CN117143316A - Bio-based honokiol organic silicon epoxy resin and preparation method thereof - Google Patents
Bio-based honokiol organic silicon epoxy resin and preparation method thereof Download PDFInfo
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- CN117143316A CN117143316A CN202311422263.7A CN202311422263A CN117143316A CN 117143316 A CN117143316 A CN 117143316A CN 202311422263 A CN202311422263 A CN 202311422263A CN 117143316 A CN117143316 A CN 117143316A
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- epoxy resin
- honokiol
- bio
- magnolol
- catalyst
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- VVOAZFWZEDHOOU-UHFFFAOYSA-N honokiol Natural products OC1=CC=C(CC=C)C=C1C1=CC(CC=C)=CC=C1O VVOAZFWZEDHOOU-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 101
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 101
- FVYXIJYOAGAUQK-UHFFFAOYSA-N honokiol Chemical compound C1=C(CC=C)C(O)=CC=C1C1=CC(CC=C)=CC=C1O FVYXIJYOAGAUQK-UHFFFAOYSA-N 0.000 title claims abstract description 80
- BYTORXDZJWWIKR-UHFFFAOYSA-N Hinokiol Natural products CC(C)c1cc2CCC3C(C)(CO)C(O)CCC3(C)c2cc1O BYTORXDZJWWIKR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 17
- 239000010703 silicon Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- -1 hydrogen siloxane Chemical group 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 26
- 238000002390 rotary evaporation Methods 0.000 claims description 21
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 9
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 9
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 3
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 3
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 3
- NAWZSHBMUXXTGV-UHFFFAOYSA-M triethyl(hexyl)azanium;bromide Chemical compound [Br-].CCCCCC[N+](CC)(CC)CC NAWZSHBMUXXTGV-UHFFFAOYSA-M 0.000 claims description 3
- FASLCARXKMYXDH-UHFFFAOYSA-M triethyl(octyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](CC)(CC)CC FASLCARXKMYXDH-UHFFFAOYSA-M 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 19
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 9
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 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 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002989 phenols Chemical group 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The application discloses a bio-based honokiol organic silicon epoxy resin and a preparation method thereof, belonging to the technical field of high polymer materials. The application takes bio-based honokiol and long-chain terminal hydrogen siloxane as raw materials to prepare the organosilicon modified honokiol-based epoxy resin, and the organosilicon modified honokiol-based epoxy resin has good flexibility and mechanical property after being solidified. The honokiol epoxy raw material source is green and sustainable, has little harm to human body, has certain tensile strength and certain toughness, expands the application field of epoxy resin, and solves the problem of dependence on petroleum-based bisphenol A epoxy resin to a certain extent.
Description
Technical Field
The application belongs to the technical field of high polymer materials, and particularly relates to a bio-based honokiol organosilicon epoxy resin and a preparation method thereof.
Background
Epoxy resins are the most widely used resins among thermosetting resins because of their excellent adhesive properties, electrical properties, chemical resistance, corrosion resistance, and are widely used in the fields of paints, adhesives, composite materials, electronic packaging, and the like. Currently, more than 90% of the commercial epoxy resins are made from diglycidyl ethers of bisphenol a. The bisphenol A diglycidyl ether is synthesized from petroleum phenol and acetone. Bisphenol a has various hazards to human health, such as carcinogenicity, mutagenicity, and reproductive toxicity, and endocrine disruptors. Therefore, the development of the environment-friendly epoxy resin capable of replacing bisphenol A epoxy resin has great significance.
Honokiol is a plant extract isolated from magnolia and has long been used as a drug and is considered safe by the food safety department. Compared with other bio-based extracts, honokiol has a difunctional monomer with both allyl and phenolic hydroxyl groups. Reactive allylic groups can be reacted with a hydrosilylation group, while phenolic hydroxyl groups can be easily substituted with other functional groups to obtain the desired structure. Meanwhile, honokiol has a benzene ring structure, so that the honokiol has a certain rigid structure. The glycidyl ether epoxy synthesized by taking honokiol as a raw material has excellent tensile strength, but the epoxy shows brittleness after solidification, so that the application of the epoxy in the field of adhesives is limited.
Disclosure of Invention
Based on the problems, the application discloses a bio-based honokiol organosilicon epoxy resin and a preparation method thereof.
In order to achieve the above purpose, the present application provides the following technical solutions:
a bio-based honokiol organosilicon epoxy resin, which has the following structural formula:
wherein n is 8 or 13, and m is 0, 1 or 2.
The silicone resin has a unique structure and properties, and when the material is subjected to external stress, the soft Si-O bonds in the structure provide good expansion and contraction elasticity to the material, and dissipate external forces through deformation. In addition, the organic silicon resin has excellent performances such as high temperature resistance, low temperature resistance, electrical insulation, aging resistance, low surface tension and the like, and the silicone chain segment is embedded into the epoxy resin through Michael addition, so that the toughness of the epoxy resin is improved.
The application also provides a preparation method of the bio-based honokiol organosilicon epoxy resin, which comprises the following steps:
(1) Mixing honokiol, epichlorohydrin and a quaternary ammonium salt catalyst at normal temperature and normal pressure, stirring at normal temperature, and carrying out etherification ring-opening reaction for 2-4 hours at the temperature of 60-100 ℃ under nitrogen to obtain chlorohydrin;
(2) Removing redundant epichlorohydrin by rotary evaporation, adding alkali, carrying out ring closure reaction for 1-12 h at 80 ℃, then adding sodium dihydrogen phosphate for neutralization, washing with water, standing, then taking out a lower organic substance, adding anhydrous sodium sulfate into the organic substance, and carrying out overnight, and removing volatile substances by rotary evaporation to obtain honokiol glycidyl ether epoxy resin;
(3) Mixing honokiol glycidyl ether epoxy resin, a hydrosilylation catalyst and a solvent, dropwise adding chain end hydrogen siloxane, heating for reaction for 5-8 hours, and removing the solvent and volatile substances by rotary evaporation to obtain the bio-based honokiol organosilicon epoxy resin.
Further, the molar ratio of honokiol to epichlorohydrin to quaternary ammonium salt catalyst is 1:25-50:0.05-0.1.
Further, the quaternary ammonium salt catalyst is any one of benzyl triethyl ammonium chloride, trioctylmethyl ammonium chloride, tetramethyl ammonium bromide, tetrapropyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, triethyl benzyl ammonium bromide, benzyl triethyl ammonium chloride, triethyl hexyl ammonium bromide and triethyl octyl ammonium bromide.
Further, the molar ratio of honokiol to alkali is 1:1-2.5. The alkali is selected from common alkaline substances such as sodium hydroxide, potassium hydroxide or ammonia water, and can be directly added into the solid, or can be added after being prepared into alkaline solution.
Further, the addition amount of the hydrosilylation catalyst is 15-20ppm of the reaction raw materials; the molar ratio of C=C in the honokiol glycidyl ether epoxy resin to Si-H in the long-chain terminal hydrogen siloxane is (1-2) to 1.
Further, the structural general formula of the long-chain terminal hydrogen siloxane is as follows:
wherein the hydrogen content is 0.26% or 0.18%, respectively, and n is 8 or 13 respectively;
the hydrosilylation catalyst is any one of Karstedt catalyst and Speier catalyst.
Further, the conditions of the hydrosilylation reaction are: the temperature is 70-90 ℃ and the time is 5-8 hours.
The present application also provides an epoxy resin material comprising: bio-based and magnolol silicone epoxy resin, curing agent and curing accelerator. The epoxy resin material comprises the following components in parts by mass: 100 parts of bio-based and magnolol organic silicon epoxy resin, 3-80 parts of curing agent and 1-3 parts of curing accelerator.
Further, the curing agent is selected from common curing agent types including anhydride or polyether amine curing agents. The curing accelerator is selected from phenols such as 2,4, 6-tris (dimethylaminomethyl) phenol.
The application also provides a preparation method of the epoxy resin material, which comprises the following steps: mixing the bio-based and magnolol organic silicon epoxy resin, a curing agent and a curing accelerator, defoaming at room temperature, pouring, and then sequentially curing at 80-120 ℃ for 2-3 hours and at 120-150 ℃ for 2-3 hours to obtain the epoxy resin material.
Compared with the prior art, the application has the following advantages and technical effects:
the application takes bio-based honokiol and long-chain terminal hydrogen siloxane as raw materials to prepare the organosilicon modified honokiol-based epoxy resin, and the organosilicon modified honokiol-based epoxy resin has good flexibility and mechanical property after being solidified. The honokiol epoxy raw material source is green and sustainable, has little harm to human body, has certain tensile strength and certain toughness, expands the application field of epoxy resin, and solves the problem of dependence on petroleum-based bisphenol A epoxy resin to a certain extent.
The preparation method is simple and flexible, the reaction condition is mild, a part of bio-based epoxy resin can be used for replacing petroleum product epoxy resin, and meanwhile, long-chain organic silicon is introduced into the epoxy resin, so that the flexibility and heat resistance of the epoxy resin product can be improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of honokiol glycidyl ether epoxy resin prepared in example 1;
FIG. 2 is a Fourier infrared spectrum of a bio-based and magnolol silicone epoxy resin prepared in examples 1-6;
FIG. 3 is a thermogravimetric plot of the bio-based and magnolol silicone epoxy resins prepared in examples 1-6;
fig. 4 is a partial enlarged view of fig. 3.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "room temperature" and "normal temperature" in the present application are all calculated at 25.+ -. 2 ℃ unless otherwise specified.
As used herein, the term "normal pressure" refers to an atmospheric pressure gauge unless otherwise specified.
The parts of the application are calculated according to the parts by mass unless otherwise specified,
the raw materials used in the following examples of the present application are all commercially available.
The application provides a bio-based honokiol organic silicon epoxy resin, which has the following structural formula:
wherein n is 8 or 13, and m is 0, 1 or 2.
The application also provides a preparation method of the bio-based honokiol organosilicon epoxy resin, which comprises the following steps:
(1) Adding honokiol, epichlorohydrin and a quaternary ammonium salt catalyst into a four-necked flask with a condenser tube and a thermometer at normal temperature and normal pressure, magnetically stirring at normal temperature, introducing nitrogen for 10 minutes, and carrying out etherification ring-opening reaction at 60-100 ℃ (preferably 80 ℃) to obtain chlorohydrin;
(2) After the reaction of the step (1) is carried out for 2-4 hours (preferably for 3 hours), removing redundant epichlorohydrin by rotary evaporation, then adding alkali into the system, continuing the ring-closure reaction for 1-12 hours (preferably for 1 hour) at 80 ℃, adding sodium dihydrogen phosphate for neutralization, washing, standing and separating liquid, taking the lower organic matters out after the system is divided into two layers, adding anhydrous sodium sulfate for overnight, and removing volatile matters by rotary evaporation to obtain honokiol glycidyl ether epoxy resin;
(3) Adding the honokiol glycidyl ether, the hydrosilylation catalyst and the solvent prepared in the step (2) into a three-neck flask, dropwise adding chain end hydrogen siloxane, heating for reaction for 5-8 hours, and removing the solvent and volatile substances by rotary evaporation to obtain the bio-based and magnolol organosilicon epoxy resin.
In some preferred embodiments of the present application, in step (1), the quaternary ammonium salt catalyst is any one of benzyl triethyl ammonium chloride, trioctylmethyl ammonium chloride, tetramethyl ammonium bromide, tetrapropyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, triethyl benzyl ammonium bromide, benzyl triethyl ammonium chloride, triethyl hexyl ammonium bromide and triethyl octyl ammonium bromide, preferably benzyl triethyl ammonium chloride. The molar ratio of the catalyst to honokiol is 0.1:1. In the step (2) of some preferred embodiments of the application, the molar ratio of the epichlorohydrin to the honokiol is (25-50) to 1, the alkali is selected from common alkaline substances such as sodium hydroxide, potassium hydroxide and ammonia water, and the alkali can be directly added into the solid or can be added after the alkali solution is prepared, and the molar ratio of the alkali to the honokiol is 2.5 to 1.
In some preferred embodiments of the present application, step (3), the hydrosilylation catalyst is added in an amount of 15-20ppm of the reaction raw material, and the hydrosilylation catalyst is any one of Karstedt catalyst and Speier catalyst, preferably Karstedt catalyst; the molar ratio of honokiol glycidyl ether epoxy to long-chain terminal hydrogen siloxane is calculated by C=C:Si-H=1-2.0 (and the molar ratio of C=C bond and Si-H is ensured to be 1-2.0). The hydrosilylation reaction conditions are as follows: the reaction temperature is preferably 70-90 ℃, preferably 80 ℃, and the reaction time is preferably 5-8 h, preferably 5h. The structural general formula of the long-chain terminal hydrogen siloxane is as follows:
wherein the hydrogen content is 0.26% or 0.18%, respectively, and n is 8 or 13, respectively.
The present application also provides an epoxy resin material comprising: bio-based and magnolol silicone epoxy resin, curing agent and curing accelerator. The epoxy resin material comprises the following components in parts by mass: 100 parts of bio-based and magnolol organic silicon epoxy resin, 3-80 parts of curing agent and 1-3 parts of curing accelerator. Preferably, the epoxy resin composition comprises 100 parts of bio-based honokiol organosilicon epoxy resin, 22-44 parts of curing agent and 1-3 parts of curing accelerator.
In some preferred embodiments of the present application, the curing agent is selected from the common classes of curing agents, including anhydride and polyetheramine curing agents. The curing accelerator is selected from phenols such as 2,4, 6-tris (dimethylaminomethyl) phenol.
The application also provides a preparation method of the epoxy resin material, which comprises the following steps: mixing the bio-based and magnolol organic silicon epoxy resin, a curing agent and a curing accelerator, defoaming at room temperature, casting, and then sequentially curing for 2-3 hours at 80-120 ℃ and 2-3 hours at 120-150 ℃ to obtain the epoxy resin material. Preferably at 120℃for 2 hours and at 150℃for 2 hours in sequence.
The time and temperature of the reaction of the different types of curing agents with the bio-based honokiol silicone epoxy resin vary greatly. The polyether amine curing agent has higher reactivity with the bio-based epoxy resin, shorter curing time and lower curing temperature, while the anhydride curing agent has opposite reactivity. Fine tuning can be performed according to the specific situation.
The instrumentation used in the following examples: magnetic stirring oil bath-DF-101S-Shanghai Lichen Instrument technology Co., ltd; rotary vane vacuum pump-SN-2 XZ-2-Shanghai instrument, inc; electrothermal blowing drying oven-DHG-9123A-New medical instruments Inc. in Jiaxing City; electronic analytical balance-JC-TP-Guangzhou Gu Wei technology Co., ltd; shore D durometer-LX-D-Wenzhou tripod Instrument manufacturing Co., ltd; universal tensile machine-CMT 4202-American MTS company; fourier infrared spectrometer-N6700-Nicolet Inc. of America; nuclear magnetic resonance apparatus-AVANCE-bruck company; thermogravimetric analyzer-SDT-2960-american TA company.
The following examples serve as further illustrations of the technical solutions of the application.
Example 1
27.96g of honokiol (0.105 mol), 485.73g of epichlorohydrin (5.25 mol) and 2.39g of benzyl triethyl ammonium chloride (0.0105 mol) are added into a three-port bottle provided with a stirrer, a constant pressure funnel and a thermometer under normal temperature and pressure, and the mixture is reacted for 3 hours at 80 ℃ under nitrogen atmosphere to obtain chlorohydrin;
excess epichlorohydrin was removed by rotary evaporation, sodium hydroxide (10.5 g,0.2625 mol) was dissolved in 15.75ml of water, and a 40wt% aqueous solution of sodium hydroxide was prepared and allowed to react at 80℃for 1 hour; adding 6.4g anhydrous sodium dihydrogen phosphate (0.0525 mol) for neutralization, washing with water, and separating; the organic layer was dried by adding 10g of anhydrous sodium sulfate. Filtering, rotary evaporating to remove volatile substances to obtain honokiol glycidyl ether epoxy resin;
3) 33.93g of honokiol glycidyl ether epoxy resin, 25g of anhydrous toluene, 0.42g of Karstedt's catalyst (15 ppm) were added to a three-necked flask equipped with a condensing reflux device; 50g of hydrogen-containing siloxane at two ends with hydrogen content of 0.18% (molar ratio of carbon-carbon double bond in magnolol glycidyl ether epoxy resin to silicon-hydrogen bond in hydrogen-containing siloxane at two ends is 2:1, structural formulaAnd n=13) is dissolved in the above system, placed in a constant pressure dropping funnel, and under nitrogen atmosphere, after the system temperature is raised to 80 ℃ and the dropping is completed within 1 hour, the temperature is kept for 5 hours after the dropping is completed, toluene is removed by vacuum rotary evaporation at 70 ℃ to obtain bio-based and magnolol organosilicon epoxy resin, which is marked as SIHOEP-0.18-2 (SIHOEP-0.18-2 has the meaning: SI is an abbreviation for silicone; HO is an abbreviation for honokiol; e (E)P is an abbreviation for epoxy; 0.18 is the hydrogen content of the silicone oil used; 2 is the molar ratio of carbon-carbon double bonds to silicon-hydrogen bonds), and has the structural formula:
where n=13 and m is 0. Theoretical epoxy values are shown in table 2.
100 parts of bio-based honokiol organic silicon epoxy resin prepared in the example, 35.6 parts of methyl hexahydrophthalic anhydride curing agent and 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol are taken, uniformly stirred and mixed, then vacuumized and defoamed for 30 seconds at 80 ℃, uniformly smeared on the surface of a steel sheet washed by ethanol according to GBT7124-2008 (adhesive tensile shear strength test method) and fixed. Resin, curing agent and curing accelerator were stirred uniformly and defoamed according to the above method, and then poured into a steel mold (for preparing a spline according to national standard GB/T1040-2006, dumbbell type 2), cured at 120℃for 2 hours and cured at 150℃for 2 hours, and the iron sheet bonding strength, tensile strength, elongation at break and hardness data of the obtained samples are shown in Table 1.
Example 2
1) 55.92g of honokiol (0.21 mol), 485.73g of epichlorohydrin (5.25 mol) and 2.39g of benzyl triethyl ammonium chloride (0.0105 mol) are added into a three-necked flask equipped with a stirrer, a constant pressure funnel and a thermometer under normal temperature and pressure, and reacted for 3 hours at 80 ℃ under nitrogen atmosphere to obtain chlorohydrin;
2) Excess epichlorohydrin was removed by rotary evaporation, sodium hydroxide (21 g,0.525 mol) was dissolved in 31.5ml of water, and a 40wt% aqueous solution of sodium hydroxide was prepared and allowed to react at 80℃for 1 hour; adding 12.8g anhydrous sodium dihydrogen phosphate (0.105 mol) for neutralization and water washing, and separating; the organic layer was dried by adding 10g of anhydrous sodium sulfate. Filtering, rotary evaporating to remove volatile substances to obtain honokiol glycidyl ether epoxy resin;
3) 24.45g of honokiol glycidyl ether epoxy resin, 25g of anhydrous toluene, 0.37g of Karstedt's catalyst (15 ppm) were added to a three-necked flask equipped with a condensing reflux device; 50g of a hydrogen-containing siloxane having 0.18% hydrogen at both ends (honokiol glycidyl ether ring)The molar ratio of the carbon-carbon double bond in the oxygen resin to the silicon-hydrogen bond in the hydrogen-containing siloxane at the two ends is 1.5:1, the structural formulaAnd n=13) is dissolved in the system, the mixture is placed in a constant pressure dropping funnel, under the nitrogen atmosphere, when the temperature of the system is raised to 80 ℃, the mixture is dropped in 1 hour, the mixture is kept for 5 hours after the dropping is finished, toluene is removed by vacuum rotary evaporation at 70 ℃ to obtain bio-based and magnolol organosilicon epoxy resin, which is marked as SIMAEP-0.18-1.5, and the structural formula is as follows:
where n=13 and m is 0 or 1. Theoretical epoxy values are shown in table 2.
100 parts of bio-based honokiol organic silicon epoxy resin prepared in the example, 29.67 parts of methyl hexahydrophthalic anhydride curing agent and 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol are taken, uniformly stirred and mixed, then vacuumized and defoamed for 30 seconds at 80 ℃, uniformly smeared on the surface of a steel sheet washed by ethanol according to GBT7124-2008 (adhesive tensile shear strength test method) and fixed. Resin, curing agent and curing accelerator were stirred uniformly and defoamed according to the above method, and then poured into a steel mold (for preparing a spline according to national standard GB/T1040-2006, dumbbell type 2), cured at 120℃for 2 hours and cured at 150℃for 2 hours, and the iron sheet bonding strength, tensile strength, elongation at break and hardness data of the obtained samples are shown in Table 1.
Example 3
1) 55.92g of honokiol (0.21 mol), 485.73g of epichlorohydrin (5.25 mol) and 4.78g of benzyl triethyl ammonium chloride (0.021 mol) are added into a three-mouth bottle provided with a stirrer, a constant pressure funnel and a thermometer under normal temperature and pressure, and the mixture is reacted for 3 hours at 80 ℃ under the nitrogen atmosphere to obtain chlorohydrin;
2) Excess epichlorohydrin was removed by rotary evaporation, sodium hydroxide (21 g,0.525 mol) was dissolved in 31.5ml of water, and a 40wt% aqueous solution of sodium hydroxide was prepared and allowed to react at 80℃for 1 hour; adding 12.8g anhydrous sodium dihydrogen phosphate (0.105 mol) for neutralization and water washing, and separating; the organic layer was dried by adding 10g of anhydrous sodium sulfate. Filtering, rotary evaporating to remove volatile substances to obtain honokiol glycidyl ether epoxy resin;
3) 16.96g of honokiol glycidyl ether epoxy resin, 25g of anhydrous toluene, 0.335g of Karstedt's catalyst (15 ppm) were added to a three-necked flask equipped with a condensing reflux device; 50g of hydrogen-containing siloxane at two ends with hydrogen content of 0.18% (molar ratio of carbon-carbon double bond in magnolol glycidyl ether epoxy resin to silicon-hydrogen bond in hydrogen-containing siloxane at two ends is 1:1, structural formulaAnd n=13) is dissolved in the system, the mixture is placed in a constant pressure dropping funnel, under the nitrogen atmosphere, when the temperature of the system is raised to 80 ℃, the mixture is dropped in 1 hour, the mixture is kept for 5 hours after the dropping is finished, toluene is removed by vacuum rotary evaporation at 70 ℃, and the bio-based and magnolol organosilicon epoxy resin is obtained and is marked as SIMAEP-0.18-1, and the structural formula is as follows:
where n=13 and m is 0, 1 or 2. Theoretical epoxy values are shown in table 2.
100 parts of bio-based honokiol organic silicon epoxy resin prepared in the example, 22.3 parts of methyl hexahydrophthalic anhydride curing agent and 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol are taken, stirred and mixed uniformly, then vacuumized and defoamed for 30 seconds at 80 ℃, and uniformly smeared on the surface of a steel sheet washed by ethanol according to GBT7124-2008 (adhesive tensile shear strength test method) and fixed. Resin, curing agent and curing accelerator were stirred uniformly and defoamed according to the above method, and then poured into a steel mold (for preparing a spline according to national standard GB/T1040-2006, dumbbell type 2), cured at 120℃for 2 hours and cured at 150℃for 2 hours, and the iron sheet bonding strength, tensile strength, elongation at break and hardness data of the obtained samples are shown in Table 1.
Example 4
1) 55.92g of honokiol (0.21 mol), 485.73g of epichlorohydrin (5.25 mol) and 4.78g of benzyl triethyl ammonium chloride (0.021 mol) are added into a three-mouth bottle provided with a stirrer, a constant pressure funnel and a thermometer under normal temperature and pressure, and the mixture is reacted for 3 hours at 80 ℃ under the nitrogen atmosphere to obtain chlorohydrin;
2) Excess epichlorohydrin was removed by rotary evaporation, sodium hydroxide (21 g,0.525 mol) was dissolved in 31.5ml of water, and a 40wt% aqueous solution of sodium hydroxide was prepared and allowed to react at 80℃for 1 hour; adding 12.8g anhydrous sodium dihydrogen phosphate (0.105 mol) for neutralization and water washing, and separating; the organic layer was dried by adding 10g of anhydrous sodium sulfate. Filtering, rotary evaporating to remove volatile substances to obtain honokiol glycidyl ether epoxy resin;
3) 19.656g of honokiol glycidyl ether epoxy resin, 25g of anhydrous toluene, 0.20g of Karstedt's catalyst (15 ppm) were added to a three-necked flask equipped with a condensing reflux device; 20g of the siloxane with hydrogen content of 0.26 percent at both ends (the molar ratio of the carbon-carbon double bond in the magnolol glycidyl ether epoxy resin to the silicon-hydrogen bond in the siloxane with hydrogen content at both ends is 2:1, the structural formula is thatAnd n=8) is dissolved in the system, the mixture is placed in a constant pressure dropping funnel, under the nitrogen atmosphere, when the temperature of the system is raised to 80 ℃, the mixture is dropped in 1 hour, the mixture is kept for 5 hours after the dropping is finished, toluene is removed by vacuum rotary evaporation at 70 ℃, and the bio-based and magnolol organosilicon epoxy resin is obtained and is marked as SIMAEP-0.26-2, and the structural formula is as follows:
where n=8 and m is 0. Theoretical epoxy values are shown in table 2.
100 parts of bio-based honokiol organic silicon epoxy resin prepared in the example, 43.5 parts of methyl hexahydrophthalic anhydride curing agent and 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol are taken, stirred and mixed uniformly, then vacuumized and defoamed for 30 seconds at 80 ℃, and uniformly smeared on the surface of a steel sheet washed by ethanol according to GBT7124-2008 (adhesive tensile shear strength test method) and fixed. Resin, curing agent and curing accelerator were stirred uniformly and defoamed according to the above method, and then poured into a steel mold (for preparing a spline according to national standard GB/T1040-2006, dumbbell type 2), cured at 120℃for 2 hours and cured at 150℃for 2 hours, and the iron sheet bonding strength, tensile strength, elongation at break and hardness data of the obtained samples are shown in Table 1.
Example 5
1) 55.92g of honokiol (0.21 mol), 485.73g of epichlorohydrin (5.25 mol) and 4.78g of benzyl triethyl ammonium chloride (0.021 mol) are added into a three-mouth bottle provided with a stirrer, a constant pressure funnel and a thermometer under normal temperature and pressure, and the mixture is reacted for 3 hours at 80 ℃ under the nitrogen atmosphere to obtain chlorohydrin;
2) Excess epichlorohydrin was removed by rotary evaporation, sodium hydroxide (21 g,0.525 mol) was dissolved in 31.5ml of water, and a 40wt% aqueous solution of sodium hydroxide was prepared and allowed to react at 80℃for 1 hour; adding 12.8g anhydrous sodium dihydrogen phosphate (0.105 mol) for neutralization and water washing, and separating; the organic layer was dried by adding 10g of anhydrous sodium sulfate. Filtering, rotary evaporating to remove volatile substances to obtain honokiol glycidyl ether epoxy resin;
3) 14.742g of honokiol glycidyl ether epoxy resin, 25g of anhydrous toluene, 0.17g of Karstedt's catalyst (15 ppm) were added to a three-necked flask equipped with a condensing reflux device; 20g of the hydrogen-containing siloxane at both ends with the hydrogen content of 0.26 percent (the molar ratio of the carbon-carbon double bond in the magnolol glycidyl ether epoxy resin to the silicon-hydrogen bond in the hydrogen-containing siloxane at both ends is 1.5:1, the structural formula is thatAnd n=8) is dissolved in the system, the mixture is placed in a constant pressure dropping funnel, under the nitrogen atmosphere, when the temperature of the system is raised to 80 ℃, the mixture is dropped in 1 hour, the mixture is kept for 5 hours after the dropping is finished, toluene is removed by vacuum rotary evaporation at 70 ℃ to obtain bio-based and magnolol organosilicon epoxy resin, which is marked as SIMAEP-0.26-1.5, and the structural formula is as follows:
where n=8, m is 0 or 1. Theoretical epoxy values are shown in table 2.
100 parts of bio-based honokiol organic silicon epoxy resin prepared in the example, 37.2 parts of methyl hexahydrophthalic anhydride curing agent and 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol are taken, stirred and mixed uniformly, then vacuumized and defoamed for 30 seconds at 80 ℃, and uniformly smeared on the surface of a steel sheet washed by ethanol according to GBT7124-2008 (adhesive tensile shear strength test method) and fixed. Resin, curing agent and curing accelerator were stirred uniformly and defoamed according to the above method, and then poured into a steel mold (for preparing a spline according to national standard GB/T1040-2006, dumbbell type 2), cured at 120℃for 2 hours and cured at 150℃for 2 hours, and the iron sheet bonding strength, tensile strength, elongation at break and hardness data of the obtained samples are shown in Table 1.
Example 6
1) 55.92g of honokiol (0.21 mol), 485.73g of epichlorohydrin (5.25 mol) and 4.78g of benzyl triethyl ammonium chloride (0.021 mol) are added into a three-mouth bottle provided with a stirrer, a constant pressure funnel and a thermometer under normal temperature and pressure, and the mixture is reacted for 3 hours at 80 ℃ under the nitrogen atmosphere to obtain chlorohydrin;
2) Excess epichlorohydrin was removed by rotary evaporation, sodium hydroxide (21 g,0.525 mol) was dissolved in 31.5ml of water, and a 40wt% aqueous solution of sodium hydroxide was prepared and allowed to react at 80℃for 1 hour; adding 12.8g anhydrous sodium dihydrogen phosphate (0.105 mol) for neutralization and water washing, and separating; the organic layer was dried by adding 10g of anhydrous sodium sulfate. Filtering, rotary evaporating to remove volatile substances to obtain honokiol glycidyl ether epoxy resin;
3) 9.828g of honokiol glycidyl ether epoxy resin, 25g of anhydrous toluene, 0.15g of Karstedt's catalyst (15 ppm) were added to a three-necked flask equipped with a condensing reflux device; 20g of the siloxane with hydrogen content of 0.26% (the molar ratio of the carbon-carbon double bond in the magnolol glycidyl ether epoxy resin to the silicon-hydrogen bond in the siloxane with hydrogen content of 1:1, structural formulaAnd n=8) is dissolved in the system, the mixture is placed in a constant pressure dropping funnel, under the nitrogen atmosphere, when the temperature of the system is raised to 80 ℃, the mixture is dropped in 1 hour, the mixture is kept for 5 hours after the dropping is finished, toluene is removed by vacuum rotary evaporation at 70 ℃ to obtain bio-based and magnolol organosilicon epoxy resin, which is marked as SIMAEP-0.26-1, and the structural formula is as follows:
where n=8 and m is 0, 1 or 2. Theoretical epoxy values are shown in table 2.
100 parts of bio-based honokiol organic silicon epoxy resin prepared in the example, 28.9 parts of methyl hexahydrophthalic anhydride curing agent and 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol are taken, uniformly stirred and mixed, then vacuumized and defoamed for 30 seconds at 80 ℃, uniformly smeared on the surface of a steel sheet washed by ethanol according to GBT7124-2008 (adhesive tensile shear strength test method) and fixed. Resin, curing agent and curing accelerator were stirred uniformly and defoamed according to the above method, and then poured into a steel mold (for preparing a spline according to national standard GB/T1040-2006, dumbbell type 2), cured at 120℃for 2 hours and cured at 150℃for 2 hours, and the iron sheet bonding strength, tensile strength, elongation at break and hardness data of the obtained samples are shown in Table 1.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of honokiol glycidyl ether epoxy resin prepared in example 1; as can be seen from the figure, the characteristic peak of about 5.25ppm of the honokiol phenolic hydroxyl groups disappeared after epoxidation. The proton peaks obtained correspond to the epoxypropyl group at about 3.9-4.3, 3.2-3.4 and 2.6-2.9 ppm. Meanwhile, other proton peaks are attributed, and the combination of the relative integral areas of the corresponding spectrum peaks can indicate that phenolic hydroxyl groups in honokiol are successfully epoxidized to obtain honokiol glycidyl ether epoxy.
FIG. 2 is a Fourier infrared spectrum of honokiol glycidyl ether epoxy and biobased honokiol silicone epoxy resin prepared in examples 1-6; as can be seen from FIG. 2, 2129cm -1 The absorption peak of the silicon-hydrogen bond at the position disappears, namely 1641cm -1 The absorption peaks of the carbon-carbon double bonds at the positions gradually decrease, and the absorption peaks of the carbon-carbon double bonds and the silicon-hydrogen bonds of SIHOEP-0.18-1 and SIHOEP-0.26-1 disappear, which indicates that the reaction is complete, and the organosilicon chain segment is successfully connected into the epoxy molecular chain.
Fig. 3 and 4 are a thermogravimetric graph and a partial enlarged view of the bio-based and magnolol silicone epoxy resin prepared in examples 1 to 6, respectively; it can be seen that the temperatures at 50% mass loss of examples 1-6 are 458.333, 462.333, 474.667, 452.000, 455.000, 464.333 ℃, respectively, and that the order of temperatures from small to large is from example 4 < example 5 < example 1 < example 2 < example 6 < example 3, corresponding to the order of epoxy values corresponding to the examples. The greater the silicone segment content, the higher the 50% mass loss temperature of the silicone epoxy resin, and the higher the thermal decomposition temperature.
Performance test:
the epoxy resin materials prepared in examples 1-6 were subjected to performance testing, and tensile performance testing was performed according to the national standard GBT 1040-2006. Tensile shear strength was tested according to the national standard GBT7124-2008 tensile shear performance. The test results are shown in Table 1.
TABLE 1
As can be seen from table 1, examples 1, 2 and 3 are compared, and as the reaction ratio of the carbon-carbon double bond to the silicon-hydrogen bond is reduced from 2 to 1, the tensile strength and shore D hardness of the cured magnolol silicone resin are gradually reduced, and the elongation at break is gradually increased. This is because as the reaction ratio approaches 1, the content of the siloxane segment in the molecular chain of the resin gradually increases, the flexibility of the molecular chain increases, the toughness of the material is improved, and the elongation at break increases from 26.51% to 45.75%. And simultaneously, the epoxy value of the resin is reduced, so that the tensile strength, the tensile shear strength and the hardness of the cured material are gradually reduced. Comparing example 1 with example 4, using different amounts of long chain hydrogen containing siloxanes at the same molar ratio of reaction, it can be seen that example 1 has a lower tensile strength than example 4 and example 1 has a greater elongation at break than example 4. This is because 0.18% of the both-end hydrogen-containing siloxanes have a molecular weight of greater than 0.26% and the silicone segment content in the segment of example 1 is greater than that of example 4, improving the toughness of the material and the elongation at break. The epoxy value of example 1 is less than example 4, such that the tensile strength, tensile shear strength and hardness of example 1 are less than example 4.
TABLE 2
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (9)
1. The bio-based honokiol organosilicon epoxy resin is characterized by comprising the following structural formula:
wherein n is 8 or 13, and m is 0, 1 or 2.
2. A method of preparing the bio-based and magnolol silicone epoxy resin of claim 1, comprising the steps of:
mixing honokiol, epichlorohydrin and a quaternary ammonium salt catalyst, and then carrying out etherification ring-opening reaction under the conditions of nitrogen and heating to obtain chlorohydrin;
performing rotary evaporation on the chlorohydrin, adding alkali, performing ring closure reaction under a heating condition, adding sodium dihydrogen phosphate, washing with water, standing, taking out a lower organic substance, adding anhydrous sodium sulfate into the organic substance, standing overnight, and performing rotary evaporation to obtain honokiol glycidyl ether epoxy resin;
mixing the honokiol glycidyl ether epoxy resin, a hydrosilylation catalyst and a solvent, dripping lengthened chain end hydrogen siloxane, heating to react, and performing rotary evaporation to obtain the bio-based honokiol organosilicon epoxy resin.
3. The preparation method of the bio-based honokiol organosilicon epoxy resin according to claim 2, wherein the molar ratio of honokiol, epichlorohydrin and quaternary ammonium salt catalyst is 1: (25-50): (0.05-0.1).
4. The method for preparing bio-based and magnolol silicone epoxy resin according to claim 3, wherein the quaternary ammonium salt catalyst is any one of benzyl triethyl ammonium chloride, trioctyl methyl ammonium chloride, tetramethyl ammonium bromide, tetrapropyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, triethyl benzyl ammonium bromide, benzyl triethyl ammonium chloride, triethyl hexyl ammonium bromide and triethyl octyl ammonium bromide.
5. The method for preparing bio-based honokiol organosilicon epoxy resin according to claim 2, wherein the molar ratio of honokiol to alkali is 1: (1-2.5).
6. The preparation method of the bio-based and magnolol organosilicon epoxy resin according to claim 2, wherein the concentration of the hydrosilylation catalyst is 15-20ppm of the reaction raw material; the molar ratio of C=C in the honokiol glycidyl ether epoxy resin to Si-H in the long-chain terminal hydrogen siloxane is (1-2) to 1.
7. The method for preparing bio-based and magnolol silicone epoxy resin according to claim 6, wherein the structural general formula of the long-chain terminal hydrogen siloxane is as follows:
wherein n is an integer of 8 or 13;
the hydrosilylation catalyst is any one of Karstedt catalyst and Speier catalyst.
8. An epoxy resin material comprising the bio-based and magnolol silicone epoxy resin of claim 1, a curing agent, and a curing accelerator.
9. A method for preparing the epoxy resin material according to claim 8, comprising the steps of: mixing the bio-based and magnolol organic silicon epoxy resin, a curing agent and a curing accelerator, defoaming at room temperature, casting, and then sequentially curing for 2-3 hours at 80-120 ℃ and 2-3 hours at 120-150 ℃ to obtain the epoxy resin material.
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