CN104098742A - Method for adjusting molecular weight of polymer - Google Patents
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- CN104098742A CN104098742A CN201310126273.6A CN201310126273A CN104098742A CN 104098742 A CN104098742 A CN 104098742A CN 201310126273 A CN201310126273 A CN 201310126273A CN 104098742 A CN104098742 A CN 104098742A
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Abstract
The invention discloses a method for adjusting the molecular weight of a polymer. The method is characterized in that a polymer contacts with a catalyst as a substrate under olefin metathesis reaction conditions, the polymer contains a carbon-carbon double bond, and the catalyst is a compound with the structure represented by formula I. The method can effectively adjust the molecular weight of existing polymers. Additionally, the method has the advantages of simplicity, easy implementation and mild reaction conditions.
Description
Technical field
The present invention relates to a kind of method of regulate polymer molecular weight.
Background technology
Along with the development of Materials science, the Application Areas of high molecular polymer constantly expands.For macromolecule polymer material, the mechanical property of material, processing rheological property, mechanical property, thermomechanical property etc. are all closely related with molecular weight and molecualr weight distribution.Molecular weight and molecualr weight distribution, as the important performance index of high molecular polymer, all receives chemist's concern all the time.But, with regard to high molecular polymerization, be often limited by synthetic method used and reaction unit for control and the adjusting of molecular weight.
In prior art, mainly comprise for the method that regulates high molecular polymer molecular weight: change catalyst system; Adopt many still series connection to carry out polyreaction; Catalyzer is repeatedly added in employing or coupling agent carries out polyreaction.Though above several method can play the effect of the molecular weight that regulates high molecular polymer, but be all confined to just start molecular weight to regulate from polymerization stage, existing high molecular polymer is difficult to carry out as requested to the adjusting of molecular weight, and then reach and optimize product structure and performance, the object of the development trade mark flexibly.
Therefore, the method that need to regulate the molecular weight of existing polymkeric substance, to optimize product structure and performance, meets the service requirements of different application occasion.
Summary of the invention
A kind of method that the object of the present invention is to provide new molecular weight to polymkeric substance to regulate.
The invention provides a kind of method of regulate polymer molecular weight, the method is included under olefin metathesis reaction condition, and the polymkeric substance as substrate is contacted with catalyzer, and described polymkeric substance contains carbon-carbon double bond, and described catalyzer is the compound shown in formula I,
In formula I, R
1for hydrogen, C
2-C
20replacement or unsubstituted thiazolinyl, C
2-C
20replacement or unsubstituted alkynyl, C
1-C
20replacement or unsubstituted alkyl, C
6-C
20replacement or unsubstituted aryl, C
1-C
20carboxylic acid ester groups, C
1-C
20replacement or unsubstituted alkoxyl group, C
2-C
20replacement or unsubstituted alkenyloxy, C
2-C
20replacement or unsubstituted chain oxy-acetylene, C
6-C
20replacement or unsubstituted aryloxy, C
1-C
20replacement or unsubstituted alkylthio, C
1-C
20replacement or unsubstituted alkyl sulphonyl or C
1-C
20replacement or unsubstituted alkyl sulfinyl;
X
1and X
2the anion ligand of respectively doing for oneself;
L
1and L
2for the neutral ligand of respectively doing for oneself, and L alternatively
1and L
2neutral ligand that can interconnection formation two coordinations;
Y is negatively charged ion;
N is the integer of 1-6.
The method according to this invention can regulate the molecular weight of existing polymkeric substance effectively.In addition, the method according to this invention is simple and easy to do, reaction conditions gentleness.
Embodiment
The invention provides a kind of method of regulate polymer molecular weight, the method is included under olefin metathesis reaction condition, and the polymkeric substance as substrate is contacted with catalyzer, (described polymkeric substance contains carbon-carbon double bond,-C=C-), described catalyzer is the compound shown in formula I
In formula I, R
1for hydrogen, C
2-C
20replacement or unsubstituted thiazolinyl, C
2-C
20replacement or unsubstituted alkynyl, C
1-C
20replacement or unsubstituted alkyl, C
6-C
20replacement or unsubstituted aryl, C
1-C
20carboxylic acid ester groups, C
1-C
20replacement or unsubstituted alkoxyl group, C
2-C
20replacement or unsubstituted alkenyloxy, C
2-C
20replacement or unsubstituted chain oxy-acetylene, C
6-C
20replacement or unsubstituted aryloxy, C
1-C
20replacement or unsubstituted alkylthio, C
1-C
20replacement or unsubstituted alkyl sulphonyl or C
1-C
20replacement or unsubstituted alkyl sulfinyl;
X
1and X
2the anion ligand of respectively doing for oneself;
L
1and L
2for the neutral ligand of respectively doing for oneself, and L alternatively
1and L
2neutral ligand that can interconnection formation two coordinations;
Y is negatively charged ion, is preferably halide-ions, more preferably iodide ion;
N is the integer of 1-6, can select according to the kind of Y.
In formula I, R
1be preferably C
6-C
20replacement or unsubstituted aryl, more preferably phenyl.
In formula I, X
1and X
2can be common various anion ligands, for example, can be halide-ions separately, is preferably chlorion;
In formula I, L
1and L
2can be common various neutral ligands separately, its specific examples can include but not limited to: phosphine, amine, thioether, Cabbeen or replacement or unsubstituted imidazolidine.Preferably, L
1and L
2for phosphine, Cabbeen or replacement or unsubstituted imidazolidine.More preferably, L
1for phosphine, L
2for replacing or unsubstituted imidazolidine.
Phosphine can be the hydrogen partial in various phosphuret-(t)ed hydrogen molecules or the compound that is all replaced formation by organic group, is preferably trialkyl phosphine, and described organic group is identical or different, can be selected from separately alkyl group (as C
1-C
10alkyl group) and replacement or unsubstituted cycloalkyl (as C
6-C
12replacement or unsubstituted cycloalkyl), be preferably selected from separately replace or unsubstituted cycloalkyl, more preferably cyclohexyl.
Replacement or unsubstituted imidazolidine can be the imidazolidine shown in formula II,
In formula II, R
2and R
3c respectively does for oneself
6-C
20replacement or unsubstituted aryl; R
2and R
3be preferably separately
r
4, R
5, R
6, R
7and R
8identical or different, can be selected from separately hydrogen or C
1-C
5alkyl; R
2and R
3more preferably
r
2and R
3more preferably
c
1-C
5the specific examples of alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl and n-pentyl.
In a kind of preferred implementation of the present invention, in formula I, R
1for phenyl, L
1for phosphine, L
2for replacing or unsubstituted imidazolidine, X
1and X
2for chlorion, Y is iodide ion.In the preferred embodiment of one of the present invention, in formula I, R is phenyl, L
1for phosphine, L
2for
x
1and X
2for chlorion, Y is iodide ion.
The method according to this invention, the compound shown in formula I can adopt the conventional method in organic synthesis field synthetic.For example: can be by the compound contact reacts shown in Lewis acid and formula III, thus obtain the compound shown in formula I,
In formula III, R
1, L
1, L
2, X
1and X
2definition with described identical above, be not described in detail in this.
The catalytic condition of compound described in Lewis acid and formula III is not particularly limited.Usually, the temperature of described contact can be 20-100 DEG C, and the mol ratio of the compound shown in Lewis acid and formula III can be 1-5:1.Described Lewis acid can be conventional selection, for example iodine.The time of described contact can be carried out appropriate selection according to the temperature contacting.Described contact is preferably carried out in non-active gas atmosphere, and described non-active gas do not refer to, with reactant and reaction product, chemically interactive compound occurs, for example: nitrogen and neutral element gas (as argon gas).The mixture that can adopt the conventional the whole bag of tricks in this area that contact is obtained carries out purifying, thereby obtains the compound shown in formula I, for example: the mixture obtaining can be carried out to column chromatography separation.Particularly, can be by the mixture obtaining aluminium sesquioxide post, and carry out wash-out using methylene dichloride as eluent, thus obtain the compound shown in formula I.
The method according to this invention, the consumption of described catalyzer can carry out appropriate selection according to the quality of the polymkeric substance as substrate, is as the criterion can realize catalysis.Usually, the 0.01-5 % by weight of the total amount that the consumption of catalyzer is described polymkeric substance, is preferably the 0.3-1 % by weight of the total amount of described polymkeric substance.
The method according to this invention, contacts the polymkeric substance that contains carbon-carbon double bond as substrate with the compound shown in formula I, intermolecular olefin metathesis reaction occurs described polymkeric substance, thereby can change the molecular weight and molecualr weight distribution of polymkeric substance.Number-average molecular weight as the polymkeric substance of substrate can be generally more than 10000.
From the angle of the change amplitude of further raising molecular weight, under the existence of at least one conditioning agent, carry out with contacting preferably of the compound shown in formula I as the polymkeric substance of substrate, described conditioning agent can be alkene.Under the existence of at least one conditioning agent, carry out described contact, can further improve the amplitude that polymericular weight and molecular weight distribution change.
Refer to and can use general formula C as the alkene of conditioning agent
nh
2nthe hydrocarbon representing, wherein, n can be more than 2 integers, is preferably the integer of 2-20.Can be monoolefine as the alkene of conditioning agent, can be also diolefin, can also be polyene hydrocarbon (, containing three above carbon-carbon double bonds in an olefin hydrocarbon molecules).
In one embodiment of the invention, described conditioning agent is alkene, can significantly reduce like this molecular weight of polymkeric substance.Preferably, described conditioning agent is alpha-olefin, can under more gentle condition, carry out so described contact.Further preferably, described conditioning agent is C
1-C
20alpha-olefin, as ethene, 1-propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-laurylene, 1-hexadecylene, 1-octadecylene and 1-icosa alkene.
The method according to this invention, the consumption of described conditioning agent can carry out appropriate selection according to the molecular weight of the polymkeric substance of expection, is not particularly limited.
The method according to this invention, the addition manner of described conditioning agent is not particularly limited, and conditioning agent once can be added in the reaction vessel contacting with the compound shown in formula I as the polymkeric substance of substrate; Also conditioning agent gradation can be added in the reaction vessel that carries out described contact, for example: part conditioning agent is contacted with the compound shown in formula I with the polymkeric substance as substrate under olefin metathesis condition, remainder conditioning agent in the process of described contact, once or gradation add.
The method according to this invention, contains carbon-carbon double bond as the polymkeric substance of substrate, and described carbon-carbon double bond can be positioned on the main chain of this polymkeric substance, also can be positioned on the side chain of this polymkeric substance.Preferably, at least partly carbon-carbon double bond is positioned on the main chain as the polymkeric substance of substrate.Can be to contain carbon-carbon double bond in the common various molecular structures in this area as the described polymkeric substance of substrate, and the polymkeric substance that need to regulate molecular weight.
Preferably, contain as the polymkeric substance of substrate the monomeric unit being formed by conjugated diene.More preferably, contain the monomeric unit being formed by conjugated diene as substrate polymer, and the monomeric unit being formed by conjugated diene is at least partly the monomeric unit that conjugated diene forms with Isosorbide-5-Nitrae-polymerization methods.
Described conjugated diene refers to the unsaturated acyclic hydrocarbon that contains conjugated double bond (,-C=C-C=C-) in molecular structure, can be the common various conjugated diene that can polymerization reaction take place forms polymkeric substance.Particularly, described conjugated diene is for being selected from divinyl, isoprene, 1,3-isoprene, 1, one or more in 3-hexadiene and 2,3-dimethylbutadiene.Preferably, described conjugated diene is divinyl and/or isoprene.
Particularly, can contain the monomeric unit being formed by conjugated diene and the monomeric unit being formed by monoolefine as the polymkeric substance of substrate.
Described monoolefine can variously can carry out the alkene that contains a carbon-carbon double bond in copolymerization and molecular structure with conjugated diene for common.For example: described monoolefine can be monovinylarene.Described monovinylarene is specifically as follows and is selected from the compound shown in formula IV,
In formula IV, R
9for C
6-C
20replacement or unsubstituted aryl.Described C
6-C
20replacement or the example of unsubstituted aryl can for but be not limited to: phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene, o-tert-butyl phenyl, a tert-butyl-phenyl, to tert-butyl-phenyl, to dodecylphenyl, 2,4-di-n-butyl phenyl, to n-propylbenzene base and 2,4-diethyl phenyl.
Described monovinylarene is specifically as follows vinylbenzene, 2-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 3, one or more in 5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene and 4-dodecyl vinylbenzene.
The present invention is in the polymkeric substance as substrate, the content of the monomeric unit being formed by conjugated diene and the monomeric unit that formed by monoolefine is not particularly limited, can carry out appropriate selection according to the source of polymkeric substance and concrete application scenario, no longer describe in detail herein.
The method according to this invention, can carry out appropriate selection according to the particular type of polymkeric substance as the content of carbon-carbon double bond in the polymkeric substance of substrate, is not particularly limited.
The method according to this invention is carried out with contacting preferably of the compound shown in formula I as the polymkeric substance of substrate under the existence of at least one organic solvent.
The kind of described organic solvent can be carried out appropriate selection according to the kind of the polymkeric substance as substrate, is as the criterion can dissolve as the polymkeric substance of substrate.Usually, described organic solvent can be alkane series solvent (comprising paraffinic hydrocarbons series solvent and naphthenic hydrocarbon series solvent), aromatic hydrocarbons series solvent, ketone series solvent and alicyclic heterocyclic series solvent (heteroatoms is preferably Sauerstoffatom).Particularly, described organic solvent can be for being selected from toluene, dimethylbenzene, chlorinated benzene, C
6-C
12replacement or unsubstituted naphthenic hydrocarbon (as: pentamethylene, normal hexane, methylcyclopentane, suberane and cyclooctane), C
2-C
20paraffinic hydrocarbons (as: Skellysolve A, normal hexane, just, normal heptane and octane), tetrahydrofuran (THF), acetone and dioxane.The consumption of described organic solvent can be that the routine of this area is selected, and no longer describes in detail herein.
The method according to this invention, described olefin metathesis reaction condition can be conventional selection.Usually, described metathesis reaction conditions comprises: temperature can be 30-150 DEG C, is preferably 50-120 DEG C.Using as the polymkeric substance of substrate and can carry out appropriate selection according to the temperature contacting the duration of contact of the compound shown in formula I, be as the criterion with the molecular weight that can obtain expection.
Describe the present invention in detail below in conjunction with embodiment.
In following examples and comparative example, the gel permeation chromatograph that it is HLC-8320 that the molecular weight and molecualr weight distribution employing of polymkeric substance is purchased from the model of TOSOH company is measured, and taking THF as moving phase, taking Narrow distribution polystyrene as standard specimen, temperature is 40 DEG C; Spectral analysis of the nuclear magnetic resonance carries out on the nuclear magnetic resonance spectrometer that to be purchased from the model of Bruker company of the U.S. be AVANCE400.
Embodiment 1-9 is used for illustrating method of the present invention.
Embodiment 1
(1) Kaolinite Preparation of Catalyst
Under nitrogen protection, in the there-necked flask of 100mL, add the compound shown in 760mg iodine, 848mg formula V (being purchased from lark prestige Science and Technology Ltd.) and 20mL methylene dichloride, stir 0.5 hour in room temperature (being 25 DEG C).To obtain mixture aluminium sesquioxide column chromatography and separate (developping agent is methylene dichloride), after the elutriant obtaining concentrates, with hexanaphthene washing, obtain the catalyzer that 1.31g is yellow solid.By the catalyzer obtaining carry out proton nmr spectra (
1h-NMR) and carbon-13 nmr spectra (
13c-NMR) analyze, confirm that the catalyzer obtaining has structure shown in formula VI.
1H-NMR(400MHz,DMSO)δ(ppm):1.35-2.06(m,33H),1.81(s,18H),2.62(m,4H),6.11(d,1H),7.38-7.50(m,5H),7.59-7.67(m,3H)。
13C-NMR(100MHz,DMSO)δ(ppm):24.8,25.5,26.2,26.3,26.4,26.6,?31.9,32.1,129.1,129.2,129.3,129.5,130.7,134.2,134.3,193.0。
In formula V and formula VI, Cy is cyclohexyl.
(2) 5 grams of butadiene-styrene copolymer (be purchased from Sinopec, the trade mark is Y031), under nitrogen protection, are dissolved in 50mL toluene, to be dissolved completely after, add wherein 5 grams of 1-octenes.After the catalyzer that adds in reaction system 5mg step (1) to prepare, be heated to 100 DEG C and react, react 2 hours, stopped reaction, drying under reduced pressure is except desolventizing.Before reaction, list in table 1 with the molecular weight and molecualr weight distribution of reacted polymkeric substance.
Table 1
Embodiment 2
5 grams of butadiene-styrene copolymer (be purchased from Sinopec, the trade mark is Y031), under nitrogen protection, are dissolved in 50mL toluene, to be dissolved completely after, add wherein 5 grams of 1-decene.After the catalyzer that adds in reaction system 15mg embodiment 1 step (1) to prepare, be heated to 100 DEG C and react, react 2 hours, stopped reaction, drying under reduced pressure is except desolventizing.Before reaction, list in table 2 with the molecular weight and molecualr weight distribution of reacted polymkeric substance.
Table 2
Embodiment 3
Adopt the method identical with embodiment 2 to process butadiene-styrene copolymer, different, react at 40 DEG C.Before reaction, list in table 3 with the molecular weight and molecualr weight distribution of reacted polymkeric substance.
Table 3
Embodiment 4
Adopt the method identical with embodiment 2 to process butadiene-styrene copolymer, different, react at 130 DEG C.Before reaction, list in table 4 with the molecular weight and molecualr weight distribution of reacted polymkeric substance.
Table 4
Can find out from the result of embodiment 2-4, the temperature that the method according to this invention is reacted by adjusting can regulate the degree of reaction in effect ground, thereby obtains having the polymkeric substance of expection molecular weight.
Embodiment 5
Adopt the method identical with embodiment 2 to process butadiene-styrene copolymer, different, replace toluene with hexanaphthene.Before reaction, list in table 5 with the molecular weight and molecualr weight distribution of reacted polymkeric substance.
Table 5
Embodiment 6
5 grams of dienites (be purchased from Sinopec, the trade mark is LCBR1403), under nitrogen protection, are dissolved in 50mL tetrahydrofuran (THF), to be dissolved completely after, add wherein 5 grams of 1-decene.After the catalyzer that adds in reaction system 15mg embodiment 1 step (1) to prepare, be heated to 60 DEG C and react, react stopped reaction, removal of solvent under reduced pressure 2 hours.Before reaction, list in table 6 with the molecular weight and molecualr weight distribution of reacted polymkeric substance.
Table 6
Embodiment 7
Adopt the method identical with embodiment 6 to process dienite, different, the consumption of 1-decene is 1 gram.Before reaction, list in table 7 with the molecular weight and molecualr weight distribution of reacted polymkeric substance.
Table 7
Embodiment 8
5 grams of dienites (are purchased from Sinopec; the trade mark is LCBR1403) under nitrogen protection; be dissolved in 50mL toluene; to be dissolved completely after; after the catalyzer that adds in reaction system 15mg embodiment 1 step (1) to prepare, be heated to 60 DEG C and react, react 2 hours; stopped reaction, removal of solvent under reduced pressure.Before reaction, list in table 8 with the molecular weight and molecualr weight distribution of reacted polymkeric substance.
Table 8
Embodiment 9
5 grams of butadiene-styrene copolymer (are purchased from Sinopec; the trade mark is SSBR2305) under nitrogen protection; be dissolved in 50mL toluene; to be dissolved completely after, add wherein 1 gram of 1-decene, after the catalyzer that adds in reaction system 15mg embodiment 1 step (1) to prepare; being heated to 60 DEG C reacts; react stopped reaction, removal of solvent under reduced pressure 6 hours.Before reaction, list in table 9 with the molecular weight and molecualr weight distribution of reacted polymkeric substance.
Table 9
。
Claims (13)
1. a method for regulate polymer molecular weight, the method is included under olefin metathesis reaction condition, and the polymkeric substance as substrate is contacted with catalyzer, and described polymkeric substance contains carbon-carbon double bond, and described catalyzer is the compound shown in formula I,
In formula I, R
1for hydrogen, C
2-C
20replacement or unsubstituted thiazolinyl, C
2-C
20replacement or unsubstituted alkynyl, C
1-C
20replacement or unsubstituted alkyl, C
6-C
20replacement or unsubstituted aryl, C
1-C
20carboxylic acid ester groups, C
1-C
20replacement or unsubstituted alkoxyl group, C
2-C
20replacement or unsubstituted alkenyloxy, C
2-C
20replacement or unsubstituted chain oxy-acetylene, C
6-C
20replacement or unsubstituted aryloxy, C
1-C
20replacement or unsubstituted alkylthio, C
1-C
20replacement or unsubstituted alkyl sulphonyl or C
1-C
20replacement or unsubstituted alkyl sulfinyl;
X
1and X
2the anion ligand of respectively doing for oneself;
L
1and L
2the neutral ligand of respectively doing for oneself, and L alternatively
1and L
2neutral ligand that can interconnection formation two coordinations;
Y is negatively charged ion;
N is the integer of 1-6.
2. method according to claim 1, wherein, R
1for C
6-C
20replacement or unsubstituted aryl, be preferably phenyl;
X
1and X
2the halide-ions of respectively doing for oneself, is preferably chlorion;
L
1and L
2respectively do for oneself phosphine, amine, thioether, Cabbeen or replacement or unsubstituted imidazolidine, L
1and L
2be preferably phosphine, Cabbeen or replacement or unsubstituted imidazolidine;
Y is halide-ions, is preferably iodide ion.
3. method according to claim 1, wherein, R
1for phenyl, L
1for phosphine, L
2for replacing or unsubstituted imidazolidine, X
1and X
2for chlorion, Y is iodide ion.
4. according to the method in claim 2 or 3, wherein, phosphine is trialkyl phosphine.
5. according to the method in claim 2 or 3, wherein, imidazolidine is the imidazolidine shown in formula II,
In formula II, R
2and R
3c respectively does for oneself
6-C
20replacement or unsubstituted aryl; R
2and R
3be preferably separately
r
4, R
5, R
6, R
7and R
8be selected from separately hydrogen or C
1-C
5alkyl; R
2and R
3more preferably
6. method according to claim 1, wherein, the consumption of described catalyzer is the 0.01-5 % by weight of the total amount of the described polymkeric substance as substrate.
7. according to the method described in claim 1 or 6, wherein, in the polymkeric substance as substrate, carbon-carbon double bond is positioned on the main chain of this polymkeric substance at least partly.
8. method according to claim 7, wherein, contains the monomeric unit being formed by conjugated diene Isosorbide-5-Nitrae-polymerization as the polymkeric substance of substrate.
9. method according to claim 8, wherein, also contains as the polymkeric substance of substrate the monomeric unit being formed by monoolefine, and described monoolefine is preferably monovinylarene, and described monovinylarene is preferably selected from the compound shown in formula IV,
In formula IV, R
9for C
6-C
20replacement or unsubstituted aryl.
10. method according to claim 8 or claim 9, wherein, described conjugated diene is selected from divinyl, isoprene, 1,3-isoprene, 1,3-hexadiene and 2,3-dimethylbutadiene.
11. methods according to claim 1, wherein, described catalyzer carries out with the contacting under the existence of at least one conditioning agent of polymkeric substance as substrate, and described conditioning agent is alkene.
12. methods according to claim 11, wherein, described alkene is monoolefine, described monoolefine is preferably alpha-olefin, more preferably C
2-C
20alpha-olefin.
13. methods according to claim 1, wherein, the condition of described contact comprises: temperature is 30-150 DEG C, is preferably 50-120 DEG C.
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| CN110272513A (en) * | 2018-03-15 | 2019-09-24 | 中国石油化工股份有限公司 | The method of post-metallocene catalyst precursor and preparation method thereof and catalyst and its application and ethylene homo |
| CN113896837A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
| CN113896836A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
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| CN110272515A (en) * | 2018-03-15 | 2019-09-24 | 中国石油化工股份有限公司 | The preparation method of ethylene copolymer |
| CN110272513A (en) * | 2018-03-15 | 2019-09-24 | 中国石油化工股份有限公司 | The method of post-metallocene catalyst precursor and preparation method thereof and catalyst and its application and ethylene homo |
| CN110272513B (en) * | 2018-03-15 | 2021-10-19 | 中国石油化工股份有限公司 | Post-metallocene catalyst precursor, preparation method thereof, catalyst, application thereof and ethylene homopolymerization method |
| CN110272515B (en) * | 2018-03-15 | 2021-10-19 | 中国石油化工股份有限公司 | Process for the preparation of ethylene copolymers |
| CN113896837A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
| CN113896836A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
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