AU2015202202B2 - Isocyanurate vinyl ester anchoring adhesive composition - Google Patents

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 adhesie can be used to firmly bond anchor pins to boreholes in concrete, steel wood, and other substrates,

Description

iSDCVANEKATE VINYL ESTER ANCHORING ADHESIVE COMPOSITION

FIELD OF THE INVENTION

This invention is directed to a» .anchoring adhesive cotsposiri'ptv used to maintain anchor pins in boreholes, wMch:':hasAxM!en^m^ssk'^'8tiEength'.and tensile strength, and inini'irtml shrinkage duringcuring,

BAGKGROIJND OF THE INVENTION

Anchoring adhesives are used to maintain anchor pins: in 'boreholes that are upside down and vertical, or horizontal, or oriented at anv angle:. The anchoring adhesives and anchor pins are useful in industrial or eoinhieicialconstmcthw applications such as bridges, airports, highways, skyscrapers, stadiums and tunnels: in a typical application, a borehole is drilled into a substrate mentlSer formed of concrete, steel, wood, or a combination thereof, or another material. Then, the interior of the boreltoie is: cleaned and scrubbed to remove dust and dirt particles, Then, the borehole ts filled with a measured amount of anchoring adhesive. Then, a driving tool is used to drive aft anchor pin into the borehole, A typical anchor pin is elongated and made of sled. The anchor pin may be threaded or non-threaded and may have a flat or pointed end. The dri ving tool may ire a hammer, or may be a power tool that employs hammering and/or rotational motion.

Some anchoring adhesives and methods of applying theftt ate disclosed in ITS, Patent 6,291,555, issued to Sudan cr al.; ITS. Patent 6,402,43d, Issued to Surjaft et ah; ITS. Patent .6,403.678, issued to Surjan et alc IIS; Patent 6,416,256, issued to Surian ei al,: ITS. Patent 6,420,458, issued to Sudan el al.; ITS, Patent 2,226,65¾ Issued to Liu et al.; and UN, Patent 7,368,170; issued to iiu et al Ihese patents are incorporated hernia by reference in their entireties.

Additional anchoring adhesives and methods of applying them are disclosed in ITS, Patent 7,411,0Hi, issued κ· Kish d al.; 1 IS. patent 7.163,971, issued to Raneich et al,; U.S, Patent 6.822,0:17, issited to Kish et al; ITS, Patent 6,228,2()7, issued to Raneich et al. and U.S. Patent 5.965.635, issued to Raneich et al. Those patents arc 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

In accordance with one aspect of the present invention, there is provided 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 present in separate capsules; 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 comprises an isocyanurate compound and a vinyl ester compound and the second part B comprises a free radical initiator.

In accordance with another aspect of the present invention, there is provided 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; 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 comprises an isocyanurate compound and a vinyl ester compound and the second part B comprises a free radical initiator; and the adhesive bond exhibits an adhesive strength of at least about 1500 psi, a compressive strength of at least about 10,000 psi, and a shrinkage not greater than about 1.6%.

In accordance with another aspect of the present invention, there is provided 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; the first part A comprising an isocyanurate compound selected from the group consisting of isocyanurate acrylates, isocyanurate diacrylates, isocyanurate triacrylates, and combinations thereof, and a 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.

Examples of the present invention are 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 examples 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 examples 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 * he roof.

BRIEF 'DESCRIPTION' OF THE DRA WINGS

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 from view of the dog-bone shaped test specimen of Fig. ).

Fig. 3 is a side view of the dog-bone shaped test, specimen of fig. I.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present itweniion is an anchoring adhesive including a first part A sad a second pan 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 3():1:, or about !:i to about if):t.

The first part A includes and isoeyanumte eahipound and a vinyl ester compound, The isocyanurate compound may be selected 1mm compounds having the following chemical formula;

Whemin each R and R' is ally 1, alkyl or aryl.

Suitably, the isocyanurate compound etth he sleeted Bom isocyanurate acrylates, isocyanurate diacrylates, isocyanurate triaerylates, arid: combinations thereof. The isocyanurate compound east he a monomer Ta polymer, and is suitably a .monomer. One particularly suitable rsoeyanuraig: compound is tris(2-hydroxy ethyl! isocyanurate triaeryhue. fins isoeyaneritte Obmixiund is a mofsom etv and is available fiosit Sitrtoliter USA, LIT: under the trade name SR36S. The structure of isocyamirate, as: exemplified: by the following structure of trisi2-hydroxy ethyl): iSoeyanUiate triaciylate, lends itself to forming un ique crosslinks with vinyl cater that strengthen the imlymer lattice and resist: elevated temperature creep:

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

wherein

Ar is a. substituted or unsuhstituted aromatic radical with a. valence of at. least two, R is independently a substituted or uosubstituted di valent radical derived front alkyl or arylalkyh R5 is a. hydroxy substituted divalent radical derived from an alkyl radical, R4 is independently a vinyl carhoxy radical or a epoxy radical provided that lire ratio of a to the number of vinyl carhoxy R4 groups is. on average for .the composition, from about 0.4 as about 2,0, and rs is front 1 to 5. A particularly suitable vinyl ester compound is available front Reichhold Chemical Co. under the tradename Norpoi Dion Ver 9165. This product contains 64.5¾ by weight, of a vinyl ester having tire folio wing chemical formula, tnid 3515% by weight vinyl toluene.

where n is from 1 to about 5 and wherein the ratio ol ri to the ierminid vinyl units is, on average for the composition, from about (),4 Its about 23, ’Πιο first part A may include about 1-3()¾ by weight of the isocy ami rate compound, suitably about 1-20¾ by weight, or about 2-lf)%>:by weight; The first pari A may include about 3-50¾ by weight of the vinyl ester eompouiKl, suitably about 5-40¾ by weight, or about 8-30¾ 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, dtaerylate or hi&cryiate moitomer, and combinations thereof, 'The additional : monomer may constitute zero to about 4038 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 chesnieal {eroxslinking} maclion between the isoeyanurate: compound and the vinyl ester compound.

The first part A may also include about: 2()-30% by combined weight of one or more idlers, suitably about· 30-7051- by weight, or about 30-6()% 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. [-4%- by weight. Suitable thixotropic agents include without limitation formed silica, polyearboxyiic 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 stray also include minor amounts of catalysis, chain extenders, flame retardants, fragrances and the like. While a catalyst may be included iti the first part A, tins catalyst is typically not a free radical initiator of the type that is typically included in tbs second part. B. Exemplary catalysts and chain extenders useful in the first part A include without limitation diethylo!-p-tojuidine, tt-dodecy 1 mercaptan, and the like.

The second pan R may Include about: 5-88¾ by weight of a free radical initiator, suitably about i0-50% by weight, or tea 15-4()¾ by weight, Suitable free radical initiators include without limitation peroxide compounds,, tertiary amine compounds, aldehyde amine compounds. organic sulfony) chlorides, ami combinations thereof. One suitable i&ee radieid initiator is available froth Arkema Inc. «rider the trade name AT'R40, This product 'is. a mixture of 401%· by weight, dihtmzpyl peroxide, 40%· by weight di.butyl phthalate, and 21)% by weight ',vat.er.

The Second part B may also: Ineldde shout 3(:fd(.!%· by weight of a thickening agent, suitably about 2063% by Weight, or about 20-50% by weight. Suitable ifcicfcening agents include without, limitation nKtnosiliea, organic and inorganic elayspand other very fine, inert particulate materiais.

The second pan B may also ίη'£&Λ·$··^^ anidunf'of zes&fci aboht 50%: by weight, suitably about 10-45% by weight of about 15-40%: by weight. Suitable liquid carriers include water and organic solvents such as alcohols,. ethers and ketones. Additionally, the second part B ntity include sutvabie aiuounts of pigments,, fillers and the like. 'Fite first part A, and second part B stray be present in separate first and second capsules and may be combined in a single cartridge, slug of package of anchoring adhesive, lire first and second capsules can be formed of glass, plastic Or a membrane material. (fine 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 anti the second part B is contained within a second, smaller capsule,, and the second capsule is contained within die first capsule.

The cartridge, slug or package of anchoring adhesive tnay contain the first and second capsules and may have a narrow, elongated shape which fits easily into the borehole. When a too! is upd to drive an anchor pin into the borehole, the first, and second capsules rupture and die lust aud second parts A and B mix together, resulting in chemical reaction, erosshnking and adhesion 'between: the anchor pin and die inner sndaces oj.' the borehole. The anchoring adhesion of the invention forms a strong adhesive bond and exhibits high tensile and compressive strengths and minimal shrinkage. f-XAMPLES

Several experimental' anchoring: adhesives Wore fminulated using the ingredient;; listed in Table L

Table 1: Anchoring Adhesive mgr^dfents :

The foregoing ingredients were formulated into anchoring: adhesive compositions, with control compositions A.7 from Illinois: Tool Works lfte, and HY-150 ifonr HilUAitengesellsehaft, and experimental compositions At 4-1. A7+-2,. A7-f—3, ,,., through ΑΊ+--95, Physical properties of Compressive StretigLh, Tensile Strength, Tensile Modules and Shrinkage were measured for many of the aficlipff ng. adhOsi-VC PAinpoisliitthSi... using, die 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 Hid isoeyanurate compound (represented by ingredient PRO 12128) in combination with the vinyl ester compound (represented by ingredient RICiM dtS.5) generally had higher compression strengths and higher tensile strengths than the: anchoring adhesives that omitted one of both of these ingredients, and also exhibited excellent (low) shrinkage values.

tabife 2: Ai^hofinfi Adhesive-CompositionsΛίΐά fet liesulK

I

50 1 w r~ 50 rz /·'**> s Γ" * >

I

Compression Testing

Anchoring adhesive ingredients Were: jinxed and molded into cylindrical samples having a 1,23 ineijj· diameter and Cinch length,, to .approximately simulate the: size and shape of anchoring adhesive typically harmed m a borehole. Πιο samples: were cured for at least 24 hours at ambient conditions, and were: placed th a universal flat plate testing machine. The samples were compressed at a rate of 0.1 inch penhinote white the force and deflection were measured until1 the sample failed or the deflection: reached 0.4 inch. Tire maximum compressive force was recorded. ifeimifolMma

Dog-bone shaped samples were molded according to the shape illustMcd: 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. E i.OOin. I TOO in, B 0,35 in, F 1.25 in. j 0.25 m. C 0.25 in. G 2.00 in. K 7.00 m, D 154.6'·' H 125 in. L 0.25 in.

Hie lest samples were placed in the groups of a large Instfon 5586 tensile tester with a 2000-lb load cell adapter and pulled at a speed of 0.2 in. per minute. 1'he force and dcflcctioivwere measured until the sample failed. The maximum tensile force was recorded.

Shrinkage Testing ΊΤιο 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 ;md compared to the mold diameter. The shrinkage was calculated: according to the equation: .Shrinkage = (1-- v-- ) x 1.0()0-

While file emkxii-iiients of the invention described heroin, are presently preferred, various modificarions and improveineias 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 f all within file meaning arid range of equivalent* are intended to be entbraceef (herein.

Claims (20)

1 BE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:

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 E present in separate capsules; 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 comprises an isocyarmrate compound and a vinyl ester compound and the second part B comprises a .free radical initiator.

2. The method of Claim 1, where! a the adhesi ve bond exhibit s an adhesive strength of at least about 1500 psi, a compressive Strength Of at least about 10,000 psi, and a shrinkage not greater than about 1,6%.

3. The method of Claim I, wherein the substrate is one of concrete, steel and wood,

4, The method of Claim 1, -wherein the borehole is upside down,

5, The method of Claim 1, wherein the borehole is horizontal

6, The method of Claim 1,. wherein the isocyanurate compound is selected from the group consisting of compounds having the following eherniea! formula:

wherein each R. and R' is ally!» alkyl or aryl.

7. The method of Claim 1, wherein the isocyanurate compound is selected from the group consisting of isocyanurate acrylates, isocyanurate diacrylates, isocyanurate triacrylates, and combinations thereof.

8. The method of Claim 1, wherein the isocyanurate compound comprises tris (2-hydroxyethyl) isocyanurate triacrylate.

9. 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 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 an 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.

10. 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. Π, The method of Claim I. whereat the free radical initiator is selected from the group consisting of peroxide compounds, tertiary amine compounds, aldehyde amine compounds, organic suifonyl chlorides, and combinations thereof.

12, 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 partB; 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 comprises ah isoeyimurate compound and a vinyl ester compound and the second part δ comprises a free radical initiator; and the adhesive bond exhibits an adhesive strength of at least about 1500 psi, a compressive strength of at least about 10,000 psi, and a shrinkage not greater than about 1.0%.

13, The method of Claim 12, wherein the isocyanurate compound Is selected from the group consisting of isocyanurate acrylates, isocyanurate diacrylates, isocyanurate triacrylates, and combinations thereof.

14. The method of Claim 12, wherein the vloyl ester compound is selected from the group consisting of compounds haying 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 9,4 to about 2.0.

15. The method of Claim 13, wherein the vinyl ester compound is selected from the group consisting of compounds having the fol lowing chemical formula:

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

16. 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.

17. The method of Claim iS, 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.

18. 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 pari 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; the first part A comprising an. isoeyarmrate compound selected from the group consisting of isocyanurate acrylates, isocyanurate diaerylates, isocyanurate triacrylates, and combinations thereof, and a 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 sultbnyl chlorides, and combinations thereof.

19. The method of Claim IS, 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 snore additional monomers, and about 20-70% by weight of one or more fillers.

20. The method of Claim 1.9, wherein the first part A comprises about 2- 19% by weight of an isocyanurate triaeryiate. about 2-20¾¾ by weight of m additional acrylate monomer, about 8-30% by weight of the vinyl ester compound, about 2-29% by weight of an additional vinyl monomer, and about 30-70% by weight of one or mots fillers. 2L The method of Claim 19, wherein the second part B comprises about 5-80% by weight of the free radical initiator, about 29-80% by weight of a thickening agent, and zero to about 50% by weight of a Kqiud carrier.

22. The method of Claim 21, wherein the second pari B comprises about 10-59% 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.