Chlorinated cycloaliphatic (meth) acrylate compositions are prepared by the reaction of chlorine at a temperature in the range from -30.degree. C. to 50.degree. C. with compositions made by reacting (meth) acrylic acid with crude dicyclopentadiene in the presence of a Friedel-Crafts catalyst such as BF.sub.3. The chlorinated compositions have a pleasant fruity odor and are useful to make homopolymers or copolymers which find use as metal coatings, inks, ultraviolet light curable coatings and the like.

BACKGROUND OF THE INVENTION 
This invention relates to chlorinated cycloaliphatic (meth) acrylate 
compositions which are the complex reaction products of chlorine with 
cycloaliphatic (meth) acrylate compositions. 
It is known from Ser. No. 951,416 filed Oct. 13, 1978 that cycloaliphatic 
(meth) acrylate compositions can be produced by reacting a crude 
dicyclopentadiene with acrylic acid or methacylic acid in the presence of 
a Friedel-Crafts catalyst such as BF.sub.3. These compounds have the 
sharp, penetrating "acrylate" odor. 
Pure dicyclopentadiene acrylate (DCPDA) is known from U.S. Pat. No. 
2,414,089 dated Jan. 14, 1947. 
The preparation of 2, 3-dibromo DCPDA is known from U.S. Pat. No. 3,143,535 
dated Aug. 4, 1964. The dibromo compound is very dense and viscous, and is 
produced by the esterification of 2,3-dibromo DCPD alcohol with acrylic 
acid. 
SUMMARY OF THE INVENTION 
The chlorinated cycloaliphatic (meth) acrylate compositions of this 
invention comprise, 
(A) about 60 to 95 percent by weight of dicyclopentadiene acrylate, 
dicyclopentadiene methacrylate, or mixtures thereof, 
(B) about 2 to 15 percent by weight of a mixture of polycyclopentadienyl 
acrylates of the formula 
##STR1## 
where R is CH.sub.2 .dbd.CZC(O)--O-- 
Z is H, or methyl 
n is 1, or 2 
m is 0 or 1 and when m is 0 there is a double bond present, 
(C) about 0 to about 21 percent by weight of a mixture of the copolymers of 
methacrylic acid or acrylic acid with adducts of cyclopentadiene with 
isoprene, piperylene, methylcyclopentadiene, or mixtures thereof, 
(D) about 0.05 to 10 weight percent of a mixture of polyacrylates having 
the repeating unit: 
##STR2## 
where R' is hydrogen or 
##STR3## 
R is CH.sub.2 .dbd.CZ--C(O)--O--, Z is hydrogen or methyl, n is 0, 1 or 2, 
and m is 0 or 1, and when m is 0, there is a double bond present in the 
cyclopentadienyl group, whereby said reaction product has substantially 
all the original acrylic unsaturation, substantially no remaining 
cyclolefinic unsaturation and has 1 to 3 chlorine atoms attached to the 
original cyclopentene ring. 
These compositions are prepared by chlorinating cycloaliphatic (meth) 
acrylate compositions with chlorine gas at a temperature in the range from 
-30.degree. to 50.degree. C. in the presence of an inert solvent. 
The compositions of this invention are useful as monomers or comonomers in 
thermosetting resins or thermoplastics. They are also useful to form metal 
coatings with good adhesion, laminates and inks since they are curable by 
ultraviolet light. The instant compositions have a pleasant fruity odor 
and their polymeric products are odor-free. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The main reactants to make the compositions of this invention are the 
products set forth in the aforementioned Ser. No. 951,416 which are 
referred to hereinafter as cycloaliphatic acrylate compositions or CAC and 
CMC for cycloaliphatic methacrylate compositions. 
These CAC or CMC compositions are chlorinated with chlorine gas at 
temperatures in the range from about -30.degree. to about 50.degree. C. 
and preferably in the range -20.degree. to 20.degree. C. in the presence 
of an inert solvent. 
Useful solvents are those that are not attacked by chlorine under the 
reaction conditions and are easily removed. Examples are halogenated 
solvents, such as methylene chloride, carbon tetrachloride, chloroform, 
methylchloroform, fluorocarbons, such as Freons.RTM., e.g., Freon 11, 12, 
21, 114, and benzene. 
If desired, the use of a solvent can be eliminated. However, the reaction 
is more difficult to carry out because of poor mixing and heat removal, 
and the temperature must be raised to the range 0.degree.-20.degree. C. in 
order to reduce the viscosity. 
After chlorination, the reaction products are washed with water several 
times. The solvents are removed by vacuum distillation and the 
polymerization of the product during the distillation step is prevented or 
inhibited by the use of a small amount of a polymerization inhibitor such 
as tertiary butyl catechol, hydroquinone, or phenothiazine. Generally, 
about 50-300 parts per million of the polymerization inhibitor will be 
used. 
The chlorinated compositions prepared herein are useful to make polymers 
alone or in combination with unsaturated monomers or unsaturated resins. 
Examples of unsaturated monomers which are polymerizable with the present 
compositions are one or more acrylates and vinyl aromatics such as 
styrene, alpha methyl styrene, halo styrenes, vinyltoluene, divinyl 
benzene, and the like, allyl compounds such as diallyl phthalate or allyl 
alcohol, olefins such as butene, diolefins such as butadiene, halogenated 
olefins such as vinyl chloride, and vinyl cyanide. 
Examples of unsaturated resins which are polymerizable with the present 
compositions are one or more unsaturated polyester resins, vinylester 
resins as described in U.S. Pat. Nos. 3,367,992, 3,564,074 and 3,594,247, 
polybutadiene and polyisoprene, styrene/butadiene copolymers and the like. 
Polymerization is accomplished by a free radical mechanism i.e. using free 
radical catalysts such as benzoyl peroxide, including initiation by 
electron and ultraviolet irradiation. 
If desired, the above thermosetting resins can be blended with an 
ethylenically unsaturated monomer mixture copolymerizable with the 
unsaturated polymers. The mixture comprises vinyl aromatic monomers such 
as styrene, alpha-methyl styrene, chlorostyrene, vinyl toluene, divinyl 
benzene, and diallyl phthalate with about 5 to about 90 weight percent of 
the chlorinated compositions of this invention. 
The thermosetting blends with the unsaturated monomer mixture should 
contain 20 to about 70 percent by weight and preferably 30 to 50 percent 
by weight of the monomer mixture based on the weight of the resin. A small 
amount of inhibitor such as tertiary butyl catechol, hydroquinone, or the 
like is added to this mixture. The amount added is generally in the range 
from about 50-300 parts per million based on the amount of unsaturated 
monomer. 
The final blend is a crosslinkable resin composition which is useful to 
make laminates. 
Laminates are made by mixing into the crosslinkable composition free 
radical forming catalysts and adding this mixture to a suitable fibrous 
substrate such as asbestos fibers, carbon fibers, fibrous glass, or 
inorganic fibers. Examples of these catalysts are benzoyl peroxide, 
tertial butyl peroxide, methylethylketone peroxide and the like. It is 
also of value to add accelerators such as cobalt naphthenate, dimethyl 
aniline, and the like. 
The crosslinkable composition is rolled, sprayed or impregnated into the 
fibrous reinforcement such as fibrous glass and cured in a manner well 
known in the art. When fibrous glass is used, it can be in any form such 
as chopped strands, filaments, glass ribbons, glass yarns, or reinforcing 
mats. 
The following examples and preparations are presented to illustrate but not 
to limit the invention. 
Preparation 1 
Glacial acrylic acid (AA) containing 0.1% methylether of hydroquinone 
(MEHQ) inhibitor and borontrifluoride etherate catalyst were premixed in a 
stainless steel feed tank and pumped with a metering pump to a mixing tee 
where they were combined with a metered stream of dicyclopentadiene (96% 
pure DCPD) inhibited with tertiary butyl catechol. This feed mixture was 
preheated and converted in a jacketed 3/8" O.D..times.0.035" 
walls.times.35" length reactor tube made of stainless steel. The reaction 
temperature was maintained by controlling the jacket temperature. The 
reaction pressure was controlled at 30-60 psig to maintain liquid phase. 
Steady state conditions were reached in 15-30 minutes. The effluent from 
the flow reactor was fed via a let-down valve to a falling film stripper 
column of 1/2" O.D..times.0.035" wall.times.46" length. The feed was 
distributed to the stripper wall via a slotted weir. The stripper 
temperature was controlled with a steam heated jacket and the pressure was 
reduced with a vacuum pump outfitted with a pressure regulator. In the 
stripper, predominantly acrylic acid/BF.sub.3 complex and acrylic acid are 
removed overhead through a rectification/demister section and recycled to 
the reactor. Overheads and bottoms were cooled and collected for mass 
balance and analysis. 
The reactor was fed at a rate of 3.24 ml/min. with a glacial acrylic 
acid/BF.sub.3 etherate mixture (2.53% BF.sub.3 etherate) and with 3.19 
ml/min. DCPD. This corresponds to a 2/1 molar ratio of acrylic acid to 
DCPD and 0.6% BF.sub.3 based on total feed. Temperatures in the reactor 
and stripper were 120.degree. C. The pressure in the stripper was 5 mm Hg. 
The residence time in the reactor was eight minutes, and about two minutes 
in the stripper. 
During a 4.5 hour period of continuous run, the following quantities were 
fed and recovered: 
______________________________________ 
Feed Product 
______________________________________ 
AA + 
BF.sub.3 Et.sub.2 O 
903.70g Bottom Product 
1248.98g (72.7%) 
DCDP 823.80g Overhead Product 
469.81g (27.3%) 
Total 1727.50g Total 1718.79g 
______________________________________ 
706.4 of the stripper bottoms were placed in a one gallon glass bottle, 
stirred and heated to 70.degree. C. 689.6 g of 70.degree. C. deionized 
water were added and the mixture was stirred for five minutes. Excellent 
phase separations were obtained with separation times of 3 to 3.5 minutes. 
The washing was repeated three times and 689 g of wet dicyclopentadiene 
acrylate concentrate were obtained. This material was dried in a two liter 
flask equipped with a magnetic stirring bar at room temperature at 12 mm 
Hg. Loss was 13.65 g or 1.98% giving 675.35 g of a bright clear liquid 
with the following properties: 
______________________________________ 
Gardner color 6-7 
Viscosity 22 cps (24.degree. C.) 
Boron 2 ppm 
Dicyclopentadiene acrylate 
83.6% 
(DCPDA) 
Polycyclopentadientyl acrylates 
12.6% 
Copolymers of acrylic acid 
1.0% 
Polyacrylates 2.8% 
______________________________________ 
Similar results are obtained when the acrylic acid is replaced with 
methacrylic acid. 
Preparation 2 
Using the identical procedure and conditions, but using a DCPD concentrate 
as feedstock the following results were obtained: 
______________________________________ 
Converisons 99.7% (based on DCPD) 
Gardner color 9-10 
Viscosity 63.9 cps (24.degree. C.) 
Dicyclopentadiene acrylate 
72.7% 
(DCPDA) 
Polycyclopentadienyl acrylates 
10.2% 
Copolymers of acrylic acid 
14.0% 
Polyacrylates 3.0% 
______________________________________ 
The above dicyclopentadiene concentrate contained 84% DCPD, 13% dimers of 
cyclopentadiene with isoprene, piperylene, etc., and 2% tricyclopentadiene 
and tetracyclopentadiene. 
Preparation 3 
237.6 pounds of dicyclopentadiene (97% pure DCPD) were inhibited with 238 g 
of methylether of hydroquinone (MEHQ) dissolved in 900 g acrylic acid. 
194.4 pounds of glacial acrylic acid containing 0.1% MEHQ inhibitor were 
loaded into a stirred 100-gallon stainless steel reactor and mixed with 
2476 g of BF.sub.3 etherate. The empty space in the reactor was filled 
with 2% O.sub.2 in nitrogen at 2-5 psig. All exposed metal surfaces were 
kept wetted with inhibited reaction mixture or by an internal spray 
system. 11.0 pounds of the inhibited DCPD were added to the kettle and the 
temperature increased to 40.degree. C. After analysis showed that the 
reaction had started, the DCPD was added at a rate of about 25 pounds/hour 
(9.6 hrs) at 50.degree.-60.degree. C. After all DCPD was added, the 
reaction was completed at 70.degree. C. in 3.2 hours. Unreacted acrylic 
acid, catalyst, and color bodies were removed by five washes with 50-65 
gallons of water at 70.degree. C. The washed material was dried for three 
hours until the kettle conditions were 69.degree. C. and 33 mm Hg. The 
product was cooled, drummed, and the MEHQ concentration adjusted to 190 
ppm. 363 pounds of cycloaliphatic composition were obtained. The yield on 
DCPD is 98.8%. The product has the following characteristics: 
______________________________________ 
Gardner color 3-4 
Viscosity 16.7 cps (at 24.degree. C.) 
Boron 5.6 ppm 
Dicyclopentadiene acrylate 
87.7% 
(DCPDA) 
Polycyclopentadienyl acrylate 
11.2% 
Copolymers of acrylic acid 
0.9% 
Polyacrylates 0.2% 
______________________________________

EXAMPLE 1 
In a 3-necked 2,000 ml round bottom flask 377.3 g (1.801 moles) of a 
cycloaliphatic acrylate composition (CAC) prepared by a method similar to 
Preparation 3 above and 1200 ml methylene chloride (1:3.4 volume ratio) 
were mixed and cooled to -10.degree. C. The flask was equipped with a 
mechanical stirrer, a thermometer, a chlorine inlet, a vent, and a bath 
capable of maintaining the reaction temperature at -10.degree. to 
-20.degree. C. during chlorine addition. The diluted CAC's were 
chlorinated with 140.5 g (1.98 moles) of chlorine over a period of 75 
minutes while agitating the solution vigorously. The work-up consisted of 
3 washes with distilled water, followed by solvent recovery under vacuum. 
Before solvent removal, 200 ppm of t-butyl catechol (TBC) based on monomer 
were added. 
The composition of the resultant product is listed in Table 1. The products 
were identified by gas chromatography and mass spectroscopy and the 
principal components are the dichlorides of di- tri- and 
tetracyclopentadiene acrylate formed by the chlorination of the 
cyclopentene bond. The finished product has about the same amber color as 
the starting material, but the odor level is reduced and the odor quality 
is pleasantly fruit-like. 
EXAMPLE 2 
Following the procedure outlined in Example 1, the same CAC was chlorinated 
with less solvent dilution. 
200.0 g of CAC (0.954 moles) were mixed with 300 ml of carbon tetrachloride 
(1:1.6 volume ratio) and reacted with 63.1 g (0.89 moles) of chlorine at 
-20.degree. C. Upon purification as in EXample 1 a slightly more viscous 
material of a composition listed in Table 1 was obtained. The color and 
odor characteristics were as in Example 1. 
TABLE 1 
______________________________________ 
Chlorination of CAC's in Solvents 
Example 1 2 
______________________________________ 
Solvent Ratio/Solvent 
1:3.4CH.sub.2 Cl.sub.2 
1:1.6 CCl.sub.4 
DCPDA Conversion .about.100% .about.100% 
Reaction condition 
-10.degree. -20.degree. C. 
DCPDA .8 .2 
(dicyclopentadienyl acrylate) 
Cl.sub.1 DCPDA 1.2 1.6 
Cl.sub.2 DCPDA 78.6 77.0 
(Cl.sub.3-4 DCPDA and 
Cl.sub.1-4 DCPDA-H)* 
13.5 20.0 
Unidentified 5.9 1.2 
______________________________________ 
*Includes chlorination products of heavy acrylates and Cl.sub.3-4 product 
of DCPDA. 
EXAMPLE 3 
Following the procedure of Example 1, 50 g (0.20 moles) of a cycloaliphatic 
composition (CAC) was chlorinated at -20.degree. C. in 300 milliliters 
methylene chloride. (1:6 volume ratio) using 20.0 g gaseous chlorine (0.28 
moles). The composition of the CAC used was 79.9% DCPDA, 11.1% 
polycyclopentadienyl acrylates (DCPDA-H) and about 9% of oligomers of 
acrylic acid with codimers of cyclopentadiene with isoprene, piperylene 
and methylcyclopentadiene, and small amounts of acrylate polymers. Work-up 
and product stabilization was as described in Example 1. 
The product had a density of 1.29 g/cm.sup.3 at 25.degree. C. and a Gardner 
color of 8-9. Its odor was faint and pleasant. 
EXAMPLE 4 
Following the general procedure of Example 1, 53.3 g (0.240 moles) of a 
cycloaliphatic product consisting of 93.0% dicyclopentadiene methacrylate 
(DCPDM), 7% of mostly tri and tetra-cyclopentadiene methacrylate and 
dicyclopentadiene (DCPD) dimethacrylate and 0.1-0.3% acrylate polymer were 
diluted to a 1:6.0 volume ratio with methylene chloride (300 ml). Chlorine 
gas (17.5 g, 0.25 moles) was added at -20.degree. C. over a period of 53 
minutes. The products were recovered as in Example 1. 
EXAMPLE 5 
In a manner similar to Example 4, 107.3 g (0.483 moles) of the same product 
were dissolved in 150 ml methylene chloride (volume ratio 2:3) and 
chlorinated at -20.degree. C. with 38.0 g (0.536 moles, of chlorine over a 
period of 111 minutes. The products were recovered as in Example 1. 
The final products from Examples 4 and 5 had gas chromatographic pattern 
very similar to the corresponding acrylate materials. The product 
consisted predominantly of the dichloride formed by the addition of 
chlorine to the cyclopentene double bond with the exclusion of the 
acrylate bond. As with the CAC products, the selectivity to dichloride was 
higher at the higher dilution level and the odor decreased and the odor 
quality improved upon chlorination. The compositions for the examples are 
listed in Table 4. 
TABLE 2 
______________________________________ 
Chlorination of CMC at two dilution levels. 
Example 4 5 
______________________________________ 
Solvent ratio/Solvent 
1:6/CH.sub.2 Cl.sub.2 
2:3/CH.sub.2 Cl.sub.2 
Conversion of CMC .about.100% 
.about.100% 
Reaction conditions -20.degree. C. 
-20.degree. C. 
DCPDM .2 .2 
(dicyclopentadienyl methacrylate) 
Cl.sub.1 DCPDM 3.7 5.5 
Cl.sub.2 DCPDM 83.0 76.5 
(Cl.sub.3-4 DCPDM and 
Cl.sub.1-4 DCPDM-H)* 13.0 16.0 
Unidentified .1 1.8 
______________________________________ 
*Includes chlorination products of heavy methacrylates and Cl.sub.3-4 
products of DCPDM. 
EXAMPLE 6 
Chlorinated CAC (Example 1) homopolymerized rapidly by free radical and 
photo initiation. 
For this composition, ultraviolet photo initiation and rapid cure was 
obtained when thin films (0.2-0.3 mls) on steel (bonderite 37) or aluminum 
panels were passed under a 200 watts U.V. lamp at 100 foot/minute line 
speed. 3-4 passes were required to obtain odor-and mar-free coatings with 
excellent adhesion. Two suitable initiator systems are 3.0% benzoin butyl 
ether or a combination of 3.0% diethoxyacetophenone and 2.0% methyl 
diethanolamine. 
EXAMPLE 7 
Chlorinated CAC (Example 1) was mixed with commercial vinyl ester resins in 
a 1:1 weight ratio. The vinyl ester resin was The Dow Chemical Company's 
vinyl ester resin XD 9002. Rapid polymerization to copolymers occurred 
during 3-4 passes under a 200 watt/linear inch mercury arc lamp at 100 
foot/minute line speed using 3% diethoxyacetophenone and 2% diethanolamine 
as the photo initiator system. The resultant coating was odor-free and had 
good solvent and mar resistance and excellent adhesion. 
EXAMPLE 8 
In a two liter flask, 320 g of butyl acrylate (50%), 12.8 g acylic acid 
(2%), 245.2 g (38%) methyl methacrylate, and 62 g (10%) of chlorinated 
product of Example 3 were copolymerized into a latex containing about 40% 
solids by an emulsion technique using sodium persulfate as the initiator. 
The solids contained about 10% by weight of the chlorinated DCPDA. 
A control latex was also made using 307.2 g (48%) of the methyl 
methacrylate and no chlorinated DCPDA. 
Films were prepared from the above latexes after thickening with Acrysol 
RM-4 a commercial latex of Rohm and Hass by casting the latexes on glass 
plates and curing. 
Coated panels were also prepared by coating the latexes on clean cold 
rolled steel panels and aluminum panels. 
When these sample films and coated panels were tested it was found that the 
latex containing the chlorinated DCPDA was equal to or better than the 
control in tensile, elongation, adhesion, solvent resistance, impact, and 
abrasion tests.