CN109096455B - Preparation method of modified alkyl phenolic tackifying resin and rubber composition thereof - Google Patents
Preparation method of modified alkyl phenolic tackifying resin and rubber composition thereof Download PDFInfo
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Abstract
The invention relates to a modified alkyl phenolic tackifying resin, which is prepared by reacting alkyl phenol formaldehyde resin with a modifier in the presence of an acid catalyst; the invention also relates to a rubber composition comprising a rubber or rubber mixture and the modified alkyl phenolic tackifying resin. The modified alkyl phenolic tackifying resin provided by the invention can improve the tackifying effect of rubber under high-temperature and high-humidity conditions, and is modified by non-hazardous solvents such as non-acetylene and the like, so that the preparation process is safe; the process does not use a solvent, so that the operation is simpler; the added modifier does not generate extra liquid or gas waste, so that the environment is protected.
Description
Technical Field
The invention relates to the technical field of phenolic resin, in particular to a preparation method of modified alkyl phenolic tackifying resin and a rubber composition thereof.
Background
The adhesiveness is the basic chemical property of the material surface, particularly in the tire industry, and the unvulcanized rubber surface must have certain adhesiveness and initial adhesion so as to integrate the rubber of each part of the tire by sticking until molding. If the adhesive material lacks adhesion, especially the synthetic rubber material, the semi-finished rubber part is not only easy to deform in size, but also can crack at the adhesive part because of expansion during molding.
Among various tackifiers, the synthetic type has higher tackifying performance than natural type, in the synthetic type tackifiers, the initial tackifying performance of non-thermal reactive alkylphenol formaldehyde resin is better than that of petroleum resin type tackifiers, and common non-thermal reactive alkylphenol formaldehyde tackifying resin has good initial tackifying performance, but the tackiness of rubber material is rapidly reduced after the rubber material is aerated or subjected to damp-heat treatment. In actual industrial production, the rubber needs to be stored, and due to adverse factors such as hot summer and high air humidity, the tackifier is required to have long-acting property, moisture resistance and high tackifying property.
The Koresin of BASF company is an alkylphenol-acetylene resin, which has excellent synergistic effects such as long-lasting effect and resistance to humidity, but has the following disadvantages: the production difficulty is high, the process is complex, the equipment requirement is high, the price is high, and acetylene used as a raw material for production has great potential safety hazard and the like.
CN105646806A discloses a method for preparing acetylene modified alkylphenol formaldehyde super tackifying resin, which comprises the steps of firstly, preparing alkylphenol formaldehyde tackifying resin by reacting alkylphenol with formaldehyde by using catalyst oxalic acid; then, according to the tackifying mechanism of Koresin, acetylene and alkylphenol formaldehyde tackifying resin are used for preparing acetylene modified alkylphenol formaldehyde super tackifying resin by adopting the reaction of catalyst zinc carboxylate. Although the tackifying resin prepared by the method has excellent long-acting tackifying capability and excellent long-acting tackifying effect under severe conditions such as high temperature, high humidity and the like, acetylene gas is used as a raw material for the tackifying resin, and high-temperature and high-pressure reaction is required for production, so that the tackifying resin is difficult to operate, has a high risk coefficient and is not beneficial to environmental protection.
Therefore, how to improve the tackifying effect of the rubber under the high-temperature and high-humidity condition, and the preparation process does not use acetylene and other gases, the simple and environment-friendly process becomes a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a modified alkyl phenolic tackifying resin which not only can improve the tackifying effect of rubber under the high-temperature and high-humidity condition, but also has safe preparation process because of adopting non-dangerous solvents such as non-acetylene and the like for modification; the process does not use a solvent, so that the operation is simpler; the added modifier does not generate extra liquid or gas waste, so that the environment is protected.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a modified alkyl phenolic tackifying resin, which comprises a small molecular substance with a molecular weight of 236.3 in the molecular weight distribution, wherein the content of the small molecular substance is less than 10%.
The modified alkyl phenolic tackifying resin provided by the invention is prepared by reacting an alkyl phenol formaldehyde resin with a modifier in the presence of an acid catalyst.
The invention also provides a process for preparing the modified alkyl phenolic tackifying resin in which an alkyl phenol formaldehyde resin is reacted with a modifier in the presence of an acid catalyst. The method may further comprise the step of neutralizing the acid catalyst with a base after the completion of the reaction.
In another aspect, the present invention provides a rubber composition comprising a rubber or rubber mixture and a modified alkyl phenolic tackifying resin of the present invention.
The invention also provides the use of the rubber composition in the production of tires and industrial rubber articles.
Compared with the prior art, the invention has at least the following beneficial effects:
the modified alkyl phenolic tackifying resin provided by the invention can improve the tackifying effect of rubber materials under high-temperature and high-humidity conditions, the hot and humid viscosity value of the rubber materials can reach 14.1 after 2 hours in the environment with the temperature of 60 ℃ and the humidity of 90%, and the preparation process is safer due to the adoption of non-dangerous solvents such as non-acetylene and the like for modification; a solvent is not used in the process, so that the operation is simpler; the added modifier does not generate extra liquid or gas waste, so that the environment is protected.
Detailed Description
The present invention relates to alkyl phenol formaldehyde tackifying resins modified with modifiers. The modified alkyl phenolic tackifying resins of the present invention are prepared by reacting an alkyl phenol formaldehyde resin with a modifier in the presence of an acid catalyst.
The reaction route of the modified alkyl phenolic tackifying resin in the invention is as follows:
the field analysis mass spectrogram of the modified alkyl phenolic tackifying resin is shown in figure 1. The mass spectrogram shows that the modified alkyl phenolic aldehyde tackifying resin contains phenolic resin polymers with normal molecular weight, and the inventor finds that the mass spectrogram also contains micromolecular compounds with the molecular weight of 236.3, and the content of the micromolecular compounds with the molecular weight of 236.3 is measured to be below 10 percent by using high performance liquid chromatography for quantification.
The micromolecule substance with the molecular weight of 236.3 contained in the modified alkyl phenolic tackifying resin is derived from at least the following conditions: (1) the unreacted part left after the reaction with the alkylphenol-formaldehyde resin by adding a modifier with a molecular weight of 236.3; (2) the added small molecular weight substance generates a substance with a molecular weight of 236.3 in the reaction process; (3) the added modifier with larger molecular weight is decomposed in the reaction process to obtain the substance with the molecular weight of 236.3.
The modified alkyl phenolic tackifying resin disclosed by the invention contains micromolecular compounds with the molecular weight of 236.3, so that the compatibility of the resin and rubber is better, the plasticity of the rubber is improved, the initial viscosity of the rubber material is also improved, and the tackifying effect of the rubber material under the high-temperature and high-humidity conditions can be greatly improved.
According to the present invention, the alkylphenol-formaldehyde resin may be modified with any modifier, provided that the resulting modified alkylphenol-formaldehyde tackifying resin necessarily contains a small molecular substance having a molecular weight of 263.3 and the content of the small molecular substance is 10% or less, for example, 10%, 8%, 7%, 6%, 5%, 4%, etc.
The small molecule substance with a molecular weight of 236.3 contained in the modified alkyl phenol formaldehyde tackifying resin of the present invention is preferably derived from the remaining unreacted portion of the modifying agent with a molecular weight of 236.3 after reaction with the alkylphenol formaldehyde resin. By the mode, the compatibility of the resin and the rubber and the plasticity of the rubber can be further improved, the initial viscosity of the rubber material can be further improved, and the tackifying effect of the rubber material under the high-temperature and high-humidity condition can be greatly improved.
Examples of modifiers useful in the present invention include, but are not limited to: 2-ethylanthraquinone, 1, 4-dimethylanthraquinone, 2, 6-dimethylanthraquinone, 2, 3-dimethylanthraquinone, 2, 4-diphenyl-4-methylpentene, 6-methylflavone, any one or a mixture of at least two of diphenylethanone hydrazone 3- (N, N-diethyl) amino-4-methoxyacetanilide, butaneyl- α -D-glucopyranose, 2,3,4, 6-tetramethyl-D-glucose, 1-ethyl-4- [2- (4-methoxyphenyl) ethynyl ] benzene, 6-phenylamino-1, 3, 5-triazine-2, 4-thiol, or 4, 4-dimethyl chalcone, where a typical but non-limiting mixture is: a mixture of 2-ethylanthraquinone and 1, 4-dimethylanthraquinone, a mixture of 6-methylflavone and 4, 4-dimethylchalcone, a mixture of 2-ethylanthraquinone, 1, 4-dimethylanthraquinone and 1-ethyl-4- [2- (4-methoxyphenyl) ethynyl ] benzene.
Any alkylphenol-formaldehyde resin may be used to form the modified alkyl phenol-formaldehyde tackifying resin of the present invention. The polymerization of alkyl phenols with formaldehyde to produce alkyl phenol formaldehyde resins is well known in the art.
The term "alkyl" in the present invention is meant to include linear and branched aliphatic alkyl substituents, preferably said alkyl is selected from the group consisting of C1-C15 alkyl, for example selected from the group consisting of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14 or C15 alkyl, preferably C4-C15 alkyl; further preferably, the alkyl group is any one of nonyl, octyl, tert-butyl or tert-octyl, more preferably any one of nonyl, octyl or tert-butyl. The alkyl groups may be substituted with conventional functional groups such as hydroxyl, amino, carboxyl, halogen, thiol or disulfide groups, etc., which should not impair the tackifying effect of the modified alkyl phenolic tackifying resins of the present invention or the rubber compositions to which the resins are added under high temperature and humidity conditions.
According to the present invention, the acid catalyst is preferably an organic acid catalyst, including any one or a mixture of at least two of oxalic acid, benzoic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid or acetic acid, wherein typical but non-limiting mixtures are: a mixture of oxalic acid and benzoic acid, a mixture of dodecylbenzenesulfonic acid and p-toluenesulfonic acid, and a mixture of benzoic acid, p-toluenesulfonic acid and acetic acid. The amount of the acid catalyst is preferably 0.1-1 part per 100 parts of the modified alkyl phenolic resin.
According to the invention, the weight ratio of the alkylphenol-formaldehyde resin to the modifier is 10 (0.1-2), such as 10:0.1, 10:0.2, 10:0.5, 10:0.8, 10:1, 10:1.2, 10:1.5, 10:1.8 or 10: 2.
The present invention also provides a process for preparing a modified alkyl phenolic tackifying resin as described hereinbefore, comprising the steps of: reacting an alkylphenol-formaldehyde resin with a modifier in the presence of an acid catalyst. The process may also include the step of neutralizing the acid catalyst after the modification reaction is complete with a base, which may be any base from caustic NaOH to amines, but is preferably triethylamine or triethanolamine.
According to the modification reaction of the invention, the resin does not need to be dissolved in the solvent, namely the solvent is not used in the whole preparation process, so that the operation is simpler, the added modifier does not generate extra liquid or gas waste, and the environment is more protected.
As noted above, any alkylphenol-formaldehyde resin may be used to form the modified alkyl phenol-formaldehyde tackifying resin of the present invention. The modification reaction may be carried out directly as a subsequent process after the phenol-formaldehyde polymerization to form the phenolic resin or may be used to modify the phenolic resin after initial production. The process can be carried out in a reactor, such as a conventional vessel or glass flask, equipped with a stirrer, heater, thermostat, feed, reflux condenser and water separator. The alkylphenol can be added with the catalyst at the beginning and reaches the desired reaction temperature or distillation temperature, and after a period of reaction, the formaldehyde water solution is added; it is also possible to add only a part of the alkylphenol at the beginning and then add the remaining part together with the formaldehyde, or to add all of the alkylphenol, the aqueous formaldehyde solution and the catalyst at the beginning, and in any case, the order of addition of the alkylphenol, the aqueous formaldehyde solution and the acid catalyst is not particularly limited in the present invention, and it is allowed to react at a desired reaction temperature or distillation temperature. After the condensation reaction is complete, the modifier is added to the reactor and held at the appropriate reaction temperature for an additional time. The reaction can be neutralized with a base and the water distilled off.
According to the invention, the phenolic aldehyde polycondensation reaction in the preparation method is generally controlled to be carried out at 100-150 ℃, and can be, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃; the time of the polycondensation reaction is 1-3 h, for example, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h or 3 h; the modification reaction is carried out at a temperature of 120-150 deg.C, such as 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C or 150 deg.C; the time of the modification reaction is 1 to 2 hours, for example, 1 hour, 1.2 hours, 1.5 hours, 1.8 hours or 2 hours.
The preparation method of the invention also comprises the following steps: the modified alkylphenol-formaldehyde resin obtained is dehydrated by heating, generally the temperature is raised to 170 ℃ or higher, the modified alkylphenol-formaldehyde resin is purified, the modified alkylphenol-formaldehyde resin is vacuumized, for example, to-0.09 MP, the vacuum degree is kept unchanged for 0.5h or more, and when the temperature of the reaction mixture is raised to 180 ℃ or higher, the purification is completed when the free phenol is less than 2%.
According to the present invention, after the above purification is completed, the method may further include: and pouring the obtained modified alkyl phenolic resin into a cooling disc while the modified alkyl phenolic resin is hot, and cooling to obtain yellow transparent blocky modified alkyl phenolic resin.
The modified alkyl phenolic tackifying resins prepared according to the present invention can be used in a wide variety of applications. The modified resins are useful, for example, as binders, dispersants, surfactants, emulsifiers, elastomers, coatings, paints, thermoplastic elastomers, engineering resins, ink components, lubricants, polymer blend components, paper additives, biomaterials, water treatment additives, cosmetic components, antistatic agents, food and beverage packaging materials, as release blenders in medical applications, and the like.
The modified alkyl phenol formaldehyde tackifying resins prepared according to the present invention may be used to form rubber compositions by mixing with rubber or rubber compounds. The amount of the modified alkyl phenol resin used is preferably 2 to 6%, for example, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5% or 6% of the total mass of the rubber composition.
The modified alkylphenolic tackifying resins prepared according to the invention can also be used as reinforcing resins for rubbers or elastomers, for which purpose they can be incorporated into the rubber or elastomer mixture which has not yet been vulcanized, either together with the crosslinking agent or separately from the crosslinking agent. Any desired delivery form of rubber may be used, such as any one or a mixture of at least two of natural rubber, butadiene rubber or styrene butadiene rubber, and other conventional additives may also be used in the rubber composition of the present invention, including but not limited to: fillers, vulcanizing agents, accelerators, activators, processing aids, for example at least one aid selected from carbon black, insoluble sulfur, accelerators, zinc oxide or scorch retarders, the specific amounts of these components being such that they can be formulated appropriately according to the actual needs by the person skilled in the art, and the invention is not particularly limited.
The modified alkyl phenol formaldehyde tackifying resins prepared according to the present invention are useful as tackifiers for rubbers and are particularly useful in the production of tires, especially winter tires, tire components, especially tire treads, subtreads, carcasses, sidewalls, reinforced sidewalls for run-flat tires, and bead apex compounds, and in the production of industrial rubber goods, preferably damping elements, roll covers, conveyor belt covers, drive belts, spun yarns, seals, golf ball cores and shoe soles, and the like.
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
(1) Adding 500g of nonyl phenol, 120g of formaldehyde aqueous solution with the mass concentration of 50% and 1g of oxalic acid with the mass fraction of more than 98% into a 2000mL four-neck flask, carrying out phenolic aldehyde polycondensation reaction, arranging an electric stirrer, a thermometer and a constant-pressure dropping funnel on the four-neck flask, starting the stirrer, starting heating, heating the reaction mixture to 100 ℃ within 30min, keeping the system boiling, refluxing at the constant temperature of 100 ℃, and reacting for 3h to obtain thermoplastic alkyl phenolic resin;
(2) adding 50g of 2-ethyl anthraquinone into the thermoplastic phenolic resin obtained in the step (1), and continuously carrying out constant-temperature reflux reaction for 2 hours to obtain modified alkyl phenolic resin;
(3) heating the obtained modified alkyl phenolic resin for dehydration, purifying the modified alkyl phenolic resin when the temperature is increased to 170 ℃, vacuumizing to-0.09 MP, keeping the vacuum degree unchanged for more than 0.5h, and finishing purification when the temperature of a reaction mixture is increased to 180 ℃ and the content of free phenol is less than 2%;
(4) and after the purification is finished, pouring the obtained modified alkyl phenolic resin into a cooling disc while the modified alkyl phenolic resin is hot, and cooling to obtain yellow transparent blocky modified alkyl phenolic resin.
Preparation example 2
(1) Adding 500g of p-tert-octylphenol, 110g of formaldehyde aqueous solution with the mass concentration of 50% and 1g of dodecylbenzene sulfonic acid with the mass fraction of more than 98% into a 2000mL four-neck flask, carrying out phenolic aldehyde polycondensation reaction, arranging an electric stirrer, a thermometer and a constant-pressure dropping funnel on the four-neck flask, starting the stirrer, starting heating, heating the reaction mixture to 100 ℃ within 30min, keeping the system boiling, refluxing at the constant temperature of 100 ℃, and reacting for 3h to obtain the thermoplastic alkyl phenolic resin;
(2) heating the thermoplastic alkyl phenolic resin obtained in the step (1) to dehydrate, adding 50g of 2,3,4, 6-tetramethyl-d-glucose when the temperature is raised to 150 ℃, and continuously carrying out reflux reaction at a constant temperature of about 150 ℃ for 2h to obtain modified alkyl phenolic resin;
(3) heating the obtained modified alkyl phenolic resin for dehydration, purifying the modified alkyl phenolic resin when the temperature is increased to 170 ℃, vacuumizing to-0.09 MP, keeping the vacuum degree unchanged for more than 0.5h, and finishing purification when the temperature of a reaction mixture is increased to 180 ℃ and the content of free phenol is less than 2%;
(4) and after the purification is finished, pouring the obtained modified alkylphenol formaldehyde resin into a cooling disc while the modified alkylphenol formaldehyde resin is hot, and cooling to obtain the yellow transparent blocky modified alkylphenol formaldehyde resin.
Preparation example 3
(1) Adding 500g of p-tert-butylphenol, 90g of formaldehyde aqueous solution with the mass concentration of 50% and 1g of dodecylbenzene sulfonic acid with the mass fraction of more than 98% into a 2000mL four-neck flask, carrying out phenolic aldehyde polycondensation reaction, arranging an electric stirrer, a thermometer and a constant-pressure dropping funnel on the four-neck flask, starting the stirrer, starting heating, heating the reaction mixture to 100 ℃ within 30min, keeping the system boiling, refluxing at the constant temperature of 100 ℃, and reacting for 3h to obtain thermoplastic alkyl phenolic resin;
(2) heating the thermoplastic alkyl phenolic resin obtained in the step (1) for dehydration, adding 50g of 4, 4-dimethyl chalcone when the temperature is raised to 150 ℃, and continuously carrying out reflux reaction at a constant temperature of about 150 ℃ for 2 hours to obtain modified alkyl phenolic resin;
(3) heating the obtained modified alkyl phenolic resin for dehydration, purifying the modified alkyl phenolic resin when the temperature is increased to 170 ℃, vacuumizing to-0.09 MP, keeping the vacuum degree unchanged for more than 0.5h, and finishing purification when the temperature of a reaction mixture is increased to 180 ℃ and the content of free phenol is less than 2%;
(4) and after the purification is finished, pouring the obtained modified alkylphenol formaldehyde resin into a cooling disc while the modified alkylphenol formaldehyde resin is hot, and cooling to obtain the yellow transparent blocky modified alkylphenol formaldehyde resin.
Preparation example 4
(1) Adding 500g of p-tert-butylphenol and 50g of 2, 4-diphenyl-4-methylpentene into a 2000mL four-necked flask, arranging an electric stirrer, a thermometer and a constant-pressure dropping funnel on the four-necked flask, starting the stirrer, heating to 140 ℃, adding 1g of p-toluenesulfonic acid with the mass fraction of more than 98%, reacting at 140 ℃ for 1h at constant temperature, adding 90g of formaldehyde aqueous solution with the mass concentration of 50% to perform phenolic aldehyde polycondensation reaction, keeping the system boiling, refluxing at 100 ℃ at constant temperature, and reacting for 3h to obtain modified alkyl phenolic resin;
(2) heating the modified alkyl phenol formaldehyde resin obtained in the step (1) for dehydration, purifying the modified alkyl phenol formaldehyde resin when the temperature is increased to 170 ℃, vacuumizing to-0.09 MP, keeping the vacuum degree unchanged for more than 0.5h, and finishing purification when the temperature of a reaction mixture is increased to 180 ℃ and the content of free phenol is less than 2%;
(3) and after the purification is finished, pouring the obtained modified alkylphenol formaldehyde resin into a cooling disc while the modified alkylphenol formaldehyde resin is hot, and cooling to obtain the yellow transparent blocky modified alkylphenol formaldehyde resin.
Preparation example 5
(1) Adding 500g of p-tert-butylphenol, 90g of formaldehyde aqueous solution with the mass concentration of 50% and 1g of dodecylbenzene sulfonic acid with the mass fraction of more than 98% into a 2000mL four-neck flask, carrying out phenolic aldehyde polycondensation reaction, arranging an electric stirrer, a thermometer and a constant-pressure dropping funnel on the four-neck flask, starting the stirrer, starting heating, heating the reaction mixture to 100 ℃ within 30min, keeping the system boiling, refluxing at the constant temperature of 100 ℃, and reacting for 3h to obtain thermoplastic alkyl phenolic resin;
(2) heating the thermoplastic alkyl phenolic resin obtained in the step (1) to dehydrate, adding 20g of diphenylethanone hydrazone and 30g of 6-methyl flavone when the temperature is raised to 150 ℃, and continuously carrying out reflux reaction at a constant temperature of about 150 ℃ for 2 hours to obtain modified alkyl phenolic resin;
(3) heating the obtained modified alkyl phenolic resin for dehydration, purifying the modified alkyl phenolic resin when the temperature is increased to 170 ℃, vacuumizing to-0.09 MP, keeping the vacuum degree unchanged for more than 0.5h, and finishing purification when the temperature of a reaction mixture is increased to 180 ℃ and the content of free phenol is less than 2%;
(4) and after the purification is finished, pouring the obtained modified alkylphenol formaldehyde resin into a cooling disc while the modified alkylphenol formaldehyde resin is hot, and cooling to obtain the yellow transparent blocky modified alkylphenol formaldehyde resin.
Comparative preparation example 1 (comparison with preparation example 3, without any modifier)
(1) Adding 500g of p-tert-butylphenol, 90g of formaldehyde aqueous solution with the mass concentration of 50% and 1g of dodecylbenzene sulfonic acid with the mass fraction of more than 98% into a 2000mL four-neck flask, carrying out phenolic aldehyde polycondensation reaction, arranging an electric stirrer, a thermometer and a constant-pressure dropping funnel on the four-neck flask, starting the stirrer, starting heating, heating the reaction mixture to 100 ℃ within 30min, keeping the system boiling, refluxing at the constant temperature of 100 ℃, and reacting for 3h to obtain thermoplastic alkyl phenolic resin;
(2) heating the thermoplastic alkyl phenolic resin obtained in the step (1) for dehydration, purifying the thermoplastic alkyl phenolic resin when the temperature is raised to 170 ℃, vacuumizing to-0.09 MP, keeping the vacuum degree unchanged for more than 0.5h, and finishing purification when the temperature of a reaction mixture is raised to 180 ℃ and the free phenol is less than 2%;
(3) and after the purification is finished, pouring the obtained thermoplastic alkylphenol formaldehyde resin into a cooling disc while the thermoplastic alkylphenol formaldehyde resin is hot, and cooling to obtain yellow transparent blocky alkylphenol formaldehyde resin.
Comparative preparation example 2 (addition of 4-methylstyrene modifier compared with preparation example 4)
(1) Adding 500g of p-tert-butylphenol and 50g of 4-methylstyrene into a 2000mL four-neck flask, arranging an electric stirrer, a thermometer and a constant-pressure dropping funnel on the four-neck flask, starting the stirrer, heating to 140 ℃, adding 1g of p-toluenesulfonic acid with the mass fraction of more than 98%, reacting at the constant temperature of 140 ℃ for 1h, adding 90g of formaldehyde aqueous solution with the mass concentration of 50% to perform phenolic polycondensation, keeping the system boiling, refluxing at the constant temperature of 100 ℃, and reacting for 3h to obtain modified alkyl phenolic resin;
(2) heating the modified alkyl phenol formaldehyde resin obtained in the step (1) for dehydration, purifying the modified alkyl phenol formaldehyde resin when the temperature is increased to 170 ℃, vacuumizing to-0.09 MP, keeping the vacuum degree unchanged for more than 0.5h, and finishing purification when the temperature of a reaction mixture is increased to 180 ℃ and the content of free phenol is less than 2%;
(3) and after the purification is finished, pouring the obtained modified alkylphenol formaldehyde resin into a cooling disc while the modified alkylphenol formaldehyde resin is hot, and cooling to obtain the yellow transparent blocky modified alkylphenol formaldehyde resin.
Comparative preparation example 3
Compared with the preparation example 1, the 2-ethyl anthraquinone is replaced by anthraquinone, and the specific operation is as follows:
(1) adding 500g of p-tert-butylphenol, 90g of formaldehyde aqueous solution with the mass concentration of 50% and 1g of dodecylbenzene sulfonic acid with the mass fraction of more than 98% into a 2000mL four-neck flask, carrying out phenolic aldehyde polycondensation reaction, arranging an electric stirrer, a thermometer and a constant-pressure dropping funnel on the four-neck flask, starting the stirrer, starting heating, heating the reaction mixture to 100 ℃ within 30min, keeping the system boiling, refluxing at the constant temperature of 100 ℃, and reacting for 3h to obtain thermoplastic alkyl phenolic resin;
(2) heating the thermoplastic alkyl phenolic resin obtained in the step (1) to dehydrate, adding 50g of anthraquinone when the temperature is raised to 150 ℃, and continuously carrying out reflux reaction at a constant temperature of about 150 ℃ for 2h to obtain modified alkyl phenolic resin;
(3) heating the obtained modified alkyl phenolic resin for dehydration, purifying the modified alkyl phenolic resin when the temperature is increased to 170 ℃, vacuumizing to-0.09 MP, keeping the vacuum degree unchanged for more than 0.5h, and finishing purification when the temperature of a reaction mixture is increased to 180 ℃ and the content of free phenol is less than 2%;
(4) and after the purification is finished, pouring the obtained modified alkyl phenolic resin into a cooling disc while the modified alkyl phenolic resin is hot, and cooling to obtain yellow transparent blocky modified alkyl phenolic resin.
Comparative preparation example 4
Compared with the preparation example 2, the specific operation of replacing 2,3,4, 6-tetramethyl-d-glucose by glucose is as follows:
(1) adding 500g of p-tert-butylphenol, 90g of formaldehyde aqueous solution with the mass concentration of 50% and 1g of dodecylbenzene sulfonic acid with the mass fraction of more than 98% into a 2000mL four-neck flask, carrying out phenolic aldehyde polycondensation reaction, arranging an electric stirrer, a thermometer and a constant-pressure dropping funnel on the four-neck flask, starting the stirrer, starting heating, heating the reaction mixture to 100 ℃ within 30min, keeping the system boiling, refluxing at the constant temperature of 100 ℃, and reacting for 3h to obtain thermoplastic alkyl phenolic resin;
(2) heating the thermoplastic alkyl phenolic resin obtained in the step (1) for dehydration, adding 50g of glucose when the temperature is raised to 150 ℃, and continuously carrying out reflux reaction at a constant temperature of about 150 ℃ for 2h to obtain modified alkyl phenolic resin;
(3) heating the obtained modified alkyl phenolic resin for dehydration, purifying the modified alkyl phenolic resin when the temperature is increased to 170 ℃, vacuumizing to-0.09 MP, keeping the vacuum degree unchanged for more than 0.5h, and finishing purification when the temperature of a reaction mixture is increased to 180 ℃ and the content of free phenol is less than 2%;
(4) and after the purification is finished, pouring the obtained modified alkyl phenolic resin into a cooling disc while the modified alkyl phenolic resin is hot, and cooling to obtain yellow transparent blocky modified alkyl phenolic resin.
The free phenol contents of the modified alkyl phenol resins obtained in the above preparation examples 1 to 5 and comparative preparation examples 1 to 4 and the commercially available KORESIN resin were measured according to chemical standard HG/T2621-1994 "gas chromatography for measuring the content of residual phenol in phenol resin", and the results are shown in tables 1 to 2.
The softening points of the modified alkylphenol-formaldehyde resins obtained in the above preparation examples 1 to 5 and comparative preparation examples 1 to 4 were measured according to national standard GB/T4507-1999 asphalt softening point measurement method (Ring and ball method), and the results are shown in tables 1 to 2.
TABLE 1 physicochemical indices of modified alkylphenol aldehyde resins obtained in preparation examples 1 to 5
Table 2 shows the physical and chemical indexes of the modified alkylphenol aldehyde resins obtained in comparative preparation examples 1 to 4
| Detecting items | Comparative preparation example 1 | Comparative preparation example 2 | Comparative preparation example 3 | Comparative preparation example 4 | KORESIN |
| Free alkylphenol/%) | 1.4 | 1.5 | 1.5 | 1.6 | 1.2 |
| Ring and ball softening point/. degree.C | 127 | 127 | 126 | 125 | 128 |
As can be seen from tables 1-2, the free alkylphenol content and the ring-and-ball softening point of the modified alkylphenol-formaldehyde resins obtained in preparation examples 1-5 are not much different from those of comparative preparation examples 1-4 and commercially available KORESIN resins, and the influence of the free alkylphenol content and the ring-and-ball softening point index of the resins on the performance of the sizing material can be eliminated.
Example 1
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of the modified alkylphenol formaldehyde resin prepared in preparation example 1 of the present invention were kneaded and subjected to a small compounding test to obtain a tire rubber.
Example 2
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of the modified alkylphenol formaldehyde resin prepared in preparation example 2 of the present invention were kneaded and subjected to a small compounding test to obtain a tire rubber.
Example 3
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of the modified alkylphenol formaldehyde resin prepared in preparation example 3 of the present invention were kneaded and subjected to a small compounding test to obtain a tire rubber.
Example 4
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of the modified alkylphenol formaldehyde resin prepared in preparation example 4 of the present invention were kneaded and subjected to a small compounding test to obtain a tire rubber.
Example 5
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of the modified alkylphenol formaldehyde resin prepared in preparation example 5 of the present invention were kneaded and subjected to a small compounding test to obtain a tire rubber.
Comparative example 1
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of the modified phenol resin prepared in comparative preparation example 1 were kneaded and subjected to a mini-compounding test to obtain a tire rubber.
Comparative example 2
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of the modified phenol resin prepared in comparative preparation example 2 were kneaded and subjected to a mini-compounding test to obtain a tire rubber.
Comparative example 3
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of the modified phenol resin prepared in comparative preparation example 3 were kneaded and subjected to a mini-compounding test to obtain a tire rubber.
Comparative example 4
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of the modified phenol resin prepared in comparative preparation example 4 were kneaded and subjected to a mini-compounding test to obtain a tire rubber.
Comparative example 5
100 parts by weight of butadiene rubber, 66 parts by weight of carbon black, 3 parts by weight of insoluble sulfur, 1 part by weight of an accelerator TMTD, 3 parts by weight of zinc oxide, 0.6 part by weight of a scorch retarder and 4 parts by weight of a commercially available KORESIN resin were mixed and subjected to a mini compounding test to obtain a tire rubber.
The performance data of the tire rubbers obtained in examples 1 to 5 and comparative examples 1 to 5 are specifically shown in tables 3 to 4.
TABLE 3 Performance data of the tire rubbers obtained in examples 1 to 5
TABLE 4 Performance data of the tire rubbers obtained in comparative examples 1 to 5
The following points can be seen from tables 3-4:
(1) as can be seen from comparison of example 3 with comparative example 1, the tire rubber obtained in example 3 is superior to comparative example 1 in both the storage tack and the hot humid tack, and it is demonstrated that the tire rubber of the present invention obtained by using the modified alkylphenol aldehyde resin can obtain more excellent storage tack and hot humid tack than the tire rubber obtained by adding the unmodified alkylphenol aldehyde resin.
(2) Comparing example 4 with comparative example 2, it can be seen that the tire rubber obtained in example 4 exhibits a storage tack and a hot and humid tack superior to those of comparative example 2, indicating that the tire rubber obtained from the alkylphenol aldehyde resin obtained by adding the 2, 4-diphenyl-4-methylpentene modifier according to the present invention can obtain a more excellent storage tack and hot and humid tack than the alkylphenol aldehyde resin obtained by adding the 4-methylstyrene modifier.
(3) As can be seen from comparison of example 1 with comparative example 3, the storage tack and hot humid tack of the tire rubber obtained in example 1 are superior to those of comparative example 3; as can be seen from comparison of example 2 with comparative example 4, the storage tack and hot and humid tack of the tire rubber obtained in example 2 are also superior to those of comparative example 4; it can be seen from this that, by using a modifier having a molecular weight of 236.3, such as 2-ethylanthraquinone, 2,3,4, 6-tetramethyl-d-glucose, etc., the present invention can exhibit more excellent storage tack and hot and humid tack than using a modifier having a molecular weight outside this range, such as anthraquinone, glucose, etc.
As can be seen by comparing the properties of the tire rubbers of examples 1-5 with comparative example 5, it is similar to tire rubbers obtained using the commercially recognized KORESIONS resin, a super tackifying resin.
In conclusion, the modified alkyl phenolic tackifying resin provided by the invention contains a micromolecule substance with the molecular weight of 236.3 in the molecular weight distribution, so that the tackifying effect of rubber materials under high-temperature and high-humidity conditions can be greatly improved by adding the modified alkyl phenolic tackifying resin into rubber; in addition, when the preparation is carried out, the preparation process is safer due to the adoption of modification by non-dangerous solvents such as non-acetylene and the like; the process does not use a solvent, so that the operation is simpler; the added modifier does not generate extra liquid or gas waste, so that the environment is protected.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (18)
1. A modified alkyl phenolic tackifying resin is characterized in that the molecular weight distribution of the modified alkyl phenolic tackifying resin contains micromolecular substances with the molecular weight of 236.3, and the content of the micromolecular substances is less than 10%;
the modified alkyl phenolic tackifying resin is prepared by reacting an alkyl phenol formaldehyde resin with a modifier in the presence of an acid catalyst;
the modifier is any one or a mixture of at least two of 2-ethyl anthraquinone, 1, 4-dimethyl anthraquinone, 2, 6-dimethyl anthraquinone, 2, 3-dimethyl anthraquinone, 2, 4-diphenyl-4-methyl pentene, 6-methyl flavone, diphenylethanone hydrazone, 3- (N, N-diethyl) amino-4-methoxy acetanilide, 1-ethyl-4- [2- (4-methoxyphenyl) ethynyl ] benzene, 6-phenylamino-1, 3, 5-triazine-2, 4-thiol or 4, 4-dimethyl chalcone;
the small molecule substance with the molecular weight of 236.3 comes from the residual unreacted part after the modifier with the molecular weight of 236.3 is reacted with the alkylphenol formaldehyde resin.
2. The modified alkyl phenol formaldehyde tackifying resin of claim 1, wherein the weight ratio of the alkyl phenol formaldehyde resin to the modifier is 10 (0.1-2).
3. The modified alkyl phenol formaldehyde tackifying resin of claim 1 wherein said alkyl groups in said alkyl phenol formaldehyde resin are C1 to C15 alkyl groups.
4. The modified alkyl phenol formaldehyde tackifying resin of claim 1 wherein said alkyl groups in said alkyl phenol formaldehyde resin are C4 to C15 alkyl groups.
5. The modified alkyl phenol formaldehyde tackifying resin of claim 1 wherein said alkyl group is any one of nonyl, octyl, t-butyl or t-octyl.
6. The modified alkyl phenol formaldehyde tackifying resin of claim 1 wherein said alkyl group is any one of nonyl, octyl or t-butyl.
7. The modified alkyl phenol formaldehyde tackifying resin of claim 1 wherein said acid catalyst is any one or a mixture of at least two of oxalic acid, benzoic acid, p-toluene sulfonic acid, dodecylbenzene sulfonic acid or acetic acid.
8. A process for the preparation of a modified alkyl phenolic tackifying resin according to any one of claims 1 to 7, comprising the steps of: reacting an alkylphenol-formaldehyde resin with a modifier in the presence of an acid catalyst.
9. The method of claim 8, further comprising the step of neutralizing the acid catalyst with a base after the reaction is complete.
10. A rubber composition comprising a rubber or rubber mixture and a modified alkyl phenolic tackifying resin of any one of claims 1 to 7.
11. The rubber composition of claim 10, wherein the rubber is any one of natural rubber, butadiene rubber or styrene-butadiene rubber or a mixture of at least two of the natural rubber, the butadiene rubber and the styrene-butadiene rubber.
12. The rubber composition of claim 10, further comprising any one or a mixture of at least two of carbon black, insoluble sulfur, accelerators, zinc oxide, or scorch retarders.
13. Use of a rubber composition as defined in any one of claims 10 to 12 for the production of tyres.
14. Use of the rubber composition according to any of claims 10 to 12 in winter tyres, tyre parts.
15. Use of the rubber composition of any one of claims 10-12 in a tire tread, subtread, carcass, sidewall, or bead apex mixture.
16. Use according to claim 15, wherein the sidewall comprises a reinforced sidewall of a run-flat tire.
17. Use of the rubber composition according to any one of claims 10 to 12 for the production of technical rubber articles.
18. Use of the rubber composition of any of claims 10-12 in a damping element, a roll cover, a conveyor belt cover, a drive belt, a spun cop, a seal, a golf ball core or a shoe sole.
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| CN116409994A (en) * | 2022-01-10 | 2023-07-11 | 山东圣泉新材料股份有限公司 | Resin carbon anode green body and preparation method thereof, green body intermediate and preparation method thereof, carbon anode and preparation method thereof |
| CN116003716A (en) * | 2022-12-30 | 2023-04-25 | 彤程化学（中国）有限公司 | Methylolated alkylphenol formaldehyde resin addition asphalt, preparation method thereof and rubber composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08134275A (en) * | 1994-11-10 | 1996-05-28 | Sumitomo Chem Co Ltd | Rubber composition excellent in processability |
| CN1863832A (en) * | 2003-10-03 | 2006-11-15 | 谢尼克特得国际有限公司 | Novolacquer alykylphenol resins, methods for the production thereof and use thereof of as tackifying and/or reinforcing resins for rubbers |
| CN101338013A (en) * | 2008-08-11 | 2009-01-07 | 华奇（张家港）化工有限公司 | Improved process for producing alkylphenols thermoplastic resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08134275A (en) * | 1994-11-10 | 1996-05-28 | Sumitomo Chem Co Ltd | Rubber composition excellent in processability |
| CN1863832A (en) * | 2003-10-03 | 2006-11-15 | 谢尼克特得国际有限公司 | Novolacquer alykylphenol resins, methods for the production thereof and use thereof of as tackifying and/or reinforcing resins for rubbers |
| CN101338013A (en) * | 2008-08-11 | 2009-01-07 | 华奇（张家港）化工有限公司 | Improved process for producing alkylphenols thermoplastic resin |
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