CN116082719A - Composite wear-resistant adhesive for passenger car tire bead openings and preparation method and application thereof - Google Patents
Composite wear-resistant adhesive for passenger car tire bead openings and preparation method and application thereof Download PDFInfo
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- CN116082719A CN116082719A CN202310200673.0A CN202310200673A CN116082719A CN 116082719 A CN116082719 A CN 116082719A CN 202310200673 A CN202310200673 A CN 202310200673A CN 116082719 A CN116082719 A CN 116082719A
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- butadiene
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000011324 bead Substances 0.000 title claims abstract description 41
- 239000000853 adhesive Substances 0.000 title claims abstract description 24
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 56
- 239000005060 rubber Substances 0.000 claims abstract description 56
- 229920003049 isoprene rubber Polymers 0.000 claims abstract description 26
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002978 peroxides Chemical class 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 8
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 8
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 8
- 229920001194 natural rubber Polymers 0.000 claims abstract description 8
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 8
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 7
- 239000008117 stearic acid Substances 0.000 claims abstract description 7
- 239000012936 vulcanization activator Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 229910052742 iron Inorganic materials 0.000 claims description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005299 abrasion Methods 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 8
- -1 alkyl peroxide Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000012933 diacyl peroxide Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 8
- 230000035882 stress Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 5
- 229920005549 butyl rubber Polymers 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000008036 rubber plasticizer Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- NSYRAUUZGRPOHS-UHFFFAOYSA-N 2-methylocta-1,3-diene Chemical compound CCCCC=CC(C)=C NSYRAUUZGRPOHS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
A composite wear-resistant adhesive for passenger car tyre bead openings and a preparation method and application thereof. The invention belongs to the field of rubber materials for tires and preparation thereof. The invention aims to improve the wear resistance, ageing resistance and deformation recovery capability of the composite wear-resistant adhesive for the child opening of the existing passenger car tire. The material is prepared from olefin rubber, reinforcing filler, koresin tackifying resin, a vulcanization activator, a plasticizer, peroxide and an anti-aging agent, wherein the olefin rubber is prepared by mixing natural rubber, butadiene rubber and iron-series butadiene-isoprene rubber, and the vulcanization activator is composed of zinc methacrylate and stearic acid.
Description
Technical Field
The invention belongs to the field of rubber materials for tires and preparation thereof, and particularly relates to a composite wear-resistant rubber for a passenger car tire bead, and a preparation method and application thereof.
Background
The bead abrasion-resistant rubber of the tire is positioned at the tire bead part and is in direct contact with the rim, and the stress from the rim and the tire body is transferred, so that the tire bead is protected. Compared with car tires, all-steel radial truck and passenger car tires bear higher stress, the tire bead is high in strength and heat generation, and higher requirements are met on the performance of the bead abrasion-resistant rubber. Therefore, on one hand, the seam allowance abrasion-resistant adhesive has better high-temperature resistance or ageing resistance; on the other hand, the bead abrasion-resistant adhesive has better deformation recovery capability so as to avoid the dimensional change of the bead part caused by the periodic stress strain action of the bead part, and further be beneficial to maintaining the whole stress condition of the tire unchanged, thereby ensuring the safety of vehicles and drivers.
Disclosure of Invention
The invention aims to improve the wear resistance, ageing resistance and deformation recovery capability of the conventional composite wear-resistant adhesive for the passenger car tire bead, and provides a composite wear-resistant adhesive for the passenger car tire bead, a preparation method and application thereof.
The invention aims to provide a composite wear-resistant adhesive for a passenger car tire bead, which is prepared from the following components in parts by weight:
100 parts of olefin rubber;
50-90 parts of reinforcing filler;
1-5 parts of Koresin tackifying resin;
3-15 parts of a vulcanization activator;
1-5 parts of peroxide;
1-5 parts of an anti-aging agent;
1-30 parts of plasticizer;
wherein the olefin rubber is prepared by mixing 20-40 parts of natural rubber, 20-40 parts of butadiene rubber and 30-50 parts of iron-based butadiene-isoprene rubber in parts by mass, and the vulcanization activator consists of 2-10 parts of zinc methacrylate and 1-5 parts of stearic acid.
Further defined, the iron-based butadiene-isoprene rubber is a gel-free butadiene-isoprene rubber produced by coordination polymerization of isoprene and butadiene with an iron-based catalyst.
Further defined, the number average molecular weight of the iron-based butadiene-isoprene rubber is 129.2w.
Further defined, the molar ratio of butadiene to isoprene during the preparation is 2:3.
further defined, the iron-based butyl rubber microstructure composition is: the molar content of 1, 2-butadiene in the butadiene structural unit was 22%, the molar content of 1, 4-butadiene was 78%, the molar content of 3, 4-isoprene in the isoprene structural unit was 84%, and the molar content of 1, 4-isoprene was 16%.
Further limited, the reinforcing filler is one or a mixture of a plurality of carbon black, white carbon black, talcum powder, ceramic powder and calcium carbonate according to any ratio.
Further defined, the anti-aging agent is one or a mixture of several of anti-aging agent RD, anti-aging agent 4020 and protective wax according to any ratio.
Further defined, the peroxide is one or a mixture of several of alkyl peroxide and diacyl peroxide in any ratio.
Still further defined, the peroxide is preferably dicumyl peroxide.
Further defined, the Koresin is prepared from p-tert-butylphenol and acetylene at high temperature and high pressureThe zinc naphthenate is prepared by polycondensation under the catalysis condition, the softening point is 135-150 ℃, and the density is 1.02-1.04g/cm 3 。
Further defined, the plasticizer is one or a mixture of a plurality of cyclic paraffin-based rubber plasticizers, aromatic-based rubber plasticizers and cycloalkyl-based rubber plasticizers in any ratio.
The invention also aims to provide a preparation method of the composite wear-resistant adhesive for the tire bead of the passenger car, which comprises the following steps:
step 1: adding olefin rubber into an internal mixer for plasticating, standing for more than 4 hours, adding reinforcing filler, vulcanizing activator, plasticizer, koresin tackifying resin and anti-aging agent for mixing to obtain a mixed rubber;
step 2: and adding the mixed rubber and the peroxide into an internal mixer for continuous mixing to obtain the composite wear-resistant rubber for the tire bead of the passenger car.
The invention further aims to provide application of the composite wear-resistant adhesive for the passenger car tire bead, which is used for preparing passenger car tires.
Compared with the prior art, the invention has the remarkable effects that:
1) The wear-resistant rubber for the tire bead of the passenger car can be improved in wear resistance and ageing resistance by introducing the iron-based catalytic butadiene-isoprene rubber. The butadiene-isoprene rubber is composed of more 1, 4-butadiene and 3, 4-isoprene structural units, so that the rubber composite material has certain flexibility, and meanwhile, the strength of the material is obviously improved, and the butadiene-isoprene rubber composite material has better wear resistance. And the iron-based catalytic butadiene-isoprene rubber has a certain content of side groups (vinyl and propenyl), so that the reactivity of the main chain double bond is reduced, and the ageing resistance of the iron-based catalytic butadiene-isoprene rubber is enhanced.
2) According to the invention, the Koresin tackifying resin is added into the iron-based butadiene-isoprene rubber, so that the wear resistance of the rubber composite material is further improved. The phenol in the Koresin can be para-position with different branching degrees and different sizes of alkyl groups, the nonpolar alkyl chain can have good compatibility with rubber, and meanwhile, the butyl-pentyl rubber propenyl side group has electronegativity and can generate certain chemical acting force with the Koresin. Therefore, compared with other rubber and tackifying resin, the iron-based butadiene-isoprene rubber can generate better winding, combination and adhesion with the Koresin in the mixing process, and can effectively improve the wear resistance of the material under the synergistic effect of the iron-based butadiene-isoprene rubber and the Koresin.
3) According to the invention, the peroxide and the zinc methacrylate reactive auxiliary agent are added into the iron-based butadiene-isoprene rubber, so that the deformation recovery capability, ageing resistance and high temperature performance of the wear-resistant rubber for the tire bead of the passenger car are obviously improved. The iron-based butyl-pentyl rubber molecular chain contains a large number of vinyl and propenyl side group double bond groups, peroxide is decomposed into free radicals in the high-temperature vulcanization process, the unique double bond structural characteristics in the butyl-pentyl rubber molecular chain can easily generate macromolecular chain crosslinking reaction under the initiation of the peroxide free radicals, the crosslinking reaction degree of side groups (propenyl and vinyl) and double bonds adjacent to carboxyl in zinc methacrylate in the subsequent vulcanization process is improved, the polymerization reaction of ZDMA is initiated, and the side groups are partially grafted in the butyl-pentyl rubber molecular chain, so that the crosslinking degree and crosslinking bond energy of the rubber composite material are improved, and the deformation recovery capacity and the high-temperature resistance of the rubber composite material are improved.
Detailed Description
The present invention will be described in further detail, clarity and completeness by the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art. For process parameters not specifically noted, reference may be made to conventional conditions.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
Reference in the following examples to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Examples 1-3: the formulas of the composite wear-resistant adhesive for the tire bead of the passenger car of the embodiment 1-3 are shown in the table 1, and the performance detection results are shown in the tables 2-3;
wherein the iron-based butadiene-isoprene rubber is gel-free butadiene-isoprene rubber prepared by coordination polymerization of isoprene and butadiene through an iron-based catalyst, the number average molecular weight is 129.2w, and the molar ratio of butadiene to isoprene in the preparation process is 2:3, the microstructure composition of the prepared iron-based butadiene-isoprene rubber is as follows: the molar content of 1, 2-butadiene in the butadiene structural unit was 22%, the molar content of 1, 4-butadiene was 78%, the molar content of 3, 4-isoprene in the isoprene structural unit was 84%, and the molar content of 1, 4-isoprene was 16%, which was designated BIR-1811.
The Koresin is prepared by polycondensing p-tert-butylphenol and acetylene under the catalysis of zinc naphthenate at high temperature and high pressure, and has a softening point of 140 ℃ and a density of 1.02g/cm 3 。
The preparation method of the composite wear-resistant adhesive for the tire bead of the passenger car disclosed in the embodiment 1-3 comprises the following steps:
step 1: adding natural rubber No. 20, butadiene rubber 9000 and iron-series butadiene-isoprene rubber into an internal mixer, wherein the filling coefficient is 0.7, plasticating for 80s at 50rpm and 90 ℃, standing for more than 4h, then adding carbon black N330, stearic acid, aromatic hydrocarbon oil, zinc methacrylate, koresin tackifying resin, age inhibitor 4020, age inhibitor RD and protective wax, wherein the filling coefficient is 0.7, and mixing for 240s at 50rpm and 110 ℃ to obtain a mixed rubber;
step 2: adding the mixed rubber and peroxide DCP into an internal mixer, and mixing for 240s at 50rpm and 100 ℃ to obtain the composite wear-resistant rubber for the tire bead of the passenger car.
Comparative example 1: this comparative example differs from example 2 in that:
the olefin rubber consists of 70 parts of natural rubber 20# and 30 parts of butadiene rubber 9000, and iron-based butadiene-isoprene rubber BIR-1811 is not added.
The preparation method of the composite wear-resistant adhesive for the passenger car tire bead comprises the following steps:
step 1: adding natural rubber No. 20 and butadiene rubber 9000 into an internal mixer, plasticating for 80s at 50rpm and 90 ℃, standing for more than 4h, then adding carbon black N330, stearic acid, aromatic hydrocarbon oil, zinc methacrylate, koresin tackifying resin, an anti-aging agent 4020, an anti-aging agent RD and protective wax, mixing for 240s at 50rpm and 110 ℃ to obtain a mixed rubber, wherein the filling coefficient is 0.7;
step 2: adding the mixed rubber and peroxide DCP into an internal mixer, and mixing for 240s at 50rpm and 100 ℃ to obtain the composite wear-resistant rubber for the tire bead of the passenger car.
The specific formulation is shown in table 1; the results of the performance tests are shown in tables 2-3.
Comparative example 2: this comparative example differs from example 2 in that: zinc methacrylate is not added;
the preparation method of the composite wear-resistant adhesive for the passenger car tire bead comprises the following steps:
step 1: adding natural rubber No. 20, butadiene rubber 9000 and iron-series butadiene-isoprene rubber into an internal mixer, plasticating for 80s at 50rpm and 90 ℃, standing for more than 4h, then adding carbon black N330, stearic acid, aromatic oil, koresin tackifying resin, an anti-aging agent 4020, an anti-aging agent RD and protective wax, mixing for 240s at 50rpm and 110 ℃ to obtain a mixed rubber, wherein the filling coefficient is 0.7;
step 2: adding the mixed rubber and peroxide DCP into an internal mixer, and mixing for 240s at 50rpm and 100 ℃ to obtain the composite wear-resistant rubber for the tire bead of the passenger car.
The specific formulation is shown in table 1; the results of the performance tests are shown in tables 2-3.
Comparative example 3: this comparative example differs from example 2 in that: no Koresin tackifying resin is added;
the preparation method of the composite wear-resistant adhesive for the passenger car tire bead comprises the following steps:
step 1: adding natural rubber No. 20, butadiene rubber 9000 and iron-series butadiene-isoprene rubber into an internal mixer, plasticating for 80s at 50rpm and 90 ℃, standing for more than 4h, then adding carbon black N330, stearic acid, aromatic hydrocarbon oil, zinc methacrylate, an anti-aging agent 4020, an anti-aging agent RD and protective wax, mixing for 240s at 50rpm and 110 ℃ to obtain a mixed rubber, wherein the filling coefficient is 0.7;
step 2: adding the mixed rubber and peroxide DCP into an internal mixer, and mixing for 240s at 50rpm and 100 ℃ to obtain the composite wear-resistant rubber for the tire bead of the passenger car.
The specific formulation is shown in table 1; the results of the performance tests are shown in tables 2-3.
Table 1 formulation of rubber composite
TABLE 2 rubber composite Properties
| Performance parameters | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile Strength | 23.62 | 23.75 | 24.27 | 22.32 | 21.31 | 20.43 |
| 100% stress at definite elongation, MPa | 3.45 | 3.53 | 3.62 | 2.31 | 2.22 | 2.53 |
| 300% stress at definite elongation, MPa | 14.51 | 14.72 | 14.97 | 11.34 | 11.21 | 12.43 |
| Elongation at break% | 538.01 | 539.64 | 540.45 | 501.3 | 500.5 | 508.5 |
| Shore hardness of | 57 | 58 | 58 | 60 | 60 | 60 |
| Tear strength, KN/m | 22.7 | 23.2 | 23.9 | 19.1 | 18.8 | 20.3 |
| DIN abrasion, mm 3 /40m | 0.1893 | 0.1852 | 0.1810 | 0.1914 | 0.1881 | 0.2724 |
| Compression set, percent | 9.63 | 8.58％ | 7.42％ | 15.14 | 16.45 | 9.91 |
TABLE 3 Properties after aging of rubber (thermal oxygen aging at 100 ℃ C. For 48 h)
| Performance parameters | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile Strength | 22.34 | 22.56 | 22.78 | 19.34 | 18.43 | 18.34 |
| 100% stress at definite elongation, MPa | 3.40 | 3.50 | 3.59 | 3.34 | 3.41 | 3.45 |
| Elongation at break% | 515.5 | 517.7 | 519.7 | 456.4 | 467.5 | 454.8 |
| Shore hardness of | 55 | 54 | 55 | 56 | 57 | 58 |
| Tear strength, KN/m | 19.3 | 19.5 | 19.9 | 16.6 | 15.9 | 16.1 |
| DIN abrasion, mm 3 /40m | 0.2093 | 0.2056 | 0.2015 | 0.2453 | 0.2043 | 0.3054 |
| Compression set, percent | 11.02 | 10.86 | 9.41 | 17.42 | 19.53 | 10.90 |
Analysis of the data in tables 2-3 shows that the compression set, abrasion resistance and aging properties of the composite material are significantly improved with the addition of the iron-based butyl rubber, zinc methacrylate and KORESIN tackifying resin. Before aging, the addition of the butyl rubber in the example 2 is compared with that in the comparative example 1, the wear resistance and compression set of the material are improved, and the tensile and tearing properties of the material are correspondingly improved. Example 2 the compression set and ageing resistance of the material was improved compared to comparative example 2 by the addition of zinc methacrylate. Example 2 the abrasion resistance of the material was improved compared to comparative example 3 by the addition of KORESIN tackifying resin. After aging, the addition of the iron-based butadiene-isoprene rubber and zinc methacrylate improves the ageing resistance of the rubber composite material.
From the comparative analysis of the above examples and comparative examples, in the composite abrasion resistant rubber for a passenger car tire bead of the present invention, iron-based catalytic butyl rubber, koresin tackifying resin, peroxide and zinc methacrylate have synergistic effects with each other in addition to their independent effects, and the concrete expression is:
firstly, the allyl side group of the butadiene-isoprene rubber has electronegativity and can generate certain chemical acting force with the Koresin tackifying resin, so that better winding, combination and adhesion are generated between the allyl side group and the Koresin tackifying resin, and the wear resistance of the material can be effectively improved under the synergistic effect of the allyl side group and the Koresin.
Secondly, the peroxide is decomposed into free radicals in the high-temperature vulcanization process, and the unique double bond structural characteristics in the butyl-isoprene rubber molecular chain can easily generate macromolecular chain crosslinking reaction under the initiation of the peroxide free radicals.
In addition, the crosslinking reaction degree of the side groups (propenyl and vinyl) adjacent to the carboxyl in the zinc methacrylate is improved in the vulcanization process, the polymerization reaction of the ZDMA is initiated, and the side groups are partially grafted into the butyl-pentyl rubber molecular chain, so that the crosslinking degree and the crosslinking bond energy of the side groups are improved, and the deformation recovery capacity and the high temperature resistance of the rubber composite material are improved.
It should be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and that the present invention is based on various embodiments under the general inventive concept, and the scope of the present invention is not limited thereto, but any person skilled in the art can make modifications or equivalents to the technical solution of the present invention within the technical scope of the present invention disclosed herein, which are all encompassed by the scope of the claims of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. The composite wear-resistant adhesive for the passenger car tyre bead is characterized by being prepared from the following components in parts by weight:
100 parts of olefin rubber;
50-90 parts of reinforcing filler;
1-5 parts of Koresin tackifying resin;
3-15 parts of a vulcanization activator;
1-5 parts of peroxide;
1-5 parts of an anti-aging agent;
1-30 parts of plasticizer;
wherein the olefin rubber is prepared by mixing 20-40 parts of natural rubber, 20-40 parts of butadiene rubber and 30-50 parts of iron-based butadiene-isoprene rubber in parts by mass, and the vulcanization activator consists of 2-10 parts of zinc methacrylate and 1-5 parts of stearic acid.
2. The composite wear-resistant rubber for a passenger car tire bead according to claim 1, wherein the number average molecular weight of the iron-based butadiene-isoprene rubber is 129.2w, and the molar ratio of butadiene to isoprene in the preparation process is 2:3, wherein the molar content of 1, 2-butadiene in the butadiene structural unit is 22%, the molar content of 1, 4-butadiene is 78%, the molar content of 3, 4-isoprene in the isoprene structural unit is 84%, and the molar content of 1, 4-isoprene is 16%.
3. The composite wear-resistant adhesive for passenger car tyre bead openings according to claim 1, wherein the reinforcing filler is one or a mixture of several of carbon black, white carbon black, talcum powder, ceramic powder and calcium carbonate.
4. The composite wear-resistant adhesive for a passenger car tire bead according to claim 1, wherein the anti-aging agent is one or a mixture of several of RD,4020 and protective wax.
5. The composite wear-resistant adhesive for a passenger car tire bead according to claim 1, wherein the peroxide is one or a mixture of several of alkyl peroxide and diacyl peroxide.
6. The composite abrasion resistant adhesive for a passenger car tire bead according to claim 5, wherein the peroxide is dicumyl peroxide.
7. The composite wear-resistant adhesive for passenger car tyre bead openings according to claim 1, wherein the Koresin tackifying resin is formed by polycondensing p-tert-butylphenol and acetylene under the catalysis of zinc naphthenate at high temperature and high pressure, and has a softening point of 135-150 ℃ and a density of 1.02-1.04g/cm 3 。
8. The composite wear-resistant rubber for a passenger car tire bead according to claim 1, wherein the plasticizer is one or a mixture of a plurality of cyclic paraffin-based rubber, aromatic-based rubber and cycloalkyl-based rubber.
9. The method for preparing the composite wear-resistant adhesive for the bead filler of the passenger car tire according to any one of claims 1 to 8, which is characterized by comprising the following steps:
step 1: adding olefin rubber into an internal mixer for plasticating, standing for more than 4 hours, adding reinforcing filler, vulcanizing activator, plasticizer, koresin tackifying resin and anti-aging agent for mixing to obtain a mixed rubber;
step 2: and adding the mixed rubber and the peroxide into an internal mixer for continuous mixing to obtain the composite wear-resistant rubber for the tire bead of the passenger car.
10. A composite wear resistant adhesive for a passenger tire bead set according to any one of claims 1 to 8 for use in the preparation of a passenger tire.
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