# Patent

## Title
Isocyanurate vinyl ester anchoring adhesive composition

## Abstract

An anchoring adhesive includes effective amounts of an isocyanurate compound and a vinyl ester compound that react and cure to form a composition having high compressive strength, high tensile strength and low shrinkage. The anchoring adhesive can be used to firmly bond anchor pins to boreholes in concrete, steel, wood, and other substrates.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application is a divisional of U.S. patent application Ser. No. 13/110,504, filed 18. May 2011. This application is herein incorporated by reference in its entirety and is made a part hereof, including but not limited to those portions which specifically appear hereinafter.


FIELD OF THE INVENTION
This invention is directed to an anchoring adhesive composition used to maintain anchor pins in boreholes, which has excellent compressive strength and tensile strength, and minimal shrinkage during curing.
BACKGROUND OF THE INVENTION
Anchoring adhesives are used to maintain anchor pins in boreholes that are upside down and vertical, or horizontal, or oriented at any angle. The anchoring adhesives and anchor pins are useful in industrial or commercial construction applications such as bridges, airports, highways, skyscrapers, stadiums and tunnels. In a typical application, a borehole is drilled into a substrate member formed of concrete, steel, wood, or a combination thereof, or another material. Then, the interior of the borehole is cleaned and scrubbed to remove dust and dirt particles. Then, the borehole is filled with a measured amount of anchoring adhesive. Then, a driving tool is used to drive an anchor pin into the borehole.
A typical anchor pin is elongated and made of steel. The anchor pin may be threaded or non-threaded and may have a flat or pointed end. The driving tool may be a hammer, or may be a power tool that employs hammering and/or rotational motion.
Some anchoring adhesives and methods of applying them are disclosed in U.S. Pat. No. 6,291,555, issued to Surjan et al.; U.S. Pat. No. 6,402,434, issued to Surjan et al.; U.S. Pat. No. 6,403,678, issued to Surjan et al.; U.S. Pat. No. 6,416,256, issued to Surjan et al.; U.S. Pat. No. 6,420,458, issued to Surjan et al.; U.S. Pat. No. 7,226,650, issued to Liu et al.; and U.S. Pat. No. 7,368,170, issued to Liu et al. These patents are incorporated herein by reference in their entireties.
Additional anchoring adhesives and methods of applying them are disclosed in U.S. Pat. No. 7,411,010, issued to Kish et al.; U.S. Pat. No. 7,163,971, issued to Rancich et al.; U.S. Pat. No. 6,822,017, issued to Kish et al.; U.S. Pat. No. 6,228,207, issued to Rancich et al. and U.S. Pat. No. 5,965,635, issued to Rancich et al. These patents are incorporated herein by reference in their entireties.
Due to the heavy duty nature of most anchor pin applications, it is important that the anchoring adhesive maintain a strong adhesive bond between the anchor pin and the borehole under a wide variety of conditions. Properties of anchoring adhesive that are considered important in end use applications include high compressive strength, high tensile strength, and low shrinkage during curing. There is a need or desire for anchoring adhesives that demonstrate improvements in these and other properties.
SUMMARY OF THE INVENTION
This present invention is directed to an anchoring adhesive that exhibits high compressive strength, high tensile strength, and low thermal shrinkage, when used to bind an anchor pin to a borehole. The anchoring adhesive includes a first part A and a second part B in a weight ratio of about 1:4 to about 40:1. The first part A includes an isocyanurate compound and a vinyl ester compound. The second part B includes a free radical initiator.
The first part A and second part B are initially separate from each other and may be present in separate capsules inside an anchoring adhesive cartridge, slug or package. During use, the cartridge, slug or package of anchoring adhesive can be placed in a borehole or immediately above a borehole. When a tool is used to drive an anchor pin into the borehole, the driving force ruptures the capsules, if present, and causes the first part A and second part B to mix together and chemically react in the interstitial spaces between the anchor pin and the interior of the borehole.
Upon mixing of the first part A and the second part B, the isocyanurate compound reacts with the vinyl ester compound to create a polymer that is believed to include uniquely shaped crosslinks which both strengthen the polymer and resist elevated temperature creep. The chemical reaction advantageously occurs quickly, with minimal set time, at ambient temperature. The anchoring adhesive provides excellent adhesion between various substrate materials that can be used for the anchor pin and the borehole.
With the foregoing in mind, it is a feature and advantage of the invention to provide an anchoring adhesive that exhibits excellent strength properties and low shrinkage during curing. These and other features and advantages of the invention will become further apparent from the following detailed description of the preferred embodiments. The detailed description is considered to be merely illustrative rather than limiting, the scope of the invention being defined by the appended claims and equivalents thereof



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a dog-bone shaped test specimen used in the tensile testing of anchoring adhesive compositions described below.
FIG. 2 is a front view of the dog-bone shaped test specimen of FIG. 1.
FIG. 3 is a side view of the dog-bone shaped test specimen of FIG. 1.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is an anchoring adhesive including a first part A and a second part B. The first part A and second part B are present in weight ratios of about 1:4 to about 40:1, suitably about 1:3 to about 30:1, or about 1:2 to about 20:1, or about 1:1 to about 10:1.
The first part A includes and isocyanurate compound and a vinyl ester compound. The isocyanurate compound may be selected from compounds having the following chemical formula:




Wherein each R and R′ is allyl, alkyl or aryl.
Suitably, the isocyanurate compound can be selected from isocyanurate acrylates, isocyanurate diacrylates, isocyanurate triacrylates, and combinations thereof. The isocyanurate compound can be a monomer or a polymer, and is suitably a monomer. One particularly suitable isocyanurate compound is tris(2-hydroxy ethyl)isocyanurate triacrylate. This isocyanurate compound is a monomer, and is available from Sartomer USA, LLC under the trade name SR368. The structure of isocyanurate, as exemplified by the following structure of tris(2-hydroxy ethyl)isocyanurate triacrylate, lends itself to forming unique crosslinks with vinyl ester that strengthen the polymer lattice and resist elevated temperature creep:




The vinyl ester compound can be a monomer or a polymer, and is suitably a polymer. The vinyl ester compound can be selected from polymers having the following chemical formula:




wherein

    
    
        Ar is a substituted or unsubstituted aromatic radical with a valence of at least two,
        R is independently a substituted or unsubstituted divalent radical derived from alkyl or arylalkyl,
        R3 is a hydroxy substituted divalent radical derived from an alkyl radical,
        R4 is independently a vinyl carboxy radical or a epoxy radical, provided that the ratio of n to the number of vinyl carboxy R4 groups is, on average for the composition, from about 0.4. to about 2.0, and
        n is from 1 to 5.
    
    


A particularly suitable vinyl ester compound is available from Reichhold Chemical Co. under the tradename Norpol Dion Ver 9165. This product contains 64.5% by weight of a vinyl ester having the following chemical formula, and 35.5% by weight vinyl toluene.




where n is from 1 to about 5 and wherein the ratio of n to the terminal vinyl units is, on average for the composition, from about 0.4 to about 2.0.
The first part A may include about 1-30% by weight of the isocyanurate compound, suitably about 1-20% by weight, or about 2-10% by weight. The first part A may include about 3-50% by weight of the vinyl ester compound, suitably about 5-40% by weight, or about 8-30% by weight. As noted above, the first part A may also include an additional monomer. Suitable monomers include without limitation a vinyl monomer, an acrylate, diacrylate or triacrylate monomer, and combinations thereof. The additional monomer may constitute zero to about 40% by weight of the first part A, suitably about 1-30% by weight, or about 2-20% by weight. When present, the additional monomer may also participate in the chemical (crosslinking) reaction between the isocyanurate compound and the vinyl ester compound.
The first part A may also include about 20-70% by combined weight of one or more fillers, suitably about 30-70% by weight, or about 30-60% by weight. Suitable fillers include without limitation glass fibers, silicon dioxide (silica), titanium dioxide, quartz sand, other sands, and combinations thereof. The first part A may also include about 0.01-10% by combined weight of one or more thixotropic agents, suitably about 0.05-5% by weight, or about 0.1-4% by weight. Suitable thixotropic agents include without limitation formed silica, polycarboxylic acid amides, urea compounds, and combinations thereof Thixotropic agents cause the anchoring adhesive to become more fluid (less viscous) as its components are mixed together.
The first part A may also include minor amounts of catalysts, chain extenders, flame retardants, fragrances and the like. While a catalyst may be included in the first part A, this catalyst is typically not a free radical initiator of the type that is typically included in the second part B. Exemplary catalysts and chain extenders useful in the first part A include without limitation diethylol-p-toluidine, n-dodecyl mercaptan, and the like.
The second part B may include about 5-80% by weight of a free radical initiator, suitably about 10-50% by weight, or about 15-40% by weight. Suitable free radical initiators include without limitation peroxide compounds, tertiary amine compounds, aldehyde amine compounds, organic sulfonyl chlorides, and combinations thereof. One suitable free radical initiator is available from Arkema Inc. under the trade name AFR40. This product is a mixture of 40% by weight dibenzoyl peroxide, 40% by weight dibutyl phthalate, and 20% by weight water.
The second part B may also include about 20-80% by weight of a thickening agent, suitably about 20-65% by weight, or about 20-50% by weight. Suitable thickening agents include without limitation monosilica, organic and inorganic clays, and other very fine, inert particulate materials.
The second part B may also include a liquid carrier in an amount of zero to about 50% by weight, suitably about 10-45% by weight or about 15-40% by weight. Suitable liquid carriers include water and organic solvents such as alcohols, ethers and ketones. Additionally, the second part B may include suitable amounts of pigments, fillers and the like.
The first part A and second part B may be present in separate first and second capsules and may be combined in a single cartridge, slug or package of anchoring adhesive. The first and second capsules can be formed of glass, plastic or a membrane material. One of the first and second capsules can be smaller than the other of the first and second capsules and contained within the other of the first and second capsules. Suitably, the first part A is contained within a first, larger capsule and the second part B is contained within a second, smaller capsule, and the second capsule is contained within the first capsule.
The cartridge, slug or package of anchoring adhesive may contain the first and second capsules and may have a narrow, elongated shape which fits easily into the borehole. When a tool is used to drive an anchor pin into the borehole, the first and second capsules rupture and the first and second parts A and B mix together, resulting in chemical reaction, crosslinking and adhesion between the anchor pin and the inner surfaces of the borehole. The anchoring adhesion of the invention forms a strong adhesive bond and exhibits high tensile and compressive strengths and minimal shrinkage.
EXAMPLES
Several experimental anchoring adhesives were formulated using the ingredients listed in Table 1.







TABLE 1







Anchoring Adhesive Ingredients










Trade Name
Supplier
Chemical Name
Purpose





C2208
ITW-Red Head
70% Methyl Methacrylate/30% Polymethylmethacrylate
Monomer/Resin


SR350
Sartomer
TRIMETHYLOLPROPANE TRIMETHACRYLATE
Monomer


SR540
Sartomer
ETHOXYLATED (4) BISPHENOL A DIMETHACRYLATE
Monomer


SR368
Sartomer
TRIS (2-HYDROXY ETHYL) ISOCYANURATE TRIACRYLATE
Monomer


SR833S
Sartomer
TRICYCLODECANE DIMETHANOL DIACRYLATE
Monomer


PRO12128
Sartomer
30% SR368/70% SR833S (proprietary composition)
Monomers


DION 9165
Reichhold
64.5% DEGBPA Vinyl Ester/35.5% Vinyl Toluene
Resin/Monomer


Ethylene Glycol
Various
Ethylene Glycol
Monomer


Pulcra 5710
Pulcra Chemical
diethylol-p-toluidine
Catalyst



Company


NDM
Arkema
n-DODECYL MERCAPTAN
Chain Extender


Fragrance 16332
Atlanta Fragrance
unknown
Fragrance



Company


Aerosil R 202
Evonik
Hydrophobically modified fumed silica
Thixotropic Agent


Aerosil R974
Evonik
Hydrophillically modified fumed silica
Thixotropic Agent


BYK-R605
BYK
Solution of polyhydroxycarboxylic acid amides
Thixotropic Agent


BYK-E401
BYK
Solution of a modified urea
Thixotropic Agent


TS720
Cabot Corp
Hydrophobically modified fumed silica
Thixotropic Agent


Micral 9400
J. M. Huber
Aluminum trihydrate
Flame Retardant



Corporation


Microglass M9132
Fibertec, Inc.
Milled glass fiber (15 μm diameter × ~150 μm Length)
Reinforcing Filler


Sand 100/140
AGSCO
Quartz Sand (100-140 mesh)
Reinforcing Filler


Silcosil 63
US Silica
Crystalline silica (<63 μm)
Reinforcing Filler


TiPure R900
DuPont
Titanium Dioxide
Pigment


AFR 40
Arkema
40% Dibenzoyl Peroxide/40% Dibutyl Pthalate/20% Water
Free Radical Initiator


Tamsil 8
TAM
microsilica
Thickening Agent


Tixogel VZ
Southern Clay
organoclay
Thickening Agent



Products


VC 80000
American Colors,
Black Iron Oxide Paste
Pigment



Inc









The foregoing ingredients were formulated into anchoring adhesive compositions, with control compositions A7. from Illinois Tool Works Inc. and HY-150 from HiltiAltengesellschaft, and experimental compositions A7+−1, A7+−2, A7+−3, . . . , through A7+−95. Physical properties of Compressive Strength, Tensile Strength, Tensileh Modules and Shrinkage were measured for many of the anchoring adhesive compositions, using the test procedures described below. The following Table 2. describes the anchoring adhesive compositions and sets forth the test results.
As shown below, the anchoring adhesives formulated using the isocyanurate compound (represented by ingredient PRO 12128) in combination with the vinyl ester compound (represented by ingredient DION 9165) generally had higher compression strengths and higher tensile strengths than the anchoring adhesives that omitted one or both of these ingredients, and also exhibited excellent (low) shrinkage values.







TABLE 2





Anchoring Adhesive Compositions And Test Results



















Controls













HY-
Crosslinker-Fiber
Catalysis


















A7
150
A7 + −1
A7 + −2
A7 + −3
A7 + −4
A7 + −5
A7 + −6
A7 + −7
A7 + −8










Resin Side (Part A)

















C2208
39.88% 

36.26% 
30.70% 
33.25% 
36.26% 
30.70% 
40.20% 
39.88% 
39.88% 


SR350












SR540


4.53%
11.51% 
8.31%
4.53%
11.51% 





PRO12128












SR833S












DION 9165












Ethylene Glycol












HET
0.50%

0.45%
0.38%
0.42%
0.45%
0.38%
0.10%
0.10%
0.90%


NDM
0.50%

0.45%
0.38%
0.42%
0.45%
0.38%
0.10%
0.90%
0.10%


F16332
0.30%

0.27%
0.23%
0.25%
0.27%
0.23%
0.30%
0.30%
0.30%


R202
3.99%

3.63%
3.07%
3.33%
3.63%
3.07%
4.02%
3.99%
3.99%


R974












BYK-605












BYK-E401












TS720












M9400
4.99%

4.53%
3.84%
4.16%
4.53%
3.84%
5.03%
4.98%
4.98%


Glass Fibers


12.47% 
12.47% 
31.17% 
49.86% 
49.88% 





Sand 100/140
49.85% 

37.40% 
37.41% 
18.70% 


50.25% 
49.85% 
49.85% 


Silicosil 63












R900

















Activator Side (Part B)

















AFR40
48.72

48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72


Tamsil 8












Tixogel VZ
 1.98

 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95

48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36

 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties

















Compressive Strength, psi
1,643
9,400  
16,494 
10,000
9,411
6,386
10,815 
15,073




Tensile Strength, psi
1,615
577
2,112
 1,874
2,608
2,924
3,467
 1,744




Tensile Modulus, ksi
1,025
187
1,036
  984
1,197
1,501
1,511
  803




Shrinkage


















Microsilica-Isocyanurate
Original























A7 + −9
A7 + −10
A7 + −11
A7 + −12
A7 + −13
A7 + −14
A7 + −15
A7 + −16
A7 + −17
A7 + −18










Resin Side (Part A)

















C2208
39.56% 
0.48%
0.54%
0.52%
39.88% 
39.88% 
39.88% 
39.88% 
39.88% 
39.88% 


SR350












SR540


13.60% 
13.07% 








PRO12128


4.09%
7.86%








SR833S












DION 9165












Ethylene Glycol












HET
0.89%
0.01%
0.01%
0.01%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%


NDM
0.89%
0.01%
0.01%
0.01%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%


F16332
0.30%
0.00%
0.00%
0.00%
0.30%
0.30%
0.30%
0.30%
0.30%
0.30%


R202
3.96%
0.05%
0.05%
0.05%
3.99%
3.99%
3.99%
3.99%
3.99%
3.99%


R974












BYK-605












BYK-E401












TS720












M9400
4.95%
0.06%
0.07%
0.07%
4.99%
4.99%
4.99%
4.99%
4.99%
4.99%


Glass Fibers

72.28% 
51.02% 
49.01% 

24.93% 

8.31%
24.93% 



Sand 100/140
49.45% 

30.61% 
29.40% 
49.85% 

49.85% 
8.31%

49.85% 


Silicosil 63

27.11% 



24.93% 

33.23% 
24.93% 



R900

















Activator Side (Part B)

















AFR40
48.72
48.72
48.72
48.72
49.5
48.72
48.72
48.72
48.72
48.72


Tamsil 8




29.7







Tixogel VZ
 1.98
 1.98
 1.98
 1.98
19.8
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95
48.95
48.95
48.95

48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36
 0.36
 0.36
 0.36
 0.99
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties

















Compressive Strength, psi

12,013 
11,042 
9,241
1,284
2,965
3,325
2,991
2,847  
3,290


Tensile Strength, psi

2,805
2,690
2,515
1,367
1,359
2,025
1,495
837
2,202


Tensile Modulus, ksi

1,300
1,144
1,191
1,022
  954
1,267
1,106
836
1,645


Shrinkage












Sand/Microsilica/Glass Fiber DOE


















A7 + −19
A7 + −20
A7 + −21
A7 + −22
A7 + −23
A7 + −24
A7 + −25
A7 + −26
A7 + −27
A7 + −28










Resin Side (Part A)

















C2208
39.88% 
39.88% 
39.88% 
39.88% 
39.88% 
39.88% 
39.88% 
39.88% 
39.88% 
39.88% 


SR350












SR540












PRO12128












SR833S












DION 9165












Ethylene Glycol












HET
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%


NDM
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%
0.50%


F16332
0.30%
0.30%
0.30%
0.30%
0.30%
0.30%
0.30%
0.30%
0.30%
0.30%


R202
3.99%
3.99%
3.99%
3.99%
3.99%
3.99%
3.99%
3.99%
3.99%
3.99%


R974












BYK-605












BYK-E401












TS720












M9400
4.99%
4.99%
4.99%
4.99%
4.99%
4.99%
4.99%
4.99%
4.99%
4.99%


Glass Fibers

49.85% 

8.31%
20.77% 
33.23% 
49.85% 
16.62% 

24.93% 


Sand 100/140



33.23% 
20.77% 
8.31%

16.62% 
24.93% 
24.93% 


Silicosil 63
49.85% 

49.85% 
8.31%
8.31%
8.31%

16.62% 
24.93% 



R900

















Activator Side (Part B)

















AFR40
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72


Tamsil 8












Tixogel VZ
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties

















Compressive Strength, psi
2,967

2,438
3,226
2,888
2,622
1,903  
3,253
2,848
3,006


Tensile Strength, psi
1,323
1,073
1,532
2,458
1,981
1,108
712
1,532
1,111
1,786


Tensile Modulus, ksi
1,100
1,010
1,039
1,346
1,116
1,021
937
1,114
1,231
1,010


Shrinkage






A7 + −29
A7 + −30
A7 + −31
A7 + −32
A7 + −33
A7 + −34
A7 + −35
A7 + −36
A7 + −37
A7 + −38










Resin Side (Part A)

















C2208
39.88% 
39.88% 
39.88% 
39.88% 








SR350




6.61%

10.17% 

20.35% 



SR540




4.07%
10.17% 
30.52% 
10.17% 




PRO12128




4.07%


30.52% 

20.35% 


SR833S




19.33% 
30.52% 


20.35% 
20.35% 


DION 9165




6.61%







Ethylene Glycol












HET
0.50%
0.50%
0.50%
0.50%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%


NDM
0.50%
0.50%
0.50%
0.50%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%


F16332
0.30%
0.30%
0.30%
0.30%
0.31%
0.31%
0.31%
0.31%
0.31%
0.31%


R202
3.99%
3.99%
3.99%
3.99%
2.34%
2.34%
2.34%
2.34%
2.34%
2.34%


R974












BYK-605












BYK-E401












TS720












M9400
4.99%
4.99%
4.99%
4.99%
5.09%
5.09%
5.09%
5.09%
5.09%
5.09%


Glass Fibers

9.97%
9.97%
9.97%
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 


Sand 100/140
24.93% 

4.99%
7.48%








Silicosil 63
24.93% 
39.88% 
34.90% 
32.40% 
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 


R900

















Activator Side (Part B)

















AFR40
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72


Tamsil 8












Tixogel VZ
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties

















Compressive Strength, psi
3,159



13,617 
12,838 
10,567 
9,812
12,303 
11,051


Tensile Strength, psi
2,344



1,501
2,528
1,860
2,772
2,385
 2,888


Tensile Modulus, ksi
1,270



1,171
1,153
1,167
1,074
1,251
  954


Shrinkage




1.57%
1.82%
1.44%
1.34%
2.03%
1.40%












High Potential Monomer Screening


















A7 + −39
A7 + −40
A7 + −41
A7 + −42
A7 + −43
A7 + −44
A7 + −45
A7 + −46
A7 + −47
A7 + −48










Resin Side (Part A)

















C2208












SR350

4.07%

30.52% 
20.35% 


19.33% 

4.07%


SR540
30.52% 
19.33% 

10.17% 

30.52% 
30.52% 
6.61%
20.35% 
4.07%


PRO12128

6.61%
20.35% 


10.17% 

4.07%

19.33% 


SR833S
10.17% 
4.07%




10.17% 
4.07%

6.61%


DION 9165

6.61%
20.35% 

20.35% 


6.61%
20.35% 
6.61%


Ethylene Glycol












HET
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%


NDM
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%


F16332
0.31%
0.31%
0.31%
0.31%
0.31%
0.31%
0.31%
0.31%
0.31%
0.31%


R202
2.34%
2.34%
2.34%
2.34%
2.34%
2.34%
2.34%
2.34%
2.34%
2.34%


R974












BYK-605












BYK-E401












TS720












M9400
5.09%
5.09%
5.09%
5.09%
5.09%
5.09%
5.09%
5.09%
5.09%
5.09%


Glass Fibers
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 


Sand 100/140












Silicosil 63
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 


R900

















Activator Side (Part B)

















AFR40
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72


Tamsil 8












Tixogel VZ
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties

















Compressive Strength, psi
10,352
11,735
10,469 
9,773
13,881 
12,235
10,530
12,643
11,751
11,719 


Tensile Strength, psi
 1,662
 2,375
2,241
1,592
2,438
 2,270
 2,237
 1,900
 2,512
2,192


Tensile Modulus, ksi
  800
  848
1,204
1,102
1,147
  886
  780
  991
  891
1,102


Shrinkage
1.46%
1.15%
1.10%
2.30%
1.55%
1.60%
1.23%
1.44%
1.28%
1.51%






A7 + −49
A7 + −50
A7 + −51
A7 + −52
A7 + −53
A7 + −54
A7 + −55
A7 + −56
A7 + −57
A7 + −58










Resin Side (Part A)

















C2208












SR350
10.17% 
10.17%
20.35% 
6.61%



10.17% 
10.17% 



SR540
30.52% 
10.17%

6.61%

23.83% 
15.26% 

30.52% 



PRO12128

10.17%
20.35% 
4.07%


25.43% 


10.16% 


SR833S

10.17%

4.07%
20.35% 
16.86% 






DION 9165



19.33% 
20.35% 


30.52% 

30.49% 


Ethylene Glycol












HET
0.25%
 0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.51%


NDM
0.25%
 0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.25%
0.51%


F16332
0.31%
 0.31%
0.31%
0.31%
0.31%
0.31%
0.31%
0.31%
0.31%
0.30%


R202
2.34%
 2.34%
2.34%
2.34%
2.34%
2.34%
2.34%
2.34%
2.34%
2.44%


R974












BYK-605












BYK-E401












TS720












M9400
5.09%
 5.09%
5.09%
5.09%
5.09%
5.09%
5.09%
5.09%
5.09%
5.08%


Glass Fibers
12.82% 
12.82%
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 
12.82% 
10.10% 


Sand 100/140












Silicosil 63
38.25% 
38.25%
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 
38.25% 
40.41% 


R900

















Activator Side (Part B)

















AFR40
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72


Tamsil 8












Tixogel VZ
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties

















Compressive Strength, psi
10,251
12,343
13,137 
12,516 
13,698 
11,655
10,095
14,668
12,084
11,657


Tensile Strength, psi
 1,896
 2,449
2,160
2,244
3,033
 2,471
 2,717
 2,738
 1,814
 2,828


Tensile Modulus, ksi
  771
  776
1,198
1,214
1,117
  824
  851
  874
  727
  971


Shrinkage
1.51%
1.57%
0.00%
1.17%
1.51%
1.45%
1.37%
1.48%
1.57%
1.69%













Filler Loading
% Filler/% Monomer/% Glass


















A7 + −59
A7 + −60
A7 + −61
A7 + −62
A7 + −63
A7 + −64
A7 + −65
A7 + −67
A7 + −68
A7 + −69










Resin Side (Part A)

















C2208












SR350












SR540












PRO12128
8.86%
6.73%
6.47%
8.26%
3.73%
7.10%
3.32%
4.10%
4.10%
10.20% 


SR833S












DION 9165
26.59% 
20.18% 
30.61% 
24.70% 
33.34% 
33.60% 
29.64% 
36.60% 
36.60% 
30.50% 


Ethylene Glycol












HET
0.44%
0.34%
0.46%
0.40%
0.46%
0.50%
0.40%
0.50%
0.50%
0.50%


NDM
0.44%
0.34%
0.46%
0.40%
0.46%
0.50%
0.40%
0.50%
0.50%
0.50%


F16332
0.27%
0.20%
0.27%
0.24%
0.27%
0.30%
0.24%
0.30%
0.30%
0.30%


R202
2.13%
1.61%
2.19%
1.94%
2.19%
2.40%
1.94%
2.40%
2.40%
2.40%


R974












BYK-605












BYK-E401












TS720












M9400
4.43%
3.36%
4.55%
4.05%
4.55%
5.00%
4.05%
5.00%
5.00%
5.00%


Glass Fibers
11.37% 
13.45% 
5.43%




5.10%
10.10% 



Sand 100/140












Silicosil 63
45.47% 
53.80% 
49.57% 
60.00% 
55.00% 
50.60% 
60.00% 
45.50% 
40.50% 
50.60% 


R900

















Activator Side (Part B)

















AFR40
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72


Tamsil 8












Tixogel VZ
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties

















Compressive Strength, psi
14,059 
9,584
14,670
13,598
14,670
9,562
11,657
14,670
10,908
14,670


Tensile Strength, psi
2,495
2,323
 2,498
 1,777
 2,117
 1,893
 2,828
 2,672
 2,505
 2,455


Tensile Modulus, ksi
1,228
1,484










Shrinkage
1.37%
1.26%
1.57%
1.36%
1.43%
1.30%
1.34%
1.43%
1.34%
1.59%














DOE
Optimization
Color and Pumpability Match


















A7 + −70
A7 + −71
A7 + −72
A7 + −73
A7 + −74
A7 + −75
A7 + −76
A7 + −77
A7 + −78
A7 + −79










Resin Side (Part A)

















C2208












SR350












SR540












PRO12128
3.32%
4.10%
8.26%
3.32%
8.26%
8.26%
4.76%
4.80%
4.69%
4.58%


SR833S












DION 9165
29.64% 
36.60% 
24.70% 
29.64% 
24.70% 
24.70% 
33.22% 
33.49% 
32.70% 
31.95% 


Ethylene Glycol








1.97%
3.85%


HET
0.40%
0.50%
0.40%
0.40%
0.40%
0.40%
0.47%





NDM
0.40%
0.50%
0.40%
0.40%
0.40%
0.40%
0.47%
0.47%
0.46%
0.45%


F16332
0.24%
0.30%
0.24%
0.24%
0.24%
0.24%
0.28%
0.47%
0.46%
0.45%


R202
1.94%
2.40%
1.94%
1.94%
1.94%
1.94%
2.00%
0.28%
0.28%
0.27%


R974







1.21%
1.57%
1.92%


BYK-605







4.71%
4.60%
4.49%


BYK-E401












TS720












M9400
4.05%
5.00%
4.05%
4.05%
4.05%
4.05%
4.67%





Glass Fibers
11.98% 

11.98% 
11.98% 
11.98% 

5.35%
5.39%
5.27%
5.14%


Sand 100/140
 











Silicosil 63
48.02%
50.60% 
48.02% 
48.02% 
48.02% 
60.00% 
48.77% 
49.17% 
48.01% 
46.90% 


R900

















Activator Side (Part B)

















AFR40
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72


Tamsil 8












Tixogel VZ
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties

















Compressive Strength, psi
14,670
13,549
11,946
14,670
12,519
14,090






Tensile Strength, psi
 2,502
 1,978
 2,031
 2,496
 2,401
 2,047






Tensile Modulus, ksi












Shrinkage
1.29%
1.36%
1.06%
1.11%
1.24%
1.30%
1.36%
















BYK E401



Color and Pumpability Match
R974/BYK605 5-Point Study
Ladder


















A7 + −80
A7 + −81
A7 + −82
A7 + −83
A7 + −84
A7 + −85
A7 + −86
A7 + −87
A7 + −88
A7 + −89










Resin Side (Part A)

















C2208












SR350












SR540












PRO12128
4.61%
4.77%
4.77%
4.75%
4.75%
4.75%
4.75%
4.75%
4.75%
4.75%


SR833S












DION 9165
32.19% 
33.26% 
33.29% 
33.19% 
33.19% 
33.19% 
33.19% 
33.19% 
33.19% 
33.19% 


Ethylene Glycol
3.88%











HET



0.47%
0.47%
0.47%
0.47%
0.47%
0.47%
0.47%


NDM
0.46%
0.47%
0.47%
0.47%
0.47%
0.47%
0.47%
0.47%
0.47%
0.47%


F16332
0.46%
0.47%
0.47%
0.29%
0.29%
0.29%
0.29%
0.29%
0.29%
0.29%


R202
0.27%
0.28%
0.28%
1.86%








R974
1.16%
1.60%
1.60%

1.00%
1.00%
2.00%
3.00%
3.00%



BYK-605
4.53%
4.68%
4.68%

0.20%
0.50%
0.70%
0.60%
1.50%



BYK-E401









0.10%


TS720












M9400



4.67%
4.67%
4.67%
4.67%
4.67%
4.67%
4.67%


Glass Fibers
5.18%
5.36%
5.36%
5.35%
5.35%
5.35%
5.35%
5.35%
5.35%
5.35%


Sand 100/140












Silicosil 63
47.26% 
48.83% 
48.87% 
48.74% 
48.74% 
48.74% 
48.74% 
48.74% 
48.74% 
48.74% 


R900

0.29%
0.21%
0.21%
0.21%
0.21%
0.21%
0.21%
0.21%
0.21%







Activator Side (Part B)

















AFR40
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72
48.72


Tamsil 8












Tixogel VZ
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties

















Compressive Strength, psi












Tensile Strength, psi












Tensile Modulus, ksi












Shrinkage














BYK E401 Ladder
TS720 Ladder
Final














A7 + −90
A7 + −91
A7 + −92
A7 + −93
A7 + −94
A7 + −95










Resin Side (Part A)













C2208








SR350








SR540








PRO12128
4.75%
4.75%
4.75%
4.75%
4.75%
4.75%


SR833S








DION 9165
33.19% 
33.19% 
33.19% 
33.19% 
33.19% 
33.15% 


Ethylene Glycol








HET
0.47%
0.47%
0.47%
0.47%
0.47%
0.47%


NDM
0.47%
0.47%
0.47%
0.47%
0.47%
0.47%


F16332
0.29%
0.29%
0.29%
0.29%
0.29%
0.28%


R202








R974





1.09%


BYK-605





0.20%


BYK-E401
0.50%
1.00%






TS720


1.00%
2.00%
3.00%



M9400
4.67%
4.67%
4.67%
4.67%
4.67%
4.95%


Glass Fibers
5.35%
5.35%
5.35%
5.35%
5.35%
4.95%


Sand 100/140








Silicosil 63
48.74% 
48.74% 
48.74% 
48.74% 
48.74% 
49.48% 


R900
0.21%
0.21%
0.21%
0.21%
0.21%
0.21%







Activator Side (Part B)













AFR40
48.72
48.72
48.72
48.72
48.72
48.72


Tamsil 8








Tixogel VZ
 1.98
 1.98
 1.98
 1.98
 1.98
 1.98


Sand 100/140
48.95
48.95
48.95
48.95
48.95
48.95


VC 80000
 0.36
 0.36
 0.36
 0.36
 0.36
 0.36







Physical Properties













Compressive Strength, psi








Tensile Strength, psi








Tensile Modulus, ksi








Shrinkage









TEST PROCEDURES USED FOR EXAMPLES
Compression Testing
Anchoring adhesive ingredients were mixed and molded into cylindrical samples having a 1.25 inch diameter and 1-inch length, to approximately simulate the size and shape of anchoring adhesive typically formed in a borehole. The samples were cured for at least 24 hours at ambient conditions, and were placed in a universal flat plate testing machine. The samples were compressed at a rate of 0.1 inch per minute while the force and deflection were measured until the sample failed or the deflection reached 0.4 inch. The maximum compressive force was recorded.
Tensile Testing
Dog-bone shaped samples were molded according to the shape illustrated in FIGS. 1-3, and were cured at ambient conditions for at least 24 hours. The dimensions A-K indicated in the drawings were as follows:
















A
0.25 in.



B
0.35 in.



C
0.25 in.



D
184.6°



E
1.00 in.



F
1.25 in.



G
2.00 in.



H
1.25 in.



I
1.00 in.



J
0.25 in.



K
7.00 in.



L
0.25 in.










The test samples were placed in the groups of a large Instron 5586 tensile tester with a 2000-lb load cell adapter and pulled at a speed of 0.2 in. per minute. The force and deflection were measured until the sample failed. The maximum tensile force was recorded.
Shrinkage Testing
The same molded samples used for compression testing were used to measure shrinkage. After the sampled were cured for 24 hours, the diameters of their bases were measured and compared to the mold diameter. The shrinkage was calculated according to the equation:




  Shrinkage
  =
  
    
      (
      
        1
        -
        
          
            sample
            ⁢
            
              
            
            ⁢
            diameter
          
          
            mold
            ⁢
            
              
            
            ⁢
            diameter
          
        
      
      )
    
    ×
    100
    ⁢
    %
  




While the embodiments of the invention described herein are presently preferred, various modifications and improvements can be made without departing from the spirit and scope of the invention. The scope of the invention is defined by the appended claims, and all changes that fall within the meaning and range of equivalents are intended to be embraced therein.

## Claims

1. A method of binding an anchor pin to a borehole formed in a substrate, comprising the steps of: placing a cartridge, slug or package of anchoring adhesive in the borehole, the anchoring adhesive including a first part A and a second part B separate from each other and present in separate capsules; wherein the first part A and the second part B are present in a weight ratio of about 1:4 to 40:1; driving an anchor pin into the borehole, rupturing the capsules and causing the first part A and the second part B to mix together; and chemically reacting the first part A and the second part B in a space between the anchor pin and an inner surface of the borehole, forming a strong adhesive bond between the anchor pin and the inner surface of the borehole; wherein the first part A prior to the chemical reaction comprises an isocyanurate compound and a vinyl ester compound in combination and the second part B comprises a free radical initiator, and the chemical reaction comprises reacting the isocyanurate compound with the vinyl ester compound; wherein the first part A comprises about 1-30% by weight of the isocyanurate compound, about 3-50% by weight of the vinyl ester compound, zero to about 40% by weight of one or more additional monomers, and about 20-70% by weight of one or more fillers; wherein the adhesive bond exhibits an adhesive tensile strength of at least about 1500 psi, a compressive strength of at least about 10,000 psi, and shrinkage not greater than about 1.6%.

2. The method of claim 1, wherein the substrate is one of concrete, steel and wood.

3. The method of claim 1, wherein the isocyanurate compound is selected from the group consisting of compounds having the following chemical formula:

4. The method of claim 3, wherein the isocyanurate compound is selected from the group consisting of isocyanurate acrylates, isocyanurate diacrylates, isocyanurate triacrylates, and combinations thereof.

5. The method of claim 4, wherein the compound comprises tris (2-hydroxyethyl) isocyanurate triacrylate.

6. The method of claim 1, wherein the vinyl ester compound is selected from the group consisting of compounds having the following chemical formula:



wherein
Ar is a substitute or unsubstituted aromatic radical with a valence of at least two,
R is independently a substituted or unsubstituted divalent radical derived from alkyl or arylalkyl,
R3 is a hydroxyl substituted divalent radical derived from an alkyl radical,
R4 is independently a vinyl carboxy radical or a epoxy radical, provided the ratio of n to the number of vinyl carboxy R4 groups is, on average for the composition, from about 0.4 to about2.0, and
n is from 1 to 5.

7. The method of claim 6, wherein the vinyl ester compound is selected from the group consisting of compounds having the following chemical formula:



wherein n is from 1 to about 5 and wherein the ratio of n to the terminal vinyl units is, on average for the composition, from about 0.4 to about 2.0.

8. The method of claim 1, wherein the free radical initiator is selected from the group consisting of peroxide compounds, tertiary amine compounds, aldehyde amine compounds, organic sulfonyl chlorides, and combinations thereof.

9. A method of binding an anchor pin to a borehole formed in a substrate, comprising the steps of: placing a cartridge, slug or package of anchoring adhesive in a borehole, the anchoring adhesive comprising a first part A and a second part B present in a weight ratio of about 1:4 to about 40:1; driving an anchor pin into the borehole, causing the first part A and the second part B to mix together; and chemically reacting the first part A and the second part B in a space between the anchor pin and an inner surface of the borehole, forming a strong adhesive bond between the anchor pin and the inner surface of the borehole; wherein the first part A prior to the chemical reaction comprises an isocyanurate compound in combination with a vinyl ester compound and the second part B comprises a free radical initiator, and the chemical reaction comprises reacting the isocyanurate compound with the vinyl ester compound; wherein the first part A comprises about 1-30% by weight of the isocyanurate compound, about 3-50% by weight of the vinyl ester compound, zero to about 40% by weight of one or more additional monomers, and about 20-70% by weight of one or more fillers; and the adhesive bond exhibits an adhesive tensile strength of at least about 1500 psi, a compressive strength of at least about 10,000 psi, and shrinkage not greater than about 1.6%.

10. The method of claim 9, wherein the isocyanurate compound is selected from the group consisting of isocyanurate acrylates, isocyanurate diacrylates, isocyanurate triacrylates, and combinations thereof.

11. The method of claim 9, wherein the vinyl ester compound is selected from the group consisting of compounds having the following chemical formula:



wherein n is from 1 to about 5 and wherein the ratio of n to the terminal vinyl units is, on average for the composition, from about 0.4 to about 2.0.

12. The method of claim 10, wherein the vinyl ester compound is selected from the group consisting of compounds having the following chemical formula:



wherein n is from 1 to about 5 and wherein the ratio of n to the terminal vinyl units is, on average for the composition, from about 0.4 to about 2.0.

13. The method of claim 9, wherein the free radical initiator is selected from the group consisting of peroxide compounds, tertiary amine compounds, aldehyde amine compounds, organic sulfonyl chlorides, and combinations thereof.

14. The method of claim 12, wherein the free radical initiator is selected from the group consisting of peroxide compounds, tertiary amine compounds, aldehyde amine compounds, organic sulfonyl chlorides, and combinations thereof.

15. A method of binding an anchor pin to a borehole formed in a substrate, comprising the steps of: placing a cartridge, slug or package of anchoring adhesive in a borehole, the anchoring adhesive comprising a first part A and a second part B present in a weight ratio of about 1:2 to about 20:1; driving an anchor pin into the borehole, causing the first part A and the second part B to mix together; and chemically reacting the first part A and the second part B in a space between the anchor pin and the inner surface of the borehole, forming a strong adhesive bond between the anchor pin and the inner surface of the borehole; wherein the first part A prior to the chemical reaction comprises an isocyanurate compound selected from the group consisting of isocyanurate acrylates, isocyanurate diacrylates, isocyanurate triacrylates, and combinations thereof, in combination with a vinyl ester compound, and the chemical reaction comprises reacting the isocyanurate compound with the vinyl ester compound; the second part B comprising a free radical initiator selected from the group consisting of peroxide compounds, tertiary amine compounds, aldehyde amine compounds, organic sulfonyl chlorides, and combinations thereof; wherein the first part A comprises about 1-30% by weight of the isocyanurate compound, about 3-50% by weight of the vinyl ester compound, zero to about 40% by weight of one or more additional monomers, and about 20-70% by weight of one or more fillers, and the adhesive bond exhibits an adhesive tensile strength of at least about 1500 psi, a compressive strength of at least 10,000 psi, and shrinkage not greater than about 1.6%.

16. The method of claim 15, wherein the first part A comprises about 2-10% by weight of an isocyanurate triacrylate, about 2-20% by weight of an additional acrylate monomer, about 8-30% by weight of the vinyl ester compound, about 2-20% by weight of an additional vinyl monomer, and about 30-70% by weight of one or more fillers.

17. The method of claim 15, wherein the second part B comprises about 5-80% by weight of the free radical initiator, about 20-80% by weight of a thickening agent, and zero to about 50% by weight of a liquid carrier.

18. The method of claim 17, wherein the second part B comprises about 10-50% by weight of the free radical initiator, about 20-50% by weight of a thickening agent, and about 15-40% by weight of a liquid carrier.