CN106349409B - A kind of method for reducing polymer molecular weight - Google Patents
A kind of method for reducing polymer molecular weight Download PDFInfo
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- CN106349409B CN106349409B CN201510427023.5A CN201510427023A CN106349409B CN 106349409 B CN106349409 B CN 106349409B CN 201510427023 A CN201510427023 A CN 201510427023A CN 106349409 B CN106349409 B CN 106349409B
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Abstract
The invention discloses a kind of method for reducing polymer molecular weight, it is included in the presence of at least one of inorganic acid salt of the inorganic acid salt selected from Ru, Rh inorganic acid salt and Pd, polymer is subjected to heating response in organic solvent, contains carbon tin key in the molecular structure of the polymer.This method can be effectively reduced the molecular weight of the polymer containing carbon tin key.This method is used to handle the coupling polymer obtained using tin as coupling center, polymer after processing is in addition to the content of high molecular weight moieties and low molecular weight part changes, the molecular size range and its no significant change of distribution of high molecular weight moieties and low molecular weight part, show that the selectivity of this method is good, other chemical bonds in polymer will not be caused to be broken.Meanwhile this method can efficiently control the degree of reaction by adjusting reaction condition, so as to obtain the polymer with expected molecular weight.In addition, the reaction condition of this method is gentle, it is simple and easy to do.
Description
Technical field
The present invention relates to a kind of method for reducing polymer molecular weight.
Background technology
With the continuous development of material science, the application field of high molecular polymer constantly expands.For high molecular polymerization
For thing material, the molecular weight and molecualr weight distribution of high polymer and the physical property of product and processing characteristics have close relationship.Point
The performance indications that son is measured and its distribution is important as high molecular polymer, are all paid close attention to by chemist all the time.Therefore, such as
What efficiently controls and adjusted the molecular weight and molecular weight distribution of high polymer, will be the key of guarantee product quality.
The method for being used to controlling and adjusting high molecular polymer molecular weight and its distribution in the prior art is mainly by changing
Become polymerization formula and polymerizing condition, such as：Change catalyst system；Polymerisation is carried out using catalyst is repeatedly added；Regulation
Catalyst amount matches；Change feeding temperature；Polymerisation is carried out using multi-floating bodies；Change polymerization temperature.It is poly- by changing
Though closing formula and polymerizing condition can play a part of adjusting molecular weight and its distribution of high molecular polymer, it is confined to from poly-
The conjunction stage begins to that molecular weight and its distribution is adjusted.
Existing polymer is also required to adjust molecular weight sometimes according to its use occasion and the difference of processing method
Section, to optimize the physical property of polymer and processing characteristics.
CN100379845C discloses a kind of method for reducing olefin copolymer molecular weight, and this method utilizes main polymer chain
On weak carbon-hydrogen link be oxidized easily, the characteristics of causing copolymer degradation, make in the presence of oxygen at a temperature of at least 60 DEG C
Olefin copolymer on main chain containing tertiary carbon atom and the base oil containing less than 0.05 weight % sulphur are in contact, so as to realize reduction alkene
The molecular weight of copolymer.
CN1117107C discloses a kind of method for the molecular weight for reducing polymeric material, and this method is included with least one
Hydroperoxides handle polymeric material, wherein, the hydroperoxides are can exist the amount that molecular weight reduces, wherein temperature
Scope is 80-250 DEG C, and the polymeric material is selected from that mole content is 16-50% EPM polymer, EPDM and it is mixed
Compound.
CN101151282B discloses a kind of molecular weight for reducing polypropylene, propylene copolymer or polypropylene miser
Method, this method include mixing a kind of azo-compound with polypropylene, propylene copolymer or the polypropylene for needing to be degraded
Close, and the mixture to obtaining heats at 160-340 DEG C.
The method of the molecular weight of above-mentioned reduction polymer is by disconnecting the carbochain on main polymer chain, so as to realize
Reduce the molecular weight of polymer.
In polymer, the particularly preparation process of synthetic rubber, addition coupling agent, which carries out coupling, to be greatly enhanced
The molecular weight of polymer, improve the physical property and processing characteristics of polymer.Wherein, conventional coupling agent includes polyfunctional stannane
Compound, such as butter of tin.But with the raising of coupling degree, some negative shadows can be brought to the processing characteristics of polymer
Ring.Also, polymer also has different requirements for coupling efficiency with the difference of application scenario.
Therefore, it is necessary to the method that the molecular weight of coupling polymer is adjusted, to optimize the physical property of polymer and processing
Performance, meet the requirement of different application occasion.
The content of the invention
It is an object of the invention to provide a kind of method for reducing polymer molecular weight, this method, which can be effectively reduced, to be contained
There is the polymer of carbon-tin key, be particularly the molecular weight reduced using tin as the polymer of coupling center.
The present inventor is in research process it was unexpectedly observed that using inorganic acid salt, Rh inorganic acid selected from Ru
Polymer containing carbon-tin key is reacted, can effectively dropped as catalyst by the compound of salt and Pd inorganic acid salt
The molecular weight of the low polymer.The present invention is completed on this basis.
The invention provides a kind of method for reducing polymer molecular weight, this method is included in depositing at least one catalyst
Under, polymer is subjected to heating response at least one organic solvent, contains carbon-tin in the molecular structure of the polymer
Key, the catalyst are selected from Ru inorganic acid salt, Rh inorganic acid salt and Pd inorganic acid salt.
The method according to the invention can be effectively reduced the polymer for containing carbon-tin key and (such as be used as coupling using tin atom
The polymer at center) molecular weight, its reason is probably：By the polymer containing carbon-tin key and inorganic acid salt, Rh selected from Ru
Inorganic acid and the Pd catalyst of inorganic acid salt contact and carry out heating response, can optionally make carbon in polymer-
Tin key disconnects, so as to reduce the molecular weight of polymer.
Also, use the method for the present invention to handle the coupling polymer obtained using tin as coupling center, handle
Polymer afterwards is in addition to the content of high molecular weight moieties and low molecular weight part changes, high molecular weight moieties and low molecule amount
Partial molecular size range and its distribution does not have significant change.This explanation is using the method for the present invention to containing carbon-tin key
Polymer is handled, and other chemical bonds in polymer will not be caused to be broken, thus the selectivity reacted is good.
Meanwhile method of the invention can efficiently control the degree of reaction by adjusting reaction condition, so as to be had
There is the polymer of expected molecular weight.
In addition, the reaction condition of the method according to the invention is gentle, and it is simple and easy to do.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the GPC spectrograms for the BS 2305 for being used as raw material in the embodiment of the present invention 1；
Fig. 2 is the GPC spectrograms for the product that the embodiment of the present invention 1 obtains；
Fig. 3 is the GPC spectrograms for the product that comparative example 1 of the present invention obtains.
Embodiment
The invention provides a kind of method for reducing polymer molecular weight, this method is included in depositing at least one catalyst
Under, polymer is subjected to heating response at least one organic solvent, contains carbon-tin in the molecular structure of the polymer
Key.
In the present invention, " at least one " refers to one or more.
The method according to the invention, the catalyst are selected from Ru inorganic acid salt, Rh inorganic acid salt and Pd inorganic acid
Salt.The inorganic acid salt of the Ru refers to the compound formed with least one hydrogen atom in Ru element substitution inorganic acids, institute
The inorganic acid salt for stating Rh refers to the compound formed with least one hydrogen atom in Rh element substitution inorganic acids, the Pd's
Inorganic acid salt refers to the compound formed with least one hydrogen atom in Pd element substitution inorganic acids.
The catalyst can be selected from is used as sun at least using Ru elements as the inorganic acid salt of cation, at least using Rh elements
The inorganic acid salt of ion and the inorganic acid salt of cation is used as at least using Pd elements.Preferably, the catalyst is selected from Ru nothing
The anaerobic hydrochlorate of oxygen hydrochlorate, Rh anaerobic hydrochlorate and Pd.It is highly preferred that the catalyst is selected from the halogenation of Ru halide, Rh
The halide of thing and Pd.The instantiation of the catalyst can include but is not limited to RuCl3、RhCl3And PdCl2。
In the present invention, the inorganic acid salt as catalyst can be free of chemical bonding water, can also contain chemical bonding water,
For example, RuCl3Can be with RuCl3·3H2O form uses, RhCl3Can be with RhCl3·3H2O form uses.
The present invention a kind of preferred embodiment in, the catalyst be Ru inorganic acid salt, such as RuCl3.With adopting
The inorganic acid salt of inorganic acid salt and/or Pd by the use of Rh is compared as catalyst, using Ru inorganic acid salt as catalyst, at remaining
The effect of more preferable catalytic reaction can be obtained in the case of condition identical.
The method according to the invention, the dosage of the catalyst can according to the species of the polymer for being reacted with
And expected molecular weight carries out appropriate selection, can realize that catalysis is defined.Usually, the dosage of the catalyst can
Think the 0.005-10 weight % of the amount of the polymer, the 0.05-5 weight % of the amount of preferably described polymer, more preferably
For the 0.5-2 weight % of the amount of the polymer.
The method according to the invention, in the molecular structure of the polymer containing carbon-tin key (i.e.,).Point
The polymer for containing carbon-tin key in subchain for example can be the polymer using tin atom as coupling center.
Specifically, the polymer can be by olefin polymer with degree of functionality be more than 2 (being preferably more than 3) tin
Polymer obtained from compound is coupled.The olefin polymer various can need to be coupled with sn-containing compound
Polymer, it is used for example as the olefin polymer of rubber.The instantiation of the olefin polymer can include but is not limited to：Conjugation
The homopolymer of alkadienes, such as polyisoprene, polybutadiene；The copolymer of monoolefine and conjugated diene, such as butadiene and benzene
The copolymer of the copolymer of ethene, butadiene and acrylonitrile.The sn-containing compound can be it is commonly used in the art it is various can
By the polymer molecular chain of more than two by the carbon-sn-containing compound of tin key connection together, its representative instance is four chlorinations
Tin.
The present invention is not particularly limited for the content of carbon in the polymer-tin key, can be according to as the poly- of raw material
The source of compound and it is different.
The method according to the invention, the organic solvent can be conventional various organic solvents, scattered that can dissolve
The polymer is defined.Usually, the organic solvent can be selected from C5-C10Straight or branched alkane, C6-C12Substitution or
Unsubstituted cycloalkane, C6-C12Substituted or unsubstituted aromatic hydrocarbons, C3-C8Ketone and C4-C8Substituted or unsubstituted fat it is miscellaneous
Ring.Specifically, the organic solvent can be selected from hexamethylene, n-hexane, pentane, toluene, dimethylbenzene, chlorobenzene, tetrahydrochysene furan
Mutter, acetone and dioxane.
The method according to the invention, the temperature conditionss of the reaction are not particularly limited, can be reacted and will not
Make reactant and reaction product that thermal decomposition occur and be defined.Usually, the temperature of the reaction can be 40-150 DEG C.Preferably,
The temperature of the reaction is 50-120 DEG C (such as 60-100 DEG C), can so be obtained higher under more gentle reaction condition
Reaction speed.The time of the heating response can be fitted according to the molecular weight of expected polymer and the temperature of reaction
When selection.Usually, the time of the reaction can be 0.5-24 hours, preferably 2-20 hours, and more preferably 5-15 is small
When, more preferably 6-12 hours.
The method according to the invention, the reaction can be carried out in oxygen-containing atmosphere, can also be by non-active gas shape
Into atmosphere in carry out, the non-active gas refer to not with reactant, reaction product and the organic solvent
The gas of interaction is learned, such as group 0 element gas (such as argon gas) and nitrogen.Usually, the reaction is entered in air atmosphere
OK.
The method according to the invention, the mixture for reacting to obtain can use the conventional method of this area to be handled, from
And obtain the polymer of molecular weight reduction.For example, can be under conditions of pressure be reduced, in the mixture obtained except dereaction
Solvent, so as to obtain the polymer of molecular weight reduction.
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following examples and comparative example, the molecular weight of polymer and its distribution are using the model commercially available from TOSOH companies
Determined for HLC-8320 gel permeation chromatograph, using tetrahydrofuran as mobile phase, using Narrow distribution polystyrene as standard specimen, temperature
For 40 DEG C.Coupling efficiency refers in polymer that the number for the strand being coupled accounts for the percentage of the total number of strand, according to
GPC results are calculated.
Embodiment 1-5 is used for the method for illustrating the present invention.
Embodiment 1
By 1g Afpols (commercially available from Sinopec, the trade mark 2305, the Afpol with
Butter of tin is as coupling agent) be dissolved in 5mL n-hexanes, it is to be dissolved completely after, add 0.01g RuCl thereto3·3H2O, will
Reaction solution is heated to 60 DEG C in air atmosphere, reacts 6 hours.Obtained mixture is dried under reduced pressure removing in vacuum drying oven
Solvent, obtain product.As the Afpol of raw material and the molecular weight of obtained product and its it is distributed in table 1
List.Fig. 1 and Fig. 2 respectively illustrates the GPC spectrograms of the Afpol as raw material and the GPC of obtained product
Spectrogram.
Comparative example 1
Reacted using method same as Example 1, unlike, without using RuCl3·3H2O, obtained product
Molecular weight and its be distributed in table 1 list.Fig. 3 is the GPC spectrograms of obtained product.
Embodiment 2
Afpol is handled using method same as Example 1, unlike, the reaction time
For 12 hours.The molecular weight of obtained product and its be distributed in table 1 is listed.
Table 1
| Numbering | Raw material | Embodiment 1 | Comparative example 1 | Embodiment 2 |
| Mn 1(×104) | 12.3 | 12.4 | 12.3 | 11.5 |
| MWD1 | 1.03 | 1.03 | 1.04 | 1.06 |
| *A1(%) | 42.6 | 48.0 | 42.7 | 56.3 |
| Mn 2(×104) | 24.2 | 24.8 | 24.3 | 22.3 |
| MWD2 | 1.01 | 1.02 | 1.02 | 1.03 |
| **A2(%) | 15.2 | 16.5 | 16.2 | 24.2 |
| Mn 3(×104) | 41.2 | 42.6 | 42.4 | 40.5 |
| MWD3 | 1.06 | 1.06 | 1.06 | 1.06 |
| ***A3(%) | 42.2 | 35.5 | 41.1 | 19.5 |
*A1=[m1/(m1+m2+m3)] × 100%
**A2=[m2/(m1+m2+m3)] × 100%
***A3=[m3/(m1+m2+m3)] × 100%
m1It is M for number-average molecular weightn 1Peak area
m2It is M for number-average molecular weightn 2Peak area
m3It is M for number-average molecular weightn 3Peak area
As it can be seen from table 1 the polymer containing carbon-tin key is handled using the method for the present invention, can be effective
Ground reduces the content of high molecular weight moieties in polymer.Also, with the polymer phase ratio of before processing, high molecular weight moieties and low
The molecular weight of molecular weight fractions and its it is distributed in and does not have significant change before and after the processing.This explanation, the method according to the invention can
Optionally disconnect carbon in polymer-tin key, without or the other chemical bonds that will not destroy substantially in polymer.
Fig. 1 to Fig. 3 is also confirmed that, the polymer containing carbon-tin key is handled using the method for the present invention, can be selected
Carbon-tin key is disconnected to property, so as to reduce the content of high molecular weight moieties in polymer.
Embodiment 3
(1) 1g Afpols are dissolved in 5mL toluene (with embodiment 1), it is to be dissolved completely after, thereto
Add 0.005g RuCl3·3H2O, reaction solution is heated to 60 DEG C in nitrogen atmosphere, reacted 8 hours.The mixture that will be obtained
Removing solvent is dried under reduced pressure in vacuum drying oven, obtains product.The molecular weight of obtained product and its be distributed in table 2 is listed.
Embodiment 4
Afpol is handled using method same as Example 3, unlike, add thereto
Enter 0.015g RuCl3·3H2O, reaction time are 6 hours.The molecular weight of obtained product and its be distributed in table 2 is listed.
Embodiment 5
Afpol is handled using method same as Example 3, unlike, reaction temperature
For 100 DEG C, the time is 6 hours.The molecular weight of obtained product and its be distributed in table 2 is listed.
Embodiment 6
Afpol is handled using method same as Example 1, unlike, without using
RuCl3·3H2O, but 0.01g RhCl are added thereto3·3H2O.The molecular weight of obtained product and its it is distributed in table 2
List.
Embodiment 7
Afpol is handled using method same as Example 3, unlike, without using
RuCl3·3H2O, but 0.01g PdCl are added thereto2.The molecular weight of obtained product and its be distributed in table 2 is listed.
Table 2
| Numbering | Raw material | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Mn 1(×104) | 12.3 | 12.5 | 11.9 | 12.4 | 12.5 | 12.3 |
| MWD1 | 1.03 | 1.03 | 1.04 | 1.03 | 1.03 | 1.03 |
| *A1(%) | 42.6 | 48.7 | 50.4 | 55.4 | 48.2 | 48.1 |
| Mn 2(×104) | 24.2 | 23.6 | 21.6 | 23.8 | 24.1 | 24.3 |
| MWD2 | 1.01 | 1.03 | 1.03 | 1.04 | 1.02 | 1.03 |
| **A2(%) | 15.2 | 16.2 | 16.0 | 24.9 | 16.5 | 16.4 |
| Mn 3(×104) | 41.2 | 41.1 | 41.6 | 42.0 | 41.6 | 41.2 |
| MWD3 | 1.06 | 1.07 | 1.05 | 1.06 | 1.06 | 1.07 |
| ***A3(%) | 42.2 | 35.1 | 33.6 | 19.7 | 35.3 | 35.5 |
*A1=[m1/(m1+m2+m3)] × 100%
**A2=[m2/(m1+m2+m3)] × 100%
***A3=[m3/(m1+m2+m3)] × 100%
m1It is M for number-average molecular weightn 1Peak area
m2It is M for number-average molecular weightn 2Peak area
m3It is M for number-average molecular weightn 3Peak area
As can be seen from Table 2, the method according to the invention can efficiently control reaction by adjusting reaction condition
Degree, so as to obtain the polymer with expected molecular weight.
Claims (9)
1. a kind of method for reducing polymer molecular weight, this method is included in the presence of at least one catalyst, by polymer
Heating response is carried out at least one organic solvent, contains carbon-tin key, the catalyst in the molecular structure of the polymer
The inorganic acid salt of inorganic acid salt, Rh and Pd inorganic acid salt selected from Ru.
2. according to the method for claim 1, wherein, the dosage of the catalyst is the 0.005-10 of the amount of the polymer
Weight %.
3. according to the method for claim 2, wherein, the dosage of the catalyst is heavy for the 0.05-5 of the amount of the polymer
Measure %.
4. according to the method for claim 3, wherein, the dosage of the catalyst is heavy for the 0.5-2 of the amount of the polymer
Measure %.
5. according to the method described in any one in claim 1-4, wherein, the catalyst is selected from Ru halide, Rh
The halide of halide and Pd.
6. according to the method described in any one in claim 1-4, wherein, the catalyst is selected from RuCl3、RhCl3With
PdCl2。
7. according to the method described in any one in claim 1-4, wherein, the polymer be using tin atom as being coupled in
The polymer of the heart.
8. according to the method described in any one in claim 1-4, wherein, the organic solvent is selected from C5-C10Straight chain or
Branched paraffin, C6-C12Substituted or unsubstituted cycloalkane, C6-C12Substituted or unsubstituted aromatic hydrocarbons, C3-C8Ketone and C4-
C8Substituted or unsubstituted alicyclic heterocyclic.
9. according to the method described in any one in claim 1-4, wherein, the reaction is entered at a temperature of 40-150 DEG C
OK.
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| 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 |
| CN1423663A (en) * | 1999-11-16 | 2003-06-11 | 伊斯曼化学公司 | Process for reducing the weight average molecular weight and melt index ratio of polyethy lenes and polyethylene products |
| CN101372518A (en) * | 2007-08-21 | 2009-02-25 | 朗盛德国有限责任公司 | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
| CN102838700A (en) * | 2012-08-23 | 2012-12-26 | 辽宁和运合成橡胶研究院有限公司 | Molecular weight distribution regulating method of 3,4-polyisoprene rubber |
| CN104098718A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for reducing molecular weight of polymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013098052A2 (en) * | 2011-12-28 | 2013-07-04 | Lanxess Deutschland Gmbh | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1423663A (en) * | 1999-11-16 | 2003-06-11 | 伊斯曼化学公司 | Process for reducing the weight average molecular weight and melt index ratio of polyethy lenes and polyethylene products |
| 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 |
| CN101372518A (en) * | 2007-08-21 | 2009-02-25 | 朗盛德国有限责任公司 | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
| CN102838700A (en) * | 2012-08-23 | 2012-12-26 | 辽宁和运合成橡胶研究院有限公司 | Molecular weight distribution regulating method of 3,4-polyisoprene rubber |
| CN104098718A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for reducing molecular weight of polymer |
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