TW202307164A - (meth)acrylate structural adhesives and methods - Google Patents

Abstract

Provided are curable (meth) acrylate structural adhesive compositions comprising a cyclic imide-containing (meth) acrylate monomer and a crosslinker, and methods, particularly methods of use.

Description

(Meth)acrylate structural adhesives and methods

Structural adhesives are known for joining one substrate to another, eg, metal to metal, metal to plastic, plastic to plastic, glass to glass. Structural adhesives are an attractive alternative to mechanical joining methods such as riveting or spot welding because structural adhesives distribute loading stresses over a large area rather than concentrating such stresses at a few points .

While known structural adhesives can have good high temperature performance and durability, the rigid joints created by these structural adhesives after curing can lead to poor impact resistance of the joined parts and subsequent failure of the joint. Furthermore, adhesives that form rigid bonds have high and non-uniform stresses distributed throughout the bond, with stress at the edges of the bond being generally higher than in the middle of the bond. High stress in rigid structural adhesives can lead to undesired distortion of the bonded material.

One approach used by the industry to increase the flexibility and toughness of structural adhesives is to incorporate elastomeric materials that can be dissolved or dispersed in curable adhesive compositions. Examples of such elastic materials may include, for example, methyl methacrylate-butadiene-styrene copolymer ("MBS"), acrylonitrile-styrene-butadiene copolymer, linear polyurethane, Acrylonitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, butadiene rubber, and natural rubber. However, these elastomeric additives can result in a high viscosity of the liquid adhesive composition, which can pose handling challenges during use. Furthermore, in the case of butadiene or other conjugated diene rubbers, elastomeric additives can reduce the oxidation resistance of the structural adhesive, which can lead to joint failure.

Good adhesion of structural adhesives to glass (non-sintered or sintered) is often quite difficult to achieve without the use of primers or reactive hot melt (eg polyurethane) adhesives. Structural adhesive compositions including acrylates are well known to cure rapidly and are insensitive to surface preparation; however, when used on glass, such adhesives are easily absorbed by high humidity conditions via transesterification and hydrolysis. ground degradation.

What is needed is a curable adhesive composition that cures rapidly to form a structural adhesive, preferably one that bonds to glass (e.g., glass-to-glass or metal-to-glass) (ideally without the need for a primer) and has Curable adhesive composition with low hydrolysis rate and low transesterification rate.

In one aspect, provided is a curable (meth)acrylate structural adhesive composition comprising: a (meth)acrylate monomer containing a cyclic imide; a crosslinking agent; and a curing initiator system; wherein the crosslinking agent is a compound represented by the following formula:

L-(R ¹ ) _q

Wherein each ^R is independently selected from a functional group represented by the following formula:

in:

^each R is independently hydrogen or methyl;

n is an integer from 1 to 5 (inclusive);

X is O, S, or NH; and

Y is a single bond or a divalent group represented by the following formula:

in:

N ' is the nitrogen bonded to the carbonyl carbon of ^R ; and

T is a divalent group selected from the group consisting of straight-chain alkylene, cyclic alkylene, unsubstituted arylylene, substituted arylylene, and combinations thereof;

q is an integer of at least 2; and

L is a q-valent organic polymer (preferably, it has a number average molecular weight of 4,000 to 54,000 grams per mole relative to polystyrene standards) comprising a compound selected from the group consisting of monomer units represented by the following formula Single unit:

Wherein R ^is a hydrogen or Z-terminated alkyl or heteroalkylene chain, wherein each Z-terminated chain can independently comprise a chain selected from secondary amine linkages, tertiary amine linkages, ether linkages, and the linkage of the group formed by combinations thereof, and wherein each Z is independently O, S, or NH;

Wherein n is an integer from 1 to 5 (inclusive), each R is ^{independently} hydrogen or alkyl, and each Z is independently O, S, or NH;

Wherein n is an integer from 1 to 5 (inclusive), each R is ^{independently} hydrogen or alkyl, and each Z is independently O, S, or NH;

wherein j is an integer less than or equal to 30, k is _{an integer less than or equal to 30, each R is independently hydrogen or alkyl, and each R is independently C 10} ^{to C} ₁₅ alkyl or C ₁₀ to C ₁₅ Alkenyl, wherein j and k are not both zero, and wherein the moieties with j and k subscripts are randomly distributed in the carbon chain;

Where m is an integer from 10 to 330 (inclusive), n is an integer from 1 to 5 (inclusive); and

its mixture;

Wherein the q-valent organic polymer L comprises less than 26000 grams per mole of monomeric units e) (if present) relative to polystyrene standards.

In another aspect, a method of joining a first substrate to a second substrate is provided, the method comprising:

providing a curable (meth)acrylate structural adhesive composition described herein, and an accelerator to form a curable adhesive mixture;

applying the curable adhesive mixture to at least a portion of a surface of the first substrate;

at least partially covering (on the surface of the first substrate) the curable adhesive mixture with at least a portion of a surface of the second substrate; and

The curable adhesive mixture is allowed to cure and form a structural (meth)acrylate adhesive (thereby joining the first substrate and the second substrate).

The term "aliphatic" refers to a saturated or unsaturated straight-chain, branched-chain, or cyclic hydrocarbon group. In certain embodiments, the term aliphatic refers to a saturated or unsaturated straight or branched chain hydrocarbon group. The term is intended to encompass, for example, alkyl, alkenyl and alkynyl.

The term "alkyl" refers to a monovalent group of an alkane radical, which is a saturated hydrocarbon. The alkyl group can be linear, branched, cyclic, or combinations thereof, and generally has 1 to 20 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n- Octyl, and ethylhexyl.

The term "alkylene" refers to a divalent group that is an alkyl group. The alkylene group can be linear, branched, cyclic, or combinations thereof. Alkylene groups generally have 1 to 20 carbon atoms. The radical centers of the alkylene group can be on the same carbon atom (ie, an alkylidene) or on different carbon atoms.

The term "alkoxy" refers to a monovalent group of formula --OR, wherein R is an alkyl group.

The term "aromatic" or "aryl" refers to a group having at least one aromatic ring. Any additional rings may be unsaturated, partially saturated, saturated, or aromatic. Optionally, the aromatic ring may have one or more additional carbocycles fused to the aromatic ring. Unless otherwise specified, aryl groups generally contain from 6 to 30 carbon atoms. In some embodiments, the aryl group contains 6 to 20, 6 to 18, 6 to 16, 6 to 12, or 6 to 10 carbon atoms. Examples of aryl groups include phenyl, naphthyl, biphenyl, phenanthrenyl, and anthracenyl.

The term "arylene" refers to a polyvalent aromatic, such as phenylene, naphthalene, and the like.

The term "cyclic" refers to a ring-closed hydrocarbon group classified as an alicyclic group, an aromatic group, or a heterocyclic group. The term "alicyclic group" refers to a cyclic hydrocarbon group having properties similar to those of an aliphatic group. "alicyclic ring" and "aliphatic ring" are used interchangeably herein. The term "aromatic group" or "aryl group" refers to a mono- or polynuclear aromatic hydrocarbon group.

The term "heteroalkylene" refers to an alkylene having one or more -CH ₂ - groups replaced by thio, oxy, or -NR ^b -, wherein R ^b is hydrogen or alkyl . A heteroalkylene group can be linear, branched, cyclic, or combinations thereof. Exemplary heteroalkylene groups include alkylene oxide or poly(alkylene oxide). That is, heteroalkylene includes at least one group of formula -(RO)-, where R is alkylene.

The term "(meth)acrylate" or "(meth)acrylic acid" used herein means the corresponding acrylate and methacrylate. Thus, for example, the term "(meth)acrylic acid" covers both methacrylic acid and acrylic acid, while the term "(meth)acrylate" covers both acrylate and meth Acrylic both. (Meth)acrylate or (meth)acrylic acid may consist of only methacrylate or methacrylic acid, respectively, or may consist of only acrylate or acrylic acid, respectively, however it is also possible to A mixture of acrylates (or acrylic and methacrylic).

As used herein, unless the context clearly requires otherwise, the word "or" generally includes the meaning of "and/or" when used.

As used herein, the term "and/or (and/or)" is used to indicate that one or both of the stated events may occur, for example, A and/or B includes (A and B) and (A or B) .

As used herein, the term "room temperature" refers to a temperature in the range of 20°C to 25°C.

As used herein, the term "substantially free" means less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight of the given composition in the composition, based on the total weight of the composition. set components.

The term "glass transition temperature" or " _Tg " refers to the temperature at which a material changes from a glassy state to a rubbery state. In this context, the term "glassy" means that the material is hard and brittle (and thus relatively easy to break) and the term "rubbery" means that the material is elastic and flexible. For a polymeric material, T _g is the critical temperature that distinguishes its glass-like behavior from rubber-like behavior. If the polymeric material is at a temperature below its _Tg , large-scale molecular motion is severely restricted because the material is essentially frozen. On the other hand, if the polymeric material is held at a temperature above its _Tg , molecular motion on the scale of its repeating units occurs, making it soft or rubbery. Any reference herein to the _Tg of a monomer refers to the _Tg of the homopolymer formed from that monomer. The glass transition temperature of polymeric materials is often determined using methods such as dynamic mechanical analysis (DMA) or differential scanning calorimetry (eg, modulated differential scanning calorimetry). Alternatively, the glass transition of a polymeric material can be calculated using the Fox Equation if the amounts of each monomer used to form the polymeric material and the _Tg are known.

In this article, when the word "comprises" and its variants appear in the specification and claims, these words do not have a restrictive meaning. Such terms are to be understood as implying the inclusion of the stated step or element, or group of steps or elements, but not the exclusion of any other step or element, or group of steps or elements. The so-called "consisting of" means to include and be limited to any item following "consisting of". Thus, the phrase "consisting of" indicates that the listed elements are required or mandatory elements and that no other elements may be present. By "consisting essentially of" is meant to include any element listed after the phrase, and is limited to other elements that do not interfere with or facilitate the activity or function specified for the listed element in the disclosure. Thus, the phrase "consisting essentially of" means that the listed elements are necessary or mandatory, but that other elements are optional and may or may not be present depending on whether they materially affect the listed The activity or function of a component. Any element or combination of elements described in this specification in an open language (for example: comprise (comprise) and its derivatives) can be regarded as otherwise described in a closed language (for example: composition (consist) and its derivatives) ) and semi-closed language (for example: basically constitute (consist essentially), and its derivatives) to describe.

The terms "preferred" and "preferably" in the embodiments of the present disclosure indicate that certain benefits may be provided under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other claims are not useful, nor is it intended to exclude other embodiments from the scope of the present disclosure.

In this application, terms such as "a (a)", "an" and "the" are not only intended to refer to singular entities, but also include general classes whose specific examples can be used as illustrations . The terms "a", "an" and "the" are used interchangeably with the term "at least one". The phrases "at least one of" and "comprise at least one of" used after a list refer to any one of the items in the list and the Any combination of two or more items.

Also herein, all numbers are assumed to be modified by the word "about" and, in certain embodiments, preferably by the word "exactly". As used herein, the term "about" in conjunction with a measured quantity refers to the variation of that measured quantity as if measured with a degree of care commensurate with the object of measurement and the precision of the measuring equipment used. Technologists expected. As used herein, "up to" a number (eg, up to 50) includes that number (eg, 50).

Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range as well as by those endpoints (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.) and any subranges (eg, 1 to 5 includes 1 to 4, 1 to 3, 2 to 4, etc.).

The phrase "in the range" or "within a range" (and similar statements) includes endpoints of the stated range.

Throughout this specification, references to "one embodiment", "an embodiment", "some embodiments" or "some embodiments" mean that at least one embodiment of the present disclosure includes a combination of the Specific features, configurations, compositions or properties described in the embodiments. Accordingly, the occurrences of these phrases in various places throughout this specification do not necessarily mean Show the same embodiment of the present disclosure. Furthermore, the particular features, configurations, compositions or characteristics may be combined in any suitable manner in one or more embodiments.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The following embodiments more specifically exemplify illustrative examples. In several places throughout this application, guidance is provided through lists of examples, which may be used in various combinations. In each case, the recited list serves only as a representative group and should not be construed as an exclusive list. Thus, the scope of the present disclosure should not be limited to the specific example structures described herein, but extends at least to structures described in the language of the claims and equivalents of those structures. Any one of the elements explicitly stated as substitutes in this specification can be explicitly included in or excluded from the scope of the patent application in any combination as desired. While various theories and possible mechanisms may have been discussed herein, such discussions should in no way be used to limit the claimable subject matter.

The disclosure provides a curable (meth)acrylate structural adhesive composition, which includes: a (meth)acrylate monomer containing cyclic imide; a crosslinking agent; and a curing initiator system. Curable compositions in embodiments of the present disclosure may further have the advantage of producing bonded structures, generally comprising glass (non-sintered or sintered), whether glass-to-glass or metal-to-glass.

Adhesives (which may also be sealants) prepared from curable compositions of the present disclosure can be prepared by combining curable structural adhesive compositions of the present disclosure with materials such as, for example, from The accelerator combination of 3M SCOTCH-WELD DP8410NS acrylic adhesive (3M Company, St. Paul, MN) was prepared. In some embodiments, the adhesive may include 10 parts of curable composition and 1 part of accelerator.

Adhesives of the present disclosure can be used, for example, to join a first substrate to a second substrate to provide a joined article. Many types of substrates can be bonded with elastic products of the present disclosure, such as, for example, metal (eg, aluminum), plastic (eg, polyamide), and glass. In particularly preferred embodiments, the substrate is glass (whether sintered or non-sintered), and the glass is bonded to another glass or the glass is bonded to metal.

In some embodiments, a first substrate can be bonded to a second substrate by mixing a curable structural adhesive composition of the present disclosure with an accelerator to form a curable adhesive mixture, the curable structural adhesive composition A cured adhesive composition is applied to at least a portion of a surface of the first substrate, the curable adhesive mixture (which is disposed on the surface of the first substrate) is at least partially coated with one of the second substrates At least a portion of the surface is covered, and the curable adhesive mixture is allowed to cure and form a structural adhesive to join the first and second substrates together. In some embodiments, the portion of a surface of the first substrate is not subjected to a surface treatment (eg, corona, flame, abrasion, or chemical primer) prior to applying the curable adhesive mixture thereto. In some embodiments, the portion of a surface of the second substrate is not subjected to a surface treatment (eg, corona, flame, abrasion, or chemical primer) prior to contact with the curable adhesive composition. In some embodiments, the first substrate and the second substrate are different materials such as, for example, metal and glass. In some embodiments, the bonded article may be, for example, an automotive component, an electronic device, or a component of an electronic device.

After curing, the curable structural adhesive compositions of the present disclosure produce bonded structures on various substrates that exhibit high adhesion, elongation, and impact resistance, even when the bonded substrates did not accept the surface prior to bonding. The same goes for processing. Curable compositions in embodiments of the present disclosure can yield adhesives that provide bonded configurations that exhibit little to no bond line readthrough, which can be particularly useful in automotive and aerospace applications, among others. The curable compositions in embodiments of the present disclosure can result in adhesives that are particularly suitable for portable electronic devices that require strong adhesives that can withstand the shocks associated with drop testing. The curable compositions in embodiments of the present disclosure can provide adhesive compositions that exhibit stretch release, which can enable rework of parts joined with these adhesives. Curable compositions in embodiments of the present disclosure can provide sealants that resist hydrolysis upon heat/humidity aging, which can be particularly useful, for example, in applications where the sealant is exposed to warm, humid conditions for extended periods of time.

Curable compositions are substantially free of liquid rubber materials (and often even substantially free of silane adhesion promoters, isocyanates, urethanes, mercaptans, epoxies) and still produce adhesives that exhibit high tack (i.e., >1000 psi), elongation (i.e., values greater than 10%, greater than 25%, greater than 50%, greater than 100%, or greater than 400%), and impact resistance (e.g., >2J) in a general overlap shear test A bonded construction, even if the bonded substrate (e.g., glass, metal, polymer) has not received a surface treatment (e.g., corona, flame, abrasion, chemical primer) prior to bonding, due to the following Describe novel crosslinking agent and monomer.

Such constructions exhibit little to no bond line read through, providing adhesive compositions that exhibit stretch release that allow the parts bonded with these adhesives to Capable of rework as well as providing a sealant that resists hydrolysis during heat/humidity aging. In some cases, compositions of the present disclosure allow the assembly to be disassembled with heat and non-wire wires.

In some embodiments, the structural (meth)acrylate adhesive formed from the curable composition described herein has at least 50%, at least 100%, at least 200%, at least 400%, at least 600%, or A minimum ultimate elongation of at least 800% and a minimum overlap shear strength of at least 1000 psi, at least 1100 psi, at least 1200 psi, at least 1300 psi, or at least 1400 psi. In some embodiments, structural (meth)acrylate adhesives formed from the curable compositions described herein can exhibit stretch release. In some embodiments, the structural (meth)acrylate adhesives formed from the curable compositions described herein resist hydrolysis upon heat/humidity aging.

The tan δ peak in dynamic mechanical analysis ("DMA") reflects the ability of a material to store or dissipate energy. A broader tan delta peak indicates that the material can dissipate energy and withstand shock over a wider frequency and/or temperature range.

In some embodiments, the structural adhesive may exhibit a cure _Tg (judged using DMA) above 70°C, which appears to impart sufficient cohesive integrity to add benefit to adhesion. In general, if the T _g is lower than this, the adhesion may be too weak to hold the load.

Cyclic imide-containing ( meth ) acrylate monomer

The cyclic imide-containing (meth)acrylate monomer includes a cyclic imide group of the following formula:

其中R¹及R²係連接以形成環系，該環系包括一或多個環(一般係兩個環)，且R³係結合至(甲基)丙烯酸酯基團(-O-C(O)-C(R)=CH₂)(其中R=H或CH₃)之伸烷基(例如，C1-C8伸烷基，且一般係伸乙基)。該環系可包括(多個)脂族環、(多個)芳族環、或兩者。在某些實施例中，該環系僅包括脂族環(一般係兩個脂族環)。

wherein R ¹ and R ² are joined to form a ring system comprising one or more rings (typically two rings), and R ³ is bound to a (meth)acrylate group (-OC(O) -C(R)=CH ₂ ) (wherein R=H or CH ₃ ) alkylene (for example, C1-C8 alkylene, and generally ethylylene). The ring system may include aliphatic ring(s), aromatic ring(s), or both. In certain embodiments, the ring system includes only aliphatic rings (typically two aliphatic rings).

In certain embodiments, the cyclic imide-containing (meth)acrylate monomer is a methacrylate of the following formula:

(甲基丙烯酸2-(六氫酞醯亞胺基)乙酯)以及其丙烯酸酯類似物。一般而言，甲基丙烯酸酯單體(其可以商標名稱MIRAMER M1089購自Miwon North America(Exton,PA))優於類似的丙烯酸酯，這係至少由於較高的穩定性及固化T_g(較佳地，高於70℃)之所得結構性黏著劑。

(2-(Hexahydrophthalimido)ethyl methacrylate) and its acrylate analogues. In general, methacrylate monomers (commercially available from Miwon North America (Exton, PA) under the trade designation MIRAMER M1089) are preferred over similar acrylates, at least due to higher stability and cure _Tg (compared to Preferably, above 70°C) of the resulting structural adhesive.

In certain embodiments of the present disclosure, the curable composition often includes at least 5 wt-% of a cyclic imide-containing (meth)acrylate monomer. In certain embodiments of the present disclosure In , the curable composition often includes up to 50 wt-% of a cyclic imide-containing (meth)acrylate monomer.

Additional monofunctional monomers

The curable composition further includes a monofunctional (meth)acrylate monomer. Examples of monofunctional (meth)acrylate monomers that may be used in embodiments of the present disclosure include 2-phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate esters, isocamphoryl (meth)acrylate, acid functional monomers such as (meth)acrylic acid, alkoxylated lauryl (meth)acrylate, alkoxylated phenol (meth)acrylate, alkoxylated Oxylated tetrahydrofurfurylmethyl (meth)acrylate, caprolactone (meth)acrylate, cyclic trimethylolpropaneformyl (meth)acrylate, ethylene glycol methyl ether methacrylate, Ethoxylated nonylphenol (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate (( Stearyl methacrylate), tetrahydrofuryl methyl (meth)acrylate, tridecyl (meth)acrylate, tetrahydrofuryl methyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylic acid Methyl ester, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, (meth) 2-ethylhexyl acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate ) 2-hydroxypropyl acrylate and 3-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylic acid 2-Ethoxypropyl or 3-ethoxypropyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, glycidyl (meth)acrylate, phosphonate Functional (meth)acrylate monomers (e.g. For example, SIPOMER PAM resin from Solvay Specialty Polymers USA, LLC or under the trade names MIRAMER SC1400 and MIRAMER SC1400A from Miwon North America (Exton, PA), N-(2-(2-oxo-1-imidazolidine (yl)ethyl)-methacrylamide (available under the tradename SIPOMER WAM II from Solvay Specialty Polymers USA, LLC. as methacrylamidoethylethylurea (“MAEEU”)) and the like, and combination.

Specific examples of monoacrylate monomers useful in embodiments of the present disclosure include isocamphoryl acrylate (commercially available from SARTOMER under the trade designation SR506, or from Evonik Performance Materials GmbH under the trade designation VISIOMER IBOA), isoborneol methacrylate, Camphenate (commercially available under the trade name SR423A from Sartomer or under the trade name VISIOMER IBOMA from Evonik Performance Materials GmbH), 2-phenoxyethyl methacrylate (commercially available from SARTOMER under the trade name SR340), methacrylic acid Cyclohexyl ester (commercially available under the trade name VISIOMER c-HMA from Evonik Performance Materials GmbH), benzyl methacrylate (commercially available under the trade name MIRAMER M1183 from Miwon North America (Exton, PA)), phenyl methacrylate ( Commercially available under the trade name MIRAMER M1041 from Miwon North America (Exton, PA)), allyl methacrylate (commercially available under the trade name VISIOMER AMA from Evonik Performance Materials GmbH), 2-hydroxyethyl methacrylate (commercially available under the trade name VISIOMER AMA from Evonik Performance Materials GmbH), 2-hydroxyethyl methacrylate (available under the trade name Names VISIOMER HEMA 97 and HEMA 98 commercially available from Evonik Performance Materials GmbH), hydroxypropyl methacrylate (commercially available under the trade names VISIOMER HPMA 97 and HPMA 98 from Evonik Performance Materials GmbH), ultra-high purity 2-hydroxy methacrylate Ethyl ester (commercially available under the trade name VISIOMER UHP HEMA from Evonik Performance Materials GmbH), methyl methacrylate (commercially available under the trade name VISIOMER MMA from Evonik Performance Materials GmbH), methacrylic acid (commercially available under the trade name VISIOMER GMAA from Evonik Performance Materials GmbH), Evonik Performance Materials GmbH), n-butyl methacrylate (commercially available under the trade name VISIOMER n-BMA from Evonik Performance Materials GmbH), isobutyl methacrylate (commercially available under the trade name VISIOMER i-BMA from Evonik Performance Materials GmbH ), glycerin formal methacrylate (commercially available under the trade name VISIOMER GLYFOMA from Evonik Performance Materials GmbH), 2-(2-butoxyethoxy)ethyl methacrylate (commercially available under the trade name VISIOMER BDGMA from Evonik Performance Materials GmbH), lauryl methacrylate (commercially available under the trade name LMA 1214 F from BASF, Florham Park, NJ), polypropylene glycol monomethacrylate (commercially available under the trade name MIRAMER M1051 from Miwon North America ( Exton, PA)), -methacryloxyethyl hydrosuccinate (commercially available under the trade name NK ESTER SA from Shin-Nakamura Co.LTD (Arimoto, Japan)), methacrylic acid 2-isocyanate Ethyl ester (commercially available from Showa Denko K.K. (Tokyo, Japan) under the trade name KarenzMOI), 2-(methacryloxy) ethyl phthalate mono((HEMA phthalate) under product code X- 821-2000 commercially available from ESSTECH, Inc., Essington, PA), 2-(methacryloxy)ethylmaleate ((HEMA maleate) available under Product No. X- 846-0000 commercially available from ESSTECH, Inc., Essington, PA), methoxydiethylene glycol methacrylate (commercially available from Shin-Nakamura under the trade designation M-20G Co.LTD (Arimoto, Japan)), methoxytriethylene glycol methacrylate (commercially available from Shin-Nakamura Co.LTD (Arimoto, Japan) under the trade name M-30G), methoxytetraethylene glycol Alcohol methacrylate (commercially available from Shin-Nakamura Co.LTD (Arimoto, Japan) under the trade name M-40G), methoxytripropylene glycol methacrylate (commercially available from Shin-Nakamura under the trade name M-30PG Co.LTD (Arimoto, Japan)), butoxydiethylene glycol methacrylate (commercially available from Shin-Nakamura Co.LTD (Arimoto, Japan) under the trade name B-20G), phenoxydiethylene glycol methacrylate Alcohol methacrylate (commercially available under the trade name PHE-1G from Shin-Nakamura Co.LTD (Arimoto, Japan)), phenoxydiethylene glycol methacrylate (commercially available under the trade name PHE-2G from Shin-Nakamura Co.LTD (Arimoto, Japan)), - Nakamura Co.LTD (Arimoto, Japan)), dicyclopentenyloxyethyl methacrylate (commercially available from Hitachi Chemical (Tokyo, Japan) under the trade name FANCRYL FA-512M), dicyclopentanyl methacrylate (commercially available under the trade name FANCRYL FA-513M from Hitachi Chemical, Tokyo, Japan), Isocamylcyclohexyl Methacrylate (commercially available under the product MM-304 from Designer Molecules, Inc. (San Diego, CA)) , 4-methacryloxyethyl trimellitic anhydride (commercially available as product A-304 from Designer Molecules, Inc. (San Diego, CA)), 2-methacryloxyethylphenylamine Formate (commercially available from Polysciences, Inc. (Warrington, PA)), trifluoroethyl methacrylate (commercially available from Hampford Research Inc. (Stratford, CT)), methacrylamide (commercially available under the trademark Name VISIOMER MAAmide commercially available from Evonik Performance Materials GmbH), 2-dimethylaminoethyl methacrylate (commercially available under the trade name VISIOMER MADAME from Evonik Performance Materials GmbH), 3-dimethyl Aminopropylmethacrylamide (commercially available under the trade name VISIOMER DMAPMA from Evonik Performance Materials GmbH), and the like, and combinations thereof.

In some embodiments, additional monofunctional (meth)acrylate monomers can act as reactive diluents for the oligomers.

In some embodiments, the additional monofunctional monomer is selected from the group consisting of methyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid, 2-(2-methacrylic acid Butoxyethoxy)ethyl ester, glyceryl formal methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, phosphonate functional (meth)acrylate monomers , and combinations thereof.

In certain embodiments of the present disclosure, curable compositions often include at least 49 wt-% of additional monofunctional monomers. In certain embodiments of the present disclosure, curable compositions often include up to 97 wt-% of additional monofunctional monomers.

crosslinking agent

The cross-linking agent of the present disclosure is a compound represented by the following formula:

L-(R ¹ ) _q wherein each R ¹ is independently selected from a functional group represented by the following formula:

其中：

in:

^each R is independently hydrogen or methyl;

n is an integer from 1 to 5 (inclusive);

X is O, S, or NH; and

Y is a single bond or a divalent group represented by the following formula:

in:

N ' is the nitrogen bonded to the carbonyl carbon of ^R ; and

T is a divalent group selected from the group consisting of straight-chain alkylene, cyclic alkylene, unsubstituted arylylene, substituted arylylene, and combinations thereof;

q is an integer of at least 2; and

L is a q-valent organic polymer comprising a monomer unit selected from the group consisting of monomer units represented by the following formula:

Wherein R ^is a hydrogen or Z-terminated alkyl or heteroalkylene chain, wherein each Z-terminated chain can independently comprise a chain selected from secondary amine linkages, tertiary amine linkages, ether linkages, and the linkage of the group formed by combinations thereof, and wherein each Z is independently O, S, or NH;

Wherein n is an integer from 1 to 5 (inclusive), each R is ^{independently} hydrogen or alkyl, and each Z is independently O, S, or NH;

Wherein n is an integer from 1 to 5 (inclusive), each R is ^{independently} hydrogen or alkyl, and each Z is independently O, S, or NH;

wherein j is an integer less than or equal to 30, k is _{an integer less than or equal to 30, each R is independently hydrogen or alkyl, and each R is independently C 10} ^{to C} ₁₅ alkyl or C ₁₀ to C ₁₅ Alkenyl, wherein j and k are not both zero, and wherein the moieties with j and k subscripts are randomly distributed in the carbon chain;

Where m is an integer from 10 to 330 (inclusive), n is an integer from 1 to 5 (inclusive); and mixtures thereof;

Wherein the q-valent organic polymer L comprises less than 26000 grams per mole of monomeric units e) (if present) relative to polystyrene standards.

In some embodiments, L further comprises monomeric units selected from the group consisting of monomeric units represented by the formula:

、

、

、及其組合，其中各R⁶獨立地係氫、選自由單體單元a)至e)所組成之群組的單體單元、及Z封端之烷基鏈，其中該Z封端之烷基鏈可包括選自由二級胺基鍵聯、三級胺基鍵聯、醚鍵聯、及其組合所組成之群組的鍵聯，且其中Z係O、S、或NH，其中理解到，單體單元f)、g)、及h)如果其等存在則並非位於L之末端。

,

,

, and combinations thereof, wherein each R is ^{independently} hydrogen, a monomeric unit selected from the group consisting of monomeric units a) to e), and a Z-terminated alkyl chain, wherein the Z-terminated alkane The base chain may include linkages selected from the group consisting of secondary amine linkages, tertiary amine linkages, ether linkages, and combinations thereof, and wherein Z is O, S, or NH, wherein it is understood , monomer units f), g), and h) are not located at the end of L if they are present.

In some embodiments, L further comprises monomeric units represented by the formula:

其中T係選自由直鏈伸烷基、環狀伸烷基、未經取代伸芳基、經取代伸芳基、及其組合所組成之群組的二價基團。在此類實施例中，L可 係具有一般結構A-B-A-B-A之嵌段共聚物，其中各A代表包括式b)之單體單元的均聚物，其中n=4，Z係O，且具有每莫耳2500至3500克(例如，每莫耳2900克)之平均分子量，而各B代表由式i)所代表之單體單元，其中理解到，單體單元i)(如果其存在)並非位於L之末端。在一些實施例中，L可具有每莫耳4000至40000克或每莫耳8000至30000克之平均分子量。

Wherein T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylylene, substituted arylylene, and combinations thereof. In such embodiments, L may be a block copolymer having the general structure ABABA, wherein each A represents a homopolymer comprising monomer units of formula b), wherein n=4, Z is O, and has An average molecular weight of 2500 to 3500 grams (for example, 2900 grams per mole), and each B represents a monomer unit represented by formula i), wherein it is understood that the monomer unit i) (if it exists) is not located in L end of In some embodiments, L can have an average molecular weight of 4000 to 40000 grams per mole or 8000 to 30000 grams per mole.

With regard to the q-valent organic polymer L, it is understood that L can be a homopolymer or a copolymer (eg, block copolymer, random copolymer). For example, homopolymer L will include only one monomer unit (ie, a), b), c), d), or e)) in the polymer chain. A block copolymer may comprise, for example, a sequence of a) monomeric units adjacent to a sequence of b) monomeric units to form a polymer chain. A random copolymer may comprise, for example, some first number of b) monomeric units randomly interspersed with some second number of a) monomeric units to form a polymer chain.

The cross-linking agent of the present disclosure represented by the formula L-(R ¹ ) _q can be prepared by methods known to those skilled in the relevant technical field and can be prepared by methods such as those described in the following documents: Cooper, SLand Guan, J. (Eds) Advances in Polyurethane Biomaterials, Chapter 4, (Elsevier Ltd., 2016) and Lin et al., "UV-curable low-surface-energy fluorinated poly(urethane-acrylates)s for biomedical applications", European Polymer Journal, Vol.44, pp.2927-2937 (2008). For example, a crosslinking agent comprising monomer units represented by formulas a) and b) may be obtained from 3M Company, St. Paul, MN under the trade name DYNAMAR HC-1101 or as Prepared as described in US Patent No. 3,436,359 (prepared by Hubin et al.)) with 2-isocyanatoethyl methacrylate ("IEM").

In some preferred embodiments, the q-valent organic polymer L comprises 10wt-% to 20wt-% monomer unit a) monomer and at least 70wt-% monomer unit b) monomer. In some embodiments, the q-valent organic polymer L comprises less than 7wt-%, less than 6wt-%, less than 5wt-%, less than 4wt-%, less than 3wt-%, less than 2wt-%, less than 1wt-%, or less than 0.5 wt-% of monomer units a) monomers, wherein R ³ is other than hydrogen. In some embodiments, the q-valent organic polymer L has a number average molecular weight of 4000 to 54000 grams per mole relative to polystyrene standards.

In certain embodiments of the present disclosure, the curable composition includes at least 2 wt-%, or at least 5 wt-% of the crosslinking agent represented by the formula L-(R ¹ ) _q . In certain embodiments of the present disclosure, the curable composition includes at most 60 wt-%, or at most 50 wt-% of the crosslinking agent represented by the formula L-(R ¹ ) _q .

Curing Initiator System

The curable composition further comprises a cure initiator system. In some embodiments, the cure initiator system is a redox initiator system, since redox reactions of one-electron transfer can be an efficient method of generating free radicals under mild conditions. Redox initiator systems have been described, for example, in Prog. Polym. Sci. 24 (1999) 1149-1204.

In some embodiments, the redox initiator system is a blend of peroxides and amines, wherein polymerization is initiated by decomposition of an organic peroxide activated by a redox reaction with an amine reducing agent. Generally speaking, peroxide is benzoyl peroxide, and Amines are tertiary amines. Aromatic tertiary amines are the most effective compounds for generating primary free radicals, and N,N-dimethyl-4-toluidine ("DMT") is the most common amine reducing agent.

In some embodiments, the redox cure initiator system comprises a barbituric acid derivative and a metal salt. In some embodiments, the barbituric acid/metal salt cure initiator system may further comprise an organic peroxide, an ammonium chloride salt (eg, benzyltributylammonium chloride), or a mixture thereof.

Examples of barbituric acid-based cure initiator systems include those having (i) barbituric acid derivatives and/or malonyl sulfamides, and (ii) organic peroxides (selected from monofunctional A redox initiator system consisting of a group consisting of sexual or multifunctional carboxylic acid peroxyesters). Can be used as barbituric acid derivatives, such as 1,3,5-trimethylbarbituric acid, 1,3,5-triethylbarbituric acid, 1,3-dimethyl-5-ethane Dimethylbarbituric acid, 1,5-dimethylbarbituric acid, 1-methyl-5-ethylbarbituric acid, 1-methyl-5-propylbarbituric acid, 5-ethyl Barbituric acid, 5-propylbarbituric acid, 5-butylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid , and thiobarbituric acid mentioned in German Patent Application No. DE-A-42 19 700.

Barbituric acid and barbituric acid derivatives disclosed in U.S. Patent Nos. 3,347,954 (Bredereck et al.) and 9,957,408 (Thompson), and European Patent Specification No. EP-B-0 059 451 The malonyl sulfonamide can be used in the embodiments of the present disclosure. Examples of preferred malonylsulfonamides are 2,6-dimethyl-4-isobutylmalonylsulfonamide, 2,6-diisobutyl-4-propylmalonylsulfonamide, 2 ,6-dibutyl-4-propylmalonylsulfonamide, 2,6-dimethyl-4-ethylmalonylsulfonamide, or 2,6-dioctyl-4-isobutylpropane Diamide sulfonamides.

Barbituric acid-based redox initiator systems generally contain monofunctional or polyfunctional peroxycarboxylates as organic peroxides. Within the meaning of the present disclosure, carbonic peroxyesters are also included in polyfunctional carboxylate peroxyesters. Suitable examples include carbonic acid-diisopropyl-peroxy diester, neodecanoic acid-tert-butyl-peroxyester, neodecanoic acid-tert-pentyl-peroxyester, maleic acid-tert-butyl Base-monoperoxyester, benzoic acid-tertiary butyl-peroxyester, 2-ethylhexanoic acid-tertiary butyl-peroxyester, 2-ethylhexanoic acid-tertiary pentyl-peroxyester , Carbonic acid-monoisopropyl ester-mono-tertiary butyl-peroxy ester, carbonic acid-dicyclohexyl-peroxy ester, carbonic acid dimyristyl-peroxy ester, carbonic acid dicetyl peroxy ester, carbonic acid-two (2-Ethylhexyl)-peroxyester, carbonic acid-tertiary butyl-peroxy-(2-ethylhexyl)ester, or 3,5,5-trimethylhexanoic acid-tertiary butyl-peroxy Oxygen ester, benzoic acid-tertiary pentyl-peroxyester, acetic acid-tertiary butyl-peroxyester, carbonic acid-di(4-tertiary butyl-cyclohexyl)-peroxyester, neodecanoic acid-iso Propylbenzene-peroxyester, trimethylacetate-tert-pentyl-peroxyester, and trimethylacetate-tert-butyl-peroxyester.

Specifically, carbonate-tertiary butyl-peroxy-(2-ethylhexyl) ester (commercially available under the trade name LUPEROX TBEC from Arkema, Inc. (King of Prussia, PA)) or 3,5,5- Trimethyl-hexanoic acid-tertiary butyl-peroxyester (commercially available under the trade designation LUPEROX 270 from Arkema, Inc. (King of Prussia, PA)) can be used as the organic peroxide according to embodiments of the present disclosure.

Metal salts useful with barbituric acid derivatives may include transition metal complexes, especially salts of cobalt, manganese, copper, and iron. When the metal salt is a copper compound, the salt may have the general formula CuX _n , where X is an organic and/or inorganic anion and n=1 or 2. Examples of suitable copper salts include copper chloride, copper acetate, copper acetylacetonate, copper naphthenate, copper salicylate, or complexes of copper with thiourea or ethylenediaminetetraacetic acid, and mixtures thereof. In some embodiments, copper naphthenates are particularly preferred.

Another redox initiator system suitable for use in embodiments of the present disclosure comprises an inorganic peroxide, an amine-based reducing agent, and an accelerator, wherein the amine can be an aromatic amine and/or an aliphatic amine, and the polymeric The accelerator is at least one selected from the group consisting of: sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate, sodium sulfite, sulfurous acid Potassium, calcium sulfite, ammonium sulfite, sodium bisulfate, and potassium bisulfate. An example of an inorganic peroxide that can be used in this system is peroxodisulfate as described in US Patent No. 8,545,225 (Takei et al.).

In some embodiments, the curable composition includes a cure initiator system comprising a metal salt (eg, copper naphthenate) and an ammonium salt (eg, benzyltributylammonium chloride). In some embodiments, the curable composition includes a cure initiator system comprising a barbituric acid derivative and a metal salt, and optionally at least one of an organic peroxide or an ammonium chloride salt.

If used, the components of the cure initiator system can be present in the curable composition in an amount sufficient to allow curing of the curable composition to have a suitable free radical reaction rate at the initiation of polymerization, such amounts can be determined by those skilled in the art Easily determined by those with ordinary knowledge. Generally, curable compositions often contain at least 0.1 wt-%, or at least 0.5 wt-% of the cure initiator system. In certain embodiments of the present disclosure, curable compositions often contain up to 10 wt-%, or up to 5 wt-% of a cure initiator system.

additive

The curable composition may optionally contain one or more conventional additives. Additives may include, for example, tackifiers, plasticizers, dyes, pigments, antioxidants, UV stabilizers, corrosion inhibitors, dispersants, wetting agents, adhesion promoters, tougheners, and fillers.

Fillers useful in embodiments of the present disclosure include, for example, fillers selected from the group consisting of micro-fibrillated polyethylene, fumed silica, talc, wollastonite, aluminosilicate Salt clays (eg, halloysite), phlogopite, calcium carbonate, kaolin clay, metal oxides (eg, barium oxide, calcium oxide, magnesium oxide, zirconia, titanium oxide, zinc oxide), nanoparticles Fillers (eg, nanosilica, nanozirconia), and combinations thereof.

Selected Embodiments of the Disclosure

In the first embodiment, a curable (meth)acrylate structural adhesive composition is provided, which includes: a (meth)acrylate monomer containing a cyclic imide; a crosslinking agent ; and a curing initiator system; wherein the crosslinking agent is a compound represented by the formula:

L-(R ¹ ) _q

Wherein each ^R is independently selected from a functional group represented by the following formula:

in:

^each R is independently hydrogen or methyl;

n is an integer from 1 to 5 (inclusive);

X is O, S, or NH; and

Y is a single bond or a divalent group represented by the following formula:

in:

N ' is the nitrogen bonded to the carbonyl carbon of ^R ; and

T is a divalent group selected from the group consisting of straight-chain alkylene, cyclic alkylene, unsubstituted arylylene, substituted arylylene, and combinations thereof;

q is an integer of at least 2; and

L is a q-valent organic polymer (preferably, it has a number average molecular weight of 4,000 to 54,000 grams per mole relative to polystyrene standards) comprising a compound selected from the group consisting of monomer units represented by the following formula Single unit:

Wherein R ^is a hydrogen or Z-terminated alkyl or heteroalkylene chain, wherein each Z-terminated chain can independently comprise a chain selected from secondary amine linkages, tertiary amine linkages, ether linkages, and the linkage of the group formed by combinations thereof, and wherein each Z is independently O, S, or NH;

Wherein n is an integer from 1 to 5 (inclusive), each R is ^{independently} hydrogen or alkyl, and each Z is independently O, S, or NH;

Wherein n is an integer from 1 to 5 (inclusive), each R is ^{independently} hydrogen or alkyl, and each Z is independently O, S, or NH;

wherein j is an integer less than or equal to 30, k is _{an integer less than or equal to 30, each R is independently hydrogen or alkyl, and each R is independently C 10} ^{to C} ₁₅ alkyl or C ₁₀ to C ₁₅ Alkenyl, wherein j and k are not both zero, and wherein the moieties with j and k subscripts are randomly distributed in the carbon chain;

Where m is an integer from 10 to 330 (inclusive), n is an integer from 1 to 5 (inclusive); and

its mixture;

Wherein the q-valent organic polymer L comprises less than 26000 grams per mole of monomeric units e) (if present) relative to polystyrene standards.

In a second embodiment, the curable composition as in the first embodiment is provided, wherein the q-valent organic polymer L of the crosslinking agent has a concentration of 4000 to 54000 grams per mole relative to a polystyrene standard. Number average molecular weight. In a third embodiment, provided is the curable composition as in the first embodiment or the second embodiment, wherein the q-valent organic polymer L of the crosslinking agent comprises 10wt-% to 20wt-% of a single Body unit a) Monomer. In a fourth embodiment, provided is a curable composition as any one of the first embodiment to the third embodiment, wherein the q-valent organic polymer L of the crosslinking agent comprises at least 70wt-% of Monomer unit b) Monomer. In a fifth embodiment, provided is a curable composition as any one of the first embodiment to the fourth embodiment, wherein the q-valent organic polymer L of the crosslinking agent comprises less than 7wt-%, Less than 6wt-%, less than 5wt-%, less than 4wt-%, less than 3wt-%, less than 2wt-%, less than 1wt-%, or less than 0.5wt-% monomer unit a) monomer, wherein ^R is not hydrogen . In a sixth embodiment, there is provided a curable composition as in any one of the first to fifth embodiments, which comprises at least 2wt-% or at least 5wt-% of the formula L-(R ¹ ) is a cross-linking agent represented by _q . In a seventh embodiment, there is provided a curable composition as in any one of the first to sixth embodiments, which comprises at most 60wt-%, or at most 50wt-% of the formula L-(R ¹ ) The cross-linking agent represented by _q .

In an eighth embodiment, provided is a curable composition as any one of the first to seventh embodiments, wherein the cyclic imide-containing (meth)acrylate monomer comprises the following Cyclic imide group of the formula:

其中R¹及R²係連接以形成環系，該環系包括一或多個環(一般係兩個環)，且R³係結合至(甲基)丙烯酸酯基團(-O-C(O)-C(R)=CH₂)(其中R=H或CH₃)之伸烷基(例如，C1-C8伸烷基，且一般係伸乙基)。在第九實施例中，所提供的是如第八實施例之可固化組成物，其中該環系僅包括脂族環(一般係兩個脂族環)。在第十實施例中，所提供的是如第九實施例之可固化組成物，其中該含環狀醯亞胺之(甲基)丙烯酸酯單體具有下式：

wherein R ¹ and R ² are joined to form a ring system comprising one or more rings (typically two rings), and R ³ is bound to a (meth)acrylate group (-OC(O) -C(R)=CH ₂ ) (wherein R=H or CH ₃ ) alkylene (for example, C1-C8 alkylene, and generally ethylylene). In a ninth embodiment, provided is the curable composition as in the eighth embodiment, wherein the ring system includes only aliphatic rings (typically two aliphatic rings). In the tenth embodiment, provided is the curable composition as in the ninth embodiment, wherein the cyclic imide-containing (meth)acrylate monomer has the following formula:

In an eleventh embodiment, provided is a curable composition as in any one of the first to tenth embodiments, comprising at least 5 wt-% of the cyclic imide-containing (methyl ) acrylate monomer. In a twelfth embodiment, provided is a curable composition as any one of the first to eleventh embodiments, which comprises at most 10 wt-% of the cyclic imide-containing (form base) acrylate monomer.

In a thirteenth embodiment, provided is the curable composition of any one of the first to twelfth embodiments, further comprising an additional monofunctional monomer. In a fourteenth embodiment, provided is the curable composition of the thirteenth embodiment, wherein the additional monofunctional monomer is selected from the group consisting of: methyl methacrylate, methyl 2-hydroxyethyl acrylate, methacrylic acid, 2-(2-butoxyethoxy)ethyl methacrylate, glycerin formal methacrylate, lauryl methacrylate, cyclohexyl methacrylate , phenyl methacrylate, phosphonate functional (meth)acrylate monomers, and combinations thereof. In a fifteenth embodiment, provided is the curable composition of the thirteenth embodiment or the fourteenth embodiment, which comprises at least 49 wt-% of the additional monofunctional monomer. In a sixteenth embodiment, provided is the curable composition of the thirteenth embodiment to the fifteenth embodiment, which comprises at most 97 wt-% of the additional monofunctional monomer.

In a seventeenth embodiment, provided is the curable composition of any one of the first to sixteenth embodiments, wherein the cure initiator system comprises a free radical initiator system. In an eighteenth embodiment, provided is the curable composition of the seventeenth embodiment, wherein the free radical initiator system comprises a metal salt (e.g., copper naphthenate) and an ammonium salt (e.g., benzyl tributylammonium chloride). In a nineteenth embodiment, there is provided The curable composition of any one of the first to eighteenth embodiments, comprising at least 0.1 wt-% (or at least 0.5 wt-%) of the curing initiator system. In a twentieth embodiment, provided is a curable composition as in any one of the first to nineteenth embodiments, comprising at most 10 wt-% (or at most 5 wt-%) of the curing agent starter system.

In the twenty-first embodiment, provided is the curable composition as any one of the first embodiment to the twentieth embodiment, wherein the q-valent organic polymer L further comprises The monomer unit of the group consisting of the represented monomer units:

、

、

、及其組合，其中各R⁶獨立地係氫、選自由單體單元a)至e)所組成之群組的單體單元、及Z封端之烷基鏈，其中該Z封端之烷基鏈可包括選自由二級胺基鍵聯、三級胺基鍵聯、醚鍵聯、及其組合所組成之群組的鍵聯，且其中Z係O、S、或NH。

,

,

, and combinations thereof, wherein each R is ^{independently} hydrogen, a monomeric unit selected from the group consisting of monomeric units a) to e), and a Z-terminated alkyl chain, wherein the Z-terminated alkane The base chain can include linkages selected from the group consisting of secondary amine linkages, tertiary amine linkages, ether linkages, and combinations thereof, and wherein Z is O, S, or NH.

In the twenty-second embodiment, provided is the curable composition as any one of the first embodiment to the twenty-first embodiment, wherein the q-valent organic polymer L further comprises represented by the following formula The single unit:

其中T係選自由直鏈伸烷基、環狀伸烷基、未經取代伸芳基、經取代伸芳基、及其組合所組成之群組的二價基團。

Wherein T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylylene, substituted arylylene, and combinations thereof.

In a twenty-third embodiment, provided is the curable composition of any one of the first to twenty-second embodiments, the composition further comprising a filler. In a twenty-fourth embodiment, provided is the curable composition of the twenty-third embodiment, wherein the filler is selected from the group consisting of: microfibrillated polyethylene, fuming dioxide Silicon, talc, wollastonite, aluminosilicate clay, phlogopite, calcium carbonate, kaolin clay, and combinations thereof.

In a twenty-fifth embodiment, provided is the curable composition of any one of the first to twenty-fourth embodiments, wherein the structural (methyl) The acrylate adhesive has a minimum ultimate elongation of at least 50%, at least 100%, at least 200%, or at least 400%, at least 600%, or at least 800%. In a twenty-sixth embodiment, provided is the curable composition of any one of the first through twenty-fifth embodiments, wherein the structural (meth)acrylate adhesive has at least 1000 psi, A minimum overlap shear strength of at least 1100 psi, at least 1200 psi, or at least 1300 psi, or at least 1400 psi.

In a twenty-seventh embodiment, provided is a method of joining a first substrate to a second substrate, the method comprising: providing the curable (meth)acrylate structural composition described herein an adhesive composition; and an accelerator for forming a curable adhesive mixture; applying the curable adhesive mixture to at least a portion of a surface of the first substrate; at least partially coating the curable adhesive mixture with the At least a portion of one surface of the second substrate is covered; and the curable adhesive mixture is cured and formed into a structural (a base) acrylate adhesive. In the twenty-eighth embodiment, provided is the method as in the twenty-seventh embodiment, wherein 10 parts of the curable (meth)acrylate structural adhesive composition and 1 part of the accelerator agent mix.

In the twenty-ninth embodiment, provided is the method of the twenty-seventh embodiment or the twenty-eighth embodiment, wherein at least one of the first substrate or the second substrate is glass. In a thirtieth embodiment, provided is the method of any one of the twenty-seventh embodiment to the twenty-ninth embodiment, wherein the first substrate and the second substrate are different materials. In a thirty-first embodiment, provided is the method of the thirtieth embodiment, wherein at least one of the first substrate or the second substrate is glass, and the other substrate is metal.

In a thirty-second embodiment, provided is the method according to any one of the twenty-seventh embodiment to the thirty-first embodiment, wherein the portion of a surface of the first substrate is The cured adhesive mixture was not subjected to surface treatment prior to application thereto.

In a thirty-third embodiment, provided is a bonded article comprising a structural adhesive bonded to a substrate prepared according to any one of the twenty-seventh to thirty-second embodiments .

example

Objects and advantages of the present disclosure are further illustrated by the following non-limiting examples, but the specific materials and their amounts detailed in these examples, as well as other conditions and details, should not be unduly interpreted to limit the present invention.

Unless otherwise stated, parts, percentages, ratios, etc. in the examples in this specification and in the rest of the specification are by weight.

analysis program

Attenuated total reflectance (ATR) FTIR spectroscopy measurement

ATR-FTIR measurements were recorded using a Thermo Nicolet iS50 FTIR (Thermo Fisher Scientific Co., Waltham, MA, USA) spectrometer equipped with a single-bounce diamond crystal and deuterated triglycine sulfate detection device. A drop of each liquid sample was placed directly on the surface of the diamond ATR crystal, and the evanescent wave could be absorbed by the liquid sample. The resulting attenuated radiation produces an ATR spectrum similar to conventional absorption spectra.

Transmission FTIR (transmission-FTIR) spectroscopy measurement

Transmission FTIR measurements were recorded using a Thermo Nicolet iS5 System FTIR (Thermo Fisher Scientific Co., Waltham, MA) spectrometer. Samples were prepared by diluting an aliquot of the reaction in toluene to provide a solution, spreading the solution on a salt plate, and drying under a stream of nitrogen.

gel permeation chromatography

The polymer was obtained by gel permeation chromatography (gel permeation chromatography, GPC) using Reliant GPC (Waters e2695 pump/autosampler Detector) with Waters 2424 evaporative light scattering detector and PL-Gel-2 column; each 300 x 7.5mm; a 3μm Mixed-E (nominal MW range up to 30,000 Daltons) and a 5μm Mixed-E -D (nominal MW range 200 to 400,000 Daltons). Stabilized with 250 ppm BHT (relative to polystyrene standards) in tetrahydrofuran at 40°C.

Overlap Shear Test

Each sample formulation was loaded separately into the 10 side of a 10:1 dual syringe cartridge dispenser, using accelerator from 3M SCOTCH-WELD DP8410NS Acrylic Adhesive (3M Company) in the 1 side of the dispenser in each case. All joints were prepared by dispensing the sample formulation and accelerator through a static mixing tip. The resulting adhesive was used to prepare samples for overlay shear test samples on sandblasted aluminum substrates, IPA wiped glass substrates, or IPA wiped sintered glass substrates. Overlap shear samples were 2.54cm x 10.16cm x 0.16cm aluminum, glass or sintered glass specimens and used 0.076 to 0.0127mm spacer beads with a 1.27cm overlap. The bond wires were clamped with long tail clips during curing and the clips were removed after 24 hours at 25°C. Testing was performed on a 5000 lb (22kN) load cell for overlapping shear. The equivalent value is the average of three samples.

Tensile test of cured film

Films of the cured composition were prepared by mixing 40 g of the sample formulation with DP8410NS from SCOTCH-WELD in a polypropylene Max 100 DAC cup (Part No. 501 221 from FlackTek, Inc., Landrum, SC). 4 g accelerator combination of Acrylic Adhesive (3M Company, St. Paul, MN). The cup was closed with a polypropylene lid and the mixture was high shear mixed at 1500 rpm (revolutions per minute) for 25 seconds at ambient temperature and pressure using a FlackTek, Inc. SPEEDEMIXER (DAC 400.2 VAC). The resulting mixture was spread between silicone-treated polyester release liners at a thickness of approximately 1 mm. The coated films were allowed to stand at room temperature for a minimum of 24 hours prior to testing. Tensile elongation measurement is carried out according to ASTM Standard ASTM Standard D638-14 "Standard Test Method for Tensile Properties of Plastics", 2015, using TYPE-V mold for sample cutting And use 100mm/min chuck test speed (crosshead test speed).

Dynamic Mechanical Analysis (“DMA”) Testing

Film samples were prepared using films prepared as described above for the "Tensile Test". Film samples were cut to approximately 6 to 7 mm width x 1 mm thickness x 50 mm length and tested on a DMAQ800 (TA Instruments Inc., New Castle, DE) using a double cantilever fixture with the following settings: Frequency = 1 Hz, Oscillation Amplitude = 15μm, and the minimum vibration force = 0.02N. The film samples were equilibrated to -75°C and held at this temperature for five minutes, followed by a 3.0°C/minute temperature ramp to 200°C. The glass transition temperature (T _g ) was found by detecting the maximum peak height of the Tan delta curve.

Preparation Example 1: Preparation of Methacryloxyurea-terminated Branched-chain Diamine Poly(tetrahydrofuran) (“HC-1101/IEM”)

DYNAMAR HC-1101 ("HC-1101") was heated at 65°C to melt the solid material and reduce its viscosity. Molten HC-1101 (245.0 g) was charged to a 3 neck round bottom flask equipped with distillation head, thermocouple, and overhead stirrer. The flask was sparged with nitrogen and heated to 70°C. To the highly viscous, heated HC-1101 was added methyl ethyl ketone (60 mL) with stirring. Subsequently, the same amount of methyl ethyl ketone was distilled off under vacuum to provide dry HC-1101. To the dried HC-1101 was added dropwise 2-isocyanatoethyl methacrylate ("IEM") (5.32 g) under nitrogen and stirring was continued at 70°C for 16 hours. Isocyanate consumption was monitored by transmission FTIR spectroscopy. The resulting material was discharged at 70°C to afford 196.2 g (78% yield) of a viscous, light yellow oil (HC-1101/IEM) which solidified upon cooling to ambient temperature.

Alternative Crosslinkers

The following crosslinkers can be prepared as substitutes for the crosslinkers prepared in Example 1. Although these do not incorporate curable (meth)acrylate structural adhesive compositions comprising cyclic imide-containing (meth)acrylate monomers, it is believed that they will provide the result of.

Alternative Preparation Example 2: Preparation of Methacrylate Functional Pure Primary Poly(tetrahydrofuran)diamine (“PPDA-6K/IEM” and “PPDA-9K/IEM”)

81) IEM-PPDA-6K (diamine Mn=5888 Dalton, X

81)

124) IEM-PPDA-9K (diamine Mn=9126 Dalton, X

124)

Linear polytetrahydrofuran diamine PPDA-6K (122.5 g) (prepared as described in U.S. Patent No. 4,833,213 (Leir et al.)) was added to a 500 mL vessel equipped with a thermocouple, stainless steel mechanical stirrer, and vacuum adapter. resin flask. The flask was heated to 75°C and kept under high vacuum overnight (14 hours). The flask was refilled with dry air and PROSTAB 5198 (44.0 mg) was added. Mix well and cool the flask to 50°C. Remove from heat source. 2-Isocyanatoethyl methacrylate (6.42 g) was added and stirred well. The previously clear viscous oil became opaque when 2-isocyanatoethyl methacrylate was mixed. After 30 minutes, all isocyanate was consumed as evidenced by transmission FTIR spectroscopy. The material was drained to provide 125.8 g (98% yield) of an opaque viscous oil which solidified upon cooling.

Linear polytetrahydrofuran diamine PPDA-9K (82.07 g) (prepared as described in U.S. Patent No. 4,833,213 (Leir et al.)) was added to a 500 mL vessel equipped with a thermocouple, stainless steel mechanical stirrer, and vacuum adapter. resin flask. The flask was heated to 75°C and kept under high vacuum overnight (16 hours). The flask was refilled with dry air and PROSTAB 5198 (23.3 mg) was added. Mix well and cool the flask to 50°C. Remove from heat source. 2-Isocyanatoethyl methacrylate (2.85 g) was added and stirred well. After 30 minutes, all isocyanate was consumed as evidenced by transmission FTIR spectroscopy. The material was discharged to afford 80.0 g (94% yield) of a viscous pale yellow oil which solidified upon cooling.

Alternative Preparation Example 3: Methacryloxyurea Terminated Polysiloxane Methacrylate ("MAUS-1K/IEM", "MAUS-5K/IEM", and "MAUS-25K/IEM") Synthesis of crosslinking agent

MAUS (methacryloxyurea-terminated polysiloxane)

MAUS-1K/IEM (Polysiloxane Mn~1000 Dalton)

MAUS-5K/IEM (Polysiloxane Mn~5000 Dalton)

MAUS-25K/IEM (Polysiloxane Mn~25000 Dalton)

For each material, silicone diamine and 2-isocyanatoethyl methacrylate ("IEM") were added to a polypropylene MAX 200 DAC cup (Part No. 501 220p-j from FlackTek, Inc., Landrum, SC). The cups were closed with polypropylene lids and the mixture was high shear mixed at 2000 rpm for one minute at ambient temperature and pressure using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC). After mixing, the mixture became hot due to the exothermic reaction. The mixture was allowed to react at ambient conditions for at least 24 hours before use.

Alternative Preparation Example 4: Synthesis of Methacrylate Functional Poly(tetrahydrofuran)diols (“THF 2000/IEM” and “THF 2900/IEM”)

26) THF 2000/IEM(X

26)

38) THF 2900/IEM(X

38)

Methacrylate functional poly(tetrahydrofuran)diols were prepared using poly(tetrahydrofuran)diols of two molecular weights (2000 g/mol and 2900 g/mol) using the following procedure.

The diol was heated at 70°C to melt. Transfer the amounts of molten diols listed in Table 5 to polypropylene MAX 200 DAC cups (Part No. 501 220p-j from FlackTek, Inc., Landrum, SC) using separate cups for each diol, followed by the addition of The amount of isocyanatoethyl methacrylate ("IEM") listed in Table 5. The cups were closed with polypropylene lids and the mixture was high shear mixed at 2000 rpm for one minute at ambient temperature and pressure using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC). The closed container was kept at 60°C in an oven. The reaction mixture was monitored over time using attenuated total reflectance ("ATR") FTIR spectroscopy. The total reaction time was 17 hours. After this time, ATR showed that the isocyanate-NCO peak at about 2264 cm ^-1 and the OH peak at 3500 cm ^-1 disappeared, and the NH peak at 3400 cm ^-1 appeared, confirming the completion of the reaction .

Alternative Preparation Example 5: Synthesis of Methacrylate Functional PLACCEL H1P ("PCL H1P/IEM")

10,000 molecular weight poly(caprolactone) diol was methacrylate functionalized using the procedure described above for poly(tetrahydrofuran) diol, in which PLACCEL H1P (200 g) was combined with 2-isocyanatoethyl methacrylate (7.19 g) at 80°C for 4 hours.

Alternative Preparative Example 6: Synthesis of Methacrylate Functional D4000 ("D4000/IEM")

To a polypropylene MAX 200 DAC cup (Part No. 501 220p-j from FlackTek, Inc., Landrum, SC) was added JEFFAMINE D4000 (100 g), 2-isocyanatoethyl methacrylate (7.8 g), and MEHQ (0.25g). The cup was closed with a polypropylene lid and the mixture was high shear mixed at 2000 rpm for one minute at ambient temperature and pressure using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC). After mixing, the mixture became hot due to the exothermic reaction. The methacrylates were allowed to react at ambient conditions for at least 24 hours before use.

Alternative Preparative Example 7: Synthesis of Methacrylate Functional EC311 ("EC311/IEM")

A polypropylene MAX 200 DAC cup (Part No. 501 220p-j from FlackTek, Inc., Landrum, SC) was charged with EC311 (100 g), 2-isocyanatoethyl methacrylate (8.0 g), and MEHQ ( 0.25g). The cup was closed with a polypropylene lid and the mixture was high shear mixed at 2000 rpm for one minute at ambient temperature and pressure using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC). After mixing, the mixture became hot due to the exothermic reaction. The methacrylates were allowed to react at ambient conditions for at least 24 hours before use.

Alternative Preparative Example 8: Synthesis of Methacrylate Functional Polymethylene Diol ("F3000/IEM")

To a polypropylene MAX 200 DAC cup (Part No. 501 220p-j from FlackTek, Inc., Landrum, SC) was added poly(bacteriochlorene) F3000 (100 g), and 2-isocyanatoethyl methacrylate ( 11.4g). The cup was closed with a polypropylene lid and the mixture was high shear mixed at 2000 rpm for one minute at ambient temperature and pressure using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC). The closed container was kept at 70°C in an oven. The reaction mixture was monitored over time using attenuated total reflectance ("ATR") FTIR spectroscopy. The total reaction time is 7 hours, after this time, ATR shows that the isocyanate-NCO peak at about 2264 cm ^-1 and the OH peak at 3500 cm ^-1 disappear, and the NH peak at 3400 cm ^-1 appears, confirming the completion of the reaction .

Example 1. Preparation of curable samples 1 to 9:

Curable samples 1 through 9 were prepared by combining the components of Table 6 in a polypropylene MAX 200 DAC cup (Part No. 501 220 from FlackTek, Inc.). After capping with a polypropylene cap, the mixture was mixed in a SPEEDMIXER (DAC 400.2 VAC from FlackTek, Inc.) at 1500 rpm for one minute (three times) with manual agitation using a wooden spatula between mixings. Samples were degassed by capping with polypropylene caps containing vents and high shear mixed under reduced pressure (35 Torr).

Example 2: Sample film and bonding test

Film coatings of the samples incorporated in Table 6 were prepared using the procedure described above. The testing procedures for tensile elongation measurements and dynamic mechanical analysis ("DMA") using the prepared film coatings were as described above. The sample film test results are shown in Tables 7 and 8 below.

The joints of the samples incorporated in Table 6 were prepared between glass, sintered glass and aluminum samples using the procedure described above. The procedure for the overlap shear test was as described above and the test results are shown in Table 9 below.

The data in Tables 7-9 show that sample formulations containing crosslinkers and monomers of the present disclosure can produce adhesives with excellent adhesion to glass without the use of primers or surface modifications.

Example 3. Glass/Glass Overlap Sheer ("OLS") Aging Test

Sample formulations 4 or 7, prepared as described above, were loaded into the 10-part side of a 10:1 dual-syringe cartridge dispenser, and in the 1-part side of the dispenser, Acrylic Adhesive from 3M SCOTCH-WELD DP8410NS (3M Company, St. Accelerator of Paul MN). All joints are made by static mixing of the adhesive composition and accelerator. Prepared for dispensing with tip. The adhesive was used to prepare overlap shear aging test specimens on sintered glass substrates prepared with isopropanol wipes and white painted aluminum substrates. Overlap shear samples with a 0.5 inch (1.27 cm) overlap were prepared on glass coupons (1/4 inch (0.635 mm) thick x 1 inch (25.4 mm) wide x 4 inches (101.6 mm) long). The bond wires were clamped with long tail clips during curing and the clips were removed after 24 hours at 25°C. Glass test specimens were conditioned at 77°F (25°C) and 50% relative humidity for 3 days, then placed in a weathering chamber. Measurements were then made at 3 weeks on a 5000 lb (22kN) load cell for overlapping shear ("OLS Aging Results"). After removing the forming chamber, the samples were allowed to equilibrate for 24 hours. The equivalent value is the average of three samples. The data are shown in Table 10.

Adhesives based on methacrylate monomers, such as those prepared with sample formulations 4 or 7, are expected to hydrolyze upon heat/humidity aging (i.e., 150°F (66°C) and 85% relative humidity) and The OLS value therefore decreases with continued aging. Surprisingly, the data in Table 10 show that adhesives prepared using Sample Formulation 4 did not performance, and suggest that the adhesive formulations of the present disclosure may have utility as sealants and advanced weathering structural adhesives.

The documents, patents and patent applications cited in the above patent applications are all incorporated herein by reference in their entirety in a consistent manner. If there is any inconsistency or conflict between the incorporated documents and this application, the information in the foregoing description shall prevail. The aforementioned implementation methods of the present disclosure are intended to enable persons with ordinary knowledge in the technical field to implement the disclosed embodiments, and should not be construed as limiting the scope of the present invention. The scope of the present invention is defined by the scope of the patent application and all its equivalents.

Claims (15)

A curable (meth)acrylate structural adhesive composition comprising: a (meth)acrylate monomer containing a cyclic imide; a cross-linking agent; and a curing initiator system; wherein the cross-linking agent The linking agent is a compound represented by the following formula: L-(R ¹ ) _q Wherein each ^R is independently selected from a functional group represented by the following formula:

in: ^each R is independently hydrogen or methyl; n is an integer from 1 to 5 (inclusive); X is O, S, or NH; and Y is a single bond or a divalent group represented by the following formula:

in: N ' is the nitrogen bonded to the carbonyl carbon of ^R ; and T is a divalent group selected from the group consisting of straight-chain alkylene, cyclic alkylene, unsubstituted arylylene, substituted arylylene, and combinations thereof; q is an integer of at least 2; and L is a q-valent organic polymer comprising monomer units selected from the group consisting of monomer units represented by the following formula:

Wherein R ^is a hydrogen or Z-terminated alkyl or heteroalkylene chain, wherein each Z-terminated chain can independently comprise a chain selected from secondary amine linkages, tertiary amine linkages, ether linkages, and the linkage of the group formed by combinations thereof, and wherein each Z is independently O, S, or NH;

Wherein n is an integer from 1 to 5 (inclusive), each R is ^{independently} hydrogen or alkyl, and each Z is independently O, S, or NH;

Wherein n is an integer from 1 to 5 (inclusive), each R is ^{independently} hydrogen or alkyl, and each Z is independently O, S, or NH;

wherein j is an integer less than or equal to 30, k is _{an integer less than or equal to 30, each R is independently hydrogen or alkyl, and each R is independently C 10} ^{to C} ₁₅ alkyl or C ₁₀ to C ₁₅ Alkenyl, wherein j and k are not both zero, and wherein the moieties with j and k subscripts are randomly distributed in the carbon chain;

Wherein, m is an integer from 10 to 330 (inclusive), and n is an integer from 1 to 5 (inclusive). The curable composition as claimed in claim 1, wherein the q-valent organic polymer L of the crosslinking agent has a number average molecular weight of 4000 to 54000 grams per mole relative to polystyrene standards, or wherein if the monomer unit e) present, the q-valent organic polymer L comprises less than 26000 grams per mole of the monomer unit e) relative to polystyrene standards. The curable composition according to claim 1, which comprises at least 2 wt-% and at most 60 wt-% of the crosslinking agent represented by the formula L-(R ¹ ) _q . The curable composition as claimed in claim 1, wherein the cyclic imide-containing (meth)acrylate monomer has the following formula:

The curable composition according to claim 1, which comprises at least 5wt-% and at most 50wt-% of the cyclic imide-containing (meth)acrylate monomer. The curable composition according to claim 1, further comprising an additional monofunctional monomer. The curable composition as claimed in item 6, wherein the additional monofunctional monomer system is selected from the group consisting of: methyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid, methyl 2-(2-Butoxyethoxy)ethyl acrylate, glyceryl formal methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, phosphonate functionality (methacrylate base) acrylate monomers, and combinations thereof. The curable composition of claim 6, comprising at least 49 wt-% and at most 97 wt-% of the additional monofunctional monomer. The curable composition according to claim 1, wherein the curing initiator system comprises a free radical initiator system. The curable composition as claimed in claim 9, wherein the free radical initiator system comprises a metal salt and ammonium salt. The curable composition according to claim 1, which comprises at least 0.1 wt-% and at most 10 wt-% of the curing initiator system. The curable composition according to claim 1, further comprising a filler. A method of bonding a first substrate to a second substrate, the method comprising: Provide a curable (meth)acrylate structural adhesive composition according to any one of claims 1 to 12, and an accelerator to form a curable adhesive mixture; applying the curable adhesive mixture to at least a portion of a surface of the first substrate; at least partially covering the curable adhesive mixture with at least a portion of a surface of the second substrate; and The curable adhesive mixture is allowed to cure and form a structural (meth)acrylate adhesive. The method according to claim 13, wherein at least one of the first substrate or the second substrate is glass. A bonded article comprising a structural adhesive bonded to a substrate prepared by the method of claim 13.