CA1274637A - Polymer concrete compositions containing water absorbent polymers - Google Patents

Abstract

ABSTRACT

Polymer concrete compositions comprising an unsaturated thermosettable resin(s) and/or ethylen-ically unsaturated monomer(s), an aggregate component and a water absorbent polymer are cured to provide polymer concrete with enhanced adhesion to substrates, especially wet concrete. A primer or coating compo-sition for concrete comprising a water absorbent polymer and an unsaturated thermosettable composition is also disclosed.

Description

~ ~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-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. 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 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~

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 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~

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 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~

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-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~

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 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 ~Z~ '7 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-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~

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~

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 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 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 . . OH

33,451-F -22-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-~-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-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~

(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 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-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 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~

, 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-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 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 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~ ~
., .

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-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.

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-&~

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-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-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-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 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-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.

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~

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~

(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).

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.

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-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).

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~

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.

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~-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_

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A curable polymer concrete composition which comprises A) 2 to 20 weight percent of an unsaturated thermo-settable composition containing 1 to 99 weight percent of one or more ethylenically unsaturated monomers and 1 to 99 weight percent of one or more ethylenically unsaturated resins, B) 75 to 97.9 weight percent 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 weight percent of a water absorbent cross-linked polymer.

2. The curable polymer concrete composition of Claim 1 wherein the amount of thermosettable composition is 8 to 15 weight percent, the amount of said aggregate is 83 to 91 weight percent, and the amount of said absorbent cross-linked polymer is from 1 to 2 weight percent.

3. The curable polymer concrete composition of Claim 1 wherein said unsaturated resin is selected from the group consisting of ethylenically unsaturated polyester resins, ethylenically unsaturated polyesteramide resins, norbornyl modified unsaturated polyester resins, norbornyl modified unsaturated poly-esteramide resins, hydrocarbon modified unsaturated poly-ester resins prepared from a resin oil hydrocarbon modified unsaturated poly-esteramide resins prepared from a resin oil vinyl ester resins, and mixtures thereof.

4. A coating composition which comprises A) 1 to 50 percent by weight of a water absorbent cross-linked polymer, and B) 50 to about 99 percent by weight of an unsaturated thermosettable composition containing 1 to 99 percent by weigilt of one or more ethylenically unsaturated monomers and 1 to 99 weight percent of one or more ethylenically unsaturated resins.

5. The coating composition of Claim 4 wherein the amount of said absorbent polymer is 3 to 15 percent by weight and the amount of said thermosettable composition is 85 to 97 percent by weight.

6. The coating composition of Claim 4 wherein said unsaturated resin is selected from the group consisting of 33,451-F -49-ethylenically unsaturated polyester resins, ethylenically unsaturated polyesteramide resins, norbornyl modified unsaturated polyester resins, norbornyl modified unsaturated polyesteramide resins, hydrocarbon modified unsaturated polyester resins prepared from a resin oil hydrocarbon modified unsaturated polyesteramide resins prepared from a resin oil vinyl ester resins, and mixture of thereof.

7. The curable polyester concrete composition of Claim 1 wherein component A is an ethylenically unsaturated monomer mixture consisting of methylmethacrylate and trimethylolpropane trimethacrylate.

8. The cured polymer concrete composition of any of Claims 1 to 3.

9. The cured coating composition of Claim 4.

33,451-F -50-