with a silane having 15 hydrolyzable groups and at least one olefinic double bond. These polymers, when cured, do not have high tensile and tear strength due to the lack of urethane groups. IJ.S. Patent 4,960,~44 discloses silane Pn~lrArped polymers with urethane groups in the polymer chain.
20 Hydrolyzable groups attached to the silicon atom are alkoxy groups with lower alkyl groups.
The silane tPrml nAt~-l polymers of this invention are easily cured at room temperature in the presence of 25 normal humidity to a hydrolytically stable solid elastomer having high tensile and tear strength and low compression set. No catalyst is required for this cure to take place although a wide variety of catalysts known to the art can be used to decrease cure times. An object 30 of the invention is to provide an organic liquid polymer endblocked with silanes cnn~Atntng ketoximes as the hydrolyzable groups that ca~ be cured at room temperature into a rubber-like elastomer or leathery adhesive when exposed to moisture.

~ w0 95/33784 ~ l 9 0 7 5 1 1 .1. ' 473 S~IPRY OF THE INVENTION
The invention provi~eE~ rYtminns;lAn~ terminated polymers having the formula:
_ _ R- -O-C-NH-Rl-NH-C-X-R2-Y-CX2CH2-Si- (O-N=C)n " " I I
O O (R3)m R5 _ P
having an average molecular weight of at least ahout 600;
wherei~ R is an organic polymer rnnt;:linin~ a h~rkhnn~
15 polyether, polythioether or polyester, Rl is a divalent organic radical, R2 is an alkylene group having at least 3 carbon atoms, X is O or NR6 where R6 is either llydlu~
or a monovalent lower alkyl group, Y is sul~ur or S-R7-S
where R7 is an alkylene thioether having 4-12 carbon 20 atoms, alkylene having 2 to 10 carbon atoms, or a substituted cyclohexyl ring group having the ~ormula:
l H3

2 5 CH2 CH
\ . /
CH2 CH- CH2 - CH2 ~ or CH2 CH-I

CH CH
CH

3 5 CH3 CH
R3 is an alkyl radical o~ 1 to 7 carbon atoms or an alkoxy radical o~ 1 to 6 carbon atoms and R4 and R5 are independently a s~tllr~tP~l straight chain or h-r~nrh~c~

w0 9sJ33784 2 1 9 0 7 5 1 ~ . 473 ~

alkyl radical of 1 to 7 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and amyl, or R4 and R5 taken together form a cyclized group, p is 2 to 3, m is O to 2, n is 1 to 3 and the sum of m and n is 3.
The invention further provides a method for the production of the above oY;m;nl cilane tPrm;nAtPd polymers . A prepolymer is f ormed by reacting a hydroYyl -terminated polymer with an organic diisocyanate to 10 produce an isocyanate tPrm;n~tPd polymer. The isocyanate tPrm;n~ted polyol is reacted with an olefinic alcohol or amine in which the olefinic group i8 sPriqrAtp~ by at least one carbon atom to give olefin tPrm;n~tPtl polyether polyol. One then reacts the olefin-tPrm;n~tPcl 15 prepolymer with a dimercaptan and a vinyl~ Y; ~ nP
The invention still furt~er provides a method for the production of the above nY;m;n~silane tGrm;n~ted polymers by reacting the isocyanate term;n~ted polyol with a 20 mercapto alcohol to produce a mercaptan tPrm~n~tecl polymer; and then reacting with a vinyloxime silane.
The invention also provides a f, l~t~d sealant, coating, foam or adhesive composition which comprises the above nY;m;nt-cilane tPrm;n~tec9 polymer in ~( Yt~lre with 25 a plasticizer, filler, and moisture scavenger as well as an optional ~-lhPCif~n promoter, catalyst, rheology m~fl;fi~r and/or crossl;nk~r.
nRrr~Tl.Rn r~R.elrRTPTION OF l~TR ~ RN~nnTMRNT
30 The invention Pn~ ~~cses organic polymers, having hydrolyzable kPt~Y;m;no silyl group at each end of each molecule as is shown by the formula described above. The kPtr~; m; n~silane- terminated polymers are prepared by forming an isocyanate tPrm;n~tPf~ polymer, or prepolymer, 35 having the general formula:

WO 95133784 T ~ i5~3 R [0- C-NH-R1 -N=C=0] p where R, R1 and p have the same meaning as above, by 5 reacting a hydroxyl t~rm;n~ted polymer with an organic diisocyante. In the preferred embodiment, the polymeric h 1 ~^kh~^,nP, noted ag R in the general f ormula can be such as hydroYyl terminated polypropylene oxide polyols, polybutyl~nP~^Y- ~1P glycol polyols, polytetr^~^thylene 10 glycol polyols, polyester polyols, polythioether polyols, polyalkylene glycol co-polymer polyols, and polyalkylene glycol-polyester copolymer polyols. These hydroxyl t~rm;n^t~l polyols are reacted with an organic diiso-cyanate f ollowing a procedure known in the prior art .
15 Some eY~mples of the organic diisocyanates are toluene diisocyanate, diphenylmethane 4, 4 ' -diisocyanate, 1, 6-hl thylene diisocyanate and isophorone diisocyanate.
The prepolymers can be converted to mercaptan- tPrml nc tPrl polymer_ by either 1) reacting with a mercapto alcohol in 20 which the mercaptan and the hydroxyl groups are sPr~rAte~l by at least two methylene groups or 2 ) or reacting with a olefinic alkylene alcohol or amine of at least three carbon atoms wherein the olefin group is sPi^,Ar~ted from the hydroxyl or amine by at least 1 carbon atom. The 25 resulting ole~in-tPrm;n~tPd polymer is then reacted with a ~ Lan, in which the mercaptan functionality i8 separated by alkylenes, alkylene ethers, alkylene thloethPrc, alkylene esters and substituted cyclohexyl rings to give mercaptan-tPrm;nAted polymers. Hydrogen 30 sulfide can also be used to obtain the mercaptan tPrm; n~tPd polymer by using at least 1 mole for each e~uivalent of olefinic polymer to ensure all olefin functionality is tPrml n~tPd with the mercaptan groups .
Because of their greater av~-l^h-l;ty, the preferred 35 ~ ans are 1,2-ethane dithiol, 1,6-hexane dithiol, 1,10-decane dithiol, 2-mercaptoethylether, 2-. !
W095/33784 219075 ~ P~,l/.l.,_.~73 ~

mercaptoethylsulfide, glycol ~i uaL~l,O acetate, glycoldimercapto propionate, p-ml~nth~n.--2,9-dithiol and ethylcyclohexane dithiol. Preferred mercapto alcohols are 2 -mercaptoethAnnl, 3 -mercapto- 1-propanol . The 5 reactions described above are disclosed in U. S . Patents 3, 923, 748, 4, 366, 307 and 4, 960, 844 the disclosure of which are incorporated herein by reference. Radical initiated coupling reaction between the olef inic ~ uu~ld, i.e., the olefin tPrminAtPd polymer and an 10 organic ~ ~ m1nrl with 2 to 4 but at least two mercaptan groups will give mercaptan tGrminAt~nl polymer as described in the following equation:
p[R7- (SH)2_4] + R- [0-C-NH-R1-NH-C-X-CH2-C=C]p -->
n n O O
R- [o-C-NH-R1-NH-C-X-CH2-C-C-S-R7- (SH) 1-3] p O O
The above straight f orward reaction is catalyzed by 0 .1 to 1_ 0 weight 96 of radical initiators such as organic peroxides or azobis alkyl nitriles. The reaction tf'mr~'rAt~lre i9 rn-intA1nPC~ between 55C and 120C with the preferred rânge between 55C and 85C.
When the mercaptan t~rm1nAted polymer is reacted with a vinyl oximino silane, vinylalkyloximino silane, vinylaryloximino silane, vinylalkylalkoxyoximino silane, vinylalkoxyoximino silane or vinylarylalkoxyoximino silane, a silane t~rm;nAt~od polymer is obtained which is preferably a li5~uid and preferably has a molecular weight of from about 1200 to about 100,000. This is also a radical initiated addition reaction between the mercaptan group of the polymer and the olef in group of the vinylnY~ n~. The preferred silane has the formula, ~ W095/33784 2 1 9075 ~ 5473 H2 C=CH- Si - ( 0 - N=C) n 1 l (R3)m R5 in which R3, R4, R5, m and n have the same description as set forth above. The ketoximino silane tPrm;n~tpd liquid polymers of the present invention are different from the prior art by having urethane groups and the sulfur atoms separated by just 2 or more carbon atoms in the polymer h;lrkhnnP and algo because of at least one fast hydrolyzable neutral ketoximino group attached to the silicon atom.
In the nnmrolln~l;n~ of an adhesive, coating, foam or sealant composition, the nT;m;nnqilane tPrm;n~tPd polymers may be used alone, but more pref erably are blended with additives known in the art for the preparation of such a&esives, sealants and coating compositions. Such non-exclusively include plasticizers, fillers, reinforcing agents, moisture sc~av~llyel~"
rheology ;f;Prs, colorants, uv stabilizers, fungicides, mildewcides, antimicrobial agents, antioT;~l~ntq, polymers, crosql;nkPrs, coupling agents, adhesion promoters, and catalysts, thixotropic agents, flame retardants, thermal and electrically cnn~ t;ve fillers, blowing agents, surfactants, heat stabilizers, and solvents etc. to tailor the composition to a specifically desired application. These usually may be added at any stage of the mixing opPr~t;nn but care should be taken to add them under anhydrous conditions to avoid introducing additional moisture.
In the preparation of a formulated adhesive, coating, foam or sealant composition, the amount of polymer to be _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . .. .. . ... ... . . . . .

4 1 ~ J., 5'--473 21 9075~
used in this invention ranges f rom above 5 to about 9 o percent by weight o_ the total composition but preferably ranges from about 15 to about 60 percent by weight of the total composition.
The polymer may be used to create a foam by those skilled in the art through the use of a low boiling point liriuid or other suitable blowing agent, an example of which is l,l-dichloro-l-fluoro ethane in combination with a 10 surfactant as a foam stabilizer.
The composition can contain a filler which may be a reinforcing silica filler, a semireinforcing filler, a non- rein~orcing f iller or mixtures thereof . Examples of 15 reinforced silica fillers are fumea silica and precipitated silica. Examples of useful silica fillers are described in U.S. Patents 3,837,878; 2,938,009;
3, 004, 859, and 3, 635, 743 which are incorporated by reference. The amounts of reinforcing filler ranges from 20 0 to about 50 percent by weight of the total composition, pre~erably f rom about 0 to about 14 percent by weight and most preferably 2 to 8 percent by weight. Use of reinforcing fillers imparts increased tensile strength of the cured composition as well as providing thixotropic 25 character to the uncured composition. A non-reinforcing or semi-reinforcing filler can also be used at levels up to 759~. These include fillers such as calcium r~rhrn~tP
and ground riuartz . Other semi - reinf orcing f illers or ~t~n.l;nrJ fillerg which are known in the art may be used.0 These include, but are not limited to silica aerogel, t~ CerJl~q earth, iron oxide, titanium oxide, aluminum oxide, zirconium silicate, calcined clay, m~r,nPf~ m oxide, talc, wollastonite, hydrated alumina, and carbon black . The total amount of all f illers in the 35 composition ranges from 09~ to about 60~6 and preferably -WO 95/33784 2 1 9 0 7 5 1 ~ 473 from about 6~ to about 55~ by weight of the overall composition .
Methyl tris- (methyl ethyl ketnl~;m;nn) silane, vinyl tris-

5 (methyl ethyl ketn~;m;nQ) silane and tetrakis- (methyl ethyl ketoximino) silane are the pr~ln-; nAnt oxime silanes used commercially as crossl; nk~rS in oxime RTV
compounds and are used to speed the cure. Also useful as cros~l; nkl ers and herein are those silanes described in U.S. patent 3,18g,576 and is hereby incorporated by reference. Crosslinker can be present in an amount of from about 0 to about 10 percent by weight of the total composition, however from about 3 to about 7 percent by weight is preferred and from about 3 to about 6 percent by weight is most preferred. Tetrafunctional alkoxy-ketoxime silanes as disclosed in U.S. Patents 4,657,967 and 4,973,623 can also be used as cro~sl;nk~rs and are incorporated herein by reference. U.S. Patent 4,705,877 describes aminohydrocarbyl substituted k~otnlr;m; nnsilanes as m-rl; n~ agents and is incorporated herein by ref erence .
Additionally, known in the art are organofunctional silanes as adhesion promoters non-exclusively including gamma-aminopropyltriethoxy silane and gamma-aminopropyltrimethoxy silane as described in U. S . Patent 4,720,530. Other adhesion promoters may include 3-glycidu~y~ru~yl trimethoxy silane or gamma-mercaptopropyl trimethoxy silane. The amount of ~ ; on promoter may 3 o range f rom about 0 to about 5 . o percent by weight of the total composition. Preferably 0.5 to 1.5 percent by weight of the total composition is used.
The composition may further contain an optional catalyst which accelerates the reaction of the polymer. Examples of catalysts, non-exclusively include organotin _ _ _ _ _ . _ _ _ _ _ . .... . .. _ . .. _ . . .

W095/33784 2 1 90i5 1 ~ 473 carboxylates such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin maleate, dialkyl tin hP~ ?tPC~ dioctyltin dilaurate, iron octanoate, zinc octanoate, lead octanoate, cobalt 5 naphthenate, amines such as diamine, and titanantes.
Dibutyltl ntl; 1~ r~te is the preferred catalyst . Use levels of catalyst can range from 0 to about 2.0 percent by weight of the total composition, preferably about 0 . 05 to about 1 percent and most preferably from about 0.2 to 10 about 0 . 5 weight percent .
The composition may also contain an optional plasticizer to improve the extrusion properties of the composition and to modify the modulus of the cured composition. Such 15 include ~hth;~ t~C, ~ t~C, and aromatic hydrocarbons.
Suitable plasticizers include dibutylrhth~l~te, dioctylrhth~l~te, triarylphosphate and substituted analogs thereof. The plasticizer is added in an amount ranging from 0 to 50 weight percent based on the overall 20 composition, preferably from about 10 to about 30 weight percent. Preferred viscosity of the plasticizer ranges from about 100 to about 1000 cps. at 25 C.
Common uv stabilizers include benzo~h~n~n~c and 25 l~ydLo~Ly~henyl benzotriazoles families, including llydlv~yl,henyl benzotriazole mr~n~ c~ and dimers.
Hydroxyphenyl benzotriazole monomers are disclosed in U.S. Patents 3,204,896; 5,097,041; 4,943,637 and 5,104,992. 2-hydroxy-4-alkoxyb~n7OphPnr~n~c are useful uv absorbers and light stabilizers. U.S. Patents 3,399,237 and 3,310,525 show cl ~ol~n~lC having benzophenone f1lnrt;r,n~l groups. The uv stability of such materials is ' _ .,v~d by mixing the polymer with from about 0.19~ to about 5 9~ based on the weight of the polymer composition of the asymmetrical dimer of this invention. Moisture S.C.v~ are preferably present in an amount of ~rom 0 ~ W095/33784 2 1 9075 1 1~11. ' 473 to about 5% by weight of the composition. Suitable moisture 8.c-v~llyt:LA non-exclusively include trifunctional or greater ~ ;m;nAs;l~nPA, molecular sieves and other moisture reactive materials. Rheology modifiers are 5 preferably present in an amount o~ from 0 to about 59~ by weight of the composition. Suitable rheology modif iers non-exclusively include smectic clay, fumed silica, castor oil, castor wax and fibers.
10 Preferred colorants for this invention are pigments and dyes. Examples of colorants are titanium dioxide, carbon black, silica, zinc oxide, and clay. It is preferably present in an amount ranging from about 5~ to about 10%
based on the weight of the solids in the layer. The 15 composition also may contain an optional bacteriostat/fungistat. The most preferred c ~ ~ is acetoxy-dimethoxydioxane. Such are preferably present in an amount of f rom about 0 . 001% to about 1. 0% by weight o~
the c, it;on.
Solvents useful for forming coating compositions include essentially any inert organic solvent that is a solvent for the other composition ~ ltC. Solvents may be ethers, ketones, hydrocarbons and halocarbons, among 25 others . The amount of solvent can be tlPtP~n; nPCI by the skilled artisan ~_p~nr9; n~ on the end use. The other optional ~- ~ AntA may be present in an amount ranging from about 0 to about 10 weight percent based on the entire composition.
The composition of the present invention can be used in the form of a one An~lr~AnPnt room temperature curing composition which is produced by mixing the above described ~AI ,, A7tA and various additives in the absence 35 of moisture and storing in a closed vessel which is impervious to moisture. The composition is cured to an WO gsl33784 2 1 9 0 7 5 ~ 473 1--elastomer by e,-~uo~uLe to atmospheric moisture at the time of use when the package is broken.
.
The following non-limiting examples serve to illustrate 5 the invention.
Rlrl~MPr,~ 1 To 2000 grams (0.5 mole) of polyu~y,uLu,uylene diol having a molecular weight 4000 is added 174.5 grams (1.0 moles) 10 of toluene diisocyanate. The reaction is carried out in the presence of nitrogen in a 3L reaction kettle equipped with a mechanical stirrer and three neck lid. The mixture i8 heated to 80C for 1-2 hours in t~e presence of 2 26 grams DABCO catalyst solution (249~ in toluene), To the above obtained prepolymer i5 mixed 58 .1 g (1. 0 moles) of allyl alcohol in the presence of 9.3 grams DABCO solution and heated at 80C for 1-2 hours with ~nnt;nllml~ stirring. The completion of the reaction is characterized by disappearance of -NCO peak in IR and GPC. To the above obtained olefinic t~rm~n~t~-fl polymer is added 94.2 g (1.0 moles) of 1,2-ethane dithiol and 4.65 g ~ lh;~1~ubuLyLullitrile and heated to 80-95C for two hours with slow stirring to prevent vortex forr-t~nn.
The mercaptan content of the polymer is conf irmed by iodometric titration and the mercaptan equivalent weight is calculated. To the - - U~L~tall polymer thus obtained is added 267 . 5 g methyl vinyl bis (2 -butanone oxime) silane (1.05 moles, 955c assay) and 5.18 g ~7nh~ n~ yLullitrile initiator and the mixture is heated at 80-95C for 2 hours with continuous stirring. The nitrogen blanket i9 kept throughout the reaction. The M.W. of the polymer at different steps i9 flf~t~rmln~rl by GPC. The final polymer is moisture sensitive therefore is stored in a nitrogen flushed closed cont~in~r. The viscosity of the polymer ranges between 900-1100 poise at 23C (90,000-110,000 cps ) .

WO 95/33784 2 1 9 0 7 5 1 f~ 9' --473 i 13 R~MPT,~ 2 An olefin tPrmin~tP1 polymer is prepared following the procedure described in Example l. The pre-polymer i8 5 prepared from l, 100 grams of polypropylene glycol polyol with hydroxyl number of 28.8, 96 grams of toluene diisocyanate and 0.30 grams of DA~3CO. The olefin tP~n1n~tPd polymer is prepared by reacting the prepolymer with 33.6 grams of allyl alcohol and 1.20 grams of DA3CO.
10 To the above polymer, 102 . 0 grams of ethylcyclohexyldimercaptan and 2 . 4 grams of azobisisoluLyLu~litrile are added and heated for 4 hours at 80C to give mer.Gl.tall terminated polymer which is then reacted with 147 grams of methyl vinyl bis (2-15 butanone oxime) silane and 3 . 0 grams of~7nh;~;~nhlltyronitrile (radical initiator) at 80C for 4 hours to give oxime silane tPrm; n~tPr~ polymer.
~MDL~ 3 20 An olefin tPrm;n~tPd polymer is prepared according to the procedure described in Example 1. 1300 Grams of polypropylene glycol polyol with a hydroxyl number of 2~3.8, 130.5 grams of toluene diisocyanate and 0.36 gram of DA3CO catalyst are heated at 80C for 1 1/2 hours to 25 give isocyanate tf~; n ltPd polymer which is converted to ole~in t~rm;n~tP~l polymer by reacting with 43.6 grams of allyl alcohol and 1.26 grams of DA~3CO catalyst at 80C
for 4 hours . To the above polymer, 173 . 8 grams of ethylene bis (3 -mercapto propionate) and 3 . 0 grams of 30 azobisisobutyronitrile are added and heated at 80C for 4 hours to give mercaptan terminated polymer which is then reacted with 191 grams o~ methyl vinyl bis (2-h~lt:lnnnP
oxime) silane and 3.4 grams of azobisisobutyronitrile at 80C for 4 hours to give oxime silane terminated polymer.

wogsl33~84 2 ~ 9 ~ 75 i r~l,u.,_ ~473 Rlr~MPL~ 4 2,4-Toluene diisocyanate (0.123 moles, 21.46 gm) having 20~ 2,6-toluene diisocyanate i.e. TDI 80/20 and 0.33 gm 2496 solution of DABCO are added to polybutyl,~nF~
having a molecular weight 4878 (300 g, 0 . 0615 moles) under nitrogen atmosphere. The mixture i8 heated to 80C
for 1-2 hours. Allyl alcohol (7.15 gm, 0.123 moles, 9956) and 1. 31 gm DABCO solution are added to the above mixture and heated to 80C for 1-2 hours with rnnt;n~ c stirring. To the polymer thus obtained 18 added (146 gm 0.123 moles, 999s) 1,2-ethane dithiol and 0.51 gm 1c;cobutyronitrile and heated for 2 hours at 80-90C.
Finally (32.9 gm, 0.1292 moles, 9596) methylvinyl bis(2-butanone oxime) silane and 0.56 gm AIBN are added to the mercaptan polymer and heated for 2 hours at 80-90C. The polymer at different steps is characterized by IR, GPC
and volumetric titration. The viscosity of the 8ilyl terminated polymer is 100,000 cps at 24C.
2 0 ~MPT,R 5 To 300 gm (0.14465 moles) propyl~n~ p~nt~nP~l;ol and polyester polyol is added 50. 4 gm (0.2893 moles) toluene diisocyanate and 0 . 37 gm DABCO catalyst solution. The polyester polyol used has a molecular weight of 2074 and hydroxyl number 54.1. The mixture is heated to 80C for 1-2 hours in a nitrogen atmosphere. Allyl alcohol 16.8 gm (0.2893 moles, 99%) and 1.5 gm DABCO solution is added and heated for 1-2 hours at 80C Qith r ~nt;n~ llc stirring. 27.3 gm (0.2893 mole, 99i) 1,2-ethane dithiol and 0.59 gm AIBN is added to olefin terminatea polymer and radical coupling is carried out at 80-90C for 2 hours with slow stirring. To the mercaptan polymer thus obtained is added 77.4 g (0.3037 moles, 9596) methyl vinyl bis (2-but~none oxime) silane and heated for 2 hours at 80-90C. The polymer is characterized at ,1; ~f~r~nt steps by IR and GPC and the -S~I content in the mercaptan WO 9s/33784 ~ g~D'~73 terminated polymer is detPrml n~d by volumetric tit~ation.
The viscosity of silyl t~-rm;n~t~rl polymer is 140, 000 cps .
at 24C.
RS~Z~MPT.R 6 297.1 g (0.102 moles) polytetramethyleneglycol having 2914 molecular weight and 385 hydroxy number i9 melted at 60 and mixed to make a homogeneous liquid and to it is added 356 g (0.204 moles) 80:20 toluene diisocyanate and 0.35 g DABCO solution. The reaction is carried at 80C
for 1-2 hours in nitrogen atmosphere. To this prepolymer is added 11.9 g (0.204 moles) allyl alcohol and 1.45 g DABCO solution. The product is heated to 80C with r~nt;m~ stirring for 1 -2 hours. The allyl tP~;n~t~l polymer thus obtained is reacted with 19.2 g (0.2040 moles) 1,2-ethane dimercaptan and 0.55 g AIBN initiator.
The temperature of the reaction is kept between 80-90C
for 2 hours. Finally 54.5 g (0.2142 moles) 95~ assay methyl vinyl bis (2 -b~t~n~n~ oxime) silane and 0 . 62 g AIBN
2 0 is added and reacted at 8 0 - 9 0 C f or 2 hours . The 8 ilyl t~o~n;n~t~d polymer thus obtained is highly viscous (1 million cps at 24.5 C).
RXZ~MP~.R 7 A polythioether polyol, 300 g (0.15 mole), having hydroxyl nu~ber 56 and molecular weight 2000 is reacted with 52.4 g (0.30 mole) of toluene diisocyanate in the presence of 0.37 g DABCO solution at 80 C for 1-2 hours.
The prepolymer thus obtained is reacted with 17 . 4 g ( 0 . 3 0 moles) of allyl alcohol in the presence of 1.5 g DABCO
catalyst solution for 1-2 hours. 28.3 g (0.30 moles) of 1, 2 ethane dithiol and 0 .15 weight96 of AIBN are added and stirred slowly for 2 hours at 80-90 C. To this mercaptan t~rm;n~t~ polymer is added 93.6 g (0.367 moles, 959i assay) methyl vinyl bis (2-butanone oxime) silane and 0.15 w095l33784 2 ~ ~ ~ 7 ~ 1 r~llu~ J5~3 weiyht 96 AIBN and reacted at 80-90 C for 2 hours to get oxime tPrm;n~tP~ polymer having viscosity 220,000 Cp8 at 23 C. Nitrogen A ~ ,r'~~re i9 kept throughout the reaction process.
~ re ~Ate ComDarison Cure rate is compared for identical polymers with varying types of silane end capping. The mercaptan terminated polymer prepared as in Example 1 is divided into three 10 reactors designated A, B and C. The polymer in reactor A
is capped with methylvinyl bis (methoxy) silane, the polymer in B is capped with methylvinyl bi~ (ethoxy) silane and the polymer in reactor C capped with methyl vinyl bis (2-butanone oxime) silane as described in 15 Example 1 for ketoximino silane. The capped polymers are prepared as sealants to compare physical properties such as curing rates and strength by the f ollowing f ormu -lations and methods.
20FnrrmllAt;nn 1 COMPONENT WEIGXT
Polyether polymer of Example 1 30.00 Di-octyl rhthAl~te 24.50 CaC03 42 . 9 25Methyl tri (2-b~ltAnnnP oxime) silane 2 . 00 Amino propyl triethoxy silane 0.50 Dibutyl tin rl;lAllr~te 0.1 F lAt;nn 2 Polyether polymer of Example 1 30 . 00 Di-octyl rhthAlAte 24.50 CaC03 43 . 00 Methyl tri (2 -butanone oxime) silane 2 . 00 35Amino propyl triethoxy silane 0 . 50 ~ WO 95/33784 2 1 9 0 7 5 1 r ~ 473 To a dou-hle rlAn~t~Ary vacuum mixer are added the polymer and plasticizer. This is mixed under vacuum.
Precipitated calcium rArhnnAte is added and mixed under vacuum. Methyloximino silane and amino propyltriethoxy 5 silane (available as A-1100 from OSI) is added to the mixture. Mixing takes place under vacuum. The mixture is discharged into tubes for storage and further eVAlllA~ir,n, 10 Sealant is produced from each poLymer using the formula~
and methods in Table 1. Cure times, cure though rates and mechanical properties are measured and listed in Table 1. Sealant prepared by f ormulation 1 or 2 with ethoxy silane capped polymer fails to cure.

Tahle 1 M~-'IJ~ Tl"DT. ~K'VJ~ K`i POLYNER./Fr)~HrTT.~rTr-o A/l A/2 B/l B/2 C/l C/2 S~CIN OVEFc TI~3 210-300 1440-4320 No No 50 135 (Ninutes) Cure Cure TAC~tFREE~ TIMl~ 210-300 ~4320 50 160 (Minute~) TENSILE STRENGTH 1.8 No Cure 1.8 1.9 (N/mm2 ) -KT~ -- 250 250 260 (~) }~NESS 45 45 43 (SHOR~ A) 20 In the following examples, a number of other polymer hArkhrn~ are evaluated as starting materials for the silane addition methods and properties are noted as f ollows woss/33784 2 1 907~ s473 Forrn~ t ion 3 COMPONENT ~ WEIG~T
Polyester polymer of Example 5 30. 00 Aromatic hydrocarbon oll 24 . 50 CaC03 43 . 00 Methyl tri (2-but~nr,n.o oxime) silane 2.00 A- 1100 0 . 50 To a double rl ~n~t~ry vacuum mixer i5 added 30 parts by 10 weight polymer and 24 . 5 pbw o~ plasticizer. This i5 mixed for 2 to 5 minutes under vacuum. Precipitated calcium r~rhnn7te is added ar,d mixed for 15 to 20 minutes under vacuum. Methyloximino silane and A-llOO is added to the mixture . Mixing takes place f or approximately 15 five minutes under vacuum. The mixture is discharged ir,to tubes for storage and further ev~ tinn.
r l~tioL 4 COMPONENT WEIGHT
Polymer of Example 7 30.00 Alkyl aryl rhn~rh~te ester 24.50 CaC03 43 . 00 Methyl tri (2 -blltAnnn~ oxime) silane 2 . 00 A- 1100 0 . 50 To a double pl~not~ry vacuum mixer is added 30 parts by weight polymer and 24 . 5 pbw of plasticizer. This is mixed f or 2 to 5 minutes under vacuum . Precipitated calcium r~rhnn~tP is added and mixed for 15 to 20 minutes 30 under vacuum. Methyloximino silane ard A-llOO is added to the mixture. Mixing takes place for apprn~ tPly f ive minutes under vacuum. The mixture is discharged ir,to tubes for storage and ~urther evaluation.

~1 W0 95/33784 2 1 9 0 7 5 1 r~ 473 TAEjI-E 2 ME~'T-TANT~AT PROPRT~TIRq:
FORM. 2 FORM. 3 FORM. 42 FORM. 4 EXA~. 4 E~AM. 5 EXAM. 6 EXAM. 7 (Minutes ) (Minutes ) TENSILE STRENGTH 1.57 0.27 7.73 1.2 (N/mm2 ) (~) T~T~nNRqS 40 12 56 37 (SHORE A) 5 r l~t;on 5 To 50 parts by weight of the polymer of Example 6 is added 5 0 parts by weight of a ' ~ f j ~Cl cumene - indole resin (softer3ing point, Ring and rall by ASTM E-28 100C) at a temperature of between 150 and 200C. The mixture 10 is prepared as a sheet on polypropylene and allowed to cool . The sheet is allowed to cure f or 15 days at room temperature after which it is exposed to 100 C for 6 hours f ollowed by an additional 9 days at room temperature. Tensile properties are as follows: tensile strength - 15 N/mm2; elnn~t~nn - 790~, hardness ( Shore A) -17 .

wog~l33784 2 1 9075 t ~ ~473 Formulation 6 Polyether polymer of Example 2 40 . 00 Di-octyl phthalate 14.50 CaC03 43 . oo Methyl tri (2 -butanone oxime) silane 2 . 00 A-1100 0.50 To a double planetary vacuum mixer is added 40 parts by 10 weight polymer and 14 . 5 pbw of plasticizer. This is mixed for 2 to 5 minutes under vacuum. Precipitated calcium c~rhnn~te is added and mixed for 15 to 20 minutes under vacuum. Methyloximino silane and A-1100 is added to the mixture . Mixing takes place f or approximately 15 five minutes under vacuum. The mixture is discharged into tubes f or storage and further evaluation. Beads of sealant are applied to glass and ~ m; nl-m substrates and allowed to cure at ambient conditions f or 7 days . Adhe -sion testing consists of an initial starting razor cut at 20 the substrate adhesive interface. Force is applied at 45 and 90 by hand and the failure mode evaluated visually. Adhesion is ranked on a scale of 1 to 6 with 1 being no ;~flhf-~linn and 6 being cohesive failure at both tensile force angles. The samples are then exposed to 25 boiling water for 15 days and re-tested using the same method. The sample consistently exhibits partial cohesive failure at 45 tensile pull and 100~ cohesive failure at 90 pull.

~E GLASS ALUMIN[~M GLASS ALUMINUM
Formulation 6 5 5 5 5 ~ WO95/33784 21 90751 r~ 9 ~473 ti orl 7 Polyether polymer of example 3 30 . 00 Di-octyl rhth;-l~te 24.50 CaC03 43 . 00 Met~yl tri (2-butanone oxime) silane 2 . 00 A- 1100 0 . 50 To a double planetary vacuum mixer is added 40 parts by 10 weight polymer ard 14 . 5 pbw of plasticizer. This i8 mixed for 2 to 5 minutes under vacuum. Precipitated calcium carbonate is added and mixed for 15 to 20 minutes under vacuum. Methyloximino silane and A-1100 are added to the mixture. Mixing take~ place for apprny;l"-tply 15 f ive minutes under vacuum. The mixture is discharged irto tubes f or storage and further ev~ t; nn . The sample is cured for 7 days at room temperature and tensile properties dPtPrm;npA by DIN 53504 type s2 and Shore a hardness by ASTM C- 661.
Fn~mll At; nn 3 COMPONENT WEIGHT
polymer of Example 1 30.00 Di-octyl rhth~l Ite 24.00 25 CaC03 43 . 00 Moisture s~ v~llger:
Oxzolidir,e (Angus Chemical) 3 . 00 3-ethyl-2-methyl-2- (3-methyl butyl ) -1, 3 - nY~ 7~ ; n-~
To a double rl~n~-t~ry vacuum mixer are added the polymer and di-octyl rhth~l~te, This is mixed for 2 to 5 minutes under vacuum. Precipitated calcium carbonate is added and mixed for 15 to 20 minutes under vacuum. The 35 moisture s~c.v~g~:~ is ther. added to the mixture. Mixing takes place f or approximately f ive minutes under vacuum .
_ _ _ _ _ .. . ..

W0 9s/33784 2 1 9 0 7 5 ~ 0s473 ~
The mixture is discharged into tubes ~or storage and further evaluation. Sealant is produced from each composition and the mechanical properties are measured and listed in Table 3 below.

TA~31~E 3 Polymer From Formul . 6 Formul . 7 Formul . 8 Example 2 Example 3 Example 1 Skin Over Time 100-150 80-100 300 (Minutes ) Tackfree Time 100-150 80-100 300-1,400 (Minutes ) Tensile Strength 2 . 3 1. 3 2 . 2 (N/Mm.2 ) Elongation 440 540 750 (~) Hardness 41 25 20 (Shore A) lor-- lAt;nn g CU.I~UN~1 WEIGHT 9 Polyether polymer of Example 1 49.50 Di-octyl rhth~le,te 9.90 Precipitated hydrated alumina 24 . 75 15Titanium dioxide 14 . 85 A-1100 0.99 Solvent cnmrnn~nt parts per hundred mixture:
Methyl chloro~orm 40 To 49.5 g of polymer is added 9.9 g of dioctyl ~hth~1~te and combined at medium speed with a high shear dispersing blade. To this mixture 24 . 75 g of alumina trihydrate and 14 . 85 g of titanium dioxide are cn~nhi nPrl at medium shear -~I W095/33784 21 ~ 0 7 5 1 I~ r 473 for 5 minutes using a high shear blade. 0.99 g of amino ethoxy silane is addefl and mixed for 1 minute at medium speed. Apprn~rim~t~ly 40 parts per hundred of methyl chlorof orm was added to the m~cture to obtain a f lowable 5 vi3cosity. Aluminum sheet cleaned with hexane is coated with the mixture to a uniform thickness. The surface is tack free between 120 and 140 minutes after application.
A 1/8 inch thick sheet of coating i8 prepared by casting the c , uulld in a mold.
Tack free time 120-150 minutes Tensile strength 3 . 6 N/mm2 Elongation 260 Shore A hardness 42 Bend Pass - no rr~rk; n~
~ XAMPLE 8 A 1 liter three neck reactor flask fitted with an 20 overhead stirrer, th~rmnm~ter and addition funnel is charged with 17.5 grams of toluene diisocyanate (O.lOM) and heated to 80 to 90 C. Polypropylene oxide diol with average molecular weight of 4000, ~200 gm, 0.05M) is added slowly. The reaction mixture is refluxed at 80 to 25 90 C for 2-4 hours and the ~IU~L~ of the rnn~lPnCAtlnn is monltored by infrared spectroscopy. 2-mercaptoeth ( 7 . 8 gm., O . lOM) is added slowly to the reaction mixture and refluxed at 90 to 100 C until the infrared spectrum of the pot sample shows no isocyanate absorption at 2265 30 cm~1 Methylvinyl bis(methylethylketoximino)silane (31.3 gm., O . lOM) and AIBN (460 mg) are added to the mercapto t-~rrnin~t~cl polyol and refluxed at 85-90 C for 3 hours to give an oximesilane tPrmin~ted liquid polyol polymer.

WO 95/33784 2 1 9 0 7 5 1 ~ ~~473 RX Z~MPT ,R 9 Example 8 i9 repeated except 3-mercaptopropanol ~92 g, 0.10M) is used. Similar results are noted.
5Fn ~m~ t ion 10 COMPONENT WEIGHT
Polymer of Example 8 or 9 30.00 Di-octyl rhth~1 ~te 24.50 CaC03 43 . 00 10Methyl tri (2 -b~lt~nnnp oxime) silane 2 . 00 A- 1100 0 . 50 To a double planetary vacuum mixer are added 30 parts by weight polymer and 24 . 5 pbw of plasticizer. This i8 15 mixed f or 2 to 5 minutes under vacuum . Precipitated calcium carbonate is added and mixed for 15 to 20 minutes under vacuum. MethylnY;mlnn silane and amino propyltrimethoxy silane (Available as A-1110 from Union Carbide) is added to the mixture. Mixing takes place for 2 0 approximately f ive minutes under vacuum. The mixture is discharged into tubes f or storage a~ld ~urther evaluation with the following results.
F 1 e 8 Pol --- r 1 e 9 Polymer Strain at Max. Load 370 270 Maximum Stress 1. 3 1. 6 Skinover Time 93-106 min. 120-150 min.
Tack free Time 107-116 min. 120-150 min.
Shore A Hardness 30 46 ~ =

Claims

What is claimed is:

1. An oximinosilane terminated polymer having the formula and having an average molecular weight of at least 1,200;
wherein R is an organic polymer having a backbone of polyether, polythioether or polyester, R1 is a divalent organic radical, R2 is an alkylene group having at least 2 carbon atoms, X is 0 or NR6 where R6 is either hydrogen or a monovalent lower alkyl group, Y is sulfur or S-R7-S
where R7 is an alkylene thioether having 4-12 carbon atoms, alkylene having 2 to 10 carbon atoms, or a substituted cyclohexyl ring group having the formula:

or R3 is an alkyl radical of 1 to 7 carbon atoms or an alkoxy radical of 1 to 6 carbon atoms and R4 and R5 are independently a saturated straight chain or branched alkyl radical of 1 to 7 carbon atoms or R4 and R5 taken together form a cyclized group, p is 2 to 3, m is 0 to 2, n is 1 to 3 and the sum of m and n is 3.

2. The oximinosilane terminated polymer of claim 1 wherein R is hydroxyl terminated polymer selected from the group consisting of polypropylene oxide polyols, polybutyleneoxide glycol polyols, polytetramethylene glycol polyols, polyester polyols, polythioether polyols, polyalkylene glycol co-polymer polyols, and polyalkylene glycol-polyester copolymer polyols.

3. The oximinosilane terminated polymer of claim 1 which is a liquid having a molecular weight in the range of from about 1,200 to about 100,000.

4. A composition comprising:
a.) the oximinosilane terminated polymer of claim 1 in an amount o from about 5% to about 90% by weight of the composition; and b.) a moisture scavenger in an amount of from 0% to about 5% by weight of the composition; and c.) a plasticizer in an amount of from 0% to about 50% by weight of the composition; and d.) a filler in an amount of from 0% to about 75% by weight of the composition.

5. A method for the production of oximinosilane terminated polymers having the formula and having an average molecular weight of at least 1,200;
wherein R is an organic liquid polymer containing a backbone of polyether, polythioether or polyester, R1 is a divalent organic radical, R2 is an alkylene group having at least 3 carbon atoms, X is 0 or NR6 where R6 is either hydrogen or a monovalent lower alkyl group, Y is sulfur or S-R7-S where R7 is an alkylene thioether having 4-12 carbon atoms, alkylene having 2 to 10 carbon atoms, or a substituted cyclohexyl ring group having the formula:

or R3 is an alkyl radical of 1 to 7 carbon atoms or an alkoxy radical of 1 to 6 carbon atoms and R4 and R5 are independently a saturated straight chain or branched alkyl radical of 1 to 7 carbon atoms or R4 and R5 taken together form a cyclized group, p is 2 to 3, m is 0 to 2, n is 1 to 3 and the sum of m and n is 3; the method comprising:
a.) reacting an isocyanate terminated polymer having the general formula:

with an olefin alcohol or amine in which the olefin group is seperated by at least one carbon atom to give olefin terminated polyether polyol;
b.) reacting the olefin-terminated polymer with a dimercaptan in which the mercaptan functionality is separated by an alkylene, alkylene ether, alkylene thioether, alkylene ester or substituted cyclohexyl rings to give a mercaptan-terminated polymer; and c.) reacting the mercaptan terminated polymer with a component selected from the group consisting of vinyl oximino silane, vinylalkyloximino silane, vinylaryloximino silane, vinylalkylalkoxyoximino silane vinylalkoxyoximino silane and vinylarylalkoxyoximino silane.

6. The method of claim 5 wherein R is a hydroxyl terminated polymer selected from the group consisting of polypropylene oxide polyols, polybutyleneoxide glycol polyols, polytetramethylene glycol polyols, polyester polyols, polythioether polyols, polyalkylene glycol co-polymer polyols, and polyalkylene glycol-polyester copolymer polyols.

7. The method of claim 5 wherein the dimercaptans are selected from the group consisting of 1,2-ethane dithiol, 1, 6-hexane dithiol, 1,10-decane dithiol, 2-mercaptoethylether, 2-mercaptoethylsulfide, glycol dimercapto acetate, glycol dimercapto propionate, p-methane-2, 9-dithiol, ethylene bis (3-mercapto propionate) and ethylcyclohexane dithiol.

8. The method of claim 5 wherein the vinyloximino silane or vinylalkoxyoximino silane has the formula,

9. A method for the production of oximinosilane terminated polymers having the formula and having an average molecular weight of at least 1,200;
wherein R is an organic liquid polymer having a backbone of polyether, polythioether or polyester, R1 is a divalent organic radical, R2 is an alkylene group having at least 2 carbon atoms, X is 0 or NR6 where R6 is either hydrogen or a monovalent lower alkyl group, Y is sulfur or S-R7-S where R7 is an alkylene thioether having 4-12 carbon atoms, alkylene having 2 to 10 carbon atoms, or a substituted cyclohexyl ring group having the formula:

or R3 is an alkyl radical of 1 to 7 carbon atoms or an alkoxy radical of 1 to 6 carbon atoms and R4 and R5 are independently a saturated straight chain or branched alkyl radical of 1 to 7 carbon atoms or R4 and R5 taken together form a cyclized group, p is 2 to 3, m is 0 to 2, n is 1 to 3 and the sum of m and n is 3; the method comprising:

a.) reacting an isocyanate terminated polymer having the general formula:

with a mercapto alcohol in which the mercaptan and the hydroxyl groups are separated by at least two methylene groups to produce a mercaptan terminated polymer; and b.) reacting the mercaptan terminated polymer with a component selected from the group consisting of vinyl oximino silane, vinylalkyloximino silane, vinylaryloximino silane, vinylalkylalkoxyoximino silane vinylalkoxyoximino silane and vinylarylalkoxyoximino silane.

10. The method of claim 9 wherein R is a hydroxyl terminated polymer selected from the group consisting of polypropylene oxide polyols, polybutyleneoxide glycol polyols, polytetramethylene glycol polyols, polyester polyols, polythiother polyols, polyalkylene glycol co-polymer polyols, and polyalkylene glycol-polyester copolymer polyols.