CN105732867B - Rare-earth isoprene rubber solution polymerization method - Google Patents
Rare-earth isoprene rubber solution polymerization method Download PDFInfo
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Abstract
A kind of rare-earth isoprene rubber solution polymerization method, comprises the following steps：(1) hexane solvent and isoprene monomer obtain anhydrous and oxygen-free hexane solvent and isoprene monomer through physical absorption and chemical treatment；(2) anhydrous and oxygen-free isoprene monomer and a part of anhydrous and oxygen-free hexane, activator and homogeneous rare earth catalyst are dispersed in activation kettle, carry out priming reaction, form activation material；(3) activation material is directly entered in prepolymerization kettle, is carried out isoprene prepolymerization, is formed the prepolymerization reaction material containing unreacted monomer and polymer；(4) prepolymerization reaction material and another part anhydrous and oxygen-free hexane are directly entered is mixed in the polymerization reaction system that reactor is composed in series entirely by 3 double ribbons with self-operated type scraper plate, carry out isoprene polymerization reaction, (5) after polymerisation terminates, polymerizate is first sufficiently mixed with age resistor in high degree of dispersion device, is subsequently introduced glue carrying object and is coated on high viscose surface and is sent into the preparation cohesion of glue storage tank.
Description
Technical field
The present invention relates to synthetic rubber solution polymerization technique, and in particular to a kind of quick, high conversion, controllable rare earth are different
Penta rubber solutions polymerization.
Background technology
Isoprene rubber (cis-1,4-polyisoprene rubber, IR), complete entitled cis- Isosorbide-5-Nitrae-polyisoprene rubber,
It is a kind of synthetic rubber formed by isoprene through polymerisation in solution, there is the chemical composition similar to natural rubber, three-dimensional knot
Structure and physical and mechanical properties, be otherwise known as natural man-made rubber, can be used alone, can also with natural rubber or other synthesize
Rubber blending.It is the ideal material for substituting natural rubber in manufacture radial heavy duty tire, light truck radial-ply tyre, passenger tyre etc.,
Process industry articles for use, medical supplies and daily necessities are additionally operable to, such as：Rubber overshoes, cord ply compound, adhesive, sealant, electric wire,
Sports articles, medical instruments etc..
Isoprene rubber can be divided into lithium system isoprene rubber, titanium system isoprene rubber and Rare Earth isoprene rubber, wherein lithium system isoamyl
Rubber is that isoprene progress anionic solution polymerization under alkyl lithium initiator effect forms, and it is homogeneous body to have catalyst
System, activity are high, and the characteristics of no gel and kiss-coating, but cis- Isosorbide-5-Nitrae structural content is low (91~92%), and only kraton gathers at present
Compound company produces, mainly with natural rubber and to improve its processing characteristics；Industrial titanium system isoprene rubber mainly uses
TiCl4-AlR3And TiCl4The class catalyst system and catalyzing of-polyimides base aluminium alkane two, the former is widely used in the isoamyl of Russia, the U.S., Japan
Rubber industry produces, and has exited production neck with closing down for Italian process units with the experience of steady production for many years, the latter
Domain；Rare Earth isoprene rubber is that isoprene carries out continuous solution polymerization in the presence of rare earth series catalysts and formed.External
There are Russian Sterlitamak companies to build up a set of 10,000 tons/year of rare-earth isoprene rubber process units, it is domestic from 20th century 60
Age has begun to rare-earth isoprene rubber production technology research, has just built up more set rare-earth isoprene rubber works successively from after 2009
Industry device, production capacity reach 160,000 tons/year, such as：Period In Maoming Lu Hua Chemical Co., Ltd.s 1.5 ten thousand tons/year of isoprene rubber devices, green grass or young crops
Her 30,000 tons of rare earths of 30,000 tons/year of isoprene rubber devices of Cohan new material limited company and Shandong Shen Chi petrochemical industry Co., Ltd of island
Isoprene rubber device, but also do not supply product to market stable mass.Integrated comparative, titanium system isoprene rubber are the current world
The maximum isoprene rubber of upper production capacity, its yield accounts for more than the 95% of world's isoprene rubber total output, but catalyst is non-equal
Phase system, active ability highest need to be prepared under low temperature (- 78 DEG C)；Variable valency metal titanium ion in catalyst makes polymer colored,
And the oxidative degradation of polymer can be accelerated, the ageing-resistant performance of rubber is influenceed, needs water elution to remove；Product gel content is high, catalysis
Agent requires height (catalyst TiCl to equipment material4, Cl-Seriously corroded), quantity of three wastes is big and intractability is big.And rare earth isoamyl
Rubber product quality is more superior, and polymer color is shallow and quality is homogeneous, and catalyst amount is few and active height, catalyst residue pair
Polymer performance does not influence, it is not necessary to washes Removal of catalyst, process condition milder, quantity of three wastes is few and processing is more held
Easily.Examined from the production technology reliability of the performance and isoprene rubber of the product demand to isoprene rubber and isoprene rubber at present
Consider, new device selection rare-earth system production Technology of Isoprene Rubber is one of the development trend in future.
In existing industrial production technology, rare-earth isoprene rubber production technology and butadiene rubber production technology are essentially identical,
The kettle of generally use 3 series connection continuous solution polymerization process, increasing with the carry out polymerization system viscosity of reaction, this is just reaction
Heat is quickly moved out bringing very big difficulty, typically using adiabatic means control polymerization temperature, polymerization temperature is not carried out harsh
Control, last kettle temperature degree reach 70~80 DEG C, and between polymeric kettle and kettle interior reaction temperature gradient is big；Isoprene polymerization initial reaction stage
Stage glue easily causes the engineering problem such as kiss-coating and pipeline blocking, it is difficult to ensure that device long-period stable operation, prior art
It is to use first kettle one to open a standby scheme to carry out periodically switching to ensure device long-term operation.Gather accordingly, with respect to isoprene
Closing the process engineering problems such as the mass transfer reacted, heat transfer, glue conveying turns into the industrialized difficult point of isoprene rubber.
CN101838361 provides a kind of catalyst for preparing high Mooney rare-earth isoprene rubber and preparation method and for isoamyl two
Alkene polymerization, using the catalyst prepared by trifluoromethanesulfonic acid rare earth compounding and alkyl aluminum, catalyst amount is 8.20 ×
10-6~11.2 × 10-6Mol catalyst/gram monomer, with bench scale device, intermittent polyreaction 4~6 is small at 20~60 DEG C
When high Mooney isoprene rubber is made.
CN202054768 provides a kind of premix kettle for being used to produce isoprene rubber, and the agitating paddle of the reactor is oblique for four
Blade profile blade and screw type blade, it is scattered uneven in reaction mass to solve only polymerisation heterogeneous catalysis at initial stage
Problem.
CN101091901 provides a kind of helix stirred reactor of interior logical cryogen, enhances polymerization process and biography
Thermal process, polymeric reaction temperature are 20~100 DEG C, 10~40g/100ml of monomer concentration, monomer conversion 70% or so, polymerization
Thing is cis-Isosorbide-5-Nitrae-structural content 94.2~95.8%, molecular weight distribution 2.89~5.12.The technology does not refer to the defeated of high viscose
Send problem, monomer concentration and during too high conversion ratio in actual continuous production, glue conveying and cohesion post-processing difficulty are very big, work
Industryization is difficult.
As can be seen here, existing industrial production technology uses adiabatic means control polymeric reaction temperature substantially, not to isoamyl two
Alkene heat of polymerization is removed and strictly controlled；Research in existing patented technology on isoprene polymerization technology is concentrated mainly on different
Premixing process and structure of reactor during penta rubber production, it is therefore intended that solve the mixed problem of initial reaction stage material and carry
For a kind of reactor for improving reaction effect, preferable effect is achieved, but do not solved from industrialization amplification angle systematically
More kettle continuous polymerization initial reaction stability, high viscosity polymerization system heat of polymerization remove and reaction temperature is controllable and high viscosity thing
The engineering problems such as material conveying.
The content of the invention
Present invention aims to overcome that prior art is insufficient, there is provided a kind of high conversion for being suitable for rare-earth isoprene rubber
The controllable solution polymerization process of rate.
The rare-earth isoprene rubber solution polymerization method of the present invention, it is deep on the basis of existing synthetic rubber solution polymerization technique
The characteristics of entering to dissect this technology used catalyst, and taken into full account in the urgent need to address in rare-earth isoprene rubber industrial production
The engineering challenges such as reaction heat removal, kiss-coating and the conveying of high viscose.Obtained surely by priming reaction and monomer prepolymerization reaction
Fixed polymerization system, solve the problems, such as that polymerization initial stage glue wall built-up and pipeline block, ensure commercial plant continuous and steady operation；Adopt
With the paradigmatic system of the complete mixed reactor of the stirring of double ribbons with self-operated type scraper plate of multi-floating bodies, solves high viscous polymerization system
It is quick to move heat problem, it is controllable stable with product quality to realize polymerization temperature；By the association for optimizing rare earth catalyst and activator
Same-action, realize polymer molecular weight, molecular weight distribution and Mooney viscosity and regulate and control online, directly appointed according to user's request production
The isoprene rubber product of the meaning trade mark, and ensure product microstructure and the stabilization of macro property between batch；By introducing high viscose glue
Liquid carrying object, glue transporting resistance is reduced, efficiently solve the transportation problem of high viscose, reduce the difficulty of industry amplification
Degree.
The present invention provides a kind of rare-earth isoprene rubber solution polymerization method, comprises the following steps：
(1) hexane solvent and isoprene monomer obtain the anhydrous and oxygen-free of high purity through physical absorption and chemical treatment
Hexane solvent and isoprene monomer；
(2) anhydrous and oxygen-free isoprene monomer and a part of anhydrous and oxygen-free hexane, activator exist with homogeneous rare earth catalyst
It is dispersed in activation kettle, priming reaction is carried out, forms activation material；
(3) activation material is directly entered in prepolymerization kettle, progress isoprene prepolymerization, and control monomer conversion 5~
15%, form the prepolymerization reaction material containing unreacted monomer and polymer；
(4) prepolymerization reaction material and another part anhydrous and oxygen-free hexane are directly entered double with self-operated type scraper plate by 3
Ribbon is mixed in the polymerization reaction system that reactor is composed in series entirely, progress isoprene polymerization reaction, 45~55 DEG C of reaction temperature,
Control the first reactor monomer conversion 30~35%；In terms of monomeric charge gross mass, the second reactor monomer conversion 25~
30%；In terms of monomeric charge gross mass, the 3rd reactor monomer conversion 20~25%, control priming reaction rare earth catalyst with
The synergy of activator, prepares rare-earth isoprene rubber；
(5) after polymerisation terminates, polymerizate is discharged by the 3rd reactor, is first filled with age resistor in high degree of dispersion device
Divide mixing, be subsequently introduced glue carrying object and be coated on high viscose surface and be sent into the preparation cohesion of glue storage tank.
Wherein, activator described in step (2) is the mixture of diisobutylaluminium hydride and triisobutyl aluminium, and hydrogenation two is different
Butyl aluminium and triisobutyl aluminium mol ratio are preferably 0.1~10:1.
Glue carrying object is preferably water described in step (5).
A part of hexane dosage is preferably 46~56kg HX/100L described in step (2).
Rare earth catalyst described in step (2) is preferably rare earth neodymium coordination isoprene polymer.
Step (2) middle rare earth catalyst amount is preferably 0.5 × 10 in terms of unit interval isoprene feedstock quality-6~
1.0×10-6Mol catalyst/gram monomer；Activator level is preferably 0.06 in terms of unit interval isoprene inlet amount quality
~3.0%；Priming reaction temperature is preferably 10~40 DEG C, and soak time is preferably 1~10min.
Prepolymerization kettle is used by the frame type agitating blade with self-operated type scraper plate and multiple layers of vanes oar Combined type stirring in step (3)
Mix, for bottom agitator preferably with the frame type agitating blade of self-operated type scraper plate, kettle top agitator is preferably multiple layers of vanes oar.
Prepolymerization technology condition in step (3)：Pre-monomer concentration preferably 10~20kg IP/100L, prepolymerization temperature
Preferably 40~50 DEG C, prepolymerization time is preferably 20~30 minutes, and bottom speed of agitator is preferably 10~50 revs/min, top
Portion's speed of agitator is preferably 80~300 revs/min.
Another part hexane dosage is preferably 20~50kg HX/100L in step (4).
Age resistor described in step (5) is preferably to polymerize phenol and the double lauryl compounds of thio-2 acid, and its mass ratio is excellent
Elect 1 as:1~1:1.5, age resistor is preferably 0.1% with respect to rare-earth isoprene rubber quality meter, addition.
The present invention has following significant progressive and positive effect compared with prior art：
1. this technology has, catalyst amount is few, reaction speed is fast, production efficiency is high, polymerisation and polymer architecture can
The characteristics of control；
2. the polymerization system stablized by priming reaction and monomer prepolymerization reaction, solve polymerization initial stage glue wall built-up and
The problem of pipeline blocks, ensure commercial plant continuous and steady operation
3. using double ribbons stirring with self-operated type scraper plate, mixed reactor solves high viscous polymerization system mass-and heat-transfer entirely
Problem, it is controllable stable with product quality to realize polymerization temperature；
4. by introducing high viscose carrying object, solves the transportation problem of isoprene rubber industrialization high viscosity glue；
5. by the synergy of priming reaction rare earth catalyst and activator, realize that set of device coproduction series Mooney glues
Spend isoprene rubber product.
6. a technique simplifies the isoprene rubber technological process of production, energy consumption without glue washing step and MONOMER RECOVERY process
It is low with material consumption, and quantity of three wastes is few.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
The experimental method of unreceipted actual conditions in example, generally according to normal condition.
Monomer conversion in prepolymerization kettle：
In the present invention, monomer conversion in prepolymerization kettle is not particularly limited, generally activates material and be directly entered pre-polymerization
In kettle, isoprene prepolymerization is carried out, controls monomer conversion 5~15%, formation contains unreacted monomer and polymer
Prepolymerization reaction material；If controlling monomer conversion to be less than 5%, cause material viscosity too low, it is steady initial stage to influence polymerisation
It is qualitative；And monomer conversion is more than 15%, meeting material viscosity is too high, causes runaway reaction, has no other beneficial effects.
Polymerization reaction system：
In the present invention, the condition of polymerization reaction system is not particularly limited, in usual polymerization reaction system, carried out different
Pentadiene polymerisation, 45~55 DEG C of reaction temperature, control the first reactor monomer conversion 30~35%；It is total with monomeric charge
Quality meter, the second reactor monomer conversion 25~30%；In terms of monomeric charge gross mass, the 3rd reactor monomer conversion 20
~25%, the synergy of priming reaction rare earth catalyst and activator is controlled, prepares rare-earth isoprene rubber；
If reaction temperature is less than 45 DEG C, it is impossible to meets polymerization temperature requirement, temperature oligomerizing speed is slow, influences to gather
Compound yield；And temperature is higher than 55 DEG C, the cis- Isosorbide-5-Nitrae structural content of polymer is caused to reduce；
If controlling the first reactor monomer conversion to be less than 30%, the difficult control of polymerization reaction late stage temperature is caused；And control
The first reactor monomer conversion is made more than 35%, may polymerisation thermal discharge remove heat energy power beyond the first polymeric kettle,
Make heat of polymerization removal difficulty big, cause polymerisation out of control；
In terms of monomeric charge gross mass, if the second reactor monomer conversion is less than 25%, cause to polymerize total conversion
Low and increase third polymerization kettle heat of polymerization removes difficulty, influences reaction stability；And control the second reactor monomer conversion big
In 30%, may polymerisation thermal discharge remove heat energy power beyond the second polymeric kettle；
In terms of monomeric charge gross mass, if the 3rd reactor monomer conversion is less than 20%, cause to polymerize total conversion
It is low；The kettle conversion ratio fundamental reaction is complete, it is difficult to more than 25%
Activator：
In the present invention, activator is not particularly limited, activator is usually diisobutylaluminium hydride and triisobutyl
The mixture of aluminium, diisobutylaluminium hydride and triisobutyl aluminium mol ratio are 0.1~10:1；Selective hydrogenation diisobutyl aluminum and
For the mixture of triisobutyl aluminium as activator, benefit is can to improve catalyst activity and realize that polymer molecule characteristic regulates and controls；
If diisobutylaluminium hydride and triisobutyl aluminium mol ratio are less than 0.1:1, then diisobutylaluminium hydride dosage is very few, causes
Activation effect is poor；And diisobutylaluminium hydride and triisobutyl aluminium mol ratio are more than 10:1, then diisobutylaluminium hydride dosage
Excessively, cause polymer molecular weight too low, it is impossible to meet application requirement.
A part of hexane dosage in step (2)：
In the present invention, a part of hexane dosage in step (2) is not particularly limited, one described in usual step (2)
Part hexane dosage is 46~56kg HX/100L；If a part of hexane dosage described in step (2) is less than 46kg HX/
100L, because dosage is very few, prepolymerization excessive velocities are caused, be difficult to control；And a part of hexane is used described in step (2)
Amount is more than 56kg HX/100L, because dosage is excessive, causes to be unfavorable for realizing that polymerization reaction heat removes scheme and optimized, has no it
His benefit.
Step (2) middle rare earth catalyst amount：
In the present invention, step (2) middle rare earth catalyst amount is not particularly limited, generally with unit interval isoamyl two
Alkene feedstock quality is calculated as 0.5 × 10-6~1.0 × 10-6Mol catalyst/gram monomer；If rare earth catalyst dosage, with unit
Time isoprene feedstock quality meter is less than 0.5 × 10-6Mol catalyst/gram monomer, because catalyst amount is very few, polymerization is anti-
Answer speed slow, polymer ultimate yield is low；And rare earth catalyst dosage, it is more than in terms of unit interval isoprene feedstock quality
1.0×10-6Mol catalyst/gram monomer, causes the waste of catalyst, and polymerization rate is fast, polymerisation stability difference and
The difficult control of temperature, has no other benefits.
Activator level：
In the present invention, activator level is not particularly limited, usual activator level, with unit interval isoprene
Inlet amount quality is calculated as 0.06~3.0%；If activator level, it is less than in terms of unit interval isoprene inlet amount quality
0.06%, because activator level is very few, activation effect is poor, can not improve polymerisation stability；And activator level, with list
Position time isoprene inlet amount quality meter is more than 3.0%, then because dosage is excessive, causes to waste, influence polymer molecule knot
Structure characteristic and application performance, have no other benefits.
Priming reaction temperature：
In the present invention, priming reaction temperature being not particularly limited, usual priming reaction temperature is 10~40 DEG C, if
Priming reaction temperature is less than 10 DEG C, then without activation effect；And priming reaction temperature, because temperature is too high, causes more than 40 DEG C
Priming reaction is excessively violent, causes runaway reaction.
Soak time：
In the present invention, soak time is not particularly limited, usual soak time is 1~10min, if soak time
Less than 1min, because how short the time is, cause activation effect poor；And soak time causes runaway reaction, has no it more than 10min
His benefit.
Prepolymerization technology condition in step (3)：
In the present invention, prepolymerization technology condition in step (3) is not particularly limited, prepolymerization in usual step (3)
Process conditions：Pre-monomer concentration 10~20kg IP/100L, 40~50 DEG C of prepolymerization temperature, 20~30 points of prepolymerization time
Clock, bottom speed of agitator are 10~50 revs/min, and top speed of agitator is 80~300 revs/min；
If pre-monomer concentration is less than 10kg IP/100L, cause reaction speed slow, polymer total recovery is low；It is and pre-
Polymeric monomer concentration is more than 20kg IP/100L, causes polymer viscosity too high, can not realize that heat of polymerization is smoothly moved out；
If prepolymerization temperature is less than 40 DEG C, because temperature is too low, causes prepolymerization reaction speed slow, can not ensure that pre-polymerization is anti-
Conversion ratio is answered, causes polymeric reaction temperature fluctuation big；And temperature is higher than 50 DEG C, cause prepolymerization reaction speed fast, cause reaction to lose
Control, has no other benefits；
If prepolymerization time is less than 20 minutes, because polymerization time is too short, cause prepolymerization reaction conversion ratio low, nothing
Method realizes polymerisation stability contorting；And polymerization time wastes more than 30 minutes, on the time, and prepolymerization conversion ratio mistake
Height, cause prepolymerization out of control, have no other benefits；
If bottom speed of agitator is less than 10 revs/min, because rotating speed is too low, cause mass-and heat-transfer effect poor；And bottom
Speed of agitator is higher than 50 revs/min, then causes reaction stability poor；
If top speed of agitator is less than 80 revs/min, because rotating speed is too low, cause mass-and heat-transfer effect poor；Existing skill
Art is hardly higher than 300 turns.
Another part hexane dosage in step (4)：
In the present invention, another part hexane dosage in step (4) is not particularly limited, it is another in usual step (4)
Part hexane dosage is 20~50kg HX/100L, if another part hexane dosage is less than 20kg HX/100L in step (4),
Because hexane dosage is too small, causing heat of polymerization to remove, effect is poor, and reaction temperature is difficult controls；And another part hexane in step (4)
Dosage is more than 50kg HX/100L, causes hexane dosage to waste, and increases energy consumption, has no other benefits.
Age resistor：
In the present invention, age resistor described in step (5) is not particularly limited, usual age resistor for polymerization phenol with it is thio
The double lauryl compounds of dipropionic acid, its mass ratio are 1:1~1:1.5, age resistor is with respect to rare-earth isoprene rubber quality meter, addition
For 0.1%；
If polymerizeing phenol and the double lauryl compounds of thio-2 acid, its mass ratio is less than 1:1.5, due to polymerizeing phenol dosage
It is very few, cause to polymerize phenol and the double lauryl synergies of thio-2 acid are poor, ageing resistace is poor；And it polymerize phenol and thio dipropyl
Sour double lauryl compounds, its mass ratio are more than 1:1, because polymerization phenol dosage is excessive, causes to polymerize phenol and thio-2 acid is double
Lauryl synergy is poor, and ageing resistace is poor.
Embodiment 1
The present embodiment is in 1m3Implement on the continuous solution polymerization device of polymeric kettle scale, specific implementation process is as follows：
(1) hexane solvent and isoprene monomer obtain the anhydrous and oxygen-free of high purity through physical absorption and chemical treatment
Hexane solvent and isoprene monomer.
(2) anhydrous and oxygen-free isoprene monomer 15kg IP/100L (136kg/h), a part of anhydrous and oxygen-free hexane 51.4kg
HX/100L (465.9kg/h), activator 4080g/h (being calculated as 3.0% with unit interval isoprene inlet amount quality), wherein
It is 10 that activator, which is diisobutylaluminium hydride with triisobutyl aluminium by mol ratio,:1 is compounded, dilute with homogeneous rare earth catalyst
Native neodymium coordination isoprene polymer 0.5 × 10-6Mol catalyst/gram monomer is dispersed in activation kettle, in 40 DEG C of conditions
Lower activation forms activation material for 1 minute；
(3) activation material be directly entered in prepolymerization kettle, carry out isoprene prepolymerization, wherein, prepolymerization kettle use by
Frame type agitating blade and the stirring of multiple layers of vanes oar combined type with self-operated type scraper plate, bottom agitator is with self-operated type scraper plate
Frame type agitating blade, 50 revs/min of bottom speed of agitator, 80 revs/min of top speed of agitator；Prepolymerization temperature 50 C, when
Between be 30 minutes, control monomer conversion 15%, form the prepolymerization reaction material containing unreacted monomer and polymer；
(4) prepolymerization reaction material and another part anhydrous and oxygen-free hexane 22kg HX/100L (299.7kg/h) are subsequently entered
Mixed entirely in the polymerization reaction system that reactor is composed in series by 3 double ribbons with self-operated type scraper plate, carry out isoprene and gather
Close and react, 55 DEG C of reaction temperature, in terms of monomeric charge gross mass, the first reactor monomer conversion 35.1%, the second reactor
Monomer conversion 27.1%, the 3rd reactor monomer conversion 22.8%, by controlling priming reaction rare earth catalyst and activation
The synergy of agent, and control hexane reasonable distribution, realize that steadily control and reaction heat are quickly moved out conversion ratio, are prepared dilute
Native isoprene rubber；
(5) after polymerisation terminates, polymerizate is discharged by the 3rd reactor, first with age resistor (with rare-earth isoprene rubber
Quality meter, addition 0.1%) it is sufficiently mixed in high degree of dispersion device, wherein age resistor is that polymerization phenol and thio-2 acid are double
Lauryl is according to mass ratio 1:1 is compounded, and is re-introduced into water (1L/h) and is coated on high viscose surface and is sent into glue storage tank standard
Standby cohesion, first reactor Stress control 0.35MPa, polymerization pressure is stable, maximum differential pressure 0.15MPa, and reactor and defeated
Hose line does not have kiss-coating.
The present embodiment polymerisation effect and gained isoprene rubber product quality are listed in Tables 1 and 2.
Embodiment 2
The present embodiment is in 1m3Implement on the continuous solution polymerization device of polymeric kettle scale, specific implementation process is as follows：
(1) hexane solvent and isoprene monomer obtain the anhydrous and oxygen-free of high purity through physical absorption and chemical treatment
Hexane solvent and isoprene monomer.
(2) anhydrous and oxygen-free isoprene monomer 20kg IP/100L (136kg/h), a part of anhydrous and oxygen-free hexane 46kg
HX/100L (316.8kg/h), activator 80g/h (being calculated as 0.06% with unit interval isoprene inlet amount quality), wherein living
It is 0.1 that agent, which is diisobutylaluminium hydride with triisobutyl aluminium by mol ratio,:1 is compounded, dilute with homogeneous rare earth catalyst
Native neodymium coordination isoprene polymer 1.0 × 10-6Mol catalyst/gram monomer is dispersed in activation kettle, in 10 DEG C of conditions
Lower activation forms activation material for 10 minutes；
(3) activation material be directly entered in prepolymerization kettle, carry out isoprene prepolymerization, wherein, prepolymerization kettle use by
Frame type agitating blade and the stirring of multiple layers of vanes oar combined type with self-operated type scraper plate, bottom agitator is with self-operated type scraper plate
Frame type agitating blade, 10 revs/min of bottom speed of agitator, 300 revs/min of top speed of agitator；40 DEG C of prepolymerization temperature, when
Between be 20 minutes, control monomer conversion 10%, form the prepolymerization reaction material containing unreacted monomer and polymer；
(4) prepolymerization reaction material and another part anhydrous and oxygen-free hexane 33kg HX/100L (448.8kg/h) are subsequently entered
Mixed entirely in the polymerization reaction system that reactor is composed in series by 3 double ribbons with self-operated type scraper plate, carry out isoprene and gather
Close and react, 50 DEG C of reaction temperature, in terms of monomeric charge gross mass, the first reactor monomer conversion 33.8%, the second reactor
Monomer conversion 25.0%, the 3rd reactor monomer conversion 22.4%, by controlling priming reaction rare earth catalyst and activation
The synergy of agent, and control hexane reasonable distribution, realize that steadily control and reaction heat are quickly moved out conversion ratio, are prepared dilute
Native isoprene rubber；
(5) after polymerisation terminates, polymerizate is discharged by the 3rd reactor, first with age resistor (with rare-earth isoprene rubber
Quality meter, addition 0.1%) it is sufficiently mixed in high degree of dispersion device, wherein age resistor is that polymerization phenol and thio-2 acid are double
Lauryl is according to mass ratio 1:1.5 are compounded, and are re-introduced into water (1L/h) and are coated on high viscose surface and are sent into glue storage tank
Prepare cohesion, first reactor Stress control 0.35MPa, polymerization pressure is stable, maximum differential pressure 0.15MPa, and reactor and
Glue conveying box line does not have kiss-coating.
The present embodiment polymerisation effect and gained isoprene rubber product quality are listed in Tables 1 and 2.
Embodiment 3
The present embodiment is in 1m3Implement on the continuous solution polymerization device of polymeric kettle scale, specific implementation process is as follows：
(1) hexane solvent and isoprene monomer obtain the anhydrous and oxygen-free of high purity through physical absorption and chemical treatment
Hexane solvent and isoprene monomer.
(2) anhydrous and oxygen-free isoprene monomer 10kg IP/100L (102kg/h), a part of anhydrous and oxygen-free hexane 56kg
HX/100L (561kg/h), activator 800g/h (being calculated as 0.6% with unit interval isoprene inlet amount quality), wherein activating
It is 0.1 that agent, which is diisobutylaluminium hydride with triisobutyl aluminium by mol ratio,:1 is compounded, with homogeneous rare earth catalyst rare earth
Neodymium coordination isoprene polymer 0.5 × 10-6Mol catalyst/gram monomer is dispersed in activation kettle, under the conditions of 10 DEG C
Activation forms activation material for 1 minute；
(3) activation material be directly entered in prepolymerization kettle, carry out isoprene prepolymerization, wherein, prepolymerization kettle use by
Frame type agitating blade and the stirring of multiple layers of vanes oar combined type with self-operated type scraper plate, bottom agitator is with self-operated type scraper plate
Frame type agitating blade, 10 revs/min of bottom speed of agitator, 300 revs/min of top speed of agitator；40 DEG C of prepolymerization temperature, when
Between be 20 minutes, control monomer conversion 5%, form the prepolymerization reaction material containing unreacted monomer and polymer；
(4) prepolymerization reaction material and another part anhydrous and oxygen-free hexane 20kg HX/100L (287kg/h) are subsequently entered by 3
Double ribbons of the platform with self-operated type scraper plate are mixed in the polymerization reaction system that reactor is composed in series entirely, and it is anti-to carry out isoprene polymerization
Should, 45 DEG C of reaction temperature, in terms of monomeric charge gross mass, the first reactor monomer conversion 30.0%, the second reactor monomer
Conversion ratio 30.0%, the 3rd reactor monomer conversion 25.0%, by controlling priming reaction rare earth catalyst and activator
Synergy, and control hexane reasonable distribution, realize that steadily control and reaction heat are quickly moved out conversion ratio, and it is different to prepare rare earth
Penta rubber；
(5) after polymerisation terminates, polymerizate is discharged by the 3rd reactor, first with age resistor (with rare-earth isoprene rubber
Quality meter, addition 0.1%) it is sufficiently mixed in high degree of dispersion device, wherein age resistor is that polymerization phenol and thio-2 acid are double
Lauryl is according to mass ratio 1:1.5 are compounded, and are re-introduced into water (1L/h) and are coated on high viscose surface and are sent into glue storage tank
Prepare cohesion, first reactor Stress control 0.35MPa, polymerization pressure is stable, maximum differential pressure 0.15MPa, and reactor and
Glue conveying box line does not have kiss-coating.
The present embodiment polymerisation effect and gained isoprene rubber product quality are listed in Tables 1 and 2.
Embodiment 4
The present embodiment is in 1m3Implement on the continuous solution polymerization device of polymeric kettle scale, specific implementation process is as follows：
(1) hexane solvent and isoprene monomer obtain the anhydrous and oxygen-free of high purity through physical absorption and chemical treatment
Hexane solvent and isoprene monomer.
(2) anhydrous and oxygen-free isoprene monomer 17.4kg IP/100L (136kg/h), a part of anhydrous and oxygen-free hexane 49kg
HX/100L (382.8kg/h), activator 800g/h (being calculated as 0.6% with unit interval isoprene inlet amount quality), wherein living
It is 0.2 that agent, which is diisobutylaluminium hydride with triisobutyl aluminium by mol ratio,:1 is compounded, dilute with homogeneous rare earth catalyst
Native neodymium coordination isoprene polymer 0.8 × 10-6Mol catalyst/gram monomer is dispersed in activation kettle, in 30 DEG C of conditions
Lower activation forms activation material for 6 minutes；
(3) activation material be directly entered in prepolymerization kettle, carry out isoprene prepolymerization, wherein, prepolymerization kettle use by
Frame type agitating blade and the stirring of multiple layers of vanes oar combined type with self-operated type scraper plate, bottom agitator is with self-operated type scraper plate
Frame type agitating blade, 30 revs/min of bottom speed of agitator, 150 revs/min of top speed of agitator；Prepolymerization temperature 45 C, when
Between be 25 minutes, control monomer conversion 12.5%, form the prepolymerization reaction material containing unreacted monomer and polymer；
(4) prepolymerization reaction material and another part anhydrous and oxygen-free hexane 28kg HX/100L (382.8kg/h) are subsequently entered
Mixed entirely in the polymerization reaction system that reactor is composed in series by 3 double ribbons with self-operated type scraper plate, carry out isoprene and gather
Close and react, 45 DEG C of reaction temperature, in terms of monomeric charge gross mass, the first reactor monomer conversion 33.8%, the second reactor
Monomer conversion 28.1%, the 3rd reactor monomer conversion 23.4%, by controlling priming reaction rare earth catalyst and activation
The synergy of agent, and control hexane reasonable distribution, realize that steadily control and reaction heat are quickly moved out conversion ratio, are prepared dilute
Native isoprene rubber；
(5) after polymerisation terminates, polymerizate is discharged by the 3rd reactor, first with age resistor (with rare-earth isoprene rubber
Quality meter, addition 0.1%) it is sufficiently mixed in high degree of dispersion device, wherein age resistor is that polymerization phenol and thio-2 acid are double
Lauryl is according to mass ratio 1:1.2 are compounded, and are re-introduced into water (1L/h) and are coated on high viscose surface and are sent into glue storage tank
Prepare cohesion, first reactor Stress control 0.35MPa, polymerization pressure is stable, maximum differential pressure 0.15MPa, and reactor and
Glue conveying box line does not have kiss-coating.
The present embodiment polymerisation effect and gained isoprene rubber product quality are listed in Tables 1 and 2.
Embodiment 5
The present embodiment is in 1m3Implement on the continuous solution polymerization device of polymeric kettle scale, specific embodiment and technique control
Make same as Example 4, it be diisobutylaluminium hydride with triisobutyl aluminium by mol ratio is 0.5 to distinguish in activator:1 is carried out
Compounding, activator level 1500g/h.
The present embodiment polymerisation effect and gained isoprene rubber product quality are listed in Tables 1 and 2.
Embodiment 6
The present embodiment is in 1m3Implement on the continuous solution polymerization device of polymeric kettle scale, specific embodiment and technique control
Make same as Example 4, it be diisobutylaluminium hydride with triisobutyl aluminium by mol ratio is 0.14 to distinguish in activator:1 enters
Row compounding, activator level 1000g/h.
The present embodiment polymerisation effect and gained isoprene rubber product quality are listed in Tables 1 and 2.
Embodiment 7
The present embodiment is in 1m3Implement on the continuous solution polymerization device of polymeric kettle scale, specific embodiment and technique control
Make same as Example 4, it be diisobutylaluminium hydride with triisobutyl aluminium by mol ratio is 0.25 to distinguish in activator:1 enters
Row compounding, activator level 600g/h..
The present embodiment polymerisation effect and gained isoprene rubber product quality are listed in Tables 1 and 2.
Embodiment 8
The present embodiment is in 1m3Implement on the continuous solution polymerization device of polymeric kettle scale, specific embodiment and technique control
Make same as Example 4, it be diisobutylaluminium hydride with triisobutyl aluminium by mol ratio is 0.33 to distinguish in activator:1 enters
Row compounding, activator level 300g/h..
The present embodiment polymerisation effect and gained isoprene rubber product quality are listed in Tables 1 and 2.
Comparative example 1
The present embodiment is in 1m3Implement on three kettle continuous solution polymerization devices of polymeric kettle scale, each polymeric kettle is traditional
Double ribbons mix reactor entirely, and specific implementation process is as follows：
It is dehydrated qualified refined hexane solvent 55kg HX/100L (510kg/h), isoprene monomer 11kgHX/100L
(102kg/h) and homogeneous rare earth catalyst (1.5 × 10-6Mol catalyst/gram monomer) be directly entered the series connection of three kettles with double
Polymerisation, polymeric reaction temperature and viscosity are carried out in the polymeric kettle of ribbon stirring to raise by kettle, concrete technology condition is：Monomer
Concentration 11kg IP/100L, first 45 DEG C of kettle reaction temperature, two 60 DEG C of kettle reaction temperatures, three 70 DEG C of kettle reaction temperatures, each kettle stop
65 minutes time.
After polymerisation terminates, polymer hexane solution is discharged by the 3rd reactor, first (anti-old with age resistor hexane solution
Agent is with respect to dry glue quality meter, addition 0.1%) merged in pipeline into glue storage tank, first reactor Stress control
0.55MPa, polymerization pressure are had larger fluctuation, maximum differential pressure 0.30MPa, glue difficulty of transportation by each kettle monomer reaction situation.
The present embodiment polymerisation effect and gained isoprene rubber product quality are listed in Tables 1 and 2.
Each embodiment polymerisation effect of table 1
Each embodiment isoprene rubber product quality of table 2
Claims (9)
1. a kind of rare-earth isoprene rubber solution polymerization method, comprises the following steps：
(1) hexane solvent and isoprene monomer obtain the anhydrous and oxygen-free hexane of high purity through physical absorption and chemical treatment
Solvent and isoprene monomer；
(2) anhydrous and oxygen-free isoprene monomer and a part of anhydrous and oxygen-free hexane, activator are activating with homogeneous rare earth catalyst
It is dispersed in kettle, priming reaction is carried out, forms activation material；
(3) activation material is directly entered in prepolymerization kettle, carries out isoprene prepolymerization, controls monomer conversion 5~15%,
Form the prepolymerization reaction material containing unreacted monomer and polymer；
(4) prepolymerization reaction material and another part anhydrous and oxygen-free hexane are directly entered by 3 double ribbons for carrying self-operated type scraper plate
In the polymerization reaction system that complete mixed reactor is composed in series, isoprene polymerization reaction, 45~55 DEG C of reaction temperature, control are carried out
First reactor monomer conversion 30~35%；In terms of monomeric charge gross mass, the second reactor monomer conversion 25~30%；
In terms of monomeric charge gross mass, the 3rd reactor monomer conversion 20~25%, control priming reaction rare earth catalyst is with activating
The synergy of agent, prepares rare-earth isoprene rubber；
(5) after polymerisation terminates, polymerizate is discharged by the 3rd reactor, is first fully mixed in high degree of dispersion device with age resistor
Close, be subsequently introduced glue carrying object and be coated on high viscose surface and be sent into the preparation cohesion of glue storage tank；
Activator described in step (2) is the mixture of diisobutylaluminium hydride and triisobutyl aluminium, diisobutylaluminium hydride and
Triisobutyl aluminium mol ratio is 0.1~10:1.
2. rare-earth isoprene rubber solution polymerization method as claimed in claim 1, it is characterised in that：Glue described in step (5)
Carrying object is water.
3. rare-earth isoprene rubber solution polymerization method as claimed in claim 1, it is characterised in that：One described in step (2)
It is 46~56kg HX/100L to divide hexane dosage.
4. rare-earth isoprene rubber solution polymerization method as claimed in claim 1, it is characterised in that：Rare earth described in step (2)
Catalyst is that rare earth neodymium is coordinated isoprene polymer.
5. rare-earth isoprene rubber solution polymerization method as claimed in claim 1, it is characterised in that：Step (2) middle rare earth is catalyzed
Agent dosage is calculated as 0.5 × 10 with unit interval isoprene feedstock quality-6~1.0 × 10-6Mol catalyst/gram monomer；Activation
Agent dosage is calculated as 0.06~3.0% with unit interval isoprene inlet amount quality；Priming reaction temperature is 10~40 DEG C, activation
Time is 1~10min.
6. rare-earth isoprene rubber solution polymerization method as claimed in claim 1, it is characterised in that：Prepolymerization kettle is adopted in step (3)
Stirred with by the frame type agitating blade with self-operated type scraper plate and multiple layers of vanes oar combined type, bottom agitator is to be scraped with self-operated type
The frame type agitating blade of plate, kettle top agitator are multiple layers of vanes oar.
7. rare-earth isoprene rubber solution polymerization method as claimed in claim 1, it is characterised in that：Prepolymerization work in step (3)
Skill condition：Pre-monomer concentration 10~20kg IP/100L, 40~50 DEG C of prepolymerization temperature, 20~30 points of prepolymerization time
Clock, bottom speed of agitator are 10~50 revs/min, and top speed of agitator is 80~300 revs/min.
8. rare-earth isoprene rubber solution polymerization method as claimed in claim 1, it is characterised in that：Another part in step (4)
Hexane dosage is 20~50kg HX/100L.
9. rare-earth isoprene rubber solution polymerization method as claimed in claim 1, it is characterised in that：Prevent described in step (5) old
Agent is polymerization phenol and the double lauryl compounds of thio-2 acid, and its mass ratio is 1:1~1:1.5, age resistor is with respect to rare earth isoamyl
Rubber mass gauge, addition 0.1%.
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| CN109776707B (en) * | 2017-11-10 | 2021-05-11 | 中国石油化工股份有限公司 | Method for producing rare earth isoprene rubber |
| CN110193890B (en) * | 2019-06-06 | 2020-05-19 | 益凯新材料有限公司 | Wet mixing continuous production method of isoprene rubber |
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| RU2374271C1 (en) * | 2008-02-27 | 2009-11-27 | Ооо "Сиарси" | Isoprene rubber and method of producing said rubber |
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| RU2374271C1 (en) * | 2008-02-27 | 2009-11-27 | Ооо "Сиарси" | Isoprene rubber and method of producing said rubber |
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