CN112521666A - Rubber composition, preparation method thereof and rubber product - Google Patents
Rubber composition, preparation method thereof and rubber product Download PDFInfo
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- CN112521666A CN112521666A CN202011482599.9A CN202011482599A CN112521666A CN 112521666 A CN112521666 A CN 112521666A CN 202011482599 A CN202011482599 A CN 202011482599A CN 112521666 A CN112521666 A CN 112521666A
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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
- 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
- C08L21/00—Compositions of unspecified rubbers
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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
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Abstract
The application relates to the technical field of rubber products, and particularly discloses a rubber composition, a preparation method thereof and a rubber product. The rubber composition comprises the following components: 100 parts of rubber, 20-80 parts of carbon black, 0.5-5 parts of vulcanizing agent, 1-10 parts of mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, wherein the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin comprises a formula (1) and a formula (2), and the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is terminated by alkylresorcinol; the preparation method of the rubber composition comprises the following steps: mixing rubber and carbon black, heating to 140-160 ℃, cooling to 80-95 ℃, adding a vulcanizing agent and mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, and mixing at 40-50 ℃ for 4-10min to obtain the rubber composition. The rubber composition of the present application has excellent adhesion properties.
Description
Technical Field
The application relates to the technical field of rubber products, in particular to a rubber composition, a preparation method thereof and a rubber product.
Background
The steel wire framework material adhesive layer depends on the initial adhesive strength, the rubber-steel wire adhesive strength retention rate, heat aging, salt aging, wet aging, steam aging and other factors, wherein the rubber material, the filler, the vulcanization system, the heat generation and the variety and quality of the adhesive are main factors influencing the adhesive performance.
In the manufacture of automobile tires, in order to improve the adhesive strength between the cord layer of the tire and the rubber, a methylene acceptor and a methylene donor are added before the rubber is vulcanized to form an adhesive system, and a resinification reaction is generated in the vulcanization process to form a vulcanized rubber-resin network, so that the physical properties and the mechanical properties of the vulcanized rubber and the adhesive force between the rubber and the cord are enhanced.
The related art improves the properties of the rubber composition by adjusting the modified adhesive resin, however, the improvement of the adhesive property of the rubber composition is not significant.
Disclosure of Invention
In order to greatly promote the adhesive property of the rubber composition, the application provides the rubber composition and the application thereof.
In a first aspect, the present application provides a rubber composition and its use, using the following technical scheme:
a rubber composition comprising the following components in parts by weight:
according to 100 parts of rubber, 20-80 parts of carbon black, 0.5-5 parts of vulcanizing agent and 1-10 parts of mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin;
wherein the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin comprises a first repeating unit represented by formula (1) and a second repeating unit represented by formula (2), and the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin is terminated with alkylresorcinol;
the first repeating unit represented by formula (1) and the second repeating unit represented by formula (2) 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 represented by the formula (1) and the second repeating unit represented by the formula (2) is in the range of 500-4000.
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, five or more.
According to 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 at least two kinds of alkyl resorcinol, carrying out chain extension reaction, and reacting for a period of time to obtain the mixed alkyl resorcinol modified cardanol-formaldehyde resin, wherein the mixed alkyl resorcinol modified cardanol-formaldehyde resin comprises at least two kinds of first repeating units and second repeating units (shown as formulas (1) and (2)) formed by alkyl resorcinol, cardanol and formaldehyde, and is terminated by alkyl resorcinol.
Applicants have found that alkylresorcinols are more reactive than resorcinols, and that alkylresorcinols react better with rubber components; also, different types of alkylresorcinols have a synergistic effect, allowing different types of alkylresorcinols molecules to be structurally complementary, and therefore the effect of mixed alkylresorcinols is superior to that of alkylresorcinols alone.
The mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin has high reaction activity with a methylene donor, and the substituent of the alkylresorcinol has better compatibility with a rubber component, so that the rubber composition has good adhesive property.
The mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin has the weight average molecular weight of 500-5000-.
The softening point of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is 80-140 ℃; more preferably, the softening point of the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin is 90 to 110 ℃.
By adopting the technical scheme, the molecular weight of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is in the range, and the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin has good viscosity.
The content of free resorcinol in the mixed alkyl resorcinol modified cardanol-formaldehyde adhesive resin is 3-15 mass%; further preferably, the content of free resorcinol in the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin is in the range of 4 to 12 mass%.
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.
When the content of free resorcinol is too high, smoke is generated in the rubber mixing process, and pungent smell is generated, so that the health of operators is not good; when the content of free resorcinol is too low, the adhesive properties of the resin are lowered.
In one embodiment, the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin further comprises a third repeating unit represented by the following formula (3),
wherein the molecular weight of the third repeat unit shown in formula (3) is 300-3000.
By adopting the technical scheme, the mixed alkyl resorcinol modified cardanol-formaldehyde adhesive resin further comprises a repeating unit (shown as a formula (3)) formed by resorcinol, cardanol and formaldehyde. The various repeating units are complementary in structure, so that the crosslinking degree of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin can be improved, and the compatibility between the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin and the rubber component can be improved.
Preferably, said R 'and said R' are independently C1-10 alkyl or C7-12 alkaryl; further preferably, said R 'and said 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 alkylaryl, the reaction activity of the alkyl resorcinol is higher, the alkyl resorcinol can better react with the reaction products of methanol, cardanol and methanol to obtain more repeating units, and thus the reaction activity of the mixed alkyl resorcinol modified cardanol-formaldehyde adhesive resin can be improved. When the number of carbon atoms of the alkyl group exceeds 10, the reactivity of the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin is lowered; in consideration of steric hindrance effect, the number of carbon atoms of alkyl in the alkylaryl is controlled within the range of 1-6, and the reaction activity of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin can be effectively improved.
In one embodiment, the rubber composition further comprises 0.5 to 5 parts of an alkylphenol sulfide and/or 0.5 to 10 parts of an alkylphenol-modified amino resin, based on 100 parts by weight of the rubber.
By adopting the technical scheme, the adhesive property, the aging resistance and the reversion resistance of the rubber composition are remarkably improved through the synergistic effect of three components of alkylphenol sulfide, alkylphenol modified amino resin and mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin in the rubber composition.
Preferably, the alkylphenol sulfide contains a repeating unit represented by formula (4):
in the formula (4), R1、R2Each independently selected from hydrogen, straight or branched C1-C20Alkyl of (C)6-C30Aryl of (C)7-C30Alkylaryl of, C7-C30At least one of aralkyl groups of (1), wherein R1And R2When not simultaneously hydrogen, x is an integer of 1-2; preferably, said R is1And said R2Each independently selected from hydrogen, straight or branched C1-C15Alkyl of (C)6-C18Aryl of (C)7-C18Alkylaryl of, C7-C18Wherein R is as defined above, wherein R is an alkyl group1And said R2Not hydrogen at the same time.
Preferably, the alkylphenol-modified amino resin includes a repeating unit represented by formula (5):
in the formula (5), R3、R4、R5Each independently is at least one of hydrogen, a residue of a substituted or unsubstituted alkylphenol after losing a hydrogen atom, a repeating unit, and R3、R4、R5At least one of which is a residue of a substituted or unsubstituted alkylphenol after the hydrogen atom has been lost.
In one embodiment, the alkylphenol sulfide has a weight average molecular weight of 500-3000; further preferably, the softening point is 70 to 120 ℃.
In one embodiment, the alkylphenol-modified amino resin has a weight average molecular weight of 1000-30000; further preferably, the softening point is 50 to 180 ℃.
The alkylphenol sulfide has good anti-reversion performance and has the double-function alkylphenol sulfide with anti-aging performance, and the alkylphenol sulfide has good compatibility with other components in the rubber composition.
In the application, each structural unit of the alkylphenol modified amino resin has a large triazine ring structure inside, the outside 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 good compatibility with rubber molecules, and meanwhile, a large number of hydroxyl structures on the benzene rings are tightly contacted with the surfaces of fillers such as carbon black and the like through H bonds, so that the rigidity of the alkylphenol modified amino resin and the compatibility of the alkylphenol modified amino resin with rubber and a filler system are ensured, in addition, the alkylphenol modified amino resin can better react with a methylene donor, and the fillers are fully mixed and dispersed through intermolecular peristalsis; in addition, imino and hydroxymethyl groups existing in the alkylphenol modified amino resin can react with rubber molecules and other components in the composition, so that the obtained rubber composition has high viscosity.
In one embodiment, the rubber composition comprises 1 to 4 parts of the alkylphenol sulfide, 1 to 6 parts of the alkylphenol-modified amino resin, 1.5 to 8 parts of the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin, based on 100 parts by weight of rubber.
Preferably, the rubber composition comprises 2 to 4 parts of the alkylphenol sulfide, 2 to 4 parts of the alkylphenol-modified amino resin and 2 to 4 parts of the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin, based on 100 parts by weight of the rubber.
By adopting the technical scheme, the formula of the alkylphenol sulfide, alkylphenol modified amino resin and mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is further optimized, so that the adhesive property, the aging resistance and the reversion resistance of the rubber composition are further improved.
Preferably, the rubber composition further comprises one or more of 1.5-8 parts by weight of an activator, 0.5-10 parts by weight of a binder, 0.5-5 parts by weight of an accelerator and 1-5 parts by weight of an anti-aging agent, based on 100 parts by weight of the rubber.
By adopting the technical scheme, the reactivity of the alkylphenol sulfide can be improved by adding the activating agent, so that the heat-resistant aging performance of the rubber composition is improved; the adhesive is added into a rubber product sizing material serving as a framework material, so that a bridge effect can be realized between rubber and a cord thread, firm chemical bonding is generated, the adhesive strength can be improved, and the cord thread coating rate is improved; the addition of the accelerator can accelerate the crosslinking reaction of sulfur and rubber molecules, and achieve the effects of shortening the vulcanization time and reducing the vulcanization temperature; by adding the anti-aging agent, the resistance of the rubber composition product to the external damage can be improved, and the aging process can be delayed or inhibited, so that the storage period and the service life of the rubber composition product are prolonged.
Preferably, the activator comprises 0.5 to 5 parts by weight of stearic acid and 1 to 10 parts by weight of zinc oxide per 100 parts by weight of rubber.
By adopting the technical scheme, zinc salt is formed in the presence of zinc oxide and stearic acid, and the zinc salt is chelated with the pendant group of the sulfur-containing accelerator, so that weak bonds are in a stable state, and further, rubber is vulcanized to generate shorter cross-linking bonds, new cross-linking bonds are added, and the cross-linking density is improved.
Preferably, the binder is a cobalt salt.
Preferably, the promoter is a promoter CZ.
Preferably, the antioxidant is antioxidant RD.
By adopting the technical scheme, the adhesion between the rubber component and the metal can be improved by adding the cobalt salt; the accelerator CZ can promote the vulcanization of sulfur and rubber, shorten the vulcanization time and improve the crosslinking density of vulcanized rubber; the anti-aging agent RD can delay or inhibit the aging process of the rubber composition product, thereby prolonging the storage life and the service life of the rubber composition product.
Preferably, the vulcanizing agent is one or more selected from sulfur, a sulfur donor, and a sulfur-containing organic compound.
Preferably, the sulfur donor is one or more of tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dithiomorphine, and caprolactam disulfide;
the sulfur-containing organic compound is one or more of alkylphenol disulfide, 1, 6-bis- (N, N-dibenzyl thiocarbamoyldithio) hexane and methylene-1, 6-disodium dithiosulfate.
Preferably, the rubber is one or more of natural rubber, isoprene rubber, styrene-butadiene rubber, polybutadiene rubber-styrene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, silicone rubber, fluororubber and urethane rubber.
Preferably, the rubber composition comprises the following components in parts by weight:
55 parts of carbon black, 6 parts of zinc oxide, 1 part of cobalt salt, 1 part of antioxidant RD, 1.5 parts of HMMM, 1.5 parts of sulfur, 1 part of accelerator CZ, 3 parts of alkylphenol sulfide, 3 parts of alkylphenol modified amino resin and 3 parts of mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, wherein the weight of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is calculated on 100 parts of rubber.
The inventors found through experiments that when the addition amounts of the alkylphenol sulfide, the alkylphenol-modified amino resin, and the alkylresorcinol-modified cardanol-formaldehyde adhesive resin are too small, the adhesive property, the mechanical property, and the vulcanization property of the rubber composition are affected; when the addition amounts of the alkylphenol sulfide, the alkylphenol-modified amino resin, and the alkylresorcinol-modified cardanol-formaldehyde adhesive resin are too large, the adhesive property, the mechanical property, the vulcanization property, and the like of the rubber composition are not significantly increased, but the raw material cost of the rubber composition is increased. The rubber composition prepared by the method has excellent adhesive property, aging resistance and reversion resistance.
In a second aspect, the present application provides a method for preparing a rubber composition, which adopts the following technical scheme:
a method of preparing a rubber composition comprising the steps of:
mixing rubber and carbon black, heating to 140-160 ℃ to prepare rubber master batch, cooling to 80-95 ℃, adding a vulcanizing agent and mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, mixing with the rubber master batch, and mixing at 40-50 ℃ for 4-10min to obtain the rubber composition.
Preferably, the activator, binder, accelerator, anti-aging agent, alkylphenol sulfide and cardanol modified amino resin are added together with the vulcanizing agent and mixed alkylresorcinol modified cardanol-formaldehyde binding resin.
By adopting the technical scheme, the rubber composition is obtained, and the preparation method is simple to operate.
Preferably, the preparation method of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin comprises the following steps:
reacting cardanol with formaldehyde under an alkaline condition, then neutralizing by acid, and then reacting with mixed alkyl resorcinol;
the mol 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 sum of the moles of alkylresorcinols used.
By adopting the technical scheme, firstly, cardanol reacts with formaldehyde under an alkaline condition, and the formaldehyde basically reacts completely; 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 resin and can also better control the chain growth reaction, thereby preparing the 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 (6);
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, the long alkyl chains may increase the compatibility of the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin with the rubber component, thereby promoting better compatibility of the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive 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 mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin network is connected with the rubber network through chemical bonds, so that the viscosity of the 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 resins of the present application, at least two alkylresorcinols are used, thereby forming at least two repeating units comprising alkylresorcinols (as shown in formula (1) and formula (2)).
In the present application, the mixed alkylresorcinol includes at least the above two alkylresorcinols. On one hand, the reaction activity of the alkyl resorcinol is stronger than that of resorcinol, and compared with single resorcinol, the alkyl resorcinol of different types is mixed, the structures of the generated products can be complemented, a synergistic effect can be formed easily with the rubber component, and the finally prepared rubber composition has a better bonding effect; on the other hand, single alkyl resorcinol is easy to sublimate and generate smoke at high temperature (100 ℃ and above), so that the problems of health, pollution and the like are easily caused.
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 70-90 ℃, 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, the cardanol reacts with formaldehyde under an alkaline condition, and then is neutralized by organic acid, in the process, a small amount of organic salt (such as dodecyl benzene sulfonic acid ammonium salt, p-toluene sulfonic acid ammonium salt and the like) generated by the reaction of an alkaline catalyst and the organic acid does not generate precipitate in the mixed alkyl resorcinol modified cardanol-formaldehyde adhesive resin, so that the water washing step in the traditional resin production process is omitted, a large amount of industrial wastewater can be reduced, the environment is protected, and water resources are saved.
Preferably, the molar ratio of the cardanol to 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 formaldehyde and the cardanol react to obtain a hydroxylated liquid, the polymerization degree of the obtained hydroxylated liquid is low, the subsequent reaction of the hydroxylated liquid and a specific amount of mixed alkylresorcinol is facilitated, and the first repeating unit and the second repeating unit shown as the formulas (1) and (2) in the application are obtained, so that the reactivity of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is improved.
Preferably, the mixed alkylresorcinol can be 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-methyl-5-tert-butylresorcinol, 2-methylresorcinol, 4-methylresorcinol, 2-methylresorcinol, and mixtures thereof, At least two of 2-cyclohexyl resorcinol, 4-tert-octyl resorcinol and styryl resorcinol.
By adopting the technical scheme, different types of alkyl resorcinol are mixed, so that the generated mixed alkyl resorcinol modified cardanol-formaldehyde adhesive resin can be complementary in structure, and a synergistic effect is more easily formed between the mixed alkyl resorcinol modified cardanol-formaldehyde adhesive resin and rubber.
In a third aspect, the present application provides a rubber product, which adopts the following technical scheme:
a rubber product is prepared from the rubber composition.
By adopting the technical scheme, the rubber product can improve the bonding strength of the rubber product.
In summary, the present application has the following beneficial effects:
1. in the rubber composition, the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin has higher reaction activity with a methylene donor, so that a substituent of the alkylresorcinol has better compatibility with rubber, and the adhesive property of the rubber composition is improved;
2. in the rubber composition, the specific alkylphenol sulfide is added, so that the aging resistance and the reversion resistance of the rubber composition are improved on the basis of optimizing and improving the adhesive property of the rubber composition, and meanwhile, the reaction of a methylene donor with resin and rubber components can be effectively promoted and the intermolecular creeping is promoted by adding the alkylphenol modified amino resin, so that the fillers can be better mixed and dispersed;
3. in the rubber composition, the adhesive property, the aging resistance and the reversion resistance of the rubber composition can be remarkably improved through the synergistic effect of three components, namely alkylphenol sulfide, alkylphenol modified amino resin and mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, and in the rubber composition, the initial adhesive strength of the rubber composition can reach above 2055KN/m, the thermal aging adhesive strength can reach above 1613KN/m, the constant-temperature constant-humidity aging adhesive strength can reach above 4KN/m, and the brine aging adhesive strength can reach above 1878 KN/m.
Detailed Description
The following examples further illustrate the present application in detail.
The sources of the raw materials are shown in table 1.
TABLE 1 sources of raw materials
Preparation example of Mixed alkylResorcinol-modified Cardanol-Formaldehyde adhesive resin
Preparation examples 1 to 6: mixing 0.5mol (151g) of cardanol, 30g of distilled water, 50ml of toluene and 0.55g of triethanolamine, gradually heating to 85 ℃, stirring for dissolving, gradually adding 0.85mol (25.5g) of solid formaldehyde, reacting for 3.5 hours at 98 ℃ under reflux, adding 1.20g of dodecylbenzene sulfonic acid for neutralization, then adding 0.66mol of mixed alkylresorcinol, reacting for 1 hour at 90 ℃, changing the distillation state, gradually heating to 160 ℃, and then carrying out reduced pressure distillation to obtain dark red mixed alkylresorcinol modified adhesive resin, namely resin 1-6; wherein, the kinds and contents of the mixed alkylresorcinols are shown in Table 1.
TABLE 1 kinds and contents of alkylresorcinols in preparation examples 1 to 6
TABLE 2 content of free Resorcinol in preparation examples 1 to 6
Preparation of alkylphenol sulfide
79.2g (0.4mol) of styrenated phenol, 30.2g (0.1mol) of distyrenated phenol, and 90g of toluene were put into a 500ml reaction flask equipped with a stirring device, a thermometer, and a reflux condenser, and 64.8g S was gradually added dropwise2Cl2(0.48mol), and simultaneously gradually raising the temperature to 85 ℃, carrying out reflux reaction for 2h, then raising the temperature to 170 ℃ and carrying out reduced pressure distillation to obtain a product, wherein the softening point of the product is 84.6 ℃, and the sulfur content of the product is 23.7%.
Preparation example of alkylphenol-modified amino resin
Adding 1.1mol of cardanol, 100ml of toluene and 0.5g of dodecylbenzene sulfonic acid into a 500ml round bottom flask provided with a stirring device, a thermometer and a reflux condenser, heating to 100 ℃, slowly adding HMMM0.26mol, controlling the reaction temperature to be about 80 ℃, reacting for 3 hours in a reflux state, heating to 185 ℃ in a distillation state, reacting for 30 minutes, reducing pressure and vacuumizing for 20 minutes, neutralizing with triethanolamine, and discharging to obtain the cardanol modified amino resin. The resin softening point was determined to be 82.5 ℃.
Examples of rubber compositions
The detection method comprises the following steps:
1. the method for detecting the adhesion performance of the steel wire comprises the following steps:
the adhesion strength of the vulcanized rubber to the steel cord was tested according to standard GB/T16586-.
The adhesive strength means the force in KN/m by which the single steel cord is drawn out in the axial direction from the embedded rubber by measuring it from the prepared sample. The greater the adhesion, the higher the adhesion strength.
In the examples of the present application, the test conditions of heat aged adhesive strength of the rubber composition were as follows: the temperature is 100 ℃, and the testing time is 168 h; test conditions for constant temperature and humidity aged adhesive strength of rubber composition: the temperature is 90 ℃, the humidity is 98%, and the testing time is 168 h; test conditions for salt water aged adhesive strength of rubber composition: soaking in 10% NaCl solution for 168 h.
2. The mechanical property testing method comprises the following steps:
and (3) carrying out mechanical property test on the rubber composition according to the requirements of the standard GB/T528-2009. The larger the mechanical property value is, the larger the crosslinking degree of the rubber material is, and the better the mechanical property is.
The stress at definite elongation means the tensile stress in MPa when the gauge length of a tensile specimen reaches a predetermined elongation. Tensile Strength-tensile stress recorded at the moment the specimen is stretched to break, in MPa.
3. Method for measuring tear strength:
the tear strength of the vulcanizates was tested according to the standard GB/T529-.
The tear strength refers to the maximum force required to continuously stretch a test specimen with or without a cut at a prescribed speed using a tensile tester until the test specimen tears. The tear strength is given in KN/m. The tearing strength is high, and the tearing resistance of the rubber is good.
4. The shore hardness test method comprises the following steps:
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.
5. DIN abrasion test method:
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 that of the test gum under the same conditions is expressed as a percentage. The larger the abrasion index, the better the abrasion resistance.
6. Method for measuring vulcanization characteristics:
the initial vulcanization characteristics of the rubber compositions were determined using a disc shear viscometer in accordance with standard GB/T1233-2008.
The rubber compositions were tested for their vulcanization characteristics according to the standard GB/T16584-. ML characterizes the shear modulus of the rubber composition when vulcanization has not occurred; the MH may characterize the shear modulus of the rubber composition as it reaches the optimum state of cure, with a higher MH value indicating a higher crosslink network density of the rubber composition.
The test conditions of ML and MH are as follows: the temperature was 160 ℃ and the test time 60 min.
7. The scorch performance test method comprises the following steps:
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.
8. The detection method of reversion performance comprises the following steps:
the rubber compound reversion performance is represented by a reversion rate Rt, and the smaller the value is, the smaller the reversion degree at the time t is, and the better the effect is, wherein t is 60 min. The calculation formula is as follows:
Rt＝(MH-Mt)/(MH-ML)×100％。
examples 1-6 and comparative example 1: the rubber composition was prepared as follows:
adding rubber, carbon black, zinc oxide and stearic acid into a 1.6L Banbury mixer (manufactured by FARREL company), mixing for 6 minutes, heating to 155 ℃, and cooling to about 90 ℃; then adding a promoter CZ, cobalt salt, an anti-aging agent RD, S, HMMM and mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, and mixing the mixture at the temperature of 50 ℃ for 5min to obtain an unvulcanized rubber composition; the rubber composition was molded on a BH-25T press (manufactured by Zhenwangbo sea test machinery works in Jiangdu district) to prepare a vulcanized rubber composition sheet or sheet, and the specific formulation is shown in Table 3.
TABLE 3 raw material compounding ratio of rubber compositions in examples 1 to 6 and comparative example 1
TABLE 4 results of adhesion Strength test (KN/m) in examples 1 to 6 and comparative example 1
As shown by combining tables 3 and 4, it was found by comparison of examples 1 to 6 that the adhesive performance of examples 2 to 5 was significantly better than that of example 1, and therefore, in the rubber composition, the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin prepared by adding mixed alkylresorcinol was better than that prepared by adding alkylresorcinol alone; and in examples 2 to 5, the more the alkylresorcinol species, the better the adhesion properties of the resulting rubber compositions, with the same total molar amount of alkylresorcinol. When the alkylresorcinol is used in the rubber composition in a type of 4 or more, the initial adhesive strength in the rubber composition is 1975KN/m or more, the heat aged adhesive strength is 1956KN/m or more, the constant temperature and humidity aged adhesive strength is 1791KN/m or more, and the salt water aged adhesive strength is 1800KN/m or more.
The initial adhesive strength, heat aged adhesive strength, constant temperature and humidity aged adhesive strength, and salt water aged adhesive strength in examples 2-6 were all much higher than those in comparative example 1, compared to comparative example 1, and therefore, the adhesive strength of the rubber composition prepared by adding the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin in the present application was superior to that of the rubber composition prepared by using the commercially available adhesive resin.
Examples 7 to 10: the difference from example 1 is that alkylphenol sulfide and alkylphenol-modified amino resin were added together with mixed alkylresorcinol-modified cardanol-formaldehyde binding resin to be kneaded, and the formulation of the rubber composition is shown in table 5.
TABLE 5 compounding ratios of raw materials for rubber compositions in examples 7 to 10
TABLE 6 results of adhesion Strength test (KN/m) in examples 7 to 10
Table 7 results of measuring vulcanization properties and mechanical properties in example 5 and examples 7 to 10
Combining tables 6 and 7, the adhesion performance of example 5 is much higher than the adhesion performance index of examples 7-8 by comparing with examples 7-8, and therefore, the adhesion performance of the rubber composition with the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin added alone is better than the rubber composition with the alkylphenol sulfide added alone and the alkylphenol-modified amino resin added alone.
As can be seen from Table 7, the reversion resistance of the rubber composition is improved more when the alkylphenol sulfide is added to the rubber composition because the reversion resistance of example 7 is lower than that of examples 5 and 8.
As can be seen from Table 7, the tensile stress at definite elongation, the tear strength, the abrasion index, the tear strength and the scorch time of example 8 are all superior to those of examples 5 and 7, and therefore, when the alkylphenol-modified amino resin is added to the rubber composition, the hardness, the vulcanization property, the scorch resistance, the abrasion resistance and the tear resistance of the rubber composition are all enhanced.
As shown in tables 6 and 7, the adhesive properties of examples 9 to 10 were enhanced and the adhesive property of example 10 was the best as compared with example 5. Among them, the adhesive property and reversion resistance of example 9 were significantly improved as compared with example 5, but the improvement of mechanical properties of example 9 was not significant, and therefore, when the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin was used together with an alkylphenol sulfide, both the adhesive property and reversion resistance of the resulting rubber composition were significantly improved; the initial adhesive strength and mechanical properties of example 10 were significantly improved as compared to example 5, but the reversion rate of vulcanization and the improvement in adhesive strength after aging were not significant in example 10, and therefore, when the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin was used in combination with the alkylphenol-modified amino resin, the initial adhesive property and mechanical properties of the resulting rubber composition were significantly improved.
Examples 11-18 and comparative example 2: the difference from example 7 is that the compounding ratio of alkylphenol sulfide, alkylphenol-modified amino resin, resin 5 and commercially available adhesive resin is different, and the formulation of the rubber composition is shown in Table 8.
TABLE 8 raw material compounding ratios of rubber compositions in examples 11 to 18 and comparative example 2
TABLE 9 results of adhesion Strength test (KN/m) in examples 11 to 18 and comparative example 2
TABLE 10 results of measuring vulcanization properties and mechanical properties in example 18 and comparative example 2
As shown in table 6 and table 9, compared with examples 5 and 8 to 10, the adhesion of example 11 was superior to that of examples 5 and 8 to 10, and thus, the adhesion performance was best when the rubber composition prepared by adding the alkylphenol sulfide, the alkylphenol-modified amino resin, and the alkylresorcinol-modified cardanol-formaldehyde adhesive resin together was added, and secondly, the rubber composition prepared by adding the alkylresorcinol-modified cardanol-formaldehyde adhesive resin and the alkylphenol sulfide, or the alkylresorcinol-modified cardanol-formaldehyde adhesive resin and the alkylphenol-modified amino resin was added, while the adhesion performance was weaker in the rubber composition prepared by adding only the alkylphenol sulfide, the alkylphenol-modified amino resin, or the alkylresorcinol-modified cardanol-formaldehyde adhesive resin.
As shown by combining Table 9 and Table 10, the comparison of examples 11-13 shows that the adhesive properties of examples 12-13 are significantly better than those of example 11, but the increase in the adhesive properties of example 13 is not significant compared to example 12 in example 13. The inventors found that, in the rubber composition, when 3 parts of the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin was used in 100 parts of the natural rubber, the adhesive property of the rubber composition was the best; when the using amount of the mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin is increased to 4 parts, the adhesive performance is not increased much, but the cost is increased; therefore, when 3 parts of the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin is used, the rubber composition is cost-optimized while ensuring excellent adhesive properties of the rubber composition.
Comparison of examples 11 and 14-15 shows that the adhesion performance of examples 14-15 is significantly better than that of example 11, but the increase in adhesion performance of example 15 is not significant compared to example 14. The inventors found that, in the rubber composition, when 3 parts of the alkylphenol sulfide is used, the adhesion property of the rubber composition is best; however, when the usage amount of the alkylphenol sulfide is increased to 4 parts, the performance is not increased much, but the cost is increased; therefore, when 3 parts of the alkylphenol sulfide is used, the rubber composition is most cost-effective while the rubber composition is excellent in adhesion and aging resistance.
Comparison of examples 11 and 16-17 shows that the adhesion performance of examples 16-17 is significantly better than example 11, but the increase in adhesion performance of example 17 is not significant compared to example 16. The inventors found that, in the rubber composition, when 3 parts of the alkylphenol-modified amino resin is used, the adhesion property of the rubber composition is best; however, when the amount of the alkylphenol-modified amino resin is increased to 4 parts, the performance is not increased much, but the cost is increased; therefore, when 3 parts of the alkylphenol-modified amino resin is used, the rubber composition is cost-optimized while the adhesive property, the vulcanization property and the mechanical property of the rubber composition are ensured to be excellent.
The adhesion, vulcanization, tensile stress at break, abrasion index, tear strength, etc. of example 18 are all significantly improved over those of examples 11-17, so when the rubber: alkylphenol sulfides: alkylphenol-modified amino resin: when the alkyl resorcinol-modified cardanol-formaldehyde adhesive resin is mixed in a ratio of 100:3:3:3, the adhesive property, vulcanization property and mechanical property of the rubber composition are all the best.
Compared with the comparative example 2, the adhesive property, the vulcanization property, the tensile stress at definite elongation, the breaking strength, the abrasion index, the tear strength and other properties of the example 18 are all superior to those of the comparative example 2, wherein the initial adhesive strength of the example 18 reaches 2151KN/m, the heat aging adhesive strength reaches 1788KN/m, the constant temperature and humidity aging adhesive strength reaches 1985KN/m, the salt water aging adhesive strength reaches 1967KN/m, the reversion rate of vulcanization is 23%, the breaking strength before aging is 26.6MPa, and the breaking strength after aging is 25.9 MPa. Therefore, the overall performance of the rubber composition made with the addition of the mixed alkylresorcinol modified cardanol-formaldehyde binding resin is superior to that of the rubber composition with the addition of the commercially available binding resin.
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 rubber composition is characterized by comprising the following components in parts by weight:
according to 100 parts of rubber, 20-80 parts of carbon black, 0.5-5 parts of vulcanizing agent and 1-10 parts of mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin;
wherein the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin comprises a first repeating unit represented by formula (1) and a second repeating unit represented by formula (2), and the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin is terminated with alkylresorcinol;
the first repeating unit represented by formula (1) and the second repeating unit represented by formula (2) 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 represented by the formula (1) and the second repeating unit represented by the formula (2) is 500-4000.
2. The rubber composition of claim 1, wherein the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin has a weight average molecular weight of 500-5000.
3. The rubber composition of claim 1, wherein the mixed alkylresorcinol-modified cardanol-formaldehyde binding resin has a softening point of 80-140 ℃.
4. The rubber composition of claim 1, wherein R' and R "are independently C1-10 alkyl or C7-12 alkaryl.
5. A rubber composition according to any one of claims 1 to 4, wherein the rubber composition further comprises 0.5 to 5 parts by weight of an alkylphenol sulfide and/or 0.5 to 10 parts by weight of an alkylphenol-modified amino resin per 100 parts by weight of the rubber.
6. The rubber composition according to claim 5, wherein the alkylphenol sulfide has a weight average molecular weight of 500-3000.
7. The rubber composition according to claim 5, wherein the alkylphenol-modified amino resin has a weight-average molecular weight of 1000-20000.
8. The rubber composition of claim 5, wherein the rubber composition comprises 1 to 4 parts by weight of the alkylphenol sulfide, 1 to 6 parts by weight of the alkylphenol-modified amino resin, and 1.5 to 8 parts by weight of the mixed alkylresorcinol-modified cardanol-formaldehyde adhesive resin, based on 100 parts by weight of the rubber.
9. The method for preparing a rubber composition according to any one of claims 1 to 8, comprising the steps of:
mixing rubber and carbon black, heating to 140-160 ℃ to prepare rubber master batch, cooling to 80-95 ℃, adding a vulcanizing agent and mixed alkylresorcinol modified cardanol-formaldehyde adhesive resin, mixing with the rubber master batch, and mixing at 40-50 ℃ for 4-10min to obtain the rubber composition.
10. A rubber article characterized in that a raw material for the rubber article comprises the rubber composition according to any one of claims 1 to 8.
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| CN114181446B (en) * | 2022-01-12 | 2023-03-31 | 北京新世纪京喜防水材料有限责任公司 | Polymer waterproof sheet, preparation method thereof and polymer waterproof coiled material |
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