Note: Descriptions are shown in the official language in which they were submitted.
--1--
~ ~OL~MER CONCRETE COMPOSITIONS
CONTAINING WAT~R ABSORBENT POL~ERS
This invention relates to polymer concrete
compositions consisting generally of a unsaturated
thermosettable resin and/or ethylenically unsaturated
monomer, an aggregate component, and a water absorbent
polymer composition.
Polymer concretes are well known from U.S.
patents 4,346,050; 4,371,639; 4,375,489 and the references
cited therein. The use of polymers in concrete is
further reviewed in "Chemical, Polymer and Fiber Addi-
tions for Low Maintenance Highways" by Hoff et al.Noyes Data Corp 1979 pages 467-511.
The use of the compositions of this invention
have been found to strengthen the compressive bond
strength of polymer concretes when used on wet or dry
substrates, such as, for example, Portland cement
concrete.
33,451-F -1-
~27~ 7
-2-
The invention concerns a curable pol~mer
concrete composition comprising
(A) 2 to 20, preferab.y 8 to 15 percent '~y
weight (pbw) of an un.satura-ted thermo-
settable compositlon containing 1 to 9g
percent by weight of one or more ethyl-
enically unsa-turated monomers and 1 to
99 weight percent of one or more ethyl-
enically unsaturated resins
(B) 75 to 97.9, preferably 83 to 91 pbw of
an aggregate comprising at least 50
percent by weight of a component
selected from the group consisting of
sand, gravel, crushed stone or rock,
silica flour, fly ash, or mixtures
thereof; and
(C) 0.1 to 5, preferably 1 to 2 pbw of a
water absorbent cross-linked polymer.
A further embodiment of the invention is a
20 - coating composition comprising
(A) 1 to 50, preferably 3 to 15 pbw of a
water absorbent cross-linked polymer and
(B) 50 to 99,.preferably 85 to 97 pbw of an
unsaturated thermos-table composition
con-taining 1 to 99 percent by weight
of one or more ethenically unsaturated
monomers and 1 to 99 weight percent
of one or more ethenically unsaturated
resins.
The invention provides unsa-turated thermoset-
table resin and/or ethylenically unsaturated monomer-
-aggregake-absorbent polymer compositions which when
c ~ 33,451-F -2-
--3--
cured with known catalyst systems give a polymer con-
crete with better compressive bonding strengths to both
wet and dry substrates such as concrete and the liXe.
The invention further provides unsaturated thermo-
settable res~n and/or ethylenically unsaturatedmonomer-absorbent polymer primer or coating com-
positions which give improved compressive bonding
stren,gths between cured polymer concretes and both wet
and dry substrates such as concrete and the li~e. As
an added benefit, certain of the cured polymer concrete
compositions of the present invention (containing a
water absorbent polymer composition) are more easily
demolded from a mold when compared to the corresponding
conventional cured polymer concrete (without a water
absorbent polymer composition).
The polymer concrete of the present invention
is especially suited for use in repair of spalled,
cracked or otherwise damaged concrete runways, highways,
oil-well platforms, parking structures, bridges and the
like especially where the concrete surface is damp or
wet. Under these conditions, the polymer concrete -
compositions of this invention provide enhanced
adhesion to said damp or wet concrete surface. These
compositions are not well sui-ted for underwater appli-
cations.
- The unsaturated thermose-ttable resins used in
this invention comprise
1. unsaturated polyester or polyesteram~ide
resins,
302. norbornyl modified unsaturated polyester
or polyesteramide resins,
3. hydrocarbon modified unsaturated poly-
ester or polyesteramide resins,
33,451-F -3-
~;~7~7
--4--
4. vinyl ester resins, or
5. mixtures of the foregoing resins.
These unsaturated resins are blended ~ith 1
to 99 percent by weight and preferably 30 to ~0 percent
by weigh-t, of one or more ethylenically unsaturated
monomers to make up the thermosetta~le~ resin compo-
sitions.
The unsaturated polyesters used in this
invention possess ~,~-unsa-turated carboxylic acid ester
groups ~lithin the polymer chains. Said unsaturated
polyesters are composed of the polymerizate of a polyol,
an ~,~-unsaturated polycarboxylic acid and, optionaily,
a saturated and/or aromatie polycarboxylie aeid.
Preparation of said unsaturated polyesters is taught by
Kirk-Othmer, Eneyclopedia of Chemical Technology, Vol.
18, pages 575-594 (1982). The unsaturated polyester-
amides used in this invention possess amide groups
within the polymer chains which are obtained by partial
replacement of the polyol by a polyamine or mixture of
polyamines.
The norbornyl modified unsaturated polyesters
or polyesteramides used in this invention have an ester
or esteramide chain, respectively, and have at least
one terminal norbornyl radical. The ester chain is
eomposed of ~he polymerizate of a polyol, an ~ unsat-
urated polycarboxylic acid and, optionally, a saturated
and/or aromatic polycarboxylic acid. The ester amide
ehain is eomposed of the polymerizate of a polyol, a
polyamine, an ~,~-unsaturated polyearboxylic acid and,
optionally, a saturated and/or aromatic polycarboxylic
33,451-F -4-
~2'~3~
~ 4633-3~4
acid. The norbornyl radical is derived from dicyclopentadiene,
dicyclopentadiene monoalcohol, polycyclopentadiene, dicyclo-
pentadiene concentrate, mixtures thereof and the like.
Preparation of said norbornyl modified unsaturated polyester3 and
polyesteramides is taught by United States 4,029,84~; 4,117,030;
4,167,542; 4,233,432; ~,2~6,367; ~,348,49g; 4,360,634; 4,409,371;
and 4,410,686.
Resin concrete compositions prepared using a dic~)~clo-
pentadiene modified unsaturated polyester resin are taught by
United 5tates Patent No. 4,228,251. Polymer concrete compositions
prepared using a norbornyl modified unsaturated polyesteramide
resin are taught by PCT Publication Number W085/01948 published
May 9, 1985.
Hydrocarbon modified unsaturated polyesters or poly-
esteramides prepared from resin oils used in this invention as
well as polymer concrete compo~itions thereof are prepared by
reacting resin oils with an ~,~-unsaturated carboxylic acid,
anhydride, or mixture thereof, and a polyol, or a polyol mixture
and, when used a diamine or a polyamine resin oils are complex
mixtures which contain dicyclopentadiene and/or indene as
component(s). The resin oils consists of three distinct types of
components: esterifiable hydrocarbon reactives including dicyclo-
pentadiene, methyl dicyclopentadiene, indene, methyl indene,
cyclopen~adiene codimer and diolefin dimers, ethylenically
unsaturated aromatic
--6--
hydrocarbon reactives including styrene, vinyl toluene
and allyl benzene, and nonreactive hydrocarbons includ-
ing aromatic, alkyl aromatic and polyalkylaromatic
hyd~ocarbons. The following examples illustrate pro-
cedures for the prepration of these hydrocarbon pol~mers.
~ Example A-l
Maleic anhydride ~306.97 g) was added to a
reactor and heated to 135C with stirring under a
nitrogen atmosphere. Water (62.04 g) was added and
immediately induced a maximum e~otherm of 143C with
the 135C temperature being reestablished within 5
minutes. Five minutes after the initial water addition,
a commercial grade resin oil designated as Resin Oil 80
~hereinafter~ -80) and produ ed by The Dow Chemical
15 Company, (115.12 g) was added to the reactor, the steam
condenser was started, and nitrogen sparging was
increased. A maximum exotherm of 142C occurred 1
minute after the initial RO-80 addition. Additional
RO-80 (115.12 g) was added 15 minutes after the initial
RO-80 addition, and 19 ml of water collected in the
Dean Stark trap was removed and recycled to the reactor.
A final portion of RO-80 (115.12 g) was added 15 minutes
later. The yellow-colored slurry was held for 30
minutes at 135C, after which time the temperature
controller was set at 160C. Thirteen minutes later,
155C was reached and a propylene glycol/dipropylene
glycol mixture (118.72 g/209.32 g) was added to the
reactor. The 160C temperature was achieved 12 minutes
later. After 2 hours at 160C, the temperature
controller was set at 205C, and this temperature was
achieved 32 minutes later. After 2.5 hours, a total of
91.5 ml of water layer and 100.5 ml of organic material
.
. 33,451-F -6-
- ~Z7~
--7--
were collected in the Dean Stark trap. The reactor was
cooled to 168C and 100 ppm of hydroguinone wer~ added.
The modified unsaturated polyester was recovered as a
transparent, light yellow-colored, tacky solid with a
final acid number of 27Ø
Based on this analysis, the esterified hydro- -
carbon reactives component (1) comprises 44.29 percent
~ by weight, the ethylenically unsaturated aromatic
hydrocarbon reactives component (2) comprises 23.80
percent by weight and the nonreactive hydrocarbons
component comprises the balance by difference.
Example A-2
Maleic anhydride (3.13 moles, 306.97 g) was
added to a reactor and heated to 135C under a nitrogen
atmosphere with stirring. Water (3.443 moles, 62.04 g)
was added and immediately induced a maximum exotherm of
143C with the 135C temperature being reestablished 2
minutes later. Five minutes after the initial water
addition, RO-80 (115.12 q) was added to the reactor.
The RO-80 used was the same as that used in Example A-8,
excep-t that partial polymerization of the ethylenically
unsaturated aromatic hydrocarbon reactives component of
the resin oil was completed prior to use of the resin
oil herein by addition of 0.23 percent by weight
azobisisobutyronitrile followed by reaction for 2 hours
at 70;C followed by addition of 0.12 percent by weight
benzoyl peroxide followed by reaction for 1 hour at
100C. A maximum exotherm of 141C occurred 1 minute
later. Air cooling of the reactor exterior reduced the
reactor temperature to 135C. A second portion of
R~-80 (115.12 g) was added 15 minutes after the initial
33,451-F -7-
~27~ 7
--8--
RO-80 addition. A final portion of RO-80 (115.~2 g~
was added 15 minutes later and the 135C reaction
temperature was reachieved 2 minutes later. After 30
minutes, a propylene glycol/dipropylene glycol mixture
(1.56 moles, 118.72 g/1.56 moles, 209.32 g) was added
to the reactor and the steam condenser was started.
Ni-trogen sparging was increased to 0.5 liter per minute,
an~ the temperature controller was set at 160C. The
160C temperature was reached 19 minutes later. After
2 hours at 160C, the temperature controller was set at
205C and this temperature was achieved 25 minutes
later. After 14.0 hours, a total of 103.5 ml of water
layer and 82 ml of organic material were collected in
the Dean Stark trap. The reactor was cooled to 165C
and 100 ppm of hydroquinone were added. The modified
unsaturated polyester was recovered as a transparent,
light yellow-colored solid with a final acid number of
11.5.
Example A-3
Maleic anhydride (3.13 moles, 306.97 g) was
added to a reactor and heated to 80C under a nitrogen
a-tmosphere with stirring. Water (3.443 moles, 62.04 g)
was added and immediately induced a maximum exotherm of
126C with a 120C temperature being established within
5 minutes. Fifteen minutes after the initial water
addition, indene (0.40 mole, 46.46 g) was added to the
reactor and th~ temperature controller was set at - -
135C. This temperature was achieved 12 minutes later.
The indene used was the same as that used in Examples
A-2, A-3, A-4 and A-5. Additional indene (0.40 mole,
46.46 g) was added 15 minutes after the initial indene
addition. A final portion of indene (0.40 mole,
33,451-F -8-
~2~637
46.46 g) was added 15 minutes later. The yellow
colored slurry was held for 30 minutes at 135C, af-;_er
which time propylene glycol (3.10 moles, 235.91 g, and
piperazine (0.312 mole, 26.88 g) were added to the
reactor. The steam condenser was started, nitrogen
sparging was increased to 2 liters per minute and the
tempera~ure controller was se-t at 160C The 160C
temperature was achieved 20 minutes later. After 2.0
hours at 160~C, the t@mperature controller was set at
205C and this temperature was achieved 11 minutes
later. After 4.0 hours, a total of 111.5 ml of water
layer and 8.5 ml of organic material were collected in
the Dean Stark trap. The reactor was cooled to 165C
and 100 ppm of hydroquinone were added. The polyester-
amide was recovered as a transparent, light amber-
-colored, solid with a final acid number of 29.2.
Example A-4
Maleic anhydride (5.00 moles, 490.3 g) was
added to a reactor and heated to 100C under a nitrogen
20 atmosphere with stirring. Water (5.50 moles, 99.11 g)
; was added and induced a maximum exotherm of 139C two
minutes later. Cooling reduced the reactor temperature
to 130C after an additional 5 minutes. Fifteen minutes
after the initial water addition, a commercial grade of
resin oil designated as Resin Oil 60 (hereinafter
RO-60) and produced by The Dow Chemical Company
(288.1 g) was added to the reactor. Capillary gas
chromatographic-mass spectroscopic analysis of the
RO 60 demonstrated the following composition: 64.36
weight percent esterifiable hydrocarbon reactives
composed of cyclopentadiene (2.95 percent), ~uta-
diene/cyclopentadiene codimers (3.96 percent),
33,451-F -9-
~ ~74~
--10--
dicyclopentadiene (45.81 percent), indene (4.37 per-
cent), isoprene/cyclopentadiene codimer (1.4~ percent~
and methylcyclopentadiene/cyclopentadiene codimer (5.78
percent); 16.14 weight percent ethylenically unsat-
urated aromatic hydrocarbon reactives composed pri-
marily of styrene and less than 1 percent vinyl
~ toluene; and 19.50 weight percent nonreactive
hydrocarbons composed of toluene (0.12 percent),
nàphthalene (0.30 percent) xylenes, ethylbenzenes,
trimethylbenzenes, methylethylbenzenes, and the like.
A maximum exotherm of 143C occurred 2 minutes later.
Cooling reduced the reactor temperature to 130C. A
second portion of Resin Oil 60 (288.1 g) was added 15
minutes after the initial RO-60 addition. A final
portion of RO-60 (288.1 g) was added 15 minutes later,
and the 130C reaction temperature was reachieved 3
minutes later. Thirty minutes after the addition of
the final portion of RO-60, propylene glycol (3.00
moles, 228.3 g) was added to the reactor, the steam
condenser was started, nitrogen sparging was increased
to 0.75 liter per minute and the temperature controller
was se~ at 160C. The 160C temperature was achieved
26 minutes later. After 2 hours at 160C, the temper-
ature controller was set at 205C and this temperature
was achieved 14 minutes later. After 10 hours, a total
of 115 ml of water layer and 174 ml of organic material
were collected into the Dean Stark trap. The reactor
was cooled to 165C and 100 ppm of hydroquinone were
added. The modified unsaturated polyester was
recovèred as a transparent, light yellow-colored solid
with a final acid number of 30.1. Mass balance calcu-
lations verified that essentially all of the hydrocar-
bon reactives and reactive ethylenically unsaturated
33,451-F -10-
~;~7~f~i37
--11--
aromatic hydrocarbons were incorporated into the poltI-
ester while in excess of 95 percent of the nonreactive
hydrocar~ons were recovered into the Dean Star~ trap.
ExamPle A-5
Maleic anhydride (5.00 moles, 490.3 g) was
- added to a reactor and heated to 100C under a nitrogen
atmosphere with stirring. Water (5.50 moles, 99.11 g)
wàs added and induced a maximum eY~otherm of 138C one
minute. later. Cooling reduced the reactor temperature
to 130C after an additional 3 minutes. Fifteen minutes
after the initial water addition, a commercial grade of
resin oil designated as RO-60 (288.1 g) was added to
the reactor. The composition of the RO-60 was iden-
tical to tha-t delineated in Example A-4. A maximum
exotherm of 143C occurred 2 minutes later. Cooling
reduced the reactor temperature to 130C. A second
portion of RO-60 (288.1 g) was added 15 minutes after
the initial RO-60 addition. A final portion of RO-60
(288.1 g) was added 15 minutes later and the 130C
reaction temperature was reachieved 3 minutes later.
Thirty minutes after the addition of the final portion
of RO-60, ethylene glycol (3.00 moles, 186.18 g) was
added to the reactor, the steam condenser was started,
nitrogen sparging was increased to 0.75 liter per
minute, and the temperature controller was set at
160C. The 160C temperature was achieved 28 minutes
later. After 2 hours at i600C, the temperature con-
troller was set at 205C and this temperature was
achieved 26 minutes later. After 8 hours, a total of
100 ml of water layer and 127 ml of organic material
were collected in the Dean Stark trap. The reactor was
cooled to 165C and 100 ppm of hydroquinone were added.
33,451-F -11-
3~
-12-
The modified unsaturated polyester was recovered as a
-transparent, light yellow-colored solid with a final
acid number of 31.7. Essen-tially all of the hydro-
carbon reactives and reactive ethylenically unsaturate.d
aromatic hydrocarbons were incorporated into the poly-
ester while the bulk of the nonreactive hydrocarbons
were recovered in the~Dean S-tark trap as determined by
mass balance calculations.
Example A-6
Maleic anhydride (2.22 moles, 217.91 g) was
added to a reactor and heated to~100C under a nitrogen
atmosphere with stirring. Water (2.44 moles, 44.05 g)
was added and induced a maximum exotherm of 136C two
minutes later. Cooling reduced the reactor temperature
to 130C after an additional 3 minutes. Fifteen minutes
after the initial water addition, a commercial grade of
resin oil designated as RO-60 (128.03 g) was added to
the reactor. The composition of the Resin Oil 60 was
identical to that delineated in Example A-4 except that
partial polymerization of the ethylenically unsaturated
aromatic hydrocarbon reactives component of the resin
oil was completed prior to the use of the resin oil
herein by addition of 0.10 percent by weight azobisiso-
butyronitrile followed by reaction for 19.5 hours at
60C. A maximum exotherm of 144C occurred 2 minutes
later. Cooling reduced the reactor temperature to
130C.: A second portion of RO-60 (128.03 g) was added
15 minutes after the initial RO-60 addition. A final
portion of RO-60 (128.03 g) was added 15 minutes later
and the 130C reaction temperature was reachieved 2 -
minutes iater. Thirty minutes after the addition of
the final portion of RO-60, propylene glycol (1.33
33,451-F -12-
-13-
moles, 101.47 g) was added to the reactor, the steam
condenser was started, nitrogen sparging was increased
to 0.50 liter per minute, and the temperature control-
ler was set at 160C. The 160C temperature was
5 achieved 17 minutes later. After 2 hours at 160C, the
temperature controller was set at 205C and this tem-
perature was achieved 15 minutes la-ter. After 5 hours
at the 205C reaction temperature, the reactor ~,7as
cooled to 165C and 100 ppm of hydroquinone were~ added.
The modified unsaturated polyester was recovered as a
transparent, light yellow-co].ored solid with a final
acid number of 38.9. Mass balance calculations ver-
ified that essentially all of the hydrocarbon reactives
and reactive ethylenically unsaturated aromatic hydro-
carbons were incorporated into the polyester while thebulk of the nonreactive hydrocarbons were recovered in
the Dean Stark trap.
Example A-7
Maleic anhydride (5.00 moles, 490.3 g) was
- 20 added to a reactor and heated to 100C under a nitrogen
atmosphere with stirring. Water (5.50 moles, 99.11 g)
was added and induced a maximum exotherm of 135C two
minutes later. Cooling reduced the reactor temperature
to 125C after an additional 5 minutes. Fifteen minutes
after the initial water addition, a commercial grade of
resin oil designated as RO-60 (326.57 g) was added to
the reactor. Capillary gas chromatographic-mass spectro-
scopic analysis of the RO-60 demonstrated the following
composition: 63.41 weight percen-t esterifiable hydro-
carbon reactives composed of cyclopentadiene (5.02 per-
cent), butadiene/cyclopentadiene codimers (3.74 percent),
dicyclopentadiene (50.51 percent), indene (3.25 percent),
33,451-F -13-
i3~
-14-
and methylcyclopentadiene/cyclopentadiene codimer (5.91
percent); 12.92 weight percent ethylenically unsaturated
aromatic hydrocarbon reactives composed of styrene
(11.48 percent) and vinyl toluene (1.44 percent); and
23.67 weight percent nonreac-tive hyarocarbons composed
of ethylbenzene (0.13 percent), xylenes (1.52 percent)
naphthalene (0.18 percent), trimethylbenzenes, di- ahd
triethylbenzenes, methylethylbenzenes, and the like.
A maximum exotherm o~ 139C occurred 3 minutes later.
Cooling reduced the reactor temperature to 125C. A
second portion of RO-60 (326.57 g) was added 15 minutes
after the initial RO-60 addition. A final portion of
RO-60 (326.57 g) was added 15 minutes later and the
125C reaction temperature was reachieved 4 minutes
later. Thirty minutes after the addition of the final
portion of RO-60, ethylene glycol (3.00 moles, 186.18 g)
was added to the reactor, the steam condenser was
started, nitrogen sparging was increased to 0.75 liter
per minute, and the tempera-ture controller was set at
160C. The 160C temperature was achieved 29 minutes
later. After 2 hours at 160C, the temperature controller
was set at 205C and this temperature was achieved 22
minutes later.~ After 10 hours, a total of 102 ml of
water layer and 145 ml of organic material were collected
in the Dean Stark trap. The reactor was cooled to
165C and 100 ppm of hydroquinone were added. The
modified unsaturated polyester was recovered as a
transparent, -light yellow-colored solid with a final
acid number of 25.1.
Example A-8
Maleic anhydride (5.00 moles, 490.3 g) was
added to a reactor and heated to 100C under a nitrogen
33,451-F -14-
~ 7~37
- 15 -
atmosphere with stirring. Water ( 5.50 moles, 99.11 g)
was added and induced a maximum exotherm of 135C two
minutes later. Cooling reduced the reactor temperature
to 125C after an additional 5 minutes. Fifteen minutes
5 after the initial water addition, a commercial grade of
resin oil designated as RO-60 (326.57 g~ was added to
the reactor. The composition of the RO-60 was identical
to that delineated in Example A-7. A maximum e~otherrn
of 139C occurred 3 minu~es later. Cooling reduced the
reactor temperature to 125C. A second portion of
RO-60 (326.57 g) was added 15 minutes after the initial
RO-60 addition. A final portion of RO~60 (326.57 g)
was added 15 minutes later and the 125C reaction
temperature was reachieved 4 minutes later. Thirty
15 minutes after the addition of the final portion of
RO-60, ethylene glycol ( 2.70 moles! 167.56 g) and
piperazine (0.30 mole, 25.84 g) were added to the
reactor, the steam condenser was started, nitrogen
sparging was increased to 0.75 liter per minute, and
20 the temperature controller was set at 160C. The 160C
temperature was achieved 22 minutes later. After 2
hours at 160C, the temperature controller was set at
205C and this temperature was achieved 26 minutes
later. After 10 hours, a total of 100 ml of water
25 layer and 169 ml of organic material were collected in
the Dean Stark trap. The reactor was cooled to 165C
and 100 ppm of hydroquinone was added. The modified
unsaturate-d polyesteramide was recovered as a transparent,
light yellow-colored solid with a final acid number of
18.5.
Blends of norbornyl modified unsaturated
polyesters and/or polyesteramides with vinyl ester
33,451-F -15-
3~
64693-3%4
resins used in this invention are taught by United States Patent
No. 4,753,982.
The blended resins can be prepared by the follo~tling
procedures.
Resin
Bisphenol A is catalytically reacted with a glycidyl
polyether of bi phenol A having an E~W of 186-192 (polyether A) at
150C under a nitrogen atmosphere for 1 hour to form a polyepoxide
having an EEW of 535. After cooling to 110C, additional
diglycldyl ether of bisphenol A (EEW = 186-192) is added with
methacrylic acid and hydroquinone and reacted to a carboxyl
content of about 2-2.5 percent. Then maleic anhydride is added to
and reacted with the vinyl ester resin. The final resin, diluted
with styrene, has a pH of 7.7 and contains approximately:
Contents
bisphenol A 7.7
diglycidyl ether of
bis A (EEW = 186-192) 36.7
methacrylic acid 9.15
maleic anhydride 1.45
styrene 45
100 . 00
Resin B
About 1 equivalent of methacrylic acid is reacted with
0.75 equivalent of an epoxy novolac having an epoxide equivalent
weight (EEW) of 175-182 and 0.25 equivalent of a glycidyl poly-
ether of bisphenol A having an EEW of 186-192. The above
reactants are heated to 115C with catalyst and hydroquinone
present
- 16 -
~Z~ '7
-17-
until the carboxylic acid content reaches a~out 1
percent. The reactants are cooled and then styrene
(containing 50 ppm of t-butyl catechol) is added. The
final resin diluted with styrene has a pH of 7.7 and
contains approxmately:
Contents
- styrene 36
methacrylic acid 20.6
epoxy novolac
10 (EEW = 175-182) 32.1
diglycidyl ether
of bis A
(EEW = 186-192) 11.3
100.00
Example B-l
(Part A)
Maleic anhydride (7.0 moles, 686.42 grams)
was added to a reactor and heated to 100C under a
nitrogen atmosphere. Water (7.10 moles, 127.94 grams)
was added. The reaction was cooled to 121C. 98
percen-t dicyclopentadiene (2.10 moles, 277.64 grams)
was added 15 minutes after the water is added. The
reactor was cooled to a 120C and a second aliquot of
98 percent dicyclopentadiene (2.10 moles, 277.64 grams)
was added. A final aliquot of 98 percent dicyclopenta-
diene (2.10 moles, 277.64 grams) was added. Later,
propylene glycol (3.78 moles, 287.66 grams) and piper
azin~ (0.420 mole, 36.18 grams) were added to the
reactor and the steam condenser was started, nitrogen
sparging was increased and the temperature controller
was set at 160C. Fifteen minutes separate each addition
of dicyclopentadiene. After 2 hours at 160C, the tem-
perature controller was set at 205C. After 14 hours,
100 milliliters o~ a water layer and 26 milliliters of
33,451-F -17-
-18-
organic material were collected. The reactor was cooled
to 168C and 100 ppm of hydroquinone were added. The
modified unsaturated polyesteramide alkyd was recovered
as a clear, light yellow colored solid with a final
acid number of 18.8.
(Part-B)
A portion o~ the modified unsaturated poly-
esteramide alkyd and Resin A which has a styrene compo-
nent and styrene are formulated as follows to provide
the indlcated weight percent of each component.
Modified
Polyesteramide
Alkyd Resin Aa Styrence
(grams/wt %) (grams /wt o/Ob) (grams/wt % )
15 164.5/47.0 50.9/8.0 134.6/45.0
136.5/39.0 101.8/16.0 111.7/45.0
108.5/31.0 152.7/24.0 88.8/45.0
Comparative Standards
192.5/55.0 none 157.5/45.0
20 none 192.5/55.0 157.5/45.0
a Total Resin A, less styrene.
b Active Resin A in formulation
c Total styrene in formulation.
- (P~rt C) -
Portions of the modified unsaturated polyester-
amide alkyd, Resin B, which has a styrene component,
and styrene are formulated as follows to provide the
indicated weight percent of each component:
33,451-F -18-
3~
--19--
Modified
Polyesteramide
Alkyd Resin A Styrene
(grams/wt %) _ (gramsa/wt o/b) (grams/~tl,_ %C)
189.0/54.0 - 54.7/10.0 106.3/36.9
154.0/4~.~ 109.4/20.0 g6.6/36.0
119.0~34.0 164.1/30.0 66.9/36.0
35.0/10.0 295.3/54.0 19.7/36.0
none - 350.0/64.0 none/36.0
Comparative Standards
224.0/64.0 none 126.0/36.0
none 224.0/64.0 126.0/36.0
Total Resin B, less styrene.
b Active Resin B in formulation
15 Total styrene in formulation.
Example B-2
(Part A)
Maleic anhydride (7.0 moles, 686.42 grams)
was added to a reactor and heated to 120C under a
nitrogen atmosphere. Water (7.10 moles, 127.94 grams)
was added. The reactor was cooled to 122C. Dicyclo-
pentadiene concentrate (278.70 grams) was added 15
minutes after the water was added. (The dicyclopenta-
diene concentrate contained 0.31 percent lights, 13.64
percent cyclopentadiene codimers and diolefin dimers,
and 86.05 percent dicyclopentadiene.) The reactor was
cooled to 120C. A second aliquot of dicyclopentadiene
concentrate (278.70 grams) was added. A final aliquot
of dyclopentadiene concentrate was added. Fifteen
minutes separate each addition of dicyclopentadiene.
.
33,451-F -19-
3~
-20-
Later, propylene glycol (3.78 moles, 278.66 grams~ and
piperazine (0.420 mole, 36.18 grams) were added to the
reactor and the steam condenser was started, nitrogen
sparying was increased and the temperature controller
was set at 160C. Af-ter 2 hours at 160C, the tempera-
ture con-troller was set at 205C. After 8.5 hours, 156
milliliters of water layer and 62.5 milliliters of
organic material were collected. The reactor was cooled
to 168C and i00 ppm of hydroquinone were added. The
modified unsaturated polyesteramide alkyd was recovered
as a clear, light yellow colored solid with a final acid
number of 28.4.
A portion of the modified unsaturated poly-
esteramide alkyd was used to prepare a 30.0 percent
sytrene-70.0 percent alkyd solution. Then 250 grams of
this solution and 250 grams of Resin B, with styrene,
were mixed to provide a solution.
Example B-3
(Part A)
Maleic anhydride (8.0 moles, 784.48 grams)
was added to a reactor and heated to 70C under a nitro-
gen atmosphere. Water (4.2 moles, 75.68 grams) was
added, followed 2 minutes later by dicyclopentadiene
concentrate (1-59.15 grams). The dicyclopentadiene
concentrate was the same as that used in Example 2.
Addi-tional dicyclopentadiene concentrate (159.15 grams)
and water (25.23 grams) were later added to the reactor.
A third aliquot of dicyclopentadiene concentrate (159.15
grams) was added. Later, a final aliquot of dicyclopenta-
diene concentrate (159.15 grams) was added and the
temperature controller was set at 110C. Fifteen minutes
33,451-F -20-
~'~7f~ 7
-21-
separated each addition of dicyclopentadiene. Later,
propylene glycol (474.86 grams) was added to the reactsr
and the steam condenser was started, nitrogen sparging
was increased and the temperature controller ~,7as set at
- 5 160C. After 2 hours at 160C, the temperature controller
was set at 205C. 188.5 Milliliters of water layer and
21.0 mi~lliliters of organic material were collected.
The reactor was cooled to 165C and 100 ppm of hydro-
~uinone were added. The modified unsaturated polyester
alkyd was recovered as a clear, liyht yello~ solid with
a final acid number of 30.3.
Example B-4
(Part A)
A dicyclopentadiene modified unsaturated ~oly-
esteramide alkyd was prepared using the method of
Example B-l.
(Part B)
A portion of the modified unsaturated poly-
esteramide alkyd, Resin B (which has a styrene compo-
nent), and styrene are formulated as follows to providethe indicated weight percent of each component:
Modified
Polyesteramide
Alkyd Resin A b Styrene c
25 (grams/wt %) (gramsa/wt % ) (grams/wt % )
325.0/50.0 101.56/10.0 223.44/40.0
260.0/40.0 203.13/20.0 186.87/40.0
Comparative Standards
370.5/57.0 - none 279.5/43.0
33,451-F -21
37
-22-
a Total Resin B, less styrene.
Active Resin B
c in formulation
Total styrene in formulation.
Vinyl ester resins (VER) are the reaction
product of about e~uivalent amounts of a monounsat-
urated monocarboxylic acid an-d a polyepoxide-. One
class of VER is described in U.S. Patent No. 3,367,992
where dicarboxylic acid half esters of hydroxyalkyl
acrylates or methacrylates are reacted with polyepoxide
resins. Bowen in U.S. Patent Nos. 3,066,112 and
3,179,623 describes the preparation of VER from mono-
carboxylic acids such as acr~lic and methacrylic acid.
Bowen also describes alternate methods of preparation
wherein a glycidyl methacrylate or acrylate is reacted
with the sodium salt of a dih~dric phenol such as
bisphenol A. VER based on epoxy novolac resins are
described in U.S. Patent No. 3,301,743 to Fekete et
al. Fekete et al. described VER where the molecular
weight of the polyepoxide is increased by reacting a
dicarboxylic acid with the polyepoxide resin as well as
acrylic acid, et in U.S. Patent No. 3,256,226. Other
difunctional compounds containing a group which is
reactive with an epoxide group, such as an amine,
mercaptan and the like, may be utilized in place of the
dicarboxylic acid. All of the above-described resins; -~
which contain the characteristic linkages
-C-OCH2CHCH2O-
. . OH
33,451-F -22-
-23-
and terminal polymerizable vinylidene groups are clas-
sified as VER.
Briefly, any of the known polyepoxides may be
employed in the preparation of the vinyl ester resins
of this invention. Useful polyepoxides are glycidyl
polyethers of both polyhydric alcohols and polyhydric
phenols, such as the diglycidyl ether of bisphenol A;
- `epox~ novolacs; epoxidized fatty acids or drying oil
aci~s; epoxidized diolefins, epoxidized di-unsaturated
acid esters as well as epoxidized unsaturated polyester,
so long as they contain more than one oxirane group per
molecule. The polyepoxides may be monomeric or poly-
meric.
Preferred polyepoxides are glycidyl poly-
ethers of polyhydric alcohols or polyhydric phenolshaving weights per epoxide group of 150 to 2000. The
polyepoxides may be nuclearly substituted with halogen,
preferably bromine. These polyepoxides are usually
made by reacting at least about two moles of any
epihalohydrin or glycerol dihalohy~rin with one mole of
the polyhydric alcohol or polyhydric phenol and a
sufficient amount of a caustic alkali to combine with
the halogen of the halohydrin. The products are char-
acterized by the presence of more than one epoxide
group per molecule, i.e., a 1,2-epoxy e~livalency
greater than one.
Ethylenically unsaturated monomers suitable
for blending with the thermosettable resin compositions
include both the alkenyl aromatic monomers such as
styrene, vinyl toluene, t-butylstyrene, chlorostyrene,
33,451-F -23-
-24-
~-methylstyrene, divinylbenzene and mixtures thereof
and the alkyl and hydroxyalkyl esters of acrylic acid
and methacrylic acid such as methyl methacrylate,
ethylacrylate, propylacrylate, sec-butylacrylate,
n-butylacrylate, cyclohexylacrylate, dicyclopentadienyl
acrylate, hydroxyethyl acrylate, hydroxypropylmethacry-
late, trimethylolpropane triacrylate, trimethylol-
propane trimethacrylate, pentaerythritol trimethacrylate,
~ and mixtures thereof. Most any vinyl monomer ma~i be
employed which is copolymerizable with the unsaturated
groups of the thermosettable resin composition.
An ethylenically unsaturated monomer or
mixture of said monomers as described above may also be
used alone to prepare the compositions of the present
invention.
Polymer concrete is a composition made by
blending of a curable component lunsaturated thermo-
settable resins and/or ethylenically unsaturated monomer
blend) and an aggregate component. The polymer concrete
composition of the present invention is prepared by
blending from 2 percen-t to 20 percent by weight of a
thermosettable resin and/or ethylenically unsaturated
monomer composition with from 75 percent to 97.9 percent
by weight of an aggregate component and from 0.1 to 5
percent by weight of a wa-ter absorbent cross-linked
polymer. The components may be blended toget~er in any
order, however, it is preferred to preblend the aggre-
gate component and the water absorbent cross-linked
polymer composition prior to addition of the unsat--
urated thermosettable resin and/or ethylenicallyunsatura-ted monomer composition.
33,451-F -24-
-25-
The aggregate component is typically sand,
gravel, crushed stone or rock, silica flour, fly ash,
and the like or mixtures thereof. Up to 50 percent by
weight of metal fines, glass fibers, synthetic fibers,
glass reinforcing mats, metal turnings, me-tal fibers,
hydrated alumina, ceramic beads or mixtures thereof may
be present in the aggregate composition. The exact
componen-ts used in the aggregate composition are
generally dictated by the physical properties required
of the cured polymer concrete composition. Thus,
optimal aggregate particle size distribution and
physical configuration can be determined by simple
preliminary experiments.
Moisture absorbent cross-linked polymers
suitable for use herein are set forth in U.S. patents
2,988,539; 3,247,171; 3,357,067; 3,393,168; 3,514,419;
3,926,891; 3,954,721; 3,980,663; 3,993,616; 3,997,484;
and 4,076,673.
- The unsaturated thermosettable resin and/or
ethylenically unsaturated monomer-absorbent cross-
linked polymer mixtures are curable by known catalyst
systems. Peroxides, such as methyl ethyl ketone
peroxides, can be used with or without known promoters,
such as cobalt octoate or cobalt naphthenate, that
function with such peroxides. Acyl peroxides, such as
- benzoyl peroxides can be used with or without promoters
such as tertiary amines, including typically dimethyl
aniline and N,N-dimethyl-p-toluidine. The concentra-
tions of catalyst and promoter are adjusted within
known limits of from 0.1 to 3.0 weight percent depen-
ding on the rate of cure desired, the magnitude of the
33,451-F -25-
7~
~26-
generated exotherm and for other known purposes.
Suitable gelation retarding agents, such as
p-benzoquinone, can be employed in the curing system.
The coating composition of the present inven-
tion is prepared by mixing from 1 percent to 50 percent
by weight of a water absorbent cross linked polyme~
with from 99 percent to 50 percent by weight of an
unsaturated-thermosettable resin and/or ethylenically
unsaturated monomer compositon. Said coating compo-
sition is typically applied to the concrete (or other)surface directly prior to application of a polymer
concrete or a polymer concrete additionally containing
a water absorbent polymer composition. The coating
composition may be left uncured prior to application of
a polymer concrete or it may be partially or totally
cured prior to said application using the aforemen-
tioned known catalyst systems. Depending on the type
of water absorbent polymer composition used, its par-
ticle size distribution, the amount used and other
known variables, the coating composition can be
adjusted in consistency to become a suspension, a
paste, a thin free-flowing liquid and the like. The
coating composition of the present invention provides
enhanced adhesion to concrete surfaces, especially
where the surface is damp or wet. The coating com-
position is not well suited for underwater applica-
tions. -
Preparation 1: Dicyclopentadiene Modified Unsaturated
Polyesteramide (Resin A)
A dicyclopentadiene modified unsaturated
polyesteramide resin was prepared in a 100 gallon
33,451-F -2~-
1~7~6~
-27-
(0.379 m3), 316 stainless steel reactor. The reactor
was eguipped with mechanical stirring, flow meter
controlled inlet lines
and associated valving for nitrogen, water, dicyclopen-
tadiene (96 percent), propylene glycol-pipera~ine
solution and styrene. The respective liquid reactants
were metered into the reactor from indi~idual drums
using calibrated drum pumps. A scale was used to
~ monitor the weight loss from each drum during pumping.
Heating and cooling were provided to the reastor jacket
via a recirculating pump for the heat transfer fluid.
Heat was provided to the heat transfer fluid reservoir
via a pair of thermostated in-line electric heaters.
Finned cooling coils with a water curtain provided for
rapid cooling when activated. The reactor overhead
section was fitted with a manway for charging solid
maleic anhydride briquettes or hydroquinone and a
steam-jacketed condensor. A chilled, water condensor
and knock-out pot fitted with a drain valve were used
to recover condensate from the steam-jacketed condensor.
Product was recovered from the reactor through a ram
valve into a 10 micron filter assembly and to a valved
drumming outlet.
The following reaction stoichiometry was
used:
maleic anhydride183.7 pounds (82.7 kg)
water 18.5 pounds (8.3 kg)
dicyclopentadiene (96%) 223.1 pounds (100.4 kg)
11.17% wt. piperazine in
propylene glycol solution86.8 pounds (39 kg)
.hydroquinone - addition 15.6 grams
- addition 258.9 grams
styrene 372.4 pounds(167. ko)
33,451-F -27-
~ ~7~ 7
-28-
The following reaction sequence was used:
Reaction Step Cumulatlve Reaction Time
.
Water addition started into
70C s-tirred solution of
maleic anhydride and hydro-
quinone (addition 1) under
0.2 Std. Cubic E't/Hour(scfh) 0 minutes
(1.57m3/s) scfh (7.87 m3/s)
nitrogen
10 Dicyclopentadiene addition
started 2 minutes
Water and dicylopentadiene
additions completed 1 hour 45 minutes
: Hydrolysis reaction
15 completed 4 hours 40 minutes
(% Zicyclopentadiene/acid
number = 1.9%/273)
Piperazine-propylene glycol
solution added temperature
20 controller set at 160C,
nitrogen s~arge set to 2 scfh 4 hours 45 minutes
(1.57 x 10 5)
Reaction at 160C completed 8 hours 35 minutes
(acid number = 139)
25 Temperature set at 205C 8 hours 45 minutes
Nitrogen sparge set at 1.4
scfm (6.6 x 10 4 m3/s) 17 hours 35 minutes
Reaction at 205C completed
and cooling started 22 hours 35 minutes
(acid number = 27.5)
Hydroquinone (addition 2),
- 2% 2 in N2 started 24 hours 5 minutes
Styrene added at 110C 25 hours 5 minutes
Styrenated resin drummedl 26 hours
1 Contained 43 percent by weight styrene
33,451-F -28-
-29-
Preparation 2: Dicyclopentadiene Modified Unsaturated
Polyesteramide with Flexibilizing
Glycol Ether Component (Resin B)
A dicyclopentadiene modified unsaturated
polyesteramide was prepare~ in a 100 gallon (0.379 m~,
316 stainless steel reactor. The reactor was equipped
r with mechanical stirring, flow meter contro~led inlet
lines and associated val~ing for nitrogen, dicyclopen-
. tadiene concentrate, propylene glycol-piperazine~
10 -polypropo~ylate of-glycerin solution, and styrene. The
dicyclopentadiene concentrate contained 99.23 ester-
ifiable hydrocarbon reactives including 81.4 percent by
weight (pbw) dicyclopentadiene 11.86 pbw isoprene
-cyclopentadiene codimer, 0.16 pbw tricyclopentadiene,
15 and 0.59 pbw methylcyclopentadiene-cyclopentadiene
codimer. The respective liquid reactants were metered
into the reactor from individual drums using calibrated
drum pumps. A scale was used to monitor the weight
loss from each drum during pumping. Heating and
20 cooling were provided to the reactor jacket via a
recirculating pump for the heat transfer fluid. Heat
was provided to the heat transfer fluid reservoir via a
pair of thermostated in line electric heaters. Finned
cooling coils with a water curtain provided for rapid
25 cooling when activated. The reactor overhead section
was fitted with a manway for charging solid maleic
anhydride briquet-tes or hydroquinone and a steam-
-jacketed condensor. A chilled water condensor and
knock-out pot fitted with a drain valve were used to
30 recover condensate from the steam-jacke-ted condensor.
Product was recovered from the reactor through a ram
valve into a 10 micron filter-assembly and to a valved
drumming outlet.
33,451-F -29-
`` ~27f~6~7
-30-
The following reaction stoichiometry ~,7as
used:
maleic anhydride 144.2 pounds (64.9 kg)
water 29.1 pounds (13.1 kg)
5 dicyclopentadiene concen- 175.5 pounds (79 kg)
trate
72.64% wt. polypropoxylate - -
of glycerin, and 4.34% wt.
piperazine in prop-~lene
glycol solution175.1 pounds(78.8 kg)
hydroquinone - addi~ion 1 5.6 grams
- addition 2 58.9 grams
styrene 372.4 pounds (167.6 kg)
The following reaction sequence was used:
Reaction Step Cumulative Reaction Time
Water addition started into
70C stirred solution of
maleic anhydride and hydro~
quinone (addition 1) under
20 0.38 scfh 0 minutes
(3 x 10 6 m3/s) nitrogen
Dicyclopentadiene concen-
trate addition started 2 minutes
Water and dicyclopentadiene . . .
25 concentrat~ additions com-
pleted 2 hours
Hydrolysis reaction
completed 4 hours 45 minutes
(acid number = 259)
33,451-F -30-
~7~
-31-
,
Piperazine-propYlene glycol-
glycerin polypropoxylate solu-
tion added, temper~ture con-
troller set at 160C, nitrogen
sparge set_to 2 scfh 5 hours
(1.57 ~10 5 m3/s)
Reaction at 160C completed
and temperature set at 205C 7 hours 45 minutes
Nitrogen sparge set at 2.8
10 scfm 15 hours 45 minutes
Reaction at 205C completed
and cooling started 19 hours 45 minutes
(acid number = 27)
Hydroquinone (addition 2~,
2% 2 in N2 started 20 hours 40 minutes
Styrene added at 110C 22 hours 40 minutes
Styrenated resin drummed1 25 hours 10 minutes
1Contained 43 percent by weight styrene
Preparation 3: Resin Oil Modified Unsaturated Polyester-
amide (Resin C~ Prepared by the Prehy-
drolysis Method
A resin oil modified unsaturated polyesteramide
resin was prepared in a 100 gallon (0.379 m3) 316 stain-
less steel reactor. The reactor was equipped with
mechanical stirring, flow meter controlled inlet lines
and associated valving for nitrogen, water, resin oil,
ethylene glycol-piperazine solution and styrene. The
resin oil used contained 63.06 percent by weight (pbw)
esterifiable hydrocarbon reactives consisting of
isoprene-cyclopentadiene codimer (1.65 pbw), indene
(4.03 pbw), methyl cyclopentadiene-cyclopentadiene
codimer (6.17 pbw), butadiene-cyclopentadiene codimer
(5.32 pbw) and dicyclopentadiene (45.89 pbw); ethyl-
enically unsaturated aromatic hydrocarbon reactives
33,451-F -31-
-32-
consisting of styrene and vinyl toluenes (15.95 pbw~;
cyclopentadiene (1.56 pb~1); and non-reactive hydro-
carbons (19.42 pbw). The respective liguid reactants
were metered into the reactor from individual drums
using calibrated drum pumps. A scale was used to
monitor the weight loss from each drum during purnping.
Heating and cooling were provided to the reactor jacket
via a recirculating pump for the heat transfer fluid.
Heat was provided to the heat transfér fluid reservoir
via a pair of thermostated in-line electric heaters.
Finned cooling coils with a water curtain provided for
rapid cooling when ac-tivated. The reactor overhead
section was fitted with a manway for charging solid
maleic anhydride briquettes or hydroquinone and a
steam-jacketed condensor. A chilled water condensor
and knock-out pot fitted with a drain valve were used
to recover condensate from the steam-jacketed con-
densor. Product was recovered from the reactor through
a ram valve into a 10 micron filter assembly and to a
valved drumming outlet.
The following reaction stoichiometry and
sequence were used:
Reaction Step Cumulative Reaction Time
Water addition (31 pounds
at 1.9 gph) started into
100C stirr2d solution of
maleic anhydride (169 lbs.)
- under 0.357 sch (2.9 xlO 6 m3/s~
nitrogen 0 minutes
First 31 pounds of (13.9 kg) water in,
start bulk addition of second
31 pounds (13.9 g kg) of water 1 hour 45 minutes
33,451-F ~32-
~Z7~ 7
-33-
All water added, reaction
temperature between 90-110C,
start recycling water and
hydrocarbon dlstillate back
5 into reactor 1 hour 50 minu~es
Start resin oil addition
(320.1 pounds at 0.66 gpm) 2 hours
(144 kg at 4.2 x 10 5 m3/s)
Resin oil addition completed.
10 temperature controller set at
135C 2 hours~55 minutes
Hydrolysis reaction completed,
recycle of water and hydrocar-
bon distillate into reactor
15 stopped 4 hours 55 minutes
~acid number = 218~
Piperazine-ethylene glycol
: solution (66.7 pounds) (30.0 kg~
added, temperature controller set
20 at 160C, nitrogen sparge set to
7.5 scfh (5.9 x 10 5 m3/s),
2,5-di-tert-butylhydroguinone-
(12.6 grams) 5 hours 50 minutes
added as process inhi~itor
25 Reaction at 160C completed,
temperature controller set at
205C 7 hours 50 minutes
(acid number = 120)
205C reached 10 hours
30 Nitrogen sparge set at 2.75
scfm (1.29 x 10 3 m3/s) 11 hours 40 minutes
Reaction at 205C completed,
cooling started, turn nitrogen
:- sparge down to 0.375 scfh 15 h~urs 30 minutes
(2.95 x 10 ~ m3/s)
Hydroquinone (58.9 grams)
added at 150C 16 hours 40 minutes
(acid number = 27)
2% 2 in N2 started at 125C 17 hours 15 minutes
33,451-F -33-
'~3 7
-34-
Styrene (372.4 pounds) (167.4 kg)
added at 110C 18 hours
Styrenated resin drummedl 19 hours 30 minutes
lContained 43 percent by weight styrene
Preparation 4: P~esin Oil Modified Unsaturated Polyester-
amide (Resin D) Prepared by the Staged
Hydrolysis Method
A resin oil modified unsaturated polyesteramide
resin was prepared using the equipment described in
Preparation 3. The resin oil used contained 57.85
percent by weight (pbw) esterifiable hydrocarbon reactives
consisting of isoprene-cyclopentadiene codimer (2.93
pbw), indene (2.58 pbw), methylcyclopentadiene-cyclopenta-
diene codimer (4.42 pbw), butadiene-cyclopentadiene
codimer (4.0 pbw) and dicyclopentadiene (43.92 pbw);
ethylenically unsaturated aromatic hydrocarbon reactives
(16.57 pbw) consisting of styrene (15.67 pbw) and vinyl
toluenes (0.90 pbw); cyclopentadiene (6.82 pbw); and
. non-reactive hydrocarbons (18.76 pbw).
The following reaction stoichiometry and
sequence were used:
Reaction Step Cumulative Reaction Time
- . Water addition (32.4 pounds
at 1.9 gph) (14.9 kg at 1.3 x 10 3 m3/s )
25 started into 70C stirred solution
of maleic anhydride (160.2 pounds)
(72.1 kg) under 0.20 scfh
(1.57 x 10-6 m3/s) nitrogen O minutes
Start resin oil addition
(332.2 pounds at 0.35 ~pm) 2 minutes
(149:5 kg at 2.21 x 10 5 m3/s )
33,451-F -34-
~Z74~ ~
., .
-35-
Resin oil and water additions
completed, temperature con-
troller set at 120C 1 hour 45 minutes
Hydrolysis reaction completed,
temperature at 118C 3 hours 10 minutes
(acid number=247.5)
Piperazine-ethylene glycol
^ solution (63.14 pounds) (28.4 kg)
added, temperature controller set
at 160C, nitrogen sparge set to
5.3 scfh (4:17 x ld 5 m3/s) 3 hours 3~ minutes
Reaction at 160C completed,
temperature controller set
at 205C 6 hours 30 minutes
(acid nu~ber = 121)
205C reached 8 hours 50 minutes
Nitrogen sp~rge set at
1.4 scfh (l.1 x 10 5 m3/s) 11 hours 30 minutes
(acid number = 41)
Reaction a-t 205C completed,
cooling started, turn nitro-
gen sparge down to 0.375
scfh (2.9 x 10 5 m3/s)
(acid number = 38) 13 hours
Hydro~uinone (58.9 grams)
added at 145;C, 2% 2 in
N2 started - 14 hours 30 minutes
Styrene (372.4 pounds)
(167.6 kg) added a-t 116C 20 hours 15 minutes
The styrenated resin was drummed after all
product was observed to be in solution. The resin
contained 43 percent by weight styrene.
Preparation 5: Methyl methacryla-te (Monomer Blend E)
Monomer grade methyl methacrylate (203.3
grams) and trimethylolpropane trimethacrylate (10.70
grams) were mixed together to give a 95/5 percent by
wei-ght blend. --
33,451-F -35-
-36-
Preparation 6: Absorbent Polymer A
A copolymer containing 52.0 rnole percent
ethyl acrylate, 28.0 mole percent sodium methac~ylate
and 20.0 mole percent sodium acrylate as 3 25% solution
in water is crosslinked using Polycup 172~(Hercules~
1.~, ,..~,
then dried and cured to provide Absorbent Pol~ner A.
' The polymer was ground to a powder which passed through
a 48 mesh standard sieve. The powder was dried at
110C for 60 minutes before using in a polymer concrete
formulation,
Preparation 7: Absorbent Polymer B
The sodium salt of a crosslinked copolymer of
acylamide and acrylic acid was prepared in the manner
set forth in U.S. 3,247,171. The copolymer contained
30 mole percent of sodium acrylate, 70 mole percent
acylamide, and 500 ppm of methylene bis(acrylamide).
The copolymer was ground to a powder which passed
through a 48 mesh standard sieve. The powder was
dried at 110C for 60 minutes before using in a polymer
concrete formation.
EXAMPLE 1
A. Dry Compressive Bond Strength of Polymer Concrete
Containing Resin A and Absorbent Polymer A
A pair of compressive strength test pieces
were prepared using a modification of standard method
ASTM C882 wherein the polymer concrete formulation was
poured onto a concrete cylinder with a sandblasted 30
degree (from the horizon) angle face. Each concrete
cylinder was contained in a plastic cylinderical mold.
~k tra~ ~
33,451-F -36-
&~
-37-
A 185.7 gram portion of Resin A ~,7as catalyzed
using 0.30 percent by weight (pbw) N,M-dimethylaniline
and 1.00 pbw benzoyl peroxide. Then 1300 grams of a
49.4/25.3/25.3 pb~l mixture of rock/number 3 blasting
'5 sand/number 4 blasting sand and 13.0 grams of Absorb~nt
Polymer A were thoroughly mixed and then stirred into
the resin solution. The rock used herein ranged in
size from 5/8 to 1/4 inch (1.59 cm to 0.63 cm). The
resulting polymer concrete was split into two equi- ~
valent aliquots which were used to prepare duplicate
compressive strength test pieces.
A tamping rod and vibrator were used to pack
the cylindrical molds containing the concrete cylinder
with a 30 degree face with the polymer concrete and
assist in removal of bubbles before gelation. After
post curing for five days at room temperature (25C),
the 3-inch (7.62) diameter by 6-inch (15.24 cm) cylin-
drical ccmpressive strength test pieces were demolded
and tested by loading along their longitudinal axes at
a loading rate of 20,000 psi (137895 kPa) per minute
until failure occurred. The ultimate load was divided
by the circular cross-sectional area to determine the
compressive bond strength of each sample. The average
of the duplicate compressive bond strength values is
given in Table I.
B. Wet Compressive Bond Strength of Polymer Concrete
Containing Resin A and Absorbent Polymer A
The method of Example 1-A was repeated except
that each concrete cylinder contained in a plastic
cylindrical mold was immersed under water for three
hours. The water was then poured off each cylinder
five minutes prior to adding the polymer concrete. The
33,451-F -37-
-38-
average of the duplicate compressive bond strength
values is given in Table I.
CONTROL l
A. Dry Compressive Bond Strenqth of Polymer Concrete
Containin~_~esin A
The method of Example l~A was repeated except
that no absorbent polymer was used in the polymer
concrete. The average of the duplicate compressive
bond strength values is given in Table I.
B. Wet Compressive Bond Strength of Polymer Concrete
Contalnlnq Res1n A
The method of Example 1-B was repeated except
- that no absorbent polymer was used in the polymer
~ concrete. The average of the duplicate compressive
bond strength values is given in Table I.
TABLE I
Compressive Bond Strength
(psi)
- Example l~A4351 (29999 kPa)
Example l-B3566 ~24587 kPa)
Control 1-A3522 (24283 kPa)
Control 1-B2214 (15265 kPa)
The polymer concrete of Resin A containing
Absorbent Polymer A (Example 1-A) exhibited the highest
compressive bond stre~gth of the series. The polymer
; concretes of Resin A containing Absorbent Polymer A
exhibited significantly higher dry and wet compressive
bond strengths versus the polymer concretes of Resin A
alone (Examples l-A and 1-B versus Controls 1-A and
1-B).
.
33,451-F -38-
-39-
EXAMPLE 2
A. ~et Compressive Bond Strength of Pol-~ner Concrete
Containin~ Resin B and Using a Resin ~-~sorbent
Polymer A Primer
A pair of compressive strenyth test pieces
were prepared using a modification of standard method
ASTM C88G ~7herein the polymer concrete formulation was
poured onto a concrete cyli~der with a sandblasted 30
degree angle face. Each concrete cylinder contained in
a plastic cylindrical mold was immersed under water for
three hours. The water was then poured off each cylinder.
A primer consisting of 1.25 grams of Absorbent
Polymer A suspended in 25.0 grams of Resin B was painted
onto the wet face of each concrete cylinder. A 185.7
gram portion of Resin B was catalyzed using 0.30 pbw
N,N-dimethylaniline and 1.00 pbw benzoyl peroxide.
Then 1300 grams of a 49.4/25.3/25.3 pbw mixture of
rock/number 3 blasting sand/number 4 blasting sand were
stirred into the resin solution. The rock used herein
ranged in size from 5/8 to 1/4 inch (1.59 cm to 0.63
cm). The resulting polymer concrete was split into two
e~uivalent aliquots which were used to prepare dupli-
cate compressive strength test pieces five minutes
after applying -the aforementioned primer and using the
method of Example l-A. The 3-inch (7.62 cm) diameter
by 6-inch (15.24 cm) cylindrical compressive strength
test pieces were tested using the method of Example
l-A. The average of-the duplica-te ~ompre-s~ive bond
strength values is given in Table II.
33,451-F -39-
-40-
CONTROL 2
A. Wet Compressive Bond Streng-th of Pol~mer Concrete
Containing Resin B and Using a Resin B Primer
The method of Example 2-A was repeated,
excep-t that a primer consisting of 25.0 grams of Res-n
B and no absorbent polymer was used on the wet face of
each concrete cylinder. The average of the duplicate
compressive ~ond strength values is given in Table II.
B. Wet Compressive Bond Stren~th of Polymer Concrete
~ Containing Resin B
The method of Example 2-A was repeated,
except that no primer was used on the wet face of each
concrete cylinder. The average of the duplicate compres-
sive bond strength values is given in Table II.
.
C. Dry Compressive Bond Strength of Po~ymer Concrete
Containing Resin B
The method of Example 2-A was repeated except
that each concrete cylinder contained in a plastic
cylindrical mold was not immersed under water but was
used dry and no primer was used on the dry face of each
concrete cylinder. The average of the duplicate compres-
sive bond strength values is given in Table II.
TABLE II
Compressive Bond Strength
(psi)
Example 2-A 4274 (29468 kPaj
Control 2-A 3666 (25276 kPa)
Control 2-B 2888 (19912 kPa)
Control 2-C 4422 (30489 kPa)
33,451-F -40-
~ z~ 7
-41-
The polymer concrete of Resin B using a P~esin
~-Absorbent Polymer A primer (Example 2A) exhi~ited
significantly increased compressive bonding st~-ength to
the wet concrete surface when compared to the polymer
concrete of Resin B using-a Resin B primer (Control
2-A) or the polymer concrete of Resin B without any
primer (Comparative Experiment 2-B). The polymer
concrete of Resin B using a Resin B-Absorbent Pol~,~mer A
~ primer (Example 2-A) provided a compressive bonding
strength on wet concrete approaching that of the
polymer concrete of Resin B on dry concrete (Control
2-C).
EXA~PLE 3
A. Wet Compressive Bond Strength of Polymer Concrete
Containing Resin C and Absorbent PolYmer A
A pair of compressive strength test pieces
- were prepared using a modification of standard method
ASTM C882 wherein the polymer concrete formulation was
poured onto a concrete cylinder with a sandblasted 30
degree angle face. Each concrete cylinder contained in
a plastic cylindrical mold was immersed under water for
twenty-four hours. The water was then poured off each
cylinder two minutes prior to adding the polymer con-
crete.
A 185.7 gram portion of Resin C was catalyzed
using ~.30 percent by weight (pbw) N,N-dimethylaniline
and 1.00 pbw benzoyl peroxide. Then 1300 grams of a
49.4/25.3/25.3 pbw mixture of rock/number 3 blasting
sand/number 4 blasting sand and 13.0 grams of Absorbent
Polymer A were thoroughly mixed and then stirred into
the resin solution. The rock used herein ranged from
5/8 to 1/4 inch (1.59 cm to 0.63 cm). The resulting
33,451-F -41-
37
-42-
polymer concrete was split into two equivalent aliquot~
which were used to prepare duplicate compressive strength
test pieces. A tamping rod and vibratoL- ~7ere used to
pack the cylindrical molds with the polymer concrete
and assist in rernoval of bubbles before gelation.
After post curing for two hours at 75C, the 3-inch
(7.52 cm) diameter by 6-inch (15.24 cm) c~linderic~l -
compressive strength test pieces were demolded and
tested using the method of Example 1-A. The average of
the duplicate compressive bond strength values is given
in Table III.
B. Wet Compressive Bond Strength of Polymer Concrete
Containing Resin C and Absorbent Pol~er B
The method of Example 3-A was repeated except
that 13.0 grams of Absorbent Polymer B was substituted
for Absorbent Polymer A. The average of the duplicate
compressive bond strength values is given in Table III.
CONTROL 3
A. Dry Compressive Bond Strength of Polymer Concrete
Containing Resin C
A pair of compressive strength test pieces
were prepared using a modification of standard method
ASTM C882 wherein the polymer concrete formulation was
poured onto a concrete cylinder with a sandblasted 30
degree angle face. Each concrete cylinder was con-
tained in a plastic cylindrical mold.
A 185.7 gram portion of Resin C was ca-talyzed
using 0.30 percent by weight (pbw) N,N-dimethylaniline
and 1.00 pbw benzoyl peroxide. Then 1300 grams of a
49.4/25.3/25.3 pbw mixture of rocX/number 3 blasting
sand/number 4 blasting sand were thoroughly mixed and
33,451-F -42-
6,3~
-43-
then stirred into the resin solution. The roc~ used
herein ranged from 5/8 to 1/4 inch (1.58 cm to 0.53
cm). The resulting polymer concrete ~las split in~o t-~70
e~uivalent aliquots which were used to prepare dupli-
cate compressive strength test pieces. A tamping rodand vibrator were used to pack the cylinderical molds
with the polymer concrete and assist in removal of
bubbles before gelation. After post curing for t~70
hours at 75C, the 3~inch (7.62 cm) diameter by 6-inch
(15.24 cm) cylinderical compressive strength test
pieces were demolded and tested using the method of
Example 1-A. The average of the duplicate compressive
bond strength values is given in Table III.
B. Wet Compressive Bond Strength of Polymer Concrete
Containing Resin C
The method of Example 3-A was repeated except
that no absorbent polymer was used in the polymer
concrete. The average of the duplicate compressive
bond strength values is given in Table III.
TABLE III
.
Compressive Bond Strength
(psi)
Example 3-A 3295 (22718 kPa)
Example 3-B 2352 (16216 kPa)
25 Control 3-A 2931 (20208 kPa)
Control 3-B 2152 (14837 kPa) -
The polymer concrete of Resin C containing
Absorbent Polymer A (Example 3-A) exhibited the highest
compressive bond strength of the series, even exceeding
that of the dry compressive bond strength control
33,451-F -43-
7f~
-44-
(Control 3-A). The polymer concrete of Resin C con-
taining Absorbent Polymer B (Example 3-B) provided a
wet compressive bond strength higher than that of the
wet compressive bond strength control (Control 3-B).
EXAMPLE 4
Dry Compressive Bond Streng~h of Polymer Concrete
Containina Resin D and Absorbent Polvmer B
.,
P. pair of-compressive st~ength test pieces
were prepared using the method of Example 1-A except
that 185.7 grams of Resin D was substituted for Resin A
and 13.0 grams of Absorbent Polymer B was substituted
for Absorbent Polymer A. The average of the duplicate
compressive bond strength values is given in Table IV.
Each polymer concrete-concrete cylinder was easily
lifted from its plas-tlc mold after post-curing was
completed.
CONTROL 4
Dry Compressive Bond Strength of Polymer Concrete
Containing Resin D
The method of Example 4 was repeated except
that no absorbent polymer was used in the polymer
concrete. The average of the duplicate compressive
bond strength values is given in Table IV. Each polymer
concrete-concrete cylinder was difficult to demold and
the plastic cylinderical molds had to be cut and peeled
away after post-curing was-completed.
.
TABLE IV
Compressive Bond Strength
(psi)
Example 4 4592 (31661 kPa)
Contr~l 4 - 2927 (20181 ~Pa)
33,451-F -44-
-45-
The polymer concrete of Resin D containing
Absorbent Polymer B (Example 4) exhibited significantly
higher dry compressive bond strength -than the polymer
concrete of Resin D alone (Control 4).
EXAMPLE 5
A. Dry Compressive Bond Strength of Polymer Concrete
Containing Monomer Blend E and Absorbent Pol~mer A
~ A pair o compressive strength test pieces
were prepared using a modification of standard method
ASTM C882 wherein the polymer concrete formulation was
poured onto a concrete cylinder with a sandblasted 30
degree angle face. Each concrete cylinder was con-
tained in a plastic cylinderical mold.
A 214.0 gram portion of Monomer Blend E was
catalyzed using 0.60 percent by weight (pbw~ N,N-di-
' methyltoluidine and 1.2 pbw benzoyl peroxide. Then
1500 grams of a 49.4/25.3/25.3 pbw mixture of rock/-
number 3 blasting sand/number 4 blasting sand, 45.0
grams of poly(methylmethacrylate) and 13.0 grams of
Absorbent Polymer A were thoroughly mixed and then
stirred into the monomer blend solution. The rock used
herein ranged in size from 5/8 to 1/4 inch (1.59 cm to
0.63 cm). The resulting polymer concrete was split
into two equivalent aliquots which were used to prepare
duplicate compressive strength test pieces. A tamping
rod and vibrator were used to pack t~e cylinderical
molds with the polymer concrete and assist in removal
of bubbles before gelation. After post curing for two
hours at 75C, the 3-inch (7.62 cm) diameter by 6-inch
(15.24 cm) cylinderical compressive strength test
pieces were demolded and tested using the method of
Example 1-A. The average of the duplicate compressive
bond strength values is given in Table V.
33,451-F -45-
~7~
-46-
B. Wet Com~ressive Bond Strenqth of Pol~Jmer Concrete
Containinq Monomer Blend E and Absorbent Pol~mer A
The method of Example 5-A was repeated except
that each concrete cylinder contained in a plastic
.5 cylinderical mold was immersed under water for tr,7enty-four
hours. The water was then poured off each cylinder two
minutes prior t~ adding the polymer concrete. The
average of the duplicate compressive bond strength
- values is given in Table V. - -
C. Dry Compressive Bond Strength of Polymer Concrete
Containing Monomer Blend E and Absorbent Polymer B
The method of Example 5-A was repeated except
that 13.0 grams of Absorbent Polymer B was substituted
for Absorbent Polymer A. The average of the duplicate
compressive bond strength values is given in Table V.
D. Wet Com~ressive Bond Strength of Polvmer Concrete
Containing Monomer Blend E and Absorbent Polymer B
The method of Example 5-B was repeated except
that 13.0 grams of Absorbent Polymer B was substituted
for Absorbent Polymer A. The average of the duplicate
compressive bond strength values is given in Table V.
CONTROL 5
Wet Compressive Bond Strength of Polymer Concrete
Containing Monomer Blend E
The method of Example 5-B was repeated except
that no absorbent polymer was used in the polvmer
concrete. The average of the duplicate compressive
bond strength values is given in Table V.
33,451-F 4~-
-47-
TABLE V
Compressive Bond Strength
(psi )
Example 5-A 4214 (29054 kPa)
5 Example 5-B 3376 (23277 kPa)
Exarnple 5-C 3904 (26917 kPa)
Exarnple 5-D 3328 (22946 kPa)
Control 5 . 2072 (1.4286 kPa)
The polymer concretes of Monomer Blend E containing
Absorbent Polymer A (Example 5-B) and Absorbent Polymer
B (Example 5-D) exhibited significantly higher wet
compressive bond strengths versus the polymer concrete
of ~lend E alone (Control 5).
33,451-F _47_
