CA1098246A

CA1098246A - Cured abrasion resistant coatings of epoxy-silanes

Info

Publication number: CA1098246A
Application number: CA246,677A
Authority: CA
Inventors: Mohammad S. Nozari
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1975-03-07
Filing date: 1976-02-26
Publication date: 1981-03-24
Also published as: SE7602448L; DE2609148A1; SE425501B; IT1064113B; BR7601347A; AU1172676A; AU503610B2; IL49108A0; GB1546887A; IL49108A; US4049861A; DE2609148C2; CH605122A5; JPS51126222A; ES445816A1; FR2303055B1; MX147060A; JPS611476B2; FR2303055A1

Abstract

ABSTRACT

Abrasion resistant coatings comprising epoxy-terminated silanes cured in the presence of high fluori-nated aliphatic sulfonic and sulfonylic catalysts are solvent and abrasion resistant.

Description

~:i.le 911,811 Abrasion re~i~tant coatin{~ bave 6~n~r~11y ~n u~ed to protect agaln~t ~ur~ace dama~e to ~ub~tr~ or exampl~ 3 optical ~ 99 are ~oat~d to prev~t ~ar~ln~ or ~cratchi~ o:f the l~n8 ~ur~ace. ~h~o ab~a~lor~ ~sl~ta21t coaklng~ ar~ ordlnarily thin coakin~;s o~ pla~ic ~ur~d ln 81~GU a~ a coatln~s on ~he sub~trate.
Many compo~itlo2ls and methods have be~n previou31y sug~,e~3ted ~or applyln~ abra~ion r~ tan~ coatln6~ ~o dam~gea~le ~ubstra~es ~ ~ut ~aoh . ~ur~ers ln ~ dir~ere~t ~ashlon. Sosne compo~itlons provide only minlmum imprQ~-mont13 in abra~lon re~l~tanc~ whil~ ther~ ar~ no'c pra~ti~able b&cau~ ofb ~xtreme proce~ing condltiolls or ~xc~ ,ro: GO~
For example ~ ~ome o~ th~ modastl~ succe~rul ~,tlng~ r~qu~re .
cure t~mperature~ of about- 150C or mor~ ~ur ~ nd~d p~riod~
`
o~ tlme. Such pr~cedure~ ~re li~ E18 ~or oo~t~g i~Rg~abl~
materlal3 ~u~h as photocondu~tî~re ~heet~ and ~}~e~tr~p~oeo-graphic 3heet~s a~ well a~ any t~mperature ~en~ltiv~ ~ub3trate ~uch a~ ~herTn~pla~tic materlal~c Even ~or ~oatln~ ~h~rmo ~ettîn~ polymer~ ~uch eonditlons cau~e w~rpine asld deoom~
posltionO
Earller methods ~or lrnpartin~; abra~;lon re~1~tanc~
~ncluded vapor deposltion o~ lno~;anic mat~rlal~ 6~, :
metal oxld~ %uch as ~12 ~ Zr2 ~ ~tc . ~ Oth~r inorl3;an1c mat~rïal~ used~ ror abrasl-on re~1:3tance coating~ ar~ di~-closed in U.S~ Patents 2~768,909 and 3,460,956. The ~ormer patent dî8C108~EI coatlngs up to 1 mlcron in thickn~ 0 hydrolyzab~. metal or~;anlc e~t~rJ3. l'hick0r c~atings are de~crlb~d a~ unde~ ra~l2 becau~ r~ductîon in tr~
parency, c~he~lon 3 and adhe~l~sn . Other coati~ bo ~ ~ncrea~
3,~ abra~lon re~i~tance lnclud~ or~anlG re~in~ and organlc~

-i~organia bl~nd~ such a~ ar0 described ln U ~ ~ . P~t~nt~

2~4~ 0~; 333~4"05~; 33~7~399~; 3,632,7~5; 3,64

3,708,22$, and 338i7~905.
~llicone polymer~ hav~ b~n lrlv~sti~;~t~d 5 abrasion r~ t coa'cln~, bul; o~t~n ~u~r rr~m brittlene~s, ~oltsen~ ~en~lviby ~nd ~oat~ n~ dl~rioultl~ ~
Ambl~unctlonal ~llicone polymer~ ~uch a3 vlnyl~ poxy-~ontalnilng ~llan~s ha~ al~o been u~ed ln ~n atJc~pt to 6Dveraom~ ~h~ d~ cult~ e~, bu~ only ~ith r~ar~inal :
lG ~uc~e~
o~ @xampl~3 Japa~ Pa~ent ~i~) No.
49-11752~ su~d Nove~sr g, :1~74 ~ ~ugge~t~ l;h~
.
~ ~p~xy~ilane a~ an abra~lon re~F3tant~ ~atin~ by ~or~nlng a pr~cond~n~ate ~r ~n epoxy~ d ~adlng ~ a~
c~galy8t ~ m~ r~a~ e~e~ rr~m~ ~s~4~ SnF4 ~r C~13~H~
NH2BF2 (~fhe2~e n 1~ 0 or~ l)o 'rhe ~ethod and co~o~ o3-s ~hown ln that re~renc~ L3 hlghly: abraaion ro~l~t~nt, but the polymer i~ no'G ~omple'cely cu~ed by th~ proce~
.;
'6augh~ ln th~ dl3cl0~ure ~2la 19 sub~t to ~F~ ol-~0 v~ at~ack~ i8 bell~e~ ~hat th~ proc~ h~n ~pp~ar3 to predo~ninat~ly cur~ onl~r on~ c~lonal 6roup of the ~p~xy~ lan~ or ~ure on~ gro~ ~ar mor~ ly ~han the o~her ~o that &` dual p~lyD~r ne~rork ~r poly-siloxane atl~ poly~poxld~ ) 18 ~ot fo~d D: :
- 25 U.8. PaOerlt~ 3,6379416 a~d 3,7~2.98i ~1~0 show cur~d epox~ 8~ e8 ~ alld these ~aterl al~ ar~ n~lther highly abra~lo~r~ ant nor ~olYent r~ t~r~t~
Th~ ¢ured product~. o~ ~h~ pr~ent ln~ 1;lon ha~e b~th ~ p0~yepQ~c:Ld~ chai3~ ar~d a p~ly~lloxane ba~k-30 bQns wlthlrl ths polymer ~tructur~0 Th0 ch~1n and 32~q~

backbone inc]uding the respective f~nction~l ends of the epocy-silane. The crosslinked polymeric products of the present invention show excellent solvent resistance to water, toluene, acetone, octane and various other organic solvents.
The present invention overcomes many of the disadvantages of the prior art.
The coatings useful in the practice of the present invention are rapid curing, highly abrasion resistant, capable of room temperature cure~
and resistant to corrosives and solvents. The low surface energy of the 10 cured coatings further prevents aclherence of foreign rnaterial to~ the surface.
These coatings may be used as protective coatings on a wide variety of sub-strates, including metal, glass, wood, ceramics, natural and synthetic polymeric materials, etc.
Accordingly, the invention provides an abrasion resistant coating on a substrate, wherein said coating is from 0.1 to 500 microns thick and `~
comprises a polymer cornprising (a) at least 15 percent by weight of units from an epoxy-terminated silane represented by the formula / \ . ~ ' CH2- CH ( R- ~ Si -~OR') O' / ~~
~ > ~ R ~ ~ OR')3 wherein R is a non-hydrolyzable divalent hydrocarbon radical of less than 20 carbon ato~s, or a divalent radical of less than 20 carbon atoms the back~
bone of which is C atoms which may be interrupted by individual atoms from the group of N and 0, the O atoms in the form of ether linkages, n is 0 or l, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula _ 3 _ %~

(CH2CH20)kZ in which k is an integer of at least 1, and Z is ~ ~ .
hydrogen or an aliphatic hydrocarbon radical of less than 10 ..
carbon atoms, and (b) up to 85 percent by weight units derived from ; materials copolymerizable with epoxy or silane groups; the .
silane being cured in the presence of a catalytically active amount of a highly fluorinated aliphatic sulfonylic or highly fluorinated aliphatic sulfonic catalyst~ a sulfonic catalyst comprising a highly fluorinated aliphatic sulfonic acid or ;:
salt thereof and a sulfonylic catalyst comprising a compound containing two highly fluorinated aliphatic sulfonyl groups attached directly to an i.mide or methylene group. :
Certain fillers, especially silica, may~be added in weight percentages of up to 50% and more, so these materials ~ :.
are not considered in the weight percentages of the polymer compositions. The coatings are from 0.1 to 500 microns, yet .
retain pre~erably ~-20 microrls.

~':

, ~

- 3a -~' ~. .

1. ) EPOXY TERMINAT~D ~II.ANES
Epoxy-termlna'G~d ~ilane~ ar~ compound~ or materlals having polymerlzable (pra~rably terminal~ epoxy, group~ and t~rminal, polymerl~bl~ 5112n~ grOllp8, the ~rldging o~ the~
5 groups belng through a non~hydrolyzable al~pha~i~ 9 aroDIa$1c, or alîphatic and arom~ttc dlvalent hydracarbon linka~ whl~h m~y have N an~or O i3tom~ ln th~ liLnk~ge rhaln. ~he O atom~
~or e~ample ~ould be wlthln the oh~,ln only a~ e~her linkage~.. .
The~e llnka~ ehalns may be generally~ ~ubstl~tuted a~ i9 well 10 ~n~wn in the art, a~ th~e ~ub~itu~nt~ on the chain do not ~r~atly aP~ect the funotlonal abillty o~ the ep~xy ~ 'cermlnated .

~ilane~ to und~r l~h~ entlal rea¢tion~ neGessary t~ poly-meri~atlon ~hroug~ th~ loxan~ or ep~xy ~mln:~l g~cup~. -Examples Or 3ubs'Gltuenta whl~ch ma~.be Pr~n~ on ~th~-~linkag~
15 or brld~in~ moietie~ ar~ ~roup~ s~ch a~ NO?~ CH3~CH2)n~H2~, methoxy~halog~n~ etc~ In general ~tru~t~al~ ~or~u~e appearln~ wlthin thl~ deso~lp1;i~ r ;~he inv~h1;10n2 ~uoh ~ubstitutiorl Or ~h~ b~id~3;1n~ moleti~s i~ d~s~

~peci~iGally ~x~lud~d by langlaa~such a~ "un~u~a~ltuk~d 20 dlvalent hydrocarbon radlcal~
E~ les ~r pre~erred ~poxy-termina~ed use~u~ ~n ~he pra¢tlce Or thl~ lnv~n~l~n ~ar'~ o~, l;he gener~l ~ormulae: .

25 [CH~-CH~R~Sl~OP~' )m and [Q\O ~R~Slt0 where R ~ a non-hydrolyz~le dlval~nt hydrocarb~ ,d~
(aliphatlc g, aromatic, or allpha~ and aroimatlc ¢o~tQlning) of' le3~1 th~ 2û carbon atom~ or a dlval~nt ~ r~ical o~ le~
than 20 carbo~ at~m~ compo~ed o~ C, H, N, S " an~ O aksms (th~e atom~ are the only atoms whlch may app~ar in-th~ ~:
backbone oP the d~ valent radlcal8 ~, the la~ in~ th~
form o~ ether 1:~ nkage~ ~ N0 two hete~at~ may b~
ad~ a.cent w~ thin th~ backbone o~ th~ dl~al~nt hy~r~ar~n :
radlcalO Thl~ de~cripti~n de~îne~ dl.~a,l~;lt hydr~c.~n radical~ ~o~ ~po~y termi nated 3il0~can~8 ln the p~sti~
~i` 'ch~ lnverl~Gion. The valu~ Or i~ i~ from 0 t~ 1, R'~
a~ aliphat~ c hydrocarbon r~lc~l 0f~ 1~8~ ~ha~ 10 ~rborl :
at~ms " an acyl radlcal ~ ~ lees th~n 10 car~an ~oaF~ , or ~
a radioal ~ rmula (CH2CH20)~CZ ln tlrhlah k i~-.an lnt~ger : l.S ~:t ~t lea~t 1 and Z ~ iB an aliphat:ic hydroclrbon ra~
Or le~ than 10 aar~n at~ml3 ~r h~dr~n" m has valu~
1 t~ 3.
~h~ a~mp~tlon~ ~mpl~ged in thi~ isltri~D~n ~a~l b~ ep~xy ~llane ~r th~ abov~ ~'ormula ~ n w~loh F Y
2U dlval~nt hydrocarbon radi~al such ~3 methyl~ne 9 ethyl~ne d~calexle~ phenglen2, cycloh~2cyl~n~, cycl~p~n'cyl~n-3 m~thylcycl~h~ylene-3 2-e~hylbll~syl~n~ " and allen~ or ~ an e~h~sr radl cal ~u~h a~ H2-CE~2-0-CH2 ~ CH2 , ~CH2~CN20~2-CH~ C~ {} 0 CH~-CH2 and -CH2~- ~ CH2 ) 3 be any allphatic hydro~rbon rad~oal; o~ 1~8~ than lU
ca~bon atom~ s~ch a~ m~thyl, ~thyl, isopr~pyl, butyl;
vlnyl, alkyl~ or any acyl r~dic~l o~ than ~ rb0n a1;o~ ~uch as rormylj a~etyl, pr~plonyl, or any ra~llGal ~ ~ri~he ~crmu}a ~¢~I2CH;~0)~ ln ~hlch k 1Z~ an lnte~r oP
at l~a~t 1~, ~or example 2, 5, and 8, and Z ~s~h~dPo~;en .
--5~

or any ~liphatic hydrvcarbon radi¢al o~ 1e~B ~harl lO sarbon at~m~ ~u~h aa methyl, ~thyl 9 leopropyl " b~tyl, vir~yl and a:Llyl O
In add~tl~n to any ~r ~h~ aboYo ~ilane~ th~
5 compo~ition~ his in~n~lorl c~n belany hydroly~ t~ ~r prec~nden~ate o~ 'ch~s ~ald ~llar~e~O These hydr~ly~ate~ ¢an be ~orm~d by the partial or c~mplet~ hydrolysl~ ~ the sllane OR' e~roup~O ~hu~ the ~erm preaonden~ate ~nclud~s siloxane~ ln whlch some or all ~ the ~illcon ato~3 ar~
10 bQnded knr~ugh QXyg~ll a~omsO The ~llowlng c~mpound~ are iïluetrative Or ~me o~ U8~ mater~ ale in the pro~0~ o~
t~ inYentl~n and ~hould not be ~on~trued a~ ieing the inventi~rl which i~ properly explain~d abo~re:
',' -6- :~

l~9B24~i ~

H2C - CH-CH2-O-CH2-CH2-si(OET)3 :

H2C - CH-CH2-CH2-Si (OOCc~3) 3 H2C - CH-CH2-CH2-Si(OcH2-c~-I=cH2) O
~ H2C~- CH-Si(OPr)3 ; ~
O
:~ J ~CH ~ - Si(OCH2CH2~H)3 :',`~:

~ ~ H2C - CH-(CH2)3-Si[O(CH3CH20)5CH3]3 :: :
: :~-:
O~

~; ~ H2C - CH- ~ Si(OcH3) ' Q~7~
~ - -CH2-CH2-Si(OcH2cH20cH3)3 ~ `:
:

O
(CH2=CH) - Si(CH-CH2)3 O~ ~' Si(CH-CH2)4 .~

~D

.

.

%~

o : :
CH2!CH~CIJ2-CH2-Si (OMe)3 ~, ~ti3~c~2-cH2-cH~ -CH2~i (OET~3 ~ H 3 113 ~H-CH2- CH2-Si (OMe)3 ~113 ., /~2 ~CH \~ - Sl (OMe) \CH: /~H2 ~l2 ' :

H2C/-~H -C~2- cN2 - sl ( oMe) 2 ~

The~ preparation of most of the above~ compounds : have been descrl~bed ~n the U.S, Patent 3,131,161 2 . ~ US E FU L MOa I ~ I E R5 The basic abrasion resistànt ~oatlng of th~s ~nventi~on ~s ~rmed ~rom ~a:n epoxy-term~na~ed :s~lane~ :
~: such as the ones ~:llustrated above and a~ highly fluorl~
nated aliphatlc sulfonic or sul~onylic~ catalyst~ Th1s;
basio composit~on, haweve~r, can be~mad~ied wit host of other copolymer:s, add~tlves, and moisture sens~
:
tive compounds wh~ch can form a t~ht matr1x w1th the ~:

.

, epoxy sllanes ~o glive abrasion resistant coating. Some of the modlfiers include~
a. ) Moisture Sens~tiYe ~ompounds Capable of Formina a T1aht Matrix wit~ Epoxy Silanes These include compounds with the general formula of RnlM(OR' ~n ~n wh~ch M ;s S~, Al, Zr, or Ti, ~ is a ~ydrocarbon group of less than 10 carbon atoms or a group composed of hydrogen, carbon . and oxygen o~ 1 ess than 20 carbon atoms. R' is an alkyl or acyl group o~ less than 10 carbon atoms, m has Yalues of 0, 1, 2 and 3 and n -:
correspondi ngl y i s 4, 3, 2, or 1 . These compounds may be used ~n a precondensate form or in some ~nstances ~n the monomeric ~orm. These compounds form a tîght matr~x with epoxy s11anes to 91ve abraston r~s~stant coat~ngs.
The followi.ng compounds are~ ustrat~ve o:~ the type of mo1sture sensiti~ve materlals~ th~t can be used ~n t~e ; ;~, process of this inventîon Si(OET~4, CH~351(0ETi3. (CH3i25~l0ET~2~ ~H~3~35l( (CH3SCH:2~2)3-S~OC23~5~ C6H55~(~ET~39 SH2-CHsitoAc33s ( 6H5CH2scH2~H2)2si(oMe)2~ ~u3c~iHsscH2(cH3)cH si(oc2H ~ ~:
CH2-CHCOOlCH2)3~ Sl(OCH)3, ~H2-Ctl(C7H~)COO~H2 51(0C2H5)3,~
C4H90~4 Tl, T~C3H7~4~ A1~C4Hg)3, (C~H5)z Al(OC2H5), ~C3H70)4Zr.
b.)~ 3~
The dlsulfone ca~lys~ work:~es~ on cation~-:
: f cally polymer,zable conlpounds, thus ~he other copolymeri~
zable materials most use~ul in the ~pro~ess of th~is ~ -i nv~nt~ on are those 11 n whi ch the comonomer i s ca~pabl e ~:
of cation~c polymerlzat10n such as styrene, methyl styrene, vinyl amides and v~nyl ethers. The best /
~ 9_ ' 3~8;~ ~

compounds, however, are the epoxy compounds su~h as 1 ,4-butanedlol d~glycid~yl ether, d~glyeidyl ether of bis-phenol A, and d ~ COOCH

5 These compounds may be copolylner1zed with the epoxy termlnated silane and a moisture sensitive compound contai ni ng Sl, Al, T; or ~r . In ~eneral al 1 compounds that can be copolymer~zed wlith an epoxy or silane func-tionali~y are useful in the process of thls inv~ntion.
o. ) Addit7ves Varlous additi~tes such as dyes~uffs, P~ne metals, metal ox~es~ conduct~ve mat~rials, 1~Y~1~n9 agents, flow contrsl agents, U.V. abs~rbers, functi~nal mater~als such: a;s magnet:~c~part~:cles,~ and many bther 1~ specit~o ma~er~als which serve a ~tven purpose can~ be added to the b~aslc r~sin sxstem to obtaln the d~s.~r~d properties. There ~s however, th~ one lim1tat~on :that~
the addit~ves c~nnot be basic materlals which would -neutral~ze the disulfone cata1yst and slow down ~the 20 react~on rate signi~icantly.
3 ~
The catalysts use~ul accordl ng to the broadest aspects of ~he pr~sent ilnvent~o~l areh~ghly fluor~nated alipha~c sulfonic a7ld sulfonyl~c comp~unds.. The~
, 25 sul~on~c materials are de~ined as a h~ghly fluor~nate~
al i pha~i c sul font G aci d or 5al t thereof . The sul fonyl i e . ~
mater~als are defin~d as ~a compound ~eo!)tain1ng two~ highly fluorlnated al~phat~c sulfonlrl groups attached directly to an imide or methylene (e.g~, -NR' ~r -C~'R").. ~he 3ulfonlc materials ma~/ be ~a~tiall~J represented by the ~ormula ( ~ 3 n wherein ~ is h,yclrogerl, am~onil~ cation or metal cation and n is t~e valence of ~.
'.rhe sulfonylic catal~sts may be partially represented by the ~ormula (RfS02 )-Q(~'~02R ~ ) :
wherein Q is a divalerlt radical selected ~rom ' ~B N9 , -CR'R" and -~ChR3 wherein ~" is selected from h~dro~en, chlorine, bromine, iodine, ~f~2-~ alkenyl o~ 3-4 carbon ; atoms, alkyl D~ 1 to 20 carbon atoms (pre~er-: ably 1 to 4), aryl of l to 2n carbon atoms ~ re~erabl~J~to~lO~and rOr exam~le, ~henyl,~ ~ ;
naphthyl, pyridyl,~benzthienyl~ etc~ and ~ :
al~ar~l of 7 to 20 carbon ato~s ~pre~erabl~
: to 1~), R' is selec~ed from hy~roF7en, Ghlorine, br~omlne, iodlne, ammonlum cat~ons or metal catlons~ :
:
and R3 is IT, alken~l (3 ko 1~ carbon atomst or aryl up to 20 carbon a~ms.
he catalysts wherein the N or~C atom honded ~o the hl~hly ~luorinated aliphatic (pre~erably:alkyl) ~roup has a ~ :
hydrogen atom bonded~thereto are actlve catalvsts. Those havin~ no hydro~en atom are laten~ and may be activated by heatl ac.ld, chelating a~ent or comblnation~ thereo~
as later exemp~lfied.
Metals use~ul in the above derinitions essen-- -tially includes all metals. ~11 metals inclusive of and :

~ 6 to the le~t of al~lnum, germ~nium~ ~ntlmony and pol~nlum on the periodic chart o~ th~ elements, and the rare earth metals can func~ion in the practice o~ this lnvention.
m e group Ia and IIa metals must be activa~ed by ~c~ds and heat or chelatlng agents and hea~3 but they are functional.
Examples o~ many metals~ includin~ lanthanum~ are provided to show tha~ all metal~ wlll work, even thou~h some would be commerc~ally use es~ becau~e o~ expense. Pre~erably the met~l~ would exclude elements 59~63, 65-71~ ~d tho~2 above 89.
Accordi~g to the Pe~lodlc T~ble in Adv~nc~d ~-9~ . h~ml~Lrl, Cotto~ ~nd ~ n~on, 2d~ Ed~ ~n~e~- ~
science publisher~3 1966y more pr~rred m~tal~ would be those o* ~roups9 I~, IIa,~Ia, VIII3 Ib~ IIb~ IVb~and ~:
15 and lantha~um, ~ltan~um, ~rconium5 chromium9 moly~denum, ~ :
manganese, cesium, ~nd gadolinium based on econom~c ~on-sideratlons.
In the practic~ o~ ~his invention, R~ and R' ~re independe~tl~ de~ined by highly fluorlnated alipha~ic radical which encompaæses ~luorlnated, satur~ed~ mono~
: valent~ aliph~t~c radicals havlng 1 to 20 car~o~ atom~.
he ~keletal ch~ln o~ the rad~cal may be stra~t, br~nched or~ u~lci~ntly large ~e~g. ~t le~8t 3 or 5 atom~) cycloaliphatic3 and may ~e Lnterrupted by dl~aIen~ oxygen atoms or trivalent nitrogen atom~ bonded only to carbon atoms. Preferably ~he chaln o~ the fluo~inated aliphatic radical doe~ not contain more thæn one het~ro atom9 iOe~3 nitrogen or oxygen, for every two c~rbon a~om~ ln the skeletal chain~ A ~ully ~luori~ated group i~ pre~erred9 but hydrogen or chlorlns atoms may be present a~ subæti-~12-t~lent~ in ~h~ ~luorin~ted aliphat:ic radlcal provld~d that not more th~n one atom of e:l ther is present in the radical for ~ach carbon atom. Preferably, the ~luoroaliphatlc rad~cal is a saturated perfluoroalkyl radical havlng a ~keïetal chs,i.n that i~ ~tr~Lght or bra~ched ~nd has a ~ormula CXF2x ~ l whereln x has a value from 1 to 18 ~
The pr~erred as~ti~re catalysts o~ th'i s ~nven-tion are tho~e compounds havin~ the formula (Rf,S02)Q~02S~f~ ~
whereln Rf and R~i are independ~ntly a highly ~luorinated alkyl group, ~nd Q i3 a divalen~ radlcal selected from -NH and -CHR-, ~herein R is sel~cted f~rom Br" Cl, I, Hg alkyl ~roups of 1 ~o 20 carbon atoms (pre~erably 1 to 4 ), alkenyl of 3 to 4 oarbon atom~ 9 aryl or aralkyl Or up to 20 carbon a~om~ (preferably up ~o 10 ) or R'X, wh~rein R' is an alkylenle group u~ up ~o ~0 carbon atoms (pr~fera~ly 1 to 4 ) and X i8 H~ Br, Cl, I, -02SP~, 2 ~ ) 2, -CH- ( GH2 )n-CQOR 3 o r -CY ( COOR2 ) 2 Br whereln R4 is H or l to 8 alkyl and n is 0 to 8, ~nd whereln R2 i~ alkyl o~ 1 to 4 oarbon atoms or phen~rla~kyl, the ~lkyl g:roup o~ whlch ha~ 1 to 4 carb~n atom~, and Y
is H, Br, C13 I~ or N02.
~nonium catlon a~ used i;n the pre~ent invent~on i~ de~lned as aations o~ ammonia, primar~., second~ryj tertiary and qu~tern~ry amines. Alkyl, arylg alkaryl3 etc., as us~d ln the pre~ent invention ~excluding :1~ type groups a~ el~ewhere de~ined~ includes such simple ~u~tl-tuted groups as are re.cognl~ed ln tk~e art as ~unctional.
e~uivalents o~ t~e groups (eOgO, -CH2C~2CH2Gl; S03~ ) --13~

insofar as its function in the present invention is con- ~ :
cerned.
Illustrative bis(perfluoroalkyl sulfonyl) protonic acids are~
Bis(trifluoromethylsulfonyl)methane Tris(trifluoromethylsulfonyl)methane Bis(trifluoromethylsulfonyl)imide Bis(trifluoromethylsulfonyl)chloromethane Bis(trif'luoromethylsulfonyl)phenylmethane Bis(perfluorobutylsulfonyl)methane Bis(perfluorobutylsulfonyl)imide Trifluoromethylsulfonic acid ~: :
Perfluorobutylsulfonic acid Perfluorooctylsulfonic acid Ethyl 6, 6-Bis(perfluoromethyl sulfonyl)

4-bromohexanoate Methyl 4, 4-Bis(perfluoromethyl sulfonyl) -2-carboxy-2-bromobutanoate Ethyl 4~ Ll-Bis(perfluoromethyl fulfonyl) -2 carboethoxy-2-nitrobutanate 1, 1, 2, 2-Tetra(trifluoromethylsulfonyl) ethan~

;::

,4~i Selectlon of a most pre~erred perfluoroalkyls~ onyl methane catalyst is dependent on the particular monomer compos~t1on in which the catalyst 1s to be used and the applicat1Qn for which the comnosit10n is to be used.
Al ~hough thei r use 7 s no~ necessary in the composi tl ons of ~he i nvellti on to effect a cure of coat~ngs of the composi~lon, it ls o~ten preferable to lnclude in addltion to the flworoalkylsulfony1 prot~nic acl d ca~alysts from about û. 01 ~o 5 perce~t and pre~era~ly about 0.1 to 2 p~rcenk of a çscond s110xane hydrolysis and condensat1~n c~atalys:t A~ is ilïus~rated 1n the ex~mples, some o~ such ~ombin~t~on o~ catalysts pro-vides synerg1st7c e~ects allo~1ng ~or tncr~sed r~e of cure oYer that obtai nabl e by the fl uoro~l kyl sul ~onyl :-~; ~5 protonic acicl catalyst alone. ~ Such s~ioxdne hydrolysis and condensation catalysts are wel l knawn and inc7ude among others organot7n omp~undls ~see U.S. Patent 3,664,997~ such as bls(aceto~ydibutylt1n) ox7da b1sLdib~yl~hexyloxy)t~n~ox7de,, phenylbutoxyt~nhydrox~de 2û and the 17ke; meta1 salts ~see U.S. Pat~nts 3~719~l~35 and 3,772,240~ such as lead 2-~thylhexoate? d~lbuty1tin dilaurate, z~nc naphthenate, ~lrconlum octoate, tetra-phenylt~tanate, and ~He l1ke; su1fur-contatn~ng org~no tin compour)ds ~see U.S. Patcn~ 39499,870) such ~s (C4Hg)25n ~5GH2COOC~Hg~2 and the like; other cata1ysts such as those d~sclosed ln U.SO Pa~en~s 3,433,~58 (vanad~llm compounds)~ 3~474,Q6~ ~zirconium alkox~des and chelates); 3,474,07û (ferr1c alkoxides); 3,491,054 (alum1num alkoxldes); 376~9~454 (l:~tanlum chelates and ~

alkox~des~; 3,714,212 (cobalt-platinum compou~ds);
etc. Epoxy catalysts may be added~ but wlth no s i gn 1 f i can t improvement observed .
Abrasion reslstance as use~ herein is expressed

5 . as percent~ge haze produoed on a sampl e of o~r~d cQat 1 ng on a 4 ml 1 ( 100 m~ cron ) cl ear col or l ess polycster film ~y the falling sand method of test ~or abrasio~
res~stance. In accordance w7th thils procedure which ~-is the same as that of ASTM Dcsignation ~68-51 (Reapproved 1972) with the modificat~on that the spe~imen platform ~rotat~d at abou~ ~Q ~pm dur1ng th~ ::
t~5t. Perc~n~ag:e h~ze prod~ the specim~n ~S th~n measured usi ng a 6ardner H~z~m~t~r (manufa~tur~ ~y -Gardner Laboratory Inc., Bethesda, Maryland~ in 15 accordan~`e with ASTM~Dest~natioo Dlû03~64 (Procedure A) (ReapproYed 1970). In some inst,a~ces the resist~tlce . of sa~ples to the abraslve action of steel wool is .
alsa dQterm~ned~ :

slJbstrate , The abrasion resistant coati?nss o~ the pr~senl:
invent10n are best used as coatillgs upon a substrateO
Matertals wh~?ch are able to prov~de use~ul ~ ?nctilons ~ut do not have satisfactory abrasion resistanc~ can be improved by ~hc addlt~on af coatt?n~s acoord~ng ~to the present 1nYention. Espectally those material~ ~
Which heretofore ha~e not been coated to tmprove th~r ~:
resi stance Wi th any great succ~ss bQcause of heat sensit~v7ty (low meltin~? point3 destrwct10n of heat unstable mater~?als~ etc. ) can be readily impro~ed ~:

~. -accord~ng to the present ~nven~ion becau~e of the abili~yof the present composl~lons to bond wl~h essen~1ally room temperature cur~ng.
Solld substrates that can be coated are the sur~aces of fibers, shee~s~ and shaped sol~d objects.
Among the solid substrates particularly useful accord-ing to ~he presen~ ~nvention are ceramic materlals (e~g., glass fused ceramic sheetlng and f~bers), metal~ ~e.g. sheets, ~i~ers, aluminum9 iron, silver, chromium and other me~als), metal o~des, thermo-plastlc res1ns ~e.g., polyesters, po1yamid~es, poly-ol~fins, polyc~rb~nates, ocrylic res1ns~ polyviny~ : :
: chloride, cellulose acetate butyrat2 etc.), thermo~et reslns (e.gO, epoxy resins, p~lys~lanes, polyslloxan~s?
etc.)~ paper, wood, natura~ rQsins (eOg. ru~b~r, gelatin~and~ ln general, any solld surface which ne~ds pra-tection from abrasion. :
Where the substrate is not naturally adherent ~.
with the composltions Qf the present inv~ntion, prlmers may be used on~the substrate. Many pr1mers are known .~ 1n ~he ar~, and their purpose ls to provide a layer to : which the coatin~ more read~ly adheres than to the or~glnal surface of the'substrate. For example, in the photograph~c artl primers arP generally used on th~ -po1yethyleneterephthalate base to lmproYe adhes;on o~
subsequent layers thereto. Such prlmers, and other known prlmers, would be usefu1 in the practlce of the present lnventlon.

3~--~B% ~i The surface of the substrate may i tsel f be treated ~o improve adherence such as by abrasion or corona :::
discharge to enhance bonding of the abras~on resistant layer thereto.
A large number of pr~mers can ~;n~ utility in the prac~lce of th~s invention and do not affect the propor~ion of the top abras10n res~stant coatlng. Some :
of ~he most useful ones, however, are the acryllc based primers such as terpolymers o~ butyl~ethacrylate~
10 methylme~hacrylate~ and methacryloxy propyl~rimethoxy silane, d~ssolve~ ~n approp~1ate solvents. The rat1D
o~ the components o~ ~he t~rpolymer can be ~far~ed over a w1de range to attain the Qpt~um prlmary propert1es : for a g1ven substr~te. This pr-Tmer when used ~n appro-15 pria~e sollvents such as 1soprQp~flacetate, is~propanol toluene-me~hanol m~xtures or other m~xed solv~nts fi~d utility ln prlming a var~ety of substrates, su~h as polycarbonates, polymethylmethacrylates, cellulose ;:
acetate ~utyrate, polystyrene9 alum~num, polyv7nyl-20 chloride3 silver halide - ~etatln emu1sions and a host of other organ~c and ~norganlc substrates. As ~ar as the polyester is concerned, t~taniaslllca, or po~y~
vinylidene chloride are the b~st prlmérs. A host of -~
other comrnercial primers such as var~ous aliphatic or 25 aromatic urethenes, caprolactohes~ epox~es9 an~d silo- : :
xanes can also F~nd utility as pr1mers for the coat-ings of the nventlon.
In ~h~ following examples whlch further illu~
strate the ~nventlon,.the sllane precondensates can be ~18--includ~d wlthln the de~inltion" belng ailane~ havlng polymerizable epQxy sub~ti~Guents on 'che moleculeO

~;

:

: ~

:~

lg-~XAMPLE 1 ~ he precondensate o~ tetrae~hoxy~llane wa~ pr~-pared by addln~ 86 ~ 4 ~ alcohol containlng 86 ~ 4 ~ water and one drop o~ Oo ll~ HCl ~o 333 ~5 k~trae~hoxysilane ln 3~3 g 5 ethanol~ The re~ulting solutlorl wa~ heated ~or on~ hour al;
78C to re~lux ln a dlstilllng fla~k and then dur~ng about 3 hours at a ~till pot temperatur~ o~ 80C. The sti:ll pot re~ldue was dilulted with an ~qual welgh~ o~ aceto~O Pr~-cor;ld~nsate~ of` other moi~ure ~ns~kl~r~ modl~ r~ w~re made 10 in accordance wlth thl~ proo~dure by ~ubstltuJGlng l~hs tetra-ethoxysilane wlth an equlv~lent amount o~ th~ ot~er mo~if'ie~. :
Thi~ 1~ mat~rlal A.

The preconden~ate Or 3(2~3-~poxy~prQ
15 ethoxysllane wa~ pr~pared b~ mixing ln a ~lask~ set: ~or ~: dlst~llation~, 160~ g 3(2,3 epoxy)propoxyl;rlm~tho~y~ilan~
in 1605 e ethanol, 800 g wat~r 11l ~ g ethanol, an~ 1 drop :~
o~ O, lN HClo ~he rl2sk was hea~ea ~o dlstlll Qxr vala-tiles to a po~ ten~p~ra~ure of 8Q"C, 3 the re~ldue ~o)1~d and .
diluted at 50% pr~cond~n~at~ with acetone or oth~r organl~
: 301V~At~ Pre~ondens~t~ o~ oth~r ~poxy te~lnated sllan~
w~re made in~a ~imi~ar man~r by ~ub ti~utlng the 3(2,3-epoxy)propoxy~rlmetho~y~llane by ~n ~ulval~nt amoun~ o~
lihe spproprla~e epOxy term1 na ced sl lan~ .

','' ~':
~.
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25~

Certain material~i are repeatedly u3ea in ~h~ ''^6~ ~ p re c~e~ecA ing example6. For th~ converliarlce o~ px~3~enting the example~ in table orm, the~e malkerials will be r~presan~ed by the ollowing syIr~ol~

A preconden~ate of M (a~ C4F9s(~2~HcF3s02 B precondan~ate of C (b) ~CF3S02) ~CHC~2~- (COOC2~5)2 r C CH~ H-CE~2-O-~CH2~3Si(OMe)3 ~c) (CF3s02)2CH-CH~C}1(1OC2 D CH3~i (OEt) 3 (~) ~CF3~02 ) 2~}~Br ~
~2 -: :
S~ 3t~ 3 ~e) ~ F3~02)2CN~ C (~
F CEI2=~CH-Si (OEt) 3 (~) ~CF3SO~) 2CE1 1 G C}I3Si ~oE~) 3 (g) ~cF3sQ2)~cHcN~cH~ 3s42)2 H 1, 4-butanediol (h~ dibutyl~in dilaurate COOC~2~ i,li B~3 etherate J prehydrolyzate o f C in Br 1~ solvent (acetone, ethanol, ~ .
and ethyl ac~tate u~ed ( j~ (CF350~2) 2C:HC~CHCH2CH2Cl inters:~hangeably) ~:

K ~> -CH;~-CH2 -Si (O~e ~ 3 (k 1 (CF3SO;2 ~ ~CHC6}1~;
C~-Si ~QElt) 3 ~ C~FgSO2) 2C~HC 6H5 d/ : ' `

M ~i (Ol:t) 4 : (m~ (C4F~SO~ CHBr (n) (C4~9~O2) 2CH~ :
(O) tCF3S02 ) 2C}~S02C~3 ~p) (C~FgSO~) 2C~ICl (q) (CF3SO;~) 2C~I~

r) (CF3S02 ~ 2CHCH~C~C~Cl C~3C ~ 2~F33 2 (~) [ (~3SS)~2C~12~2 (u~ CF3S02 ) 2C~1 3 :~
~v~ Nl [ (C~3S02 ) 2C~
(w) zn E (CF3S02 ~ 2CH] ;2 (X) Pb 1 1CF3S0;2 ) ~CH~ 2 (yj ~:[ ~C~3S02) ~CE~2 (z~ ~g~CF3~02)2~r laa~ C4FgSO;~~N~~OjCF3 : ~;

~b) NI14 (CP'3SO 2 ) zCBr (cc) Pb(S02CF3) 2 ~ ~
ldd) ~Qal (CF3S02)2CNI ~ ~ :
~e~ ) ~ (CF3S02 l 2~
~) oxalic acld ) P;~5 : :
(hh) CF3S03H

:.

, The tabulation o~ example~ i~ generally thought to speak f'or it~el~ but ~ome example do require expl~nation.
All example~, unless otherwise lndlcated u~e ethanol or ethanol/water ~olvent systems. All percentage haze values are based upon the ~alling sand test (ASTM
Designation Dg68-5l) unless otherwise indicat~d. Egamples 25 34 are com~aritive examples of prior ~rt proc~s~es o~ cureO
Examples 49-60 show that the c~taly~ts of the present invention cure silane groups as well a~ epoxy groups, this 0 ln it elf ~eing nove~ and uno~viou~
Examples 73 and 74 sho~ ~he latency of ce~t~in cat~ ts, whil~ examples 75 an~ 76 shQw how that l~t~nt effect can be activated (~y acid ~nd heat)~ ~ample 77 simllarly ~hows that lat~nt c~taly~t~ ca~ be actlvated ~y a chelating compound ~nd heat.
It is belleved that :the catalysts of this invention produce si~;nl~icantly ~mproved abra~ion resi~tant coa~ing~ ;
from monomers known in the art by not only catalyz~ng both functlonal terminal groups, but al~o by causlrlg the silane 20 groups to react with ~u:~ic~ent speed that the r~pid cure of the epo~y group~ does not r~tr~c~ the f~reedom o~ movement o~ the growing molecules to such a degree that thk silane group~ will not cure. B~r taking rapid meacurement~ o* ~ree epoxide content and ~ree slloxane content, it is s~en that 25 by the time 80% of~ the epoxy groupæ are reac~ed, at least 10~ of the siloxane groups are re~c~ed. It is thought that khi~ relative rate o~ reactlon o~ these groups ~s importar~t to the novel propert~es in the product.
The use of the catal~sts o~ t~e present invention readil~ e~fect this type o~ cure at temperatures about lO~C

~ 2~

as well as at conventional elevated temperature~ by placing the reactl~e epoxy-termlnated sllox~ne monomers in caralytic proximity to a catalytically active amount o~ the catalysts of this invention.
me coatings o~ this invenklon are generally use~ul wherever the additlon o~ ~ abrasion reslst~nt coating would be desl~able~ ~uch ob~ious area~ o~ utility lnclude coatings on glas5 or plastic optic lense3~ on re~lective sheeki~g such as street sign~, intenslfylng Qcresn~ ~ known i~ the radio- :
graphic and ~el~ted arts~ protection o~ photoconductl~e and electrophotoconductive sur~ace~, on thermographi~ and photo-thermc~r~phlc fftemen~sS ~e:~ and countertop ~ur~a~e~ ~e~
cially cuttin~ sur~àces), ~r~llc c~ramic coatln~ on c&r bod~es), boat hulls ~nd any other sur~ace sub~ect to ahrasionO
S~rpri~ingl~, the flex~ility of the compositior.s o~ the present ln~ention is extr~rn21y high ~or ~uch a hard abrasion re~istant materi~l. Som~ compositions in fllm ~orm : can be sub~ected to a bend around a one inch diameter tube without cracking or s~re~s mark~. Thi8 i~ a de~ree o~
20 ~le~ibility ~ar grea~er than tha~ o* prlor art abrasl~n :
resi~tant materi~ls o~ ~ny commercial value.
The term epo~y-terminatad silane has ~een used generall~ throughou~ the~peci~ic~tion, but as cle~rly~hown by one o~ the ætructural *ormul~e used in de~cr~.bing certain epoxy-subæt~tu~ed silanes, the ep~xy group doe~ not hav~ to be te~minal (iOe~, a 1,2 epo~y group)0 An~ epo~y group in a position on the chain whlch is capable o~ polymerl~ing a~
epoxy groups are k~own to polymerize i~ included on the term :~
epoxy-termlnated siloxane~ For example9 th~ epoxy groups on the æaturated ring~ ar~ not. truly t~rmlnal but are ~9_ prepared by any of the process~s ~or hydrnly2ing silanas that are known ~n the art. General7y, about 1 to 6 moles of water per mole of s~loxane acid and an acid ca~alyst are used. Su~tab1e ac~d catalysts are llsted S in UiS. Patent 3,776,881 and procedure for the prepara~
tlon cf the pre ondensates is descr~bed in U.SO Patent 2,404,426~ of the precondensa~es o~ the epoxy-terminated 57 lanes (and the method used for the precondensates in the examples~ are preferably prepared by adding 5 to :

6 moles o~ wa~er in an equal weight o~:ethanol con-taining about 0.5 m~ equlYalent of hydrogen chlor~de to one mole o~ th~ ~poxy-~e~m~nated s~lane ~n an~e~ual ~ :
amount o~ ethanol. The m~x~ure ls then he~ted ~n a distilling apparatus to a bottoms temperature of about 80C . to remoYe ekhanol 1 eaYl ng the precondensate ~s ~:
s~lll bottoms.
The precondensates of th~ mo~sture s~nsitive mod~ier (compounds of khe ~ormula RmM~OR')n are preferably pr~p~ared 1n a method slmilar to that for the epoxy~terminated s~1anes us~ng, hawever, 2 to 3 :
; moles of wa~er, wlth or w~thout the addit~on o~ ethanQl.
The pr~condensdtes~are ready for use as prepared but : ~, may be stab~l~2ed a3a-n~t further condens~ation by the addit~on of an appropriate solven~ such as acetone. : :
It ~s known in the art that wi:th the use o~ any acid catalyst, baslc sites and basic ingredi:ents compi~-cate the effectiveness o~ the system. For example, ba ic nitrogens may exlst in the aliphatic cha~n of the epoxy-term~ndted s11anes in the present invent10n. Howeveri ~hese basic n7trogens tend to form eleotronic bonds w~th -3o-f~

the acid ca~alyst and inh~b~ft ~he1r act~vlffty. In cofm-pos~ions where such bas~c s~tes or basic moleties are present~ the amoun~ of catalyst necessary to effect a catalytïfcally active concentratffffon ~s 1ncreased. It 5 m1ght a1so be desirable to 10wer the pH o~ the system to blfock the basic si~es. Such groups as diva1ent su1fur (C-S~f and aromatic r1ngs have simff1ar inhtbffting ef~ects ~-upon the cata1yst . They do not compl ete1y prevent poly-m.eri zat~ on, but do ~ nhi b1 t ~ff t .
f 10 Among other pre~erred ffffub~trates to be coated ~:
in the pre~ent in:ue~tio~ ~re p~int~fd su~aces ~:inclufding ~crylic ce~m auto paint6)9 ma~r~le ~ur~ces, po}yesters (e~g~, polyethyl~ne terephthalate),:~in~hed photo~
, gr~phic products ~by de~ it~on, print~f9 ~ilm3g tr3n~- ~
15 parenclf--ffæ3 negative~ micrff-ff~lch~f~ motion picture f1~m, : :
micro~ilm, pr~n~ing plate~ and t~e llke), a~d works of ~ ~
art . -:
, :A pa~ticularly use*ul coating incluae3 ~illed resin compo~lt.ions~ reC;in ltfsel~ mufs~ still contain 20 ~t l.efa~ 15 per ent by weight o~ units derived ~rom an ~:~
epoxy-~ermi~a~ed silane~ bu~:will still be use~ul with : up to 50 wsl6ht percen~ o~ the tot~l ~y~tem (reduclng :: the epoxy ilane o~ the ~otal coatln~ sy~tem to 7n5 percent although s~ percent o~ th~ resin3 as ~lller~
25 Par~cularly g~od ~i~ler~ include tita~ia and ~llica~
A f'urther ~urpri~ing f act in the practlce of' thls invention ls that when two oatalys~s were ~ombined wlbh an epoxy-terminated ~llane, one a ca'calyst f'or epoxy poly~
merizatlon (BF3, monoethylamlne) and one f`or sllane 30 polymerizatlon (dibutyltln dilaurate), and the composltion wa~ heated ln an oven for a prolongsd time, th~ composltion did not cure to a hardness comp~rable ~o identical composi ; tlons cured with highly ~luorinated allphatic sul~onyllc and sul~onic catalysts. In view Or the ~ac~ that the cata~
lys~ used in the practice o~ this lnventlon wer~ not known as ca~alysts for siloxane~, thi3 re~ult is notew~rthy. ~ :

~, :

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An abrasion resistant coating on a substrate, wherein said coating is from 0.1 to 500 microns thick and comprises a polymer comprising (a) at least 15 percent by weight of units from an epoxy-terminated silane represented by the formula or wherein R is a non-hydrolyzable divalent hydrocarbon radical of less than 20 carbon atoms, or a divalent radical of less than 20 carbon atoms the backbone of which is C atoms which may be interrupted by individual atoms from the group of N and O, the O atoms in the form of ether linkages, n is 0 or 1, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula (CH2CH2O)kZ
in which k is an integer of at least 19 and Z is hydrogen or an aliphatic hydrocarbon radical of less than 10 carbon atoms, and (b) up to 85 percent by weight units derived from materials copoly-merizable with epoxy or silane groups, the silane being cured in the presence of a catalytically active amount of a highly fluorinated aliphatic sulfonylic or highly fluorinated aliphatic sulfonic catalyst, a sulfonic catalyst com-prising a highly fluorinated aliphatic sulfonic acid or salt thereof and a sulfonylic catalyst comprising a compound containing two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or methylene group.

2. The abrasion resistant coating of claim 1, wherein the surface of the substrate is coated with a primer to enhance bonding between the coating and the substrate.

3. The abrasion resistant coating of claim 1, wherein the remainder of the polymer is derived from units formed in copolymerization with epoxy resins, styrene, methylstyrene, vinyl amides, vinyl ethers, and compounds of the formula:
RmM(OR')n wherein M is Si, Al, Zr or Ti R is selected from hydrocarbon groups of less than 10 carbon atoms or groups composed of hydrogen, carbon and oxygen of less than 20 carbon atoms, R1 is alkyl or acyl of fewer than 10 carbon atoms, m is 0, 1, 2 and 3, and n is 4, 3, 2 or 1, and m plus n equals 3 or 4.

4. The abrasion resistant coating of claim 1, wherein said sulfonic and sulfonylic catalyst are selected from the formulae:
(RfSO3)nR and (RfSO2)-Q-(SO2Rf') wherein R is selected from hydrogen, ammonium cation and metal cation and n is the valence of R, Rf and Rf' are independently highly fluorinated aliphatic groups, and Q is selected from , and wherein R' is selected from hydrogen, chlorine, bromine, iodine, ammonium cation, or metal cation R" is selected from hydrogen, chlorine, bromine, iodine, RfSO2, alkenyl or 3 to 4 carbon atoms, alkyl of 1 to 20 carbon atoms, aryl of up to 20 carbon atoms, and alkaryl of up to 20 carbon atoms, and R3 is H, alkenyl of 3 to 4 carbons and aryl of up to 20 carbons.

5. The abrasion resistant coating of claim 1, wherein said highly fluorinated sulfonyl catalyst is represented by the formula:
(RfSO2)-Q-(O2SR?) wherein Rf and R? are independently a highly fluorinated alkyl group, and Q is a divalent radical selected from -NH- and -CHR-wherein R is selected from Br, Cl, I, H, alkyl groups of 1 to 20 carbon atoms, alkenyl of 3 to 4 carbon atoms, aryl or aralkyl of up to 20 carbon atoms, or R'X, wherein R' is an alkylene group of up to 20 carbon atoms and X is H, Br, Cl, I, -O2SRf, -CH(O2SRf)2, , or -CY(COOR2)2 wherein R4 is H or 1 to 8 carbon alkyl and n is 0 to 8, and wherein R2 is alkyl of 1 to 4 carbon atoms or phenylalkyl, the alkyl group of which has 1 to 4 carbon atoms, and Y is H, Br, Cl, I or NO2.

6. The abrasion resistant coating of claim 4 or 5, wherein Rf and Rf' represent perfluorinated alkyl groups.

7. The abrasion resistant coating of claim 1, further comprising at least some filler up to 50 weight-percent of the coating.

8. The abrasion resistant coating of claim 1, 2 or 3, further com-prising pigments or dyes.

9. The abrasion resistant coating of claim 1, 2 or 3, further com-prising heat stabilizers.

10. The abrasion resistant coating of claim 1, 2 or 3, wherein the substrate comprises a polyester.

11. The abrasion resistant coating of claim 1, 2 or 3, wherein the substrate comprises an acrylic resin.

12. The abrasion resistant coating of claim 1, 2 or 3, wherein the substrate is glass.

13. The abrasion resistant coating of claim 1, 2 or 3, wherein the substrate comprises a polycarbonate.

14. The abrasion resistant coating of claim 1, 2 or 3, wherein the substrate comprises a cellulose acetate butyrate.

15. The abrasion resistant coating of claim 7, wherein said filler comprises titania and silica.

16. The abrasion resistant coating of claim 1, 2 or 3, wherein said substrate comprises a finished photographic product.

17. The abrasion resistant coating of claim 1, 2 or 3, wherein said substrate is a painted surface.

18. The abrasion resistant coating of claim 1, 2 or 3, wherein said substrate is metal.

19. A film from 0.1 to 500 microns thick comprising a polymer having at least 15 percent by weight of units derived from an epoxy-terminated silane represented by the formula:
or wherein R is a non-hydrolyzable divalent hydrocarbon radical of less than 20 carbon atoms, or a divalent radical of less than 20 carbon atoms the backbone of which is C atoms which may be interrupted by individual atoms from the group of N and 0, the 0 atoms in the form of ether linkages, n is 0 or 1, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula (CH2CH2O)kZ
in which k is an integer of at least 1, and Z is hydrogen or an aliphatic hydrocarbon radical of less than 10 carbon atoms, the silane being cured in the presence of a catalytically active amount of a highly fluorinated aliphat-ic sulfonylic or highly fluorinated aliphatic sulfonic catalyst, a sulfonic catalyst comprising a highly fluorinated aliphatic sulfonic acid or salt thereof and a sulfonylic catalyst comprising a compound containing two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or methyl-ene group, said polymer further comprising up to 85 percent by weight of units derived from epoxy compounds copolymerizable with the silane or epoxy groups of the epoxy-terminated silane.

20. The film of claim 19 wherein said catalyst is represented by the formulae:
(RfSO3)nR and (RfSO2)-Q-(SO2Rf') wherein R is selected from hydrogen, ammonium cation and metal cation and n is the valence of R, Rf and Rf' are independently highly fluorinated aliphatic groups, and Q is selected from -?R', -?R'R" and -?=CHR3 wherein R' is selected from hydrogen, chlorine, bromine, iodine, ammonium cation, or metal cation, R" is selected from hydrogen, chlorine, bromine, io-dine, RfSO2, alkenyl of 3 to 4 carbon atoms, alkyl of 1 to 20 carbon atoms, aryl of up to 20 carbon atoms, and alkaryl of up to 20 carbon atoms and R3 is H, alkenyl of 3 to 4 carbons and aryl of up to 20 carbons.

21. The film of claim 19 wherein said catalyst is represented by the formula:
(RfSO2)Q(O2SR?) wherein Rf and R? are independently a highly fluorinated aliphatic group.
and Q is a divalent radical selected from -NH- and -CHR-wherein R is selected from Br, Cl, I, H, alkyl groups of 1 to 20 carbon atoms, alkenyl of 3 to 4 carbon atoms, aryl or aralkyl of up to 20 carbon atoms, or R'X, wherein R' is an alkylene group of up to 20 carbon atoms and X is H, Br, Cl, I, -O2SRf, -CH(O2SRf)2, , or -CY(COOR2)2 wherein R4 is H or 1 to 8 carbon alkyl and n is 0 to 8, and wherein R2 is alkyl of 1 to 4 carbon atoms or phenylalkyl, the alkyl group of which has 1 to 4 carbon atoms, and Y is H, Br, Cl, I or NO2.

22. The film of claim 19, wherein said catalyst is represented by the formula (RfSO2)Q(O2SR?) wherein Rf and R? are independently a highly fluorinate alkyl group, and Q
is a divalent radical selected from -NH- and -CHR- wherein R is selected from Br, Cl, I, H, alkyl groups of 1 to 20 carbon atoms, alkenyl of 3 to 4 carbon atoms, aryl or aralkyl of up to 20 carbon atoms, or R'X, wherein R' is an alkylene group of up to 20 carbon atoms and X is H, Br, Cl, I, -O2SRf, -CH(O2SRf)2, -CH-(CH2)n-COOR4, or -CY(COOR2)2 Br wherein R4 is H or 1 to 8 carbon alkyl and n is 0 to 8, and wherein R2 is alkyl of 1 to 4 carbon atoms or phenylalkyl, the alkyl group of which has 1 to 4 carbon atoms, and Y is H, Br, Cl, I or NO2.

23. A method of forming an abrasion resistant coating of from 0.1 to 500 microns thickness on a substrate which comprises curing a composition comprising at least 15 percent by weight units derived from an epoxy-terminated silane represented by the formula:

or wherein R is a non-hydrolyzable divalent hydrocarbon radical of less than 20 carbon atoms, or a divalent radical of less than 20 carbon atoms the backbone of which is C atoms which may be interrupted by individual atoms from the group of N and O, the O atoms in the form of ether linkages, n is 0 or 1, and R' is an aliphatic hydrocarbon radical of less than 10 carbon atoms, an acyl radical of less than 10 carbon atoms, or a radical of the formula (CH2CH2O)kZ
in which k is an integer of at least 1, and Z is hydrogen or an aliphatic hydrocarbon radical of less than 10 carbon atoms, and up to 85 percent by weight of units derived from materials copolymerizable with epoxy or silane groups, the silane being in catalytic proximity to a catalytically active amount of a highly fluorinated aliphatic sulfonic or sulfonylic catalyst, a sulfonic catalyst comprising a highly fluorinated aliphatic sulfonic acid or salt thereof and sulfonylic catalyst comprising a compound containing two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or methylene group, and bonding said composition to said substrate.

24. The method of claim 23 wherein said bonding is effected by in situ cure of said composition upon said substrate.

25. The method of claim 24 wherein a primer is applied to said substrate prior to said in situ cure.

26. The method of claim 23 wherein the remainder of the composition is derived from units formed in copolymerization with epoxy resins, styrene, methylstyrene, vinyl amides, vinyl ethers, and compounds of the formula:
RmM(OR')n wherein M is Si, Al, Zr or Ti R is selected from hydrocarbon groups of less than 10 carbon atoms or groups composed of hydrogen, carbon and oxygen of less than 20 carbon atoms, R1 is alkyl or acyl of fewer than 10 carbon atoms, m is 0, 1, 2 and 3, and n is 4, 3, 2 or 1, and m plus n equals 3 or 4.

27. The method of claim 23, 24 or 26, wherein said catalyst is represented by the formulae:
(RfSO3)nR
and (RfSO2)-Q-(SO2Rf') wherein R is selected from hydrogen, ammonium cation and metal cation and n is the valence of R, Rf and Rf' are independently highly fluorinated aliphatic groups, and Q is selected from , and wherein R' is selected from hydrogen, chlorine, bromine, iodine, ammonium cation, or metal cation R" is selected from hydrogen, chlorine, bromine, iodine, RfSO2, alkenyl of 3 to 4 carbon atoms, alkyl of 1 to 20 carbon atoms, aryl of up to 20 carbon atoms, and alkaryl of up to 20 carbon atoms and R3 is H, alkenyl of 3 to 4 carbons and aryl of up to 20 carbons.

28. The method of claim 23, 24 or 26, wherein the highly fluorinated aliphatic sulfonylic catalyst is represented by the formula:
(RfSO2)Q(O2SR?) wherein Rf and R? are independently a highly fluorinated aliphatic group, and Q is a divalent radical selected from -NH- and -CHR- wherein R is selected from Br, C1, I, H, alkyl groups of 1 to 20 carbon atoms, alkenyl of 3 to 4 carbon atoms, aryl or aralkyl of up to 20 carbon atoms, or R'X, wherein R' is an alkylene group of up to 20 carbon atoms and X is H, Br, Cl, I, -O2SRf, -CH(O2SRf)2, , or CY(COOR2)2 wherein R4 is H or 1 to 8 carbon alkyl and n is 0 to 8, and wherein R2 is alkyl of 1 to 4 carbon atoms or phenylalkyl, the alkyl group of which has 1 to 4 carbon atoms, and Y is H, Br, Cl, I, or NO2.