CN115124672A - 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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- CN115124672A CN115124672A CN202210769823.5A CN202210769823A CN115124672A CN 115124672 A CN115124672 A CN 115124672A CN 202210769823 A CN202210769823 A CN 202210769823A CN 115124672 A CN115124672 A CN 115124672A
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- cresol
- formaldehyde resin
- reaction
- cresol formaldehyde
- sulfate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 56
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- -1 aldehyde compound Chemical class 0.000 claims abstract description 16
- 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 13
- 239000002783 friction material Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 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
- 239000002904 solvent Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 239000002253 acid Substances 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
- 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
- 230000009471 action Effects 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
- 230000029936 alkylation Effects 0.000 abstract description 8
- 150000001335 aliphatic alkanes Chemical group 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 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
- 238000001816 cooling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-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
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- PQBOTZNYFQWRHU-UHFFFAOYSA-N 1,2-dichlorobutane Chemical compound CCC(Cl)CCl PQBOTZNYFQWRHU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000007731 hot pressing 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
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change 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
- 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
- 230000007935 neutral effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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- 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 as well as a preparation method and an application thereof, wherein the preparation method of the o-cresol formaldehyde resin comprises the following reaction steps of: carrying out alkylation reaction on o-cresol and dichloroalkane to obtain an intermediate I; and carrying out polycondensation reaction on the intermediate I and an aldehyde compound to generate the o-cresol formaldehyde resin. According to the preparation method, firstly, an alkane chain of dichloroalkane is connected between two o-cresol by alkylation to obtain an intermediate I, and the intermediate I is subjected to polycondensation with formaldehyde to obtain o-cresol formaldehyde resin, wherein the o-cresol formaldehyde resin has the advantages of good flexibility and stable performance, and has good application in preparation of 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 condensation polymerization of o-cresol and aldehyde compounds under acid catalysis, and a three-dimensional structure with high crosslinking density is easy to form. The condensate is rich in phenolic aldehyde skeleton, has the characteristics of basically no change of epoxy value when the softening point is changed, low melt viscosity and the like, and shows excellent process stability and processing manufacturability.
At present, the method for synthesizing the o-cresol formaldehyde resin comprises the following steps: the o-cresol formaldehyde resin with high molecular mass and low molecular mass distribution is synthesized by adopting an acid stepwise catalysis method, but the synthesized o-cresol formaldehyde resin has low toughness and the whole synthesis step is complicated. For another example, patent CN106608957A discloses a method for synthesizing a polyvinyl acetal modified phenolic resin, which, although successfully toughening phenolic resin, has a risk of gelation.
Because the o-cresol formaldehyde resin synthesized by the prior art has the problems of high water absorption of a condensate, high brittleness, poor mechanical property and the like, the application scene is limited, and the requirements of high and new technical fields of automobiles, electronics, aerospace, national defense and the like on high-performance composite materials are difficult to meet.
Disclosure of Invention
Aiming at the problems of the prior art, the application provides an o-cresol formaldehyde resin and a preparation method and application thereof.
The preparation method of the o-cresol formaldehyde resin comprises the following reaction sequentially under the action of a sulfate catalyst:
carrying out alkylation reaction on o-cresol and dichloroalkane to obtain an intermediate I;
and carrying out 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 o-cresol is 1: 1.8-2.
Optionally, the temperature of the alkylation reaction 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 mass of the sulfate catalyst added in the alkylation reaction is 0.2-0.5% of that of o-cresol;
the mass of the sulfate catalyst added in the polycondensation reaction is 0.2-0.5% of that of o-cresol.
Optionally, 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 product acid and residual dichloroalkane;
and after the polycondensation reaction is finished, adding a solvent for dissolving, removing the sulfate catalyst, and then dehydrating and removing the solvent to obtain the o-cresol formaldehyde resin.
Optionally, removing the product acid and the residual dichloroalkane under negative pressure (-0.04 Mpa);
optionally, hot water is used for eluting the sulfate catalyst, and the temperature is 65-90 ℃.
Optionally, the conditions of dehydration and solvent removal are as follows: the temperature is raised to 160 ℃ under normal pressure.
The application also provides the o-cresol formaldehyde resin prepared by the preparation method.
The application also provides an application of the o-cresol formaldehyde resin in preparing a friction material.
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 method has the following technical effects:
(1) the method comprises the steps of successfully connecting an alkane chain of dichloroalkane into the middle of two o-cresol-formaldehyde through alkylation reaction to obtain an intermediate, and performing polycondensation on the intermediate and formaldehyde to obtain a modified o-cresol-formaldehyde resin product, wherein the product has stable performance and the modified o-cresol-formaldehyde resin has excellent flexibility;
(2) the alkylation mode is adopted to link the alkane in the dichloroalkane to the o-cresol formaldehyde resin, so that the problem of gelation is prevented;
(3) the production is carried out by adopting a one-pot method, the alkylation and polycondensation reactions both adopt a sulfate catalyst, the reaction is carried out in the same reactor, special post-treatment is not required, and the production process is simple.
Drawings
FIG. 1 is a flow chart of the preparation method of o-cresol formaldehyde resin in the present application.
Detailed Description
The technical solutions described in the present application will be further described with reference to the following embodiments, but the present 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 carrying out polycondensation reaction on the intermediate I and an aldehyde compound to generate the o-cresol formaldehyde resin.
On one hand, an alkane chain is introduced into an o-cresol formaldehyde resin structure through alkylation reaction of dichloroalkane and o-cresol, so that the o-cresol formaldehyde resin is modified, the cross-linking density is reduced, and the toughness is improved; on the other hand, the operation steps are simple, and the alkylation conditions are simple.
The above-mentioned o-cresol is previously melted to facilitate mixing of the dichloroalkanes.
The aldehyde compound is at least one of formaldehyde, paraformaldehyde and butyraldehyde. Wherein the formaldehyde is in the form of an aqueous formaldehyde solution, such as a 37 wt% 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; preferably 1.4-dichlorobutane or 1.3-dichloropropane, which have 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 above alkylation and polycondensation reactions may be the same or different.
The alkylation reaction with o-cresol, for example 1, 2-dichloroethane, is as follows:
the polycondensation reaction of intermediate I and formaldehyde is as follows:
in the alkylation reaction, the molar ratio of dichloroalkane to o-cresol is 1.05-1.1: 2, and slight excess dichloroalkane can promote full utilization of o-cresol, so that a large amount of intermediate I is generated, on one hand, the main reaction in the polycondensation reaction is the polycondensation reaction of the intermediate 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 temperature of the alkylation reaction is 40-80 ℃, and the reaction time is 2-4 h; 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 mass of the sulfate catalyst added in the alkylation reaction is 0.2-0.5% of that of o-cresol; the mass of the sulfate catalyst added in the polycondensation reaction is 0.2-0.5% of that of o-cresol.
In one embodiment, the alkylation reaction and the polycondensation reaction are conducted in the same reaction vessel. The production is carried out by adopting a one-pot method, the alkylation and polycondensation reactions both adopt a sulfate catalyst, the reaction is carried out in the same reactor, special post-treatment is not required, and the production process is simple.
In one embodiment, the method further comprises: after the alkylation reaction is finished, removing product acid and residual dichloroalkane; the purpose of this step is to reduce side reactions.
And after the polycondensation reaction is finished, adding a solvent for dissolving, removing the sulfate catalyst, and then dehydrating and removing the solvent to obtain the o-cresol formaldehyde resin.
Wherein the conditions for removing the product acid and the residual dichloroalkane are as follows: the vacuum degree is-0.04 Mpa, and the temperature is 105-125 ℃.
The solvent is at least one of methyl isobutyl ketone (MIBK), toluene and methanol;
eluting the sulfate catalyst by hot water at the temperature of 65-90 ℃;
the conditions of dehydration and solvent removal are as follows: the temperature is raised to 160 ℃ under normal pressure.
If the product acid and the residual dichloroalkane are not removed after the alkylation reaction is finished, the side reaction and the subsequent polycondensation reaction products are complicated; the technological parameters are as follows: the temperature, the vacuum degree, the catalyst dosage, the raw material proportion and the like need to meet the requirements, and if the requirements do not meet the requirements, the product is not clear, side reactions are increased, and the quality of the final product is influenced.
The application also provides the o-cresol formaldehyde resin prepared by the preparation method.
The application also provides an application of the o-cresol formaldehyde resin in preparing a friction material.
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
Adding 1000kg of preheated and melted o-cresol into a high-level metering tank through a special pump, metering into a reaction kettle, then adding 1746kg of 1, 2-dichloroethane and 300kg of sodium bisulfate, heating to 60 ℃, carrying out alkylation reaction for 3 hours, and after the reaction is finished, removing HCl and dichloroethane as products under the vacuum degree of-0.04 Mpa at 120 ℃;
adding 236kg of formaldehyde and 200kg of supplemented sodium bisulfate, heating to 100 ℃, carrying out polycondensation reaction for 5h, adding 700kg of methyl isobutyl ketone to dissolve resin after the reaction is finished, adding deionized water at 75 ℃, stirring, and washing with water until no sodium bisulfate exists; then heating to dehydrate and desolventize to 160 ℃ under normal pressure; and discharging and cooling to obtain 1630kg of tawny solid o-cresol formaldehyde resin.
Example 2
Adding 1000kg of preheated and melted o-cresol into a high-position metering tank through a special pump, metering into a reaction kettle, then adding 1746kg of 1, 2-dichloropropane and 300kg of sodium bisulfate, heating to 60 ℃, carrying out alkylation reaction for 3 hours, and after the reaction is finished, removing HCl and 1, 2-dichloropropane which are products at 115 ℃ and the vacuum degree of-0.04 Mpa;
adding 236kg of formaldehyde and 200kg of supplemented sodium bisulfate, heating to 100 ℃, carrying out polycondensation reaction for 5h, adding 700kg of methyl isobutyl ketone to dissolve resin after the reaction is finished, adding deionized water at 75 ℃, stirring, and washing with water until no sodium bisulfate exists; then heating to dehydrate and desolventize to 160 ℃ under normal pressure; discharging, cooling to obtain 1598kg of tawny solid o-cresol formaldehyde resin.
Example 3
Adding 1000kg of preheated and melted o-cresol into a high-level metering tank through a special pump, metering into a reaction kettle, then adding 1755kg of 1, 2-dichlorobutane and 300kg of sodium bisulfate, heating to 60 ℃, carrying out alkylation reaction for 3 hours, and removing HCl and 1, 2-dichlorobutane from the product at 110 ℃ and the vacuum degree of-0.04 Mpa after the reaction is finished;
adding 236kg of formaldehyde and 200kg of supplemented sodium bisulfate, heating to 105 ℃, carrying out polycondensation reaction for 4h, adding 700kg of methyl isobutyl ketone to dissolve resin after the reaction is finished, adding deionized water at 75 ℃, stirring, and washing until no sodium bisulfate exists; then heating to dehydrate and desolventize to 160 ℃ under normal pressure; discharging, cooling to obtain 1622kg of tawny solid o-cresol formaldehyde resin.
Example 4
Adding 1000kg of preheated and melted o-cresol into a high-order metering tank through a special pump, metering into a reaction kettle, then adding 1755kg of 1, 2-dichloroethane and 250kg of sodium bisulfate, heating to 60 ℃, carrying out alkylation reaction for 3 hours, and removing HCl and 1, 2-dichloroethane as products at 120 ℃ and a vacuum degree of-0.04 Mpa after the reaction is finished;
adding 236kg of formaldehyde and 150kg of supplemented sodium bisulfate, heating to 100 ℃, carrying out polycondensation reaction for 5h, adding 700kg of methyl isobutyl ketone to dissolve resin after the reaction is finished, adding deionized water at 75 ℃, stirring, and washing with water until no sodium bisulfate exists; then heating to dehydrate and desolventize to 160 ℃ under normal pressure; discharging, cooling to obtain 1537kg of tawny solid o-cresol formaldehyde resin.
Comparative example 1
Adding 1000kg of preheated and melted o-cresol into a high-level metering tank by using a special pump, metering and adding into a reaction kettle, then adding 236kg of formaldehyde and 200kg of oxalic acid, heating to 100 ℃, carrying out polycondensation for 5 hours, adding 700kg of methyl isobutyl ketone dissolved resin after the reaction is finished, adding 75 ℃ of deionized water, stirring, pouring into a funnel, and washing to be neutral; and then heating to remove the solvent to 160 ℃ under normal pressure, removing phenol under reduced pressure, keeping the vacuum degree above-0.09 Mpa, removing to 195 ℃ for 2 hours, stopping the outflow of feed liquid, discharging the product, and cooling to obtain 1063kg of light yellow transparent solid resin.
The o-cresol formaldehyde resins prepared in examples 1 to 4 and comparative example 1 of the present application were subjected to the following performance test, and the test results are shown in table 1:
TABLE 1 Performance testing of O-cresol formaldehyde resins
| Phenolic resin | Speed of convergence/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 are prepared by respectively using the o-cresol formaldehyde resins of the embodiments 1-4 and the comparative example 1, and the friction material 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. The preparation method comprises the following steps:
mixing materials: weighing the raw materials according to the proportion, adding into a high-speed mixer, and stirring for 30min to obtain 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 under the pressure of 16MPa, keeping the pressure for 5min in the hot-pressing process, and opening the die to deflate for 4 times within five minutes before keeping the pressure.
And (3) heat treatment: and (3) putting the sample wafer subjected to hot press molding into an oven, carrying out heat treatment for 12h at the temperature of 160 ℃, and cooling to obtain the friction material sample wafer. Taking examples 1 and 2 and comparative examples 1 and 2 under the same conditions, samples of the 4 obtained friction materials were subjected to constant speed test in accordance with GB5763-2008, and the test results are shown in Table 2.
TABLE 2 Friction coefficient and wear Rate
Generally, the better the resin flexibility, the higher the coefficient of friction of the friction material; the better the resin is resistant to heat, the more stable the coefficient of friction of the friction material. As can be seen from Table 2, the friction coefficient and stability of examples 1 and 2 are higher than those of comparative example 1, which shows that the flexibility of the method for alkylation modification of o-cresol formaldehyde resin by using dichloroalkane is higher than that of the unmodified o-cresol formaldehyde resin. In addition, the wear rates of examples 1 and 2 are lower than those of comparative example 1, which shows that the method for modifying the o-cresol formaldehyde resin by alkylation of the dichloroalkane improves the wear resistance of the phenolic resin.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present application shall be subject to the appended claims.
Claims (10)
1. The preparation method of the o-cresol formaldehyde resin is characterized by sequentially carrying out 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 carrying out polycondensation reaction on the intermediate I and an aldehyde compound to generate the o-cresol formaldehyde resin.
2. The method for preparing o-cresol formaldehyde resin according to claim 1, wherein the aldehyde compound is at least one of formaldehyde, paraformaldehyde and butyraldehyde;
the dichloro alkane 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 preparing the o-cresol formaldehyde resin according to claim 1, wherein the molar ratio of the dichloroalkane to the o-cresol is 1.05-1.1: 2;
the molar ratio of the aldehyde compound to o-cresol is 1: 1.8-2.
4. The preparation method of the o-cresol formaldehyde resin according to claim 1, wherein the alkylation reaction temperature is 40-80 ℃, and the reaction time is 2-4 h;
the temperature of the polycondensation reaction is 90-110 ℃, and the reaction time is 4-6 h.
5. The method for preparing the o-cresol formaldehyde resin according to claim 1, wherein the sulfate catalyst is added in two batches, wherein the sulfate catalyst added in the alkylation reaction accounts for 0.2-0.5% of the mass of o-cresol;
the mass of the sulfate catalyst added in the polycondensation reaction is 0.2-0.5% of that of o-cresol.
6. The method of claim 5, wherein the alkylation reaction and the polycondensation reaction are performed in the same reaction vessel.
7. The method for preparing the o-cresol formaldehyde resin according to claim 6, further comprising: after the alkylation reaction is finished, removing product acid and residual dichloroalkane;
and after the polycondensation reaction is finished, adding a solvent for dissolving, removing the sulfate catalyst, and then dehydrating and removing the solvent to obtain the o-cresol formaldehyde resin.
8. The o-cresol formaldehyde resin prepared by the preparation method of any one of claims 1 to 7.
9. Use of the o-cresol formaldehyde resin according to claim 8 for the preparation of a friction material.
10. A friction material comprising the orthocresol formaldehyde resin as claimed in claim 8, comprising the following components in percent 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117299096A (en) * | 2023-11-30 | 2023-12-29 | 明硕环境科技集团股份有限公司 | Iron oxyhydroxide desulfurizing agent based on resin substrate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2022
- 2022-06-30 CN CN202210769823.5A patent/CN115124672B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 乙东旭等: "高邻位邻甲酚醛树脂的制备及表征", 《塑料工业》, vol. 51, no. 2, pages 23 - 30 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117299096A (en) * | 2023-11-30 | 2023-12-29 | 明硕环境科技集团股份有限公司 | Iron oxyhydroxide desulfurizing agent based on resin substrate and preparation method thereof |
| CN117299096B (en) * | 2023-11-30 | 2024-03-15 | 明硕环境科技集团股份有限公司 | Iron oxyhydroxide desulfurizing agent based on resin substrate and preparation method thereof |
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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 |