CN111253896B - Epoxy adhesive and preparation method and application thereof - Google Patents
Epoxy adhesive and preparation method and application thereof Download PDFInfo
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- CN111253896B CN111253896B CN202010147921.6A CN202010147921A CN111253896B CN 111253896 B CN111253896 B CN 111253896B CN 202010147921 A CN202010147921 A CN 202010147921A CN 111253896 B CN111253896 B CN 111253896B
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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Abstract
The invention relates to an epoxy adhesive and a preparation method and application thereof, wherein the adhesive comprises an epoxy resin component and a curing agent component, wherein the epoxy resin component comprises 80-94.5 wt% of epoxy resin containing long-chain alkyl and polyurethane, 5-19.5 wt% of low-viscosity flexible epoxy resin and 0.5-1 wt% of coupling agent a; the curing agent comprises the following components in percentage by weight: 80 to 90 percent of polythiol, 1 to 5 percent of monoalkanolamine, 5 to 15 percent of tertiary amine urea, 0.5 to 1 percent of coupling agent b and 0.1 to 1 percent of defoaming agent. The epoxy adhesive is particularly suitable for occasions needing quick fixation at normal temperature or low temperature, and has particularly short fixation time and high flexibility.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to an epoxy adhesive as well as a preparation method and application thereof.
Background
The epoxy resin adhesive has excellent thermo-mechanical property, good chemical resistance and processing property, has good adhesive force to various base materials, and is widely applied to the fields of material bonding, fixing, packaging and the like. Ordinary epoxy resins are hard and brittle, and therefore, efforts to improve the flexibility of epoxy resins from the viewpoint of physical modification and molecular structure are one of the important issues. At present, two main directions are provided for developing flexible epoxy, firstly, a soft segment unit is introduced into an epoxy resin molecular structure, such as a siloxane unit, a long-chain fatty alcohol and the like, and the toughening mode is more traditional, so that a large space is provided for further reducing stress, improving temperature resistance and the like; and secondly, an elastomer toughening agent such as liquid nitrile rubber and organic silicon is added, the viscosity of the epoxy resin can be obviously increased by the toughening mode, and certain limitation is brought to preparation and partial molding application.
Polythiol curing agents are most commonly used in order to allow rapid curing of epoxy resins under some ambient conditions, either at ambient or low temperatures. The polythiol is a room-temperature or low-temperature rapid curing agent, is not cured when being used alone, can realize rapid curing at low temperature under the action of accelerators such as tertiary amine and the like, and can be applied to low-temperature operation or occasions needing rapid fixing, such as road repair in winter and rapid fixing of wiring harnesses. Because the polythiol curing agent contains the sulfur flexible chain segment, the epoxy resin can be obviously toughened, and meanwhile, the polythiol has higher refractive index and can be applied to a transparent system. The epoxy cured in 5 minutes on the market mostly has the operation time of 1-2 minutes, generally, when the epoxy is applied at low temperature, the flexibility of the epoxy can not meet the requirement, when the epoxy is subjected to repeated low temperature or large external force, the colloid or the substrate can not release stress through deformation, the internal stress can be amplified, and the bonding strength and the flexibility can not bear the stress, so that the epoxy is easy to crack. Flexibilizers and plasticizers can be used to improve the low temperature properties of the epoxy, resulting in a certain elongation at break. With this modification, mineral or metallic fillers are generally used to obtain adhesives with better properties at-20 ℃. However, at lower temperatures, the performance of the matrix resin and the curing agent is mainly required to achieve good performance.
Disclosure of Invention
Based on the above, there is a need for a flexible two-component epoxy adhesive capable of being rapidly fixed at normal temperature or low temperature and a preparation method thereof.
An epoxy adhesive comprises an epoxy resin component and a curing agent component, wherein the epoxy resin component comprises 80-94.5 wt% of epoxy resin containing long-chain alkyl and polyurethane, and the structural units of the epoxy resin are shown as a formula (I) and a formula (II):
r is a divalent non-aromatic long-chain hydrocarbon group containing 9 or more carbons in the main chain, and X is a divalent polyether group;
and n is an integer of 1 to 20.
The structural unit shown in the formula (I) contains long-chain alkyl, and the structural unit shown in the formula (II) contains long-chain alkyl and polyurethane, so that the epoxy resin containing long-chain alkyl and polyurethane can have good flexibility, has higher elongation, lower elastic modulus, higher impact resistance and heat resistance compared with the traditional rubber or ethylene oxide modified flexible epoxy resin, and has good compatibility with other epoxy resins, and the epoxy resin is matched with a curing agent component, so that the epoxy adhesive not only can quickly fix a base material or a device, but also can not remarkably reduce the operation time, and meanwhile, the problem that the low-temperature flexibility of the quick-curing epoxy adhesive on the market cannot meet the requirement can be solved, and the epoxy resin serving as an adhesive raw material has a quick-curing effect and keeps excellent flexibility when being applied at low temperature, impact resistance and vibration resistance.
In one embodiment, the divalent non-aromatic long-chain hydrocarbon group having 9 or more carbons in the main chain is selected from an alkylene group or an alkenylene group, and the alkylene group or the alkenylene group may have a substituent.
In one embodiment, the epoxy resin component further comprises 5 to 19.5 weight percent of a low viscosity flexible epoxy resin, and the epoxy equivalent of the low viscosity flexible epoxy resin is 300 to 600 g/eq.
In one embodiment, the epoxy resin component further comprises 0.5 to 1 weight percent of a coupling agent a.
The curing agent comprises the following components in percentage by weight: 80 to 90 percent of polythiol, 1 to 5 percent of monoalkanolamine, 5 to 15 percent of tertiary amine urea, 0.5 to 1 percent of coupling agent b and 0.1 to 1 percent of defoaming agent.
In one embodiment, the coupling agent a is a weakly acidic epoxy silane coupling agent, and the coupling agent b is a strongly basic amino silane coupling agent; preferably, the coupling agent a is a commercially available product KH-560, A-187, Z-6040 or GF-81, and the coupling agent b is a commercially available product KH-550, ND-42, GF-90 or KBM-803.
In one embodiment, the polythiol is a polythiol having a terminal end containing three thiol groups or four thiol groups. For example, commercially available products: polypropylene glycol-2-hydroxythiol Capcure3800, low-odor polythiol QE-340M.
In one embodiment, the monoethanolamine is one of ethanolamine, 3-propanolamine, isopropanolamine, 2-amino-1-butanol, and isobutanolamine. Preferably, the monoethanolamine is ethanolamine.
In one of themIn one embodiment, the tertiary amine urea has the formula [ R2NXNH]2CO]In the formula: x is C2～C3R is C1～C2Alkyl chain of (2). Preferably, the tertiary amine-containing urea compound is 1, 3-bis [3- (dimethylamino) propyl group]Urea.
In one embodiment, the defoaming agent is a silicon-free defoaming agent, preferably, the defoaming agent is a polyolefin, polyvinyl ether, polyacrylate or polyester.
In one embodiment, the weight ratio of the epoxy resin component to the curing agent component is (60-100) as the epoxy resin component and (100) as the curing agent component.
The preparation method of the adhesive comprises the following steps:
preparation of the epoxy resin component: under the atmosphere of protective gas, mixing and stirring the epoxy resin containing long-chain alkyl and polyurethane and the low-viscosity flexible epoxy resin until the epoxy resin and the low-viscosity flexible epoxy resin are soaked, adjusting the temperature to be 45-65 ℃, adding the coupling agent a, stirring and mixing uniformly, vacuumizing and removing bubbles to obtain colorless to light yellow transparent liquid;
preparation of the curing agent component: in the atmosphere of protective gas, polythiol, monoalkanolamine and tertiary amine urea are stirred and mixed uniformly; adjusting the temperature to 25-35 ℃, adding the coupling agent b and the defoaming agent, stirring and mixing uniformly, and vacuumizing to remove bubbles to obtain colorless to light yellow transparent liquid.
The adhesive and the adhesive prepared by the preparation method are applied to bonding of plastics, metals, glass, wood, ceramics, rubber, elastic masonry materials, fixing of elastic circuits, cable boots or fillet keys. Preferably, the method is applied to occasions needing ultra-clear bonding lines.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
An epoxy adhesive of an embodiment can be rapidly fixed at normal or low temperature, has high transparency, low odor, easy mixing at the time of application, and high strength and flexibility after curing.
The epoxy adhesive comprises an epoxy resin component and a curing agent component, wherein the epoxy resin component comprises 80-94.5% by weight of epoxy resin containing long-chain alkyl and polyurethane,
r is a divalent non-aromatic long-chain hydrocarbon group containing 9 or more carbons in the main chain, and X is a divalent polyether group; n is an integer of 1 to 20.
The structural unit shown in the formula (I) contains long-chain alkyl, and the structural unit shown in the formula (II) contains long-chain alkyl and polyurethane, so that the epoxy resin containing long-chain alkyl and polyurethane can have good flexibility, has higher elongation, lower elastic modulus, higher impact resistance and heat resistance compared with the traditional rubber or ethylene oxide modified flexible epoxy resin, and has good compatibility with other epoxy resins, and the epoxy resin is matched with a curing agent component, so that the epoxy adhesive not only can quickly fix a base material or a device, but also can not remarkably reduce the operation time, and meanwhile, the problem that the low-temperature flexibility of the quick-curing epoxy adhesive on the market cannot meet the requirement can be solved, and the epoxy resin serving as an adhesive raw material has a quick-curing effect and keeps excellent flexibility when being applied at low temperature, impact resistance and vibration resistance.
Specifically, n in formula (i) may be any integer from 1 to 20, preferably any integer from 1 to 5, and n may be 1,2, or 5.
In one embodiment, the epoxy resin containing long chain hydrocarbon groups and polyurethane groups comprises 80% to 94.5% of the total weight of the epoxy resin component. The epoxy resin component of the present embodiment is based on an epoxy resin containing a long-chain hydrocarbon group and a urethane group, and in such a range, the obtained overall properties such as fixation speed, flexibility, heat resistance, and the like are good. Wherein the epoxy resin containing long chain hydrocarbon groups and polyurethane groups may comprise 80%, 82%, 85%, 88%, 90%, or 94.5% by weight of the total epoxy resin component.
In one embodiment, R is a divalent non-aromatic long chain hydrocarbon group having 9 or more carbons in the main chain. Preferably, it may be selected from:
(a1)–(CH2)r–
(a2)
wherein, formula (a)1) Wherein r is an integer of 10 to 16, specifically, r can be 10, 12, 13, 14 or 16; formula (a)2) Are structural units derived from dimer acid.
In one embodiment, X is a divalent polyether group. Preferably, it may be selected from:
(b1)–(CH2)u–O)v–
(b2)–(CH2–CH(–CH3)–O)w–
(b3)–(CH2–CH(–CH2–CH3)–O)x–
wherein u is an integer of 1 to 20, preferably u is an integer of 1 to 4; v, w and x are integers from 1 to 40; the polyether radical (b) preferably has a molecular weight in the range from 1000 to 3000 g/mol.
The long-chain hydrocarbon group in the structural units shown in the formulas (I) and (II) is selected from the structural formula (a) and the polyether group is selected from the structural formula (b), so that the prepared adhesive has better impact resistance and heat resistance when used at low temperature or normal temperature, and has better compatibility with other epoxy resins.
In one embodiment, the long chain hydrocarbon group and urethane group containing epoxy resin is prepared from a polyglycidyl ether of bisphenol A, a long carbon chain dibasic acid, and an epoxy-terminated urethane. Polyglycidyl ethers of bisphenol A such as EPON828 of Hexion, south Asia NPEL-128, R-140 of Mitsui; the long carbon chain dibasic acid refers to dibasic acid with more than 11 carbons such as dodecanedioic acid and dimer acid; epoxy-terminated polyurethanes are obtained by reacting Toluene Diisocyanate (TDI) with a polyol (polyether diol) at an NCO/OH ratio of 2 to 2.5. Epoxy resins containing long chain hydrocarbon groups and polyurethane groups contain a block structure.
Specifically, Toluene Diisocyanate (TDI) is a mixed isomer of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, or 100% of 2, 4-toluene diisocyanate. The main types sold in the market are TDI-100, TDI-80 and TDI-65. Preferred are TDI-100 and TDI-80.
The polyether diols used here are the polymerization products of ethylene oxide, 1, 2-propylene oxide, 1, 2-or 2, 3-butylene oxide, tetrahydrofuran or mixtures thereof. Preferred are hydroxyl terminated polypropylene glycols. The polyether diols preferably have molecular weights in the range from 1000 to 3000g/mol, such as PPG1000, PPG 2000.
Further, the epoxy resin component also comprises 5 to 19.5 weight percent of low viscosity flexible epoxy resin, the epoxy equivalent weight of the low viscosity flexible epoxy resin is 300 to 600g/eq, and specifically, the epoxy equivalent weight can be 350g, 400, 440, 500, 560 or 600.
The low-viscosity flexible epoxy resin within the epoxy equivalent range is selected, the viscosity of the epoxy resin is less than 500cps, the epoxy resin has better compatibility with epoxy resin containing long-chain alkyl and polyurethane, the flexibility of epoxy resin components can be mutually enhanced, the viscosity of the adhesive is adjusted through a certain addition proportion, the epoxy diluent with the epoxy equivalent of about 200g/eq is more adaptive to the epoxy resin containing long-chain alkyl and polyurethane, and the performance of the obtained adhesive is better.
Further, the low-viscosity flexible epoxy resin accounts for 5-19.5 wt% of the epoxy resin component, and can be mutually promoted with 80-94.5 wt% of the epoxy resin containing long-chain alkyl and polyurethane, so that the flexibility of the whole adhesive is improved, and specifically, the low-viscosity flexible epoxy resin can account for 5%, 10.5%, 12%, 15%, 18% or 19.5 wt%.
In one embodiment, the low viscosity flexible epoxy resin is a polyol-derived polyglycidyl ether, preferably polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, or the like. Excellent flexibility, extensibility and impact resistance can be imparted to the system. For example, commercially available products: CY208 from Huntsman, HX-116 from Hopo.
Further, the epoxy resin component also comprises 0.5 to 1 weight percent of coupling agent a;
the curing agent comprises the following components in percentage by weight: 80 to 90 percent of polythiol, 1 to 5 percent of monoalkanolamine, 5 to 15 percent of tertiary amine urea, 0.5 to 1 percent of coupling agent b and 0.1 to 1 percent of defoaming agent.
The coupling agent a represents a coupling agent of the epoxy resin component, and the coupling agent b represents a coupling agent of the curing agent component.
Specifically, the coupling agent a is a weakly acidic epoxy silane coupling agent, and the coupling agent b is a strongly basic amino silane coupling agent; when the epoxy resin component and the curing agent component are mixed, the coupling agent a and the coupling agent b have a synergistic interaction effect in the adhesive, so that the bonding strength of the adhesive and a base material is improved. In a specific example, the coupling agent a is a commercially available product KH-560, A-187, Z-6040 or GF-81, and the coupling agent b is a commercially available product KH-550, ND-42, GF-90 or KBM-803.
Further, the polythiol in the curing agent component is a low-odor modified polythiol containing three thiol groups or four thiol groups, having excellent flexibility and adhesion, and such modified polythiol can be used with an odor masking agent or an odor absorbent or by structural modification, and particularly preferred is low-odor polythiol QE-340M from Pentium polypropylene glycol-2-hydroxythiol Capcure3800 or Toray Japan. Compared with polythiol and rapid curing agent modified amine, the polythiol curing agent contains a sulfur flexible chain segment, and can obviously toughen epoxy resin.
Compared with tertiary amine urea and monoalcohol amine, the traditional curing accelerators K54 and BDMA have longer fixing time when matched with mercaptan, but the tertiary amine urea, monoalcohol amine and modified polythiol are matched to ensure quick fixing, do not obviously reduce the operation time and simultaneously improve the toughness of the epoxy resin component.
In the curing agent components, 80-90% of polythiol is selected, which is beneficial to toughening the epoxy resin components and can realize rapid curing. In particular, the modified polythiol can be present in an amount of 80%, 84%, 86%, 88%, or 90%.
Further, the monoalkanolamine is one of ethanolamine, 3-propanolamine, isopropanolamine, 2-amino-1-butanol and isobutanolamine. Preferably, the monoethanolamine is ethanolamine. In the curing agent system, a promoting system formed by mixing the mono-alcohol amine and the tertiary amine urea can realize the quick fixation of the epoxy adhesive to a base material or a device.
Tertiary amine urea is solvent-free and has the structural formula [ R2NXNH]2CO]In the formula: x is C2～C3R is C1～C2Alkyl chain of (2). Preferably 1, 3-bis [3- (dimethylamino) propyl group]Urea.
When the tertiary amine urea is selected and compounded with the mono-alcohol amine and the polythiol, the rapid fixation can be ensured, and the operation time is not remarkably reduced.
The defoaming agent in the curing agent component is a silicon-free defoaming agent such as polyolefin, polyvinyl ether, polyacrylate or polyester, preferably a commercial product BYK-A500,
Or MOK-6025, which is a silicon-free high-efficiency defoaming agent, does not reduce the adhesive strength to a substrate, and has excellent compatibility in a polar system.
In one embodiment, the mixing weight ratio of the epoxy resin component and the curing agent component is 100 (60-100), and the system is less sensitive to the glue preparation amount of the curing agent, and is preferably in the range of 100 (90-100). The components begin to solidify after being mixed, the viscosity of the components can quickly rise, and the amount of one-time glue preparation can be reduced as much as possible. The two-component epoxy adhesive mixed according to the proportion is cured at normal temperature or low temperature, and has low shrinkage rate and good peeling resistance. After being completely cured, the epoxy adhesive can resist various chemical substances and solvents, and is an excellent insulator.
The method for preparing the epoxy adhesive of the embodiment includes steps S000 to S300:
step S000: preparation of epoxy resins containing long-chain hydrocarbon groups and polyurethane groups: adding polyether glycol into a round-bottom flask, heating at the temperature of 110-. At this point dodecanedioic acid, the polyglycidyl ether of bisphenol A and the catalyst are added separately. Regulating the reaction temperature, stirring at constant temperature for a certain time, transferring into a container, and cooling for later use.
Step S100: preparation of the epoxy resin component: under the atmosphere of protective gas, adding the epoxy resin containing long-chain alkyl and polyurethane and the low-viscosity flexible epoxy resin according to the proportion, setting the temperature at 45-65 ℃, mixing and stirring until the epoxy resin and the low-viscosity flexible epoxy resin are soaked, adding the coupling agent a, stirring and mixing uniformly, and then vacuumizing to remove bubbles to obtain an epoxy resin component;
specifically, the protective gas is nitrogen; the epoxy resin containing long-chain alkyl and polyurethane and the low-viscosity flexible epoxy resin are firstly stirred and soaked at a low speed of 400-600rpm, then stirred at a medium speed of 800-1000rpm for 100-150 min, and the temperature is set to be 45-65 ℃;
further, adding an epoxy coupling agent, and then stirring at a rotation speed of 800-1000rpm for 10-30 min at a medium speed, wherein the temperature is set to be 45-65 ℃; finally, reducing the stirring speed to 400-600rpm, vacuumizing and removing bubbles for 10-30 min, and setting the temperature to be 45-65 ℃; stopping stirring, using a filter, and directly filling the mixture into a double tube by matching with a 100-mesh filter screen for filtering.
Step S200: preparation of the curing agent component: under the atmosphere of protective gas, adding polythiol, monoalkanolamine and tertiary amine urea at the temperature of 25-45 ℃, stirring and mixing uniformly, adding coupling agent b and defoamer, stirring and mixing uniformly, and vacuumizing to remove bubbles to obtain a curing agent component;
specifically, the protective gas is nitrogen; stirring and mixing polythiol, hydramine and tertiary amine urea, and stirring at the rotation speed of 800-1000rpm for 100-150 min at the temperature of 25-45 ℃; then adding an amino coupling agent b and a defoaming agent, and stirring at the rotation speed of 800-; finally, reducing the stirring speed to 400-600rpm, vacuumizing and removing bubbles for 10-30 min, and setting the temperature to be 25-45 ℃; stopping stirring, using a filter, and directly filling the mixture into a double tube by matching with a 100-mesh filter screen for filtering.
Step S300: and centrifuging the double-tube packaged epoxy adhesive at the room temperature for 2min at the rotating speed of 2000rpm by using a centrifuge, removing bubbles, and storing the finished product at the room temperature.
When the preparation method is double-tube packaging, the tube barrel is only required to be inserted into a glue gun to discharge a small amount of glue solution when in use, so that the two sides are ensured to flow uniformly and freely. If automatic mixing of the resin and curing agent is desired, a mixing nozzle is connected to the automatic mixer to begin dispensing the adhesive. When manually mixed, the desired amount of the adhesive was discharged and thoroughly mixed for 15 seconds. When packaged in a bulk container, the mixture is mixed thoroughly in the above weight ratio for about 15 seconds.
The epoxy adhesive is suitable for bonding plastics, metals, glass, wood, ceramics, rubber, masonry materials needing elasticity, fixed elastic circuits, cable boots and fillet keys. Is very suitable for occasions needing ultra-clear bonding lines.
When the adhesive is used for bonding base materials, the adhesive comprises the following steps:
uniformly coating the flexible epoxy adhesive formed by mixing on the surface of one substrate or two substrates to be connected;
at the appropriate time the coating is complete and the two substrates are in contact with each other;
preventing the parts from moving during the curing process, if necessary applying contact pressure;
curing was completed at room temperature.
For high strength structural members, the substrate surface can be cleaned of contaminants such as paint, oxide films, oil, dust, mold release agents, and all other surface contaminants.
The resin and the curing agent are free of volatile matters, low in odor and favorable for use environment and operators.
The epoxy adhesive disclosed by the invention at least has the following advantages:
1) the epoxy resin component of the invention is epoxy resin containing long chain alkyl and polyurethane group in the molecular structure, has good flexibility, and has higher elongation, lower elastic modulus, higher impact resistance and heat resistance compared with the traditional rubber or ethylene oxide modified flexible epoxy resin, and simultaneously has good compatibility with other epoxy resins. The epoxy adhesive is compounded with the low-viscosity flexible epoxy resin, has good compatibility with the epoxy resin containing long-chain alkyl and polyurethane, can mutually enhance the flexibility of the epoxy resin, and is matched with a curing system of polythiol, monoalcohol amine and tertiary amine urea to realize the quick fixation of the epoxy adhesive to a substrate or a device, wherein the fixation time can reach 5-6min, and the operation time is not obviously reduced. The super-flexible epoxy resin component and the flexible curing agent component are mixed, so that the epoxy adhesive can be quickly fixed on a base material or a device, and the problem that the low-temperature flexibility of the epoxy adhesive which is quickly cured in the market cannot meet the requirement can be solved. When the two-component epoxy resin adhesive is applied at low temperature, the two-component epoxy resin adhesive not only has the effect of quick curing, but also keeps excellent flexibility, impact resistance and vibration resistance.
2) The mixed two-component epoxy resin adhesive is cured at normal temperature or low temperature, has low shrinkage rate and good peeling resistance, and after being completely cured, the epoxy resin can resist various chemical substances and solvents, thereby being an excellent insulator.
The invention is further illustrated, but not limited, by the following specific examples.
Polyether glycol: polypropylene glycol PPG1000, polypropylene glycol PPG2000, available from dow;
TDI: TDI-80, available from Pasteur;
bisphenol a type epoxy resin: EPON828, available from hansen;
low viscosity flexible epoxy resin: CY208, epoxy equivalent 425 g/eq; purchased from hensman; HX-116, epoxy equivalent 500g/eq, available from Hopo.
Polythiol: capcure3800, purchased from Yingchuang, QE-340M, purchased from Toray Japan;
tertiary amine urea: 1, 3-bis [3- (dimethylamino) propyl ] urea, purchased from Aikang;
mono-alcohol amine: ethanolamine, available from dow;
coupling agent: KH550, KH560, available from the national pharmacy group;
defoaming agent: BYK-A500 from Pico Chemicals;
modified fatty amine: 2914UF, purchased from winning creations;
accelerator (b): BDMA, purchased from nova chemical;
accelerator (b): k54, purchased from winning creations.
The components, weight percentage contents and performance test results of the adhesives of examples 1-8 and comparative examples 1-6 are shown in tables 1 and 2; the preparation methods of the adhesives of examples 1 to 8 and comparative examples 1 to 6 are the same.
The preparation method of the adhesive comprises the following steps:
preparation of epoxy resins containing long-chain hydrocarbon groups and polyurethane groups: adding 416g of PPG2000 (or 208g of PPG1000) into a 5-liter round-bottom flask, heating at 110 ℃ for vacuum dehydration for 3 hours, cooling and introducing nitrogen for protection, then adding 80g of TDI-80, uniformly stirring, heating to 70 ℃ for reaction, cooling and introducing nitrogen for protection when the NCO content is monitored to be half of the initial content in real time by a toluene di-n-butylamine method, adding 31g of glycidol, fully stirring, and heating to 60 ℃ for reaction for 3 hours. 519g of dodecanedioic acid, 2942g of the polyglycidyl ether of bisphenol A EPON828 and 12.2g of ethyltriphenylphosphorodiodiamidite were then added in each case. The reaction temperature is adjusted to 100 ℃, the mixture is stirred for 4 hours at constant temperature, the mixture is transferred into a container, and the prepared epoxy resin with two epoxy equivalent weights is cooled for standby.
Preparation of the epoxy resin component: the ingredients of the resin components given in tables 1,2 were processed to prepare in the given amounts (weight ratio). The preparation method comprises the following steps: in the nitrogen atmosphere, adding epoxy resin components into a high-speed stirring reaction kettle, stirring and infiltrating at a low speed of 500rpm, and then stirring at a medium speed of 800rpm for 120min, wherein the temperature is set to 50 ℃; then adding a coupling agent, and stirring at the rotation speed of 1000rpm for 20min at medium speed, wherein the temperature is set to 50 ℃; and finally, reducing the stirring speed to 500rpm, vacuumizing to remove bubbles for 20min, setting the temperature to be 50 ℃, stopping stirring, and directly filling the mixture into a double tube by using a filter and matching with a 100-mesh filter screen for filtering.
Preparation of the curing agent component: likewise, the ingredients of the curing agent component given in table 1, table 2 were processed to prepare in the given amounts (weight ratio). Under the nitrogen atmosphere, adding (polythiol, monoalkanolamine and tertiary amine urea)/or modified fatty amine into a high-speed stirring reaction kettle, and stirring at the rotating speed of 800rpm for 120min at a medium speed, wherein the temperature is set to be 30 ℃; then adding a coupling agent and a defoaming agent, and stirring at the rotation speed of 1000rpm for 20min at a medium speed, wherein the temperature is set to 30 ℃; and finally, reducing the stirring speed, vacuumizing to remove bubbles for 20min, setting the temperature to be 30 ℃, stopping stirring, and directly filling the mixture into a double tube by using a filter and matching with a 100-mesh filter screen for filtering.
After the resin component and the curing agent component are obtained, testing is carried out by means of glue discharging and gluing of a mixed glue gun according to the using method of the epoxy adhesive, and the performance and the method of the test are as follows:
the operation time is as follows: the time from the preparation of the adhesive to the maintenance of the service performance of the adhesive. Under standard circumstances, 2g of the mixed gum was applied in an egg tart cup and slid with a toothpick until the time when the scratch was unrecoverable.
Fixing time: under the conditions of certain temperature, pressure and the like, the time required for the adhesive in the assembly to be cured to 0.1MPa is obtained. Under the standard environment, the carbon steel after polishing treatment is evenly glued, lapped and fixed, the timing is started, one end of a lapping piece is hung on a 3.1Kg weight sleeve, and if the lapping piece is pulled open, the preliminary fixed time is judged to be longer than the required time. If the mobile terminal cannot be pulled open, the preliminary fixed time is judged to be less than the requirement.
Shear strength: a longitudinal tensile shear force was applied to the faying surface of the test piece, and the maximum load that the test piece can bear was measured. Under the standard environment, the carbon steel after the polishing treatment is evenly glued, lapped and fixed, after timing for 24 hours, a testing machine is started, and the carbon steel is loaded at a stable speed within 10 mm/min. The maximum load of the test specimen to shear failure was recorded and the length and width of the faying surface of the test specimen was measured and the tensile shear strength was calculated.
Peel strength: the maximum force required to peel the materials from the contact surface per unit width was measured by a T-peel test using neoprene rubber against neoprene rubber, and a peel force was applied to the unbonded end of the sample to peel the sample along the bonding line.
Cold and hot impact: to test the ability to withstand cold and thermal shock conditions, a cold and thermal shock tester was used, with a 30min exposure at-40 ℃ and a rapid transition to an exposure at 85 ℃ for 30min, and this was repeated 100 times.
TABLE 1
TABLE 2
As can be seen from Table 1, the two-component epoxy adhesive of the present invention can be applied to the occasions requiring rapid fixing at normal temperature or low temperature, and not only has the effect of rapid fixing, but also maintains excellent flexibility.
As is clear from Table 2, the comparative examples 1 to 3 are different from the examples in the kind of epoxy resin in the epoxy resin component, and from the results, under the condition of the same total content, when the epoxy resin adopts low-viscosity flexible epoxy resin to be matched with bisphenol A epoxy resin EPON828, the epoxy resin containing long-chain hydrocarbon group and polyurethane group, the low-viscosity flexible epoxy resin to be matched with the bisphenol A epoxy resin EPON828 or the bisphenol A epoxy resin EPON828 is independently adopted, on the comprehensive evaluation of the operation time, the fixing time, the shearing strength, the peeling strength and the cold and hot impact resistance of the adhesive, the epoxy resin containing long-chain alkyl and polyurethane group and the low-viscosity flexible epoxy resin are not used in a compounding way according to the proportion, this is because the epoxy resin containing a long-chain hydrocarbon group and a urethane group has excellent flexibility with the low-viscosity flexible epoxy resin.
The difference between the comparative examples 4-6 and the examples is that the curing agents are different in types, and the polythiol of the comparative examples 4-5 is mixed with the traditional accelerators k54 and BDMA, and the results show that although the polythiol can be rapidly cured at room temperature or low temperature, the operation time cannot be obviously reduced, the fixing time is obviously longer compared with the curing agents adopting polythiol, monoalcohol amine and tertiary amine urea, and the invention shows that the tertiary amine urea, monoalkanolamine and polythiol can ensure rapid fixing and simultaneously ensure the flexibility of the epoxy resin adhesive. Comparative example 6 using the rapid-curing modified fatty amine 2914UF, it is clear from the results that peel strength and cold-heat impact resistance are significantly inferior to those of the present invention.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. An epoxy adhesive comprises an epoxy resin component and a curing agent component, and is characterized in that the epoxy resin component comprises 80-94.5 wt% of epoxy resin containing long-chain alkyl and polyurethane, and the epoxy resin comprises structural units shown as a formula (I) and a formula (II):
r is a divalent non-aromatic long-chain hydrocarbon group containing 9 or more carbons in the main chain, and X is a divalent polyether group;
n is an integer of 1 to 20;
the epoxy resin component also comprises 5 to 19.5 weight percent of low-viscosity flexible epoxy resin, and the epoxy equivalent of the low-viscosity flexible epoxy resin is 300 to 600 g/eq;
the epoxy resin component also comprises 0.5 to 1 weight percent of coupling agent a;
the curing agent comprises the following components in percentage by weight: 80 to 90 percent of polythiol, 1 to 5 percent of monoalkanolamine, 5 to 15 percent of tertiary amine urea, 0.5 to 1 percent of coupling agent b and 0.1 to 1 percent of defoaming agent;
the structural formula of the tertiary amine urea is [ R ]2NXNH]2CO]In the formula: x is C2～C3R is C1～C2Alkyl chain of (2).
2. The adhesive of claim 1, wherein the divalent non-aromatic long-chain hydrocarbon group containing 9 or more carbons in the main chain is selected from an alkylene group and an alkenylene group.
3. The adhesive of claim 2 wherein the alkylene or alkenylene group has a substituent.
4. The adhesive of claim 1 wherein the low viscosity flexible epoxy resin is a polyol derived polyglycidyl ether.
5. The adhesive of claim 4,
the low-viscosity flexible epoxy resin is polypropylene glycol diglycidyl ether or 1, 4-butanediol diglycidyl ether.
6. The adhesive according to claim 1, wherein the coupling agent a is a weakly acidic epoxy silane coupling agent, and the coupling agent b is a strongly basic amino silane coupling agent.
7. The adhesive of claim 1, wherein the polythiol is a polythiol having a terminal end containing three thiol groups or four thiol groups.
8. The adhesive of claim 1, wherein the mono-alcohol amine is one of ethanolamine, 3-propanol amine, isopropanol amine, 2-amino-1-butanol, and isopropanol amine.
9. The adhesive of claim 1 wherein the tertiary amine urea is 1, 3-bis [3- (dimethylamino) propyl ] urea.
10. The preparation method of the adhesive according to any one of claims 1 to 9, which is characterized by comprising the following steps:
preparation of the epoxy resin component: under the atmosphere of protective gas, adding the epoxy resin containing long-chain alkyl and polyurethane and the low-viscosity flexible epoxy resin according to the proportion, setting the temperature at 45-65 ℃, mixing and stirring until the epoxy resin and the low-viscosity flexible epoxy resin are soaked, adding the coupling agent a, stirring and mixing uniformly, vacuumizing and removing bubbles to obtain an epoxy resin component;
preparation of the curing agent component: under the atmosphere of protective gas, adding polythiol, monoalkanolamine and tertiary amine urea at the temperature of 25-45 ℃, stirring and mixing uniformly, adding coupling agent b and defoaming agent, stirring and mixing uniformly, and vacuumizing to remove bubbles to obtain the curing agent component.
11. The adhesive according to any one of claims 1 to 9 and the adhesive prepared by the preparation method of claim 10 are applied to bonding any two of plastic, metal, glass, wood, ceramic, rubber and elastic masonry materials, or the adhesive is used for fixing an elastic circuit, a cable boot or a fillet key.
12. Use according to claim 11, in applications where ultra-clear bond lines are required.
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