CN117164788A - Preparation method of phenolic resin for friction material - Google Patents
Preparation method of phenolic resin for friction material Download PDFInfo
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- CN117164788A CN117164788A CN202311444001.0A CN202311444001A CN117164788A CN 117164788 A CN117164788 A CN 117164788A CN 202311444001 A CN202311444001 A CN 202311444001A CN 117164788 A CN117164788 A CN 117164788A
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- phenolic resin
- eugenol
- phenol
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- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 73
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 73
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002783 friction material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 119
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 112
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005770 Eugenol Substances 0.000 claims abstract description 32
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229960002217 eugenol Drugs 0.000 claims abstract description 32
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 24
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 238000010438 heat treatment Methods 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 46
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 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 35
- 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 34
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 34
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 34
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000004327 boric acid Substances 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 5
- 229920003987 resole Polymers 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 description 38
- 238000006297 dehydration reaction Methods 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 21
- 238000004821 distillation Methods 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- -1 boric acid ester Chemical class 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 235000019492 Cashew oil Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 229940059459 cashew oil Drugs 0.000 description 1
- 239000010467 cashew oil Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003335 steric effect Effects 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
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The application provides a preparation method of phenolic resin for friction materials, which adopts nitrile rubber to modify eugenol, and utilizes the modified eugenol to replace part of phenol, and after polycondensation reaction with formaldehyde, the prepared phenolic resin not only maintains good mechanical property and toughness, but also has high temperature resistance equivalent to that of unmodified resol. The friction material can bring good high-temperature stability, has excellent mechanical properties, and can be suitable for more application scenes.
Description
Technical Field
The application relates to the technical field of friction matrix materials, in particular to a preparation method of phenolic resin for friction materials.
Background
Phenolic resin is a thermosetting synthetic resin, has the advantages of easily obtained raw materials, low price, good mechanical property, weather resistance, corrosion resistance, water resistance and certain heat resistance, is widely applied to the industries of aviation, traffic, military, electronic products and the like, is a main base material of friction material parts in structures such as automobile brake pads, speed changers and the like, is obtained by polycondensation reaction of phenol and formaldehyde, and is connected through a methylene, so that the rotational freedom degree of chain links is small, the density of benzene rings is high, and the brittleness of the phenolic resin is finally high.
With the increasing performance requirements of friction materials, conventional phenolic resin cannot meet the friction requirements, and the phenolic resin is easy to crack after the shear stress caused by friction force is excessive, so that the toughening treatment of the phenolic resin becomes an important research direction of the current phenolic resin, and the toughening treatment of the current phenolic resin mainly comprises two directions of raw material modification toughening and component optimization toughening, and the application aims to provide the toughening phenolic resin so as to solve the problem of low toughness of the current phenolic resin.
In the prior art, aiming at the toughening scheme surrounding phenolic resin, the raw material phenol is partially replaced, wherein common replacement raw materials comprise tung oil, cashew oil and lignin, the raw materials contain phenol structures, meanwhile, phenol has a certain long carbon chain, the polymerization degree can be reduced to a certain extent by utilizing the steric effect of the long carbon chain, and part of energy can be absorbed by the long carbon chain under the action of shear stress, so that the toughening purpose is achieved. However, such toughening modifications also reduce the high temperature resistance of the resulting phenolic resin.
Disclosure of Invention
In view of the above, the application provides a preparation method of phenolic resin for friction materials, which aims to improve the toughness of the phenolic resin and maintain certain high temperature resistance.
The technical scheme of the application is realized as follows: the application provides a preparation method of phenolic resin for friction materials, which comprises the following steps:
step one, mixing eugenol, liquid nitrile rubber, benzoyl peroxide and ethyl acetate, heating to 60-80 ℃, stirring under nitrogen atmosphere for reaction for 6-8 hours, adding methanol, stirring for precipitation, and filtering to obtain a filter cake to obtain modified eugenol;
step two, after mixing the modified eugenol, phenol, sodium hydroxide and formaldehyde, heating to 50-80 ℃, stirring and reacting for 1-5 hours, and dehydrating the product to obtain phenolic resin for friction materials, wherein the modified eugenol: phenol: the mass ratio of formaldehyde is (1-4): (25-30): 10.
in the scheme, eugenol is adopted as a modified component of the resol, the eugenol has a carbon chain on a benzene ring, the carbon chain length is short, the toughening effect of direct modification is not ideal, double bonds are considered on the carbon chain of the eugenol, and the eugenol can be subjected to grafting reaction with nitrile rubber to grow the carbon chain, so that the nitrile rubber is adopted as a grafting modifier of the eugenol, benzoyl peroxide is adopted as an initiator to carry out grafting reaction, the modified eugenol with a longer carbon chain structure is obtained, and meanwhile, phenol is adopted as a main raw material and then reacts with formaldehyde to obtain the modified phenol-formaldehyde resin.
In some embodiments, the second step may further comprise mixing the modified eugenol, cardanol, phenol, catalyst and formaldehyde, heating to 50-80 ℃, stirring for 1-5h, and dehydrating the product to obtain phenolic resin for friction material, modified eugenol: cardanol: phenol: the mass ratio of formaldehyde is (1-4): (2-8): (25-30): 10.
in the above embodiment, compared with the modified eugenol, the structure of cardanol is more single, the cardanol has a relatively single longer carbon chain structure, and unlike the modified eugenol in which a reticular carbon chain may exist, the cardanol can be added as a further toughening modification component, so that adjacent reticular carbon chains are combined with each other, thereby obtaining the resin with higher structural strength and good toughness.
In some embodiments, the modified eugenol: the mass ratio of cardanol is 1:2.
In some embodiments, the second step may further comprise mixing the modified eugenol, cardanol, phenol, boric acid and toluene, heating to 80-100deg.C, stirring for 30-60min, and drying by distillation to obtain borate, wherein the mass ratio of the total mass of the modified eugenol, cardanol and phenol to boric acid is 2:1; then mixing boric acid ester with phenol, sodium hydroxide and formaldehyde, heating to 50-80 ℃, stirring and reacting for 1-5h, and dehydrating the product to obtain phenolic resin for friction materials, wherein in the reaction process, the eugenol is modified: cardanol: total amount of phenol: the mass ratio of formaldehyde is (1-4): (2-8): (25-30): 10, wherein the total amount of phenol: the mass ratio of boric acid is 1: (0.05-0.15).
In order to further improve the heat resistance, in the above embodiment, a part of phenol is preferentially reacted with boric acid together with the modified eugenol and cardanol to obtain a borate ester, and the introduction of boric acid enables the modified eugenol, cardanol and phenol to be riveted with each other to obtain a more uniform crosslinked structure, and the introduction of a boron-oxygen bond improves the heat resistance and environmental protection of the resin.
In some embodiments, in step one, eugenol: the mass ratio of the nitrile rubber is 1: (10-40).
In some embodiments, step one, after obtaining the filter cake, further comprises flushing the filter cake with methanol 2-3 times and drying.
On the other hand, the application also provides phenolic resin for the friction material, which is prepared by adopting the preparation method.
Compared with the prior art, the preparation method of the phenolic resin for the friction material has the following beneficial effects:
according to the friction material, by introducing part of eugenol modified by nitrile rubber as a toughening modifier, good toughening performance is obtained, and meanwhile, the obtained phenolic resin has good heat resistance.
Detailed Description
The following description of the embodiments of the present application will clearly and fully describe the technical aspects of the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to fall within the scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the application belong. If the definitions set forth in this section are contrary to or otherwise inconsistent with the definitions set forth in the patents, patent applications, published patent applications and other publications incorporated herein by reference, the definitions set forth in this section are preferentially set forth in the definitions set forth herein.
The number average molecular weight of the liquid nitrile rubber used in the following preparation examples and examples was 50000Da.
Preparation example 1
Respectively weighing 1kg of eugenol, 10kg kg of liquid nitrile rubber, 0.1kg kg of benzoyl peroxide and 40kg kg of ethyl acetate, heating to 60 ℃ under nitrogen atmosphere, stirring at 100rpm for reaction for 6h, adding 40kg methanol, stirring for precipitation, filtering, and drying a filter cake to obtain the modified eugenol.
Preparation example 2
Respectively weighing eugenol 1kg, liquid nitrile rubber 40kg, benzoyl peroxide 0.5kg and ethyl acetate 100kg, mixing, heating to 80 ℃ under nitrogen atmosphere, stirring at 100rpm for reaction for 8 hours, adding 100kg of methanol, stirring for precipitation, filtering, and drying a filter cake to obtain the modified eugenol.
Preparation example 3
Respectively weighing 1kg of eugenol, 10kg of liquid nitrile rubber, 0.1kg of benzoyl peroxide and 40kg of ethyl acetate, heating to 60 ℃ under nitrogen atmosphere after mixing, stirring at 100rpm for reaction for 6 hours, then adding 40kg of methanol, stirring for precipitation, filtering, taking filter cakes, respectively flushing the filter cakes with 10kg of methanol, and drying to obtain the modified eugenol after flushing.
Comparative preparation example 1
Respectively weighing 1kg of eugenol, 1kg of liquid nitrile rubber, 0.01kg of benzoyl peroxide and 10kg of ethyl acetate, mixing, heating to 60 ℃ under nitrogen atmosphere, stirring at 100rpm for reaction for 6 hours, adding 10kg of methanol, stirring for precipitation, filtering, and drying a filter cake to obtain the modified eugenol.
Comparative preparation example 2
Respectively weighing 1kg of eugenol, 100kg of liquid nitrile rubber, 1kg of benzoyl peroxide and 200kg of ethyl acetate, mixing, heating to 80 ℃ under nitrogen atmosphere, stirring at 100rpm for reaction for 8 hours, adding 200kg of methanol, stirring for precipitation, filtering, taking a filter cake, and drying to obtain the modified eugenol.
Example 1
Mixing 1kg of modified eugenol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat and stirring for 5 hours, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain the phenolic resin.
Example 2
Mixing 1kg of modified eugenol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat and stirring for 5 hours, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain the phenolic resin.
Example 3
Mixing 1kg of modified eugenol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde prepared in preparation example 3, heating to 50 ℃, preserving heat and stirring for 5 hours, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain phenolic resin.
Comparative example 1
Taking 1kg of modified eugenol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde prepared in comparative preparation example 1, mixing, heating to 50 ℃, preserving heat and stirring for 5 hours, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain phenolic resin.
Comparative example 2
Taking 1kg of modified eugenol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde prepared in comparative preparation example 1, mixing, heating to 50 ℃, preserving heat and stirring for 5 hours, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain phenolic resin.
Comparative example 3
Mixing 1kg of liquid nitrile rubber, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat and stirring for 5 hours, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain the phenolic resin.
Comparative example 4
Mixing 1kg of eugenol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat and stirring for 5 hours, decompressing, distilling and dehydrating, pouring into a mould after dehydrating, heating to 120 ℃, and curing to obtain the phenolic resin.
Blank examples
The blank example adopts 26kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, after mixing, the temperature is raised to 50 ℃, the mixture is kept warm and stirred for 5 hours, then reduced pressure distillation and dehydration are carried out, after dehydration is finished, the mixture is poured into a die, the temperature is raised to 120 ℃, and the phenolic resin is obtained after solidification.
The phenolic resins prepared in examples 1 to 3, comparative examples 1 to 4 and blank examples described above were subjected to performance tests, specifically, thermal weight loss analysis, friction performance test, compressive strength and flexural strength, respectively.
Thermal weight loss analysis:
and testing the obtained phenolic resin on a thermal analysis system, wherein the atmosphere is air, the heating speed is 20 ℃/min, and the thermal decomposition temperature is tested.
Friction performance test:
the obtained phenolic resin is subjected to friction experiments by a constant-speed friction tester, and the friction coefficients and the wear rates at 100 ℃ and 300 ℃ are respectively tested according to GB-5763-98.
The data results shown in the following table were obtained:
as can be seen from the above test data, the nitrile rubber modified eugenol adopted by the application is used as a partial substitute raw material, after the phenol and formaldehyde are replaced to carry out polycondensation to prepare the phenolic resin, compared with the conventional unmodified resol, the obtained resin has the advantages of obvious enhancement of compressive strength and bending strength, and obvious enhancement of toughness of the phenolic resin. Meanwhile, the heat resistance is almost unchanged, compared with comparative example 4 obtained by replacing conventional eugenol and comparative example 3 obtained by partially replacing and modifying nitrile rubber, the phenolic resin obtained by modifying the eugenol by the nitrile rubber has stronger comprehensiveness, and the eugenol alternative of comparative example 4 can be seen that although the obtained phenolic resin has a certain improvement on friction performance, the improvement is not obvious, the toughness improvement is extremely low, and on the contrary, the heat resistance is reduced to a certain extent. Phenolic resin prepared by the scheme of the nitrile rubber partial replacement modification of comparative example 3 has a certain improvement on toughness data, and has a certain reduction on thermal decomposition and friction performance.
Considering that the nitrile rubber is possibly subjected to reaction modification with the eugenol, on one hand, unsaturated bonds in the nitrile rubber are subjected to chain extension after being reacted with allyl groups of the eugenol, so that a flexible chain segment is increased for benzene rings of the eugenol, and on the other hand, methoxy groups in the eugenol possibly subjected to addition reaction with partial unsaturated bonds in the nitrile rubber, so that eugenol with a complex network structure is obtained, and the eugenol with the complex network structure participates in the condensation polymerization process of phenol and formaldehyde, so that on one hand, the complex network structure provides steric hindrance, excessively high dense benzene ring accumulation is avoided, the toughness is improved, and on the other hand, phenolic hydroxyl exposed in the eugenol with the complex network structure is subjected to condensation polymerization with formaldehyde, so that the high temperature resistance of the obtained phenolic resin is good.
Example 4
Taking 1kg of modified eugenol, 2kg of cardanol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde prepared in preparation example 1, mixing, heating to 50 ℃, preserving heat and stirring for 5 hours, carrying out reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain phenolic resin.
Example 5
Taking 1kg of modified eugenol, 1kg of cardanol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde prepared in preparation example 1, mixing, heating to 50 ℃, preserving heat and stirring for 5 hours, carrying out reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain phenolic resin.
Example 6
Taking 1kg of modified eugenol, 3kg of cardanol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde prepared in preparation example 1, mixing, heating to 50 ℃, preserving heat and stirring for 5 hours, carrying out reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain phenolic resin.
Comparative example 5
Mixing 1kg of eugenol, 2kg of cardanol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat and stirring for 5 hours, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain the phenolic resin.
Comparative example 6
Mixing 2kg of cardanol, 25kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat and stirring for 5 hours, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain the phenolic resin.
The phenolic resins prepared in examples 4 to 6 were subjected to performance tests, respectively, and the results are shown in the following table:
in a further scheme of the application, a part of cardanol is added into the raw materials for phenol substitution, and experiments show that the addition of cardanol has excellent reinforcing effect on the mechanical properties, particularly toughness, of phenolic resin, and the effect on toughness increase is remarkable because of the longer branched carbon chain structure in cardanol, so that the friction performance and toughness of the obtained phenolic resin are remarkably improved, but the corresponding thermal decomposition performance is reduced to a certain extent by matching with the modified eugenol. Meanwhile, according to the data of comparative examples 5 and 6, compared with the toughening modification of the conventional eugenol, the modified eugenol and cardanol seem to have certain coordination action, and after the modified eugenol and cardanol are used for replacing part of phenol together for polycondensation reaction, the toughness of the obtained phenolic resin is improved, and the thermal decomposition performance is improved. The reason is considered that the addition of cardanol forms a linking structure, and links the network structure formed by the modified eugenol, thereby improving flexibility between dispersed eugenol systems. But at the same time, the addition of cardanol also brings about greater steric hindrance, so that the phenol system with high polymerization degree between the dispersed eugenols becomes more 'loose'. Thereby reducing the alarm high temperature performance.
Example 7
Mixing 1kg of modified eugenol, 2kg of cardanol, 10kg of phenol, 1.25kg of boric acid and 40kg of toluene, heating to 80 ℃, stirring for reacting for 60min, cooling to 60 ℃, steaming toluene to dryness under reduced pressure to obtain boric acid ester, mixing the boric acid ester with the rest 15kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat, stirring for 5h, distilling under reduced pressure for dehydration, pouring into a die after dehydration is completed, heating to 120 ℃, and curing to obtain phenolic resin.
Example 8
Mixing 1kg of modified eugenol, 2kg of cardanol, 10kg of phenol, 3.75kg of boric acid and 40kg of toluene, heating to 100 ℃, stirring for reacting for 30min, cooling to 60 ℃, steaming toluene to dryness under reduced pressure to obtain boric acid ester, mixing the boric acid ester with the rest 15kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat, stirring for 5h, distilling under reduced pressure for dehydration, pouring into a die after dehydration is completed, heating to 120 ℃, and curing to obtain phenolic resin.
Comparative example 7
Mixing 1kg of modified eugenol, 10kg of phenol, 1.25kg of boric acid and 40kg of toluene, heating to 80 ℃, stirring for reacting for 60min, cooling to 60 ℃, steaming toluene to dryness under reduced pressure to obtain boric acid ester, mixing boric acid ester with the rest 15kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat, stirring for 5h, carrying out reduced pressure distillation and dehydration, pouring into a mould after dehydration is completed, heating to 120 ℃, and curing to obtain phenolic resin.
Comparative example 8
Mixing 2kg of cardanol, 10kg of phenol, 1.25kg of boric acid and 40kg of toluene, heating to 80 ℃, stirring for reacting for 60min, then cooling to 60 ℃, steaming toluene under reduced pressure until the mixture is dried to obtain borate, mixing the borate with the rest 15kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat and stirring for 5h, performing reduced pressure distillation and dehydration, pouring into a die after dehydration, heating to 120 ℃, and curing to obtain phenolic resin.
Comparative example 9
Mixing 10kg of phenol, 1.25kg of boric acid and 40kg of toluene, heating to 80 ℃, stirring for reacting for 60min, cooling to 60 ℃, steaming toluene to dryness under reduced pressure to obtain boric acid ester, mixing the boric acid ester, the rest 15kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 50 ℃, preserving heat and stirring for 5h, carrying out reduced pressure distillation and dehydration, pouring into a mould after dehydration is finished, heating to 120 ℃, and curing to obtain phenolic resin.
The phenolic resins prepared in examples 7 to 8 and comparative examples 7 to 9 were subjected to performance tests, respectively, to obtain the results shown in the following table:
as can be seen from the data of the above examples, the phenolic resin prepared by the method further improves the high temperature resistance on the premise of retaining the toughness properties such as good compressive strength and bending strength by pre-reacting the modified eugenol, cardanol, part of phenol and boric acid to prepare boric acid ester and then performing polycondensation reaction on the boric acid ester and the rest of phenol, and as can be seen from the data of comparative examples 7-9, when at least one of the modified eugenol and cardanol is omitted from the raw materials, the corresponding phenolic resin cannot meet the corresponding requirements, therefore, it can be seen that the unexpected effect is obtained after the three raw materials pass through the pre-step, and the fact that the adding of boric acid forms an in-situ reaction point is considered to enable the modified eugenol, cardanol and part of phenol to mutually graft react to form a complex network system, the toughness of the obtained phenolic resin is enhanced due to the long carbon chain in the system, and the complex network structure and the high-density polymerization structure brought by phenol can still retain good compressive property of the resin itself; and due to the introduction of boron atoms, the benzene rings where different phenolic hydroxyl groups are located are combined more tightly, and the bond energy of boron-oxygen bonds is high, so that the thermal decomposition temperature is increased, and a better heat-resistant effect is brought.
Example 9
Mixing 2kg of modified eugenol, 27kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 70 ℃, preserving heat and stirring for 3 hours, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain the phenolic resin.
Example 10
Mixing 4kg of the modified eugenol prepared in preparation example 1, 30kg of phenol, 1kg of sodium hydroxide and 10kg of formaldehyde, heating to 80 ℃, preserving heat and stirring for 1h, performing reduced pressure distillation and dehydration, pouring into a mould after dehydration, heating to 120 ℃, and curing to obtain the phenolic resin.
The results of the performance tests of the phenolic resins prepared in example 9 and example 10 are shown in the following table:
the foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (7)
1. The preparation method of the phenolic resin for the friction material is characterized by comprising the following steps of:
step one, mixing eugenol, liquid nitrile rubber, benzoyl peroxide and ethyl acetate, heating to 60-80 ℃, stirring under nitrogen atmosphere for reaction for 6-8 hours, adding methanol, stirring for precipitation, and filtering to obtain a filter cake to obtain modified eugenol;
step two, after mixing the modified eugenol, phenol, sodium hydroxide and formaldehyde, heating to 50-80 ℃, stirring and reacting for 1-5 hours, and dehydrating the product to obtain phenolic resin for friction materials, wherein the modified eugenol: phenol: the mass ratio of formaldehyde is (1-4): (25-30): 10.
2. the method for producing a phenolic resin for friction materials according to claim 1, wherein the second step is to mix modified eugenol, cardanol, phenol, sodium hydroxide and formaldehyde, heat up to 50-80 ℃, stir and react for 1-5 hours, and then dehydrate the product to obtain the phenolic resin for friction materials, wherein the modified eugenol: cardanol: phenol: the mass ratio of formaldehyde is (1-4): (2-8): (25-30): 10.
3. the method for producing a phenolic resin for friction material according to claim 2, wherein the modified eugenol: the mass ratio of cardanol is 1:2.
4. The method for preparing phenolic resin for friction material as claimed in claim 1, wherein the second step is that after mixing the modified eugenol, cardanol, phenol, boric acid and toluene, heating to 80-100 ℃, stirring and reacting for 30-60min, and then distilling and drying to obtain borate, wherein the mass ratio of the total mass of the modified eugenol, cardanol and phenol to boric acid is 2:1 when preparing the borate; then mixing the obtained borate with phenol, sodium hydroxide and formaldehyde, heating to 50-80 ℃, stirring and reacting for 1-5h, and dehydrating the product to obtain the phenolic resin for the friction material, wherein in the reaction process, the eugenol is modified: cardanol: total amount of phenol: the mass ratio of formaldehyde is (1-4): (2-8): (25-30): total amount of phenol: the mass ratio of boric acid is 1: (0.05-0.15).
5. The method of producing a phenolic resin for friction material as claimed in claim 1, wherein in the first step, eugenol: the mass ratio of the nitrile rubber is 1: (10-40).
6. The method of producing a phenolic resin for friction materials as claimed in claim 1, wherein in the first step, after obtaining the cake, further comprising flushing the cake with methanol 2 to 3 times and drying.
7. A phenolic resin for friction materials, characterized in that it is prepared by the preparation method according to any one of claims 1 to 6.
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