CN106084108A - A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber - Google Patents
A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber Download PDFInfo
- Publication number
- CN106084108A CN106084108A CN201610413640.4A CN201610413640A CN106084108A CN 106084108 A CN106084108 A CN 106084108A CN 201610413640 A CN201610413640 A CN 201610413640A CN 106084108 A CN106084108 A CN 106084108A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- amidino groups
- isoprene rubber
- alkyl compound
- groups rare
- 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
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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/08—Isoprene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber, belongs to diolefin polymerization field.The method comprises the following steps: by amidino groups rare earth alkyl compound, joins in eggplant type bottle, adds solvent and monomer, add alkyl aluminum toluene solution, stirring 5 ~ 15min, adds the organic boronic saline solution that toluene dissolves, reaction is placed in the oil bath pan of 25 ~ 60 DEG C, stirring, reaction 5 ~ 360min, after reaction terminates, under stirring, add a large amount of industrial alcohol until polymer separates out completely, prepare isoprene rubber.The method uses amidino groups rare earth compound, adds chain-transferring agent, the isoprene rubber narrow molecular weight distribution of preparation, the advantages such as Mooney viscosity is adjustable.
Description
Technical field
The invention belongs to diolefin polymerization field, prepare isoprene rubber particularly to a kind of amidino groups rare earth alkyl compound
Method.
Background technology
Double olefin copolymer, because containing double bond in structure, can use sulfur cross-linking so that linear structure becomes netted
Structure, for rubber.Isoprene is the monomer of isoprene rubber, and isoprene rubber has 4 kinds of stereoregular structures: cis-Isosorbide-5-Nitrae-
Poly-isoprene rubber, trans-Isosorbide-5-Nitrae-poly-isoprene rubber, 3,4-poly-isoprene rubbers and 1, the poly-isoprene rubber of 2-.Wherein, cis-Isosorbide-5-Nitrae-poly-different
Penta rubber, because its chemical composition, stereochemical structure and mechanical property are quite similar with natural rubber, also referred to as " synthesis of natural rubber
Glue ", also it is a kind of rubber of extremely paying close attention to of research staff.Trans-Isosorbide-5-Nitrae-poly-isoprene rubber is also referred to as gutta-percha, has shape memory
Function.First two rubber is all the isoprene rubber kind that nature exists.1,2-poly-isoprene rubber is because of structural instability, seldom
Can obtain.3,4-isoprene rubbers are a kind of kinds of anti-slippery rubber, are also the emphasis of research, and research shows, 3,4-poly-isoamyls
Diene is used for high-performance tire, has significant oil resistivity, resistance to water, water penetration, a breathability, excellent anti-slippery, simultaneously
Heat is little, can be widely applied to submarine cable, high-performance tire etc..
Rare earth catalyst can aggregate into the side-product in petroleum refinery process, such as ethylene, propylene, butylene and aromatic hydrocarbon
The synthetic rubber of various performances.Rare earth IR is the raw catelyst kind that first China develop, and has technique relatively easy, product
Can be stable, the advantages such as product post processing is simple.Synthesize the rare earth catalyst of isoprene rubber at present, mainly have neodecanoic acid rare earth, ring
Several big kinds such as alkanoic acid rare earth, phosphate ester rare earth, and industrial applications.
Summary of the invention
It is an object of the invention to provide a kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber, the method uses
Amidino groups rare earth compound, adds chain-transferring agent, the isoprene rubber narrow molecular weight distribution of preparation, the advantages such as Mooney viscosity is adjustable.
A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber, comprises the following steps:
Eggplant type bottle except water deoxygenation is put in glove box, weighs 16 ~ 20mg amidino groups rare earth alkyl compound, join eggplant type bottle
In, add 5 ~ 10ml solvent and refined isoprene monomer, wherein, the mol ratio of monomer and catalyst be (1000:1) ~
(2000:1)；Add the alkyl aluminum toluene solution of the 1M concentration of 100 ~ 500 μ L, stir 5 ~ 15min, add 1 ~ 5ml toluene and dissolve
Organic boronic saline solution, the most boratory quality is 20 ~ 30mg, reaction is placed in the oil bath pan of 25 ~ 60 DEG C, stirring,
Reaction 5 ~ 360min, after reaction terminates, under stirring, adds a large amount of industrial alcohol until polymer separates out completely.Will polymerization
Thing is put in the vacuum drying oven of 40 ~ 50 DEG C, is dried, and prepares poly-isoprene rubber, and the change of dried poly-isoprene rubber weight exists
In 0.001g, calculate productivity by weighing.
Wherein, described amidino groups rare earth alkyl molecular structure of compounds formula is:
Wherein, Ln is rare earth element, for the one in scandium, yttrium or all lanthanide series；Preferably neodymium, yttrium；
R is the one in ph, pyridine or tBu.
Described solvent is toluene, one in chlorobenzene, pentane, normal hexane or hexamethylene.
Described alkyl aluminum is the one in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium or three amyl group aluminum
Or it is several.
Described organic borate is [Ph3C][B(C6F5)4] or [PhMe2NH][B(C6F5)4One in].
The method that the amidino groups rare earth alkyl compound that the present invention provides prepares isoprene rubber, compared to prior art, has
Following advantage:
In the isoprene rubber of preparation, 3,4-structural contents comparatively speaking, are not the highest, have rigidity and flexible nature concurrently, have again
Anti-slippery structure, compared to high by 3, for the isoprene rubber of 4-structural content, during solving post-treatment, filler is not easy
The problem being mixed into, decreases the energy consumption of calendering process.
The method uses amidino groups rare earth compound, adds chain-transferring agent, the isoprene rubber narrow molecular weight distribution of preparation, Mooney
The advantages such as viscosity is adjustable.
Detailed description of the invention
In order to further illustrate technical scheme, below in conjunction with embodiment, the preferred embodiment of the invention is entered
Line description.
Embodiment 1
100ml eggplant type bottle except water deoxygenation is put in glove box, weighs 16mg amidino groups yttrium alkyl compound and join 100ml eggplant
In type bottle, add 5ml toluene, the isoprene monomer that 1.022g is refined；Add the triisobutyl aluminium first of the 1M concentration of 100 μ L
Benzole soln, stirs 5min, adds [the Ph that 1ml toluene dissolves3C][B(C6F5)4] solution, wherein [Ph3C][B(C6F5)4] quality
For 20mg, reaction is placed in the oil bath pan of 25 DEG C, stirring, reacts 10min, after reaction terminates, under stirring, add a large amount of
Industrial alcohol is until polymer separates out completely.Polymer is put in the vacuum drying oven of 40 DEG C, be dried, until dried poly-
Till polymer weight change is in 0.001g, the productivity of polymer is 100%.Testing through GPC, the weight average of polyisoprene divides
Son amount is 240,000, and number-average molecular weight is 160,000, and molecular weight distribution is 1.5, and through infrared test analysis, 3,4-structural contents are
75%。
Embodiment 2
100ml eggplant type bottle except water deoxygenation is put in glove box, weighs 20mg amidino groups neodymium alkyl compound and join 100ml eggplant
In type bottle, add 10ml normal hexane, the isoprene monomer that 10g is refined；Add the triisobutyl aluminium first of the 1M concentration of 500 μ L
Benzole soln, stirs 15min, adds [the PhMe that 5ml toluene dissolves2NH][B(C6F5)4] solution, wherein [PhMe2NH][B
(C6F5)4] quality be 30mg, reaction is placed in the oil bath pan of 60 DEG C, stirring, react 360min, reaction terminate after, stirring
Under state, add a large amount of industrial alcohol until polymer separates out completely.Polymer is put in the vacuum drying oven of 40 DEG C, dry
Dry, till the change of dried polymer weight is in 0.001g, the productivity of polymer is 100%.Test through GPC, poly-
The weight average molecular weight of isoprene is 320,000, and number-average molecular weight is 18.8 ten thousand, and molecular weight distribution is 1.7, divides through infrared test
Analysis, 3,4-structural contents are 74.5%.
Embodiment 3
100ml eggplant type bottle except water deoxygenation is put in glove box, weighs 20mg amidino groups neodymium alkyl compound and join 100ml eggplant
In type bottle, add 10ml chlorobenzene, the isoprene monomer that 10g is refined；The triethyl aluminum toluene of the 1M concentration adding 300 μ L is molten
Liquid, stirs 15min, adds [the PhMe that 5ml toluene dissolves2NH][B(C6F5)4] solution, wherein [PhMe2NH][B(C6F5)4]
Quality is 30mg, reaction is placed in the oil bath pan of 40 DEG C, stirring, reacts 360min, after reaction terminates, under stirring, adds
Enter a large amount of industrial alcohol until polymer separates out completely.Polymer is put in the vacuum drying oven of 40 DEG C, be dried, until being dried
After polymer weight change in 0.001g till, the productivity of polymer is 100%.Test through GPC, polyisoprene
Weight average molecular weight is 420,000, and number-average molecular weight is 300,000, and molecular weight distribution is 1.4, and through infrared test analysis, 3,4-structures contain
Amount is 76.5%.
Embodiment 4
100ml eggplant type bottle except water deoxygenation is put in glove box, weighs 16mg amidino groups neodymium alkyl compound and join 100ml eggplant
In type bottle, add 10ml hexamethylene, the isoprene monomer that 10g is refined；Add the triethyl aluminum toluene of the 1M concentration of 200 μ L
Solution, stirs 15min, adds [the Ph that 4ml toluene dissolves3C][B(C6F5)4] solution, wherein [Ph3C][B(C6F5)4] quality
For 22mg, reaction is placed in the oil bath pan of 50 DEG C, stirring, reacts 240min, after reaction terminates, under stirring, add big
Amount industrial alcohol is until polymer separates out completely.Polymer is put in the vacuum drying oven of 40 DEG C, be dried, until dried
Till polymer weight change is in 0.001g, the productivity of polymer is 100%.Test through GPC, the weight average of polyisoprene
Molecular weight is 480,000, and number-average molecular weight is 300,000, and molecular weight distribution is 1.6, and through infrared test analysis, 3,4-structural contents are
73%。
Embodiment 5
100ml eggplant type bottle except water deoxygenation is put in glove box, weighs 18mg amidino groups neodymium alkyl compound and join 100ml eggplant
In type bottle, add 10ml chlorobenzene, the isoprene monomer that 10g is refined；The triethyl aluminum toluene of the 1M concentration adding 100 μ L is molten
Liquid, stirs 15min, adds [the Ph that 3ml toluene dissolves3C][B(C6F5)4] solution, wherein [Ph3C][B(C6F5)4] quality be
25mg, is placed in reaction in the oil bath pan of 40 DEG C, stirring, reacts 300min, after reaction terminates, under stirring, adds a large amount of
Industrial alcohol is until polymer separates out completely.Polymer is put in the vacuum drying oven of 40 DEG C, be dried, until dried poly-
Till polymer weight change is in 0.001g, the productivity of polymer is 100%.Testing through GPC, the weight average of polyisoprene divides
Son amount is 520,000, and number-average molecular weight is 290,000, and molecular weight distribution is 1.79, and through infrared test analysis, 3,4-structural contents are
75.2%。
Claims (5)
1. the method that an amidino groups rare earth alkyl compound prepares isoprene rubber, it is characterised in that comprise the following steps:
Eggplant type bottle except water deoxygenation is put in glove box, weighs 16 ~ 20mg amidino groups rare earth alkyl compound, join eggplant type bottle
In, add 5 ~ 10ml solvent and refined isoprene monomer, wherein, the mol ratio of monomer and catalyst be (1000:1) ~
(2000:1)；Add the alkyl aluminum toluene solution of the 1M concentration of 100 ~ 500 μ L, stir 5 ~ 15min, add 1 ~ 5ml toluene and dissolve
Organic boronic saline solution, the most boratory quality is 20 ~ 30mg, reaction is placed in the oil bath pan of 25 ~ 60 DEG C, stirring,
Reaction 5 ~ 360min, after reaction terminates, under stirring, adds a large amount of industrial alcohol until polymer separates out completely, will polymerization
Thing is put in the vacuum drying oven of 40 ~ 50 DEG C, is dried, and prepares poly-isoprene rubber.
2. require, according to right 1, the method that described amidino groups rare earth alkyl compound prepares isoprene rubber, it is characterised in that described
Amidino groups rare earth alkyl molecular structure of compounds formula be:
Wherein, Ln is rare earth element, for the one in scandium, yttrium or all lanthanide series；
R is the one in ph, pyridine or tBu.
3. require, according to right 1, the method that described amidino groups rare earth alkyl compound prepares isoprene rubber, it is characterised in that described
Solvent be for the one in toluene, chlorobenzene, pentane, normal hexane or hexamethylene.
4. require, according to right 1, the method that described amidino groups rare earth alkyl compound prepares isoprene rubber, it is characterised in that described
Alkyl aluminum be one or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium or three amyl group aluminum.
5. require, according to right 1, the method that described amidino groups rare earth alkyl compound prepares isoprene rubber, it is characterised in that described
Organic borate be [Ph3C][B(C6F5)4] or [PhMe2NH][B(C6F5)4One in].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610413640.4A CN106084108A (en) | 2016-06-14 | 2016-06-14 | A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610413640.4A CN106084108A (en) | 2016-06-14 | 2016-06-14 | A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106084108A true CN106084108A (en) | 2016-11-09 |
Family
ID=57845754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610413640.4A Pending CN106084108A (en) | 2016-06-14 | 2016-06-14 | A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106084108A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087508A (en) * | 2019-12-30 | 2020-05-01 | 复旦大学 | Coordination chain transfer polyisoprene system based on amidino rare earth alkyl compound |
| CN112592421A (en) * | 2020-11-22 | 2021-04-02 | 复旦大学 | Method for preparing isoprene multi-block region copolymer by chain shuttle reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1939221A2 (en) * | 2006-12-28 | 2008-07-02 | Bridgestone Corporation | A method for producing functionalized cis-1,4polydienes having high cis-1,4-linkage content and high functionality |
| CN101400707A (en) * | 2006-03-10 | 2009-04-01 | 独立行政法人理化学研究所 | Polymerization catalyst composition for polymerization of isoprene compound |
| CN104017121A (en) * | 2014-06-02 | 2014-09-03 | 复旦大学 | Method for preparation of isoprene and myrcene regional block copolymers by chain transfer reaction |
| CN105085720A (en) * | 2014-05-15 | 2015-11-25 | 中国石油化工股份有限公司 | Composition for rare earth catalyst, rare earth catalyst, preparation method and application of rare earth catalyst and isoprene polymerization method |
-
2016
- 2016-06-14 CN CN201610413640.4A patent/CN106084108A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101400707A (en) * | 2006-03-10 | 2009-04-01 | 独立行政法人理化学研究所 | Polymerization catalyst composition for polymerization of isoprene compound |
| EP1939221A2 (en) * | 2006-12-28 | 2008-07-02 | Bridgestone Corporation | A method for producing functionalized cis-1,4polydienes having high cis-1,4-linkage content and high functionality |
| CN105085720A (en) * | 2014-05-15 | 2015-11-25 | 中国石油化工股份有限公司 | Composition for rare earth catalyst, rare earth catalyst, preparation method and application of rare earth catalyst and isoprene polymerization method |
| CN104017121A (en) * | 2014-06-02 | 2014-09-03 | 复旦大学 | Method for preparation of isoprene and myrcene regional block copolymers by chain transfer reaction |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087508A (en) * | 2019-12-30 | 2020-05-01 | 复旦大学 | Coordination chain transfer polyisoprene system based on amidino rare earth alkyl compound |
| CN112592421A (en) * | 2020-11-22 | 2021-04-02 | 复旦大学 | Method for preparing isoprene multi-block region copolymer by chain shuttle reaction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101563398B (en) | Branched polymers and methods for their synthesis and use | |
| CN107406474A (en) | Organic zinc compound comprising polyolefin polystyrene block copolymer and preparation method thereof | |
| BRPI0500273B1 (en) | Process for the preparation of low branching polybutadiene and sulfur-vulcanizable elastomeric mixtures | |
| JP2006124707A (en) | Method for producing polybutadiene having low content of branch | |
| KR20110112315A (en) | Conjugated diene polymer manufacturing method, polybutadiene, and rubber composition utilizing the same | |
| Shen et al. | A new strategy to produce low-density polyethylene (LDPE)-based composites simultaneously with high flame retardancy and high mechanical properties | |
| CN103172870A (en) | Polyhedral oligomeric silsesquioxane (POSS) modified double-bond containing elastomer and preparation method thereof | |
| CN107314246B (en) | SiO2- polyolefin composite anti-drag agent solution in-situ synthetic method | |
| BR112013003741B1 (en) | CATALYST COMPONENT FOR OLEFINE POLYMERIZATION, ITS PREPARATION METHODS, CATALYST FOR OLEFINE COPOLIMERIZATION OR HOMOPOLIMERIZATION, AND ITS USE | |
| CN106084108A (en) | A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber | |
| TR201802338T4 (en) | Process for preparing 1,3-butadiene and styrene copolymers and their use in vulcanizable elastomeric compositions. | |
| Zheng et al. | Controlled Chain‐Scission of Polybutadiene by the Schwartz Hydrozirconation | |
| CN104177529B (en) | Ternary RE EP rubbers and preparation method thereof | |
| CN104125967B (en) | For preparing the bulk polymerization of polydiene | |
| CN106699946A (en) | High-density polyethylene resin, and preparation method and application thereof | |
| CN110121513A (en) | Modified conjugated diene quasi polymer and rubber composition comprising it | |
| CN104017121B (en) | The method being prepared the region block copolymer of isoprene, myrcene by chain transfer reaction | |
| RU2626967C2 (en) | Method for producing 1,4-cis-polybutadiene | |
| CN104245749B (en) | The manufacture method of polymerization catalyst composition, polymerization catalyst composition, the manufacture method of polymer composition and polymer composition | |
| CN116589503A (en) | Iron-phosphorus complex, composite catalyst, syndiotactic 1, 2-polybutadiene, modified rare earth butadiene rubber and preparation method and application thereof | |
| Nimpaiboon et al. | Role of gel content on the structural changes of masticated natural rubber | |
| CN105330773A (en) | Composition for rare earth catalyst, rare earth catalyst, and preparation method and application thereof | |
| TWI671323B (en) | Polybutadiene and rubber composition | |
| CN103980772B (en) | A kind of nitroso-fluoro-elastomers soaker and preparation technology thereof | |
| JP5990426B2 (en) | Method for producing polymerization catalyst composition and polymerization catalyst composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161109 |
|
| WD01 | Invention patent application deemed withdrawn after publication |