CN114672074B - 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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- CN114672074B CN114672074B CN202011549573.1A CN202011549573A CN114672074B CN 114672074 B CN114672074 B CN 114672074B CN 202011549573 A CN202011549573 A CN 202011549573A CN 114672074 B CN114672074 B CN 114672074B
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- resin
- phenol
- rubber
- xylene
- resorcinol
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 59
- 239000005060 rubber Substances 0.000 title claims abstract description 59
- -1 xylene modified phenolic resin Chemical class 0.000 title claims abstract description 49
- 239000008096 xylene Substances 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229920005989 resin Polymers 0.000 claims abstract description 80
- 239000011347 resin Substances 0.000 claims abstract description 80
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 18
- 238000006482 condensation reaction Methods 0.000 claims abstract description 17
- 150000002989 phenols Chemical class 0.000 claims abstract description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 13
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 10
- 239000005011 phenolic resin Substances 0.000 claims abstract description 8
- 239000000370 acceptor Substances 0.000 claims abstract description 7
- ZCJGPLOQDMFGAR-UHFFFAOYSA-N formaldehyde;1,2-xylene Chemical compound O=C.CC1=CC=CC=C1C ZCJGPLOQDMFGAR-UHFFFAOYSA-N 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 63
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- 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
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 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
- 239000002994 raw material Substances 0.000 claims description 6
- UIFVCPMLQXKEEU-UHFFFAOYSA-N 2,3-dimethylbenzaldehyde Chemical compound CC1=CC=CC(C=O)=C1C UIFVCPMLQXKEEU-UHFFFAOYSA-N 0.000 claims description 5
- MSFGJICDOLGZQK-UHFFFAOYSA-N 5-ethylbenzene-1,3-diol Chemical compound CCC1=CC(O)=CC(O)=C1 MSFGJICDOLGZQK-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 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
- 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 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
- 239000003054 catalyst Substances 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
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 4
- 229960001553 phloroglucinol Drugs 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
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229920000877 Melamine resin 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
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 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
- 229940092714 benzenesulfonic acid Drugs 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 238000004513 sizing Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000000779 smoke Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 17
- 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
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000020169 heat generation Effects 0.000 description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 7
- 239000002318 adhesion promoter Substances 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 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
- 238000009472 formulation Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010410 layer Substances 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
- 238000003860 storage Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001070 adhesive effect 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
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical class O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 229920000728 polyester Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011369 resultant mixture Substances 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
- 230000000391 smoking effect Effects 0.000 description 1
- 230000003068 static effect Effects 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
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 dimethylbenzene modified phenolic resin, which comprises the following components: (1) a rubber component; (2) Xylene modified phenolic 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 and aldehyde compounds, and has low content of volatile micromolecules, and no smoke phenomenon basically occurs in the mixing process of sizing materials. The active dimethylbenzene formaldehyde resin can be subjected to condensation reaction with the phenolic compound, and enters the main chain of the resin, a larger side chain structure which is easy to cause dynamic performance reduction is not formed basically, and in addition, the hygroscopicity of the resin can be improved by introducing the dimethylbenzene structure; the more reactive second phenolic compound may provide faster cure crosslinking speeds 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 properties of rubber articles such as tires, conveyor belts, and rubber hoses are 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 methylene donors and methylene acceptors, is a conventional method of improving the adhesion properties of rubber to reinforcing materials. The mechanism is as follows: the methylene acceptor reacts with the methylene donor and the methylene acceptor interpenetrates the rubber matrix by bonding, which has a significant effect on the properties of the final rubber article.
In the rubber industry, resorcinol and resorcinol formaldehyde resins are commonly used for the adhesion of rubber to reinforcing materials, and although resorcinol can provide excellent properties to rubber, resorcinol is susceptible to sublimation and smoke during use, which is not beneficial to environmental and occupational health. Although resorcinol formaldehyde resins reduce the content of free resorcinol, they still do not solve the problem of smoke and are susceptible to moisture and caking during transportation or storage. In order to further solve the problems of smoke generation and caking, styrene-modified resorcinol formaldehyde resins have been developed which have low free phenol content and are not prone to moisture absorption and caking, but the use of styrene introduces a small pendant structure of phenethyl groups outside the molecular main chain, which in turn leads to a decrease in dynamic heat build-up properties.
In general, phenol formaldehyde resins are commonly used as reinforcing resins in the rubber industry and are not used substantially as rubber adhesion promoters due to their slow cure rate. For this reason, there is a patent to use a resorcinol-modified phenol formaldehyde resin having a high activity to increase the curing and crosslinking speed thereof, and to use it as a rubber adhesion promoter. As in patent US20050137379, a modified phenol-formaldehyde resin prepared from 1-30% by weight of an alkylphenol, 1-25% by weight of resorcinol and 45-98% by weight of phenol as phenolic raw materials is used as a rubber adhesion promoter. Although the use of resorcinol improves the curing crosslinking rate of the modified resin, the presence of alkyl groups in the alkylphenol side chains also adversely affects the dynamic heat buildup.
Disclosure of Invention
In order to solve the defects existing in the prior art. The invention adopts active dimethylbenzene formaldehyde resin, phenol and at least one second phenol compound with activity higher than that of phenol as raw materials to develop the dimethylbenzene modified phenolic resin used as a rubber adhesion promoter, and the dimethylbenzene modified phenolic resin has low content of volatile small molecules and basically does not generate smoke phenomenon. The active dimethylbenzene formaldehyde resin can be subjected to condensation reaction with the phenolic compound, and enters the main chain of the resin, so that a larger side chain structure which is easy to cause dynamic performance reduction is not formed, and in addition, the hygroscopicity of the resin can be improved by introducing the dimethylbenzene structure; the second, more reactive phenolic compound can provide a suitable cure crosslinking rate for the resin or compound.
The invention provides a dimethylbenzene modified phenolic resin, which has the structural formula:
in the formula (II), m, n and r are natural numbers, wherein 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 phenolic resins used as methylene acceptors;
(3) A methylene donor.
In the invention, the dimethylbenzene modified phenolic resin is prepared by condensation reaction of active dimethylbenzene formaldehyde resin, phenol and at least one second phenolic compound with activity higher than that of phenol serving as raw materials with formaldehyde.
Wherein, the weight percentages of the xylenol formaldehyde resin, the phenol and at least one second phenol compound with activity higher than that of the phenol in the resin are respectively as follows: 5wt% -30wt%, 50wt% -90 wt%, 5wt% -30 wt%; preferably, the weight percentage is 5 to 30 percent, 50 to 80 percent and 5 to 20 percent.
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;
wherein the number average molecular weight of the dimethylbenzaldehyde resin is 200-2000; preferably 200 to 1000.
Wherein the oxygen content of the dimethylbenzaldehyde resin is 5-20wt%; preferably 7wt% to 15wt%.
In the present invention, the second phenolic compound used for the xylene modified phenolic resin is selected from the group consisting of: any one or a combination of at least two of resorcinol, phloroglucinol, 5-methyl resorcinol, 5-ethyl resorcinol, and the like; preferably resorcinol.
Resorcinol has about 10 to 15 times as much activity as phenol due to the activation of meta-bisphenol hydroxyl groups (Resorcinol Chemistry, technology and application. Raj b. Durairaj. P181.). Based on the same mechanism, the activity of 5-alkyl substituted resorcinol and phloroglucinol is higher than resorcinol. Therefore, the addition of a proper amount of high-activity phenolic compounds can obviously improve the reactivity 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, the 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 xylene modified phenolic resin is obtained by heating and distilling out moisture and other volatile small molecules.
Wherein the 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 and the like; preferably, it is one or more of C1-C15 alkylbenzenesulfonic acids.
Wherein the terminator is selected from one or more of sodium hydroxide, triethanolamine, N-methyldiethanolamine, diazabicyclo (1, 8-diazabicyclo undec-7-ene) and the like; preferably sodium hydroxide.
Wherein the temperature of the condensation reaction is 60-120 ℃; preferably at 100 ℃.
Wherein the time of the condensation reaction is 5-180 min; preferably 30min.
Wherein the temperature of the heating distillation is 100-200 ℃; preferably 180 ℃.
Wherein the temperature rising distillation time is 30-180 min; preferably 60min.
Wherein, the feeding sequence of the reaction materials can be as follows: the preparation method comprises the steps of mixing xylene formaldehyde resin, phenol and at least one second phenolic compound to perform a pre-reaction, and then adding formaldehyde to perform a condensation reaction; or the xylene formaldehyde resin is pre-reacted with phenol or part of phenol, then part of phenol and at least one second phenol compound are added for mixing, and formaldehyde is added for condensation reaction; or pre-reacting xylene formaldehyde resin with phenol or partial phenol, adding partial formaldehyde for condensation, adding partial phenol and at least one second phenolic compound for mixing, and adding formaldehyde for condensation reaction; the preferred order of addition: the xylene formaldehyde resin is pre-reacted with part of phenol, then part of phenol and at least one second phenolic compound are added to be mixed, such as resorcinol, and formaldehyde is added to be subjected to condensation reaction, wherein the reaction process is as follows:
in the first step, the reaction equation for the pre-reaction of the xylenecarboxaldehyde 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;
the bonding resins commonly used in the modern rubber industry are resorcinol formaldehyde resins and styrenated resorcinol formaldehyde resins. The resorcinol formaldehyde resin has high molecular structure of free resorcinol (generally more than 10 wt%) and is easy to absorb moisture and agglomerate, and has smoking phenomenon in use.
The styrenated resorcinol formaldehyde resin has nonpolar phenethyl side groups, and the side groups are easy to generate vibration friction heat to influence the dynamic performance of the tire although the moisture absorption and caking of the resin are improved.
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 m is less than or equal to 20.
Styrene-modified resorcinol formaldehyde 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, some commercially available modified phenol formaldehyde resins for use as rubber adhesion promoters are prepared by the condensation reaction of alkylphenols, phenol, 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 phenol resins. The presumed structural formula is as follows:
in the formula (VII), m, n and r are natural numbers, wherein 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 discloses a xylene modified phenolic resin, which is characterized in that nonpolar xylene is connected into a main chain of a phenolic resin molecular structure, so that the occurrence of side groups is avoided, the moisture absorption and dynamic heat generating performance of the phenolic resin are improved, and simultaneously, a second phenolic compound with higher activity is added 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 natural rubber.
In the invention, the methylene donor is selected from one or more of hexamethylenetetramine, hexamethoxymethyl melamine, hexaethoxymethyl melamine and the like; preferably, it is hexamethoxymethyl melamine.
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 between 1:5 and 5:1.
The weight ratio of the rubber component to the dimethylbenzene modified phenolic resin is 100:0.5-100: 5; preferably, the ratio of the components is 100:1-100: 3.
in the invention, the rubber composition further comprises an additive, wherein the additive is one or more selected from carbon black, a vulcanizing agent, an accelerator, stearic acid, zinc oxide, an antioxidant, softening oil, cobalt salt, white carbon black, a silane coupling agent and the like.
In the present invention, the xylene modified phenolic resin can be mixed into the rubber composition in the same manner as the same type of 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 vulcanizing agent, accelerator and adhesion accelerator 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 step two.
Wherein the vulcanizing agent, the accelerator and the adhesion promoter are added in the second step and/or the third step independently.
In the present invention, an internal mixer such as a Banbury mixer is used in combination.
In the first step, the mixing temperature is 150-155 ℃; preferably 150 ℃.
In the second step, the mixing temperature is 90-150 ℃; preferably 145 ℃.
In the third step, the mixing temperature is 90-150 ℃; preferably, it is 90 to 100 ℃.
Preferably, the rubber composition formed may be further shaped and vulcanized.
The invention also provides application of the rubber composition containing the xylene modified phenolic resin in tire products.
The tire product is a bonding part between rubber such as a carcass and a belt layer of a tire and a cord (polyester/steel wire).
The beneficial effects of the invention include: when the modified phenolic resin is added into rubber as a rubber adhesion promoter for use, the physical friction heat generation between a resorcinol resin network and a rubber network and between the resorcinol resin network and an adhesive layer is reduced due to the fact that dimethylbenzene is added into a phenolic resin main chain structure instead of a side chain modification mode, so that loss factors are reduced, dynamic heat generation of the rubber is reduced, the internal structure of the 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 groups 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 further described in detail with reference to the following specific examples. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common knowledge and common knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
In the invention, the raw materials of the dimethylbenzaldehyde resin, phenol, resorcinol and formaldehyde are all industrial grade. The formaldehyde concentration is 36.7-37.1%. P-toluenesulfonic acid (PTSA) and sodium hydroxide are chemically pure reagents.
Reference example 1
The commercial A resin was a resorcinol formaldehyde resin with a softening point of 105℃and a free resorcinol content of 12.5% by weight.
Reference example 2
The commercial B resin was a styrene-modified resorcinol-formaldehyde resin with a softening point of 108.7deg.C and a free resorcinol content of 1.21wt%.
Reference example 3
The commercial C resin is an alkylphenol-modified resorcinol-formaldehyde resin with a softening point of 104.1℃and a free phenol content of 0.27% by weight.
Example 1
Into 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, and the mixture was heated to 90 ℃. 115g of formaldehyde (37% aqueous solution) were then slowly added 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 ℃ for distillation and water removal, and phenol removal in vacuum at 180 ℃ is carried out (less than 100 torr), so that the xylene modified resorcinol-formaldehyde resin is obtained, wherein the softening point is 102.3 ℃, the content of free 5-methyl resorcinol is 0.23wt%, and the content of free phenol is 0.16wt%.
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, and the mixture was heated to 90 ℃. 110g of formaldehyde (37% aqueous solution) are then slowly added 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 ℃ for distillation and water removal, and phenol removal in vacuum at 180 ℃ is carried out (less than 100 torr), so that the xylene modified resorcinol-formaldehyde resin is obtained, wherein the softening point is 105.1 ℃, the content of free 5-ethyl resorcinol is 0.51wt%, and the content of free phenol is 0.29wt%.
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 and the mixture was heated to 90 ℃. Then 80g of formaldehyde (37% aqueous solution) was slowly added 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 ℃ for distillation and water removal, and phenol removal in vacuum at 180 ℃ is carried out (less than 100 torr), so that the xylene modified resorcinol-formaldehyde resin is obtained, wherein the softening point is 104.0 ℃, the content of free resorcinol is 0.80wt%, and the content of free phenol is 0.13wt%.
Example 4
To a 1000ml round bottom flask equipped with a stirred, temperature controlled, reflux condenser was added 60g of xylene formaldehyde resin, 90g of phenol, and 0.5g of p-toluene sulfonic acid and the mixture was heated to 90 ℃. Then 50g of formaldehyde (37% aqueous solution) was slowly added and incubated for 30 minutes. After the reaction was completed, 110g of phenol, 30g of resorcinol were added thereto, and after melt-mixing was completed, the mixture was brought to 90℃and then 60g of formaldehyde (37% aqueous solution) was slowly added thereto, and the mixture was kept for 30 minutes. Adding 0.35g of sodium hydroxide (30% aqueous solution), neutralizing, heating to 170 ℃ for distillation and water removal, and removing phenol in vacuum at 180 ℃ for less than 100torr to obtain the xylene modified resorcinol-formaldehyde resin, wherein the softening point is 106.5 ℃, the content of free resorcinol is 0.12wt% and the content of free phenol is 0.31wt%.
Example 5
The commercial resins A, B and C selected in reference examples 1 to 3 were subjected to hygroscopic tests with the xylene modified phenolic resins prepared in examples 1 to 4 of the present invention under conditions of 40℃and 70% relative humidity, and stored for 24 hours, 48 hours and 72 hours, with the test results shown in Table 1 below:
table 1 moisture absorption test of resin under damp-heat conditions (%)
As can be seen from the data in Table 1, the xylene modified phenolic resin prepared in the examples of the present invention has significantly improved moisture absorption properties compared to resorcinol-formaldehyde resins (commercial A resins), comparable to styrene modified resorcinol-formaldehyde resins (commercial B resins).
Example 6
The xylene modified resorcinol-formaldehyde resins prepared in examples 1-4 of the present invention were tested against commercially available A, B, C resins in the belt speed layer formulation.
Wherein the rubber formulation was refined according to the formulation shown in Table 2, wherein the amount of each component to be blended was based on each 100 parts by mass of rubber (phr).
Table 2 rubber application test formulation
The mixing process of the sizing material is as follows:
in the first step, the rubber component, carbon black, silica, zinc oxide, and an anti-aging agent (TMQ and 6 PPD) were mixed at about 150℃with a Banbury mixer, and kneaded to prepare a masterbatch.
In the second step, samples of the adhesive resins (xylene-modified resorcinol-formaldehyde resins) prepared in comparative examples A, B, and C and examples 1,2,3, and 4 of the present invention, respectively, and cobalt salts were mixed into a masterbatch obtained by Banbury mixer mixing at a temperature of about 145 ℃.
In the third step, insoluble sulfur (OT 20), accelerator (TBBS), methylene acceptor-HMMM (65%) listed in Table 2 was added to the mixture at 90 to 100℃and the resultant mixture was left overnight at a constant temperature of about 23℃and a relative humidity of 50%. Then, the sulfur-change instrument was measured for vulcanization, shape, and optimum degree of vulcanization at 160 ℃.
Test data for the modified vulcanized rubber compositions shown in Table 3. The tensile property is tested by using GB/T528-2009, the vulcanization condition of the sizing material before aging is 160 ℃ for 15min, and the hot air aging condition of the sizing material is 100 ℃ for 24h; the hardness is tested by GB/T531.1-2008;
the vulcanization performance is Alpha Technologies MDR sulfur transformer, and the reference standard is: GB/T16584-1996 and GB/T1233-2008 standards, measured at 160℃in an arc of 1℃and 1.67 Hz. In an oscillation disc thiorheometer, a sizing material sample is subjected to constant-amplitude oscillation shearing force, and the torque of an oscillation net disc embedded in the sizing material sample at the vulcanization temperature is measured;
the vulcanization conditions used for the adhesive properties of the steel cord are: the specification of the steel cord is 155 ℃ multiplied by 40 min: 3+9+15.0.22+1, tested in accordance with standard ASTM D1871-2004.
Dynamic heat generation DMA detection conditions: 30-80 ℃/3K/11Hz/10N/15 μm.
Compression heating, and referring to detection standard ISO4666-4-2007, the detection conditions are constant temperature 55 ℃, preheating time 30min, test time 25min, static load 100N, dynamic load 700N and frequency 10HZ.
TABLE 3 rubber compound Properties
According to the properties of the rubber materials in Table 3, the rubber materials containing the xylene modified resorcinol-formaldehyde resin prepared in the examples of the present invention have longer scorch time (T10) and better scorch safety, and the vulcanization time (T90) is similar to that of the commercial resin B (styrene modified resorcinol-formaldehyde resin), with reference to the commercial resin A (resorcinol-formaldehyde resin). The sizing materials containing the xylene modified resorcinol-formaldehyde resins prepared in examples 1-4 of the present invention had tensile strength before and after aging that was slightly better than commercial resin A/B, slightly better than commercial resin C or equivalent. The steel wire pullout force data (Table 3: steel cord adhesion properties) show that the compounds containing the xylene modified resorcinol-formaldehyde resins prepared in examples 1-4 of the present invention are improved to varying degrees.
In the dynamic heat generation (DMA) test of the sizing material of the xylene modified resorcinol formaldehyde resin prepared in the embodiments 1-4, the dynamic modulus (G' and high temperature mechanical property) at 60 ℃ is close to that of the commercial resin A and is superior to that of the commercial resin B/C; tan delta at 60 ℃ is lower than that of the commercial resin, which shows that the rubber compound mixed by the xylene modified resorcinol-formaldehyde resins prepared in the examples 1-4 has low hysteresis loss and low heat generation. In the compression heat generation test, the intermediate end temperature and the permanent deformation degree of the xylene modified resorcinol-formaldehyde resins prepared in examples 1 to 4 of the invention are similar to those of the commercial A resin and lower than those of the commercial B/C resin; the results of the compression heat generation test intuitively demonstrate that the xylene-modified resorcinol-formaldehyde resins prepared in examples 1 to 4 of the present invention have low heat generation properties.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that would occur to one skilled in the art are included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is defined by the appended claims.
Claims (9)
1. A rubber composition containing a xylene modified phenolic resin, characterized in that the rubber composition comprises at least the following components:
(1) A rubber component;
(2) Xylene modified phenolic resins used as methylene acceptors;
(3) A methylene donor;
wherein the dimethylbenzene modified phenolic resin is prepared by condensation reaction of active dimethylbenzene formaldehyde resin, phenol and at least one second phenol compound with activity higher than that of the phenol serving as raw materials with formaldehyde; the weight percentages of the xylenol formaldehyde resin, the phenol and at least one second phenol compound with activity higher than that of the phenol in the total mass of the xylenol formaldehyde resin and the phenol raw materials are respectively as follows: 5wt% -30wt%, 50wt% -90 wt%, 5wt% -30 wt%;
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 second phenolic compound used in the xylene modified phenolic resin is selected from the group consisting of: any one or a combination of a plurality of resorcinol, phloroglucinol, 5-methyl resorcinol and 5-ethyl resorcinol.
2. A rubber composition according to claim 1,
the number average molecular weight of the dimethylbenzaldehyde resin is 200-2000; the oxygen content of the dimethylbenzaldehyde resin is 5-20wt%.
3. The rubber composition according to claim 1, wherein the rubber component is selected from natural rubber, synthetic rubber or a combination thereof; the synthetic rubber is selected from one or more of cis-1, 4-polyisoprene, polybutadiene, polychloroprene, copolymer of isoprene and butadiene, copolymer of acrylonitrile and isoprene, copolymer of styrene and butadiene and isoprene, butyl rubber, ethylene propylene diene monomer, and copolymer of styrene and butadiene.
4. The rubber composition according to claim 1, wherein the methylene donor is selected from one or more of hexamethylenetetramine, hexamethoxymethyl melamine, and hexaethoxymethyl melamine.
5. The rubber composition according to claim 1, wherein the weight ratio of the methylene donor to the xylene modified phenolic resin is between 1:10 and 10:1; and/or the weight ratio of the rubber to the xylene modified phenolic resin is 100:0.5-100: 5.
6. The rubber composition according to claim 1, further comprising an additive selected from one or more of carbon black, vulcanizing agent, accelerator, stearic acid, zinc oxide, antioxidant, softening oil, cobalt salt, white carbon black, and silane coupling agent.
7. The rubber composition as described in claim 1, wherein the method for producing the xylene modified phenolic resin in the rubber composition comprises the steps of:
under the action of a catalyst, the 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 and distilled to obtain moisture and other volatile small molecules, so that the xylene modified phenolic resin is obtained.
8. The rubber composition according to claim 7, wherein the catalyst is one or more selected from 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-diazabicyclo undec-7-ene); the second phenolic compound is selected from: any one or a combination of a plurality of resorcinol, phloroglucinol, 5-methyl resorcinol and 5-ethyl resorcinol; the temperature of the condensation reaction is 60-120 ℃; the time of the condensation reaction is 5-180 min; the temperature of the heating distillation is 100-200 ℃; the temperature rising distillation time is 30-180 min.
9. Use of the rubber composition containing a xylene modified phenolic resin according to any of the claims 1-6 in a tyre product.
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| CN105623188A (en) * | 2015-10-21 | 2016-06-01 | 彤程化学（中国）有限公司 | Cardanol modified phenol formaldehyde resin used as binding agent for rubber and rubber 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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