CN115260607B - Rubber composition with low content of volatile organic compounds and preparation method thereof - Google Patents
Rubber composition with low content of volatile organic compounds and preparation method thereof Download PDFInfo
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- CN115260607B CN115260607B CN202210933607.XA CN202210933607A CN115260607B CN 115260607 B CN115260607 B CN 115260607B CN 202210933607 A CN202210933607 A CN 202210933607A CN 115260607 B CN115260607 B CN 115260607B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 85
- 239000005060 rubber Substances 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 68
- 239000002781 deodorant agent Substances 0.000 claims abstract description 41
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- -1 sulfonyl hydrazine compound Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 15
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims abstract description 13
- 238000007670 refining Methods 0.000 claims abstract description 7
- 239000006229 carbon black Substances 0.000 claims description 23
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 19
- 239000005062 Polybutadiene Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 229920002857 polybutadiene Polymers 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 244000043261 Hevea brasiliensis Species 0.000 claims description 13
- 229920003052 natural elastomer Polymers 0.000 claims description 13
- 229920001194 natural rubber Polymers 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 12
- 239000001993 wax Substances 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- 230000003712 anti-aging effect Effects 0.000 claims description 10
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 6
- 239000004200 microcrystalline wax Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000010692 aromatic oil Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 241000196324 Embryophyta Species 0.000 claims description 4
- PIBIAJQNHWMGTD-UHFFFAOYSA-N 1-n,3-n-bis(4-methylphenyl)benzene-1,3-diamine Chemical compound C1=CC(C)=CC=C1NC1=CC=CC(NC=2C=CC(C)=CC=2)=C1 PIBIAJQNHWMGTD-UHFFFAOYSA-N 0.000 claims description 3
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000002199 base oil Substances 0.000 claims description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012990 dithiocarbamate Substances 0.000 claims description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 3
- 229960002447 thiram Drugs 0.000 claims description 3
- YZRSLFIRGZJTAZ-UHFFFAOYSA-N 2-cyclohexyl-3-sulfanylideneisoindol-1-one Chemical compound S=C1C2=CC=CC=C2C(=O)N1C1CCCCC1 YZRSLFIRGZJTAZ-UHFFFAOYSA-N 0.000 claims 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 1
- 230000001877 deodorizing effect Effects 0.000 abstract description 11
- 230000002829 reductive effect Effects 0.000 abstract description 11
- 150000003254 radicals Chemical class 0.000 abstract description 10
- 238000004073 vulcanization Methods 0.000 abstract description 9
- ISNKSXRJJVWFIL-UHFFFAOYSA-N (sulfonylamino)amine Chemical group NN=S(=O)=O ISNKSXRJJVWFIL-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001299 aldehydes Chemical class 0.000 abstract description 3
- 230000036541 health Effects 0.000 abstract description 3
- 238000007342 radical addition reaction Methods 0.000 abstract description 3
- 238000007347 radical substitution reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 239000004636 vulcanized rubber Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- 239000002174 Styrene-butadiene Substances 0.000 description 11
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 7
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical group O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000006757 chemical reactions by type Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 101100149706 Arabidopsis thaliana SMR10 gene Proteins 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000003988 headspace gas chromatography Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- KTRQRAQRHBLCSQ-UHFFFAOYSA-N 1,2,4-tris(ethenyl)cyclohexane Chemical compound C=CC1CCC(C=C)C(C=C)C1 KTRQRAQRHBLCSQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000756137 Hemerocallis Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 210000000777 hematopoietic system Anatomy 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage 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
-
- 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
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- 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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a rubber composition with low content of volatile organic compounds and a preparation method thereof, wherein the rubber composition uses sulfonyl hydrazides compounds as chemical deodorant, and the sulfonyl hydrazides compounds are added in two stages of a masterbatch stage and a final refining stage, so that the volatile organic compounds in different stages are better removed, wherein: the sulfonyl hydrazides added in the masterbatch section can be decomposed in advance to form free radicals, so that free radical addition and free radical substitution reactions occur; the sulfonyl hydrazine compound added in the final refining section can not be decomposed in advance, the sulfonyl hydrazine group can react with aldehyde and ketone compounds, and simultaneously, the sulfonyl hydrazine group can react with volatile organic compounds generated in the vulcanization process in the vulcanization stage, so that the deodorizing effect of the chemical deodorizing agent is improved. The sulfonyl hydrazine compound is used as the deodorant, so that the odor of the tire can be reduced, the content of volatile organic compounds in the tire can be reduced radically, and the sulfonyl hydrazine compound has important practical significance in the aspect of protecting the health of tire manufacturers and consumers.
Description
Technical Field
The invention belongs to the technical field of tires, and particularly relates to a rubber composition with low content of volatile organic compounds and a preparation method thereof.
Background
The tire is processed by rubber and a large amount of chemical additives, on one hand, the rubber and the chemical additives contain certain volatile organic compounds and unpleasant odor, on the other hand, various chemical reactions which are difficult to predict can also occur between the rubber and the additives due to the high temperature required in the processing process, so that a large amount of Volatile Organic Compounds (VOC) are generated, and the malodor odor of the tire is aggravated.
VOCs are extremely harmful, and human bodies are exposed in environments with high concentration of VOCs for a long time, and dizziness and nausea are caused by light and heavy diseases, which cause damage to nervous systems, immune systems, respiratory systems, hematopoietic systems and livers, even cause leukemia, and cause death. The tire generates a large amount of volatile organic compounds in the whole life cycle of production, storage, transportation, assembly and use, and has great necessity and urgency for developing a tire with low volatile organic compounds for protecting the health of relevant practitioners and consumers.
In order to reduce volatile organic compounds in tires and improve odor problems of tires, three main ways are currently adopted: firstly, an essence masking method is disclosed in CN102602246A, for example, an aromatic tire and a production method thereof are disclosed, wherein high-temperature resistant aromatic plant essence is fixedly connected in the tread, the sidewall and the airtight layer of the aromatic tire, and is added during mixing of rubber materials of the tread, the sidewall and the airtight layer, so that the tire emits aromatic odor, and the problem of the method is that volatile organic matters in the tire cannot be reduced by using the essence, and the emission of the volatile organic matters is aggravated; secondly, an adsorption method is disclosed in CN112321908A, such as a rubber material composition, a rubber compound, a preparation method thereof and a spare tire, wherein the active carbon with the particle size less than or equal to 10 mu m is matched with natural rubber and butadiene rubber to reduce the release of pungent odor in the rubber material and the spare tire, and maintain good physical and mechanical properties; thirdly, a physical barrier method, such as CN110951175a, discloses a low-odor barrier layer compound, a method for preparing the same, a low-odor tire and a method for preparing the tire by using the low-odor barrier layer compound, wherein halogenated butyl rubber or BIMSM (brominated isobutylene/para-methylstyrene copolymer) elastomer rubber is used in the barrier layer compound, no anti-aging agent is added, and the barrier layer compound uses a vulcanizing agent and an accelerator as materials with lower odor, so that the purpose of reducing odor is achieved by adding the barrier layer on the surface of a tread rubber of a conventional tire. As another example, CN111675939a discloses a method for reducing the odor of a pneumatic tire and a low-odor tire, in which butyl rubber, natural rubber, carbon black, a dispersant, a resin, zinc oxide, stearic acid, and sulfur are dissolved in an organic solvent to prepare a rubber mixed solution, and the rubber mixed solution is applied to the surface of an unvulcanized green tire, and the low-odor tire is obtained after vulcanization. This method has the disadvantage of requiring a physical barrier layer on the outer surface of the tyre, adding to the process steps and complexity.
At present, the rubber used in the tire industry is mainly natural rubber, butadiene rubber and styrene butadiene rubber. Researches show that the volatile organic compounds of the vulcanized rubber mainly comprise chemical substances such as aldehyde ketone, amine, olefin, benzothiazole and the like (China rubber, 2019,35,34-38.), in addition, the styrene-butadiene rubber also comprises polymerized monomer styrene, and butadiene rubber mainly comprises butadiene oligomer 1,2, 4-trivinylcyclohexane, and the volatile organic compounds are also main factors causing peculiar smell of the tire. How to provide a simple and effective technical method capable of reducing the volatile organic compounds of the tire from the root so as to improve the odor of the tire is a technical problem to be solved.
Disclosure of Invention
In view of the shortcomings of the prior art, an object of the present invention is to provide a rubber composition having a low content of volatile organic compounds, which has lower volatile organic compounds, and a method for producing the same, which radically reduces the odor of tires.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for producing a rubber composition having a low content of volatile organic compounds, the rubber composition using a sulfonyl hydrazide-based compound as a chemical deodorant; in the preparation process of the rubber composition, the chemical deodorant is added in two times, firstly, a part of chemical deodorant is added in a masterbatch section, and then the rest chemical deodorant is added in a final smelting section; wherein: the mass ratio of the chemical deodorant added in the masterbatch section to the chemical deodorant added in the final smelting section is 1: (0.5-2). The chemical structural formula of the sulfonyl hydrazides compound is as follows:wherein R is selected from alkyl or aryl; by a means ofThe sulfonyl hydrazide compound is preferably 4,4' -oxo-bis-benzenesulfonyl hydrazide, and has the structural formula +.>
Further, the rubber composition comprises 100 parts of matrix rubber, 50-80 parts of filler, 0-10 parts of silane coupling agent, 1-5 parts of zinc oxide, 1-5 parts of stearic acid, 2-6 parts of chemical anti-aging agent, 1-5 parts of protective wax, 0-20 parts of operating oil, 0-20 parts of resin, 1-5 parts of vulcanizing agent, 0.3-3.0 parts of accelerator, 0-1 part of scorch retarder and 1-5 parts of chemical deodorant. In one aspect, the base rubber includes natural rubber and butadiene rubber. In another aspect, the base rubber includes styrene butadiene rubber and butadiene rubber. Wherein:
the natural rubber is selected from one of SIR20#, SMR10#, SMR20#, SVR L, SCR 5#, SCR WF, and SVR 3L is preferably used as the natural rubber.
The butadiene rubber is selected from one of NiBR and NdBR, and preferably NiBR is used as the butadiene rubber.
The styrene-butadiene rubber is selected from SBR 4602, SBR 763B, SBR1502, SBR 1763 and SBR 1723, preferably SBR 4602 is used as the styrene-butadiene rubber.
The carbon black is selected from N115, N134, N220, N234, N326, N330, N375, N550 and N660, and preferably N330 is used as the carbon black.
The filler comprises 30-50 parts of carbon black and 0-50 parts of white carbon black; the white carbon black is one of 855GR, 1165MP and 7000GR, and 1165MP is preferably used as the white carbon black.
The silane coupling agent is selected from one of X75s, X50s, si69 and NXT, and preferably X75s is used as the silane coupling agent.
The chemical antioxidant is at least one selected from antioxidant RD, antioxidant 4010NA, antioxidant DTPD, antioxidant TMPPD and antioxidant 6 PPD.
The protective wax is at least one selected from microcrystalline wax OK15001, rhine 111 and microcrystalline wax P type.
The operating oil is at least one selected from environment-friendly aromatic oil, naphthenic oil and plant base oil, and preferably the operating oil is environment-friendly aromatic oil.
The resin is at least one selected from hydrocarbon resin, coumarone resin and hydrocarbon resin mixture, preferably hydrocarbon resin is used.
The vulcanizing agent is at least one selected from common sulfur, insoluble sulfur and sulfur master batch S-80, and the sulfur master batch S-80 is preferably used as the vulcanizing agent.
The accelerator may be at least one selected from the group consisting of sulfenamides, guanidine, thiazole, dithiocarbamate, thiourea and thiuram, and sulfenamide accelerators are preferably used, and accelerator CBS is more preferably used.
The scorch retarder is N-cyclohexylthio-phthalimide (CTP).
The preparation method of the rubber composition with low content of volatile organic compounds comprises the following steps:
and (3) a masterbatch section: putting matrix rubber, filler, silane coupling agent, zinc oxide, stearic acid, chemical anti-aging agent, protective wax, operating oil, resin and part of chemical deodorant into an internal mixer together, controlling the rotating speed to be 20-80rpm, controlling the upper bolt pressure to be 3.0-5.0MPa, mixing for 1-5min, discharging rubber when the mixing temperature reaches 155 ℃, obtaining M1-section masterbatch, and cooling for standby;
and (3) final refining: adding the cooled M1-section masterbatch, a vulcanizing agent, an accelerator, a scorch retarder and a chemical deodorant into an internal mixer, controlling the rotating speed to be 15-30rpm, discharging rubber when the temperature reaches 100 ℃, and cooling to obtain an unvulcanized rubber composition.
The action mechanism of the chemical reaction type deodorant (chemical deodorant for short) using the sulfonyl hydrazine compound is as follows:
the sulfonyl hydrazides have higher reactivity, and the reaction with volatile organic compounds in tires is mainly divided into two types: firstly, utilizing sulfonyl hydrazine groups to participate in the reaction, wherein in the following formula (a), the sulfonyl hydrazine groups and aldehyde and ketone carry out nucleophilic addition reaction; and secondly, active free radicals generated by the decomposition of sulfonyl hydrazine groups are used for participating in the reaction, and the active free radicals are used for carrying out free radical addition or free radical substitution reaction with amine, olefin and benzothiazole, wherein the reaction mechanism is shown in the following formulas (b) - (d).
From the above chemical reaction, it is theoretically possible to eliminate volatile organic compounds in vulcanized rubber by using sulfonyl hydrazides as chemical deodorizing agents, and accordingly, we have provided a rubber composition having a low content of volatile organic compounds.
Compared with the prior art, the invention has the advantages that:
(1) According to the invention, the sulfonyl hydrazine compound is used as a chemical reaction type deodorant, and the sulfonyl hydrazine compound is subjected to chemical reaction with different volatile organic compounds by utilizing the self reaction activity in the process of processing the rubber composition into the tire, so that the application range is wide, the deodorizing effect is durable, no rebound is caused, and no new volatile organic compounds are generated. The sulfonyl hydrazine compound is used as the deodorant in the tire, so that the odor of the tire can be reduced, the content of volatile organic compounds in the tire can be reduced radically, and the sulfonyl hydrazine compound has important practical significance in the aspect of protecting the health of tire manufacturers and consumers.
(2) According to the invention, the sulfonyl hydrazine compound is used as a chemical reaction type deodorant, and is added into a mother smelting section and a final smelting section respectively, so that volatile organic compounds in different stages are removed better, and the application range of the sulfonyl hydrazine compound is widened. Wherein: the sulfonyl hydrazides added in the masterbatch section can be decomposed in advance to form free radicals, so that free radical addition and free radical substitution reactions occur; the sulfonyl hydrazine compound added in the final refining section can not be decomposed in advance, the sulfonyl hydrazine group can be subjected to nucleophilic addition reaction with aldehyde and ketone compounds, and meanwhile, the sulfonyl hydrazine group can be subjected to corresponding reaction with volatile organic compounds generated in the vulcanization process in the vulcanization stage, so that the deodorizing effect of the chemical deodorizing agent is improved.
(3) The invention uses the odor grade evaluation and the qualitative and semi-quantitative results of volatile organic compounds to jointly measure the quality of the odor, thereby fundamentally explaining the odor source and the odor grade of the tire, and the two evaluation methods are combined to eliminate the interference of adverse factors, so that the odor evaluation of the tire is more comprehensive and accurate.
Detailed Description
The present invention will be further described with reference to examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
In addition, the preparation processes in the following examples are conventional means in the art unless specifically described, and therefore, will not be described in detail; the parts in the following embodiments refer to parts by weight.
A method for producing a rubber composition having a low content of volatile organic compounds, the rubber composition using a sulfonyl hydrazide-based compound as a chemical deodorant; the chemical structural formula of the sulfonyl hydrazides compound is as follows:wherein R is selected from alkyl or aryl; the sulfonyl hydrazides are preferably 4,4' -oxo-bis-benzenesulfonyl hydrazides.
Further, the rubber composition comprises 100 parts of matrix rubber, 50-80 parts of filler, 0-10 parts of silane coupling agent, 1-5 parts of zinc oxide, 1-5 parts of stearic acid, 2-6 parts of chemical anti-aging agent, 1-5 parts of protective wax, 0-20 parts of operating oil, 0-20 parts of resin, 1-5 parts of vulcanizing agent, 0.3-3.0 parts of accelerator, 0-1 part of scorch retarder and 1-5 parts of chemical deodorant. In one aspect, the base rubber includes natural rubber and butadiene rubber. In another aspect, the base rubber includes styrene butadiene rubber and butadiene rubber. Wherein:
the natural rubber is selected from one of SIR20#, SMR10#, SMR20#, SVR L, SCR 5#, SCR WF, and SVR 3L is preferably used as the natural rubber.
The butadiene rubber is selected from one of NiBR and NdBR, and preferably NiBR is used as the butadiene rubber.
The styrene-butadiene rubber is selected from SBR 4602, SBR 763B, SBR1502, SBR 1763 and SBR 1723, preferably SBR 4602 is used as the styrene-butadiene rubber.
The carbon black is selected from N115, N134, N220, N234, N326, N330, N375, N550 and N660, and preferably N330 is used as the carbon black.
The filler comprises 30-50 parts of carbon black and 0-50 parts of white carbon black; the white carbon black is one of 855GR, 1165MP and 7000GR, and 1165MP is preferably used as the white carbon black.
The silane coupling agent is selected from one of X75s, X50s, si69 and NXT, and preferably X75s is used as the silane coupling agent.
The chemical antioxidant is at least one selected from antioxidant RD, antioxidant 4010NA, antioxidant DTPD, antioxidant TMPPD and antioxidant 6 PPD.
The protective wax is at least one selected from microcrystalline wax OK15001, rhine 111 and microcrystalline wax P type.
The operating oil is at least one selected from environment-friendly aromatic oil, naphthenic oil and plant base oil, and preferably the operating oil is environment-friendly aromatic oil.
The resin is at least one selected from hydrocarbon resin, coumarone resin and hydrocarbon resin mixture, preferably hydrocarbon resin is used.
The vulcanizing agent is at least one selected from common sulfur, insoluble sulfur and sulfur master batch S-80, and the sulfur master batch S-80 is preferably used as the vulcanizing agent.
The accelerator may be at least one selected from the group consisting of sulfenamides, guanidine, thiazole, dithiocarbamate, thiourea and thiuram, and sulfenamide accelerators are preferably used, and accelerator CBS is more preferably used.
The scorch retarder is N-cyclohexylthio-phthalimide (CTP).
Examples 1 to 3 and comparative examples 1 to 3
In examples 1 to 3 and comparative examples 1 to 3, rubber compositions were prepared using natural rubber and butadiene rubber as base rubber components in the amounts shown in Table 1, according to the following procedures:
and (3) a masterbatch section: adding natural rubber, butadiene rubber, carbon black, zinc oxide, stearic acid, a chemical anti-aging agent, protective wax, operating oil, resin and a chemical deodorant into an internal mixer, controlling the rotating speed to 70rpm, controlling the upper bolt pressure to be 4MPa, mixing for 3min, discharging rubber when the mixing temperature reaches 155 ℃, obtaining M1-section masterbatch, and cooling for later use.
And (3) final refining: adding the cooled M1-section master batch, a vulcanizing agent, an accelerator, a scorch retarder and a chemical deodorant into an internal mixer, mixing at 20rpm until the temperature reaches 100 ℃, discharging rubber, and cooling to obtain an unvulcanized rubber composition.
TABLE 1 raw materials consumption Meter for examples 1-3 and comparative examples 1-3
*1. Natural rubber: standard gum SVR 3L, commercially available.
*2. Butadiene rubber: niBR from the well petrochemical company.
*3. Carbon black: carbon black N330, from Cabot Chemical co.ltd.
*4. Zinc oxide: from the Tianli zinc industry.
*5. Stearic acid: from tylotheca brownification.
*6. Chemical anti-aging agent: age resister 4020, from san jose chemical industry.
*7. Protective wax: rhine 111, from Rhine chemistry.
*8. Operating oil: environment friendly oil NAP from Krama.
*9. Resin: hydrocarbon resin from Lu Huahong brocade.
*10. Vulcanizing agent: sulfur masterbatch S-80 from Yangguhua Taai.
*11. And (3) an accelerator: accelerator CBS, from kemelic chemical.
*12. Scorch retarder: scorch retarder CTP, from Dai Ruike.
*13. Chemical deodorant: 4,4' -oxo-bis-benzenesulfonyl hydrazide (OBSH), commercially available.
The unvulcanized rubber compositions obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to the following tests: the unvulcanized rubber was tested for vulcanization characteristics according to GB/T16584-1996. Vulcanizing the unvulcanized rubber composition on a flat vulcanizing machine at 160 ℃ for 10min to obtain a vulcanized rubber composition. The following tests were carried out on the vulcanized rubber composition: the hardness test of the vulcanized rubber is carried out according to GB/T531.1-2008, the tensile stress and strain performance test of the vulcanized rubber is carried out according to GB/T528-2009, and the density test of the vulcanized rubber is carried out according to GB/T533-2008, and the test results are shown in Table 2.
TABLE 2 comparison of the processability of the rubber compounds of examples 1-3 and comparative examples 1-3 with the physical properties of the vulcanizates
Odor evaluation: the vulcanized rubber is put into a 1L odor bottle, sealed, subjected to heat preservation treatment at 25 ℃ for 24 hours and 80 ℃ for 2 hours respectively, and then subjected to odor evaluation. Odor ratings were tested according to the VDA-270 odor rating criteria, the odor ratings are shown in Table 3. In the odor evaluation, five evaluators score, the scores with larger differences are removed, the rest scores are averaged, and the average value is determined as the odor grade of the sample. The odor evaluation results of the vulcanized rubber compositions of comparative examples 1 to 3 and examples 1 to 3 are shown in Table 4.
TABLE 3 odor rating scoring criteria
The volatile organic compounds of the rubber compositions after vulcanization were analyzed by static headspace-gas chromatography mass spectrometry, and the peak areas of the volatile organic compounds of comparative examples 1 to 3 and examples 1 to 3 are shown in Table 4.
TABLE 4 odor evaluation results and peak areas of respective volatile organic compounds of comparative examples 1 to 3 and examples 1 to 3
Note that: ND represents unidentified.
As can be seen from the odor evaluation data in table 4, in terms of first and second odor grades: comparative examples 2-3 and examples 1-3, which used OBSH as a chemical deodorant, each achieved a reduction in odor level, with the best odor improvement using example 3 in a 1:2 ratio of OBSH in the masterbatch stage and the final stage, with odor levels of 4.2 (25 ℃ x 24 h) and 4.7 (80 ℃ x 2 h), respectively. 2. Volatile organic content: in comparative examples 2-3 and examples 1-3, which used OBSH as a chemical deodorizing agent, the peak areas of volatile organic compounds were significantly reduced, wherein in example 3, which used a ratio of 1:2 in the masterbatch stage to the final stage, no cyclohexylamine and aniline were detected, and the peak areas of the other three volatile organic compounds were reduced by 96%, 65% and 78%, respectively, with the best reduction effect of the volatile organic compound content.
Examples 4 to 6 and comparative examples 4 to 6
In examples 4 to 6 and comparative examples 4 to 6, styrene-butadiene rubber and butadiene rubber were used as base rubber components, and rubber compositions were prepared according to the following procedures in the amounts of raw materials shown in Table 5:
and (3) a masterbatch section: adding styrene-butadiene rubber, carbon black, white carbon black, a silane coupling agent, zinc oxide, stearic acid, a chemical anti-aging agent, protective wax, operating oil, resin and a chemical deodorant into an internal mixer, controlling the rotating speed to 70rpm, controlling the upper bolt pressure to be 4MPa, mixing for 5min, discharging rubber when the mixing temperature reaches 155 ℃, obtaining M1-section masterbatch, and cooling for standby;
and (3) final refining: adding the cooled M1-section master batch, a vulcanizing agent, an accelerator, a scorch retarder and a chemical deodorant into an internal mixer, mixing at 20rpm until the temperature reaches 100 ℃, discharging rubber, and cooling to obtain an unvulcanized rubber composition.
TABLE 5 raw material consumption Meter for comparative examples 4 to 6 and examples 4 to 6
*1. Styrene-butadiene rubber: SBR 4602 from trinse.
*2. Butadiene rubber: niBR from the well petrochemical company.
*3. Carbon black: carbon black N330, from Cabot Chemical co.ltd.
*4. White carbon black: white carbon 1165MP from Solvay.
*5. Silane coupling agent: x75s from south kyo daylily.
*6. Zinc oxide: from the Tianli zinc industry.
*7. Stearic acid: from tylotheca brownification.
*8. Chemical anti-aging agent: age resister 4020, from san jose chemical industry.
*9. Protective wax: rhine 111, from Rhine chemistry.
*10. Operating oil: environment friendly oil NAP from Krama.
*11. Resin: hydrocarbon resin from Lu Huahong brocade.
*12. Vulcanizing agent: sulfur masterbatch S-80 from Yangguhua Taai.
*13. And (3) an accelerator: accelerator CBS, from kemelic chemical.
*14. Scorch retarder: scorch retarder CTP, from Dai Ruike.
*15. Chemical deodorant: OBSH (4, 4' -oxybisbenzenesulfonyl hydrazide) is commercially available.
The unvulcanized rubber composition obtained was subjected to the following test: the unvulcanized rubber was tested for vulcanization characteristics according to GB/T16584-1996. Vulcanizing the unvulcanized rubber composition on a flat vulcanizing machine at 160 ℃ for 15min to obtain a vulcanized rubber composition. The following tests were carried out on the vulcanized rubber composition: the hardness test of the vulcanized rubber according to GB/T531.1-2008, the tensile stress and strain performance test of the vulcanized rubber according to GB/T528-2009 and the density test of the vulcanized rubber according to GB/T533-2008 are shown in Table 6.
Table 6 comparison of the processability of the rubber compounds of comparative examples 4 to 6 and examples 4 to 6 with the physical properties of the vulcanized rubber
The data in Table 6 shows that examples 4-6, which used different proportions of OBSH as chemical deodorizing agent in the masterbatch stage and the final stage, had little change in crosslink density, prolonged cure time, and some improvement in physical properties as compared to comparative example 4. Whereas examples 4-6 were consistent in processability and physical properties as compared to comparative examples 5-6.
Odor evaluation: the vulcanized rubber is put into a 1L odor bottle, sealed, subjected to heat preservation treatment at 25 ℃ for 24 hours and 80 ℃ for 2 hours respectively, and then subjected to odor evaluation. Odor ratings were tested according to the VDA-270 odor rating criteria, the odor ratings are shown in Table 7. In the odor evaluation, five evaluators score, the scores with larger differences are removed, the rest scores are averaged, and the average value is determined as the odor grade of the sample. The odor evaluation results of comparative examples 4 to 6 and examples 4 to 6 are shown in Table 8.
TABLE 7 odor rating scoring criteria
The volatile organic compounds of the rubber compositions after vulcanization were analyzed by static headspace-gas chromatography mass spectrometry, and the peak areas of the volatile organic compounds of comparative examples 4 to 6 and examples 4 to 6 are shown in Table 8.
Table 8 odor evaluation results and peak areas of respective volatile organic compounds of comparative examples 4 to 6 and examples 4 to 6
Note that: ND represents unidentified.
As can be seen from the odor evaluation data of table 8, in terms of first, odor rating: comparative examples 5-6 and examples 4-6, which used OBSH as a chemical deodorant, each achieved a reduction in odor grade, with OBSH using example 6 in a 1:2 ratio in the masterbatch stage and the final stage, with odor grades of 4.2 (25 ℃ x 24 h) and 4.7 (80 ℃ x 2 h), respectively, with the best odor improving effect. 2. Volatile organic content: in both comparative examples 5-6 and examples 4-6, which used OBSH as a chemical deodorizing agent, the peak areas of volatile organic compounds were significantly reduced, wherein in example 6, which used a ratio of 1:2 in the masterbatch stage to the final stage, no cyclohexylamine and aniline were detected, and the peak areas were reduced by 41%, 38% and 77%, respectively, for the other three volatile organic compounds, with the best volatile organic compound content reduction.
According to the invention, the sulfonyl hydrazine compound with a chemical deodorizing function is added into the formula, so that the content of volatile organic compounds in the rubber composition is greatly reduced, the odor grade of the rubber composition is also obviously reduced, and the physical properties of the rubber composition are not greatly changed after the chemical deodorizing agent is added, so that the invention is particularly suitable for preparing low-odor tires.
It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. A process for producing a rubber composition having a low content of volatile organic compounds, characterized by: the rubber composition uses sulfonyl hydrazides as chemical deodorant; in the preparation process of the rubber composition, the chemical deodorant is added in two times, firstly, a part of chemical deodorant is added in a masterbatch section, and then the rest chemical deodorant is added in a final smelting section; wherein: the mass ratio of the chemical deodorant added in the masterbatch section to the chemical deodorant added in the final smelting section is 1: (0.5-2); the chemical structural formula of the sulfonyl hydrazides compound is as follows:wherein R is selected from alkyl, or aryl.
2. A process for producing a rubber composition having a low content of volatile organic compounds, characterized by: the rubber composition uses sulfonyl hydrazides as chemical deodorant; in the preparation process of the rubber composition, the chemical deodorant is added in two times, firstly, a part of chemical deodorant is added in a masterbatch section, and then the rest chemical deodorant is added in a final smelting section; wherein: the mass ratio of the chemical deodorant added in the masterbatch section to the chemical deodorant added in the final smelting section is 1: (0.5-2); the sulfonyl hydrazine compound is 4,4' -oxo-bis-benzenesulfonyl hydrazine.
3. The method for producing a rubber composition having a low content of volatile organic compounds according to claim 1, characterized in that: the rubber composition comprises 100 parts of matrix rubber, 50-80 parts of filler, 0-10 parts of silane coupling agent, 1-5 parts of zinc oxide, 1-5 parts of stearic acid, 2-6 parts of chemical anti-aging agent, 1-5 parts of protective wax, 0-20 parts of operating oil, 0-20 parts of resin, 1-5 parts of vulcanizing agent, 0.3-3.0 parts of accelerator, 0-1 part of scorch retarder and 1-5 parts of chemical deodorant.
4. A process for producing a rubber composition having a low content of volatile organic compounds as claimed in claim 3, characterized in that: the method comprises the following steps:
and (3) a masterbatch section: putting matrix rubber, filler, silane coupling agent, zinc oxide, stearic acid, chemical anti-aging agent, protective wax, operating oil, resin and part of chemical deodorant into an internal mixer together, controlling the rotating speed to be 20-80rpm, controlling the upper bolt pressure to be 3.0-5.0MPa, mixing for 1-5min, discharging rubber when the mixing temperature reaches 155 ℃, obtaining M1-section masterbatch, and cooling for standby;
and (3) final refining: adding the cooled M1-section masterbatch, a vulcanizing agent, an accelerator, a scorch retarder and a chemical deodorant into an internal mixer, controlling the rotating speed to be 15-30rpm, discharging rubber when the temperature reaches 100 ℃, and cooling to obtain an unvulcanized rubber composition.
5. The method for producing a rubber composition having a low content of volatile organic compounds as claimed in claim 4, wherein: the base rubber includes natural rubber and butadiene rubber.
6. The method for producing a rubber composition having a low content of volatile organic compounds as claimed in claim 4, wherein: the base rubber comprises styrene-butadiene rubber and butadiene rubber.
7. The method for producing a rubber composition having a low content of volatile organic compounds according to any one of claims 3 to 6, characterized in that: the filler comprises 30-50 parts of carbon black and 0-50 parts of white carbon black; the chemical antioxidant is at least one selected from antioxidant RD, antioxidant 4010NA, antioxidant DTPD, antioxidant TMPPD and antioxidant 6 PPD; the protective wax is at least one selected from microcrystalline wax OK15001, rhine 111 and microcrystalline wax P type.
8. The method for producing a rubber composition having a low content of volatile organic compounds according to any one of claims 3 to 6, characterized in that: the operating oil is at least one of environment-friendly aromatic oil, naphthenic oil and plant base oil; the resin is at least one selected from hydrocarbon resin, coumarone resin and hydrocarbon resin mixture; the vulcanizing agent is at least one selected from common sulfur, insoluble sulfur and sulfur master batch S-80.
9. The method for producing a rubber composition having a low content of volatile organic compounds according to any one of claims 3 to 6, characterized in that: the accelerator is at least one selected from sulfenamides, guanidine, thiazole, dithiocarbamate, thiourea and thiuram; the scorch retarder is selected fromN-cyclohexylthio-phthalimide.
10. A rubber composition having a low content of volatile organic compounds, characterized in that: which is prepared by the preparation method according to any one of claims 1 to 9.
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| CN102391550A (en) * | 2011-09-07 | 2012-03-28 | 际华三五三七制鞋有限责任公司 | Natural rubber white odorless spongy cushion for in situ color-protecting shoes and preparation method thereof |
| CN105419007A (en) * | 2015-12-30 | 2016-03-23 | 四川君格橡胶制品有限公司 | Tasteless formulation inner tube sizing material and processing process thereof |
| CN109467870A (en) * | 2018-10-29 | 2019-03-15 | 北方华锦化学工业股份有限公司 | A kind of low smell highly resistance, which is leapt high, flows ABS resin and preparation method thereof |
| JP2019189747A (en) * | 2018-04-24 | 2019-10-31 | 住友ゴム工業株式会社 | Rubber composition for tire tread and tire |
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| CN102391550A (en) * | 2011-09-07 | 2012-03-28 | 际华三五三七制鞋有限责任公司 | Natural rubber white odorless spongy cushion for in situ color-protecting shoes and preparation method thereof |
| CN105419007A (en) * | 2015-12-30 | 2016-03-23 | 四川君格橡胶制品有限公司 | Tasteless formulation inner tube sizing material and processing process thereof |
| JP2019189747A (en) * | 2018-04-24 | 2019-10-31 | 住友ゴム工業株式会社 | Rubber composition for tire tread and tire |
| CN109467870A (en) * | 2018-10-29 | 2019-03-15 | 北方华锦化学工业股份有限公司 | A kind of low smell highly resistance, which is leapt high, flows ABS resin and preparation method thereof |
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