CN104861095A - Method for reducing polymer molecular weight - Google Patents
Method for reducing polymer molecular weight Download PDFInfo
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- CN104861095A CN104861095A CN201410067350.XA CN201410067350A CN104861095A CN 104861095 A CN104861095 A CN 104861095A CN 201410067350 A CN201410067350 A CN 201410067350A CN 104861095 A CN104861095 A CN 104861095A
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Abstract
The invention discloses a method for reducing polymer molecular weight. The method comprises that in the presence of a VIII group metal inorganic salt, a polymer undergoes a heating reaction in at least one organic solvent, wherein the molecular structure of the polymer contains a C-Sn bond. The method effectively reduces molecular weight of the polymer containing the C-Sn bond. The method is used for treating a coupled polymer with Sn as a coupling center. The treated polymer has changed content of a high molecular weight part and a lower molecular weight part, has almost no change of molecular weight and distribution of the high molecular weight part and the lower molecular weight part, has good selectivity and does not cause fracture of other chemical bonds of the polymer. Through adjustment of reaction conditions, a reaction degree can be effectively controlled so that the polymer with desired molecular weight is obtained. The method allows mild reaction conditions and is simple and easy.
Description
Technical field
The present invention relates to a kind of method reducing polymericular weight.
Background technology
Along with the development of Materials science, the Application Areas of high molecular polymer constantly expands.For macromolecule polymer material, the molecular weight and molecualr weight distribution of superpolymer and the physical property of product and processing characteristics have close relationship.Molecular weight and distribution thereof, as the important performance index of high molecular polymer, all receive the concern of chemist all the time.Therefore, how effectively controlling and regulate molecular weight and the molecular weight distribution of superpolymer, will be the key ensureing quality product.
For controlling and regulating the method for high molecular polymer molecular weight and distribution thereof mainly by changing polymerization formula and polymerizing condition in prior art, such as: change catalyst system; Employing is repeatedly added catalyzer and is carried out polyreaction; Regulate catalyst levels proportioning; Change feeding temperature; Multi-floating bodies is adopted to carry out polyreaction; Change polymerization temperature.Though can play regulate the molecular weight of high molecular polymer and the effect of distribution thereof by changing polymerization formula and polymerizing condition, be all confined to from polymerization stage with regard to molecular weight and distribution thereof are regulated.
Existing polymkeric substance, according to the difference of its use occasion and working method, also needs to regulate molecular weight, with the physical property of aggregation thing and processing characteristics sometimes.
CN100379845C discloses a kind of method reducing olefin copolymer molecular weight, the method utilizes the weak C-H on main polymer chain easily oxidized, cause the feature of copolymer degradation, to make on main chain containing the olefin copolymer of tertiary carbon atom in the presence of oxygen at the temperature of at least 60 DEG C and contact containing the base oil being less than 0.05 % by weight sulphur, thus realizing reducing the molecular weight of olefin copolymer.
CN1117107C discloses a kind of method reducing the molecular weight of polymer materials, the method comprises with at least one hydroperoxide process polymer materials, wherein, the amount existence that described hydroperoxide reduce can make molecular weight, wherein temperature range is 80-250 DEG C, and described polymer materials is selected from EPM polymkeric substance, EPDM and its mixture that mole content is 16-50%.
CN101151282B discloses a kind of method reducing the molecular weight of polypropylene, propylene copolymer or polypropylene miser, polypropylene, propylene copolymer or polypropylene that the method comprises a kind of azo-compound and needs carry out degrading mix, and heat at 160-340 DEG C the mixture obtained.
The method of the molecular weight of above-mentioned reduction polymkeric substance is all by making the carbochain on main polymer chain disconnect, thus realization reduces the molecular weight of polymkeric substance.
In polymkeric substance, particularly elastomeric preparation process, add coupling agent and carry out the molecular weight that coupling greatly can improve polymkeric substance, improve physical property and the processing characteristics of polymkeric substance.Wherein, conventional coupling agent comprises polyfunctional stannane compound, such as tin tetrachloride.But, along with the raising of coupling degree, serve negative impact can to the processing characteristics band of polymkeric substance.Further, polymkeric substance, with the difference of application scenario, also has different requirement for coupling efficiency.
Therefore, need the method that the molecular weight of coupling polymer is regulated, with the physical property of aggregation thing and processing characteristics, meet the service requirements of different application occasion.
Summary of the invention
The object of the present invention is to provide a kind of method reducing polymericular weight, the method effectively can reduce polymkeric substance containing carbon-Xi key, particularly reduce the molecular weight of the polymkeric substance using tin as coupling center.
The present inventor is surprised to find that in research process, is reacted by the inorganic acid salt containing group VIII metallic element, effectively can reduce the molecular weight of this polymkeric substance with the polymkeric substance containing carbon-Xi key.Complete the present invention on this basis.
The invention provides a kind of method reducing polymericular weight, under the method is included in the existence of the inorganic acid salt of at least one group VIII metal, polymkeric substance is carried out reacting by heating at least one organic solvent, containing carbon-Xi key in the molecular structure of described polymkeric substance.
The molecular weight of the polymkeric substance (as using tin atom as the polymkeric substance of coupling center) containing carbon-Xi key effectively can be reduced according to method of the present invention, its reason may be: reacted by the inorganic acid salt of the polymkeric substance containing carbon-Xi key and at least one group VIII metal, carbon-Xi the key in polymkeric substance optionally can be made to disconnect, thus the molecular weight of polymkeric substance can be reduced.
And, method of the present invention is adopted to process the coupling polymer obtained using tin as coupling center, polymkeric substance after process except the content of high molecular weight moieties and low molecular weight part changes, the molecular size range of high molecular weight moieties and low molecular weight part and distribution not considerable change thereof.This illustrates and adopts method of the present invention to process the polymkeric substance containing carbon-Xi key, and other chemical bond in polymkeric substance can not be caused to rupture, and the selectivity of thus reacting is good.
Meanwhile, method of the present invention can control the degree of reacting effectively by regulating reaction conditions, thus obtains the polymkeric substance with expection molecular weight.
In addition, gentle according to the reaction conditions of method of the present invention, and simple and easy to do.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the GPC spectrogram of the styrene-butadiene copolymer 2305 being used as raw material in the embodiment of the present invention 1;
Fig. 2 is the GPC spectrogram that the embodiment of the present invention 1 obtains product;
Fig. 3 is the GPC spectrogram of the product that comparative example 1 of the present invention obtains.
Embodiment
The invention provides a kind of method reducing polymericular weight, under the method is included in the existence of the inorganic acid salt of at least one group VIII metal, polymkeric substance is carried out reacting by heating at least one organic solvent, containing carbon-Xi key in the molecular structure of described polymkeric substance.
In the present invention, " at least one " refers to one or more.
According to method of the present invention, the inorganic acid salt of described group VIII metal refers to the compound formed with at least one hydrogen atom in group VIII metallic element displacement mineral acid, can be common various using group VIII metallic element as cationic inorganic acid salt, be preferably the anaerobic hydrochlorate of group VIII metal, be more preferably the halogenide of group VIII metal.Described group VIII metallic element is preferably selected from ferro element, nickel element and cobalt element, is more preferably ferro element.
One of the present invention preferred embodiment in, the described inorganic acid salt containing group VIII metal is FeCl
2.Be FeCl at the described halogenide containing group VIII metal
2time, can, under more gentle condition, more effectively make the carbon-Xi key in polymkeric substance disconnect.
According to method of the present invention, in the molecular structure of described polymkeric substance containing carbon-Xi key (that is,
).Polymkeric substance containing carbon-Xi key in molecular chain can be such as the polymkeric substance using tin atom as coupling center.
Particularly, described polymkeric substance can for the polymkeric substance that be more than 2 by the olefin polymer functionality tin compound of (being preferably more than 3) carries out coupling and obtain.Described olefin polymer can be the various polymkeric substance carrying out coupling with tin compound that needs, such as, be used as the olefin polymer of rubber.The specific examples of described olefin polymer can include but not limited to: the homopolymer of conjugated diene, as polyisoprene, polyhutadiene; The multipolymer of monoolefine and conjugated diene, as the multipolymer of divinyl and cinnamic multipolymer, divinyl and vinyl cyanide.The various sn-containing compounds that the polymer molecular chain of more than two can be linked together by carbon-Xi key that described tin compound can be commonly used for this area, its representative instance is tin tetrachloride.
The present invention is not particularly limited for the content of carbon-Xi key in described polymkeric substance, can be different according to the source of the polymkeric substance as raw material.
According to method of the present invention, the inorganic acid salt of described group VIII metal plays the effect of catalyzer in the method for the invention, its consumption can carry out appropriate selection according to the molecular weight of kind and expection for carrying out the polymkeric substance reacted, is as the criterion can realize catalysis.Usually, the consumption of the inorganic acid salt of described group VIII metal can be the 0.005-10 % by weight of the amount of described polymkeric substance, is preferably the 0.05-5 % by weight of the amount of described polymkeric substance, is more preferably 0.5-2 % by weight.
According to method of the present invention, described organic solvent for conventional various organic solvents, can be as the criterion can dissolve described polymkeric substance.Usually, described organic solvent can be selected from C
5-C
10straight or branched alkane, C
6-C
12substituted or unsubstituted naphthenic hydrocarbon, C
6-C
12substituted or unsubstituted aromatic hydrocarbons, C
3-C
8ketone and C
4-C
8substituted or unsubstituted alicyclic heterocyclic.Particularly, described organic solvent can be selected from hexanaphthene, normal hexane, Skellysolve A, toluene, dimethylbenzene, chlorinated benzene, tetrahydrofuran (THF), acetone and dioxane.
According to method of the present invention, the temperature condition of described reaction is not particularly limited, can carry out reacting and reactant and reaction product generation thermolysis can not be made to be as the criterion.Usually, the temperature of described reaction can be 40-150 DEG C.Preferably, the temperature of described reaction is 50-120 DEG C (as 60-100 DEG C), under comparatively gentle reaction conditions, can obtain higher speed of response like this.The time of described reacting by heating can carry out appropriate selection according to the molecular weight of polymkeric substance of expection and the temperature of reaction.Usually, the time of described reaction can be 0.5-24 hour.
According to method of the present invention, the mixture be obtained by reacting can adopt the ordinary method of this area to process, thus obtains the polymkeric substance of molecular weight reduction.Such as, under the condition reducing pressure, the solvent in the mixture be obtained by reacting can be removed, thus obtain the polymkeric substance of molecular weight reduction.
The present invention is described in detail below in conjunction with embodiment.
In following examples and comparative example, the molecular weight of polymkeric substance and distribution thereof adopt the gel permeation chromatograph that to be purchased from the model of TOSOH company be HLC-8320 to measure, and being moving phase with tetrahydrofuran (THF), take Narrow distribution polystyrene as standard specimen, and temperature is 40 DEG C.Coupling efficiency refers in polymkeric substance, and the number of coupled molecular chain accounts for the per-cent of the overall number of molecular chain, calculates according to GPC result.
Embodiment 1-5 is for illustration of method of the present invention.
Embodiment 1
2 grams of Afpols (be purchased from Sinopec, the trade mark is 2305, and this Afpol is using tin tetrachloride as coupling agent) are dissolved in 10mL normal hexane, to be dissolved completely after, add 0.02 gram of FeCl wherein
2, reaction solution is heated to 60 DEG C, reacts 6 hours.The mixture obtained drying under reduced pressure in vacuum drying oven, except desolventizing, is obtained product.List in Table 1 as the Afpol of raw material and the molecular weight of the product obtained and distribution thereof.Fig. 1 and Fig. 2 respectively illustrates GPC spectrogram as the Afpol of raw material and the GPC spectrogram of product that obtains.
Comparative example 1
The method identical with embodiment 1 is adopted to react, unlike, do not use FeCl
2, molecular weight and the distribution thereof of the product obtained are listed in Table 1.Fig. 3 is the GPC spectrogram of the product obtained.
Embodiment 2
The method identical with embodiment 1 is adopted to process Afpol, unlike, the reaction times is 12 hours.Molecular weight and the distribution thereof of the product obtained are listed in Table 1.
Table 1
| Numbering | Raw material | Embodiment 1 | Comparative example 1 | Embodiment 2 |
| M n 1（×10 4） | 12.3 | 12.5 | 12.2 | 11.3 |
| MWD 1 | 1.03 | 1.03 | 1.04 | 1.06 |
| *A 1（%） | 42.6 | 48.4 | 42.9 | 56.6 |
| M n 2（×10 4） | 24.2 | 24.9 | 24.4 | 22.3 |
| MWD 2 | 1.01 | 1.02 | 1.02 | 1.03 |
| **A 2（%） | 15.2 | 16.8 | 16.1 | 24.4 |
| M n 3（×10 4） | 41.2 | 42.6 | 42.3 | 40.5 |
| MWD 3 | 1.06 | 1.06 | 1.06 | 1.06 |
| ***A 3（%） | 42.2 | 34.8 | 41.0 | 19.0 |
*A
1=[m
1/(m
1+m
2+m
3)]×100% **A
2=[m
2/(m
1+m
2+m
3)]×100% ***A
3=[m
3/(m
1+m
2+m
3)]×100%
M
1for number-average molecular weight is M
n 1peak area m
2for number-average molecular weight is M
n 2peak area m
3for number-average molecular weight is M
n 3peak area
As can be seen from Table 1, adopt method of the present invention to process the polymkeric substance containing carbon-Xi key, effectively can reduce the content of high molecular weight moieties in polymkeric substance.Further, with polymer phase ratio before treatment, the molecular weight of high molecular weight moieties and low molecular weight part and be distributed in before and after process and do not have considerable change.This illustrates, can optionally make the carbon-Xi key in polymkeric substance disconnect according to method of the present invention, and other chemical bond that can not or substantially can not destroy in polymkeric substance.
Fig. 1 to Fig. 3 also confirms, adopts method of the present invention to process the polymkeric substance containing carbon-Xi key, optionally can disconnect carbon-Xi key, thus reduces the content of high molecular weight moieties in polymkeric substance.
Embodiment 3
(1) 2 grams of Afpols (with embodiment 1) are dissolved in 10mL toluene, to be dissolved completely after, add 0.01 gram of FeCl wherein
2, reaction solution is heated to 60 DEG C, reacts 8 hours.The mixture obtained drying under reduced pressure in vacuum drying oven, except desolventizing, is obtained product.Molecular weight and the distribution thereof of the product obtained are listed in table 2.
Embodiment 4
The method identical with embodiment 3 is adopted to process Afpol, unlike, add 0.03 gram of FeCl wherein
2, the reaction times is 6 hours.Molecular weight and the distribution thereof of the product obtained are listed in table 2.
Embodiment 5
The method identical with embodiment 3 is adopted to process Afpol, unlike, temperature of reaction is 100 DEG C, and the time is 6 hours.Molecular weight and the distribution thereof of the product obtained are listed in table 2.
Table 2
| Numbering | Raw material | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| M n 1（×10 4） | 12.3 | 12.4 | 11.8 | 12.5 |
| MWD 1 | 1.03 | 1.03 | 1.04 | 1.04 |
| *A 1（%） | 42.6 | 49.5 | 50.9 | 57.2 |
| M n 2（×10 4） | 24.2 | 23.7 | 21.8 | 23.8 |
| MWD 2 | 1.01 | 1.04 | 1.03 | 1.04 |
| **A 2（%） | 15.2 | 16.9 | 16.5 | 26.1 |
| M n 3（×10 4） | 41.2 | 41.0 | 41.8 | 42.1 |
| MWD 3 | 1.06 | 1.08 | 1.05 | 1.06 |
| ***A 3（%） | 42.2 | 33.6 | 32.6 | 16.7 |
*A
1=[m
1/(m
1+m
2+m
3)]×100%
**A
2=[m
2/(m
1+m
2+m
3)]×100%
***A
3=[m
3/(m
1+m
2+m
3)]×100%
M
1for number-average molecular weight is M
n 1peak area
M
2for number-average molecular weight is M
n 2peak area
M
3for number-average molecular weight is M
n 3peak area
As can be seen from Table 2, effectively can control the degree of reacting according to method of the present invention by regulating reaction conditions, thus the polymkeric substance with expection molecular weight can be obtained.
Claims (7)
1. reduce a method for polymericular weight, polymkeric substance is carried out reacting by heating under being included in the existence of the inorganic acid salt of at least one group VIII metal by the method at least one organic solvent, containing carbon-Xi key in the molecular structure of described polymkeric substance.
2. method according to claim 1, wherein, the consumption of the inorganic acid salt of described group VIII metal is the 0.005-10 % by weight of the amount of described polymkeric substance.
3. method according to claim 1 and 2, wherein, the inorganic acid salt of described group VIII metal is selected from the halogenide of group VIII metal.
4. method according to claim 3, wherein, the inorganic acid salt of described group VIII metal is FeCl
2.
5. method according to claim 1, wherein, described polymkeric substance is the polymkeric substance using tin atom as coupling center.
6. method according to claim 1, wherein, described organic solvent is selected from C
5-C
10straight or branched alkane, C
6-C
12substituted or unsubstituted naphthenic hydrocarbon, C
6-C
12substituted or unsubstituted aromatic hydrocarbons, C
3-C
8ketone and C
4-C
8substituted or unsubstituted alicyclic heterocyclic.
7. method according to claim 1, wherein, described reaction is carried out at the temperature of 40-150 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340091A (en) * | 1999-12-13 | 2002-03-13 | 埃克森美孚化学专利公司 | Molecular weight reduction of olefin copolymers |
| CN1758997A (en) * | 2003-03-25 | 2006-04-12 | 因温斯特技术公司 | Process for controlling molecular weight of polymer |
| CN101372517A (en) * | 2007-08-21 | 2009-02-25 | 朗盛德国有限责任公司 | Method for metathesis decomposition of nitrile rubbers |
| CN101628972A (en) * | 2008-07-14 | 2010-01-20 | 青岛生物能源与过程研究所 | Method for preparing poly (ethylene succinate) |
-
2014
- 2014-02-26 CN CN201410067350.XA patent/CN104861095B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340091A (en) * | 1999-12-13 | 2002-03-13 | 埃克森美孚化学专利公司 | Molecular weight reduction of olefin copolymers |
| CN1758997A (en) * | 2003-03-25 | 2006-04-12 | 因温斯特技术公司 | Process for controlling molecular weight of polymer |
| CN101372517A (en) * | 2007-08-21 | 2009-02-25 | 朗盛德国有限责任公司 | Method for metathesis decomposition of nitrile rubbers |
| CN101628972A (en) * | 2008-07-14 | 2010-01-20 | 青岛生物能源与过程研究所 | Method for preparing poly (ethylene succinate) |
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