CN117164789A - Preparation method and application of phenolic resin with narrow molecular weight distribution - Google Patents
Preparation method and application of phenolic resin with narrow molecular weight distribution Download PDFInfo
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- CN117164789A CN117164789A CN202311245092.5A CN202311245092A CN117164789A CN 117164789 A CN117164789 A CN 117164789A CN 202311245092 A CN202311245092 A CN 202311245092A CN 117164789 A CN117164789 A CN 117164789A
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- phenolic resin
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- phenolic
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 86
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 84
- 238000009826 distribution Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 34
- 229920001971 elastomer Polymers 0.000 claims abstract description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 52
- 230000002829 reductive effect Effects 0.000 claims description 34
- 238000010992 reflux Methods 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000004821 distillation Methods 0.000 claims description 29
- 150000002989 phenols Chemical class 0.000 claims description 28
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 28
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 28
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- -1 olefin compound Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 4
- 239000001739 pinus spp. Substances 0.000 claims description 4
- 229940036248 turpentine Drugs 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 18
- 238000002156 mixing Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001336 alkenes Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The application relates to the field of preparation of phenolic resin for rubber tires, and particularly discloses a preparation method and application of phenolic resin with narrow molecular weight distribution. The preparation method of the phenolic resin mainly comprises the following steps: controlling the polymerization reaction rate through saturated monoalcohol to obtain phenolic resin and modified phenolic resin with weight average molecular weight of 1700-2300 and molecular weight distribution (Mw/Mn) below 1.9; the rubber obtained by mixing the rubber has good processability and excellent cohesiveness.
Description
Technical Field
The application relates to the field of rubber tires, in particular to a preparation method and application of a phenolic resin with narrow molecular weight distribution.
Background
In rubber tire products, nylon, steel wire, etc. are generally used as their supporting frame structure to increase the strength of rubber, and an adhesive material (methylene acceptor) is generally added to bond the supporting frame structure and the rubber. Resorcinol or phenol formaldehyde resin is often used as a methylene acceptor adhesive material in the prior art, but free phenol in resorcinol or resin can release toxic smog in the rubber mixing process, and the conventional phenol formaldehyde resin has wider molecular weight distribution and poor rubber compatibility, and has poor dispersion performance in rubber and affected mixing uniformity, so that the mechanical property and processing property of rubber materials are poor.
Currently, the prior art is improved to synthesize more phenolic resin with narrow molecular weight distribution, the Hua Ji patent CN103923284B discloses a method for preparing phenolic resin by a two-phase method, the Shandong holy spring patent CN102585124B discloses a method for preparing phenolic resin with narrow molecular weight distribution, the method is used for preparing phenolic resin with narrow molecular weight distribution, the compatibility of the resin and rubber is increased, better processability is provided, but a large amount of solvent is needed in the preparation of the two-phase method, the physiological toxicity of the solvent is high, the production process steps of the holy spring patent are complex, and the post-process time of the product process is long
Disclosure of Invention
The application provides a preparation method and application of a phenolic resin with narrow molecular weight distribution, in order to solve the problems of toxic solvents and complex process in the preparation process of the phenolic resin with narrow molecular weight distribution.
In a first aspect, the present application provides a preparation method of a phenolic resin with narrow molecular weight distribution, which adopts the following technical scheme:
a preparation method of a phenolic resin with narrow molecular weight distribution comprises the following steps: adding a phenolic compound and an acidic catalyst into a reactor; regulating the reaction temperature, adding saturated monoalcohol, dropwise adding 37% formaldehyde aqueous solution, and carrying out heat preservation and reflux for reaction; and distilling under reduced pressure after atmospheric distillation to obtain the phenolic resin with narrow molecular weight distribution.
By adopting the technical scheme, the saturated monoalcohol with single functionality is used for carrying out reversible reaction with the phenolic compound and is hung on two sides of a molecular chain, so that the polymerization reaction is more gentle to a certain extent, the solubility of the saturated monoalcohol in the macromolecular phenolic resin is better than that of the macromolecular phenolic resin in water, the saturated monoalcohol is more soluble in the macromolecular phenolic resin when layering occurs in the later stage of polymerization, the inhibition effect on continuous polymerization of the macromolecular phenolic resin is larger, the inhibition effect on the micromolecular phenolic resin is smaller, and the polymerization chain length of the phenolic resin in a polymerization system tends to be close by controlling the polymerization reaction rate of the macromolecular phenolic resin and the micromolecular phenolic resin, so that the phenolic resin with narrower molecular weight distribution is obtained; removing water, unreacted phenols and alcohols by distillation to obtain purer phenolic resin; finally, a phenolic resin having a suitable weight average molecular weight and a molecular weight distribution (Mw/Mn) of 1.9 or less is obtained.
In a specific embodiment, the method further comprises the following steps after adding the phenolic compound and the acidic catalyst to the reactor: heating to 130-150 ℃, adding olefin compound, and carrying out heat preservation reflux reaction for 2-3h; the reaction temperature is regulated to 80-100 ℃; the reaction time of heat preservation and reflux after the dropwise adding of 37% formaldehyde aqueous solution is 2-3h.
By adopting the technical scheme, the hydroxyl and methylene in the molecular structure of the phenolic resin are easy to oxidize, and the phenolic resin is thermally decomposed at the use temperature of over 250 ℃, so that the heat resistance and oxidation resistance of the phenolic resin are affected. In addition, the benzene ring in the phenolic resin molecule is connected by only one methylene, so that the density of benzene ring groups in the structure is large, the steric hindrance is large, the rotational freedom degree is small, and the final toughness of the phenolic resin is poor. The phenolic resin is modified by the olefin compound, and an olefin chain segment is introduced into the phenolic resin, so that the toughness, heat resistance, ageing resistance and other performances of the phenolic resin are improved.
In a specific embodiment, the phenolic compound is one or more of phenol, m-cresol, resorcinol; the acid catalyst is one or more of oxalic acid, hydrochloric acid and p-toluenesulfonic acid, and the dosage of the acid catalyst is 5 per mill-1% of the mass of the phenolic compound.
By adopting the technical scheme, the types of the phenolic compounds influence the polymerization rate, the molecular chain structure and the like of the polymer resin, and the application can select phenol, m-cresol, resorcinol or a mixture of a plurality of phenol, m-cresol, resorcinol to promote the polymerization process rate and adjust the performance of the generated resin; in the preparation process of the phenolic resin, the acid catalysis phenolic resin has high reaction speed, good heat resistance and strong corrosion resistance, the variety and the dosage of the acid catalyst have influence on the quality of the final phenolic resin, one or more of the acid catalysts are preferably selected to improve the quality of the resin, the reaction rate, the heat resistance, the corrosion resistance and other performances are improved, the polymerization rate is slow due to the fact that the dosage of the acid catalyst is too small, the quality of the final resin is influenced by the fact that the dosage of the catalyst is too large, and the catalyst addition amount in the range has polymerization efficiency and resin quality.
In a specific embodiment, the phenolic compound comprises: 50-100 parts of phenol, 0-30 parts of m-cresol and 0-20 parts of resorcinol; the acid catalyst is p-toluenesulfonic acid.
By adopting the technical scheme, the structure, molecular weight and other performances of the prepared phenolic resin are regulated through the selection and content proportion of various phenolic compounds; the acid catalyst preferably has better catalysis effect on the toluenesulfonic acid, which is probably due to the fact that the toluenesulfonic acid has a benzene ring structure similar to that of a phenolic compound, and the p-toluenesulfonic acid and the phenolic compound have better compatibility, so that the catalyst is more beneficial to catalysis, the consumption of the catalyst is reduced, and the polymerization rate is improved.
In a specific embodiment, the olefin compound is one or more of styrene, isobutene and turpentine, and the amount of the olefin compound is 10% -50% of the mass fraction of the phenolic compound; or the olefinic compound is used in an amount of 20% of the phenolic compound mass fraction.
By adopting the technical scheme, the specific olefin is selected to introduce the corresponding olefin chain segment into the resin, so that the toughness, heat resistance, ageing resistance and other performances of the phenolic resin are improved, the modification performance in the dosage range of the olefin compound is better, the toughness, heat resistance and other performances of the resin can be influenced by too little olefin compound, the dispersibility of the phenolic resin is poor due to too much olefin compound, and the bonding effect is reduced.
In a specific embodiment, the saturated monoalcohol is a saturated monoalcohol having a boiling point of 85 to 120 ℃, and the amount of the saturated monoalcohol is 5 to 15% of the weight fraction of the phenolic compound.
By adopting the technical scheme, the alcohol with the boiling point of 85-120 ℃ is basically alcohol with 3-5 carbon atoms, the carbon chain of the saturated monoalcohol is too short to better inhibit the polymerization of the phenolic compound and the aldehyde, and the carbon chain of the saturated monoalcohol is too long to easily influence the integral polymerization rate of the phenolic resin and the molecular weight of the final phenolic resin; the alcohols selected by the application are saturated monoalcohols with the boiling point of 85-120 ℃, have low solubility in water, and can be recycled in layers after reduced pressure distillation. The obtained phenolic resin is applied to rubber and has better processability and mechanical property. The amount of saturated monoalcohol is preferably 5-15% of the phenolic compound mass fraction to ensure that the saturated monoalcohol acts effectively to inhibit long chain resins, resulting in a narrower molecular weight distribution of the final resin.
In a specific embodiment, the saturated monoalcohol is n-butanol and the saturated monoalcohol is used in an amount of 10% by weight of the phenolic compound.
By adopting the technical scheme, the n-butanol is selected to have proper carbon chain length, and the saturated monoalcohol is matched with the saturated monoalcohol with the dosage of 10 percent of the mass fraction of the phenolic compound, so that the saturated monoalcohol can realize better effect of inhibiting macromolecular phenolic polymerization in the polymerization process.
In a specific embodiment, the phenolic resin has an aldehyde to phenol molar ratio of 0.55 to 0.73.
By adopting the technical scheme, when the proportion is lower than the above proportion, the softening point of the resin is low, the resin is difficult to form, and when the proportion is higher than the above proportion, the resin is easy to gel and solidify; the balance of easy molding and gel prevention is achieved within the above range; the molar ratio is preferably 0.60 to 0.70.
In a specific embodiment, the reduced pressure distillation temperature is 160-180deg.C, the reduced pressure distillation time is 30-60min, and the reduced pressure distillation pressure is-0.07 to-0.09 Mpa.
By adopting the technical scheme, the impurities such as water, unreacted phenols, alcohols and the like are removed through distillation by setting the distillation process parameters, so that purer resin is obtained, and the final phenolic resin has high purity and excellent performance.
In a second aspect, the application provides the use of a phenolic resin prepared by the method for preparing a phenolic resin of narrow molecular weight distribution as defined in any one of claims 1 to 9,
the following technical scheme is adopted: the prepared phenolic resin is used for preparing rubber.
By adopting the technical scheme, the phenolic resin with narrow molecular weight distribution is used for preparing the rubber, and the phenolic resin has good dispersibility and strong adhesiveness in the rubber.
In summary, the application has the following beneficial effects:
1. according to the application, saturated monoalcohol is added to participate in the polymerization of phenolic resin, so that phenolic resin and modified phenolic resin with weight average molecular weight of 1700-2300 and molecular weight distribution (Mw/Mn) of less than 1.9 are obtained; the rubber obtained by mixing the rubber has good processability and excellent cohesiveness.
2. The saturated monoalcohol is further selected to be saturated monoalcohol with 3-5 carbon atoms and the boiling point of the saturated monoalcohol is 85-120 ℃, so that the saturated monoalcohol can be recycled in a layering way after reduced pressure distillation; and the molecular weight distribution of the final resin is made narrower.
3. The application controls the mole ratio of aldehyde to phenol of the phenolic resin to be 0.55-0.73, and realizes easy molding and gel prevention balance in the range.
Detailed Description
The present application will be described in further detail with reference to examples. The starting materials used in the examples are all of the conventional commercial grades or are obtainable by conventional processes.
Example 1
200g of phenol, 1g of p-toluenesulfonic acid and the temperature of 140 ℃ are added into a 1L four-neck flask with a temperature control, stirring, reflux condensing tube and constant pressure dropping funnel, the temperature is reduced to 90 ℃ after the reaction is carried out for 2 hours, 20g of n-butanol is added, 120g of 37% formaldehyde aqueous solution is then added dropwise, the reaction is carried out for 2.5 hours after the heat preservation and reflux, the atmospheric pressure is distilled to 160 ℃, the reduced pressure distillation under the pressure of-0.07 Mpa is carried out until the temperature in a kettle is 180 ℃ and the temperature is kept for 60 minutes, and then 234g of modified phenolic resin is obtained, the softening point is 102 ℃, the weight average molecular weight is 1900, and the molecular weight distribution Mw/Mn is 1.76.
Example 2
200g of phenol, 2g of oxalic acid, 20g of n-propanol are added into a 1L four-neck flask with a temperature control, stirring, reflux condensing tube and constant pressure dropping funnel, the temperature is raised to 100 ℃, then 110g of 37% formaldehyde aqueous solution is added dropwise, the heat preservation reflux reaction is carried out for 2 hours, normal pressure distillation is carried out to 180 ℃, the temperature in a kettle is reduced to 180 ℃ under-0.08 Mpa, and after 30 minutes, 205g of modified phenolic resin is obtained, the softening point is 96 ℃, the weight average molecular weight is 1700, and the molecular weight distribution Mw/Mn is 1.80.
Example 3
To a 1L four-neck flask equipped with a temperature control, stirring, reflux condenser and constant pressure dropping funnel, 160g of phenol, 40g of resorcinol and 2g of oxalic acid are added, the temperature is raised to 130 ℃, 40g of styrene is added, the temperature is kept for reflux reaction for 2 hours, the temperature is reduced to 90 ℃, 20g of tertiary amyl alcohol is added, then 115g of 37% formaldehyde aqueous solution is added dropwise, the temperature is kept for reflux reaction for 2 hours, atmospheric distillation is carried out to 160 ℃, the pressure is reduced to-0.09 Mpa until the temperature in the kettle is 180 ℃, and after the temperature is kept for 30 minutes, 229g of phenolic resin is obtained, the softening point is 107 ℃, and the weight average molecular weight is 1800, and the Mw/Mn is 1.82.
Example 4
To a 1L four-neck flask equipped with a temperature control, stirring, reflux condenser and constant pressure dropping funnel, 160g of phenol, 40g of resorcinol, 1g of p-toluenesulfonic acid, heating to 100 ℃, adding 18g of n-butanol, then dropwise adding 100g of 37% formaldehyde aqueous solution, carrying out heat preservation reflux reaction for 2h, carrying out normal pressure distillation to 170 ℃, carrying out reduced pressure distillation at-0.09 Mpa until the temperature in the kettle is 180 ℃, and keeping for 60min to obtain 229g of modified phenolic resin, wherein the aldehyde-phenol molar ratio of the resin is 0.6, the softening point is 97 ℃, the weight average molecular weight is 2300, and the Mw/Mn is 1.79.
Example 5
To a 1L four-necked flask equipped with a temperature-controlled, stirred, reflux condenser and constant pressure dropping funnel, 160g of phenol, 40g of resorcinol, 1g of p-toluenesulfonic acid, heating to 100 ℃, adding 18g of n-butanol, then dropwise adding 91.5g of 37% aqueous formaldehyde solution, carrying out heat preservation reflux reaction for 2h, carrying out normal pressure distillation to 170 ℃, carrying out reduced pressure distillation at-0.09 Mpa until the temperature in the kettle is 180 ℃, and keeping for 60min to obtain 229g of modified phenolic resin, wherein the molar ratio of aldehyde to phenol of the resin is 0.55, the softening point is 85 ℃, the weight average molecular weight is 2200, and the Mw/Mn of the molecular weight distribution condition is 1.87.
Example 6
To a 1L four-neck flask equipped with a temperature control, stirring, reflux condenser and constant pressure dropping funnel, 160g of phenol, 40g of resorcinol, 1g of p-toluenesulfonic acid, heating to 100 ℃, adding 18g of n-butanol, then dropwise adding 121.5g of 37% formaldehyde aqueous solution, carrying out heat preservation reflux reaction for 2h, carrying out normal pressure distillation to 170 ℃, carrying out reduced pressure distillation at-0.09 Mpa until the temperature in the kettle is 180 ℃, and keeping for 60min to obtain 229g of modified phenolic resin, wherein the molar ratio of aldehyde to phenol of the resin is 0.73, the softening point is 108 ℃, and the weight average molecular weight is 2300, and the Mw/Mn is 1.85.
Example 7
200g of phenol, 1g of p-toluenesulfonic acid and the like are added into a 1L four-neck flask with a temperature control, stirring, reflux condensing tube and constant pressure dropping funnel, the temperature is raised to 140 ℃, 40g of turpentine is added, the temperature is kept for 2 hours, the temperature is reduced to 80 ℃, 20g of absolute ethyl alcohol is added, then 120g of 37% formaldehyde aqueous solution is added dropwise, the temperature is kept for 2.5 hours, the atmospheric distillation is carried out to 160 ℃, the reduced pressure distillation under the pressure of-0.07 Mpa is carried out until the temperature in the kettle is 180 ℃, and the temperature is kept for 60 minutes, thus obtaining 223g of modified phenolic resin with the softening point of 92 ℃, the weight average molecular weight of 2200 and the molecular weight distribution Mw/Mn of 1.85.
Example 8
200g of phenol, 1g of p-toluenesulfonic acid and 20g of n-hexanol are added into a 1L four-neck flask with a temperature control, stirring, reflux condensing tube and constant pressure dropping funnel, the temperature is raised to 140 ℃, 40g of turpentine is added, the temperature is kept for 2 hours, the temperature is reduced to 90 ℃, 120g of 37% formaldehyde aqueous solution is added dropwise, the temperature is kept for 2.5 hours, the normal pressure distillation is carried out to 160 ℃, the pressure is reduced to-0.07 Mpa and the temperature in the kettle is 180 ℃ and the temperature is kept for 60 minutes, so that 234g of modified phenolic resin is obtained, the softening point is 102 ℃, the weight average molecular weight is 2100, and the molecular weight distribution Mw/Mn is 1.88.
Example 9
200g of phenol, 1g of p-toluenesulfonic acid and the temperature of 140 ℃ are added into a 1L four-neck flask with a temperature control, stirring, reflux condensing tube and constant pressure dropping funnel, the temperature is reduced to 90 ℃ after the reaction is carried out for 2 hours, 8g of n-butanol is added, 120g of 37% formaldehyde aqueous solution is then added dropwise, the reaction is carried out for 2.5 hours after the heat preservation and reflux, the atmospheric pressure is distilled to 160 ℃, the reduced pressure distillation of-0.07 Mpa is carried out until the temperature in the kettle is 180 ℃ and the temperature is kept for 60 minutes, so that 227g of modified phenolic resin is obtained, the softening point is 100 ℃, the weight average molecular weight is 1900, and the molecular weight distribution Mw/Mn is 1.89.
Example 10
200g of phenol, 1g of p-toluenesulfonic acid and the temperature of 140 ℃ are added into a 1L four-neck flask with a temperature control, stirring, reflux condensing tube and constant pressure dropping funnel, the temperature is reduced to 90 ℃ after the reaction is carried out for 2 hours, 32g of n-butanol is added, 120g of 37% formaldehyde aqueous solution is then added dropwise, the reaction is carried out for 2.5 hours after the heat preservation and reflux, the atmospheric pressure is distilled to 160 ℃, the reduced pressure distillation under the pressure of-0.07 Mpa is carried out until the temperature in a kettle is 180 ℃ and the temperature is kept for 60 minutes, and then 234g of modified phenolic resin is obtained, the softening point is 102 ℃, the weight average molecular weight is 1900, and the molecular weight distribution Mw/Mn is 1.87.
Comparative example 1
200g of phenol, 1g of p-toluenesulfonic acid and the temperature of 140 ℃ are added into a 1L four-neck flask with a temperature control, stirring, reflux condensing tube and constant pressure dropping funnel, the temperature is reduced to 90 ℃ after the reaction is carried out for 2 hours, 120g of 37% formaldehyde aqueous solution is added dropwise after the reaction is carried out for 2.5 hours after the reaction is carried out for 2 hours after the reaction is carried out for 2.5 hours after the reaction is carried out for 160 ℃, the temperature in a kettle is 180 ℃ after the distillation is carried out under reduced pressure of-0.07 Mpa, and 228g of modified phenolic resin with the softening point of 100 ℃ and the weight average molecular weight of 1700 and the Mw/Mn of 1.99 are obtained.
Comparative example 2
200g of phenol, 2g of oxalic acid and 110g of 37% formaldehyde aqueous solution are added into a 1L four-neck flask with a temperature control, stirring, reflux condensing tube and a constant pressure dropping funnel, heated to 100 ℃, then subjected to reflux reaction for 2 hours under heat preservation, distilled to 180 ℃ under normal pressure, distilled to 180 ℃ under reduced pressure of-0.08 Mpa, and kept at the temperature in the kettle of 180 ℃ for 30 minutes, so as to obtain 205g of modified phenolic resin, wherein the softening point is 90 ℃, and the weight average molecular weight is 1700, and the Mw/Mn is 2.21.
Comparative example 3
To a 1L four-neck flask equipped with a temperature control, stirring, reflux condenser and constant pressure dropping funnel, 160g of phenol, 40g of resorcinol and 2g of oxalic acid are added, the temperature is raised to 130 ℃, 40g of styrene is added, the temperature is kept for reflux reaction for 2 hours, the temperature is reduced to 90 ℃, then 115g of 37% formaldehyde aqueous solution is added dropwise, the temperature is kept for reflux reaction for 2 hours, the atmospheric pressure is distilled to 160 ℃, the pressure of-0.09 Mpa is reduced to 180 ℃ and the temperature in the kettle is kept for 30 minutes, and 221g of phenolic resin with the softening point of 105 ℃ and the weight average molecular weight of 1900 and the Mw/Mn of 2.28 is obtained.
Comparative example 4
160g of phenol, 40g of resorcinol and 1g of p-toluenesulfonic acid are added into a 1L four-neck flask with a temperature control, stirring, reflux condensing tube and a constant pressure dropping funnel, the temperature is raised to 100 ℃, then 100g of 37% formaldehyde aqueous solution is added dropwise, the heat preservation reflux reaction is carried out for 2 hours, the normal pressure distillation is carried out to 170 ℃, the temperature in a kettle is 180 ℃ under the reduced pressure of-0.09 Mpa, and the temperature is kept for 60 minutes, thus 229g of modified phenolic resin is obtained, the aldehyde-phenol molar ratio of the resin is 0.65, the softening point is 97 ℃, the weight average molecular weight is 2300, and the Mw/Mn is 2.18.
Performance test
1. GPC tests were carried out on the phenolic resins obtained in examples 1 to 10 and comparative examples 1 to 4. GPC test instrument information: brands Waters, liquid chromatography host model e2695, differential photodetector host model 2414, column WATERS STYRAGEL HR 0.5.5 (tetrahydrofuran), WATERS STYRAGEL HR (tetrahydrofuran), WATERS STYRAGEL HR (tetrahydrofuran), mobile phase tetrahydrofuran.
Table 1: GPC test results of phenolic resins obtained in examples 1 to 10 and comparative examples 1 to 4
As can be seen in combination with Table 1, the phenolic resins Dp prepared in examples 1-10 are all less than 1.9, with a narrower molecular weight distribution; however, in the comparative examples 1, 2, 3 and 4, which correspond to examples 1, 2, 3 and 4, except that no saturated monoalcohol was added thereto for modification, GPC results of the obtained resins showed that Dp was higher than that of the corresponding examples. Therefore, the molecular weight distribution of the phenolic resin obtained by modifying the phenolic resin by adding the protective monoalcohol is narrower; by combining examples 1, 7, 8, saturated monoalcohols, preferably with a boiling point of 85 to 120 ℃, can be obtained; by combining examples 1, 9, 10, a preferred proportion of saturated monoalcohols of 5% to 15% can be obtained.
2. The experimental formulations of the phenolic resins prepared in examples 1-10 and comparative examples 1-4 in rubber preparation are shown in Table 2 below:
table 2: formula of rubber prepared from phenolic resin prepared in examples 1-10 and comparative examples 1-4
The specific preparation steps of the rubber composition are as follows:
firstly, mixing rubber components at 150 ℃ by using a Farrel internal mixer to prepare master batch;
in a second step, the resins prepared in examples 1 to 10 and comparative examples 1 to 4 were mixed with cobalt salt at 145℃into a masterbatch obtained by mixing in a Farrel mixer.
Thirdly, adding and mixing the rest components of insoluble sulfur, an accelerator DZ, an accelerator NS-80, a scorch retarder CTP, a methylene acceptor HMMM, an antioxidant 4020 and the like listed in the table 2 at the temperature of 90-100 ℃ to obtain a modified vulcanized rubber mixture, and standing the modified vulcanized rubber mixture at the constant temperature of 23-25 ℃ and the relative humidity of 40-80% overnight. Then, the sulfur transformer vulcanization, shape and optimum degree of vulcanization were measured at 150 ℃. To evaluate the mechanical properties thereof.
The test data of the modified vulcanized rubber composition are shown in Table 3.
Steel cord adhesion properties (N) vulcanization conditions used: 160 ℃ for 20min, and the specification of the rigid cord; 2+2 x 0.25ht, tested in standard ASTM D1871-2004; the test results are shown in Table 4.
Table 3: mooney viscosity contrast
As can be seen from a combination of examples 1-10, comparative examples 1-4 and Table 3, the synthetic phenolic resins of examples 1-10 have lower Mooney viscosities and better dispersion properties and are more processable.
Table 4: t-pullout force vs (number of samples N > 5) N/2+3 x 0.3HT steel wire
As can be seen in the combination of examples 1-10, comparative examples 1-4 and Table 4, the adhesive properties of the phenolic resins synthesized using the present application (examples 1-6) were superior to those of the phenolic resins polymerized without the addition of saturated monoalcohol (comparative examples 1-4) and other phenolic resins not within the preferred range (examples 7-10) before the rubber aging, and the adhesive properties of the rubber prepared from the resins of examples 1-6 were still superior to the results of the corresponding comparative examples 1-4, examples 7-10 after the aging; according to the application, the phenolic resin with narrow molecular weight distribution is finally obtained through the polymerization of the optimized saturated monoalcohol and the phenolic resin, and the phenolic resin is used for improving the dispersibility, the cohesiveness and the ageing resistance in rubber.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. A preparation method of a phenolic resin with narrow molecular weight distribution is characterized by comprising the following steps: the preparation method comprises the following steps: adding a phenolic compound and an acidic catalyst into a reactor; regulating the reaction temperature, adding saturated monoalcohol, dropwise adding 37% formaldehyde aqueous solution, and carrying out heat preservation and reflux for reaction; and distilling under reduced pressure after atmospheric distillation to obtain the phenolic resin with narrow molecular weight distribution.
2. The method for producing a narrow molecular weight distribution phenolic resin according to claim 1, wherein: the method further comprises the following steps after the phenolic compound and the acid catalyst are added into the reactor: heating to 130-150 ℃, adding olefin compound, and carrying out heat preservation reflux reaction for 2-3h; the reaction temperature is regulated to 80-100 ℃, and the reaction time of heat preservation and reflux after the dropwise addition of 37% formaldehyde aqueous solution is 2-3h.
3. The method for producing a narrow molecular weight distribution phenolic resin according to claim 1, wherein: the phenolic compound is one or more of phenol, m-cresol and resorcinol; the acid catalyst is one or more of oxalic acid, hydrochloric acid and p-toluenesulfonic acid, and the dosage of the acid catalyst is 5 per mill-1% of the mass of the phenolic compound.
4. A process for preparing a narrow molecular weight distribution phenolic resin in accordance with claim 3, wherein: the phenolic compounds include: 50-100 parts of phenol, 0-30 parts of m-cresol and 0-20 parts of resorcinol; the acid catalyst is p-toluenesulfonic acid.
5. The method for producing a narrow molecular weight distribution phenolic resin according to claim 2, characterized in that: the olefin compound is one or more of styrene, isobutene and turpentine, and the dosage of the olefin compound is 10% -50% of the mass fraction of the phenolic compound; or the olefinic compound is used in an amount of 20% of the phenolic compound mass fraction.
6. The method for producing a narrow molecular weight distribution phenolic resin according to claim 1, wherein: the saturated monoalcohol is saturated monoalcohol with the boiling point of 85-120 ℃, and the dosage of the saturated monoalcohol is 5-15% of the mass fraction of the phenolic compound.
7. The method for producing a narrow molecular weight distribution phenolic resin according to claim 6, wherein: the saturated monoalcohol is n-butanol, and the dosage of the saturated monoalcohol is 10% of the mass fraction of the phenolic compound.
8. The method for producing a narrow molecular weight distribution phenolic resin according to claim 1, wherein: the mole ratio of aldehyde to phenol of the phenolic resin is 0.55-0.73.
9. The method for producing a narrow molecular weight distribution phenolic resin according to claim 1, wherein: the reduced pressure distillation temperature is 160-180deg.C, the reduced pressure distillation time is 30-60min, and the reduced pressure distillation pressure is-0.07-0.09 Mpa.
10. Use of a phenolic resin prepared by the method for preparing a phenolic resin with a narrow molecular weight distribution according to any one of claims 1 to 9, characterized in that: the phenolic resin is used for preparing rubber.
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|---|---|---|---|---|
| GB750233A (en) * | 1953-03-26 | 1956-06-13 | British Resin Prod Ltd | Improvements in modified phenol-aldehyde resins |
| CN101023111A (en) * | 2004-09-24 | 2007-08-22 | 茵迪斯佩克化学公司 | Modified phenolic novolak resins and applications thereof |
| CN109160986A (en) * | 2018-08-22 | 2019-01-08 | 江苏麒祥高新材料有限公司 | A kind of modified metacresol-phenol-formaldehyde resin, preparation method and its rubber composition |
| CN112457459A (en) * | 2020-10-20 | 2021-03-09 | 江苏麒祥高新材料有限公司 | Modified resorcinol formaldehyde resin, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB750233A (en) * | 1953-03-26 | 1956-06-13 | British Resin Prod Ltd | Improvements in modified phenol-aldehyde resins |
| CN101023111A (en) * | 2004-09-24 | 2007-08-22 | 茵迪斯佩克化学公司 | Modified phenolic novolak resins and applications thereof |
| CN109160986A (en) * | 2018-08-22 | 2019-01-08 | 江苏麒祥高新材料有限公司 | A kind of modified metacresol-phenol-formaldehyde resin, preparation method and its rubber composition |
| CN112457459A (en) * | 2020-10-20 | 2021-03-09 | 江苏麒祥高新材料有限公司 | Modified resorcinol formaldehyde resin, preparation method and application thereof |
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| Title |
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| 苏涛 等: ""用松节油或重松节油制备高软化点萜烯酚醛树脂"", 《林产化学与工业》, vol. 18, no. 03, 23 September 1998 (1998-09-23), pages 39 - 48 * |
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