CN115124672B - O-cresol formaldehyde resin and preparation method and application thereof - Google Patents
O-cresol formaldehyde resin and preparation method and application thereof Download PDFInfo
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- CN115124672B CN115124672B CN202210769823.5A CN202210769823A CN115124672B CN 115124672 B CN115124672 B CN 115124672B CN 202210769823 A CN202210769823 A CN 202210769823A CN 115124672 B CN115124672 B CN 115124672B
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- formaldehyde resin
- cresol
- cresol formaldehyde
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- sulfate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 65
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims abstract description 56
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 31
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 22
- -1 aldehyde compound Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002783 friction material Substances 0.000 claims abstract description 12
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 15
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 5
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229920006231 aramid fiber Polymers 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 4
- 239000002006 petroleum coke Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052683 pyrite Inorganic materials 0.000 claims description 4
- 239000011028 pyrite Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000010455 vermiculite Substances 0.000 claims description 4
- 229910052902 vermiculite Inorganic materials 0.000 claims description 4
- 235000019354 vermiculite Nutrition 0.000 claims description 4
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 32
- 230000029936 alkylation Effects 0.000 abstract description 7
- 150000001335 aliphatic alkanes Chemical group 0.000 abstract description 4
- 150000002883 o-cresols Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PQBOTZNYFQWRHU-UHFFFAOYSA-N 1,2-dichlorobutane Chemical compound CCC(Cl)CCl PQBOTZNYFQWRHU-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The application discloses an o-cresol formaldehyde resin and a preparation method and application thereof, wherein the preparation method of the o-cresol formaldehyde resin comprises the following reactions sequentially carried out under the action of a sulfate catalyst: carrying out alkylation reaction on o-cresol and dichloroalkane to obtain an intermediate I; and (3) performing polycondensation reaction on the intermediate I and an aldehyde compound to generate the o-cresol formaldehyde resin. According to the application, an alkane chain of dichloroalkane is connected into the middle of two o-cresols through alkylation to obtain an intermediate I, and the intermediate I is polycondensed with formaldehyde to obtain the o-cresol formaldehyde resin, so that the o-cresol formaldehyde resin has good flexibility and stable performance, and has good application in preparing friction materials.
Description
Technical Field
The application relates to the technical field of phenolic resin, in particular to o-cresol formaldehyde resin and a preparation method and application thereof.
Background
The o-cresol formaldehyde resin is a high molecular compound formed by polycondensation of o-cresol and aldehyde compounds under the catalysis of acid, and is easy to form a three-dimensional structure with high crosslinking density. The condensate is rich in phenolic skeleton, has the characteristics of basically unchanged epoxy value, low melt viscosity and the like when the softening point is changed, and has excellent process stability and processing manufacturability.
Currently, the method for synthesizing o-cresol formaldehyde resin includes: the acid step-by-step catalysis method is adopted to synthesize the o-cresol formaldehyde resin with high molecular mass and low molecular mass distribution, but the toughness of the synthesized o-cresol formaldehyde resin is not high, and the whole synthesis step is complex. As another example, patent CN106608957a discloses a synthetic method of polyvinyl acetal modified phenolic resin, which, although successfully toughening the phenolic resin, has a gel risk.
Because the o-cresol formaldehyde resin synthesized by the prior art has the problems of high water absorption, large brittleness, poor mechanical properties and the like of a cured product, the application scene is limited, and the requirements of high-performance composite materials in high and new technical fields such as automobiles, electronics, aerospace, national defense and the like are hardly met.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides o-cresol formaldehyde resin and a preparation method and application thereof.
The preparation method of the o-cresol formaldehyde resin comprises the following steps of:
carrying out alkylation reaction on o-cresol and dichloroalkane to obtain an intermediate I;
and (3) performing polycondensation reaction on the intermediate I and an aldehyde compound to generate the o-cresol formaldehyde resin.
Optionally, the aldehyde compound is at least one of formaldehyde, paraformaldehyde and butyraldehyde.
Optionally, the dichloroalkane is at least one of dichloromethane, 1, 2-dichloroethane, 1-dichloropropane, 1, 2-dichloropropane, 1, 3-dichloropropane and 1, 4-dichlorobutane.
Optionally, the sulfate catalyst is at least one of sodium bisulfate, ferric sulfate, zinc sulfate and calcium sulfate.
Optionally, the molar ratio of the dichloroalkane to the o-cresol is 1.05-1.1:2; preferably 1.05:2.
Optionally, the molar ratio of the aldehyde compound to the o-cresol is 1:1.8-2.
Optionally, the alkylation reaction temperature is 40-80 ℃ and the reaction time is 2-4 h.
Optionally, the temperature of the polycondensation reaction is 90-110 ℃ and the reaction time is 4-6 h.
Optionally, the sulfate catalyst is added in two batches, wherein the added sulfate catalyst for alkylation reaction is 0.2-0.5% of the mass of o-cresol;
the added sulfate catalyst for the polycondensation reaction is 0.2-0.5% of the mass of the o-cresol.
Alternatively, the alkylation reaction and the polycondensation reaction are carried out in the same reaction vessel.
Optionally, the preparation method further comprises: after the alkylation reaction is finished, removing the product acid and the rest dichloroalkane;
after the polycondensation reaction is finished, adding a solvent to dissolve, removing the sulfate catalyst, and then dehydrating and desolventizing to obtain the o-cresol formaldehyde resin.
Optionally, negative pressure (-0.04 Mpa) is used for removing the product acid and the rest dichloroalkane;
optionally, hot water is used to elute the sulfate catalyst at a temperature of 65-90 ℃.
Optionally, the conditions of dehydration and desolventizing are as follows: the temperature is raised to 160 ℃ at normal pressure.
The application also provides the o-cresol formaldehyde resin prepared by the preparation method.
The application also provides application of the o-cresol formaldehyde resin in preparing friction materials.
The application also provides a friction material containing the o-cresol formaldehyde resin, which comprises the following components in percentage by mass:
18% of o-cresol formaldehyde resin, 19% of aramid fiber, 10% of glass fiber, 9% of alumina, 9% of pyrite powder, 9% of graphite, 6% of vermiculite, 4% of petroleum coke powder, 4% of barium sulfate and 12% of molybdenum disulfide.
Compared with the prior art, the application has at least the following technical effects:
(1) According to the application, alkane chains of dichloroalkane are successfully connected into two o-cresol formaldehyde intermediates through alkylation reaction to obtain an intermediate, and the intermediate is polycondensed with formaldehyde to obtain a modified o-cresol formaldehyde resin product, so that the modified o-cresol formaldehyde resin has stable performance and excellent flexibility;
(2) Alkane in dichloro alkane is linked into o-cresol formaldehyde resin in an alkylation mode, so that the problem of gel is prevented;
(3) The method adopts a one-pot method to produce, the alkylation and the polycondensation are both carried out by adopting sulfate catalysts, the reaction is carried out in the same reactor, no special post-treatment is needed, and the production process is simple.
Drawings
FIG. 1 is a flow chart showing a method for producing an orthocresol formaldehyde resin according to the present application.
Detailed Description
The technical scheme of the application is further described below with reference to the specific embodiments, but the application is not limited thereto.
Referring to fig. 1, an embodiment of the present application provides a method for preparing an o-cresol formaldehyde resin, which sequentially performs the following reactions under the action of a sulfate catalyst:
carrying out alkylation reaction on o-cresol and dichloroalkane to obtain an intermediate I;
and (3) performing polycondensation reaction on the intermediate I and an aldehyde compound to generate o-cresol formaldehyde resin.
On one hand, alkane chains are introduced into the structure of the o-cresol formaldehyde resin through alkylation reaction of dichloro alkane and o-cresol, so that the o-cresol formaldehyde resin is modified, the crosslinking density of the o-cresol formaldehyde resin is reduced, and the toughness of the o-cresol formaldehyde resin is improved; on the other hand, the operation steps are simple, and the alkylation conditions are simple.
The o-cresol is melted in advance so as to facilitate the mixing of the dichloroalkane.
The aldehyde compound is at least one of formaldehyde, paraformaldehyde and butyraldehyde. Wherein formaldehyde is in the form of an aqueous formaldehyde solution, for example a 37wt% aqueous formaldehyde solution.
The dichloroalkane is at least one of dichloromethane, 1, 2-dichloroethane, 1-dichloropropane, 1, 2-dichloropropane, 1, 3-dichloropropane and 1, 4-dichlorobutane; preference is given to 1.4-dichlorobutane or 1.3-dichloropropane having a relatively long chain length.
The sulfate catalyst is at least one of sodium bisulfate, ferric sulfate, zinc sulfate and calcium sulfate. The sulfate catalysts used in the alkylation and polycondensation reactions described above are the same or different.
Taking 1, 2-dichloroethane as an example, the alkylation reaction with o-cresol is as follows:
the polycondensation reaction of intermediate I with formaldehyde is as follows:
in the alkylation reaction, the molar ratio of the dichloroalkane to the o-cresol is 1.05-1.1:2, and a small excess of dichloroalkane can promote the full utilization of the o-cresol, so that a large amount of intermediates I are generated, on one hand, the main reaction in the polycondensation reaction is the polycondensation reaction of the intermediates I and formaldehyde, on the other hand, the later dephenolization step is omitted, and the process is simpler.
In the polycondensation reaction, the molar ratio of the aldehyde compound to the o-cresol is 1:1.8-2.
In one embodiment, the alkylation reaction temperature is 40-80 ℃ and the reaction time is 2-4 hours; the temperature of the polycondensation reaction is 90-110 ℃ and the reaction time is 4-6 h.
In one embodiment, the sulfate catalyst is added in two batches, wherein the added sulfate catalyst for alkylation reaction is 0.2-0.5% of the mass of o-cresol; the added sulfate catalyst for polycondensation is 0.2-0.5% of the weight of o-cresol.
In one embodiment, the alkylation and polycondensation reactions are carried out in the same reaction vessel. The method adopts a one-pot method to produce, the alkylation and the polycondensation are both carried out by adopting sulfate catalysts, the reaction is carried out in the same reactor, no special post-treatment is needed, and the production process is simple.
In one embodiment, the preparation method further comprises: after the alkylation reaction is finished, removing the product acid and the rest dichloroalkane; the purpose of this step is to reduce side reactions.
After the polycondensation reaction is finished, adding a solvent for dissolution, removing a sulfate catalyst, and then dehydrating and desolventizing to obtain the o-cresol formaldehyde resin.
Wherein, the conditions for removing the product acid and the rest dichloroalkane are as follows: vacuum degree-0.04 Mpa, temperature 105-125 deg.c.
The solvent is at least one of methyl isobutyl ketone (MIBK), toluene and methanol;
washing the desulphurized catalyst with hot water at 65-90 ℃;
the conditions for dehydration and desolventizing are as follows: the temperature is raised to 160 ℃ at normal pressure.
If the product acid and the rest dichloroalkane are not removed after the alkylation reaction is finished, the side reaction and the subsequent polycondensation reaction products are complex; the process parameters are as follows: the temperature, the vacuum degree, the catalyst consumption, the raw material proportion and the like are required to meet the requirements, if not, the product is undefined, side reactions are increased, and the quality of the final product is affected.
The application also provides the o-cresol formaldehyde resin prepared by the preparation method.
The application also provides application of the o-cresol formaldehyde resin in preparing friction materials.
The application also provides a friction material containing the o-cresol formaldehyde resin, which comprises the following components in percentage by mass:
18% of o-cresol formaldehyde resin, 19% of aramid fiber, 10% of glass fiber, 9% of alumina, 9% of pyrite powder, 9% of graphite, 6% of vermiculite, 4% of petroleum coke powder, 4% of barium sulfate and 12% of molybdenum disulfide.
Example 1
1000kg of preheated and melted o-cresol is added into a high-level metering tank through a special pump, then 1746kg of 1, 2-dichloroethane, 300kg of sodium bisulfate are added into the high-level metering tank, the temperature is raised to 60 ℃ for alkylation reaction for 3 hours, and after the reaction is finished, the products of HCl and dichloroethane are removed under 120 ℃ and the vacuum degree is minus 0.04 Mpa;
adding 236kg of formaldehyde and 200kg of supplementary sodium bisulfate, heating to 100 ℃, carrying out polycondensation reaction for 5 hours, adding 700kg of methyl isobutyl ketone to dissolve resin after the reaction is finished, adding 75 ℃ deionized water, stirring, and washing until sodium bisulfate is absent; then heating to dehydrate and desolventize to 160 ℃ under normal pressure; and discharging and cooling to obtain 1630kg of tan solid-like o-cresol formaldehyde resin.
Example 2
1000kg of preheated and melted o-cresol is added into a high-level metering tank through a special pump, then 1746kg of 1, 2-dichloropropane and 300kg of sodium bisulfate are added into the high-level metering tank, the temperature is raised to 60 ℃ for alkylation reaction for 3 hours, and after the reaction is finished, products HCl and 1, 2-dichloropropane are removed at 115 ℃ and the vacuum degree is-0.04 Mpa;
adding 236kg of formaldehyde and 200kg of supplementary sodium bisulfate, heating to 100 ℃, carrying out polycondensation reaction for 5 hours, adding 700kg of methyl isobutyl ketone to dissolve resin after the reaction is finished, adding 75 ℃ deionized water, stirring, and washing until sodium bisulfate is absent; then heating to dehydrate and desolventize to 160 ℃ under normal pressure; discharging and cooling to obtain 1598kg of a tan solid-like o-cresol formaldehyde resin.
Example 3
1000kg of preheated and melted o-cresol is added into a high-level metering tank through a special pump, then 1755kg of 1, 2-dichlorobutane and 300kg of sodium bisulfate are added into the high-level metering tank, the temperature is raised to 60 ℃ for alkylation reaction for 3 hours, and after the reaction is finished, the products of HCl and 1, 2-dichlorobutane are removed under the vacuum degree of-0.04 Mpa at 110 ℃;
adding 236kg of formaldehyde and 200kg of supplementary sodium bisulfate, heating to 105 ℃, carrying out polycondensation reaction for 4 hours, adding 700kg of methyl isobutyl ketone to dissolve resin after the reaction is finished, adding 75 ℃ deionized water, stirring, and washing until sodium bisulfate is absent; then heating to dehydrate and desolventize to 160 ℃ under normal pressure; and discharging and cooling to obtain 1622kg of tan solid-like o-cresol formaldehyde resin.
Example 4
1000kg of preheated and melted o-cresol is added into a high-level metering tank through a special pump, then 1755kg of 1, 2-dichloroethane is added, 250kg of sodium bisulfate is added, the temperature is raised to 60 ℃ for alkylation reaction for 3 hours, and after the reaction is finished, the products HCl and 1, 2-dichloroethane are removed under the vacuum degree of-0.04 Mpa at 120 ℃;
adding 236kg of formaldehyde and 150kg of supplementary sodium bisulfate, heating to 100 ℃, carrying out polycondensation reaction for 5 hours, adding 700kg of methyl isobutyl ketone to dissolve resin after the reaction is finished, adding 75 ℃ deionized water, stirring, and washing until sodium bisulfate is absent; then heating to dehydrate and desolventize to 160 ℃ under normal pressure; then, the mixture was discharged and cooled to obtain 1537kg of a tan solid-like o-cresol formaldehyde resin.
Comparative example 1
1000kg of preheated and melted o-cresol is added into a high-level metering tank by a special pump, then 236kg of formaldehyde and 200kg of oxalic acid are added into a reaction kettle, the temperature is raised to 100 ℃ and polycondensation reaction is carried out for 5 hours, 700kg of methyl isobutyl ketone is added into dissolved resin after the reaction is finished, 75 ℃ of deionized water is added into the mixture for stirring, and the mixture is poured into a funnel for washing until the mixture is neutral; then the temperature is increased to 160 ℃ for dehydration and desolventizing under normal pressure, the pressure is reduced for dephenolization, the vacuum degree is more than-0.09 Mpa, no feed liquid flows out after the dehydration is carried out for 2 hours at 195 ℃, the product is discharged, and 1063kg of light yellow transparent solid resin is obtained after cooling.
The o-cresol formaldehyde resins prepared in examples 1 to 4 of the present application and comparative example 1 were subjected to the following performance tests, and the test results are shown in table 1:
TABLE 1 o-cresol formaldehyde resin Performance test
| Phenolic resin | Speed aggregation/s | viscosity/P | Free phenol/% | Molecular weight |
| Example 1 | 55 | 1.356 | 0.5 | Mw＝5447 |
| Example 2 | 50 | 1.416 | 0.3 | Mw＝5765 |
| Example 3 | 53 | 1.355 | 0.4 | Mw＝5563 |
| Example 4 | 54 | 1.378 | 0.4 | Mw＝5663 |
| Comparative example 1 | 62 | 1.588 | 1.5 | Mw＝2861 |
The material materials were prepared using the o-cresol formaldehyde resins of examples 1 to 4 and comparative example 1, respectively, and the friction material components thereof were as follows in mass percent: 18% of o-cresol formaldehyde resin, 19% of aramid fiber, 10% of glass fiber, 9% of alumina, 9% of pyrite powder, 9% of graphite, 6% of vermiculite, 4% of petroleum coke powder, 4% of barium sulfate and 12% of molybdenum disulfide. Prepared by the following method:
mixing materials: weighing the raw materials according to the proportion, adding the raw materials into a high-speed mixer, and stirring for 30min to obtain the uniformly dispersed mixed raw materials.
Hot press molding: pouring the uniformly dispersed mixed raw materials into a die, hot-pressing and molding by a hot press at the temperature of 150 ℃ and the pressure of 16MPa, maintaining the pressure for 5min in the hot-pressing process, and opening the die and deflating for 4 times within five minutes before the pressure maintaining.
And (3) heat treatment: and (3) placing the sample wafer subjected to hot press molding into an oven, preserving heat for 12 hours at 160 ℃, performing heat treatment, and cooling to obtain the friction material sample wafer. Taking examples 1 and 2 and comparative examples 1 and 2 under the same conditions, the 4 obtained friction material samples were subjected to constant speed test according to GB5763-2008, and the test results are shown in Table 2.
Table 2 coefficient of friction and wear rate
Generally, the better the resin flexibility, the higher the coefficient of friction of the friction material; the better the heat resistance of the resin, the more stable the friction coefficient of the friction material. As is clear from Table 2, the friction coefficients and stability of examples 1 and 2 of the present application are higher than those of comparative example 1, indicating that the flexibility of the process of the present application using the dichloro alkane type alkylated modified o-cresol formaldehyde resin is higher than that of the unmodified o-cresol formaldehyde resin. In addition, examples 1 and 2 each have a lower abrasion rate than comparative example 1, demonstrating that the method of the present application improves the abrasion resistance of phenolic resins by alkylating and modifying o-cresol resins with dichloroalkanes.
The above examples merely represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the patent. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of the application should be assessed as that of the appended claims.
Claims (9)
1. A preparation method of o-cresol formaldehyde resin is characterized in that under the action of sulfate catalyst, the following reactions are sequentially carried out:
carrying out alkylation reaction on o-cresol and dichloroalkane to obtain an intermediate I;
performing polycondensation reaction on the intermediate I and an aldehyde compound to generate the o-cresol formaldehyde resin;
the mol ratio of the dichloro alkane to the o-cresol is 1.05-1.1:2;
the molar ratio of the aldehyde compound to the o-cresol is 1:1.8-2.
2. The method for producing an o-cresol formaldehyde resin according to claim 1, wherein the aldehyde compound is at least one of formaldehyde, paraformaldehyde and butyraldehyde;
the dichloroalkane is at least one of dichloromethane, 1, 2-dichloroethane, 1-dichloropropane, 1, 2-dichloropropane, 1, 3-dichloropropane and 1, 4-dichlorobutane;
the sulfate catalyst is at least one of sodium bisulfate, ferric sulfate, zinc sulfate and calcium sulfate.
3. The method for producing an o-cresol formaldehyde resin according to claim 1, wherein the alkylation reaction temperature is 40 to 80 ℃ and the reaction time is 2 to 4 hours;
the temperature of the polycondensation reaction is 90-110 ℃ and the reaction time is 4-6 h.
4. The method for producing an o-cresol formaldehyde resin according to claim 1, wherein the sulfate catalyst is added in two batches, wherein the amount of the sulfate catalyst added in the alkylation reaction is 0.2 to 0.5% by mass of the o-cresol;
the added sulfate catalyst for the polycondensation reaction is 0.2-0.5% of the mass of the o-cresol.
5. The method for producing an o-cresol formaldehyde resin according to claim 4, wherein the alkylation reaction and the polycondensation reaction are carried out in the same reaction vessel.
6. The method for producing an o-cresol formaldehyde resin according to claim 5, further comprising: after the alkylation reaction is finished, removing the product acid and the rest dichloroalkane;
after the polycondensation reaction is finished, adding a solvent to dissolve, removing the sulfate catalyst, and then dehydrating and desolventizing to obtain the o-cresol formaldehyde resin.
7. An o-cresol formaldehyde resin produced by the production method according to any one of claims 1 to 6.
8. The use of the o-cresol formaldehyde resin according to claim 7 for the preparation of friction materials.
9. A friction material comprising the o-cresol formaldehyde resin according to claim 7, characterized by comprising the following components in mass percent:
18% of o-cresol formaldehyde resin, 19% of aramid fiber, 10% of glass fiber, 9% of alumina, 9% of pyrite powder, 9% of graphite, 6% of vermiculite, 4% of petroleum coke powder, 4% of barium sulfate and 12% of molybdenum disulfide.
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| US4731423A (en) * | 1986-08-13 | 1988-03-15 | The Dow Chemical Company | Meta-halo-phenolic alkylation products and epoxy systems |
| JPS6377832A (en) * | 1986-09-18 | 1988-04-08 | Nippon Kayaku Co Ltd | Production of dimethylole compound of o-cresol binuclear substance |
| CN106220804A (en) * | 2016-08-12 | 2016-12-14 | 江苏三吉利化工股份有限公司 | A kind of synthetic method of ultra-pure o-cresol formaldehyde epoxy resin |
| CN109306040A (en) * | 2017-07-26 | 2019-02-05 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it |
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| US4731423A (en) * | 1986-08-13 | 1988-03-15 | The Dow Chemical Company | Meta-halo-phenolic alkylation products and epoxy systems |
| JPS6377832A (en) * | 1986-09-18 | 1988-04-08 | Nippon Kayaku Co Ltd | Production of dimethylole compound of o-cresol binuclear substance |
| CN106220804A (en) * | 2016-08-12 | 2016-12-14 | 江苏三吉利化工股份有限公司 | A kind of synthetic method of ultra-pure o-cresol formaldehyde epoxy resin |
| CN109306040A (en) * | 2017-07-26 | 2019-02-05 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it |
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Denomination of invention: Ortho formaldehyde resin and its preparation method and application Granted publication date: 20231205 Pledgee: China Co. truction Bank Corp Fuyang Yingdong sub branch Pledgor: Hangmo technology new materials (Fuyang) Co.,Ltd. Registration number: Y2024980037393 |