CN106750666A - A kind of preparation method and applications of plant polyphenol base rubber accelerator - Google Patents
A kind of preparation method and applications of plant polyphenol base rubber accelerator Download PDFInfo
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- CN106750666A CN106750666A CN201611034924.9A CN201611034924A CN106750666A CN 106750666 A CN106750666 A CN 106750666A CN 201611034924 A CN201611034924 A CN 201611034924A CN 106750666 A CN106750666 A CN 106750666A
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- Prior art keywords
- rubber
- plant polyphenol
- accelerator
- preparation
- plant
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- 235000013824 polyphenols Nutrition 0.000 title claims abstract description 70
- 150000008442 polyphenolic compounds Chemical class 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004073 vulcanization Methods 0.000 claims abstract description 19
- 239000012467 final product Substances 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000010355 oscillation Effects 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract 5
- 235000019441 ethanol Nutrition 0.000 claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000010058 rubber compounding Methods 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- -1 silica compound Chemical class 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 4
- GGCJLWBMJYGIRE-UHFFFAOYSA-N ethanol;formaldehyde Chemical compound O=C.CCO GGCJLWBMJYGIRE-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 47
- 239000002585 base Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000006870 function Effects 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000013539 mentalization-based treatment Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000010057 rubber processing Methods 0.000 description 4
- 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 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 235000001508 sulfur Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- HARGZZNYNSYSGJ-JTQLQIEISA-N Dihydrotanshinone I Chemical compound C1=CC2=C(C)C=CC=C2C(C(=O)C2=O)=C1C1=C2[C@@H](C)CO1 HARGZZNYNSYSGJ-JTQLQIEISA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DPAJXTFPOAFNQG-ILKKLZGPSA-N [La].NC(=S)S.C(CC)N[C@@H](CCO)C(=O)O Chemical compound [La].NC(=S)S.C(CC)N[C@@H](CCO)C(=O)O DPAJXTFPOAFNQG-ILKKLZGPSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HOEFWOBLOGZQIQ-UHFFFAOYSA-N morpholin-4-yl morpholine-4-carbodithioate Chemical compound C1COCCN1C(=S)SN1CCOCC1 HOEFWOBLOGZQIQ-UHFFFAOYSA-N 0.000 description 1
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 1
- ILSQBBRAYMWZLQ-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-propan-2-ylpropan-2-amine Chemical compound C1=CC=C2SC(SN(C(C)C)C(C)C)=NC2=C1 ILSQBBRAYMWZLQ-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 125000004402 polyphenol group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- JYPIENNPOPULKF-UHFFFAOYSA-N s-butylthiohydroxylamine Chemical class CCCCSN JYPIENNPOPULKF-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/72—2-Mercaptobenzothiazole
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
Abstract
The invention discloses a kind of preparation method and applications of plant polyphenol base rubber accelerator, (1) will be dissolved in formaldehyde ethanol solution containing the secondary amine of rubber promotion base and stir;(2) it is refluxed in acid adjustment water-bath;(3) by plant polyphenol addition absolute ethyl alcohol, acid adjustment sonic oscillation continues to react;(4) by product in stand at low temperature, filtering;(5) distilled water, plant polyphenol Quito function promoter is added to separate out filtrate, washing, suction filtration, drying obtain final product final product.Collection promotes the vulcanization of rubber, white carbon surface modified and prevents the multiple actions such as ageing of rubber with one, it is a kind of Multifunctional rubber accelerator, with it is environment-friendly the characteristics of, the preparation condition of the multifunctional assistant is gentle, and byproduct of reaction is few, and yield is high, low cost, meet the requirement of " green chemical industry ", be applied in silica compound that the strength and extension property and dynamic mechanical of rubber can be effectively improved, can be in green tire tread rubber.
Description
Technical field
The invention belongs to the preparation method technical field of accelerator, and in particular to a kind of plant polyphenol base rubber accelerator
Preparation method and applications.
Background technology
Rubber chemicals are the important auxiliary materials of rubber industry.By traditional classification, rubber chemicals are divided into vulcanization aid, protection
Auxiliary agent, processing aid and other major classes of special functional rubber chemicals four.In rubber industry, although auxiliary dosage is relatively very
It is small, but very important effect is played to product processing and the improvement of application performance.The development of rubber chemicals gradually shows height
The features such as relative molecular mass, multi-functional, high-performance, greenization, Composite.
Thiofide is the very important rubber processing aids of a class, and traditional rubber accelerator only serves promotion
Vulcanization of rubber crosslinking, the effect for shortening cure time.In sulfidation, the functional group of vulcanization accelerator take part in vulcanization instead
Should, form the suspension side chain in vulcanization reaction later stage, these pendent groups, not having to the raising of rubber composite performance has
The help of benefit.And these rubber tradition accelerator can also migrate or discharge poisonous small molecule, band in use
Carry out environmental pollution.Therefore exploitation " one multipotency ", the multi-functional accelerator of rubber of " environment-friendly high-efficiency " be rubber chemicals field very
Important research contents.
Into the nineties in 20th century, internationally famous tyre company Goodyear, Michelin, Bridgeston etc. are pushed away in succession
It is " green tire " (or the fuel-saving tire) of purport to have gone out to save fuel oil and reduce waste gas discharge, with common radial phase
Energy consumption than green tire is greatly reduced.Thus greatly developing for " green tire " has greatly promoted the hair of " Green Additives "
Exhibition.Prepare the developing direction that environmentally friendly, efficient, multi-functional rubber accelerator is current rubber chemicals both at home and abroad.
Current white carbon black/solution polymerized butadiene styrene rubber balanced constant is the conventional ligand for preparing High-performance green tire tread glue
System, but white carbon particle diameter is small, surface polarity greatly with the poor compatibility of rubber, therefore easily reunite and be difficult to disperse.Therefore white carbon
Surface is needed to be modified, stuffing surface modification agent usually used at present includes titanate coupling agent and silane coupler etc..But this
There is the shortcomings of produce small molecule and poor storage stability in poor processability, modifying process in the surface modifier of a little small molecules.
Develop with promoting the vulcanization of rubber and improve the Multifunctional rubber accelerator of white carbon-rubber interface effect to cause that people's is wide
General concern.
Because the accelerator containing secondary amine can produce carcinogen nitrosamine in sulfidation, exist to health latent
Threatening.Therefore in recent ten years, external several top auxiliary agent manufacturer input substantial contributions and technical force develop into
Work(some without nitrosamine or the accelerator new varieties to nitrosamine safety, the relatively more representational N- for having a Flexsys companies
Double benzothiazoles sulfenamide (TBSI) of the tert-butyl group -2-, N- cyclohexyl-bis- (2-[4-morpholinodithio) secondary sulphonyl of Uniroyal companies
Amine (ESVE or CBSA) and the N- oxygen diethylidene sulphide amino formyl-N- tert. butyl sulphenamides of Goodyear companies
(OTTOS), these sulfenamide type accelerators can be used as the substitute of NOBS, DIBS and OTOS.Flexsys companies develop
Success two is hydrated six methines, 1,6 pairs of thiosulfuric acid disodiums (i.e. DHTS or HTS), can form the hybrid cross-linked network of flexible.This
Planting cross-linked structure can suppress the change of the aging cross-linked structure and crosslink density for causing of over cure, high temperature vulcanized and anoxybiotic, Jin Erfang
Physical property deterioration only relevant with reverting and dynamic property decline.But these modified accelerator are still present unitary function
Shortcoming, and molecular weight is low, easily separates out.
Current white carbon black/solution polymerized butadiene styrene rubber balanced constant is the conventional ligand for preparing High-performance green tire tread glue
System, therefore exploitation causes the extensive concern of people for the multifunctional assistant of white carbon system.Patent 200810220321.7 will
2- benzothiazolyl mercaptans and alkali soluble are subsequently adding chlorocarbon base silane in organic solvent, it is reacted be prepared for collection promote vulcanization,
The Multifunctional rubber processing aid of the functions such as plasticising and reinforcement.Patent 201210013339.6 is sweet by coupling agent γ-shrink
Oily ether propyl trimethoxy silicane reacts under certain condition with mutual-amido two polyaniline (PPDA), is prepared for white carbon surface
Novel multifunctional additive that is modified and preventing ageing of rubber double action.Willow face etc. synthesizes two kinds of rare earth rubber accelerator paddy
Propylhomoserin aminodithioformic acid lanthanum (La-GDTC) and N- phenyl-N'- (γ-triethoxysilane)-propyl group-thiocarbamide (STU), knot
Fruit finds that both rare earth accelerator have the double action for improving curingprocess rate and improving filler-rubber interface.These are prepared
Method technique is all harsher, and production cost is higher, and molecular weight product is low, it is difficult to improve consumption it is big when easily separate out lack
Point.
The content of the invention
There is unitary function for the accelerator being modified present in prior art and molecular weight is low, the technology for easily separating out is asked
Topic, it is an object of the invention to provide a kind of preparation method and applications of plant polyphenol base rubber accelerator, wherein, plant is more
The preparation method of phenolic group Multifunctional rubber accelerator, the selection, proportioning, reaction temperature, time and pH value including raw material etc., and
The separation of product, method of purification.Plant polyphenol Quito functional rubber is promoted to be applied to the technology of rubber, including addition component,
Method etc. and addition sequence (being added together with white carbon).It is i.e. specifically related to a kind of with plant polyphenol as matrix, using " one pot two
Footwork " prepares plant polyphenol Quito function promoter, and preparing has " the promotion vulcanization of rubber ", " white carbon surface is modified " and " prevent
It is only aging " etc. the multi-functional rubber processing aids with one, and application technology of the New-type adjuvant in silica compound.
The technical scheme that the present invention takes is:
A kind of preparation method of plant polyphenol base rubber accelerator, it is characterised in that specifically include following steps:
(1) by a certain amount of secondary amine containing rubber promotion base, it is dissolved in the ethanol solution of 100ml formaldehyde, formaldehyde:
The volume ratio of ethanol is 6:94ml/ml, secondary amine quality:The mass volume ratio of anhydrous ethanol solvent is 1:5-10g/ml, stirring
10-20min, makes mixture fully dissolve;
(2) with acid regulation PH=3-6, mixture is inserted in the there-necked flask of 500ml specifications, in 70-90 DEG C of water-bath
Condensing reflux stirs 3-6h, and heating stirring makes formaldehyde fully be reacted with secondary amine;
(3) by a certain amount of plant polyphenol add absolute ethyl alcohol in, plant polyphenol:The mass volume ratio of anhydrous ethanol solvent
It is 1:5-10g/ml, with acid regulation pH value 3-6, sonic oscillation 5min;Plant polyphenol ethanol solution is added prepared by step (2)
Continue to react 3-9h in solution;Plant polyphenol fully participates in reaction, and the synthesis of new accelerator is completed jointly, molten in course of reaction
Liquid color is gradually transparent;
(4) by product at -10 DEG C stand at low temperature 2 days, make unreacted imines separate out, be filtrated to get filtrate;
(5) by distilled water and filtrate by volume 4:1 ratio mixing, plant polyphenol Quito function promotes in mixed process
Agent is separated out, and is then washed 3 times, suction filtration, 60 DEG C of drying 6h, obtains final product final product.
Further, it is MBT or the tertiary fourths of N- to promote the secondary amine of base containing rubber in the step (1)
Base -2-[4-morpholinodithio sulfenamide.
Further, obtained final product is plant polyphenol base rubber accelerator in the step (5), and its molecular weight is
611-682。
Further, 1-3phr plant polyphenol bases rubber accelerator is replaced into the accelerator in former rubber compounding.Above-mentioned system
Accelerator obtained in Preparation Method is applied to the preparation method of rubber, it is characterised in that specifically include following steps:
(1) banburying:By plant polyphenol Quito functional rubber accelerator and white carbon in mass ratio 1:12.5 are added to together
In banbury, 70-90 DEG C of mixing a period of time 10min of control melting temperature, it is therefore an objective to make sizing material tentatively be mixed with inserts
Close;
(2) mill:Sizing material after banburying is carried out into compressing tablet on a mill, the sulphur of blend glue stuff mass ratio 0.9% is added
Huang, it is thin logical 6 times as the crosslinking agent of the vulcanization of rubber, bottom sheet after triangle bag is beaten, obtain elastomeric compound;
(3) determine:The glue of 5g or so is cut off on elastomeric compound, be placed on vulcameter set the cure time of elastomeric compound as
90s;
(4) shape:To be vulcanized under the certain temperature and pressure of elastomeric compound, obtained vulcanizate.
Further, the temperature in the step (4) is 160 DEG C, and pressure is 10M Pa, and cure time determines for vulcameter
Time be 90s.
Beneficial effects of the present invention are:
It is primary raw material that the present invention uses bio-based materials plant polyphenol, is prepared for the multi-functional rubber for silica compound
Promoter for rubber.
Multifunctional rubber accelerator of the invention has advantages below:
1. collection promotes the vulcanization of rubber, white carbon surface modified and prevents the multiple actions such as ageing of rubber and one, is a kind of
Multifunctional rubber accelerator.
2. plant polyphenol is a kind of biomaterial, and from nature, therefore the multifunctional assistant has environment-friendly spy
Point.
3. the preparation condition of the multifunctional assistant is gentle, and byproduct of reaction is few, and yield is high, and low cost meets " greenization
The requirement of work ".
4. it is applied in silica compound that the strength and extension property and dynamic mechanical of rubber can be effectively improved, can Ying Yu
In green tire tread rubber.
5. it is applied to dialogue carbon blacksurface to be modified to a certain extent in silica compound, improves the reinforcement of white carbon
Effect.
Multifunctional rubber accelerator of the invention is applied in rubber, is had the advantage that:
1. the accelerator in original formulation can wholly or in part be replaced, with curing efficiency higher, while improving vulcanization
The crosslink density of glue.
2. the interaction of white carbon-rubber can be improved, the dispersion of white carbon is improved, so as to improve strong the stretching property of rubber
Energy.
3. acted on certain anti-aging, improve the service life of rubber.
4. it is applied in silica compound that the dynamic mechanical of rubber can be effectively improved, can be in green tire tire
In the glue of face.
5. the time of scorch for being applied to vulcanizate in silica compound increases, the vulcanized rubber for improving to a certain extent
Processed safely performance.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of TPM in the present invention.
Fig. 2 is the infrared spectrogram of TPN in the present invention.
Fig. 3 is influence figures of the TPM and TPN to SSBR2557A rubber vulcanization characteristics.
Specific embodiment
The preparation of the plant polyphenol base rubber accelerator TPM of embodiment 1
A kind of preparation method of plant polyphenol base rubber accelerator, specifically includes following steps:
(1) 10g MBTs (MBT) are weighed, is dissolved in the ethanol solution of 50ml formaldehyde, stirred at room temperature
10min;
(2) PH=3 is adjusted with hydrochloric acid, 6h is refluxed in 70 DEG C of water-baths;
(3) by 10g plant polyphenols addition 50ml absolute ethyl alcohols, PH=3, sonic oscillation 5min are adjusted with hydrochloric acid;
(4) in the solution for adding step (2) to prepare plant polyphenol ethanol solution in step (3), continue anti-at 70 DEG C
Answer 9h;
(5) by product at -10 DEG C stand at low temperature 2 days, make unreacted MBT separate out, filtering;
(6) filtrate is added into distilled water, plant polyphenol Quito function promoter is separated out, is then washed 3 times, suction filtration, 60 DEG C
Drying 6h, obtains final product final product, and form is light brown powder TPM, and yield is 67%.
The preparation of the plant polyphenol base rubber accelerator TPN of embodiment 2
A kind of preparation method of plant polyphenol base rubber accelerator, specifically includes following steps:
(1) 10g N tert butyl benzothiazole 2 sulfenamides (NS) are weighed, are dissolved in the ethanol solution of 100ml formaldehyde,
10min is stirred at room temperature;
(2) PH=4 is adjusted with hydrochloric acid, 3h is refluxed in 80 DEG C of water-baths;
(3) by 10g plant polyphenols addition 100ml absolute ethyl alcohols, PH=4, sonic oscillation 5min are adjusted with hydrochloric acid;
(4) in the solution for adding step (2) to prepare plant polyphenol ethanol solution in step (3), continue anti-at 80 DEG C
Answer 5h;
(5) by product at -10 DEG C stand at low temperature 2 days, make unreacted NS separate out, filtering;
(6) filtrate is added into distilled water, plant polyphenol Quito function promoter is separated out, is then washed 3 times, suction filtration, 80 DEG C
Drying 6h, obtains final product final product, and form is light brown powder TPN, and yield is 70.7%.
The preparation of the plant polyphenol base rubber accelerator TPM of embodiment 3
A kind of preparation method of plant polyphenol base rubber accelerator, specifically includes following steps:
(1) 10g MBTs (MBT) are weighed, is dissolved in the ethanol solution of 100ml formaldehyde, stirred at room temperature
10min;
(2) PH=6 is adjusted with hydrochloric acid, 3h is refluxed in 90 DEG C of water-baths;
(3) by 10g plant polyphenols addition 100ml absolute ethyl alcohols, PH=6, sonic oscillation 5min are adjusted with hydrochloric acid;
(4) in the solution for adding step (2) to prepare plant polyphenol ethanol solution in step (3), continue anti-at 90 DEG C
Answer 3h;
(5) by product at -10 DEG C stand at low temperature 3 days, make unreacted MBT separate out, filtering;
(6) filtrate is added into distilled water, plant polyphenol Quito function promoter is separated out, is then washed 3 times, suction filtration, 60 DEG C
Drying 6h, obtains final product final product, and form is light brown powder TPM, and yield is 74.6%.
The structural characterization of embodiment 4TPM and TPN
The TPM and embodiment synthesized in embodiment 1 and 3 using fourier transform infrared spectroscopy (FTIR) to synthesis
The TPN synthesized in 2 carries out structural characterization.
The infrared curve of TP can be seen that 3200~3600cm from Fig. 1-1Belong to stretching for O-H keys in Tea Polyphenols (TP)
Contracting vibration, 1200cm-1It is the absworption peak of Tea Polyphenols C-O keys.Fig. 1 TPM are carried out into contrast discovery with figure TP, TPM is in 1650-
2000cm-1There is the quartet of phenyl ring in place, and in 3200~3600cm-1There is absworption peak wide at place, belongs to Tea Polyphenols O-H keys
Stretching vibration, 1200cm-1There is a small absworption peak at place, can belong to Tea Polyphenols C-O keys.To sum up analyze, some features of TPM
Absworption peak is consistent with some characteristic peaks of captax, while also some essential characteristic peaks containing TP, in sum, have prepared
Go out new rubber chemicals TPM.
It can be seen that being located at 3300cm in the IR curves of NS from Fig. 2-1Left and right is the characteristic peak of NH, 3050cm-1Left and right
Small peak is the stretching vibration of aromatic ring, 2920cm-1Peak is the stretching vibration of saturation C-H, 1450cm-1、1420cm-1Left and right is virtue
The skeleton stretching vibration of ring, 754cm-1Left and right is the substitution characteristic absorption of ortho position two on aromatic ring.
The IR curves of TPN can be seen that 3200~3600cm from Fig. 2-1Belong to the flexible of O-H keys in Tea Polyphenols (TP)
Vibration, 1200cm-1It is the absworption peak of Tea Polyphenols C-O keys.In 754cm-1Left and right is the substitution feature suction of ortho position two on aromatic ring
Receive, this is the characteristic absorption peak of phenyl ring, and originally accelerator NS is in 3300cm-1NH characteristic peaks disappear, and illustrate that accelerator NS and tea are more
Phenol reacts Mannich reaction, and TPN is successfully prepared out.
The plant polyphenol base rubber accelerator of embodiment 5 is applied to the preparation method of rubber
(1) knead:By 137.5g ESSBR2535E add banbury in, then by 50g white carbons, 5g plant polyphenols base promote
Enter agent TPM and Si69 4g to be added in banbury together, auxiliary material zinc oxide 3g, stearic acid 1g, DPG 1.5g are added, close
Mix 10min in mill.Above-mentioned mixing initial temperature is 70 DEG C, mixing 70 turns/min of rotating speed, and mixing total time is 8min;
(2) mill:Sizing material after banburying is carried out into compressing tablet on a mill, adds 1.76g Sulfurs thin logical 6 times, beat triangle
Bottom sheet after bag;
(3) vulcanization sizing:To be vulcanized under 160 DEG C of elastomeric compound, 10MPa pressure, cure time is to be determined by vulcameter
Technique sulfurizing time t90, you can obtain vulcanizate.
The plant polyphenol base rubber accelerator of embodiment 6 is applied to the preparation method of rubber
(1) knead:By 137.5g ESSBR2535E add banbury in, then by 50g white carbons, 5g plant polyphenols base promote
Enter agent TPN and Si69 4g to be added in banbury together, auxiliary material zinc oxide 3g, stearic acid 1g, DPG 1.5g are added, close
Mix 10min in mill.Above-mentioned mixing initial temperature is 70 DEG C, mixing 70 turns/min of rotating speed, and mixing total time is 8min;
(2) mill:Sizing material after banburying is carried out into compressing tablet on a mill, adds 1.76g Sulfurs thin logical 6 times, beat triangle
Bottom sheet after bag;
(3) vulcanization sizing:To be vulcanized under 160 DEG C of elastomeric compound, 10MPa pressure, cure time is to be determined by vulcameter
Technique sulfurizing time t90, you can obtain vulcanizate.
Reference examples using prior art Central Plains rubber compounding it is traditional captax substitution embodiment 5 and 6 in TPM or
TPN, the vulcanization characteristics curve of elastomeric compound is as shown in Figure 3.
From figure 3, it can be seen that adding curingprocess rates and traditional captax (reference examples) of the TPM and TPN to white carbon
Promote vulcanization activity be more or less the same, and vulcanizate highest moment of torsion all higher than reference examples sizing material, this explanation TPM and TPN
The crosslink density of vulcanizate can be improved.
The physical and mechanical properties of vulcanizate is as shown in table 1.
The influence of table 1TPM, TPN to vulcanized mechanical
From table 1 it follows that compared to control group, the tensile strength of TPM and TPN vulcanizates, tearing strength, break and stretch
Rate long and hardness all increase.Illustrate that TPM and TPN dialogue carbon blacksurface can be modified to a certain extent, improve white carbon
Strengthening action.And after aging 48h at 100 DEG C, the stretching strength retentivity of TPM and TPN vulcanizates is above control group, says
Bright TPM and TPN also have the effect for preventing ageing of rubber.
General principle of the invention is as follows:
Plant polyphenol is the general name of more than the 30 kinds of Polyphenols and its derivative extracted from plant, has rich on its strand
Rich hydroxyl, with molecular weight and molecular weight distribution wider higher.Technical grade other plant polyphenol is from plant, trees
Extracted in skin, root, leaf, therefore cost is relatively low.There is substantial amounts of phenolic hydroxyl group, mean molecule quantity is 432 left in plant polyphenol structure
The right side, will be big than general traditional rubber accelerator.Phenolic hydroxyl group on plant polyphenol can form hydrogen with the hydroxyl on white carbon
Key and free radical can be adsorbed, can be as the surface modifier of white carbon and age resistor, with the potentiality applied in rubber.
This paper is by plant polyphenol and formaldehyde, imines rubber accelerator (MBT or the N- tert-butyl groups -2-[4-morpholinodithio
Sulfenamide) reaction be prepared for new Multifunctional rubber accelerator, multi-functional accelerator collection " the promotion vulcanization of rubber ", " hard charcoal
Black surface is modified " and " preventing ageing of rubber " etc. it is multi-functional with integrally, for the excellent green tire of processability provides multi-functional
Natural, green, efficient New Processing Aid provide practical basis.
This project is based on plant polyphenol and is rich in phenolic hydroxyl group, and phenolic hydroxyl group faces a more active premise of benzene ring hydrogen,
Under acid catalysis, phenolic hydroxyl group faces a benzene ring hydrogen can occur Mannich addition reaction with formaldehyde, secondary amine (or ammonia).By choosing
The secondary amine (such as MBT or N tert butyl benzothiazole 2 sulfenamide) for promoting base with rubber is selected, just
Plant polyphenol base rubber accelerator can be prepared.And on plant polyphenol base rubber accelerator retain phenolic hydroxyl group can with it is white
Hydroxyl on carbon black forms hydrogen bond and can adsorb free radical, therefore have can be as the surface modifier of white carbon and anti-old
Agent.Therefore the tea-polyphenol base rubber accelerator has " the promotion vulcanization of rubber ", " white carbon surface is modified " and " prevents rubber simultaneously
It is aging " etc. function.It is a kind of Multifunctional rubber processing aid of environmental protection.
The above is not limitation of the present invention, it should be pointed out that:Come for those skilled in the art
Say, on the premise of essential scope of the present invention is not departed from, some changes, remodeling, addition can also be made or replaced, these improvement
Protection scope of the present invention is also should be regarded as with retouching.
Claims (6)
1. a kind of preparation method of plant polyphenol base rubber accelerator, it is characterised in that specifically include following steps:
(1) by a certain amount of secondary amine containing rubber promotion base, it is dissolved in the ethanol solution of 100ml formaldehyde, formaldehyde:Ethanol
Volume ratio be 6:94ml/ml, secondary amine quality:The mass volume ratio of anhydrous ethanol solvent is 1:5-10g/ml, stirs 10-
20min, makes mixture fully dissolve;
(2) with acid regulation PH=3-6, mixture is inserted in there-necked flask, the condensing reflux stirring 3- in 70-90 DEG C of water-bath
6h, heating stirring makes formaldehyde fully be reacted with secondary amine;
(3) by a certain amount of plant polyphenol add absolute ethyl alcohol in, plant polyphenol:The mass volume ratio of anhydrous ethanol solvent is 1:
5-10g/ml, with acid regulation pH value 3-6, sonic oscillation 5min;Plant polyphenol ethanol solution is added the solution of step (2) preparation
It is middle to continue to react 3-9h;Reaction is gradually transparent to solution colour;
(4) by product at -10 DEG C stand at low temperature 2 days, make unreacted imines separate out, be filtrated to get filtrate;
(5) by distilled water and filtrate by volume 4:1 ratio mixing, function promoter analysis in plant polyphenol Quito in mixed process
Go out, then wash 3 times, suction filtration, 60 DEG C of drying 6h obtain final product final product.
2. a kind of preparation method of plant polyphenol base rubber accelerator according to claim 1, it is characterised in that the step
(1) it is MBT or N tert butyl benzothiazole 2 sulfenamide to promote the secondary amine of base containing rubber in.
3. a kind of preparation method of plant polyphenol base rubber accelerator according to claim 1, it is characterised in that the step
(5) obtained final product is plant polyphenol base rubber accelerator in, and its molecular weight is 611-682.
4. application of the accelerator obtained in preparation method in rubber according to claim 1, it is characterised in that by 1-3phr
Accelerator in the former rubber compounding of plant polyphenol base rubber accelerator substitution.
5. accelerator obtained in preparation method is applied to the preparation method of rubber according to claim 1, it is characterised in that tool
Body comprises the following steps:
(1) banburying:By plant polyphenol Quito functional rubber accelerator and white carbon in mass ratio 1:12.5 are added to banburying together
In machine, 70-90 DEG C of mixing 10min of control melting temperature makes sizing material tentatively be mixed with inserts;
(2) mill:Sizing material after banburying is carried out into compressing tablet on a mill, the Sulfur of blend glue stuff mass ratio 0.9% is added, made
It is the crosslinking agent of the vulcanization of rubber, it is thin logical 6 times, bottom sheet after triangle bag is beaten, obtain elastomeric compound;
(3) determine:The glue of 5g or so is cut off on elastomeric compound, it is 90s to be placed on vulcameter and set the cure time of elastomeric compound;
(4) shape:To be vulcanized under the certain temperature and pressure of elastomeric compound, obtained vulcanizate.
6. accelerator is applied to the synthetic method of vulcanizate according to claim 5, it is characterised in that in the step (4)
Temperature be 160 DEG C, pressure be 10M Pa, cure time be vulcameter determine time 90s.
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