CN116041670A - Acid modified epoxy resin and preparation method and application thereof - Google Patents
Acid modified epoxy resin and preparation method and application thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 97
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 97
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 150000007524 organic acids Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000012778 molding material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 150000004665 fatty acids Chemical group 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000007142 ring opening reaction Methods 0.000 claims description 6
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 6
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 238000010292 electrical insulation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- KCFOLUKWAIAKFB-UHFFFAOYSA-N CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br Chemical compound CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br KCFOLUKWAIAKFB-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000005452 bending Methods 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 235000003441 saturated fatty acids Nutrition 0.000 description 5
- -1 coatings Substances 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000012772 electrical insulation material Substances 0.000 description 4
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- RZWDOHOQSSGFOR-UHFFFAOYSA-N bromo-ethyl-triphenyl-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Br)(C=1C=CC=CC=1)(CC)C1=CC=CC=C1 RZWDOHOQSSGFOR-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 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 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- 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
- C09J163/10—Epoxy resins modified by unsaturated compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to an acid modified epoxy resin, a preparation method and application thereof. The invention uses organic acid monomer as modifier to react with epoxy resin, through the copolymerization of carboxyl of organic acid monomer and epoxy resin,the flexible groups are introduced into the epoxy resin, so that the crosslinking network of the epoxy resin is changed, the activity of molecules is improved, the toughness of the cured epoxy resin is enhanced, the problems of high curing brittleness, easy cracking, no impact resistance and the like of the epoxy resin are effectively solved, and the application range of the basic epoxy resin is enlarged. The invention adopts a one-step method to modify the epoxy resin, has simple reaction steps and is easy to operate. The acid modified epoxy resin provided by the invention has high toughness, and the impact strength is 2.78KJ/m 2 The improvement ratio can reach 28%, the tensile strength is above 76MPa, the elongation at break is above 3.26%, the bending strength is above 115.6MPa, and the mechanical property is excellent.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an acid modified epoxy resin, a preparation method and application thereof.
Background
As an important general thermosetting resin, the epoxy resin has the advantages of excellent adhesive property, mechanical property, wear resistance, electrical insulation property, chemical stability, small curing shrinkage, good technological property and the like, and is widely applied to the fields of composite materials, adhesives, coatings, electrical insulation materials, molding materials, injection molding materials and the like. However, the cured epoxy resin has the disadvantages of high crosslinking density, low toughness, fatigue resistance and poor impact resistance, and the application of the epoxy resin in some high-technology fields is limited. For this reason, toughening of epoxy resins has become the focus of its application, and many researchers have made extensive research.
At present, the toughening approaches for epoxy resins can be divided into 3 categories: (1) The rubber elastomer, thermoplastic resin, rigid inorganic filler, thermotropic liquid crystal polymer and the like are utilized to form a two-phase structure for toughening; (2) Forming a semi-interpenetrating network type polymer by continuously penetrating thermoplastic plastics into an epoxy resin network for toughening; (3) The flexibility of the crosslinked network is improved by changing the chemical structure composition of the crosslinked network (such as introducing a 'soft segment' into the crosslinked network), thereby realizing toughening. At present, starting from the molecular structure of epoxy resins, how to synthesize high-toughness epoxy resins containing flexible chain segments is always a hot spot for research.
Chinese patent CN 103113716a reports a preparation method of a dimer acid modified epoxy resin toughened carbon fiber prepreg, which reacts dimer acid with active carboxyl groups with epoxy resin at 120-160 ℃ for 2-6 hours under the action of an organic salt catalyst to obtain dimer acid modified epoxy resin, wherein the epoxy resin adopts one or more of bisphenol a glycidyl ether, bisphenol F glycidyl ether, bisphenol AD type epoxy resin and alicyclic epoxy resin. However, the impact strength of the modified epoxy resin prepared by the method can be improved by about 20%, the toughness of the epoxy resin is improved only, and the application range is still narrow.
Disclosure of Invention
The invention aims to provide an acid modified epoxy resin, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of acid modified epoxy resin, which comprises the following steps:
and heating and mixing the epoxy resin, the organic acid monomer, the organic salt catalyst and the benzene solvent in a protective atmosphere to perform ring-opening reaction to obtain the acid modified epoxy resin.
Preferably, the temperature of the ring-opening reaction is 135-145 ℃, and the heat preservation time is 3-4 h.
Preferably, the mass ratio of the epoxy resin to the organic salt catalyst is 100:1-10;
the mass ratio of the epoxy resin to the organic acid monomer is 1:0.3-0.6;
the mass ratio of the epoxy resin to the benzene solvent is 1:0.1-0.6.
Preferably, the organic acid monomer is a fatty acid.
Preferably, the fatty acid comprises one or more of saturated fatty acid and unsaturated fatty acid.
Preferably, the organic salt catalyst comprises one or more of tetrabutylammonium bromide, cetyltrimethylammonium bromide and ethyl triphenyl phosphonium bromide.
Preferably, the epoxy resin is epoxy resin E-51; the benzene solvent is dimethylbenzene.
Preferably, the heating and mixing are as follows: introducing a protective gas into an organic salt catalyst, epoxy resin and an organic acid monomer for premixing to obtain a premix; heating the premix to 50-55 ℃ to dissolve the organic acid monomer in the premix, and then mixing with the benzene solvent.
The invention also provides the acid modified epoxy resin obtained by the preparation method.
The invention also provides application of the acid modified epoxy resin in composite materials, adhesives, coatings, electrical insulation materials, molding materials or injection molding materials.
The invention provides a preparation method of acid modified epoxy resin. According to the invention, the organic acid monomer is used as a modifier to react with the epoxy group of the epoxy resin, and the carboxyl of the organic acid monomer is copolymerized with the epoxy resin, so that the flexible group is introduced into the epoxy resin, the epoxy resin cross-linking network is changed, the activity of molecules is improved, and the toughness of the cured epoxy resin is enhanced, thereby improving the toughness of the epoxy resin, effectively solving the problems of high curing brittleness, easy cracking, no impact resistance and the like of the epoxy resin, and expanding the application range of the basic epoxy resin. The invention adopts a one-step method to modify the epoxy resin, has simple reaction steps and is easy to operate.
The invention also provides the acid modified epoxy resin obtained by the preparation method. The acid modified epoxy resin provided by the invention has high toughness, wherein the impact strength is 2.78KJ/m 2 The improvement ratio can reach 28 percent, and the tensile strength is more than 76MPaThe breaking elongation is more than 3.26 percent, the bending strength is more than 115.6MPa, and the mechanical property is excellent.
The invention also provides application of the acid modified epoxy resin in composite materials, adhesives, coatings, electrical insulation materials, molding materials or injection molding materials. The acid modified epoxy resin provided by the invention has high toughness, is especially suitable for composite material stress members and high-performance structural adhesives, and can obviously improve the mechanical properties of products.
Detailed Description
The invention provides a preparation method of acid modified epoxy resin, which comprises the following steps:
and heating and mixing the epoxy resin, the organic acid monomer, the organic salt catalyst and the benzene solvent in a protective atmosphere to perform ring-opening reaction to obtain the acid modified epoxy resin.
In the present invention, the epoxy resin is preferably epoxy resin E-51; the organic acid monomer is preferably a fatty acid; the fatty acid preferably comprises one or more of saturated fatty acid and unsaturated fatty acid; the saturated fatty acids preferably comprise C 14:0 Saturated fatty acids, C 16:0 Saturated fatty acids and C 18:0 One or more of saturated fatty acids; the unsaturated fatty acid is preferably C 18:1 Unsaturated fatty acids; the organic salt catalyst preferably comprises one or more of tetrabutylammonium bromide, cetyltrimethylammonium bromide and ethyl triphenyl phosphorus bromide, more preferably ethyl triphenyl phosphorus bromide; the benzene solvent is preferably xylene; the mass ratio of the epoxy resin to the organic acid monomer is preferably 1:0.3-0.6, more preferably 1:0.4-0.5; the mass ratio of the epoxy resin to the organic salt catalyst is preferably 100:1-10, more preferably 100:3-8, and even more preferably 100:5-6; the mass ratio of the epoxy resin to the benzene solvent is preferably 1:0.1-0.6, more preferably 1:0.3-0.5. In a specific embodiment of the present invention, the organic acid monomer preferably employs C that is unreacted in the dimer acid polymerization 14:0 、C 16:0 、C 18:0 Saturated fatty acids or C 18:1 Unsaturated fatty acid to realize the recycling of waste liquidThe utilization of the method can protect the environment and reduce the production cost.
In the present invention, the protective atmosphere is preferably nitrogen; the heated mixing is preferably: introducing a protective gas into an organic salt catalyst, epoxy resin and an organic acid monomer for premixing to obtain a premix; heating the premix to 50-55 ℃ to dissolve the organic acid monomer in the premix, and then mixing with the benzene solvent.
In the present invention, the temperature of the ring-opening reaction is preferably 135 to 145 ℃, more preferably 138 to 143 ℃, and the holding time is preferably 3 to 4 hours, more preferably 3.5 hours.
The invention also provides the acid modified epoxy resin obtained by the preparation method. The acid modified epoxy resin provided by the invention has high toughness, wherein the impact strength is 2.78kJ/m 2 The improvement ratio can reach 28%, the tensile strength is above 76MPa, the elongation at break is above 3.26%, the bending strength is above 115.6MPa, and the mechanical property is excellent.
The invention also provides application of the acid modified epoxy resin in composite materials, adhesives, coatings, electrical insulation materials, molding materials or injection molding materials. The acid modified epoxy resin provided by the invention has high toughness, is especially suitable for composite material stress members and high-performance structural adhesives, and can obviously improve the mechanical properties of products.
The following describes the invention in detail with reference to examples for further illustration of the invention, but they should not be construed as limiting the scope of the invention.
Example 1
At N 2 200g of epoxy resin E-51 and 60g of C are reacted under protection 18:1 Adding unsaturated acid into four-mouth bottle, adding 12g organic salt catalyst cetyl trimethyl ammonium bromide, heating to 50deg.C, and standing for C 18:1 After the unsaturated acid is completely dissolved, 225mL of dimethylbenzene is added, the reaction system is continuously heated to 135 ℃, and the reaction is stopped after continuously stirring for 3 hours, so as to obtain the acid modified epoxy resin.
Example 2
At N 2 200g of epoxy resin E-51 and 60g of C are reacted under protection 18:0 Adding saturated acid into a four-mouth bottle, adding 12g of organic salt catalyst ethyl triphenyl phosphonium bromide, heating to 50 ℃, and keeping the temperature at C 18:0 And after the saturated acid is completely dissolved, 225mL of dimethylbenzene is added, the reaction system is continuously heated to 135 ℃, and the reaction is stopped after the reaction system is continuously stirred for 3 hours, so that the acid modified epoxy resin is obtained.
Example 3
At N 2 200g of epoxy resin E-51 and 80g of C are reacted under protection 16:0 Adding saturated acid into a four-mouth bottle, adding 12g of organic salt catalyst butyl ammonium bromide, heating to 50 ℃, and keeping the temperature at C 16:0 And after the saturated acid is completely dissolved, 225mL of dimethylbenzene is added, the reaction system is continuously heated to 135 ℃, and the reaction is stopped after the reaction system is continuously stirred for 3 hours, so that the acid modified epoxy resin is obtained.
Example 4
At N 2 200g of epoxy resin E-51 and 100g of C are reacted under protection 14:0 Adding saturated acid into a four-mouth bottle, adding 12g of organic salt catalyst ethyl triphenyl phosphonium bromide, heating to 50 ℃, and keeping the temperature at C 14:0 And after the saturated acid is completely dissolved, 225mL of dimethylbenzene is added, the reaction system is continuously heated to 135 ℃, and the reaction is stopped after the reaction system is continuously stirred for 3 hours, so that the acid modified epoxy resin is obtained.
Example 5
At N 2 200g of epoxy resin E-51 and 120g of C are reacted under protection 18:1 Adding unsaturated acid into four-mouth bottle, adding 12g of organic salt catalyst ethyl triphenyl phosphonium bromide, heating to 50deg.C, and standing for C 18:1 After the unsaturated acid is completely dissolved, 225mL of dimethylbenzene is added, the reaction system is continuously heated to 135 ℃, and the reaction is stopped after continuously stirring for 3 hours, so as to obtain the acid modified epoxy resin.
The acid-modified epoxy resins and conventional resins prepared in examples 1 to 5 of the present invention were subjected to epoxy equivalent weight, viscosity, volatility and chromaticity tests according to GB/T22314, and the results are shown in Table 1.
TABLE 1 Performance test results of acid-modified epoxy resins prepared in examples 1 to 5 of the present invention
As can be seen from Table 1, the fatty acid in the acid-modified epoxy resin prepared by the invention reacts with the epoxy resin, and the viscosity and the epoxy equivalent are obviously changed, so that the invention successfully realizes the modification of the epoxy resin.
The acid modified epoxy resin and the unmodified epoxy resin prepared in examples 1 to 5 of the present invention were subjected to performance test by the following methods: the acid-modified epoxy resins and the unmodified epoxy resins prepared in examples 1 to 5 were cured with the same aliphatic polyamide-based curing agent (flexible curing agent PA 651 ) Curing is carried out under the same curing condition, after the curing agent and the epoxy resin are mixed in a ratio of 1:1, the constant temperature curing is carried out for 2 hours from room temperature (25 ℃), then the temperature is slowly raised to 70 ℃ and is kept for 2 hours, finally the temperature is raised to 125 ℃ and is kept for 0.5 hour, and then the sample preparation test is carried out, and the results are shown in table 1.
TABLE 1 Performance data for acid-modified epoxy resins prepared in examples 1 to 5
As can be seen from table 1, compared with the unmodified epoxy resin, the acid-modified epoxy resins prepared in examples 1 to 5 of the present invention have higher impact strength and tensile strength, and significantly improved both bending strength and elongation at break, and thus the acid-modified epoxy resins prepared in the present invention have high toughness and excellent comprehensive mechanical properties.
As can be seen from the above examples, the acid-modified epoxy resin provided by the present invention has high toughness, in which the impact strength is 2.78KJ/m 2 The improvement ratio can reach 28%, the tensile strength is above 76MPa, the elongation at break is above 3.26%, the bending strength is above 115.6MPa, and the combination is realizedExcellent mechanical properties.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. The preparation method of the acid modified epoxy resin comprises the following steps:
and heating and mixing the epoxy resin, the organic acid monomer, the organic salt catalyst and the benzene solvent in a protective atmosphere to perform ring-opening reaction to obtain the acid modified epoxy resin.
2. The preparation method according to claim 1, wherein the temperature of the ring-opening reaction is 135-145 ℃ and the holding time is 3-4 h.
3. The preparation method according to claim 1, wherein the mass ratio of the epoxy resin to the organic salt catalyst is 100:1-10;
the mass ratio of the epoxy resin to the organic acid monomer is 1:0.3-0.6;
the mass ratio of the epoxy resin to the benzene solvent is 1:0.1-0.6.
4. A method of preparation according to claim 1 or 3, wherein the organic acid monomer is a fatty acid.
5. The method according to claim 4, wherein the fatty acid comprises a saturated fatty acid and an unsaturated fatty acid.
6. A method of preparing according to claim 1 or 3, wherein the organic salt catalyst comprises one or more of tetrabutylammonium bromide, cetyltrimethylammonium bromide and ethyltriphenylphosphine bromide.
7. A method of preparation according to claim 1 or 3, wherein the epoxy resin is epoxy resin E-51; the benzene solvent is dimethylbenzene.
8. The method of claim 1, wherein the heating and mixing is: introducing a protective gas into an organic salt catalyst, epoxy resin and an organic acid monomer for premixing to obtain a premix; heating the premix to 50-55 ℃ to dissolve the organic acid monomer in the premix, and then mixing with the benzene solvent.
9. An acid-modified epoxy resin obtained by the production method according to any one of claims 1 to 8.
10. Use of the acid-modified epoxy resin of claim 9 in composites, adhesives, coatings, electrical insulation, molding materials or injection molding materials.
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CN202211638624.7A CN116041670A (en) | 2022-12-20 | 2022-12-20 | Acid modified epoxy resin and preparation method and application thereof |
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