CN1037848C - Production of butadiene-styrene block copolymer - Google Patents
Production of butadiene-styrene block copolymer Download PDFInfo
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- CN1037848C CN1037848C CN95107917A CN95107917A CN1037848C CN 1037848 C CN1037848 C CN 1037848C CN 95107917 A CN95107917 A CN 95107917A CN 95107917 A CN95107917 A CN 95107917A CN 1037848 C CN1037848 C CN 1037848C
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Abstract
The present invention relates to a method of preparing a butadiene-styrene block copolymer. The present invention prepares a butadiene-styrene copolymer with a styrene homopolymerization block, a butadiene homopolymerization block, a butylbenzene atactic copolymerization block and a styrene homopolymerization block by a high temperature polymerization method; the product has the advantages of high elongation rate and proper melt index. The method of the present invention has the advantages of easy operation and high productive efficiency; the obtained product can be used in various application fields of general butadiene-styrene block copolymers. The obtained product can be especially used as plastic modifying agents, etc.
Description
The present invention relates to a kind of manufacture method of butadiene-styrene block copolymer, particularly relate to a kind of preparation method who has high elongation rate, suitable melting index, reaches the butadiene-styrene block copolymer of certain degree of hardness.
As everyone knows, adopt three-step approach or coupling method to produce the block butylbenzene copolymer, need three steps of branch to feed in raw material at least, the reaction times is more than 1～2 hour.Two steps of bibliographical information are mixed reinforced method, though can reduce once reinforced operation, because of the performance of its product performance not as the aforesaid method products obtained therefrom, thereby fail to realize suitability for industrialized production.
U.S. Pat 4600749 provides that a kind of what improve elongation, oil-proofness is the butylbenzene copolymer manufacture method of four or six blocks at least, its temperature of reaction is usually at 30～100 ℃, reaction times is very long, particularly when preparation above high elongation rate of six blocks or oil resistant butadiene-styrene block copolymer, process complexity, production efficiency are not high.
The object of the present invention is to provide a kind of manufacture method of simple to operation, butadiene-styrene block copolymer rapidly and efficiently, this method is particularly suitable for the manufacturing of high elongation rate butadiene-styrene block copolymer thermoplastic elastomer.
The present invention finds, suitably improves and the controlled polymerization temperature, can in controlled scope polymerization rate obviously be increased, thereby significantly shorten polymerization time, enhances productivity greatly.Simultaneously, improve polymerization temperature and also can impel the random copolymerization of vinylbenzene and divinyl, thereby form long random styrene-butadiene rubber block, it is different from the excessive block of usually said gradation type.Owing to the existence of this random styrene-butadiene rubber block, improved the elongation of product, improved the performance of product.
Therefore, purpose of the present invention can be by realizing in the method that surpasses the high temperature polymerization reaction under the conventional polymerization temperature.Butylbenzene benzene segmented copolymer manufacture method of the present invention comprises the steps:
(1) in polymerization reactor, adds inert solvent, first vinylbenzene and initiator organolithium compound respectively, under suitable polymerization temperature, carry out the first step polyreaction;
(2) after the first step reaction finishes, add divinyl, second batch of vinylbenzene again, under suitable polymerization temperature, carry out the second step polyreaction;
(3) after second step, reaction finished, add terminator, finish reaction.
As required, carrying out for second when reaction step, also can suitably add the initiator organolithium compound.
If needed, after second step, reaction was finished, can be that also identical polymerization temperature of second step continues to divide many endorsements solely to add vinylbenzene or divinyl down, perhaps adds vinylbenzene and divinyl, simultaneously to form segmented copolymer.Add in the process of polymerization single polymerization monomer in above-mentioned continuation, also can add an amount of initiator organolithium compound simultaneously.
Said polymerization reactor can be various reaction flasks, or has the metal polymerization reaction kettle of stirring.
Said vinylbenzene and divinyl are the polymerization-grade monomer, with preceding drying again and remove impurity and handle.In the present invention, the vinylbenzene of first adding (being designated as S1) is 1/1.0～1/1.5 (weight ratio) with the feeding quantity of the vinylbenzene (being designated as S2) of second batch of adding than (being designated as S1/S2), be preferably 1/1.1～1/1.3 (weight ratio), the feed molar ratio of vinylbenzene (being designated as S) total amount and divinyl (being designated as B) total amount (be designated as S total/B is total) is 10/90～90/10 (weight ratio), is preferably 25/75～75/25 (weight ratio).
Said initiator organolithium can be alkyl lithium compounds, for example n-Butyl Lithium, s-butyl lithium etc.The add-on of organolithium is by the molecular weight decision of required polymkeric substance.The molecular weight of polymkeric substance of the present invention is 10000～500000, can determine the consumption of organolithium thus.Mentioned as the front, in the present invention, also can in the reaction of second step, add basic lithium.Add the segmented copolymer that organolithium can form two kinds of structures, the elongation of product is further improved, have higher using value.In the present invention, having added basic lithium generally is that organolithium is added in two batches, the organolithium of first adding (being designated as Li1) is generally 0.01～0.30 (mol ratio) with the amount ratio (being designated as Li2/Li1) of the organolithium (being designated as Li2) of second batch of adding, is preferably 0.05～0.2 (mol ratio).Obviously, organolithium also can divide more batches of addings in the present invention.
Said inert solvent can be alkane, naphthenic hydrocarbon, aromatic hydrocarbons or its mixture, for example hexane, heptane, hexanaphthene etc.
Said terminator is for polyreaction terminator commonly used, as water, methyl alcohol, ethanol or Virahol etc.
Said suitable polymerization temperature is 60 ℃～100 ℃ for the first step polyreaction, is preferably 70 ℃～90 ℃; For 60 ℃～150 ℃ of the second step polyreactions, be preferably 80 ℃～140 ℃.
In the preparation process of butadiene-styrene block copolymer of the present invention, need not add polar compound as activator, thereby simplify polymerization process, particularly help the carrying out of solvent recuperation process.Certainly, adding polar compound in preparation process also is fine.Said polar compound is for making common used polar compound, for example tetrahydrofuran (THF), glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dme, tetraethyleneglycol dimethyl ether and tetramethyl quadrol etc. in the butylbenzene copolymer.
Butadiene-styrene block copolymer manufacture method of the present invention equally also is applicable to monovinylarene and the segmented copolymer of conjugated diene, for example vinylbenzene and isoprene block copolymer, vinyl toluene and butadiene block copolymer, vinyl toluene and the isoprene copolymer etc. of making other.
Key of the present invention just is under higher temperature range condition, in polymerization process, add in the stage of vinylbenzene and divinyl, at first form the butadiene homopolymerization block, the reaction heat of polymerizing butadiene process not only need not removed, and can utilize it to improve the polymeric kettle temperature, impel in the butadiene homopolymerization later stage because high temperature changes divinyl and cinnamic random copolymerization reaction over to formation random styrene-butadiene rubber block, along with divinyl is all finished conversion, generate vinylbenzene homopolymerization block at last.We know that the add-on of monomer and solvent is determined in the polymerization process, so the thermal capacitance of corresponding polymerization reaction heat and polymerization system is certain, then the temperature rise of polymer fluid is certain.Therefore, difference along with the initial polymerization reaction temperature, with causing secondary polymerization reaction temperature difference, that is to say that process can be controlled the temperature of random copolymerization reaction by control initial polymerization temperature in polymerization, thereby the length of the random copolymerization of butylbenzene block of control and the quality of control product can be carried out.
Method of the present invention also can adopt high temperature reactive measures such as similar gradual change temperature control method, sectional temperature-controlled mode except that with above-mentioned not removing the hot natural heating mode, or constant temperature segmentation reaction under higher temperature.Be the best wherein, have advantages such as efficient energy-saving and simplified control in (adiabatic relatively) mode that heats up naturally of not removing reaction heat.
Method gained butadiene-styrene block copolymer of the present invention can have high elongation and suitable hardness and melting index, particularly still has high elongation and suitable hardness and melting index in multipolymer under the styrene content condition with higher.The prepared butadiene-styrene block copolymer of method of the present invention can be used for the various Application Areass of general butadiene-styrene block copolymer, for example tackiness agent or asphalt modifier etc., be particularly useful for to have the occasion of high elongation rate and suitable melting index, for example be used as plastic modifier etc.
The technological process of butadiene-styrene block copolymer manufacture method of the present invention is comparatively simple, polymerization velocity is fast, its the first step is reacted and can be made transformation efficiency reach 100% in about 3 minutes, and the transformation efficiency of the second step reaction reaches 100% and only needs about 6 minutes, whole polymerization time can foreshorten to about 10 minutes, thereby had improved plant factor and production efficiency greatly.
Below will the present invention is described in further detail by embodiment, but the present invention is not limited to this.
Embodiment 1
With refining nitrogen 10 liters of stainless steel polymeric kettles are replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add the 200g drying respectively and eliminate vinylbenzene, the 6000ml drying of impurity and eliminate hexanaphthene, and the 16.5ml n-Butyl Lithium of impurity, under 82～87 ℃, carry out the first step reaction.After 2.9 minutes, the first step reaction is finished, and then in still, add the 220.0g drying and eliminate vinylbenzene, the 580g drying of impurity and eliminate divinyl, the 500ml drying of impurity and eliminate the hexanaphthene of impurity, under 84～120 ℃, carry out the reaction of second step.After 4.9 minutes, the reaction of second step is finished, and adds terminator immediately and finishes reaction.The gained polymerization product after tested, its elongation is 1052%, shore hardness is 84, melting index is 13.3g/10min.
Comparative example 1
With refining nitrogen 10 liters of stainless steel polymeric kettles are replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add the 200g drying respectively and eliminate vinylbenzene, the 6000ml drying of impurity and eliminate hexanaphthene, and the 16.5ml n-Butyl Lithium of impurity, under 82～87 ℃, carry out the first step reaction.After 3.0 minutes, the first step reaction is finished, and then in still, add the 220.0g drying and eliminate vinylbenzene, the 580g drying of impurity and eliminate divinyl, the 500ml drying of impurity and eliminate the hexanaphthene of impurity, under 80～110 ℃, carry out the reaction of second step.After 6.3 minutes, the reaction of second step is finished, and adds terminator immediately and finishes reaction.The gained polymerization product after tested, its elongation is 769%, shore hardness is 92, melting index is 1.33g/10min.
Comparative example 2
With refining nitrogen 10 liters of stainless steel polymeric kettles are replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add the 200g drying respectively and eliminate vinylbenzene, the 6000ml drying of impurity and eliminate hexanaphthene, 0.5ml tetrahydrofuran (THF), and the 19.0ml n-Butyl Lithium of impurity, under 60 ℃, carry out the first step reaction.After 30 minutes, the first step reaction is finished, and adds the 580g drying then and eliminate the divinyl of impurity, carry out the reaction of second step under 90 ℃ in still.Through after 60 minutes, the reaction of second step is finished again, adds the 220.0g drying then immediately and eliminates vinylbenzene, the 500ml drying of impurity and eliminate the hexanaphthene of impurity, then carries out three-step reaction under 80 ℃.After 30 minutes, three-step reaction is finished, and adds terminator immediately and finishes reaction.The gained polymerization product is tested, and its elongation is 720%, and it is 96 that Shao Shi just spends, and melting index is 0.1g/10min.
Embodiment 2
With refining nitrogen 5 liters of stainless steel polymeric kettles are replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add the 120g drying respectively and eliminate vinylbenzene, the 2750ml drying of impurity and eliminate hexanaphthene, and the 15.7ml n-Butyl Lithium of impurity, under 82～90 ℃, carry out the first step reaction.After 2.5 minutes, the first step reaction is finished, and then in still, add the 132.5g drying and eliminate vinylbenzene, the 347.5g drying of impurity and eliminate divinyl, the 500ml drying of impurity and eliminate the hexanaphthene of impurity, and the 1.0ml n-Butyl Lithium, under 81～125 ℃, carry out the reaction of second step.After 4.3 minutes, the reaction of second step is finished, and adds terminator immediately and finishes reaction.The gained polymerization product is tested, and its elongation is 1064%, and shore hardness is 88, and melting index is 2.28g/10min.
Embodiment 3
With refining nitrogen 5 liters of stainless steel polymeric kettles are replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add the 115g drying respectively and eliminate vinylbenzene, the 2750ml drying of impurity and eliminate hexanaphthene, and the 8.4ml n-Butyl Lithium of impurity, under 78～90 ℃, carry out the first step reaction.After 3.3 minutes, the first step reaction is finished, and then in still, add the 137.5g drying and eliminate vinylbenzene, the 347.5g drying of impurity and eliminate divinyl, the 500ml drying of impurity and eliminate the hexanaphthene of impurity, and the 2.0ml n-Butyl Lithium, under 74～108 ℃, carry out the reaction of second step.After 8.1 minutes, the reaction of second step is finished, and adds terminator immediately and finishes reaction.The gained polymerization product is tested, and its elongation is 897%, and shore hardness is 89, and melting index is 9.5g/10min.
Embodiment 4
With refining nitrogen 5 liters of stainless steel polymeric kettles are replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add the 115g drying respectively and eliminate vinylbenzene, the 2750ml drying of impurity and eliminate hexanaphthene, and the 8.4ml n-Butyl Lithium of impurity, under 82～90 ℃, carry out the first step reaction.After 3.0 minutes, the first step reaction is finished, and then in still, add the 137.5g drying and eliminate vinylbenzene, the 347.5g drying of impurity and eliminate divinyl, the 500ml drying of impurity and eliminate the hexanaphthene of impurity, and the 2.0ml n-Butyl Lithium, under 80～118 ℃, carry out the reaction of second step.After 5.5 minutes, the reaction of second step is finished, and adds terminator immediately and finishes reaction.The gained polymerization product is tested, and its elongation is 993%, and shore hardness is 88, and melting index is 18.1g/10min.
Embodiment 5
With refining nitrogen 5 liters of stainless steel polymeric kettles are replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add the 115g drying respectively and eliminate vinylbenzene, the 2750ml drying of impurity and eliminate hexanaphthene, the 15.3ml n-Butyl Lithium of impurity, under 84～90.5 ℃, carry out the first step reaction.After 2.5 minutes, the first step reaction is finished, and then in still, add the 137.5g drying and eliminate vinylbenzene, the 347.5g drying of impurity and eliminate divinyl, the 500ml drying of impurity and eliminate the hexanaphthene of impurity, and the 2.0ml n-Butyl Lithium, under 83～126 ℃, carry out the reaction of second step.After 4.1 minutes, the reaction of second step is finished, and adds terminator immediately and finishes reaction.The gained polymerization product is tested, and its elongation is 1053%, and shore hardness is 85, and melting index is 18.6g/10min.
Embodiment 6
With refining nitrogen 5 liters of stainless steel polymeric kettles are replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add the 120g drying respectively and eliminate vinylbenzene, the 2750ml drying of impurity and eliminate hexanaphthene, the 16.9ml n-Butyl Lithium of impurity, under 82～91.5 ℃, carry out the first step reaction.After 2.5 minutes, the first step reaction is finished, and then in still, add the 132.5g drying and eliminate vinylbenzene, the 347.5g drying of impurity and eliminate divinyl, the 500ml drying of impurity and eliminate the hexanaphthene of impurity, and the 2.0ml n-Butyl Lithium, under 82～124.5 ℃, carry out the reaction of second step.After 4.6 minutes, the reaction of second step is finished, and adds terminator immediately and finishes reaction.The gained polymerization product is tested, and its elongation is 1027%, and shore hardness is 90, and melting index is 6.26g/10min.
Claims (3)
1. the preparation method of a butadiene-styrene block copolymer is characterized in that this preparation method comprises the steps:
1) in polymerization reactor, adds inert solvent, first vinylbenzene and initiator organolithium compound, under 60～100 ℃, carry out the first step reaction;
2) after the first step reaction finishes, add divinyl and second batch of vinylbenzene again, under 60～150 ℃, carry out the reaction of second step;
3) after second step, reaction finished, add terminator, finish reaction.
2. the preparation method according to the said butadiene-styrene block copolymer of claim 1 is characterized in that the temperature of said the first step reaction is 70～90 ℃.
3. the preparation method according to claim 1 or 2 said butadiene-styrene block copolymers is characterized in that the temperature of said second step reaction is 80～140 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107917A CN1037848C (en) | 1995-08-04 | 1995-08-04 | Production of butadiene-styrene block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107917A CN1037848C (en) | 1995-08-04 | 1995-08-04 | Production of butadiene-styrene block copolymer |
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| Publication Number | Publication Date |
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| CN1123797A CN1123797A (en) | 1996-06-05 |
| CN1037848C true CN1037848C (en) | 1998-03-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN95107917A Expired - Lifetime CN1037848C (en) | 1995-08-04 | 1995-08-04 | Production of butadiene-styrene block copolymer |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0704674A2 (en) * | 2007-12-14 | 2009-08-11 | Petroflex Ind E Com S A | process for the preparation of 1,3-butadiene and styrene copolymer containing in its main chain random segment, followed by block with differentiated structure of the homopolymeric or copolymeric main chain, functionalized and product obtained from it |
| CN102887980B (en) * | 2011-07-20 | 2015-04-22 | 中国石油化工集团公司 | Styrene-butadiene copolymer as well as preparation method and application thereof |
| CN105985488B (en) * | 2015-02-03 | 2018-08-17 | 中国石油化工股份有限公司 | Butylbenzene copolymer and preparation method thereof and rubber composition and vulcanized rubber |
| CN107236101A (en) * | 2016-03-29 | 2017-10-10 | 中国石油化工股份有限公司 | SB and preparation method thereof and application of the SB in sole |
| CN112812250B (en) * | 2021-01-06 | 2023-08-29 | 宁波金海晨光化学股份有限公司 | Preparation method of styrene thermoplastic elastomer |
| CN114685740A (en) * | 2022-04-25 | 2022-07-01 | 宁波金海晨光化学股份有限公司 | Preparation method of styrene thermoplastic elastomer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4089913A (en) * | 1974-01-10 | 1978-05-16 | Sumitomo Chemical Company, Limited | Process for producing transparent block copolymer resin |
| US5256736A (en) * | 1991-05-08 | 1993-10-26 | Phillips Petroleum Company | Tapered block copolymers of conjugated dienes and monovinylarenes |
| EP0654488A1 (en) * | 1993-11-15 | 1995-05-24 | Phillips Petroleum Company | Tapered block copolymers of monovinylarenes and conjugated dienes |
| US5438103A (en) * | 1994-03-23 | 1995-08-01 | Phillips Petroleum Company | Block copolymers of monovinylaromatic and conjugated diene monomers |
-
1995
- 1995-08-04 CN CN95107917A patent/CN1037848C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4089913A (en) * | 1974-01-10 | 1978-05-16 | Sumitomo Chemical Company, Limited | Process for producing transparent block copolymer resin |
| US5256736A (en) * | 1991-05-08 | 1993-10-26 | Phillips Petroleum Company | Tapered block copolymers of conjugated dienes and monovinylarenes |
| EP0654488A1 (en) * | 1993-11-15 | 1995-05-24 | Phillips Petroleum Company | Tapered block copolymers of monovinylarenes and conjugated dienes |
| US5438103A (en) * | 1994-03-23 | 1995-08-01 | Phillips Petroleum Company | Block copolymers of monovinylaromatic and conjugated diene monomers |
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| CN1123797A (en) | 1996-06-05 |
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