CN113621119A - Xylene-modified resorcin aldehyde resin and rubber composition thereof - Google Patents
Xylene-modified resorcin aldehyde resin and rubber composition thereof Download PDFInfo
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- CN113621119A CN113621119A CN202010373202.6A CN202010373202A CN113621119A CN 113621119 A CN113621119 A CN 113621119A CN 202010373202 A CN202010373202 A CN 202010373202A CN 113621119 A CN113621119 A CN 113621119A
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- Prior art keywords
- xylene
- resorcinol
- resin
- rubber
- formaldehyde resin
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical class OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229920001971 elastomer Polymers 0.000 title claims abstract description 46
- 239000005060 rubber Substances 0.000 title claims abstract description 46
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 74
- 239000008096 xylene Substances 0.000 claims abstract description 30
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 claims abstract description 27
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 11
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 7
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 6
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 6
- 229920001194 natural rubber Polymers 0.000 claims abstract description 6
- -1 xylene modified resorcinol-formaldehyde Chemical class 0.000 claims description 37
- 238000006482 condensation reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 16
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical class OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 238000005804 alkylation reaction Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 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 6
- 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
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 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
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-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
- 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
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229960001755 resorcinol Drugs 0.000 abstract description 44
- 239000000463 material Substances 0.000 abstract description 10
- 230000020169 heat generation Effects 0.000 abstract description 7
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 3
- 238000004513 sizing Methods 0.000 abstract 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 20
- 238000010992 reflux Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 230000003472 neutralizing effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000000370 acceptor Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a rubber-framework material adhesion promoting resin, namely a xylene resin modified resorcinol aldehyde resin, which is used for replacing or partially replacing an aralkyl small side group structure in a resin by introducing a nonpolar xylene structure into a resorcinol resin main chain, so that frictional heat caused by vibration of the aralkyl small side group is reduced, and dynamic heat generation performance is improved. The invention also discloses a rubber composition, which comprises the following components: (i) a rubber component selected from natural rubber or synthetic rubber; (ii) a methylene donor; (iii) a xylene-modified resorcin aldehyde resin as a methylene acceptor. The sizing material test finds that the xylene modified resorcinol aldehyde resin has more excellent performance in the aspects of mechanical strength, dynamic performance and steel wire adhesion of the vulcanized sizing material.
Description
Technical Field
The invention relates to the field of rubber resin processing, in particular to a rubber adhesion promoter (xylene modified resorcinol aldehyde resin) and a preparation method and application thereof.
Background
An adhesive system is often employed between the carcass material and the rubber, particularly during tire manufacture. The mechanism of action is generally believed to be: during vulcanization, methylene provided by the methylene donor reacts with the methylene acceptor, and a three-dimensional network cross-linked structure is formed between the rubber and the framework material, so that the bonding force between the rubber and the framework material is improved. The resorcinol resin methylene acceptors which are common at present comprise resorcinol, resorcinol phenolic resin, aralkyl resorcinol formaldehyde resin and the like.
Resorcinol has a long use history, but is easy to sublimate and smoke in the mixing and processing process, pollutes the environment and has a large risk to occupational health, so that resorcinol-formaldehyde resin is generated, is a linear structure generated by condensation polymerization of resorcinol and formaldehyde, the fuming problem in the rubber material production process is relieved to a great extent, but the problem is not completely solved, and due to the damage of crystallinity, phenolic hydroxyl groups with strong polarity in the resorcinol-formaldehyde resin cause the resin to be easy to absorb moisture and agglomerate, so that the use of the resin is influenced.
Then, aralkylated (styrenated) resorcinol-formaldehyde resins such as US5021522, US7074861 and the like have appeared, which not only further reduce fuming but also greatly improve the moisture absorption problem, but the aralkyl group in the aralkylated resorcinol-formaldehyde resin exists in the form of a pendant group, which is very liable to generate heat by molecular vibration friction, resulting in large dynamic heat generation of the compound. The viscoelastic hysteresis heat generation of the rubber material is an important influence factor of the fatigue damage of the rubber material, and is directly related to the performance and the service life of the rubber product.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention introduces a nonpolar xylene structure into a main chain of the resorcinol aldehyde resin to replace or partially replace an aralkyl small side group structure in the resorcinol aldehyde resin, so that the hygroscopicity of the resorcinol aldehyde resin is improved, meanwhile, the frictional heat caused by the vibration of the aralkyl small side group is reduced, and the dynamic heat generation performance of the rubber compound is improved.
An object of the present invention is to provide a xylene-modified resorcin aldehyde resin and a method for preparing the same.
It is still another object of the present invention to provide a rubber composition comprising the above xylene-modified resorcinol-based resin.
Specifically, the present invention provides the following means to achieve the above object.
The invention provides a xylene-modified resorcinol aldehyde resin, wherein the molecule of the xylene-modified resorcinol aldehyde resin has a characteristic structure shown in a formula (1):
wherein m and n are natural numbers, m is more than or equal to 1 and less than or equal to 20, and n is more than or equal to 1 and less than or equal to 30; preferably, 1. ltoreq. m.ltoreq.15, 1. ltoreq. n.ltoreq.20.
R is selected from H, alkyl of C1-C8, aralkyl containing C1-C6 substituent; preferably, R is selected from H, methyl, ethyl or phenethyl;
r' is H;
r' is selected from H, C1-C8 alkyl, aralkyl containing C1-C6 substituent,
Preferably, R "is H.
The invention also provides a preparation method (method I) of the xylene modified resorcinol aldehyde resin, which comprises the following steps: under the acidic condition, the resorcinol compound and the olefin compound are firstly subjected to alkylation reaction and then subjected to condensation reaction with the xylene formaldehyde resin to prepare the xylene modified resorcinol aldehyde resin.
The method comprises the following specific steps: heating resorcinol to 120-150 ℃ for melting, adding a catalyst, adjusting the pH value to 1-5, then adding an olefin compound for alkylation reaction, adding xylene formaldehyde resin into a system after the alkylation reaction is finished, further performing condensation reaction, adding a terminator after the condensation reaction is finished, adjusting the pH value to 4-7, then heating to 150-180 ℃ for atmospheric distillation and reduced pressure distillation, and obtaining the xylene modified resorcinol aldehyde resin.
The temperature of the alkylation reaction is 120-150 ℃; preferably, the temperature is 120-140 ℃.
The alkylation reaction time is 5-120 min; preferably, the time is 10-60 min.
The temperature of the condensation reaction is 90-150 ℃; preferably, the temperature is 90-130 ℃.
The condensation reaction time is 5-120 min; preferably, the time is 10-60 min.
The terminator is selected from one or more of NaOH, triethanolamine, N-methyldiethanolamine, diazabicyclo (1, 8-diazabicycloundecen-7-ene) and the like; preferably, it is NaOH.
Further, in the preparation process, no olefin compound may be added, and the preparation process comprises the following steps: under the acidic condition, the resorcinol compound and the xylene formaldehyde resin are subjected to condensation reaction to prepare the xylene modified resorcinol aldehyde resin (method II).
The method specifically comprises the following two methods:
method I-1: heating resorcinol to 120-150 ℃ for melting, adding a catalyst, adjusting the pH value to 1-5, then adding xylene formaldehyde resin into the system, further carrying out condensation reaction, adding a terminator after the condensation reaction is finished, adjusting the pH value to 4-7, then heating to 150-180 ℃ for atmospheric distillation and reduced pressure distillation, and obtaining the xylene modified resorcinol aldehyde resin.
The temperature of the condensation reaction is 120-150 ℃; preferably, the temperature is 120-140 ℃.
The condensation reaction time is 5-120 min; preferably, the time is 10-60 min.
The terminator is selected from one or more of NaOH, triethanolamine, N-methyldiethanolamine, diazabicyclo (1, 8-diazabicycloundecen-7-ene) and the like; preferably, it is NaOH.
Method II-2: dissolving resorcinol in water at 40-100 ℃, adding xylene formaldehyde resin into the system, performing a pre-condensation reaction, adding a catalyst, adjusting the pH to 1-5, further performing a condensation reaction, adding a terminator after the condensation reaction is completed, adjusting the pH to 4-7, and then heating to 150-180 ℃ to perform normal pressure distillation and reduced pressure distillation to obtain the xylene modified resorcinol aldehyde resin.
The temperature of the pre-condensation reaction is 40-100 ℃; preferably, the temperature is 60 to 100 ℃.
The pre-condensation reaction time is 5-120 min; preferably, the time is 10-60 min.
The temperature of the condensation reaction is 40-100 ℃; preferably, the temperature is 60 to 100 ℃.
The condensation reaction time is 5-120 min; preferably, the time is 10-60 min.
The terminator is selected from one or more of NaOH, triethanolamine, N-methyldiethanolamine, diazabicyclo (1, 8-diazabicycloundecen-7-ene) and the like; preferably, it is NaOH.
Furthermore, in all the reaction processes, after the condensation reaction of the xylene formaldehyde resin is completed, an aldehyde compound can be added to further carry out the condensation reaction so as to meet the requirements of other indexes of the product.
Wherein the xylene formaldehyde resin has a structure as shown in formula (2):
in the formula (2), p is more than or equal to 0 and less than or equal to 10, and q is more than or equal to 0 and less than or equal to 20.
Preferably, the number average molecular weight of the xylene formaldehyde resin is 200-2000; further preferably, the number average molecular weight of the xylene formaldehyde resin is 200 to 1000.
Preferably, the oxygen content of the xylene formaldehyde resin is 5 wt% to 20 wt%; further preferably, the oxygen content of the xylene formaldehyde resin is 7-15 wt%.
In the above method of the present invention, the acidic condition is provided by a catalyst, and the catalyst suitable for the present invention is selected from one or more of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, benzenesulfonic acid, benzenedisulfonic acid, C1-C15 alkylbenzene sulfonic acid, naphthalenesulfonic acid, and the like; preferably, p-toluenesulfonic acid.
In the above process of the present invention, the olefin compound is selected from one or more of styrene, methylstyrene, ethylstyrene, divinylbenzene, etc.; preferably, the olefinic compound is styrene.
In the above method of the present invention, the aldehyde compound is selected from one or more of formaldehyde, trioxymethylene, acetaldehyde, paraldehyde, butyraldehyde, valeraldehyde, caproaldehyde, furfural, benzaldehyde, and the like. Further preferably, the aldehyde compound is formaldehyde.
In the method, the mass ratio of the resorcinol compound to the olefin compound is 100: 0-100: 100; preferably, the ratio is 100: 0-100: 80.
When the mass of the olefin compound is 0, the olefin compound is completely substituted by the xylene formaldehyde resin, and the xylene modified resorcinol aldehyde resin does not contain small side group functional groups introduced by the olefin compound. Corresponding to embodiments 1 to 4 of the present invention.
In the method, the mass ratio of the resorcinol compound to the xylene formaldehyde resin is 100: 10-100: 150; preferably, it is 100: 10-100: 100.
the invention also provides the xylene modified resorcinol aldehyde resin prepared by the method.
The invention also provides application of the xylene modified resorcinol aldehyde resin in preparation of rubber compositions.
The xylene-modified resorcinol aldehyde resin is used as a methylene acceptor for preparing a rubber composition.
The rubber compositions are preferably used for the production of tires, hoses and tapes.
The invention also provides a rubber composition, which comprises the following components:
(i) a rubber component selected from the group consisting of natural rubber and synthetic rubber;
(ii) a methylene donor;
(iii) the xylene-modified resorcinol aldehyde resin methylene acceptor is described.
According to the rubber composition of 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.
The rubber composition of the present invention contains one or more methylene donors.
The term "methylene donor" refers to a compound capable of producing a reactive methylene structure under heated conditions, the resulting methylene structure being capable of reacting with resorcinol, resorcinol-formaldehyde resin, xylene-modified resorcinol-based resin to form a crosslinked network. Methylene donors useful in the present invention include, but are not limited to, one or more of Hexamethylenetetramine (HMT), Hexamethoxymethylmelamine (HMMM), hexaethoxymethylmelamine, and the like; preferably Hexamethoxymethylmelamine (HMMM).
The weight ratio of the methylene donor to the xylene-modified resorcinolic aldehyde resin in the rubber composition of the present invention can be varied. Generally, the weight ratio is in the range of 1: 10 to 10: 1. The best weight ratio is 1: 5-5: 1.
The rubber composition of the present invention may further comprise various additives used in rubber materials, such as carbon black, vulcanizing agent, accelerator, stearic acid, zinc oxide, antioxidant, softening oil, cobalt salt, and the like. The sulfur is usually used as a vulcanizing agent, the amount is well known to those skilled in the art, and 0.5-10 parts by weight of sulfur is added to 100 parts by weight of rubber.
According to the rubber composition of the present invention, the xylene-modified resorcinol-based resin can be incorporated 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: a first step of mixing a rubber and additive components other than a vulcanizing agent, an accelerator and an adhesion promoter to form a mixture; a second step of mixing the xylene-modified resorcinol aldehyde resin into the mixture formed in the first step; in a third step, the methylene donor is mixed into the mixture formed in the second step.
Wherein the vulcanizing agent, the accelerator and the adhesion promoter are added in the second step and/or the third step independently of one another. According to the method for producing the rubber composition of the present invention, an internal mixer such as a Banbury mixer; preferably, the mixing temperature of the first step is 150-155 ℃; preferably, the temperature of the second step and the third step is 90-150 ℃.
Preferably, the formed rubber composition can be further shaped and vulcanized.
The invention also provides the use of the rubber composition in the production of a composite material.
The composite material is a composite material which needs to be tightly combined with a steel wire or a fiber material, such as a tire, a rubber tube, an adhesive tape and the like.
The invention has the beneficial effects that: the invention introduces a nonpolar xylene structure into a main chain of the resorcinol resin to replace or partially replace an aralkyl small side group structure in the resin, thereby reducing frictional heat generation caused by vibration of the aralkyl small side group and improving dynamic heat generation performance. The modified resin provided by the invention is applied to rubber, and can obviously improve the mechanical strength, dynamic property and steel wire bonding property of vulcanized rubber.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following examples. 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, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, 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 present invention, the softening point testing apparatus for the resin is Mettler Toledo FP90 heat value analysis system + FP83 HT.
In the present invention, the free phenol content of the resin was tested using Waters H Class ultra performance liquid chromatography.
In the present invention, the moisture absorption of the resin is carried out at a temperature of 25 ℃ and a relative humidity of 70%.
Reference ratio 1 (Resorcinol Formaldehyde resin)
Adding 110g of resorcinol into a round-bottom flask provided with a stirring, temperature control and reflux condenser, heating to 120 ℃ for melting, adding 0.2g of p-toluenesulfonic acid, dropwise adding 46g of 37% liquid aldehyde, then neutralizing, heating to 160 ℃, distilling and dehydrating to obtain the resorcinol-formaldehyde resin, wherein the resin softening point is 106 ℃, and the free resorcinol is 14.7%.
Reference ratio 2 (styrenated resorcinol formaldehyde resin)
Adding 110g of resorcinol into a round-bottom flask provided with a stirring, temperature control and reflux condenser, heating to 120 ℃ for melting, adding 0.5g of p-toluenesulfonic acid, adding 60g of styrene for alkylation reaction, dropwise adding 50g of 37% liquid aldehyde after the alkylation reaction is finished, then neutralizing, heating to 160 ℃, distilling and dehydrating to obtain the styrenated resorcinol-formaldehyde resin, wherein the softening point of the resin is 115 ℃, and the free resorcinol is 1.1%.
Example 1
Adding 60g of resorcinol and 0.2g of p-toluenesulfonic acid into a round-bottom flask with a stirring, temperature control and reflux condenser, controlling the temperature to 130 ℃ to melt the resorcinol, starting stirring, then slowly adding 50g of xylene formaldehyde resin (2602 resin), carrying out reflux reaction for 20min, adding 10g of 37% liquid aldehyde, carrying out reflux reaction for 10min, then neutralizing, heating to 160 ℃, distilling and dehydrating to obtain the xylene modified resorcinol formaldehyde resin, wherein the resin softening point is 104.4 ℃, and the free resorcinol is 13.6%.
Example 2
Adding 55g of resorcinol, 0.8g of p-toluenesulfonic acid and a small amount of water into a round-bottom flask provided with a stirring, temperature control and reflux condenser, controlling the temperature to 80 ℃, stirring until the resorcinol is dissolved, then adding 50g of xylene formaldehyde resin (2602 resin), carrying out reflux reaction at 100 ℃ for 30min, then neutralizing, heating to 160 ℃, distilling and dehydrating to obtain the xylene modified resorcinol formaldehyde resin, wherein the resin softening point is 82 ℃ and the free resorcinol is 14.7%.
Example 3
To a 250ml round bottom flask equipped with a stirred, temperature controlled, reflux condenser was added 40g resorcinol, a small amount of water, temperature controlled to 100 ℃, and stirred until resorcinol dissolved. Then 60g of xylene formaldehyde resin (2602 resin) is added, reflux reaction is carried out for 60min at 100 ℃, 0.5g of p-toluenesulfonic acid is added, reflux heat preservation is carried out for 10min, neutralization is carried out, heating is carried out to 180 ℃, distillation and dehydration are carried out, and the xylene modified resorcinol formaldehyde resin is obtained, wherein the resin softening point is 131 ℃, and the free resorcinol is 2.4%.
Example 4
To a 250ml round bottom flask equipped with a stirred, temperature controlled, reflux condenser was added 40g resorcinol, a small amount of water, temperature controlled to 100 ℃, and stirred until resorcinol dissolved. Then adding 50g of xylene formaldehyde resin (2602 resin), carrying out reflux reaction at 100 ℃ for 40min, adding 0.4g of p-toluenesulfonic acid, carrying out reflux insulation for 10min, neutralizing, heating to 160 ℃, distilling and dehydrating to obtain the xylene modified resorcinol formaldehyde resin, wherein the resin softening point is 109 ℃, and the free resorcinol is 5.6%.
Example 5
Adding 100g of resorcinol and 0.5g of p-toluenesulfonic acid into a round-bottom flask with a stirring, temperature control and reflux condenser, heating to 130 ℃ for melting, adding 50g of styrene for reaction, adding a small amount of water, cooling to below 100 ℃, adding 10g of xylene formaldehyde resin (2602 resin), carrying out reflux reaction for 10min, adding 40g of 37% liquid aldehyde, neutralizing, heating to 160 ℃, and carrying out distillation and dehydration to obtain the xylene modified resorcinol formaldehyde resin, wherein the resin softening point is 112.5 ℃ and the free resorcinol is 1.2%.
Example 6
Adding 100g of resorcinol and 0.5g of p-toluenesulfonic acid into a round-bottom flask with a stirring, temperature control and reflux condenser, heating to 130 ℃ for melting, adding 5g of styrene, adding a small amount of water after the reaction is finished, cooling to below 100 ℃, adding 120g of xylene formaldehyde resin (2602 resin), carrying out reflux reaction for 10min, then neutralizing, heating to 160 ℃, and carrying out distillation and dehydration to obtain the xylene modified resorcinol formaldehyde resin, wherein the resin softening point is 107.7 ℃ and the free resorcinol is 1.5%.
Example 7
Adding 100g of resorcinol and 0.5g of p-toluenesulfonic acid into a round-bottom flask with a stirring, temperature control and reflux condenser, heating to 130 ℃ for melting, adding 30g of styrene, adding a small amount of water after the reaction is finished, cooling to below 100 ℃, adding 120g of xylene formaldehyde resin (2602 resin), carrying out reflux reaction for 20min, then neutralizing, heating to 160 ℃, and carrying out distillation and dehydration to obtain the xylene modified resorcinol formaldehyde resin, wherein the resin softening point is 109.4 ℃, and the free resorcinol is 0.8%.
Example 8
The moisture absorption of the xylene-modified resorcinol resins prepared in the reference examples was verified, and the test results are shown in table 1.
As can be seen from the data in table 1, the moisture absorption properties of the xylene-modified resorcinol-formaldehyde resins prepared in the examples of the present invention are greatly improved as compared to resorcinol-formaldehyde resins, which are comparable to low moisture absorption styrenated resorcinol-formaldehyde resins.
Example 9
Xylene modified resorcinol-formaldehyde resins prepared according to examples 1, 4-7 of the present invention were tested in rubber formulations and compared to commercially available resorcinol resins having similar softening points and free phenol contents.
The commercial A resin is resorcinol-formaldehyde resin with softening point of 103 ℃ and free resorcinol of 13.9%. Compared with the inventive example 1. The commercial B resin is styrene modified resorcinol formaldehyde resin with softening point of 106 ℃ and free resorcinol of 1.4%. Compared with the inventive examples 4 to 7.
The rubber formulation was refined in accordance with the formulation shown in Table 1, wherein the compounding amounts of the respective components were based on 100 parts by mass of rubber (phr).
Firstly, rubber, carbon black, zinc oxide and stearic acid are subjected to banburying mixing at the temperature of about 150 ℃ by a Banbury mixer, and are mixed to prepare master batch.
In the second step, the binder resin prepared in examples 1 and 4 to 7 of the present invention, a commercially available A resin or a commercially available B resin, a cobalt salt and an antioxidant were mixed into a master batch at a temperature of about 145 ℃.
Thirdly, adding insoluble sulfur, a promoter and HMMM (65%) at 90-100 ℃ for mixing, and placing the product obtained by mixing in an environment with a constant temperature of about 23 ℃ and a relative humidity of 50% overnight. The vulcanization characteristics were then determined at 150 ℃ and the mechanical properties, the dynamic heat generation (RPA2000) and the wire adhesion of the vulcanizates were determined by press vulcanization.
Comparing inventive example 1 with a commercial A resin, inventive examples 4-7 with a commercial B resin, the data in Table 3 shows: the rubber compound containing the xylene modified resorcinol resin prepared by the embodiment of the invention has better tensile strength before and after aging, tensile strength at break and steel cord adhesion before and after aging than the corresponding commercial resin, and meanwhile, in the table 3, the tan delta for representing dynamic loss is obviously lower than that of the commercial resin, which shows that the resorcinol resin which has higher performance than the commercial product and is used as a methylene acceptor can be prepared by using the method of the invention.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (11)
1. A xylene-modified resorcinolic aldehyde resin characterized by having a characteristic structure represented by the formula (1):
wherein the content of the first and second substances,
m and n are natural numbers, m is more than or equal to 1 and less than or equal to 20, and n is more than or equal to 1 and less than or equal to 30;
r is selected from alkyl of H, C1-C8 and aralkyl containing C1-C6 substituent;
r' is H;
r' is selected from H, C1-C8 alkyl, aralkyl containing C1-C6 substituent,
2. A preparation method of a xylene modified resorcinol-formaldehyde resin is characterized by comprising the following steps:
the method I comprises the following steps: under the acidic condition, carrying out alkylation reaction on resorcinol compounds and olefin compounds, and then carrying out condensation reaction on the resorcinol compounds and xylene formaldehyde resin to obtain the xylene modified resorcinol formaldehyde resin; or
Method II: under the acidic condition, carrying out condensation reaction on resorcinol compound and xylene formaldehyde resin to obtain the xylene modified resorcinol formaldehyde resin.
3. The method of claim 2, wherein the method I comprises the specific steps of: heating resorcinol to 120-150 ℃ for melting, adding a catalyst, adjusting the pH value to 1-5, then adding an olefin compound for alkylation reaction, adding xylene formaldehyde resin into a system after the alkylation reaction is finished, further performing condensation reaction, adding a terminator after the condensation reaction is finished, adjusting the pH value to 4-7, then heating to 150-180 ℃ for atmospheric distillation and reduced pressure distillation, and obtaining the xylene modified resorcinol aldehyde resin;
the method II comprises the following specific steps:
method II-1: heating resorcinol to 120-150 ℃ for melting, adding a catalyst, adjusting the pH value to 1-5, then adding xylene formaldehyde resin into the system, further performing condensation reaction, adding a terminator after the condensation reaction is finished, adjusting the pH value to 4-7, then heating to 150-180 ℃ for normal pressure distillation and reduced pressure distillation, and obtaining the xylene modified resorcinol aldehyde resin; or
Method II-2: dissolving resorcinol in water at 40-100 ℃, adding xylene formaldehyde resin into the system, performing a pre-condensation reaction, adding a catalyst, adjusting the pH to 1-5, further performing a condensation reaction, adding a terminator after the condensation reaction is completed, adjusting the pH to 4-7, and then heating to 150-180 ℃ for atmospheric distillation and reduced pressure distillation to obtain the xylene modified resorcinol aldehyde resin.
4. The method of claim 2, wherein the xylene-formaldehyde resin has a structure according to formula (2):
in the formula (2), p is more than or equal to 0 and less than or equal to 10, and q is more than or equal to 0 and less than or equal to 20.
5. The method of claim 2, wherein the xylene formaldehyde resin has a number average molecular weight of 200 to 2000; and/or the oxygen content of the xylene formaldehyde resin is 5-20 wt%; and/or, the acidic condition is provided by a catalyst selected from one or more of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, benzenesulfonic acid, benzene disulfonic acid, C1-C15 alkylbenzene sulfonic acid, naphthalene sulfonic acid; and/or, the olefin compound is selected from one or more of styrene, methyl styrene, ethyl styrene and divinyl benzene; and/or the mass ratio of the resorcinol compound to the xylene formaldehyde resin is 100: 10-100: 150; and/or the mass ratio of the resorcinol compound to the olefin compound is 100: 0-100: 100.
6. The method of claim 3, wherein the terminating agent is selected from one or more of NaOH, triethanolamine, N-methyldiethanolamine, diazabicyclo (1, 8-diazabicycloundecen-7-ene); and/or in the method I, the temperature of the alkylation reaction is 120-150 ℃, and the temperature of the condensation reaction is 90-150 ℃; and/or in the method II-1, the condensation reaction temperature is 120-150 ℃; and/or in the method II-2, the temperature of the pre-condensation reaction is 40-100 ℃, and the temperature of the condensation reaction is 40-100 ℃.
7. A xylene-modified resorcinol aldehyde resin produced by the method as claimed in any one of claims 2 to 6.
8. Use of the xylene-modified resorcinol aldehyde resin according to claim 1 or 7 in a rubber composition.
9. A rubber composition, comprising the following components:
(i) a rubber component selected from the group consisting of natural rubber and synthetic rubber;
(ii) a methylene donor;
(iii) a methylene acceptor comprising a xylene-modified resorcinolic aldehyde resin selected from the group consisting of the xylene-modified resorcinolic aldehyde resins described in claim 1 or 7.
10. The rubber composition of claim 9, wherein the rubber component is selected from natural rubber, synthetic rubber, or combinations thereof, the synthetic rubber being selected from one or more of cis-1, 4-polyisoprene, polybutadiene, polychloroprene, copolymers of isoprene and butadiene, copolymers of acrylonitrile and isoprene, copolymers of styrene and butadiene and isoprene, butyl rubber, ethylene propylene diene monomer, and copolymers of styrene and butadiene; and/or the methylene donor is selected from one or more of hexamethylenetetramine, hexamethoxymethylmelamine and hexaethoxymethylmelamine; and/or the weight ratio of the methylene donor to the modified resorcinol-formaldehyde resin is 1: 5-5: 1; and/or, 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 and a cobalt salt.
11. Use of the rubber composition according to claim 10 in the production of a composite material.
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