CA2146816A1 - Process and composition for preparing a dental polymer product - Google Patents

Process and composition for preparing a dental polymer product

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Publication number
CA2146816A1
CA2146816A1 CA002146816A CA2146816A CA2146816A1 CA 2146816 A1 CA2146816 A1 CA 2146816A1 CA 002146816 A CA002146816 A CA 002146816A CA 2146816 A CA2146816 A CA 2146816A CA 2146816 A1 CA2146816 A1 CA 2146816A1
Authority
CA
Canada
Prior art keywords
preparing
polymer composition
substituted
unsubstituted
acid
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.)
Abandoned
Application number
CA002146816A
Other languages
French (fr)
Inventor
Joachim E. Klee
Wc Walter Leube
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dentsply GmbH
Original Assignee
Joachim E. Klee
Wc Walter Leube
Dentsply Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Joachim E. Klee, Wc Walter Leube, Dentsply Gmbh filed Critical Joachim E. Klee
Publication of CA2146816A1 publication Critical patent/CA2146816A1/en
Abandoned legal-status Critical Current

Links

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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/834—Chemically modified polymers by compounds containing a thiol group
    • C08G18/835—Unsaturated polymers modified by compounds containing a thiol group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2270/00—Compositions for creating interpenetrating networks
    • 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
    • Y10S525/903—Interpenetrating network
    • 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
    • Y10S525/922—Polyepoxide polymer having been reacted to yield terminal ethylenic unsaturation

Abstract

Process and composition for preparing a dental polymer product Abstract The invention concerns a process for preparing a polymer composition, that is free-radical/photochemical and thermal curing epoxide-methacrylate and/or isocyanate-methacrylate adhesives in broadest terms, dental/medical adhesives, and dental restoratives. Furthermore the dual curing epoxide-methacrylate and/or isocyanate-methacrylate adhesives can be used in the optical industry, in optoelectronics and microelectronics, for example for the adhesion of complicated optical components in the combination glass/ glass, glass/metal. Advantageous is the small shrinkage during polymerization and the good mechanical properties in combination with thepossibility of step-wise or one-step polymerization.

Description

21A681fi . /'723 -~ac~ss cnd c~mpa5itian rar ~,~2?,.~ c a G2nra/~atyi. erpr~ dL~c:

, le inven~icn re!a_s .a c den~21 c_mpcsitiGn ar '~it cr a2: ~5 i'Cr prêp2~ Ing 3 ~,ciymer, ~c _ pracess ,cr srs?annç szid pclymzrs a, Id pclymer -rccL!G, abtair;c~i hsfay, na-~cbiy er ric al .e~rh.

ectc~graund at' ~he inventian Oental ':iling ma;erials m2inly c~r;sis, CT liquid pclymefr~-_ie argcnic mancr,ien ênG' cr yclyme~s, re--_~ive diil!efrts, paiymeri~ ^S,icn initie~cri, s;a~ ^fs, _r,c "ile~s. -I .~ese c .r"pas~tS m2-e.riêls nê~e ,~.eir çcad mêc enic~l prr~pef;ieC such æS Ais~
F,'e:~urel s.rariS."s, hi~5ii c^mcrassive s;uênsu;s and u ,air hea.~dnesa. ,~ur;"a ",Gra ulêy ê e pclishe~le e~id it iS pGsJibiz to êdius; ~Jhêir dyc. 1 n_ mcsi " s~tæntl~J u tac' r'-,cr;a-.. rl,ar, êrs es;~r~ af mea~ cGyle--~es êr,d Aicher muitif~nc icrê} alc-anc(ês ..r .sac~cl.e as s~ich 2s :ha cismzi~necyle-ta ar bispi zncl-,, digiyc,cyi at. IS-, i lra, ,2"z ~ism.êi~i2^~t^
I~e~a!S~

Cr,e c1' ~1''.5 ri~i2in disê_v2ntê ~ês usinG c~m csi.ês ê9 dê. ,.alt nitina mêtanJs jst ~7e ~ ~ :
rtlea~ive~ nisr~shrlr~cê~zG~i' ars~rlic ~Icncmef~ ririct-ciymên~-Jcn~ li.e hrrKê__ -e~ 'S55 ,he~I~fe~ Gwnê:'l'e~ 'c~ir,i,ê~ nceJSic~ci Si!3~2~s!er;;~.2~_.Ca.C_r.~i~n C ên;21 c^mccsii2s si-cw ê _i-iri.~kcse G-; ~ Ic ~1.;0 ~G~ a. -1~ is we!l kncwn u~i2'. ~J'~ê s-.rinkege dirFi.y derencs Gn ,~ e mcler-~iê~ wei~ cr .Giy- . ~
meriz--~le araanic r~icncmsrs. On U ie a~hêr Aênc. inc. ê_sinc maleralem~êi~r;ts ar -~ ; .
s.' r mcncmerâ êre c3mbinec wiir ê n inc. 3êâing visc lsi,l air ~1 ie resin. rnef-l5r3 r~
2c;lve diii ~eniâ, 5uc l 2s 3ii526t.'~iyienêslycalG3~llêil~lec-/lc-r~2s~ êr3 rleC-S_eî J '3 a~;cir -2 cwer viscc~si~l ênc~he pcs_i3iiiiy .c inc,lcGrê-.e .. e ~3cirsd cma-!n; af iilæ~s. ~ :~
; cwe~J~Sr,;~ e~ en;,~ awêrs3iêiiv3!~Jriis.~ ririkê-_3~ U'iê.~ise~Jes.;~r^~
2r. 7clê 1 ~ c Ici-~h i~a~ Fl:~c ;~eshylêriçi~Jc-lcime-., .cc. Ji2iê. -~

Mc~ê5~JG~, c_r.~fenticrêl ! 15êd c_mpcsltss Sî ~C,w ii . s!e.i~fê!~/ tGW sê!. -^~hs5icn ;G
t^ê hl r e~^ls 2nd cerêmics~ In ni:me~cus e:<pcril~.snt_ ~;sir.c sp~ xics pai~/r efs 2nd ;~
r m~'~2_.-~/12 _s .ar ~.._ pr_?er2.icn cr !i5:`ls ( I.Pc~ ic:.. ?~ P_ly~l.C:._.m. ;a , .... _ . _ . , _ _ ~ , _ _. .. .. ... . .. . ..

21468~

(1CS2! ,c 1, J.Aopl.C~rom. ~4 (1g91) 6^2, Paiym. 31 (19SO) 2C66, ) multirJr,ase sys;ems werê obtainee wh~c.n have insuric.ent rr,ec. ,anical, .nermzi ênd c?tic--l prooer.ies or wnicn result in mic.opnas2 se?cr2t2d ,oalymers (Ac;â Pclymeric~ 3~ -(1987) Sd7 and DO 2~6/ 31 ) wi~h insu"icient adhesion ta teeth and ceramics.

Description of the invention Therefor it is the object of the invention to provide â proc2ss and composition for preparing a polymer composition for dental purposes exhibiting â low shrinkage and a high se!f-adhesion to cPramics and metals.

This object is avanc~d by a proc~ss according to claim 1.
Preferably the mac. omonomers have a generally forrnula I or ll~

Jx D--C ~ ~--Clx wherein A and O are unsaturated moieties, B is a moiety arisen rrom a diepoxide or a diisocyanate and C is a HX-residue selected from the graup consisting of -OH, `~
-C00H, -NH2. -NH-, -SH. `
~-....,'., The macromonomers I and ll peferably are a,~terminated poly (epoxide~arboxylic `~
acid) macromonomers of formulas M-1, M~ and M-9, ~ ~terminated poly(epoxide-amine) macromonomers of formulas M-2 to M-5, M-10 and M-11 or a,~Jterminated poly(epoxide-phenol) macromonomers of formulas M~, M-7 and M-12 are described -in the following literature (J. Klee, H.-H. Horhold, H. Schutz, Acta Polym. 42 (1991) 17-20, J. Klee et. al. Polym. 8ull. 27 (1992) 511-517) and in the patent literature (DO
277 689, 00 279 607, OE-P 42 17 761.8). They are cAaracterized by the struc~uresM-1 t~ M-12 ~O~I~f OJ~R7l0~R I O~
R~ OH OH OH n CH R, M-1 '. ' ~.
.

~ i . . ^ . . ~ - . ~ : -` -`- 21~fi~16 R~ OH OH R3 OH n OH R~ M-2 ~O~R~N,R2~
R1 OH OH R3 R3 OH n OH Rl M-3 ~O~I~R~I~O~ ~ ~, Rl OH R~ OH OH R3 OH R~ M

~l~R~ R~`N~--o~
R~ OH R3 R3 OH OH R3 R3 OH R~ M-5 Rl . OH OH OH n OH Rl M~

"

o R~ OH L OH OH n OH R~

O~a~2l0 I R ~Ol~R~--o~ ;
R~ OH l CH OH n CH t M-3 21468~.6 ~I R~N~ [ ~--O~;~lO~R~N~
O R3 OH L OH OH I n OH R~ O

D~R2~R2 O R3 OH L OH R3 OH n OH R3 O M~

~R~R'--~R~~N~R~
O R3 OH OH R3 R3 OH n OH R3 M-11 ~R~ ~fo,R.~o~--N~R~
O R3 OH OH OH n OH R3 O M-12 wherein R is a residue derived from 2 diepoxide, notably a residue of the following ,ormula ~: :
~~ ~~~o~

whereby ~ is C(CH3)2, -CH2-, -O-, -S-, -CO-, -S02-R1 denotes hydrogen or a substituted or unsubstituted C1 to C12 alkyl group or an oxyalkyl group, C2 to C12 alkenyl group, C5 to C12 cyc~oalkyl, C6 to C12 aryl orC7 to C12 aralkyl . ~ -, ~:
.: ~

21~6816 - ~ ~
. . , R2 is a ~ir~nc:ioncl surstituted or unsuostirutGd Cl to C12 _ik`11 srclJo, C2 to C12 aikenyi group, Cs ;o C12 CJC!OCII~YI~ CO to C12 ar~l or C7 o C12 ar21kyl, ~3 den~es hydrcsen or c suostituted ar unsuosii;utEd C1 to C12 21kyl srauo, C2 - .
tc C12 21kenyl srouo, C~ to C12 cyc!oalkyl, C~ o C12 2ryl or C7 to C12 ar-lkyl,R~ is a substitute~ or unsucstituted CO to C12 aryl, such 2S .;~

where~y X is C(CH3)2, ~H2-, -O-, ~-, -CO-, -S02-and n is an integers of n =1, 2, 3, 4, 5, 6, /, 8 Macromonomers M-1, M-2, M-3, M~ are synthesisEd in twr~ steps. At first by re3c~tion or excessive bisphenol-A dialycidyl ether OGc3A, bisphenol-F digiycidyl ether DGcBf, butanediol diglycidyl et~her 8000Gc, tet~r2hydro tEre?htalic acid diglycidyl ether or diglycidyl aniline and methacrylic acid MAA (x~2y) an oligomer mi%urE is . :. -;
obtained. This mixture c~ntains the bismethacrylate OT DGc~A (Bis-GMA, n=~) along with mono-GMA and unreacted OGc~A as we!l as aov~Qrned bv the er~cxid~omo-nomer ratio. The formation af macromonomers ,ollows in a sacond reaction af OGc3A and mono-GiVA, respec;ive!~ with pr,mary mona2mines ta M-2, disarond2r~
diamines to M-3 (J. KleQ et al. Polym.8ull. 27 (19S2) 511-~1/, 00 2/ ~-ol), carboxylic2cids to M-1 (OE 421~751.8), orbipnenols ;o M~ (J. E. KleQ ~t_l., Ac;aPolym. 44 (1993)163).

x ~ --~7 Y I Cl~ AC [ o~iScoSmae9es ] ~ ~

r'firs; s;age 1 ,R~ 2h, ~Ci~
oiigomets ~ JY ,<H

q--b~;2--x~ -~x--~
Rl OH L OH OH I n CH R.
: ..' '-;
M-1 (X=COO), M-2 (R2=NR_ X= -) M-3 'X=NR3). ~ !x=o!
s - 2~6816 During the epoxide ring cleavage by carboxylic acids an amount of approximately 20 -% of the e~oxide groups is opened to the c~rresponding primary alcohols. Conse~
quently, macromonorners M-1, M-2, M-3 cnd M~ contairls booth types af malecules having primary andlor s~condary alcohol units.

Macromonomers M4 and M-5 are prepared by one- or two-step reactions ~f the die-paxides, primary monoamines ar disecondary diamines and 2,3~poxypropyl-meth-acrylate using amine in excess and a mol ratio a~b, and 2c+a=~. rne macromono-mers M4 and M-5 also obtainable by ~emminating reaction of ~ amino tenninated prepolymers with 2,3-epoxypropyl-methacrylate (D0 277689, J.Klee, H.-H. Horhold,H.Schutz, Acta Polym. 42 (1991)17-20).
- .

a ~R ~ ~ b HN~ 2 NH ~ c R3 R3 o ~0~ 1 `N I R~N~R~
R~ OH R3 R3 OH OH R3 ~3 OH R
M-5, M~ (R3NH2) Instant of amines also were used bisphenols or dicarboxylic acids to produce macro-monomers M-7 and M~, respectively.

o ., ..
x ~R ~ ~ y ~O'R2`N''Y ' ~ [oltjs9t~stt 9ts ]
Rt P`3 ~ -~ . .
[oligomers ] HX,R2~XH 2h. 90 C e .'' `, ~'~ ~;

'`N~f ~`R~X,R2~x~ N~ `
Rl R3 aH OH OH n OH R3 R, M-9 (X=COO), M-10 (R2=NR~3 X= -), M-11 (X=NR3), M-12 ~X=0) y;.i'.` .~:~' ` ' ' , ' ., : : :
--: 2146816 Macromonomers M-~ ~o M-12 are orepared by one- or ~vo-step reactions of the di-epoxides, primary monoamines, disecondary diamines, dicarboxylic acids, or phe~
nols and amino alkyl methac.~ylates.

The polymer composition comprises a,~erminated poly(urethane) macromonomers, terminated poly(urea) macromonomers or ~,~terminated polylthiourethane) macromonomers of the following formulas M-13 to M-24 which are polymerizable in a mixture with di-or polyepoxides and/or di- or polyisocyanates and polyamines and/or primary monoamines andlor disecondary diamines or dicarb-oxylic acids, dicarboxylic acid anhydrides, diphenols, or dithioles~

~0~ ,N~O~ ,O ~!~ o~ ~o ~o~
R2 R4 ~ R4 ~R2 ~ h o o n M-13 Rl OH H H OH R
`R4~ ~R~ R4 o n M-14 ; . ~

R1 H R3 R3 IH IH _ IR3 R3 H Rl :
D~` ,~N`R--~N~R,N~N`R,~ ~ R2~ ~b R, fH R3 R~ H H R3 R3 OH R, . ~ ;
O~N~R,N~N~R,~ R2 ~
o L n M-16 R, OH Hl H IOH R, D:~O~S`R~S~N~?~S~p,S~~ ~ M-17 ;

~ ~' 21468~;6 ~ ~;

D`y R~ ~ R~ y ~R~ ~ R~ y R3 y~ M-18 J`y R~ E~R~ r R~ ~R~ y R3 y~ M-19 --y R~ b~R~Ny R~ ~R~ y A~

J~YO~R,OS~N~R,NYN~ N~ ,NyO~ ~Oy~ M-21 ~;

yO~R,~,N`R'Nyo`R~dN` hYN`P'Y~ M-22 yO~R~N~ ~N~S~R~S~N~ h~-~ ,oy~ M-23 ~ ~
`''"''" ~' Rl IR3 l H Rl3 P~3 1 I H R3 It J~yO~ ~N~fN~R_NyN~R~N`2'Ny `R~
L n M-24 :~

21~6816 wnerein R is a residue derived ,rom ê diisocyanate, notably a residue of the ,ollowin~
formL~la - -~XJ~

R1 denotes hydrogen or a substituted ar unsubstituted C1 to C12 alkyi group, C2 to C12 alkenyl group, Cs to C12 cycloalkyl, C6 to C12 aryl or C7 to C
aralkyl R2 is a difunctional substituted or unsubstituted C1 to C12 alkyl sroup, C2 to C12 alkenyl group, Cs to C12 cycloalkyl, C6 to C12 aryl or C7 to C12 aralkyl R3 denotes hydrogen or a substituted or unsubstituted C1 to Cl2 alkyl group, C2 to C12 alkenyl group, C~ to C12 cyc!oalkyl, C6 to C12 aryl or C7 to C12 aralkyl,R4 is a substituted or unsubstituted C6 to C12 aryl, such as ~x~ ~
whereby X is C(CI 13)2, -CH2-, -O-, -S-, -C0-, S02-andnisanintegersofn=1,2,3,4,5,6,7,8,...

It is possible to use the polymer composition as an one-part composition or as two part-composition. A two-part composition wnich is mixed immediately berore use contains for example the ,'ollowin~ substancas in the parts A and B ~

part A: macromonomer, reactive diluent, di- or polyepoxide or di-or polyisocyan2te ~ -and polymerization initiator part B: macromonomer, reactivediluent, coinitiator2nd amine ordicarboxylicacid, dicarboxylicacid anhydride, diphenol, ordithiol, respective!y.

The cornosition contains 1 to 99 mol-% of a macromonomer relative to to said mono-mers, preferably 10 to 90 mol-~/~ of a macromonomer relative to to s2id monomers, most preferably 30 to 70 mol-% of a macromonomer relative to to sêmd monomers. ~ ~
:: . - .

21~6~

The prep2red adhesives, edhesive cements and composites are polymeriz2ble In ~ ~ ~
hvo dirrerent polymerization reactions, namely in a free-radical/pho~ochemic21 and a ~ ~-thermal polymeriz2tion re2ction which may run subsequently or simultaneausly. In ; -~
both cases interpenetrating networks or semi-lPNs were prepared depending on the -comonomer used for the addition reaction namely if palyamines, primary mono-amines, disecondary diamines or dicarboxylic acids, dicarboxylic acid anhydrides, diphenols or dithiols were used for epoxide-addition polymerization.
The methacrylate networks and the epoxide networks and linear polymers, respecti-vely are compatible. The invented polymer compositions exnibit advantageous me-chanical properties and a small shrinkage during polymerization.

The invented polymer compositions may contain reactive diluents such as diethy-leneglycoldimethacrylate, triethyleneglycoldimethacryiate, polypropyleneglycoldi- ~ -methecryl2te, methacrylate substiruted spiroortho esters, glycarintrimeth2cryi2te, furfurylmethacrylate, urethandimethacrylate, Bis-GMA in a content or 5 to 5G wt-%. -;

The invented polymer compositions may contain stabilisers such as hydroquinon or2,6-di-tert.butyl-p-cresol.

The invented polymer c~mpositions may comprise redox-initiator systems such as ~ ;
azobisisobutyronitril, dibenzoylperoxid/amine, Cu-acetyl2cetonatelLi-sulfin2te, tri-alkylbcranes or photo initiators sucn as benzoinmethylether, benzilke~al, camphor quinon or acylphosphinoxides in contents or 0,1 to 3 wt-%.

When using the invented polymer compositions as composite, fillers can be mixed into the epoxide/macromonomer or isocyanate/macromonomer matrix. As fillers wereused inorganic gl2sses such as barium-alumosilicat glasses, silica gels, xero gels or inorganic compounds such 2S La203, ZrO2, ~iPOa, CaWOa, ~aW04, Sr~2, ~i20 or organic fillers such as broken organic polymers The invented polymer compositions reveals interesting mechanical properties suchas a high flexural and compressi~e strength, a low expansion, good adhesion to metal, glass and ceramics, a low shrinkage and a high radio-opacity between RO= 2 and 10 mm/mm Al depending on the nature of the filler used - -` 214681~
-:

When applying the invented dual curing material as 2dhesive, the visr,osi~/ and the adhesion properties af the materi21 are adjustable througn evalu2tion of the macro-manomer and the chain length of these. In many cas2s reactive diluents are necas~
sary for the US2 of the invented materials.

Reference example 1 Preparation of macromonomer M-2 (n=1, R= -OC6~4-C(CH3)~C6H40-~ R1- CH3-, R3= -C6H4COOC4H9) 20,000 9 (58,75 mmol) bisphenol-A diglycidyl ether, 5,058 g (58,75 mmol) methacrylic acid, 0,253 9 triethylbenzylammoniumchlorid, 0,194 g 2,6-di-tert.-butyl~.esol (BHT), ~ ~
7,747 g triethyleneglycoldimethacrylate and 5,677 9 (29,38 mmol) p-amino-benzoic ~ ;
butyl ester were mixed and reacted ror 16 hours at 80 ~C. In the IR-spectrum of the . .-macromonomer no absorption of epoxide groups at 915 cm-1 was ,ound.

Refefence examp/e 2 Preparation or macromonomer M-3 (n=1, R= -OC6H4-c(c~'l3)2-c6H4o-~ R1= C~3-, R2= -(CH2)40(CH2)4-, R3= C6HSCH2-) ~ -:

150,000 9 (0,441 mol) bispnenol-A diglycidyl ether, 37,935 9 (o~4a1 mol) methacrylic :
acid, 2,000 9 triethylbenzyiammonium chloride, 1,115 g 2,6-di-tert.-butyl-p~resol (BHT) and 111,65 9 ethoxylated 8is-GMA were homogeneously mixed under slow heating.
The mixture was kept for two hours at 90 C. After this time 75,020 9 (0,221 mol) N,N'-dibenzyl-5-oxanon2nediamine-1,9 were added to the mixture while stirring and was kept for additional two hours at 90 C. The obtained methacrylate terminated macromonomer is soluble iri organic sol~ents such as chloroform, I~MF and THF. In the IR-spectrum no absorption of epoxide groups at 915 and 3050 cm-1 was obser~/ed. A new aosorption of ester groups was found at 1720 cr~

Refefence example 3 Preparation of mac. omonomer M-5 (n=l, R= -OC6H4-C(C~'i3)2-Csi 140- ~1= C! t3-R2= -(C.'1~)4C)(C~2)4-, R3= C6~5CH2-) 11 ~`. ~-' ':' -` 2 1 ~ 6 8 1 6 :

20,000 9 (58,75 mmol) bisphenol-A diglycidyl ether and 40,012 9 (117,50 mmol) N,N'-dibenzyl-5-oxanon2nedi2mine-1,9 were homogeneous~y mixed under slow heating. rnemixture w2S keot ,;or ~vo hours at 90 C. After this time 16,704 9 (117,50 mmol) 2,3-epoxypropyl methacrylate were added to the mixture while stirring and were kept for another two hours at 90 C. The obtained methacrylate terminated macromonomer is .
soluble in organic solvents such as chlcroform, DMF and THF. In ~e IR-spectn m no absorption of epoxide groups at 915 and 3050 cm~1 were observed.
.
Refe~ence example 4 - . .
"~
Preparation of maomonomerM-21 (n=1, R1=CH3-, R2=-C~2C~2'~ :
R4 = -(cH2)2<~(cH2)2~(c~2)2-~ ) `R~O~R~Nys~R~s~ ~o~R~o~
O n -:
CH~

R ~ M-21 15,000 9 (67,790 mmol) isophorondiisocyanate, 6,1~9 9 ( 33,8gSmmol) 1,8-dimercapto-3,6-dioxaoctane, 8,822 9 (67,790 mmol) hydroxyethylmethacrylate ~nd 0,C60 9 BHT
were homogeneously mixed and reacted for 8h hours at 45 ~C. rf e obtained macromo-nomer does not show an absorption of the isocyanate group at 2200 cm~1 in the IRspectrum.

Example 1~5 3,0 9 (15,4 mmol) 3(4),8(9)-8is(aminomethyl)tricyclo-5.2.1Ø 2-5-decan TCD and 10,5 9 ~.
(30,8 mmol) 2,2-8is~4~2,3~poxypropoxy)phenyl]propane DGEBA were mixed ~o give the epoxide-amine addition polymer AP. Direrent amounts (see table 1) of macromono-mer M-5 (n=~, R= -C~C6H4-C(CH3)2~C6H4~-. R1= C;~3-, R2= -(CH2)4C)(CH2)¢-~ R3= C6HSC~2) N, N'-Oibenzyl-N, N'-bis-(2-hydroxy-3-methacryloyloxyoropyl)-5~xanonandiamin-1,9.

, .

- 21~8~6 and 0.5% photo initietor IRGACU~E 6i1 (Ciba Geigy) were cdded and the parts thorougnly mixed. To remove gas buboles the mixture was exposed to vacuum Ot an oil pump and then rilled into moulds to prepare test samples for dynamic mechanic analysis (DMA). Methacrylate groups were polymerized upon exposure to UV light of a s~roboscope UV lamp ror 6 minutes. rnen the samples were aiready stiff ~nough to be released from the mould. The polymeri-zation or zpoxide with amine was then completed by storing over night at 85C.
The glass transition temperatures of the resulting materials were determined by dif-ferential scanning calorimetry (DSC) and the maximum of tan ~ in DMA. Results are shown in table 1. Only one glass transition appears. Under scanning electron micro-scope phase separation is not being found (resolution 500 nm).
.~:
Table 1: Composition and glass temperatures of IPN and homopolymers of M-5 and ~ ;
AP

. . Example originâlly weight-in quantity of ¦ ratio of Tg ¦ Tg - - ~ ;
M-5/AP (DSC) ¦ (DMA) ;
. DGE3A ¦ TCD M-~ _ 7 ~ L--mmol wt-% C C
M-5 ~ ¦ 10.0 16.0 100/0 10 18 1 2,00 ¦ 5.8~ 1 0.57 1 2.941 25.7041 13 ¦ 90/10 9 20 2 5,00 1 14,69 1 1, 3 1 7,71 1 1929 30.81 1 7_/25 37 36 3 10,C0 ¦ 30,84 ¦ 3,00 ¦ 15,42 ¦ 13.5û 21,61 50/50 60 69 4 10,50 1 30,84 1 3.00 1 15,42 ! 450 7,~0 25175 98 103 ~ 10,50 L 30.84 ¦ 3.00 ¦ 15,42 1 1,94 3,11 10/90 140 125 AP 10.50 ¦ 30,84 ¦ 3,00 ¦ 15,42 ¦ -= 0/100 154 156 . . .
Example 6 (one-paste systemJ

3,000 9 of macromonomer M-2 of reference ex.,mple 1 and 1,142 9 (3,35 mmol) bispnenol-A diglycidyl ether, 1,142 g (3,35 mmol) N,N -Oibenzyl-5-oxanonandi2mine-1,9 and 0,02 9 camphor quinon were homogeneously mixed and polymerized as described in example 1-5. The shrinkage of the photochemical polymerization is û,68 vol-% and of the thermal cddition polymerization 2,44 vol-%. ; ~
,.
.

13 ~ -~
: ~ ' , ~ .. .. . . .

. . .
. .,. --. : ~
. - ~: - ,: . ,:. :: , . ,, :

21~6~16 E~amp/e 7 (one-paste sysremJ

3,000 9 of mac. omonomer M-2 of rererence example 1 were homogeneously mixed with 1,1429 (3,35 mmol) bisphenol-A diglycidyl ether, 0,8069 (3,35 mmol) N,N'~i-benzyl-ethylenediamine and 0,029 camphor ~uinon and polymerized as desc,ii~ed in examPIe 1-5. The shrinkage of the photochemical polymerization is 0,56 vol-% and of the then~nal addition polymerization 3,43 vol-%.

Examp/e 8 (one-pastesyst~mJ

3,000 9 of macromonomer M-2 of reference example 1 were homogeneously mixed with1,142 9 (3,35 mmol) bisphenol-A diglycidyl ether, 0,176 9 (1,34 mmol) N,N-dipropylen-triamine and 0,02g camphar quinon and polymerized as described in example 1-5.
A shrinkage of dV= 3,5%, dV= 1,8% was measured wnich is caused by the photo- -chemical step and dV= 1,7% which is caused by the thermal epoxide-amine additionpolymerization.

Example 9 rtNo-paste sysfem) : .

Part A) .
2,000 9 of macromonomer M-2 of r~ference example 1 were homcgeneously mixed with4,246 9 (3,35 mmol) Araldit-F, 0,054 g dibenzoylperoxide 19,500 9 of a mixiure of CaW04ZrO2 (4:1) and 0,100 9 aerosil.

Part B) 2,000 9 of macromonamer M-2 of reference example 1 were homogeneously mixed with1,086 9 ( 5,59 mmol) 3(4),8(9)-bis(amino methyl)-tricyclo-5.2.1Ø2-6~ecan, 0,054 9 N,N-bis(,B-hydroxyethyl)-p-aminobenzoic acid e~hylester, 9,441 9 of a mixture ofCaWO4 / Zr2 (4:1 ) and 0,100 9 aerosil.

Parts A and ~ were mixed immediately before use in a weight ratio of 2:1 and poly-merized for 10 minutes at 37 C. The shrinkage was measured as follows:
dV= 0,99 vol.-% and the radia-apacity R0= 8,3 mm/mm Al.

- 21~6~16 Examp/e 10 (two-paste sys~m) Part A) 10,000 9 cf macromonamer M-3 of reference example 2 were homageneously-mixed : :
with 7,010 9 (20,60 mmol) Araldit MY-790, 0,010 9 dibenzoylperoxide and 23,000 g8arium-Alumosilicate-glass and 0,100 9 aerosil.

Part 8) 2,000 9 of maaomonomer M-3 of reference example 2 were homogeneously mixed with 2,001 9 (1~,30 mmol) 3(4),8(9)-bis(amino methyl)-tricyclo-5 2 1Ø2 6-decan, 0,015 9 N,Nbis(,B-hydroxyethyl)-p-aminobenzoic acid ethyl ester, 2~,aoo 9 Barium-Alumo- - ~ -silicate-glass and 0,100 9 aerosil.
' ' . - ~.`
Parts A and 8 were mixed immediately before use in a weignt ratio or 1:0,706 andpolymerized at 37 C for 10 minutes. The shrinkage was measured of dV= 1,55 vol.-%.

Example 11 (two-paste system) Part A) 10,000 g of macromonomer M-5 of reference example 3 were homogeneously mixed with 7,010 9 (20,60 mmol) Araldit MY-790 and 0,010 9 dioenzoylperoxide.

Part 8) 10,000 9 of macromonomer M-5 of reference example 3 were homogeneously mixed with 2,001 9 (10,30 mmol) 3(4),8(9)~is(amino methyl)-tricyclo-5 2.1 0 2-6-decan and 0,015 g N,N-bis(,~-hydroxy-ethyl)~p-aminobenzoicacid ethyl ester.
.~ --. . -Parts A and 8 were mixed immediately before use in a weight ratio of 1:0,707. The first polymerization step occurs during radiation at ~ > 365 nm ior 360 seconds and the second step as thermal epoxide-amine polymerization at 85 ~C for 16 hours The following values were measured: Tg = 6g C, ~V = 1,75 vol -%

:, ,. . .

`~-` 21~6~16 Example 12 (one-,oaste system) 8,6~0 g (7,~5 mmol) of mac.omonomer M-~ of reference examole 3 (R= ~C~H4~(C'rl3)2-Ctj~4o-, R1= C:~3-, R2= -(CH2)40(C~2)4-, R3= C6H5Ci~2-), 3,707 9 ;riethyleneglycoldimeth-acrylate, 1,359 (3,62 mmol) 3(4),8(9)-8is(aminomethyl)tricyclo-5.2.1Ø 2--decan, 2,467 9 (7,~5 mmol) bisphenol-A diglycidyl ether, 0,124 9 camphor quinon and 0,124 g N,N-bis(,~-hydroxy-athyl)-p-toluidine were mixed homogenously immeadely befor use. Asmal layer of this mixture was put on a ceramic tooth and polymenzed with visir~le light for 40 seconds. Thereaffer a composite lP.H (Oe Trey Oentsply) was applied to this layer and polymerizQd for 40 seconds. Then material was reacted ,or 24 hours at 37~C.
After this time the adhesion of the material is 7,4 _ 1,3 MPa.

C~mpar,json example (Acta Polym. 3~ (1987) 547) 7,000 9 (13,66 mmol) Bis-GMA, 3,000 9 triethyleneglycoldimethacrylate, 5,096~ g (14,97 mmol) bisphenol-A diglycidyl ether, 4,9179 (14,97 mmol) N,N -Oibenzyl-3,6-dioxaoctanediamine-1,8 (Acta Polym. 3~ (1987) Sa7 and 00 226731), 0,050 9 camphor quinon and 0,0050 9 N,N~is(,B-hydroxy~thyl)-,o-toluidine were mixed homogenouslyimmeadely befor use. A smal layer of this mixture was put on a ceramic tooth andpolymerized with visir le light for 40 seconds. Thereafter a composite TP.H (De Trey Dentsply) was applied to this layer and polymerized for 40 seconds. Then the material was reacted in water for 24 hours at 37~C. After this time the adhesion of the material is 4,1 1,2 MPa.

Example 13 (fwo-yaste systemJ
5,000 9 (7,532 mmol) of M-21, 1,373 9 (7,532 mmol) 1,8-dimercapto-3,6-dioxaoctane, 2,564 9 (7,532 mmol) bisphenol-A diglycidyl ether, 0,089 g camphor quinon and 0,089 g N,N-bis(~-hydroxy~thyl)-p-toluidine were mixed homogenously immeadely befor use. A . -smal layer of this mixture was put on a ceramic tooth and polymerized with visible light for 40 secclnds. Thereafter a composite TP.H (De Trey Dentsply) was applied to this layer and polymerized for ~0 sec?nds. Then the material was reacted in water for 24 hours at 37C. After this time the adhesion of the material is 6,9 ~ 0,7 MPa.

~:.

Claims (25)

1.A process for preparing a polymer composition comprising the steps of A preparing a liquid mixture of (i) at least one monomer having at least two double bonds, (ii) at least one polyaddition component having at least two moieties capable ofaddition reaction selected from the groups consisting of epoxide or isocyanate moieties and (iii) at least two H-active components having at least two HX-residues selected from the group consisting of -OH, -COOH, -NH2, -NH-, -SH
8 polymerizing said monomer (i) and C subjecting said polyaddition component (ii) and said H-active component (iii) to a polyaddition reaction whereby steps 8 and C are carried out either simulta-neously or one after the other characterized in that for preparing a single-phase polymer composition having interpenetrating network with a single glass transition temperature from 1 to 99 mol-% of a macromonomer relative to said monomer (i) are copolymerized in step 8 whereby said macromonomer has a molecular weight at at least 600 and contains at least one structural unit whichis of the same type as a repetitive units produced in step 8.
2. A process for preparing a polymer composition as claimed in claim 1 wherein the said macomonomers comprises of the following fonmulas I and II
I II
wherein A and D are unsaturated moieties, B is a moiety derived from a diepoxide or a diisocyanate and C is at least a moiety having two H-active residues selected from the group consisting of -OH, -COOH, -NH2, -NH-, -SH
3. A process for preparing a polymer composition as claimed in claim 1 where-in said macromonomers are .alpha.,.omega.-terminated poly (epoxide-carboxylic acid) macromo-nomers of formulas M-1, M-8 and M-9, .alpha.,.omega.-terminated poly(epoxide-amine) macro-monomers of formulas M-2 to M-5, M-10 and M-11 or .alpha.,.omega.-terminated poly (epoxide-phenol) macomonomers of formulas M-6, M-7 and M-12 M-10 wherein R is a residue derived from a diepoxide, notably a residue of the following formula whereby X is C(CH3)2, -CH2-, -O-, -S-, -CO-, -SO2-R1 denotes hydrogen or a substituted or unsubstituted C1 to C12 alkyl group or an oxyalkyl group, C2 to C12 alkenyl group, C5 to C12 cycloalkyl, C6 to C12 aryl orC7 to C12 aralkyl R2 is a difunctional substituted or unsubstituted C1 to C12 alkyl group, C2 to C12 alkenyl group, C5 to C12 cycloalkyl, C6 to C12 aryl or C7 to C12 aralkyl, R3 denotes hydrogen or a substituted or unsubstituted C1 to C12 alkyl group, C2 to C12 alkenyl group, C5 to C12 cycloalkyl, C6 to C12 aryl or C7 to C12 aralkyl,R4 is a substituted or unsubstituted C6 to C12 aryl, such as whereby X is C(CH3)2, -CH2-, -O-, -S-, -CO-, -SO2-and n is an integers of n =1, 2, 3, 4, 5, 6, 7, 8,
4. A process for preparing a polymer composition as claimed in claim 1 wherein said macromonomers having at least one repetitive unit selected of the group of urethanes, ureas or thioureas of the following formulas M-13 to M-24:

M-14 M-19 M-24 wherein R is a residue derived from a diisocyanate, notably a residue of the following formula R1 denotes hydrogen or a substituted or unsubstituted C1 to C12 alkyl group, C2 to C12 alkenyl group, C5 to C12 cycloalky, C5 to C12 aryl or C7 to C12 aralkyl R2 is a difunctional substituted or unsubstituted C1 to C12 alkyl group, C2 to C12 alkenyl group, C5 to C12 cycloalkyl, C5 to C12 aryl or C7 to C12 aralkyl R3 denotes hydrogen or a substituted or unsubstituted C1 to C12 alkyl group, C2 to C12 alkenyl group, C5 to C12 cycloalkyl, C6 to C12 aryl or C7 to C12 aralkyl,R4 is a substituted or unsubstituted C5 to C12 aryl, such as whereby X is C(CH3)2, -CH2-, -O-, -S-, -CO-, -SO2-and n is an integers of n =1, 2, 3, 4, 5, 6, 7, 8
5. A process for preparing a polymer composition as claimed in claim 1 wherein said macromonomers and addition polymers are com-prised in a weight ratio between 1: 99 % and 99: 1 %, preferable in a weight ratio between 10: 90 % and 90: 10 %, most preferable in a weight ratio between 30: 70 %
and 70: 30 %.
6. A process for preparing a polymer composition as claimed in claim 1 wherein said reactive diluent is triethyleneglycol bismethacrylate, diethyleneglycol bismethacryl-ate, dioxolan bismethacrylate, vinyl-, vinylen- or vinylidenacrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicyloortho esters, ethoxylated Bis-GMA in a content of 5 to 50 wt-%.
7. A process for preparing a polymer composition as claimed in claim 1 wherein said di- or polyepoxide is bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, novo-lakepoxides, N,N,N',N'-tetraglycidyl diaminodiphenylmethan or .DELTA.3-tetrahydrophtha-lic acid diglycidyl ester.
8. A process for preparing a polymer composition as claimed in claim 1 wherein said primary monoamine is benzylamine, 1-adamantanamine, .alpha.-phenethylamine and ethanol amine and as disecondary diamines N,N'-dibenzyl-ethylenediamine, N,N'-dimethyl-ethylenedi-amine, N,N'-dibenzyl-3,6-dioxaoctandi-amine-1,8, N,N'-diben-zyl- 5-oxanonandiamine-1,9, N,N'-dibenzyl-(2,2,4)/(2,4,4)-trimethylhexamethylenedi-amine and as polyamines N,N-dipropylenetriamine, tripropylenetetramine, isopho-rondiamine, (2,2,4)/ (2,4,4)-trimethylhexamethylenediamine-1,6, 3(4),8(9)- bis(amino methyl)tricyclo-5.2.1Ø2.5-decan or O,O'-bis-amino(polypropyleneglycol).
9. A process for preparing a polymer composition as claimed in claim 1 wherein said diisocyanate is toluendiisocyanate, hexamethylenediisocyanate, 2,2,4-(2,4,4)-tri-methylhexamethylendiisocyanate, isophorondiisocaanate or 4,4'-diphenylmethane-diisocyanate.
10. A process for preparing a polymer composition as claimed in claim 1 wherein said dicarboxylic acid is a substituted or unsubstituted aliphatic, araliphatic, cycloali-phatic (bi- and tricyclic) and/or aromatic dicarboxylic acids such as succinic acid, adipic acid, hexahydrophthalic acid, phthalic acid, terephthalic acid.
11. A process for preparing a polymer composition as claimed in claim 1 wherein said dicarboxylic acid anhydride is a substituted or unsubstituted aliphatic, ar-aliphatic, cycloaliphatic (bi- and tricyclic) and/or aromatic dicarboxylic acid anhydri-des such as succinic acid anhydride, methylsuccinic acid anhydride, hexahydro-phthalic acid anhydride, dichlormaleic acid anhydride, tetrahydro phthalic acid anhydride, phthalic acid and 3,4,5,6-tetrachloro-7,7-difluoro-3,6-endomethylene tetrahydro phthalic acid anhydride.
12. A process for preparing a polymer composition as claimed in claim 1 wherein said phenol is a substituted or unsubstituted phenols such as phenol, resorcinol, hydroquinon, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxy sulphone.
13. A process for preparing a polymer composition as claimed in claim 1 wherein said dithiole is a substituted or unsubstituted aliphatic, araliphatic, cycloaliphatic (bi-and tricyclic) and/or aromatic dithioles such as thiocole, 1,8-dimer-capto-3,6-dioxa-octane, 1,7-dimercapto-3,5-dioxaheptane, 1,9-dimercapto-5-oxa-nonane, 1,14-di-mercapto-5,10-dioxatetradecane, mercapto acid-1,4-butandiol ester, 4,4'-oxydithio-phenol.
14. A process for preparing a polymer composition as claimed in claim 1 whereby additional compounds which undergo polyaddition with di- and polyepoxides an added notably as cyanuric acid, melamine- and urea-formaldehyde-resins, amides, di- and polyisocyanates or inorganic acids such as phosphoric acid or phosphonicacid.
15. A process for preparing a polymer composition as claimed in claim 1 wherein said photo initiator is benzoinmethylether, benzilketal, camphor quinon, acylphos-phinoxides in a ratio of 0,1 to 3 wt-%.
16. A process for preparing a polymer composition as claimed in claim 1 wherein said thermal initiators azobisisobutyronitril or dibenzoylperoxid in a portion of 0,1 to 3 wt-% or redox initiator systems.
17. A process for preparing a polymer composition as claimed in claim 1 polymeriz-ing photochemically for 10 to 300 seconds having a rapid fixation followed by the thermal polymerization in a temperature range of 20 to 200 °C during 0,5 to 40 hours.
18. A process for preparing a polymer composition as claimed in claim 1 polymeriz-ing in two thermal initiated steps whereas the first polymerization occurs at 35 to 130 °C for 10 to 60 seconds and the second polymerization occurs at 20 to 200 °C for 0.5 to 40 hours.
19. A process for preparing a polymer composition as claimed in claim 1 wherein said filler is an inorganic glass such as barium-alumosilicat glass, xerogel or an inor-ganic compound such as La2O3, ZrO2, BiPO4, CaWO4, BaWO4, SrF2, Bi2O3 or an organic fitler such as a particle polymer.
20. A process for preparing a polymer composition as claimed in claim 1 containing dye pigments.
21. A process for preparing a polymer composition as claimed in claim 1 prepared as a two-part system comprising two pastes, which require mixing prior to their applica-tion.
22. A process for preparing a polymer composition as claimed in claim 1 wherein said interpenetrating network comprises at least one network polymer and at least one linear addition polymer.
23. A kit of parts performing the process according to claim 1 comprises a component of (i) at least one monomer having at least two double bonds, and a second component of (ii) at least one polyaddition component having at least two moieties capable ofaddition reaction selected from the groups consisting of epoxide or isocyanate moieties and (iii) at least two H-active components having at least two HX-residues selected from the group consisting of -OH, -COOH, -NH2, -NH-, -SH
24. Polymer composition composition by a process according to claims 1
25. Artificial teeth composed of a polymer of claim 24.
CA002146816A 1994-04-22 1995-04-11 Process and composition for preparing a dental polymer product Abandoned CA2146816A1 (en)

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FI116294B (en) 2005-10-31
FI951909A0 (en) 1995-04-21
EP0678533A3 (en) 1998-01-28
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EP0678533B1 (en) 2004-09-01
DE69533433T2 (en) 2005-01-13
DE69533433D1 (en) 2004-10-07
FI951909A (en) 1995-10-23
EP0678533A2 (en) 1995-10-25
NO951494L (en) 1995-10-23
US5876210A (en) 1999-03-02
NO309610B1 (en) 2001-02-26

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