CA1196749A - Polymerizate of (allyl carbonate) and aliphatic polyurethane having acrylic unsaturation - Google Patents
Polymerizate of (allyl carbonate) and aliphatic polyurethane having acrylic unsaturationInfo
- Publication number
- CA1196749A CA1196749A CA000413951A CA413951A CA1196749A CA 1196749 A CA1196749 A CA 1196749A CA 000413951 A CA000413951 A CA 000413951A CA 413951 A CA413951 A CA 413951A CA 1196749 A CA1196749 A CA 1196749A
- Authority
- CA
- Canada
- Prior art keywords
- group
- polyurethane
- chosen
- allyl carbonate
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/14—Esters of polycarboxylic acids
- C08F218/16—Esters of polycarboxylic acids with alcohols containing three or more carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/92—Polyurethane having terminal ethylenic unsaturation
Abstract
Abstract Discloses a monomeric composition of a polyol(allyl carbonate) and a polyurethane having terminal acrylate functionality, and a polymer thereof.
Description
1~6~4~
POLYMFRTZATE OF (ALLYL CARBONATE) AND ALIPaATIC
POLYURETHANE ~AVI~G ACRYLIC UNSATURATION
1 De~cription of the Inveneion Polmerizates of alipbatic polyol(allyl carbonate) ~re char~cter-ized by hardne~, impact resi~tance, ~nd optic~l clarity. ~owever, for certain applica~ion~, increased impact resi~tance and hardness ~re de~ir-~ble. In ~he past, it has not been posaible to obtain the~e desired propertie~ ~ithout degradation of other propertie~, for example9 ~ithout incressed yellowing 9 snd ha~e.
It ha~ no~ been found ~hat a polymeri~at~ of an nliphatic diol bi~(allyl carbonate) h~ving increased impact ~trength and sub~tantially no degradation in op~ical propertie~ or increase in yellowing may be prepared by the addi~ion of R poly carb~ic e~ter, i.e., ~ polyure~hane, having ~er~i-nal scrylRte functionality. It ba~ further been found tha~ a copolymeriza~e of p~lyol(~llyl carbonate) and an a~rylate capped r~nomer, prepolymer, oligomer, or low molecular weight poly~er ha~in8 internal polyureth~ne func-tionality exhibit~ enhsnced i~pact ~trength, and aubatanti~lly no increa~ed yello~ing when c~mpared with ~ bomopolymerizate of polyol(allyl c~rbonate).
Deta1ed De0cription of the Invention It ha~ no~ been found that the addition to 8 mon~meric polyol (allyl carbon~te) of a high ~olecular ~ei~ht monomer, oligo~er, prçpolymer, or polymer having A mGlecular weight bel~w nbout 3500, characteri~ed by internal polyurethane b~nda and terminal acrylate unc~ionality increase~
the impact 0treng~h of the polyol(allyl csrbonate) poly~erizate ~i~hout increa~ed yellowing. It ha~ further been found that c copolyDeri~ate of 4 ~
1 diol bis (allyl csrbonste) with 8 high molecular weight mon~er, oligomer, or low molecular weight polymer or prepolymer having internal polyurethane functionality and terminal acrylste functionality has higher impact ~trength than nn equivalent polyol(Allyl carbonate) homopolymer~
According to the method herein contemplsted, nn effective smount of n material having internal polyurethane functionality and terminal scryl~te functionality iB added to a polyol(allyl ~arbonate) monomer, whereby to pro~ide 8 liquid co~position of a major portion of pclyol(sllyl c~rbonate) monomer and a minor portion o the m~terial having interaal polyurethane funetionAlity and te~minal aclylate functionalityO The resulting liquid c~mpo~ition i3 polymerized, e.g., by free radical initi-sted polymeri~ation through the nllyl and acrylate functionality to proYide a copolymerizate of a major portion of polyol(~llyl carbonaee) ~nd 8 minor portion of ehe materiAl hsving ineernal polyurethane functionality~ i.e., poiyur~thane material.
By an ~ffective ~mount of the scrylsted polyurethane material iB
meant an ~mount sufficiene to provide a measurable enhancement of impace ~tren8th. Thi~ i~ at lea~t about 3 weight percent, nnd generelly ~bo~e about 10 ~eight percent. However, the ~ount ~hould be belo~ nbout 50 weight percent and preferably below about 40 weight percent in order to retain the desired optical propertie~ and ohemical re~i~tance of the polyol-(~llyl csrbonste). It has ge~erally been found that a loading of in exces~
of nbout 10 weight percent of the terminal acrylate polyurethane provides a Dignificant increa~e in ~verage ampact atrength relative to that of ~he ~olyol(allyl c~rbonate) homopolymerizate~ while lGsdings of polyurethane ~ith terminal ~crylate functionality above about 20 to 30 weight percent provide An even higher increase in the impact streng~h relative to th~t of
POLYMFRTZATE OF (ALLYL CARBONATE) AND ALIPaATIC
POLYURETHANE ~AVI~G ACRYLIC UNSATURATION
1 De~cription of the Inveneion Polmerizates of alipbatic polyol(allyl carbonate) ~re char~cter-ized by hardne~, impact resi~tance, ~nd optic~l clarity. ~owever, for certain applica~ion~, increased impact resi~tance and hardness ~re de~ir-~ble. In ~he past, it has not been posaible to obtain the~e desired propertie~ ~ithout degradation of other propertie~, for example9 ~ithout incressed yellowing 9 snd ha~e.
It ha~ no~ been found ~hat a polymeri~at~ of an nliphatic diol bi~(allyl carbonate) h~ving increased impact ~trength and sub~tantially no degradation in op~ical propertie~ or increase in yellowing may be prepared by the addi~ion of R poly carb~ic e~ter, i.e., ~ polyure~hane, having ~er~i-nal scrylRte functionality. It ba~ further been found tha~ a copolymeriza~e of p~lyol(~llyl carbonate) and an a~rylate capped r~nomer, prepolymer, oligomer, or low molecular weight poly~er ha~in8 internal polyureth~ne func-tionality exhibit~ enhsnced i~pact ~trength, and aubatanti~lly no increa~ed yello~ing when c~mpared with ~ bomopolymerizate of polyol(allyl c~rbonate).
Deta1ed De0cription of the Invention It ha~ no~ been found that the addition to 8 mon~meric polyol (allyl carbon~te) of a high ~olecular ~ei~ht monomer, oligo~er, prçpolymer, or polymer having A mGlecular weight bel~w nbout 3500, characteri~ed by internal polyurethane b~nda and terminal acrylate unc~ionality increase~
the impact 0treng~h of the polyol(allyl csrbonate) poly~erizate ~i~hout increa~ed yellowing. It ha~ further been found that c copolyDeri~ate of 4 ~
1 diol bis (allyl csrbonste) with 8 high molecular weight mon~er, oligomer, or low molecular weight polymer or prepolymer having internal polyurethane functionality and terminal acrylste functionality has higher impact ~trength than nn equivalent polyol(Allyl carbonate) homopolymer~
According to the method herein contemplsted, nn effective smount of n material having internal polyurethane functionality and terminal scryl~te functionality iB added to a polyol(allyl ~arbonate) monomer, whereby to pro~ide 8 liquid co~position of a major portion of pclyol(sllyl c~rbonate) monomer and a minor portion o the m~terial having interaal polyurethane funetionAlity and te~minal aclylate functionalityO The resulting liquid c~mpo~ition i3 polymerized, e.g., by free radical initi-sted polymeri~ation through the nllyl and acrylate functionality to proYide a copolymerizate of a major portion of polyol(~llyl carbonaee) ~nd 8 minor portion of ehe materiAl hsving ineernal polyurethane functionality~ i.e., poiyur~thane material.
By an ~ffective ~mount of the scrylsted polyurethane material iB
meant an ~mount sufficiene to provide a measurable enhancement of impace ~tren8th. Thi~ i~ at lea~t about 3 weight percent, nnd generelly ~bo~e about 10 ~eight percent. However, the ~ount ~hould be belo~ nbout 50 weight percent and preferably below about 40 weight percent in order to retain the desired optical propertie~ and ohemical re~i~tance of the polyol-(~llyl csrbonste). It has ge~erally been found that a loading of in exces~
of nbout 10 weight percent of the terminal acrylate polyurethane provides a Dignificant increa~e in ~verage ampact atrength relative to that of ~he ~olyol(allyl c~rbonate) homopolymerizate~ while lGsdings of polyurethane ~ith terminal ~crylate functionality above about 20 to 30 weight percent provide An even higher increase in the impact streng~h relative to th~t of
- 2 -1 the polyol(sllyl carbonate) homopolynerizaee while retaining optical tranDparency and clarity~
~ owever, a~ounts of the scrylate terminated polyurethane above about 40 to 50 weigh~ percent ~hould be avoided ina~much a8 nt level~ of the ~crylate terminated polyureth~ne above about 40 to 50 weight percent, basis total organics, the chemical resiatance of the polymeri~ate begins to declina ~elative to that of the polyol(allyl carbona~e). aoweYer, higher levels of acryl~te ter~inated polyurethane ~ay be utilized ~here chemical re~istance i9 not essential.
The te~inally scrylic polyurethane~ herein contemplat2d, includ- -ing dithiocarb&myl e~eers, as will be de~cribed mo~e fully hereinbelo~, preferably ha~e a moleeular weight of ~rom about 350 eo about 3500, ~d preferably from about 500 to ~bou~ 2000. Hi8her ~olecular weight termi-nslly acrylic polyurechanes do not appear to provide ~uffieient arrylate acti~ity for ehe degree of polymerization and cro~ linking deslred while ter~inally acrylic polyureth~nes ha~ing a ~oleculsr ~eight belo~ about 300 do not appear to offer ~ufficiene ~olecul~r weight or poly~rethane func~
tionnlity to provide the deaired enhanrenent of the physical propertie~ of ~he re~ulting polymerirate.
~olyol(allyl carbonate) mon~mer~, such a~ diol bis(allyl carbo~- -nteD), triol tris(allyl carbonate~ nd higher h~mologuea, ~hi~h ~ay be ~opolymerized by the method of thi~ invention ar~ normally aliphatic liquid allyl rarbonates, e.g., glycol bia(allyl carbonat~) compound~, in which the allyl groups may be substituted at the 2 position with a halogen, notably chlorine or bromi~e, or a 1 to 4 carbon alkyl group~ generally ~ ~ethyl or ethyl group. For diol bis(allyl carbonate~) the glycol re~id~e ~ay be an alkylene, alkylene ether, alkylene polyether5 alkylene carbonaee, or 7~S~
cycloahphatic group having from 2 to 10 carbon6 ~nd oxygen~. Exempl~ry diol bi~(allyl carbonate) monomer~ are repre~ented by the formula:
O O
.. ..
Rl - 0 - C - 0 - R2 ~ - C 0 - R3 where Rl ~nd R3 are allyl or ~ub~tituted allyl groupa, and R2 iB ~ defined below. Rl and R3 are independently repre~ented by the formula: -Rl H2C ~ C- CH2-~here Rl mny be hydrogen, halogen, or ~ 1 to 4 c~rbon alkyl group. Spe-cific exa~ple~ of Rl and R3 include allyl, 2-chloro~llyl, 2 bromo~llyl, 2-iodo~llyl, Z-fluoro~llyl, 2w~ethallyl, 2-eshylallyl, 2-iaepropylallyl, 10 2-n-propylallyl, ~nd 2-n-butylallyl group~. Most cG~monly, Rl ~nd R3 ~re allyl groupR, H2C ~ C~ - CH2-. Such compound~ ~nd ~ethods for makin~ them are di~clo~ed in ~. S. Patents 2,3~0,567 and 2,403,113.
Speciiic ax~mple~ of a2 ~re alkylene groups 8uch A~ ethylene, trimetbylene, ~ethylethylene, tets&methyle~e, ethylethyl~ne, pentamethylene, hexamethylene, 2-methylhe~2me~hylene, ~cesmethylene, ~nd dec~methyle~e group~, ~lkylene ather g~oup8 auch ~ -C~2~0-c~2-s -~H2C~2-0-CH2C~2 3 -C~2-0-CH2-C~2-- ~nd -CH2C~2CH2-0-CH2 CH2C~2-, ~lkyle~e poly~tber groups ~uch ~ CH2CH2 -0-CM2CH2-0-CH2C~2-O-cH2c~20-cH2c~2 &nd C~2 CH2 group~, ~lkylene c~rbon~te groups such ~ C~CH2 -O~C0-0-CH2CK2 ant -C~2CH2-0-C0-0-CH2CU2-0-C0-0-CH2 C~2-0-C0-OCH2CH2- groups, ~nd cyclo ali- -phatic groups, as 1,4 cyclohexane dimethanol bi~ (Nllyl carbonate~. Most commonly, R2 i3 -CH2Ca2-, CH2CH2-0-C~2C~2-, or -C~2C~2-O C~CH2-~-C~C~
Specific exsmple~ of diol bi~(allyl carbonate) mon~Ders u~eful in c~rrying ou~ the method herein contemplated include ~thylene glycol bi~
(2-chlor~llyl carbonate), diethylene gly~31 bi~2-~etballyl c~rbonate~, -;7~
1 triethylene glycol bis(allyl carbonate), propyle~e glycol bi3(2-e~hylallyl carbonate), 1,3-propanediol bi~(allyl c~rbonate), 1,3-butanediol bis~allyl carbonate), l,4-butanediol bis(2-bromoallyl carbonste) 9 dipropylene glycol bis(~llyl carbonate), trimethylene glycol bis~2-ethylallyl carbonate), and pentamethylene glycol bi~allyl carbonate).
Com~ercially important diol bi~allyl carbonate~ monomers which ~ay be polymerized by the method herein conte~plated ~re:
O O
.. ,.
CH2 - CH-CH2-(:)-C-O-C~2-CH2-0-CH2CH2-0-Ctl2 CH2-0-C-O-CH2C~ D~ CH2, O O
.. ..
CH2 ~ CH-CH2-0-C-O-C'tl2CH2-0-CH2CH2-0-C-OCH?-C~1 2.CH2, O O
.. ..
and CH2 ~ CH-CH2-~-C-D-CH2CH2-0-C-O-C8~-C~ ~ CH2.
The method~ of thi~ invention ~ay al~o be utili~ed ~o ccpolymerize 1,4 cyclohexane di~ethanol bis(allyl carbonate)~ snd to copoly~eri~e triol tria(allyl carbonatea) a~ described in U.S. Patent 4,144,~62 eo Stevens for TRIALLYL CARBONATE MONOMERS. The pol~methane~ h~ving terminal ~crylic groups which can be copoly~eri~ed according to this invention Are characteri~ed by ter~inal acrylate group~, i.2., acrylic ~cid groupa, methacrylic ~cid groups, ethyl acrylic acid group~, ~ethyl acrylate group~, ~ethyl meth-ncrylate groups, ethyl methacryl2te groups5 or the like, a~d internal carbamate bond6, including dithiocarb~ate bonda.
Whenever the terms "polyurathane having ter~inal acrylate func- -tionality", "acrylated urethane oligomer", "acrylated carbamyl esterl', or "polyacrylate having internal carbamate bonds", are used herein, they are used interchangeably and ~ynonymou~ly.
_ 5 _ ~a~
Whenever the terms "urethane", "carbamate", and "carbamyl" are used herein, they are intended to interchangeably and synonymously refer to the sulfur analogs, unless the contrary shall be clearly indicated by the context.
The polyurethsnes having terminal acrylate functionality which can be copolymerized according to ~his invention are normally li~uid, ali-phatic diacrylate, triacrylate, and tetra acrylate polyurethanes.
According to one exemplification herein contemplated, the poly-acrylate having internal polyurethane, including dithiocarbamate, functionality has the formula:
(I) RIIIo X
[H2C = C - C - O - R ~-~~ ~ NH2 - C - X
~ O X R3 L~2 C = C - C - O - R ~~~] -NH2 - C - X
while according to an alternative exemplification, the polyacrylate having internal polyurethane functionality has the formula:
(II) RIII X
O "
LH2 C = C C 0 ----R - X - C~ 1 2-Y
LH2C = 1 C - 0 - RVI X X] 2-z ~....
1 i.e., - (IIa) RIII
O
[H2C e C ~ C -- O ~ RIV --------X--C--3y NH2_y NH
C~X
X
~f~
RV E~4 O O
~12C 3 ~ - C - O - RVI --X-C ~ 1 NH2-~
wbsre omega i6 ~uch as to proYide the desir~d molerular ~eight.
In For~ulae (I), (II), and (lIa) R~II and BV are independently chosen from the group consisting cf -H and -CH3, RIV ~nd RVI are inde-pendently cho~en from the group con~isting of Cl to Clo alkyl~, including branched alkyls. Most commonly RIV and RVI are -CH2CH2-, y and ~ are inde-pendently 1 or 2, X is cho~en fro~ the group con~isting of osygan and 8ul-fur. In Formula I R3 i~ chosen frGm the group consisting of ~lkylene groupsa ~lkylene e~her group~, alkylene polyether groupa, alkylene carbonate group3, aromatic group~, polyureehsn~ group~, ~nd polythiourethane group~. In Formula II
R3 iB derived from the reactions of polyols with aliphatic and aromatic polyisocyanates, i.e., R3 i9 polyurethane. In Formula IIa, R4 i~ derived fr~r the di-i~oryanate, and Rs i~ independenely ~ C2 to Cl~ ~Ikylene group derived from the diol.
The acrylaee terminated polyurethane of Formula I may be prepared by reacting two moles of an alkali metal hydroxy carbamate, LHO_RIV___NH_C_X~ Na , or [(HO-R~ )2N-C-X~ Na with a mole of an alkyl dichloride, Cl-R3-Cl, whereby to form a diol having internal carbamate bonds, including dithio-carbamate bonds, H0--R ---NH-C-X-r T~ lR3 H0--R V---NH-C-X_ X
~H0-R ---~2N-C-X-Ho-RIv NH Rc x ! or --R ---~ 2N-C-X__ ~3 ~H--R -----]2N-C_X_ which may then be reacted with an acrylic acid.
According to one exemplification of preparing the polyacrylate of Formula 1, 2-N-hydroxy ethyl carbamic acid sodium salt may be reacted with 1,5-dichloropentane to glve 1,5-bis(2-N-hydroxy ethyl carbamyl)pentane, '7~
2(HOCH2CM2NH-C-0) Na~ ~ ClCH2CH2CH2 CH2CH2Cl~
o HOCU2CH2NH-C-O-ClH2 r.H "
The resulting 1,5-bis~2-N hydroxy ethyl carbamyl) pentane may ~hen be reacted with acrylic acid to give the corre~ponding bis(acrylate).
Ho-cH ~cH2-NH-c-Q-cH2 lH2 HO-CH2CH2-NH-C-O-C~2 o 2 CH2-CH-C-OH--~
O O
CH2-CH-C-0-CH2cH2-NH-c-O-lH2 CH2 ~ 2H20 o O CH2 CH2~(CH-C-O-CM2CH2-NH-C-0 CN2 According to an alternative exempliiicaticn of preparing the poly-acrylate of formula I, diethanol amine may be reacted with carbon di~ulide in the pre~ence of cau~tic ~oda to yield ~odium ethyl dithiocarbamate;
i 7~
~aO~
(HOCH2CH2 ) 2NH + CS2 ~q S
1(HOCH2CH2)2NC-S]
Thereafter a saturated dichloride, ~.g., bi~-~2-chloroethyl) formal, i3 ddded to the aqueous 801ution to bia-(2-hydroxyethyl) dithiocarbamyl ethyl formal, S
2 [(HOCH2CH2)2NC-S]- N~
+ Cl - C~2CH2 - C~OCH3~2 CH2CH2Cl S
(HOCH2C}12 ) -~C-S-CI H2 C~OGH3)2 ~ 2NaCl.
S
(lBOCH2CM2 ) 2NC-S-C112 This material i~ then reacted with ethyl~crylic acid to for~ bis-(2-hydro~y ethyl)dithiocarbamyl 2thyl for~l tetr~acryl~te, [CH2~G(CH2c~3)c-o-cH2cH2lzNc-s-cH2 c(oCH3~2 O S C~2 1CH2~C(CH2CH3C-O-CH2CH2]2-NC- CH2 7~
1 The acrylate ter~inated polyurethane of formula II may be pre-pared by various methods that are well known in ~he i~ocyanate art. For exsmple, the acrylate ter~inated polyurethane of Formula II ~ay be pr~pared by r~acting 2 mole~ of a diol monoacrylate Witll a diisocyanate, RIII
l O
2cx2~c-c-o--RIv--oH ~ O~C~-R3-N=C=0 RIII
l O O
CH2~C-C-O---RlV-----O-C-N~
~III R3 O
. ..
H2~C-C---RIV 0-C-NH
For example, ethylene ~lycol diisocyanate may be r~acted ~ith two mole~ of hydroxy ethyl Rcrylate to give ethyle~e glycol diurethane bis(ethyl acrylate), O O
.. .-H0-C N~-CH2CH2-NHC-0~ ~
o .
2 CH2~CH-C-0-CH2CH20H
O O
,. ..
C~2~C~-C -O-C~2C~2 -O-C-NH
O C~2 CH2~CX-C-0-C~2CH2-0-C- NH
The acrylate terminated polyurethane of formuls IIa may be for~ed by reacting an excess of ~ diiaocyanate with a diol9 whereby to for~ a polyurethane having terminal isocyanate functionali~y, e~g., O~C~N-RA-N~C aO ~ ~O-RB-OII :~' o o 0 ~ C ~ N - RA ~ NH - C - 0 -~B~CCNH - RA ~ NC - O - R~0 - C - ~H RA ~ ~ ~ C 8 O, where n i~ 0 or an i~teger frol 1 to 50 or more, and generslly fro~ 1 to 10.
The re~ulting polyurethane dii~ocyanate~ ~hich may be ~ynonymously referred to a~ a polymer, ~ prepolymer, or sn Dli2o~er, i~ thereafter reacted with a material having acrylic and hydroxyl functionality, e.g., a mono arrylate of 8 diol, the mono acrylate ester ha~ing hydroxyl functionality, o .-0 2H2C~C~R~ Co-C(R~V)-(C~2)m-o~l 4 O O O O
(~C~N -RA-NH-C -O RB~ OCN~I-RA-NH-C -OWRB~ OC -NH-RA-~=C~O~
O O
li 11 (IIIa)H2C~C~R~ CO-C(RIV)-(CH2)m-0-5~N~
O O O
RA-MH-C-O-RB~ OC~ RA-NH-C -O-RB~ p-O-C-N~d-~
O O
a2CAC(RIII)C0-C(RIV)-(C~2)n-0-C-N~ .
While ~he inve~tion i~ illustrated ~ith respec~ ~o ~liph&tic diol bi~(allyl carbonates) and aliphatic polyurethane~ having terminal acrylate functionality, it i~ to be understo~d that the cyclic and aro~atic (allyl carbonateD) and the cyclic and sro~atic polyuretb~ne~ with termi-nal acrylate group~ may b~ u~ed. ThiR iB espç ially ~o in ~pplic~tion~
where hi~h optical indice~ of ~efraction are r~quired, or where Bome diRcoloration and yellowing may be tolerated.
i7~
1 The polymerizstion of the polyol (allyl carbon~te) composition iA initiated by the creation of ~ctive centers, e.g., free radical~.
U~eful free radical initi~tor~ ~re organic peroxy c~mpounds. The organic peroxy compound~ include: i~obutyryl peroxide; di(2-ethylhe~yl) p~roxy-dicarbonate; ~cetyl cyclohexan~ ~ulfonyl pero~ide; di(secbu~yl) peroxydi- -carbonate; diisopropyl pero~ydicarbonate; 2,4-dichlorobenzoyl peroxide9 ~-butyl peroxypivalste; decanoyl peroxide; lauroyl peroxidej propionyl peroxide; 2,5 dimethyl-2,5-bi~(2-ethyl hexylpero~y) hexane; acetyl perox-ide; ~uccinic acid pero~ide; t-buSyl peroxyoctoate; ben~oyl pero~ide;
p-chloroben~oyl pero~ide; t-b~tyl peroxyiaobutyrate; t-butyl pero~y~aleic acid; bia(l-hydrosycyclohexyl) peroxide, l-hydroxy~ hydroperoxy dicyclo-hexyl pero~ide; t-butyl peroxyi~opropyl carbonate; 2~5-dimethyl 2,5~bi~-(ben~oylperoxy) he~ane; t-butyl peroxyacetate; methyl e~hyl ~e~one pe~o~ide~;
ti-t-butyl diperoxyphthalate and t-butyl pero~ybenzoate. Al00 useful nre diazo compounds, e.g., azo i~obutyryl nitrile.
E~pecially prefesred ini~iutors are tho~e ~hat do n~t discolo~
the resulting polymerizate. Exe~plary are diisopropyl pero~ydic~rbonate and ben~oyl peroxide.
According to ~ne particula~ly pref¢rred e~emplificaeiQn herein contemplated, a liquid oomposition ia prepared containing fro~ about 80 to about 90 pe~cent diethylene ~lycol bi~(allyl csrban~ee) ant bala~ce ure-thane oli~mer with acrylic fu~ctionality ha~ing the Gtructure repre~ented by repre~entation IIa, and a molecular weîght of about 1300 ~o about 1500.
To this liquid compo~ition i~ added about 3.0 weight percent diisop~opyl-pero~ydicarbona~e, ba~ eight of the diethylene glycol bis(allyl c~rbon- -hte~. The compo~ition i~ plac2d in a mold in nn Anerobic at~o~phere, and the liquid co~po~ition i~ ~]Lowly he~ted fro~ roo~ temperAture to ~bout ~¢~
100 degree~ Centigrade over a period of 18 hours. ~he re~u1~ing h~rd poly-meri~ate ca~t in the for~ of the mold e~hibita an enhanced impact ~trength.
The following e~smple~ are illustr~tive oi the ~ethGd of thiD
invention.
EXAM LE I
A ~eries of te~t~ ~ere run to deter~ine the effe t of the addi-tion of ~crylated polyurethane on the Notched Izod Strength of ~ diol bis-(allyl carhonate) polymer.
Five aheet~ were prepared by ca~ting a solution of PPG Indu~trie~, Inc. CR-39~ diethylene ~lycol bis(allyl carbon~te) containing 3.5 weight percent i~opropyl peroxydicsrbonAte between a pair of gl~ss ~heets ~ep~-r~ted by a one-eighth inch g~sket. l~e c~stings were cured ~ccording to the following cure cycle:
Elap~ed Time ~hours) Temperatureg C
2 ~
201~ 4~
14 5~
16 - 54.5 ~0 61 24 g8 . 1 100 7~
l Five sheets were prepared by ca~ting a ~olu~ion of 8705 ~eight percent PPG Industriea, Inc. CR-39~ diethylene ~lycol bi~allyl csrbon3te) snd 12.5 weight percent Thiokol Chemical Co. WITHANE~-893, 1300 ~olec~lar weight diacrylated urethane oligomer, ba~i~ total mon~mer~, and 3.5 weight percent i~opropyl pero~ydic~rbonate, b~ weight Df diethylene ~ly~ol bi~(allyl carbonate). The aolution w~e cu~ed ~ccording to the abovQ cure cycle.
Both ~eCs of fiYe ~heets ~ere cue into four ~pe~ime~s per ~heet.
Each ~peci~en wa~ notched and subjected t~ n I od Notched Impact Teat.
The results sho~n in Table I were obtained:
Table I - Izod Notched I~pace Strengths In ~oot-Pounds/Inch of One-Eighth Insh Sheet 8 Sheeta 1 to 5: Diethylene Glycol Bi~(Allyl Carbonate) Sheet l Sheet 2 Sheet 3 Sheet 4 Sheet 5 Teat 1 0.51 0.23 0.24 0.31 0.~3 Te~t 2 0.24 0.31 0.3l 3.31 0.31 Tese 3 0.24 0.31 0.24 0.31 0.31 Te~t 4 0.40 0.31 0.24 0.46 0.31 20 Min. 0.24 0.23 0.24 0.31 0.23 ~ax. 0.51 0.31 0.31 0.46 0.31 Mesn 0.348 0.290 0.258 0.34B 0.290 Variance 0.0174 0.0016 0.00123 0.00563 0.0016 Std. Dev. 0.132 0.040 0.035 0.075 a.o40 Average of 20 Tests ~ 0.32 7~3 1 Sheets 6 to 10: Diethylene Glycol Bis(Allyl Carbonate) ~ 12.5 Weighe Percent Polyurethane With Terminal Acrylate Sheet 6 Sheet 7 Sheet 8Sheet 9 Sheet 10 Test 10.30 0.46 0.38 0.37 0.48 Test 20.75 0.24 0.51 0.31 0.39 Test 30.53 0.49 0.44 0.53 0.32 Test 40.29 0.23 -- 0.46 0.32 Min. 0.29 0.23 0.31 0.32 0.32 Max. 0.53 0.51 0.53 0.45 0.48 Mean 0.543 0.390 0.4180.378 0.378 Variance 0.082a 0.014 0.009 0.005 0.005 Std. Dev. 0.288 0.119 0.097 0.076 0.076 Average of 19 Tests --- --- 0.043 ---The 35 percent increase in I~od Notched Impact Test strength was ~tatintically nignificant at ehe 99.5 percent confidencF level.
EXAMPLE II
A series of tests were run to deter~ine the effect of the addi-tion of acrylAted urethane on the ~oeched Izod Strength of a diol bi~allyl carbonate) polymer.
Five sheets were prepared by casting ~ solution of PPG Industries, Inc. CR-39~ diethylene glycol bis(allyl carbonate~ containing 3.S weight per-cent inopropyl peroxydicarbonate between a pair of glass sheets separated ~ 16 -i 7 ~ ~
1 by a one-eigheh inch ga~ket. The c~ting~ were rured according to ehe following cure cycle:
~lap~ed Time (hours) Temperature ~C
2 ~4 6 ~6 lS 54.5 23 7g 24 .1 150 ~i~e ~heet~ were prepared by casting a ~olution of 75 ~eight percent PPG Indu0trie~, Inc. CR 39~ diethylene glycol bi~all~l carbonaee) and 25 veight percent Thiokol Chemical Co~ UVITHANE~-893, 1300 ~olecular ~eight, diacrylated urethane oligomar, basi~ tot~l ~ono~er~, a~d 3.5 w~ight percent isopropyl peroxydicarbonate, basis weight of diethylene glycol bi~(~llyl carbonate). The Dolution wa~ cured s~cording to the above cure cycl~. -~:~.¢.~i741~
l BoCh seta of five ~heets were eut into individual apeci~ens.
Each ~peciman W~8 notched ~nd ~ubjected to ~n I~od Notehed Impact Te~t.
The result~ shown in Table II ~ere Gbtained:
Table II - Izod Notched I~pact Strengtha In Foot-Pound~/lnch of One-Eighth Inch Sheet~
Sheet~ 1 to 5: Diethylene Glycol Bis(Allyl Csrbonate) Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Test l 0.42 0.41 0032 0.~0 0.50 Te~t 2 0.25 0.48 0.38 0.46 Teat 3 0.49 0.48 0.39 0.47 Test 4 0.32 0.31 0.38 Test 5 0.40 0.39 0.S5 Te~t 6 0.46 0.46 0.46 Te~t 7 0.62 Te~t 8 Min. 0.25 0.32 0.32 0.31 0.38 ~a~. 0.49 0.48 0.32 0.4S 0.62 ~an 0.39 0.43 0.32 0.38 0.49 Variance 0.015 0.003 --- 0.0023 0.005B
Std. Dev~ 0.12 0.06 --- 0.048 0.076 Average ~ 0.43 7~3 1 Sheet~ 6 to 10: Diethylene Glycol ~is(Allyl Carbonate) ~ 25 ~eight Percent Polyurethane With Terminal Acrylate Sheet 6Sheet 7 Sheet 8 Sheet 9 Sheet 10 TeAt 1 0.54 0.53 0.50 0 53 0.62 Tcst 2 0.54 0.60 0.38 0.45 0.62 Te~t 3 0.54 Q.30 0.54 0.53 0.46 Test 4 0.54 0.59 0.67 0.53 0.45 Te~t 5 0.54 0~60 0.54 0.53 0-54 Te~t 6 0.62 0.59 0.54 0.45 0.53 lO Te~t 7 0.54 0.60 0.54 ___ 0.62 Test 8 0.54 ~in. 0.54 0.30 0.38 0.45 0.45 Max. 0.62 0.60 0.67 0.53 0.62 Me~n 0.55 0.54 0.53 0.50 0.55 V~riance 0.0008 0.012 0.0072 0.0017 0.0055 Std. Dev. 0.028 0.11 0.085 0.041 0.074 Average ~ 0,54 The 17 perceot increa~e in the Izod Notched I~pact Strength ~a~
stati~ticslly ~ignificant at the 99.9 percent cnnfide~ce l~vel.
Example III
A cerie~ of tests ~ere conducted to deter~i~e the steel b~ll impact ctrength of one ~ixteenth inch thick ~heet~.
7~
1 Ten ~heet~ were prepared by ca~ting a solution of PPG Industrie3, Inc. CR-39~ diethylene glycol bi~(811yl carbonate) containing 3.5 weight percent i~opropyl peroxydicarbonate between a pair of gla8s sheee~ ~ep~r~ted by ~ one sixteenth inch gasket.
Ten Aheet~ were prepured by c~ting a ~ol~tion of 87.5 weight percent PPG Industries~ Inc. CR-39~ diethylene ~lycol bi~(allyl carbon~te) and 12.5 wei~ht percent Thiokol ChemicAl Co. UVITHANE~-893 diacrylated urethane oligomer, baais toeal ~onomera, and 3.5 ~eight percent i~opropyl peroxydicsrbonate, bRsis weight of diethylene glycol bi~(allyl carbonate), a~ described Above.
Ten sheet~ were prepared by cssting ~ solution of 75 ~eighe per-cene PPG Intuseries, Inc. CR-39~ diethylene glycol bis(allyl c~rbonate~ and 25 weight percent Thiokol Che~icAl Co. W IT~ANE~-893 diacrylated urethane oligo~er, ba~is total ~ono~ers, ~nd 3.5 ~ei8ht percent i~op~opyl peroxydi-carbonate, bs~i~ weight of diethylene glycol bis~allyl carbonate), a~ -described ~bove.
All of the aample~ ~ere cured according to the follo~ing c~re cyC 1P
E1APBed Time (hour~) Temperature, C
0 ~2 8 l~7 4~
1~ ~4.5 - 2~ -jjt79~
Elapsed Tlme (hours) Temperature, C
22 6~
24.1 100 Each of the sheets were tested in accordance with American National Standards Institute Standard Z 87.1-1979. The apparatus was the same as that described in the standard at section 5.1.4.1.6, paragraph 4, except that a 1.5 inch diameter guide tube extended to within 2 inches of the sample.
The following results were obtained:
TABLE III
Steel Ball Impact Test Diethylene Glycol Diethylene Glycol Diethylene Glycol Bis(Allyl Carbonate Bis + 12.5~ (Allyl Bis(Allyl Carbonate) Carbonate ~ 25~ Diacrylate + 12.5~ Diacrylate Urethane Oligomer Material Urethane Oligomer Diameter (inches) Numer of Castings 10/16 o 0 0 broken in successive impacts 11/16 0 0 o with diEferent 12/16 1 0 0 diameter steel 13/16 4 1 0 balls Number Surviving 16/16 inch steel balls 1 0 7 - 21 _ 7~
1 ~x8mple IV
A serie~ of tea~a ~ere conducted to determine the Gardner ~teel ball impnct ~trength of one eighth inch thick heets.
Ten ~heets were prepared by casting a aolutioD of PPG Industries, Inc. CR-39~ diethylene glycol bi~(allyl carbon~te) containing 3.5 weight percent i~opropyl pero~ydicarbonate beeween a pair of glaa~ ahee~s ~eparated by ~ one-eighth inch ga~ket.
Ten sheets ~ere prepared by castin8 a aolution of 87.5 weight percent PPG Indu~tries, Inc. CR-39~ diethylene glycol bi~(~llyl carbon~te) and 12.5 ~ei8ht percent Thiokol Chemical Co. UVITHANE~-893 di2crylated urethane olig~mer, ~asis total monomers, snd 3.5 weight percent isopropyl peroxydicarbonate, b2sis weight of diethylene glycol bis~allyl ~rbon~te), ~8 described abo~e.
Ten ~heet~ ~ere prep~red by cnsting ~ ~olution ~f 75 weight per-cent PPG Induatrie3, Inc. C~-39~ diethylene glycol bi~(allyl s~rbonate) and 25 weight percent Thiokol Chemical Co. WIT~ANE~-893 diacrylated urethane oligomer, baaiq total ~on~mer~, and 3.5 weight percent i~opropyl pero~ydi-c~rbon~te, bnsis weight of diPthylene ~lycol bia(~llyl c~rbon~te)~
deacribed nbove.
All of the ~ample~ w~re cured accGrding to the following cure cycle:
Elapaed Time (hour~) Temper~ture, C
4 ~5 ~6 ~¢~
Elapsed Ti~e (hour~) Temperature~ 'C
~3 79 ~4.1 100 ~ach ~heet wa~ ~ubjected to a Gardner I~pact Strength Test, in which eash sbeet was ~ubjected to an increasingly hi8her i~pact, until the sheet failed. The follo~in& results ~ere obtained:
TABLE IV
Gardner I~p~ct Test~ s~f ~lat Sheees (1/8") ~t-lba Required to Break Len~e~ Uaing Multiple Increaaing Impacts Average Bresk (an "~" denotea a sample break; a "-" denote~ ~ur~ival~ Ft-lbs 0.17 0.33 0.50 0.67 0.83 1.00 1.17 1.33 1~0 1.67 PPG CR-39~ Diethylene Glycol Bis(Allyl Carbonate) ~opolymer -- X
X
- - ~ X 0.63 X
;7~
Gardner Impact Tests of Flat Sheets (1/8") Ft-lbs Required to Break Len~es Using Multiple Increasing Impacts Aversge Break (an "X" denotss a sample break; a "-" denotes survival) Ft-lbs 0.17 0.33 0.50 0.67 0.83 1.00 1.17 1.33 1.50 1.67 87.5X PPG CR-39~ Diethylene Glycol Bis(Allyl Carbonate) ~ 12.5~ Thiokol "UVITHANE" 393 Polyurethane with Terminzl Acrylate Functionality X
X
X 1.1 y X
X
X
X
75Z PPG CR-39~ ~iethylene Glycol Bi~Allyl Carbonate) 1 25% Thiokol "~VIT~ANE" 893 Polyurethane with Ter~inal Acrylate Functionality -- X
-- -- -- X
~ 1.3 -- -- X
-- -- -- X
-- -- X
-- -- X
-- -- -- X
-- -- X
-- -- X
While the invention has been de3cribed with respect to certain preferred exemplifications and embodiment~, the scope of the inveneion i~
not to be limited thersby, but i8 solely defined by the claims Appended hereto.
- 2~ -
~ owever, a~ounts of the scrylate terminated polyurethane above about 40 to 50 weigh~ percent ~hould be avoided ina~much a8 nt level~ of the ~crylate terminated polyureth~ne above about 40 to 50 weight percent, basis total organics, the chemical resiatance of the polymeri~ate begins to declina ~elative to that of the polyol(allyl carbona~e). aoweYer, higher levels of acryl~te ter~inated polyurethane ~ay be utilized ~here chemical re~istance i9 not essential.
The te~inally scrylic polyurethane~ herein contemplat2d, includ- -ing dithiocarb&myl e~eers, as will be de~cribed mo~e fully hereinbelo~, preferably ha~e a moleeular weight of ~rom about 350 eo about 3500, ~d preferably from about 500 to ~bou~ 2000. Hi8her ~olecular weight termi-nslly acrylic polyurechanes do not appear to provide ~uffieient arrylate acti~ity for ehe degree of polymerization and cro~ linking deslred while ter~inally acrylic polyureth~nes ha~ing a ~oleculsr ~eight belo~ about 300 do not appear to offer ~ufficiene ~olecul~r weight or poly~rethane func~
tionnlity to provide the deaired enhanrenent of the physical propertie~ of ~he re~ulting polymerirate.
~olyol(allyl carbonate) mon~mer~, such a~ diol bis(allyl carbo~- -nteD), triol tris(allyl carbonate~ nd higher h~mologuea, ~hi~h ~ay be ~opolymerized by the method of thi~ invention ar~ normally aliphatic liquid allyl rarbonates, e.g., glycol bia(allyl carbonat~) compound~, in which the allyl groups may be substituted at the 2 position with a halogen, notably chlorine or bromi~e, or a 1 to 4 carbon alkyl group~ generally ~ ~ethyl or ethyl group. For diol bis(allyl carbonate~) the glycol re~id~e ~ay be an alkylene, alkylene ether, alkylene polyether5 alkylene carbonaee, or 7~S~
cycloahphatic group having from 2 to 10 carbon6 ~nd oxygen~. Exempl~ry diol bi~(allyl carbonate) monomer~ are repre~ented by the formula:
O O
.. ..
Rl - 0 - C - 0 - R2 ~ - C 0 - R3 where Rl ~nd R3 are allyl or ~ub~tituted allyl groupa, and R2 iB ~ defined below. Rl and R3 are independently repre~ented by the formula: -Rl H2C ~ C- CH2-~here Rl mny be hydrogen, halogen, or ~ 1 to 4 c~rbon alkyl group. Spe-cific exa~ple~ of Rl and R3 include allyl, 2-chloro~llyl, 2 bromo~llyl, 2-iodo~llyl, Z-fluoro~llyl, 2w~ethallyl, 2-eshylallyl, 2-iaepropylallyl, 10 2-n-propylallyl, ~nd 2-n-butylallyl group~. Most cG~monly, Rl ~nd R3 ~re allyl groupR, H2C ~ C~ - CH2-. Such compound~ ~nd ~ethods for makin~ them are di~clo~ed in ~. S. Patents 2,3~0,567 and 2,403,113.
Speciiic ax~mple~ of a2 ~re alkylene groups 8uch A~ ethylene, trimetbylene, ~ethylethylene, tets&methyle~e, ethylethyl~ne, pentamethylene, hexamethylene, 2-methylhe~2me~hylene, ~cesmethylene, ~nd dec~methyle~e group~, ~lkylene ather g~oup8 auch ~ -C~2~0-c~2-s -~H2C~2-0-CH2C~2 3 -C~2-0-CH2-C~2-- ~nd -CH2C~2CH2-0-CH2 CH2C~2-, ~lkyle~e poly~tber groups ~uch ~ CH2CH2 -0-CM2CH2-0-CH2C~2-O-cH2c~20-cH2c~2 &nd C~2 CH2 group~, ~lkylene c~rbon~te groups such ~ C~CH2 -O~C0-0-CH2CK2 ant -C~2CH2-0-C0-0-CH2CU2-0-C0-0-CH2 C~2-0-C0-OCH2CH2- groups, ~nd cyclo ali- -phatic groups, as 1,4 cyclohexane dimethanol bi~ (Nllyl carbonate~. Most commonly, R2 i3 -CH2Ca2-, CH2CH2-0-C~2C~2-, or -C~2C~2-O C~CH2-~-C~C~
Specific exsmple~ of diol bi~(allyl carbonate) mon~Ders u~eful in c~rrying ou~ the method herein contemplated include ~thylene glycol bi~
(2-chlor~llyl carbonate), diethylene gly~31 bi~2-~etballyl c~rbonate~, -;7~
1 triethylene glycol bis(allyl carbonate), propyle~e glycol bi3(2-e~hylallyl carbonate), 1,3-propanediol bi~(allyl c~rbonate), 1,3-butanediol bis~allyl carbonate), l,4-butanediol bis(2-bromoallyl carbonste) 9 dipropylene glycol bis(~llyl carbonate), trimethylene glycol bis~2-ethylallyl carbonate), and pentamethylene glycol bi~allyl carbonate).
Com~ercially important diol bi~allyl carbonate~ monomers which ~ay be polymerized by the method herein conte~plated ~re:
O O
.. ,.
CH2 - CH-CH2-(:)-C-O-C~2-CH2-0-CH2CH2-0-Ctl2 CH2-0-C-O-CH2C~ D~ CH2, O O
.. ..
CH2 ~ CH-CH2-0-C-O-C'tl2CH2-0-CH2CH2-0-C-OCH?-C~1 2.CH2, O O
.. ..
and CH2 ~ CH-CH2-~-C-D-CH2CH2-0-C-O-C8~-C~ ~ CH2.
The method~ of thi~ invention ~ay al~o be utili~ed ~o ccpolymerize 1,4 cyclohexane di~ethanol bis(allyl carbonate)~ snd to copoly~eri~e triol tria(allyl carbonatea) a~ described in U.S. Patent 4,144,~62 eo Stevens for TRIALLYL CARBONATE MONOMERS. The pol~methane~ h~ving terminal ~crylic groups which can be copoly~eri~ed according to this invention Are characteri~ed by ter~inal acrylate group~, i.2., acrylic ~cid groupa, methacrylic ~cid groups, ethyl acrylic acid group~, ~ethyl acrylate group~, ~ethyl meth-ncrylate groups, ethyl methacryl2te groups5 or the like, a~d internal carbamate bond6, including dithiocarb~ate bonda.
Whenever the terms "polyurathane having ter~inal acrylate func- -tionality", "acrylated urethane oligomer", "acrylated carbamyl esterl', or "polyacrylate having internal carbamate bonds", are used herein, they are used interchangeably and ~ynonymou~ly.
_ 5 _ ~a~
Whenever the terms "urethane", "carbamate", and "carbamyl" are used herein, they are intended to interchangeably and synonymously refer to the sulfur analogs, unless the contrary shall be clearly indicated by the context.
The polyurethsnes having terminal acrylate functionality which can be copolymerized according to ~his invention are normally li~uid, ali-phatic diacrylate, triacrylate, and tetra acrylate polyurethanes.
According to one exemplification herein contemplated, the poly-acrylate having internal polyurethane, including dithiocarbamate, functionality has the formula:
(I) RIIIo X
[H2C = C - C - O - R ~-~~ ~ NH2 - C - X
~ O X R3 L~2 C = C - C - O - R ~~~] -NH2 - C - X
while according to an alternative exemplification, the polyacrylate having internal polyurethane functionality has the formula:
(II) RIII X
O "
LH2 C = C C 0 ----R - X - C~ 1 2-Y
LH2C = 1 C - 0 - RVI X X] 2-z ~....
1 i.e., - (IIa) RIII
O
[H2C e C ~ C -- O ~ RIV --------X--C--3y NH2_y NH
C~X
X
~f~
RV E~4 O O
~12C 3 ~ - C - O - RVI --X-C ~ 1 NH2-~
wbsre omega i6 ~uch as to proYide the desir~d molerular ~eight.
In For~ulae (I), (II), and (lIa) R~II and BV are independently chosen from the group consisting cf -H and -CH3, RIV ~nd RVI are inde-pendently cho~en from the group con~isting of Cl to Clo alkyl~, including branched alkyls. Most commonly RIV and RVI are -CH2CH2-, y and ~ are inde-pendently 1 or 2, X is cho~en fro~ the group con~isting of osygan and 8ul-fur. In Formula I R3 i~ chosen frGm the group consisting of ~lkylene groupsa ~lkylene e~her group~, alkylene polyether groupa, alkylene carbonate group3, aromatic group~, polyureehsn~ group~, ~nd polythiourethane group~. In Formula II
R3 iB derived from the reactions of polyols with aliphatic and aromatic polyisocyanates, i.e., R3 i9 polyurethane. In Formula IIa, R4 i~ derived fr~r the di-i~oryanate, and Rs i~ independenely ~ C2 to Cl~ ~Ikylene group derived from the diol.
The acrylaee terminated polyurethane of Formula I may be prepared by reacting two moles of an alkali metal hydroxy carbamate, LHO_RIV___NH_C_X~ Na , or [(HO-R~ )2N-C-X~ Na with a mole of an alkyl dichloride, Cl-R3-Cl, whereby to form a diol having internal carbamate bonds, including dithio-carbamate bonds, H0--R ---NH-C-X-r T~ lR3 H0--R V---NH-C-X_ X
~H0-R ---~2N-C-X-Ho-RIv NH Rc x ! or --R ---~ 2N-C-X__ ~3 ~H--R -----]2N-C_X_ which may then be reacted with an acrylic acid.
According to one exemplification of preparing the polyacrylate of Formula 1, 2-N-hydroxy ethyl carbamic acid sodium salt may be reacted with 1,5-dichloropentane to glve 1,5-bis(2-N-hydroxy ethyl carbamyl)pentane, '7~
2(HOCH2CM2NH-C-0) Na~ ~ ClCH2CH2CH2 CH2CH2Cl~
o HOCU2CH2NH-C-O-ClH2 r.H "
The resulting 1,5-bis~2-N hydroxy ethyl carbamyl) pentane may ~hen be reacted with acrylic acid to give the corre~ponding bis(acrylate).
Ho-cH ~cH2-NH-c-Q-cH2 lH2 HO-CH2CH2-NH-C-O-C~2 o 2 CH2-CH-C-OH--~
O O
CH2-CH-C-0-CH2cH2-NH-c-O-lH2 CH2 ~ 2H20 o O CH2 CH2~(CH-C-O-CM2CH2-NH-C-0 CN2 According to an alternative exempliiicaticn of preparing the poly-acrylate of formula I, diethanol amine may be reacted with carbon di~ulide in the pre~ence of cau~tic ~oda to yield ~odium ethyl dithiocarbamate;
i 7~
~aO~
(HOCH2CH2 ) 2NH + CS2 ~q S
1(HOCH2CH2)2NC-S]
Thereafter a saturated dichloride, ~.g., bi~-~2-chloroethyl) formal, i3 ddded to the aqueous 801ution to bia-(2-hydroxyethyl) dithiocarbamyl ethyl formal, S
2 [(HOCH2CH2)2NC-S]- N~
+ Cl - C~2CH2 - C~OCH3~2 CH2CH2Cl S
(HOCH2C}12 ) -~C-S-CI H2 C~OGH3)2 ~ 2NaCl.
S
(lBOCH2CM2 ) 2NC-S-C112 This material i~ then reacted with ethyl~crylic acid to for~ bis-(2-hydro~y ethyl)dithiocarbamyl 2thyl for~l tetr~acryl~te, [CH2~G(CH2c~3)c-o-cH2cH2lzNc-s-cH2 c(oCH3~2 O S C~2 1CH2~C(CH2CH3C-O-CH2CH2]2-NC- CH2 7~
1 The acrylate ter~inated polyurethane of formula II may be pre-pared by various methods that are well known in ~he i~ocyanate art. For exsmple, the acrylate ter~inated polyurethane of Formula II ~ay be pr~pared by r~acting 2 mole~ of a diol monoacrylate Witll a diisocyanate, RIII
l O
2cx2~c-c-o--RIv--oH ~ O~C~-R3-N=C=0 RIII
l O O
CH2~C-C-O---RlV-----O-C-N~
~III R3 O
. ..
H2~C-C---RIV 0-C-NH
For example, ethylene ~lycol diisocyanate may be r~acted ~ith two mole~ of hydroxy ethyl Rcrylate to give ethyle~e glycol diurethane bis(ethyl acrylate), O O
.. .-H0-C N~-CH2CH2-NHC-0~ ~
o .
2 CH2~CH-C-0-CH2CH20H
O O
,. ..
C~2~C~-C -O-C~2C~2 -O-C-NH
O C~2 CH2~CX-C-0-C~2CH2-0-C- NH
The acrylate terminated polyurethane of formuls IIa may be for~ed by reacting an excess of ~ diiaocyanate with a diol9 whereby to for~ a polyurethane having terminal isocyanate functionali~y, e~g., O~C~N-RA-N~C aO ~ ~O-RB-OII :~' o o 0 ~ C ~ N - RA ~ NH - C - 0 -~B~CCNH - RA ~ NC - O - R~0 - C - ~H RA ~ ~ ~ C 8 O, where n i~ 0 or an i~teger frol 1 to 50 or more, and generslly fro~ 1 to 10.
The re~ulting polyurethane dii~ocyanate~ ~hich may be ~ynonymously referred to a~ a polymer, ~ prepolymer, or sn Dli2o~er, i~ thereafter reacted with a material having acrylic and hydroxyl functionality, e.g., a mono arrylate of 8 diol, the mono acrylate ester ha~ing hydroxyl functionality, o .-0 2H2C~C~R~ Co-C(R~V)-(C~2)m-o~l 4 O O O O
(~C~N -RA-NH-C -O RB~ OCN~I-RA-NH-C -OWRB~ OC -NH-RA-~=C~O~
O O
li 11 (IIIa)H2C~C~R~ CO-C(RIV)-(CH2)m-0-5~N~
O O O
RA-MH-C-O-RB~ OC~ RA-NH-C -O-RB~ p-O-C-N~d-~
O O
a2CAC(RIII)C0-C(RIV)-(C~2)n-0-C-N~ .
While ~he inve~tion i~ illustrated ~ith respec~ ~o ~liph&tic diol bi~(allyl carbonates) and aliphatic polyurethane~ having terminal acrylate functionality, it i~ to be understo~d that the cyclic and aro~atic (allyl carbonateD) and the cyclic and sro~atic polyuretb~ne~ with termi-nal acrylate group~ may b~ u~ed. ThiR iB espç ially ~o in ~pplic~tion~
where hi~h optical indice~ of ~efraction are r~quired, or where Bome diRcoloration and yellowing may be tolerated.
i7~
1 The polymerizstion of the polyol (allyl carbon~te) composition iA initiated by the creation of ~ctive centers, e.g., free radical~.
U~eful free radical initi~tor~ ~re organic peroxy c~mpounds. The organic peroxy compound~ include: i~obutyryl peroxide; di(2-ethylhe~yl) p~roxy-dicarbonate; ~cetyl cyclohexan~ ~ulfonyl pero~ide; di(secbu~yl) peroxydi- -carbonate; diisopropyl pero~ydicarbonate; 2,4-dichlorobenzoyl peroxide9 ~-butyl peroxypivalste; decanoyl peroxide; lauroyl peroxidej propionyl peroxide; 2,5 dimethyl-2,5-bi~(2-ethyl hexylpero~y) hexane; acetyl perox-ide; ~uccinic acid pero~ide; t-buSyl peroxyoctoate; ben~oyl pero~ide;
p-chloroben~oyl pero~ide; t-b~tyl peroxyiaobutyrate; t-butyl pero~y~aleic acid; bia(l-hydrosycyclohexyl) peroxide, l-hydroxy~ hydroperoxy dicyclo-hexyl pero~ide; t-butyl peroxyi~opropyl carbonate; 2~5-dimethyl 2,5~bi~-(ben~oylperoxy) he~ane; t-butyl peroxyacetate; methyl e~hyl ~e~one pe~o~ide~;
ti-t-butyl diperoxyphthalate and t-butyl pero~ybenzoate. Al00 useful nre diazo compounds, e.g., azo i~obutyryl nitrile.
E~pecially prefesred ini~iutors are tho~e ~hat do n~t discolo~
the resulting polymerizate. Exe~plary are diisopropyl pero~ydic~rbonate and ben~oyl peroxide.
According to ~ne particula~ly pref¢rred e~emplificaeiQn herein contemplated, a liquid oomposition ia prepared containing fro~ about 80 to about 90 pe~cent diethylene ~lycol bi~(allyl csrban~ee) ant bala~ce ure-thane oli~mer with acrylic fu~ctionality ha~ing the Gtructure repre~ented by repre~entation IIa, and a molecular weîght of about 1300 ~o about 1500.
To this liquid compo~ition i~ added about 3.0 weight percent diisop~opyl-pero~ydicarbona~e, ba~ eight of the diethylene glycol bis(allyl c~rbon- -hte~. The compo~ition i~ plac2d in a mold in nn Anerobic at~o~phere, and the liquid co~po~ition i~ ~]Lowly he~ted fro~ roo~ temperAture to ~bout ~¢~
100 degree~ Centigrade over a period of 18 hours. ~he re~u1~ing h~rd poly-meri~ate ca~t in the for~ of the mold e~hibita an enhanced impact ~trength.
The following e~smple~ are illustr~tive oi the ~ethGd of thiD
invention.
EXAM LE I
A ~eries of te~t~ ~ere run to deter~ine the effe t of the addi-tion of ~crylated polyurethane on the Notched Izod Strength of ~ diol bis-(allyl carhonate) polymer.
Five aheet~ were prepared by ca~ting a solution of PPG Indu~trie~, Inc. CR-39~ diethylene ~lycol bis(allyl carbon~te) containing 3.5 weight percent i~opropyl peroxydicsrbonAte between a pair of gl~ss ~heets ~ep~-r~ted by a one-eighth inch g~sket. l~e c~stings were cured ~ccording to the following cure cycle:
Elap~ed Time ~hours) Temperatureg C
2 ~
201~ 4~
14 5~
16 - 54.5 ~0 61 24 g8 . 1 100 7~
l Five sheets were prepared by ca~ting a ~olu~ion of 8705 ~eight percent PPG Industriea, Inc. CR-39~ diethylene ~lycol bi~allyl csrbon3te) snd 12.5 weight percent Thiokol Chemical Co. WITHANE~-893, 1300 ~olec~lar weight diacrylated urethane oligomer, ba~i~ total mon~mer~, and 3.5 weight percent i~opropyl pero~ydic~rbonate, b~ weight Df diethylene ~ly~ol bi~(allyl carbonate). The aolution w~e cu~ed ~ccording to the abovQ cure cycle.
Both ~eCs of fiYe ~heets ~ere cue into four ~pe~ime~s per ~heet.
Each ~peci~en wa~ notched and subjected t~ n I od Notched Impact Teat.
The results sho~n in Table I were obtained:
Table I - Izod Notched I~pace Strengths In ~oot-Pounds/Inch of One-Eighth Insh Sheet 8 Sheeta 1 to 5: Diethylene Glycol Bi~(Allyl Carbonate) Sheet l Sheet 2 Sheet 3 Sheet 4 Sheet 5 Teat 1 0.51 0.23 0.24 0.31 0.~3 Te~t 2 0.24 0.31 0.3l 3.31 0.31 Tese 3 0.24 0.31 0.24 0.31 0.31 Te~t 4 0.40 0.31 0.24 0.46 0.31 20 Min. 0.24 0.23 0.24 0.31 0.23 ~ax. 0.51 0.31 0.31 0.46 0.31 Mesn 0.348 0.290 0.258 0.34B 0.290 Variance 0.0174 0.0016 0.00123 0.00563 0.0016 Std. Dev. 0.132 0.040 0.035 0.075 a.o40 Average of 20 Tests ~ 0.32 7~3 1 Sheets 6 to 10: Diethylene Glycol Bis(Allyl Carbonate) ~ 12.5 Weighe Percent Polyurethane With Terminal Acrylate Sheet 6 Sheet 7 Sheet 8Sheet 9 Sheet 10 Test 10.30 0.46 0.38 0.37 0.48 Test 20.75 0.24 0.51 0.31 0.39 Test 30.53 0.49 0.44 0.53 0.32 Test 40.29 0.23 -- 0.46 0.32 Min. 0.29 0.23 0.31 0.32 0.32 Max. 0.53 0.51 0.53 0.45 0.48 Mean 0.543 0.390 0.4180.378 0.378 Variance 0.082a 0.014 0.009 0.005 0.005 Std. Dev. 0.288 0.119 0.097 0.076 0.076 Average of 19 Tests --- --- 0.043 ---The 35 percent increase in I~od Notched Impact Test strength was ~tatintically nignificant at ehe 99.5 percent confidencF level.
EXAMPLE II
A series of tests were run to deter~ine the effect of the addi-tion of acrylAted urethane on the ~oeched Izod Strength of a diol bi~allyl carbonate) polymer.
Five sheets were prepared by casting ~ solution of PPG Industries, Inc. CR-39~ diethylene glycol bis(allyl carbonate~ containing 3.S weight per-cent inopropyl peroxydicarbonate between a pair of glass sheets separated ~ 16 -i 7 ~ ~
1 by a one-eigheh inch ga~ket. The c~ting~ were rured according to ehe following cure cycle:
~lap~ed Time (hours) Temperature ~C
2 ~4 6 ~6 lS 54.5 23 7g 24 .1 150 ~i~e ~heet~ were prepared by casting a ~olution of 75 ~eight percent PPG Indu0trie~, Inc. CR 39~ diethylene glycol bi~all~l carbonaee) and 25 veight percent Thiokol Chemical Co~ UVITHANE~-893, 1300 ~olecular ~eight, diacrylated urethane oligomar, basi~ tot~l ~ono~er~, a~d 3.5 w~ight percent isopropyl peroxydicarbonate, basis weight of diethylene glycol bi~(~llyl carbonate). The Dolution wa~ cured s~cording to the above cure cycl~. -~:~.¢.~i741~
l BoCh seta of five ~heets were eut into individual apeci~ens.
Each ~peciman W~8 notched ~nd ~ubjected to ~n I~od Notehed Impact Te~t.
The result~ shown in Table II ~ere Gbtained:
Table II - Izod Notched I~pact Strengtha In Foot-Pound~/lnch of One-Eighth Inch Sheet~
Sheet~ 1 to 5: Diethylene Glycol Bis(Allyl Csrbonate) Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Test l 0.42 0.41 0032 0.~0 0.50 Te~t 2 0.25 0.48 0.38 0.46 Teat 3 0.49 0.48 0.39 0.47 Test 4 0.32 0.31 0.38 Test 5 0.40 0.39 0.S5 Te~t 6 0.46 0.46 0.46 Te~t 7 0.62 Te~t 8 Min. 0.25 0.32 0.32 0.31 0.38 ~a~. 0.49 0.48 0.32 0.4S 0.62 ~an 0.39 0.43 0.32 0.38 0.49 Variance 0.015 0.003 --- 0.0023 0.005B
Std. Dev~ 0.12 0.06 --- 0.048 0.076 Average ~ 0.43 7~3 1 Sheet~ 6 to 10: Diethylene Glycol ~is(Allyl Carbonate) ~ 25 ~eight Percent Polyurethane With Terminal Acrylate Sheet 6Sheet 7 Sheet 8 Sheet 9 Sheet 10 TeAt 1 0.54 0.53 0.50 0 53 0.62 Tcst 2 0.54 0.60 0.38 0.45 0.62 Te~t 3 0.54 Q.30 0.54 0.53 0.46 Test 4 0.54 0.59 0.67 0.53 0.45 Te~t 5 0.54 0~60 0.54 0.53 0-54 Te~t 6 0.62 0.59 0.54 0.45 0.53 lO Te~t 7 0.54 0.60 0.54 ___ 0.62 Test 8 0.54 ~in. 0.54 0.30 0.38 0.45 0.45 Max. 0.62 0.60 0.67 0.53 0.62 Me~n 0.55 0.54 0.53 0.50 0.55 V~riance 0.0008 0.012 0.0072 0.0017 0.0055 Std. Dev. 0.028 0.11 0.085 0.041 0.074 Average ~ 0,54 The 17 perceot increa~e in the Izod Notched I~pact Strength ~a~
stati~ticslly ~ignificant at the 99.9 percent cnnfide~ce l~vel.
Example III
A cerie~ of tests ~ere conducted to deter~i~e the steel b~ll impact ctrength of one ~ixteenth inch thick ~heet~.
7~
1 Ten ~heet~ were prepared by ca~ting a solution of PPG Industrie3, Inc. CR-39~ diethylene glycol bi~(811yl carbonate) containing 3.5 weight percent i~opropyl peroxydicarbonate between a pair of gla8s sheee~ ~ep~r~ted by ~ one sixteenth inch gasket.
Ten Aheet~ were prepured by c~ting a ~ol~tion of 87.5 weight percent PPG Industries~ Inc. CR-39~ diethylene ~lycol bi~(allyl carbon~te) and 12.5 wei~ht percent Thiokol ChemicAl Co. UVITHANE~-893 diacrylated urethane oligomer, baais toeal ~onomera, and 3.5 ~eight percent i~opropyl peroxydicsrbonate, bRsis weight of diethylene glycol bi~(allyl carbonate), a~ described Above.
Ten sheet~ were prepared by cssting ~ solution of 75 ~eighe per-cene PPG Intuseries, Inc. CR-39~ diethylene glycol bis(allyl c~rbonate~ and 25 weight percent Thiokol Che~icAl Co. W IT~ANE~-893 diacrylated urethane oligo~er, ba~is total ~ono~ers, ~nd 3.5 ~ei8ht percent i~op~opyl peroxydi-carbonate, bs~i~ weight of diethylene glycol bis~allyl carbonate), a~ -described ~bove.
All of the aample~ ~ere cured according to the follo~ing c~re cyC 1P
E1APBed Time (hour~) Temperature, C
0 ~2 8 l~7 4~
1~ ~4.5 - 2~ -jjt79~
Elapsed Tlme (hours) Temperature, C
22 6~
24.1 100 Each of the sheets were tested in accordance with American National Standards Institute Standard Z 87.1-1979. The apparatus was the same as that described in the standard at section 5.1.4.1.6, paragraph 4, except that a 1.5 inch diameter guide tube extended to within 2 inches of the sample.
The following results were obtained:
TABLE III
Steel Ball Impact Test Diethylene Glycol Diethylene Glycol Diethylene Glycol Bis(Allyl Carbonate Bis + 12.5~ (Allyl Bis(Allyl Carbonate) Carbonate ~ 25~ Diacrylate + 12.5~ Diacrylate Urethane Oligomer Material Urethane Oligomer Diameter (inches) Numer of Castings 10/16 o 0 0 broken in successive impacts 11/16 0 0 o with diEferent 12/16 1 0 0 diameter steel 13/16 4 1 0 balls Number Surviving 16/16 inch steel balls 1 0 7 - 21 _ 7~
1 ~x8mple IV
A serie~ of tea~a ~ere conducted to determine the Gardner ~teel ball impnct ~trength of one eighth inch thick heets.
Ten ~heets were prepared by casting a aolutioD of PPG Industries, Inc. CR-39~ diethylene glycol bi~(allyl carbon~te) containing 3.5 weight percent i~opropyl pero~ydicarbonate beeween a pair of glaa~ ahee~s ~eparated by ~ one-eighth inch ga~ket.
Ten sheets ~ere prepared by castin8 a aolution of 87.5 weight percent PPG Indu~tries, Inc. CR-39~ diethylene glycol bi~(~llyl carbon~te) and 12.5 ~ei8ht percent Thiokol Chemical Co. UVITHANE~-893 di2crylated urethane olig~mer, ~asis total monomers, snd 3.5 weight percent isopropyl peroxydicarbonate, b2sis weight of diethylene glycol bis~allyl ~rbon~te), ~8 described abo~e.
Ten ~heet~ ~ere prep~red by cnsting ~ ~olution ~f 75 weight per-cent PPG Induatrie3, Inc. C~-39~ diethylene glycol bi~(allyl s~rbonate) and 25 weight percent Thiokol Chemical Co. WIT~ANE~-893 diacrylated urethane oligomer, baaiq total ~on~mer~, and 3.5 weight percent i~opropyl pero~ydi-c~rbon~te, bnsis weight of diPthylene ~lycol bia(~llyl c~rbon~te)~
deacribed nbove.
All of the ~ample~ w~re cured accGrding to the following cure cycle:
Elapaed Time (hour~) Temper~ture, C
4 ~5 ~6 ~¢~
Elapsed Ti~e (hour~) Temperature~ 'C
~3 79 ~4.1 100 ~ach ~heet wa~ ~ubjected to a Gardner I~pact Strength Test, in which eash sbeet was ~ubjected to an increasingly hi8her i~pact, until the sheet failed. The follo~in& results ~ere obtained:
TABLE IV
Gardner I~p~ct Test~ s~f ~lat Sheees (1/8") ~t-lba Required to Break Len~e~ Uaing Multiple Increaaing Impacts Average Bresk (an "~" denotea a sample break; a "-" denote~ ~ur~ival~ Ft-lbs 0.17 0.33 0.50 0.67 0.83 1.00 1.17 1.33 1~0 1.67 PPG CR-39~ Diethylene Glycol Bis(Allyl Carbonate) ~opolymer -- X
X
- - ~ X 0.63 X
;7~
Gardner Impact Tests of Flat Sheets (1/8") Ft-lbs Required to Break Len~es Using Multiple Increasing Impacts Aversge Break (an "X" denotss a sample break; a "-" denotes survival) Ft-lbs 0.17 0.33 0.50 0.67 0.83 1.00 1.17 1.33 1.50 1.67 87.5X PPG CR-39~ Diethylene Glycol Bis(Allyl Carbonate) ~ 12.5~ Thiokol "UVITHANE" 393 Polyurethane with Terminzl Acrylate Functionality X
X
X 1.1 y X
X
X
X
75Z PPG CR-39~ ~iethylene Glycol Bi~Allyl Carbonate) 1 25% Thiokol "~VIT~ANE" 893 Polyurethane with Ter~inal Acrylate Functionality -- X
-- -- -- X
~ 1.3 -- -- X
-- -- -- X
-- -- X
-- -- X
-- -- -- X
-- -- X
-- -- X
While the invention has been de3cribed with respect to certain preferred exemplifications and embodiment~, the scope of the inveneion i~
not to be limited thersby, but i8 solely defined by the claims Appended hereto.
- 2~ -
Claims (24)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A copolymer of (A) an aliphatic diol bis(allyl carbonate) having the formula where R1 and R2 are independently chosen from the groups consisting of hydrogen, C1, F, Br, and C1 to C4 alkyl groups, and R2 is chosen from the group consisting of alkylene groups, alkylene ether groups, alkylene polyether groups, and alkylene carbonate groups; and (B) a polyurethane having terminal acrylate functionality.
2. The copolymer of Claim 1 wherein the polyurethane has the formula chosen from the group consisting of (I) , and (II) where RIII and RV are independently chosen from the group consisting of H and -CH3, RIV and RVI are inde-pendently chosen from the group consisting of C1 to C10 alkyls, m and n are independently integers from 1 to 10, y and z are independently 1 or 2, and x is chosen from the group consisting of oxygen and sulfur.
3. The copolymer of claim 2 wherein R3 is a discretionary group-ing of the form [(CH2)a (OCH2)b Oc]
where a is an integer from 2 to 20, b is 0 or an inte-ger from 1 to 3, and c is 0 or an integer from 1 to 10.
where a is an integer from 2 to 20, b is 0 or an inte-ger from 1 to 3, and c is 0 or an integer from 1 to 10.
4. The copolymer of claim 3 wherein RIII and RV are each hydro-gen, RIV and RVI are independently selected from the group consisting of -CH2-, and -C2H4, y and z are independently 1 or 2, and R3 is an alkylene polyether having the formula [(CH2CH2O)d(CH2CH2)]
where d is an integer from 1 to 5.
where d is an integer from 1 to 5.
5. The copolymer of claim 2 wherein R1 and R2 are H, and R2 is an alkylene polyether having the formula [(CH2CH2O)eCH2CH2]
where e is an integer from 1 to 3.
where e is an integer from 1 to 3.
6. The copolymer of claim 2 wherein R3 is a polyurethane group.
7. The copolymer of Claim 1 wherein the copolymer contains from about 75 to about 95 weight percent aliphatic diol bis(allyl carbonate), balance polyurethane having terminal acrylate functionality, basis weight of the total aliphatic diol bis (allyl carbonate) and polyurethane.
8. A liquid composition comprising:
(A) an aliphatic diol bis(allyl carbonate) having the formula where R1 and R2 are independently chosen from the groups consisting of hydrogen, C1, F, Br, and C1 to C4 alkyl groups, and R2 is chosen from the group consisting of alkylene groups, alkylene ether groups, alkylene polyether groups, and alkylene carbonate groups; and (B) a polyurethane having terminal acrylate functionality.
(A) an aliphatic diol bis(allyl carbonate) having the formula where R1 and R2 are independently chosen from the groups consisting of hydrogen, C1, F, Br, and C1 to C4 alkyl groups, and R2 is chosen from the group consisting of alkylene groups, alkylene ether groups, alkylene polyether groups, and alkylene carbonate groups; and (B) a polyurethane having terminal acrylate functionality.
9. The composition of Claim 8 wherein the polyurethane has the formula chosen from the group consisting of (I) , and (II) where RIII and RV are independently chosen from the group consisting of H and -CH3, RIV and RVI are inde-pendently chosen from the group consisting of C1 to C10 alkyls, m and n are independently integers from 1 to 10, y and z are independently 1 or 2, and x is chosen from the group consisting of oxygen and sulfur.
10. The composition of Claim 8 wherein R3 is a discretionary grouping of the form [(CH2)a (OCH2)b Oc]
where a is an integer from 2 to 20, b is 0 or an integer from 1 to 3, and c is 0 or an integer from 1 to 10.
where a is an integer from 2 to 20, b is 0 or an integer from 1 to 3, and c is 0 or an integer from 1 to 10.
11. The composition of Claim 10 wherein RIII and RV are each hydrogen, RIV and RVI are independently selected from the group consisting of -CH2-, and -C2H4-, y and z are independently 1 or 2, and R3 is an alkylene polyether having the formula [(CH2CH2O)d(CH2CH2)]
where d is an integer from 1 to 5.
where d is an integer from 1 to 5.
12. The composition of Claim 9 wherein R1 and R2 are H, and R2 is an alkylene polyether having the formula [(CH2CH2O)eCH2CH2]
where e is an integer from 1 to 3.
where e is an integer from 1 to 3.
13. The composition of Claim 9 wherein R3 is a polyurethane group.
14. The composition of Claim 8 containing from about 75 to about 95 weight percent aliphatic diol bis (allyl carbonate), balance poly-urethane, basis weight of the total aliphatic diol bis(allyl carbonate) and polyurethane.
15. A method of increasing the impact strength of diol bis(allyl carbonate) polymerizates comprising adding an effective amount of a poly-urethane having terminal acrylate functionality to the diol bis(allyl carbonate), and thereafter polymerizing the resulting composition.
16. The method of Claim 15 wherein the polyurethane has the formula chosen from the group consisting of (I) , and (II) where RIII and RV are independently chosen from the group consisting of H and -CH3, RIV and RVI are inde-pendently chosen from the group consisting of C1 to C10 alkyls, m and n are independently integers from 1 to 10, y and z are independently 1 or 2, and x is chosen from the group consisting of oxygen and sulfur.
17. The method of claim 16 wherein R3 is a discretionary group-ing of the form [(CH2)a(OCH2)b Oc]
where a is an integer from 2 to 20, b is 0 or an inte-ger from 1 to 3, and c is 0 or an integer from 1 to 10.
where a is an integer from 2 to 20, b is 0 or an inte-ger from 1 to 3, and c is 0 or an integer from 1 to 10.
18. The method of claim 17 wherein RIII and RV are each hydro-gen, RIV and RVI are independently selected from the group consisting of -CH2-, and -C2H4, y and z are independently 1 or 2, and R3 is an alkylene polyether having the formula [(CH2CH2O)d(CH2CH2)]
where d is an integer from 1 to 5.
where d is an integer from 1 to 5.
19. The method of claim 16 wherein R' and R" are H, and R2 is an alkylene polyether having the formula [(CH2CH2O)eCH2CH2]
where e is an integer from 1 to 3.
where e is an integer from 1 to 3.
20. The method of claim 16 wherein R3 is a polyurethane group.
21. The method of Claim 15 wherein the copolymer contains from about 75 to about 95 weight percent aliphatic diol bis(allyl carbonate), balance polyurethane, basis weight of the total aliphatic diol bis(allyl carbonate) and polyurethane.
22. A copolymer of a polyol (allyl carbonate) and a polyurethane having terminal acrylate functionality.
23. A liquid composition comprising a polyol (allyl carbonate) and a polyurethane having terminal acrylate functionality.
24, A method of increasing the impact strength of a polyol(allyl carbonate) comprising adding an effective amount of a polyurethane having terminal acrylate functionality to the monomeric polyol (allyl carbonate) and thereafter polymerizing the resulting composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US314,267 | 1981-10-23 | ||
| US06/314,267 US4360653A (en) | 1981-10-23 | 1981-10-23 | Polymerizate of (allyl carbonate) and aliphatic polyurethane having acrylic unsaturation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1196749A true CA1196749A (en) | 1985-11-12 |
Family
ID=23219270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000413951A Expired CA1196749A (en) | 1981-10-23 | 1982-10-21 | Polymerizate of (allyl carbonate) and aliphatic polyurethane having acrylic unsaturation |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4360653A (en) |
| EP (1) | EP0078170B1 (en) |
| AU (1) | AU537736B2 (en) |
| CA (1) | CA1196749A (en) |
| DE (1) | DE3271578D1 (en) |
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| WO2009017690A2 (en) * | 2007-07-26 | 2009-02-05 | Henkel Corporation | Curable epoxy resin-based adhesive compositions |
| RU2726363C2 (en) | 2013-03-14 | 2020-07-13 | ПиПиДжи ИНДАСТРИЗ ОГАЙО, ИНК. | Polyurethanes, articles and coatings obtained from them, and methods for production thereof |
| CN107924116B (en) | 2015-09-03 | 2021-06-15 | 光学转变公司 | Multilayer photochromic articles |
| MX2022006809A (en) | 2019-12-05 | 2022-07-11 | Ppg Ind Ohio Inc | Curable compositions. |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3297745A (en) * | 1962-04-05 | 1967-01-10 | Robertson Co H H | Ethylenically unsaturated di-and tetra-urethane monomers |
| US3979426A (en) * | 1971-08-12 | 1976-09-07 | Ppg Industries, Inc. | Radiation-sensitive diacrylates |
| US3872042A (en) * | 1972-02-01 | 1975-03-18 | Buckbee Mears Co | Plastic lenses and method of making same |
| US3907865A (en) * | 1973-06-20 | 1975-09-23 | Kansai Paint Co Ltd | Photopolymerizable vinylurethane monomer |
| US4017646A (en) * | 1975-12-11 | 1977-04-12 | Ralston Purina Company | Process for producing pH modified protein filaments |
| FR2363546A1 (en) * | 1976-09-07 | 1978-03-31 | Poudres & Explosifs Ste Nale | ALLYLIC-ACRYLIC MIXED MONOMERS, THEIR PREPARATION AND POLYMERS THEREOF |
| US4125671A (en) * | 1977-05-06 | 1978-11-14 | Thiokol Corporation | Acrylated dithiocarbamyl esters |
-
1981
- 1981-10-23 US US06/314,267 patent/US4360653A/en not_active Expired - Lifetime
-
1982
- 1982-09-20 AU AU88529/82A patent/AU537736B2/en not_active Ceased
- 1982-10-21 CA CA000413951A patent/CA1196749A/en not_active Expired
- 1982-10-25 DE DE8282305650T patent/DE3271578D1/en not_active Expired
- 1982-10-25 EP EP82305650A patent/EP0078170B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4360653A (en) | 1982-11-23 |
| AU8852982A (en) | 1983-04-28 |
| EP0078170A1 (en) | 1983-05-04 |
| DE3271578D1 (en) | 1986-07-10 |
| EP0078170B1 (en) | 1986-06-04 |
| AU537736B2 (en) | 1984-07-12 |
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