CN102558441A - Synthetic method of solution polymerized butadiene-isoprene rubber - Google Patents
Synthetic method of solution polymerized butadiene-isoprene rubber Download PDFInfo
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- CN102558441A CN102558441A CN2010106228780A CN201010622878A CN102558441A CN 102558441 A CN102558441 A CN 102558441A CN 2010106228780 A CN2010106228780 A CN 2010106228780A CN 201010622878 A CN201010622878 A CN 201010622878A CN 102558441 A CN102558441 A CN 102558441A
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Abstract
The invention relates to a polymerization method for producing solution polymerized butadiene-isoprene rubber. The polymerization method comprises the following steps of: copolymerizing butadiene and isoprene in a hydrocarbon solvent at 0-130 DEG C in the presence of organic lithium as an initiator and tetrahydrofurfuryl alcohol as a structure regulator and after polymerization reaction basically completes, adding a coupling agent with functionality of 2-4 into the copolymer to perform the coupling reaction. The tetrahydrofurfuryl alcohol is used as the structure regulator, so as to obtain a 1,2-structure content adjustable random copolymer rubber.
Description
Technical field
The present invention relates to the polymerization method of soluble polybutaamyl-rubber (IBR), more particularly, relate to have different 1, the polymerization method of the star-like soluble polybutaamyl-rubber of 2-structural content.
Background technology
Bibliographical information, glycol dimethyl ether (1G) be as regulator, can regulate that contents of ethylene surpasses 60.0% in the polyhutadiene.But this alcohol ether has two big shortcomings as regulator: the one, can not be from hexane direct separation; The 2nd, coupling efficiency is near 0.Therefore ethylene glycol diethyl ether and the ethylene glycol dibutyl ether in this compounds can not satisfy TR.
The method that relates to synthetic divinyl of a kind of use butyllithium and diglyme (2G) and isoprene copolymer among the JP 82/87406, but the transformation efficiency of this method is not high.
US 4; 530; Mention in 985 when using diethyl carbitol to prepare wide distribution polyisoprene,, prove when adding coupling agent not had the active site in the system owing to cross the early stopping polyreaction and/or disturb linked reaction can not obtain star-type polymer as regulator.This patent has been set forth all regulators in the past, confirms that they had the early stopping polymerization and/or disturbed the link coupled effect.This patent is found to use a kind of new ether, i.e. formula R
1-O-CH
2-CH (R
2)-O-C (R
3) (R
4)-O-R
5(R wherein
1Alkyl for 2-18 carbon atom; R
2And R
3Alkyl for hydrogen or 1-4 carbon atom; R
4Alkyl for hydrogen or 1-6 carbon atom; R
5Alkyl for 1-18 carbon atom) ether replaces conventional alcohol ether, has improved the coupling situation, but compound itself is difficult to obtain.
US 5; 008; 343 disclose a kind of method for preparing no block polymer, comprise be selected from least two kinds of compounds in divinyl, isoprene and the vinylbenzene in inert organic solvents at organolithium compound as the ethylene glycol bisthioglycolate alkyl oxide of catalyzer and following formula as anionoid polymerization in the presence of the promotor:
R
1-O-CH
2-CH(R
3)-O-R
2
R wherein
3Be hydrogen, methyl or ethyl, R
1And R
2For having the alkyl of different carbonatomss, be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl or the tertiary butyl, and the total number of carbon atoms in the alkyl is 5-7.According to this patent, obtained no block polymer than high-vinyl-content through a large amount of use promotors.
CN 100362030C discloses a kind of method that adopts terepthaloyl moietie ethyl tertbutyl ether to prepare soluble polybutaamyl-rubber as structure regulator.But this structure regulator can't remove from polymer solvent fully, reclaims solvent there is influence in subsequent polymerisation reaction.
Summary of the invention
Based on above-mentioned prior art situation, contriver of the present invention has carried out research extensively and profoundly in the anionoid polymerization field of conjugated diene, in the hope of developing a kind of preparation vinyl, and promptly 1, the 2-structural content is adjustable, the polymerization method of soluble polybutaamyl-rubber.The result is unexpected to be found through adopting tetrahydrofurfuryl alcohol ether (ETE) as regulator divinyl and isoprene to be carried out solution polymerization; Can fully regulate the contents of ethylene in the gained multipolymer; For example under certain regulator consumption, can in 8～85 weight % scopes, regulate arbitrarily contents of ethylene, and very little to the coupling effectiveness affects; This structure regulator can remove from polymer solvent fully simultaneously, reclaims solvent subsequent polymerisation reaction is had no effect.
The purpose of this invention is to provide a kind of technology simple, be suitable for extensive implement and can satisfy various 1, the method for the star-like soluble polybutaamyl-rubber of production of 2-structural content.
Therefore, the present invention relates to a kind of polymerization method of producing soluble polybutaamyl-rubber, be included in 0～130 ℃, preferred 10-130 ℃; Preferred 10-120 ℃, preferred 10-110 ℃, preferred 20-130 ℃; Preferred 20-120 ℃, preferred 20-110 ℃, preferred 10-100 ℃; Preferred 10-90 ℃, preferred 10-80 ℃, preferred 20-100 ℃; Preferred 20-90 ℃, in varsol, carry out the copolymerization of divinyl and isoprene at organolithium down as structure regulator as initiator and ETE under preferred 20-80 ℃ the temperature, and polymerization basic complete after the adding coupling agent carry out coupling.
Of the present invention this will become cheer and bright with other purposes, feature and advantage after the detailed description with reference to the intact the application of advantages.
Description of drawings
Fig. 1 is in the multipolymer that obtains according to embodiment of the invention 1-9 1, the graphic representation of the relation of 2-structural content and ETE consumption;
In the multipolymer that Fig. 2 obtains according to embodiment of the invention 10-18 for explanation 1, the graphic representation of the relation of 2-structural content and ETE consumption;
Fig. 3 is the multipolymer GPC spectrogram that obtains according to the embodiment of the invention 1;
Embodiment
In the method for the invention, used polymerization single polymerization monomer is the mixture of divinyl and isoprene, and wherein isoprene content is 10%～50% based on the monomer total mass; Preferred 15%～50%, preferred 20%～50%, preferred 25%～50%; Preferred 15%～45%, butadiene content correspondingly is 90%～50%, preferred 85%～50%; Preferred 80%～50%, preferred 75%～50%, preferred 85%～55%.
In the method for the invention, used varsol is hexanaphthene, raffinate oil or the mixed solvent (weight ratio of hexanaphthene and normal hexane is 70: 30～90: 10) of hexanaphthene and normal hexane, and it is 10～20 weight % that the consumption of said solvent should make monomeric concentration.
In the method for the invention, used initiator is to be selected from the following compound any: C
1-C
7Lithium alkylide, C
6-C
12Lithium aryl, C
7-C
14Aralkyl lithium or C
3-C
6The naphthenic base lithium, like lithium ethide, propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium, naphthyl lithium etc., preferred n-Butyl Lithium or s-butyl lithium.The consumption of organic lithium initiator is selected according to the molecular weight size of required polymkeric substance.General initiator amount is that every 100g monomer need add 0.3～2.5mmol.
In the method for the invention, polyreaction is structure regulator with ETE, and the concentration of said ETE in monomer and solvent is 0.0001～0.15 weight %; Preferred 0.001～0.15 weight %, preferred 0.0015～0.15 weight %, preferred 0.004～0.15 weight %; Preferred 0.005～0.15 weight %, preferred 0.01～0.15 weight %, preferred 0.015～0.15 weight %; Preferred 0.02～0.15 weight %, preferred 0.03～0.15 weight %, preferred 0.05～0.15 weight %; Preferred 0.08～0.15 weight %, preferred 0.10～0.15 weight %.
In the method for the invention, the reaction later stage adopts the coupling agent of 2～4 functionality to carry out coupling usually.The instance of said coupling agent comprises Vinylstyrene, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, silicon tetrachloride or tin tetrachloride, preferred silicon tetrachloride.The mol ratio of said coupling agent and organic lithium initiator is 0.10: 1～0.25: 1.
Random copolymers of the present invention is preferably through interrupter method production., at first monomer and solvent are joined in the reactor drum for this reason, then structure regulator and organic lithium initiator are joined respectively in the reactor drum, in 10～120 minutes reaction times, the back adds coupling agent again, and coupling time is 10～40 minutes.
Polymerization process of the present invention can be carried out in 0～130 ℃ TR, preferably under 30～100 ℃, carries out, and it is liquid that polymerization pressure should keep polymerization system, generally at 0.05～1MPa, selects 0.1～0.5MPa usually.
When polymerization and linked reaction end, handle polymer fluid, to stop reactive polymer, avoid it to contact with airborne oxygen.Terminator commonly used is Virahol, water, ethanol etc.In addition, before polymer precipitation, add a small amount of anti-aging agent usually, for example oxidation inhibitor such as 2,6 di tert butyl 4 methyl phenol etc. are precipitated out polymkeric substance then in excess ethyl alcohol.The consumption of terminator is generally the 0.2-5% that needs the trigger monomer quality, and the consumption of anti-aging agent is generally the 0.1-10% that needs the trigger monomer quality.
Polymerisate can obtain as follows: be added with the direct desolventizing of polymers soln of anti-aging agent after will stopping, or above-mentioned polymers soln is made solvent and water form azeotrope with devaporation and is removed.Wet polymer obtains product through dry and granulation again.
The present invention obtains difference 1, random fourth penta multipolymer of 2-structural content through ETE is used as structure regulator.Along with the continuous increase of asymmetrical ether consumption, in the gained multipolymer 1, the 2-structural content also constantly increases, and has guaranteed the degree of randomness of butadiene-isoprene rubber.
Through adopting ETE as structure regulator and be used in combination coupling agent, can obtain different 1, the star-like soluble polybutaamyl-rubber of 2-structural content, and other regulation system is difficult in the polymerization later stage and carries out successfully coupling, guarantees that multipolymer is a hub-and-spoke configuration.In addition, ETE itself can remove from polymer solvent fully, reclaims solvent subsequent polymerisation reaction is had no effect.
The present invention has following advantage:
1.ETE active high, consumption is few, takes conveniently;
2. its synthesis route is simple, and production cost is low, can directly purchase from market;
3. guaranteed the activity of spike in the polymerization process, and the successful coupling of ability;
4. the various polymerization solvent system is used in reaction, as raffinate oil, hexanaphthene and hexanaphthene/hexane mixed solvent system, need not to add again other auxiliary adjustment agent in the system, polymeric reaction temperature can fix on 30～100 ℃;
5. polyreaction can obtain difference 1 through the add-on of adjustment ETE, the star-like soluble polybutaamyl-rubber of 2-structural content, and its regulation range is 8～85 weight %;
6.ETE adding little to the molecular weight and the distribution influence thereof of product.
7.ETE itself can remove from polymer solvent fully, reclaims solvent subsequent polymerisation reaction is had no effect.
Embodiment
The following example is used to describe the present invention, but never means the present invention is constituted any restriction, and in contrast, the applicant only regards it as one of optimum implementation of the various technical solutions of the present invention.
In the following example, specifications of raw materials and treating process are following: divinyl is industrial polymerization-grade, directly uses; Isoprene is industrial polymerization-grade, under the high pure nitrogen protection, uses behind the adding gama-alumina drying and dehydrating; Hexanaphthene, raffinate oil or the mixed solvent of hexanaphthene and normal hexane is a technical grade, need to add the gama-alumina drying and dehydrating more than three days, feed the high pure nitrogen oxygen of half a hour before use possibly exist in the system of removing; Initiator is n-Butyl Lithium or s-butyl lithium; Structure regulator ETE is common commercially available prod, and it is for use that process adds the sodium backflow, back feeding nitrogen bubble is handled in distillation.In the present invention, BD representes divinyl, and IP representes isoprene.
Embodiment 1Hexanaphthene/normal hexane mixed solvent (=82/18, weight ratio) system is synthesized star-like soluble polybutaamyl-rubber (BD/IP=75/25, weight ratio)
Be aggregated in 5 liters of stainless steel cauldrons and carry out, reaction kettle finds time to fill nitrogen (high purity nitrogen) pump drainage three times after hexanaphthene/normal hexane embathes, and reaction kettle adopts deep fat heating and cold oil cooling, and hot oil temperature is set at 30 ℃, and the cold oil temperature is set at 10 ℃.Hexanaphthene/normal hexane 2600g, ETE 0.003g, divinyl 291.38g, isoprene 97.13g are made with extra care at first disposable adding.Use deep fat reacting by heating material then; When the question response temperature in the kettle rose to 30 ℃, control deep fat and cold oil ratio made temperature of charge keep stable; Disposable then adding is killed assorted and is caused with n-Butyl Lithium 14ml (0.3M hexanaphthene/hexane solution), initiated polymerization.Add the 0.65mmol silicon tetrachloride behind the polyreaction 40min and carry out linked reaction, disposable adding 0.5ml Virahol stops and 0.5g anti-aging agent 1520 (Switzerland vapour Bagong department product) behind the coupling 30min, synthesizes star-like soluble polybutaamyl-rubber.The polyreaction original pressure is 0.1MPa, and the reaction kettle mixing speed is set at 200rpm, and the gained glue adopts devaporation to remove solvent.The molecular weight of sample, MWD and coupling efficiency adopt gel permeation chromatography (day island proper Tianjin Class-LC10A cohesion permeation chromatography) to measure, and microtexture adopts nuclear-magnetism wave of oscillation spectrometer (Switzerland Bruker400MHz NMR) to measure.
Embodiment 2-9Hexanaphthene/normal hexane mixed solvent (=82/18, weight ratio) system is synthesized star-like soluble polybutaamyl-rubber (BD/IP=75/25, weight ratio)
The test of microtexture is identical with embodiment 1 in copolymer method and the polymkeric substance, and difference is that ETE adds according to design flow, and concrete add-on is seen table 1.
1 of ETE add-on, polymerisate; 2-structural content, molecular weight, MWD, coupling efficiency are measured the result and are seen table 1; Visible by table 1: the star-like soluble polybutaamyl-rubber prepared according to the present invention can successfully carry out linked reaction, and 1 in the multipolymer, and the 2-structural content is controlled.
The molecular parameter of the star-like soluble polybutaamyl-rubber of table 1 and microtexture
| The experiment number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| ETE(g) | 0.003 | 0.03 | 0.05 | 0.15 | 0.45 |
| 1，2-(％) | 9.0 | 14.5 | 20.7 | 29.0 | 52.2 |
| Mp | 120，324 | 142，124 | 132，424 | 122，952 | 121，005 |
| Mw/Mn | 1.37 | 1.41 | 1.44 | 1.40 | 1.38 |
| S(％) | 68.75 | 71.58 | 67.51 | 70.25 | 57.44 |
Table 1 (continuing)
| The experiment number | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| ETE(g) | 0.9 | 1.5 | 3.0 | 4.5 |
| 1，2-(％) | 65.5 | 78.3 | 82.3 | 84.5 |
| Mp | 115，478 | 138，032 | 145，578 | 144，235 |
| Mw/Mn | 1.46 | 1.41 | 1.37 | 1.41 |
| S(％) | 61.85 | 64.14 | 58.12 | 52.92 |
Annotate:
ETE (g): tetrahydrofurfuryl alcohol ether;
1,2-(%): total contents of ethylene in the multipolymer;
Mp: peak molecular weight;
Mw/Mn: MWD;
S (%): coupling efficiency.
Can be found out by table 1: the adding of ETE is little to the molecular weight and the MWD influence of multipolymer, and polymerization reaction late stage can be carried out linked reaction smoothly, and coupling efficiency can reach more than 50%.
Accompanying drawing 1 shows under certain condition, and in the product 1, the 2-structural content is directly proportional with the ETE add-on, according to design requirements, can in 15%～85% scope, regulate.
Polymerization result shows: carry out the synthetic of soluble polybutaamyl-rubber with ETE as regulator, can obtain difference 1, the star copolymer of 2-structural content.
A part of soluble polybutaamyl-rubber to has wherein carried out physical and mechanical properties mensuration, and the result is as shown in table 2.Visible by table 2; Star-like butadiene-isoprene rubber that synthesizes and common rare earth butadiene-isoprene rubber (Nd-BIR, Sinopec Qilu Petroleum Chemistry Co. Inst. development product, according to Jiao Zhimin etc. in " rare earth butadiene-isoprene rubber performance and the research of in tread rubber, using "; Rubber industry; The 49th volume the 8th phase (2002), disclosed method preparation in the 462-466 page or leaf) relatively, have better physical and mechanical properties.
The physical and mechanical properties of the star-like soluble polybutaamyl-rubber of table 2
Embodiment 10-18The hexanaphthene system is synthesized star-like soluble polybutaamyl-rubber (BD/IP=65/35, weight ratio)
The test of microtexture is identical with embodiment 1 in copolymer method and the polymkeric substance; Difference is that the polymer solvent system changes hexanaphthene 2600g into, and kick off temperature changes 50 ℃ into, and ETE adds according to design flow; Concrete add-on and polymerisate 1, the 2-structural content is seen table 3.
The microtexture of the star-like soluble polybutaamyl-rubber of table 3
| The experiment number | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 |
| ETE(g) | 0.003 | 0.03 | 0.05 | 0.15 | 0.45 |
| 1，2-(％) | 8.0 | 13.4 | 16.6 | 25.1 | 49.1 |
Table 3 (continuing)
| The experiment number | Embodiment 15 | |
Embodiment 17 | |
| ETE(g) | 0.9 | 1.5 | 3.0 | 4.5 |
| 1，2-(％) | 62.4 | 73.2 | 76.2 | 77.4 |
The physical and mechanical properties of the star-like soluble polybutaamyl-rubber of table 4
Embodiment 19Hexanaphthene/normal hexane mixed solvent (=82/18, weight ratio) system is synthesized star-like soluble polybutaamyl-rubber (BD/IP=50/50, weight ratio)
The test of microtexture is identical with embodiment 1 in copolymer method and the polymkeric substance, and difference is that the raw material add-on should be hexanaphthene/normal hexane 2600g mutually, divinyl 194.25g, and isoprene 194.25g, ETE 0.9g, kick off temperature are 70 ℃.The product physical and mechanical properties is seen table 5.
The physical and mechanical properties of the star-like soluble polybutaamyl-rubber of table 5
Embodiment 20The system of raffinating oil is synthesized star-like soluble polybutaamyl-rubber (BD/IP=75/25, weight ratio)
The test of microtexture is identical with embodiment 1 in copolymer method and the polymkeric substance, and difference is that the polymer solvent system changes the 2600g that raffinates oil into, and ETE 0.45g, kick off temperature are 50 ℃.The product physical and mechanical properties is seen table 6.
The physical and mechanical properties of the star-like soluble polybutaamyl-rubber of table 6
Claims (13)
1. a polymerization method of producing soluble polybutaamyl-rubber is included in 0～130 ℃, preferred 10-130 ℃; Preferred 10-120 ℃, preferred 10-110 ℃, preferred 20-130 ℃; Preferred 20-120 ℃, preferred 20-110 ℃, preferred 10-100 ℃; Preferred 10-90 ℃, preferred 10-80 ℃, preferred 20-100 ℃; Preferred 20-90 ℃, in varsol, carry out the copolymerization of divinyl and isoprene at organolithium down as structure regulator as initiator and tetrahydrofurfuryl alcohol ether under preferred 20-80 ℃ the temperature, and polymerization basic complete after the coupling agent of adding 2～4 functionality carry out linked reaction.
2. according to each method of aforementioned claim, it is characterized in that organolithium is to be selected from the following compound any: C
1-C
6Lithium alkylide, C
6-C
12Lithium aryl, C
7-C
14Aralkyl lithium, C
3-C
6The naphthenic base lithium.
3. according to each method of aforementioned claim, it is characterized in that organolithium is n-Butyl Lithium or s-butyl lithium.
4. according to each method of aforementioned claim, it is characterized in that varsol is a hexanaphthene.
5. according to each method of aforementioned claim, it is characterized in that varsol is for raffinating oil.
6. according to each method of aforementioned claim, it is characterized in that varsol is the mixed solvent system that hexanaphthene and normal hexane are formed, wherein hexanaphthene and normal hexane weight ratio are 70: 30～90: 10.
7. according to each method of aforementioned claim, it is characterized in that isoprene content is 10%～50% based on the monomer total mass, preferred 15%～50%; Preferred 20%～50%, preferred 25%～50%, preferred 15%～45%; And butadiene content is 90%～50% based on the monomer total mass, preferred 85%～50%, preferred 80%～50%; Preferred 75%～50%, preferred 85%～55%.
8. according to each method of aforementioned claim, it is 10～20 weight % that the consumption that it is characterized in that varsol should make monomer concentration.
9. according to each method of aforementioned claim, it is characterized in that temperature of reaction is 30～100 ℃.
10. according to each method of aforementioned claim, it is characterized in that the concentration of tetrahydrofurfuryl alcohol ether in monomer and solvent is 0.0001～0.15 weight %, preferred 0.001～0.15 weight %; Preferred 0.0015～0.15 weight %, preferred 0.004～0.15 weight %, preferred 0.005～0.15 weight %; Preferred 0.01～0.15 weight %, preferred 0.015～0.15 weight %, preferred 0.02～0.15 weight %; Preferred 0.03～0.15 weight %; Preferred 0.05～0.15 weight %, preferred 0.08～0.15 weight %, preferred 0.10～0.15 weight %.
11., it is characterized in that coupling agent is to be selected from any of following compound: Vinylstyrene, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, silicon tetrachloride, tin tetrachloride, preferred silicon tetrachloride according to each method of aforementioned claim.
12. according to each method of aforementioned claim, the mol ratio that it is characterized in that coupling agent and organolithium is 0.10: 1～0.25: 1.
13., it is characterized in that contents of ethylene is 8%～85% in the gained multipolymer according to each method of aforementioned claim.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716598A (en) * | 2021-01-04 | 2022-07-08 | 北京化工大学 | Preparation method of butadiene-isoprene copolymer, butadiene-isoprene copolymer and tread rubber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5448003A (en) * | 1992-04-06 | 1995-09-05 | The Goodyear Tire & Rubber Company | Synthesis of rubbery polymer using anionic polymerization modifier |
| CN1814640A (en) * | 2005-01-31 | 2006-08-09 | 中国石化北京燕化石油化工股份有限公司 | Method for polymerizing soluble polybutaamyl-rubber |
| 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 |
-
2010
- 2010-12-29 CN CN2010106228780A patent/CN102558441A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5448003A (en) * | 1992-04-06 | 1995-09-05 | The Goodyear Tire & Rubber Company | Synthesis of rubbery polymer using anionic polymerization modifier |
| CN1814640A (en) * | 2005-01-31 | 2006-08-09 | 中国石化北京燕化石油化工股份有限公司 | Method for polymerizing soluble polybutaamyl-rubber |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716598A (en) * | 2021-01-04 | 2022-07-08 | 北京化工大学 | Preparation method of butadiene-isoprene copolymer, butadiene-isoprene copolymer and tread rubber |
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Application publication date: 20120711 |