CN102863576A - Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same - Google Patents
Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same Download PDFInfo
- Publication number
- CN102863576A CN102863576A CN2012103023928A CN201210302392A CN102863576A CN 102863576 A CN102863576 A CN 102863576A CN 2012103023928 A CN2012103023928 A CN 2012103023928A CN 201210302392 A CN201210302392 A CN 201210302392A CN 102863576 A CN102863576 A CN 102863576A
- Authority
- CN
- China
- Prior art keywords
- polyisoprene rubber
- conditioning agent
- composite structure
- preparation
- organolithium
- 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
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the field of preparation of chemicals, in particular to a compound structure modifier for preparing 3,4-isoprene rubber and a method for preparing 3,4-isoprene rubber by using the same. The compound structure modifier combines a tertiary amine-type structure modifier and an anionic surfactant, wherein the molar ratio of the tertiary amine-type structure modifier to the anionic surfactant is 0.2 to 20; the tertiary amine-type structure modifier may be N, N, N', N'-tetramethyl ethylene diamine, trimethylamine, triethylanmine, pentamethyldiethylenetriamine or hexamethylphosphoric triamide; and the anionic surfactant is C4 to C20 alkane sulfonate. According to the preparation method provided by the invention, at a relative high polymerization temperature, the content of the 3,4 structure of the polymers can be effectively modified, and the content of the 3,4 structure of the obtained products is over 70 percent. When the polymers are applied to tire tread rubber of automobile tires, the tire tread is quite high in wet skid resistance and low in rolling resistance.
Description
Technical field
The invention belongs to the chemical preparation field, specifically a kind of composite structure conditioning agent that is applicable to prepare 3,4-polyisoprene rubber and for the preparation of the method for 3,4-polyisoprene rubber.
Background technology
Along with the construction of high-grade highway and improving constantly of automobile speed per hour, people have proposed more and more higher requirement to the security of automobile, and hauling ability and wet-sliding resistant performance become the important indicator of weighing tyre performance.3,4-polyisoprene (3,4-Polyisoprene, be called for short 3,4-PIp) on the building block of rubber larger side group arranged, so that both had excellent wet-sliding resistant performance with the tread rubber of its preparation, there is not again the serious living heat of styrene-butadiene rubber(SBR) (SBR), so receive much concern.
At present the method for preparation 3,4-polyisoprene rubber has anionic polymerization and polycomplexation legal, and polycoordination mainly contains titanium system, iron system, and rare earths etc., titanium are that rubber is because the chemical valence of titanium elements is unstable, so that ageing of rubber is accelerated; The rubber gels content of iron system preparation is higher, affects the performance of rubber; 3 of the preparation of Rare Earth, 4-polyisoprene rubber 3,4 structural contents are higher, but the rare earth catalyst synthesis technique is harsh, and be difficult for preserving, be not suitable for industrialization.The rubber impurities of anionic polymerization preparation is less, and molecular weight can be controlled, and technique is relatively simple, and industrialization has certain feasibility.
Mentioned among the US3536690 take sodium and some organism (fluorochemical) as catalyzer and prepare 3,4-polyisoprene rubber, but this initiator system is nonhomogeneous system, the initiator utilization ratio is low, and severe reaction conditions, and productive rate is not high, is unfavorable for industrialization.
US4894425, having mentioned the employing asymmetrical ether among the US5336739 is the polyisoprene rubber that structure regulator prepares high 3,4 content, but preparation technology's more complicated of present asymmetrical ether, the domestic industry product is less, needs import, and cost is higher.
Mention among the JP7638356 take the naphthyl lithium as initiator, tetrahydrofuran (THF) is that structure regulator causes isoprene in hexane, can obtain high by 3, the polyisoprene rubber of 4 structural contents, but the preparation process condition of naphthyl lithium is harsh, has increased production cost, and the regulating power of tetrahydrofuran (THF) is with the rising reduction of temperature, reaction will be cooled off when reaching a high temperature, and technique is complicated.
Mentioned the method for synthetic 3, the 4-polyisoprene rubber of a kind of employing anionoid polymerization among the US5667402, the method is received as structure regulator take TMEDA and alkoxyl group, can obtain 3,4 structural contents at 3 more than 80%, the 4-polyisoprene rubber.But because the cost of sodium alkylate is higher, increased the production cost of rubber, and sodium tert-amyl alcohol and hexanaphthene difficulty separate, aftertreatment technology is complicated.
Yang Xingkun etc. have studied take hexanaphthene as solvent, and n-Butyl Lithium is that initiator, dioxane (DOX) prepare 3,4-polyisoprene rubber for polar modifier, find that dioxane increases regulating power with temperature and descends, and regulating power is unstable.
Consider feasibility and the production cost of suitability for industrialized production, reaction must guarantee faster speed of reaction, and this just need to have higher temperature of reaction.And for polar modifier, temperature is higher, and its regulating power is more weak.Under industrialized optimal temperature (50-70 ℃), the regulating power of most of polar modifier all a little less than.Therefore seek the polar modifier that is fit to polymerization under the high temperature and just become the key that lithium is the polyisoprene rubber of synthetic high 3,4 structural contents of initiator system.
Summary of the invention
The object of the invention is to provide a kind of composite structure conditioning agent that is applicable to prepare 3,4-polyisoprene rubber and for the preparation of the method for 3,4-polyisoprene rubber.
The technical solution used in the present invention is for achieving the above object:
A kind of composite structure conditioning agent that is applicable to prepare 3,4-polyisoprene rubber, the composite structure conditioning agent is the mixture of tertiary amines structure regulator and anion surfactant; Wherein the mol ratio of tertiary amines structure regulator and anion surfactant is 0.2-20, and described tertiary amines structure regulator is N, N, N ', N '-Tetramethyl Ethylene Diamine, Trimethylamine, triethylamine, PMDETA or HMPA; Described anion surfactant is C
4-C
20Alkylsulfonate.
Described tertiary amines structure regulator is N, N, N ', N '-Tetramethyl Ethylene Diamine; Described anion surfactant is sodium laurylsulfonate, dodecyl sodium sulfonate potassium, Sodium dodecylbenzene sulfonate or Potassium dodecylbenzenesulfonate.
The composite structure conditioning agent is for the preparation of 3, the method of 4-polyisoprene rubber, in polymerization reaction kettle, add first organic solvent, add again isoprene monomer, then described composite structure conditioning agent is added in the polymerization reaction system, adopt organolithium that system is killed assorted, is able to polymerization after killing assorted the end under the initiation of organolithium, the condition of polymerization is to be 4-5h in 0 ℃ of-100 ℃ of polymerization time under nitrogen protection; Add terminator and anti-aging agent after reaction finishes, last vacuum drying treatment namely obtains 3,4-polyisoprene rubber.
The mol ratio of described tertiary amines structure regulator and organolithium is 0.01-10, and the mol ratio of anion surfactant and organolithium is 0.01-5; Described tertiary amines structure regulator is N, N, N ', N '-Tetramethyl Ethylene Diamine, Trimethylamine, triethylamine, PMDETA or HMPA; Described anion surfactant is C
4-C
20Alkylsulfonate; Described organolithium is C
1-C
6Lithium alkylide, C
6-C
12Lithium aryl, C
7-C
14Aralkyl lithium or C
3-C
12The cycloalkyl lithium.
Described organic solvent is hexanaphthene, normal hexane, Skellysolve A, normal heptane, one or more mixtures in toluene, the tetrahydrofuran (THF), in the described polymerization reaction kettle organic solvent and the isoprene monomer that adds mixed, the massfraction of monomer is 8%-25% in its mixed solution.
Described terminator is water, methyl alcohol, ethanol or Virahol; Wherein the terminator consumption is 1-1.5 times of organolithium amount of substance.
Described anti-aging agent is 2,6 ditertiary butyl p cresol, tert-butyl catechol or 2,2 '-methylene radical-two (4-methyl-6-tert-butylphenol); Wherein aging inhibitor dosage is the 0.05-2% of monomer total mass.
The present invention has advantages of:
The present invention is applicable to the structure regulator of high 3,4 structural contents of adjusting polyisoprene rubber of suitability for industrialized production, namely still has higher regulating power under higher temperature.Adopt composite structure conditioning agent of the present invention to obtain the polyisoprene of high 3,4 structural contents, the composite structure conditioning agent is to temperature-insensitive, and regulating power is more stable, has simplified polymerization technique.These polymkeric substance are used for the rubber item of doughnut etc., will give the good anti-slippery of tire and low-rolling-resistance.
Embodiment
Further specify the characteristics of this research below in conjunction with embodiment, but scope of the present invention is not limited to these embodiment.
The present invention prepares 3, the method of 4-polyisoprene rubber is under the anionoid polymerization condition, take organolithium as initiator, take tertiary amines structure regulator and anion surfactant mixture as structure regulator, in organic solvent, make the isoprene monomer polymerization, adding terminator and anti-aging agent after polyreaction is finished.Wherein polymerization temperature is 0 ℃-100 ℃, preferred 30 ℃-70 ℃, and polymerization time 0.5-5 hour, preferred 4-5 hour.
Described organic solvent is hexanaphthene, normal hexane, Skellysolve A, normal heptane, one or more mixtures in toluene or the tetrahydrofuran (THF); When described normal hexane mixes with hexanaphthene, take mass ratio as 1:4.
The massfraction of isoprene monomer is 8%-25% in the described polyreaction organic solvent, preferred 10%-20%.
Described organolithium is initiator, and selected organolithium is C
1-C
6Lithium alkylide, C
6-C
12Lithium aryl, C
7-C
14Aralkyl lithium or C
3-C
12The cycloalkyl lithium, preferred lithium ethide, isopropyl lithium, s-butyl lithium, tert-butyl lithium, uncle's octyl group lithium, dodecyl lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-tolyl lithium or cyclohexyl lithium or 4-butyl cyclohexyl lithium; More preferably n-Butyl Lithium or s-butyl lithium are take n-Butyl Lithium as best.
Described tertiary amines structure regulator is N, N, N ', N '-Tetramethyl Ethylene Diamine, Trimethylamine, triethylamine, PMDETA or HMPA; Preferred N, N, N ', N '-Tetramethyl Ethylene Diamine (TMEDA).Its tertiary amines structure regulator consumption is 0.01-10:1 for the mol ratio with organolithium, and is preferred: 0.1-2:1.
Described anion surfactant is C
4-C
20Alkylsulfonate, such as sodium laurylsulfonate (SDBS), dodecyl sodium sulfonate potassium, Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate is preferably Sodium dodecylbenzene sulfonate.The mol ratio of its anion surfactant and organolithium is 0.01-5:1, preferred 0.05-0.5:1.
Described terminator is water, methyl alcohol, ethanol, Virahol.Take ethanol as main, the 1-1.5 that its terminator consumption is the organic lithium initiator amount of substance doubly.
Described anti-aging agent is 2,6 ditertiary butyl p cresol, tert-butyl catechol, 2,2 '-methylene radical-two (4-methyl-6-tert-butylphenol), and take 2,6 ditertiary butyl p cresol as main, wherein aging inhibitor dosage is the 0.05-2% of monomer total mass.
Embodiment 1
Carry out in 5 liters of polymeric kettles, paradigmatic system is through high-purity N
2After the displacement; under the high pure nitrogen protection; in still, add hexanaphthene 3000ml and isoprene monomer 500ml mixing according to this; the monomer mass mark is 14.5% in the mixed solution; then in reactor, add structure regulator TMEDA(0.25mol/L again) 13.8ml, Sodium dodecylbenzene sulfonate (0.1mol/L) 17.2ml, reactor is warming up to 50 ℃ of constant temperature; kill assorted rear n-Butyl Lithium (0.43mol/L) 8ml that adds, then carry out polyreaction.Reaction pressure is 0.1-0.3MPa.Polyreaction 4 hours, add terminator ethanol 0.2g and anti-aging agent 2,6-ditertbutylparacresol 3.4g, glue settles out in ethanol, then under 40 ℃ through air dry oven dry 3 hours, at vacuum drying oven dry 48 hours again, obtain high 3,4 content and be 72% 3, the 4-polyisoprene rubber, Mn is 104896, and molecular weight distribution is 1.18.
Embodiment 2-6
Carry out in 5 liters of polymeric kettles, paradigmatic system is through high-purity N
2After the displacement deoxidation, under high pure nitrogen protection, add hexanaphthene 3000ml in the still according to this and isoprene 500ml mixes, the monomer mass mark is 14.5% in the mixed solution; Then in reactor, add structure regulator TMEDA(0.25mol/L again) and Sodium dodecylbenzene sulfonate (0.1mol/L), the proportioning of structure regulator and n-Butyl Lithium sees Table one, be warming up to respectively 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ of constant temperature, kill assorted rear n-Butyl Lithium (0.43mol/L) 12.5ml that adds, then carry out polyreaction.Reaction pressure is 0.1-0.3MPa.Polyreaction 4 as a child adds terminator ethanol 0.2g and anti-aging agent 3.4g, and glue settles out in ethanol, then under 40 ℃ through dry 3 hours of air dry oven, obtained the glue sample in dry 48 hours at vacuum drying oven again, the test result of glue sample sees Table one.
Comparative Examples 1-5
Experimental technique only is not add SDBS in the reactor polymerization reaction system with embodiment 2-6.The test result of product sees Table one.
Table one
Application examples 1-2 and contrast application examples 6
Get above-described embodiment and prepare gained 3,10～20 parts of 4-polyisoprene rubbers are compound with 85～90 parts of natural rubbers, compound rear respectively with sulphur, captax (captax is 2-thiol benzothiazole MBT), zinc oxide, antioxidant 2246(antioxidant 2246 is 2,2 '-methylene-bis (4-methyl-6-tert.-butyl phenol)), stearic acid, carbon black carries out blend, prescription and test result see Table two, can be found out by table two, along with 3, the increase of 4-polyisoprene rubber content, the anti-slippery index of blend has improved 0.07-0.14 than Comparative Examples 6, rolling resistance index has improved 0.02-0.05 than Comparative Examples, and abrasion and living thermal distortion are little.
Table two
| Application examples 1 | Application examples 2 | Comparative Examples 6 | |
| Natural rubber/phr | 90 | 80 | 100 |
| 3,4-polyisoprene rubber/phr | 10 | 20 | 0 |
| Anti-slippery index (50km/h) | 1.07 | 1.14 | 1.00 |
| Rolling resistance index (50km/h) | 0.98 | 0.95 | 1.00 |
| Living heat/℃ | 136 | 137 | 135 |
| Abrasion (mm 3） | 105 | 110 | 100 |
Prescription/phr: carbon black 50, zinc oxide 3, captax 1.2, sulphur 3, antioxidant 22462, stearic acid 1; 3,4-polyisoprene rubber: 3,4-content 71%, Tg-8 ℃, relative molecular weight (Mn) 20 * 10
4, ML(1+4) 100 ℃ 60.
Claims (7)
1. composite structure conditioning agent that is applicable to prepare 3,4-polyisoprene rubber, it is characterized in that: the composite structure conditioning agent is the mixture of tertiary amines structure regulator and anion surfactant; Wherein the mol ratio of tertiary amines structure regulator and anion surfactant is 0.2-20, and described tertiary amines structure regulator is N, N, N ', N '-Tetramethyl Ethylene Diamine, Trimethylamine, triethylamine, PMDETA or HMPA; Described anion surfactant is C
4-C
20Alkylsulfonate.
2. by the composite structure conditioning agent that is applicable to prepare 3,4-polyisoprene rubber claimed in claim 1, it is characterized in that: described tertiary amines structure regulator is N, N, N ', N '-Tetramethyl Ethylene Diamine; Described anion surfactant is sodium laurylsulfonate, dodecyl sodium sulfonate potassium, Sodium dodecylbenzene sulfonate or Potassium dodecylbenzenesulfonate.
3. a composite structure conditioning agent claimed in claim 1 is for the preparation of 3, the method of 4-polyisoprene rubber, it is characterized in that: in polymerization reaction kettle, add first organic solvent, add again isoprene monomer, then described composite structure conditioning agent is added in the polymerization reaction system, adopt organolithium that system is killed assorted, is able to polymerization after killing assorted the end under the initiation of organolithium, the condition of polymerization is to be 4-5h in 0 ℃ of-100 ℃ of polymerization time under nitrogen protection; Add terminator and anti-aging agent after reaction finishes, last vacuum drying treatment namely obtains 3,4-polyisoprene rubber.
4. composite structure conditioning agent claimed in claim 3 is characterized in that for the preparation of the method for 3,4-polyisoprene rubber: the mol ratio of described tertiary amines structure regulator and organolithium is 0.01-10, and the mol ratio of anion surfactant and organolithium is 0.01-5; Described tertiary amines structure regulator is N, N, N ', N '-Tetramethyl Ethylene Diamine, Trimethylamine, triethylamine, PMDETA or HMPA; Described anion surfactant is C
4-C
20Alkylsulfonate; Described organolithium is C
1-C
6Lithium alkylide, C
6-C
12Lithium aryl, C
7-C
14Aralkyl lithium or C
3-C
12The cycloalkyl lithium.
5. composite structure conditioning agent claimed in claim 3 is for the preparation of 3, the method of 4-polyisoprene rubber, it is characterized in that: described organic solvent is hexanaphthene, normal hexane, Skellysolve A, normal heptane, one or more mixtures in toluene, the tetrahydrofuran (THF), in the described polymerization reaction kettle organic solvent and the isoprene monomer that adds mixed, the massfraction of monomer is 8%-25% in its mixed solution.
6. composite structure conditioning agent claimed in claim 3 is characterized in that for the preparation of the method for 3,4-polyisoprene rubber: described terminator is water, methyl alcohol, ethanol or Virahol; Wherein the terminator consumption is 1-1.5 times of organolithium amount of substance.
7. composite structure conditioning agent claimed in claim 3 is characterized in that for the preparation of the method for 3,4-polyisoprene rubber: described anti-aging agent is 2,6 ditertiary butyl p cresol, tert-butyl catechol or 2,2 '-methylene radical-two (4-methyl-6-tert-butylphenol); Wherein aging inhibitor dosage is the 0.05-2% of monomer total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210302392.8A CN102863576B (en) | 2012-08-23 | 2012-08-23 | Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210302392.8A CN102863576B (en) | 2012-08-23 | 2012-08-23 | Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102863576A true CN102863576A (en) | 2013-01-09 |
| CN102863576B CN102863576B (en) | 2014-11-19 |
Family
ID=47442727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210302392.8A Expired - Fee Related CN102863576B (en) | 2012-08-23 | 2012-08-23 | Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102863576B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224578A (en) * | 2013-01-29 | 2013-07-31 | 富阳经略化工技术有限公司 | Ethylene propylene diene monomer and preparation method thereof |
| CN104628951A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Structure regulator for anionic polymerization and anionic polymerization method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894425A (en) * | 1986-05-31 | 1990-01-16 | Huels Aktiengesellschaft | Preparation of polyisoprene having high content of 1,2- and 3,4-structural units by anionic polymerization |
| CN101007860A (en) * | 2006-01-28 | 2007-08-01 | 中国石油化工股份有限公司 | Method for synthesizing vinyl solution-polymerization butadiene-isoprene rubber adopting composite regulation system |
| CN101062964A (en) * | 2007-05-21 | 2007-10-31 | 北京化工大学 | Method for synthesizing star amphiphilic rubber |
-
2012
- 2012-08-23 CN CN201210302392.8A patent/CN102863576B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894425A (en) * | 1986-05-31 | 1990-01-16 | Huels Aktiengesellschaft | Preparation of polyisoprene having high content of 1,2- and 3,4-structural units by anionic polymerization |
| CN101007860A (en) * | 2006-01-28 | 2007-08-01 | 中国石油化工股份有限公司 | Method for synthesizing vinyl solution-polymerization butadiene-isoprene rubber adopting composite regulation system |
| CN101062964A (en) * | 2007-05-21 | 2007-10-31 | 北京化工大学 | Method for synthesizing star amphiphilic rubber |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224578A (en) * | 2013-01-29 | 2013-07-31 | 富阳经略化工技术有限公司 | Ethylene propylene diene monomer and preparation method thereof |
| CN103224578B (en) * | 2013-01-29 | 2015-03-11 | 富阳经略化工技术有限公司 | Ethylene propylene diene monomer and preparation method thereof |
| CN104628951A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Structure regulator for anionic polymerization and anionic polymerization method |
| CN104628951B (en) * | 2013-11-12 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of anionic polymerisation structure regulator and a kind of anionic polymerisation process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102863576B (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1326884C (en) | Modified polymers with a high content of cis-position double bonds, a process for their production as wall as their use | |
| EP3059258B1 (en) | Modified conjugated diene-based polymer, method for preparing same, and rubber composition comprising same | |
| EP3101036B1 (en) | Modified conjugated diene polymer, a modified rubber composition containing same, and method for preparing modified conjugated diene polymer | |
| US9868795B2 (en) | Vinyl modifier composition and processes for utilizing such composition | |
| US6812277B2 (en) | Tire with component comprised of a blend of polybutadiene-rich rubber composition which contains a minor portion of styrene-rich styrene/isoprene elastomer | |
| EP2360189B1 (en) | Conjugated diene polymer manufacturing method, polybutadiene, and rubber composition utilizing the same | |
| KR101909756B1 (en) | Aminosilane initiators and functionalized polymers prepared therefrom | |
| CN104119578A (en) | Rubber composition for tread of truck radial tire with low hysteresis loss | |
| CN105001467B (en) | Wet masterbatch of NdBR and its preparation method and application | |
| CN106661283B (en) | Rubber composition for tire and pneumatic tire | |
| EP2871191B1 (en) | Method for producing polybutadiene, polybutadiene, rubber composition and tire | |
| Braum et al. | Silica grafted with epoxidized liquid polybutadienes: its behavior as filler for tire tread compounds | |
| EP3450468A1 (en) | Process for producing modified polymer, modified polymer, rubber composition, and tire | |
| TW202041539A (en) | Hydrogenated conjugated diene polymer, polymer composition, crosslinked body and tire | |
| CN102863576B (en) | Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same | |
| EP3106469B1 (en) | Modified conjugated diene polymer, modified rubber composition comprising same, and method for preparing modified conjugated diene polymer | |
| EP2746331A1 (en) | Rubber composition for tire, and pneumatic tire | |
| US20110196063A1 (en) | Rubber composition for tread and tire using the rubber composition | |
| CN105121477A (en) | Catalyst for use in polymerization of conjugated diene, conjugated diene polymer and modified conjugated diene polymer each produced using said catalyst, methods respectively for producing said polymers, rubber composition for tires, and rubber composition for rubber belts | |
| JP3731521B2 (en) | Modified diene polymer rubber, method for producing the same, and rubber composition | |
| CN102199232A (en) | Anion trigger system and polymerization method for synthesizing trans polybutadiene and copolymer thereof | |
| CA1208845A (en) | Elastomers and tyres containing them | |
| CN106715479B (en) | Conjugated-diolefin (co) polymer shares catalyst, conjugated diolefin polymer, modified conjugated diene polymer, polybutadiene and the composition comprising aforementioned substances | |
| KR102549890B1 (en) | Method for producing modified conjugated diene-based polymer, modified conjugated diene-based polymer, polymer composition, crosslinked product and tire | |
| CN112409520B (en) | Preparation of polybutadiene and catalyst thereof by homogeneous rare earth catalyst |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141119 Termination date: 20210823 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |