CN104098742B - A kind of method of regulate polymer molecular weight - Google Patents
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Abstract
The invention discloses a kind of method of regulate polymer molecular weight, the method is included under olefin metathesis reaction condition, and the polymer as substrate is contacted with catalyst, and described polymer contains carbon-carbon double bond, and described catalyst is the compound shown in formula I. The method according to this invention can regulate the molecular weight of existing polymer effectively. In addition, the method according to this invention is simple and easy to do, reaction condition gentleness. ?
Description
Technical field
The present invention relates to a kind of method of regulate polymer molecular weight.
Background technology
Along with the development of material science, the application of high molecular polymer constantly expands. For macromolecule polymer material, the mechanical performance of material, processing rheological property, mechanical property, thermodynamic property etc. are all closely related with molecular weight and molecualr weight distribution. Molecular weight and molecualr weight distribution, as the important performance indications 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 polymerisation; Catalyst is repeatedly added in employing or coupling agent carries out polymerisation. 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 polymer, to optimize product structure and performance, meets the instructions for use 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 polymer 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 polymer as substrate is contacted with catalyst, and described polymer contains carbon-carbon double bond, and described catalyst is the compound shown in formula I,
In formula I, R1For hydrogen, C2-C20Replacement or unsubstituted thiazolinyl, C2-C20Replacement or unsubstituted alkynyl, C1-C20Replacement or unsubstituted alkyl, C6-C20Replacement or unsubstituted aryl, C1-C20Carboxylic acid ester groups, C1-C20Replacement or unsubstituted alkoxyl, C2-C20Replacement or unsubstituted alkenyloxy, C2-C20Replacement or unsubstituted chain oxy-acetylene, C6-C20Replacement or unsubstituted aryloxy group, C1-C20Replacement or unsubstituted alkylthio group, C1-C20Replacement or unsubstituted alkyl sulphonyl or C1-C20Replacement or unsubstituted alkyl sulfinyl;
X1And X2The anion ligand of respectively doing for oneself;
L1And L2For the neutral ligand of respectively doing for oneself, and L alternatively1And L2Can be connected to each other the neutral ligand that forms two coordinations;
Y is anion;
N is the integer of 1-6.
The method according to this invention can regulate the molecular weight of existing polymer effectively. In addition, the method according to this invention is simple and easy to do, reaction condition gentleness.
Detailed description of the invention
The invention provides a kind of method of regulate polymer molecular weight, the method is included under olefin metathesis reaction condition, and the polymer as substrate is contacted with catalyst, (described polymer contains carbon-carbon double bond,-C=C-), described catalyst is the compound shown in formula I
In formula I, R1For hydrogen, C2-C20Replacement or unsubstituted thiazolinyl, C2-C20Replacement or unsubstituted alkynyl, C1-C20Replacement or unsubstituted alkyl, C6-C20Replacement or unsubstituted aryl, C1-C20Carboxylic acid ester groups, C1-C20Replacement or unsubstituted alkoxyl, C2-C20Replacement or unsubstituted alkenyloxy, C2-C20Replacement or unsubstituted chain oxy-acetylene, C6-C20Replacement or unsubstituted aryloxy group, C1-C20Replacement or unsubstituted alkylthio group, C1-C20Replacement or unsubstituted alkyl sulphonyl or C1-C20Replacement or unsubstituted alkyl sulfinyl;
X1And X2The anion ligand of respectively doing for oneself;
L1And L2For the neutral ligand of respectively doing for oneself, and L alternatively1And L2Can be connected to each other the neutral ligand that forms two coordinations;
Y is anion, is preferably halide ion, more preferably iodide ion;
N is the integer of 1-6, can select according to the kind of Y.
In formula I, R1Be preferably C6-C20Replacement or unsubstituted aryl, more preferably phenyl.
In formula I, X1And X2Can be common various anion ligands, for example, can be halide ion separately, is preferably chlorion;
In formula I, L1And L2Can be common various neutral ligands separately, its instantiation can include but not limited to: phosphine, amine, thioether, Cabbeen or replacement or unsubstituted imidazolidine. Preferably, L1And L2For phosphine, Cabbeen or replacement or unsubstituted imidazolidine. More preferably, L1For phosphine, L2For replacing or unsubstituted imidazolidine.
Phosphine can be the hydrogen partial in various hydrogen phosphide 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 C1-C10Alkyl group) and replacement or unsubstituted cycloalkyl (as C6-C12Replacement 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, R2And R3C respectively does for oneself6-C20Replacement or unsubstituted aryl; R2And R3Be preferably separatelyR4、R5、R6、R7And R8Identical or different, can be selected from separately hydrogen or C1-C5Alkyl; R2And R3More preferablyR2And R3More preferablyC1-C5The instantiation of alkyl can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group and n-pentyl.
In a kind of preferred embodiment of the present invention, in formula I, R1For phenyl, L1For phosphine, L2For replacing or unsubstituted imidazolidine, X1And X2For chlorion, Y is iodide ion. In the preferred embodiment of one of the present invention, in formula I, R is phenyl, L1For phosphine, L2ForX1And X2For 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 haptoreaction shown in lewis acid and formula III, thus obtain the compound shown in formula I,
In formula III, R1、L1、L2、X1And X2Definition 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 suitable 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 product, chemically interactive compound occurs, for example: nitrogen and group 0 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 alundum (Al2O3) post, and carry out wash-out using carrene as eluant, eluent, thus obtain the compound shown in formula I.
The method according to this invention, the consumption of described catalyst can carry out suitable selection according to the quality of the polymer as substrate, is as the criterion can realize catalysis. Usually, the 0.01-5 % by weight of the total amount that the consumption of catalyst is described polymer, is preferably the 0.3-1 % by weight of the total amount of described polymer.
The method according to this invention, contacts the polymer that contains carbon-carbon double bond as substrate with the compound shown in formula I, intermolecular olefin metathesis reaction occurs described polymer, thereby can change the molecular weight and molecualr weight distribution of polymer. Number-average molecular weight as the polymer 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 polymer 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 polymer molecular weight and molecular weight distribution change.
Refer to and can use general formula C as the alkene of conditioning agentnH2nThe 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 (, 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 polymer. Preferably, described conditioning agent is alpha-olefin, can under more gentle condition, carry out so described contact. Further preferably, described conditioning agent is C1-C20Alpha-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 suitable selection according to the molecular weight of the polymer 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 polymer 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 polymer 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 polymer of substrate, and described carbon-carbon double bond can be positioned on the main chain of this polymer, also can be positioned on the side chain of this polymer. Preferably, at least partly carbon-carbon double bond is positioned on the main chain as the polymer of substrate. Can be to contain carbon-carbon double bond in the common various molecular structures in this area as the described polymer of substrate, and the polymer that need to regulate molecular weight.
Preferably, contain as the polymer 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 polymer. Particularly, described conjugated diene is for being selected from butadiene, isoprene, 1,3-isoprene, 1, one or more in 3-hexadiene and 2,3-dimethyl butadiene. Preferably, described conjugated diene is butadiene and/or isoprene.
Particularly, can contain the monomeric unit being formed by conjugated diene and the monomeric unit being formed by monoolefine as the polymer of substrate.
Described monoolefine can variously can carry out the alkene that contains a carbon-carbon double bond in combined polymerization 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, R9For C6-C20Replacement or unsubstituted aryl. Described C6-C20Replacement 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 styrene, 2-methyl styrene, 4-t-butyl styrene, 4-methyl styrene, 3,5-diethylbenzene ethene, 3, one or more in 5-di-n-butyl styrene, 4-n-propylbenzene ethene and 4-dodecyl styrene.
The present invention is in the polymer 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 suitable selection according to the source of polymer and concrete application scenario, no longer describe in detail herein.
The method according to this invention, can carry out suitable selection according to the particular type of polymer as the content of carbon-carbon double bond in the polymer 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 polymer of substrate under the existence of at least one organic solvent.
The kind of described organic solvent can be carried out suitable selection according to the kind of the polymer as substrate, is as the criterion can dissolve as the polymer of substrate. Usually, described organic solvent can be alkane series solvent (comprising alkane series solvent and cycloalkane series solvent), aromatic hydrocarbons series solvent, ketone series solvent and alicyclic heterocyclic series solvent (hetero atom is preferably oxygen atom). Particularly, described organic solvent can be for being selected from toluene, dimethylbenzene, chlorobenzene, C6-C12Replacement or unsubstituted cycloalkane (as: pentamethylene, n-hexane, methyl cyclopentane, cycloheptane and cyclooctane), C2-C20Alkane (as: pentane, n-hexane, just, normal heptane and normal octane), oxolane, 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 polymer of substrate and can carry out suitable selection according to the temperature contacting the time 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 polymer is purchased from the model of TOSOH company is measured, and taking THF as mobile 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 chemical analyser 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 carrene, stir 0.5 hour in room temperature (being 25 DEG C). To obtain mixture alundum (Al2O3) column chromatography and separate (solvent is carrene), after the eluent obtaining concentrates, with cyclohexane washing, obtain the catalyst that 1.31g is yellow solid. By the catalyst obtaining carry out proton nmr spectra (1H-NMR) and carbon-13 nmr spectra (13C-NMR) analyze, confirm that the catalyst 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 BSs (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 catalyst that adds in reaction system 5mg step (1) to prepare, be heated to 100 DEG C and react, react 2 hours, stop reaction, drying under reduced pressure is except desolventizing. Before reaction, list in table 1 with the molecular weight and molecualr weight distribution of reacted polymer.
Table 1
Embodiment 2
5 grams of BSs (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 catalyst that adds in reaction system 15mg embodiment 1 step (1) to prepare, be heated to 100 DEG C and react, react 2 hours, stop reaction, drying under reduced pressure is except desolventizing. Before reaction, list in table 2 with the molecular weight and molecualr weight distribution of reacted polymer.
Table 2
Embodiment 3
Adopt the method identical with embodiment 2 to process BS, different, react at 40 DEG C. Before reaction, list in table 3 with the molecular weight and molecualr weight distribution of reacted polymer.
Table 3
Embodiment 4
Adopt the method identical with embodiment 2 to process BS, different, react at 130 DEG C. Before reaction, list in table 4 with the molecular weight and molecualr weight distribution of reacted polymer.
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 polymer of expection molecular weight.
Embodiment 5
Adopt the method identical with embodiment 2 to process BS, different, replace toluene with cyclohexane. Before reaction, list in table 5 with the molecular weight and molecualr weight distribution of reacted polymer.
Table 5
Embodiment 6
5 grams of dienites (be purchased from Sinopec, the trade mark is LCBR1403), under nitrogen protection, are dissolved in 50mL oxolane, to be dissolved completely after, add wherein 5 grams of 1-decene. After the catalyst that adds in reaction system 15mg embodiment 1 step (1) to prepare, be heated to 60 DEG C and react, react 2 hours, stop reaction, removal of solvent under reduced pressure. Before reaction, list in table 6 with the molecular weight and molecualr weight distribution of reacted polymer.
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 polymer.
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 catalyst that adds in reaction system 15mg embodiment 1 step (1) to prepare, be heated to 60 DEG C and react, react 2 hours; stop reaction, removal of solvent under reduced pressure. Before reaction, list in table 8 with the molecular weight and molecualr weight distribution of reacted polymer.
Table 8
Embodiment 9
5 grams of BSs (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 catalyst that adds in reaction system 15mg embodiment 1 step (1) to prepare; being heated to 60 DEG C reacts; react 6 hours, stop reaction, removal of solvent under reduced pressure. Before reaction, list in table 9 with the molecular weight and molecualr weight distribution of reacted polymer.
Table 9
。
Claims (24)
1. a method for regulate polymer molecular weight, the method is included in olefin metathesis reaction conditionUnder, the polymer as substrate is contacted with catalyst, described polymer contains carbon-carbon double bond, described in urgeAgent is the compound shown in formula I,
In formula I, R1For hydrogen, C2-C20Replacement or unsubstituted thiazolinyl, C2-C20Replacement or do not getThe alkynyl in generation, C1-C20Replacement or unsubstituted alkyl, C6-C20Replacement or unsubstituted aryl,C1-C20Carboxylic acid ester groups, C1-C20Replacement or unsubstituted alkoxyl, C2-C20Replacement or do not replaceAlkenyloxy, C2-C20Replacement or unsubstituted chain oxy-acetylene, C6-C20Replacement or unsubstitutedAryloxy group, C1-C20Replacement or unsubstituted alkylthio group, C1-C20Replacement or unsubstituted alkyl sulphurAcyl group or C1-C20Replacement or unsubstituted alkyl sulfinyl;
X1And X2The anion ligand of respectively doing for oneself;
L1And L2The neutral ligand of respectively doing for oneself, and L alternatively1And L2Can be connected to each other and form two coordinationsNeutral ligand;
Y is anion;
N is the integer of 1-6.
2. method according to claim 1, wherein, R1For C6-C20Replacement or unsubstitutedAryl;
X1And X2The halide ion of respectively doing for oneself;
L1And L2Respectively do for oneself phosphine, amine, thioether, Cabbeen or replacement or unsubstituted imidazolidine;
Y is halide ion.
3. method according to claim 2, wherein, R1For phenyl.
4. method according to claim 2, wherein, X1And X2The chlorion of respectively doing for oneself.
5. method according to claim 2, wherein, L1And L2For phosphine, Cabbeen or replacementOr unsubstituted imidazolidine.
6. method according to claim 2, wherein, Y is iodide ion.
7. method according to claim 1, wherein, R1For phenyl, L1For phosphine, L2For replacingOr unsubstituted imidazolidine, X1And X2For chlorion, Y is iodide ion.
8. according to the method described in any one in claim 2-7, wherein, phosphine is trialkyl phosphine.
9. according to the method described in any one in claim 2-7, wherein, imidazolidine is formula II instituteThe imidazolidine showing,
In formula II, R2And R3C respectively does for oneself6-C20Replacement or unsubstituted aryl.
10. method according to claim 9, wherein, R2And R3Respectively do for oneselfR4、R5、R6、R7And R8Be selected from separately hydrogen or C1-C5Alkyl.
11. methods according to claim 9, wherein, R2And R3Respectively do for oneself
12. methods according to claim 1, wherein, the consumption of described catalyst is described conductThe 0.01-5 % by weight of the total amount of the polymer of substrate.
13. according to the method described in claim 1 or 12, wherein, and in the polymer as substrate,Carbon-carbon double bond is positioned on the main chain of this polymer at least partly.
14. methods according to claim 13, wherein, contain by being total to as the polymer of substrateThe monomeric unit that yoke alkadienes Isosorbide-5-Nitrae-polymerization forms.
15. methods according to claim 14, wherein, as the polymer of substrate also contain byThe monomeric unit that monoolefine forms.
16. methods according to claim 15, wherein, described monoolefine is monovinylarene.
17. methods according to claim 16, wherein, described monovinylarene is selected from formula IVShown compound,
In formula IV, R9For C6-C20Replacement or unsubstituted aryl.
18. methods according to claim 14, wherein, described conjugated diene be selected from butadiene,Isoprene, 1,3-isoprene, 1,3-hexadiene and 2,3-dimethyl butadiene.
19. methods according to claim 1, wherein, described catalyst and the polymerization as substrateThe contact of thing is carried out under the existence of at least one conditioning agent, and described conditioning agent is alkene.
20. methods according to claim 19, wherein, described alkene is monoolefine.
21. methods according to claim 20, wherein, described monoolefine is alpha-olefin.
22. methods according to claim 21, wherein, described monoolefine is C2-C20α-alkeneHydrocarbon.
23. methods according to claim 1, wherein, the condition of described contact comprises: temperature is30-150℃。
24. methods according to claim 23, wherein, the condition of described contact comprises: temperatureFor 50-120 DEG C.
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