CN108570134B - Alkylphenol modified amino resin, preparation method and application - Google Patents
Alkylphenol modified amino resin, preparation method and application Download PDFInfo
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Abstract
The invention discloses alkylphenol modified amino resin, a preparation method and application thereof. An alkylphenol-modified amino resin comprising a structural unit represented by the formula (I):
wherein R is1、R2、R3、R4、R5、R6Each independently represents a hydrogen atom represented by the formula: -CH2-R' is a group represented by the formula: -CH2-or a group represented by formula (la): -CH2-R' -represents a group; r ' represents a group obtained by removing one hydrogen atom from the active site on the benzene ring of the alkylphenol, and R ' is a residue obtained by removing one hydrogen atom from R '; wherein R is1、R2、R3、R4、R5、R6Is represented by the formula: -CH2-R' represents a group; the alkylphenol modified amino resin comprises 1-15 unit body structural units shown in the formula (I). When the alkylphenol modified amino resin is added into rubber to react with other substances in rubber materials, a large amount of alcohol cannot be released, so that environmental pollution is caused, and meanwhile, bubbles cannot be easily generated in the rubber to influence the quality of products.
Description
Technical Field
The invention relates to the field of rubber, in particular to alkylphenol modified amino resin, a preparation method and application.
Background
Amino resins (melamine-formaldehyde, benzoguanamine-formaldehyde and urea-formaldehyde (urea-formaldehyde) resins) refer to thermosetting resins prepared by condensation polymerization of amino-containing compounds and aldehydes, and are widely used in coatings, adhesives, plastics or tanning materials, and in shrink-proof and crease-resistant treatments of fabrics and papers.
An alcohol etherified melamine formaldehyde resin which is important in amino resin is mainly added into steel cord fabric and belt ply rubber in the form of hexamethoxy methyl melamine (HMMM) with high etherification degree in the rubber industry, and a methylene donor is provided and is used as an accelerant for adhesion of rubber and steel cord fabric, so that the adhesive property of the rubber is improved.
However, the use of HMMM in rubber is currently limited to this, and studies for preparing functional resins by modifying specific functional groups of HMMM are rarely seen.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides alkylphenol modified amino resin, a preparation method and application.
One of the objects of the present invention is to provide an alkylphenol-modified amino resin.
Comprising a structural unit represented by formula (I):
wherein R is1、R2、R3、R4、R5、R6Each independently represents a hydrogen atom represented by the formula: -CH2-R' is a group represented by the formula: -CH2-or a group represented by formula (la): -CH2-R' -represents a group;
r ' represents a group obtained by removing one hydrogen atom from the active site on the benzene ring of the alkylphenol, and R ' is a residue obtained by removing one hydrogen atom from R '; wherein R is1、R2、R3、R4、R5、R6Is represented by the formula: -CH2-R' represents a group;
the alkylphenol modified amino resin comprises 1-15 unit body structural units shown in the formula (I), preferably 4-10 unit body structural units shown in the formula (I);
the softening point of the alkylphenol modified amino resin is 50-180 ℃, and preferably 60-160 ℃.
The second purpose of the invention is to provide a preparation method of alkylphenol modified amino resin.
The method comprises the following steps:
the method comprises the following steps of carrying out catalytic reaction on hydroxymethyl melamine or etherified hydroxymethyl melamine and alkylphenol to obtain a unit body structural unit shown in a formula (I), further carrying out polymerization reaction, and finally neutralizing to obtain the alkylphenol modified amino resin.
Preferably:
the amino resin is prepared by taking hexamethylol melamine (formula II) or etherified hexamethylol melamine (formula III) as a raw material, carrying out acid catalytic reaction on the hexamethylol melamine (formula II) or etherified hexamethylol melamine (formula III) and alkylphenol to obtain a unit body structural unit shown in a formula (I), further carrying out polymerization reaction, and finally neutralizing the obtained product, wherein the reaction process is as follows:
wherein R is1、R2、R3、R4、R5、R6Each independently represents a hydrogen atom represented by the formula: -CH2-R' is a group represented by the formula: -CH2-or a group represented by formula (la): -CH2-R' -represents a group;
r 'H is alkylphenol, R' represents a group of alkylphenol with one hydrogen atom removed from an active site on a benzene ring, and R 'is a residue of R' with one hydrogen atom removed; wherein R is1、R2、R3、R4、R5、R6Is represented by the formula: -CH2-R' represents a group; r7Is selected from alkyl groups having 1 to 10 carbon atoms, and the number of carbon atoms is preferably 1 to 4.
The R' H is selected from linear chain or branched chain, saturated or unsaturated alkyl phenol which is mono-substituted or multi-substituted by one or more halogen or sulfur atoms, and the substituent group of the alkyl phenol contains 0-60 carbon atoms, preferably 0-30 carbon atoms; the phenols are one or more of phenol, cresol, xylenol, ethylphenol, allylphenol, tert-butylphenol, amylphenol, heptylphenol, octylphenol, 2, 4-di-tert-butylphenol, 2-thio-di-p-tert-octylphenol, nonylphenol, decylphenol, dodecylphenol, bisphenol A and cardanol.
The catalyst is an acidic catalyst and is selected from one or more of organic acid and inorganic acid; the organic acid catalyst is preferably one or more of trifluoroacetic acid, trichloroacetic acid, dodecylbenzene sulfonic acid, benzene sulfonic acid, acetic acid and oxalic acid; the inorganic acid catalyst is preferably one or more of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid and nitric acid;
preferably, the methylol melamine is selected from methylol melamine containing 1-6 methylol structures; more preferably 3 to 6;
preferably, 1-6 hydroxymethyl groups in the etherified methylol melamine are subjected to etherification reaction with alcohol; more preferably 3 to 6;
preferably, the molar ratio of the alkylphenol modified amino resin to the methylolmelamine or etherified methylolmelamine to the alkylphenol is 1: 1-1: 6, preferably 1: 3-1: 6.
preferably, the preparation method of the alkylphenol modified amino resin comprises the following steps: adding alkylphenol and an acidic catalyst into a reaction bottle provided with a stirring device, a thermometer and a reflux condenser, adding or not adding an organic solvent, heating to completely dissolve the alkylphenol, slowly adding etherified methylol melamine or methylol melamine, controlling the reaction temperature to be about 70-200 ℃, reacting for 0.5-10 h, changing the distillation state to be heated to 150-220 ℃, decompressing, vacuumizing, neutralizing, and discharging to obtain the alkylphenol modified amino resin.
The ether bonds in the raw materials are partially removed in the reaction process through the reaction of the former stage, and the residual ether bonds in the raw materials can be completely removed under the high-temperature reduced-pressure vacuum condition of the latter stage. Because the ether linkages present in the resin structure are unstable during processing, alcohol species are generated which affect their processability for incorporation into rubber or other articles.
The invention also aims to provide the application of the alkylphenol modified amino resin in rubber or rubber compositions.
Particularly in the application of the rubber composition in the tire, the rubber composition (such as the tire and the like) using the resin can further improve the modulus, the hardness, the tensile strength, the tear resistance and the aging resistance of the rubber compound and reduce the rolling resistance, the abrasion and the like of the rubber compound compared with a blank rubber compound (namely, the rubber composition without using the alkylphenol modified amino resin).
HMMM is itself a 6-functionalized monomeric compound, and the idealized HMMM, i.e. the fully etherified amino resin, is extremely symmetric, with only one of its functional groups: alkoxy, as shown in formula III. Since the etherification degree cannot reach 1: 6 (highest), so that said fully etherified amino resin always has a little imino groups and methylol groups present. Formula IV (R represents alkyl) is a partially alkylated HMMM amino resin containing alkoxy, imino, methylol groups, etc. The triazine ring skeleton structure has higher rigidity, methylene groups of one carbon atom are connected among triazine rings, the triazine rings are highly crosslinked, the possibility of deformation in the molecule is lower, and the structure function has the characteristic of brittle and hard resin; the branch or branch derived from the triazine ring skeleton can be vividly described as a three-head six-arm, and the performance of amino resin is changeable, namely the six arms are different and formed by the combination of the three arms in an intricate arrangement; meanwhile, HMMM can easily react with polymers with functional groups such as hydroxyl, carboxyl, amido and the like, and can easily perform intramolecular polycondensation reaction through the hydroxyl and polycondensation reaction among other amino resin molecules, so that the HMMM is crosslinked into a three-dimensional network structure through chemical reaction; these characteristics determine that functional resins can be prepared by modifying certain reactive groups of HMMM, allowing them to be used in tire formulations for maximum efficacy.
The alkylphenol modified amino resin is composed of a plurality of unit body structural units shown in formula (I), and the structure of the unit body can be artificially designed with functional groups by relatively changing a synthesis process route, a raw material ratio and the like according to needs. The inside of the structural unit of the alkylphenol modified amino resin is a triazine ring structure with larger rigidity, the outside of the structural unit is an alkylphenol structure containing a large number of benzene rings with rigid structures and alkyl chains, the alkyl chains on the benzene rings can keep better compatibility with rubber molecules, and meanwhile, a large number of hydroxyl structures on the benzene rings are in close contact with the surface of the filler; this structural feature ensures the rigidity of the resin and the compatibility of the resin with both the rubber and filler system. In addition, imino groups present in small amounts are reactive and can react with rubber molecules and other components of the composition. The specific functional structures and active groups of the alkylphenol modified amino resin can well interact with each component in the rubber composition, so that the rubber composition tire containing the resin has good control performance and processing performance.
Compared with the traditional amino resin, the alkylphenol modified amino resin has the remarkable characteristic that ether bonds are completely reacted in the modification process through process control, a large amount of alcohol cannot be released when the alkylphenol modified amino resin is added into rubber to react with other substances in rubber materials, so that the environmental pollution is caused, and meanwhile, bubbles are not easily generated in the rubber to influence the quality of products.
The preparation method provided by the invention has the advantages of simple process, mild reaction conditions, safety, reliability and easy realization of industrialization;
the modified resin provided by the invention is added into the rubber material, so that the modulus, hardness, tensile strength, tear resistance and aging resistance of the rubber material can be further improved, and the rolling resistance, abrasion and the like of the rubber material are reduced.
Drawings
FIG. 1 is a chart of the IR spectra measured in example 1, the IR spectrum of the mixture before the reaction and the IR spectrum of the product after the reaction, respectively; the infrared detection result shows that: 3384.2cm-1Is the water peak in air and the absorption peak of OH bond in the sample, 2853.5cm-1Is a methylene C-H symmetric stretching vibration absorption peak, 2927.2cm-1Is methylene C-H asymmetric stretching vibration absorption, 1552.0cm-1～1464.9cm-1Is a skeleton vibration absorption peak of benzene ring, 1083.8cm-1Is the absorption peak of stretching vibration of C-O-C bond, 1016.5cm-1Is CH3C-O stretching vibration of-O. After the reaction, most of infrared spectrum signal peaks are widened, and 1083.8cm is simultaneously generated-1And 1016.5cm-1The two signals disappear, which shows that the alkylphenol and the raw material have condensation reaction, and the C-O stretching vibration signal disappears after the alcohol is removed. The reacted resin has no C-O-C bond.
FIG. 2 is a chart of the IR spectra measured in example 3, the IR spectrum of the mixture before the reaction and the IR spectrum of the product after the reaction, respectively; the infrared detection result shows that: 3389.4cm-1Is the water peak in air and the absorption peak of OH bond in the sample, 2953.5cm-1Is methylene C-H asymmetric stretching vibration absorption, 1513.4cm-1～1486.2cm-1Is a skeleton vibration absorption peak of benzene ring, 1083.5cm-1Is an extension of a C-O-C bondAbsorption peak of contraction vibration, 1015.7cm-1Is CH3C-O stretching vibration of-O. After the reaction, most of infrared spectrum signal peaks are widened, and 1083.5cm is simultaneously generated-1And 1015.7cm-1The two signals disappear, which shows that the alkylphenol and the raw material have condensation reaction, and the C-O stretching vibration signal disappears after the alcohol is removed. The reacted resin has no C-O-C bond.
Detailed Description
The present invention will be further described with reference to the following examples.
TABLE 1
The types of instruments used in the examples of the present invention and their sources are shown in table 2:
TABLE 2
1.1 preparation and Performance testing of phenolic resins
Testing of softening point:
the softening point of the phenolic resin was tested using the FP900 calorific value analysis system according to the standard ASTM D3461-97 (2007).
Example 1
Adding 1.2mol of p-tert-butylphenol, 100ml of toluene and 0.5g of dodecylbenzenesulfonic acid into a 500ml round bottom flask provided with a stirring device, a thermometer and a reflux condenser, heating to 100 ℃ to completely dissolve the p-tert-butylphenol, slowly adding HMMM0.3mol, controlling the reaction temperature to be about 80 ℃ and reacting for 3 hours under a reflux state, heating to 215 ℃ under a distillation state to react for 30 minutes, vacuumizing under reduced pressure for 20 minutes, neutralizing with triethanolamine, and discharging to obtain the p-tert-butylphenol modified amino resin. The resin softening point was determined to be 132.6 ℃.
Examples 2 to 6
The procedure for producing the alkylphenol-modified amino resin in example 1 was repeated except for changing the kind of alkylphenol. See table 3 below for specific data.
TABLE 3
Example 7
Adding 1.4mol of 2, 2-thio-di-p-tert-octylphenol and bisphenol A mixed phenol, 100ml of dimethylbenzene and 1.0g of nitric acid into a 500ml round bottom flask provided with a stirring device, a thermometer and a reflux condenser, heating to completely dissolve the mixed alkylphenol, slowly adding 0.3mol of hydroxymethyl melamine, controlling the reaction temperature to be about 135 ℃ for reaction for 8 hours, heating to 190 ℃ in a distillation state, decompressing and vacuumizing for 20 minutes, neutralizing with sodium hydroxide, and discharging to obtain the 2, 2-thio-di-p-tert-octylphenol and bisphenol A mixed phenol modified amino resin. The resin softening point was determined to be 128.6 ℃.
Example 8
Adding 1.4mol of p-cresol and 1.0g of trichloroacetic acid into a 500ml round-bottom flask provided with a stirring device, a thermometer and a reflux condenser, slowly adding 0.3mol of methylol melamine, controlling the reaction temperature to be 180 ℃, reacting for 3 hours under a reflux state, raising the temperature to 165 ℃ under a distillation state, vacuumizing under reduced pressure for 20 minutes, neutralizing by potassium hydroxide, and discharging to obtain the p-cresol modified amino resin. The resin softening point was determined to be 118.3 ℃.
Examples 9 to 11
The procedure for producing an alkylphenol-modified amino resin in example 7 was repeated except for changing the kind of alkylphenol. See table 4 below for specific data.
TABLE 4
| Examples | Example 8 | Example 9 | Example 10 | Example 11 |
| Class of alkylphenols | Para-cresol | Dodecyl phenol | P-tert-octylphenol | P-tert-butylphenol |
| Softening Point (. degree. C.) | 108.3 | 92.5 | 122.0 | 130.6 |
Example 12
Adding 1.55mol of cardanol, 1.5g of phosphoric acid and 100ml of xylene into a 500ml round-bottom flask provided with a stirring device, a thermometer and a reflux condenser, slowly adding 0.3mol of hexamethoxy methyl melamine, controlling the reaction temperature to be 120 ℃, reacting for 8h, then raising the temperature to 210 ℃ in a distillation state, keeping for 60min, reducing the pressure, vacuumizing for 30min, neutralizing with sodium hydroxide, and discharging to obtain the cardanol modified amino resin. The resin softening point was determined to be 90.1 ℃.
Comparative example
The cardanol amino resin is prepared from HMMM and cardanol as raw materials according to the preparation method provided in U.S. Pat. No. US20080103283A1
Adding 29.01g of HMMM, 70.46g of cardanol and 0.58g of 40% p-toluenesulfonic acid catalyst (isopropanol is used as a solvent) into a reaction kettle, stirring and reacting under the condition of introducing nitrogen for protection, gradually heating to 160 ℃, and keeping the temperature at 160 ℃ for reaction for 4 hours to obtain the cardanol amino resin which is viscous at normal temperature.
Example 12 compared with comparative example, in example 12, alkylphenol reacted with amino resin, ether bond of hexamethoxymethylmelamine reacted completely, alkylphenol lost hydrogen atom at carbon atom at benzene ring position, and comparative example, hydroxyl group position of alkylphenol lost hydrogen atom. In addition, the preparation temperature, the reaction time and other process conditions of the two resins are different, the final states of the products are also different, the product obtained in example 12 is solid and is easier to store, transport and apply, and the sample obtained in the comparative example is viscous and is not beneficial to industrial production and application.
1.2 preparation and Performance testing of rubber compositions
EXAMPLE 13 preparation of rubber composition
The properties of the resin in the rubber composition were evaluated based on the p-tert-butylphenol-modified amino resin prepared in example 1. The experimental formulation is shown in table 5 below:
TABLE 5
In the first stage, styrene-butadiene rubber, natural rubber, carbon black, white carbon black, zinc oxide, stearic acid, wax, CJ44, an antioxidant, and the alkylphenol-modified amino resin prepared according to the method of example 1 were mixed in a Banbury mixer at 150 ℃ to prepare a rubber masterbatch. Then in the second stage, sulfur and an accelerant are mixed into a proper amount of rubber master batch at the temperature of 150 ℃. The two-stage masterbatch discharged from the internal mixer is milled in an XK-160 open mill (the mixing temperature is 50 ℃ and the mixing time is 10 min). The test compositions were subjected to a storage test at a constant room temperature of 25 ℃ and a relative humidity of 45%.
EXAMPLE 14 Performance testing of rubber compositions
1.2.1 testing of vulcanization characteristics
The rubber compositions were tested for their vulcanization characteristics according to the standard GB/T16584-.
ML-the minimum moment or force, in units of N.m or N, can characterize the shear modulus of the rubber composition when unvulcanized;
MH, the flat, maximum, highest torque or force achieved in a given time, in units of N m or N, characterizes the shear modulus of the rubber composition at the time of achieving the optimum state of cure, with a higher value of MH indicating a higher cross-linked network density of the rubber composition;
1.2.2 testing of tensile Properties
The vulcanized rubber was tested for tensile stress at definite elongation, tensile strength at break according to standard GB/T528-.
Stress at definite elongation-tensile stress in MPa when the gauge length of a tensile specimen reaches a specified elongation.
Tensile Strength-tensile stress recorded at the moment the specimen is stretched to break, in MPa.
1.2.3 determination of tear Strength
The tear strength of the vulcanizates was tested according to the standard GB/T529-. Tear Strength-the test specimens with or without cuts were continuously pulled at a specified speed using a tensile tester until the maximum force required to tear the test specimens. The tear strength is given in KN/m. The tearing strength is high, and the tearing resistance of the rubber is good.
1.2.4 measurement of scorch Properties
The scorch performance of the unvulcanized rubber composition was tested according to standard GB/T1233-. The test temperature used in the experiment was, and the large rotor was used for the test.
Scorch time reflects the safety of the rubber composition during processing, with longer scorch times indicating greater safety of operation.
1.2.5 Shore hardness test
The Shore hardness of the rubber compositions after vulcanization is evaluated according to the standard GB/T531.1-2008.
The higher the hardness value, the higher the rigidity of the rubber composition.
1.2.6DIN abrasion
The index of consumption of vulcanized rubber is tested according to the standard GB/T9867-2008.
The ratio of the abrasion loss of the standard gum to the abrasion loss of the experimental gum under the same condition. Expressed in percent. The smaller the abrasion index, the better the abrasion resistance.
1.2.7 loss factor
The ratio of loss modulus to elastic modulus is the ratio of the energy dissipated per cycle to the maximum stored energy over a cycle. The smaller the value of the loss factor tan at 60 ℃ is, the smaller the rolling resistance is indicated.
After tests on various performances of the rubber compound with the alkylphenol modified amino resin formula, the data are shown in tables 6-7:
TABLE 6
TABLE 7
As can be seen from the data in tables 6 to 7, compared with the blank rubber material, the alkylphenol modified amino resin prepared in this embodiment 1 has stronger tensile property, tear resistance, thermo-oxidative aging resistance, tensile strength at break and hardness before and after aging, and also has higher abrasion index, modulus, longer scorching time and lower loss factor, and significantly improves the performance of the rubber material.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. An alkylphenol-modified amino resin characterized by being composed of a structural unit represented by the formula (I):
wherein R is1、R2、R3、R4、R5、R6Each independently represents a hydrogen atom represented by the formula: -CH2-R' is a group represented by the formula: -CH2-or a group represented by formula (la): -CH2-R' -represents a group;
r ' represents a group obtained by removing one hydrogen atom from the active site on the benzene ring of the alkylphenol, and R ' is a residue obtained by removing one hydrogen atom from R '; wherein R is1、R2、R3、R4、R5、R6Is represented by the formula: -CH2-R' represents a group;
the alkylphenol modified amino resin comprises 1-15 unit body structural units shown in the formula (I);
the softening point of the alkylphenol modified amino resin is 50-180 ℃;
the alkylphenol modified amino resin is prepared by a method comprising the following steps:
adding alkylphenol and an acidic catalyst into a reaction bottle provided with a stirring device, a thermometer and a reflux condenser, adding or not adding an organic solvent, heating to completely dissolve the alkylphenol, slowly adding etherified methylol melamine or methylol melamine, controlling the reaction temperature to be 70-200 ℃, reacting for 0.5-10 h, changing the distillation state and adjusting the temperature to be 150-220 ℃, decompressing, vacuumizing, neutralizing, and discharging to obtain the alkylphenol modified amino resin;
the alkylphenol is one or more of cresol, xylenol, ethylphenol, allylphenol, tert-butylphenol, pentylphenol, heptylphenol, octylphenol, 2, 4-di-tert-butylphenol, 2-thio-di-p-tert-octylphenol, nonylphenol, decylphenol, dodecylphenol and cardanol.
2. The alkylphenol-modified amino resin of claim 1, wherein:
the alkylphenol modified amino resin comprises 4-10 unit body structural units shown in the formula (I).
3. The alkylphenol-modified amino resin of claim 1, wherein:
the softening point of the alkylphenol modified amino resin is 60-160 ℃.
4. A method for producing an alkylphenol-modified amino resin as claimed in any one of claims 1 to 3, characterized by comprising:
adding alkylphenol and an acidic catalyst into a reaction bottle provided with a stirring device, a thermometer and a reflux condenser, adding or not adding an organic solvent, heating to completely dissolve the alkylphenol, slowly adding etherified methylol melamine or methylol melamine, controlling the reaction temperature to be 70-200 ℃, reacting for 0.5-10 h, changing the distillation state and adjusting the temperature to be 150-220 ℃, decompressing, vacuumizing, neutralizing, and discharging to obtain the alkylphenol modified amino resin;
the alkylphenol is one or more of cresol, xylenol, ethylphenol, allylphenol, tert-butylphenol, pentylphenol, heptylphenol, octylphenol, 2, 4-di-tert-butylphenol, 2-thio-di-p-tert-octylphenol, nonylphenol, decylphenol, dodecylphenol and cardanol.
5. The process for producing an alkylphenol-modified amino resin as claimed in claim 4, characterized in that:
the amino resin is prepared by taking hexamethylol melamine (formula II) or etherified hexamethylol melamine (formula III) as a raw material, carrying out acid catalytic reaction on the hexamethylol melamine (formula II) or etherified hexamethylol melamine (formula III) and alkylphenol to obtain a unit body structural unit shown in a formula (I), further carrying out polymerization reaction, and finally neutralizing the obtained product, wherein the reaction process is as follows:
wherein R is1、R2、R3、R4、R5、R6Each independently represented by the formula: -CH2-R' is a group represented by the formula: -CH2-or a group represented by formula (la): -CH2-R' -represents a group;
r ' represents a group obtained by removing one hydrogen atom from the active site on the benzene ring of the alkylphenol, and R ' is a residue obtained by removing one hydrogen atom from R '; wherein R is1、R2、R3、R4、R5、R6Is represented by the formula: -CH2-R' represents a group; r7Selected from alkyl groups having 1 to 10 carbon atoms.
6. The process for producing an alkylphenol-modified amino resin as claimed in claim 5, characterized in that:
R7selected from alkyl with 1-4 carbon atoms.
7. The process for producing an alkylphenol-modified amino resin as claimed in claim 4, characterized in that:
the catalyst is an acidic catalyst and is selected from one or more of organic acid and inorganic acid;
the methylol melamine is selected from methylol melamine containing 1-6 methylol structures;
1-6 hydroxymethyl groups in the etherified methylol melamine are etherified;
the molar ratio of the methylol melamine or etherified methylol melamine to the alkylphenol is 1: 1-1: 6.
8. the process for producing an alkylphenol-modified amino resin as claimed in claim 7, characterized in that:
the organic acid catalyst is one or more of trifluoroacetic acid, trichloroacetic acid, dodecylbenzene sulfonic acid, benzene sulfonic acid, acetic acid and oxalic acid;
the inorganic acid catalyst is one or more of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid and nitric acid;
the methylol melamine is selected from methylol melamine containing 3-6 methylol structures;
3-6 hydroxymethyl groups in the etherified methylol melamine are etherified;
the molar ratio of the methylol melamine or etherified methylol melamine to the alkylphenol is 1: 3-1: 6.
9. use of the alkylphenol-modified amino resin as claimed in any one of claims 1 to 3 in rubber or rubber compositions.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3293212A (en) * | 1963-06-24 | 1966-12-20 | American Cyanamid Co | Thermosetting reaction product of hexakis-(alkoxymethyl) melamines and bisphenols |
| US4393181A (en) * | 1982-06-30 | 1983-07-12 | Shell Oil Company | Polyfunctional phenolic-melamine epoxy resin curing agents |
| US4436853A (en) * | 1982-08-20 | 1984-03-13 | The Goodyear Tire & Rubber Company | Phenol-melamine resins for improving rubber to metal adhesion |
| US4605696A (en) * | 1985-09-27 | 1986-08-12 | The Goodyear Tire & Rubber Company | Enhanced adhesion of rubber to reinforcing materials through the use of phenolic esters |
| JP4394978B2 (en) * | 2004-03-09 | 2010-01-06 | 住友ゴム工業株式会社 | Rubber composition for belt layer steel cord and steel cord coated thereby |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7326765B1 (en) * | 2002-08-16 | 2008-02-05 | Palmer International, Inc. | Melamine ring-containing co-polymers; methods of making and using the same |
-
2017
- 2017-03-09 CN CN201710137378.XA patent/CN108570134B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3293212A (en) * | 1963-06-24 | 1966-12-20 | American Cyanamid Co | Thermosetting reaction product of hexakis-(alkoxymethyl) melamines and bisphenols |
| US4393181A (en) * | 1982-06-30 | 1983-07-12 | Shell Oil Company | Polyfunctional phenolic-melamine epoxy resin curing agents |
| US4436853A (en) * | 1982-08-20 | 1984-03-13 | The Goodyear Tire & Rubber Company | Phenol-melamine resins for improving rubber to metal adhesion |
| US4605696A (en) * | 1985-09-27 | 1986-08-12 | The Goodyear Tire & Rubber Company | Enhanced adhesion of rubber to reinforcing materials through the use of phenolic esters |
| JP4394978B2 (en) * | 2004-03-09 | 2010-01-06 | 住友ゴム工業株式会社 | Rubber composition for belt layer steel cord and steel cord coated thereby |
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| CN108570134A (en) | 2018-09-25 |
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