Arylcyclobutenes

Abstract

Arylclobutene-containing multi-functional monomers are useful in the preparation of arylcyclobutene-based polymer coatings. Compositions comprising one or more arylclobutene-containing multi-functional monomers and one or more oligomers comprising as polymerized units one or more arylcyclobutene monomer provide arylcyclobutene-based polymer coatings having reduced stress. Such compositions are useful in the manufacture of electronic devices.

Claims

1. A dry film structure comprising a support sheet; a layer of a polymer on the support sheet, the polymer comprising polymerized units of one or more monomers of formula (1) ##STR00013## wherein each A is independently chosen from CR.sup.3R.sup.4O, C(O)O, and C(O)NH; each B is independently chosen from CR.sup.3R.sup.4 and C(O); each R is independently chosen from halo, cyano, hydroxy, carboxy, C.sub.1-6 alkoxy, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.2-6 alkenyl, carboxy C.sub.1-6 alkyl, (CO)C.sub.1-6 alkyl, -G-(CO)C.sub.1-6 alkyl, (CO)-G-C.sub.1-6 alkyl, OC.sub.4-20 aryl, (CO)C.sub.4-20, aryl, -G-(CO)C.sub.4-20 aryl, and (CO)-G-C.sub.4-20 aryl; each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently chosen from H, C.sub.1-10 alkyl, C.sub.2-10 alkenyl, C.sub.2-10 alkynyl, and C.sub.4-15 aryl; Z is an organic radical having 2 to 50 carbon atoms; G is O or N(R).sub.2; each R is independently chosen from H, C.sub.1-6 alkyl, C.sub.4-10 aryl, and C.sub.7-15 aralkyl; x is the number of R groups and is an integer of from 0 to 2; m is an integer of from 1 to 6; n is an integer of from 0 to 5; and m+n=3 to 6; and a cover sheet on the polymer layer.

2. The dry film structure of claim 1 wherein m=1 to 4.

3. The dry film structure of claim 1 wherein n=0 to 3.

4. The dry film structure of claim 1 wherein A is CR.sup.3R.sup.4O or C(O)O.

5. The dry film structure of claim 1 wherein Z has one or more ether linkages, one or more hydroxyl moieties, or a combination of one or more ether linkages and one or more hydroxyl moieties.

6. The dry film structure of claim 1 wherein each R.sup.1 and R.sup.2 is independently chosen from H, C.sub.1-10 alkyl, and C.sub.2-10 alkenyl.

7. The dry film structure of claim 1 wherein B is CR.sup.3R.sup.4.

8. The dry film structure of claim 1 wherein the support sheet is a polyester sheet or a polyimide sheet.

9. The dry film structure of claim 1 wherein the cover sheet is polyethylene.

10. The dry film structure of claim 1 wherein the polymer of the polymer layer further comprises polymerized units of one or more arylcyclobutene oligomers of formula ##STR00014## wherein B.sup.1 is an n-valent linking group; Ar is a polyvalent aryl group and the carbon atoms of the cyclobutene ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar; m is an integer of 1 or more; n is an integer of 1 or more; and each R.sup.10 is a monovalent group.

11. The dry film structure of claim 10 wherein the polymer layer further comprises one or more photoactive compounds.

12. A method of forming a film on a substrate comprising: providing a substrate; providing the dry film structure of claim 1; removing the cover sheet; laminating the polymer layer to a surface of the substrate; and removing the support sheet.

Description

EXAMPLE 1: SYNTHESIS OF TRIMETHYLOLPROPANE PROPOXYLATE TRI(ACRYLATEBENZOCYCLOBUTENE)COMPOUND (9)

(1) A 2000 mL three-necked, round bottomed flask with bottom drain port, outfitted with a mechanical stirrer, pressure equalizing addition funnel and condenser with attached nitrogen inlet was charged with potassium acetate (125.6 g, 1.28 mol) and deionized (DI) water (60 mL). The solution was stirred for 10 min. and then trimethylolpropane propoxylate triacrylate having an average of 2 propoxylate groups (107.1 g, 165.9 mmol), 100 mL dimethylformamide (DMF), palladium acetate (0.27 g, 1.18 mmol) and tri(o-tolyl)phosphine (1.14 g, 3.75 mmol) were added to the vessel and the mixture was sparged with nitrogen with stirring for 30 min. The pressure equalizing addition funnel was charged with a solution of 3-bromobenzocyclobutane (91.46 g, 499.6 mmol) in DMF (50 mL). This solution was then de-gassed via nitrogen sparge for 20 min. The reaction solution was slowly heated to 80 C. followed by slow addition of the 3-bromobenzocyclobutane. Reaction completeness was monitored by the disappearance of 3-bromobenzocyclobutane via gas chromatography, which took 27 hr. Toluene (200 mL) was added to the solution which was then cooled to room temperature. The aqueous layer, which was laden with suspended solids, was removed via the reactor bottom drain. The organic layer was filtered over a pad of celite via vacuum filtration. The filtrate was washed with deionized water, resulting in an emulsion which would not separate. The emulsion was filtered again through celite to separate the organic and aqueous layers. The organic layer was isolated, dried over anhydrous magnesium sulfate, filtered and condensed to afford the product as a clear yellow colored viscous oil. Yield: 140.4 g (88.9%).

EXAMPLES 2-5

(2) The procedure of Example 1 was repeated except that the trimethylolpropane propoxylate triacrylate having an average of 2 propoxylate groups was replaced with trimethylolpropane triacrylate (no ethoxylate groups, Compound 10) or with trimethylolpropane ethoxylate triacrylate having the average number of ethoxylated groups indicated in Table 1.

(3) TABLE-US-00001 TABLE 1 Average Ethoxylate Chain Example Compound No. Length 2 6 1 3 7 2 4 8 5 5 10 0

EXAMPLE 6

(4) A 500 mL two-necked, round bottomed flask with rubber septum and condenser with attached nitrogen inlet was charged with 3-acrylic acid benzocyclobutene (30.17 g, 173.2 mmol), chloroform (100 mL) and DMF (0.10 mL). A solution of thionyl chloride (23.60 g, 198.4 mmol) in chloroform (20 mL) was added via syringe over 15 min. The solution was stirred for 60 min. at room temperature followed by heating to 45 C. for 1 hr. Toluene (75 mL) was added to the vessel and the solution condensed on a rotary evaporator to afford benzocyclobutene acryloyl chloride (BCB-AA acid chloride) as a light tan colored solid in quantitative yield. .sup.1H NMR (500 MHz, Chloroform-d) 7.83 (d, J=15.5 Hz, 1H), 7.41 (dd, J=7.6, 1.4 Hz, 1H), 7.29 (dd, J=1.3, 0.7 Hz, 1H), 7.13 (dd, J=7.6, 0.9 Hz, 1H), 6.59 (d, J=15.4 Hz, 1H), 3.24 (s, 4H).

EXAMPLE 7: SYNTHESIS OF PENTAERYTHRITOL TRIALLYL ETHER BENZOCYCLOBUTENE ACRYLIC ACIDCOMPOUND (3)

(5) A 1000 mL three necked round bottomed flask outfitted with a mechanical stirrer (Teflon paddle), a pressure equalizing addition funnel was charged with pentaerythritol triallyl ether (NEOALLYL P-30) (111.9 g, 436.5 mmol), toluene (300 mL) and triethylamine (56.61 g, 559.4 mmol). The addition funnel was charged with a solution of BCB-AA acid chloride (88.96 g, 461.8 mmol) from Example 6 in toluene (100 mL), which was then added dropwise to the reaction mixture over 45 min. The solution was then heated to 90 C. for 9.5 hr. The solution was then filtered through a 38 mm (1.5 inch) thick silica gel plug on a 350 mL fritted glass funnel. Hexane:ethyl acetate (80:20, 200 mL) was used as the washing solvent. The filtrate was condensed to afford an orange colored viscous oil, which was taken up in hexanes (300 mL) and placed into a freezer for 3 days. The solution was filtered and condensed to afford the product as a viscous dark yellow colored oil. Yield: 178.0 g (93.97%). .sup.1H NMR (500 MHz, Chloroform-d) 7.67 (dd, J=15.9, 3.1 Hz, 1H), 7.36 (dd, J=7.6, 1.5 Hz, 1H), 7.31-7.18 (m, 1H), 7.13-6.94 (m, 1H), 6.39 (d, J=16.0 Hz, 1H), 5.97-5.78 (m, 2H), 5.27 (dd, J=17.3, 1.7 Hz, 2H), 5.15 (dd, J=10.5, 1.6 Hz, 2H), 4.30 (s, 2H), 3.97 (d, J=5.4 Hz, 4H), 3.52 (s, 4H), 3.20 (s, 3H).

EXAMPLE 8: SYNTHESIS OF TRIMETHYOLPROPANE ALLYL ETHERBIS(BENZOCYCLOBUTENE ACRYLIC ACID)COMPOUND (5)

(6) A 500 mL two-necked, round bottomed flask with magnetic stir bar, rubber septum and condenser with attached nitrogen inlet served as the vessel for this reaction. The vessel was charged with BCB-AA acid chloride (28.59 g, 148.4 mmol) from Example 6, toluene (150 mL), triethylamine (19.35 g, 191.2 mmol) and trimethyolpropane allyl ether (27.62 g, 128.9 mmol). The solution was heated to 50 C. for 3 hr. after which time a catalytic amount of DMAP was added. The solution was heated for an additional 5 hr. at 50 C. and then filtered while hot. The filtrate was washed with deionized water and a saturated ammonium chloride solution. The organic layer was isolated, dried over anhydrous magnesium sulfate, filtered and condensed to afford the crude material which was purified by automated flash chromatography on silica gel. The resulting product was then taken up into ethyl acetate:hexanes (20:80, 200 mL) and placed in a freezer for 48 hr. The solution was then filtered and condensed in-vacuo. The resulting oil was taken up into dichloromethane (200 mL) and washed with a saturated sodium bicarbonate solution doped with 1% NaOH. The organic layer isolated, dried over anhydrous magnesium sulfate, filtered and condensed to afford the product Compound (5) as a clear yellow colored oil. Yield: 34.65 g (72.4%). .sup.1H NMR (500 MHz, Chloroform-d) 7.67 (d, J=15.9 Hz, 1H), 7.36 (d, J=7.4 Hz, 1H), 7.26 (s, 1H), 7.07 (d, J=7.5 Hz, 1H), 6.39 (d, J=16.0 Hz, 1H), 5.89 (ddt, J=17.3, 10.6, 5.4 Hz, 2H), 5.27 (dd, J=17.3, 1.7 Hz, 2H), 5.16 (dd, J=10.4, 1.7 Hz, 2H), 4.19 (d, J=1.0 Hz, 2H), 3.97 (d, J=5.4 Hz, 4H), 3.40 (s, 4H), 3.20 (s, 4H), 1.52 (q, J=7.5 Hz, 2H), 0.91 (t, J=7.5 Hz, 3H).

EXAMPLE 9: SYNTHESIS OF TRIMETHYLOLPROPANE DIALLYL ETHERBENZOCYCLOBUTENE ACRYLIC ACIDCOMPOUND (4)

(7) The procedure of Example 8 was repeated except that the following amounts of materials were used: BCB-AA acid chloride from Example 6 (40.98 g, 212.7 mmol), toluene (200 mL), triethylamine (29.11 g, 287.7 mmol) and trimethylolpropane allyl ether (18.18 g, 104.3 mmol). The product was isolated as a clear orange colored viscous oil. Yield: 36.02 g (71.6%). .sup.1H NMR (500 MHz, Chloroform-d) 7.68 (d, J=15.9 Hz, 2H), 7.35 (dd, J=7.6, 1.4 Hz, 2H), 7.24 (s, 2H), 7.06 (d, J=7.6 Hz, 2H), 6.39 (d, J=16.0 Hz, 2H), 5.89 (ddt, J=17.2, 10.7, 5.5 Hz, 1H), 5.37-5.23 (m, 1H), 5.17 (dd, J=10.4, 1.6 Hz, 1H), 4.25 (d, J=2.1 Hz, 4H), 3.98 (d, J=5.5 Hz, 2H), 3.44 (s, 2H), 3.19 (s, 8H), 1.59 (q, J=7.6 Hz, 2H), 0.96 (t, J=7.6 Hz, 3H).

EXAMPLE 10: SYNTHESIS OF COMPOUND (24)

(8) A 500 mL two-necked, round bottomed flask with a magnetic stir bar, rubber septum and condenser with attached nitrogen inlet was charged with BCB-AA acid chloride from Example 6 (13.91 g, 72.2 mmol), toluene (150 mL) and triethylamine (8.86 g. 87.6 mmol). Amine terminated propoxylated trimethylolpropane having a total of 5-6 propoxylate groups (JEFFAMINE T-403, Huntsman Corporation) (10.33 g, 21.5 mmol) was then added to the solution via syringe through the rubber septum. The solution was then heated to 90 C. for 8 hr. The solution was filtered while hot, washed with dilute (1 wt %) NaOH, dried over anhydrous magnesium sulfate, filtered and condensed. The isolated material was then purified via automated flash chromatography over silica gel. The resulting product (Compound 24) was a yellow colored solid. Yield: 13.89 g (68.0%). .sup.1H NMR (400 MHz, Chloroform-d) 7.56 (d, J=15.7 Hz, 3H), 7.27 (s, 3H), 7.15 (d, J=7.3 Hz, 3H), 6.98 (d, J=7.7 Hz, 3), 6.53-6.08 (m, 3H), 4.33-4.06 (m, 3H), 3.68-3.21 (m, 18H), 3.19-2.99 (m, 12H), 1.49-1.33 (m, 2H), 1.30-0.99 (m, 9H), 0.93-0.67 (m, 3H).

(9) ##STR00009##

EXAMPLES 11-14: SYNTHESIS OF COMPOUNDS (25-28)

(10) The general procedure of Example 9 was repeated except that BCB-AA acid chloride from Example 6 was reacted with each of the following polyol compounds to provide Compounds (25-28). For each of Compounds (25-27), 3 equivalents of BCB-AA acid chloride were used for each equivalent of polyol compound, and 4 equivalents of BCB-AA acid chloride were used to prepare Compound (28).

(11) ##STR00010##

(12) TABLE-US-00002 TABLE 2 Example Compound n1 + No. No. R.sup.23 n2 + n3 + n4 11 25 C.sub.2H.sub.5 4-5 12 26 H 10-11 13 27 H 16-18 14 28 CH.sub.2O(CH.sub.2CH(CH.sub.3).sub.n4OH 6-7

EXAMPLE 15: SYNTHESIS OF COMPOUND (29)

(13) The general procedure of Example 9 was repeated except that 4 equivalents of BCB-AA acid chloride from Example 6 were reacted with pentaerythritol to provide Compound (29).

EXAMPLE 16: SYNTHESIS OF 1-MEO-TRIS-BENZOCYCLOBUTENE-ACRYLATE COMPOUND (11)

(14) Bromobenzocyclobutene (91.5 g, 0.5 mol) and chlorobenzene(anhydrous, 2500 mL) were charged into a four-neck 5 L flask equipped with mechanical stir, condenser, N.sub.2 (in and outlet) and thermometer. The reaction mixture was heated to 120 C., and N-bromosuccinimide (111.3 g, 0.625 mol) was gradually charged over 30 min., followed by slowly feeding a mixture of a free radical azo compound source (VAZO 68) (14.0 g, 0.05 mol) and chlorobenzene (500 mL) over 30 min. Then the reaction mixture was heated to 133 C. (mild reflux) and kept at that temperature for 6 hr. The mixture was then cooled to room temperature overnight, and chlorobenzene was removed by vacuum evaporation. The crude product was extracted with hexane. After removal of hexane, 1-bromo-bromobenzocyclobutene (1-BrBrBCB) (80-85 C./0.35 torr, 90 g, ca. 93% purity) was obtained by vacuum distillation.

(15) The 1-BrBrBCB (90.0 g, 0.49 mol), anhydrous THF (100 mL), and sodium methoxide (200 g, 0.93 mol, 2-5 wt % in methanol) were charged into a 1000 mL four-neck flask equipped with a condenser, N.sub.2 (in and outlet), and mechanical stirrer. The reaction mixture was heated to 75 C. and held at this temperature for 6 hr. After reaction, the reaction mixture was poured into 400 mL of hexane, and washed with DI water six times (6100 mL). The solvent in the separated organic layer was removed by evaporator, and the colorless product 1-methoxy-bromobenzocyclobutene (1-MeOBrBCB) was obtained by vacuum distillation (80 g, 62-65 C./0.39 torr, yield, 76%).

(16) Trimethylolpropane propoxylate triacrylate (TMPPTA, 32.24 g, 0.05 mol), toluene (anhydrous, 30 g), N-methyldicyclohexylamine (39.07 g, 0.20 mol) were charged into a 500 mL four-neck flask equipped with additional funnel, N.sub.2 (in and outlet), and magnetic stirrer, and thermometer. 1-MeOBrBCB (32.0 g, 0.15 mol) and toluene (anhydrous, 30 g) were charged into an addition funnel, followed by N.sub.2 bubbling for 20 min. In a dry glove box, a catalyst solution of tris(dibenzylideneacetone)dipalladium (0.916 g, 1.0 mmol), tri-tert-butylphosphine (0.425 g, 2.1 mmol) and toluene (anhydrous, 20 g) was prepared. This catalyst solution was stirred for 20 min. under N.sub.2, and then transferred into the reaction flask via a syringe. Next, the MeOBrBCB/toluene solution was added dropwise from the additional funnel over 60 min. After addition was complete, the reaction mixture was stirred at room temperature for 48 hr. After reaction, the reaction mixture was poured into 500 mL of hexane, and washed with DI water (100 mL water with 5 mL acetic acid) six times (6100 mL). The resulted product (Compound 11) (43 g, yield, 82%) was obtained by removing solvent (toluene, hexane) under vacuum.

EXAMPLE 17: SYNTHESIS OF PENTAERYTHRITOL TRIS(1-MEOBCB) ALLYL ETHERCOMPOUND (16)

(17) Pentaerythritol triallylether (NEOALLYL P-30, 12.72 g, 0.05 mol), toluene (anhydrous, 30 g), and N-methyldicyclohexylamine (39.07 g, 0.20 mol) were charged into a 500 mL four-neck reaction flask equipped with an addition funnel, N.sub.2 (in and outlet), magnetic stirrer, and thermometer. 1-MeOBrBCB (32.0 g, 0.15 mol) and toluene (anhydrous, 30 g) were charged into an addition funnel, followed by N.sub.2 bubbling for 20 min. In a dry glove box, a catalyst solution of tris(dibenzylideneacetone)dipalladium (0.916 g, 1.0 mmol), tri-tert-butylphosphine (0.425 g, 2.1 mmol) and toluene (anhydrous, 20 g) was prepared. This catalyst solution was stirred for 20 min under N.sub.2, and then transferred into the reaction flask via a syringe. 1-MeOBrBCB/toluene solution was dropwise added to the flask over 60 min. After addition was complete, the reaction mixture was kept stirring at room temperature for 48 hr. After reaction, the reaction mixture was poured into 500 mL of hexane, and washed with DI water (100 mL water with 5 mL acetic acid) 6 times (6100 mL). The resulting product (Compound 16) (37 g, yield, 82%) was obtained by removing solvent (toluene, hexane) under vacuum.

EXAMPLE 18: PREPARATION OF FORMULATION 1

(18) In a 250 mL brown bottle, 6.16 g of 2,1,5-di azonaphthoquinone (DNQ) sulfonic ester of 4,4-((2-hydroxyphenyl)methylene)bis(2,3,6-trimethylphenol) with an average 65 mole % of esterified phenols as photoactive compound (PAC) was dissolved in 1.39 g dipropylene glycol dimethyl ether (PROGLYDE DMM, The Dow Chemical Company), 3.75 g methyl 3-methoxypropionate (MMP) and 0.16 g propylene glycol methyl ether acetate (PGMEA) and 2.64 g of a 5 wt % solution of a silicon-containing surfactant (DCT L-7604) in MMP solvent. Next, 23.32 g of a 50 wt % solution of Compound (25) from Example 11 in MMP as crosslinker was added along with 57.30 g of a 40.85 wt % arylcyclobutene oligomer solution in PROGLYDE DMM solvent and 5.28 g of a 50 wt % triethoxysilylpropylmaleamic acid in PGMEA as adhesion promoter. The arylcyclobutene oligomer solution was a B-staged reaction mixture with on average 69 mole % benzocyclobutene acrylic acid (BCB-AA) and 31 mole % bis(benzocyclobutene vinyl) dimethylsiloxane (DVS-BCB). The bottle was rolled for 12 hours to form a homogeneous solution. After de-foaming, the solution was filtered through a 0.45 m nylon filter before use.

EXAMPLES 19-22: FORMULATIONS 2-5

(19) The procedure of Example 18 was repeated except that the crosslinker solution was a 50 wt % MMP solution the compounds shown in Table 3.

(20) TABLE-US-00003 TABLE 3 Example Formulation No. Compound No. 19 2 26 20 3 27 21 4 28 22 5 29

EXAMPLE 23: FORMULATION 6

(21) The procedure of Example 18 was repeated except that the crosslinker solution used was replaced with 23.51 g of a 39.68 wt % solution of an oligomer comprising only as polymerized units a monomer of Compound 25 in PROGLYDE DMM solvent.

EXAMPLE 24: FORMULATION 7

(22) The procedure of Example 18 was repeated except that the crosslinker solution used was replaced with 23.54 g of a 39.62 wt % solution of an oligomer comprising only as polymerized units a monomer of Compound 25 in 3-methoxy-1-butyl acetate.

EXAMPLE 25

(23) Solutions of each of Formulations 1-7 and a Control sample were spin coated on 200 mm prime grade silicon wafers using a Site Trac TT5-XP coater at 1450 rpm for 30 seconds followed by a hotplate bake of 120 C. for 90 seconds to further remove solvent. The film thickness was approximately 6.5 m. The coated wafers were then thermally cured in a Blue M Ultra-Temp oven (Model IGF-6680E-4) under nitrogen at 200 C. for 100 min. Oxygen levels were maintained at <100 ppm for the entire process. The final film thickness was approximately 6.1 m. Film stress was measured within 2 hr. of removal from the furnace. The Control sample was a commercially available benzocyclobutene material, CYCLOTENE 6505, available from Dow Electronic Materials. The Control did not contain any monomers of the invention, nor any oligomers comprising any monomers of the invention.

(24) Residual stress of the cured polymeric film was measured on a FLX-3300-T Thin Film Stress Measurement System from TOHO Technology. Duplicate wafers were prepared for each Formulation and the average of two measurements was reported as the residual stress value. The residual stress .sub.film is defined in Equation 1

(25) $\begin{array}{cc}{}_{\mathrm{film}}=\left(\frac{E}{1-}\right)\frac{t_s^2}{6t_{f}R}& \mathrm{Equation}1\end{array}$
where .sub.film is residual stress, t.sub.s is thickness of the silicon substrate, t.sub.f is the coating thickness, and R is the radius as defined in Equation 2. E is the Modulus of Silicon and v is Poisson's ratio. These values are constant and are defined as E=169.0 GPa and v=0.0641 (See Hoperoft, M A, J. Micromechanical Systems, Vol 19, No 2, April 2010. Page 237, Table V.).

(26) $\begin{array}{cc}R=\frac{L^2}{8B}& \mathrm{Equation}2\end{array}$
L is the scan length and B is the wafer bow, which is defined as the deviation of the center point of the median surface of a free, un-clamped wafer from the median surface to the reference plane. The residual stress values for the polymer films from each of Formulations 1-7 and the Control are reported in Table 4. As can be seen from these data, the compositions of the present invention provide significant reduction in residual stress as compared to the commercially available Control.

(27) TABLE-US-00004 TABLE 4 Formulation No. Stress Value (MPa) 1 24.08 2 20.51 3 16.18 4 24.95 5 24.14 6 24.77 7 24.46 Control 29.05

EXAMPLE 26: SYNTHESIS OF COMPOUNDS (30-39)

(28) The general procedure of Example 1 is repeated except that equivalents of 3-bromobenzocyclobutane used is varied and/or the trimethylolpropane propoxylate triacrylate having an average of 2 propoxylate groups is replaced with trimethylolpropane triacrylate, pentrerythritol triacrylate, pentaerythritol tetraacrylate, or propoxylated pentaerythritol tetraacrylate and is expected to prepare Compounds (30-39) having the following general formula as described in Table 5.

(29) ##STR00011##

(30) TABLE-US-00005 TABLE 5 Compound p t R.sup.5 E 30 2 1 CH.sub.3 CH.sub.3 31 2 2 CH.sub.3 CH.sub.3 32 0 2 CH.sub.3 33 1 2 H CH.sub.3 34 0 2 OH 35 0 1 O(CO)CHCH.sub.2 36 0 2 O(CO)CHCH.sub.2 37 0 3 O(CO)CHCH.sub.2 38 1 1 CH.sub.3 OCH(CH.sub.3)CH.sub.2O(CO)CHCH.sub.2 39 1 2 CH.sub.3 OCH(CH.sub.3)CH.sub.2O(CO)CHCH.sub.2

EXAMPLE 27: SYNTHESIS OF COMPOUNDS (40-54)

(31) The general procedure of Example 1 is repeated except that equivalents of 3-bromobenzocyclobutane used is varied and the trimethylolpropane propoxylate triacrylate having an average of 2 propoxylate groups is replaced with dipentaerythritol pentaacrylate, ditrimethylolpropane tetraacrylate, or ethoxylated dipentaerythritol pentaacrylate and is expected to prepare Compounds (40-54) having the following general formula as described in Table 6 where AG is the sum of the terminal acrylate groups, or [(3(k+a))+(3(z+u))].

(32) ##STR00012##

(33) TABLE-US-00006 TABLE 6 Compound r k + z a u AG R.sup.a R.sup.b 40 0 1 1 1 3 C.sub.2H.sub.5 C.sub.2H.sub.5 41 0 2 1 1 2 C.sub.2H.sub.5 C.sub.2H.sub.5 42 0 3 1 1 1 C.sub.2H.sub.5 C.sub.2H.sub.5 43 0 1 1 0 4 CH.sub.2OH 44 0 2 1 0 3 CH.sub.2OH 45 0 3 1 0 2 CH.sub.2OH 46 1 1 1 0 4 CH.sub.2OH 47 1 2 1 0 3 CH.sub.2OH 48 1 4 1 0 1 CH.sub.2OH 49 2 1 1 0 4 CH.sub.2OH 50 2 2 1 0 3 CH.sub.2OH 51 0 1 0 0 5 52 0 2 0 0 4 53 0 3 0 0 3 54 0 5 0 0 1

EXAMPLES 28: FORMULATIONS 8-10

(34) The procedure of Example 18 is repeated with similar results expected except that the crosslinker solution is a 50 wt % MMP solution the compounds shown in Table 7.

(35) TABLE-US-00007 TABLE 7 Example Formulation No. Compound No. 28 8 31 29 9 35 30 10 38 31 11 42 32 12 47