CN115232274B - Benzoxazine oligomer toughening agent based on long fatty chain phenol and preparation method and application thereof - Google Patents
Benzoxazine oligomer toughening agent based on long fatty chain phenol and preparation method and application thereof Download PDFInfo
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000012745 toughening agent Substances 0.000 title claims abstract description 96
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000002028 Biomass Substances 0.000 claims abstract description 117
- 239000003822 epoxy resin Substances 0.000 claims abstract description 73
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 73
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 17
- -1 amine compounds Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 150000002989 phenols Chemical class 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 52
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 8
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 claims description 6
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 claims description 6
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 claims description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 5
- 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 5
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 5
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- KVVSCMOUFCNCGX-UHFFFAOYSA-N cardol Chemical compound CCCCCCCCCCCCCCCC1=CC(O)=CC(O)=C1 KVVSCMOUFCNCGX-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- UFMJCOLGRWKUKO-UHFFFAOYSA-N cardol diene Natural products CCCC=CCC=CCCCCCCCC1=CC(O)=CC(O)=C1 UFMJCOLGRWKUKO-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000006683 Mannich reaction Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000007142 ring opening reaction Methods 0.000 description 7
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003177 cardiotonic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- RVRHBLSINNOLPI-UHFFFAOYSA-N Lythridin Natural products COc1ccc(cc1OC)C2CC(CC3CCCCN23)OC(=O)CC(O)c4ccc(O)cc4 RVRHBLSINNOLPI-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- LTNZEXKYNRNOGT-UHFFFAOYSA-N dequalinium chloride Chemical compound [Cl-].[Cl-].C1=CC=C2[N+](CCCCCCCCCC[N+]3=C4C=CC=CC4=C(N)C=C3C)=C(C)C=C(N)C2=C1 LTNZEXKYNRNOGT-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229930003811 natural phenol Natural products 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to a benzoxazine oligomer toughening agent based on long-fatty-chain phenol, and a preparation method and application thereof. Biomass phenolic compounds containing long fatty side chains and biomass amine compounds containing long fatty chains are used as raw materials, a Mannich reaction is adopted to synthesize single-ring biomass benzoxazine containing long fatty side chains, a ring-opening polymerization is carried out to generate an oligomer, and the oligomer is used as a biomass toughening agent of epoxy resin. Blending the biomass toughening agent with epoxy resin according to a certain proportion, and heating and curing to obtain an epoxy-benzoxazine resin cured product. The biomass toughening agent is in a liquid state, and is very favorable for blending with epoxy resin. The toughness of the epoxy resin is increased by the long-fat side chain, the maximum elongation at break of the cured product reaches 14.3%, and the elongation at break is improved by 52% compared with that of the cured product without the toughening agent; the maximum impact strength reaches 55.3KJ/m 2 Compared with the non-toughening agent, the biological toughening agent is improved by 170%, so that the biological toughening agent has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of toughening agents, and particularly relates to a benzoxazine oligomer toughening agent taking cardanol as a phenol source, and a preparation method and application thereof.
Background
The epoxy resin is a thermosetting resin containing active epoxy groups, and has wide application in the fields of electronic equipment, aerospace, insulating materials, high-performance composite materials and the like because of excellent mechanical properties, heat resistance, excellent electrical insulation properties and the like. However, unmodified epoxy resins are brittle after curing, limiting their application and therefore require toughening modification in most applications.
At present, researchers at home and abroad conduct a great deal of research in the direction of improving the toughness of the epoxy resin. For example: oligomers, rubber elastomers, thermotropic liquid crystalline polymers, rigid nanoparticles, and the like are added to improve the toughness of the epoxy resin. However, rubber elastomer modification, while greatly improving the toughness of the material, often compromises the stiffness (e.g., modulus of elasticity and strength) and heat resistance of the material. The thermal liquid crystal polymer toughened epoxy resin has basically unchanged modulus, heat resistance and other performances, but has difficult raw material sources and synthesis, high cost and high melting point, and is easy to cause processing difficulty. The rigid nanoparticle modification method often encounters the problem that agglomeration easily occurs during the dispersion process, and good dispersion in epoxy resin is not easily achieved. The oligomer toughening agent can maintain good dispersibility and compatibility in an epoxy system while improving the toughness of the epoxy resin, and has simple processing technology, thereby attracting wide attention of people.
Today, with exhaustion of petroleum resources and aggravation of environmental pollution, development of biomass raw materials to replace petroleum-based raw materials is urgent. The benzoxazine resin has good compatibility with epoxy resin, can be blended with the epoxy resin, and a plurality of researchers have dedicated to synthesis and application of biomass benzoxazine toughening agent, for example, CN201210549497.3 discloses a cardanol-aromatic diamine type benzoxazine which is blended with the epoxy resin for curing, and has the impact strength of 43KJ/m 2 The toughness of a certain epoxy resin system is improved; sun Haoran A cardanol-aniline benzoxazine is synthesized, and after the cardanol-aniline benzoxazine is blended with the traditional diamine benzoxazine for curing, the elongation at break of a cured product is increased from 2.98% to 3.38%, so that the toughening effect is achieved to a certain extent. The disclosed benzoxazine toughening agents are all in their monomeric form to toughen the blend system. However, research on using benzoxazine oligomer as a toughening agent and toughening epoxy resin has not been reported yet. The monocyclic benzoxazine is subjected to thermal ring-opening polymerization to prepare a linear oligomer, so as to form a molecular chain framework. If long-chain phenol is used as a phenol source to synthesize the benzoxazine oligomer, the long-chain phenol is equivalent to a long-chain fat contained in the phenol source to be linked to a main chain of the benzoxazine, and the long-chain phenol can be used as a molecular structural unit with a toughening effect. For this purpose, the present invention is proposed.
Disclosure of Invention
The invention aims to provide a biomass toughening agent, in particular to a benzoxazine oligomer biomass toughening agent taking long-fatty-chain phenol as a phenol source and a preparation method thereof, which not only improve the toughness of an epoxy resin cured product, but also solve the problems that a common epoxy resin toughening agent needs solvent assistance with an epoxy resin system and has poor compatibility.
The invention adopts long fatty chain biomass amine as raw material to synthesize single ring benzoxazine monomer, and generates benzoxazine oligomer with side group containing long fatty chain and thermoplasticity through simple heating ring-opening polymerization. When the benzoxazine oligomer is used as an epoxy resin toughening agent, a large amount of phenolic hydroxyl groups generated after ring opening polymerization can participate in the epoxy resin curing reaction, so that the compatibility of the benzoxazine oligomer and the epoxy resin is enhanced. In order to further improve the toughness of the epoxy resin, the invention selects the biomass phenol containing long fat side chains, and can form larger free volume, thereby further improving the toughness of an epoxy resin curing system.
In order to solve the problem caused by the exhaustion of petroleum resources, the invention adopts biomass raw materials to synthesize the full biomass benzoxazine oligomer, and further uses the full biomass benzoxazine oligomer as an epoxy resin biomass toughening agent.
In order to solve the problem of compatibility of the benzoxazine and the epoxy resin, the invention adopts the natural phenol containing long fatty side chains as a biomass phenol source of the benzoxazine, and the prepared benzoxazine monomer and the prepared benzoxazine oligomer are all in liquid state, so that the compatibility of the benzoxazine and the epoxy resin is increased.
In order to solve the problem of high brittleness of the cured epoxy resin, the invention designs and synthesizes the benzoxazine oligomer toughening agent containing long fatty side chains. The method comprises the steps of selecting biomass amine with a long-fatty chain structure as a biomass amine source of benzoxazine, and selecting biomass phenol with a long-fatty side chain as a biomass phenol source of a benzoxazine oligomer toughening agent.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the biomass toughening agent for the epoxy resin curing system has a structure shown in a formula I II or a formula IV:
wherein,,
R 1 ＝-(CH 2 ) 11 -CH 3 ，-(CH 2 ) 13 -CH 3 ,-(CH 2 ) 17 -CH 3 or- (CH) 2 ) 8 -CH＝CH-(CH 2 ) 7 -CH 3 ；
R 2 = -H, -OH or-CH 3 ；
R 3 ＝-C 15 H 31-2n ；
n＝2-100。
According to the invention, the preparation method of the biomass toughening agent comprises the following steps:
synthesizing a biomass benzoxazine monomer containing a long-fatty side chain by taking a biomass amine compound containing a long-fatty chain structure, a biomass phenol compound containing a long-fatty side chain and formaldehyde as raw materials, namely a biomass toughening agent of a formula III;
further, the biomass benzoxazine monomer containing the long-fat side chain is subjected to heating ring-opening polymerization to obtain the biomass benzoxazine oligomer containing the long-fat side chain, namely the biomass toughening agent with the structure shown in the formula IV.
According to the invention, it is preferred that the temperature for synthesizing the biomass benzoxazine monomer containing long aliphatic side chains is 80-120 ℃ and the reaction time is 5-12 hours.
According to the invention, the temperature of the ring-opening polymerization of the biomass benzoxazine monomer containing long fatty side chains is preferably 100-220 ℃, and the ring-opening polymerization time is 8-24 hours.
According to the invention, preferably, the preparation method of the biomass toughening agent comprises the following steps:
(1) Mixing a biomass amine compound containing a long fatty chain structure, a biomass phenol compound containing a long fatty side chain and formaldehyde, reacting for 5-12 hours at the temperature of 80-120 ℃, washing with a sodium hydroxide aqueous solution after the reaction, washing with water to be neutral, and drying in vacuum to obtain a biomass benzoxazine monomer containing a long fatty side chain, namely a biomass toughening agent with a structure of formula III;
(2) Adding 5-20% of p-tert-butylphenol into the biomass benzoxazine monomer containing the long-fat side chain, uniformly mixing, and heating for ring-opening polymerization to obtain the biomass benzoxazine oligomer containing the long-fat side chain, namely the biomass toughening agent with the structure shown in the formula IV.
According to the invention, preferably, the molar ratio of the biomass phenolic compound containing long fatty side chains, the biomass amine compound containing long fatty chain structures and formaldehyde is 1:1: (2-2.8).
According to the invention, preferably, the biomass phenolic compound containing long fat side chains is any one of urushiol, cardol and cardanol.
According to the present invention, the biomass amine having a long fatty chain structure is preferably any one of dodecylamine, octadecylamine, and oleylamine.
According to the invention, a preparation method of the benzoxazine oligomer biomass toughening agent containing long fatty side chains comprises the following steps of:
reacting a biomass amine compound containing a long fatty chain structure, a biomass phenol compound containing a long fatty side chain with formaldehyde at a reaction temperature of 80-120 ℃ for 5-12 hours, washing the obtained product with methanol for multiple times, filtering and vacuum drying to obtain a benzoxazine monomer, namely the biomass toughening agent with the structure shown in formula III;
adding initiator p-tert-butylphenol into benzoxazine monomer, mixing them uniformly, ring-opening curing for 8-24 hr in oven whose polymerization temperature is 100-220 deg.C so as to obtain the benzoxazine oligomer, namely the invented biomass toughening agent with formula IV.
The invention also provides application of the structural compound shown in the formula I II or the formula IV as a toughening agent of an epoxy resin curing system.
The invention also provides an epoxy-benzoxazine resin condensate, which comprises the following raw materials in parts by mass:
97.5-90 parts of epoxy resin and 2.5-10 parts of biomass toughening agent of structural compound shown in formula I II or formula IV.
According to the invention, the epoxy resin toughening curing system further comprises a curing agent, wherein the adding amount of the curing agent is 20-30% of the total mass of the epoxy resin and the biomass toughening agent.
According to the present invention, the above-mentioned method for preparing an epoxy-benzoxazine resin cured product comprises the steps of:
and (3) blending the biomass toughening agent and epoxy resin according to the mass ratio, adding a curing agent to obtain an epoxy resin blend, and respectively curing the epoxy resin blend at 100 ℃, 150 ℃ and 200 ℃ for 2 hours to obtain an epoxy-benzoxazine resin cured product.
The benzoxazine biomass toughening agent containing long fatty side chains prepared by the invention has the following synthetic reaction equation:
the beneficial effects of the invention are as follows:
1. the biomass amine source containing the long-fatty chain structure and the biomass phenol source containing the long-fatty side chain are used as raw materials, and the benzoxazine monomer containing the long-fatty side chain and the benzoxazine oligomer biomass toughening agent containing the long-fatty side chain are designed and synthesized, so that the raw materials are low in price and easy to obtain, the cost is reduced, and the requirements of green sustainable development materials are met.
2. The benzoxazine oligomer biomass toughening agent containing long fatty side chains has a large amount of active phenolic hydroxyl groups, and the state of the benzoxazine oligomer biomass toughening agent is liquid, and the phenolic hydroxyl groups contained in the benzoxazine oligomer toughening agent can react with epoxy groups to increase the compatibility of the benzoxazine oligomer biomass toughening agent and an epoxy resin blend. Meanwhile, the epoxy resin can be directly mixed with epoxy resin without solvent, thereby reducing environmental pollution. .
3. The long-fatty chain structure and the long-fatty side chain structure of the benzoxazine oligomer biomass toughening agent containing the long-fatty side chain can increase the toughness of the epoxy resin. The benzoxazine biomass toughening agent containing long fatty side chains can be obviously improvedHigh toughness of epoxy resin, wherein the maximum elongation at break of the epoxy-benzoxazine monomer resin curing system and the epoxy-benzoxazine oligomer resin curing system are respectively 13.6% and 14.3%, respectively, which are improved by 45% and 52% compared with the non-toughened epoxy resin curing system (9.4%), respectively, and the maximum impact strength is 46.9KJ/m respectively 2 And 55.3KJ/m 2 Compared with the non-toughened epoxy resin curing system (20.5 KJ/m 2 ) The improvement is 129% and 170%, respectively. The maximum elongation at break of the commercial epoxy resin toughening agent carboxyl terminated nitrile rubber (CTBN) toughened epoxy resin is about 10 percent, and the maximum impact strength is 25KJ/m 2 Left and right.
4. T with best toughening effect of benzoxazine biomass toughening agent g All at 140 deg.c or above. T when traditional commercial epoxy resin toughening agent carboxyl terminated nitrile rubber has best toughening effect g At about 100 ℃. Therefore, the benzoxazine biomass toughening agent containing long fatty side chains has less thermal property loss than a commercial toughening agent.
5. The content of the toughening agent is 7.5% when the benzoxazine oligomer biomass toughening agent containing long fatty side chains has the best effect of toughening the epoxy resin, and the content of the toughening agent is below 10%. The CTBN content of the traditional commercial toughening agent (CTBN) when the toughening effect of the epoxy resin is best is more than 15%, so that the toughening effect of the commercial toughening agent can be achieved by adopting a small load.
Drawings
FIG. 1 is an infrared spectrum of a benzoxazine monomer in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of benzoxazine monomer in example 1;
FIG. 3 is an infrared spectrum of the benzoxazine oligomer of example 1;
FIG. 4 is a nuclear magnetic resonance spectrum of the benzoxazine oligomer of example 1;
FIG. 5 is a graph comparing elongation at break after toughening the epoxy resin with different amounts of benzoxazine monomers and oligomers in test example 1;
FIG. 6 is a graph comparing tensile strength of epoxy resins toughened with benzoxazine monomers and oligomers at different levels in test example 1;
FIG. 7 is a graph comparing impact strength after toughening epoxy resins with different amounts of benzoxazine monomers and oligomers in test example 1;
FIG. 8 is a graph of DMA (dynamic thermal mechanical analysis) comparisons after toughening epoxy resins with different amounts of benzoxazine monomers in test example 1;
fig. 9 is a graph comparing DMA (dynamic thermo-mechanical analysis) after toughening epoxy with different content of benzoxazine oligomer in test example 1.
Detailed Description
In the following, the technical solutions of the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the embodiments are only representative embodiments of some but not all embodiments of the present invention, and all other embodiments obtained by those skilled in the art without making any creative effort are within the protection scope of the present invention. In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1: benzoxazine monomer synthesized based on oleylamine and cardanol and preparation method of oligomer thereof
(1) The method comprises the steps of reacting oleylamine, cardanol and formaldehyde according to a molar ratio of 1:1:2, reacting for 10 hours at a reaction temperature of 80 ℃ by using triethylamine as a catalyst, washing the obtained product with methanol aqueous solution for multiple times, and then drying in vacuum to obtain the oleylamine type benzoxazine monomer biomass toughening agent containing long fat side chains, wherein the yield is 85%.
(2) Weighing a certain amount of the benzoxazine monomer synthesized in the step (1), adding an initiator p-tert-butylphenol with the mass percent of the biomass benzoxazine monomer of 8%, uniformly mixing, and carrying out ring opening and curing in an oven with the polymerization temperature of 160 ℃ for 12 hours to obtain the benzoxazine oligomer biomass toughening agent containing long fat side chains.
Referring to fig. 1 and fig. 2, the infrared and nuclear magnetic spectra of the oleamide benzoxazine monomer biomass toughening agent containing long fatty side chains prepared in the embodiment are shown. Benzoxazine monomer at 1240cm -1 (C-O-C, asymmetry)Stretching) 1069cm -1 (C-O-C, symmetrical stretching) and 964cm -1 Characteristic peaks at (oxazine ring backbone vibration and C-H face bending outwards) indicate oxazine ring formation. Except C-H aliphatic (2926 and 2854cm -1 ) And aliphatic double bond (3007 cm) -1 ) Other characteristic peaks besides the stretching vibration of (2) include CH2 (1372 cm -1 ) And C-N-C (1118 cm) -1 ) Is not symmetrical to the vibration of the expansion and contraction. At 4.85ppm (s, O-CH) 2 -N) and 3.96ppm (s, N-CH) 2 -Ar), confirming the formation of oxazine rings.
1 H NMR(400MHz,CDCl 3 ,ppm)：5.81-5.90ppm(1H,m,-HC＝),5.36-5.45ppm(2H,m,-HC＝CH-),5.01-5.21ppm(2H,m,＝CH 2 ),4.85ppm(2H,s,O-CH 2 -N),3.96ppm(2H,s,N-CH 2- Ar),2.53ppm(2H,t,-CH 2 N-),1.57ppm(2H,m,-CH 2 CH 3 ),1.41-1.28ppm(30H,m,-CH 2 -),0.90ppm(3H,t,-CH 3 ) The map is shown in fig. 2.
Referring to fig. 3 and fig. 4, the infrared and nuclear magnetic spectra of the benzoxazine oligomer biomass toughening agent containing long fatty side chains prepared in the embodiment are shown. Benzoxazine monomer is 964cm -1 The infrared characteristic peak of oxazine ring disappears and the infrared characteristic peak is in 3306cm -1 Hydroxyl characteristic peaks appear in the region. Oxazine ring at 4.85ppm (O-CH) 2 -N) and 3.96ppm (N-CH) 2 -Ar) the signal peak at 3.79ppm was lost, a new signal peak was present, ascribed to N-CH after oxazine ring opening 2 Ar signal peak.
1 H NMR(400MHz,CDCl 3 ,ppm)：6.70-6.85ppm(3H,ArH),3.79ppm(2H,N-CH 2 -Ar),2.53ppm(2H,-CH 2 N-),1.57ppm(2H,CH 2 CH 3 ),1.41-1.28ppm(30H,-CH 2 -),0.90ppm(3H,-CH 3 ) The map is shown in fig. 4.
EXAMPLE 2 preparation of benzoxazine monomer and its oligomer based on Synthesis of dodecyl amine and cardiotonic phenol
(1) And (3) reacting the dodecyl amine, the heart-strengthening phenol and the formaldehyde according to the molar ratio of 1:1:2.2, using triethylamine as a catalyst, reacting for 6 hours at the reaction temperature of 85 ℃, washing the obtained product with a sodium hydroxide aqueous solution, washing with water to be neutral, separating liquid, and drying in vacuum to obtain the dodecylamine type benzoxazine monomer biomass flexibilizer containing long fat side chains, wherein the yield is 78%.
(2) Weighing a certain amount of the benzoxazine monomer synthesized in the step (1), adding an initiator p-tert-butylphenol with the mass percent of 13% into the benzoxazine monomer, uniformly mixing, and carrying out ring-opening curing for 24 hours in an oven with the polymerization temperature of 100 ℃ to obtain the furanmethylamine type benzoxazine oligomer biomass toughening agent containing long fatty side chains.
EXAMPLE 3 preparation of benzoxazine monomer and oligomer thereof based on Synthesis of Shidiamine and urushiol
(1) And (3) reacting the dodecyl amine, the urushiol and the formaldehyde according to the molar ratio of 1:1:2.5, using triethylamine as a catalyst, reacting for 5 hours at the reaction temperature of 110 ℃, washing the obtained product with sodium bicarbonate aqueous solution, washing with water to be neutral, separating liquid, and drying in vacuum to obtain the dodecylamine benzoxazine monomer biomass flexibilizer containing long fat side chains, wherein the yield is 82%.
(2) Weighing a certain amount of the benzoxazine monomer synthesized in the step (1), adding an initiator p-tert-butylphenol with the mass percent of 5% into the benzoxazine monomer, uniformly mixing, and carrying out ring opening curing for 10 hours in an oven with the polymerization temperature of 150 ℃ to obtain the dodecylamine type benzoxazine oligomer biomass toughening agent containing long fatty side chains.
Example 4 preparation of benzoxazine monomer and its oligomer based on Synthesis of Temantamine and cardiotonic phenol
(1) And (3) reacting the decamine, the heart-strengthening phenol and formaldehyde according to the molar ratio of 1:1:2.8, using triethylamine as a catalyst, reacting for 8 hours at the reaction temperature of 120 ℃, washing the obtained product with sodium carbonate aqueous solution, washing with water to be neutral, separating liquid, and drying in vacuum to obtain the tetradecylamine type benzoxazine monomer biomass toughening agent containing long fat side chains, wherein the yield is 86%.
(2) Weighing a certain amount of benzoxazine monomer synthesized in the step (1), adding initiator p-tert-butylphenol with the mass percent of 20% into the benzoxazine monomer, uniformly mixing, and carrying out ring-opening curing for 8 hours in an oven with the polymerization temperature of 180 ℃ to obtain the tetradecylamine type benzoxazine oligomer biomass toughening agent containing long fatty side chains.
Example 5 preparation of benzoxazine monomer and oligomer thereof based on octadecylamine and urushiol Synthesis
(1) Reacting octadecylamine, urushiol and formaldehyde according to the molar ratio of 1:1:2.3, using triethylamine as a catalyst, reacting for 6 hours at the reaction temperature of 85 ℃, washing the obtained product with water for three times, separating liquid, and drying in vacuum to obtain the octadecylamine type benzoxazine monomer biomass toughening agent containing long fat side chains, wherein the yield is 75%.
(2) Weighing a certain amount of benzoxazine monomer synthesized in the step (1), adding initiator p-tert-butylphenol with the mass percent of the monomer being 10%, uniformly mixing, and carrying out ring opening curing for 12 hours in an oven with the polymerization temperature being 160 ℃ to obtain the octadecylamine type benzoxazine oligomer biomass toughening agent containing long fatty side chains.
Comparative example 1 epoxy resin cured product without toughening agent
Adding metered curing agent into epoxy resin, heating, stirring, mixing uniformly, placing into an oven, and respectively curing at 100 ℃, 150 ℃ and 200 ℃ for 2 hours to obtain an epoxy resin curing system. And performing performance test on the system.
Test example 1
The biomass toughening agent prepared in the example 1 and the epoxy resin are mixed according to the mass ratio of (2.5-10): (97.5-90) blending, adding a curing agent to obtain an epoxy resin blend, and respectively curing the epoxy resin blend at 100 ℃, 150 ℃, 200 ℃ and 250 ℃ for 2 hours to obtain an epoxy-benzoxazine resin cured product, which is marked as a sample 1-8, wherein the sample 1-4 adopts the benzoxazine monomer biomass toughening agent containing long aliphatic side chains in the embodiment 1, and the sample 5-8 adopts the benzoxazine oligomer biomass toughening agent containing long aliphatic side chains in the embodiment 1.
The performance index of the epoxy resin curing systems of samples 1-8 and comparative example 1 are tested as shown in Table 1.
TABLE 1 Performance parameters of different epoxy resin curing systems
As can be seen from table 1:
(1) The epoxy-benzoxazine resin cured products (samples 1-8) after the addition of the biomass toughening agent had increased elongation at break, increased impact strength, reduced tensile strength, and reduced glass transition temperature compared to the epoxy resin cured system without the toughening agent (comparative example 1).
(2) With the increase of the content of the single-ring benzoxazine biomass toughening agent (the content of the toughening agent used in samples 1-4 is 2.5%, 5%, 7.5% and 10%) respectively, the elongation at break of the epoxy-benzoxazine resin cured product is increased and then reduced, the impact strength is increased and then reduced, the tensile strength is gradually reduced, and the glass transition temperature is increased and then reduced. Wherein the elongation at break and impact strength at 7.5% of the toughening agent content (sample 3) are maximum at 13.6% and 46.9KJ/m, respectively 2 The epoxy resin is improved by 45 percent and 129 percent compared with pure epoxy resin.
(3) With the increase of the content of the benzoxazine oligomer biomass toughening agent (the content of the toughening agent used in samples 5-8 is 2.5%, 5%, 7.5% and 10% respectively), the elongation at break of the epoxy-benzoxazine resin cured product is increased, the impact strength is increased firstly and then reduced, the tensile strength is reduced, and the glass transition temperature is reduced. Wherein the elongation at break and impact strength at 5% of the toughening agent content (sample 6) are maximum at 14.3% and 55.3KJ/m, respectively 2 The epoxy resin is improved by 52 percent and 170 percent respectively compared with pure epoxy resin.
(4) Compared with the toughening effect of the epoxy resin by using the biomass toughening agent with the same content of the benzoxazine monomer and the oligomer, the breaking elongation, the impact strength and the glass transition temperature of the epoxy-benzoxazine oligomer resin curing system are higher than those of the epoxy-benzoxazine monomer resin curing system, and the tensile strength is lower than that of the epoxy-benzoxazine monomer resin curing system. Description: the benzoxazine oligomer biomass toughening agent has a toughening effect stronger than that of a benzoxazine monomer biomass toughening agent, and has small thermal property loss.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. The biomass toughening agent for the epoxy resin curing system is characterized by having a structure shown in a formula IV:
wherein,,
R 1 ＝-(CH 2 ) 11 -CH 3 ，-(CH 2 ) 13 -CH 3 ,-(CH 2 ) 17 -CH 3 or- (CH) 2 ) 8 -CH＝CH-(CH 2 ) 7 -CH 3 ；
R 2 = -H, -OH or-CH 3 ；
R 3 ＝-C 15 H 31-2n ；
n＝2-100。
2. A method of preparing the biomass toughening agent of claim 1, comprising the steps of:
synthesizing a biomass benzoxazine monomer containing a long fatty side chain by taking a biomass amine compound containing a long fatty chain structure, a biomass phenol compound containing a flexible side chain and formaldehyde as raw materials;
and (3) carrying out heating ring-opening polymerization on the biomass benzoxazine monomer containing the long-fat side chain to obtain a biomass benzoxazine oligomer containing the long-fat side chain, namely the biomass toughening agent with the structure shown in the formula IV.
3. The method for preparing the biomass toughening agent according to claim 2, wherein the temperature for synthesizing the biomass benzoxazine monomer containing the long-fat side chain is 80-120 ℃ and the reaction time is 5-12 hours.
4. The method for preparing a biomass toughening agent according to claim 2, wherein the temperature of the ring-opening polymerization of the biomass benzoxazine monomer containing the long-fat side chain is 100-220 ℃, and the ring-opening polymerization time is 8-24 hours.
5. The method for preparing the biomass toughening agent according to claim 2, wherein the method for preparing the biomass toughening agent comprises the following steps:
(1) Mixing a biomass amine compound containing a long fatty chain structure, a biomass phenol compound containing a long fatty side chain and formaldehyde, reacting for 5-12 hours at the temperature of 80-120 ℃, washing with a sodium hydroxide aqueous solution after the reaction, washing with water to be neutral, and drying in vacuum to obtain a biomass benzoxazine monomer containing a long fatty side chain;
(2) Adding 5-20% of p-tert-butylphenol into the biomass benzoxazine monomer containing the long-fat side chain, uniformly mixing, and heating for ring-opening polymerization to obtain the biomass benzoxazine oligomer containing the long-fat side chain, namely the biomass toughening agent with the structure shown in the formula IV.
6. The method for preparing the biomass toughening agent according to claim 2 or 3, wherein the molar ratio of the biomass phenolic compound containing the flexible side chain, the biomass amine compound containing the long-fatty-chain structure and formaldehyde is 1:1: (2-2.8).
7. The method for preparing a biomass toughening agent according to claim 2 or 3, wherein the biomass phenolic compound containing a flexible side chain is any one of cardol, urushiol and cardanol.
8. The method for preparing the biomass toughening agent according to claim 2, wherein the biomass amine containing the long-fatty chain structure is any one of dodecylamine, octadecylamine and oleylamine.
9. Use of a structural compound of formula IV according to claim 1 as a toughening agent for epoxy curing systems.
10. An epoxy-benzoxazine resin condensate, which comprises a structural compound shown in a formula IV in claim 1, and comprises the following raw materials in parts by mass:
97.5-90 parts of epoxy resin and 2.5-10 parts of biomass toughening agent of structural compound shown in formula IV in claim 1.
11. The epoxy-benzoxazine resin cured product according to claim 10, wherein the epoxy resin toughening curing system further comprises a curing agent, and the addition amount of the curing agent is 20% -30% of the total mass of the epoxy resin and the biomass toughening agent.
12. The method for producing an epoxy-benzoxazine resin cured product according to claim 10, comprising the steps of:
and (3) blending the biomass toughening agent and the epoxy resin according to the mass ratio, adding a curing agent to obtain an epoxy resin blend, and respectively curing the epoxy resin blend at 100 ℃, 150 ℃, 200 ℃ and 250 ℃ for 2 hours to obtain an epoxy-benzoxazine resin cured product.
13. The method for preparing the epoxy-benzoxazine resin cured product according to claim 12, wherein the mass ratio of the biomass toughening agent to the epoxy resin is (2.5-10): (97.5-90) blending.
14. The method for producing an epoxy-benzoxazine resin cured product according to claim 12, wherein the mass ratio of the curing agent to the blend is (20-30): 100.
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| CN103012841A (en) * | 2012-12-18 | 2013-04-03 | 四川大学 | Cardanol-aromatic diamine type benzoxazine flexibilizer as well as preparation method and purposes thereof |
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| CN103012841A (en) * | 2012-12-18 | 2013-04-03 | 四川大学 | Cardanol-aromatic diamine type benzoxazine flexibilizer as well as preparation method and purposes thereof |
| CN109081895A (en) * | 2018-07-27 | 2018-12-25 | 贵州理工学院 | A kind of self toughening benzoxazine thermosetting resin and preparation method thereof |
| WO2021238004A1 (en) * | 2020-05-23 | 2021-12-02 | 苏州大学 | Biomass benzoxazine-based shape memory resin, preparation method therefor, and application thereof |
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