CN1861649A - Preparation process of rare earth catalyst for diolefines polymerizing copolymerizing - Google Patents

Preparation process of rare earth catalyst for diolefines polymerizing copolymerizing Download PDF

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CN1861649A
CN1861649A CN 200610016949 CN200610016949A CN1861649A CN 1861649 A CN1861649 A CN 1861649A CN 200610016949 CN200610016949 CN 200610016949 CN 200610016949 A CN200610016949 A CN 200610016949A CN 1861649 A CN1861649 A CN 1861649A
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alcohol
molecular weight
rare earth
ndcl
catalyst
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董为民
任长友
李桂连
姜连升
张学全
王佛松
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

A process for preparing the RE catalyst used for the polymerization or copolymerization of diolefine includes such steps as proportionally adding the alkoxide of the RE halide (LnX3 .nROH), monomer and the saturated hydrocarbon solution of alkyl aluminum into reactor under protection of N2, and ageing at 40-100 deg.C for 5min -24 hr.

Description

The preparation method who is used for the rare earth catalyst of diolefin polymerization or copolymerization
Technical field
The invention belongs to the preparation method of the rare earth catalyst that is used for diolefin polymerization or copolymerization.
Background technology
Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences uses the rare earth resources of China's abundant as far back as early sixties, has carried out the research of rare earth catalyst tactic polymerization, and has openly reported with the form of paper at first: YCl 3With AlEt 3The nonhomogeneous system of forming can be synthesized the polyhutadiene of high-cis (95%) structure in order to catalysis, but catalytic activity not high (Science Bulletin, 1964, (4): 335-337).Add a spot of ethanol and can improve the catalytic activity of rare earth chloride.Discover that further alcohol just shows active (Chinese science, 1980, (2): 127-135) with the aluminum alkyls reaction after must at first forming title complex with rare earth chloride according to certain mol proportion again.
Binary catalyst catalysis diolefin polymerization or copolymerization that rare earth chloride alcohol adduct and aluminum alkyls are formed, catalyst levels is higher, and polymerization activity lower (use polymer chemistry, J.Appl.Polym.Chem., 2005,97:1279-1283).
Improve the Preparation of catalysts temperature, will cause catalytic activity to reduce.When the preparation catalyzer, add small amounts of monomer, though can improve the system viscosity, help the dispersion of catalyzer, activity is not significantly influenced (Chinese science, 1980, (2): 127-135).
Summary of the invention
The objective of the invention is for catalysis diolefin polymerization after solving the binary rare-earth catalyzer and in preparation process, not adding monomer or add monomer or the active low problem of copolymerization, provide a kind of preparation method who is used for the rare earth catalyst of diolefin polymerization or copolymerization: press alcohol adduct, the monomer of rare earth halide, the order of aluminum alkyls is mixed, the high temperature ageing is treated the catalyzer that obtains after the solution changes color to be used for the activity that polymerization can increase substantially monomer polymerization.
The catalyzer that the present invention proposes is the alcohol adduct (LnX with rare earth halide 3NROH), aluminum alkyls and monomer are formed.Wherein:
Ln is neodymium (Nd) or praseodymium (Pr);
X is chlorine (Cl) or bromine (Br).
Alcohol (ROH) comprising: various straight chain alcohols, branched-chain alcoho or aromatic alcohol, and as ethanol (EtOH), propyl alcohol (PrOH), butanols (BuOH), amylalcohol (PtOH), hexanol (HxOH), octanol (OtOH), nonyl alcohol (NOH), decyl alcohol (DOH), lauryl alcohol (DoOH), 16 carbon alcohol (HdOH), octadecanol (OdOH), Virahol (Pr iOH), isopropylcarbinol (Bu iOH), isooctyl alcohol (EHOH), hexalin (ChOH), phenylcarbinol or benzyl alcohol (BzOH).
N＝1.5-4。
Monomer comprises: divinyl, isoprene or pentadiene.
Aluminum alkyls comprises: trialkylaluminium or alkyl-al hydride wherein, are preferably triisobutyl aluminium (Al (i-Bu) 3), triethyl aluminum (AlEt 3), diisobutyl aluminium hydride (Al (i-Bu) 2H) or ADEH (AlEt 2H).
Step and the condition of implementing the rare earth catalyst preparation method who is used for diolefin polymerization and copolymerization of the present invention are as follows:
Alcohol adduct (the LnX that under nitrogen protection, in exsiccant catalyst preparation device, adds above-mentioned rare earth halide successively 3NROH), monomer, the saturated hydrocarbon solution of aluminum alkyls (Al).The mol ratio of mol ratio between each component: Al and Ln is 10～200, and the mol ratio of monomer and Ln is 2～50.After 40～100 ℃ of following ageings were treated solution changes color in 5 minutes～24 hours, obtain being used for the rare earth catalyst of diolefin polymerization or copolymerization.
This catalyzer is applicable to diolefin polymerization or copolymerization, is aggregated in the organic solvent existence and also can carries out under solvent-free situation down; Adopting stable hydrocarbon hexane, hexanaphthene, heptane, hydrogenated gasoline or sherwood oil when carrying out solution polymerization is solvent, and monomer concentration is 8～20g/100mL, and catalyst levels Ln is 5 * 10 with the monomer ratio -7～1.0 * 10 -5Mol/g, polymerization temperature are 0～100 ℃, and polymerization time is 0.5 hour～5 hours; Reaction with contain 1% 2, the ethanolic soln of 6-di-tert-butyl methyl phenol stops, the polymkeric substance that in excess ethyl alcohol, settles out, after the washing with alcohol extruding, in 40 ℃ of drying under reduced pressure 24 hours, the calculating monomer conversion of weighing.
The alcohol adduct that consists of rare earth halide, aluminum alkyls and the monomer of this catalyzer; Ageing at high temperature has higher catalyzed polymerization activity, can make that suitable-1,4 structural content is higher than 95.8%, the high-molecular weight polyisoprene.
Suitable-1,4 structural content with the infrared measurement polymkeric substance.Measure the molecular weight and the molecular weight distributing index of polymkeric substance with gel permeation chromatography (GPC).
Embodiment
The present invention proposes following examples as further instruction.
Embodiment 1:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al (i-Bu) of the divinyl hexane solution of the 1.0mol/L of 3EHOH, 3mL and the 2.0mol/L of 3mL 3Hexane solution is added the hexane of 14mL.At this moment, the mol ratio of Al and Nd is 20, and the mol ratio of divinyl and Nd is 10, and in 70 ℃ of ageings 15 minutes, catalyst color was a yellow-green colour, obtained being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add hexane, the isoprene (300g) of 440mL and the catalyzer of above-mentioned preparation of 2560mL.This moment, monomer concentration was 10g/100mL, and Nd/ isoprene ratio is 1.0 * 10 -6Mol/g.After 1 hour, get isoprene polymerization product 223g in reaction under 50 ℃, transformation efficiency 74%, recording suitable-1,4 structural content through infrared spectra is 95.9%, and recording number-average molecular weight through GPC is 1568000, and molecular weight distribution is 1.82.
Comparative example 1:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al of the 2.0mol/L of 3EHOH and 3mL (i-Bu) 3Hexane solution is added the hexane of 17mL.At this moment, the mol ratio of Al and Nd is 20, and ageing is 1 hour under room temperature, and catalyst color is an oyster white, obtains being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add hexane, the isoprene (300g) of 440mL and the catalyzer of above-mentioned preparation of 2560mL.This moment, monomer concentration was 10g/100mL, and Nd/ isoprene ratio is 1.0 * 10 -6Mol/g.50 ℃ are reacted down after 1 hour, get isoprene polymerization product 84g, transformation efficiency 28% (embodiment 1 is 74%).Recording suitable-1,4 structural content through infrared spectra is 96.0%, and recording number-average molecular weight through GPC is 1786000, and molecular weight distribution is 1.89.
Comparative example 2:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al of the 2.0mol/L of 3EHOH and 3mL (i-Bu) 3Hexane solution is added the hexane of 17mL.At this moment, the mol ratio of Al and Nd is 20, in 70 ℃ of following ageings 15 minutes, obtains being used for the rare earth catalyst of diolefin polymerization and copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add hexane, the isoprene (300g) of 440mL and the catalyzer of above-mentioned preparation of 2560mL.This moment, monomer concentration was 10g/100mL, and Nd/ isoprene ratio is 1.0 * 10 -6Mol/g.After 1 hour, get isoprene polymerization product 39g in reaction under 50 ℃, transformation efficiency 13% (embodiment 1 is 74%), recording suitable-1,4 structural content through infrared spectra is 95.9%, and recording number-average molecular weight through GPC is 1626000, and molecular weight distribution is 1.75.
Comparative example 3:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al (i-Bu) of the divinyl hexane solution of the 1.0mol/L of 3EHOH, 3mL and the 2.0mol/L of 3mL 3Hexane solution is added the hexane of 14mL.At this moment, the mol ratio of Al and Nd is 20, and the mol ratio of divinyl and Nd is 10, and ageing is 1 hour under room temperature, and catalyst color is an oyster white, obtains being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add hexane, the isoprene (300g) of 440mL and the catalyzer of above-mentioned preparation of 2560mL.This moment, monomer concentration was 10g/100mL, and Nd/ isoprene ratio is 1.0 * 10 -6Mol/g.After 1 hour, get isoprene polymerization product 78g in reaction under 50 ℃, transformation efficiency 26% (embodiment 1 is 74%), recording suitable-1,4 structural content through infrared spectra is 95.9%, and recording number-average molecular weight through GPC is 1639000, and molecular weight distribution is 1.69.
Embodiment 2:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only to replace in 24 hours in 70 ℃ of ageings 15 minutes in 40 ℃ of following ageings.
This moment is as follows with the result of its gained polyisoprene: polymerisate 203g, transformation efficiency are 68%, and recording suitable-1,4 structural content through infrared spectra is 95.7%, and recording number-average molecular weight through GPC is 1573000, and molecular weight distribution is 1.87.
Embodiment 3:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only to replace in 5 minutes in 70 ℃ of ageings 15 minutes in 100 ℃ of following ageings.
This moment is as follows with the result of its gained polyisoprene: polymerisate 210g, transformation efficiency are 70%, and recording suitable-1,4 structural content through infrared spectra is 96.0%, and recording number-average molecular weight through GPC is 1733000, and molecular weight distribution is 1.78.
Embodiment 4:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only replace divinyl with isoprene.
This moment is as follows with the result of its gained polyisoprene: polymerisate 205g, transformation efficiency are 72%, and recording suitable-1,4 structural content through infrared spectra is 96.0%, and recording number-average molecular weight through GPC is 1468000, and molecular weight distribution is 1.82.
Embodiment 5:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only replace divinyl with pentadiene.
This moment is as follows with the result of its gained polyisoprene: polymerisate 207g, transformation efficiency are 72%, and recording suitable-1,4 structural content through infrared spectra is 95.9%, and recording number-average molecular weight through GPC is 1498000, and molecular weight distribution is 1.71.
Embodiment 6:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al (i-Bu) of the divinyl hexane solution of the 1.0mol/L of 3EHOH, 0.6mL and the 2.0mol/L of 30mL 3Hexane solution.At this moment, the mol ratio of Al and Nd is 200, and the mol ratio of divinyl and Nd is 2, and in 70 ℃ of ageings 15 minutes, catalyst color was a yellow-green colour, obtained being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add hexanaphthene, the isoprene (300g) of 440mL and the catalyzer of above-mentioned preparation of 2560mL.This moment, monomer concentration was 10g/100mL, and Nd/ isoprene ratio is 1.0 * 10 -6Mol/g.After 5 hours, get isoprene polymerization product 283g in reaction under 50 ℃, transformation efficiency 94%, recording suitable-1,4 structural content through infrared spectra is 95.9%, and recording number-average molecular weight through GPC is 368000, and molecular weight distribution is 9.82.
Embodiment 7:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al (i-Bu) of the divinyl hexane solution of the 1.0mol/L of 3EHOH, 15mL and the 2.0mol/L of 1.5mL 3Hexane solution is added the hexane of 2mL.At this moment, the mol ratio of Al and Nd is 10, and the mol ratio of divinyl and Nd is 50, and in 70 ℃ of ageings 15 minutes, catalyst color was a yellow-green colour, obtained being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add heptane, the isoprene (300g) of 440mL and the catalyzer of above-mentioned preparation of 2560mL.This moment, monomer concentration was 10g/100mL, and Nd/ isoprene ratio is 1.0 * 10 -6Mol/g.After 4 hours, get isoprene polymerization product 48g in reaction under 0 ℃, transformation efficiency 16%, recording suitable-1,4 structural content through infrared spectra is 95.8%, and recording number-average molecular weight through GPC is 368000, and molecular weight distribution is 1.62.
Embodiment 8:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 2.4 * 10 successively -3The NdCl of mol 3The Al (i-Bu) of the divinyl hexane solution of the 1.0mol/L of 3EHOH, 24mL and the 2.0mol/L of 24mL 3Hexane solution.At this moment, the mol ratio of Al and Nd is 20, and the mol ratio of divinyl and Nd is 10, and in 70 ℃ of ageings 15 minutes, catalyst color was a yellow-green colour, obtained being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add hydrogenated gasoline, the isoprene (240g) of 350mL and the catalyzer of above-mentioned preparation of 2650mL.This moment, monomer concentration was 8g/100mL, and Nd/ isoprene ratio is 1.0 * 10 -5Mol/g.After 0.5 hour, get isoprene polymerization product 228g in reaction under 100 ℃, transformation efficiency 95%, recording suitable-1,4 structural content through infrared spectra is 95.5%, and recording number-average molecular weight through GPC is 278000, and molecular weight distribution is 8.12.
Embodiment 9:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al (i-Bu) of the divinyl hexane solution of the 1.0mol/L of 3EHOH, 3mL and the 2.0mol/L of 3mL 3Hexane solution is added the hexane of 11mL.At this moment, the mol ratio of Al and Nd is 20, and the mol ratio of divinyl and Nd is 10, and in 70 ℃ of ageings 15 minutes, catalyst color was a yellow-green colour, obtained being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add sherwood oil, the isoprene (600g) of 880mL and the catalyzer of above-mentioned preparation of 2120mL.This moment, monomer concentration was 20g/100mL, and Nd/ isoprene ratio is 5.0 * 10 -7Mol/g.After 3 hours, get isoprene polymerization product 468g in reaction under 50 ℃, transformation efficiency 78%, recording suitable-1,4 structural content through infrared spectra is 95.5%, and recording number-average molecular weight through GPC is 1678000, and molecular weight distribution is 1.65.
Embodiment 10:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al (i-Bu) of the divinyl hexane solution of the 1.0mol/L of 3EHOH, 3mL and the 2.0mol/L of 3mL 3Hexane solution is added the hexane of 11mL.At this moment, the mol ratio of Al and Nd is 20, and the mol ratio of divinyl and Nd is 10, and in 70 ℃ of ageings 15 minutes, catalyst color was a yellow-green colour, obtained being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add the isoprene (600g) of 880mL and the catalyzer of above-mentioned preparation.This moment, monomer concentration was 20g/100mL, and Nd/ isoprene ratio is 5.0 * 10 -7Mol/g.After 3 hours, get isoprene polymerization product 546g in reaction under 50 ℃, transformation efficiency 91%, recording suitable-1,4 structural content through infrared spectra is 95.9%, and recording number-average molecular weight through GPC is 1358000, and molecular weight distribution is 1.69.
Embodiment 11:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 34EtOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 165g, transformation efficiency are 55%, and recording suitable-1,4 structural content through infrared spectra is 95.8%, and recording number-average molecular weight through GPC is 1441000, and molecular weight distribution is 1.98.
Embodiment 12:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33PrOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 172g, transformation efficiency are 57%, and recording suitable-1,4 structural content through infrared spectra is 95.8%, and recording number-average molecular weight through GPC is 1275000, and molecular weight distribution is 1.87.
Embodiment 13:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33BuOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 168g, transformation efficiency are 56%, and recording suitable-1,4 structural content through infrared spectra is 95.6%, and recording number-average molecular weight through GPC is 1266000, and molecular weight distribution is 1.77.
Embodiment 14:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33PtOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 155g, transformation efficiency are 55%, and recording suitable-1,4 structural content through infrared spectra is 95.9%, and recording number-average molecular weight through GPC is 1311000, and molecular weight distribution is 1.92.
Embodiment 15:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33HxOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 175g, transformation efficiency are 58%, and recording suitable-1,4 structural content through infrared spectra is 95.6%, and recording number-average molecular weight through GPC is 1471000, and molecular weight distribution is 1.94.
Embodiment 16:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33HtOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 182g, transformation efficiency are 61%, and recording suitable-1,4 structural content through infrared spectra is 95.7%, and recording number-average molecular weight through GPC is 1491000, and molecular weight distribution is 1.76.
Embodiment 17:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33OtOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 179g, transformation efficiency are 60%, and recording suitable-1,4 structural content through infrared spectra is 95.7%, and recording number-average molecular weight through GPC is 1563000, and molecular weight distribution is 1.77.
Embodiment 18:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33NOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 175g, transformation efficiency are 58%, and recording suitable-1,4 structural content through infrared spectra is 95.9%, and recording number-average molecular weight through GPC is 1353000, and molecular weight distribution is 1.82.
Embodiment 19:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33DOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 167g, transformation efficiency are 56%, and recording suitable-1,4 structural content through infrared spectra is 95.8%, and recording number-average molecular weight through GPC is 1543000, and molecular weight distribution is 1.73.
Embodiment 20:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33DoOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 162g, transformation efficiency are 54%, and recording suitable-1,4 structural content through infrared spectra is 95.8%, and recording number-average molecular weight through GPC is 1397000, and molecular weight distribution is 1.78.
Embodiment 21:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33HdOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 172g, transformation efficiency are 58%, and recording suitable-1,4 structural content through infrared spectra is 95.8%, and recording number-average molecular weight through GPC is 1462000, and molecular weight distribution is 1.73.
Embodiment 22:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33OdOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 153g, transformation efficiency are 51%, and recording suitable-1,4 structural content through infrared spectra is 95.5%, and recording number-average molecular weight through GPC is 1647000, and molecular weight distribution is 1.86.
Embodiment 23:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33Pr iOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 186g, transformation efficiency are 62%, and recording suitable-1,4 structural content through infrared spectra is 95.8%, and recording number-average molecular weight through GPC is 1561000, and molecular weight distribution is 1.72.
Embodiment 24:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33Bu iOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 159g, transformation efficiency are 56%, and recording suitable-1,4 structural content through infrared spectra is 95.6%, and recording number-average molecular weight through GPC is 1511000, and molecular weight distribution is 1.88.
Embodiment 25:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 31.5EHOH replace NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 164g, transformation efficiency are 55%, and recording suitable-1,4 structural content through infrared spectra is 95.7%, and recording number-average molecular weight through GPC is 1632000, and molecular weight distribution is 1.79.
Embodiment 26:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 32.5EHOH replace NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 178g, transformation efficiency are 59%, and recording suitable-1,4 structural content through infrared spectra is 95.6%, and recording number-average molecular weight through GPC is 1461000, and molecular weight distribution is 1.78.
Embodiment 27:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33ChOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 172g, transformation efficiency are 57%, and recording suitable-1,4 structural content through infrared spectra is 95.8%, and recording number-average molecular weight through GPC is 1398000, and molecular weight distribution is 1.84.
Embodiment 28:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdCl 33BzOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 159g, transformation efficiency are 56%, and recording suitable-1,4 structural content through infrared spectra is 95.6%, and recording number-average molecular weight through GPC is 1368000, and molecular weight distribution is 1.78.
Embodiment 29:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with NdBr 33EHOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 144g, transformation efficiency are 48%, and recording suitable-1,4 structural content through infrared spectra is 95.7%, and recording number-average molecular weight through GPC is 1268000, and molecular weight distribution is 1.82.
Embodiment 30:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with PrCl 33EHOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 168g, transformation efficiency are 56%, and recording suitable-1,4 structural content through infrared spectra is 95.9%, and recording number-average molecular weight through GPC is 1592000, and molecular weight distribution is 1.79.
Embodiment 31:
As catalyst preparation method and the polymerizing condition among the embodiment 1, only with PrBr 33EHOH replaces NdCl 33EHOH.
This moment is as follows with the result of its gained polyisoprene: polymerisate 138g, transformation efficiency are 46%, and recording suitable-1,4 structural content through infrared spectra is 95.6%, and recording number-average molecular weight through GPC is 1672000, and molecular weight distribution is 1.74.
Embodiment 32:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al (i-Bu) of the divinyl hexane solution of the 1.0mol/L of 3EHOH, 3mL and the 2.0mol/L of 3mL 3Hexane solution is added the hexane of 14mL.At this moment, the mol ratio of Al and Nd is 20, and the mol ratio of divinyl and Nd is 10, and in 70 ℃ of ageings 15 minutes, catalyst color was a yellow-green colour, obtained being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add hexane, the divinyl (300g) of 484ml and the catalyzer of above-mentioned preparation of 2516mL.This moment, monomer concentration was 10g/100mL, and Nd/ divinyl ratio is 1.0 * 10 -6Mol/g.After reacting 1 hour under 50 ℃, get polymerizing butadiene product 231g, transformation efficiency 77%, suitable-1,4 structural content that records divinyl through infrared spectra is 98.3%, instead-1,4 structural contents are that 1.2%, 1,2 content structural contents are 0.5%, recording number-average molecular weight through GPC is 1861000, and molecular weight distribution is 1.71.
Embodiment 33:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add 3.0 * 10 successively -4The NdCl of mol 3The Al (i-Bu) of the divinyl hexane solution of the 1.0mol/L of 3EHOH, 3mL and the 2.0mol/L of 3mL 3Hexane solution is added the hexane of 14mL.At this moment, the mol ratio of Al and Nd is 20, and the mol ratio of divinyl and Nd is 10, and in 70 ℃ of following ageings 15 minutes, the color of catalyzer was a yellow-green colour, obtains being used for the rare earth catalyst of diolefin polymerization or copolymerization.
Under nitrogen protection, in the autoclave of the dry deoxygenation of 5L, add hexane, the divinyl (240g) of 387ml, the isoprene (60g) of 88ml and the catalyzer of above-mentioned preparation of 2525mL.This moment, monomer concentration was 10g/100mL, and Nd/ monomer ratio is 1.0 * 10 -6Mol/g., get butadiene-isoprene copolymer and close product 231g, transformation efficiency 77% after 1 hour in reaction under 50 ℃, suitable-1,4 structural content that records divinyl through infrared spectra is 98.3%, anti--1,4 structural contents are that 1.2%, 1,2 content structural contents are 0.5%, polyisoprene suitable-1,4 structural contents are that 97.2%, 3,4 structural contents are 2.8%, recording number-average molecular weight through GPC is 1861000, and molecular weight distribution is 1.71.

Claims (1)

1, a kind of preparation method who is used for the rare earth catalyst of diolefin polymerization or copolymerization, this catalyzer is the alcohol adduct (LnX with rare earth halide 3NROH), aluminum alkyls and monomer are formed; Wherein:
Ln is neodymium or praseodymium;
X is a chlorine or bromine;
Alcohol roh comprises: various straight chain alcohols, branched-chain alcoho or aromatic alcohol, as ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, nonyl alcohol, decyl alcohol, lauryl alcohol, 16 carbon alcohol, octadecanol, Virahol, isopropylcarbinol, isooctyl alcohol, hexalin, phenylcarbinol or benzyl alcohol;
n＝1.5-4；
Monomer comprises: divinyl, isoprene or pentadiene;
Aluminum alkyls comprises: trialkylaluminium or alkyl-al hydride wherein, are preferably triisobutyl aluminium, triethyl aluminum, diisobutyl aluminium hydride or ADEH;
It is characterized in that the step and the condition of its preparation are as follows: the alcohol adduct (LnX that under nitrogen protection, in exsiccant catalyst preparation device, adds rare earth halide successively 3NROH), monomer, the saturated hydrocarbon solution of aluminum alkyls; The mol ratio of mol ratio between each component: Al and Ln is 10～200, and the mol ratio of monomer and Ln is 2～50; After 40～100 ℃ of following ageings were treated solution changes color in 5 minutes～24 hours, obtain being used for the rare earth catalyst of diolefin polymerization or copolymerization.
CN 200610016949 2006-06-16 2006-06-16 Preparation process of rare earth catalyst for diolefines polymerizing copolymerizing Pending CN1861649A (en)

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CN102234356A (en) * 2010-04-30 2011-11-09 青岛伊科思新材料股份有限公司 Method for producing rare-earth isoprene butadiene rubber
WO2012075964A1 (en) 2010-12-09 2012-06-14 中国石油化工股份有限公司 Neodymium based homogeneous phase rare earth catalyst and use thereof
CN103450373B (en) * 2012-05-28 2016-04-27 中国石油化工股份有限公司 Rare earth catalyst composition and rare earth catalyst and application thereof
CN106916240A (en) * 2015-12-25 2017-07-04 中国石油天然气股份有限公司 Method for preparing rare earth isoprene rubber catalyst
CN114075307A (en) * 2020-08-13 2022-02-22 中国石油天然气股份有限公司 Rare earth catalyst and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN102234356A (en) * 2010-04-30 2011-11-09 青岛伊科思新材料股份有限公司 Method for producing rare-earth isoprene butadiene rubber
CN102234356B (en) * 2010-04-30 2013-03-06 青岛伊科思新材料股份有限公司 Method for producing rare-earth isoprene butadiene rubber
WO2012075964A1 (en) 2010-12-09 2012-06-14 中国石油化工股份有限公司 Neodymium based homogeneous phase rare earth catalyst and use thereof
CN103450373B (en) * 2012-05-28 2016-04-27 中国石油化工股份有限公司 Rare earth catalyst composition and rare earth catalyst and application thereof
CN106916240A (en) * 2015-12-25 2017-07-04 中国石油天然气股份有限公司 Method for preparing rare earth isoprene rubber catalyst
CN106916240B (en) * 2015-12-25 2019-06-11 中国石油天然气股份有限公司 Method for preparing rare earth isoprene rubber catalyst
CN114075307A (en) * 2020-08-13 2022-02-22 中国石油天然气股份有限公司 Rare earth catalyst and preparation method and application thereof
CN114075307B (en) * 2020-08-13 2024-03-26 中国石油天然气股份有限公司 Rare earth catalyst and preparation method and application thereof

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