CN113929874A - Epoxy resin composition and preparation method thereof - Google Patents
Epoxy resin composition and preparation method thereof Download PDFInfo
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- CN113929874A CN113929874A CN202111357247.5A CN202111357247A CN113929874A CN 113929874 A CN113929874 A CN 113929874A CN 202111357247 A CN202111357247 A CN 202111357247A CN 113929874 A CN113929874 A CN 113929874A
- Authority
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- China
- Prior art keywords
- epoxy resin
- epoxy
- resin composition
- curing agent
- aromatic amine
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 90
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- -1 polysiloxane Polymers 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 12
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 14
- CIJZQCDLMKUXNM-UHFFFAOYSA-N trimethyl-[methylsilyloxy(diphenyl)silyl]oxysilane Chemical compound C[SiH2]O[Si](O[Si](C)(C)C)(C1=CC=CC=C1)C1=CC=CC=C1 CIJZQCDLMKUXNM-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 7
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 7
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 7
- 150000004984 aromatic diamines Chemical class 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 claims description 5
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 239000012745 toughening agent Substances 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 4
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004382 potting Methods 0.000 claims description 3
- 239000003566 sealing material Substances 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000004985 diamines Chemical class 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 229920000090 poly(aryl ether) Polymers 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 125000003700 epoxy group Chemical group 0.000 description 9
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 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 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011208 reinforced composite material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LJWZTCGLNIQHNW-UHFFFAOYSA-N 1,3-bis(dibutylamino)propan-2-ol Chemical compound CCCCN(CCCC)CC(O)CN(CCCC)CCCC LJWZTCGLNIQHNW-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 description 1
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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
- C08G59/18—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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to an epoxy resin composition and a preparation method thereof. The invention provides a preparation method of an epoxy resin composition, which comprises the following steps: carrying out pre-reaction on epoxy-terminated polysiloxane and an aromatic amine curing agent to obtain a modified aromatic amine curing agent; and mixing epoxy resin with the modified aromatic amine curing agent to obtain the epoxy resin composition. The epoxy resin composition prepared by the invention has good high temperature resistance and high toughness, the tensile strength of the epoxy resin composition prepared by the invention is 91-98 MPa, the elongation at break is 5.2-6.7%, the impact strength is 34.2-43.6 MPa, and the initial thermal decomposition temperature is higher than 300 ℃.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an epoxy resin composition and a preparation method thereof.
Background
As an important high polymer material, the epoxy resin is a thermosetting resin with better comprehensive performance. The composite material has the advantages of good mechanical property, good adhesive property, good chemical stability, good electrical insulation property and easy forming and processing, and can be widely applied to the fields of aerospace, national defense and military industry, wind power blades, rail transit, light weight of automobiles, pressure vessels and sports leisure as a composite material matrix resin. However, epoxy resins also have some disadvantages, such as poor toughness and poor high temperature resistance of the cured product, and cannot satisfy long-term use at high temperature. These have all significantly restricted the use of epoxy resins in some fields.
The organosilicon is a compound which is synthesized artificially, the main chain skeleton is formed by alternately connecting silicon atoms and oxygen atoms, and other organic chain segments or functional groups are also connected to the silicon atoms. From the structure, the organic silicon is a compound with both inorganic and organic characteristics, has excellent flexibility, can reduce the internal stress of the cured epoxy resin, makes up for the insufficient toughness of the epoxy resin, and realizes the toughening of the epoxy resin. Meanwhile, the organic silicon has excellent high-temperature resistance.
According to the Chinese patent CN101475731A, polysiloxane is co-modified by polyether and silsesquioxane, and then the modified polysiloxane is mixed with epoxy resin and a curing agent to obtain an epoxy resin composite material, although the toughness of the epoxy resin is improved, the solubility parameters of the epoxy resin and the polysiloxane are greatly different, the direct addition of the polysiloxane into the epoxy resin can cause phase separation of the two components, and the cured network is not uniform, so that the heat resistance and the flexibility of the blend are not obviously improved.
Disclosure of Invention
In view of the above, the present invention is directed to an epoxy resin composition and a method for preparing the same. The epoxy resin composition prepared by the preparation method provided by the invention has high temperature resistance and high toughness.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of an epoxy resin composition, which comprises the following steps:
mixing an aromatic amine curing agent and epoxy-terminated polysiloxane, and carrying out pre-reaction to obtain a modified aromatic amine curing agent;
mixing epoxy resin and the modified aromatic amine curing agent to obtain the epoxy resin composition;
the temperature of the pre-reaction is 140-150 ℃, and the time is 1-3 h.
Preferably, the aromatic amine curing agent comprises an aromatic diamine.
Preferably, the aromatic diamine comprises one or more of m-phenylenediamine, p-phenylenediamine, benzidine, diaminodiphenylmethane, diaminodiphenylmethanesulphone, diaminodiphenyloxide, an aryletherdiamine and a polyaryletherdiamine.
Preferably, the epoxy-terminated polysiloxane comprises one or more of epoxy-terminated tetramethyldisiloxane, epoxy-terminated octamethyltetrasiloxane and epoxy-terminated tetramethyldiphenyltrisiloxane.
Preferably, the epoxy resin includes one or more of a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a bisphenol a type epoxy resin, and a novolac epoxy resin.
Preferably, the mass ratio of the aromatic amine curing agent to the epoxy-terminated polysiloxane is 100: (5-20).
Preferably, the mass ratio of the epoxy resin to the modified aromatic amine curing agent is 100: (20 to 50).
Preferably, when the epoxy resin composition is prepared, the preparation raw materials further comprise an epoxy diluent, a toughening agent and a coupling agent.
The invention also provides the epoxy resin composition prepared by the preparation method.
The invention also provides application of the epoxy resin composition in carbon fiber composite materials, glass fiber reinforced composite materials, adhesives, semiconductor sealing materials, potting materials, coating materials and coatings.
According to the invention, epoxy-terminated polysiloxane and an aromatic amine curing agent are pre-reacted according to a certain proportion, and in the pre-reaction, epoxy groups in the epoxy-terminated polysiloxane and amino groups of the aromatic amine curing agent are reacted to form a block copolymer, so that the epoxy-terminated siloxane modified aromatic amine curing agent is obtained. From the view of molecular structure, the modified aromatic amine curing agent obtained by pre-reaction has redundant amino and imino, and meanwhile, flexible silicon-oxygen bonds (Si-O-Si) are introduced into the molecules of the modified aromatic amine curing agent.
And mixing the modified aromatic amine curing agent with epoxy resin to obtain the epoxy resin composition. Compared with the organosilicon/aromatic amine curing agent obtained by physical blending, the modified aromatic amine curing agent prepared by the invention is more uniformly distributed in epoxy resin and has better compatibility with the epoxy resin and the aromatic amine. When the epoxy resin composition is cured, amino groups and imino groups in the modified aromatic amine curing agent react with epoxy groups to form chemical bonds, and siloxane groups in the modified aromatic amine curing agent are in network connection with epoxy resin crosslinking networks through the chemical bonds, so that the epoxy resin composition plays a role of network nodes to a certain extent, improves the high temperature resistance of a cured product, and improves the toughness of the cured product.
The examples of the invention show that: the epoxy resin composition prepared by the invention has the advantages of tensile strength of 91-98 MPa, elongation at break of 5.2-6.7%, impact strength of 34.2-43.6 MPa, initial thermal decomposition temperature higher than 300 ℃ and good thermal stability.
Detailed Description
The invention provides a preparation method of an epoxy resin composition, which comprises the following steps:
mixing an aromatic amine curing agent and epoxy-terminated polysiloxane, and carrying out pre-reaction to obtain a modified aromatic amine curing agent;
mixing epoxy resin and the modified aromatic amine curing agent to obtain the epoxy resin composition;
the temperature of the pre-reaction is 140-150 ℃, and the time is 1-3 h.
In the present invention, the raw materials are preferably those commercially available, unless otherwise specified.
In the present invention, the epoxy-terminated polysiloxane preferably includes one or more of epoxy-terminated tetramethyldisiloxane, epoxy-terminated octamethylcyclotetrasiloxane and epoxy-terminated tetramethyldiphenyltrisiloxane, and more preferably is epoxy-terminated tetramethyldisiloxane, epoxy-terminated octamethylcyclotetrasiloxane or epoxy-terminated tetramethyldiphenyltrisiloxane. In the invention, the end-epoxy-terminated tetramethyldisiloxane is formed by connecting epoxy groups at two ends of a tetramethyldisiloxane main chain; the epoxy-terminated octamethylcyclotetrasiloxane is formed by connecting epoxy groups at two ends of an octamethylcyclotetrasiloxane main chain; the epoxy-terminated tetramethyl diphenyl trisiloxane is formed by connecting epoxy groups at two ends of a main chain of tetramethyl diphenyl trisiloxane.
In the present invention, the epoxy-terminated polysiloxane preferably includes those commercially available or prepared by itself.
In the present invention, the method for preparing the epoxy-terminated polysiloxane preferably comprises the steps of:
performing cation ring-opening polymerization reaction on organopolysiloxane such as tetramethyldisiloxane, octamethylcyclotetrasiloxane, tetramethyldiphenyltrisiloxane and tetramethyldisiloxane under the action of concentrated sulfuric acid catalyst to obtain hydrogen-terminated polysiloxane;
and carrying out hydrosilylation reaction on the hydrogen-terminated polysiloxane and an epoxy group-containing alkene monomer under the action of a chloroplatinic acid catalyst to obtain the epoxy-terminated siloxane.
In the present invention, the organosiloxane preferably comprises tetramethyldisiloxane, octamethylcyclotetrasiloxane or tetramethyldiphenyltrisiloxane. In the present invention, the epoxy group-containing ethylenic monomer preferably includes allyl glycidyl ether. In the present invention, the temperature of the cationic ring-opening polymerization reaction is preferably 25 ℃ and the reaction time is 8 hours. In the invention, the temperature of the hydrosilylation reaction is preferably 70 ℃, and the reaction time is 12 h.
In the present invention, the aromatic amine curing agent preferably includes an aromatic diamine; the aromatic diamine preferably comprises one or more of m-phenylenediamine (MPD), p-phenylenediamine, benzidine, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), diaminodiphenoxy and an aryletherdiamine and a polyaryletherdiamine, and is further preferably m-phenylenediamine (MPD), p-phenylenediamine, benzidine, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), diaminodiphenoxy, an aryletherdiamine or a polyaryletherdiamine.
In the present invention, the mass ratio of the aromatic amine curing agent to the epoxy-terminated polysiloxane is preferably 100: (5-20).
In the present invention, the pre-reaction step preferably comprises:
under the condition of the temperature of 90-100 ℃, epoxy-terminated polysiloxane is added into an aromatic amine curing agent while stirring for reaction, then the temperature is raised to 140-150 ℃, and the pre-reaction is carried out for 1-3 h under the protection of nitrogen, so as to obtain the modified aromatic amine curing agent.
The apparatus for the pre-reaction is not particularly limited in the present invention, and a 500mL four-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser and a nitrogen introducing device is specifically used in the examples of the present invention.
After the modified aromatic amine curing agent is obtained, the epoxy resin and the modified aromatic amine curing agent are mixed to obtain the epoxy resin composition.
In the present invention, the epoxy resin preferably includes one or more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, and glycidyl amine type, bisphenol a type epoxy resin, and novolac epoxy resin. In the invention, the glycidyl ether type epoxy resin is preferably AFG-90; the glycidyl ester type epoxy resin is preferably TDE-85; the glycidyl amine type epoxy resin is preferably AG-80; the bisphenol A epoxy resin is preferably E-51 or E-44; the novolac epoxy resin is preferably F-51.
In the present invention, the mass ratio of the epoxy resin to the modified aromatic amine curing agent is preferably 100: (20 to 50).
The mixing mode of the epoxy resin and the modified aromatic amine curing agent is not particularly limited, and the epoxy resin and the modified aromatic amine curing agent can be uniformly mixed.
After the mixing, the present invention preferably further includes vacuum defoaming the mixed solution obtained by the mixing, and the vacuum defoaming is not particularly limited in the present invention, and may be performed by a vacuum defoaming operation well known to those skilled in the art.
In the present invention, when the epoxy resin composition is prepared, the preparation raw materials preferably further include an epoxy diluent, a toughening agent and a coupling agent.
In the present invention, the epoxy diluent, the toughening agent and the coupling agent are preferably added while the epoxy resin and the modified aromatic amine curing agent are mixed.
In the present invention, the epoxy diluent preferably includes one or more of phenyl glycidyl ether, o-tolyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, carbadodecyl glycidyl ether, carbatridecyl glycidyl ether, carbatetradecyl glycidyl ether, 1, 4-butanediol diglycidyl ether, and ethylene glycol diglycidyl ether.
In the invention, the toughening agent preferably comprises one or more of carboxyl-terminated nitrile rubber, hydroxyl-terminated nitrile rubber, amino-terminated polyurethane, polyether sulfone, polyether ether ketone, polycarbonate and polyetherimide;
in the present invention, the coupling agent preferably includes one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
The invention also provides the epoxy resin composition obtained by the preparation method in the technical scheme.
The invention also provides application of the epoxy resin composition in the technical scheme in carbon fiber composite materials, glass fiber reinforced composite materials, adhesives, semiconductor sealing materials, potting materials, coating materials and coatings.
In order to further illustrate the present invention, the following examples are given to illustrate the epoxy resin composition and the preparation method thereof, but they should not be construed as limiting the scope of the present invention.
Example 1
Carrying out hydrosilylation reaction on tetramethyl disiloxane and alkene monomer containing epoxy group under the action of chloroplatinic acid catalyst, wherein the reaction temperature is 70 ℃, and the reaction time is 12h to obtain the epoxy-terminated tetramethyl disiloxane
100g of diaminodiphenylmethane was charged into a 500mL four-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser and a nitrogen gas introducing device, heated in an oil bath, preheated to 90 ℃, and 5g of terminal-epoxy-tetramethyldisiloxane was added while stirring with opening a nitrogen gas valve. Then, the temperature is raised to 140 ℃, and the reaction is carried out for 2 hours under the protection of nitrogen, thus obtaining the modified aromatic amine curing agent.
100 parts by weight of AG-80 was mixed with 20 parts by weight of the prepared modified aromatic amine curing agent to obtain an epoxy resin composition.
Example 2
Carrying out cation ring-opening polymerization reaction on tetramethyldiphenyl trisiloxane and tetramethyldisiloxane under the action of a concentrated sulfuric acid catalyst at the reaction temperature of 25 ℃ for 8 hours to obtain hydrogen-terminated polytetramethylenedisiloxane;
and then carrying out hydrosilylation reaction on the hydrogen-terminated polytetramethylene disiloxane and an epoxy group-containing alkene monomer under the action of a chloroplatinic acid catalyst, wherein the reaction temperature is 70 ℃, and the reaction time is 12 hours, so as to obtain the epoxy-terminated tetramethyldiphenyl trisiloxane.
100g of m-phenylenediamine was charged into a 500mL four-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser and a nitrogen introducing device, heated in an oil bath, preheated to 90 ℃ and opened with a nitrogen valve, and 15g of terminal-epoxy-tetramethyldiphenyltrisiloxane was added with stirring. Then, the temperature is raised to 140 ℃, and the reaction is carried out for 1h under the protection of nitrogen, thus obtaining the modified aromatic amine curing agent.
100 parts by weight of E-51 epoxy resin was mixed with 30 parts by weight of the prepared modified aromatic amine curing agent to obtain an epoxy resin composition.
Example 3
The preparation of terminal-epoxy tetramethyldiphenyltrisiloxane is as in example 2.
Adding 100g of Diamino Diphenyl Sulfone (DDS) into a 500mL four-neck flask provided with a thermometer, a mechanical stirrer, a reflux condenser and a nitrogen introducing device, heating by an oil bath, preheating the DDS to 100 ℃, opening a nitrogen valve, adding 10g of epoxy-terminated tetramethyl diphenyl trisiloxane while stirring, subsequently heating to 140 ℃, and reacting for 2 hours under the protection of nitrogen to obtain the modified aromatic amine curing agent.
100 parts by weight of AFG-90 was mixed with the obtained 20 parts by weight of the modified aromatic amine curing agent to obtain an epoxy resin composition.
Example 4
The preparation of the terminal-epoxy tetramethyldisiloxane is as in example 1.
Adding 100g of benzidine into a 500mL four-neck flask provided with a thermometer, a mechanical stirrer, a reflux condenser and a nitrogen introducing device, heating by an oil bath, preheating to 90 ℃, opening a nitrogen valve, adding 15g of epoxy-terminated tetramethyldisiloxane while stirring, heating to 150 ℃, and reacting for 1h under the protection of nitrogen to obtain the modified aromatic amine curing agent.
100 parts by weight of E-44 was mixed with 40 parts by weight of the modified aromatic amine curing agent thus prepared to obtain an epoxy resin composition.
Example 5
The preparation of the terminal-epoxy octamethyltetrasiloxane differs from example 2 only in that tetramethyldiphenyl trisiloxane is replaced by octamethyltetrasiloxane).
100g of diaminodiphenyl ether bisphenol A (BDAP) is added into a 500mL four-neck flask provided with a thermometer, a mechanical stirrer, a reflux condenser and a nitrogen introducing device, the flask is heated by an oil bath, the temperature is preheated to 100 ℃, a nitrogen valve is opened, 15g of epoxy-terminated octamethyltetrasiloxane is added while stirring, then the temperature is raised to 140 ℃, and the reaction is carried out for 3 hours under the protection of nitrogen, thus obtaining the modified aromatic amine curing agent.
100 parts by weight of F-51 and 50 parts by weight of the modified aromatic amine curing agent thus prepared were mixed to obtain an epoxy resin composition.
Comparative example 1
100 parts by weight of E-51 bisphenol A epoxy resin was mixed with 30 parts by weight of diaminodiphenylmethane to obtain an epoxy resin composition.
Comparative example 2
Uniformly mixing 100 parts by weight of E-51 bisphenol A epoxy resin, 30 parts by weight of diaminodiphenylmethane and 20 parts by weight of liquid nitrile rubber to obtain the epoxy resin composition.
Comparative example 3
100 parts by weight of E-51, 30 parts by weight of DDM and 20 parts by weight of aminopropylmethylsiloxane were mixed to obtain an epoxy resin composition.
After vacuum defoaming is carried out on the epoxy resin compositions obtained in the examples 1-6 and the comparative examples 1-3, curing is carried out, and performance test is carried out on the obtained cured product; the curing process comprises the following steps: curing at 100 deg.C for 2h, heating to 140 deg.C for 2h, and continuing heating to 180 deg.C for 2 h.
The mechanical properties are tested according to the GB/T2567-2008 standard, the thermal stability, namely the initial decomposition temperature, is tested by a thermogravimetric analysis method, and the test conditions are as follows: n is a radical of2In the atmosphere, the temperature rise rate is 10 ℃/min, the test is carried out by taking the 1% weight loss temperature as the initial decomposition temperature, and the test results are shown in table 1.
TABLE 1 Performance test results of epoxy resin compositions
From the test results of table 1, it can be seen that: the tensile strength of the epoxy resin composition is 91-98 MPa, and the elongation at break is 5.2-6.7%, so that the epoxy resin composition prepared by the invention has high elongation at break, good mechanical strength and excellent mechanical properties. Meanwhile, the initial thermal decomposition temperature of the epoxy resin composition prepared by the invention is higher than 300 ℃, and the epoxy resin composition has good thermal stability. Therefore, the epoxy resin composition prepared by the invention can meet the use requirements of products with high elongation, high temperature resistance and high fatigue resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of an epoxy resin composition comprises the following steps:
mixing an aromatic amine curing agent and epoxy-terminated polysiloxane, and carrying out pre-reaction to obtain a modified aromatic amine curing agent;
mixing epoxy resin and the modified aromatic amine curing agent to obtain the epoxy resin composition;
the temperature of the pre-reaction is 140-150 ℃, and the time is 1-3 h.
2. The method of claim 1, wherein the aromatic amine curing agent comprises an aromatic diamine.
3. The method of claim 2, wherein the aromatic diamine comprises one or more of m-phenylenediamine, p-phenylenediamine, benzidine, diaminodiphenylmethane, diaminodiphenylmethanesulphone, diaminodiphenoxy, an aromatic ether diamine, and a polyarylether diamine.
4. The method of claim 1, wherein the epoxy-terminated polysiloxane comprises one or more of epoxy-terminated tetramethyldisiloxane, epoxy-terminated octamethyltetrasiloxane and epoxy-terminated tetramethyldiphenyltrisiloxane.
5. The method according to claim 1, wherein the epoxy resin comprises one or more of a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a bisphenol a type epoxy resin, and a novolac epoxy resin.
6. The production method according to any one of claims 1 to 4, wherein the mass ratio of the aromatic amine curing agent to the epoxy-terminated polysiloxane is 100: (5-20).
7. The preparation method according to claim 1, wherein the mass ratio of the epoxy resin to the modified aromatic amine curing agent is 100: (20 to 50).
8. The method according to claim 1, wherein the epoxy resin composition is prepared from raw materials further comprising an epoxy diluent, a toughening agent and a coupling agent.
9. An epoxy resin composition produced by the production method according to any one of claims 1 to 8.
10. Use of the epoxy resin composition according to claim 9 in carbon fiber composites, glass fiber reinforced composites, adhesives, semiconductor sealing materials, potting materials, coating materials and paints.
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