Two part adhesive compositions and methods of making bonded articles

Abstract

A two part adhesive composition includes a first part and a second part. The first part comprises methyl methacrylate; a block copolymer of methyl methacrylate and a block copolymer of at least one of a C4-C9 alkyl acrylate or a C4-C9 alkyl methacrylate or a C2-4 hydroxyalkyl acrylate or a C2-4 hydroxyalkyl methacrylate; a free radical initiator including at least one of a peroxide initiator or a hydroperoxide initiator; and a radical inhibitor. The second part comprises methyl methacrylate; a crosslinking agent having two or more acrylate groups, methacrylate groups, or a combination thereof; an acrylic monomer including at least one of a phosphate group and a phosphonate group; and vanadyl acetylacetonate. A method of making a bonded article using the two part adhesive composition is also described.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 459,518, filed April 14, 2023, the disclosure of which is incorporated herein by reference in its entirety. Background Technology

[0003] Adhesives are known to be used to bond one substrate to another, such as bonding metal to metal, metal to plastic, plastic to plastic, and glass to glass. Structural adhesives are an attractive alternative to mechanical joining methods such as riveting or spot welding because they distribute load stress over a larger area rather than concentrating it at a few points. Structural adhesives also produce cleaner and quieter products because they dampen vibrations and reduce noise. Furthermore, structural adhesives can be used to bond a variety of materials, sometimes without requiring extensive surface preparation.

[0004] Certain curable acrylic adhesive compositions are disclosed in the following: U.S. Patent Nos. 5,206,288 (Gosiewski), 5,863,989 (Taguchi), 6,852,801 (Briggs), 8,067,500 (Hisha), 10,392,532 (Doe) and 11,098,225 (Sasaki), U.S. Patent Application Publication No. 2019 / 0136102 (Hurlburt), International Patent Application Publication No. WO2021 / 051257 (Sun), European Patent Application Publication No. 4130179 (published February 8, 2023), and Japanese Patent Application Publication Nos. 2014088458 (published May 15, 2014) and 2003 / 165806 (published June 10, 2003). Summary of the Invention

[0005] This disclosure provides a composition that can be used, for example, as a sealant or adhesive (e.g., a structural adhesive).

[0006] In one aspect, this disclosure provides a two-part adhesive composition having a first part and a second part. The first part comprises methyl methacrylate; the methyl methacrylate is mixed with C4-C9 alkyl acrylate or C4-C9 alkyl methacrylate or C4-C9 alkyl acrylate. 2-4 Hydroxyalkyl esters or C methacrylate 2-4The second part comprises a block copolymer of at least one of hydroxyalkyl esters; a free radical initiator, including at least one of a peroxide initiator or a hydroperoxide initiator; and a free radical inhibitor. The second part comprises methyl methacrylate; a crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof; an acrylic monomer comprising at least one of a phosphate group or a phosphonate group; and vanadium acetylacetonate.

[0007] In another aspect, this disclosure provides a two-part adhesive composition comprising a first part comprising methyl methacrylate; a poly(methyl methacrylate)-poly(((meth)acrylate) n-butyl)-poly(methyl methacrylate) triblock copolymer; cumene hydroperoxide; a free radical inhibitor; corn starch; and pyrolytic silica; and a second part comprising methyl methacrylate; methacrylic acid; a crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof; an acrylic monomer comprising at least one of phosphate groups or phosphonate groups; at least one elastomer; a free radical inhibitor; acetylacetonate vanadyl; wax; and pigment.

[0008] On the other hand, this disclosure provides a first portion of a two-part adhesive composition. The first portion comprises methyl methacrylate, methyl methacrylate with C4-C9 alkyl acrylate or C4-C9 alkyl methacrylate or C4-C9 alkyl acrylate. 2-4 Hydroxyalkyl esters or C methacrylate 2-4 A block copolymer of at least one of hydroxyalkyl esters, a free radical initiator containing at least one of a peroxide initiator or a hydroperoxide initiator, a free radical inhibitor, and starch.

[0009] In another aspect, this disclosure provides a second portion of the two-part adhesive composition. The second portion comprises a monomer and vanadium acetylacetonate, wherein the monomer comprises: methyl methacrylate; a non-cyclic crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof; an acrylic monomer comprising at least one of phosphate groups or phosphonate groups; methacrylic acid; and combinations thereof.

[0010] In another aspect, this disclosure provides a method for manufacturing an adhesive article. The method includes combining a first portion and a second portion of the two-part adhesive composition disclosed herein with a free radical initiator to provide an adhesive; applying the adhesive to at least one of a first substrate or a second substrate; adhering the first substrate and the second substrate using the adhesive; and allowing the adhesive to at least partially cure to manufacture the adhesive article.

[0011] In another aspect, this disclosure provides an article of articles bonded with the two-part composition disclosed herein and / or manufactured by the methods disclosed herein.

[0012] As used in this article:

[0013] The term "alkyl group" and the prefix "alkane" have only C-C and CH bonds and include straight-chain, branched, and cyclic groups. In some embodiments, unless otherwise specified, the alkyl group has up to 30 carbons (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6, or 5 carbons). The cyclic group can be monocyclic or polycyclic and, in some embodiments, has 3 to 10 cyclic carbon atoms and other alkyl substituents;

[0014] As used herein, “aryl” and “aromatic” include carbocyclic aromatic rings or ring systems, for example, having one, two, or three rings and optionally containing at least one heteroatom (e.g., O, S, or N) in the ring, which is optionally substituted by up to five substituents, including one or more alkyl groups (e.g., methyl or ethyl) having up to four carbon atoms, alkoxy groups, halogen groups (i.e., fluorine, chlorine, bromine, or iodine), hydroxyl groups, or nitro groups having up to four carbon atoms, examples of which include phenyl, naphthyl, biphenyl, fluorenyl, furanyl, thiophene, pyridinyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrroleyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, and thiazolyl.

[0015] The term "acrylic" refers to acrylic and methacrylic polymers, oligomers, and monomers.

[0016] "Curement" refers to the manufacture of polymer chains from one or more monomers; and

[0017] The term "(meth)acryl" refers to acryl (also known in the art as acryloyl and acrylyl) and / or methacryl (also known in the art as methacryloyl and methacrylyl)).

[0018] Terms such as “a,” “an,” “the,” and “the” are not intended to refer to a single entity, but rather to encompass a general category of specific examples that can be used to illustrate the point. The terms “a,” “an,” “the,” and “the” are used interchangeably with the term “at least one (kind).”

[0019] The phrase "including at least one of..." followed by a list means including any item in the list or any combination of two or more items in the list.

[0020] In this document, the term "comprising" and its variations are not intended to be limiting wherever they appear in the specification and claims. Such terms are to be understood as implying inclusion of the stated elements or groups of elements, but not excluding any other elements or groups of elements. The phrase "consisting of" means including and limited to what follows the phrase "consisting of". Thus, the phrase "consisting of" indicates that the listed elements are required or mandatory, and that no other elements may be present. Any element or combination of elements referenced in this specification in open-ended language (e.g., including and its derivatives) is considered to be additionally referenced in closed-ended language (e.g., consisting and its derivatives).

[0021] The term "crosslinking" refers to linking polymers together through covalent chemical bonds (usually via crosslinking molecules or groups) to form a network polymer. Crosslinked polymers are generally characterized by insolubility, but can be swollen in the presence of suitable solvents. The term "crosslinking" includes partial crosslinking.

[0022] "Open time" can be understood as the amount of time before the adhesive becomes too hard to bond well to the substrate. More specifically, open time is defined as the time during which a mixed adhesive remains unbonded and still achieves 80% or more of the lap shear strength that would be achievable if the adhesive were mixed and immediately bonded between two adherends.

[0023] Unless otherwise specified, all numerical ranges include their endpoints and the non-integer values ​​between them (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0024] The features and advantages of this disclosure will be further understood upon consideration of the specific embodiments and the appended claims. Attached Figure Description

[0025] The accompanying drawings are generally shown by way of example, but are not limited to the various embodiments discussed in this disclosure.

[0026] Figure 1 This is a graph showing the energy storage modulus versus time for Examples M-2, M-3, M-4, M-6, M-8, and M-9, as well as Explanatory Example M-1. Detailed Implementation

[0027] This disclosure provides a two-part adhesive composition. The first and second parts comprise methyl methacrylate. In some embodiments, based on the total weight of the first part of the two-part adhesive composition, the first part comprises 25 to 65 wt%, 35 to 55 wt%, or 40 to 50 wt% of methyl methacrylate. In some embodiments, based on the total weight of the second part of the two-part adhesive composition, the second part comprises 20 to 60 wt%, 25 to 50 wt%, or 30 to 45 wt% of methyl methacrylate. Methyl methacrylate is commercially available from several suppliers, including Evonik Performance Materials GmbH under the trade name “VISIOMER MMA”.

[0028] The first portion of the two-part adhesive composition of this disclosure comprises a free radical initiator, which includes at least one of a peroxide initiator or a hydroperoxide initiator. Examples of free radical initiators that can be used to practice the free radical initiators of this disclosure include cumene hydroperoxide, p-menthane hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, diisopropylbenzene disperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, tert-butyl peracetate, and tert-butyl peroxybenzoate. In some embodiments, the free radical initiator is present in an amount of 0.1% to 3.5% by weight, 0.5% to 3.5% by weight, or 1% to 3% by weight, based on the total weight of the first portion.

[0029] In some embodiments, the two-part adhesive composition is free of acyl chlorides, or contains no more than 0.05% by weight of acyl chlorides based on the total weight of the two-part adhesive composition. In some embodiments, the first part of the two-part adhesive composition is free of acyl chlorides, or contains no more than 0.05% by weight of acyl chlorides based on the total weight of the first part. Acyl chlorides as desired adjuvant initiators are reported in U.S. Patent No. 10,392,532 (Doe). Examples of acyl chlorides include sulfonyl chlorides, such as p-toluenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, 4,4'-oxobis(benzenesulfonyl chloride), and diacyl chlorides.

[0030] The second portion of the two-part adhesive composition disclosed herein comprises vanadium acetylacetonate. Vanadium acetylacetonate is also known as "vanadium bis(2,4-pentanedione)oxide (IV)," "vanadium acetylacetonate (IV)," and VO(acac)₂. In some embodiments, vanadium acetylacetonate is present in amounts of 0.05 wt% to 2 wt%, 0.25 wt% to 1.5 wt%, or 0.5 wt% to 1 wt% based on the total weight of the second portion. When the first and second portions of the two-part adhesive composition are combined, vanadium reduces hydroperoxide or peroxide and is oxidized from vanadium +4 to vanadium +5.

[0031] In some embodiments, the second part is substantially free of other reducing agents and / or accelerators. In some embodiments, the second part is substantially free of thioureas (e.g., pyridylthiourea), amines (e.g., primary amines, secondary amines, tertiary amines, pyridines such as 3,5-diethyl-1,2-dihydro-1-phenyl-2-propylpyridine, hydroxyethyltoluidine, N,N-dimethyl-4-toluidine, imidazoles, and quinolines), aldehyde-amine condensates, and other metal salt reducing agents (e.g., cobalt acetylacetonate, copper acetylacetonate, copper phthalocyanine, zinc acetylacetonate, iron acetylacetonate, titanium acetylacetonate, vanadium (III) acetylacetonate, vanadium (III) pentylene diketone, vanadium (III) naphthenate, vanadium (IV) naphthenate, copper naphthenate, and copper salicylate). In the context of this document, "substantially free of" means amounts less than 0.05 wt%, 0.01 wt%, 0.005 wt%, or 0.001 wt% based on the total weight of the second part, and includes 0 wt%.

[0032] The first portion of the two-part adhesive composition of this disclosure comprises a free radical inhibitor. In some embodiments, the second portion of the two-part adhesive composition of this disclosure comprises a free radical inhibitor. Examples of suitable free radical inhibitors include benzoquinone, naphthoquinone, butylated hydroxytoluene (BHT), hydroquinone, p-methoxyhydroquinone (MEHQ), and combinations thereof. In some embodiments, the free radical inhibitor is present in an amount of 0.05 wt% to 2.0 wt%, 0.25 wt% to 2.0 wt%, or 0.5 wt% to 1.5 wt% based on the total weight of the first portion. In some embodiments, the free radical inhibitor is present in the first portion in an amount of at least half the weight of the free radical initiator. In some embodiments, the free radical inhibitor is present in the second portion in an amount of 0.05 wt% to 1.0 wt%, 0.1 wt% to 0.5 wt%, or 0.05 wt% to 0.25 wt% based on the total weight of the second portion. Higher amounts of free radical inhibitor compared to the second portion are generally used to prevent gelling in the first portion, which comprises peroxide or hydroperoxide.

[0033] The first portion of the two-part adhesive composition disclosed herein comprises a block copolymer. The block copolymer contains hard segments and soft segments. The soft segments and the amorphous hard segments form an amorphous phase, and a portion of the hard segments crystallizes to form crystalline microdomains that can serve as physical crosslinking domains. Such block copolymers are commonly referred to as thermoplastic elastomers. In some embodiments, the block copolymer in the first portion is an acrylic copolymer, including poly(methyl methacrylate) (PMMA) hard segments. The soft segments of the block copolymer may be formed from monomers of acrylates or methacrylates, such as those having C4-C9 alkyl side chains, or mixtures thereof. Examples of monomers that can be used to form the second block include n-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, acrylates of the aforementioned methacrylates, and mixtures thereof. In some embodiments, monomers that can be used to form the soft segments include acrylic acid C. 2-4 Hydroxyalkyl esters or C methacrylate 2-4 Hydroxyalkyl esters, such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropyl methacrylate.

[0034] In some embodiments, the block copolymer is a triblock copolymer of methyl methacrylate / C4-C9 alkyl acrylate or C4-C9 alkyl methacrylate / methyl methacrylate. In some embodiments, the block copolymer is made of PMMA and poly(butyl acrylate) or poly(butyl methacrylate), and is a poly(methyl methacrylate)-poly((n-butyl methacrylate))-poly(methyl methacrylate) triblock copolymer. In some embodiments, the block copolymer contains about 70% PMMA and 30% poly(n-butyl acrylate). The block copolymer may have a number average molecular weight of up to about 120,000 g / mol. Suitable commercially available materials for use in block copolymers include those from Kuraray, Chiyoda City, Japan, under the trade name “ABC KURARITY LA2330”, and those from Arkema, King of Prussia, Pa., under the trade name “NANOSTRENGTH”.

[0035] In some embodiments, based on the total weight of the first portion of the two-part adhesive composition, the first portion comprises 20 to 60 wt%, 25 to 50 wt%, or 30 to 45 wt% of block copolymers, including any of those block copolymers defined above in any of its embodiments.

[0036] In some embodiments, the second portion of the two-part adhesive composition comprises a block copolymer as defined above in any of its embodiments. However, the second portion may additionally or alternatively comprise other elastomers (e.g., acrylic core / shell polymers; styrene-butadiene / methacrylate core / shell polymers; and acrylonitrile-butadiene rubber). As shown in the following examples, other elastomers suitable for the second portion are not suitable for the first portion because they cause the first portion to gel upon exposure to a temperature of 120℉ (49°C).

[0037] Various elastomers are suitable for the second part, provided that the elastomer is a polymeric material that exhibits rubber-like elasticity at room temperature. Examples of elastomers suitable for the second part include various synthetic rubbers, such as the aforementioned acrylic copolymers, methyl methacrylate-butadiene-styrene copolymers (MBS), acrylonitrile-styrene-butadiene copolymers, linear polyurethanes, acrylonitrile-butadiene rubber, styrene-butadiene rubber, styrene-butadiene-styrene rubber, polystyrene / EPDM (ethylene / propylene / conjugated diene copolymer), chloroprene rubber, butadiene rubber, and natural rubber. Elastomers suitable for the second part can be core-shell graft copolymers having a "rubber-like" core and a "hard" shell. Examples of useful core-shell graft copolymers are those in which a "hard" monomer (such as styrene, acrylonitrile, or methyl methacrylate) is grafted onto a rubber-like core made of a polymer of a "soft" or "elastic" monomer (such as butadiene or ethyl acrylate). Based on the total weight of the second part, the amount of elastomer present in the second part may be 5% to 35% by weight, 10% to 35% by weight, or 15% to 30% by weight.

[0038] The second portion of the two-part adhesive composition of this disclosure further comprises an acrylic monomer containing a phosphate ester group or a phosphonate ester group. Useful acrylic monomers containing phosphate ester groups or phosphonate ester groups include ethylene glycol methacrylate phosphates (e.g., available under the trade names “MIRAMER SC1400” and “MIRAMER SC1400A” from Miwon North America, Exton, Pennsylvania, and under the trade name “EBACRYL 168” from Allnex, Alpharetta, GA) and phosphates of poly(propylene glycol) monomethacrylates (e.g., available under the trade name “SIPOMER PAM” from Solvay Novecare, Cranbury, NJ). Vinylphosphonic acid may also be useful. In some embodiments, the second portion of the two-part adhesive composition of this disclosure further comprises an acrylic monomer containing a phosphate ester group. Based on the total weight of the second part, phosphonate or phosphate-functionalized acrylic monomers may be present in the second part, for example, at most 5 wt%, 4 wt%, or 3 wt%. In some embodiments, based on the total weight of the second part, phosphonate or phosphate-functionalized acrylic monomers are present in an amount of at least 0.5 wt%, 1 wt%, 1.5 wt%, or 1.9 wt%. Such monomers can be used, for example, to enhance adhesion to metal substrates.

[0039] It has now been found that changing the weight percentage of acrylic monomers containing phosphate or phosphonate groups in the formulation has a surprising effect on the curing speed and "open time" of the adhesive; increasing the amount of such monomers in the second part can decrease the curing speed and increase the open time. In some embodiments, the acrylic monomers containing phosphate or phosphonate groups are present in an amount of 1.85% to 2.15% by weight based on the total weight of the second part. In these embodiments, after mixing the first and second parts, the adhesive typically and advantageously has an open time of at least about 15 to 20 minutes. In some embodiments, the acrylic monomers containing phosphate or phosphonate groups are present in an amount of 2.25% to 3% by weight based on the total weight of the second part. In these embodiments, after mixing the first and second parts, the adhesive typically and unexpectedly has an open time of at least about 40 to 60 minutes. In the absence of acrylic monomers containing phosphate or phosphonate groups, the adhesive typically has an open time of less than five minutes after mixing the first and second parts. These effects can... Figure 1This was observed in the rheological data shown. In the curves, the opening time can be considered as the time until the slope increases. This time is similar to the opening time determined using the lap shear assessment described herein. The opening time is sometimes referred to as the working time.

[0040] The second portion of the two-part adhesive composition comprises a crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof. In some embodiments, both the first and second portions of the two-part adhesive composition comprise a crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof. In some embodiments, the second portion of the two-part adhesive composition comprises a crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof, but the first portion does not comprise such a crosslinking agent. Suitable crosslinking agents having two or more acrylate groups, methacrylate groups, or combinations thereof include diacrylates of glycols, such as ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, butane-1,3-dimethyl diacrylate, pentanediol diacrylate, hexanediol diacrylate (including 1,6-hexanediol diacrylate), heptahydrate diacrylate, octanediol diacrylate, nonanediol diacrylate, decanediol diacrylate, dimethacrylate of any of the foregoing diacrylates, and combinations thereof. Further suitable crosslinking agents include polyol polyacrylates, such as glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate, dipentaerythritol tetraacrylate, methacrylates of the aforementioned acrylates, and combinations thereof. Further suitable crosslinking agents include polyfunctional acrylate oligomers comprising two or more acrylate groups. Polyfunctional acrylate oligomers may be urethane acrylate oligomers, epoxy acrylate oligomers, polyester acrylates, polyether acrylates, polyacrylate acrylates, methacrylates of any of the aforementioned acrylates, or combinations thereof. In some embodiments, the crosslinking agent is a noncyclic crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof. Noncyclic means that the crosslinking agent does not contain any aromatic or non-aromatic rings. For example, a noncyclic crosslinking agent does not contain aromatic rings, non-aromatic carbocyclic rings, or heterocyclic rings (i.e., rings including N, O, or S as ring members) of any size. Based on the total weight of the second portion, the amount of crosslinking agent present in the second portion may be 5% to 35% by weight, 10% to 35% by weight, or 15% to 30% by weight. Based on the total weight of the first portion, these amounts may each be a useful amount of crosslinking agent in the first portion. In some embodiments, the first portion does not contain a crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof.

[0041] In some embodiments, the second portion of the two-part adhesive composition comprises an acrylic monomer containing a carboxylic acid group. In some embodiments, both the first and second portions of the two-part adhesive composition comprise acrylic monomers containing carboxylic acid groups. In some embodiments, the second portion of the two-part adhesive composition comprises an acrylic monomer containing a carboxylic acid group, but the first portion does not contain an acrylic monomer containing a carboxylic acid group. In some embodiments, the acrylic monomer containing a carboxylic acid group is present in the second portion in amounts of 5% to 20% by weight, 5% to 15% by weight, or 7.5% to 12.5% ​​by weight, based on the total weight of the second portion. These amounts may each be a useful amount of acrylic monomer containing a carboxylic acid group in the first portion based on the total weight of the first portion. In some embodiments, the first portion does not contain an acrylic monomer containing a carboxylic acid group. Examples of suitable acrylic monomers containing a carboxylic acid group include methacrylic acid, acrylic acid, β-acryloyloxyethyl hydrosuccinate, and β-methacryloyloxyethyl hydrosuccinate. Many acrylic monomers containing carboxylic acid groups are commercially available, such as methacrylic acid, available under the trade name "VISIOMER GMAA" from Evonik Performance Materials GmbH, and β-methacryloyloxyethyl hydrosuccinate, available under the trade name "NK ESTER SA" from Shin-Nakamura Co. Ltd., Arimoto, Japan. In some embodiments, the acrylic monomer containing the carboxylic acid group is at least one of acrylic acid or methacrylic acid. In some embodiments, the acrylic monomer containing the carboxylic acid group is methacrylic acid.

[0042] In some embodiments, at least one of the first or second portion of the two-part adhesive composition comprises an additional acrylic monomer, such as any of the acrylic monomers described below. In some embodiments, the second portion of the two-part adhesive composition comprises an additional acrylic monomer, but the first portion does not contain an additional acrylic monomer. In some embodiments, the additional acrylic monomer is present in an amount of at least 5% by weight and at most 25% by weight, 20% by weight, 15% by weight, or 10% by weight, respectively, based on the total weight of the second or first portion.

[0043] Examples of other suitable acrylic monomers include those containing hydroxyl groups, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and 3-hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, caprolactone mono(meth)acrylate (available under the trade name "SR-495B" from Sartomer) and other poly(e-caprolactone) mono[2-(meth)acryloyloxyethyl] esters, poly(e-caprolactone) mono[2-acryloyloxyethyl] esters, 2-hydroxy-3-alkoxy methacrylate, 2-hydroxy-3-alkoxy acrylate, and polyethylene glycol monoacrylate and methacrylate. Many acrylic monomers containing hydroxyl groups are commercially available, such as 2-hydroxyethyl methacrylate (available under the trade names "VISIOMERHEMA 97" and "VISIOMER HEMA 98" from Evonik Performance Materials, Inc.), hydroxypropyl methacrylate (available under the trade names "VISIOMER HPMA 97" and "VISIOMER HPMA 98" from Evonik Performance Materials, Inc.), ultra-high purity 2-hydroxyethyl methacrylate (available under the trade name "VISIOMER UHP HEMA" from Evonik Performance Materials, Inc.), polypropylene glycol monomethacrylate (available under the trade name "MIRAMER M1051" from Amgen North America, Exton, Pennsylvania), and CH2=CHC(O)O(CH2CH2O). 7-9 H (e.g., purchased under the trade name "BLEMMER" from Nippon Oil & Fats Company, Tokyo, Japan). Part I, Part II, or both may also be free of monomers containing hydroxyl groups, including any of the monomers mentioned above.

[0044] Other suitable examples of acrylic monomers include at least one of alkyl acrylates or alkyl methacrylates. The alkyl group of the alkyl acrylate or alkyl methacrylate may be straight-chain, branched, or cyclic (including polycyclic) and may have 2 to 14, 2 to 12, or 2 to 10 carbon atoms. Examples include lauryl methacrylate and isobornyl methacrylate. Such monomers are available from a variety of commercial sources, such as isobornyl acrylate purchased under the trade name “SR506” from Sartoma or under the trade name “VISIOMER IBOA” from Evonik Performance Materials, isobornyl methacrylate purchased under the trade name “SR423A” from Sartoma or under the trade name “VISIOMER IBOMA” from Evonik Performance Materials, and lauryl methacrylate purchased under the trade name “LMA 1214 F” from BASF, Florham Park, NJ. Part 1, Part 2, or both may also be free of straight-chain, branched, or cyclic (including polycyclic) alkyl acrylates and alkyl methacrylates having 2 to 14, 2 to 12, or 2 to 10 carbon atoms.

[0045] Other suitable examples of acrylic monomers include 2-phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, alkoxylated lauryl (meth)acrylate, alkoxylated phenol (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, caprolactone (meth)acrylate, cyclic (meth)acrylate trimethylolpropane methyl acetal, ethylene glycol methyl ether (meth)acrylate, ethoxylated phenol (meth)acrylate nonyl acrylate, isodecanyl (meth)acrylate, isooctyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), tetrahydrofurfuryl (meth)acrylate, tridecyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, allyl (meth)acrylate, and (meth)acrylate. Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, n-dodecyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxypropyl acrylate or 3-ethoxypropyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, glycidyl acrylate, N-(2-(2-oxo-1-imidazolyl)ethyl)methacrylamide and methacryloylaminoethylvinyl urea (“MAEEU”) (available under the trade name “SIPOMERWAM II” from Solvay Specialty Polymers USA, LLC) and combinations thereof. Part I, Part II, or both may also be free of any of these monomers.

[0046] In some embodiments, at least one of the first or second portion of the two-part adhesive composition of this disclosure may contain other components that can be used, for example, in sealant and adhesive compositions. For example, at least one of the first or second portion may include at least one of the following: plasticizers (e.g., aliphatic and aromatic hydrocarbons, alkyl esters, alkyl ethers, aryl esters, and aryl ethers), tackifiers, corrosion inhibitors, UV stabilizers, antioxidants, flame retardants, thixotropic agents (such as pyrolytic silica), dyes, pigments (e.g., iron oxide, brick dust, carbon black, and titanium dioxide), reinforcing agents (e.g., silica, magnesium sulfate, calcium sulfate, and beryllium aluminum silicate), clays (such as bentonite), other suitable fillers (e.g., glass beads, talc, and calcium metasilicate), dispersants, wetting agents, waxes, adhesion promoters (e.g., silane coupling agents), antistatic agents, thermally and / or electrically conductive particles, foaming agents, and hollow polymers or ceramic microspheres (e.g., glass bubbles). In some embodiments, at least one of the first or second portion of the two-part adhesive composition of this disclosure contains fillers. Examples of fillers that can be used in some embodiments of the two-part compositions of this disclosure include at least one of the following: microfibrillated polyethylene, pyrolytic silica, talc, wollastonite, aluminosilicate clay (e.g., halloysite), phlogopite, calcium carbonate, kaolin, metal oxides (e.g., barium oxide, calcium oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide), and nanoparticle fillers (e.g., nano-silica, nano-zirconia). These components may be present in any suitable amount in at least one of the first or second parts. The first part, the second part, or both may also be free of any of these components.

[0047] In some embodiments, the two-part adhesive composition is free of silsesquioxane, or contains no more than 0.05% by weight of silsesquioxane based on the total weight of the two-part adhesive composition. In some embodiments, the two-part adhesive composition is free of polyhedral oligomeric silsesquioxane, or contains no more than 0.05% by weight of polyhedral oligomeric silsesquioxane based on the total weight of the two-part adhesive composition.

[0048] In some embodiments, at least one of the first or second portion comprises pyrolytic silica. In some embodiments, the pyrolytic silica is present in the first portion in amounts of 1% to 10% by weight, 2% to 8% by weight, or 3% to 7% by weight, based on the total weight of the first portion. If present in the second portion, these amounts of pyrolytic silica may each be used in the second portion based on the total weight of the second portion. In some embodiments, at least one of the first or second portion comprises a pigment, which may be any of the pigments described above. In some embodiments, the second portion comprises carbon black. Any suitable amount of pigment (in some embodiments, carbon black) may be useful. Useful levels of pigment or carbon black include up to 2% by weight, 1.5% by weight, 1% by weight, or 0.5% by weight based on the total weight of the second portion. In some embodiments, the second portion comprises glass beads. Any suitable amount of glass beads may be useful, including up to 5% by weight, 3% by weight, 2% by weight, or 1% by weight based on the total weight of the second portion.

[0049] In some embodiments, the first portion of the two-part adhesive composition of this disclosure further comprises starch. In some embodiments, both the first and second portions of the two-part adhesive composition comprise starch. In some embodiments, the first portion of the two-part adhesive composition comprises starch, but the second portion does not. The starch may be natural starch or treated starch. Examples of suitable natural starches include corn, cassava, rice, wheat, soybean, pea, potato, sweet potato, sago, and amaranth starch. Examples of treated starches include those obtained by chemical or physical modification of any of the natural starches described above. Examples of treated starches obtained by chemical modification include etherified starch, esterified starch, cross-linked starch, dextrin, and oxidized starch. Examples of physical modification of starch include electromagnetic radiation treatment, radio frequency treatment, and hydrothermal treatment. In some embodiments, the starch is corn starch. In some embodiments, starch is present in the first portion in an amount of 5% to 20% by weight, 5% to 15% by weight, or 7.5% to 12.5% ​​by weight, based on the total weight of the first portion. These quantities can each be used individually as a useful amount of starch in the second part based on the total weight of the second part. In some embodiments, the starch used in practicing this disclosure may have an average particle size of 1 micrometer (μm) to 200 μm or 5 μm to 100 μm.

[0050] In some embodiments, the second portion of the two-part adhesive composition of this disclosure further comprises a wax. In some embodiments, both the first and second portions of the two-part adhesive composition comprise a wax. In some embodiments, the second portion of the two-part adhesive composition comprises a wax, but the first portion does not. Wax can be used, for example, to aid surface curing of the acrylic adhesive composition upon contact with air, and to reduce the evaporation of methyl methacrylate. The wax can be any common wax known in the art. Examples of suitable waxes include paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, Fischer-Tropsch wax, oxidized Fischer-Tropsch wax, functionalized wax, fatty amide wax, and any combination thereof. Examples of commercially available waxes include those from Sasol Wax under the trade name “SASAOLWAX H1”, Honeywell under the trade names “AC-400” and “AC-575P”, Marcus Oil Company under the trade name “MC-400”, Eastman Chemical under the trade name “EPOLENE C-18”, Sinopharm under the trade name “Wax 58”, and BYK USA Inc. under the trade name “BYK-S782”. Based on the total weight of the second part, the wax may be present in the second part in amounts, for example, at least 0.5% by weight, 1% by weight, 1.5% by weight, or 1.9% by weight, and at most 5% by weight, 4% by weight, or 3% by weight. If the wax is included in the first part, these amounts may also be used in the first part.

[0051] This disclosure provides a first portion of a two-part adhesive composition. The first portion comprises methyl methacrylate, methyl methacrylate with C4-C9 alkyl acrylate or C4-C9 alkyl methacrylate or C4-C9 alkyl acrylate. 2-4 Hydroxyalkyl esters or C methacrylate 2-4The first component comprises a block copolymer of at least one of hydroxyalkyl esters, a free radical initiator containing at least one of a peroxide initiator or a hydroperoxide initiator, a free radical inhibitor, and starch. Each of these components may be any of the solvents described above in any of its embodiments. In some embodiments, the block copolymer is a poly(methyl methacrylate)-poly(((meth)acrylate) n-butyl)-poly(methyl methacrylate) triblock copolymer. In some embodiments, the free radical initiator is cumene hydroperoxide. In some embodiments, the free radical initiator is present in an amount of 0.5% to 3.5% by weight based on the total weight of the first component, and the free radical inhibitor is present in an amount of at least half the weight of the free radical initiator. In some embodiments, the starch is corn starch. In some embodiments, typically and advantageously, the first component is stabilized at 120℉ (49°C) for at least one month, as shown in the examples below. The first component may be mixed with a second component as disclosed herein. The first component may also be usefully combined with different compositions containing different reducing agents to form an adhesive composition. Suitable reducing agents include any of the amines, thioureas, and other metal salts mentioned above, as well as combinations thereof.

[0052] This disclosure provides a second portion of a two-part adhesive composition. The second portion comprises a monomer and vanadium acetylacetonate. The monomer comprises: methyl methacrylate; a noncyclic crosslinker having two or more acrylate groups, methacrylate groups, or combinations thereof; an acrylic monomer comprising at least one of phosphate groups or phosphonate groups; and methacrylic acid. The noncyclic crosslinker having two or more acrylate groups, methacrylate groups, or combinations thereof and the acrylic monomer comprising at least one of phosphate groups or phosphonate groups may be any of those described above in any of its embodiments. It should be understood that while other components may be present in the second portion, other monomers may not be present in the second portion when the monomer is referred to as being composed of the above-listed components. In some embodiments, the second portion also comprises an elastomer as described above in any of its embodiments. In some embodiments, the second portion is substantially free of thiourea, amines, and other metal salt reducing agents. In some embodiments, the acrylic monomer comprising at least one of phosphate groups or phosphonate groups is present in an amount ranging from 1.85% by weight to 2.15% by weight, based on the total weight of the second portion. In some embodiments, the acrylic monomer containing phosphate ester groups or phosphonate ester groups is present in an amount of 2.25% to 3% by weight, based on the total weight of the second portion. The second portion may be mixed with the first portion as disclosed herein. The second portion may also be effectively combined with different compositions containing different oxidants to form adhesive compositions.

[0053] The first and second parts of a two-part composition can be combined in any suitable volume ratio. For example, the first and second parts can be combined in volume ratios ranging from about 5:1 to about 1:5, about 2:1 to about 1:2, about 1.5:1 to 1:1.5, or about 1:1. Manufacturing two-part free radical curable adhesive compositions having approximately equal volumes of first and second parts is challenging because such compositions typically require the inclusion of monomers as free radical initiators in the same part.

[0054] The first and second portions can be located in any suitable system or kit for containing, mixing, and dispensing the first and second portions. This system can be suitable for large-scale industrial applications or small-scale applications. Any system may include a first chamber and a second chamber for storing the respective first and second portions. The dimensions of the chambers may be set to suit any application and formed of plastic, metal, or any other suitable material. A dispenser may be adapted to receive the first and second portions and dispense the mixture of the first and second portions onto a substrate. The dispenser may be used to facilitate mixing of the first and second portions, or a mixing chamber may be located upstream of the dispenser and in fluid communication with the first and second chambers. The mixing chamber may be adapted to rotate to facilitate mixing, or the mixing chamber may include multiple baffles to induce rotation of the first and second portions.

[0055] To facilitate movement of the first and second portions, the system may include elements such as one or more plungers or one or more pumps. One or more plungers may be used in a handheld system. In these embodiments, a user may push one or both plungers between at least a first position and a second position to force the first and second portions through the system. If one plunger is present, the first and second portions can be dispensed in equal volumes or a predetermined volume ratio.

[0056] Pumps can be used in industrial applications where a large or continuous supply of a first and a second portion is dispensed. These systems may include one or more pumps in fluid communication with the first and second chambers. The one or more pumps may be located downstream of the first and second chambers, but upstream of the mixing chamber. In embodiments of a system in which two pumps are in fluid communication with the respective first and second chambers, the pumps may be adapted or controlled to pump equal volumes of the first and second portions, or to pump different amounts of the portions according to a predetermined volume ratio.

[0057] The compositions disclosed herein can be used, for example, to bond a first substrate to a second substrate to provide an adhesive article. Therefore, this disclosure provides a method of manufacturing an adhesive article. The method includes combining a first portion and a second portion of the two-part adhesive composition disclosed herein to provide an adhesive; applying the adhesive to at least one of the first or second substrates; adhering the first and second substrates using the adhesive; and at least partially curing the adhesive to manufacture the adhesive article. Many types of substrates can be bonded to the compositions disclosed herein, such as metals (e.g., stainless steel or aluminum), glass (e.g., which may be coated with indium tin oxide), polymers (e.g., plastics, rubber, thermoplastic elastomers, or thermosetting materials), or composite materials. Composite materials can be made from any two or more constituent materials with different physical or chemical properties. When components are combined to manufacture composite materials, materials with properties different from those of the individual components are generally obtained. Some examples of available composite materials include fiber-reinforced polymers (e.g., carbon fiber-reinforced epoxy resins and glass-reinforced plastics), metal matrix composites, and ceramic matrix composites. Useful adhesive polymer substrates include polymers such as acrylonitrile butadiene styrene (ABS), polycarbonate (PC), PC / ABS blends, polyvinyl chloride (PVC), polyester, polyurethane (PUR), thermoplastic elastomers (TPE), polystyrene, poly(methyl methacrylate) (PMMA), polyvinyl chloride (PVC), and combinations thereof. The substrate may also include a metallic coating on such polymers. The compositions disclosed herein can be used, for example, to bond electronic products as well as automotive and aerospace components.

[0058] After at least partial curing, a crosslinked composition is typically obtained, and if fully cured, it can be suitable as a structural adhesive for bonding two adherends. In such applications, the composition is typically sandwiched between the adherends and cured at least partially; for example, sufficient to achieve at least the desired level of bond strength.

[0059] While it is impractical to list specific curing temperatures applicable to all situations, generally speaking, suitable temperatures are in the range of about 23°C to about 200°C. In some embodiments, advantageously, the composition can be cured at room temperature (e.g., 23°C to 30°C) for, for example, at least 60 minutes, 90 minutes, 120 minutes, 6 hours, 12 hours, 24 hours, 48 ​​hours, or 72 hours to at least partially cure the composition.

[0060] As shown in the examples below, the two-part adhesive composition of this disclosure can be cured at room temperature to provide an adhesive with a glass transition temperature in the range of 125°C to 155°C, 130°C to 150°C, or 140°C to 145°C. In many advantageous embodiments, the adhesive, made from the first and second parts of the mixed two-part adhesive composition, is bonded to worn aluminum and provides a significant lap shear strength of at least 2000 psi. The adhesive bonded portion is remarkably resistant to high temperatures and freezing, retaining 90% of the lap shear strength, as shown in the examples below. The adhesive can bond a wide variety of materials, including metals and fiber-reinforced plastics, with good bond strength, for example, even at high temperatures and in some embodiments in water or high humidity.

[0061] Some implementation schemes disclosed herein

[0062] In a first embodiment, this disclosure provides a two-part adhesive composition comprising a first part comprising methyl methacrylate; methyl methacrylate and C4-C9 alkyl acrylate or C4-C9 alkyl methacrylate or C4-C9 alkyl acrylate 2-4 Hydroxyalkyl esters or C methacrylate 2-4The disclosure provides a block copolymer of at least one of hydroxyalkyl esters; a free radical initiator, including at least one of a peroxide initiator or a hydroperoxide initiator; and a free radical inhibitor; a second portion comprising methyl methacrylate; a crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof; an acrylic monomer comprising at least one of a phosphate group or a phosphonate group; and acetylacetonate vanadyl. In a second embodiment, the disclosure provides a two-part adhesive composition according to the first embodiment, wherein the first portion further comprises starch. In a third embodiment, the disclosure provides a two-part adhesive composition according to the second embodiment, wherein the starch is corn starch. In a fourth embodiment, the disclosure provides a two-part adhesive composition according to any one of the first to third embodiments, wherein the block copolymer is a poly(methyl methacrylate)-poly(((meth)acrylate) n-butyl)-poly(methyl methacrylate) triblock copolymer. In a fifth embodiment, the disclosure provides a two-part adhesive composition according to any one of the first to fourth embodiments, wherein the free radical initiator is a hydroperoxide initiator, and wherein the hydroperoxide initiator is cumene hydroperoxide. In a sixth embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to fifth embodiments, wherein the second part further comprises an elastomer. In a seventh embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to sixth embodiments, wherein the second part further comprises at least one of acrylic acid or methacrylic acid, in some embodiments being methacrylic acid. In an eighth embodiment, this disclosure provides a two-part adhesive composition comprising a first part comprising methyl methacrylate, a poly(methyl methacrylate)-poly(((meth)acrylate) n-butyl)-poly(methyl methacrylate) triblock copolymer; cumene hydroperoxide; a free radical inhibitor; corn starch; and pyrolytic silica; and a second part comprising methyl methacrylate; methacrylic acid; a crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof; an acrylic monomer comprising at least one of phosphate groups or phosphonate groups; at least one elastomer; a free radical inhibitor; acetylacetonate vanadyl; a wax; and a pigment.

[0063] In a ninth embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to eighth embodiments, wherein the crosslinker having two or more acrylate groups is a non-cyclic crosslinker. In a tenth embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to ninth embodiments, wherein, based on the total weight of the first and second parts of the two-part adhesive composition, the first part comprises 25% to 65% by weight, 35% to 55% by weight, or 40% to 50% by weight of methyl methacrylate, and the second part comprises 20% to 60% by weight, 25% to 50% by weight, or 30% to 45% by weight of methyl methacrylate. In an eleventh embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to tenth embodiments, wherein, based on the total weight of the first part, a free radical initiator is present in an amount of 0.5% to 3.5% by weight. In a twelfth embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to eighth embodiments, wherein a free radical inhibitor is present in an amount of at least half the weight of the free radical initiator. In a thirteenth embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to twelfth embodiments, wherein an acrylic monomer comprising at least one of phosphate ester groups or phosphonate groups is present in an amount ranging from 1.85 wt% to 2.15 wt% or from 1.85 wt% to 3 wt% based on the total weight of the second part. In a fourteenth embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to twelfth embodiments, wherein an acrylic monomer comprising at least one of phosphate ester groups or phosphonate groups is present in an amount ranging from 2.25 wt% to 3.5 wt% or from 2.25 wt% to 3 wt% based on the total weight of the second part. In a fifteenth embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to fourteenth embodiments, wherein the two-part adhesive composition is free of acyl chlorides or contains no more than 0.05 wt% acyl chlorides based on the total weight of the two-part adhesive composition. In a sixteenth embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to fifteenth embodiments, wherein the second part is substantially free of thiourea, amines and other metal salt reducing agents, and / or wherein the monomers in the second part consist of: methyl methacrylate; a crosslinking agent having two or more acrylate groups, methacrylate groups or combinations thereof; an acrylic monomer containing at least one of phosphate groups or phosphonate groups; and methacrylic acid.In the seventeenth embodiment, this disclosure provides a two-part adhesive composition according to any one of the first to sixteenth embodiments, wherein the first part and the second part are packaged in a first container and a second container, respectively, and wherein the volume ratio of the first container to the second container is in the range of 1.5:1 to 1:1.5.

[0064] In an eighteenth embodiment, this disclosure provides a method for manufacturing an adhesive article comprising a first substrate and a second substrate, the method comprising combining a first portion and a second portion of a two-part adhesive composition according to any one of the first to seventeenth embodiments to provide an adhesive, applying the adhesive to at least one of the first substrate or the second substrate, adhering the first substrate and the second substrate using the adhesive, and at least partially curing the adhesive to manufacture the adhesive article. In a nineteenth embodiment, this disclosure provides the method according to the eighteenth embodiment, wherein the first portion and the second portion are combined in a volume ratio in the range of 1.5:1 to 1:1.5. In a twentieth embodiment, this disclosure provides the method according to the eighteenth or nineteenth embodiment, wherein at least one of the first substrate or the second substrate comprises at least one of a metal, glass, polymer, or composite material. In a twenty-first embodiment, this disclosure provides an article manufactured by the method according to any one of the eighteenth to twentyth embodiments.

[0065] In a twenty-second embodiment, this disclosure provides a first portion of a two-part adhesive composition, the first portion comprising methyl methacrylate, methyl methacrylate with C4-C9 alkyl acrylate or C4-C9 alkyl methacrylate or C4-C9 alkyl acrylate. 2-4 Hydroxyalkyl esters or C methacrylate 2-4The disclosure provides a block copolymer of at least one of hydroxyalkyl esters, a free radical initiator comprising at least one of a peroxide initiator or a hydroperoxide initiator, a free radical inhibitor, and starch. In a twenty-third embodiment, the disclosure provides a first portion of the two-part adhesive composition according to the twenty-second embodiment, wherein the starch is corn starch. In a twenty-fourth embodiment, the disclosure provides a first portion of the two-part adhesive composition according to the twenty-second or twenty-third embodiment, wherein the block copolymer is a poly(methyl methacrylate)-poly(((meth)acrylate) n-butyl)-poly(methyl methacrylate) triblock copolymer. In a twenty-fifth embodiment, the disclosure provides a first portion of the two-part adhesive composition according to any one of the twenty-second to twenty-fourth embodiments, wherein the free radical initiator is a hydroperoxide initiator, and wherein the hydroperoxide initiator is cumene hydroperoxide. In a twenty-sixth embodiment, this disclosure provides a first portion of a two-part adhesive composition according to any one of embodiments twenty-two to twenty-five, wherein the first portion comprises 25% to 65% by weight, 35% to 55% by weight, or 40% to 50% by weight of methyl methacrylate based on the total weight of the first portion of the two-part adhesive composition. In a twenty-seventh embodiment, this disclosure provides a first portion of a two-part adhesive composition according to any one of embodiments twenty-two to twenty-six, wherein a free radical initiator is present in an amount of 0.5% to 3.5% by weight based on the total weight of the first portion. In a twenty-eighth embodiment, this disclosure provides a first portion of a two-part adhesive composition according to any one of embodiments twenty-two to twenty-seven, wherein a free radical inhibitor is present in an amount of at least half the weight of the free radical initiator. In a twenty-ninth embodiment, this disclosure provides a first portion of a two-part adhesive composition according to any one of embodiments twenty-two to twenty-eight, wherein the first portion is free of acyl chloride, or comprises no more than 0.05% by weight of acyl chloride based on the total weight of the first portion of the two-part adhesive composition.

[0066] In a thirtieth embodiment, this disclosure provides a second portion of a two-part adhesive composition comprising a monomer and vanadium acetylacetonate, wherein the monomer comprises: methyl methacrylate; a non-cyclic crosslinker having two or more acrylate groups, methacrylate groups, or combinations thereof; an acrylic monomer comprising at least one of phosphate groups or phosphonate groups; and methacrylic acid. In a thirty-first embodiment, this disclosure provides a second portion of the two-part adhesive composition according to the thirty-first embodiment, wherein the second portion further comprises an elastomer. In a thirty-second embodiment, this disclosure provides a second portion of the two-part adhesive composition according to the thirty-first or thirty-first embodiment, wherein the acrylic monomer comprising at least one of phosphate groups or phosphonate groups is present in an amount ranging from 1.85% to 2.15% by weight or from 1.85% to 3% by weight, based on the total weight of the second portion. In a thirty-third embodiment, this disclosure provides a two-part adhesive composition according to any one of embodiments thirty to thirty-one, wherein an acrylic monomer comprising at least one of phosphate ester groups or phosphonate ester groups is present in an amount ranging from 2.25% to 3.5% by weight or from 2.25% to 3% by weight, based on the total weight of the second part. In a thirty-fourth embodiment, this disclosure provides a two-part adhesive composition according to any one of embodiments thirty to thirty-three, wherein the second part comprises 20% to 60% by weight, 25% to 50% by weight, or 30% to 45% by weight of methyl methacrylate, based on the total weight of the second part of the two-part adhesive composition. In a thirty-fifth embodiment, this disclosure provides a second part of a two-part adhesive composition according to any one of embodiments thirty to thirty-four, wherein the second part is substantially free of thiourea, amines, and other metal salt reducing agents.

[0067] The purposes and advantages of this disclosure are further illustrated by the following non-limiting embodiments, but the specific materials and quantities referenced in these embodiments, as well as other conditions and details, should not be regarded as undue limitations on this disclosure.

[0068] Example

[0069] Unless otherwise stated, all parts, percentages, ratios, etc., in the embodiments and the remainder of this specification are by weight. The following abbreviations are used in this section: in = inch, g = gram, kg = kilogram, lb = pound, kN = kilonewton, N = newton, lb = 1 kilonewton. f=pounds of force, min = minutes, s = seconds, ℃ = degrees Celsius, ℉ = degrees Fahrenheit, Hz = hertz, J = joule, ° = degrees, cm = centimeters, mm = millimeters, psi = pounds per square inch, and rpm = revolutions per minute.

[0070] Table 1: List of Materials

[0071]

[0072] Test methods

[0073] Overlap-shear (OSL) test

[0074] Overlap shear test samples were prepared on aluminum (Al) substrates and fiber-reinforced plastics (FRP) using the mixed adhesives prepared by Examples A-1, B-1, B-2 to B-9, and Explanatory Examples M-1 and M-2 to M-9. The aluminum specimen samples (obtained from Joseph t. Ryerson and Son, Inc., Coon Rapids, MN) were 2.54 cm × 10.16 cm × 0.16 cm (1 in × 4 in × 1 / 16 in) and were prepared using one of three methods: (1) wiping with methyl ethyl ketone (MEK) solvent only before bonding, or (2) manually grinding with a pad of the trade name "SCOTCH BRITE" (3M Company, St. Paul, MN) and then wiping with MEK solvent before bonding, or (3) chemically etching with a solution of sulfuric acid and sodium dichromate. All green and red substrates (obtained from Plastics International, Eden Prairie, MN) were 6.35 mm × 25.4 mm × 101.6 mm (1 / 4 in × 1 in × 4 in). The green FRP substrate was available as a laminated G-10 / FR-4 glass epoxy resin, and the red FRP was available under the trade name “GPO-3” (NEMA grade glass mat reinforced polyester). A 1.27 cm (1 / 2 in) overlap was used when preparing the overlap shear samples. The adhesive layer was clamped with a long-tail clip during curing, and the clamps were removed after 24 hours at 25°C. The lap shear test was run on a Material Testing Systems Insight 30 EL instrument (obtained from MTS Systems Corporation, Eden Prairie, MN), using a 5,620 lb (25 kN) pressure sensor for aluminum samples and a 2,250 lb (10 kN) pressure sensor for plastic samples. The aluminum lap shear test was run at 2.54 mm (0.1 in) / min, and the plastic lap shear test was run at 50.8 mm (2 in) / min. Peak stress values ​​(psi) are reported, and each value is the average of three samples.

[0075] Side impact test

[0076] All bonded sections were prepared by dispensing the adhesive onto chemically etched aluminum specimens using a static mixing tip. The aluminum specimens (obtained from Joseph T. Ryerson & Sons) measured 2.54 cm × 10.16 cm × 0.16 cm (1 in × 4 in × 1 / 16 in) and were chemically etched with a solution of sulfuric acid and sodium dichromate. Side impact samples were bonded with a 1.27 cm (0.5 in) overlap. The adhesive layer was clamped with a long-tail clamp during curing and removed after 24 hours at 25°C (77℉). The side to be impacted was polished using a grinder to create a sample where the adhesive and aluminum substrate were flush. Samples were tested on a CP9050 impact pendulum (obtained from Instron, Norwood, MA), where the sample was held in the clamp and impacted at the edge of the bonded area. Test parameters were ISO 179-1, using a 21.6 J hammer dropped at a 150.0° angle.

[0077] Bell Peel Strength Test

[0078] The Bell peel test was based on ASTM D-3167, using a Material Testing Systems Insight 30EL instrument (obtained from MTS Systems Corporation, with some modifications). A 1in × 7in × 0.063in (2.54cm × 17.8cm × 0.16cm) chemically etched 2024 T3 Alclad aluminum strip (obtained from Erickson Metals of Minnesota, CoonRapids, MN) and a 1in × 10in × 0.020in (2.54cm × 25.4cm × 0.051cm) chemically etched 2024... Test samples were prepared using T3 Alclad aluminum strips (obtained from Ericsson Metals, Minnesota). Chemical etching was performed using a solution of sulfuric acid and sodium dichromate. A mixed adhesive was applied to both strips (except for a 3-inch (7.6 cm) section of the 10-inch (25.4 cm) strip). 17-mil (0.043 cm) spacer beads, made from Mosz, 40-mesh VI grade soda-lime glass spheres, were lightly sprinkled onto the adhesive, and the two strips were bonded together using a 15-lb (6.8 kg) roller to press the aluminum strips together. The samples were then held together at room temperature (approximately 25°C (77°F)) using eight long-tail clips for at least 24 hours to allow the adhesive to cure. Agent. Note that the 3-inch (7.6 cm) portion of the thinner aluminum extends beyond the 7-inch (17.8 cm) portion of the bonded aluminum strip. Test the samples using a roller peel test fixture. Insert the thinner aluminum strip through the rollers of the floating roller device and clamp it with the lower clamps. Use a 200 lb (0.9 kN) pressure sensor and test the samples at a rate of 6 in (15.24 cm) / min. Test two or three samples and report the average. Report the peel strength in pounds per line inch. Report the peel strength as the average over 3 in (7.6 cm) (i.e., 1.5 in (3.8 cm) to 4.5 in (11.4 cm)).

[0079] Mud application agent test

[0080] Ten overlap shear samples were prepared using an aluminum specimen measuring 2.54 cm × 10.16 cm × 0.16 cm (1 in × 4 in × 1 / 16 in) (obtained from Joseph T. Ryerson & Son, Inc., Kuhn Rapids, Minnesota). The specimens were hand-ground using a mat labeled “SCOTCH BRITE” (3M, St. Paul, Minnesota) and then wiped with MEK solvent before bonding. The OLS samples were bonded with a 1.27 cm (0.5 in) overlap and the adhesive was allowed to cure for at least 24 hours. Five of the ten samples served as controls and were stored in the laboratory under ambient conditions. The remaining five OLS samples were carefully wrapped in 100% cotton wadding. The wrapped samples were placed in a bag labeled “ZIPLOC” (SC Johnson and Son, Inc., Racine, WI) and distilled water was added in an amount ten times the total weight of the cotton wadding used. The bag was sealed and placed inside a second identical bag, also sealed. The double-bag sample was then placed on an aluminum tray and placed in an oven set to 71°C (160°F) for two weeks. After two weeks in the 71°C (160°F) oven, the sample was immediately placed in a freezer at -17.8°C (0°F) for two hours. After two hours in the freezer, the sample was thawed for two hours and then immediately subjected to a standard lap shear test at 2.54 mm (0.1 in) / min using a 5620 lb (25 kN) pressure sensor. Both the mud-covering sample and the control sample were tested simultaneously using the lap shear test, and the "% strength retention" was calculated based on the average of all controls.

[0081] Dynamic mechanical analysis (DMA)

[0082] Films of the cured compositions were prepared by extruding the mixed adhesives of Examples A-1, B-1, and B-2 through B-9 as a two-part composition onto a silicone polyester liner using a static mixer to create Mixed Adhesives Explanatory Examples M-1 and M-2 through M-9. Using a second silicone polyester liner, an adhesive film was prepared between the two liners to a thickness of approximately 1 mm (0.04 in) using a simple doctor blade coater. The adhesive film was allowed to cure at room temperature for at least 24 hours prior to testing.

[0083] Membrane samples were cut into pieces approximately 5 mm to 6 mm wide × 1 mm thick × 57 mm long (0.20 in to 0.24 in × 0.04 in × 2.25 in) and tested using a tension clamp on a DMA850 (TA Instruments Inc., New Castle, DE, Newcastle, Dlaiv) with the following settings: frequency = 1 Hz, strain = 0.1%, and minimum oscillation force = 0.001 N. The membrane samples were equilibrated to -50 °C (122 °F) and held at this temperature for five minutes, then gradually increased to 200 °C (392 °F) at a rate of 3.0 °C (37.4 °F) / min. The peak value of the loss tangent was reported as the glass transition temperature (T0). g ).

[0084] Opening time test of Example M-6

[0085] As previously described in the “Overlap Shear Test” section, worn aluminum overlap shear specimens were used. Ten overlap shear specimens (five bonded samples) were used for the “t=0” data, and six overlap shear specimens (three bonded samples) were used for each of the t=15, 20, 25, and 30 minute test specimens. Adhesive was applied to half of the overlap shear specimen, and a stopwatch was started. On the five “t=0” specimens, the bond closed immediately. At the corresponding times on the stopwatch, the bond closed on the 15, 20, 25, and 30 minute specimens. After allowing all overlap shear specimens to cure for at least 24 hours, the overlap shear specimens were tested as described in the “Overlap Shear Test” section above. The average psi value of each of the 15, 20, 25, and 30 minute specimens was compared to the average psi value of the “t=0” specimens. The average psi values ​​of the 15, 20, 25, and 30 minute specimens were then reported as a percentage of the average psi value of the “t=0” specimens.

[0086] Open time is defined as the time during which a mixed adhesive can remain unbonded and still achieve 80% or more of the overlap shear strength that would be achievable when the adhesive is mixed and immediately bonded between two adherents (in this case, worn aluminum).

[0087] Accelerated storage lifetime testing of Part A embodiments

[0088] Load the various A-part formulations into the "10" part side of the 10:1 cartridge and place the plunger on both sides of the cartridge. Cap the cartridge and place it in an oven at 120℉ (49℃). Remove the cartridge from the oven every one to two weeks to allow it to cool, and place it in a cartridge dispenser. Dispense the binder (2 mL to 3 mL) from the cartridge. Note whether the binder flows out of the cartridge properly or whether the binder has gelled (or partially gelled).

[0089] Rheological testing (energy storage modulus relative to time)

[0090] Tests were performed using an ARES-G2 rheometer with TRIOS software (purchased from TA Instruments). Disposable aluminum parallel plates (25mm diameter) were used, connected to upper and lower stainless steel mounting brackets with a 0.5mm gap. A frequency of 1Hz was used at a constant temperature of 25°C. Both axial force adjustment and automatic strain adjustment were employed during measurements.

[0091] Rheological testing (viscosity)

[0092] Tests were performed using an ARES-G2 rheometer with TRIOS software. A 25 mm diameter, 0.09896 rad stainless steel cone plate was used. The sample was pre-shorn at 20.0 lb / s. The sample was then gradually increased from 20.0 lb / s to 0.1 lb / s. Measurements were performed at 25 °C.

[0093] Part A Examples

[0094] Example A-1

[0095] Example A-1 was prepared in a 5000 g scale by combining the components in the amounts indicated in Table 2 in a 2-gallon biaxial Ross mixer (model PVM-2, Charles Ross & Son Company, Hauppauge, NY) equipped with anchor / scraper and dispersing blades. First, MMA and BHT were added to the mixer, and mixing was initiated with the anchor blade set to 50 rpm and the dispersing blade set to 2683 rpm. After mixing for approximately 5 minutes, BCP was slowly added over approximately 8 minutes. Mixing continued for 32 minutes, at which point the BCP was completely dissolved. Next, starch was slowly added over approximately 5 minutes, followed by silica, also slowly added over approximately 5 minutes. After the silica was completely added, the kettle temperature was maintained at 96℉ (36°C), and the material was mixed for an additional 25 minutes (anchor blade at 50 rpm and dispersing blade at 2683 rpm). Then, CHP was added, and mixing continued for an additional 10 minutes using the same settings. Finally, while continuing mixing, the material was degassed, and a vacuum of approximately 22 inches (559 mm) Hg was applied. After degassed, the material was vented.

[0096] Explanation of Example A-2

[0097] Illustrative Example A-2 was prepared in a 125 g scale by combining the components indicated in Table 2 in a polypropylene MAX 200 DAC cup (FlackTek, Inc., Landrum, SC, South Carolina). First, MMA, BHT, and the copolymer were combined and rapidly mixed at 2250 rpm for 4 minutes using a DAC 400.2 VAC (FlackTek). This mixing was repeated 12 times until the copolymer was dissolved. Next, starch and silica were added, followed by mixing at 2250 rpm for 4 minutes, and then cooling in a freezer for 5 minutes. The mixture was again mixed at 2250 rpm for 4 minutes, followed by cooling in a freezer for 5 minutes. Next, CHP was added to the mixture and rapidly mixed at 1750 rpm for 4 minutes, followed by cooling in a freezer for 5 minutes. The final adhesive resin mixture was then degassed by covering the mixing cup with a polypropylene cap containing vent holes and mixed under high shear for 2 minutes at a reduced pressure of 0.68 psi (approximately 35 torr).

[0098] Explanation of Example A-3

[0099] Illustrative Example A-3 was prepared in 70 g units by combining the components indicated in Table 2 in a polypropylene MAX 100 DAC cup (Sonchong Corporation). First, MMA and MBTBMP were combined and rapidly mixed for 4 minutes at 1500 rpm using a DAC 400.2 VAC (Sonchong Corporation). Next, NBR was added, followed by mixing at 1750 rpm for 4 minutes. Then, CSP was added, and the material was mixed at 2250 rpm for 4 minutes, followed by cooling in a freezer for approximately 5 minutes. This mixing and cooling process was repeated three times. CHP was then added to the mixture and rapidly mixed at 1750 rpm for 2 minutes, followed by cooling in a freezer for 5 minutes. The final binder resin mixture was then degassed by covering the mixing cup with a polypropylene cap containing vent holes and mixed under high shear for 2 minutes under reduced pressure of 0.68 psi (approximately 35 Torr).

[0100] Explanation of Example A-4

[0101] Explanatory Example A-4 was prepared in the same manner as Explanatory Example A-3, except that MEHQ was used instead of MBTBMP and the materials were added in the amounts indicated in Table 2.

[0102] Illustrative Examples A-5 and A-6

[0103] Illustrative Example A-5 was prepared in 60g increments by combining the components indicated in Table 2 in a polypropylene MAX 100 DAC cup (Sonchong Corporation). Finally, MMA, BHT, NBR, and CSP (if present) were combined and rapidly mixed for 4 minutes at 2250 rpm using a DAC 400.2VAC (Sonchong Corporation). This mixing was repeated, and the material was cooled in a freezer for 5 minutes. Next, starch and silica were added, followed by mixing at 2250 rpm for 4 minutes. This mixing was repeated, followed by cooling in a freezer for approximately 5 minutes. CHP was then added to the mixture and rapidly mixed for 4 minutes at 1750 rpm, followed by cooling in a freezer for 5 minutes. The final binder resin mixture was then degassed by covering the mixing cup with a polypropylene cap containing vent holes and mixed under high shear for 2 minutes under reduced pressure of 0.68 psi (approximately 35 Torr).

[0104] Explanation of Example A-7

[0105] Illustrative Example A-7 was prepared in 60g increments by combining the components indicated in Table 2 in a polypropylene MAX 100 DAC cup (Sonchong Corporation). First, MMA, BHT, and CSP were combined and rapidly mixed at 2250 rpm for 4 minutes using a DAC 400.2 VAC (Sonchong Corporation), and then cooled in a freezer. This mixing was repeated three times. Next, starch and silica were added, followed by mixing at 2250 rpm for 4 minutes and cooling in a freezer. This mixing was repeated. Then, CHP was added to the mixture and rapidly mixed at 1750 rpm for 4 minutes, followed by cooling in a freezer for 5 minutes. The final binder resin mixture was then degassed by covering the mixing cup with a polypropylene cap containing vent holes and mixed under high shear for 2 minutes under reduced pressure of 0.68 psi (approximately 35 Torr).

[0106] Table 2: Part A Examples (Ex) and Illustrative Examples (IE) (Quantities are in weight %)

[0107]

[0108] Accelerated storage lifetime tests were performed on Ex A-1 and IE A-2 through IE A-7. The results are shown in Table 3 below.

[0109] Table 3: Accelerated storage life test results for Ex A-1 and IE A-2 to IE A-7 at 120℉ (49℃)

[0110]

[0111] Part B Examples

[0112] Explanatory Examples B-1 and Examples B-2 to B-5 and B-7 to B-9

[0113] Explanatory Examples B-1 and Examples B-2 to B-5 and Examples B-7 to B-9 were prepared by combining the components in the amounts indicated in Table 4 in a polypropylene MAX 60 or 100 DAC cup (Sonchong Corporation). First, MMA, MAA, XL, phosphate ester, BHT, and VaAcAc were combined and rapidly mixed at 2250 rpm for 4 minutes using a DAC 400.2 VAC (Sonchong Corporation) until the VaAcAc was completely dissolved. Then, NBR was added, and the mixture was rapidly mixed at 2250 rpm for 4 minutes, followed by another 4 minutes at 2250 rpm. Next, CSP was added to the rapid mixer cup, and the mixture was rapidly mixed at 2250 rpm for 4 minutes, followed by cooling in a freezer for 5 minutes. This was repeated three times. Then, wax, CB, and GS were added, and the mixture was rapidly mixed at 2250 rpm for 4 minutes, followed by cooling in a freezer for 5 minutes. The final adhesive resin mixture was then degassed by covering the mixing cup with a polypropylene cap containing vent holes and mixed under high shear for 2 minutes at a reduced pressure of 0.68 psi (approximately 35 torr). Parts A and B were then loaded separately onto each side of a 1:1 dual syringe dispenser.

[0114] Example B-6

[0115] Example B-6 was prepared on a 5000 g scale by combining the components in the amounts indicated in Table 4 in the same mixer used for Example A-1. First, MMA, MAA, XL, phosphate ester, BHT, and VaAcAc were added to the mixer, and mixing was initiated with the anchor blade set to 54 rpm and the dispersing blade set to 3267 rpm. After approximately 30 minutes in the mixing vessel, the temperature was 114℉ (46°C). Then, NBR was added, and mixing continued for 24 minutes with the same mixer settings. Next, CSP was added, and mixing continued for 45 minutes. The vessel temperature was 110℉ (43°C). Next, wax, CB, and GS were added, and mixing continued with the anchor blade at 54 rpm and the dispersing blade at 3850 rpm. Mixing continued for 20 minutes. The vessel temperature was 111℉ (44°C). Finally, the material was degassed while mixing continued, and a vacuum of approximately -22 inches to -23 inches (559 mm to 584 mm) Hg was achieved. After degassing, the material is emptied. Then, the materials from parts A and B are loaded onto each side of the 1:1 dual syringe dispenser, respectively.

[0116] Table 4: Part B Examples (Ex) and Illustrative Examples (IE) (Quantities are in weight %)

[0117]

[0118] Hybrid Part A and Part B Examples

[0119] Explanatory Examples (IE) M-1 and Examples (Ex) M-2 to M-9

[0120] For IE M-1 and Ex M-2 to Ex M-9, Example A-1 and Part B indicated below were mixed at a 1:1 ratio. Overlap shear (OLS) tests were performed on 1) worn aluminum, 2) MEK-rubbed aluminum, 3) chemically etched aluminum, 4) green FRP, and 5) red FRP using the test methods described above. Additionally, side impact (SI) and Bell peel strength (BPS) tests were performed, and the results are shown in Table 5. Rheological tests (storage modulus versus time) were performed on IE M-1 and Ex M-2 to Ex M-4, Ex M-6, Ex M-8, and Ex M-9, and the results are shown in Table 5. Figure 1 middle.

[0121] Table 5: Results of IE M-1 and Examples M-2 to M-9

[0122]

[0123] Ex M-6 was subjected to a mud coating test and DMA. Ex M-6 exhibited a 90% retention rate and a glass transition temperature of 143°C after the mud coating test. The open time of Ex M-6 was evaluated using the aforementioned open time test and was found to be between 15 and 20 minutes. The results are shown in Table 6 below.

[0124] Table 6: Opening Time Assessment of Example M-6

[0125]

[0126] The foregoing description, given to enable those skilled in the art to practice this disclosure protected by the claims, should not be construed as a limitation on the scope of this disclosure, which is defined by the claims and all their equivalents.

Claims

1. A two-part adhesive composition, said two-part adhesive composition comprising: The first part, which includes: Methyl methacrylate; Methyl methacrylate with C4-C9 alkyl acrylate or C4-C9 alkyl methacrylate or C4-C9 alkyl acrylate 2-4 Hydroxyalkyl esters or C methacrylate 2-4 A block copolymer of at least one of hydroxyalkyl esters; Free radical initiators, said free radical initiators including at least one of peroxide initiators or hydroperoxide initiators; and Free radical inhibitors; and Part Two, Part Two includes: Methyl methacrylate; A crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof; Acrylic monomers containing at least one of phosphate ester groups or phosphonate ester groups; and Vanadyl acetylacetonate.

2. The two-part adhesive composition of claim 1, wherein the first part further comprises starch.

3. The two-part adhesive composition according to claim 1 or 2, wherein the two-part adhesive composition is free of acyl chloride, or contains no more than 0.05% by weight of acyl chloride based on the total weight of the two-part adhesive composition.

4. The two-part adhesive composition according to any one of claims 1 to 3, wherein the free radical initiator is the hydroperoxide initiator, and wherein the hydroperoxide initiator is cumene hydroperoxide.

5. The two-part adhesive composition according to any one of claims 1 to 4, wherein the free radical initiator is present in an amount of 0.5% to 3.5% by weight based on the total weight of the first part, and wherein the free radical inhibitor is present in an amount of at least half the weight of the free radical initiator.

6. The two-part adhesive composition according to any one of claims 1 to 5, wherein the block copolymer is a poly(methyl methacrylate)-poly((meth)acrylate n-butyl acrylate)-poly(methyl methacrylate) triblock copolymer.

7. The two-part adhesive composition according to any one of claims 1 to 6, wherein the acrylic monomer comprising at least one of phosphate ester groups or phosphonate ester groups is present in an amount ranging from 1.85% by weight to 3% by weight, based on the total weight of the second part.

8. The two-part adhesive composition according to any one of claims 1 to 7, wherein the second part further comprises an elastomer.

9. The two-part adhesive composition according to any one of claims 1 to 8, wherein the second part further comprises at least one of acrylic acid or methacrylic acid.

10. The two-part adhesive composition according to any one of claims 1 to 9, wherein the second part is substantially free of thiourea, amines and other metal salt reducing agents.

11. The two-part adhesive composition according to any one of claims 1 to 10, wherein the second part comprises a monomer consisting of: methyl methacrylate; a crosslinking agent having two or more acrylate groups, methacrylate groups, or combinations thereof; an acrylic monomer comprising at least one of phosphate groups or phosphonate groups; and methacrylic acid.

12. The two-part adhesive composition according to any one of claims 1 to 11, wherein the crosslinker having two or more acrylate groups, methacrylate groups or combinations thereof is a non-cyclic crosslinker.

13. A method for manufacturing an adhesive article comprising a first substrate and a second substrate, the method comprising: The first portion and the second portion of the two-part adhesive composition according to any one of claims 1 to 12 are combined to provide an adhesive; The adhesive is applied to at least one of the first substrate or the second substrate; The first substrate and the second substrate are adhered using the adhesive; as well as The adhesive is cured at least partially to manufacture the bonded article.

14. The method of claim 13, wherein the first portion and the second portion are combined in a volume ratio ranging from 1.5:1 to 1:1.

5.

15. A first portion of a two-part adhesive composition, the first portion comprising: Methyl methacrylate; Methyl methacrylate with C4-C9 alkyl acrylate or C4-C9 alkyl methacrylate or C4-C9 alkyl acrylate 2-4 Hydroxyalkyl esters or C methacrylate 2-4 A block copolymer of at least one of hydroxyalkyl esters; A free radical initiator, wherein the free radical initiator comprises at least one of a peroxide initiator or a hydroperoxide initiator; Free radical inhibitors; and starch.

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