CN115141330B - Novel alkyl phenol-formaldehyde vulcanized resin, and preparation method and composition thereof - Google Patents
Novel alkyl phenol-formaldehyde vulcanized resin, and preparation method and composition thereof Download PDFInfo
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- CN115141330B CN115141330B CN202210987086.6A CN202210987086A CN115141330B CN 115141330 B CN115141330 B CN 115141330B CN 202210987086 A CN202210987086 A CN 202210987086A CN 115141330 B CN115141330 B CN 115141330B
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- 229920005989 resin Polymers 0.000 title claims abstract description 63
- 239000011347 resin Substances 0.000 title claims abstract description 63
- -1 alkyl phenol-formaldehyde Chemical compound 0.000 title claims abstract description 19
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 title claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000002351 wastewater Substances 0.000 abstract description 8
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 11
- 238000004821 distillation Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzylether Substances C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08G8/28—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The application discloses a novel alkyl phenol-formaldehyde vulcanized resin, a preparation method and a composition thereof, wherein the preparation method comprises the following steps: s1, adding alkylphenol and an alkaline catalyst into a reaction vessel; s2, after heating, adding solid formaldehyde, stirring and reacting until no obvious turbidity matters exist, and continuing stirring; s3, adding a halogenated hydrocarbon modifier, and stirring for reaction; s4, heating and distilling at normal pressure, and then distilling under reduced pressure to remove water generated by the reaction, thereby obtaining the alkyl phenol-formaldehyde vulcanized resin. The preparation method provided by the application is simple and feasible, low in cost, little in generated wastewater, small in environmental pollution, and the prepared alkyl phenol-formaldehyde vulcanized resin has improved flex cracking property.
Description
Technical Field
The application belongs to the field of fine chemical engineering, and relates to a novel alkyl phenol-formaldehyde vulcanized resin, a preparation method and a composition thereof.
Background
Butyl rubber has unique excellent performances of air tightness, dielectric property, oil resistance, oxygen resistance, ozone resistance, acid and alkali resistance and the like, and has wide application. Butyl rubber is a low unsaturation rubber with only a small number of double bonds in the molecule, which is typically crosslinked or vulcanized by one of three basic methods, with sulfur, para-quinone dioxime, and alkyl phenol-formaldehyde resins. The vulcanization with alkyl phenol resin has many advantages, and is mainly characterized by excellent thermal aging resistance and chemical stability.
There are many methods for preparing the vulcanized resin, such as using NaOH as a catalyst, neutralizing and washing with water, and distilling to remove water to obtain the resin. Hexamethylene tetramine is used as a catalyst, and the synthesized vulcanized resin has lower hydroxymethyl group, but has poorer vulcanization performance. The diamine modified method is adopted to prepare the novel vulcanized resin, but the method still adopts the traditional base catalysis, the neutralization and the water washing are adopted, and the preparation mode of the product is obtained through distillation. And the dibenzyl ether bridge generated in the post-treatment process is reduced by adopting a flash evaporation process after resin is obtained by step polymerization, neutralized and washed, so that the high-activity and high-hydroxymethyl resin is produced. All the methods can generate a large amount of water washing wastewater, and the pollution problem is serious.
The organic base catalytic reaction is adopted, and the water washing step is avoided by adopting a toluene extraction mode; and the high-performance vulcanized resin is obtained by adopting the technologies of neutralization toluene extraction, stepwise reaction and flash evaporation, the extraction solves the problem of part of wastewater, but the amount of the generated wastewater is still larger.
In the prior art, a great deal of wastewater is generated, so that serious environmental pollution is caused, and therefore, a new preparation method for preparing the alkyl vulcanized phenolic resin needs to be developed, the generation amount of process wastewater is reduced, and meanwhile, the prepared alkyl phenolic vulcanized resin also has good mechanical property and processing property.
Disclosure of Invention
In order to overcome the defects in the prior art, the application provides a novel alkyl phenol-formaldehyde vulcanized resin and a preparation method thereof, and provides a flexible chain modified vulcanized resin and a preparation method thereof.
The method is realized by the following technical scheme:
a novel alkylphenol-formaldehyde-cured resin has the following structural formula:
wherein R is 1 Is an aliphatic long chain having a carbon number of from 4 to 20, preferably 4 or 8,R 2、 R 3 Each independently is one or more of an aliphatic long chain or a polyether long chain, the aliphatic long chain or the polyether long chain has a carbon number of 4-20, n, m is a natural number of 0-6, preferably 1-4.
Further, the novel alkylphenol-based cured resin is obtained by the following reaction formula:
wherein X is 1 R 2 X 2 、X 1 R 3 Is halogenated hydrocarbon, X 1 、X 2 Each independently is one of Br or Cl, R 2 、R 3 Each independently is an aliphatic long chain or a polyether long chain having 4 to 20 carbon atoms, n, m is a natural number of 0 to 6, preferably 1 to 4.
The application also provides a preparation method of the novel alkyl phenol formaldehyde vulcanized resin, which comprises the following steps:
s1: adding alkylphenol and a basic catalyst to a reaction vessel;
s2: after heating, adding solid formaldehyde in batches, stirring and reacting until no obvious turbidity matters exist, and continuously stirring for 1-3 hours, preferably 2 hours;
s3: adding a halogenated hydrocarbon modifier, and stirring for reaction;
s4: and (3) heating and distilling to 140-150 ℃ under normal pressure, and then distilling under reduced pressure to remove a small amount of water generated by the reaction, thereby obtaining the alkyl phenol-formaldehyde vulcanized resin. If the distillation temperature is lower than 140 ℃, the softening point of the alkyl phenol-formaldehyde vulcanized resin is not in accordance with the requirement, and the performance of the alkyl phenol-formaldehyde vulcanized resin is further affected; if the distillation temperature is higher than 150 ℃, the mechanical properties and processability of the alkylphenol-formaldehyde-cured resin are affected.
Further, the alkylphenol is one or more of p-tert-octylphenol, p-tert-butylphenol or dodecylphenol.
Further, the alkaline catalyst is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, diethylamine or triethylamine.
Further, the amount of the basic catalyst is 0.2 to 3% by mass, preferably 0.3 to 1.1% by mass, of the alkylphenol.
Further, in step S2, the ratio of the solid formaldehyde to the alkylphenol in step S1 is (1.5-2.1): 1, preferably (1.8-2.0): 1. the dosage ratio of solid formaldehyde to alkylphenol is higher than 2.1:1, excessive solid formaldehyde residue can cause severe resin scorching; the dosage ratio of solid formaldehyde to alkylphenol is less than 1.5:1, the resin has a small amount of hydroxymethyl groups and a poor softening point, resulting in poor resin properties and poor physical properties.
Further, in step S2, the temperature is raised to 80-90 ℃, preferably 80 ℃, and solid formaldehyde is added in batches. The temperature is controlled within the range of 80-90 ℃ to facilitate the reaction to be complete.
Specifically, in step S3, the structural formula of the halogenated hydrocarbon modifier is X 1 R 2 X 2 Or X 1 R 3 Wherein X is 1 、X 2 Each independently is one of Br or Cl, R 2、 R 3 Each independently is an aliphatic long chain or a polyether long chain having 4 to 20 carbon atoms.
Further, in step S3, the halogenated hydrocarbon modifier X 1 R 2 X 2 The molar amount of the halogenated hydrocarbon modifier X is 0.5 to 0.6 times that of the alkaline catalyst in the step S1 1 R 3 The molar amount of the catalyst is 1.0 to 1.2 times that of the alkaline catalyst in the step S1; the slightly excessive halogenated hydrocarbon modifier can completely react the alkaline catalyst without affecting the performance of the product.
Further, in step S3, the stirring reaction time is 1 to 3 hours, preferably 1 hour. Too short stirring time results in a low softening point of the resin; if the stirring time is too long, the hydroxymethyl content in the resin is small, and if the stirring time is too long or too short, the physical properties and scorch of the resin are adversely affected.
Specifically, in step S4, the reduced pressure distillation temperature is 140-150 ℃, the reduced pressure distillation time is 30-60min, the reduced pressure distillation pressure is-0.07-0.09 Mpa, the reduced pressure distillation temperature is 145 ℃, the reduced pressure distillation time is 40min, and the distillation pressure is-0.09 Mpa.
The application also provides a composition comprising the novel alkyl phenol-formaldehyde cured resin.
Compared with the prior art, the application has the following beneficial effects:
1. the application adopts solid formaldehyde as a reactant, uses alkali catalysis and a flexible chain modification method to neutralize alkali, does not use the steps of acid neutralization and water washing in the preparation process, introduces flexible chains into vulcanized resin while greatly reducing the generation of wastewater, and improves the flex cracking performance of rubber; 2. the preparation method provided by the application is simple and feasible, low in cost and small in environmental pollution.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a preparation method provided by the application;
FIG. 2 is a hydrogen nuclear magnetic resonance spectrum of example 2;
FIG. 3 is an infrared spectrum of example 2;
FIG. 4 is a hydrogen nuclear magnetic resonance spectrum of example 3;
fig. 5 is an infrared spectrum of example 3.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
S1, putting 206g of p-tert-octylphenol and 2g of liquid alkali solution (aqueous solution with 32% of sodium hydroxide content) into a 1000mL four-necked flask with a stirrer, a thermometer and a condenser;
s2: heating to completely melt the p-tert-octylphenol, starting stirring, heating to 80 ℃, adding 60g of solid formaldehyde in batches within 60 minutes, stirring at 80 ℃ for reaction until no obvious white turbidity matters exist, and continuing stirring for 2 hours;
s3: 1.1g of 1, 4-dichlorobutane was added and stirred for 40min;
s4: and (3) distilling at normal pressure to 145 ℃ to remove water, vacuumizing to-0.09 Mpa, maintaining at 140 ℃ and-0.09 Mpa for 30min, and discharging to obtain the alkyl phenolic vulcanized resin, wherein the softening point of the resin is 92.3 ℃ and the hydroxymethyl content is 9.7%.
Examples 2 to 9
Examples 2-9 are similar to example 1 with specific reactant amounts and reaction conditions shown in Table 1.
Table 1.
The softening point and the hydroxymethyl content of the resin can influence the performance of the resin, the softening point of the finally prepared alkyl phenol-formaldehyde vulcanized resin is preferably 85-110 ℃, and if the softening point of the alkyl phenol-formaldehyde vulcanized resin is too low, the polymerization degree of the resin is too low, the resin is not easy to store and the physical property is poor; if the softening point of the alkylphenol-type vulcanized resin is too high, the dispersibility thereof is poor, and the performance and use thereof are also affected.
The hydroxymethyl content represents hydroxymethyl and active ether bond, the hydroxymethyl is a functional group, the hydroxymethyl is utilized to vulcanize the resin in the reaction, and if the hydroxymethyl content is too low, the vulcanization function can not be completely satisfied.
The resin structure obtained in example 2 is as follows:
FIG. 2 is a hydrogen nuclear magnetic resonance spectrum of example 2, wherein a, b, c are characteristic peaks of p-tert-octyl phenol substituent-p-tert-octyl phenol substituent of the raw material used; d is the peak of p-tert-octylphenol benzene ring; e is the methylene peak generated by polymerization of p-tert-octylphenol; f is the peak position of the p-tert-octylphenol hydroxyl and ether bond generated by polymerization, and the positions are overlapped; g is 3.55ppm, and a peak of 1, 6-dichlorohexane modified alkyl ether bond attached to phenolic hydroxyl group appears. Fig. 3 is an infrared spectrum of example 2.
The resin structure obtained in example 3 is as follows:
fig. 4 is a hydrogen nuclear magnetic resonance spectrum of example 3, and referring to fig. 2, the basic peak positions in fig. 4 are not marked. A in fig. 4 shows that a multiple ether peak of dichloro-triethyl ether modified bond to phenolic hydroxyl group appears at 3.6-3.8 ppm. FIG. 5 is an infrared spectrum of example 3, 1050cm of FIG. 5 -1 An obvious ether bond peak resulted from the modification of the dichloro-triethyl ether appears.
Comparative example 1
S1: 206.2g of p-tert-octylphenol and 6g of aqueous alkali solution (aqueous solution having a sodium hydroxide content of 32%) were charged into a 1000mL four-necked flask equipped with a stirrer, a thermometer and a condenser;
s2: heating to completely melt p-tert-octylphenol, stirring, heating to 80deg.C, dropwise adding 166g of liquid formaldehyde (formaldehyde content of 37%) in 20 min, reacting at 80deg.C for 2 hr, neutralizing with acid to pH=6-7, standing for 40min for layering, and separating upper water layer; the resin layer of the lower layer is washed twice by water;
s3: distilling at normal pressure to 135 deg.C, vacuumizing to-0.095 Mpa, and maintaining at 135 deg.C and-0.095 Mpa for 30min to obtain vulcanized resin with softening point of 90.2 deg.C and hydroxymethyl content of 10%.
Performance testing
The vulcanized resins obtained in examples 1 to 9 and comparative example 1 were each added to a rubber composition for performance test, and the formulation of the rubber composition is shown in Table 2.
Table 2.
| Sequence number | Name of the name | Parts by mass (portions) |
| 1 | Butyl rubber (IIR) | 95 |
| 2 | Carbon black (N330) | 32 |
| 3 | Carbon black (N220) | 30 |
| 4 | Castor oil | 5.5 |
| 5 | Paraffin 9332F | 2 |
| 6 | Zinc oxide | 5 |
| 7 | Stearic acid | 1 |
| 8 | Comparative example 1 or resins produced in any of examples 1-9 | 10 |
| 9 | Neoprene glue A-90 | 5 |
In the first step, the rubber components are mixed by a Farrel internal mixer at about 150 ℃ to prepare master batch, and the rubber discharging temperature is controlled at 165-170 ℃.
In the second step, the vulcanized resin of comparative example 1 or any one of examples 1 to 9 shown in Table 2 and neoprene A-90 were added to the mixture at 90 to 100 ℃. Then, the vulcanization by a thiometer, the shape and the optimum vulcanization degree were measured to evaluate the mechanical properties, and the test data of the modified vulcanized rubber composition are shown in tables 3, 4 and 5.
Wherein tensile properties were tested using GB/T528-2009; the hardness is tested by GB/T531.1-2008; the vulcanization performance is that a high-iron sulfur transformer is adopted, and the reference is that the standard is adopted: GB/T16584-1996 and GB/T1233-2008 standards, measured at 150℃in an arc of 1℃and 1.67 Hz. In an oscillating disc thiorheometer, a sizing material sample is subjected to an oscillating shearing force with constant amplitude, and the torque of an oscillating disc embedded in the sizing material sample at the vulcanization temperature is measured; the vulcanization conditions used: 180 ℃ x 35min, tested in accordance with standard ASTM D1871-2004; the flex crack test was performed using GB/T13934-2006.
TABLE 3 test results
Table 4.
TABLE 5 results of Flex crack test
Comparing the above test results, it is known that the alkyl phenol-formaldehyde cured resins provided in examples 1 to 9 are comparable to or even better than comparative example 1 in terms of aging resistance and tensile properties, but the resins of examples 1 to 9 are significantly better in terms of flex cracking properties than comparative example 1, since part of the flexible long chain is incorporated into the resin, improving the flexibility of the resin.
In summary, the application uses solid formaldehyde and alkali catalysis, and uses a flexible chain modification method to neutralize alkali, the preparation method does not involve the processes of acid neutralization and water washing, the flexible chain is introduced into the vulcanized resin while greatly reducing the generation of wastewater, and the flex cracking performance of rubber is improved.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.
Claims (10)
1. The preparation method of the alkyl phenol-formaldehyde vulcanized resin is characterized by comprising the following steps of:
s1: adding alkylphenol and a basic catalyst to a reaction vessel;
s2: after heating, adding solid formaldehyde, stirring and reacting until no obvious turbidity matters exist, and continuing stirring;
s3: adding a halogenated hydrocarbon modifier for stirring reaction, wherein the structural formula of the halogenated hydrocarbon modifier is X 1 R 2 X 2 Or X 1 R 3 Wherein X is 1 、X 2 Each independently is one of Br or Cl, R 2 、R 3 Each independently is an aliphatic long chain or a polyether long chain having 4 to 20 carbon atoms;
s4: heating and distilling at 145-150 ℃ under normal pressure, and then distilling under reduced pressure to remove water generated by the reaction to obtain alkyl phenolic aldehyde vulcanized resin;
in the step S3, the halogenated hydrocarbon modifier X 1 R 2 X 2 The molar amount of the halogenated hydrocarbon modifier X is 0.5 to 0.6 times that of the alkaline catalyst in the step S1 1 R 3 The molar amount of the catalyst is 1.0 to 1.2 times that of the alkaline catalyst in the step S1;
in the step S2, the molar ratio of the solid formaldehyde to the alkylphenol in the step S1 is (1.5-2.1): 1.
2. the method for producing an alkylphenol-based cured resin according to claim 1, wherein the alkylphenol is one or more of p-tert-octylphenol, p-tert-butylphenol and dodecylphenol.
3. The method for preparing an alkyl phenol formaldehyde resin according to claim 1, wherein the basic catalyst is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, diethylamine and triethylamine.
4. The method for preparing alkylphenol-based vulcanized resin according to claim 1, wherein the amount of the basic catalyst is 0.2-3% by mass of the alkylphenol
5. The method for producing an alkylphenol-based vulcanized resin according to claim 1, wherein the basic catalyst is used in an amount of 0.3 to 1.1% by mass of the alkylphenol.
6. The method for producing an alkylphenol-type vulcanized resin according to claim 1, wherein in the step S2, the molar ratio of the solid formaldehyde to the alkylphenol in the step S1 is (1.8-2.0): 1.
7. a process for the preparation of an alkylphenol-type curable resin according to claim 3, wherein in step S2, the temperature is raised to 80 to 90 ℃.
8. The process for producing an alkylphenol-type vulcanized resin as set forth in claim 3, wherein in the step S3, the stirring reaction time is 1 to 3 hours.
9. An alkylphenol-type vulcanized resin produced by the production process according to any one of claims 1 to 8.
10. A composition comprising an alkylphenol-type vulcanized resin produced by the production process according to any one of claims 1 to 8.
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Citations (5)
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|---|---|---|---|---|
| US3039978A (en) * | 1957-11-29 | 1962-06-19 | Exxon Research Engineering Co | Covulcanizing butyl rubber and a high unsaturation rubber with a 2, 6-dihalomethyl alkylphenol resin |
| CH607099A5 (en) * | 1969-05-20 | 1978-11-30 | Hoechst Ag | |
| JP2003176328A (en) * | 2001-12-12 | 2003-06-24 | Hodogaya Chem Co Ltd | Method for producing resol resin |
| CN1560103A (en) * | 2004-02-25 | 2005-01-05 | 耿国庆 | Preparation process for mixed alkylphenol aldehyde resin condensation compound |
| CN107686544A (en) * | 2016-08-04 | 2018-02-13 | 彤程化学（中国）有限公司 | A kind of method of organic base catalytic synthesizing alkyl phenol formaldehyde curing resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104204015B (en) * | 2012-03-27 | 2015-12-09 | 田冈化学工业株式会社 | Resol type is to octyl group phenolic aldehyde formaldehyde cocondensation resin and manufacture method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3039978A (en) * | 1957-11-29 | 1962-06-19 | Exxon Research Engineering Co | Covulcanizing butyl rubber and a high unsaturation rubber with a 2, 6-dihalomethyl alkylphenol resin |
| CH607099A5 (en) * | 1969-05-20 | 1978-11-30 | Hoechst Ag | |
| JP2003176328A (en) * | 2001-12-12 | 2003-06-24 | Hodogaya Chem Co Ltd | Method for producing resol resin |
| CN1560103A (en) * | 2004-02-25 | 2005-01-05 | 耿国庆 | Preparation process for mixed alkylphenol aldehyde resin condensation compound |
| CN107686544A (en) * | 2016-08-04 | 2018-02-13 | 彤程化学（中国）有限公司 | A kind of method of organic base catalytic synthesizing alkyl phenol formaldehyde curing resin |
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