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Document Type and Number:
WIPO Patent Application WO/1981/003657
Kind Code:
Diacrylate and dimethacrylate esters corresponding to the formula (FORMULA) wherein R and R' are hydrogen or methyl and A is either a sigma ((Alpha)) bond; a (CH2)n radical where n is an integer that may vary from one through four; or phenylene, or an alkyl derivative thereof. The new adamantane containing difunctional olefinic monomers can then be polymerized, or copolymerized with other acrylic type olefinic monomers to produce polymers with unusual physical properties, including unusual hardness, inertness to degradable agents, and resistance to heat.

Bellmann V, Nguyen G.
Application Number:
Publication Date:
December 24, 1981
Filing Date:
June 09, 1981
Export Citation:
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Battelle, Memorial Inst
International Classes:
C08F20/10; B32B27/30; C07C17/10; C07C61/135; C07C69/00; C07C69/54; C08F20/00; C08F20/28; C08J7/04; (IPC1-7): C07C69/54; C08F20/20; C08J7/04
Foreign References:
Other References:
CHEMICAL ABSTRACTS, Volume 89, No. 14, published October 2, 1978, (Columbus, Ohio, US), S.S. NOVIKON et al. "Synthesis and Polymerization of Unsaturated Adamantane Derivatives", see page 1, the Abstract No. 110434q, Izv. Akad. Nauk SSSR, Ser. Khim. 1977 (12), 2765-7 cited in the application
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1. A cαπpound having the formula wherein R is a radical selected frαn the grcup consisting of hydro gen or methyl; R1 is a radical selected frαn the group consisting of hydrogen or eiihyl; and A is either a sigma ( ) bond; or a radi • cal satisfying the formula (QL^n where n is an integer of fron 1 through 4; or phenylene; or an alkyl derivative of phenylene.
2. C ipounds according to cläiπfl, where R = H or α^ R1 = H or CHj A is a sigma {*£ bond.
3. Ccπpounds according to clai 1, where R = H or CH, R* = Hor C j .
4. A coirposite material which will withstand more than 24 hours immersion in chlorinated solvents without significant da age, com prising: (a) a clear Substrate of organic glass; and (b) a very fine coating of crosslinked polymers resulting from the polymerizaticn of mcnomers described in Claims 1, 2, or 3.
5. A coπposite material as described in claim 4 where the thick ness of the coating is in the ränge of 2 to 8 microns.
6. Crosslinked polymers obtained by the polymerization of the ccπpounds of claim 1, 2, or 3, or the copolymerization of mixtures thereof.
7. Crosslinked resins obtained by copolymerizing the ccπpounds of claim 1, 2, or 3 in admixture with other copolymerizahle acrylic monαners.
8. The crosslinked resins of claim 7, as obtained by. thermal, freeradical, or photoinitialed polymerization methods.
9. The crosslinked resins of claim 7 having outstanding ther¬ mal resistance, up to the ränge of 400450°C.
10. The crosslinked resins of claim 7 having kncop hardness exceeding 25.
11. Cαnpounds of the formula ftherein R and R' are hydrogen or methyl and A is a bond, a ethylene, an ethylene or a phenylene group.
12. Coπpounds according to claim '11, selected fron the group consisting of the follσwing diesters: Adamantanediol acrylate and methacrylate; di ethyladamantanediol acrylate and methacrylate; adamantanedimethylol acrylate and methacrylate; dimethyladamantanedimethylol acrylate and methacrylate; di(hydroxyethyl)adamantane acrylate and methacrylate; dimethyldi(hydroxyethyl)adamantane acrylate and methacryla¬ te; di(hydroxyphenyl)adamantane acrylate and methacrylate; dimethyldi(hydroxyphenyl)adamantane acrylate and methacry¬ late.
13. Crosslinked polymers obtained by the polymerization of the coπpounds of claim 11 or 12 or the eopolvmerization of mixtures the¬ reof.
14. Crosslinked resins obtained by copolymerizing the c rpounds of claim 12 in admixture with other copolymerizable acrylic monomers.
15. The crosslinked resins of claim 14, as obtained by ther¬ mal, radical or photoinitiated polymerization methods.
16. The crosslinked resins of claim 14 having outstanding ther mal resistance, i.e. up to 400 450°C.
17. The crosslinked resins of claim 14 having KNCGP hardness better than 25.
18. Clear Substrates made of organic glasses coated with a 2 to 8 Λtm layer of crosslinked polymer resulting frcm the polymeri¬ zaticn of monomers according to claim 1, which will withstand more than 24 hrs immersion in chlorimated solvents without significant damage.
19. The cαcpound of claim 1 wherein A is a sigma bond.
20. The cαipound of claim 1 wherein A is CH2 or CH2CH2.
21. The coπpound of claim 1 wherein A is a phenylene group.
22. The cαipound of claim 19, 20, or 21 wherein R and R' both are hydrogen.
23. The cαipound of claim 19, 20, or 21 wherein R and R1 both are methyl groups.
24. The cαipound of claim 19, 20 or 21 wherein R is hydrogen and R* is a methyl group.
25. The ccπpound of claim"19T 20 or 21 wherein R is a methyl group and R1 is hydrogen. E.
_ i _



The preseπt ' invention concerns new unsaturated esters (I) of adamantane diols and of adamantane containing dihydroxy- orπpounds (II) , the polymerizaticn thereof and the cross-linked polymers re- sulting fron such polymerization..

The new ester mcnomers have the formula (I) ,


Wherein the R. and R' are hydrogen or methyl group and A is ei¬ ther a sigma (σ bond, a radical satisfying the formula (CH 2 )n, a phenylene or an alkyl derivative thereof.

W at follcws is LIST I hich lists some specific examples frcm FORMULA (I) ;


1. Diacrylate and dimethacrylate esters of 1,3-adamantane diol R = H; R' = H, CH 3 ; A = sigma {<r) bond

2. Diacrylate and dimethacrylate esters of l,3-dimethyl-5,7-ada-

raantane diol

R = C^; R « = H, CI^; A = sigma (tf) bond

3. Diacrylate and dimethacrylate esters of l,3-bis-(hydroxyme- ς thyl) adamantane

R = H R* = H, C^; A = -O^-

4. Diacrylate and dimethacrylate esters of l,3-dimethyl-5 ,7-bis- (hydroxymethyl) -adamantane Q R = CR-,; R' = H, CH 3 ; A = -CH j -

5. Diacrylate and dimethacrylate esters of l ,3-bis-(2-hydroxy- ethyl) -adamantane

R = H; R » = H, C^; A = - H 2 - H 2 - 5

6. Diacrylate and dimethacrylate esters of l,3-dimethyl-5 ,7-bis-

(2-hydroxyethyl) -adamantane

R = CHg; R' = H, CH 3 ; A = -CHg-CH j -

Q 7. Diacrylate and dimethacrylate esters of l,3-bis-(p-hydroxy- phenyl)-adamantane

R = H; R' = H, OL.; A = <->

8. Diacrylate and dimethacrylate esters of l,3-dimethyl-5 ,7-bis- 5 (p-hydroxyphenyl) -adamantane

R = C^; R 1 = H, O^; A = ~ ^>

Thus, the new mcnomers of the invention, i.e. the acrylic and methacrylic esters of the corresponding di-hydroxy containing ada- Q mantanes (II) , are bifuncticnal, cαrpounds, a ccndition for obtai- ning, by the polymerization thereof, cross-linked type resins having unusual hardness, inertness to degradation agents and resistance to heat.


Esters of unsaturated acids and hydroxy-containing adamantane

cαπpounds are already kncwn. Thus, DULING et al (US? 3,533,947 and 3,639,362) disclose the mono-acrylates of l-hydroxy-adamantane and of other hydroxy-adamantanes alkylated on the others bridge-head po- sitions of the cage. Also S.S. NQVTKOV et al, Izvestiya A ade ii Nauk 2 SSSR, fl2l 2765, (1977), report the preparation of acrylates and me- thacrylates of mono substituted adamantane cαrpounds of formula BO-R-M in which Ad represents the adamantane cage and R represents the groups methylene, ethylene, -^^-OL-O-CO-, -CH^-CH ^ -O-CO-O^-. Also, REINHARDT (USP 3,342,880) discloses the preparation and the polymerizaticn of adamantyl methacrylate and of

3,3 I -dimethylacryl-l,l l -bis-adamantane, the latter giving a cross-link¬ ed resin.

Nöw, all the mcnofuncticnal cnomers of the above prior-art pro- vide straight chain polymer resins the properties of which do not 5 come up to the level of cross-linked polymers and the difu cticnal mcnαner mentioned above, although it provides a cross-linked poly¬ mer, is rather expensive and not well suitεd for industrial develop- ments.


Thus, one object of the present inventicn is to provide new a- damantane monαners containing two olefinic groups suitable for a- king, by polymerizaticn, or cσpolymerization with other monαners, 5 cross-linked resins with unusual physical properties.

Another object of the invention is to provide adamantane poly¬ merizable difuncticnal monαners, the adamantane cage of which is se¬ paratem fron the polymerizable functiα by means of a ccnnecting chain the length of which can be varied in order that polymers and copo- Q lymers with a r nge of properties can be obtained by using appropria- te mixtures of different mcnαners and copolymerizing such mixtures.

Still another object of the invention is to prcpose new difunc¬ ticnal adamantane moncmers which can be preparsd according to well defined and relatively inexpertsive routes. 5 Still another object of the invention is to furnish difunctio- nal adamantane polymerizable mcnomers which can easily and cheaply be polymerized by different methcds, i.e. ther ally, by means of free

radicals or photcchemically, thus ensuring a great versatility of end-uses.

Other objects of the invention will bec ne apparent to thcse skilled in the art frcm the detailed discussicn that follows:


The preferred ccπpounds in the inventicn are the acrylates and ethacrylates of 1,3-adamantane diol, of l,3-bis(hydroxymethyl)-a- damantane, of l,3-bis(2-hydroxyethyl)-adamantane ; of l,3-bis-(p-hy- droxyphenyl)-adamantane, and also the corresponding hcmologs with methyl grcups in positicn 5 and 7 of the adamantane cage. All the- se monαners are liσuids or solids which can be polymerized easily either ther ally (around 150°C) or in the presence of radical ini- tiators such as EL -, organic peroxides such as benzoyl peroxide, dicumyl peroxide, lauroyl peroxide or azobis-isobutyronitrile and other cαrmcn Initiators. These mcnomers can also be polymerized by irradiation with actinic sources stich as ultraviolet light (prefe- rably belσw 3-20 ran) , and electron bea s. Ihe monomers can be polymerized either individually or copoly¬ merized as mixtures of two or several other monomers. Said other mo¬ nαners can be selected from difuncticnal mon ners according to the inventicn or from mcnomers of the prior-art including monofunctio- nal monαners or polyfuncticnal moncmers. A ong the monofunctional mono ers, acrylic acid, acrylamide, and alkyl acrylates can be menr- tioned; among the polyfuncticnal raonαners, ethylene glycol diacry¬ late, hexanediol diacrylate, and tri ethylol propane triacrylate can be mentioned. The ratio of ?T>M to the copoly ers may ränge from 1:0 to 1:1. The polymers of the inventicn are hard, transparent resins which resist attack by heat and solvents and which have many end-uses. De- pending on the ethod of polymerizaticn, hardnesses in the ränge of 30(KNCOP) and more can be attained and the weight losses on being subjected to tenperatures in the ränge of 400-450°C are only about cne third of the losses for cross-linked resins fron conventional monomers.

Therefore, the new resins can be used in many high teπperatu-

re applicaticns an , also, for iπ roving the εcratch and solvent re¬ sistance of organic glasses by means of coatings only a few microns thick.


The new monomers of the inventicn can be obtained according to several different routes sσne of which will be surπmarized in the fol- lowing text belcw by y of illustraticn.

Aäamantane itself is available ccrπmercially and is generally obtained frc the catalyzed rearrangement of tricyclic cαrpounds. Thus, for instanca, the bridge-head dimethyl hvdrccarbon can be ob¬ tained frαn acenaphtεne by hydrogenaticn (reacticn φ ) and sucsεcuent rearrangement in the presence of lewis acids (reaction(Z) ) .

Another similar method ccnsists in the hydrogenation of dime¬ thyl dicyclopentadiene (reaction > ) and the subsequent rearrange¬ ment of the hydrogenätεd tricyclo cαrpound into dimethyladamantane (reaction(2a) ) .

Then, dimet yl adamantane can be oxidized (reacticn (3) ) with

CrO, in acetic acid to the corresponding diol (Ila) such as describ- ed, for instance in French Patent No 1.461.287 , or brcminatεd to the corresponding dibrαrD-coiηpound (III) with brαnine in the preseπce

5 of boren tribrαιu.de and AlBr 3 (reaction (4) ) .

(Hα ) L Π.)

l_ the dibrαno-corrpDund (III) , as well as the diol (Ila) , can be cenverted to the corresponding dicarboxylic acid by reacticn with for ic acid in cc centrated H 2 S0 4 , (reacticn (D ) then the eiaeid is esterified with a lcwer alcohol (reaction (§) ) and the octair.ed es- ter is reduced to the corresponding diol (Ilb) with lithium al rai-

2Q niun hydride (reactiσnß ) :

Alternativel , the dibrαno-coπpound (III) can be converted to the corresponding diacetic acid derivative (IV) , for instance by hea- ting with vinylidene Chloride in sulfuric acid (reaction ( ) ) , accor¬ ding to K. EOTT, Chem.Ber. 101, 564-573 (1968) . The diacid being the- reafter esterified and the ester reduced with LiAlH. in a manner a- nalcgous to reactions ( ) and (l) above (reactions (6 ) and (j ) ) to give the dimethylol cαtpound (IIc) .

(H e)

However , sir e the sequence of reactions (§) , (§ ) and (x^ does not provide very gcod yields, a two stage analcgous sequence of reactions involving the corresponding mcnobrαno-adamantane derivative is pre- ferably used. In this sequence, dimethyl adamantane is first ono- brominated using refluxing brαnine (reaction _y ) and the di ethyl- -brαno-adamantane is converted to the mono- ethyl-carboxylic acid by the same type of reaction as reacticn ) above, after which the mono-carboxylic coπpound is brominated yielding l-brσno-3-carboxy- methyl-5,7-dimethyl adamantane which then is once more reactεd with vinylidene Chloride in H 2 S0 4 according to (8) to give, finally, the diacetic acid (IV) :

The dibrcmo-dimethyl-adaraantane (III) can also be reacted with phenols according to the conditions disclosed in LSP 3,594 ,427 (re¬ action (9) ) to give the desirεd bishydroxyphenyl ccrcpounds (Ild) . This is illustrated by the following scheme involving ordinary unsubsti- tuted phenol:

(I d)

It should be pointed out that the sa e reactions can be used for obtaining the corresponding non-methylated adamantane bishydro- xy-compounds

Nσw, the cαπpounds of formula (II) can be converted to the mo¬ nαners (I) by esterification, preferably with acrylyl chloride or methacrylyl chloride in the presence of a tertiary amine, according to well kncwn techniques (see for example CS? 3,533,947) . The reac- tiαi is carried out by dissolving the alcohol in a solvent such as benzene, toluene tetrahydrofurane or the like, adding a tertiary a- mine to the mixture in molar excess relative to the alcchol, and than slcwly adding the acid chloride thereto. The amine used preferably is triethylamine, although other tertiary amines such as pyridine, tributylamine, N,N,N' ,N'-tetramethyl-ethylenediamine, triethylene- diamine, picolines, quinoline and the like can be eπployed. Upon ad- dition of the acid chloride, the initial reaction that takes place involves the formaticn of a cαiplex between it and the amine. Slcw addition of the acid chloride is continued preferably until the a- mount added is in molar excess of the alcchol. The resulting slur- ry is then stirred at a temperature in the ränge of 10-80°C, prefe¬ rably 20-60°C, to effect the esterification reacticn. A teπperatu- re above 80°C ≤hould be avoidecT in most instances as this tends to cause a messy reacticn, and it is most preferable to maintain the tenperature in the ränge of 25-60°C. Time required for ccmpletion of the reacticn will depend upen the reacticn tenperature used, but generally is in the ränge of 1-20 hours.

As the reacticn cecurs the amine-aeid chloride cαiplex is re- placed by an amine HC1 complex which is insoluble in the solvent. ϊhe alkylada antyl-acrylate product on the other hand remains in so- lution. After completion of the reaction, the mixture is filtered to remove the amine-HCl cαiplex and the solvent is ranoved by eva- poration. The crude product ester obtained is a nearly colorless li¬ quid or solid which can be purified by liquid partition chrαnatogra- Phy, by column chromatography (on A1 2 0 3 ) or, when crvstallization oecurs, by recrysta11ization in a suitable solvent. The purified pro- duets are colorless liquids or solids. In the absence of suitable stabilizing additives, the liquids may, in seme cases, polymerise spcntanecusly on storage but this generally cecurs slcwly enough to allow end use application beforehand.

For polymerizing the mcn ners of the invention, conventional techniques can be used. For instance, the monomers can be heated,


either pure or in admixture with other monαners, at teπperatures whe- re polymerizaticn will cccur theππally. Teπperatures in the ränge of 150°C and over are ordinärily suitable.

Otherwise, free radical prαnoters or irradiation in the presen- ce of photoinitiators can be used when polymerization is to be car- ried out at lewer tenperature, e.g. roem tenperature. Conditions for photόpolymerization are also conventicnal and can be found in the follcwing referεnces: U.V. Curinq Science K Technology, Editor: Tech¬ nology Marketing Corp. (1978) Stamford, Conn.06902, USA. For instance, a coating of protective polymer according to the inventicn can be applied on organic glasses made, for exa ple, of transparent resins such as polycarbonate or polymethacrylate. For this, the mcnomers of the inventicn (either pure or in admixture with other monαners) and a photoinitiator are applied as a thin layer o- ver the surface of said organic glass and the whole is subjectεd to irradiation for periods ranging from a few seconds to several minu- tes by means of ultraviolet radiatien, e.g. a high pressure ercu- ry lanp, the emission of which is- airnly in the ultraviolet wavelengths (300-330 nm) or the Short visible wavelengths. The pie- ~ ~ es of organic glasses thus acquire a ver hard, solvent-resistant and transparent protective film enabling the to be used in appli- catiens where resistance to solvents, especially chlorinated solvents, and echanical abuse is a problem, e.g. transparent construetien pla- tes, cptical material, etc... " The exarrples below further illustrate the inventicn in roore de- tail.


Exaπple 1

Preparation of the diacrylate ester of l,3-dimethyl-5 ,7-adaman- tane-diol

(Coπpound (I) , R = CK j ; R » = H)

a) Oxidaticn of 1,3-dimethyladamantane with chrαiiic anhydride: This reaction was carried out as described in French Patent No. 1.461.287 and gave the corresponding diol in yields of about 85%.

b) Ξsterification of diol (Ila) with acrylyl chloride 9.55 g (48.6 mmole) of l,3-dimethyl-5,7-adamantane-diol were dissolved in a solution of 14 ml (100 mmole) of triethyla ine in 400 ml of anhydrous tetrahydrofurane (THF) at 40°C. The solution was kept between 40 and 50°C while adding, dropwise with stirring, 8.1 ml (100 mmole) of acrylyl chloride. The addition lasted 45 min. Stir¬ ring was ccntinued for 1 hr afterwards and the insoluble triethyl¬ amine hydrochloride was re oved by filtration. The solid was dried and weighted, the result corresponding practically to the expectεd theoretical weight and shcwing that the reaction is about quantita¬ tive. The filtrate was concentrated under reduced pressure (12 Torr; below 50°C) until 14,8 g of the crude diacrylate was obtained. The crυde product was easily purified by colu n chr natography on ' Al 2 03 using hexane or Chloroform as eluent. MP of the pure diacrylate was 45,5- 46°C. The NMR spectru was taken in CEC1-, using TMS as the internal Standard. The chemical shifts are given in ppm (2) .

-1.00 (s,6H) : -^- H^ ; 1.20 (s,2H) : adamantane-O^- ; 1.86 (s,8H) : adamantane-C^- ; 2.48 "" (s ,2E) : adamantane-CΣ^- ; 5.65 (m (ccπplex), 6H) :- - O-CH=CH 2 . Exaπple 2

Preparati i of diacrylate and dimethacrylate ester of 1,3- i- methyl-5,7-bis-(2-hydroxymethyl)adamantane a) Dibrαnination of di ethyladamantane (reaction@) .

Thi-s ibrαninaticn to l,3-dimethyl-5,7-dibrαnoadamantane can be carried out according to kncwn techniques using brαnine in the presence of Lewis acids such as AlBr., and BBr-,. The present prepa- raticn was performed according to E.R. TALATY et al, J. Chem, Soc. (C) 1968, 1902. Thus, 328 g of dimethyladamantane (2 ole) were treat- ed with 1.04 1 of anhydrous brαnine in the presence of 50 ml 3Br-, and 2.2 g of AlBr 3 to give 510 g of the desired product (80% yield) .

b) Conversicn of the dibrαno-dimethyl-adamantane (III) or the cor- respcrsding dihydroxy-ccπpound (Ila) to the ccrrespcnding dicarboxy- lic acid (lila) . This reacticn was carried out according to the directions gi¬ ven in French Patent Nö 1.476.992. Thus, treating 165 g (0.51 mole) of l,3-dimethyl-5,7-dibrαnoadamantane in 1.8 1 of sulfuric acid (103%

H 2 SO ιi equiv.) with 190 ml of HCOOH at 10°C gave, after hydrolysis, 121.3 g of the desired dicarboxylic acid (yield 94%) .

Similar results were obtained when using, as the starting mar- terial, the corresponding l,3-dimethyl-5,7-adamantane-diol.

c) Esterification of the dimethyl-adamantane-dicarboxylic acid (lila)

Esterification of the above ccπpound can be performed according to conventicnal techniques, e.g. by the direct interaction with a lewer alcchol such as M≥OH, ΞtOH in the presence of catalysts such as B S0 4 , B 3 , tosylic acid and the like. Another reute is the con- version of the diacid into its dichloride followed by reaction of the latter with the lewer alcchols. Thus, 31 g (0.12 mole) of 1,3-di- methyladamantane-5,7-dicarboxylic acid was boiled for 4 hours under reflux with 160 ml S0C1 2 . The excess of thicnyl chloride was remov- ed under reduced pressure and the residue was dissolved into 100 ml

CC1 4 to which was added an excess of absolute ethanol. The solvent and excess alcchol were stripped off and the crude diester was dis- tilled under reduced pressure " (B.P./0.8 Torr: 135 - 139°C); yield

34,9 g (92%) NMR spectru (CC1 4 ; TMS; ppmδ). 0.92 (s,6H): -C-Ol j ; 1.17 (s,2H) : adamantane-CH 2 -;

1.23 (t,6H, J = 7.2 eps) : -CHg (of ethoxy);

1.48 (s , SB) adamantane-OL ;

1.82 (s , 2H) : adamantane-OL ;

4.10 (g,4H, J = 7.2 eps) : -O^- (of ethoxy) .

d) Reducticn of the diroethyl-adamantane dicarboxylate with LiAlH. (reaction ) .

Six g of lithium-aluminum hydride (0.158 mole) was stirred with 200 ml of absolute ether and to this was added dropwise 24.15 g (0.078 mole) of diethyl l,3-dimethyladamantane-5,7-dicarboxylate in 50 ml of absolute ether at a rate such as to maintain gentle refluxing of the solvent. Refluxing was centinued for 2 hrs and the excess LiAlH. was decoπposed with moist AcOEt. The reaction mixture was aeidifi- ed with 20% H 2 S0 4 which gave, by crystallizaticn, 15.3 g of 1,3-di- methyl-5,7-bis(hydroxymethyl)-adamantane(Ilb) which was collected by filtratien. Another 1.8 g crop was obtained frαn the filträte af¬ ter separating the water phase and evaporating the organic layer.

Yield was 17.1 g (97%) . MP was 158-161 °C. Eecrystallization from e- thyl acetate afforded a prcduct MP 160-162°C. NMR spectrum (BMSO-dg + CDC1 3 , TMS, ppm tf) . 0.87 (s,6H) : -^-CH-,; 1.10 (s,12H) : adamantane-CEL-;

3.16 (d,4H, J = 6 eps) : -O^-CH; 3,93 (t,2H, J = 6 eps) : -CE^-CH.

e) Esterificaticn of the l,3-dimethyl-5 ,7-bis(hydroxymethyl) -adaman- tane (Ilb) into the corresponding diacrylic and dimethacrylic esters (I) , R - CH,; R 1 = H, CH.,; A ~ -CE,-.

1. Reacticn with acrvlyl chloride.

Tb a solution of 11.15 g of l,3-dimethyi-5 ,7-bis(hydroxymethyl)-a- da antane (49.7 mmole) in 280 ml of benzene and 16.7 ml (120 mmole) of triethylamine was added, dropwise at reem tenperature, 8.84 ml (109 mmole) of acrylyl chloride over a 45 min period. The tenpera¬ ture rose to abeut 40 °C and triethylamine hydrochloride separated. The Suspension was further stirred ~ f or 1 hr at 40 °C after which it was filtered and the solid was washed with benzene. The co bined wa≤- hings and filtrate were extracted with, successively, water, satu- rated aqueous NaHC0 3 , 5% HC1 and finally water. The benzene solution was dried on anhydrous Na 2 SO. and cencentratsd below 40°C, leaving a viscous colorless residue that crystallized on standing in the cold. Yield 13.2 g (80%) of diacrylate (I) , R = CΣ^; R' = H; A = -CB^-. i The prcduct was crystallized fron ΞtOH-H p O giving colorless crystals having a MP 49-50.5 °C. pm )

1.16 (s,12H) : adamantane-QL-;

3.80 (s,4H) : -O^O-;

5.6-6.7 (cαiplex , 6H) :

2. Reacticn with ethacrylyl-chloride

Mεthacryl chloride (12.3 ml, 127.3 mmole) was added dropwise at 40°C to a solution of 12.97 g (57.8 mmole) of l,3-dimethyl-5 ,7-bis (hydroxy ethyl) adamantane in 315 ml of dry benzene containing 17.7 ml (127.3 mmole) of Et 3 . After the additien was ccπplete, stirring was ° -

chloride was filtered off and washed with benzene. The. combined fil¬ trate . and washings were scrubbed as described abvove in the case of the diacrylate and, after drying the organic phase and evaporating the solvent, 18.7 g (90%) of the dimethycrylate (I) , R = R' = CHj; 5 A = -CB -, was recovered as a. viscous residue. This. was further pu¬ rified by column chromatography on Al 7 0 3 using CHC1-, as eluent. A- nalysis showed that it was reasonably pure but it dit not crystal- lize.

NMR spectrum (CDCL,, TMS, ppmS " ) 10 0.87 (s,6H): -y-CB-. ;

1,18 (s,12H) : ada antane-CE^-;

1.97 (d,6H, J = Λ 1 eps) : -CEL (of the methacryl group)

Exaπple "* 3

20 Preparation of diacrylate and dimethacrylate esters of 1,3-di- methyl-5,7-bis(2-hydroxyethyl)adamantane (I) , R = CH^- R* = H, CH 3 ; A = -O^- f^-

a) 1,3-dim8thyl-5,7-adamantanediacetic-acid diethylester 25 l,3-dimethyl-5 " ,7-adamantanediacetic acid (IV) was prepared by kncwn techniques (K. BOTT, Chem.Ber. ,101, 564(1968). Esterification can be achieved by the same conventional techniques mentioned under Exaπple 2C. Thus, 28.7 g of l,3-dimethyl-5,7-adamantane diacetic a- eid (0.10 mole) was boiled with an excess of absolute ethanol and 30 1.2 ml ccncentrated sulfuric acid for 12 hrs under reflux to yield 31.7 g of diethyl ester (91%) BP 0.45 Tbrr 140 - 145°C.

NMR Spectrum- (CC1. solution, TMS as infernal Standard, ppm (S) 0.85 (s,6H) : -C-CBg 1.20 (s,12H): adamantane-OL- 35 : -0- H2-CH 3

4.05 (q,4H, J = 7 eps) : -O-O^-O^

b) 1,3-dimethyl-5,7-bis(2-hydroxyethyl)adamantane (IIc) The diol (IIc) was obtained by reducing the l,3-dimethyl-5,7-a- damantanediacetic acid diethylester with Lithium aluminum hydride: To 7.5 g LiAlH 4 (197.6 mmole) in 250 ml dry ether was added 30.2 g of diester (89.8 mmole) dissolved in 50 ml ether at such a rate that a gentle refluxing of the solvent is aintained. Refluxing was con- tinued for an additional 2 hrs after which time the excess LiAlH 4 was deccnposed with ethyl acetate and water. The reaction mixture was acidified with H 2 S0 4 20% and filtered, leaving 6.15 g of diol IIc. A further 13.3 g of diol was obtained frαn the filtrate after separating and evaporating the organic layer. Yield 19.45 g (86%) of diol (IIc) MP: 133 - 135°C (frcm ether) . NMR Spectrum (DMSO-d g solution, TMS as infernal Standard, ppm {*?)

0.77 (s,6H) : - -Cϊ^ 1.04 (s,12H) : adamantane-CHJ- 1.27 (t,4H, J = 7.5 eps) : -OL-CE -O- 3.43 (t,4H, J = 7.5 eps) : -C^-CH j - -

c) Esterificatien of 1,3-dimethyl-5,7-bis(2-hydroχyethyl)ada¬ mantane into the corresponding diacrylic and dimethacrylic esters,

(I) , R = CH^, R 1 = H, CH 3 ; A = -CH j -CHg-

1. Reaction with acrylyl chloride

To 5 g of l,3-dimethyl-5,7-bis-(2-hydroxyethyl)adamantane (19.8 iαnole) in 120 ml dry tetrahydrofurane (THF) containing 6.08 ml tri¬ ethylamine (43.6 mmole) was added 3.52 ml acrylyl chloride (43.6 mo- le) during a 25 min period, while maintaining the tenperature at 45 - 50°C. Stirring was centinued for 5 hrs at 60°C. The preeipitated tri¬ ethylamine hydrochloride was filtered off and washed with THF. The filtrate and washings were evaporated to dryness and the residue re- dissolved in benzene. The benzene was successively extracted with water, saturated bicarbonate solution and water and finally dried. Evaporation of the solvent provided 6.7 g (94%) of diacrylate (I) , R = CH j ; R» = H A = -O^-σ^-. Further purification was achieved by

column chromatography cn l-O^ using Chloroform as the eluent. TMS as infernal Standard, pp (5 * ) 1.11 (s,12H) : adamantane-Q^- 1.45 (t,4H, J = 7.5 eps) : -CH 2 -CH 2 -0- 4.15 (t,4H, J = 7.5 eps) : -O^-O^-O- 5.6 - 6.6 (cαiplex m,6H) : -C-CH=CH 2


2.Reaction with methacrylyl chloride

The sa e condition as for the reaction with acrylyl chloride were found suitable, except for using instead 4.2 ml methacrylyl chlo¬ ride (43.6 mmole). The yielή was 7.3 g (95%) of dimethacrylate (I) , R = R' = CH 3 , A = -CIL-CH--. Further purification was achieved by column chromatography on A10-. using Chloroform as the eluent.

NMR Spectrum (CC1 Λ solution, TMS as infernal Standard, pp (S) 0.83 (s,6H): - -CH 3 1.13 (s,12H) : adamantane-CH-- - 1.48 (t,4H, J = 7.5 eps): - H 2 -CH 2 -0- ^ H 3

1.92 (d,6H, J = 1 eps): C=C

4.12 (t,4H, J = 7.5 eps) : -CH 2 - K 2 -0-

Examole 4

Preparaticn of diacrylate and dimethacrylate esters of 1,3-bis- (2-hydroxyethyl)adamantane

(I) , R = H; R' = H, CH 3 ; A = -O^-O^-

a) 1,3-adamantane-diacetic acid diethylester

Esterification of cαπ ercially available 1,3-adamantane diace¬ tic acid (Aldrich Chemical Co,Inc.) can be achieved by conventional techniques as mentioned heretofore. In this case, the acid chlo i- de ethod was used. Thus, 20.8 g of 1,3-adamantane-diacεtic acid (82.4 mmole) was boiled with 100 ml thionylchloride under reflux for 4 hrs. The excess thionylchloride was then evaporated off and the resulting

crude acid chloride was dissolved in 65 ml carbon tetrachloride and subseσuently treated with an excess absolute ethanol. The solvent and excess alcohol were stripped off and the crude diester was dis- tilled under vacum. .

BP 0.1 Tbrr = 149°-150°C. Yield 22.6 g (89%).

NMR spectrum (CC1 4 solution, TMS as infernal Standard, pp (3)

1.17 (t,6H, J = 7cps) : -O H 2 - H 3

1.33 - 1,63: (ccπplex m,12Ξ) adamantane-CH 2 -

1.97 (s,4H) : -O^-C-



2 (m,2H) : adamantane-C-H

4.05 (q,4H, J = 7cps) : -0-CH 2 - H 3

b) 1,3-bis-(2-hydroxyethyl)adamantane This diol can be obtained b reducing the 1,3-adamantane-dia- cetic acid diethylester with lithium aluminium hydride:

To 5.65 g LiAlH 4 (148.9 mmole) in 185 ml dry ether was added 22.5 g of the diester (73 mmole) in 40 ml ether at such a rate as to maintain the solvent under gentle reflux. Refluxing was continu- ed for a further 2.5 hrs and, thereafter, the excess LiAlH 4 was de¬ ccnposed with ethylacetate and water. The reaction mixture was aci- dified with 20% H-SO. and the organic layer was separated and wash- ed to neutrality ' with water. Crystals of the pure diol then separa¬ ted. Yield 12.6 g (77%) NMR Spectrum (EMSO-d g solution, TMS as infernal Standard, ppm S)

1.95 (m,2H) : adamantane -C-H 3.48 (t,4H, J = 7.5 eps): H^- H^-CH 4.08 (s,2H)

c) Esterifieaticn of 1,3-bis(2-hydroxyethyl)adamantane to give the corresponding diacrylic and dimethacrylic esters (I), R = H, R' = H,CH 3 ; A = -CK^- H j - 1. Reacticn with acrylyl chloride To 5 g (22.3 mmoles) of 1,3-bis(2-hydroxyethyl)adamantane in

120 ml of dry benzene containing 6.83 ml of triethylamine (49.1 mmo- les) was added, at 45°C, 3.97 ml acrylyl chloride (49.1 oles) . Stir¬ ring was continued for 5 hrs at 60°C, and the precipitated triethyl¬ amine hydrochloride was filtered off and washed with benzene. The combined filtrate and washings were extracted with water, saturat¬ ed bicarbonate solution and water and finally dried. Evaporation of the solvent yielded 7.0 g (95%) of diacrylate

(I), R = R* = H; A = -CS -CEL-. Further purification was achieved by column chromatography on A1 2 0 3 .using Chloroform as the eluent. rd, ppm _S) .

5.6 - 6.6 (cαiplex , 6H) : -C0-CH=CH 2

2. Reaction with methacrylyl-chloride

The sa e conditions were used as with the previous case but 4.74 rnl (49.1 mmoles) of methacrylyl chloride was used instead of the acrylyl chloride. The yield was 7.78 g (97%) of dimethacrylate (I), R = H; R' = CH 3 ; = -CH 2 - H 2 - Further purification was carci- ed out by column chromatography (A1 2 0 3 ; CHCU) .

NMR Spectrum (CDC1 3 , TMS as infernal Standard, ppm (S) . f(Coπplex m,12H) : adarcantane-CH~

1.17 - 1.80.

(t,4H, J = 7.5 eps) : -O^-O^-O-


I ~

1.96 (d,6H, J = 1 eps): -C-OC 0

~"2. (m,2H): adamantane -C-H

Example 5


Preparation of diacrylate and dimethacrylate esters of 1,3-di- methyl-5,7-bis(p-hydroxyphenyl)adamantane (I) , R = CI^, R « = H,OΪ 3 , A =-<3-

5 a ) 1 r 3-dimethyl-5,7-bis(p-hvdroxyphenyl)adamantane (Ild)

Afamantane bisphenols can be readily made available from the corresponding dibrαncderivatives and phenol according to US 3,594,427. Thus, 112 g of l,3-dimethyl-5,7-dibrαnoadamantane (III) (0.35 m) (see Exaπple 2a) and 900 g of phenol were heated together at 170°C for

10 6 hrs. After terminatioπ of the evolution of HBr, the mixture was heated to 220°C for a further 2 hrs pericd and the excess phenol was distilled off. The reaction mixture was poured into warm water and the white precipitate was filtered, washed with warm water and dri¬ ed at 80°C under vacuum. Yield 117.8 g (97%) . The product was recrys-

15 tallyzed fron toluene. MP: 222° - 224°C.

b) Ξsterifieaticn of the l,3-dimethyl-5,7-bis(p-hydroxyphenyl)a- da antane into the corresponding diacrylic and dimethacrylic esters (I) , R = CH,; R = H, CH^; A = > .


1. Reaction with acrylyl chloride

To 5 g of 1,3-dimethy1-5,7-bis(p-hydroxyphenyl)adamantane (14.3 nsnoles) ' in 120 ml dry tetrahydrofurane containing 4.4 ml triethyl¬ amine (31.6 mmoles) was added 2.55 ml acrylyl chloride (31.6 mmoles) 25 during 25 min, while maintaining a reaction tenperature of 45-50°C. Stirring was centinued for 4 hrs at 60°C and the solvent was evapo¬ rated under vacuum. The crude reaction product ( 7 g) was crystal- lyzed fron ethyl acetate. The yield was 5.2 g (80%) of pure diacry¬ late (I) , R = CH 3 ; R« = H; A = p-Ph; MP: 145-147°C. 30 NMR Spectrum

0.95 (s,6H): -C-CH 3 1.23 (s,2H) : adamantane-CH 2 - 1.55 (s,8H) : adamantane-CH 2 - 1.85 (s,2H) : adamantane-CH^- ' 35 5.8 - 6.8 (cαiplex m,6H) : - -CH^^


7.05 (d,4H, J = 9 eps)

:arαnatic C-H 7.42 (d,4H, J = 9 eps)

2. Reacticn with methacrylyl chloride

This was performed as above but using, instead of the acrylyl chloride, 3.04 ml of methacrylyl chloride (31.6 mmole) . The yiel of dimethacrylate (I) , R = R 1 = CH 3 ; A =Ci> was 5.6 g (81%) MP: 159.5 - 161°C (fron ethyl acetate) , NMR Spectrum

0.95 (s,6H): - -0^ 1.23 (s,2H) : adamantane-O^- 1.57 (s,8H) : adamantane-CH«- 1.87 (s,2H) : adamantane-CϊL- H 3

2.03 (d,6H, J 1 eps) OC-C=C


.aromatic C-H

While pr-phenylene was used .in this example, it is expected that alkyl derivatives of phenylene could also be so utilized.

Example 6

Thermal and free radical polymerization of some monomers of LIST I a) Thermal polymerization of the diacrylates.

The diacrylates (I) were subjeeted to heating neat at tenpera¬ ture ranging frαn 150 - 200°C unfil they had cαipletely hardened. Eequired heating ti es were extremely variable, ranging frcm seve¬ ral minutes to several hours.

The cαrpounds, identified by their substituants, the polymeri-

zation conditions and the results on hardness are summarized in Ta- ble 1 below.


Thermal polymerization of adamantane diacrylates (I)

b) Free radical catalyzed polymerization- of the diacrylates and dimethacrylates.

The diacrylates and dimethacrylates (I) were free radical po¬ lymerized using small amounts of Standard initiator catalysts and teπperatures of 20 to 150°C depending on the kind of initiator. In this manner, very hard, colorless, transparent, highly cross-link- ed resins were obtained which were infusible and found inεoluble in all solvents tried. The solvents tried were 1,1,1-trichlorcethane; Chloroform; 1,2-dichloroethane; benzene; toulene; "rylene; acetone; methyl ethyl ketone; and butyl acetate. Examples are summarized be- lσw using lauroyl peroxide as the initiator. Co pounds (I) are iden- tified by their substituents R and R' .


Free radical polymerization of adamantane diacrylates and di- methacrylates (I) .

Example 7

Photopolymerization of so e monomers of LIST I

The monαners of formula (I) in liquid fo m, either neat (melt- ed) or dissolved in other liquid olefinic cαrpounds (e.g. acrylic acid, acrylates or acrylamides) were mixed with small amounts of Stan¬ dard photoinitiators (e.g. aromatic ketones) and spread with conven¬ tional means (including a doktor knife, painting, spraying and dip- ping) as thin layers (e.g. 1 to 10 u) over transparent plates of or- _0 ganic glasses (e.g. polymethacrylates (LUCITE) or polycarbonates (MA - ROLCN, Bayer) . Then, the coated plates were photopoly erized at var- rious teπperatures for periods ranging from a few seconds to about a minute using a ultraviolet light source. The organic glasses thus coated were totally inert when immersed into chlorinated solvents 5 (e.g. CΞC1 3 , trichlorethylene, o-dichlorobenzene, etc.) whereas non coated. controls will either swell or dissolve under the same condi¬ tions. Coatings obtained frαn ccnventi al monomers such as hexane- diol diacrylate, trimethylol-pröparie triacrylate or pentaerythritol tri- and tetra-acrylates were much less effective in the protecticn Q of organic glasses toward outside solvents. Further, the coatings ade according to the inventicn were generally very hard and effec- tively protected the organic glasses frαn scratches resulting from accidental ccntacts with hard objects. Also their adhesive power was excellent and they could not be removed frαn such Substrates by u- 5 sual mechanical means.

Table 3, belcw, summarizes sαne results obtained from various cαπpounds (I) identified again by the nature of their substituents R, R' and A which were photopolymerized in the presence of 1% of ben- zophenone as films about 5.8 u thick deposited on Substrates of either 0 alu inum, polyester (MYLAR) , polymethacrylate (LUCITE) or polycar- bonate (MACROLON) and placed for 1 min at 25 an fron a PHILIPS HOK 1 W ultraviolet laπp, at the teπperatures indicated in the table. Mixtures cf mcnαπers (I) and conventional mcnαners as well as con¬ trols obtained frαn ccnventicnal monomers and two of the bare Subs¬ 5 trate are also included in the table.

A B E 3



Although the exaπples have been limited to methylene and ethy- lene, the propylene and butylene are additional hαnologs that one skilled in the art would expect to form similar cαipounds with but only a slight loss in hardness and strength properties.