CN113651846B - Method for modifying rubber by cardanol derivative - Google Patents
Method for modifying rubber by cardanol derivative Download PDFInfo
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- CN113651846B CN113651846B CN202111071273.1A CN202111071273A CN113651846B CN 113651846 B CN113651846 B CN 113651846B CN 202111071273 A CN202111071273 A CN 202111071273A CN 113651846 B CN113651846 B CN 113651846B
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- cardanol
- rubber
- phenolic resin
- derivative
- reacting
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- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical class OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 title claims abstract description 71
- 229920001971 elastomer Polymers 0.000 title claims abstract description 30
- 239000005060 rubber Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 16
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 43
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 43
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- CBVJWBYNOWIOFJ-UHFFFAOYSA-N chloro(trimethoxy)silane Chemical compound CO[Si](Cl)(OC)OC CBVJWBYNOWIOFJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004103 aminoalkyl group Chemical group 0.000 claims abstract description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 24
- 229920001568 phenolic resin Polymers 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- QHQNYHZHLAAHRW-UHFFFAOYSA-N 2-trimethoxysilylethanamine Chemical compound CO[Si](OC)(OC)CCN QHQNYHZHLAAHRW-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- BHWUCEATHBXPOV-UHFFFAOYSA-N 2-triethoxysilylethanamine Chemical compound CCO[Si](CCN)(OCC)OCC BHWUCEATHBXPOV-UHFFFAOYSA-N 0.000 claims description 2
- 101000878595 Arabidopsis thaliana Squalene synthase 1 Proteins 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 19
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000011521 glass Substances 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 229910000077 silane Inorganic materials 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 244000226021 Anacardium occidentale Species 0.000 description 5
- 235000020226 cashew nut Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- -1 aminosiloxane Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010466 nut oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the field of rubber modification, and particularly relates to a method for modifying rubber by using a cardanol derivative. The invention firstly provides a preparation method of a cardanol diffractant, which comprises the following steps: s1: reacting the epoxy cardanol with trimethoxy chlorosilane to obtain an intermediate 1; s2: and (3) reacting the intermediate 1 with aminoalkyl trialkoxysilane to obtain the cardanol derivative. According to the invention, the phenolic hydroxyl of the epoxidized cardanol and the epoxy group on the alkyl chain are modified by using silane at the same time to obtain the novel rubber modifier. When the modifier is used for modifying phenolic resin-nitrile rubber, the phenolic resin-nitrile rubber has better bonding property to a glass substrate.
Description
Technical Field
The invention relates to the field of rubber modification, and particularly relates to a method for modifying rubber by using a cardanol derivative.
Background
Cardanol is the main component of cashew nut shell oil, and is the byproduct of cashew nut oil, easy to extract, low in cost, and renewable, and the components in cardanol are roughly as follows (R.Auvergne, S.Caillol, G.David, B.J. -P Pascault, Biobased Thermosettingepoxy: Present and Future, Chemical Reviews 2014,114(2),1082 + 1115.).
The structure is that a 15-carbon alkyl chain containing 0-3 double bonds is arranged at the meta position of phenol, phenolic hydroxyl and the alkyl chain have great transformation potential, and the phenol structure of the phenol-formaldehyde resin can also be used as a component of a main chain of the phenol-formaldehyde resin.
CN108586686A discloses an epoxy cardanol/aminosiloxane synergistically modified phenolic resin and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing the epoxy cardanol and phenol, and adding the alkaline catalyst, the aminosiloxane and the paraformaldehyde in batches to prepare the epoxy cardanol/aminosiloxane synergistically modified phenolic resin. The excellent performances of the epoxy cardanol and the amino siloxane are combined, so that the molecular weight increase of the resin modified by the cardanol can be reduced, the viscosity of the synthetic resin is increased rapidly, the fluidity is poor, the microstructure of the subsequent phenolic foam is influenced, and the toughness of the phenolic foam is negatively influenced; meanwhile, halogen-free flame retardant elements, namely nitrogen and silicon, are introduced into the foam structure, so that the problem that the flame retardant property of the cardanol-based phenolic foam is reduced due to the introduction of a long carbon chain of cardanol is solved, and the complex process of additionally adding a flame retardant and the risk of separating out the flame retardant are avoided.
CN111154054A discloses a method for modifying phenolic resin with cardanol and rubber, comprising the following steps: (1) taking raw material phenol as a solvent, and enabling double bonds on a cardanol side chain to have an addition reaction with rubber alpha carbon under the action of an initiator to obtain a mixture of phenol and cardanol grafted rubber; (2) adding formaldehyde and an acid catalyst into the mixture to perform polycondensation reaction on the phenol and the cardanol grafted rubber in the mixture and the formaldehyde; (3) dehydrating to 180 ℃ in vacuum under the condition that the vacuum degree is less than 0.09Mpa, stopping reaction, and discharging to obtain the cardanol and rubber modified phenolic resin. The method can obviously improve the wear resistance, flexibility, compatibility and storage stability of the phenolic resin, and the process adopts a solvent-free process, meets the requirement of environmental protection and does not cause pollution to the environment.
CN113087866A discloses a preparation method and application of cashew phenolic resin. The preparation method comprises the following steps: (1) mixing cardanol, aldehyde substances and a catalyst, and carrying out polymerization reaction to obtain a prepolymer; (2) dehydrating the prepolymer obtained in the step (1), adding an amine compound containing methylene, stirring until a solid is formed, heating, and cooling to obtain a cashew phenolic resin; the catalyst is one of hypophosphorous acid, phosphorous acid or composite acid; the composite acid is a combination of phosphoric acid and sulfurous acid, a combination of phosphoric acid and oxalic acid, or a combination of ammonium hypophosphite and sulfuric acid. By controlling the reaction steps and selecting the catalyst, the yellow cashew phenolic resin can be prepared, and has excellent high-temperature resistance, high mechanical strength and good wear resistance.
It can be seen that when cardanol is used to modify phenolic resin, cardanol is generally used as a component of the main chain of phenolic resin, and is mainly used for increasing toughness and wear resistance of phenolic resin or rubber.
Disclosure of Invention
The invention aims to provide a method for modifying rubber by using a cardanol derivative, which can enable the modified rubber resin to have good adhesive property and is particularly suitable for bonding glass substrates.
The purpose of the invention is realized by the following technical scheme.
In one aspect, the invention provides a preparation method of a cardanol derivative, which comprises the following steps:
s1: reacting the epoxy cardanol with trimethoxy chlorosilane to obtain an intermediate 1;
s2: and (3) reacting the intermediate 1 with aminoalkyl trialkoxysilane to obtain the cardanol derivative.
Further, in S1, the epoxy value of the epoxidized cardanol is 8% to 10%.
Further, in S1, the reaction is carried out in an aprotic solvent.
Further, in S1, the aprotic solvent is at least one selected from benzene, toluene, pyridine, THF, diethyl ether, 1, 4-dioxane, dichloromethane, chloroform, DMF, DMSO, or acetonitrile.
Further, in S1, the molar ratio of the epoxidized cardanol to the trimethoxychlorosilane is 1:1-10, alternatively 1:1-8, 1:1-5, 1:1-3, 1:1-1.5, 1:1-1.2, or 1:1. Preferably 1: 1.1-1.5.
Further, in S1, the reaction is carried out under the condition of excess trimethoxy chlorosilane.
Further, in S1, a base is used in the reaction.
Further, in S1, the base is selected from an organic base, optionally at least one of triethylamine, diisopropylethylamine, or pyridine. Triethylamine is preferred.
Further, in S1, the molar ratio of the epoxidized cardanol to the alkali is 1:1-20, alternatively 1:1-15, 1:1-10, 1:1-5, 1:1-3, 1:1-1.5, or 1:1. Preferably 1: 2-3.
Further, in S2, the aminoalkylalkoxysilane is selected from at least one of aminoethyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltrimethoxysilane or aminopropyltriethoxysilane.
Further, in S2, the molar ratio of the intermediate 1 to the aminoalkyl trialkoxysilane is 1:0.3 to 0.7, preferably 1: 0.5-0.7.
Further, in S2, the reaction is carried out in an aprotic solvent.
Further, in S2, the aprotic solvent is at least one selected from benzene, toluene, pyridine, THF, diethyl ether, 1, 4-dioxane, dichloromethane, chloroform, DMF, DMSO, or acetonitrile.
Further, the reaction solvents described in S2 and S1 are the same.
Further, in S2, the reaction temperature is 50-70 ℃.
In another aspect, the present invention provides a method for modifying rubber using the cardanol derivative, comprising the steps of:
SS 1: heating and reacting the cardanol derivative with phenolic resin to obtain modified phenolic resin;
SS 2: adding nitrile rubber under the condition of heating to obtain the modified rubber.
Furthermore, in SS1, the mass ratio of the cardanol derivative to the phenolic resin is 1: 3-5.
Furthermore, in SS2, the mass ratio of the nitrile rubber to the cardanol derivative is 10-15: 1.
Further, in SS1 and SS2, the heating temperature is 60 to 100 ℃.
Further, the phenolic resin is a linear phenolic resin and is obtained by polymerizing phenol and formaldehyde, and the polymerization degree is preferably 4-12.
Further, the acrylonitrile-butadiene rubber has an acrylonitrile content of 30-40% and a Mooney viscosity of 70-80.
The invention has the advantages that:
1. according to the invention, the phenolic hydroxyl of the epoxidized cardanol and the epoxy group on the alkyl chain are modified by using silane at the same time to obtain the novel rubber modifier.
2. The modified rubber compounded by the modifier, the phenolic resin and the nitrile rubber has better adhesive property and is particularly suitable for being used on glass substrates.
Detailed Description
Unless otherwise stated, the materials used in the invention are obtained by commercial means, wherein the cardanol four-component content is more than or equal to 99 percent, and the compositions are as follows
Calculated, the average relative molecular mass of the cardanol with the composition is 300.68g/mol, and the double bond content is 0.634mol/100 g; if all of the double bonds in the final product are fully epoxidized, the theoretical epoxy value is about 9.68%, which is the theoretical maximum epoxy value.
Preparation method of epoxidized cardanol
Dissolving 100g of cardanol in DCM1000mL, adding 200mL of 30% hydrogen peroxide and 100mL of formic acid, reacting for 5h under the condition of DCM reflux, separating an organic phase after the reaction is finished, washing the organic phase for 2 times with water, wherein the dosage is 200mL each time, drying the organic phase, and removing the solvent under reduced pressure to obtain 95g of epoxidized cardanol with the epoxy value of 9.1%.
Wherein the epoxy value of the epoxidized cardanol can be adjusted by changing parameter conditions in the method according to needs.
The method for detecting the epoxy value in the present invention is referred to GB/T1677-2008 "determination of epoxy value of plasticizer", and the epoxy value is defined as "the content of oxygen in an oxirane group per 100g of sample, and is referred to as the epoxy value".
Example 1
Preparation method of cardanol derivative
1mol of epoxidized cardanol and 1.5mol of trimethoxy chlorosilane are dissolved in 2000ml of THF, 2mol of triethylamine is added, and reaction is carried out for 12 hours. The solvent and excess trimethoxychlorosilane were removed under reduced pressure to give a residue containing intermediate 1. DMF3000mL was added and stirred well, followed by the addition of 0.3mol of aminoethyl trimethoxysilane, heating to 70 ℃ and reaction for 4 h. After completion of the reaction, DMF was removed under reduced pressure to obtain a residue containing the cardanol derivative, and the residue was suspended in 1000mL of ethyl acetate, stirred uniformly, and then filtered. And removing ethyl acetate from the filtrate under reduced pressure to obtain the cardanol derivative.
Preparation of modified rubber using the cardanol derivative
Taking 100g of the cardanol derivative, adding 500g of linear phenolic resin (with the polymerization degree of 6), heating to 80 ℃, reacting for 3h, adding 1200g of nitrile rubber (JSR N232SH, ACN ═ 35, Mooney viscosity of 77), continuously keeping 80 ℃, reacting for 2h, and cooling to 20-30 ℃ to obtain the modified rubber.
Example 2
Preparation method of cardanol derivative
1mol of epoxidized cardanol and 1.1mol of trimethoxy chlorosilane are dissolved in 2000mL of chloroform, 2mol of triethylamine is added, and the reaction is carried out for 8 hours. The solvent and excess trimethoxychlorosilane were removed under reduced pressure to give a residue containing intermediate 1. Adding 3000mL of toluene, stirring uniformly, then adding 0.7mol of aminopropyl trimethoxy silane, heating to 60 ℃, and reacting for 6 h. After completion of the reaction, toluene was removed under reduced pressure to obtain a residue containing the cardanol derivative, and the residue was suspended in 1000mL of ethyl acetate, stirred well, and then filtered. And removing ethyl acetate from the filtrate under reduced pressure to obtain the cardanol derivative.
Preparation of modified rubber using the cardanol derivative
Taking 100g of the cardanol derivative, adding 300g of linear phenolic resin (with the polymerization degree of 10), heating to 80 ℃, reacting for 3h, adding 1200g of nitrile rubber (JSR N236H, ACN ═ 32, Mooney viscosity of 72), continuously keeping 80 ℃, reacting for 2h, and cooling to 20-30 ℃ to obtain the modified rubber.
Example 3
1mol of epoxidized cardanol and 2mol of trimethoxy chlorosilane are dissolved in 3000mL of pyridine and reacted for 8 hours. The solvent and excess trimethoxychlorosilane were removed under reduced pressure to give a residue containing intermediate 1. THF (3000 mL) is added and stirred uniformly, then aminopropyltrimethoxysilane (0.5 mol) is added, the temperature is raised to 70 ℃, and the reaction is carried out for 6 h. After completion of the reaction, THF was removed under reduced pressure to obtain a residue containing the cardanol derivative, and the residue was suspended in 1000mL of ethyl acetate, stirred well, and then filtered. And removing ethyl acetate from the filtrate under reduced pressure to obtain the cardanol derivative.
Preparation of modified rubber using the cardanol derivative
Taking 100g of the cardanol derivative, adding 500g of linear phenolic resin (with the polymerization degree of 10), heating to 80 ℃, reacting for 3h, adding 1200g of nitrile rubber (JSR N224SH, ACN ═ 37, Mooney viscosity of 70), continuously keeping 80 ℃, reacting for 2h, and cooling to 20-30 ℃ to obtain the modified rubber.
Comparative example 1
The difference from example 1 is that in preparing the modified rubber, epoxidized cardanol is used instead of the cardanol derivative.
Comparative example 2
The difference from example 1 is that aminopropyltrimethoxysilane was used in an amount of 1 mol.
Comparative example 3
The difference from example 1 is that no trimethoxychlorosilicon was used for the modification.
Examples of effects
The adhesive properties of the products were evaluated using the shear strength test. Specifically referring to determination of tensile shear strength (rigid material to rigid material) of GB/T7124-.
Table 1 tensile shear strength data
It can be seen that when the cardanol derivative is used for modifying phenolic resin-nitrile rubber, the rubber obtained through modification has good bonding performance on a glass substrate. From the data of comparative example 2, it can be seen that when the amount of aminoalkylalkoxysilane used in the preparation of the derivative is too large, the cardanol derivative may lose a certain crosslinking property, and the binding ability of the final modified rubber may be reduced; the data of comparative example 3 shows that the derivatization of the cardanol hydroxyl group in the application also has a large influence on the final gluing effect.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (4)
1. A preparation method of cardanol derivatives comprises the following steps:
s1: reacting the epoxy cardanol with trimethoxy chlorosilane to obtain an intermediate 1;
s2: reacting the intermediate 1 with aminoalkyl trialkoxysilane to obtain the cardanol derivative;
in S1, the epoxy value of the epoxidized cardanol is 8% -10%;
in S1, the molar ratio of the epoxidized cardanol to the trimethoxychlorosilane is 1: 1-3;
s1 and S2, wherein the reaction is carried out in an aprotic solvent selected from at least one of benzene, toluene, pyridine, THF, dichloromethane, chloroform and DMF;
in S2, the molar ratio of the intermediate 1 to the aminoalkyl trialkoxysilane is 1: 0.3-0.7.
2. The method according to claim 1, wherein a base is used in the reaction in S1.
3. The method according to claim 1, wherein in S2, the aminoalkylalkoxysilane is at least one selected from the group consisting of aminoethyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltrimethoxysilane and aminopropyltriethoxysilane.
4. A method for modifying rubber with a cardanol derivative obtained by the production method according to any one of claims 1 to 3, comprising the steps of:
SS 1: heating and reacting the cardanol derivative with phenolic resin to obtain modified phenolic resin;
SS 2: adding nitrile rubber under the condition of heating to obtain the modified rubber.
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CN103554442A (en) * | 2013-11-20 | 2014-02-05 | 哈尔滨师范大学 | Cardanol derivative curing agent and preparation method thereof |
CN103554063A (en) * | 2013-11-06 | 2014-02-05 | 河南省化工研究所有限责任公司 | Preparation method of cardanol glycidyl ether with high epoxy value |
WO2021037799A1 (en) * | 2019-08-28 | 2021-03-04 | Basf Coatings Gmbh | A cardanol-derivatives modified polymer and a coating composition comprising the same |
CN112794828A (en) * | 2021-01-13 | 2021-05-14 | 广东宏力达合成材料科技有限公司 | Epoxidized dicamba carbonate type plasticizer |
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CN103554063A (en) * | 2013-11-06 | 2014-02-05 | 河南省化工研究所有限责任公司 | Preparation method of cardanol glycidyl ether with high epoxy value |
CN103554442A (en) * | 2013-11-20 | 2014-02-05 | 哈尔滨师范大学 | Cardanol derivative curing agent and preparation method thereof |
WO2021037799A1 (en) * | 2019-08-28 | 2021-03-04 | Basf Coatings Gmbh | A cardanol-derivatives modified polymer and a coating composition comprising the same |
CN112794828A (en) * | 2021-01-13 | 2021-05-14 | 广东宏力达合成材料科技有限公司 | Epoxidized dicamba carbonate type plasticizer |
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