CN105622845A - Hydrogenated multi-arm star butadiene/isoprene random copolymer, preparation method thereof and application thereof - Google Patents
Hydrogenated multi-arm star butadiene/isoprene random copolymer, preparation method thereof and application thereof Download PDFInfo
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Abstract
The invention discloses a hydrogenated multi-arm star butadiene/isoprene random copolymer. The random copolymer is the multi-arm star random copolymer formed by taking hydrogenated butadiene and pentadiene random copolymer as a single arm, and a preparation method is characterized in that the butadiene/isoprene random copolymer is synthesized, the multi-arm star random copolymer is coupled by a coupling agent, and finally the hydrogenated multi-arm star butadiene/isoprene random copolymer is obtained through a hydrogenation reaction. The method has the advantages of simple operation, low equipment requirement, and low cost; the prepared hydrogenated multi-arm star butadiene/isoprene random copolymer has an analogous ethylene propylene copolymer polymer arm, has good high temperature resistance and shearing performance as well as strong thickening capability on a lubricating oil, and can better keep the lubrication performance of the lubricating oil under high temperature and high shear conditions.
Description
Technical field
The present invention relates to a kind of hydrogenation multi-arm star butadiene/isoprene random copolymer and its preparation method and application, belong to lubricant tackifier field.
Background technology
Lubricating oil index improver is again lubricant tackifier, it is produce a kind of additive that lubricating oil is conventional, it is mainly used in I. C. engine oil, hydraulic oil, automatic transmission fluid and gear oil, its consumption is only second to detersive and dispersant in lubricating oil, it plays the effect in two in lubricating oil, one to make oil body that namely temperature-insensitive to add the lubricating oil after viscosity index improver not rare at high temperature, and low temperature is not thick, and two is the viscosity improving low-viscosity oil.
The macromolecular organic compound that lubricating oil viscosity index agent is had anti-shear performance by some is formed, they are dissolved in lubricating oil, elongation is expanded when high temperature, strengthen the resistance between lubricating oil molecule, make the unlikely decline of lubricating oil viscosity too big, keep certain viscosity, form certain thickness oil film, play due lubrication. And when low temperature these organic compound crimp shrinkage, be suspended in lubricating oil, resistance between lubricating oil molecule thus reduce, make lubricating oil viscosity will not increase too much, in order to avoid causing engine start difficulty, increasing and wearing and tearing.
Bibliographical information thinks that straight chain polymer is conducive to improving the polymer thickening capabilities to lubricating oil, but molecular weight is too big, lubricating oil is when high temperature or high shear, macromolecular chain easily disconnects, after polymer chain rupture, the lubricants performance of lubricating oil declines, and therefore lubricating oil viscosity index improver is generally adopted the star structure of multi-arm.
It is good that ethylene-propylene copolymer (OCP) viscosity index improver has excellent thickening capabilities, good oxidation stability and shear stability, is a kind of medium-to-high grade lubricating oil viscosity index improver. EP rubbers is typically under Ziegler-Natta catalyst effect polymerisation in solution and forms, can obtain ethylene with vanadium series catalyst (such as vanadium oxytrichloride) and rubber that propylene units is evenly distributed, but the ethylene-propylene copolymer of straight chain can not meet the instructions for use of top-grade lubricating oil.
United States Patent (USP) 5, 460, 739 disclose a kind of three block star polymers being hydrogenated with polyisoprene/polybutadiene/polyisoprene, it includes polyisoprene blocks and the polybutadiene block with the molecule combination of (EP-EB-EP') n-X structure, the wherein outer block of polyisoprene of EP to be number-average molecular weight be 6500-85000, EB is 1 with at least 85% butadiene, 4-polymerization and number-average molecular weight are the polybutadiene block of 1500-15000, EP' is number-average molecular weight is the polyisoprene blocks of 1500-55000, wherein the content of polybutadiene is lower than 15%, EP/EP' is than for 0.75:1-7.5:1, X is polyalkenyl coupling agent core, and n is (EP-EB-EP') average of the every star-shaped molecule formed by the polyalkenyl coupling agent reaction of every mole of arm 2 or above mole. the contents of ethylene being wherein hydrogenated with polybutadiene segments increases, and can improve thickening effect, but, when this base polymer comprises block polybutadiene segment, it is easily formed polyethylene crystallization after polybutadiene 1.4-polymerized unit hydrogenation, affects the cryogenic property of lubricating oil.
Summary of the invention
For a series of defects that thickening of lubricating oils agent in prior art exists, it is an object of the invention to provide a kind of hydrogenation multi-arm star butadiene/isoprene random copolymer having and being similar to ethylene-propylene copolymer polymeric arms, the high temperature resistant cutting performance of this polymer is good, the thickening capabilities of lubricating oil is strong, under high temperature and shear conditions, remain to keep well the greasy property of lubricating oil.
Another object of the present invention is to be in that offer one is simple to operate, equipment requirements is low, cost is low, the method preparing described hydrogenation multi-arm star butadiene/isoprene random copolymer.
3rd purpose of the present invention be in that to provide described described hydrogenation multi-arm star butadiene/isoprene random copolymer as viscosity improver application in thickening of lubricating oils, using described copolymer as lubricating oil viscosity index improver, the thickening capabilities of lubricating oil is strong, under high temperature and shear conditions, remain to keep well the greasy property of lubricating oil.
The invention provides a kind of hydrogenation multi-arm star butadiene/isoprene random copolymer, be the multi-arm star random copolymer that single armed is constituted by the butadiene hydrogenated and pentadiene random copolymer, this multi-arm star random copolymer has structure shown in formula 1:
[Bi1-Ei2-Bi3-Ei4����Bi(m-3)-Ei(m-2)-Bi(m-1)-Eim]n-X
Formula 1
Wherein,
B is hydrogenated butadiene polymer segment;
E is hydrogenated polyisoprene segment;
I1��im is the degree of polymerization of each B or E, and i1��im is each independently selected from 1��10;
N is polymeric arms number, and n is 2��20;
X is coupling agent residue;
The molecular weight of single armed is 4��100,000, and molecular weight distribution is 1.01��1.2;
The total mass ratio of hydrogenated butadiene polymer segment and hydrogenated polyisoprene segment is 5��50:95��50.
The hydrogenation multi-arm star butadiene/isoprene random copolymer of the present invention also includes following preferred version:
In preferred hydrogenation multi-arm star butadiene/isoprene random copolymer, the average degree of polymerization of B is 1��5, and the average degree of polymerization of E is 5��10.
Preferred hydrogenation multi-arm star butadiene/isoprene random copolymer middle-molecular-weihydroxyethyl is distributed as 1.01��1.1.
In preferred hydrogenation multi-arm star butadiene/isoprene random copolymer, polymeric arms number n is 4��10.
The segment in hydrogenated butadiene polymer segment in preferred hydrogenation multi-arm star butadiene/isoprene random copolymer with 1,2-construction unit accounts for the 10��40% of hydrogenated butadiene polymer segment gross mass; It most preferably is 10��30%.
The unit segment in hydrogenated polyisoprene segment in preferred hydrogenation multi-arm star butadiene/isoprene random copolymer with 3,4-structure accounts for the 5��25% of hydrogenated polyisoprene segment gross mass; It most preferably is 5��15%.
Preferred hydrogenation multi-arm star butadiene/isoprene random copolymer has in hydrogenated polyisoprene segment the unit segment of 1,2-structure account for hydrogenated polyisoprene segment gross mass��5%.
Preferred hydrogenation multi-arm star butadiene/isoprene random copolymer molecular weight is 20��1,000,000, it is most preferred that be 40��800,000.
The preparation method that present invention also offers described hydrogenation multi-arm star butadiene/isoprene random copolymer, comprises the following steps:
Step 1): activator and organic solvent are joined in polymerization reaction kettle after mix homogeneously, temperature reaction still to 50��100 DEG C;
Step 2): to step 1) reactor in add initiator, controlling temperature is 40��115 DEG C, adds the mix monomer of butadiene and isoprene continuously lentamente in reactor, after being added dropwise to complete, continues reaction 20��60 minutes;
Step 3): step 2) reacted after, in reactor add coupling agent, react further 40��80 minutes, obtain multi-arm star butadiene/isoprene random copolymer virgin rubber;
Step 4): step 3) the multi-arm star butadiene/isoprene random copolymer virgin rubber that obtains adopts Ni/Al catalyst system and catalyzing to carry out hydrogenation under 60��110 DEG C of temperature conditions, after hydrogenation completes, purify, multi-arm star butadiene/isoprene random copolymer must be hydrogenated.
The preparation method of the hydrogenation multi-arm star butadiene/isoprene random copolymer of the present invention also includes following preferred version:
Butadiene and isoprene 5��50:95��50 in mass ratio mixing in preferred preparation method.
In preferred preparation method, the hydrogenation time is 2��5h, to ensure that in polyisoprene segments, the hydrogenation ratio of unsaturated double-bond is not less than 95%.
In preferred preparation method, butadiene and isoprene monomer gross mass percent concentration in a solvent is 5��30%.
Activator described in preferred preparation method mass percent concentration in a solvent is��0.1%.
In preferred preparation method, activator is oxolane.
In preferred preparation method, the addition of initiator is the 1��5% of butadiene and the total quality of isoprene. Described initiator amount can select by molecular weight of product as required, it is necessary to molecular weight of product high, the consumption of initiator somewhat reduces, it is necessary to molecular weight of product low, then the consumption of initiator is somewhat added.
In preferred preparation method, initiator is lithium alkylide, including butyl lithium or isobutyl group lithium.
In preferred preparation method, the consumption of coupling agent is the 0.2��3% of butadiene and isoprene monomer gross mass.
In preferred preparation method, coupling agent is one or more in dichlorodimethylsilane, trichloromethyl silane, Silicon chloride., butter of tin and divinylbenzene.
In preferred preparation method, the coupling efficiency of coupling agent is not less than 95%.
In preferred preparation method, solvent can be typically used for any solvent during solution polymerized butadiene styrene rubber produces. Modal solvent includes one or more mixing of hexamethylene, normal hexane, benzene, toluene and dimethylbenzene.
The multi-arm butadiene of the present invention-polyisoprene copolymers virgin rubber method for hydrogenation is undertaken by existing conventional method, it is preferred to undertaken by patent 201110008911.5 method, adopts Ni/Al catalyst, it is preferable that Al/Nimol ratio is 3.0��3.8. Hydrogenation conditions must be enough to make the isoprene unsaturated bond of at least 95% to hydrogenate.
Multi-arm butadiene-polyisoprene copolymers purification after the hydrogenation of the present invention presses conventional method purification of the prior art, it is preferably and is undertaken by patent CN1067898A method, Ni content��10mg/Kg, Al content��10mg/Kg, Li content��5mg/Kg in dry glue powder after glue purification process.
Present invention also offers the application of described hydrogenation multi-arm star butadiene/isoprene random copolymer, this application is that as viscosity improver, described hydrogenation multi-arm star butadiene/isoprene random copolymer is applied to thickening of lubricating oils.
Preferred application process is that as viscosity improver, described hydrogenation multi-arm star butadiene/isoprene random copolymer is applied to multi-stage combustion engine thickening of lubricating oils.
Hydrogenating multi-arm star butadiene/isoprene random copolymer addition in lubricating oil in preferred application process is 5��25wt%.
The lubricating oil of the present invention can be natural, mineral or synthetic lubricant fluid. Natural lubricating oils includes animal and plant oil, such as Oleum Ricini; Mineral oil includes the lubricating oil fraction being derived from crude oil, coal or shale, and this fraction is likely to carry out some and processes, as acid clay, solvent or selective hydration process; Synthetic lubricant fluid includes the hydrocarbon polymer of synthesis, modified oxyalkylene polymer and ester lubricant, and they are known in the art. These lubricating oil are preferably used for the crankcase lubricating oil of spark ignition and compression ignition engine, and water conservancy system lubricating oil, metal working fluid and automatically deliver liquid.
The present invention with the addition of the lubricant oil composite of hydrogenation multi-arm butadiene/isoprene random copolymer also can contain other additive, such as preservative, antioxidant, detergent, pour-point depressant and one or more other viscosity index improvers etc.
Beneficial effects of the present invention: on the basis of three block star polymers of present invention hydrogenation polyisoprene/polybutadiene/polyisoprene in the prior art, the present invention have devised a kind of star polymer having and being similar to ethylene-propylene copolymer polymeric arms, have been surprisingly found that, this hydrogenation multi-arm star butadiene/isoprene random copolymer is strong to the thickening capabilities of lubricating oil, lubricating oil is made to remain to keep well greasy property under high temperature and shear conditions, experimental results demonstrate multi-arm hydrogenated styrene/isoprene star random copolymer stable chemical performance that the present invention prepares, its resistance to oxidation, resistant to shearing, oil-soluble and good with the compatibility of lubricating oil, except lubricating oil is had good thickening capabilities, also there is outstanding anti-shear stability and viscosity temperature characteristic, modified oil body index is more than 150, after shearing, viscosity conservation rate reaches 90%, may be added in various lubricant oil composite, particularly the multi-stage combustion engine oil of large span, it is possible to be efficiently modified their viscosity index (VI). the preparation method of the present invention, by being slowly added in conjunction with suitable reaction temperature, can effectively control butadiene and the structural generation of pentadiene random copolymer arm, and the molecular weight of polymer and coupling degree can control, and coupling efficiency can reach more than 95%. and the preparation method easy control of reaction conditions of the present invention, production cost are low, it is easy to accomplish industrialized production.
Detailed description of the invention
Following example are further intended to illustrate present disclosure rather than the protection domain of restriction the claims in the present invention.
In embodiment, the molecular weight of polymer, coupling efficiency, coupling degree chromatograph of gel permeation measure, and GPC testing standard is undertaken by Q/SH019.05.P.003 (05) 1998; Degree of hydrogenation adopts iodometric determination.
Lubricants performance measures: joined by the hydrogenated polystyrene of synthesis-isoprene star random copolymer in the neutral lubricating base oils of 150SN with the ratio of 1%, 40 DEG C of kinematic viscosity 31.20mm of 150SN neutral base oil2/ s, 100 DEG C of kinematic viscosity 5.33mm2/ s, pour point-15 DEG C.
The kinematic viscosity of lubricating oil 40 DEG C and 100 DEG C is measured, by method mensuration lubricating oil viscosity index improver thickening capabilities (D) of SH/T0566-93, by the method mensuration lubricating oil low-temperature startup of GB/T6538-2000, the shear stability by the method mensuration lubricating oil of SH/T0103-2007, the method calculating oil body index by GB/T1995-88 by the method for GB/T265-88. Wherein thickening capabilities is calculated as follows:
N=Vt-Vb
In formula: N thickening capabilities, mm2/s
VtAdded with 100 DEG C of kinematic viscositys of the sample of viscosity index improver, mm2/ s;
Vb100 DEG C of kinematic viscositys of base oil, mm2/s��
Shear stable index is calculated as follows:
In formula: ViOil product shears viscosity when first 100 DEG C, mm2/ s;
VfOil product shears viscosity when latter 100 DEG C, mm2/ s;
V0Viscosity during base oil 100 DEG C, mm2/s��
The hydrogenation multi-arm star butadiene/isoprene random copolymer of embodiment 1��9 all prepares by the following method:
Concrete preparation method:
Step 1): activator and organic solvent are joined in polymerization reaction kettle after mix homogeneously, temperature reaction still to 80 �� 10 DEG C;
Step 2): to step 1) reactor in add initiator, controlling temperature is 75 �� 10 DEG C, adds the mix monomer of butadiene and isoprene continuously lentamente in reactor, after being added dropwise to complete, continues reaction about 40 minutes;
Step 3): step 2) reacted after, in reactor, add coupling agent, further reaction effect in 60 minutes, obtains multi-arm star butadiene/isoprene random copolymer virgin rubber;
Step 4): step 3) the multi-arm star butadiene/isoprene random copolymer virgin rubber that obtains adopts Ni/Al catalyst system and catalyzing to carry out hydrogenation under 85 �� 10 DEG C of temperature conditions, after hydrogenation completes, purify, multi-arm star butadiene/isoprene random copolymer must be hydrogenated.
Embodiment 1
Composite number average molecular weight is the butadiene/isoprene random copolymer of 10.3 ten thousand, adopt dichlorodimethylsilane that copolymer is carried out coupling, copolymer is carried out hydrogenation after completing by coupling reaction, and steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=7:3 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
Comparative example 1
Generated data molecular weight is the butadiene/isoprene random copolymer of 12.4 ten thousand, and copolymer is carried out hydrogenation, and steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=7:3 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
Embodiment 2
Composite number average molecular weight is the butadiene/isoprene random copolymer of 8.0 ten thousand, adopt methyl trichlorosilane that copolymer is carried out coupling, copolymer is carried out hydrogenation after completing by coupling reaction, and steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=7:3 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
Embodiment 3
Composite number average molecular weight is butadiene, the isoprene random copolymer of 6.5 ten thousand, adopt Silicon chloride. that copolymer is carried out coupling, copolymer is carried out hydrogenation after completing by coupling reaction, and steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=7:3 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
Embodiment 4
Composite number average molecular weight is butadiene, the isoprene random copolymer of 5.1 ten thousand, adopt divinylbenzene that copolymer is carried out coupling, control the addition of divinylbenzene, copolymer is carried out hydrogenation after completing by coupling reaction, steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=7:3 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
Comparative example 2
Composite number average molecular weight is the triblock copolymer of the isoprene/butadiene/isoprene of 5.3 ten thousand, then adopt divinylbenzene that copolymer is carried out coupling, control the addition of divinylbenzene, copolymer is carried out hydrogenation after completing by coupling reaction, and steam condenses, obtains copolymer after drying. Wherein Ip/Bu/Ip '=40/20/40, Bu has the 1 of at least 85% butadiene, 4-polymerized unit, join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
Embodiment 5
Composite number average molecular weight is the butadiene/isoprene random copolymer of 4.5 ten thousand, adopt divinylbenzene that copolymer is carried out coupling, control the addition of divinylbenzene, copolymer is carried out hydrogenation after completing by coupling reaction, steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=7:3 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
The contrast of the performance of the modification of lubricating oils of table 1 dissimilar arm number copolymer
Note: 150SN base oil, 100 DEG C of kinematic viscositys are 5.33.
The contrast of the performance of table 2 block and atactic polymer modification of lubricating oils
Note: 150SN base oil, 100 DEG C of kinematic viscositys are 5.33.
Embodiment 6
Composite number average molecular weight is the butadiene/isoprene random copolymer of 5.2 ten thousand, adopt divinylbenzene that copolymer is carried out coupling, control the addition of divinylbenzene, copolymer is carried out hydrogenation after completing by coupling reaction, steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=9:1 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
Embodiment 7
Composite number average molecular weight is the butadiene/isoprene random copolymer of 5.1 ten thousand, adopt divinylbenzene that copolymer is carried out coupling, control the addition of divinylbenzene, copolymer is carried out hydrogenation after completing by coupling reaction, steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=8:2 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
Embodiment 8
Composite number average molecular weight is the butadiene/isoprene random copolymer of 5.1 ten thousand, adopt divinylbenzene that copolymer is carried out coupling, control the addition of divinylbenzene, copolymer is carried out hydrogenation after completing by coupling reaction, steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=6:4 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
Embodiment 9
Composite number average molecular weight is the butadiene/isoprene random copolymer of 5.3 ten thousand, adopt divinylbenzene that copolymer is carried out coupling, control the addition of divinylbenzene, copolymer is carried out hydrogenation after completing by coupling reaction, steam condenses, obtains copolymer, wherein atactic polymer Ip/Bu=5:5 after drying. Join in 150SN neutrality lubricating base oils in the ratio of 1%, test its 40 DEG C and 100 DEG C of kinematic viscositys (calculating oil body index by this) and diesel injector shear index, shear stability, pour point.
The Ip/Bu impact on lubricants performance in table 3 random copolymer
Note: 150SN base oil, 100 DEG C of kinematic viscositys are 5.33.
Table 4 present invention prepares the Specifeca tion speeification of random copolymer
Claims (16)
1. hydrogenation multi-arm star butadiene/isoprene random copolymer, it is characterised in that be the multi-arm star random copolymer that single armed is constituted by the butadiene hydrogenated and pentadiene random copolymer, there is structure shown in formula 1:
[Bi1-Ei2-Bi3-Ei4����Bi(m-3)-Ei(m-2)-Bi(m-1)-Eim]n-X
Formula 1
Wherein,
B is hydrogenated butadiene polymer segment;
E is hydrogenated polyisoprene segment;
I1��im is the degree of polymerization of each B or E, and i1��im is each independently selected from 1��10;
N is polymeric arms number, and n is 2��20;
X is coupling agent residue;
The molecular weight of single armed is 4��100,000, and molecular weight distribution is 1.01��1.2;
The total mass ratio of hydrogenated butadiene polymer segment and hydrogenated polyisoprene segment is 5��50:95��50.
2. hydrogenation multi-arm star butadiene/isoprene random copolymer as claimed in claim 1, it is characterised in that the average degree of polymerization of B is 1��5, and the average degree of polymerization of E is 5��10.
3. hydrogenation multi-arm star butadiene/isoprene random copolymer as claimed in claim 1, it is characterised in that polymeric arms number n is 4��10.
4. hydrogenation multi-arm star butadiene/isoprene random copolymer as claimed in claim 1, it is characterised in that the segment in hydrogenated butadiene polymer segment with 1,2-construction unit accounts for the 10��40% of hydrogenated butadiene polymer segment gross mass.
5. hydrogenation multi-arm star butadiene/isoprene random copolymer as claimed in claim 4, it is characterised in that the segment in hydrogenated butadiene polymer segment with 1,2-construction unit accounts for the 10��30% of hydrogenated butadiene polymer segment gross mass.
6. hydrogenation multi-arm star butadiene/isoprene random copolymer as claimed in claim 1, it is characterised in that the unit segment in hydrogenated polyisoprene segment with 3,4-structures accounts for the 5��25% of hydrogenated polyisoprene segment gross mass.
7. hydrogenation multi-arm star butadiene/isoprene random copolymer as claimed in claim 6, it is characterised in that the unit segment in hydrogenated polyisoprene segment with 3,4-structures accounts for the 5��15% of hydrogenated polyisoprene segment gross mass.
8. the preparation method of the hydrogenation multi-arm star butadiene/isoprene random copolymer described in an any one of claim 1��7, it is characterised in that comprise the following steps:
Step 1): activator and organic solvent are joined in polymerization reaction kettle after mix homogeneously, temperature reaction still to 50��100 DEG C;
Step 2): to step 1) reactor in add initiator, controlling temperature is 40��115 DEG C, adds the mix monomer of butadiene and isoprene continuously lentamente in reactor, after being added dropwise to complete, continues reaction 20��60 minutes;
Step 3): step 2) reacted after, in reactor add coupling agent, react further 40��80 minutes, obtain multi-arm star butadiene/isoprene random copolymer virgin rubber;
Step 4): step 3) the multi-arm star butadiene/isoprene random copolymer virgin rubber that obtains adopts Ni/Al catalyst system and catalyzing to carry out hydrogenation under 60��110 DEG C of temperature conditions, after hydrogenation completes, purify, multi-arm star butadiene/isoprene random copolymer must be hydrogenated.
9. preparation method as claimed in claim 8, it is characterised in that butadiene and isoprene 5��50:95��50 in mass ratio mix.
10. preparation method as claimed in claim 8, it is characterised in that the described hydrogenation time is 2��5h, to ensure that in polyisoprene segments, the hydrogenation ratio of unsaturated double-bond is not less than 95%.
11. preparation method as claimed in claim 8, it is characterised in that butadiene and isoprene monomer gross mass percent concentration in a solvent is 5��30%.
12. preparation method as claimed in claim 8, it is characterised in that described activator mass percent concentration in a solvent is��0.1%; Described activator is oxolane.
13. preparation method as claimed in claim 8, it is characterised in that the addition of initiator is the 1��5% of butadiene and the total quality of isoprene; Described initiator is lithium alkylide.
14. preparation method as claimed in claim 8, it is characterised in that the consumption of described coupling agent is the 0.2��3% of butadiene and isoprene monomer gross mass; Described coupling agent is one or more in dichlorodimethylsilane, trichloromethyl silane, Silicon chloride., butter of tin and divinylbenzene.
15. the application of the hydrogenation multi-arm star butadiene/isoprene random copolymer as described in any one of claim 1��7, it is characterised in that be applied to thickening of lubricating oils as viscosity improver.
16. apply as claimed in claim 15, it is characterised in that hydrogenation multi-arm star butadiene/isoprene random copolymer addition in lubricating oil is 1��15wt%.
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| CN1350013A (en) * | 2000-10-19 | 2002-05-22 | 中国石油化工股份有限公司 | Star-shaped conjugated diolefine-styrene block copolymer and its prepn |
| CN1576359A (en) * | 2003-07-01 | 2005-02-09 | 英菲诺姆国际有限公司 | Viscosity index improvers for lubricating oil compositions |
| CN101817911A (en) * | 2009-02-26 | 2010-09-01 | 中国石油化工股份有限公司 | Star block copolymer prepared from isoprene, butadiene and styrene, and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110105498A (en) * | 2019-05-15 | 2019-08-09 | 大连理工大学 | One kind is suitable for single silicon hydrogen functionalization star polymer and preparation method thereof of Si―H addition reaction chemical reaction |
| CN110105498B (en) * | 2019-05-15 | 2021-07-30 | 大连理工大学 | Mono-silicon-hydrogen functionalized star polymer suitable for hydrosilylation chemical reaction and preparation method thereof |
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