CN108203486A - Preparation method of environment-friendly oil-extended styrene-butadiene rubber - Google Patents
Preparation method of environment-friendly oil-extended styrene-butadiene rubber Download PDFInfo
- Publication number
- CN108203486A CN108203486A CN201611187533.0A CN201611187533A CN108203486A CN 108203486 A CN108203486 A CN 108203486A CN 201611187533 A CN201611187533 A CN 201611187533A CN 108203486 A CN108203486 A CN 108203486A
- Authority
- CN
- China
- Prior art keywords
- environment
- preparation
- parts
- friendly type
- type oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920003048 styrene butadiene rubber Polymers 0.000 title abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229920001971 elastomer Polymers 0.000 claims abstract description 40
- 239000005060 rubber Substances 0.000 claims abstract description 40
- 229920000126 latex Polymers 0.000 claims abstract description 25
- 239000004816 latex Substances 0.000 claims abstract description 25
- 238000011049 filling Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000008234 soft water Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 239000010692 aromatic oil Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 8
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000004945 emulsification Methods 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- NEUOBESLMIKJSB-UHFFFAOYSA-J tetrasodium;tetraacetate Chemical compound [Na+].[Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O NEUOBESLMIKJSB-UHFFFAOYSA-J 0.000 claims 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000839 emulsion Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 2
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000001112 coagulating effect Effects 0.000 abstract 1
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000711 cancerogenic effect Effects 0.000 description 6
- 231100000315 carcinogenic Toxicity 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- -1 Alkyl hydroxylamine Chemical compound 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012432 intermediate storage Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000010091 synthetic rubber production Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZLCCLBKPLLUIJC-UHFFFAOYSA-L disodium tetrasulfane-1,4-diide Chemical compound [Na+].[Na+].[S-]SS[S-] ZLCCLBKPLLUIJC-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of environment-friendly oil-extended styrene-butadiene rubber, which comprises the following steps: (1) sequentially adding soft water, an emulsifier, an electrolyte, a reducing agent, tert-dodecyl mercaptan, styrene and butadiene in a nitrogen atmosphere, reducing the temperature to 5-8 ℃, adding an initiator p-menthane hydroperoxide, and adding a terminator D600 to terminate the reaction when the conversion rate reaches 60% to obtain basic latex; the terminator D600 comprises the following components: n-isopropylhydroxylamine and tetraethylenepentamine; (2) and uniformly mixing the base latex and the filling oil emulsion, adding the mixture into a dilute sulfuric acid solution with the concentration of 0.4-0.6%, stirring, coagulating, washing and drying to obtain a crude rubber finished product.
Description
Technical field
The invention belongs to synthetic rubber production technical field, more particularly to a kind of improved high combinated styrene content environment-friendly type is filled
Oily butadiene-styrene rubber preparation method.
Background technology
Emulsion polymerized styrene butadiene rubber is global yield highest, the high synthetic rubber kind of consumption figure maximum, is mainly used in automobile
The fields such as tire, industrial conveyor, sebific duct.Oil classification whether is filled by it, emulsion polymerized styrene butadiene rubber can be divided into non-oil-filled series
Product and oil-filled series of products；By the textural classification of polymer, it is 23.5% that emulsion polymerized styrene butadiene rubber, which can be divided into styrene-content,
High structural type and higher combinated styrene content (31%, 35%, 40%) series of products.
With the enhancing of countries in the world environmental consciousness, some countries and regions, which are limited in rubber, uses condensed-nuclei aromatics
The higher high aromatic oil of compounds content and the rubber for filling such oil.European Union is about disabling condensed ring containing excess in tire production
The instruction (2005/69/EC) of the toxic rubber filling oil such as the aromatic naphtha of aromatic hydrocarbons is required in 1 day January in 2010 in tire production
Middle completely forbid uses toxic rubber oil.The filling that instruction regulation puts goods on the market is oily and for manufacturing condensed ring in the filling oil of tire
Aromatic hydrocarbons (PAHs) content is less than 3%；8 kinds of carcinogenic aromatic hydrocarbons total contents are less than 10mg/L.
SBR1769/1739 is the oil-extended styrene buadiene rubber of environment-friendly type, is the oil-extended styrene buadiene rubber of current usage amount maximum
The upgrading products of SBR1721, the cementing conjunction styrene-content in basis is 40.0%, the low condensed ring virtue of 37.5 parts of filling in 100 parts of glue
Hydrocarbon ils (or naphthenic oil), PAHs contents are less than 3% in oil product, and 8 kinds of carcinogenic aromatic hydrocarbons total contents are less than 10mg/L, are ring type fillings
Aromatic naphtha (or naphthenic oil) and the butadiene-styrene rubber without nitrosamine are protected, is widely used in cross-ply, radial tyre of passenger car
In light radial truck tire and other rubbers.
The production of SBR1769/1739 is divided into the production of base latex and two stages of filling of environment-friendly aromatic oil.With it is other
Emulsion polymerization process is the same, and SBR1769/1739 base latex polymerization processes are also required to use terminator.In the prior art, it is newborn
Most of terminator used in liquid polymerization (as being used for producing styrene butadiene rubber latex) is by dimethyl dithiocarbamate, two
Alkyl hydroxylamine, sodium nitrite composition.This unfavorable conditions combined is dialkylhydroxyamines and dimethyl dithiocarbamic acid
Salt is the precursor of Carcinogenic Nitrosamines, in the acidic environment of latex gel, easily forms secondary amine, secondary amine and nitrating agent such as Asia
Reaction of nitrogen oxides present in sodium nitrate, air forms carcinogenic substance-nitrosamine.It is an object of the present invention to provide one effectively
Terminator, the presence of no nitrosamine parent cannot also generate stability nitrosamine, meet what European Union formulated for this problem
The Principles of Chemistry TRGS552, and ensure that product is stablized, it also avoids in production and mixing and other process, generates carcinogenic
Object nitrosamine.
About the free-radical emulsion polymerization terminator for not generating nitrosamine, document discloses many kinds, major in the world
Synthetic rubber production company begins one's study new polymerization terminator, to substitute the dimethyl dithiocarbamic acid for easily forming secondary amine
Salt, dialkylhydroxyamines, to eliminate the formation of nitrosamine.
The method for having been proposed solving to form nitrosamine in United States Patent (USP) US4985326 and US5177164, the former adopts
Make the method for free radical polymerization termination with the carbodithioic acid phenol acids of non-nitrous amine precursor；The latter advocates only to be used alone more
For vulcanized sodium as reaction terminating agent, sodium polysulfide used is Na2S4, for 0.02-0.5phm, (phm is relative to 100 parts to dosage
The addition of pure monomer), the polymer of generation is made to be free of nitrosamine.But carbodithioic acid phenol acids is expensive, more sulphur
Change sodium and easily form sediment in the duct.
Isopropylhydroxyla or salt are used in US5384372, and as terminator, specific type has N- isopropylhydroxylas, second
Sour isopropylhydroxyla, hydrochloric acid isopropylhydroxyla, sulfuric acid isopropylhydroxyla, addition 0.05-0.2phm, Adding Way is with passing
The Adding Way of system process termination agent is identical, and the addition of its aqueous solution is reached in the polymerisation for requiring conversion ratio.It is but single
Solely using isopropylhydroxyla or salt, the environmentally friendly butadiene-styrene rubber properties of product of production are than traditional handicraft butadiene-styrene rubber as terminator
Difference cannot get the accreditation of tire applications client.
Invention content
The purpose of the invention is to avoid in emulsion polymerization SBR1769/1739 rubber process and product is prepared generation,
Carcinogenic substance-nitrosamine is remained, after traditional low temperature emulsion polymerisation process synthesis SBR1769/1739 latex, is had using specific
The terminator of effect terminates free-radical emulsion polymerization reaction, prepares SBR1769/1739 base latex, does not have nitrosamine in the process
The presence of parent cannot also generate stability nitrosamine, meet European Union and be directed to the Principles of Chemistry TRGS552 that this problem is formulated, and really
It protects properties of product to stablize, the tensile strength and stress at definite elongation of product are above domestic similar product.
It is an object of the present invention to emulsion polymerisation process synthesize SBR1769/1739 base latex after, using D600 for termination
Agent can effectively terminate SBR1769/ using the compound of N- isopropylhydroxylas and tetren as reaction terminating agent
1739 free-radical emulsion polymerizations react, and do not generate nitrosamine.0.05~0.1 part of N- isopropylhydroxylas in D600, four ethylenes five
0.3~0.4 part of amine.
Tetren is a kind of vulcanization accelerator of low toxicity, can be compounded well with N- isopropylhydroxylas, to the poly- fourth of breast
Benzene rubber has vulcanization facilitation well, can properly increase the performance of SBR1769/1739 products.
In order to achieve the above objectives, the present invention provides a kind of preparation method of environment-friendly type oil-extended styrene buadiene rubber, including following step
Suddenly：
(1) in nitrogen atmosphere, soft water, emulsifier, electrolyte, reducing agent, tert-dodecyl mercaptan, styrene are sequentially added
And butadiene, when cooling the temperature to 5 DEG C~8 DEG C, initiator hydrogen peroxide is added in Meng's alkane, when the conversion ratio of monomer reaches 60%
When, it adds in terminator D600 and terminates reaction, obtain base latex；The component that the terminator D600 is included is：N- isopropyl hydroxyls
Amine and tetren；
(2) by base latex with after filling fat liquor blending uniformly, being added to a concentration of 0.4%~0.6% dilute sulfuric acid
In solution, stirring after cohesion, washs drying, obtains raw rubber finished product.
The preparation method of environment-friendly type oil-extended styrene buadiene rubber of the present invention, in step (1), the parts by weight of each polymeric component
Number is preferably：
The preparation method of environment-friendly type oil-extended styrene buadiene rubber of the present invention, wherein, the terminator D600 each components
Parts by weight are preferably：0.05~0.1 part of N- isopropylhydroxylas, 0.3~0.4 part of tetren.
The preparation method of oil-extended styrene buadiene rubber of the present invention, these, it is preferred to, by the N- isopropylhydroxylas and
Tetren adds in stirred tank, and terminator D600 is made under agitation, and is sent to intermediate storage tank storage, intermediate storage tank bottom
Portion is equipped with back-mixing pump.On this condition, N- isopropylhydroxylas and tetren can be kept to be sufficiently mixed, and keeps solution
Homogeneity, so as to ensure the stable quality of final products.
The preparation method of environment-friendly type oil-extended styrene buadiene rubber of the present invention, wherein, the emulsifier is preferably disproportionated pine
Fragrant acid potash soap, parts by weight are preferably 4.0~5.0 parts.
The preparation method of environment-friendly type oil-extended styrene buadiene rubber of the present invention, wherein, component that the electrolyte includes and
Parts by weight are preferably：0.2~0.3 part of phosphoric acid, 0.3~0.5 part of potassium hydroxide, 0.03 part of tetrasodium salt of EDTA and ten
0.1~0.2 part of dialkyl benzene sulfonic acids sodium.
The preparation method of environment-friendly type oil-extended styrene buadiene rubber of the present invention, wherein, component that the reducing agent includes and
Parts by weight are preferably：0.01 part of ferrous sulfate, 0.03~0.05 part of rongalite and tetrasodium salt of EDTA
0.025 part.
The preparation method of environment-friendly type oil-extended styrene buadiene rubber of the present invention, in step (2), the condition of stirring is preferably：
Temperature 60 C~65 DEG C, time 5~10 minutes.
The preparation method of environment-friendly type oil-extended styrene buadiene rubber of the present invention, in step (2), the filling fat liquor includes
Component and part be preferably：
21.5~23.5 parts of TDAE environment-friendly aromatic oils (or naphthenic oil),
11.7~12.0 parts of water,
2.8~3.0 parts of isproportionated potassium rosinate.
Technical solution of the present invention is specific as follows：
(1) first to polymeric kettle carry out vacuum, nitrogen replace, successively by soft water, emulsifier, electrolyte solution, reducing agent,
Tert-dodecyl mercaptan, styrene, butadiene are added in polymeric kettle, when polymeric kettle temperature is down to 5 DEG C~8 DEG C, is added in and are caused
Agent hydrogen peroxide carries out polymerization experiment, when conversion ratio reaches 60%, adds in terminator and terminate reaction, obtain to Meng's alkane
SBR1769/1739 base latex；
(2) by after SBR1769/1739 base latex, with filling fat liquor blending uniformly, it is added to a concentration of 0.5%
In dilution heat of sulfuric acid, stirring, at 60 DEG C~65 DEG C, the time is 5 minutes~10 minutes for temperature control, after cohesion, washs drying, obtains
To raw rubber finished product.
The polymeric component and parts by weight that above-mentioned steps (1) include be：
The emulsifier be isproportionated potassium rosinate, preferably 4.0~5.0 parts of parts by weight.
The component and part that the electrolyte includes is：
The component and part that the reducing agent includes is：
0.01 part of ferrous sulfate
0.03~0.05 part of rongalite
0.025 part of tetrasodium salt of EDTA
The component and part that the terminator D600 is included is：
0.05~0.1 part of N- isopropylhydroxylas
0.3~0.4 part of tetren
The component and part that the filling fat liquor includes is：
21.5~23.5 parts of TDAE environment-friendly aromatic oils (or naphthenic oil)
11.7~12.0 parts of water
2.8~3.0 parts of isproportionated potassium rosinate.
Advantageous effect of the present invention：
In SBR1769/1739 base latex polymerisations, terminated freely using the specific effective terminator of the present invention
Emulsion polymerization reacts, and finally prepares SBR1769/1739 products, and the presence of no nitrosamine parent in the process also cannot
Stable nitrosamine is generated, nitrosamine specified in the oil-filled glue product of environment-friendly type does not detect, meets European Union and is formulated for this problem
The Principles of Chemistry TRGS552, and properties of product are suitable with the general combinated styrene content oil-extended styrene buadiene rubber of non-environmental protection type, environmental protection
35 minutes 300% stress at definite elongations of the oil-filled glue vulcanizate of type are higher than the oil-filled glue respective performances 0.5Mpa of non-environmental protection.
Specific embodiment
The present invention is described further for the following examples, but not thereby limiting the invention.
Embodiment 1
(1) vacuum is carried out to polymeric kettle first, nitrogen is replaced.Successively by soft water, emulsifier, electrolyte solution, reducing agent,
Tert-dodecyl mercaptan, styrene, butadiene are added in polymeric kettle, when polymeric kettle temperature is down to 7 DEG C, add in initiator peroxide
Change hydrogen to Meng's alkane, carry out polymerization experiment, when conversion ratio reaches 60%, add in terminator D600 and terminate reaction, obtain SBR1739
Base latex；
(2) by after SBR1739 base latex, with filling fat liquor blending uniformly, it is added to a concentration of 0.5% dilute sulfuric acid
In solution, stirring, at 62 DEG C, the time is 7 minutes for temperature control, after cohesion, washs drying, obtains raw rubber finished product.
The component and part that above-mentioned steps (1) emulsion polymerization includes is：
The emulsifier isproportionated potassium rosinate and its number are：4.5 part
The component and number that the electrolyte includes be：
The component and number that the reducing agent includes be：
0.01 part of ferrous sulfate
0.04 part of rongalite
0.025 part of tetrasodium salt of EDTA
The component and number that the terminator D600 is included be：
0.05 part of N- isopropylhydroxylas
0.30 part of tetren
The component and part that the filling fat liquor includes is：
22.5 parts of TDAE environment-friendly aromatic oils
11.8 parts of water
2.9 parts of isproportionated potassium rosinate
After testing, N-nitrosodimethylamine is not contained in SBR1739 samples, is environment-friendly type oil-extended styrene buadiene rubber.
Embodiment 2
(1) vacuum is carried out to polymeric kettle first, nitrogen is replaced.Successively by soft water, emulsifier, electrolyte solution, reducing agent,
Tert-dodecyl mercaptan, styrene, butadiene are added in polymeric kettle, when polymeric kettle temperature is down to 5 DEG C, add in initiator peroxide
Change hydrogen to Meng's alkane, carry out polymerization experiment, when conversion ratio reaches 60%, add in terminator D600 and terminate reaction, obtain SBR1739
Base latex；
(2) by after SBR1739 base latex, with filling fat liquor blending uniformly, it is added to a concentration of 0.5% dilute sulfuric acid
In solution, stirring, at 60 DEG C, the time is 5 minutes for temperature control, after cohesion, washs drying, obtains raw rubber finished product.
The component and part that above-mentioned steps (1) emulsion polymerization includes is：
The emulsifier isproportionated potassium rosinate and its number are：4.0 part
The component and number that the electrolyte includes be：
The component and number that the reducing agent includes be：
0.01 part of ferrous sulfate
0.03 part of rongalite
0.025 part of tetrasodium salt of EDTA
The component and number that the D600 is included be：
0.1 part of N- isopropylhydroxylas
0.4 part of tetren
The component and part that the filling fat liquor includes is：
21.5 parts of TDAE environment-friendly aromatic oils
11.7 parts of water
2.8 parts of isproportionated potassium rosinate
After testing, N-nitrosodimethylamine is not contained in SBR1739 samples, is environment-friendly type oil-extended styrene buadiene rubber.
Embodiment 3
(1) vacuum is carried out to polymeric kettle first, nitrogen is replaced.Successively by soft water, emulsifier, electrolyte solution, reducing agent,
Tert-dodecyl mercaptan, styrene, butadiene are added in polymeric kettle, when polymeric kettle temperature is down to 8 DEG C, add in initiator peroxide
Change hydrogen to Meng's alkane, carry out polymerization experiment, when conversion ratio reaches 60%, add in terminator D600 and terminate reaction, obtain SBR1739
Base latex；
(2) by after SBR1739 base latex, with filling fat liquor blending uniformly, it is added to a concentration of 0.5% dilute sulfuric acid
In solution, stirring, at 65 DEG C, the time is 10 minutes for temperature control, after cohesion, washs drying, obtains raw rubber finished product.
The component and part that above-mentioned steps (1) emulsion polymerization includes is：
The emulsifier isproportionated potassium rosinate and its number are：5.0 part
The component and number that the electrolyte includes be：
The component and number that the reducing agent includes be：
0.01 part of ferrous sulfate
0.05 part of rongalite
0.025 part of tetrasodium salt of EDTA
The component and number that the terminator D600 is included be：
0.07 part of N- isopropylhydroxylas
0.33 part of tetren
The component and part that the filling fat liquor includes is：
23.5 parts of TDAE environment-friendly aromatic oils
12.0 parts of water
3.0 parts of isproportionated potassium rosinate
After testing, N-nitrosodimethylamine is not contained in SBR1739 samples, is environment-friendly type oil-extended styrene buadiene rubber.
Comparative example 1
(1) vacuum is carried out to polymeric kettle first, nitrogen is replaced.Successively by soft water, emulsifier, electrolyte solution, reducing agent,
Tert-dodecyl mercaptan, styrene, butadiene are added in polymeric kettle, when polymeric kettle temperature is down to 5 DEG C, add in initiator peroxide
Change hydrogen to Meng's alkane, carry out polymerization experiment, when conversion ratio reaches 60%, it is whole to add in terminator sodium dimethyl dithiocarbamate
It only reacts, obtains non-environmental protection SBR1739 base latex (i.e. SBR1721 base latex).
(2) it is dilute with the uniform rear addition a concentration of 0.5% of filling fat liquor blending by non-environmental protection SBR1739 base latex
In sulfuric acid solution, stirring, at 60 DEG C, the time is 5 minutes for temperature control, after cohesion, washs drying, obtains raw rubber finished product.
The component and part that above-mentioned steps (1) emulsion polymerization includes is：
Mentioned emulsifier isproportionated potassium rosinate, parts by weight are 4.5 parts
The component and part that above-mentioned electrolyte includes is：
The component and part that above-mentioned reducing agent includes is：
0.01 part of ferrous sulfate
0.03 part of rongalite
0.025 part of tetrasodium salt of EDTA
The component and part that the filling fat liquor includes is：
22.5 parts of TDAE environment-friendly aromatic oils
11.8 parts of water
2.9 parts of isproportionated potassium rosinate
After testing, N-nitrosodimethylamine carcinogenic substance is contained in comparative example non-environmental protection SBR1739 samples.
1 embodiment 1 of table and the detection of 1 properties of product of comparative example
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
It should all belong to the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of environment-friendly type oil-extended styrene buadiene rubber, which is characterized in that include the following steps：
(1) in nitrogen atmosphere, soft water, emulsifier, electrolyte, reducing agent, tert-dodecyl mercaptan, styrene and fourth are sequentially added
Diene when cooling the temperature to 5 DEG C~8 DEG C, adds in initiator hydrogen peroxide to Meng's alkane, when the conversion ratio of monomer reaches 60%,
It adds in terminator D600 and terminates reaction, obtain base latex；The component that the terminator D600 is included is：N- isopropylhydroxylas and
Tetren；
(2) by base latex with after filling fat liquor blending uniformly, being added to a concentration of 0.4%~0.6% dilution heat of sulfuric acid
In, stirring after cohesion, washs drying, obtains raw rubber finished product.
2. the preparation method of environment-friendly type oil-extended styrene buadiene rubber according to claim 1, which is characterized in that in step (1), respectively
The parts by weight of polymeric component are：
3. the preparation method of environment-friendly type oil-extended styrene buadiene rubber according to claim 1 or 2, which is characterized in that the termination
The parts by weight of agent D600 each components are：0.05~0.1 part of N- isopropylhydroxylas, 0.3~0.4 part of tetren.
4. the preparation method of environment-friendly type oil-extended styrene buadiene rubber according to claim 3, which is characterized in that by the N- isopropyls
Base azanol and tetren add in stirred tank, and terminator D600 is made under agitation.
5. the preparation method of environment-friendly type oil-extended styrene buadiene rubber according to claim 1 or 2, which is characterized in that the emulsification
Agent is isproportionated potassium rosinate, and parts by weight are 4.0~5.0 parts.
6. the preparation method of environment-friendly type oil-extended styrene buadiene rubber according to claim 1 or 2, which is characterized in that the electrolysis
The component and part that matter includes is：0.2~0.3 part of phosphoric acid, 0.3~0.5 part of potassium hydroxide, tetrasodium salt of EDTA
0.03 part and 0.1~0.2 part of neopelex.
7. the preparation method of environment-friendly type oil-extended styrene buadiene rubber according to claim 1 or 2, which is characterized in that the reduction
The component and part that agent includes is：0.01 part of ferrous sulfate, 0.03~0.05 part of rongalite and ethylenediamine tetraacetic
0.025 part of acetic acid tetrasodium salt.
8. the preparation method of environment-friendly type oil-extended styrene buadiene rubber according to claim 1, which is characterized in that in step (2), stir
The condition mixed is：Temperature 60 C~65 DEG C, time 5~10 minutes.
9. the preparation method of environment-friendly type oil-extended styrene buadiene rubber according to claim 1, which is characterized in that in step (2), institute
Stating the component and part that filling fat liquor includes is：
21.5~23.5 parts of TDAE environment-friendly aromatic oils (or naphthenic oil),
11.7~12.0 parts of water,
2.8~3.0 parts of isproportionated potassium rosinate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187533.0A CN108203486A (en) | 2016-12-20 | 2016-12-20 | Preparation method of environment-friendly oil-extended styrene-butadiene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187533.0A CN108203486A (en) | 2016-12-20 | 2016-12-20 | Preparation method of environment-friendly oil-extended styrene-butadiene rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108203486A true CN108203486A (en) | 2018-06-26 |
Family
ID=62604283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611187533.0A Pending CN108203486A (en) | 2016-12-20 | 2016-12-20 | Preparation method of environment-friendly oil-extended styrene-butadiene rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108203486A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111518324A (en) * | 2019-02-03 | 2020-08-11 | 中国石油天然气股份有限公司 | Environment-friendly oil-extended styrene-butadiene rubber and preparation method thereof |
| CN111560096A (en) * | 2019-02-14 | 2020-08-21 | 中国石油天然气股份有限公司 | Preparation method of styrene butadiene rubber |
| CN114805686A (en) * | 2021-01-19 | 2022-07-29 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288014A (en) * | 1999-09-09 | 2001-03-21 | 阿托费纳化学股份有限公司 | Composite for inhibiting nitrosamine for quick stopping free-radical emulsion polymerization |
| CN104927127A (en) * | 2014-03-20 | 2015-09-23 | 南京扬子石化金浦橡胶有限公司 | Production method of environment-friendly butadiene styrene rubber |
| CN105985455A (en) * | 2015-02-15 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of low-odor oil-extended styrene-butadiene rubber |
-
2016
- 2016-12-20 CN CN201611187533.0A patent/CN108203486A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288014A (en) * | 1999-09-09 | 2001-03-21 | 阿托费纳化学股份有限公司 | Composite for inhibiting nitrosamine for quick stopping free-radical emulsion polymerization |
| CN104927127A (en) * | 2014-03-20 | 2015-09-23 | 南京扬子石化金浦橡胶有限公司 | Production method of environment-friendly butadiene styrene rubber |
| CN105985455A (en) * | 2015-02-15 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of low-odor oil-extended styrene-butadiene rubber |
Non-Patent Citations (2)
| Title |
|---|
| 何天白 等: "《功能高分子与新技术》", 31 January 2001, 化学工业出版社 * |
| 朱洪法: "《精细化工常用原材料手册》", 31 December 2003, 金盾出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111518324A (en) * | 2019-02-03 | 2020-08-11 | 中国石油天然气股份有限公司 | Environment-friendly oil-extended styrene-butadiene rubber and preparation method thereof |
| CN111518324B (en) * | 2019-02-03 | 2022-08-05 | 中国石油天然气股份有限公司 | Environment-friendly oil-extended styrene-butadiene rubber and preparation method thereof |
| CN111560096A (en) * | 2019-02-14 | 2020-08-21 | 中国石油天然气股份有限公司 | Preparation method of styrene butadiene rubber |
| CN114805686A (en) * | 2021-01-19 | 2022-07-29 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber and preparation method thereof |
| CN114805686B (en) * | 2021-01-19 | 2024-03-01 | 中国石油天然气股份有限公司 | Oil-extended styrene butadiene rubber and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102070751B (en) | Paracril | |
| CN104945817B (en) | A kind of itaconate/butadiene copolymer type biological engineering rubber and preparation method thereof | |
| CN105778002B (en) | Method for preparing carboxylated styrene-butadiene rubber by emulsion polymerization | |
| CN105837752B (en) | Preparation method of cold-resistant nitrile rubber | |
| CN109776726B (en) | Preparation method of styrene butadiene rubber and styrene butadiene rubber | |
| US8119728B2 (en) | Storage-stable, hydroxy-modified microgel latices | |
| CN108203486A (en) | Preparation method of environment-friendly oil-extended styrene-butadiene rubber | |
| EP2242802A2 (en) | Hydrolysis-resistant polyamide-elastomer mixtures, molded parts produced therefrom and use thereof | |
| CN101735391B (en) | Composition for terminating emulsion polymerized styrene butadiene rubber without producing nitrosamine | |
| CN105837753B (en) | Preparation method of carboxyl nitrile rubber | |
| CN108203523A (en) | Preparation method of oil-extended styrene-butadiene rubber | |
| CN105732847B (en) | Composition for terminating emulsion polymerization without producing nitrosamines | |
| CN105837754B (en) | Preparation method of carboxyl nitrile rubber | |
| CN111019046A (en) | Preparation method of nitrile rubber | |
| CN102952237A (en) | Preparation method of epoxidized nitrile rubber | |
| CN111518324B (en) | Environment-friendly oil-extended styrene-butadiene rubber and preparation method thereof | |
| CN111763285B (en) | Methyl styrene-butadiene rubber and preparation method thereof | |
| CN115304711A (en) | Modified emulsion polymerized styrene-butadiene rubber latex, modified emulsion polymerized styrene-butadiene rubber and preparation method of modified emulsion polymerized styrene-butadiene rubber latex and modified emulsion polymerized styrene-butadiene rubber | |
| CN1217960C (en) | Preparation method of emulsion polymerized rubber without nitroso compound | |
| CN110357988B (en) | Composition for terminating free radical polymerization reaction and preparation method of styrene butadiene rubber | |
| CN111560096B (en) | Preparation method of styrene butadiene rubber | |
| CN103421146B (en) | Preparation method of nitrile rubber with high acrylonitrile content | |
| CN114805686B (en) | Oil-extended styrene butadiene rubber and preparation method thereof | |
| RU2771752C1 (en) | Nitrile butadiene latex, dip latex composition, dip product | |
| CN1221575C (en) | Polymerized rubber containing chloroparaffins and its preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180626 |