CN103804735A - Preparation method of modified oil-extended powder styrene-butadiene rubber - Google Patents

Preparation method of modified oil-extended powder styrene-butadiene rubber Download PDF

Info

Publication number
CN103804735A
CN103804735A CN201210455259.6A CN201210455259A CN103804735A CN 103804735 A CN103804735 A CN 103804735A CN 201210455259 A CN201210455259 A CN 201210455259A CN 103804735 A CN103804735 A CN 103804735A
Authority
CN
China
Prior art keywords
add
parts
attapulgite
preparation
styrene
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.)
Granted
Application number
CN201210455259.6A
Other languages
Chinese (zh)
Other versions
CN103804735B (en
Inventor
魏绪玲
刘宝勇
杨珊珊
付含琦
魏玉丽
梁滔
龚光碧
郑聚成
李晶
徐典宏
艾纯金
朱晶
丛日新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN201210455259.6A priority Critical patent/CN103804735B/en
Publication of CN103804735A publication Critical patent/CN103804735A/en
Application granted granted Critical
Publication of CN103804735B publication Critical patent/CN103804735B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A preparation method of modified oil-extended powder styrene-butadiene rubber comprises the steps of sequentially adding water, styrene, an emulsifier and a molecular weight regulator into a polymerization kettle, replacing with nitrogen, adding butadiene, isoprene and attapulgite, stirring and heating, adding an initiator when the temperature of the polymerization kettle reaches 30-60 ℃, stirring, reacting for 5-8 hours at the polymerization temperature of 30-60 ℃, and adding a terminator to prepare styrene-butadiene copolymer latex; and adding the prepared styrene-butadiene copolymer latex, water, an anti-aging agent and rubber filling oil into a condensation kettle, stirring for 2-3 hours at a condensation temperature of 50-80 ℃, adding an isolating agent, stirring and heating for 1-2 hours, adding a condensing agent, adjusting the pH value of a system to be 7-13, keeping the temperature at 40-80 ℃, stirring for 1-3 hours, and then washing, dehydrating and drying to obtain the modified oil-filled powder styrene-butadiene rubber. The prepared modified oil-extended powder styrene-butadiene rubber has the following properties: the particle size of the particles is 0.5-1.50 mm, the mass percentage content of the combined styrene is 23.5-40.0%, the Mooney viscosity ML (1+4) is 40-60 at 100 ℃, the 300% stress at definite elongation is 16-25 MPa, the tensile strength is more than or equal to 17.0MPa, the elongation at break is more than or equal to 600%, the water content is less than or equal to 1.0%, and the powder forming rate is more than or equal to 99.5%.

Description

The preparation method of the oil-filled powder styrene butadiene rubber of a kind of modification
Technical field
The present invention relates to the preparation method of powdered rubber, particularly relate to the preparation method of the oil-filled powder styrene butadiene rubber of a kind of modification.
Background technology
Powdered rubber is for bulk or sheet rubber, is only the form that changes rubber, and does not change the essential property of rubber.Powdered rubber has that mixing time is short, power consumption is little, dump temperature is low and the advantage such as final dispersion is better.Along with the progress of Rubber processing industry, the purposes of powdered rubber is more and more extensive, and demand is increasing, and new variety and new grades continue to bring out.
Attapulgite be a kind of have unique natural nano layer chain molecule structure containing Shuifu County's alumina magnesia silicate, be generally white, grey, light green or light brown, specific surface area 400 ~ 500m 2/ g, chemical composition is with SiO 2, MgO, Al 2o 3be main, be with reserves abundant, cheap in Soviet Union of China Anhui one.Because its special structure has superior rheological, adsorptivity, catalytic, fillibility and thermotolerance, be used widely in fields such as petroleum drilling, discoloring agent, catalyzer, coating, rubber and plastic and heat-resistant insulation materials.
CN200780006286.2 discloses a kind of oil-extended natural rubber, and it can improve breaking tenacity and the wear resistant of rubber combination, particularly, by emulsified extender oil being added into natural rubber latex Ruzhong, then solidifies and dry resulting materials and obtaining.CN201010104801.4 discloses a kind of rubber tire filling of improving the low hysteresis loss of rubber tyre and preparation method thereof, and this rubber tire filling comprises that each raw material of following weight part makes: saturation isomerism alkane oil, the saturated hydrocarbon ils of LAL, naphthenic oil and saturated aromatic hydrocarbon oil; Its preparation method comprises: after each raw material is mixed, carry out Cross-linked reaction, obtain the product of bromine number in 15, cooling discharge, to obtain final product.CN200910013774.7 discloses a kind of preparation method of oil-extended montmorillonite-extended solution co-coagulating rubber, and organic modification montmonrillonite, oil, coupling agent, anti-aging agent are joined in rubber solutions, stirs 1-30 minute; In above-mentioned solution, pass into water vapour, utilize fractionation by distillation device, solvent oil is steamed and reclaimed; Drying makes oil-extended montmorillonite-extended solution co-coagulating rubber.CN200710091680.2 discloses a kind of method of preparing oil-extended rubber, it comprises (a) one by using tensio-active agent to make to contain iodine number to be no less than 135 vegetables oil emulsification to prepare a kind of step of emulsion oil-in-water, (b) one mixes described vegetables oil emulsion and a kind of modified natural rubber latex, then the step of slaking, (c) one by step (b) thus in the mixture that makes solidify the step that makes niggerhead, a kind of oil-extended rubber being made by this preparation method, and a kind of rubber composition for tire and tire that has used this oil-extended rubber.CN201010192008.4 discloses a kind of preparation method of oil-filled type paracril/palygorskite nano composite material, and its technological process comprises the following steps successively, A: the emulsification of attapulgite modification and aromatic hydrocarbon oil; B: attapulgite is mixed with nitrile rubber with the mixed solution of oil in water emulsion, form uniform mixing solutions through stirring; C: add flocculation agent to flocculate, by throw out dehydration, oven dry, add the mixing even postcure of various Synergist S-421 95s to make oil-filled type paracril/palygorskite nano composite material.CN200910129810.6 discloses a kind of preparation method of oil-filled styrene butadiene rubber SBR 1712/palygorskite nano composite material, its preparation technology comprises modification, attapulgite and the styrene-butadiene rubber(SBR) blend of attapulgite successively, after oil-filled, the flocculation dewatering of styrene-butadiene rubber(SBR)/palygorskite nano composite material, mixing, sulfuration, make product again, in the method with sodium hexametaphosphate solution modified attapulgite.CN200410034219.X discloses a kind of polycrystalline state compound composition that can be applicable to the fields such as Rubber processing and preparation method thereof, employing is usually used in the powder of rubber filler and strengthening agent etc. and makes nucleome material, coated through mixed crystal at nucleome material surface, rubber filler and strengthening agent can contain attapulgite.CN200610125573.2 discloses the preparation method of a kind of attapulgite and natural rubber nano composite material, its technological process comprises ultrasonic dispersion, modification, blend is solidifying, ironed, washing altogether, dehydration, mixing and sulfuration, technical characterstic of the present invention is by ultrasonic dispersion, modification and the emulsion blending altogether method such as solidifying make attapulgite be dispersed in natural rubber matrix with nanocrystalline form, and have good associativity with natural rubber matrix, thereby improve the performance of rubber item.CN200910233719.9 discloses reinforcing filler for rubber latex product and preparation method thereof and purposes, it is made up of base-material, dispersion agent, surface treatment agent, emulsion and water, and wherein surface treatment agent is any in bentonite, Mierocrystalline cellulose, wilkinite, attapulgite.It is rubber plastic deodorant that CN201010204175.6 discloses a kind of natural non-metallic minerals, is made up of medical stone, six ring stones, diatomite, tourmalinite, attapulgite clay.Ding Yonghong, Sun Chuanjin, the superfine people of Yao has studied the physicals of different attapulgite modified by silane coupling agent filling SBR cross-linked rubbers in " attapulgite is filled the performance study of SBR ", and with bound rubber research reinforcement mechanism, experiment is carried out in-situ modified to attapulgite, in the preparation process of attapulgite/SBR matrix material, after mixing with SBR, attapulgite directly to the properties-correcting agent that adds metering in rubber unvulcanizate, completes the modification to attapulgite.Li Juan in " the attapulgite filling rubber research " take attapulgite as raw material, make filler through surface modification treatment, be filled in rubber and go, performance to filled rubber is studied, experiment is that 325 object attapulgites are put in baking oven to the modification of attapulgite, after 250 ℃ of roasting 2h, puts in high-speed mixer, coupling agent is sprayed in the system of 2000r/min high-speed rotation, stir 10min.Shou Wenjuan, Wan Chaoying, the people such as Zhang Yong adopt two-[γ-(triethoxysilicane) propyl group]-tetrasulfide (Si69) to carry out modification to attapulgite in " research of Properties of Carboxylated Styrene Butadiene Rubber reinforced with modified Attapulgite ", and prepared carboxylic styrene-butadiene rubber (CSBR)/attapulgite composite material by mechanical blending, study interaction and stress softening behavior between curability, mechanical property, filler and the rubber matrix of matrix material.Xu Qing, Zhang Shenjing, the people such as Wang Bin make attapulgite after 4mol/L hcl acidifying is processed in " chemical modification of silane coupling agent to attapulgite ", under ul-trasonic irradiation, disperse about 20min, add γ-(methacryloxypropyl) propyl trimethoxy silicane (abbreviation silane coupling agent), prepare attapulgite modified.Sun Chuanjin, Ding Yonghong, the superfine people of Yao adopts the method for prehydrolysis in " preparation and the performance study of organic attapulgite soil/SBR matrix material ", attapulgite is carried out to organic surface modifying with silane coupling agent KH-845-4, and prepare organic attapulgite/SBR matrix material, study physicals and the structure of this matrix material.
US4306994A has introduced a sulfurized rubber composition that contains attapulgite.JP2004182827 has introduced a kind of resin of filling attapulgite.JP2006131718 has introduced a kind of have good wet braking ability and the rubber of low-rolling-resistance, has filled attapulgite in the course of processing.US6395076, JP62085985A, GB2009782 GB2408048 etc. have introduced the matrix material that contains attapulgite.
Current research has attapulgite and nitrile rubber mechanical blending, adds attapulgite or attapulgite modified but mostly be in Rubber processing process, and the method exists attapulgite easily floating and bring the problem of dust pollution.
Summary of the invention
The object of the present invention is to provide a kind of attapulgite that adds in copolymer latex preparation process to prepare the method for the oil-filled powder styrene butadiene rubber of modification.The method attapulgite and styrene-butadiene latex copolymerization, the effect that has good original position to strengthen to rubber, has improved the processing characteristics of rubber, as tensile strength and 300% stress at definite elongation; And efficiently solve prior art in Rubber processing process, add attapulgite nanometer material, due to the easily floating pollution problem bringing of nano material, also solve the scattering problem of nano material, in the method nano material disperse simpler, dispersion effect is better.
Technical scheme of the present invention is:
First in polymeric kettle, add successively water, vinylbenzene, emulsifying agent, molecular weight regulator, with after nitrogen replacement, add divinyl, isoprene, attapulgite, stirring heating adds initiator in the time that polymeric kettle temperature reaches 30~60 ℃, stirs, then under 30~60 ℃ of polymerization temperatures, react 5~8 hours, add terminator, make copolymerization of butylbenzene latex; In cohesion still, add the copolymerization of butylbenzene latex, water, anti-aging agent, the rubber filling oil that make again, under 20~60 ℃ of condensation temperatures, stir 2~3 hours, add separant, stirring heating 1~2 hour, adds flocculation agent, regulation system pH value is 7~13, remain on 40~80 ℃, stir 1~3 hour, then through washing, dehydration, the dry oil-filled powder styrene butadiene rubber of modification that obtains.
The concrete preparation process of the present invention is as follows:
1) preparation of copolymerization of butylbenzene latex: take butadiene styrene total amount as 100 mass parts, in polymeric kettle, add successively 50~150 parts of water, 40 parts of vinylbenzene, 2~10 parts of emulsifying agents, 0.1~1.2 part of molecular weight regulator, with after nitrogen replacement, add 60 parts of divinyl, 15~40 parts of isoprene monomers, 0.5 ~ 5 part of attapulgite, stir, heating, in the time that reaching 30~60 ℃, polymeric kettle temperature adds 0.1~0.4 part of initiator, stir 0.8~1h, then under 30~60 ℃ of polymerization temperatures, react 5~8 hours, add 0.1~0.5 part of terminator, make copolymerization of butylbenzene latex.
2) condensation powdering: the copolymerization of butylbenzene latex that adds 100 mass parts to make in cohesion still, add 20~100 parts of water, under 20~60 ℃ of condensation temperatures, add 0.2~0.5 part of anti-aging agent, 0.1~1.0 part of rubber filling oil, stir 2~3 hours, add 5~20 portions of separants, stirring heating 1~2 hour, add 5~20 parts of flocculation agent, regulation system pH value is 7~13, stirs and within 1~3 hour, carries out slaking, then through washing, dehydration, the dry oil-filled powder styrene butadiene rubber of modification that obtains at 40~80 ℃.
Attapulgite is a kind of crystalloid hydrous magnesium aluminium silicate mineral, has unique layer chain-like structure feature, in its structure, has crystal lattice, contains the Na of non-quantitative in crystal +, Ca2 +, Fe3 +, Al3 +, crystal is needle-like, fibrous or fiber collection shape.Its desirable chemical molecular formula is: Mg 5(H 2o) 4[Si 4o 10] 2(OH) 24H 2o.Have the intermediate structure between chain-like structure and laminate structure, its structural formula is as Fig. 1.Suspension is met not flocculation sediment of dielectric medium.Main physical and chemical performance and processing performance have: positively charged ion interchangeability, water-absorbent, adsorption bleaching, large specific surface area (9.6~36m 2/ g) and colloid index and allowance for expansion.
The basic structure of attapulgite is divided into three levels.The one, the thickness length of brilliant bundle.Because rod is brilliant the tightst in the intrafascicular gathering of crystalline substance, therefore, brilliant bundle ratio more tiny or tiny brilliant Shu Suozhan is larger, and the microstructure of recessed soil is just looser, and vice versa.The 2nd, the state of aggregation of brilliant bundle.If brilliant interfascicular is parallel tight gathering more, microstructure is just fine and close.Otherwise if brilliant bundle is loose staggered arrangement at three-dimensional space, brilliant interfascicular interval is large, microstructure is just loose.The 3rd, in microstructure, whether be formed with built on stilts hole, crack etc.If so, microstructure is just loose.In sum, the microstructure of attapulgite has brilliant, the brilliant bundle of rod, three different levels of aggregate.
The adsorptivity of attapulgite depends on surface-area and Surface Physical Chemistry structure and the ionic condition that it is larger, and its adsorption comprises physical adsorption and chemisorption.The essence of physical adsorption is the surfaces externally and internally that by Fan get Hua Li, adsorption molecule is adsorbed on to attapulgite.The chemisorption of attapulgite is its adsorbing important embodiment.Its absorption is several adsorption centers that the surface based on attapulgite may exist: the weak electron that the displacement of (1) silicon-oxy tetrahedron layer internal cause isomorphism produces is supplied with Sauerstoffatom, and they are very weak with the effect of absorption core.(2) at fiber edge and metallic cation (Mg 2+) complex bound negative water molecules (H 2o -), can with OH -absorption karyomorphism becomes hydrogen bond.(3) the Si-OH base being formed by the bond rupture of Si-O-Si bridging oxygen on tetrahedrallayer outside surface not only can be accepted ion, and can mutually combine with the absorption molecule of crystal outside surface; Can form covalent linkage with some organic reagent.(4) the non-equivalence isomorphism of crystal chemistry composition displacement (Al 3+or Fe 3+to Mg 2+) and add the coordinated water (H causing 2o -, OH -) lose and electrical adsorption center that the charge unbalance that produces forms.
The principle of rubber latex and attapulgite copolymerization is: first, due to the physical adsorption performance of attapulgite, by Fan get Hua Li, divinyl, styrene monomer are adsorbed on to the surfaces externally and internally of attapulgite; The second, there is duct in attapulgite, and monomer enters the duct of attapulgite, reacts, together with it is copolymerized to closely with rubber at this; The 3rd, the Si-OH base being formed by the bond rupture of Si-O-Si bridging oxygen on tetrahedrallayer outside surface not only can be accepted ion, and can mutually combine with the absorption molecule of crystal outside surface, form covalent linkage with latex and some auxiliary agent as emulsifying agent, and the effect that has original position to strengthen.
In a word, attapulgite as a kind of chain laminate structure containing Shuifu County's magnesium silicate clay mineral, its crystal is very thin, inside configuration multi-pore channel, appearance is concavo-convex alternate, has very large interior external surface area, the polar organic molecular energy of certain size scope enters its duct, therefore attapulgite and latex copolymerization, the effect that has good original position to strengthen to rubber, therefore the tensile strength of rubber and stress at definite elongation are improved.And attapulgite being joined to directly mixing in rubber cement in polymerization process, attapulgite is difficult for floating formation floating dust and contaminate environment.
Time prepared by copolymer latex of the present invention, emulsifying agent used is Sulfates, Sulfonates, preferably disproportionated rosin soap; Consumption is 2~10 parts, preferably 4 ~ 6 parts.
Time prepared by copolymer latex of the present invention, molecular weight regulator used is selected from tert-dodecyl mercaptan, uncle's ten carbon mercaptan, uncle's 14 carbon mercaptan, uncle's 16 carbon mercaptan, preferred tertiary DDM dodecyl mercaptan; Consumption is 0.1~1.2 part, preferably 0.4 ~ 0.6 part.
Time prepared by copolymer latex of the present invention, isoprene add-on used is 15~40 parts, preferably 20 ~ 25 parts.
Time prepared by copolymer latex of the present invention, Attapulgite consumption is 0.5 ~ 5 part, preferably 1 ~ 2 part.
Time prepared by copolymer latex of the present invention, polymerization temperature is 30~60 ℃, preferably 40 ~ 50 ℃.
Time prepared by copolymer latex of the present invention, initiator used adopts diazoamino compound or persulphate, and preferably diazoamino compound, as diazoamino acid sodium; Consumption is 0.1~0.4 part, preferably 0.2 ~ 0.3 part.
Time prepared by copolymer latex of the present invention, terminator used is selected from Sodium dimethyldithiocarbamate 40min, quinhydrones; Consumption is 0.1~0.5 part, preferably 0.2 ~ 0.3 part.
When condensation powdering of the present invention, anti-aging agent used is N-Octyl-N '-phenyl-ρ-Ursol D, styrenated phenol etc., optimization styrene phenol; Consumption is 0.2~0.5 part, preferably 0.3~0.5 part.
When condensation powdering of the present invention, rubber filling oil used is naphthenic oil, aromatic hydrocarbons wet goods (according to IISRP specification, S* Saybolt Viscosity is less than 2000SUS), preferred aromatic hydrocarbons oil; Consumption is 0.1~1.0 part, preferably 0.2~0.5 part.
When condensation powdering of the present invention, condensation temperature is 20~60 ℃, preferably 20~30 ℃.
When condensation powdering of the present invention, separant used is inorganic salts, as sodium-chlor, magnesium sulfate etc., and preferably sodium-chlor; Consumption is 5~20 parts, preferably 10~15 parts.
When condensation powdering of the present invention, flocculation agent used is inorganic acids, as sulfuric acid, hydrochloric acid etc., and preferably sulfuric acid; Concentration is 2 ~ 10mol/L, preferably 2 ~ 4mol/L; Consumption is 5~20 parts, preferably 10~15 parts.
When condensation powdering of the present invention, system pH is 7~13, preferably 7~9.
When condensation powdering of the present invention, curing temperature is 40~80 ℃, preferably 40~50 ℃; Time is 1~3 hour, preferably 2~3 hours.
The oil-filled powder styrene butadiene rubber performance of modification that the inventive method is prepared: grain diameter 0.5~1.50mm, combined styrene quality percentage composition 23.5~40.0%, Mooney viscosity ML (1+4) 100 ℃40~60,300% stress at definite elongation 16~25MPa, tensile strength>=17.0MPa, tensile yield>=600%, moisture content≤1.0%, powder formation rate>=99.5%.
Attapulgite of the present invention can be the attapulgite of commercially available non-modified, also can be the attapulgite of acidified modification, described method of modifying is: in agitator, add 100 mass parts water, add 10 ~ 30 parts of attapulgites, start agitator and be stirred to attapulgite formation suspension, 3 ~ 10 parts of scattered attapulgite suspension are joined in beaker, add 10 ~ 20 parts of the hydrochloric acid of 3 ~ 6mol/L, at 60 ~ 80 ℃, stir and obtain attapulgite hydrochloric acid soln, add 0.3 ~ 1 part of quaternary ammonium salt solution, stir 1 ~ 2 hour, then through washing, filter, dry, obtain attapulgite modified.
The object of attapulgite being carried out to modification is to improve the disperse properties of particle in polymkeric substance, or improves the bonding properties of particle to polymkeric substance.Acidified modified mechanism: attapulgite is after acid soak, and inner tetrahedron and octahedral structure are partly dissolved; Undissolved octahedral structure plays a supportive role, and number of perforations is increased, and specific surface area increases.Meanwhile, often contain the impurity such as carbonate in attapulgite duct, acidification can be removed the impurity being distributed in attapulgite duct on the one hand, makes duct dredging; On the other hand, due to the positively charged ion interchangeability of attapulgite, the H that radius is less +can displace attapulgite interlayer portion K +, Na +, Ca 2+and Mg 2+plasma, increases pore volume.Many factors is improved the multiple performance such as attapulgite adsorptivity, decolourising property after modification.The surface property of the organic attapulgite soil after quaternary surfactant modification changes lipophilicity into by wetting ability, stronger to organic absorption property, is more conducive to oily filling.
Attapulgite's surface has many alkyl, and surface is hydrophilic oleophobic property, easily forms aggregate, and the attapulgite after quaternary ammonium salt-modified, has more lipophilicity, makes oil-filled more abundant, simpler.
In the present invention, in attapulgite modified process, attapulgite consumption is 10 ~ 30 parts, preferably 15 ~ 20 parts.
In the present invention, in attapulgite modified process, required scattered attapulgite quantities of suspension is 3 ~ 10 parts, preferably 3 ~ 8 parts.
In the present invention, in attapulgite modified process, used salt acid concentration is 3 ~ 6mol/L, and consumption is 10 ~ 20 parts; Preferred concentration 4 ~ 6mol/L, consumption is 15 ~ 20 parts.
In the present invention, in attapulgite modified process, quaternary ammonium salt used is Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide etc., preferably cetyl trimethylammonium bromide; Consumption is 0.3 ~ 1 part, preferably 0.5 ~ 0.8 part.
In the present invention, in attapulgite modified process, temperature is 60 ~ 80 ℃, preferably 65 ~ 75 ℃.
Accompanying drawing explanation
Fig. 1 attapulgite crystalline structure figure ([001] face projection)
Embodiment
Further illustrate the present invention below in conjunction with embodiment, but and the scope of unrestricted the claims in the present invention protection.
Raw material sources:
Divinyl (B), vinylbenzene (S): CNPC's Lanzhou Petrochemical is produced; Attapulgite, acid, quaternary ammonium salt: commercially available prod; Other auxiliary agent provides by CNPC's Lanzhou Petrochemical, and grade is industrial goods.
Test set: rubber mixing machine VH-109, vulcanizing press RCM × 24-100T, plasticator SK-160B, mooney's viscosimeter SMV-300RT, universal testing machine INSTRON5546, FM11 type High Temperature Furnaces Heating Apparatus, electronic balance AE100.
Testing method: particle diameter: adopted sieve method, and divided to sieve for 4 times with Tyler sieve 12,16,20,28 orders and measure, particle size range 0.5~1.5mm; Combined styrene quality percentage composition: GB/T8658-1998; Mooney viscosity: GB/T 1232.1-2000; 300% stress at definite elongation, tensile strength, tensile yield: GB/T528-2009; Moisture content: GB/T 24131-2009; Powder formation rate: weighting method.
Embodiment 1
1. the preparation of copolymerization of butylbenzene latex: add successively 80 parts of water, 40 parts of vinylbenzene, 6 parts of disproportionated rosin soaps, 0.6 part of tert-dodecyl mercaptan in polymeric kettle, with after nitrogen replacement, add 60 parts of divinyl, 25 parts of isoprene monomers, 3 parts of attapulgites, stir, heat, in the time that polymeric kettle temperature reaches 35 ℃, add 0.2 part of diazoamino acid sodium, stir 0.8h, then under 35 ℃ of polymerization temperatures, react 6 hours, add 0.4 part of Sodium dimethyldithiocarbamate 40min, make copolymerization of butylbenzene latex.2. condensation powdering: the copolymerization of butylbenzene latex that adds 100 mass parts to make in cohesion still, add 60 parts of water, under 40 ℃ of condensation temperatures, add 0.4 part of styrenated phenol, 0.4 part of rubber filling oil, stir 3 hours, add 8 parts of sodium-chlor, stirring heating 1 hour, add the sulfuric acid that 8 parts of concentration are 2mol/L, regulation system pH value is 9, stirs and within 3 hours, carries out slaking, then through washing, dehydration, the dry oil-filled powder styrene butadiene rubber of modification that obtains at 40 ℃.Product performance test result is as follows: grain diameter 0.5~1.50mm, combined styrene quality percentage composition 23.5%, 100 ℃ 50 of Mooney viscosity ML (1+4), 300% stress at definite elongation 18.2MPa, tensile strength 18.3MPa, tensile yield 605%, moisture content 0.9%, powder formation rate 99.8%.
Comparative example 1
Experiment condition is with embodiment 1, just not by attapulgite and styrene-butadiene latex copolymerization, directly to oil-filled cohesion after styrene-butadiene latex polymerization.Experimental result: grain diameter 0.5~4.00mm, combined styrene quality percentage composition 23.5%, Mooney viscosity ML (1+4) 100 ℃35,300% stress at definite elongation 17.3MPa, tensile strength 17.5MPa, tensile yield 560%, moisture content 1.2%, powder formation rate 92%.
Embodiment 2
1. the preparation of copolymerization of butylbenzene latex: add successively 110 parts of water, 40 parts of vinylbenzene, 6 parts of disproportionated rosin soaps, 0.9 part of tert-dodecyl mercaptan in polymeric kettle, with after nitrogen replacement, add 60 parts of divinyl, 35 parts of isoprene monomers, 1.5 parts of attapulgites, stir, heat, in the time that polymeric kettle temperature reaches 45 ℃, add 0.4 part of diazoamino acid sodium, stir 1h, then under 45 ℃ of polymerization temperatures, react 7 hours, add 0.5 part of Sodium dimethyldithiocarbamate 40min, make copolymerization of butylbenzene latex.2. condensation powdering: the copolymerization of butylbenzene latex that adds 100 mass parts to make in cohesion still, add 30 parts of water, under 30 ℃ of condensation temperatures, add 0.2 part of styrenated phenol, 1.0 parts of rubber filling oils, stir 2 hours, add 10 parts of magnesium sulfate, stirring heating 2 hours, add the hydrochloric acid that 15 parts of concentration are 10mol/L, regulation system pH value is 10, stirs and within 3 hours, carries out slaking, then through washing, dehydration, the dry oil-filled powder styrene butadiene rubber of modification that obtains at 30 ℃.Product performance test result is as follows: grain diameter 0.5~1.50mm, combined styrene quality percentage composition 24.5%, 100 ℃ 60 of Mooney viscosity ML (1+4), 300% stress at definite elongation 19.0MPa, tensile strength 17.5MPa, tensile yield 620%, moisture content 0.9%, powder formation rate 99.7%.
Comparative example 2
Experiment condition is with embodiment 2, just not by attapulgite and styrene-butadiene latex copolymerization, directly to oil-filled cohesion after styrene-butadiene latex polymerization.Experimental result: grain diameter 0.5~3.00mm, combined styrene quality percentage composition 24.5%, Mooney viscosity ML (1+4) 100 ℃45,300% stress at definite elongation 17.8MPa, tensile strength 17.0MPa, tensile yield 510%, moisture content 1.0%, powder formation rate 94%.
Embodiment 3
1. the preparation of copolymerization of butylbenzene latex: add successively 50 parts of water, 40 parts of vinylbenzene, 2 parts of disproportionated rosin soaps, 1.2 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 60 parts of divinyl, 15 parts of isoprene monomers, 0.5 part of attapulgite, stir, heat, in the time that polymeric kettle temperature reaches 30 ℃, add 0.4 part of diazoamino acid sodium, stir 1h, then under 30 ℃ of polymerization temperatures, react 5 hours, add 0.5 part of Sodium dimethyldithiocarbamate 40min, make copolymerization of butylbenzene latex.2. condensation powdering: get 100 parts of copolymerization of butylbenzene latex that make and add cohesion still, add 20 parts of WATER AS FLOW MEDIUM, under 50 ℃ of condensation temperatures, add 0.2 part of N-Octyl-N '-phenyl-ρ-Ursol D, 0.2 part of rubber filling oil, stir 2 hours, add 5 parts of sodium-chlor, stirring heating 1 hour, adds the sulfuric acid that 10 parts of concentration are 4mol/L, regulation system pH value is 9, within 3 hours, carries out slaking, then obtains polymer beads through washing, dewater, being dried 40 ℃ of stirrings.Product performance test result is as follows: grain diameter 0.5~1.50mm, combined styrene quality percentage composition 23.5%, 100 ℃ 45 of Mooney viscosity ML (1+4), 300% stress at definite elongation 18.6MPa, tensile strength 18.0MPa, tensile yield 610%, moisture content 1.0%, powder formation rate 99.5%.
Comparative example 3
Experiment condition is with embodiment 3, just not by attapulgite and styrene-butadiene latex copolymerization, directly to oil-filled cohesion after styrene-butadiene latex polymerization.Experimental result: grain diameter 0.5~3.50mm, combined styrene quality percentage composition 23.5%, Mooney viscosity ML (1+4) 100 ℃40,300% stress at definite elongation 17.0MPa, tensile strength 16.9MPa, tensile yield 550%, moisture content 2.0%, powder formation rate 95%.
Embodiment 4
1. the preparation of copolymerization of butylbenzene latex: add successively 150 parts of water, 40 parts of vinylbenzene, 10 parts of disproportionated rosin soaps, 1.2 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 60 parts of divinyl, 40 parts of isoprene monomers, 5 parts of attapulgites, stir, heat, in the time that polymeric kettle temperature reaches 60 ℃, add 0.4 part of diazoamino acid sodium, stir 0.8h, then under 50 ℃ of polymerization temperatures, react 5 hours, add 0.5 part of Sodium dimethyldithiocarbamate 40min, make copolymerization of butylbenzene latex.2. condensation powdering: get 100 parts of copolymerization of butylbenzene latex that make and add cohesion still, add 20 parts of WATER AS FLOW MEDIUM, under 40 ℃ of condensation temperatures, add 0.5 part of N-Octyl-N '-phenyl-ρ-Ursol D, 1.0 parts of rubber filling oils, stir 2 hours, add 20 parts of sodium-chlor, stirring heating 1 hour, adds the sulfuric acid that 20 parts of concentration are 6mol/L, regulation system pH value is 13, within 1 hour, carries out slaking, then obtains polymer beads through washing, dewater, being dried 80 ℃ of stirrings.Product performance test result is as follows: grain diameter 0.8~1.50mm, combined styrene quality percentage composition 24.5%, 100 ℃ 50 of Mooney viscosity ML (1+4), 300% stress at definite elongation 21MPa, tensile strength 18.6MPa, tensile yield 605%, moisture content 1.0%, powder formation rate 99.5%.
Comparative example 4
Experiment condition is with embodiment 4, just not by attapulgite and styrene-butadiene latex copolymerization, directly to oil-filled cohesion after styrene-butadiene latex polymerization.Experimental result: grain diameter 0.5~3.0mm, combined styrene quality percentage composition 23.5%, Mooney viscosity ML (1+4) 100 ℃43,300% stress at definite elongation 18.0MPa, tensile strength 17.5MPa, tensile yield 580%, moisture content 1.5%, powder formation rate 92%.
Embodiment 5
1. the modification of protruding rod soil: in agitator, add 100 mass parts water, add 10 parts of attapulgites, start agitator and be stirred to attapulgite formation suspension, 10 parts of scattered attapulgite suspension are joined in beaker, add 20 parts of the hydrochloric acid of 6mol/L, at 60 ℃, stir and obtain attapulgite hydrochloric acid soln, add 0.3 part of quaternary ammonium salt solution, stir 2 hours, then through washing, filtration, dry, obtain attapulgite modified.2. the preparation of copolymerization of butylbenzene latex: add successively 50 parts of water, 40 parts of vinylbenzene, 2 parts of disproportionated rosin soaps, 1.2 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 60 parts of divinyl, 15 parts of isoprene monomers, 0.5 part of attapulgite, stir, heat, in the time that polymeric kettle temperature reaches 30 ℃, add 0.4 part of diazoamino acid sodium, stir 1h, then under 30 ℃ of polymerization temperatures, react 5 hours, add 0.5 part of Sodium dimethyldithiocarbamate 40min, make copolymerization of butylbenzene latex.3. condensation powdering: get 100 parts of copolymerization of butylbenzene latex that make and add cohesion still, add 20 parts of WATER AS FLOW MEDIUM, under 50 ℃ of condensation temperatures, add 0.2 part of N-Octyl-N '-phenyl-ρ-Ursol D, 0.2 part of rubber filling oil, stir 2 hours, add 5 parts of sodium-chlor, stirring heating 1 hour, adds the hydrochloric acid that 10 parts of concentration are 8mol/L, regulation system pH value is 9, within 3 hours, carries out slaking, then obtains polymer beads through washing, dewater, being dried 40 ℃ of stirrings.Product performance test result is as follows: grain diameter 0.5~1.50mm, combined styrene quality percentage composition 23.5%, 100 ℃ 45 of Mooney viscosity ML (1+4), 300% stress at definite elongation 18.6MPa, tensile strength 18.0MPa, tensile yield 610%, moisture content 1.0%, powder formation rate 99.5%.
Comparative example 5
Experiment condition is with embodiment 5, just not by attapulgite modified and styrene-butadiene latex copolymerization, directly to oil-filled cohesion after styrene-butadiene latex polymerization.Experimental result: grain diameter 0.5~3.0mm, combined styrene quality percentage composition 23.5%, Mooney viscosity ML (1+4) 100 ℃43,300% stress at definite elongation 18.0MPa, tensile strength 17.5MPa, tensile yield 580%, moisture content 1.5%, powder formation rate 92%.
Embodiment 6
1. the modification of protruding rod soil: in agitator, add 100 mass parts water, add 20 parts of attapulgites, start agitator and be stirred to attapulgite formation suspension, 8 parts of scattered attapulgite suspension are joined in beaker, add 15 parts of the hydrochloric acid of 6mol/L, at 80 ℃, stir and obtain attapulgite hydrochloric acid soln, add 1 part of quaternary ammonium salt solution, stir 2 hours, then through washing, filtration, dry, obtain attapulgite modified.2. the preparation of copolymerization of butylbenzene latex: add successively 150 parts of water, 40 parts of vinylbenzene, 10 parts of disproportionated rosin soaps, 1.2 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 60 parts of divinyl, 40 parts of isoprene monomers, 4 parts attapulgite modified, stir, heat, in the time that reaching 60 ℃, polymeric kettle temperature adds 0.4 part of diazoamino acid sodium, stir 0.8h, then under 60 ℃ of polymerization temperatures, react 5 hours, add 0.5 part of Sodium dimethyldithiocarbamate 40min, make copolymerization of butylbenzene latex.3. condensation powdering: get 100 parts of copolymerization of butylbenzene latex that make and add cohesion still, add 20 parts of WATER AS FLOW MEDIUM, under 50 ℃ of condensation temperatures, add 0.5 part of N-Octyl-N '-phenyl-ρ-Ursol D, 0.8 part of rubber filling oil, stir 2 hours, add 20 parts of magnesium sulfate, stirring heating 1 hour, adds the hydrochloric acid that 20 parts of concentration are 10mol/L, regulation system pH value is 13, within 1 hour, carries out slaking, then obtains polymer beads through washing, dewater, being dried 80 ℃ of stirrings.Product performance test result is as follows: grain diameter 0.8~1.50mm, combined styrene quality percentage composition 24.5%, 100 ℃ 58 of Mooney viscosity ML (1+4), 300% stress at definite elongation 23.4MPa, tensile strength 20.3MPa, tensile yield 615%, moisture content 1.0%, powder formation rate 99.6%.
Comparative example 6
Experiment condition is with embodiment 6, just not by attapulgite and styrene-butadiene latex copolymerization, directly to oil-filled cohesion after styrene-butadiene latex polymerization.Experimental result: grain diameter 0.5~3.50mm, combined styrene quality percentage composition 23.5%, Mooney viscosity ML (1+4) 100 ℃40,300% stress at definite elongation 17.0MPa, tensile strength 16.9MPa, tensile yield 550%, moisture content 2.0%, powder formation rate 95%.

Claims (15)

1. the preparation method of the oil-filled powder styrene butadiene rubber of modification, to add copolymerization of butylbenzene latex in cohesion still, water, anti-aging agent, rubber filling oil, under 20~60 ℃ of condensation temperatures, stir 2~3 hours, add separant, stirring heating 1~2 hour, add flocculation agent, regulation system pH value is 7~13, remain under 40~80 ℃ of curing temperatures, stir 1~3 hour, then through washing, dehydration, the dry oil-filled powder styrene butadiene rubber of modification that obtains, it is characterized in that: described copolymerization of butylbenzene latex is made by following methods: in polymeric kettle, add successively water, vinylbenzene, emulsifying agent, molecular weight regulator, with after nitrogen replacement, add divinyl, isoprene monomer, attapulgite, stirring heating, in the time that reaching 30~60 ℃, polymeric kettle temperature adds initiator, stir, then under 30~60 ℃ of polymerization temperatures, react 5~8 hours, add terminator, make copolymerization of butylbenzene latex.
2. preparation method according to claim 1, it is characterized in that the copolymerization of butylbenzene latex in 100 mass parts, in described cohesion still, the add-on of water is 20~100 parts, the add-on of anti-aging agent is 0.2~0.5 part, the add-on of rubber filling oil is 0.1~1.0 part, the add-on of separant is 5~20 parts, and the add-on of flocculation agent is 5~20 parts.
3. preparation method according to claim 1, it is characterized in that the butadiene styrene total amount in 100 mass parts, in described polymeric kettle, the add-on of water is that 50~150 parts, cinnamic add-on are that 40 parts, the add-on of emulsifying agent are that 2~10 parts, the add-on of molecular weight regulator are 0.1~1.2 part, the add-on of divinyl is that 60 parts, the add-on of isoprene monomer are that 15~40 parts, the add-on of attapulgite are 0.5 ~ 5 part, the add-on of initiator is 0.1~0.4 part, and the add-on of terminator is 0.1~0.5 part.
4. preparation method according to claim 1, is characterized in that in described cohesion still, condensation temperature is 20~30 ℃.
5. preparation method according to claim 1, is characterized in that in described cohesion still, system pH is 7~9.
6. preparation method according to claim 1, is characterized in that in described cohesion still, curing temperature is 40~50 ℃; Time is 2~3 hours.
7. preparation method according to claim 3, is characterized in that described isoprene monomer add-on is 20 ~ 25 parts.
8. want the preparation method described in 3 according to right, it is characterized in that described attapulgite add-on is 1 ~ 2 part.
9. preparation method according to claim 1, is characterized in that in described polymeric kettle, polymerization temperature is 40 ~ 50 ℃.
10. according to the preparation method described in claim 1 or 3, it is characterized in that described attapulgite is the attapulgite of acidified modification, described method of modifying is: in agitator, add 100 mass parts water, add 10 ~ 30 parts of attapulgites, start agitator and be stirred to attapulgite formation suspension, 3 ~ 10 parts of scattered attapulgite suspension are joined in beaker, add 10 ~ 20 parts of the hydrochloric acid of 3 ~ 6mol/L, at 60 ~ 80 ℃, stir and obtain attapulgite hydrochloric acid soln, add 0.3 ~ 1 part of quaternary ammonium salt solution, stir 1 ~ 2 hour, then through washing, filter, dry, obtain attapulgite modified.
11. preparation methods according to claim 10, is characterized in that described attapulgite add-on is 15 ~ 20 parts.
12. preparation methods according to claim 10, is characterized in that described scattered attapulgite quantities of suspension is 3 ~ 8 parts.
13. preparation methods according to claim 10, is characterized in that described concentration of hydrochloric acid is 4 ~ 6mol/L, and consumption is 15 ~ 20 parts.
14. preparation methods according to claim 10, is characterized in that described quaternary ammonium salt is Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide; Consumption is 0.5 ~ 0.8 part.
15. preparation methods according to claim 10, is characterized in that described temperature is 65 ~ 75 ℃.
CN201210455259.6A 2012-11-14 2012-11-14 Preparation method of modified oil-extended powder styrene-butadiene rubber Active CN103804735B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210455259.6A CN103804735B (en) 2012-11-14 2012-11-14 Preparation method of modified oil-extended powder styrene-butadiene rubber

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210455259.6A CN103804735B (en) 2012-11-14 2012-11-14 Preparation method of modified oil-extended powder styrene-butadiene rubber

Publications (2)

Publication Number Publication Date
CN103804735A true CN103804735A (en) 2014-05-21
CN103804735B CN103804735B (en) 2016-06-08

Family

ID=50702153

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210455259.6A Active CN103804735B (en) 2012-11-14 2012-11-14 Preparation method of modified oil-extended powder styrene-butadiene rubber

Country Status (1)

Country Link
CN (1) CN103804735B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304860A (en) * 2013-06-16 2013-09-18 北京化工大学 Tire tread rubber without zinc oxide
CN105733047A (en) * 2014-12-11 2016-07-06 中国石油天然气股份有限公司 Nitrile rubber/attapulgite nano composite material, vulcanized rubber and preparation method thereof
CN106893161A (en) * 2017-04-11 2017-06-27 安徽省明美矿物化工有限公司 A kind of rubber containing attapulgite and preparation method thereof
CN107189496A (en) * 2017-07-13 2017-09-22 长春工业大学 A kind of modification illite preparation method for improving natural rubber performance
CN107236081A (en) * 2017-06-29 2017-10-10 襄阳福源兴盛科技有限公司 A kind of carboxylic acid styrene-butadiene latex
CN107805327A (en) * 2016-09-08 2018-03-16 中国石油天然气股份有限公司 Oil-extended ternary integrated rubber and preparation method thereof
CN115806741A (en) * 2021-09-14 2023-03-17 中国石油化工股份有限公司 Filling oil for styrene butadiene rubber and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1569906A (en) * 2003-07-17 2005-01-26 中国石油天然气股份有限公司 Method for preparing powdered rubber through continuous coagulation
CN102190741A (en) * 2010-03-19 2011-09-21 中国石油天然气股份有限公司 Method for coagulating rubber latex
CN102295815A (en) * 2010-06-25 2011-12-28 中国石油天然气股份有限公司 Preparation method of styrene butadiene rubber grafted isoprene polymer powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1569906A (en) * 2003-07-17 2005-01-26 中国石油天然气股份有限公司 Method for preparing powdered rubber through continuous coagulation
CN102190741A (en) * 2010-03-19 2011-09-21 中国石油天然气股份有限公司 Method for coagulating rubber latex
CN102295815A (en) * 2010-06-25 2011-12-28 中国石油天然气股份有限公司 Preparation method of styrene butadiene rubber grafted isoprene polymer powder

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李瑜等: "《季铵盐改性凹凸棒土及处理含有废水》", 《非金属矿》 *
杨晋涛等: "《原位乳液聚合制备聚苯乙烯丁二烯橡胶/凹凸棒石纳米复合材料》", 《现代化工》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304860A (en) * 2013-06-16 2013-09-18 北京化工大学 Tire tread rubber without zinc oxide
CN105733047A (en) * 2014-12-11 2016-07-06 中国石油天然气股份有限公司 Nitrile rubber/attapulgite nano composite material, vulcanized rubber and preparation method thereof
CN107805327A (en) * 2016-09-08 2018-03-16 中国石油天然气股份有限公司 Oil-extended ternary integrated rubber and preparation method thereof
CN106893161A (en) * 2017-04-11 2017-06-27 安徽省明美矿物化工有限公司 A kind of rubber containing attapulgite and preparation method thereof
CN107236081A (en) * 2017-06-29 2017-10-10 襄阳福源兴盛科技有限公司 A kind of carboxylic acid styrene-butadiene latex
CN107189496A (en) * 2017-07-13 2017-09-22 长春工业大学 A kind of modification illite preparation method for improving natural rubber performance
CN115806741A (en) * 2021-09-14 2023-03-17 中国石油化工股份有限公司 Filling oil for styrene butadiene rubber and preparation method thereof
CN115806741B (en) * 2021-09-14 2024-04-09 中国石油化工股份有限公司 Filling oil for styrene butadiene rubber and preparation method thereof

Also Published As

Publication number Publication date
CN103804735B (en) 2016-06-08

Similar Documents

Publication Publication Date Title
CN103804735A (en) Preparation method of modified oil-extended powder styrene-butadiene rubber
Kang et al. Effect of graphene oxide (GO) on hydration of tricalcium silicate (C3S)
Han et al. A review on the development and application of graphene based materials for the fabrication of modified asphalt and cement
Jing et al. From graphene oxide to reduced graphene oxide: Enhanced hydration and compressive strength of cement composites
Tian et al. Research on modifier and modified process for rubber-particle used in rubberized concrete for road
CN101381488A (en) Kaolin/rubber nano compound material with strengthening and obstructing dual property
CN103804530A (en) Preparation method of modified powdered styrene butadiene rubber
CN103359753B (en) Preparation method of kaolin-silane embedded intercalating modified complex
CN1079409C (en) Process for preparing clay-rubber nm-class composite material
GB2370280A (en) Lightweight rubber composition containing clay
JP2003192833A (en) Preparation and use of nanocomposite material of elastomer and exfoliated clay platelet formed in situ within elastomer matrix and product including tire having at least one component comprising the same
Turhan et al. Preparation and characterization of poly (vinylalcohol)/modified bentonite nanocomposites
KR20130048743A (en) Liquid curable composition
JP6833251B2 (en) Organic-inorganic composite for rubber reinforcement, its manufacturing method and rubber composition for tires containing it
CN104371152A (en) Clay/rubber nano composite material prepared from compound modified clay
CN101508801B (en) Method for preparing oil-filled styrene butadiene rubber SBR1712/attapulgite stone nano-composite material
Jia et al. Advances in rubber/halloysite nanotubes nanocomposites
CN105153750A (en) Wear-resistant surface modified calcium carbonate filler and preparation method thereof
CN105061837B (en) A kind of method that industry half wet process is attapulgite modified
Yin et al. Mechanical properties and micro-mechanism of cement-based materials strengthened by in-situ organic-inorganic polymerization
Wang et al. Fabrication of MoS2-based environment friendly modifier via tannic acid assisted diethylenetriamine co-deposition for the preparation of composite SBS modified asphalt
CN103804529B (en) Preparation method of modified styrene butadiene rubber
CN104650303B (en) Preparation method of modified oil-extended high-performance powdered styrene-butadiene rubber
CN103724736B (en) The original position of rubber/clay nano composite material is organically-modified-preexpanding preparation method
CN104650421B (en) Preparation method of rice hull ash modified styrene butadiene rubber

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant