CN104628898A - Olefin polymerization termination method - Google Patents
Olefin polymerization termination method Download PDFInfo
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- CN104628898A CN104628898A CN201310560453.5A CN201310560453A CN104628898A CN 104628898 A CN104628898 A CN 104628898A CN 201310560453 A CN201310560453 A CN 201310560453A CN 104628898 A CN104628898 A CN 104628898A
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Abstract
The invention provides an olefin polymerization termination method, which includes: (1) carrying out olefin polymerization reaction to obtain a to-be-terminated polymerization solution; and (2) under a stirring condition, adding a terminating agent solution into the to-be-terminated polymerization solution, with the terminating agent solution being a phenolic substance organic solution with a concentration of less than 100g/L. According to the method provided by the invention, by using the phenolic substance organic solution with a concentration of less than 100g/L as the terminating agent solution, termination can be carried out effectively, and the terminated glue solution has a gel content of almost zero, the glue solution viscosity is greatly reduced, and thereby the equipment loss and cost are both reduced.
Description
Technical field
The present invention relates to a kind of olefin polymerization termination method.
Background technology
Industrialization commodity polyisoprene rubber and natural gum structural similitude, have excellent green strength and cured properties, meet high-performance tire at a high speed, energy-conservation, safety, development in environmental protection etc. needs.Rare-earth isoprene rubber produces the method mainly adopting continuous solution polymerization, be polymerized to add anti-aging agent in backward glue, terminator and viscosity-depression agent, be transported to after mixing in glue tank and store, because rare-earth isoprene rubber molecular weight is large, molecular weight distribution is narrow, and the degree of branching is low, viscosity is very large, all brings very large difficulty to reaction terminating and glue conveying.
In existing production technology, generally select water or other alcohols materials to make terminator, namely in glue surge tank, water is added or alcohols material makes terminator, because water and alcohols material are polar material, bad with the intermiscibility of nonpolar polymers soln, the viscosity of adding rare-earth isoprene rubber is large especially, a lot of active centre is wrapped in cannot contacts with terminator by macromolecular chain, can not stop completely, and produce being cross-linked between chemical bond, even form gel, have a strong impact on the quality of product.
CN1919881A discloses a kind of polymerization process stopping the polyreaction of conjugated diene polymer, the method uses the aldehydes matter solution of 100-400g/L to stop, aldehydes matter strength of solution is high, but due to terminator consumption little, join with the aldehydes matter of high density like this and be in fact difficult to mix completely with the glue in still, play termination.
Summary of the invention
The object of the invention is the feature stopped for the high viscosity difficulty of rare-earth isoprene rubber successive polymerization glue, a kind of olefin polymerization termination method that effectively can reduce gelatin viscosity, reduce gel content is provided.
For realizing aforementioned object, the invention provides a kind of olefin polymerization termination method, wherein, the method comprises: (1) carries out olefinic polyreaction, obtains polymeric solution to be stopped; (2) under agitation, in polymeric solution described to be stopped, add terminator solution, described terminator solution is the organic solution of concentration lower than the aldehydes matter of 100g/L.
Method of the present invention makes terminator solution by working concentration lower than the organic solution of the aldehydes matter of 100g/L, make it possible to effectively stop, and in the glue after stopping, gel content is almost 0, and gelatin viscosity reduces greatly, and equipment loss and cost can also be made thus all to reduce.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of olefin polymerization termination method, wherein, the method comprises:
(1) carry out olefinic polyreaction, obtain polymeric solution to be stopped;
(2) under agitation, in polymeric solution described to be stopped, add terminator solution, described terminator solution is the organic solution of concentration lower than the aldehydes matter of 100g/L.
According to method of the present invention, the organic solution of preferred described terminator solution to be concentration the be aldehydes matter of 0.1-50g/L, the more preferably organic solution of described terminator solution to be concentration the be aldehydes matter of 1-3g/L.So can viscosity reduction reduce gel content further, the ageing resistance of rubber can be improved simultaneously.
According to method of the present invention, the range of choices of described aldehydes matter is wider, described aldehydes matter is oxidation inhibitor class aldehydes matter, for the present invention, preferred described aldehydes matter is 4, one or more in 6-dioctyl thiomethyl ortho-cresol (being commonly called as oxidation inhibitor 1520), 2,6 di tert butyl 4 methyl phenol (being commonly called as antioxidant 264) and β-positive octadecanol ester (being commonly called as antioxidant 1076) of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid.So can viscosity reduction reduce gel content further, the ageing resistance of rubber can be improved simultaneously.
In the present invention, the solvent phase that the organic solvent in the organic solution of preferred described aldehydes matter and polyreaction use is same, so can reduce follow-up separation circuit.
According to method of the present invention, preferred described aldehydes matter is the mixture of 4,6-dioctyl thiomethyl ortho-cresol and β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, and the weight ratio of the two is preferably 0.1-10:1.So can viscosity reduction reduce gel content further, the ageing resistance of rubber can be improved simultaneously.
According to method of the present invention, wherein, the speed that adds of preferred described terminator solution is 0.3-0.6g/ (min ﹒ 100g polymkeric substance).So can viscosity reduction reduce gel content further, the ageing resistance of rubber can be improved simultaneously.
According to method of the present invention, preferred described agitation condition comprises: stirring velocity is 1-10Hz, so can viscosity reduction reduce gel content further, can improve the ageing resistance of rubber simultaneously.
According to method of the present invention, preferably in aldehydes matter, in the polymkeric substance in polymeric solution to be stopped described in the consumption of described terminator solution is not less than, the amount in active centre, specifically can select according to needs.
According to method of the present invention, in polymeric solution to be stopped preferably, the content of polymkeric substance is 10-20 % by weight.
Method of the present invention is suitable for various types of polyreaction, and described in preferred steps (1), olefinic polyreaction carries out as follows: under olefin polymerization conditions, under chain initiator, solvent exist, is contacted by alkene with olefin polymerization catalysis.
According to method of the present invention, described alkene is preferably the conjugated diene of C4-C6, is more preferably one or more in divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2,3-dimethylbutadiene, most preferably is isoprene.
According to method of the present invention, described solvent is preferably aliphatic saturated hydrocarbon and/or alicyclic hydrocarbon, is preferably the alkane of C5-C10 and/or the naphthenic hydrocarbon of C5-C10, as being one or more in pentane, iso-pentane, hexane, hexanaphthene, heptane and octane.
According to method of the present invention, described olefin polymerization catalysis can be one or more in rare earth catalyst, Titanium series catalyst and lithium-based catalyst, specifically can select according to needs.
According to method of the present invention, described olefin polymerization conditions can be that the routine of this area is selected, and for the present invention, preferred described olefin polymerization conditions comprises: polymerization temperature is 10-60 DEG C, and polymerization pressure is 0.1-1Mpa.
Method of the present invention is suitable for batchwise polymerization and is also suitable for successive polymerization, wherein, is particularly suitable for successive polymerization.So can reduce gel content, improve rubber quality, reduce the loss that glue viscosity reduces equipment and the energy.
In the present invention, shore hardness measures according to Shore durometer method (Shao Er hardness) GB/T531.1-2008, the test determines that tear strength specifies according to GB/T529-2008, the test determines that tension set specifies according to GB/T7759-1996, pull apart elongation, 300% and surely stretch the test determines specified according to GB/T528-2009, the method that gel content specifies according to the standard SH/T1050-1991 of petrochemical industry measures, and the testing method that gelatin viscosity specifies according to GB/T10247-2008 measures.
In the present invention, monomer conversion be the isoprene added weight be polymerized after the per-cent of the weight of polyisoprene that obtains.
Embodiment 1
(1) polymerizing catalyst is, rare earth catalyst, active ingredient is neodymium caprate, its content is 6mmol/L, promotor is aluminium agent triisobutyl aluminium, electron donor is aluminium diethyl monochloride, and also containing isoprene, solvent is hexane, neodymium caprate: aluminium agent: aluminium diethyl monochloride: isoprene=1:12:3:50(mol ratio), identical below, solvent is hexane, and control polymerization temperature is 30-50 DEG C, polymerization pressure is 0.3-0.4Mpa, after polymerization-stable, the content obtaining polyisoprene is the polymerization glue of 13 % by weight, and viscosity is 96587cp;
(2) under agitation, agitation condition comprises: stirring velocity 2Hz, the hexane solution that often liter contains 264 of 2g anti-aging agent is added in glue surge tank, the add-on of 264 is 0.5 % by weight of polyisoprene quality, it is 0.3g/ (min ﹒ 100g polymkeric substance) that the hexane solution of 264 adds speed, carry out termination reaction, the glue character after termination and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 1.
Comparative example 1
Step (1) is identical with embodiment 1, unlike working concentration in: step (2) be the hexane solution of 264 of 300g/L as terminator solution, all the other conditions are all identical.Glue character and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 1.
Table 1
Data from table 1, can find out the rubber mechanical property that embodiment 1 and comparative example 1 obtain and quality index roughly the same, but not containing gel in the rubber of embodiment 1, and the rubber of comparative example 1 contains the gel of definite composition, increases the difficulty of post-treatment to a certain extent.And the rubber gelatin viscosity of the rubber gelatin viscosity comparative example far away 1 of embodiment 1 is low, illustrates thus, method of the present invention can obtain not containing the rare-earth isoprene rubber of gel, and can effectively reduce glue viscosity.
Embodiment 2
(1) polymerizing catalyst is rare earth catalyst, and solvent is hexane, and control polymerization temperature between 30-50 DEG C, polymerization pressure is between 0.3-0.4Mpa, and after polymerization-stable, the content obtaining polyisoprene is the polymerization glue of 12.3 % by weight, and viscosity is 90365cp;
(2) under agitation, agitation condition comprises: stirring velocity 3Hz, the hexane solution that often liter contains 264 of 2.6g anti-aging agent is added in glue surge tank, the add-on of 264 is 0.4 % by weight of polyisoprene quality, it is 0.4g/ (min ﹒ 100g polymkeric substance) that the hexane solution of 264 adds speed, carry out termination reaction, glue character and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 2.
Comparative example 2
Step (1) is identical with embodiment 2, unlike: in glue surge tank, add the hexane solution that concentration is 264 of 280g/L in step (2), the add-on of 264 is 0.4 % by weight of polyisoprene quality, carry out termination reaction, then water is added, the add-on of water is 100 times of catalyst active center's amount of substance, about polyisoprene quality 0.4 % by weight.Glue character and glue are through condensing the physical property mark characterization result of dry post-consumer polymer in table 2.
Table 2
Data from table 2, can find out the rubber mechanical property that embodiment 2 and comparative example 2 obtain and quality index roughly the same, but the rubber of embodiment 2 is not containing gel, and although comparative example 2 adds water makees terminator, but the gel still containing definite composition in rubber, increases the difficulty of post-treatment to a certain extent.And the rubber gelatin viscosity of the rubber gelatin viscosity comparative example far away 2 of embodiment 2 is low, illustrates thus, method of the present invention can obtain not containing the rare-earth isoprene rubber of gel, and can effectively reduce glue viscosity.
Embodiment 3
(1) polymerizing catalyst is rare earth catalyst, and solvent is hexane, and control polymerization temperature between 30-50 DEG C, polymerization pressure is between 0.3-0.4Mpa, and after polymerization-stable, the content obtaining polyisoprene is the polymerization glue of 11.9 % by weight, and viscosity is 84692cp;
(2) under agitation, agitation condition comprises: stirring velocity 1Hz, often liter of hexane solution containing 2.2g antioxidant 264 is added in glue surge tank, the add-on of 264 is 0.4 % by weight of polyisoprene quality, it is that 0.6g/ (min ﹒ 100g polymkeric substance) carries out termination reaction that the hexane solution of 264 adds speed, and glue character and glue are through condensing the physical property mark characterization result of dry post-consumer polymer in table 3.
Comparative example 3
Step (1) is identical with embodiment 3, unlike: in glue surge tank, add the hexane solution that concentration is 264 of 300g/L in step (2), the add-on of 264 is 0.4 % by weight of polyisoprene quality, carry out termination reaction, then the aqueous solution (concentration is 100g/L) of sodium oleate is added, the add-on of water is 100 times of the amount of catalyst substance, about polyisoprene quality 0.4 % by weight, the add-on of sodium oleate is 0.6% of the about polyisoprene quality of polyisoprene.Glue character and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 3.
Table 3
Data from table 3, can find out the rubber mechanical property that embodiment 3 and comparative example 3 obtain and quality index roughly the same, but the rubber of embodiment 3 is not containing gel, and although comparative example 3 adds aqueous solution sodium oleate makees terminator, but the gel still containing definite composition in rubber, increases the difficulty of post-treatment to a certain extent.And the rubber gelatin viscosity of the rubber gelatin viscosity comparative example far away 3 of embodiment 3 is low, illustrates thus, method of the present invention can obtain not containing the rare-earth isoprene rubber of gel, and can effectively reduce glue viscosity.
Embodiment 4
(1) polymerizing catalyst is rare earth catalyst, and solvent is hexane, and control polymerization temperature is 30-50 DEG C, polymerization pressure 0.3-0.4Mpa, and after polymerization-stable, the content obtaining polyisoprene is the polymerization glue of 12 % by weight, and viscosity is 89453cp;
(2) under agitation, agitation condition comprises: stirring velocity 3Hz, often liter of hexane solution containing 3g oxidation inhibitor 1520 is added in glue surge tank, the add-on of oxidation inhibitor 1520 is 0.6 % by weight of polyisoprene quality, it is 0.3g/ (min ﹒ 100g polymkeric substance) that the hexane solution of oxidation inhibitor 1520 adds speed, carry out termination reaction, the glue character after termination and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 4.
Comparative example 4
Step (1) is identical with embodiment 4, unlike working concentration in: step (2) be the hexane solution of the oxidation inhibitor 1520 of 300g/L as terminator solution, all the other conditions are all identical.Glue character and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 4.
Table 4
Data from table 4, can find out the rubber mechanical property that embodiment 4 and comparative example 4 obtain and quality index roughly the same, but not containing gel in the dry glue of embodiment 4, and the rubber of comparative example 4 contains the gel of definite composition, increases the difficulty of post-treatment to a certain extent.And the rubber gelatin viscosity of the rubber gelatin viscosity comparative example far away 4 of embodiment 4 is low, illustrates thus, method of the present invention can obtain not containing the rare-earth isoprene rubber of gel, and can effectively reduce glue viscosity.
Embodiment 5
(1) polymerizing catalyst is rare earth catalyst, and solvent is hexane, and control polymerization temperature is 30-50 DEG C, polymerization pressure 0.3-0.4Mpa, and after polymerization-stable, the content obtaining polyisoprene is the polymerization glue of 13.1 % by weight, and viscosity is 99472cp;
(2) under agitation, agitation condition comprises: stirring velocity 4Hz, often liter of hexane solution containing 2.5g oxidation inhibitor 1706 is added in glue surge tank, the add-on of oxidation inhibitor 1706 is 0.5 % by weight of polyisoprene quality, it is 0.4g/ (min ﹒ 100g polymkeric substance) that the hexane solution of oxidation inhibitor 1706 adds speed, carry out termination reaction, the glue character after termination and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 5.
Comparative example 5
Step (1) is identical with embodiment 5, unlike working concentration in: step (2) be the hexane solution of the oxidation inhibitor 1706 of 280g/L as terminator solution, all the other conditions are all identical.Glue character and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 5.
Table 5
Data from table 5, can find out the rubber mechanical property that embodiment 5 and comparative example 5 obtain and quality index roughly the same, but not containing gel in the dry glue of embodiment 5, and the rubber of comparative example 5 contains the gel of definite composition, increases the difficulty of post-treatment to a certain extent.And the rubber gelatin viscosity of the rubber gelatin viscosity comparative example far away 5 of embodiment 5 is low, illustrates thus, method of the present invention can obtain not containing the rare-earth isoprene rubber of gel, and can effectively reduce glue viscosity.
Embodiment 6
(1) polymerizing catalyst is rare earth catalyst, and solvent is hexane, and control polymerization temperature is 30-50 DEG C, polymerization pressure 0.3-0.4Mpa, and after polymerization-stable, the content obtaining polyisoprene is the polymerization glue of 13.6 % by weight, and viscosity is 99453cp;
(2) under agitation, agitation condition comprises: stirring velocity 4Hz, the hexane solution that often liter contains 1.5g oxidation inhibitor 1520 and 1.5g antioxidant 1076 is added in glue surge tank, add that total amount is polyisoprene quality 0.6 % by weight of oxidation inhibitor 1520 and antioxidant 1076, the speed that always adds of oxidation inhibitor 1520 and antioxidant 1076 is 0.3g/ (min ﹒ 100g polymkeric substance), carry out termination reaction, the glue character after termination and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 6.
Comparative example 6
Step (1) is identical with embodiment 6, unlike: use the hexane solution that oxidation inhibitor 1520 and oxidation inhibitor 1706 total concn are 300g/L as terminator solution (ratio of two kinds of oxidation inhibitor is identical with embodiment 6) in step (2), all the other conditions are all identical.Glue character and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 6.
Table 6
Data from table 6, can find out the rubber mechanical property that embodiment 6 and comparative example 6 obtain and quality index roughly the same, but not containing gel in the dry glue of embodiment 6, and the rubber of comparative example 6 contains the gel of definite composition, increases the difficulty of post-treatment to a certain extent.And the rubber gelatin viscosity of the rubber gelatin viscosity comparative example far away 6 of embodiment 6 is low, illustrates thus, method of the present invention can obtain not containing the rare-earth isoprene rubber of gel, and can effectively reduce glue viscosity.
Embodiment 7
(1) polymerizing catalyst is rare earth catalyst, and solvent is hexane, and control polymerization temperature is 30-50 DEG C, polymerization pressure 0.3-0.4Mpa, and after polymerization-stable, the content obtaining polyisoprene is the polymerization glue of 12.1 % by weight, and viscosity is 89553cp;
(2) under agitation, agitation condition comprises: stirring velocity 3Hz, often liter of hexane solution containing 3g oxidation inhibitor 1520 is added in glue surge tank, the add-on of oxidation inhibitor 1520 is 0.6 % by weight of polyisoprene quality, it is 0.3g/ (min ﹒ 100g polymkeric substance) that the hexane solution of oxidation inhibitor 1520 adds speed, carry out termination reaction, the glue character after termination and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 7.
Embodiment 8
Step (1) is identical with embodiment 7, unlike: in step (2), stirring velocity becomes 0.2Hz.Glue character and glue are through condensing the physical property characterization result of dry post-consumer polymer in table 7.
Table 7
Data from table 7, can find out the rubber mechanical property that embodiment 7 and embodiment 8 obtain and quality index roughly the same, but not containing gel in the dry glue of embodiment 7, and the rubber of embodiment 8 contains the gel of definite composition, increases the difficulty of post-treatment to a certain extent.
More than describe the preferred embodiment of the present invention in detail, but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. an olefin polymerization termination method, is characterized in that, the method comprises:
(1) carry out olefinic polyreaction, obtain polymeric solution to be stopped;
(2) under agitation, in polymeric solution described to be stopped, add terminator solution, described terminator solution is the organic solution of concentration lower than the aldehydes matter of 100g/L.
2. method according to claim 1, wherein, the organic solution of described terminator solution to be concentration the be aldehydes matter of 0.1-50g/L.
3. method according to claim 2, wherein, the organic solution of described terminator solution to be concentration the be aldehydes matter of 1-3g/L.
4. according to the method in claim 1-3 described in any one, wherein, described aldehydes matter is 4,6-dioctyl thiomethyl ortho-cresol, 2,6-di-tert-butyl-4-methy phenol and β-(3,5-di-tert-butyl-hydroxy phenyl) one or more in the positive octadecanol ester of propionic acid, the solvent phase that the organic solvent in the organic solution of described aldehydes matter and polyreaction use with.
5. according to the method in claim 1-3 described in any one, wherein, described aldehydes matter is 4,6-dioctyl thiomethyl ortho-cresol and β-(3,5-di-tert-butyl-hydroxy phenyl) mixture of the positive octadecanol ester of propionic acid, the weight ratio of the two is 0.1-10:1.
6. according to the method in claim 1-3 described in any one, wherein, the speed that adds of described terminator solution is 0.3-0.6g/ (min ﹒ 100g polymkeric substance).
7. according to the method in claim 1-3 described in any one, wherein, described agitation condition comprises: stirring velocity is 1-10Hz.
8. in polymeric solution to be stopped according to the method in claim 1-3 described in any one, wherein, the content of polymkeric substance is 10-20 % by weight.
9. according to the method in claim 1-3 described in any one, wherein, described in step (1), olefinic polyreaction carries out as follows:
Under olefin polymerization conditions, under chain initiator, solvent exist, alkene is contacted with olefin polymerization catalysis.
10. method according to claim 9, wherein, described alkene is the conjugated diene of C4-C6; Described solvent is aliphatic saturated hydrocarbon and/or alicyclic hydrocarbon; Described olefin polymerization catalysis is one or more in rare earth catalyst, Titanium series catalyst and lithium-based catalyst.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109957048A (en) * | 2017-12-14 | 2019-07-02 | 中国石油化工股份有限公司 | Halogenation monoolefine-conjugated diene copolymer solution preparation method |
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Application publication date: 20150520 |