CN102070736A - Component and preparation method of rare-earth catalyst for synthesizing high cis-1,4-polyisoprene - Google Patents
Component and preparation method of rare-earth catalyst for synthesizing high cis-1,4-polyisoprene Download PDFInfo
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- CN102070736A CN102070736A CN2009102304265A CN200910230426A CN102070736A CN 102070736 A CN102070736 A CN 102070736A CN 2009102304265 A CN2009102304265 A CN 2009102304265A CN 200910230426 A CN200910230426 A CN 200910230426A CN 102070736 A CN102070736 A CN 102070736A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 title 1
- 230000002194 synthesizing effect Effects 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 5
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 4
- 230000004224 protection Effects 0.000 claims abstract 2
- 230000032683 aging Effects 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000007172 homogeneous catalysis Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims 2
- 238000004220 aggregation Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 claims 1
- 230000029087 digestion Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 238000004513 sizing Methods 0.000 claims 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 229940126062 Compound A Drugs 0.000 abstract 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- 238000012662 bulk polymerization Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 238000003483 aging Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 4
- 244000286663 Ficus elastica Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000019628 coolness Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- -1 rare earth compound Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a homogeneous-phase rare-earth catalyst for the polymerization of isoprene. The homogeneous-phase rare-earth catalyst is prepared through the hybrid reaction of a rare-earth compound A as a main catalyst, alkyl aluminum B as an assistant catalyst and a halide C. A preparation method comprises the following steps of: uniformly mixing the three components of the A, the B and the C in hydrogasoline, and reacting for 15 minutes to 24 hours at a temperature of 0-50 DEG C. The polymerization is implemented by adopting a bulk polymerization process under the protection of high-purity N2 (nitrogen), and a monomer is transformed into a polymer by sequentially adding the isoprene and the catalysts to react for a certain time. The catalyst has high catalytic activity and can be used for preparing polyisoprene of which the molecular weight is 0.2 million to 1 million, the gel content is 0.5-18 percent, and the content of a cis-1,4 structure is larger than 96 percent. Moreover, the investment on the polymerization is reduced, the energy consumption is low, and the pollution is small.
Description
(1) technical field
The present invention relates to the macromolecular material synthetic technology.Rare-earth catalysis system is the most significant synthetic rubber catalyst system of finding over nearly 40 years, has greatly expanded the scope and the intension of Zieler-Natta tactic polymerization.At present, no matter from basic science and industrial application angle, the innovation of rare-earth catalysis system and expansion are still one of research focus.
(2) background technology
Be applied to 1, the homogeneous phase rare earth catalyst system of 3-diolefin polymerization has the characteristics such as relative molecular mass of feeding in raw material accurately, react evenly, be convenient to the controlled polymerization product, economical and technical more superior than heterogeneous catalyst, so cause people's attention.In the three-way catalyst that rare earth compound/aluminum alkyls/muriate is formed, muriatic kind and consumption are bigger to catalyzer phase and polymerization activity influence.By the chloro aluminum alkyls is that the rare earth catalyst activity of the 3rd component is higher, but easily forms nonhomogeneous system.Some hydrochloric ether or chlorosilane can be mixed with homogeneous catalyst system, but polymerization activity is lower.
(3) summary of the invention
The purpose of invention is to seek a kind of suitable chlorine part, is mixed with homogeneous catalyst system under proper reaction conditions, and a kind of polymerization process of rare earth diolefin is provided, and rare earth catalyst synthesizes high-cis-1, the 4-polyisoprene.And provide a kind of molecular weight of controlling polymers and the affected hardly method for preparing catalyst of molecular weight distribution and microtexture.
The present invention is with anhydrous AlCl
3Be dissolved in Al (i-Bu)
3In be mixed with certain density solution as the 3rd component, with Nd (octa)
3And Al (i-Bu)
3Be mixed with homogeneous catalysis system, implement the isoprene homopolymerization.
(4) embodiment
Starting material
Rubber plant of isoprene (Ip) Qilu Petrochemical company polymerization-grade product, high boiling point things such as stopper are removed in distillation before using, and get 34 ℃ of cuts, and are standby after dry two weeks through active molecular sieve.
Rubber plant of solvent Qilu Petrochemical company polymerization-grade hydrogenated gasoline, 68 ℃ of-72 ℃ of cuts are got in distillation before using, and are standby after dry two weeks through active molecular sieve.
Catalyzer (Nd) isocaprylic acid neodymium, the laboratory self-control.
Rubber plant of promotor (Al) Beijing Yanshan Petrochemical Company produces triisobutyl aluminium, is made into 2.5mol/L concentration gasoline solution and uses.
The rich Dihua worker company limited in promotor (Cl) Tianjin produces the anhydrous AlCl of analytical pure
3, be dissolved in Al (i-Bu)
3Being made into 0.1mol/L concentration solution uses.
Analysis test method:
Intrinsic viscosity adopts toluene to make solvent by determination of ubbelohde viscometer.Probe temperature is 30 ℃; Calculation formula:
[η]＝2.0×10
-4M
η 0.728。
Micmstructure of polymer and cis-1, the 4-structural content is measured by the German BRUKER ANAVCE500 of company type nuclear magnetic resonance spectrometer.
Experimental technique:
Preparation of catalysts:
With the 10ml polymerizing pipe clean, oven dry, pump drainage, with 3 coolings of nitrogen replacement, add the catalyst component of calculated amount successively.Then polymerizing pipe is put into water bath with thermostatic control, the ageing certain hour.
Polymerization experiment:
With the 10ml polymerizing pipe clean, oven dry, pump drainage, with 3 coolings of nitrogen replacement, add 5g monomer isoprene, catalyzer; Behind the constant temperature polymerization certain hour, add the ethanolic soln termination reaction that contains anti-aging agent-264.With the polymkeric substance drying to constant weight.
Embodiment 1
Al/Nd=50 (mol ratio, down with), Cl/Nd=3 (mol ratio, down with) joins through oven dry, pump drainage, in the 10ml of nitrogen replacement polymerizing pipe successively according to the order of addition(of ingredients) of Nd-Cl-Al.Then polymerizing pipe is put into ice bath, ageing 1h, gained catalyzer are the lavender clear solution.
Add 5g monomer I p and the above-mentioned catalyzer that makes, Nd/Ip=2 * 10 in the polymerizing pipe
-4(mol ratio, down together) in 50 ℃ of following polymerization 5h, stops dried packaged polymkeric substance 5.1119g, and monomer conversion reaches 100%, catalytic efficiency 1742g/gNd, and the calculating viscosity-average molecular weight is M
η=3.61 * 10
5, recording its cis-1, the 4-structural content is greater than 96%.
Embodiment 2
With embodiment 1, catalyzer ageing temperature is 20 ℃.Get polymkeric substance 5.2192g, monomer conversion is 100%, and catalytic efficiency is 1742g/gNd, and viscosity-average molecular weight is M
η=3.52 * 10
5
Embodiment 3
With embodiment 1, catalyzer ageing temperature is 50 ℃.Get polymkeric substance 3.8004g, monomer conversion 76%, catalytic efficiency 1324g/gNd.As seen catalyzer activity under higher ageing temperature has downtrending, and higher in lesser temps ageing activity.Instability when showing active centre high temperature has the part active centre at least because of the decomposition inactivation, causes the decline of catalytic activity.
Embodiment 4
Experimental procedure is with embodiment 1, Al/Nd=35.Get polymkeric substance 3.25g, monomer conversion 65%, catalytic efficiency 1132g/gNd, viscosity-average molecular weight is M
η=2.87 * 10
5
Embodiment 5
With embodiment 1, polymerization temperature is reduced to 0 ℃.Get polymerisate 3.2510g, monomer conversion 65.0%, catalytic efficiency 1132g/gNd, viscosity-average molecular weight is M
η=4.15 * 10
5
Embodiment 6
With embodiment 1, polymerization temperature is 20 ℃.Obtain polymerisate 4.5660g, monomer conversion 91.3%, catalytic efficiency 1590g/gNd, viscosity-average molecular weight is M
η=3.87 * 10
5Raise with polymerization temperature, the relative molecular weight of product reduces, and may be because the rising of temperature more helps taking place due to the chain transfer reaction.
Embodiment 7
Experimental procedure is with embodiment 1, and catalyst system three component ageings are Nd-Al-Cl in proper order.Obtaining polymerisate is 4.0100g, and monomer conversion is 80%, and catalytic efficiency is 1394g/gNd, viscosity-average molecular weight M
η=1.98 * 10
5As seen catalyzer activity under this order of addition(of ingredients) is lower, and the polymkeric substance relative molecular weight that obtains is on the low side.
Claims (3)
1. one kind is used for synthetic high-cis-1, and the novel rare-earth catalyst system of 4-polyisoprene is characterized in that adopting homogeneous catalysis system and bulk technique to implement.Be aggregated under high-purity N 2 protections and carry out, successively monomer and catalyzer are added aggregation container, polymerization at a certain temperature all changes into polymkeric substance until monomer.Need not aftertreatment and solvent monomer recovery process.
2. the method for synthetic high three-dimensional regularity diolefin according to claim 1 is characterized in that polymerizing condition is: Nd/Ip＜2 * 10
-4(mol ratio), Al/Nd=25-70 (mol ratio), polymerization temperature 0-60 ℃, polymerization time 0.5-10 hour, monomer conversion was greater than 95%, and product is the transparence sizing material.Catalytic efficiency is greater than 1600g/gNd, product cis-1, and 4-content is more than 96%.
3. the method for synthetic high three-dimensional regularity diolefin according to claim 1 is characterized in that the Preparation of catalysts condition is: 0-60 degree centigrade of ageing temperature, and digestion time 15min-24h, order of addition(of ingredients) is Nd-Cl-Al.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102304265A CN102070736A (en) | 2009-11-19 | 2009-11-19 | Component and preparation method of rare-earth catalyst for synthesizing high cis-1,4-polyisoprene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037588A (en) * | 2015-07-23 | 2015-11-11 | 北京理工大学 | Isoindole rare earth metal catalyst, preparation method and application |
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- 2009-11-19 CN CN2009102304265A patent/CN102070736A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037588A (en) * | 2015-07-23 | 2015-11-11 | 北京理工大学 | Isoindole rare earth metal catalyst, preparation method and application |
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Application publication date: 20110525 |