CN105418868B - Boron modified phenolic resin, preparation method and friction material - Google Patents
Boron modified phenolic resin, preparation method and friction material Download PDFInfo
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- CN105418868B CN105418868B CN201510924941.9A CN201510924941A CN105418868B CN 105418868 B CN105418868 B CN 105418868B CN 201510924941 A CN201510924941 A CN 201510924941A CN 105418868 B CN105418868 B CN 105418868B
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- phenolic resin
- dihydroxymethyl
- modified phenolic
- boron modified
- phenol
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 25
- -1 Boron modified phenolic resin Chemical class 0.000 title claims abstract description 19
- 239000002783 friction material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title description 6
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 24
- 239000005011 phenolic resin Substances 0.000 claims abstract description 24
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- UZJQAPIBSXPJON-UHFFFAOYSA-N (2,3-dimethylphenyl)methanediol Chemical compound CC1=CC=CC(C(O)O)=C1C UZJQAPIBSXPJON-UHFFFAOYSA-N 0.000 claims description 9
- VNMZUQPYTXUYJM-UHFFFAOYSA-N [4-(hydroxymethyl)-2,5-dimethylphenyl]methanol Chemical class CC1=CC(CO)=C(C)C=C1CO VNMZUQPYTXUYJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- ZQQIVMXQYUZKIQ-UHFFFAOYSA-N (2,3-dimethylphenyl)methanol Chemical compound CC1=CC=CC(CO)=C1C ZQQIVMXQYUZKIQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HFEMEUJQAUJONY-UHFFFAOYSA-N [3-(hydroxymethyl)-2,4-dimethylphenyl]methanol Chemical class CC1=CC=C(CO)C(C)=C1CO HFEMEUJQAUJONY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 2
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical class CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005885 boration reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KDSNMBNNCZRNPP-UHFFFAOYSA-N [5-(hydroxymethyl)-2,4-dimethylphenyl]methanol Chemical compound CC1=CC(C)=C(CO)C=C1CO KDSNMBNNCZRNPP-UHFFFAOYSA-N 0.000 description 3
- 238000002679 ablation Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ANDHMKAFIBKYRZ-UHFFFAOYSA-N [2-(hydroxymethyl)-3,5-dimethylphenyl]methanol Chemical class CC=1C=C(C(=C(C1)C)CO)CO ANDHMKAFIBKYRZ-UHFFFAOYSA-N 0.000 description 2
- XZIJJWSDPKUXJQ-UHFFFAOYSA-N [3-(hydroxymethyl)-2,5-dimethylphenyl]methanol Chemical class CC1=CC(CO)=C(C)C(CO)=C1 XZIJJWSDPKUXJQ-UHFFFAOYSA-N 0.000 description 2
- CASQRVMMWAYGHI-UHFFFAOYSA-N [4-(hydroxymethyl)-2,3-dimethylphenyl]methanol Chemical class CC1=C(C)C(CO)=CC=C1CO CASQRVMMWAYGHI-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical group CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 1
- RYHGQTREHREIBC-UHFFFAOYSA-N 3,4-dimethylbenzene-1,2-diol Chemical compound CC1=CC=C(O)C(O)=C1C RYHGQTREHREIBC-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CKYOUYSBIZYHNU-UHFFFAOYSA-N [2-(hydroxymethyl)-3,4-dimethylphenyl]methanol Chemical class CC1=CC=C(CO)C(CO)=C1C CKYOUYSBIZYHNU-UHFFFAOYSA-N 0.000 description 1
- VEUQLUPXQJDUJB-UHFFFAOYSA-N [2-(hydroxymethyl)-3,6-dimethylphenyl]methanol Chemical class CC1=CC=C(C)C(CO)=C1CO VEUQLUPXQJDUJB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
- F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
- F16D69/02—Composition of linings ; Methods of manufacturing
- F16D69/025—Compositions based on an organic binder
- F16D69/026—Compositions based on an organic binder containing fibres
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to a kind of boron modified phenolic resin, wherein including the multiple compounds of the structure with Formulas I.The invention further relates to prepare the method for the phenolic resin and use the resin as the friction material of binding agent.
Description
Technical field
The present invention relates to a kind of novel phenolic resins and its manufacture method, novel phenolic resins tool prepared in accordance with the present invention
There is the characteristics of heat-resist, intensity is high, and can be employed to make the adhesive of phenolic moulding powder, friction material etc..
Background technology
Phenolic resin is to realize industrialized synthetic resin earliest in the world, so far the existing history of last 100 yearses, due to it
Raw material is easy to get, cheap, and production technology and equipment are simple, it is often more important that its excellent mechanical performance, heat resistance, resistance to burning
Corrosion energy, electrical insulation properties, dimensional stability, molding processibility and fire resistance, phenolic resin turn into the Ministry of Industry
The indispensable material of door, but with the development of industrial expansion, particularly space flight and aviation and other national defence sophisticated technologies.Tradition
Phenolic resin fragility is big, poor toughness and relatively low heat resistance limit it as the application of high performance material.In order to adapt to
Application in terms of auto industry, Aero-Space and national defense industry, it is necessary to be modified to phenolic resin, improve its heat resistance and
Toughness etc..
In order to improve the performance of phenolic resin, there is the phenolic resin with boron modification, and be reported in heat resistance, wink
When heat-resisting quantity, ablation resistance, increase in terms of mechanical property, boron modified phenolic resin is used for rocket, guided missile and space and flown
The fields such as row device, are used as excellent ablation resistant material.It is anti-using boric acid and phenol that most common boron, which improves phenolic resin method,
Phenyl-borate should be generated, then is reacted with paraformaldehyde or formalin, the phenolic resin of 1 boracic is generated.Boron bakelite resin
Solidfied material reaches 70% in 900 DEG C of Residual carbon, decomposes peak temperature and is up to 625 DEG C.In addition introduced in boron phenolic molecular structure
Flexible larger-B-O- keys, toughness and mechanical property increase；The three-dimensional cross-linked structure of boracic, makes its resistance in cured product
Ablation property and resistance to neutron irradiation performance are better than general phenolic resin.The bending strength of obtained carbon cloth boron phenolic laminate
420MPa, shear strength is up to 39.7MPa；Oxygen-acetylene mass ablative rate only 0.0364g/s is lower than carbon/barium phenolic materials
20%.
The content of the invention
The purpose of the present invention is to propose to a kind of new technical scheme, it uses different monomers to synthesize the phenolic aldehyde of boron modification
Resin, to improve the heat resistance and water resistance of phenolic resin.
Another object of the present invention is to propose a kind of preparation method of boron modified phenolic resin.
Boron modified phenolic resin proposed by the present invention includes the multiple compounds of the structure with Formulas I：
Wherein be that n is integer between 1 to 30, such as 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,
17、18、19、20、21、22、23、24、25、26、27、28、29、30.The mean molecule quantity of the phenolic resin preferably 500~
1500, more preferably 800~1200, most preferably 1000~1100.Maximum molecular weight is no more than 20000.
Those skilled in the art are readily apparent that the structure of Formulas I should be the structure of the fractions of phenolic resin of the present invention, still
Generally so.Specifically, it is impossible to ensure that all strands have a boration benzene in the phenolic resin according to the present invention
The terminal of phenol.Due to the inexactness of polymerisation, some strand two ends may be all by boration, some possibility two ends
All by boration, but in general, their not main components, wherein one end of most of strands is by boration.Right
This situation is expressed in claim with "comprising".
According to the present invention, preparing the raw material of boron modified phenolic resin mainly includes dihydroxymethyl dimethylbenzene, phenols and boric acid.
Can be used for the present invention dihydroxymethyl dimethylbenzene include dihydroxymethyl ortho-xylene, dihydroxymethyl paraxylene,
Dihydroxymethyl meta-xylene or their mixture.These can be obtained by the way that dimethylbenzene is carried out into double methylolations.Dihydroxy
The example of methyl ortho-xylene includes 1,4- dihydroxymethyl -2,3- dimethyl benzenes, 1,2- dihydroxymethyl -3,4- dimethyl benzenes；Two
The example of methylol paraxylene include 1,4- dihydroxymethyl -2,5- dimethyl benzenes, 1,2- dihydroxymethyl -3,5- dimethyl benzenes,
1,3- dihydroxymethyl -2,5- dimethyl benzenes；The example of dihydroxymethyl meta-xylene includes 1,3- dihydroxymethyl -4,6- dimethyl
Benzene, 1,3- dihydroxymethyl -2,6- dimethyl benzenes, 1,2- dihydroxymethyl -3,5- dimethyl benzenes.Wherein preferred 1,4- dihydroxymethyls-
2,3- dimethyl benzenes, 1,4- dihydroxymethyl -2,5- dimethyl benzenes, 1,4- dihydroxymethyl -2,5- dimethyl benzenes, 1,3- dihydroxy first
Base -4,6- dimethyl benzene, 1,3- dihydroxymethyl -2,4- dimethyl benzenes, most preferably 1,3- dihydroxymethyl -4,6- dimethyl benzenes.
When synthesizing dihydroxymethyl dimethylbenzene through methylolation by dimethylbenzene, obtained product typically mixture has one kind in mixture
Principal product and one or two kinds of accessory substance.These accessory substances can be used for the binding agent of friction material, therefore when in use
Without separation.For example, with to dimethyl benzene synthesize 1,3- dihydroxymethyl -2,5- dimethyl benzenes when, can also obtain less amount of 1,
4- dihydroxymethyl -2,5- dimethyl benzenes and 1,2- dihydroxymethyl -3,6- dimethyl benzenes.Therefore, certain is used when the present invention is mentioned
During dihydroxy dimethylbenzene, however not excluded that it is using this kind of material as the scheme of the mixture of main component, wherein synthesis bar may be contained
The a small amount of accessory substance produced under part.
Can be used for the present invention phenol include but is not limited to phenol, cresols, xylenol, nonyl phenol, bisphenol-A, Bisphenol F,
Resorcinol, anacardol or their mixture, wherein preferably use phenol, cresols, this can preferably obtain higher heat-resisting
Property.
Present invention use acid can make as catalyst, the in the prior art acid catalyst for novolak resin
With typical example includes hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid and p-methyl benzenesulfonic acid etc., wherein it is preferred that p-methyl benzenesulfonic acid.
In the present invention, in the case where polymerized monomer only includes phenol with dihydroxymethyl dimethylbenzene, the mol ratio of the two is
1.0：0.5-0.9, excessive phenol can cause free phenol content increase in resin.If the too high levels of methylol dimethylbenzene, meeting
Cause the molecular weight of resin too high, cause product to be easy to gel.In another embodiment of the invention, a small amount of first is used
Aldehyde participates in chain reaction.Introducing formaldehyde makes chain reaction become easy, can shorten gel when product is used and take time, so as to reduce
The molding time of downstream product, improves production efficiency.The scope of the amount of introducing formaldehyde and the mol ratio of phenol 0.01~0.2, it is excellent
Select 0.05~0.1 scope.
In the present invention, determine mainly to consider the molal quantity of phenol during boric acid consumption, the molal quantity of boric acid can be phenol molal quantity
2~15% between, between preferably 3~10%.Boron atom and phenolic hydroxyl group formation B-O keys, play crosslinking agent between resin chain
Effect.
The method for preparing the phenolic resin of the present invention comprises the following steps：
1) phenol and methylol dimethylbenzene is made to carry out condensation reaction in the presence of acid catalyst.Condensation is generally at 80-120 DEG C
Temperature range carry out.Present invention preferably employs the method for gradient increased temperature.In a detailed embodiment, it is condensed 1 at 80 DEG C
Hour, then reacted 1 hour at 90 DEG C, be finally warming up to 100 DEG C and keep constant temperature 3 hours, reaction carries out distillation dehydration after terminating.
All phenol and methylol dimethylbenzene can disposably be fed intake, add catalyst and start reaction.It is preferred that, in order to anti-
The incipient stage answered suppresses the generation of heat, can first add phenol and catalyst, methylol dimethylbenzene is then added portionwise.
2) after above-mentioned condensation reaction finishes and sloughs water, boric acid is added in reactor according to quantity.Reaction is higher
At a temperature of carry out, such as 120~200 DEG C, more preferably preferably 130~180 DEG C, 140~160 DEG C.After the completion of reaction under reduced pressure
Distillation dehydration.It is preferred that, it can be under reduced pressure dehydrated, be dehydrated more preferably under 8000Pa pressure with side border ring.
One of the characteristics of preparation method of the present invention is that boric acid is added after the condensation reaction of phenol and methylol benzene, without
It is first to be reacted with phenol, then polymerize again with methylol benzene.
Another aspect of the present invention which uses foregoing novel phenolic resins there is provided a kind of friction material.Such as existing skill
Known to art, friction material includes resinoid bond, reinforcing material and filler.Conventional reinforcing fiber include asbestos, steel fibre,
Glass fibre, carbon fiber, organic fiber, mineral fibres.Conventional filler such as graphite, molybdenum disulfide, talcum powder, mica, sulphur
Sour barium, calcium carbonate, aluminum oxide etc..Typical preparation method is to be well mixed each material, through hot-forming, then carries out hot place
Reason.
Disc brake pad, drum-type brake pad piece, brake ribbon, brake shoe, clutch can be made according to the friction material of the present invention
Device piece, special-shaped friction plate.
Brief description of the drawings
Fig. 1 to Fig. 4 is thermal weight loss at 600 DEG C of embodiment 1, embodiment 2, comparative example 1 and the gained sample of comparative example 2 respectively
Measurement figure.
Embodiment
Embodiment 1：
By phenol 445g, dimethylbenzene, which be 1,4- dihydroxymethyl -2,3- dimethyl benzenes 358g, oxalic acid 4.45g is put into has
In thermometer, agitating device, the 1000ml reaction vessels of reflux condenser, 80 DEG C of constant temperature is heated to 1 hour, then rising
Temperature is to 90 DEG C, and constant temperature 1 hour is finally warming up to 100 DEG C, constant temperature 3 hours terminates reaction and carries out air-distillation dehydration, heating rises
Temperature adds 20g boric acid, well mixed then vacuum distillation is dehydrated to obtain the new phenolic resin of 758g under 8000Pa pressure to 150 DEG C.
Implement 2：
Phenol 450g, 1,3- dihydroxymethyl -4,6- dimethyl benzenes 250g, sulfuric acid 4.45g are put into thermometer, stirred
In the 1000ml reaction vessels for mixing device, reflux condenser, 80 DEG C of constant temperature is heated to 1 hour, be then warming up to 90 DEG C,
Constant temperature 1 hour, is finally warming up to 100 DEG C, constant temperature 3 hours, adds 60 grams of formaldehyde and continues isothermal reaction 2 hours, end react into
Row air-distillation, heats to 150 DEG C, adds 30g boric acid, is well mixed and then vacuum distillation takes off under 8000Pa pressure
Water, obtains the new phenolic resin of 718g.
Comparative example 1：
Phenol 500g, 37% formalin 301g, oxalic acid 5g are put into thermometer, agitating device, backflow
In the 1000ml reaction vessels of condenser, 80 DEG C of constant temperature is heated to 1 hour, be then warming up to 90 DEG C, constant temperature 1 hour,
100 DEG C are finally warming up to, constant temperature 3 hours terminates reaction and carries out air-distillation, 150 DEG C is heated to, then under 8000Pa pressure
Vacuum distillation, obtains 530g phenolic resin.
Comparative example 2：
Phenol 500g, 37% formalin 301g, oxalic acid 5g are put into thermometer, agitating device, backflow
In the 1000ml reaction vessels of condenser, 80 DEG C of constant temperature is heated to 1 hour, be then warming up to 90 DEG C, constant temperature 1 hour,
100 DEG C are finally warming up to, constant temperature 3 hours terminates reaction and carries out air-distillation, is heated to 150 DEG C, adds 30g boric acid, and mixing is equal
The even and then vacuum distillation under 8000Pa pressure, obtains 535g phenolic resin.
The thermal weight loss of each embodiment and comparative sample is measured under 600 DEG C and air ambient, as a result as shown in table 1.Examination
Test result to show, substantially low thermal weight loss is shown according to the boron modified phenolic resin of the present invention.Wherein, embodiment 2 product
Thermal weight loss is significantly lower than the description of product of embodiment 1, is using
The thermal weight loss test data contrast table of table 1.
With the sample preparation friction material of above-described embodiment, preparing raw material is by percentage to the quality：Phenolic resin 15%,
Aramid fiber 10%, copper fiber 10%, calcium sulfate crystal whiskers 10%, molybdenum disulfide 2%, graphite 10%, aluminum oxide 3%, flyash
20%th, barium sulfate is filled to 100%, wherein, the length of aramid fiber and copper fiber is 100~300 μm.
It is prepared via a method which：
1. material is mixed.After each component raw material is weighed by proportioning, add in high-speed mixer and stir 20min, obtain group
Divide uniform mixed material.
2. it is hot-forming.The material mixed is put into mould, at 150 DEG C ± 5 DEG C of temperature and 15MPa pressure by
Hot press is hot-forming, 3~5min of dwell time in hot pressing, first three minute domestic demand breathing a mould of pressurize 2~3 times.
3. heat treatment.Hot-forming print is put into air dry oven, 180 DEG C are to slowly warm up to, protected at 180 DEG C
Warm 12h is heat-treated, and friction material finished product is obtained after cooling.
Table 2 gives the coefficient of friction and wear rate of embodiment and comparative example product.
The constant speed experimental machine test data of table 2. is contrasted
Claims (10)
1. a kind of boron modified phenolic resin, wherein including the multiple compounds of the structure with Formulas I：
Wherein it is that n is integer between 1 to 30.
2. the boron modified phenolic resin described in claim 1, wherein preparing raw material mainly include dihydroxymethyl dimethylbenzene, phenols and
Boric acid.
3. boron modified phenolic resin according to claim 2, wherein, the dihydroxymethyl dimethylbenzene is Isosorbide-5-Nitrae-dihydroxy first
Base -2,3- dimethyl benzenes, 1,4- dihydroxymethyl -2,5- dimethyl benzenes, 1,4- dihydroxymethyl -2,5- dimethyl benzenes, 1,3- dihydroxies
Methyl -4,6- dimethyl benzenes, 1,3- dihydroxymethyl -2,4- dimethyl benzenes.
4. boron modified phenolic resin according to claim 3, wherein, the dihydroxymethyl dimethylbenzene is 1,3- dihydroxy first
Base -4,6- dimethyl benzenes.
5. boron modified phenolic resin according to claim 2, wherein, the mol ratio of phenol and dihydroxymethyl dimethylbenzene is 1.0：
0.5-0.9。
6. boron modified phenolic resin according to claim 2, wherein, the molal quantity of boric acid is the 3~10% of phenol molal quantity
Between.
7. containing formaldehyde in boron modified phenolic resin according to claim 2, preparing raw material, the mol ratio of formaldehyde and phenol exists
0.05~0.1 scope.
8. boron modified phenolic resin according to claim 1, wherein, the mean molecule quantity of the phenolic resin 800~
1200。
9. preparing the method for any one of the claim 1-6 boron modified phenolic resin, comprise the following steps：
1) phenol and methylol dimethylbenzene is made to carry out condensation reaction in the presence of acid catalyst；
2) after above-mentioned condensation reaction finishes and sloughs water, add boric acid and be further condensed.
10. a kind of friction material, it contains the boron modified phenolic resin described in claim any one of 1-8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1817928A (en) * | 2006-03-09 | 2006-08-16 | 同济大学 | Production of modified phenolic resin with high boron content |
| CN101805435A (en) * | 2010-04-19 | 2010-08-18 | 山东圣泉化工股份有限公司 | Preparation method of boron modified phenolic resin |
| CN103709348A (en) * | 2013-12-25 | 2014-04-09 | 湖南中野高科技特种材料有限公司 | Production method for anti-ablation temperature-resistant phenolic resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817928A (en) * | 2006-03-09 | 2006-08-16 | 同济大学 | Production of modified phenolic resin with high boron content |
| CN101805435A (en) * | 2010-04-19 | 2010-08-18 | 山东圣泉化工股份有限公司 | Preparation method of boron modified phenolic resin |
| CN103709348A (en) * | 2013-12-25 | 2014-04-09 | 湖南中野高科技特种材料有限公司 | Production method for anti-ablation temperature-resistant phenolic resin |
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