CN109810209A - A kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers - Google Patents
A kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers Download PDFInfo
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Abstract
The present invention relates to Polymer Synthesizing fields, particularly disclose a kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers.The preparation method of the hydrogenated styrene-butadiene-styrene block copolymers; it is characterized by: under inert gas shielding; using organolithium as catalyst; styrene is placed in progress one-step polymerization reaction in cyclohexane solvent; composite construction regulator is added simultaneously; then addition butadiene carries out two sections of polymerization reactions, and styrene is added after the completion of polymerization and carries out three sections of copolyreaction, obtains adding the basic glue SBS of hydrogen；Using homogeneous rhodium series catalysts to adding hydrogen to carry out hydrogenation with basis glue SBS, product is obtained.Rationally, hydrogenation catalyst dosage is less for present invention process design, and catalyst activity and selectivity is high, and reaction condition is mild, product purity and high income, is suitable for wide popularization and application.
Description
(1) technical field
The present invention relates to Polymer Synthesizing field, in particular to a kind of hydrogenated styrene-butadiene-styrene block copolymers
Preparation method.
(2) background technique
Styrene-Butadiene-Styrene Block Copolymer (SBS) belongs to basic material, is widely used in rubber product, plastics
The big field of modifying agent, adhesive and asphalt modifier etc. four, due to containing double bond on its strand, weatherability and thermal stability are not
Foot, limits its application.Hydrogenated styrene-butadiene-styrene block copolymers (SEBS) are by the soft segment in SBS ---
Polybutadiene adds hydrogen to be saturated to form polyethylene-poly-1-butylene block, is a kind of widely used novel block copolymer, is more
The effective ways for the defects of mending SBS weatherability and insufficient thermal stability.Compared with SBS, SEBS has a series of excellent performances,
Such as heat-resisting oxygen, ozone resistance, uvioresistant, creep-resistant property, can be widely applied to modifying plastics, high polymer alloy, height
The fields such as performance sealant, adhesive and auto industry.
Block copolymer SBS mainly uses anionic solution polymerization method to synthesize, and passes through addition in polymerization process
Structure regulator adjusts its each block concentration, its is made to meet hydrogenation needs.After corresponding catalyst is added in active SBS,
It is passed through hydrogen and carries out selective hydrogenation, control the degree of hydrogenation on phenyl ring less than 5%, and butadiene segment degree of hydrogenation is greater than 98%, i.e.,
The SEBS that can be required.The research emphasis of hydrogen addition technology is the optimization of hydrogenation catalyst.
SBS, which adds hydrogen to study more catalyst, to be had: (1) traditional catalyst, traditional hydrogenation catalyst have heterogeneous and equal
Point of phase catalyst.1. heterogeneous catalysis be by VIII race's Metal Supported over celite, heterogeneous catalysis activity low and item
Part is harsh, need to carry out at high temperature under high pressure, causes polymer to decompose and is gelled with reaction system, causes energy consumption excessively high, simultaneous reactions
The influence of system viscosity and polymer steric hindrance also adversely affects catalyst activity, thus increase catalyst amount, and
And catalyst is also to be improved to conjugated diene unit hydrogenation selectivity.2. homogeneous catalyst, homogeneous catalyst system has transition
Metal carboxylate or alkoxide compound, such as the chela of complex compound and iron, cobalt and nickel that cobaltous dichloride and amide or urea are formed
The product that conjunction object etc., i.e. organo-metallic compound are reacted in a solvent with reducing agent, homogeneous catalyst activity is higher,
A small amount of catalyst can be obtained satisfied plus hydrogen effect under low-temp low-pressure, if the condition that selection is suitable, also can be improved catalyst
Selectivity, even if the unsaturated double-bond of conjugated diene unit preferentially adds hydrogen.But homogeneous catalyst also has a negative side, i.e.,
Homogeneous catalyst needs to mix and could sufficiently show under the premise of constantly pipetting product its activity immediately in its each ingredient, reappears
Property is poor.In addition homogeneous catalyst stability is poor, needs the extemporaneous preparation before adding hydrogen every time.(2) metallocene catalyst, metallocene
Hydrogenation catalyst is a kind of novel hydrogenation catalyst, is the hot spot studied at present, is the revolution of SBS hydrogen addition technology, it
The shortcomings that overcoming traditional hydrogenation technique, with the height that catalyst activity is high, concentration is low, dosage is few, reaction condition is mild, stable
Hydrogenation rate and fabulous degree of hydrogenation, hydrogenation reaction high repeatability and other advantages, make its residue in final polymeric articles
Content is extremely low, can save purification removing process, and simplification of flowsheet is reduced investment outlay.Recent domestic SEBS industry metaplasia
Production. art mostly uses metallocene hydrogenation catalyst, such as Ba Ling petrochemical industry, U.S. Shell, Japanese Asahi Chemical Industry etc..(3) noble metal
Complex compound catalyst, the noble metal homogeneous catalysis agent such as ruthenium (Ru), rhodium (Rh) because its high activity, highly selective and hydrogenation products without
Gelatin phenomenon is concerned, and the application in high polymer selective hydration receives more and more attention, and in recent years, noble metal is urged
Agent is mainly that ruthenium catalyst system is also used for SBS and adds hydrogen, it is shown that hydrogenation activity is high, reaction condition is mild, selectivity is good etc.
Advantage.
Recently as the exploitation and development of new catalyst, hydrogenation technique technology also has corresponding development.It is reported that China
In the research that SBS hydrogenation reaction forms SEBS, mainly using nickel system, cobalt system metal or luxuriant titanium as hydrogenation catalyst.
CN104226365A discloses a kind of preparation method of novel hydrogenation catalyst for synthesizing SEBS, which belongs to luxuriant titanium and urge
Change system.CN101423569A discloses the method for a kind of selection of styrene/conjugated diene polymers plus hydrogen, with bicyclic penta 2
Alkene titanium chloride is major catalyst, and hydrogenation reaction 1 hour, degree of hydrogenation was greater than 98%.CN1834113B discloses a kind of rhodium system catalysis
Agent is catalyzed the method for hydrotreating of conjugated diene in the presence of organic solvent-free.CN1865294A discloses a kind of hydrogenated styrene analog
The preparation method of block copolymer, the patent, to adding hydrogen-based plinth relatively to carry out catalytic hydrogenation, are processed using metallocene-titanium catalyst
The better SEBS of performance.Chlorination (triphenylphosphine) rhodium complex is used for acrylonitrile-butadiene-benzene second by British patent 2070023A
Carbon carbon selectivity is carried out in the unsaturated organic polymer of alkene copolymer etc. and adds hydrogen, and this method carries out in aqueous emulsion.
From the point of view of patent literature report and commercial practice, nickel system, cobalt system catalyst system catalysis SBS hydrogenation plus hydrogen
Time is longer, and degree of hydrogenation is lower, and luxuriant titanium catalyst system is not easy to store as hydrogenation catalyst, easy in inactivation, wants to reaction condition
Ask harsher.In recent years, noble metal catalyst be also applied to butylbenzene copolymer plus hydrogen, the noble metal catalysts such as Rh, Ru, Pd
Because of its high activity, the features such as highly selective and reaction condition is mild, especially contains in high polymer and easily polymerize with being reduced group
Object (such as nitrile rubber) in selective hydrogenation application it is more and more extensive.SBS is carried out plus hydrogen prepares SEBS block copolymer,
Seek the catalyst system that a kind of activity is high, hydrogenation degree is high, selectivity is good, not only there is important theory significance, but also there is reality
Industrial application background, studying at present more is catalyzed by ruthenium complexes system, and adds hydrogen for SBS to Rhodium Complexes Catalyzed system
Research have not been reported.
(3) summary of the invention
That in order to compensate for the shortcomings of the prior art, the present invention provides a kind of catalyst amounts is few, activity and selectivity is high, reaction item
The preparation method of the mild hydrogenated styrene-butadiene-styrene block copolymers of part.
The present invention is achieved through the following technical solutions:
A kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers, includes the following steps:
(1) under inert gas shielding, using organolithium as catalyst, it is anti-that styrene is placed in progress one-step polymerization in cyclohexane solvent
It answers, while composite construction regulator is added, butadiene is then added and carries out two sections of polymerization reactions, benzene second is added after the completion of polymerization
Alkene carries out three sections of copolyreaction, obtains adding the basic glue SBS of hydrogen；
(2) product is obtained to adding hydrogen to carry out hydrogenation with basis glue SBS using homogeneous rhodium series catalysts.
The present invention is added composite construction regulator to prepare and adds hydrogen-based plinth glue, use in the presence of organic lithium initiator
Homogeneous rhodium series catalysts are to adding the selection of hydrogen-based plinth glue plus hydrogen；Composite construction regulator can carry out spirit to the structure for adding hydrogen-based plinth glue
Quick adjusting, composite construction regulator does not influence hydrogenation reaction almost without residual after reaction.
In step (1), inert gas is nitrogen, and organolithium is n-BuLi, and butadiene is polymer grade butadiene, composite junction
Structure regulator is the structure regulator that ether compound and aminated compounds compound.
Wherein, the ether compound is glycol ether or propylene glycol, and aminated compounds is tetramethyl-ethylene base diamines
Or pentamethyldivinyltriamine；The compounding molar ratio of ether compound and aminated compounds is 0.1-5.0.
The molar ratio of composite construction regulator and organolithium is 0.1-1.0, adds the hydrogen to be with the molecular weight of basis glue SBS
65000-150000, wherein the mass ratio of butadiene and styrene is 30:70-40:60, and the mass fraction of vinyl is 30-
70%。
In step (2), the homogeneous rhodium series catalysts are made of the major catalyst that molar ratio is 1-15 and co-catalyst,
In, major catalyst is rhodium compound, and co-catalyst is phosphine compound.
The preparation method of the homogeneous rhodium series catalysts is to be placed in a reaction flask phosphine compound, is dissolved with ethyl alcohol, nitrogen
Heating Water after displacement three times is stirred at reflux to being completely dissolved；After rhodium compound is dissolved with ethyl alcohol, importing fills phosphine compound
Reaction flask in, constant temperature water bath reaction after, reaction product is filtered, washed in nitrogen atmosphere to get product.
Wherein, it is trimethyl that rhodium compound, which is four carbonyl of dichloro, two rhodium, radium chloride, rhodium caprylate or rhodium nitrate, phosphine compound,
Phosphine, triphenylphosphine, tri isopropyl phosphine or tributylphosphine.
Add hydrogen basis glue SBS in the presence of homogeneous rhodium series catalysts, is passed through pressurized with hydrogen, is heated to hydrogen temperature under stirring
Degree carries out hydrogenation reaction, and homogeneous rhodium series catalysts dosage is the 0.01-0.3%, hydrogenation temperature 40-180 of basic glue SBS mass
DEG C and the love time be 20-300min, hydrogenation pressure 0.5-3.5MPa.
The present invention, as hydrogenation catalyst, controls hydrogenation temperature, hydrogenation time, hydrogenation pressure using homogeneous rhodium series catalysts
With the reaction conditions such as speed of agitator, the SEBS that degree of hydrogenation is greater than 99% can be prepared.
Process provided by the invention, has the advantages that
(1) plus the microstructure of hydrogen-based plinth glue SBS has decisive influence to hydrogenation reaction, is prepared by SEBS to its structure control
Key link in journey, structure regulator dosage used in this method is lower, adjusts high sensitivity to structure；
(2) this method reaction condition is mild, and less than 70 DEG C, hydrogenation pressure controls within 1MPa hydrogenation temperature；
(3) the catalyst amount base of this method, reaction time are no more than 1 hour, degree of hydrogenation >=99%.
Rationally, hydrogenation catalyst dosage is less for present invention process design, and catalyst activity and selectivity is high, reaction condition temperature
With product purity and high income, suitable for wide popularization and application.
(4) specific embodiment
The present invention will be further detailed in the following examples, but the range being not intended to limit the present invention.
Embodiment 1:
(common N under inert gas protection2Make protection gas), it is original with the existing polymer grade butadiene of company, self-produced styrene
Material selects glycol ether/tetramethyl-ethylene base diamines compounding structure regulator using n-BuLi as anionic catalyst,
In the item that monomer ratio (St/Bd) is 30/70,5 hours reaction time, 60 DEG C of reaction temperature, structure regulator/catalyst are 0.1
The basic glue SBS for being suitble to add hydrogen is synthesized under part, calculating 1,2 structural contents in SBS product through infra-red sepectrometry is 28.7%.
Embodiment 2:
Experimentation is with embodiment 1, and structure regulator selects propylene glycol/pentamethyldivinyltriamine, knot in experimentation
Structure regulator/Li is 1.0, and calculating 1,2 structural contents in SBS product through infra-red sepectrometry is 65.7%.
Embodiment 3:
Experimentation is with embodiment 1, and structure regulator selects propylene glycol/pentamethyldivinyltriamine, knot in experimentation
Structure regulator/Li is 0.5, and calculating 1,2 structural contents in SBS product through infra-red sepectrometry is 45.2%.
Embodiment 4:
(common N under inert gas protection2Make protection gas), it is original with the existing polymer grade butadiene of company, self-produced styrene
Material selects glycol ether/tetramethyl-ethylene base diamines compounding structure regulator using n-BuLi as anionic catalyst,
Under conditions of monomer ratio (St/Bd) is 30/70, reaction 5 hours, 60 DEG C of reaction temperature, structure regulator/catalyst are 0.5
Synthesis is suitble to plus the basic glue SBS of hydrogen.
It takes a certain amount of ligand tri isopropyl phosphine that reaction flask is added, is dissolved with ethyl alcohol, take a certain amount of rhodium compound chlorination
Rhodium is poured into after being dissolved with ethyl alcohol in the reaction flask for filling phosphine compound, isothermal reaction certain time, by reaction product in nitrogen gas
It is filtered, washed in atmosphere, can be obtained and add hydrogen final catalyst.
It will add hydrogen-based plinth glue SBS in the presence of above-mentioned catalyst, and be passed through pressurized with hydrogen, be heated to hydrogenation temperature under stiring
Hydrogenation reaction is carried out, hydrogenation catalyst dosage is 0.02g/100gSBS, and 50 DEG C of hydrogenation temperature, hydrogenation time 50min adds hydrogen pressure
Power 1.0MPa is 98.9% using nuclear magnetic resonance spectroscopy test degree of hydrogenation.
Embodiment 5:
Ligand is become triphenylphosphine in catalyst preparation process with embodiment 4 by experimentation, and rhodium based compound becomes octanoic acid
Rhodium, other conditions are constant, are 99.8% using nuclear magnetic resonance spectroscopy test degree of hydrogenation.
Embodiment 6:
Ligand is become tributylphosphine in catalyst preparation process, rhodium based compound becomes nitric acid with embodiment 4 by experimentation
Rhodium, other conditions are constant, are 97.6% using nuclear magnetic resonance spectroscopy test degree of hydrogenation.
Embodiment 7:
Experimentation is with embodiment 5, and it is 0.3g/100gSBS that experimentation, which changes catalyst amount, and other conditions are constant, utilizes
It is 99.9% that nuclear magnetic resonance spectroscopy, which tests degree of hydrogenation,.
Embodiment 8:
Experimentation changes 180 DEG C of hydrogenation temperature with embodiment 5, experimentation, and other conditions are constant, utilize nuclear magnetic resonance spectroscopy
Testing degree of hydrogenation is 96.9%.
Embodiment 9:
Experimentation is with embodiment 5, and it is 300min that experimentation, which changes hydrogenation time, and other conditions are constant, utilize nuclear magnetic resonance
Hydrogen spectrum test degree of hydrogenation is 99.9%.
Embodiment 10:
Experimentation is with embodiment 5, and it is 3.5MPa that experimentation, which changes hydrogenation pressure, and other conditions are constant, utilize nuclear magnetic resonance
Hydrogen spectrum test degree of hydrogenation is 99.5%.
Claims (8)
1. a kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers, it is characterized in that, include the following steps:
(1) under inert gas shielding, using organolithium as catalyst, styrene is placed in progress one-step polymerization reaction in cyclohexane solvent,
Composite construction regulator is added simultaneously, butadiene is then added and carries out two sections of polymerization reactions, styrene is added after the completion of polymerization
Three sections of copolyreaction are carried out, obtain adding the basic glue SBS of hydrogen；(2) using homogeneous rhodium series catalysts to add hydrogen basis glue SBS into
Row hydrogenation, obtains product.
2. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 1, feature
Be: in step (1), inert gas is nitrogen, and organolithium is n-BuLi, and butadiene is polymer grade butadiene, composite construction
Regulator is the structure regulator that ether compound and aminated compounds compound.
3. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 1, feature
Be: in step (1), the molar ratio of composite construction regulator and organolithium is 0.1-1.0, adds the molecule of the basic glue SBS of hydrogen
Amount is 65000-150000, wherein the mass ratio of butadiene and styrene is 30:70-40:60, and the mass fraction of vinyl is
30-70%。
4. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 1, feature
Be: in step (2), the homogeneous rhodium series catalysts are made of the major catalyst that molar ratio is 1-15 and co-catalyst, wherein
Major catalyst is rhodium compound, and co-catalyst is phosphine compound.
5. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 1, feature
It is: in step (2), adds hydrogen basis glue SBS in the presence of homogeneous rhodium series catalysts, be passed through pressurized with hydrogen, stirs lower heating
Hydrogenation reaction is carried out to hydrogenation temperature, homogeneous rhodium series catalysts dosage is the 0.01-0.3% of basic glue SBS mass, hydrogenation temperature
It is 20-300min, hydrogenation pressure 0.5-3.5MPa for 40-180 DEG C and love time.
6. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 2, feature
Be: the ether compound is glycol ether or propylene glycol, and aminated compounds is tetramethyl-ethylene base diamines or pentamethyl
Diethylene triamine；The compounding molar ratio of ether compound and aminated compounds is 0.1-5.0.
7. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 4, feature
Be: the preparation method of the homogeneous rhodium series catalysts is to be placed in a reaction flask phosphine compound, is dissolved with ethyl alcohol, nitrogen is set
Heating Water after changing three times is stirred at reflux to being completely dissolved；After rhodium compound is dissolved with ethyl alcohol, importing fills phosphine compound
In reaction flask, after constant temperature water bath reaction, reaction product is filtered, washed in nitrogen atmosphere to get product.
8. the preparation method of the hydrogenated styrene-butadiene-styrene block copolymers according to claim 4 or 7, special
Sign is: the rhodium compound be four carbonyl of dichloro, two rhodium, radium chloride, rhodium caprylate or rhodium nitrate, phosphine compound be trimethyl-phosphine,
Triphenylphosphine, tri isopropyl phosphine or tributylphosphine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111157565A (en) * | 2020-01-20 | 2020-05-15 | 极晨智道信息技术(北京)有限公司 | Method for analyzing hydrogenation degree of styrene butadiene rubber SEBS (styrene-butadiene-styrene block copolymer) by utilizing nuclear magnetic resonance technology |
| CN111205416A (en) * | 2020-03-18 | 2020-05-29 | 山东润科化工股份有限公司 | Preparation method of styrene-butadiene-styrene block copolymer |
| CN113278119A (en) * | 2021-07-08 | 2021-08-20 | 广东众和高新科技有限公司 | Hydrogenated styrene-butadiene block copolymer and preparation method and application thereof |
| CN115895094A (en) * | 2022-10-27 | 2023-04-04 | 泉州匹克鞋业有限公司 | Composition for ultralight elastic sole and preparation method thereof |
| CN115947880A (en) * | 2023-03-10 | 2023-04-11 | 南京聚隆科技股份有限公司 | Preparation method of SEBS (styrene-ethylene-butadiene-styrene) by catalytic hydrogenation of ionic liquid-ruthenium/rhodium phosphine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111157565A (en) * | 2020-01-20 | 2020-05-15 | 极晨智道信息技术(北京)有限公司 | Method for analyzing hydrogenation degree of styrene butadiene rubber SEBS (styrene-butadiene-styrene block copolymer) by utilizing nuclear magnetic resonance technology |
| CN111205416A (en) * | 2020-03-18 | 2020-05-29 | 山东润科化工股份有限公司 | Preparation method of styrene-butadiene-styrene block copolymer |
| CN113278119A (en) * | 2021-07-08 | 2021-08-20 | 广东众和高新科技有限公司 | Hydrogenated styrene-butadiene block copolymer and preparation method and application thereof |
| CN115895094A (en) * | 2022-10-27 | 2023-04-04 | 泉州匹克鞋业有限公司 | Composition for ultralight elastic sole and preparation method thereof |
| CN115947880A (en) * | 2023-03-10 | 2023-04-11 | 南京聚隆科技股份有限公司 | Preparation method of SEBS (styrene-ethylene-butadiene-styrene) by catalytic hydrogenation of ionic liquid-ruthenium/rhodium phosphine |
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