CN112175528A - High-stability instant adhesive and preparation method thereof - Google Patents

High-stability instant adhesive and preparation method thereof Download PDF

Info

Publication number
CN112175528A
CN112175528A CN202011093188.0A CN202011093188A CN112175528A CN 112175528 A CN112175528 A CN 112175528A CN 202011093188 A CN202011093188 A CN 202011093188A CN 112175528 A CN112175528 A CN 112175528A
Authority
CN
China
Prior art keywords
component
composition
tensile strength
ethylene
cyanoacrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011093188.0A
Other languages
Chinese (zh)
Inventor
林闪光
叶善明
庞涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Paifeite New Material Technology Co ltd
Original Assignee
Zhejiang Paifeite New Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Paifeite New Material Technology Co ltd filed Critical Zhejiang Paifeite New Material Technology Co ltd
Priority to CN202011093188.0A priority Critical patent/CN112175528A/en
Publication of CN112175528A publication Critical patent/CN112175528A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention is a solution by providing cyanoacrylate compositions which provide improved thermal and moisture properties upon curing, by combining, in general terms, (a) a cyanoacrylate component, (b) a reaction product of (i) ethylene, methyl acrylate, in combination with a monomer having a carboxylic acid cure site; (ii) a copolymer of ethylene and methyl acrylate, and a combination of (i) and (ii), (c) comprising at least two (meth) acrylate functional groups, and (d) an anhydride component. The invention also relates to a method of bonding two substrates together, which comprises applying a composition as described above to at least one of the substrates and then mating the substrates together. Furthermore, the invention relates to a process for the preparation of the composition according to the invention. The instant adhesive composition provided by the invention has enhanced heat and humidity aging performance and high stability in a heat and humidity environment.

Description

High-stability instant adhesive and preparation method thereof
Technical Field
The invention relates to an instant adhesive, in particular to a high-stability instant adhesive. Meanwhile, the invention also provides a preparation method of the high-stability instant adhesive.
Background
Flash glues, i.e. cyanoacrylate adhesive compositions, are well known for their wide use. However, since the flash gels are thermoplastic in nature, they tend to soften with increasing temperature and when the Tg of the material is exceeded, the cured product begins to flow and also begins to degrade and degrade with increasing temperature and decreasing physical properties. As a result, the existing instant adhesive is very difficult to use under the condition of high temperature (more than or equal to 120 ℃) exposure, and therefore, the use is limited.
Disclosure of Invention
As noted above, the present invention relates to an instant adhesive, cyanoacrylate composition, which provides improved thermal and moisture properties when cured.
More specifically, an instant adhesive comprising: (a) a cyanoacrylate component, (b) a rubber toughening agent consisting of (i) the reaction product of ethylene, methyl acrylate, in combination with a monomer having a carboxylic acid cure site, (ii) a dimer of ethylene and propylene acrylate, and combinations of (i) and (ii), (c) a component containing at least two (meth) acrylate functional groups, and (d) an anhydride component.
Wherein the cyanoacrylate component comprises at least one cyanoacrylate monomer which may select a wide variety of substituents, for example, from H2C ═ C (CN) -COOR, wherein R is selected from C1-15Alkyl radical, C2-15Alkoxyalkyl radical, C3-15Cycloalkyl radical, C2-15Alkenyl radical, C6-15Aralkyl radical, C5-15Aryl radical, C2-15An allyl haloalkyl group. Desirably, the cyanoacrylate monomer is selected from at least one of methyl cyanoacrylate, ethyl 2-cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate (e.g., n-butyl 1-2-cyanoacrylate), octyl cyanoacrylate, allyl cyanoacrylate, 13-methoxyethyl cyanoacrylate, and combinations thereof. Particularly desirably, the cyanoacrylate monomer comprises ethyl 2-cyanoacrylate.
The cyanoacrylate component should be included in the composition in an amount of from about 50% to about 99.98% by weight of the total composition; desirably, from about 70% to about 85% by weight.
The rubber toughening component may be selected from one of several possibilities. One such possibility is the reaction product of ethylene, methyl acrylate, in combination with a monomer having a carboxylic acid cure site. For example, the rubber toughening component may be an ethylene acrylic elastomer, such as available from DupontTMCommercial, trade name: vamac, such as VAMAC N123 and VAMAC B-124. DuPont reports it as a masterbatch of ethylene/acrylic elastomer. DuPont material VAMAC G is a similar copolymer but does not contain fillers for providing color or stabilizers. The VAMAC VCS rubber appears to be the base rubber from which the remaining members of the VAMAC product line are blended. VAMAG VCS (also known as VAMAC MR) is a reaction product of ethylene, methyl acrylate, combined with a monomer having a carboxylic acid cure site, and once formed, is substantially free of processing aids such as the release agent octadecylamine, complex organophosphate esters and/or stearic acid, and antioxidants such as substituted phenols.
Recently, DuPont has been offered to the market under the tradenames VAMAC VMX 1012 and VCD 6200, which are rubbers made from ethylene and methyl acrylate. It is believed that the VAMAC VMX 1012 rubber has little carboxylic acid in the polymer backbone, like the VAMAC VCS rubber, the VAMAC VMX 1012 and VCD 6200 rubbers are essentially free of processing aids such as the release agents octadecylamine, complex organophosphates and/or stearic acid, and antioxidants such as substituted diphenylamines. All of these VAMAC elastomeric polymers are useful herein above.
In one variation, the reaction product so formed is substantially free of processing aids and antioxidants. Processing aids are mold release agents such as octadecyl amine (commercially available under the trade name ARMEEN 18D from Akzo Nobel, reported by DuPont), complex organic phosphate esters (commercially available under the trade name VANFRE VAM from RT van der bilt co., inc.), stearic acid, and/or polyethylene glycol ether waxes. The antioxidant is a substituted diphenylamine (commercially available from Uniroyal Chemical under the trade name NAUGARD 445), reported by DuPont.
Alternatively, the rubber toughening component is a dimer of ethylene and methyl acrylate. In a variation of this alternative, the dimer thus formed is substantially free of processing aids and antioxidants. Of course, the rubber toughening agent may be a combination of the reaction product of the preceding stage and the dimer of that stage, either or both of which may be substantially free of processing aids and antioxidants.
The rubber toughening component should be present at a concentration of from about 1.5% to about 20% by weight, for example from about 5% to about 15% by weight, with from about 8% to about 10% being particularly preferred.
The component comprising at least two (meth) acrylate functional groups should be an aliphatic compound having at least two (meth) acrylate functional groups, preferably at the end of the aliphatic chain, although side groups along the aliphatic chain are suitable. Specifically, it may be hexanediol dimethacrylate and hexanediol diacrylate, or ditrimethylolpropane tetraacrylate and trimethylolpropane trimethacrylate.
For example, the component comprising at least two (meth) acrylate functional groups may have the formula:
Figure BDA0002722856620000031
wherein A is C4-C30An aliphatic chain which may optionally comprise heteroatoms chosen from O, N and S, and wherein said chain is optionally substituted by one or more acrylate and/or methacrylate functional groups and/or one or more C1-C10Alkyl substitution; wherein R is1And R2May be the same or different and are each optionally selected from H and C1To C6An alkyl group.
Suitably, the component having at least two (meth) acrylate functional groups has the formula:
Figure BDA0002722856620000032
wherein R is1And R2Identical or different and selected from H or Me; wherein X is C4-C30An alkyl chain which may optionally comprise heteroatoms selected from the group consisting of O, N and S, and wherein said chain is optionally substituted with one or more acrylate and/or methacrylate functional groups, and/or one or more C1-C10An alkyl group.
X may be C4To C30Alkyl chains, e.g. X may be C4Alkyl chains, or C5Alkyl chains, or C6Alkyl chains, or C7Alkyl chains, or C8Alkyl chains or C9Alkyl chains, or C10Alkyl chains, or C11Alkyl chains, or C12An alkyl chain.
The component having at least two (meth) acrylate functional groups may be selected from:
Figure BDA0002722856620000041
the component comprising at least two (meth) acrylate functional groups should be present at a concentration of about 0.5% to about 20% by weight, for example about 1% to about 15% by weight, about 5% to about 20% by weight. 10% by weight is particularly desirable.
The anhydride component should be an aromatic component such as phthalic anhydride or a fully or partially hydrogenated form thereof, although other anhydrides may or may not be used with phthalic anhydride (or a fully or partially hydrogenated form thereof).
The anhydride component should be present at a concentration of about 0.05 wt.% to about 5 wt.%, for example about 0.1 wt.% to about 1 wt.%, with about 0.5 wt.% being particularly preferred.
Agents imparting heat resistance may also be added. Included among these agents are certain sulfur-containing compounds, such as sulfonates, sulfinates, sulfates, and sulfites.
For example, the compositions of the present invention may optionally contain additives that impart heat resistance, such as 2-sulfobenzoic anhydride, triethylene glycol di (p-toluenesulfonate), trifluoroethyl p-toluenesulfonate, dimethyldioxol-4-ylmethylhydroquinone-toluenesulfonate, p-toluenesulfonate, methanesulfonic anhydride, 1, 3-propylene sulfite, dioxathiolene dioxide, 1, 8-naphthalenesulfonate, sultone 1, 3-propane, sultone 1, 4-butene, allylphenylsulfone, 4-fluorophenylsulfone, dibenzothiophenesulfone, bis (4-fluorophenyl) sulfone, ethyl p-toluenesulfonate, trifluoromethanesulfonic anhydride.
Accelerators may be included in the instant adhesive compositions of the present invention, such as any one or more selected from the group consisting of calixarenes and oxalates, diatomaceous earth, crown ethers, cyclodextrins, poly (ethylene glycol) di (meth) acrylates, ethoxylated hydroxyl compounds, and combinations thereof.
For example, for calixarenes, the aromatics in the following structure are useful herein:
Figure BDA0002722856620000051
wherein R is1Is alkyl, alkoxy, substituted alkyl or substituted alkoxy; r2Is H or alkyl; n is 4, 6 or 8.
One particularly desirable calixarene is tetrabutyltetra [ 2-ethoxy-2-oxyethoxy ] calixarene-4-arene.
Various crown ethers are known, having the formula:
Figure BDA0002722856620000052
can be used herein alone or in combination, for example, 15 crown 5, 18 crown 6, dibenzo 18 crown 6, benzo 15 crown 5-dibenzo 24 crown 8, dibenzo 30 crown 10, tribenzo 18 crown-6, 1, 2-naphthalene-15-crown-5, 3,4, 5-naphthalene 1-16-crown-5, 1, 2-methyl-benzo-18-crown-6, 1, 2-methylbenzo-5, 6-methylbenzo-18-crown-6, 1, 2-tert-butyl-18-crown-6, 1, 2-vinylbenzo-15-crown-5, 1, 2-vinylbenzo-18-crown-6, 1, 2-tert-butylcyclohexyl 1-18-crown-6, asymmetric-dibenzo-22-crown-6 and 1, 2-benzo-1, 4-benzo-5-oxo-20-crown-7.
Among the diatom coronas, many are also known and have been reported in the literature. Such as a typical silastic crown. Specific examples of zucchini compounds that can be used in the compositions of the present invention include:
Figure BDA0002722856620000061
dimethylsiloxane-11-crown-4;
Figure BDA0002722856620000062
dimethylsiloxane-14-crown-5;
Figure BDA0002722856620000063
and dimethylsiloxane-17-crown-6.
Many cyclodextrins can be used in conjunction with the present invention. For example, those described and claimed in U.S. patent No. 5,312,864(Wenz), the disclosure of which is expressly incorporated herein by reference as a hydroxy derivative of an α, β, or γ -cyclodextrin that is at least partially soluble in the compound.
For example, poly (ethylene glycol) di (meth) acrylates suitable for use herein include those of the following structures:
Figure BDA0002722856620000071
where n is greater than 3, for example in the range of 3 to 12, it is particularly desirable that n is 9. More specific examples include PEG 200DMA (n is about 4), PEG 400DMA (n is about 9), PEG 600DMA (n is about 14) and PEG 800DMA (n is about 19), where the number (e.g., 400) represents the average molecular weight of the diol portion of the molecule excluding the two methacrylate groups, expressed in grams/mole (i.e., 400 g/mol). A particularly desirable PEG DMA is PEG 400 DMA.
Among the ethoxylated hydroxyl compounds (or ethoxylated fatty alcohols that may be used), suitable ones may be selected from those in the following structures:
Figure BDA0002722856620000072
wherein C ismMay be a linear or branched alkyl or alkenyl chain, m is an integer between 1 and 30, such as 5 to 20, n is an integer between 2 and 30, such as 5 to 15, and R may be H or an alkyl group, such as C1-6An alkyl group.
When used, the accelerators included in the above structures should be included in the composition in an amount in the range of about 0.01% to about 10% by weight, such as in the range of about 0.1% to about 0.5% by weight. Desirably about 0.4% by weight of the total composition.
Stabilizers are also commonly found in instant adhesive compositions. The stabilizer may include one or more of a free radical stabilizer and an anionic stabilizer, each of identity and quantity being well known to those of ordinary skill in the art.
Commonly used free radical stabilizers include hydroquinone, while commonly used anionic stabilizers include boron trifluoride, boron trifluoride etherate, sulfur trioxide (and its hydrolysis products), sulfur dioxide and methane sulfonic acid.
Other additives may be included to impart additional physical properties such as improved impact resistance (e.g., citric acid), thickness (e.g., polymethyl methacrylate), thixotropy (e.g., fumed silica), and color. These other additives may be used individually in the compositions of the present invention in amounts of from about 0.05% to about 20% by weight, for example from about 1% to 15% by weight, preferably from 5% to 10%. For example, more specifically, citric acid may be used in the composition of the present invention in an amount of 5 to 500ppm, preferably 10 to 100 ppm.
In another aspect, a method of bonding two substrates together is provided, the method comprising applying a composition as described above to at least one substrate and then mating the substrates for a sufficient time to enable the adhesive to bond. For many applications, the substrate should be held by the composition in less than about 150 seconds, and depending on the substrate, as little as about 30 seconds. In addition, the composition should develop shear strength, as well as side impact strength and fracture toughness, on the substrates to which it has been applied.
In another aspect, a method of making the above-described instant adhesive composition is provided. The method includes providing a cyanoacrylate component, an acrylate component, a rubber toughening component, and a component comprising at least two (meth) acrylate functional groups, and mixing to form an instant adhesive (cyanoacrylate) composition.
Drawings
Fig. 1 shows the initial tensile strength of shot blasted mild steel (GBMS), aluminum and polycarbonate substrate flash gum formulations 1 to 7.
Figure 2 shows the tensile strength performance of the instant glue formulations 1 to 7 on GBMS after aging at 100 ℃ over time.
Fig. 3 shows the percent retention of initial tensile strength on GBMS for the instant glue formulations 1 to 7 after heat aging at 100 ℃ for 3, 6 and 12 weeks.
Figure 4 shows the tensile strength performance on GBMS of formulations 1 to 7 after aging at 120 ℃ over time.
Fig. 5 shows the percent retention of initial tensile strength on GBMS for the instant glue formulations 1 to 7 after heat aging at 120 ℃ for 3, 6 and 12 weeks.
Figure 6 shows the tensile strength performance on GBMS of the instant adhesive formulations 1 to 7 after aging over time at 40 ℃, 98% relative humidity.
Fig. 7 shows the percent retention of initial tensile strength on GBMS for the instant glue formulations 1 to 7 after heat aging at 40 ℃, 98% relative humidity for 3, 6 and 12 weeks.
Fig. 8 shows the initial tensile strength of the flash adhesive formulations 8 to 14 on GBMS and stainless steel substrates.
Fig. 9 shows the percent retention of initial tensile strength of the instant adhesive formulations 8-14 on GBMS and stainless steel after heat aging at 40 ℃, 98% relative humidity.
Fig. 10 shows the percent retention of initial tensile strength on GBMS for the instantaneous glue formulations 8 to 14 after heat aging at 65 ℃, 95% relative humidity for 2 weeks and 6 weeks.
Detailed description of the preferred embodiments
These aspects of the invention are further illustrated by the following examples.
The present invention provides an instant adhesive composition comprising:
(a) a cyanoacrylate component, a silicone oil component,
(b) a rubber toughening agent consisting of (i) the reaction product of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site in combination, (ii) a dimer of ethylene and methyl acrylate, and a combination of (i) and (ii),
(c) a component containing at least two (meth) acrylate functional groups, and
(d) an acid anhydride component.
The composition of the invention is particularly suitable for bonding steel substrates.
In one embodiment, the fugitive glue component comprises ethyl-2-cyanoacrylate present in an amount of from about 70% by weight of the total composition to about 98% by weight of the total composition, for example ethyl-2-cyanoacrylate may be present in an amount of about 85% by weight of the total composition.
The component comprising at least two (meth) acrylate functional groups may be 1, 6-hexanediol diacrylate, and may be present in an amount of about 0.5 wt% to about 10 wt% of the total composition. For example, the instant adhesive composition of the present invention may comprise from about 5% to about 10% by weight of 1, 6-hexanediol diacrylate.
The anhydride component may be tetrahydrophthalic anhydride and may be present in an amount of about 0.1% to about 1% by weight of the total composition.
The composition may further comprise stabilizers, such as sulfur dioxide and methanesulfonic acid.
In one embodiment, the cyanoacrylate component is ethyl-2-cyanoacrylate, the anhydride component is tetrahydrophthalic anhydride, and the component comprising at least two (meth) acrylate functional groups is 1, 6-hexanediol diacrylate.
In one embodiment, the rubber toughening agent is present at about 5% to about 15% by weight when the cyanoacrylate component is present at about 80% to about 90% by weight, said component comprising at least two (meth) acrylate functional groups present in an amount of about 0.5% to about 10% by weight of the total composition, and the anhydride component present in an amount of about 0.1% to about 1% by weight.
In another embodiment, the instant adhesive composition of the present invention further comprises an additive for imparting heat resistance. For example, the composition of the present invention may further comprise a sulfur-containing compound, such as ethylene sulfite or naphthalene sultone.
Additives for imparting heat resistance may be present, for example, in an amount of about 0.05% to about 5% of the total composition. For example, the additive may be present in an amount of about 1% or about 2% by weight.
The compositions of the present invention may comprise a naphthalene sultone. The composition of the present invention may comprise ethylene sulfite. The compositions of the present invention may contain one or more additives that impart thermal resistance. For example, the composition may comprise ethylene sulfite and naphthalene sultone.
Desirably, the compositions of the present invention exhibit enhanced thermal properties. Advantageously, when the compositions of the present invention are cured at room temperature between two substrates (each made of steel), they remain greater than about 40% of their initial tensile strength for about 3 weeks after exposure to a temperature of about 120 ℃ for a period of time.
Additionally, when the composition of the present invention is cured at room temperature between two substrates, each of which is made of steel, upon exposure to a temperature of about 40 ℃, advantageously retains greater than about 70% of its initial tensile strength for a period of about 3 weeks at a relative humidity of about 98%.
For example, when the composition of the present invention is cured at room temperature between two substrates, each made of steel, it advantageously retains greater than about 75% of its initial tensile strength upon exposure to a temperature of about 40%, at a relative humidity of about 98%, for a period of about 3 weeks.
The present invention provides an instant adhesive composition comprising:
(a) a cyanoacrylate component, a silicone oil component,
(b) a rubber toughening agent consisting of (i) the reaction product of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site in combination, (ii) a dimer of ethylene and methyl acrylate, and a combination of (i) and (ii),
(c) a component containing at least two (meth) acrylate functional groups, and
(d) an acid anhydride component;
wherein when both substrates cured at room temperature are constructed of steel, about 40% of their initial tensile strength is retained after a relative humidity of about 98% and exposure to a temperature greater than about 120 ℃ for a period of about 3 weeks. Providing an instant adhesive composition with enhanced heat and wet aging properties is a long standing problem in the adhesive industry. The compositions of the present invention provide a solution to this need.
The present invention provides a method of bonding two substrates together comprising applying to at least one substrate an instant adhesive composition comprising:
(a) a cyanoacrylate component, a silicone oil component,
(b) a rubber toughening agent consisting of (i) the reaction product of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site in combination, (ii) a dimer of ethylene and methyl acrylate, and a combination of (i) and (ii),
(c) a component containing at least two (meth) acrylate functional groups, and
(d) an acid anhydride component.
Suitably, at least one of the substrates is made of steel. Desirably, the bond formed between two substrates by the composition of the present invention exhibits excellent heat aging properties when cured, e.g., after exposure to elevated temperatures, i.e., temperatures above room temperature, even under high humidity conditions, e.g., at 98% relative humidity.
The effect of hexanediol diacrylate (HDDA) and various additives on the heat and humidity aging of the instant adhesive compositions was carried out.
The HDDA was added in an amount of 5-10% with the addition of tetrahydrophthalic anhydride (THPA) to see if wet aging could be improved.
A fixed time study was performed on each formulation in table 1. The addition of naphthalene sultone and ethylene sulfite resulted in a slightly delayed fixation time (table 1, formulation 2), while all other formulations showed the same or faster fixation time.
Figure BDA0002722856620000121
Figure BDA0002722856620000131
Formulation 1 is a standard flexible CA formulation comprising:
ethyl-2-cyanoacrylate, a rubber toughening agent comprising (i) the reaction product of ethylene, methyl acrylate combined with a monomer having a carboxylic acid cure site, (ii) a copolymer of ethylene and methyl acrylate, and (i) and (ii) and a stabilizer. The rubber used in formulation 1 above is supplied under the tradename VAMAC VCS 5500. The stabilizers used in the above formula 1 were methanesulfonic acid and SO2Combinations of (a) and (b). Formulations 2 through 7 included formulation 1 with additional additives added in the weight percentages provided.
FIG. 1 shows the initial tensile strength of various CA formulations on GBMS, aluminum and polycarbonate.
Tensile strength was determined according to Henkel (Henkel) STM 700 for determining the shear strength of the adhesive using lap shear samples.
The initial tensile strength was generally similar to the control sample (formulation 1). The addition of ethylene sulfite and naphthalene sultone improves the adhesion of the polycarbonate, while high levels of HDDA result in a small reduction in the initial tensile strength of GBMS.
Figure 2 shows the tensile strength of various instantized adhesive formulations on GBMS aged at 100 ℃.
The benefits of adding ethylene sulfite and naphthalene sultone are apparent. Without the additives, the control sample (formulation 1) retained about 22% of its initial tensile strength after 12 weeks, while the formulations comprising a combination of ethylene sulfite and naphthalene sultone (formulations 2 and 3) retained about 40% of its initial tensile strength after 12 weeks.
The added 5% HDDA (formula 4) showed an excellent retention of about 55% after 1000 hours, but after 12 weeks, the retention dropped to about 40%; tensile strength retention similar to formulations 2 and 3 was thus obtained.
Formulation 7, which contained 7.5% HDDA, THPA, ethylene sulfite and naphthalene sultone, was particularly high in tensile strength when measured on GBMS aged at 100 ℃.
Figure 3 shows the percent retention of initial tensile strength for formulations 1 through 7 when evaluated on GBMS after heat aging at 100 ℃ for 3, 6, or 12 weeks.
After 1000 hours (6 weeks), formulation 7 retained about 75% of its original tensile strength, and, impressively, after 2000 hours (12 weeks), formulation 7 retained its original strength: about 65% of the tensile strength. Figure 4 shows the tensile strength of various fugitive glue formulations on GBMS aged at 120 ℃.
Figure 5 shows the percent retention of initial tensile strength of formulations 1 to 7 evaluated on GBMS after heat aging at 120 ℃ for 3, 6 or 12 weeks.
Each of formulations 2 through 7 maintained about 40% of the initial tensile strength after 1000 hours and about 20% of the initial tensile strength after 2000 hours. In contrast, formulation 1, which did not contain any additives, retained 12% of the initial tensile strength after 1000 hours, while only 2% of the tensile strength was retained after 2000 hours.
Advantageously, the additives present in formulations 2 to 7 significantly increase the percent retention of the initial tensile strength compared to the corresponding instantaneous glue formulations in the absence of said additives.
Formulations 1 to 7 were also evaluated after humid aging. The tensile strength of each formulation was determined on GBMS substrates after heat aging at 40 ℃, 98% relative humidity. The tensile strength evaluation results after heat aging under humid conditions are shown in fig. 6.
Formulations 3 and 7, both containing tetrahydrophthalic anhydride (THPA), showed good strength retention after 500 hours. Thereafter, the tensile strength of formulation 3 (formulation containing only THPA) was significantly reduced compared to that of formulation 7.
Formulation 5, which contained 7.5% hexanediol diacrylate, retained 34% initial tensile strength after heating on a GBMS substrate for 500 hours at 40 ℃, 98% relative humidity. This initial tensile strength level was substantially maintained after 2000 hours.
Figure 7 shows the percentage of initial tensile strength retained for each of formulations 1 through 7 after heat aging at 40 ℃ at 98 ℃ relative humidity on a GBMS substrate.
Formulation 7 exhibited about 75% initial tensile strength retention after 1000 hours and about 60% initial tensile strength retention after 2000 hours.
The combination of tetrahydrophthalic anhydride (THPA) and hexanediol diacrylate (HDDA) appears to have a synergistic effect when included as an additive in the instant adhesive composition, since the tensile strength retention of formulation 7 is significantly higher, it contains two additives, except for formulations 3 or 5, which includes one rather than two additives.
Preferably, formulation 7 retained its initial tensile strength of about 60% after 2000 hours. This initial tensile strength retention was much higher on average than the same duration for any formulation without THPA and HDDA. In fact, this retention level is about twice the value obtained for formulations 1 to 6 when tested under the same conditions.
Further studies were subsequently performed to investigate the wet ageing achieved using an instantaneous glue formulation comprising HDDA and THPA (see table 2).
In addition to examining the effect of different levels of HDDA, a number of formulations were prepared that varied the levels of THPA, ethylene sulfite and naphthalene sultone.
Figure BDA0002722856620000151
Figure BDA0002722856620000161
Figure BDA0002722856620000171
Formulations 9 through 14 included formulation 8 with additional additives at the weight percentages provided.
The initial tensile strength of each formulation was studied on GBMS and Stainless Steel (SS).
Slight variations were observed between the respective formulations of table 1 and table 2, however, those skilled in the art will appreciate that such variations can be attributed to slight variations in, for example, laboratory conditions, adhesive age, and samples used. Generally, the initial tensile strength of each formulation did not change significantly for the different steel substrates (see fig. 8). FIG. 9 shows the percent retention of the initial tensile strength of formulations 8-14 on GBMS and stainless steel after heat aging at 40 ℃, 98% relative humidity.
Desirably, excellent wet aging is observed on GBMS as well as stainless steel substrates. Compared to formulation 8, formulations 9-14 retained about 80% of their initial strength after 1000 hours at 40 ℃, 98% relative humidity on GBMS.
The percent retention of initial tensile strength was even better for stainless steel substrates, with the percent retention of formulations 9-14 being 75-115% of the initial value after 1000 hours at 40 ℃, 98% relative humidity; formulation 8 retained about 17% of the initial tensile strength value after the same heat and moisture exposure as compared to the control sample.
The percent retention of initial tensile strength after heat aging of the formulation at 65 ℃, 95% relative humidity was tested on GBMS (see figure 10). Control formulation 8 retained about 30% of its initial tensile strength after 1000 hours.
Formulations 9 and 11 exhibited excellent durability. Formulation 9, which contained 7.5% HDDA and 0.5% THPA, retained about 60% of its initial tensile strength after 1000 hours, while formulation 11, which also contained 1% naphthalene sultone, retained about 85% of its initial tensile strength after 1000 hours.
The retention of the initial tensile strength of the formulations containing vinyl sulfite is significantly lower than those formulations containing HDDA and THPA but no vinyl sulfite. Thus, when tested on GBMS substrates after heat aging at 65 ℃ at 95% relative humidity, the addition of ethylene sulfite adversely affects the wet aging results.
Advantageously, on GBMS, excellent wet aging was observed for the instantaneous glue formulation comprising HDDA and THPA. The addition of naphthalene sultone further improves the percent retention of initial tensile strength observed after humid heat aging. Although the addition of ethylene sulfite proved to be detrimental when heat aged at 65 ℃ and a relative humidity of 95%, this is not the case when heat aged at 40 ℃ and a relative humidity of 98%, wherein the retention percentage of the initial tensile strength after 1000 hours is observed between 80% and 100% on the GBMS and stainless steel substrates.
Formulation 9 contained THPA and HDDA as additives, and the initial tensile strength retention after humid heat aging was clear due to the additives. Formulation 9 retained approximately twice the initial tensile strength observed for the GBMS substrate after 3 weeks of heat aging at 40 ℃, 98% relative humidity as compared to the control sample. This trend was also observed after 6 and 12 weeks of heat aging.
The percentage of initial tensile strength observed for formulation 9 was even more significant on the stainless steel substrate, the initial strength was substantially maintained, even after heat aging at 40 deg.C, 98% relative humidity, and an increase in tensile strength was even observed after 6 weeks for the stainless steel substrate.
Thus, the instant adhesive composition comprises: (a) a cyanoacrylate component, (b) a rubber toughening component consisting of: (i) ethylene, the reaction product of methyl acrylate in combination with a monomer having carboxylic acid cure sites, (ii) the binary copolymer ethylene and methyl acrylate, and combinations of (i) and (ii), (c) when a component comprising at least two (meth) acrylate functional groups (e.g., HDDA) and (d) an anhydride component (e.g., THPA) are cured at room temperature, both substrates made of steel, have excellent retention of initial tensile strength after heat aging at 40 ℃ at 98% relative humidity. The composition advantageously retains greater than about 75% of its initial tensile strength after heat aging at 40 ℃ for about 3 weeks at 98% relative humidity. Additionally, the composition retains greater than about 40% of the initial tensile strength after exposure to a temperature of about 120 ℃ for a period of about 3 weeks.
The initial tensile strength and thermal properties of the compositions containing the thermal resistance imparting additive are shown in table 3.
Figure BDA0002722856620000181
Figure BDA0002722856620000191
The thermal properties measured for formulations 16 to 21 are particularly good after heat aging of the formulations on a GBMS substrate for 3 weeks at 120 ℃. In addition, formulation 19, which contained 1.0 wt% tetrafluoroisophthalonitrile, exhibited excellent thermal properties and exhibited a tensile strength of about 22MPa after heat aging at 120 ℃ for 6 weeks.
Further adhesive compositions are provided in table 4.
Figure BDA0002722856620000201
Formulations 22 and 23 demonstrated the greatest initial tensile strength when measured on a GBMS substrate after 1 week of curing at room temperature.
Comparison of the properties of formulation 22 and formulation 23 shows that the heat resistance imparting agent tetrafluoroisophthalonitrile was incorporated in the composition of the present invention.
Formulations 24 and 25 containing allyl CA were also shown to be effective, with an increase in tensile strength observed after 3 and 6 weeks of heat aging at 100 ℃.
Formulation 26, which contained allyl CA as the cyanoacrylate component, had an initial tensile strength of about 16MPa on GBMS substrates after 1 week of curing at room temperature. The tensile strength was improved after heat aging at 100 ℃ for 3 weeks and 6 weeks. Additionally, the tensile strength of the formulation after heat aging at 120 ℃ for 3 weeks was about 23 MPa.
When used herein with reference to the present invention, the terms "comprises/comprising" and the terms "having/including" are used to specify the presence of stated features, integers, steps or components but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable combination.

Claims (11)

1. An instant adhesive composition comprising:
(a) a cyanoacrylate component, a silicone oil component,
(b) a rubber toughening agent consisting of (i) the reaction product of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site in combination, (ii) a dimer of ethylene and methyl acrylate, and a combination of (i) and (ii),
(c) a component containing at least two (meth) acrylate functional groups, and
(d) an anhydride component;
wherein when both substrates cured at room temperature are constructed of steel, about 40% of their initial tensile strength is retained after a relative humidity of about 98% and exposure to a temperature greater than 120 ℃ for a period of about 3 weeks.
2. The composition of claim 1, further comprising a filler.
3. A composition according to claim 2, characterized in that said filler is selected from the group consisting of carbon black, silica and combinations thereof.
4. A composition according to claim 1, characterized in that it further comprises a stabilizing amount of an acidic stabilizer and a free radical inhibitor.
5. A composition according to claim 1, wherein said rubber toughening agent is present in an amount of from about 1.5% to about 20% by weight.
6. A composition according to claim 1, characterized in that the cyanoacrylate component is selected from the structure H2A material within C (CN) -COOR, wherein R is selected from C1-15Alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl.
7. A composition according to claim 6, characterized in that the cyanoacrylate component comprises ethyl-2-cyanoacrylate.
8. A composition according to claim 1, characterized in that the composition further comprises an accelerator component selected from the group consisting of calixarenes, oxaloarenes, silacoronenes, cyclodextrins, crown ethers, polyethylene glycol di (meth) acrylates, ethoxylated hydroxyl compounds, and combinations thereof.
9. A composition according to claim 8, wherein said calixarene is tetrabutyltetra [ 2-ethoxy-2-oxoethoxy ] calix-4-arene.
10. A method of bonding two substrates together comprising the steps of:
applying a composition according to claim 1 to at least one substrate and mating the substrates to each other for a sufficient period of time to allow an adhesive to be formed from the composition between the mated substrates.
11. A process for preparing the composition of the instant adhesive according to claim 1, characterized by comprising the steps of:
providing a cyanoacrylate component, a rubber toughening agent, the rubber toughening agent is composed of the following components: (i) a reaction product of ethylene, methyl acrylate, and a monomer having a carboxylic acid cure site combined, (ii) a binary copolymer of ethylene and methyl acrylate, and combinations of (i) and (ii), and a component containing at least two (meth) acrylate functional groups, and mixed to form a composition.
CN202011093188.0A 2020-10-14 2020-10-14 High-stability instant adhesive and preparation method thereof Pending CN112175528A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011093188.0A CN112175528A (en) 2020-10-14 2020-10-14 High-stability instant adhesive and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011093188.0A CN112175528A (en) 2020-10-14 2020-10-14 High-stability instant adhesive and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112175528A true CN112175528A (en) 2021-01-05

Family

ID=73949872

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011093188.0A Pending CN112175528A (en) 2020-10-14 2020-10-14 High-stability instant adhesive and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112175528A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101258211A (en) * 2005-07-11 2008-09-03 汉高公司 Toughened cyanoacrylate compositions
CN108463525A (en) * 2015-11-06 2018-08-28 汉高知识产权控股有限责任公司 Cyanoacrylate compositions
CN110591569A (en) * 2019-09-17 2019-12-20 浙江派菲特新材料科技有限公司 Environment-friendly low-whitening instant adhesive
CN111278878A (en) * 2017-10-27 2020-06-12 汉高知识产权控股有限责任公司 Cyanoacrylate compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101258211A (en) * 2005-07-11 2008-09-03 汉高公司 Toughened cyanoacrylate compositions
CN108463525A (en) * 2015-11-06 2018-08-28 汉高知识产权控股有限责任公司 Cyanoacrylate compositions
CN111278878A (en) * 2017-10-27 2020-06-12 汉高知识产权控股有限责任公司 Cyanoacrylate compositions
CN110591569A (en) * 2019-09-17 2019-12-20 浙江派菲特新材料科技有限公司 Environment-friendly low-whitening instant adhesive

Similar Documents

Publication Publication Date Title
KR102593346B1 (en) Cyanoacrylate composition
KR102657838B1 (en) Cyanoacrylate composition
EP2121777B1 (en) Cyanoacrylate compositions incorporating graphite platelets
KR20190011744A (en) Two-part cyanoacrylate curable adhesive system
JP4748156B2 (en) 2-Cyanoacrylate composition
CN110741055B (en) Cyanoacrylate compositions
JP4084187B2 (en) Cyanoacrylate compositions curable to flexible polymeric materials
WO2010029134A1 (en) Toughened cyanoacrylate compositions
CN112175528A (en) High-stability instant adhesive and preparation method thereof
GB2577817A (en) Cyanoacrylate compositions
JP2844946B2 (en) Adhesive composition
TWI806962B (en) Cyanoacrylate compositions
CN115768845A (en) Cyanoacrylate compositions
JPH0657215A (en) Elastomer-containing adhesive composition
JP2004315710A (en) Alphacyanoacrylate adhesive composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210105