CN112592448B - Mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, preparation method thereof, rubber composition and rubber product - Google Patents
Mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, preparation method thereof, rubber composition and rubber product Download PDFInfo
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- CN112592448B CN112592448B CN202011482598.4A CN202011482598A CN112592448B CN 112592448 B CN112592448 B CN 112592448B CN 202011482598 A CN202011482598 A CN 202011482598A CN 112592448 B CN112592448 B CN 112592448B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The application relates to the technical field of rubber, and particularly discloses a mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, a preparation method thereof, a rubber composition and a rubber product. The adhesive resin comprises a first repeating unit shown in a formula (I) and a second repeating unit shown in a formula (II), and the adhesive resin is terminated by alkylresorcinol; the sum of the weight average molecular weight of the first repeating unit shown in the formula (I) and the weight average molecular weight of the second repeating unit shown in the formula (II) is 500-; the softening point of the binding resin is 80-140 ℃. The preparation method of the adhesive resin comprises the following steps: cardanol is reacted with formaldehyde under alkaline conditions, then neutralized with acid, and subsequently reacted with mixed alkylresorcinols. The adhesive resin prepared by the method has good dispersibility in rubber materials and good binding power.
Description
Technical Field
The application relates to the technical field of rubber, in particular to a mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, a preparation method thereof, a rubber composition and a rubber product.
Background
In the manufacture of automobile tires, in order to improve the adhesive strength between the cord layer and the rubber, workers in the art usually add an adhesive system before the rubber is vulcanized, so that an adhesive resinification reaction is generated during the vulcanization process to form a vulcanized rubber-adhesive resin network, thereby enhancing the physical properties and mechanical properties of the vulcanized rubber and the adhesive force between the rubber and the cord.
The adhesive system is generally formed by polymerizing a methylene acceptor and a methylene donor, wherein the commonly used methylene acceptor is mainly resorcinol and resorcinol formaldehyde adhesive resin; as the methylene donor, hexamethylenetetramine, methylolmelamine, methoxymethylmelamine or the like is mainly used. Among them, the methylene acceptor must have high reactivity to react rapidly with methylene released from the donor to form a crosslinked network in the rubber matrix rapidly.
However, the resorcinol or high resorcinol content adhesive resin which is a methylene acceptor commonly used at present has poor reactivity, and the adhesive effect of an adhesive system is general.
Disclosure of Invention
In order to enhance the adhesive effect of the adhesive resin, the application provides a mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, a preparation method thereof, a rubber composition and a rubber product.
In a first aspect, the application provides a mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, which adopts the following technical scheme:
a mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin comprising a first repeating unit represented by formula (i) and a second repeating unit represented by formula (ii), and which is end-capped with an alkylresorcinol;
the first repeating unit represented by the formula (I) and the second repeating unit represented by the formula (II) are as follows:
wherein R 'and R' are each independently alkyl or alkaryl, a and b are each independently 1 or 2; and is
When R 'is the same as R', a and b are different;
when R 'is different from R', a and b are the same or different;
n is 0, 1, 2 or 3;
the sum of the weight average molecular weight of the first repeating unit shown in the formula (I) and the weight average molecular weight of the second repeating unit shown in the formula (II) is 500-;
the mass fraction of free resorcinol in the adhesive resin is 3-15%;
the softening point of the binding resin is 80-140 ℃.
By adopting the technical scheme, the mixed alkyl resorcinol modified cardanol-formaldehyde adhesive resin comprises at least two first repeating units and second repeating units (shown as formulas (I) and (II)) formed by alkyl resorcinol, cardanol and formaldehyde, and is terminated by alkyl resorcinol. And the sum of the weight average molecular weight of the first repeating unit of the structure shown in the formula (I) and the weight average molecular weight of the second repeating unit of the structure shown in the formula (II) is 500-4000, so that the adhesive resin has good adhesive capacity and can improve the adhesive strength between the cord layer and the rubber.
First, the adhesive resin of the present application is an adhesive resin modified with mixed alkylresorcinol, and the adhesive resin obtained in the present application has a moderate content of free resorcinol as compared with an adhesive resin modified with resorcinol (unsubstituted), so that when the adhesive resin obtained is used in a rubber processing heating process, a fuming phenomenon is reduced, and the process is impaired in terms of environmental and human health hazards. Meanwhile, the adhesive property of the obtained rubber composition is better under the premise of reducing the fuming phenomenon. And secondly, compared with resorcinol, the alkyl resorcinol and formaldehyde have higher reaction activity and faster reaction efficiency due to the introduction of the substituent groups, and the prepared rubber product has better adhesive property and low content of free resorcinol.
In addition, cardanol has a longer alkyl chain containing unsaturated double bonds in a molecular structure, the alkyl chain has reaction activity, and the compatibility of the alkyl chain and rubber is better than that of short-chain alkylphenol, so that the dispersibility of rubber and filler can be improved; in addition, the substituent of the mixed alkylresorcinol has better compatibility with rubber than that of the single alkylresorcinol, so that when the adhesive resin is used for preparing the rubber composition, the raw materials can better interact and disperse, the heat generation and energy consumption are reduced, and the obtained rubber composition has better adhesive property. Therefore, when the prepared rubber composition is used for a steel cord ply of a tire, the tire is firmer, and the tire can be endowed with longer service life.
In the present application, free resorcinol means substituted and unsubstituted resorcinol, and the content of free resorcinol means the total content of substituted and unsubstituted resorcinol.
In one embodiment, the mass fraction of free resorcinol in the adhesive resin is 8-13%. The inventors found that when the free resorcinol content is less than 8%, fuming does not occur but the adhesion ability is slightly poor; at a free resorcinol content of greater than 13%, the adhesion is better but there is a significant fuming phenomenon. In the present application, the free resorcinol content is preferably 8.8-12.3%, more preferably 9%, 9.1%, or 8.8%.
In this application, alkylresorcinol refers to substituted resorcinol, and the substituents may be alkyl, alkaryl. Also commonly referred to as "substituted resorcinols".
Mixed alkylresorcinols refer to mixtures of at least two alkylresorcinols, wherein the species of alkylresorcinols can be two, three, four or more.
The softening point of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is 80-140 ℃; further preferably 89.4-130.1 deg.C, 91.5-115.5 deg.C; further preferably 108.5 ℃, 110 ℃, 115.5 ℃.
The adhesive resin has a high softening point, which shows that the adhesive resin has excellent temperature resistance.
Preferably, the adhesive resin further includes a third repeating unit represented by the following formula (III),
wherein the weight average molecular weight of the third repeating unit represented by the formula (III) is 300-3000.
By adopting the technical scheme, the adhesive resin further comprises a repeating unit (shown as a formula (III)) formed by resorcinol, cardanol and formaldehyde. The adhesive resin has at least three kinds of repeating units (shown as formulas (I) to (III)), and the three kinds of repeating units are structurally complementary, so that the crosslinking degree of the adhesive resin can be improved, and the adhesive performance of the adhesive resin can be improved.
Preferably, the R 'and R' are independently C1-10 alkyl or C7-12 alkaryl; further preferably, said R 'and R' are independently C1-8 alkyl; still further preferably, said R' and R "are independently methyl, ethyl, propyl, isopropyl, butyl or isobutyl.
By adopting the technical scheme, R 'and R' are independently C1-10 alkyl or C7-12 alkaryl, the reaction activity of the alkyl resorcinol is higher, the reaction with the reaction products of formaldehyde, cardanol and formaldehyde can be better carried out, more repeating units are obtained, and the viscosity of the adhesive resin can be improved. When the number of carbon atoms of the alkyl group exceeds 10, a steric hindrance effect occurs, resulting in a decrease in the reactivity of the binder resin, so that the reactivity of the binder resin can be effectively improved by controlling the number of carbon atoms of the alkyl group within a range of 1 to 10 in the present application.
Preferably, the molecular weight of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is 500-5000.
By adopting the technical scheme, the molecular weight of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is in the range, and the adhesive resin has good viscosity.
In a second aspect, the application provides a preparation method of a mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, which adopts the following technical scheme:
a preparation method of mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin comprises the following preparation steps:
reacting cardanol with formaldehyde under an alkaline condition, then neutralizing by acid, and then reacting with mixed alkyl resorcinol;
the molar ratio of the cardanol to the formaldehyde is (1: 1.8) - (1: 1);
the molar ratio of the cardanol to the mixed alkylresorcinol is (1: 2) - (2: 1).
The moles of mixed alkylresorcinols refer to the total number of moles of alkylresorcinols used.
By adopting the technical scheme, firstly, cardanol reacts with formaldehyde under an alkaline condition, and at the moment, the formaldehyde basically reacts to obtain hydroxylation liquid; and then adding mixed alkyl resorcinol, starting to carry out chain growth reaction, and reacting for a period of time to obtain the mixed alkyl resorcinol modified cardanol-formaldehyde adhesive resin. The preparation method can better control the repeating units in the adhesive resin and can also better control the chain growth reaction, thereby preparing the adhesive resin with better viscosity.
In the application, cardanol is a faint yellow liquid obtained by carrying out reduced pressure distillation on cashew nut shell oil, and the structure of the faint yellow liquid is shown as a formula (IV);
wherein n is 0, 1, 2 or 3.
Because the long-chain alkyl is positioned at the meta position of the phenolic hydroxyl, the cardanol has high reaction activity. Furthermore, long alkyl chains may increase the compatibility of the binding resin with the rubber, thereby promoting better compatibility of the binding resin network with the gum network. In addition, when n in the long-chain alkyl of the cashew phenol is not 0, 0-3 double bonds are arranged on the alkyl chain, the double bonds on the long alkyl chain react with sulfur in the rubber vulcanization process, and the adhesive resin network and the rubber network are connected through chemical bonds, so that the viscosity of the adhesive resin can be enhanced.
In this application, alkylresorcinol refers to resorcinol substituted with one or more alkyl groups. Mixed alkyl resorcinols contain the structure shown below:
wherein R 'and R' are each independently alkyl or alkaryl, a and b are each independently 1, 2 or 3; and when R 'is the same as R', a and b are different; when R 'is different from R', a and b are the same or different.
In preparing the adhesive resin of the present application, at least two alkylresorcinols are used, thereby forming at least two repeating units comprising the alkylresorcinols (as shown in formula (I) and formula (II)).
In the application, the mixed alkyl resorcinol at least comprises the two alkyl resorcinols, on one hand, the reaction activity of the alkyl resorcinol is stronger than that of the resorcinol, and compared with the single resorcinol, the alkyl resorcinols with different types are mixed, the structures of the generated products can be complementary, the synergistic effect can be formed more easily with the rubber compound, and the adhesion effect can be better; on the other hand, compared with the problems that single resorcinol is easy to sublimate and generate smoke at high temperature (100 ℃ and above), and is easy to cause health and pollution, the mixed alkyl resorcinol is used, and the smoke is basically avoided during production, so that the influence on workers can be reduced, and the environment is protected.
Preferably, the preparation method of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin comprises the following preparation steps: mixing cardanol, distilled water, an organic solvent and an alkaline catalyst, heating to 70-100 ℃, dropwise adding formaldehyde, reacting for 0.5-3h, then adding an organic acid for neutralization, finally adding mixed alkyl resorcinol, reacting for 0.5-2h at 80-100 ℃, heating to 160-175 ℃, and distilling under reduced pressure to obtain the mixed alkyl resorcinol modified cardanol formaldehyde adhesive resin;
the organic solvent is at least one selected from toluene, xylene, ethanol and tetrahydrofuran;
the alkaline catalyst is selected from one or more of ammonia water, diethylamine, triethylamine, diethanolamine, triethanolamine and 1, 8 diazabicyclo [5.4.0] undec-7-ene;
the organic acid is selected from any one of dodecyl benzene sulfonic acid and p-toluenesulfonic acid.
By adopting the technical scheme, firstly cardanol reacts with formaldehyde under an alkaline condition, and then the cardanol is neutralized by organic acid, in the whole preparation process, a small amount of organic salt generated by the reaction of an alkaline catalyst and the organic acid is prevented from generating precipitate in the adhesive resin, so that the water washing step in the production process of the traditional adhesive resin can be omitted, a large amount of industrial wastewater can be reduced, and the environment protection and water resource saving are facilitated.
Preferably, the mol ratio of the cardanol to the formaldehyde is (1: 1.5) - (1: 1.1); the molar ratio of the cardanol to the mixed alkylresorcinol is (1: 1.5) - (1: 0.8).
By adopting the technical scheme, under the alkaline condition, the using amount of formaldehyde is larger than that of cardanol, the cardanol and the cardanol react to obtain a hydroxylated liquid, the polymerization degree of the obtained hydroxylated liquid is small, the subsequent reaction of the hydroxylated liquid and the mixed alkylresorcinol with a specific using amount is facilitated, the first repeating unit and the second repeating unit shown as the formulas (I) and (II) in the application are obtained, and therefore the adhesive property of the adhesive resin is improved.
Further preferably, the mixed alkylresorcinol can be selected from the mixed alkylresorcinols selected from the group consisting of 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 6-methylresorcinol, 2, 4-dimethylresorcinol, 2,5, -dimethylresorcinol, 2, 6-dimethylresorcinol, 2-ethylresorcinol, 2, 4-diethylresorcinol, 2, 6-diethylresorcinol, 2-methyl-4-ethylresorcinol, 2-propylresorcinol, 2-allylresorcinol, 2-butylresorcinol, 4-butylresorcinol, 2-isobutylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, 2-methylresorcinol, 2-propylresorcinol, 2-allylresorcinol, 2-butylresorcinol, 2-tert-butylresorcinol, and mixtures thereof, At least two of 2-methyl-5-tert-butyl resorcinol, 2-cyclohexyl resorcinol and 4-tert-octyl resorcinol.
Further preferably, the mixed alkylresorcinol is a "mixed alkylresorcinol at 97% mass fraction and having an average molecular weight of 145 g/mol", and the alkylresorcinol of the "mixed alkylresorcinol at 97% mass fraction and having an average molecular weight of 145 g/mol" has: 2-methylresorcinol, resorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-ethylresorcinol, 2, 5-dimethylresorcinol, 2-propylresorcinol, 2, 4-dimethylresorcinol, 2-methyl-4-ethylresorcinol, 2-allylresorcinol, 4-butylresorcinol, 4-tert-butylresorcinol and 4-tert-octylresorcinol.
Further preferably, the mixed alkylresorcinol is a "mixed alkylresorcinol having a mass fraction of 90% and an average molecular weight of 140 g/mol", and the alkylresorcinol of the "mixed alkylresorcinol having a mass fraction of 90% and an average molecular weight of 140 g/mol" has: 2-methylresorcinol, resorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-ethylresorcinol, 2, 5-dimethylresorcinol, 2-propylresorcinol, 2, 4-dimethylresorcinol, 2-methyl-4-ethylresorcinol, 2-allylresorcinol, 4-butylresorcinol, 4-tert-octylresorcinol.
By adopting the technical scheme, the mixed alkylresorcinol at least comprises the two alkylresorcinols, and the alkylresorcinols of different types are mixed, so that the structures of the generated products can be complementary, a synergistic effect can be formed easily with rubber, and the bonding effect is better. In the application, the mixed alkyl resorcinol has more types, the reaction activity of the mixed alkyl resorcinol is better than that of a single type of resorcinol, and the prepared adhesive resin has better adhesive force.
The inventors found that when the free resorcinol content is less than 8%, fuming does not occur but the adhesion ability is slightly poor; at a free resorcinol content of greater than 13%, the adhesion is better but there is a significant fuming phenomenon. In the present application, the free resorcinol content is preferably 8 to 13%, more preferably 9%.
In a third aspect, the present application provides a rubber composition comprising the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin as described above.
Mixing rubber, carbon black, zinc oxide and HMMM to obtain a master batch; then the mixed alkylresorcinol modified cardanol-formaldehyde binding resin, the anti-aging agent, the accelerator, the cobalt salt and the sulfur are added into the master batch and mixed, and the rubber composition can be prepared.
By adopting the technical scheme, the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin and rubber are easier to form a synergistic effect, and the adhesive effect is better. The mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin has good compatibility and reaction activity with rubber, and can promote uniform dispersion of the filler and the auxiliary agent through molecular creeping in the rubber mixing process.
In a fourth aspect, the present application provides a rubber article prepared using the rubber composition as described above.
A rubber flat plate or sheet can be obtained by vulcanizing and molding the rubber composition; or the rubber composition is extruded in the form of a molded article to obtain a molded product.
Through adopting above-mentioned technical scheme, the rubber products of this application system are difficult for the fracture, and the wholeness can be better.
In summary, the present application has the following beneficial effects:
1. the adhesive resin comprises at least two first repeating units and second repeating units (shown as formulas (I) and (II)) formed by alkyl resorcinol, cardanol and formaldehyde, and is terminated by the alkyl resorcinol, so that the adhesive resin has good adhesive capacity, can improve the adhesive strength between a cord layer and rubber, and has good adhesive force;
2. the adhesive resin obtained by mixing the alkylresorcinol has good activity, and the more the alkylresorcinol is mixed, the better the adhesive force of the rubber is when the prepared adhesive resin is used for preparing the rubber, and the better the adhesive force can reach 2015 KN/m;
3. the adhesive resin prepared by the method has good dispersibility in the sizing material;
4. in the application, the long alkyl chain of the cardanol can increase the compatibility of the adhesive resin and rubber, so that the adhesive resin network and the rubber network are better compatible, and the adhesive effect and the dispersion effect are better; in addition, the double bonds on the long alkyl chains react with sulfur in the rubber vulcanization process to connect the adhesive resin network and the rubber network through chemical bonds, so that the viscosity of the adhesive resin can be enhanced;
5. this application is when preparing adhesive resin, at first cardanol reacts with formaldehyde under alkaline condition, then with organic acid neutralization, in whole preparation process, a small amount of organic salt that alkaline catalyst and organic acid reaction generated can not generate the sediment in adhesive resin to can remove the washing step in traditional adhesive resin production process, can reduce a large amount of industrial waste water, be favorable to environmental protection, water economy resource.
Detailed Description
The present application will be described in further detail with reference to examples.
The starting materials used in the examples are all commercially available and are shown in Table 1 below.
TABLE 1 Source Table of the respective raw materials
Note:
the average molecular weight of the "97% mass fraction mixed alkylresorcinol" was 145 g/mol. Included among the alkylresorcinols are: 2-methylresorcinol, resorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-ethylresorcinol, 2, 5-dimethylresorcinol, 2-propylresorcinol, 2, 4-dimethylresorcinol, 2-methyl-4-ethylresorcinol, 2-allylresorcinol, 4-butylresorcinol, 4-tert-octylresorcinol.
The "90% mass fraction mixed alkylresorcinol" has an average molecular weight of 140 g/mol. Included among the alkylresorcinols are: 2-methylresorcinol, resorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-ethylresorcinol, 2, 5-dimethylresorcinol, 2-propylresorcinol, 2, 4-dimethylresorcinol, 2-methyl-4-ethylresorcinol, 2-allylresorcinol, 4-butylresorcinol, 4-tert-octylresorcinol.
Examples
Adhesive resin examples
Binder resin example 1
Adding 0.5mol (151g) of cardanol, 20g of distilled water, 50ml of toluene and 1.0g of triethylamine into a reaction bottle with a stirring device, a thermometer and a reflux condenser, gradually heating to 85 ℃, gradually adding 0.9mol (27g) of solid formaldehyde, reacting for 3 hours in a reflux state, then adding 1.71g of p-toluenesulfonic acid for neutralization, then adding 97% of mixed alkylresorcinol 0.5mol (72.5g), reacting for 2 hours at 90 ℃, changing the distillation state, gradually heating to 170 ℃, then carrying out reduced pressure distillation, discharging to obtain 230g of red mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin with the weight-average molecular weight of 4423.
Binder resin example 2
Adding 0.5mol (151g) of cardanol, 20g of distilled water, 50ml of toluene and 1.0g of triethanolamine into a reaction bottle with a stirring device, a thermometer and a reflux condenser, gradually heating to 85 ℃, gradually adding 0.8mol (24g) of solid formaldehyde, reacting for 3 hours in a reflux state, then adding 1.15g of p-toluenesulfonic acid for neutralization, subsequently adding 0.4mol (56g) of 90% mixed alkylresorcinol, reacting for 2 hours at 90 ℃, gradually heating to 170 ℃ after changing the distillation state, then carrying out reduced pressure distillation, and discharging to obtain 205g of red mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin with the weight-average molecular weight of 3823.
Binder resin example 3
Adding 0.5mol (151g) of cardanol, 20g of distilled water, 50ml of xylene and 0.75g of DBU (1, 8 diazabicyclo [5.4.0] undec-7-ene) into a reaction flask with a stirring device, a thermometer and a reflux condenser, gradually increasing the temperature to 98 ℃, gradually adding 1mol (81g) of 37% liquid formaldehyde, reacting for 3 hours under reflux, then adding 0.94g of p-toluenesulfonic acid for neutralization, subsequently adding a mixture of 0.27mol (30g) of resorcinol, 0.1mol (20g) of 4-methylresorcinol, 0.14mol (20g) of 2, 5-dimethylresorcinol, 0.11mol (15g) of 2-ethylresorcinol, reacting for 2 hours at 90 ℃, gradually increasing the temperature to 170 ℃ after changing the distillation state, then carrying out reduced pressure distillation, discharging to obtain 239g of mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin in red color, its weight average molecular weight was 4823.
Binder resin example 4
Adding 0.5mol (151g) of cardanol, 30g of distilled water, 50ml of toluene and 0.60g of diethanolamine into a reaction bottle with a stirring device, a thermometer and a reflux condenser, gradually heating to 95 ℃, gradually adding 18g (0.60mol) of solid formaldehyde, reacting for 2 hours under reflux, then adding 1.86g of dodecylbenzenesulfonic acid for neutralization, then adding 0.29mol (40g) of 90 mass percent mixed alkylresorcinol and 0.27mol (30g) of resorcinol, reacting for 0.5 hour at 95 ℃, gradually heating to 160 ℃ after changing the distillation state, then carrying out reduced pressure distillation, discharging, and obtaining 220g of red mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin with the weight-average molecular weight of 2888.
Binder resin example 5
0.5mol (151g) of cardanol, 20g of distilled water, 50ml of toluene and 0.55g of triethanolamine were added to a reaction flask with a stirring device, a thermometer and a reflux condenser, the temperature was gradually increased to 100 ℃, 0.75mol (22.5g) of solid formaldehyde was gradually added, the mixture was reacted for 2 hours under reflux, then 1.20g of dodecylbenzenesulfonic acid was added for neutralization, then 0.21mol (30g) of 97% by mass mixed alkylresorcinol, 0.1mol (20g) of 4-methylresorcinol, 0.06mol (10g) of 2-propylresorcinol and 0.18mol (20g) of resorcinol were added, the mixture was reacted for 0.5 hours at 90 ℃, the distillation state was changed, the temperature was gradually increased to 160 ℃, then reduced pressure distillation was carried out, and discharging was carried out to obtain 231g of red mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin having a weight average molecular weight of 3696.
Binder resin example 6
0.5mol (151g) of cardanol, 20g of distilled water, 50ml of xylene and 0.75g of DBU (1, 8 diazabicyclo [5.4.0] undec-7-ene) were added to a reaction flask with a stirring device, a thermometer and a reflux condenser, gradually heated to 98 ℃, 0.9mol (27g) of formaldehyde was gradually added, reacted for 3 hours under reflux, then 0.94g of p-toluenesulfonic acid was added for neutralization, then a mixture of 0.5mol (55.1g) of 2-methylresorcinol and 0.5mol (69.08g) of 2-ethylresorcinol was added, after reaction for 2 hours at 90 ℃, the distilled state was changed and gradually heated to 170 ℃, then distillation under reduced pressure was carried out, and discharge was carried out to obtain 283g of red mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin having a weight average molecular weight of 3494.
Binder resin example 7
0.5mol (151g) of cardanol, 20g of distilled water, 50ml of xylene and 0.75g of DBU (1, 8 diazabicyclo [5.4.0] undec-7-ene) were added to a reaction flask with a stirring device, a thermometer and a reflux condenser, gradually heated to 98 ℃, 0.55mol (16.5g) of solid formaldehyde was gradually added, reacted for 3 hours under reflux, then 0.94g of p-toluenesulfonic acid was added for neutralization, then a mixture of 0.15mol (16.52g) of 2-methylresorcinol, 0.10mol (12.41g) of 2, 4-dimethylresorcinol was added, after 2 hours reaction at 90 ℃, the distilled state was changed and gradually heated to 170 ℃ after 2 hours reaction, then reduced pressure distillation was carried out, and discharge was carried out to obtain 185g of red mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin having a weight-average molecular weight of 2994.
Adhesive resin examples 8-10 differ from adhesive resin example 1 only in the choice of the mixed alkylresorcinol, as shown in table 2.
TABLE 2 selection of mixed alkylresorcinols for adhesive resin examples 8-10
| 0.5mol of mixed alkylresorcinols | Binder resin example 8/mol | Binder resin example 9/mol | Binder resin example 10mol |
| 2-Methylresorcinol | 0.2 | 0.2 | 0.2 |
| 2-Ethylresorcinol l | 0.1 | 0.1 | 0.1 |
| 2-methyl-4-ethyl resorcinol | 0.2 | 0.1 | |
| 2-propylresorcinol | 0.1 | 0.05 | |
| 2-butylresorcinol | 0.05 | ||
| 2-cyclohexyl resorcinol | 0.1 |
Comparative adhesive resin example
Adhesive resin comparative example differs from adhesive resin example 1 only in that the mixed alkylresorcinol is replaced by resorcinol, as specified below:
adding 0.5mol (151g) of cardanol, 20g of distilled water, 50ml of toluene and 1.0g of triethylamine into a reaction bottle with a stirring device, a thermometer and a reflux condenser, gradually heating to 85 ℃, gradually adding 0.9mol (27g) of solid formaldehyde, reacting for 3 hours in a reflux state, then adding 1.71g of p-toluenesulfonic acid for neutralization, subsequently adding 0.5mol (55g) of resorcinol, reacting for 2 hours at 90 ℃, gradually heating to 170 ℃ after changing the distillation state, then carrying out reduced pressure distillation, discharging to obtain 212g of red mixed alkyl resorcinol modified cardanol-formaldehyde adhesive resin, wherein the weight-average molecular weight of the resin is 4323.
Adhesive resin Performance test
The resulting adhesive resin was subjected to measurement of softening point and free resorcinol content according to the relevant specifications of ASTM D3461-14.
Table 3 below shows the results of softening point, free resorcinol and weight average molecular weight of the adhesive resins obtained in adhesive resin examples 1-10 and adhesive resin comparative example.
TABLE 3 basic Properties test Table for adhesive resins
The binder resin is suitable for rubber mixing when the softening point of the binder resin is 85 to 140 ℃.
The free resorcinol content of the adhesive resin is 8-13%, preferably 9%; when the content of the free resorcinol is 8.8-9.9%, the adhesive resin has good adhesive capacity and is not fuming; when the free resorcinol in the adhesive resin is less than 8%, fuming is not generated but the adhesive ability is slightly poor; when the free resorcinol content in the adhesive resin is much greater than 13%, the adhesive capacity is good but there is a certain fuming phenomenon.
Examples of rubber compositions
The preparation method of the rubber composition example of the application is as follows:
adding rubber, carbon black (N234), stearic acid, zinc oxide and HMMM into a Banbury mixer (manufactured by FARREL company), mixing and heating to 155 ℃ to obtain master batch;
the master batch was cooled to 90 ℃, and then mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin, antioxidant RD, sulfur (OT20), accelerator CZ and cobalt salt were added, and then the temperature was adjusted to 50 ℃, and kneaded at 50 ℃ for 5min, thereby obtaining rubber.
Rubber composition examples 1-7 differ only in the selection of different mixed alkylresorcinol modified cardanol-formaldehyde binding resins, see in particular table 4.
Table 4 rubber compositions examples 1-6 and comparative rubber compositions the raw material usage table.
Rubber Performance testing
1. Adhesive strength
The rubber samples obtained in rubber examples 1 to 6 and rubber comparative example 1 were tested for adhesion strength to steel cords according to the standard GB/T16586-.
Adhesive strength: embedding a single steel cord into the rubber samples prepared in rubber examples 1 to 6 and rubber comparative example 1, then pulling out the single steel cord from the rubber composition in the axial direction of the single steel cord, and measuring the force required for pulling out the single steel cord, the unit of the force being-KN/m;
the larger the force required to draw out the single steel cord, the larger the adhesive ability of the adhesive resin, and the higher the adhesive strength.
The rubber samples of rubber examples 1 to 6 and rubber comparative example 1 were each tested for their adhesive strength before aging, heat aging (100 ℃, 168 hours), constant temperature aging (0 ℃, 98% humidity, 168 hours) and salt water aging (10% NaCl aqueous solution, 168 hours) and specifically tested as shown in Table 5 below.
TABLE 5 examination of the adhesive Properties of the rubbers
As can be seen from the data in Table 5, the combination of different types of alkylresorcinols, as compared with the resorcinol alone, results in a complementary structure of the adhesive resin, which is more likely to have a synergistic effect with natural rubber, and a better adhesive effect with rubber. The more alkylresorcinol species are mixed in the adhesive resin, the better the adhesive strength of the rubber is, and the best adhesive resin can be 2015KN/m when the adhesive resin is used for preparing rubber.
The dispersion grades of rubber examples 1 to 6 and rubber comparative example 1 and the blank example were measured, and the results are shown in Table 5.
The detection method of the dispersion grade is as follows:
the dispersion of carbon black in the rubber was tested according to the standard GB/T6030-2006.
The test specimens are rated against a set of standard pictures stored in slides or electronic text using a zonal viewing technique. The degree of dispersion of carbon black was evaluated by displaying an image of the sample collected by a black-and-white camera or a CCD camera and a standard picture on a monitor (display) simultaneously using a divisional optical microscopy technique.
TABLE 6 visual Dispersion rating and corresponding Dispersion quality level
| Visual Dispersion Scale | Level of dispersion quality |
| 9-10 | Is very good |
| 8 | Good taste |
| 7 | Can accept |
| 5-6 | Uncertainty |
| 3-4 | Difference between |
| 1-2 | Is very poor |
TABLE 7 rubber Dispersion Scale detection Table
As can be seen from the data in Table 7, when the adhesive resin prepared by the method is applied to rubber, the dispersion grade of the adhesive resin is improved from 6.5 to more than 8, and the compatibility and the dispersion performance of each component in a rubber, filler, adhesive resin and auxiliary agent system can be effectively improved by adding the adhesive resin prepared by the method, so that the dispersion grade is improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin, characterized by comprising a first repeating unit represented by formula (i) and a second repeating unit represented by formula (ii), and the adhesive resin being terminated with alkylresorcinol;
the first repeating unit represented by the formula (I) and the second repeating unit represented by the formula (II) are as follows:
wherein R 'and R' are each independently alkyl or alkaryl, a and b are each independently 1 or 2; and is
When R 'is the same as R', a and b are different;
when R 'is different from R', a and b are the same or different;
n is 0, 1, 2 or 3;
the sum of the weight average molecular weights of the first repeating unit shown in the formula (I) and the second repeating unit shown in the formula (II) is 500-;
the mass fraction of free resorcinol in the adhesive resin is 3-15%;
the softening point of the binding resin is 80-140 ℃.
2. The mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin according to claim 1, characterized in that: the adhesive resin further includes a third repeating unit represented by the following formula (III),
wherein the weight average molecular weight of the third repeating unit represented by the formula (III) is 300-3000.
3. The mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin according to claim 1, characterized in that: the R 'and R' are independently C1-10 alkyl or C7-12 alkaryl.
4. The mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin according to any one of claims 1 to 3, characterized in that: the weight average molecular weight of the binder resin is 500-5000 and the softening point is 85-120 ℃.
5. A method of making the mixed alkylresorcinol-modified cardanol-formaldehyde binding resin according to any of claims 1-4, characterized in that: the method comprises the following steps:
reacting cardanol with formaldehyde under an alkaline condition, then neutralizing by acid, and then reacting with mixed alkyl resorcinol;
the molar ratio of the cardanol to the formaldehyde is (1: 1.8) - (1: 1);
the molar ratio of the cardanol to the mixed alkylresorcinol is (1: 2) - (2: 1).
6. The method for preparing mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin according to claim 5, characterized in that: the mol ratio of the cardanol to the formaldehyde is (1: 1.5) - (1: 1.1);
the molar ratio of the cardanol to the mixed alkylresorcinol is (1: 1.5) - (1: 0.8).
7. The method for preparing mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin according to claim 5, characterized in that: the preparation method comprises the following preparation steps:
mixing cardanol, distilled water, an organic solvent and an alkaline catalyst, heating to 70-100 ℃, dropwise adding formaldehyde, reacting for 0.5-3h, then adding an organic acid for neutralization, finally adding mixed alkyl resorcinol, reacting for 0.5-2h at 80-100 ℃, heating to 160-175 ℃, and distilling under reduced pressure to obtain the adhesive resin;
the organic solvent is at least one selected from toluene, xylene, ethanol and tetrahydrofuran;
the alkaline catalyst is selected from one or more of ammonia water, diethylamine, triethylamine, diethanolamine, triethanolamine and 1, 8 diazabicyclo [5.4.0] undec-7-ene;
the organic acid is any one selected from dodecyl benzene sulfonic acid and p-toluenesulfonic acid.
8. The method for preparing mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin according to claim 5, characterized in that: the mixed alkylresorcinol is selected from the group consisting of 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 6-methylresorcinol, 2, 4-dimethylresorcinol, 2,5, -dimethylresorcinol, 2, 6-dimethylresorcinol, 2-ethylresorcinol, 2, 4-diethylresorcinol, 2, 6-diethylresorcinol, 2-methyl-4-ethylresorcinol, 2-propylresorcinol, 2-butylresorcinol, 4-butylresorcinol, 2-isobutylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, 2-methyl-5-tert-butylresorcinol, 2-cyclohexylresorcinol, 2-butylresorcinol, 4-butylresorcinol, 2-isobutylresorcinol, 2-tert-butylresorcinol, 4-butylresorcinol, 2-methyl-5-tert-butylresorcinol, and mixtures thereof, At least two of 4-tert-octylresorcinol.
9. A rubber composition characterized by: the adhesive resin composition comprising the mixed alkylresorcinol-modified cardanol-formaldehyde resin according to any one of claims 1 to 4 or the mixed alkylresorcinol-modified cardanol-formaldehyde resin produced according to the production method of any one of claims 5 to 8.
10. A rubber article characterized by: a raw material for the rubber article comprises the rubber composition according to claim 9.
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| CN102718934A (en) * | 2012-06-14 | 2012-10-10 | 北京彤程创展科技有限公司 | Cashew nut shell oil modified resorcinol bonding resin and preparation method thereof |
| CN104448177A (en) * | 2014-12-25 | 2015-03-25 | 常州常京化学有限公司 | Modified phenolic resin and preparation method and application thereof |
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| CN102718934A (en) * | 2012-06-14 | 2012-10-10 | 北京彤程创展科技有限公司 | Cashew nut shell oil modified resorcinol bonding resin and preparation method thereof |
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