CN112341973B - Two-component normal-temperature cured epoxy resin elastomer composition and preparation method thereof - Google Patents
Two-component normal-temperature cured epoxy resin elastomer composition and preparation method thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 150
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 150
- 229920001971 elastomer Polymers 0.000 title claims abstract description 43
- 239000000806 elastomer Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 21
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 15
- 239000004814 polyurethane Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000004593 Epoxy Substances 0.000 claims description 24
- 239000000853 adhesive Substances 0.000 claims description 24
- 230000001070 adhesive effect Effects 0.000 claims description 24
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 13
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 13
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 13
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 13
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- -1 alkyl glycidyl ether Chemical compound 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 5
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 5
- WECUIGDEWBNQJJ-UHFFFAOYSA-N 4-phenylbutan-2-amine Chemical compound CC(N)CCC1=CC=CC=C1 WECUIGDEWBNQJJ-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- LYUQWQRTDLVQGA-UHFFFAOYSA-N 3-phenylpropylamine Chemical compound NCCCC1=CC=CC=C1 LYUQWQRTDLVQGA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical group CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 claims description 3
- UBLYEVLMRSPMOG-UHFFFAOYSA-N cyclopentylmethanamine Chemical compound NCC1CCCC1 UBLYEVLMRSPMOG-UHFFFAOYSA-N 0.000 claims description 3
- IPBPLHNLRKRLPJ-UHFFFAOYSA-N oxan-4-ylmethanamine Chemical compound NCC1CCOCC1 IPBPLHNLRKRLPJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims 1
- 244000060011 Cocos nucifera Species 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 229920006332 epoxy adhesive Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- DWJJIZUJXNFHSW-UHFFFAOYSA-N octadecan-9-amine Chemical compound CCCCCCCCCC(N)CCCCCCCC DWJJIZUJXNFHSW-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000001320 hippocampus Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QGLWBTPVKHMVHM-MDZDMXLPSA-N (e)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C\CCCCCCCCN QGLWBTPVKHMVHM-MDZDMXLPSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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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
-
- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4057—Carbamates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a two-component normal temperature curing epoxy resin elastomer composition and a preparation method thereof, wherein the two-component normal temperature curing epoxy resin elastomer composition comprises the following raw materials in parts by weight: and (3) epoxy resin of component A: 100 parts of epoxy resin, 10 to 20 parts of rubber modified epoxy resin and/or polyurethane modified epoxy resin and 8 to 15 parts of epoxy resin active diluent; b, epoxy resin curing agent: 100 parts of liquid monoamine curing agent, 12.5 to 45 parts of polyurethane prepolymer and 4.5 to 11.5 parts of adhesion promoter; the weight ratio of the component A to the component B is 1: 0.80-1.20. The elastomer composition has the advantages of high normal-temperature curing speed, high bonding strength, high elongation at break, good low-temperature flexibility, strong tear resistance and impact resistance, capability of realizing elastic bonding and wide application prospect.
Description
Technical Field
The invention relates to an epoxy resin adhesive, in particular to a two-component normal-temperature curing epoxy resin elastomer adhesive composition, a preparation method and an application method.
Background
Since the middle of the twentieth century, with the successive proposition of various adhesion theories, the deep development of basic research works such as adhesive chemistry, adhesive rheology, adhesive failure mechanism and the like has led to the rapid development of adhesive performance, variety and application. Because of the characteristics of high bonding strength, strong universality and the like, the epoxy adhesive has been called as a universal adhesive and is widely applied in the fields of aviation, aerospace, automobiles, machinery, construction, chemical engineering, light industry, electronics, electrical appliances, daily life and the like.
The normal temperature curing epoxy resin adhesive has received wide attention due to the advantages of time saving, workload reduction, simple process, energy saving, environmental protection and the like. The normal temperature curing epoxy resin adhesive forms a three-dimensional network structure after crosslinking and curing, has high crosslinking density and large internal stress, leads to brittleness, poor impact toughness and easy generation of cracks and fissures of epoxy resin curing substances, and has main mechanical properties particularly shown in large tensile strength, but has small elongation at break and poorer fatigue resistance, thereby seriously limiting the application of the epoxy resin adhesive in the technical field of engineering.
Chinese patent CN 102936478A, the product is solidified under the condition of room temperature, the shearing strength is 9-12 MPa, the tensile strength is 20-30 MPa, and the elongation is only 100-150%. Chinese patent CN 104479107A, the product is cured for 24-168 h at 25-80 ℃, the tensile strength is 20-35 MPa, and the elongation at break is 10-100%. Chinese patent CN 104119827A, the adhesive is composed of epoxy resin, mercapto compound, toughening agent, acid anhydride and filler, and is completely cured at 25 ℃ for 48 hours, the shear strength is 25-36 MPa, the tensile strength is 42-63 MPa, and the elongation at break is low. Other Chinese patents, CN 106281160A, CN 106117513A, CN 110016321A, CN 110373143A and the like, have high tensile strength and low elongation at break, and cannot realize elastic bonding. Therefore, the most important objective at present is to adopt an adhesive elastic bonding technology with high bonding strength and high elastic deformation to ensure the application requirements of certain specific occasions, so that the stress distribution is uniform in the service process, and the damage caused by stress concentration can not be generated.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a two-component normal-temperature curing epoxy resin elastomer composition and a preparation method thereof, which are used for realizing normal-temperature curing and elastic bonding of epoxy resin, and have high strength and high elongation at the same time.
In order to achieve the purpose, the invention adopts the following technical scheme:
a two-component normal temperature curing epoxy resin elastomer composition comprises an A-component epoxy resin and a B-component epoxy resin curing agent;
the composite material comprises the following raw materials in parts by weight:
and (3) epoxy resin of component A:
epoxy resin 100 parts
10 to 20 portions of rubber modified epoxy resin and/or polyurethane modified epoxy resin
8-15 parts of epoxy resin reactive diluent;
b, epoxy resin curing agent:
100 portions of liquid monoamine curing agent
12.5 to 45 portions of polyurethane prepolymer
4.5-11.5 parts of an adhesion promoter;
wherein the weight ratio of the epoxy resin of the component A to the epoxy curing agent of the component B is 1.
Preferably, the epoxy resin is liquid bisphenol A type glycidyl ether epoxy resin, the epoxy value is 0.48 to 0.54eq/100g, and the viscosity at 23 ℃ is 10000 to 18000mPa.s. Specifically, the trade designations Epon 828 (Shell), aradite6010 (Ciba), DER 331 (Dow), ERL 2774 (U.C.C.), CYD-128 (China petrochemical), NPEL-128 (south Asia resin works, taiwan), E-51 (Ministry of chemical industry), R-140 (Mitsui), 618, etc.
Preferably, the rubber modified epoxy resin is mainly nitrile rubber modified epoxy resin, the epoxy equivalent is 200-500 g/eq, the elastomer content is 5-50%, and the viscosity at 25 ℃ is 10000-1000000mPa.s. Specifically, commercial brands, such as HyPox RA 840, hyPox RA 1340, hyPox RF 16213, hyPox RA 95, and the like, may be purchased by CVC corporation.
Preferably, the polyurethane modified epoxy resin has an epoxy equivalent of 150 to 450g/eq, an elastomer content of 2 to 25 percent and a viscosity of 10000 to 1000000mPa.s at 25 ℃. Commercial brands such as Hypox UA10, hyPox UA11, NPER-133L (commercially available from south Asia, taiwan, china), and the like, commercially available from CVC; DER852, DER858, DER791, etc. are commercially available from Dow chemical, USA, etc. Wherein, the rubber modified epoxy resin and the polyurethane modified epoxy resin are uniformly mixed according to any mass ratio.
Preferably, the epoxy reactive diluent is one or a mixture of C12-14 alkyl glycidyl ether, 1,4-butanediol diglycidyl ether and trimethylolpropane triglycidyl ether.
Preferably, the liquid monoamine curing agent mainly refers to liquid aliphatic amines (such as octylamine, decylamine, cocoamine, oleylamine, etc.) having a molecular structure containing 2 active hydrogen atoms, liquid alicyclic amines (such as cyclohexylmethylamine, cyclopentylmethylamine, 4-aminomethyl tetrahydropyran, etc.), liquid aromatic amines (such as 1-methyl-3-phenylpropylamine, 3-phenyl-1-propylamine, etc.), liquid polyether amines (HUNTSMAN corporation)
M-2005，
M-2070，
XTJ-435，
XTJ-436, etc.) and the like in an arbitrary ratio by mass ratio.
Preferably, the polyurethane prepolymer mainly refers to polyester system polyurethane prepolymer and polyether system polyurethane prepolymer, the NCO (isocyanate group) content of the polyurethane prepolymer is 1.5-15%, and the viscosity at 80 ℃ is 300-5000 mPa.s. Including but not limited to commercial products including, in particular, but not limited to, polyester TDI systems, HC-5589, HC-5691, HC-5985, HC-5980C, HC-5595, and the like, commercially available from Hippocampus polymer technology, inc.; h1325 H1330, H1342, H1350, H1358, etc., commercially available from Zibo Huatian chemical Co., ltd. Polyether TDI systems, specifically, H2125A, H2128A, H2133A, H2143A, H2165, H2153A, H2143B and the like, can be purchased and obtained from Zibo Huatian chemical industry Co., ltd; HC-8535, HC-8692, HC-6580, HC-6595, HC-6692, etc., commercially available from Hippocampus Hecheng Polymer technology, inc.
Preferably, the adhesion promoter of the present invention is a mixture of a product of addition reaction of diethylenetriamine and propylene oxide butyl ether (trade mark 593 curing agent), cardanol and diphenol propane, and the mass ratio of the mixture is the product of addition reaction of diethylenetriamine and propylene oxide butyl ether: cardanol: diphenolylpropane = (0.2 to 1.1): (3-8): (1-3.5).
A preparation method of a two-component normal-temperature cured epoxy resin elastomer composition comprises the following steps:
step one, preparing epoxy resin of component A: heating a reaction kettle to 50-100 ℃, adding epoxy resin, epoxy resin reactive diluent and rubber modified epoxy resin or/and polyurethane modified epoxy resin into the reaction kettle according to the proportion, continuously stirring for 10-100 min, removing bubbles, and cooling to room temperature to obtain component A epoxy resin;
step two, preparing a component B epoxy resin curing agent: heating the reaction kettle to 50-150 ℃, adding a liquid monoamine curing agent, removing water, slowly adding the polyurethane prepolymer according to the proportion, and continuously stirring for 10-600 min; finally, adding the adhesion promoter, continuously stirring for 10-100 min, removing bubbles, and cooling to room temperature to obtain a component B epoxy resin curing agent;
when in use, the epoxy resin A and the epoxy curing agent B are mixed and stirred for 3-5 min at room temperature according to the proportion to obtain the epoxy resin mixed liquid composition capable of being cured at normal temperature, construction is carried out according to construction requirements, elastic bonding can be realized after curing at normal temperature for 1-2 days, and the application prospect is wide.
The first step and the second step are not limited by time sequence.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention uses the universal epoxy resin E-51, and simultaneously introduces the rubber modified epoxy resin and/or the polyurethane modified epoxy resin with good compatibility and flexibility, thereby improving and improving the flexibility of the epoxy resin cured product; and secondly, the reactive diluent used in the epoxy resin can directly participate in the curing reaction of the epoxy resin and become a part of a cross-linked network of the epoxy resin cured product, and compared with a non-reactive diluent, the reactive diluent can increase the stability of the epoxy resin cured product, simultaneously provide toughness and avoid volatilization of an organic solvent, is more environment-friendly and is beneficial to application and popularization.
According to the invention, a polyurethane prepolymer with excellent flexibility and liquid monoamine are used for carrying out prepolymerization reaction (isocyanate group and amino group are reacted) to obtain an epoxy resin curing agent component with excellent flexibility, and the epoxy resin curing agent component reacts with epoxy resin to obtain an elastomer material with excellent performance.
The adhesion promoter used in the present invention is a product of addition reaction of diethylenetriamine and propylene oxide butyl ether (trade mark 593 curing agent), which can increase the open time of the product under normal temperature conditions, and a mixture of cardanol and diphenol propane, which can promote the reactivity of epoxy resin and improve the low temperature toughness of the cured product.
Experimental results show that the normal-temperature curing speed of the epoxy adhesive can be adjusted according to construction requirements, the adhesive strength is high, the tensile elongation at break is high, the low-temperature flexibility is good, the tear resistance and the impact resistance are high, the elastic adhesion of the epoxy adhesive is realized, and the epoxy adhesive has wide application prospects in the fields of roads, bridges, building engineering and the like.
The invention is not only focused on the selection of single components, but also on the selection of each component and the further control of the coordination and the proportion among the components, thereby obtaining the technical effect of the invention with excellent final performance.
Drawings
FIG. 1 is a graph of viscosity-temperature increase of a mixed solution of example 1 at different temperatures;
FIG. 2 is a graph of viscosity-temperature increase of the mixed solution of example 2 at different temperatures;
FIG. 3 is a graph of viscosity-temperature increase of the mixed solution of example 3 at different temperatures;
FIG. 4 is a graph of viscosity-temperature increase of the mixed solution of example 4 at different temperatures;
FIG. 5 is a graph of viscosity-temperature increase of the mixed solution of example 5 at different temperatures;
FIG. 6 is a graph of viscosity-temperature increase of the mixed solution of example 6 at different temperatures;
FIG. 7 is a graph of viscosity-temperature increase of the mixed solution of example 7 at different temperatures;
FIG. 8 is a graph of viscosity-temperature increase of the mixed solution of example 8 at different temperatures.
Detailed Description
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
the embodiment provides a two-component normal-temperature curing epoxy resin elastomer composition and a preparation method thereof, and the two-component normal-temperature curing epoxy resin elastomer composition comprises the following raw materials in parts by weight:
1) And (3) epoxy resin of component A: 100 parts of epoxy resin (E-51, ba ling petrochemical), 11.8 parts of rubber modified epoxy resin (HyPox RA 1340, CVC company) and 14.2 parts of epoxy reactive diluent (1,4-butanediol diglycidyl ether);
2) B, epoxy curing agent: 100 parts of a liquid monoamine curing agent (9-octadecylamine, sovereil chemicals), 41.5 parts of a polyurethane prepolymer (HC-9975, shanghai Hecheng polymer), 5.64 parts of an adhesion promoter (593: cardanol: diphenol propane = 0.53;
wherein the weight ratio of the epoxy resin of the component A to the epoxy curing agent of the component B is 1:1;
3) The preparation method of the two-component normal temperature curing epoxy resin elastomer composition comprises the following steps:
step one, preparing epoxy resin of component A: heating a reaction kettle to 60 ℃, adding epoxy resin, epoxy resin reactive diluent and rubber modified epoxy resin or/and polyurethane modified epoxy resin into the reaction kettle according to the proportion, continuously stirring for 50min and removing bubbles, cooling to room temperature, discharging, detecting, packaging and storing to obtain the component A epoxy resin;
step two, preparing a component B epoxy resin curing agent: heating the reaction kettle to 85 ℃, adding 9-octadecenylamine, removing water, slowly adding the polyurethane prepolymer according to the proportion, and continuously stirring for 200min; then, adding an adhesion promoter, continuously stirring for 30min, removing bubbles, cooling to room temperature, discharging, detecting, packaging and storing to obtain a B-component epoxy resin curing agent;
when in use, the component A epoxy resin and the component B epoxy curing agent are stirred according to the mass ratio for 3-5 min and are uniformly mixed under the condition of normal temperature, and then the double-component normal temperature curing epoxy resin mixed solution is obtained. And in the operable time, the mixed solution is uniformly coated on a base surface, and the maintenance is completed to obtain the epoxy resin elastomer with high tensile strength, high elongation at break, good low-temperature flexibility, excellent wear resistance and tear resistance.
Example 2:
1) And (3) epoxy resin of component A: 100 parts of epoxy resin (E-51, taiwan south Asia resin factory, china), 17.4 parts of polyurethane modified epoxy resin (NPER-133L, taiwan south Asia resin factory, china), and 11 parts of epoxy resin reactive diluent (6.6 parts of C12-14 alkyl glycidyl ether and 4.4 parts of trimethylolpropane triglycidyl ether);
2) B, epoxy curing agent: liquid monoamine curing agent (A)
M-2005, XTJ-435, XTJ-436, mixed according to a molar mass ratio of 1: cardanol: diphenolylpropane =0.25:5.80:1.56 7.61 parts;
wherein the weight ratio of the epoxy resin of the component A to the epoxy curing agent of the component B is 1;
3) The preparation method refers to example 1, except that, in the step one, the temperature of the reaction kettle is 65 ℃, and the time is 60min; and step two, the temperature is 75 ℃, and the reaction time is 240min.
Example 3:
1) And (3) epoxy resin of component A: 100 parts of epoxy resin (E-51, ba ling petrochemical), 9.2 parts of rubber modified epoxy resin (HyPox RF 95, CVC company) and 6.5 parts of polyurethane modified epoxy resin (NPER-133L, south Asia resin of China), 15.7 parts in total, and 13.7 parts of epoxy resin reactive diluent (1,4-butanediol diglycidyl ether 6.3 parts, C12-14 alkyl glycidyl ether 7.4 parts, junqian new material (Shenzhen) Co., ltd.);
2) B, epoxy curing agent: 100 parts of liquid monoamine curing agents (cyclohexylmethylamine and cyclopentylmethylamine mixed according to a molar ratio of 1, 0.78), 19.5 parts of polyurethane prepolymer (H1342, zibovas chemical limited), 8.48 parts of adhesion promoter (593: cardanol: diphenolylpropane = 0.29;
wherein the weight ratio of the epoxy resin of the component A to the epoxy curing agent of the component B is 1.13;
3) The preparation method refers to example 1, except that, in the step one, the temperature of the reaction kettle is 75 ℃, and the time is 45min; and step two, the temperature is 85 ℃, and the reaction time is 300min.
Example 4:
1) And (3) epoxy resin of component A: 100 parts of epoxy resin (NPEL-128, south Asia, taiwan, ltd.); 8.7 parts of rubber modified epoxy resin (HyPox RA 1340, CVC company) and 5.1 parts of polyurethane modified epoxy resin (DER 858, dow chemical USA), wherein the total parts are 13.8 parts; 8.9 parts of epoxy reactive diluent (1.6 parts of C12-14 alkyl glycidyl ether, 3.3 parts of 1,4-butanediol diglycidyl ether and 4 parts of trimethylolpropane triglycidyl ether);
2) B, epoxy curing agent: 100 parts of liquid monoamine curing agent (1-methyl-3-phenylpropylamine, 3-phenyl-1-propylamine, mixed according to a molar mass ratio of 1: 0.59), 38.2 parts of polyurethane prepolymer (HC-5980C, shanghai he cheng polymer company), 5.14 parts of adhesion promoter (593: cardanol: diphenol propane = 0.31;
wherein the weight ratio of the epoxy resin of the component A to the epoxy curing agent of the component B is 1.03;
3) The preparation method refers to example 1, except that, in the step one, the temperature of the reaction kettle is 80 ℃, and the time is 30min; and step two, the temperature is 90 ℃, and the reaction time is 180min.
Example 5:
1) And (3) epoxy resin of component A: 100 parts of epoxy resin (NPEL-128, south Asia resin of Taiwan) 16.2 parts of polyurethane modified epoxy resin (HyPox UA11, CVC), 10.1 parts of epoxy resin reactive diluent (2.6 parts of trimethylolpropane triglycidyl ether, 7.5 parts of C12-14 alkyl glycidyl ether);
2) B, epoxy curing agent: liquid monoamine curing agents (9-octadecylamine, cocoylamine,
M-2005, 4-aminomethyl tetrahydropyran, 3-phenyl-1-propylamine, in a molar ratio of 1:0.38:0.51:0.21:0.60 portion), 27.7 portions of polyurethane prepolymer (H1330, zibohuatian chemical Co., ltd.), and adhesion promoter (according to the mass ratio of 593: cardanol: diphenolylpropane =0.52:7.0:3.1 10.62 parts;
wherein the weight ratio of the epoxy resin of the component A to the epoxy curing agent of the component B is 1;
3) The preparation method refers to example 1, except that, in the step one, the temperature of the reaction kettle is 90 ℃, and the time is 25min; and step two, the temperature is 95 ℃, and the reaction time is 170min.
Example 6:
this example provides a two-component normal temperature cured epoxy resin elastomer composition and a preparation method thereof, which are substantially the same as those in example 3, except that: the components for preparing the component B epoxy resin curing agent and the mass thereof are as follows: a polyurethane prepolymer: 5.1 parts of HC-8535, 17.3 parts of HC-6580, 10.11 parts of an adhesion promoter (593: cardanol: diphenol propane = 1.05; the mixing mass ratio of the component A to the component B is 1; the other raw materials, procedures and parameters were the same as those of example 5.
Example 7:
this example provides a two-component normal temperature cured epoxy resin elastomer composition and a preparation method thereof, which are substantially the same as example 4 except that: the components for preparing the component B epoxy resin curing agent and the mass fraction thereof are as follows: 100 parts of liquid monoamine curing agent (1-methyl-3-phenylpropylamine, cocoamine and 9-octadecylamine mixed according to a molar ratio of 1: 5.6 parts of H2165, 8.2 parts of H1358, 8.24 parts of an adhesion promoter (593: cardanol: diphenol propane =0.71: 2.53 by mass ratio) and 0.91 parts of the component A and the component B in a mixing ratio of 1. The other raw materials, steps and parameters were the same as those in example 5.
Example 8:
this example provides a two-component normal temperature curable epoxy resin elastomer composition and a method for preparing the same, which is substantially the same as example 5 except that: the components for preparing the component B epoxy resin curing agent and the mass fraction thereof are as follows: liquid monoamine curing agent (A)
XTJ 435, 1-methyl-3-phenylpropylamine, 9-octadecylamine, mixed according to a molar ratio of 1:5.3 parts of HC-5980C, 12.8 parts of H2125A, 9.10 parts of an adhesion promoter (593: cardanol: diphenol propane = 0.55. The other raw materials, steps and parameters were the same as those in example 5.
The performance test method comprises the following steps:
firstly, testing a viscosity increase curve of the mixed solution at 20 ℃,30 ℃,40 ℃, 50 ℃ and 60 ℃ according to an embodiment, wherein the test method refers to GB/T22314-2008 'method for measuring viscosity of plastic epoxy resin', and the result is shown in figure 1, and as shown in the figure, the mixed solution can be operated for a long time at 20-30 ℃, so that the construction requirement can be met; as the temperature increases, the pot life is shorter, with a faster open time.
From mixing to finishing of construction, the A, B components must be controlled within the usable time range so as to be controlled within a proper viscosity range (i.e., viscosity of less than 3000mPa. S at 20-30 ℃); as shown in table 1, different operating times are provided at different temperature ranges in order to ensure that complex construction requirements can be smoothly performed.
And (III) referring to GB/T16777 'test method for waterproof building coatings' and the results shown in Table 2, the curing period and the bonding period of validity after construction of the mixed solution are determined by selecting proper curing days according to different temperature conditions, so that reliable reference is provided for construction within the bonding period of validity.
And (IV) testing mechanical properties, namely mixing A, B components in proportion, stirring and mixing uniformly, injecting the mixture into a dumbbell type test mold, placing the prepared test mold at normal temperature for 1 day, curing at 60 ℃ for 4 days, placing the test mold at normal temperature for one day, and testing the tensile strength and the elongation at break of the test mold according to a method of GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, wherein the results are shown in Table 3.
TABLE 1 usable working time of mixed liquid of epoxy resin and epoxy hardener
TABLE 2 days of curing and days of bonding validity after the construction of the epoxy resin and curing agent mixture
TABLE 3 results of room temperature tensile test (test temperature 23. + -. 1 ℃ C.)
| Test sample | Tensile strength/MPa | Elongation at break/%) |
| Example 1 | 8.67 | 402 |
| Example 2 | 7.88 | 436 |
| Example 3 | 9.20 | 366 |
| Example 4 | 14.21 | 258 |
| Example 5 | 11.87 | 376 |
| Example 6 | 6.54 | 387 |
| Example 7 | 8.12 | 311 |
| Example 8 | 13.58 | 287 |
As shown in Table 1, the usable construction time of the mixed liquid of the epoxy resin and the epoxy curing agent is shown, the epoxy resin adhesive prepared by the invention has a long working life at 20 ℃,30 ℃ and 40 ℃, can meet the construction requirements of different occasions, and has a wide application prospect. As shown in Table 2, the curing days and the bonding effective period days after the construction of the mixed solution of the epoxy resin and the curing agent are shown, the curing time of the epoxy resin adhesive prepared by the invention is different between 10 ℃ and 50 ℃, and a proper formula can be selected according to the construction requirements; meanwhile, the surface drying has different bonding effective periods, and the next bonding operation can be carried out within the range according to the requirement. From the results of the normal temperature tensile test in table 3, it can be seen that the epoxy resin adhesive has excellent normal temperature tensile properties and can achieve elastic adhesion well at an experimental temperature of 23 ± 1 ℃.
The test results of the above embodiments show that the epoxy adhesive of the invention has high elasticity, good low-temperature flexibility and large bonding strength after room temperature curing. The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed herein.
Claims (8)
1. A two-component normal temperature cured epoxy resin elastomer adhesive is characterized by comprising an A-component epoxy resin and a B-component epoxy resin curing agent; the composite material comprises the following raw materials in parts by weight:
and (3) epoxy resin of component A:
epoxy resin 100 parts
10 to 20 portions of rubber modified epoxy resin and/or polyurethane modified epoxy resin
8-15 parts of epoxy resin reactive diluent;
b, epoxy resin curing agent:
100 portions of liquid monoamine curing agent
12.5 to 45 portions of polyurethane prepolymer
4.5-11.5 parts of an adhesion promoter;
wherein the weight ratio of the epoxy resin of the component A to the curing agent of the component B is 1:0.80 to 1.20;
the liquid monoamine curing agent is selected from cyclohexylmethylamine, cyclopentylmethylamine, 4-aminomethyl tetrahydropyran, 1-methyl-3-phenylpropylamine, 3-phenyl-1-propylamine, oleylamine, and the like,
M-2005、
M-2070、
XTJ-435、
XTJ-436, coconut amine or a mixture thereof; the content of isocyanate group in the polyurethane prepolymer is 1.5-15%; the adhesion promoter is diethylenetriamine and propylene oxide butylThe mixture of the ether reaction product, cardanol and diphenol propane is the product of addition reaction of diethylenetriamine and propylene oxide butyl ether according to mass ratio: cardanol:
diphenolylpropane = (0.2 to 1.1): (3-8): (1-3.5);
the preparation method of the component B epoxy resin curing agent comprises the following steps: heating a reaction kettle to 50-150 ℃, adding a liquid monoamine curing agent, removing moisture, slowly adding the polyurethane prepolymer according to the proportion, and continuously stirring for 10-600 min; and finally, adding the adhesion promoter, continuously stirring for 10-100 min, removing bubbles, cooling to room temperature and storing to obtain the component B epoxy resin curing agent.
2. The two-component ambient temperature curing epoxy resin elastomer adhesive as claimed in claim 1, wherein the epoxy resin is liquid bisphenol A type glycidyl ether epoxy resin, the epoxy value is 0.48-0.54 eq/100g, and the viscosity at 23 ℃ is 10000-18000mPa.s.
3. The two-component normal temperature curing epoxy resin elastomer adhesive according to claim 1, wherein the rubber modified epoxy resin is nitrile rubber modified epoxy resin, the epoxy equivalent is 200-500 g/eq, the elastomer content is 5-50%, and the viscosity at 25 ℃ is 10000-1000000mPa.s.
4. The two-component normal temperature curing epoxy resin elastomer adhesive according to claim 1, wherein the epoxy equivalent of the polyurethane modified epoxy resin is 150 to 450g/eq, the elastomer content is 2 to 25%, and the viscosity at 25 ℃ is 10000 to 1000000mpa.s.
5. The two-component normal temperature curing epoxy resin elastomer adhesive according to claim 3 or 4, wherein the rubber modified epoxy resin and the polyurethane modified epoxy resin are mixed in any proportion by mass.
6. The two-component ambient temperature curing epoxy resin elastomer adhesive as claimed in claim 1, wherein the epoxy resin reactive diluent is one or more of C12-14 alkyl glycidyl ether, 1,4-butanediol diglycidyl ether and trimethylolpropane triglycidyl ether.
7. The two-component ambient temperature curing epoxy resin elastomer adhesive as claimed in claim 1, wherein the polyurethane prepolymers are polyester system polyurethane prepolymers and polyether system polyurethane prepolymers, and have an isocyanate group content of 1.5 to 15% and a viscosity of 300 to 5000mpa.s at 80 ℃.
8. A method for preparing the two-component normal temperature curing epoxy resin elastomer adhesive according to any one of claims 1 to 7, which is characterized by comprising the following steps:
step one, preparing component A epoxy resin: heating a reaction kettle to 50-100 ℃, adding epoxy resin, epoxy resin reactive diluent, rubber modified epoxy resin and polyurethane modified epoxy resin into the reaction kettle according to the proportion, continuously stirring for 10-100 min, removing bubbles, cooling to room temperature and storing to obtain the component A epoxy resin;
step two, preparing a component B epoxy resin curing agent: heating the reaction kettle to 50-150 ℃, adding a liquid monoamine curing agent, removing water, slowly adding the polyurethane prepolymer according to the proportion, and continuously stirring for 10-600 min; finally, adding the adhesion promoter, continuously stirring for 10-100 min, removing bubbles, cooling to room temperature and storing to obtain the component B epoxy resin curing agent;
when in use, the component A epoxy resin and the component B epoxy resin curing agent are stirred according to the proportion for 3-5 min and are uniformly mixed under the normal temperature state, and the normal temperature curing epoxy resin glue solution is obtained.
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| CN113502032B (en) * | 2021-06-04 | 2023-01-10 | 东莞爱的合成材料科技有限公司 | High-toughness resin composition and preparation method and application thereof |
| CN113999638A (en) * | 2021-12-17 | 2022-02-01 | 江苏天康电子合成材料有限公司 | Novel environment-friendly corrosion-resistant sealant and preparation method thereof |
| CN114456755B (en) * | 2021-12-30 | 2024-03-12 | 江苏中科科化新材料股份有限公司 | Epoxy resin composition, preparation method and application thereof |
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