CN114672074A - Rubber composition containing xylene modified phenolic resin and application thereof - Google Patents
Rubber composition containing xylene modified phenolic resin and application thereof Download PDFInfo
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- CN114672074A CN114672074A CN202011549573.1A CN202011549573A CN114672074A CN 114672074 A CN114672074 A CN 114672074A CN 202011549573 A CN202011549573 A CN 202011549573A CN 114672074 A CN114672074 A CN 114672074A
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- Prior art keywords
- xylene
- resin
- rubber
- phenol
- resorcinol
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 60
- 239000005060 rubber Substances 0.000 title claims abstract description 60
- -1 xylene modified phenolic resin Chemical class 0.000 title claims abstract description 40
- 239000008096 xylene Substances 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000002989 phenols Chemical class 0.000 claims abstract description 25
- 238000006482 condensation reaction Methods 0.000 claims abstract description 17
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000005011 phenolic resin Substances 0.000 claims abstract description 8
- 239000000370 acceptor Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 150000003384 small molecules Chemical class 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 54
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- MSFGJICDOLGZQK-UHFFFAOYSA-N 5-ethylbenzene-1,3-diol Chemical compound CCC1=CC(O)=CC(O)=C1 MSFGJICDOLGZQK-UHFFFAOYSA-N 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- 229920003051 synthetic elastomer Polymers 0.000 claims description 4
- 239000005061 synthetic rubber Substances 0.000 claims description 4
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 claims description 3
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 3
- 229960001553 phloroglucinol Drugs 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 70
- 239000011347 resin Substances 0.000 abstract description 70
- 238000002156 mixing Methods 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000391 smoking effect Effects 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000002318 adhesion promoter Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000020169 heat generation Effects 0.000 description 8
- 229920001568 phenolic resin Polymers 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical class O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical class O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000003000 phloroglucinols Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention discloses a rubber composition containing xylene modified phenolic resin, which comprises the following components: (1) a rubber component; (2) xylene-modified phenol resins used as methylene acceptors; (3) a methylene donor. The xylene modified phenolic resin is prepared by condensation reaction of active xylene formaldehyde resin, phenol, at least one second phenolic compound with activity higher than that of the phenol and an aldehyde compound, the content of volatile small molecules of the resin is low, and the phenomenon of smoking is basically avoided in the mixing process of rubber materials. The active xylene formaldehyde resin can perform condensation reaction with a phenolic compound and enter a main chain of the resin, so that a larger side chain structure which is easy to cause reduction of dynamic performance is basically not formed, and in addition, the moisture absorption of the resin can be improved due to the introduction of a xylene structure; the more reactive second phenolic compound can provide a faster cure crosslinking speed for the resin or compound.
Description
Technical Field
The invention belongs to the technical field of rubber synthesis, and relates to a rubber composition containing xylene modified phenolic resin and application thereof.
Background
The performance of rubber articles, such as tires, conveyor belts, hoses, and the like, is greatly affected by the quality of the bond between the rubber and the reinforcing material, as well as the mechanical properties of the vulcanized rubber matrix in which the reinforcing material is used.
The use of two-component systems, including a methylene donor and a methylene acceptor, is a conventional method of improving the adhesion of rubber to reinforcing materials. The mechanism is as follows: the methylene acceptor reacts with the methylene donor, and the two are interpenetrated in the rubber matrix in a bonding mode, so that the performance of the final rubber product is obviously influenced.
In the rubber industry, resorcinol and resorcinol-formaldehyde resins are commonly used for adhesion of rubber to reinforcing materials, and although resorcinol can provide excellent properties to rubber, resorcinol is prone to sublimation and smoking during use, and is not environmentally friendly and occupational health friendly. Although resorcinol-formaldehyde resins reduce the content of free resorcinol, they do not solve the problem of smoking and are prone to moisture and caking during transportation or storage. In order to further solve the problems of smoke generation and caking, styrene modified resorcinol-formaldehyde resin is developed, the resin has low free phenol and is not easy to absorb moisture and cake, but the use of styrene introduces a phenethyl small side group structure outside a molecular main chain, which can cause the reduction of dynamic heat generation performance.
Phenol-formaldehyde resins are generally used in the rubber industry as reinforcing resins and are not used substantially as rubber adhesion promoters due to their slow cure rate. For this purpose, there is a patent that resorcinol-modified phenol-formaldehyde resin having a high reactivity is used to increase the curing and crosslinking speed thereof and is used as a rubber adhesion promoter. For example, patent US 2005013737379 uses a modified phenol-formaldehyde resin prepared by using 1-30 wt% of alkylphenol, 1-25 wt% of resorcinol and 45-98 wt% of phenol as phenolic raw materials as a rubber adhesion promoter. Although the use of resorcinol improves the cure crosslinking speed of the modified resin, the presence of the alkyl group of the alkylphenol side chain adversely affects the dynamic heat buildup properties.
Disclosure of Invention
In order to solve the defects in the prior art. The xylene modified phenolic resin used as the rubber adhesion promoter is developed by adopting active xylene formaldehyde resin, phenol and at least one second phenolic compound with activity higher than that of phenol as raw materials, and the xylene modified phenolic resin has low content of volatile micromolecules and basically does not generate a smoking phenomenon. The active xylene formaldehyde resin can perform condensation reaction with a phenolic compound and enter a main chain of the resin, so that a larger side chain structure which is easy to cause reduction of dynamic performance cannot be formed, and in addition, the moisture absorption of the resin can be improved due to the introduction of the xylene structure; the more reactive second phenolic compound can provide a suitable cure crosslinking speed for the resin or compound.
The invention provides a xylene modified phenolic resin, which has a structural formula as follows:
in the formula (II), m, n and r are natural numbers, m is less than or equal to 20, n is less than or equal to 20, and r is less than or equal to 20;
the invention also provides a rubber composition containing the xylene modified phenolic resin, which at least comprises the following components:
(1) a rubber component;
(2) xylene-modified phenol resins used as methylene acceptors;
(3) a methylene donor.
In the invention, the xylene modified phenolic resin is prepared by condensation reaction of active xylene formaldehyde resin, phenol and at least one second phenolic compound with activity higher than that of phenol as raw materials with formaldehyde.
The mass percentages of the xylene formaldehyde resin, the phenol and at least one second phenolic compound with activity higher than that of the phenol in the total mass of the xylene formaldehyde resin and the phenolic raw materials in the resin are respectively as follows: 5 wt% -30 wt%, 50 wt% -90 wt%, 5 wt% -30 wt%; preferably, it is 5 wt% to 30 wt%, 50 wt% to 80 wt%, 5 wt% to 20 wt%.
Wherein the xylene formaldehyde resin has a characteristic structure as shown in the following:
in the formula (I), p is less than or equal to 20, and q is less than or equal to 20;
wherein the number average molecular weight of the xylene formaldehyde resin is 200-2000; preferably, the weight is 200-1000.
Wherein the oxygen content of the xylene formaldehyde resin is 5 wt% -20 wt%; preferably, it is 7 wt% to 15 wt%.
In the present invention, the second phenolic compound used for the xylene-modified phenolic resin is selected from: any one or a combination of at least two of resorcinol, phloroglucinol, 5-methylresorcinol, 5-ethylresorcinol, etc.; preferably, resorcinol.
Resorcinol is about 10-15 times more active than phenol due to the activation of the meta-bisphenol hydroxyl group (Resorcinol Chemistry, Technology and application. raj b. durairaj. p 181.). Based on the same mechanism, 5-alkyl substituted resorcinols and phloroglucinols are more active than resorcinols. Therefore, the addition of a proper amount of high-activity phenolic compound can obviously improve the reaction activity of the phenol formaldehyde resin.
In the invention, the preparation method of the xylene modified phenolic resin comprises the following steps: under the action of a catalyst, xylene formaldehyde resin, phenol, at least one second phenolic compound and formaldehyde are subjected to condensation reaction, a proper amount of terminator is added, and the temperature is raised to distill out water and other volatile small molecules, so that the xylene modified phenolic resin is obtained.
Wherein the catalyst is selected from one or more of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, benzene sulfonic acid, benzene disulfonic acid, C1-C15 alkyl benzene sulfonic acid, naphthalene sulfonic acid and the like; preferably one or more of C1-C15 alkylbenzene sulfonic acids.
Wherein the terminator is selected from one or more of sodium hydroxide, triethanolamine, N-methyldiethanolamine, diazabicyclo (1, 8-diazabicycloundecen-7-ene), and the like; preferably, sodium hydroxide.
Wherein the temperature of the condensation reaction is 60-120 ℃; preferably, it is 100 ℃.
Wherein the condensation reaction time is 5-180 min; preferably, it is 30 min.
Wherein the temperature of the temperature rising distillation is 100-200 ℃; preferably, it is 180 ℃.
Wherein the time of the temperature rise distillation is 30-180 min; preferably, it is 60 min.
Wherein, the feeding sequence of the reaction materials can be as follows: xylene formaldehyde resin, phenol and at least one second phenolic compound are mixed for pre-reaction, and then formaldehyde is added for condensation reaction; or the xylene formaldehyde resin is firstly pre-reacted with phenol or partial phenol, then partial phenol and at least one second phenolic compound are added for mixing, and then formaldehyde is added for condensation reaction; or the xylene formaldehyde resin is pre-reacted with phenol or partial phenol, partial formaldehyde is added for condensation, partial phenol and at least one second phenolic compound are added for mixing, and then the formaldehyde is added for condensation reaction; the preferred sequence of addition: the xylene formaldehyde resin is pre-reacted with a portion of phenol, then a portion of phenol is added and mixed with at least one second phenolic compound, such as resorcinol, and then formaldehyde is added for condensation reaction, wherein the reaction process is as follows:
in the first step, the reaction equation for the pre-reaction of xylene formaldehyde resin with a portion of phenol is as follows:
in the formula (III), p is less than or equal to 20, and q is less than or equal to 20;
in the second step, the reaction equation of the condensation reaction of the pre-reaction product of the previous step with part of phenol, resorcinol and formaldehyde is as follows:
in the formula (IV), q is less than or equal to 20; m is less than or equal to 20, n is less than or equal to 20, and r is less than or equal to 20;
common bonding resins used in the modern rubber industry are resorcinol-formaldehyde resins and styrenated resorcinol-formaldehyde resins. The resorcinol-formaldehyde resin has high free resorcinol (generally more than 10wt percent) in the molecular structure, is easy to absorb moisture and agglomerate, and has a smoking phenomenon in use.
The styrenated resorcinol-formaldehyde resin has nonpolar phenethyl side groups, and although moisture absorption and blocking of the resin are improved, the side groups are easy to generate vibration friction heat, so that the dynamic performance of a tire is influenced.
The structural formulas of the resorcinol-formaldehyde resin and the styrene-modified resorcinol-formaldehyde resin are as follows:
resorcinol-formaldehyde resin:
in the formula (V), m is a natural number and is less than or equal to 20.
Styrene-modified resorcinol-formalin resin:
in the formula (VI), m and n are natural numbers, m is less than or equal to 20, and n is less than or equal to 20.
In addition, certain commercially available modified phenol-formaldehyde resins for use in rubber adhesion promoters are prepared by the condensation reaction of alkyl phenols, resorcinol, and formaldehyde. The alkylphenol can adjust the polarity of the resin and improve the moisture absorption of the resin, but the alkyl side group of the alkylphenol is also a structure which is easy to generate vibration friction heat; resorcinol can increase the reactivity of the phenol resin. It is presumed to have the following structural formula:
in the formula (VII), m, n and r are natural numbers, m is less than or equal to 20, n is less than or equal to 20, and r is less than or equal to 20;
the xylene modified phenolic resin of the invention is prepared by bonding nonpolar xylene into the main chain of the molecular structure of the phenolic resin, thereby avoiding the occurrence of the side group, improving the moisture absorption and dynamic heat generation performance of the phenolic resin, and simultaneously adding a second phenolic compound with higher activity to provide higher reaction activity.
In the present invention, the rubber component may be Natural Rubber (NR), synthetic rubber or a combination thereof; the synthetic rubber includes, but is not limited to, one or more of cis-1, 4-polyisoprene (BR), polybutadiene, polychloroprene, copolymers of isoprene and butadiene, copolymers of acrylonitrile and isoprene, copolymers of styrene and butadiene and isoprene, butyl rubber, EPDM, copolymers of styrene and butadiene, and the like; preferably, it is natural rubber.
In the present invention, the methylene donor is selected from one or more of hexamethylenetetramine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, and the like; preferably hexamethoxymethylmelamine.
In the invention, the weight ratio of the methylene donor to the xylene modified phenolic resin is 1: 10-10: 1; preferably, the weight ratio is 1: 5-5: 1.
The weight ratio of the rubber component to the xylene modified phenolic resin is 100: 0.5-100: 5, or less; preferably, the ratio is 100: 1-100: 3.
in the invention, the rubber composition further comprises an additive, wherein the additive is selected from one or more of carbon black, a vulcanizing agent, an accelerator, stearic acid, zinc oxide, an antioxidant, softening oil, a cobalt salt, white carbon black, a silane coupling agent and the like.
In the present invention, the xylene-modified phenolic resin may be mixed into the rubber composition in the same manner as a similar methylene acceptor product.
The invention also provides a preparation method of the rubber composition, which comprises the following steps: step one, mixing rubber and additive components except a vulcanizing agent, an accelerant and an adhesion promoter to form a mixture; step two, mixing the xylene modified phenolic resin into the mixture formed in the step one; and step three, mixing the methylene donor into the mixture formed in the second step.
Wherein the vulcanizing agent, the accelerator and the adhesion promoter are added independently in step two and/or step three.
In the present invention, an internal mixer such as a Banbury mixer is used for the mixing.
In the first step, the mixing temperature is 150-155 ℃; preferably 150 deg.c.
In the second step, the mixing temperature is 90-150 ℃; preferably, it is 145 ℃.
In the third step, the mixing temperature is 90-150 ℃; preferably, the temperature is 90-100 ℃.
Preferably, the formed rubber composition can be further shaped and vulcanized.
The invention also provides the application of the rubber composition containing the xylene modified phenolic resin in tire products.
The tire product is the bonding part of rubber and cord thread (polyester/steel wire) such as a tire body, a belt ply and the like of the tire.
The beneficial effects of the invention include: when the modified phenolic resin is used as a rubber adhesion promoter and added into rubber, xylene is added into a phenolic resin main chain structure instead of a side chain modification mode, so that increase of physical friction heat generation among a resorcinol resin network, a rubber network and an adhesive layer is reduced, loss factors are reduced, dynamic heat generation of the rubber is reduced, the internal structure of tire rubber is protected, and the use safety and the service life of the tire are improved. In addition, the addition of the dimethylbenzene reduces the mass ratio of hygroscopic phenolic hydroxyl in the resin, improves the caking phenomenon in the storage or transportation process of the resin and improves the stability of the resin.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
In the invention, the used raw materials of xylene formaldehyde resin, phenol, resorcinol and formaldehyde are all industrial grade. The concentration of formaldehyde is 36.7-37.1%. P-toluenesulfonic acid (PTSA), sodium hydroxide are chemically pure reagents.
Reference ratio 1
The commercial A resin was a resorcinol-formaldehyde resin with a softening point of 105 ℃ and a free resorcinol content of 12.5 wt.%.
Reference ratio 2
The commercially available B resin was a styrene-modified resorcinol-formaldehyde resin having a softening point of 108.7 ℃ and a free resorcinol content of 1.21 wt.%.
Reference ratio 3
The commercial C resin was an alkylphenol-modified resorcinol-formaldehyde resin having a softening point of 104.1 ℃ and a free phenol content of 0.27% by weight.
Example 1
To a 1000ml round bottom flask equipped with a stirred, temperature controlled, reflux condenser was added 25g of xylene formaldehyde resin, 190g of phenol, 25g of 5-methylresorcinol, and 0.5g of p-toluene sulfonic acid, mixed and heated to 90 ℃. Then 115g formaldehyde (37% aqueous solution) was added slowly and incubated for 30 minutes. After the reaction is finished, 0.35g of sodium hydroxide (30% aqueous solution) is added for neutralization, then the temperature is raised to 170 ℃, water is distilled off, and phenol is removed in vacuum at 180 ℃ (less than 100torr), so that the xylene modified resorcinol-formaldehyde resin is obtained, wherein the softening point of the xylene modified resorcinol-formaldehyde resin is 102.3 ℃, the content of free 5-methyl resorcinol is 0.23 wt%, and the content of free phenol is 0.16 wt%.
Example 2
To a 1000ml round bottom flask equipped with a stirred, temperature controlled, reflux condenser was added 60g of xylene formaldehyde resin, 200g of phenol, 30g of 5-ethyl resorcinol, and 0.5g of p-toluene sulfonic acid, mixed and heated to 90 ℃. Then 110g formaldehyde (37% aqueous solution) was slowly added and incubated for 30 minutes. After the reaction, 0.35g of sodium hydroxide (30% aqueous solution) is added for neutralization, then the temperature is raised to 170 ℃, water is distilled off, and phenol is removed in vacuum at 180 ℃ under the condition of less than 100torr, so that the xylene modified resorcinol-formaldehyde resin is obtained, wherein the softening point of the xylene modified resorcinol-formaldehyde resin is 105.1 ℃, the content of free 5-ethyl resorcinol is 0.51 wt%, and the content of free phenol is 0.29 wt%.
Example 3
To a 1000ml round bottom flask equipped with a stirred, temperature controlled, reflux condenser was added 90g of xylene formaldehyde resin, 150g of phenol, 60g of resorcinol, and 0.5g of p-toluene sulfonic acid, mixed and heated to 90 ℃. Then 80g of formaldehyde (37% in water) was added slowly and incubated for 30 minutes. After the reaction is finished, 0.35g of sodium hydroxide (30% aqueous solution) is added for neutralization, then the temperature is raised to 170 ℃, water is distilled off, and phenol is removed in vacuum at 180 ℃ (less than 100torr), so that the xylene modified resorcinol-formaldehyde resin is obtained, wherein the softening point of the xylene modified resorcinol-formaldehyde resin is 104.0 ℃, the content of free resorcinol is 0.80 wt%, and the content of free phenol is 0.13 wt%.
Example 4
To a 1000ml round bottom flask equipped with a stirring, temperature control, reflux condenser was added 60g of xylene formaldehyde resin, 90g of phenol, and 0.5g of p-toluene sulfonic acid, mixed and heated to 90 ℃. Then 50g formaldehyde (37% aqueous solution) was slowly added and incubated for 30 minutes. After the above reaction was completed, 110g of phenol and 30g of resorcinol were added, melted and mixed uniformly to 90 ℃, and then 60g of formaldehyde (37% aqueous solution) was slowly added thereto and kept for 30 minutes. Adding 0.35g of sodium hydroxide (30% aqueous solution), neutralizing, heating to 170 ℃, distilling to remove water, and removing phenol under vacuum at 180 ℃ (less than 100torr) to obtain the xylene modified resorcinol-formaldehyde resin, wherein the softening point of the xylene modified resorcinol-formaldehyde resin is 106.5 ℃, the content of free resorcinol is 0.12 wt%, and the content of free phenol is 0.31 wt%.
Example 5
Carrying out a moisture absorption experiment on the commercial resins A, B and C selected according to the reference proportions of 1-3 and the xylene modified phenolic resin prepared in the embodiments 1-4 of the invention under the test conditions of 40 ℃, 70% of relative humidity and 24h, 48h and 72h of storage time, wherein the test results are shown in the following table 1:
TABLE 1 moisture absorption test (%)
As can be seen from the data in Table 1, the xylene-modified phenol formaldehyde resins prepared in the examples of the present invention have significantly improved moisture absorption properties as compared to the resorcinol formaldehyde resin (commercially available A resin) and are comparable to the styrene-modified resorcinol formaldehyde resin (commercially available B resin).
Example 6
The xylene modified resorcinol-formaldehyde resin prepared in the embodiments 1-4 of the invention is compared with commercially available resins A, B and C in a rubber belt velocity layer formula for test verification.
The rubber formulation was refined in accordance with the formulation shown in table 2, wherein the compounding amounts of the respective components were based on 100 parts by mass of rubber (phr).
TABLE 2 rubber application test formulation
The rubber material mixing process comprises the following steps:
in the first step, a rubber component, carbon black, silica, zinc oxide, and an antioxidant (TMQ and 6PPD) were mixed at about 150 ℃ by a Banbury mixer, and kneaded to prepare a master batch.
In the second step, samples of the adhesive resins (xylene-modified resorcinol-formalin resins) commercially available in reference examples A, B and C and prepared in examples 1, 2, 3 and 4 of the present invention, and cobalt salts, respectively, were mixed into a master batch obtained by mixing in a Banbury mixer at a temperature of about 145 ℃.
Thirdly, adding insoluble sulfur (OT20), an accelerator (TBBS) and methylene acceptor-HMMM (65%) listed in Table 2 at 90-100 ℃ for mixing, and placing the mixed product in an environment with a constant temperature of about 23 ℃ and a relative humidity of 50% overnight. Then, the vulcanization, shape and optimum vulcanization degree were measured at 160 ℃.
The test data for the modified vulcanizate compositions are shown in Table 3. Wherein, the tensile property is tested by GB/T528-2009, the vulcanization condition of the rubber material before aging is 160 ℃, 15min, and the hot air aging condition of the rubber material is 100 ℃, 24 h; the hardness is tested by GB/T531.1-2008;
the vulcanization performance was measured using an Alpha Technologies MDR sulfur apparatus, with reference to the following standards: GB/T16584 + 1996 and GB/T1233 + 2008, measured at 160 ℃, 1 ℃ arc and 1.67 Hz. In an oscillating disc sulfur analyzer, a rubber material sample is subjected to an oscillating shearing force with constant amplitude, and the torque of an oscillating net disc embedded in the rubber material sample at a vulcanization temperature is measured;
the vulcanization conditions adopted for the adhesion performance of the steel cord are as follows: the specification of the steel cord is as follows at 155 ℃ for 40 min: 3+9+15 x 0.22+1, tested according to the standard ASTM D1871-2004.
Dynamic heat generation DMA detection conditions: 30-80 ℃ at 3K/11Hz/10N/15 μm.
And (3) generating heat by compression, referring to a detection standard ISO4666-4-2007, wherein the detection conditions are that the constant temperature is 55 ℃, the preheating time is 30min, the test time is 25min, the static load is 100N, the dynamic load is 700N, and the frequency is 10 HZ.
TABLE 3 rubber stock Properties
As can be seen from the properties of the compounds in Table 3, compounds containing xylene-modified resorcinol-formaldehyde resins prepared according to the examples of the present invention have a longer scorch time (T10) and better scorch safety, and the curing time (T90) is similar to that of the commercial resin B (styrene-modified resorcinol-formaldehyde resin), based on the commercial resin A (resorcinol-formaldehyde resin). The compound tensile strengths of the xylene-modified resorcinol-formaldehyde resins prepared in examples 1-4 of this invention before and after aging were better than the commercial resins A/B, slightly better than or comparable to the commercial resin C. The steel wire withdrawal force data (Table 3: steel cord adhesion properties) show that compounds containing the xylene-modified resorcinol-formaldehyde resin prepared in examples 1-4 of the present invention are improved to varying degrees.
In the dynamic heat generation (DMA) test of the rubber compound of the xylene modified resorcinol-formaldehyde resin prepared in the embodiments 1 to 4 of the invention, the dynamic modulus (G', high temperature mechanical property) at 60 ℃ is close to that of the commercial resin A and is better than that of the commercial resin B/C; the tan delta at 60 ℃ is lower than that of the commercial resin, indicating that compounds compounded with xylene-modified resorcinol-formaldehyde resins prepared according to examples 1-4 of the present invention have low hysteresis loss and low heat build-up. In the compression heat generation test, the middle final temperature and the permanent deformation degree of the xylene modified resorcinol-formaldehyde resin prepared in the embodiments 1-4 of the invention are similar to those of the commercial A resin and are lower than those of the commercial B/C resin; the results of the compression heat generation test intuitively demonstrate that the xylene-modified resorcinol-formalin resins prepared in examples 1-4 of the present invention have low heat buildup properties.
The protection content of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, which is set forth in the following claims.
Claims (11)
1. A rubber composition containing a xylene-modified phenolic resin, characterized in that it comprises at least the following components:
(1) a rubber component;
(2) xylene-modified phenol resins used as methylene acceptors;
(3) a methylene donor;
the xylene modified phenolic resin is prepared by condensation reaction of active xylene formaldehyde resin, phenol and at least one second phenolic compound with activity higher than that of phenol as raw materials with formaldehyde; the mass percentages of the xylene formaldehyde resin, the phenol and at least one second phenolic compound with higher activity than the phenol in the total mass of the xylene formaldehyde resin and the phenolic raw materials are respectively as follows: 5 wt% -30 wt%, 50 wt% -90 wt%, 5 wt% -30 wt%.
2. The rubber composition according to claim 1, wherein the second phenolic compound used for the xylene-modified phenolic resin is selected from: any one or more of resorcinol, phloroglucinol, 5-methyl resorcinol and 5-ethyl resorcinol.
3. The rubber composition according to claim 1, wherein the xylene formaldehyde resin has the following characteristic structure:
in the formula (I), p is less than or equal to 20, and q is less than or equal to 20;
the number average molecular weight of the xylene formaldehyde resin is 200-2000; the oxygen content of the xylene formaldehyde resin is 5 wt% -20 wt%.
4. The rubber composition of claim 1, wherein the rubber component is selected from the group consisting of natural rubber, synthetic rubber, or combinations thereof; the synthetic rubber is one or more selected from cis-1, 4-polyisoprene, polybutadiene, polychloroprene, a copolymer of isoprene and butadiene, a copolymer of acrylonitrile and isoprene, a copolymer of styrene, butadiene and isoprene, butyl rubber, ethylene propylene diene rubber and a copolymer of styrene and butadiene.
5. The rubber composition of claim 1, wherein the methylene donors are selected from one or more of hexamethylenetetramine, hexamethoxymethylmelamine, hexaethoxymethylmelamine.
6. The rubber composition according to claim 1, wherein the weight ratio of the methylene donor to the xylene-modified phenol resin is 1: 10 to 10: 1; and/or the weight ratio of the rubber to the xylene modified phenolic resin is 100: 0.5-100: 5, or more.
7. The rubber composition of claim 1, further comprising an additive selected from one or more of carbon black, a vulcanizing agent, an accelerator, stearic acid, zinc oxide, an antioxidant, a softening oil, a cobalt salt, white carbon, and a silane coupling agent.
8. The xylene modified phenolic resin is characterized by having the following structural formula:
in the formula (II), m, n and r are natural numbers, m is less than or equal to 10, n is less than or equal to 20, and r is less than or equal to 20.
9. A preparation method of xylene modified phenolic resin is characterized by comprising the following steps: under the action of a catalyst, xylene formaldehyde resin, phenol, at least one second phenolic compound and formaldehyde are subjected to condensation reaction, a terminator is added, and the temperature is raised to distill out water and other volatile small molecules, so that the xylene modified phenolic resin is obtained.
10. The method for preparing xylene-modified phenolic resin according to claim 9, wherein said catalyst is selected from one or more of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, benzenesulfonic acid, benzenedisulfonic acid, C1-C15 alkylbenzenesulfonic acid, naphthalenesulfonic acid; the terminator is selected from one or more of NaOH, triethanolamine, N-methyldiethanolamine and diazabicyclo (1, 8-diazabicycloundecen-7-ene); the second phenolic compound is selected from: any one or more of resorcinol, phloroglucinol, 5-methylresorcinol and 5-ethylresorcinol; the temperature of the condensation reaction is 60-120 ℃; the condensation reaction time is 5-180 min; the temperature of the temperature rising distillation is 100-200 ℃; the time of the temperature rising distillation is 30-180 min.
11. Use of a rubber composition comprising a xylene-modified phenolic resin according to any one of claims 1-7 or a xylene-modified phenolic resin according to claim 8 in a tire product.
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| CN1726254A (en) * | 2002-12-13 | 2006-01-25 | 茵迪斯佩克化学公司 | Phenolic modified resorcinolic resins for rubber compounding |
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