CN104098718A - Method for reducing molecular weight of polymer - Google Patents
Method for reducing molecular weight of polymer Download PDFInfo
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- CN104098718A CN104098718A CN201310126398.9A CN201310126398A CN104098718A CN 104098718 A CN104098718 A CN 104098718A CN 201310126398 A CN201310126398 A CN 201310126398A CN 104098718 A CN104098718 A CN 104098718A
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- group viii
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Abstract
The invention discloses a method for reducing a molecular weight of a polymer. The method includes a step of carrying out a heating reaction, in at least one organic solvent, between the polymer and at least one substance containing a metal element in the VIII group, wherein the substance containing the metal element in the VIII group is selected from a simple substance of the metal element in the VIII group and a salt of the metal element in the VIII group. A molecular structure of the polymer contains a carbon-silicon bond. According to the method, the molecular weight of the polymer can be reduced effectively while other chemical bonds in the polymer are free from being broken. Meanwhile, according to the method, a reaction a degree can be controlled effectively through adjustment of reaction conditions, thereby obtaining the polymer having an expected molecular weight. In addition, the method in the invention is mild in reaction conditions and is simple and convenient to carry out.
Description
Technical field
The present invention relates to a kind of method that reduces 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 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 distribution thereof, as the important performance index of high molecular polymer, all receive chemist's concern all the time.But, with regard to high molecular polymerization, for the control of molecular weight and distribution thereof with regulate and be often limited by synthetic method used and reaction unit.
In prior art for regulating the method for high molecular polymer molecular weight and distribution thereof mainly to comprise: change catalyst system; Adopt many still series connection to carry out polyreaction; Employing is repeatedly added catalyzer and is carried out polyreaction; In polymerization process, add coupling agent and carry out coupling.Though above several method can play, regulate the molecular weight of high molecular polymer and the effect of distribution thereof, be all confined to just start molecular weight and distribution thereof to regulate from polymerization stage.
In addition, add coupling agent polymkeric substance is carried out to the molecular weight that coupling can greatly improve polymkeric substance, improve the over-all properties of polymkeric substance, wherein, conventional coupling agent comprises polyfunctional silane compound.But, along with the raising of coupling degree, serve negative impact also can to the processing characteristics band of polymkeric substance.And polymkeric substance, with the difference of application scenario, also has different requirements for coupling efficiency.
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
The object of the present invention is to provide a kind of method that reduces polymericular weight, the method can reduce the molecular weight of the polymkeric substance that contains carbon-silicon key effectively.
The present inventor is surprised to find that in research process, under the existence of halogen simple substance, the simple substance of the salt of group VIII metallic element and/or group VIII metallic element and the polymkeric substance that contains carbon-silicon key are carried out to reacting by heating, can effectively reduce the molecular weight of this polymkeric substance.Completed on this basis the present invention.
The invention provides a kind of method that reduces polymericular weight, the method is included under the existence of halogen simple substance, polymkeric substance and at least one material containing group VIII metallic element are carried out to reacting by heating at least one organic solvent, the described material containing group VIII metallic element is selected from the simple substance of group VIII metallic element and the salt of group VIII metallic element, contains carbon-silicon key in the molecular structure of described polymkeric substance.
The method according to this invention can reduce the molecular weight of polymkeric substance effectively, its reason may be: by the polymkeric substance that contains carbon-silicon key and halogen simple substance and be selected from the simple substance of group VIII metallic element and the salt of group VIII metallic element at least one material carry out reacting by heating, can optionally make the carbon-silicon key in polymkeric substance disconnect, thereby can reduce the molecular weight of polymkeric substance.
And, adopt method of the present invention to process usining the coupling polymer that silicon obtains as coupling center, the molecular weight of the polymkeric substance after processing and distribution thereof are compared with the molecular weight and the distribution thereof that form the base polymer of this coupling polymer, not considerable change.This explanation adopts method of the present invention to process the polymkeric substance that contains carbon-silicon key, can not cause other chemical bond in polymkeric substance to rupture, thereby the selectivity of reaction is good.
Meanwhile, method of the present invention can be controlled the degree of reaction effectively by adjusting reaction conditions, thereby obtains having the polymkeric substance of expection molecular weight.
In addition, the reaction conditions of the method according to this invention is gentle, and simple and easy to do.
Accompanying drawing explanation
Accompanying drawing is to be 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:
Gel permeation chromatography (GPC) spectrogram of the product that Fig. 1 obtains for the polymkeric substance prepared according to embodiments of the invention 3 steps (1) and step (2), wherein, A is the GPC spectrogram of the styrene-butadiene copolymer as stock polymer prepared of step (1), and B is the GPC spectrogram of the product that obtains of step (2).
Embodiment
The invention provides a kind of method that reduces polymericular weight, the method is included under the existence of halogen simple substance, and polymkeric substance and at least one material containing group VIII metallic element are carried out to reacting by heating at least one organic solvent.
The method according to this invention, the described material containing group VIII metallic element is selected from the simple substance of group VIII metallic element and the salt of group VIII metallic element.The salt of described group VIII metallic element can variously be usingd group VIII metallic element as cationic salt for common, is preferably the anaerobic hydrochlorate of group VIII metallic element, more preferably the muriate of group VIII metallic element.Described group VIII metallic element is preferably selected from ferro element, ruthenium element and osmium element, more preferably ferro element.
Of the present invention a kind of preferred embodiment in, described material chosen from Fe simple substance, FeCl containing group VIII metallic element
2and FeCl
3.Of the present invention a kind of more preferred embodiment in, the described material containing group VIII metallic element is iron simple substance.When the described material containing group VIII metallic element is iron simple substance, can, under more gentle condition, more effectively make the silicon-carbon bonds in polymkeric substance disconnect.
The method according to this invention, described halogen simple substance can be F
2, Cl
2, Br
2or I
2, be preferably I
2.
In a kind of most preferred embodiment of the present invention, the described compound containing group VIII metallic element is iron simple substance, and described halogen simple substance is I
2.
(that is, the method according to this invention, contain carbon-silicon key in the molecular structure of described polymkeric substance
).The polymkeric substance that contains carbon-silicon key in molecular chain for example can be for usining the polymkeric substance of Siliciumatom as coupling center.
Particularly, described polymkeric substance can be for being that the silicon compound more than 2 (being preferably more than 3) carries out the polymkeric substance that coupling obtains by olefin polymer by functionality.Described olefin polymer can need to carry out with silicon compound the polymkeric substance of coupling for various, for example, 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.Described silicon compound can be the conventional various silicon-containing compounds that two above polymer molecular chains can be linked together by carbon-silicon key in this area, and its representative instance is tetrachloro silicane.
The present invention is not particularly limited for the content of carbon-silicon key in described polymkeric substance, can be according to the source of the polymkeric substance as raw material and difference.
The method according to this invention, the described material containing group VIII metallic element and the effect that halogen simple substance plays catalyzer in the method for the invention, its consumption can carry out appropriate selection according to the molecular weight of the kind of the polymkeric substance for reacting and expection, can realize catalysis, is as the criterion.Usually, the consumption of the described material containing group VIII metallic element 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.The amount of described halogen simple substance can be carried out appropriate selection according to the described amount of substance containing group VIII metallic element.Usually, the weight ratio of described halogen simple substance and the described material containing group VIII metallic element can be 0.5-5:1, is preferably 1-3:1.
The method according to this invention, described organic solvent can, for conventional various organic solvents, 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
12replacement or unsubstituted naphthenic hydrocarbon, C
6-C
12replacement or unsubstituted aromatic hydrocarbons, C
3-C
8ketone and C
4-C
8replacement or unsubstituted alicyclic heterocyclic.Particularly, described organic solvent can be selected from toluene, dimethylbenzene, chlorinated benzene, hexanaphthene, normal hexane, tetrahydrofuran (THF), acetone and dioxane.
The method according to this invention, the condition of described reacting by heating is not particularly limited, can react and can not make reactant and reaction product generation thermolysis be as the criterion.Usually, the temperature of described reacting by heating can be 40-150 ℃, is preferably 50-120 ℃.The time of described reacting by heating can be carried out appropriate selection according to the molecular weight of polymkeric substance and the temperature of reacting by heating of expection.Usually, the time of described reacting by heating can be 0.5-24 hour.
The method according to this invention, the mixture that described reacting by heating obtains can adopt the ordinary method of this area to process, thereby obtains the polymkeric substance that molecular weight reduces.For example, the mixture that reacting by heating can be obtained removes desolventizing in vacuum drying oven, thereby obtains the polymkeric substance that molecular weight reduces.
Below in conjunction with embodiment, describe the present invention in detail.
In following examples and comparative example, the molecular weight of polymkeric substance and distribution thereof and coupling efficiency (CE) adopt and to be purchased the gel permeation chromatograph that the model from TOSOH company is HLC-8320 and to measure, take tetrahydrofuran (THF) as moving phase, take Narrow distribution polystyrene as standard specimen, temperature is 40 ℃.Described 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.
Embodiment 1-6 is used for illustrating method of the present invention.
Embodiment 1
(1) 2 grams of low-cis-polybutadiene rubber (be purchased from Sinopec, the trade mark is LCBR1403) are dissolved in 10mL toluene, to be dissolved completely after, add wherein 0.01 gram of iron powder, in this solution, add 0.02 gram of iodine, reaction solution is heated to 70 ℃, react 6 hours simultaneously.The mixture obtaining drying under reduced pressure in vacuum drying oven, except desolventizing, is obtained to product.
The molecular weight of the product obtaining as low-cis-polybutadiene rubber and the step (1) of raw material and being distributed in table 1 is listed.
Comparative example 1
Adopt the method identical with embodiment 1 to react, different, do not use iron powder, the molecular weight of the product obtaining and being distributed in table 1 is listed.
Comparative example 2
Adopt the method identical with embodiment 1 to react, different, do not use elemental iodine, the molecular weight of the product obtaining and being distributed in table 1 is listed.
Embodiment 2
Adopt the method identical with embodiment 1 to process low-cis-polybutadiene rubber, different, the reaction times is 2 hours.The molecular weight of the product obtaining and being distributed in table 1 is listed.
Table 1
*CE=[m
1/(m
1+m
2)]×100%
M
1for number-average molecular weight is M
n 1peak area
M
2for number-average molecular weight is M
n 2peak area
As can be seen from Table 1, adopt method of the present invention to process the polymkeric substance that contains carbon-silicon key, the coupling efficiency of polymkeric substance declines, thereby can effectively reduce the molecular weight of polymkeric substance.And, with process before polymer phase ratio, the molecular weight of high molecular part and low molecular weight part and being distributed in does not have considerable change before and after processing.This explanation, the method according to this invention can optionally make the carbon-silicon key in polymkeric substance disconnect, and can or substantially can not destroy other chemical bond in polymkeric substance.
Embodiment 3
(1) prepare butadiene-styrene copolymer
By high pure nitrogen displacement 3 times for 5L polymerization reaction kettle; in high pure nitrogen protection downhill reaction still, add the mixed solvent of 2300 grams of hexanaphthenes and normal hexane (wherein; the weight ratio of hexanaphthene and normal hexane is 80:20), 241 grams of divinyl, 197 grams of vinylbenzene and 1.4mL be as the tetrahydrofurfuryl alcohol ethyl ether of structure regulator; be warming up to 50 ℃; (solvent is the mixed solvent of above-mentioned hexanaphthene and normal hexane to add 22mL n-butyllithium solution; concentration is 0.23M), carry out the polyreaction of 30min.Then, in the mixture obtaining to polymerization, add 3.5mL coupling agent SiCl
4solution (solvent is the mixed solvent of above-mentioned hexanaphthene and normal hexane, and concentration is 0.16M), continues reaction 30min.Then, add 0.5mL terminator Virahol, reaction is incorporated as the anti-aging agent of 0.4 % by weight of divinyl and cinnamic total amount after 5min (purchased from Beijing Jiyi Chemicals Co., Ltd., the trade mark is 1075 and 1520, by 1075 and 1520, by weight 1:1, with the mixed solvent of above-mentioned hexanaphthene and normal hexane, be made into 20wt% solution), stir.The mixture obtaining is dry except desolventizing, obtain butadiene-styrene copolymer.
(2) butadiene-styrene copolymer of being prepared by 2 grams of steps (1) is dissolved in 10mL toluene, to be dissolved completely after, add wherein 0.01 gram of iron powder, in this solution, add 0.02 gram of iodine simultaneously, be heated to 100 ℃, react 4 hours.The mixture obtaining drying under reduced pressure in vacuum drying oven, except desolventizing, is obtained to product.
The molecular weight of butadiene-styrene copolymer prepared by step (1) and being distributed in table 2 is listed, the molecular weight of the product that step (2) obtains and being distributed in table 3 is listed, the GPC spectrogram of the product that polymkeric substance prepared by step (1) and step (2) obtain provides in Fig. 1, wherein, A is the GPC spectrogram of the styrene-butadiene copolymer as stock polymer prepared of step (1), and B is the GPC spectrogram of the product that obtains of step (2).
Embodiment 4
Adopt the method identical with embodiment 3 to prepare butadiene-styrene copolymer, and the employing method identical with embodiment 3 steps (2) processed butadiene-styrene copolymer, different is, the consumption of elemental iodine is 0.0016 gram, the consumption of iron powder is 0.0016 gram, temperature of reaction is 110 ℃, and the time is 12 hours.The molecular weight of the product obtaining and being distributed in table 3 is listed.
Embodiment 5
Adopt the method identical with embodiment 3 to prepare butadiene-styrene copolymer, and the employing method identical with embodiment 3 steps (2) processed butadiene-styrene copolymer, different is, adopt 10mL chlorinated benzene as solvent, the consumption of elemental iodine is 0.1 gram, the consumption of iron powder is 0.03 gram, and temperature of reaction is 60 ℃, and the time is 12 hours.The molecular weight of the product obtaining and being distributed in table 3 is listed.
Table 2
| M n 1(×10 4） | MWD 1 | M n 2(×10 4） | MWD 2 | CE*（%） |
| 35.1 | 1.08 | 13.2 | 1.03 | 45 |
*CE=[m
1/(m
1+m
2)]×100%
M
1for number-average molecular weight is M
n 1peak area
M
2for number-average molecular weight is M
n 2peak area
Table 3
*CE=[(m
1+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 Figure 1, adopt method of the present invention to carry out reacting by heating to containing the polymkeric substance of carbon-silicon key in molecular structure, can optionally make at least part of carbon-silicon bond rupture in polymer molecular structure, thereby reduce the content of high molecular part.
From the result of table 2 and table 3, it can also be seen that, the method according to this invention can be controlled the degree of reaction effectively by adjusting reaction conditions, thereby can access the polymkeric substance with expection molecular weight.
Embodiment 6
Adopt the method identical with embodiment 3 to prepare butadiene-styrene copolymer, and the employing method identical with embodiment 3 steps (2) processed butadiene-styrene copolymer, different is to add 0.01 gram of iron protochloride, 0.02 gram of elemental iodine, temperature of reaction is 100 ℃, and the time is 12 hours.The molecular weight of the product obtaining and being distributed in table 4 is listed.
Table 4
| M n 1(×10 4） | MWD 1 | M n 2(×10 4） | MWD 2 | CE*（%） |
| 37.1 | 1.06 | 13.6 | 1.03 | 40 |
*CE=[m
1/(m
1+m
2)]×100%
M
1for number-average molecular weight is M
n 1peak area
M
2for number-average molecular weight is M
n 2peak area.
Claims (10)
1. a method that reduces polymericular weight, the method is included under the existence of halogen simple substance, polymkeric substance and at least one material containing group VIII metallic element are carried out to reacting by heating at least one organic solvent, the described material containing group VIII metallic element is selected from the simple substance of group VIII metallic element and the salt of group VIII metallic element, contains carbon-silicon key in the molecular structure of described polymkeric substance.
2. method according to claim 1, wherein, the weight ratio of described halogen simple substance and the described material containing group VIII metallic element is 0.5-5:1.
3. method according to claim 1 and 2, wherein, described halogen simple substance is I
2.
4. method according to claim 1, wherein, the 0.005-10 % by weight of the amount that the consumption of the described material containing group VIII metallic element is described polymkeric substance.
5. method according to claim 1, wherein, the salt of described group VIII metallic element is selected from the muriate of group VIII metallic element.
6. according to the method described in any one in claim 1,2,4 and 5, wherein, described group VIII metallic element is ferro element.
7. according to the method described in any one in claim 1,2 and 4, wherein, described material chosen from Fe simple substance, FeCl containing group VIII metallic element
2and FeCl
3.
8. method according to claim 1, wherein, described polymkeric substance is to using the polymkeric substance of Siliciumatom as coupling center.
9. method according to claim 1, wherein, described organic solvent is selected from C
5-C
10straight or branched alkane, C
6-C
12replacement or unsubstituted naphthenic hydrocarbon, C
6-C
12replacement or unsubstituted aromatic hydrocarbons, C
3-C
8ketone and C
4-C
8replace or unsubstituted alicyclic heterocyclic.
10. method according to claim 1, wherein, described reacting by heating is carried out at the temperature of 40-150 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349409A (en) * | 2015-07-20 | 2017-01-25 | 中国石油化工股份有限公司 | Method for reducing molecular weight of polymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108018A (en) * | 1985-11-20 | 1987-06-17 | 奥西蒙特公司 | New functionalized perfluoropolyethers and preparation method thereof |
-
2013
- 2013-04-12 CN CN201310126398.9A patent/CN104098718B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108018A (en) * | 1985-11-20 | 1987-06-17 | 奥西蒙特公司 | New functionalized perfluoropolyethers and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王超等: "通过金属促进的碳-硅键的选择性切断和重排合成硅杂环戊二烯", 《中国化学会第28届学术年会第6分会场摘要集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349409A (en) * | 2015-07-20 | 2017-01-25 | 中国石油化工股份有限公司 | Method for reducing molecular weight of polymer |
| CN106349409B (en) * | 2015-07-20 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of method for reducing polymer molecular weight |
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