CN103087260A - Method and catalyst for preparing high cis-polybutadiene by gas-phase polymerization - Google Patents
Method and catalyst for preparing high cis-polybutadiene by gas-phase polymerization Download PDFInfo
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Abstract
The invention discloses a method and catalyst for preparing high cis-polybutadiene by gas-phase polymerization. The catalyst is mixed by five components, wherein the first component is a rare-earth compound; the second component is alkyl aluminum, alkyl aluminium hydride or alkylaluminoxane; the third component is alkyl chloride or alkyl aluminum chloride; the fourth component is magnesium chloride, silicon dioxide, carbon black or aluminum oxide; the fifth component is any one or combination of more of nano silicon dioxide, nano carbon black, nano aluminum oxide, nano titanium dioxide, nano antimony trioxide, nano calcium carbonate, nano talcum powder and nano montmorillonite; and the mol ratio of the first component to the second component is 1:(20-100), the mol ratio of the first component to the third component is 1:(1-10), the ratio of the molar weight of the first component to the mass of the fourth component is 1:(2000-200000), and the mass ratio of the fifth component to the fourth is 1:(0.125-200). Butadiene and a catalyst are subjected to gas-phase polymerization reaction at 40-70 DEG C for more than 30 minutes to obtain the high cis-1,4-polybutadiene rubber particles.
Description
Technical field
The present invention relates to a kind of preparation method of gas phase polymerization process and catalyzer thereof of high-cis-1，4-polybutadiene.
Background technology
Rare earth catalyst is the effective catalyst of synthetic height stereoregular structure rubber.Divinyl can carry out tactic polymerization under the rare earth catalyst effect, synthetic high-cis-1，4-polybutadiene.Rare earth catalyst is comprised of Primary Catalysts rare-earth salts (or rare earth alcoholate), promotor and the 3rd component that can discharge halogen atom usually.Wherein, promotor can be any in aluminum alkyls, alkyl aluminium hydride, aluminum alkoxide.The 3rd component that can discharge halogen atom can be any in halogenated alkane, chloro aluminum alkyls.The existing domestic and international production technique of high-cis-1，4-polybutadiene is solution polymerization.Polymkeric substance in this technique, divinyl and catalyst system all are dissolved in solvent (as normal hexane etc.), and reaction system is homogeneous phase.Yet for ease of conducting heat and production process regulates and controls, the solid holdup in reaction system is only generally 8-10wt%, and solvent is up to more than 90wt%, directly causes the aftertreatment long flow path, device is many, energy consumption is high, and brings the pressure of many environmental protection and secure context.
Gas-phase polymerization process is to produce now that a kind of relative energy consumption of synthetic resins (as polyethylene, polypropylene etc.) is lower, the comparatively simple common technology of flow process, can directly obtain granular polyolefine, and need not to use solvent.Compare with solution polymerization, cohesion and sepn process are greatly easy, and processing safety is high, and investment is low with running cost, and environmental pollution is few.It is reported, Bayer company once predicted butadiene gas-phase polymerization 20% left and right that can reduce production costs, and can get rid of the power consumption operation relevant to solvent (solvent refining, reclaim, the operating unit such as dry), only this just can save energy 80%, also can reduce the investment approximately 25% of founding the factory simultaneously.
Yet, vapor phase process is applied to the rubber preparation has certain difficulty.Its reason is that mainly rubber is the elastomerics of very easily adhesion, between the initial reaction stage rubber grain with regard to inter-adhesive formation large particle and even caking, thereby cause mobility of particle poor, reaction heat is difficult for distributing, and implode or catalyst deactivation even occur.At present, produce in the rubber process in vapour phase polymerization, prevent that the agglomerating method of product adhesion from mainly containing following two kinds: polyreaction is carried out below the polymer glass temperature or is used dispersion agent.
Though the polymerization of carrying out below second-order transition temperature can prevent conglomeration, because polymerization temperature is too low, react very slow.
Another kind prevents that the method for rubber adhesion, caking from being: in the process of catalyst monomer polymerization, introduce inorganic particulate as dispersion agent simultaneously in reactor, and keep dispersion agent to be in certain concentration in whole reactor.Because dispersion agent can be scattered between rubber grain, play iris action, thereby play the effect that prevents that rubber is clamminess, obtain granular rubber.And along with the increase of dispersant dosage, barriering effect is better, and then anti-adhesion effects is better.But when dispersant dosage was less, the iris action between rubber grain died down, and dispersion agent also can cause between particle, bridging occuring and gather also sometimes, and anti-adhesion effects will descend greatly, does not even have antiseized effect.So, to be clamminess, be granular rubber and need be used relatively large dispersion agent in this polymerization technique.There are some researches show, when carrying out polyreaction under higher temperature (higher than second-order transition temperature), pressure, obtain granular rubber, the inorganic particulate content in polymkeric substance needs up to more than 9wt%.Therefore, although this method plays certain anti-adhesion effects, obtain granular rubber and need introduce relatively large inorganic particulate, affect processing and the application performance of rubber.
Summary of the invention
The gas phase polymerization process and the catalyzer thereof that the purpose of this invention is to provide a kind of high-cis-1，4-polybutadiene, the nanoparticle of its introducing is few and can effectively avoid polymerisate to stick together.
For achieving the above object, the technical solution used in the present invention is: the described mixture that is formed by five components for the catalyzer of butadiene gas-phase polymerization, wherein,
The first component is the rare earth compound of structure as shown in formula I,
In formula I, Ln is neodymium or pr-nd enriched product; R is alkoxyl group, carboxylic acid group, phosphate or phosphonate group; Second component is any in aluminum alkyls, alkyl aluminium hydride, alkylaluminoxane;
The 3rd component is any in alkyl chloride, chlorination aluminum alkyls;
The 4th component is magnesium chloride, silicon-dioxide, carbon black or aluminum oxide;
BSA is nanoparticle, described nanoparticle be in nano silicon, nano carbon black, nano-aluminium oxide, nano titanium oxide, nanmeter antimong trioxide, nano-calcium carbonate, nanomete talc powder, nano imvite any or appoint several combinations;
The C atomicity of the alkyl in described second component aluminum alkyls, alkyl aluminium hydride, alkyl chloride is 1-4;
The C atomicity of the alkyl in described the 3rd component alkyl chloride, chlorination aluminum alkyls is 1-4;
The mol ratio of described the first component and second component is 1:20～100, the mol ratio of the first component and the 3rd component is 1:1～10, the molar weight of the first component is 1:2000～200000 with the ratio of the quality of the 4th component, and the mass ratio of BSA and the 4th component is 1:0.125～200;
The particle diameter of described the 4th component is 10～250 μ m;
The particle diameter of described BSA is 5～300nm;
A kind of preparation method of catalyzer is characterized in that, comprises the following steps:
Under atmosphere of inert gases, first add the first component under 0～40 ℃ of condition in the container, then add and to dissolve the first component, second component and can dissolve the solvent of the 3rd component again, then add successively sequentially second component, the 3rd component, the 4th component; Stir and extract solvent after the first component, second component and the 3rd component are dissolved fully; Add successively sequentially more described solvent, BSA; Extract described solvent after stirring, obtain pulverous described catalyzer.
Described solvent is saturated alkane or alkyl substituent aromatic compound;
Described solvent is hexanaphthene, normal hexane, normal heptane, toluene, dimethylbenzene, ethylbenzene.
A kind of vapour phase polymerization that adopts is produced high method along the polyisoprene rubber particle, it is characterized in that: divinyl and described catalyzer are carried out vapour phase polymerization under 40～70 ℃, reaction is more than 30 minutes, obtain highly along the polyisoprene rubber particle, the massfraction that in product, nanoparticle accounts for polymkeric substance can be low to moderate 0.1wt%.
The technique of existing other Butadiene vapour phase polymerizations is utilize first, second, third and fourth component and make catalyzer.In polymerization process, carry out vapour phase polymerization by the catalyst divinyl, introduce inorganic particulate as dispersion agent simultaneously in reactor, and make it keep certain concentration in whole reactor.Because dispersion agent can be scattered between rubber grain, play iris action, thereby play the effect that prevents that rubber is clamminess, obtain granular rubber.And along with the increase of dispersant dosage, barriering effect is better, and then anti-adhesion effects is better.But when dispersant dosage was less, the iris action between rubber grain died down, and dispersion agent also can cause between particle, bridging occuring and gather also sometimes, and anti-adhesion effects will descend greatly, does not even have antiseized effect.So, to be clamminess, be granular rubber in this polymerization technique and need be used relatively large dispersion agent.There are some researches show when carrying out polyreaction under higher temperature (higher than second-order transition temperature), pressure, obtain granular rubber, the dispersant in polymkeric substance needs up to more than 9wt%.And the present invention breaks through tradition, introduces the nanoparticle of superhigh specific surface area in catalyst preparation process, makes it become the part of catalyzer.In polymerization process, divinyl carries out polymerization under the catalysis of this catalyzer, can directly obtain the granular rubber that is not clamminess, wherein the nanoparticle content in polymkeric substance is lower, can be low to moderate 0.1wt%, fundamentally solve the problem that in rubber, the inorganic particulate too high levels has a negative impact to rubber performance.By contrast as can be known, the present invention does not need to add dispersion agent in polymerization process again, and the nano inoganic particle content in polymkeric substance is lower, the rubber grain that available can be good.
Description of drawings
Fig. 1 is embodiment 1 gained rubber grain scanning electron microscope (SEM) photograph.
Fig. 2 is Comparative Examples 1 gained rubber grain scanning electron microscope (SEM) photograph.
Embodiment
Further illustrate the present invention below by example:
Embodiment 1
(1) catalyzer preparation
Catalyzer is by Nd (naph)
3, Al (i-Bu)
3, AlEtCl
2, particle size range silicon-dioxide and five kinds of components such as the nanoparticle carbon black of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is normal hexane, wherein the first component Nd (naph)
3Amount be 1.2mmol, second component Al (i-Bu)
3Amount be 96mmol, the 3rd component AlEtCl
2Amount be 7.2mmol, the amount of the 4th components silica is 4.8g, the amount of BSA carbon black is 2.9g, makes powder catalyst A
116.81g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyst A that makes under nitrogen protection
116.81g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 70 ℃ were reacted 1 hour, and obtained polymerisate 2879.1g through the aftertreatment drying.Calculate catalyst A
1Catalytic activity be 2.4 * 10
6G ﹒ mol
-1﹒ h
-1Characterize by Fourier transform infrared spectrometer, in the polymerisate that obtains, the content of cis-1，4-polybutadiene is 93.5%.Because carbon black in product can't separate, the content that calculates carbon black in product is 0.1wt%.Can obviously be observed by Fig. 1, the gained rubber product is not clamminess, and has good particle form.
Comparative Examples 1
(1) catalyzer preparation
Catalyzer is by Nd (naph)
3, Al (i-Bu)
3, AlEtCl
2, four kinds of components of the silicon-dioxide of particle size range in 10-250 μ m form, in catalyst preparation process, solvent for use is normal hexane.The first component Nd (naph) wherein
3Amount be 1.2mmol, the amount of second component MAO is 96mmol, the 3rd component AlEtCl
2Amount be 7.2mmol, the amount of the 4th components silica is 4.8g, makes pulverous catalyst A
29.1g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyst A that makes under nitrogen atmosphere
27.9g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, begin polymerization under 70 ℃, the particle diameter that adds simultaneously 2.9g be the carbon black of 5-300nm as dispersion agent, reacted 1 hour, obtain polymerisate 2874.4g through the aftertreatment drying.Calculate catalyst A
2Catalytic activity be 2.4 * 10
6G ﹒ mol
-1﹒ h
-1Characterize by Fourier transform infrared spectrometer, in the polymerisate that obtains, the content of cis-1，4-polybutadiene is 93.5%.Because carbon black in product can't separate, calculate that in product, content of carbon black is 0.1wt%.Can obviously observe products therefrom by Fig. 2 and be clamminess, particle adhesion becomes piece.
Contrast as can be known the catalyst A of embodiment 1 with Comparative Examples 1 by embodiment 1
1Be comprised of first, second, third and fourth and BSA carbon black, the BSA carbon black is as the part of catalyzer; And the catalyst A of Comparative Examples 1
2Only formed by first, second, third and fourth component.Embodiment 1 carries out respectively the vapour phase polymerization of divinyl under identical condition with Comparative Examples 1, different is that Comparative Examples 1 adds carbon black as dispersion agent in polymerization process.In embodiment 1 and Comparative Examples 1 gained polymerisate, the content of carbon black is 0.1wt%.Can obviously be observed by electromicroscopic photograph, embodiment 1 products therefrom is not clamminess, and has good particle form; And Comparative Examples 1 products therefrom is clamminess, and particle adhesion becomes piece.The method in embodiment 1 that illustrates has played antiseized effect.Thereby as can be known, under the condition that the inorganic particulate content of carbon black is identical in product, adopt the method for the invention to carry out the vapour phase polymerization of catalyzer preparation and divinyl, can effectively prevent the adhesion of rubber, obtain comparatively desirable rubber grain.
Embodiment 2
(1) catalyzer preparation
Catalyzer is by Nd (OiPr)
3, Al (i-Bu)
3, Al
2Et
3Cl
3, particle size range magnesium chloride and five kinds of components such as the nanoparticle silicon-dioxide of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (OiPr)
3Amount be 1.0mmol, second component Al (i-Bu)
3Amount be 30.0mmol, the 3rd component Al
2Et
3Cl
3Amount be 1.0mmol, the amount of the 4th component magnesium chloride is 50.0g, the amount of BSA silicon-dioxide is 50.0g, makes powder catalyst B
1107.2g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyst B that makes under nitrogen protection
1107.2g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 60 ℃ were reacted 1 hour, and obtained polymerisate 751.6g through the aftertreatment drying.Calculate catalyst B
1Catalytic activity is 7.5 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.2%.Because silicon-dioxide in product can't separate, calculate that in product, dioxide-containing silica is 6.67wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Comparative Examples 2
(1) catalyzer preparation
Catalyzer is by Nd (OiPr)
3, Al (i-Bu)
3, Al
2Et
3Cl
3, four kinds of components such as the magnesium chloride of particle size range in 10-250 μ m form, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (OiPr)
3Amount be 1.0mmol, second component Al (i-Bu)
3Amount be 30.0mmol, the 3rd component Al
2Et
3Cl
3Amount be 1.0mmol, the amount of the 4th component magnesium chloride is 50.0g, makes powder catalyst B
257.1g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyst B that makes under nitrogen atmosphere
257.1g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 60 ℃ begin reaction, the particle diameter that adds simultaneously 50g be the silicon-dioxide of 5-300nm as dispersion agent, reacted 1 hour, obtain polymerisate 751.0g through the aftertreatment drying.Calculate catalyst B
2Catalytic activity is 7.5 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with comparative example 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.2%.Because silicon-dioxide in product can't separate, calculate that in product, dioxide-containing silica is 6.67wt%.Can obviously observe products therefrom and be clamminess, particle adhesion becomes piece.
Contrast as can be known the catalyst B of embodiment 2 with Comparative Examples 2 by embodiment 2
1Be comprised of first, second, third and fourth and BSA, the BSA nano silicon is as the part of catalyzer; And the catalyst B of Comparative Examples 2
2Only formed by first, second, third and fourth component.Embodiment 2 carries out respectively the vapour phase polymerization of divinyl under identical condition with Comparative Examples 2, different is that Comparative Examples 2 adds silicon-dioxide as dispersion agent in polymerization process.In embodiment 2 and Comparative Examples 2 gained polymerisates, the content of silicon-dioxide is 6.67wt%.Can obviously observe, embodiment 2 products therefroms are not clamminess, and have good particle form; And Comparative Examples 2 products therefroms are clamminess, and particle adhesion becomes piece.The method in embodiment 2 that illustrates has played antiseized effect.Thereby as can be known, under the condition that the inorganic particulate dioxide-containing silica is identical in product, adopt the method for the invention to carry out the vapour phase polymerization of catalyzer preparation and divinyl, can effectively prevent the adhesion of rubber, obtain comparatively desirable rubber grain.
Embodiment 3
(1) catalyzer preparation
Catalyzer is by Nd (P
204)
3, Al (Me)
2H, Al
2Et
3Cl
3, the aluminum oxide of particle size range in 10-250 μ m
Five kinds of components such as the nanoparticle talcum powder with particle size range in 5-300nm form, and in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (P
204)
3Amount be 1.0mmol, second component Al (Me)
2The amount of H is 100.0mmol, the 3rd component Al
2Et
3Cl
3Amount be 8.0mmol, the amount of the 4th component aluminum oxide is 20.5g, the talcous amount of BSA is 72.4g, makes powder catalyst C
1102.3g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer C that makes under nitrogen protection
1102.3g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 50 ℃ were reacted 1 hour, and obtained polymerisate 942.1g through the aftertreatment drying.Calculate catalyzer C
1Activity is 9.42 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 95.0%.Because talcum powder in product can't separate, calculate that in product, talcum powder content is 7.5wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Comparative Examples 3
(1) catalyzer preparation
Catalyzer is by Nd (P
204)
3, Al (Me)
2H, Al
2Et
3Cl
3, the aluminum oxide of particle size range in 10-250 μ m
Form Deng four kinds of components, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (P
204)
3Amount be 1.0mmol, second component Al (Me)
2The amount of H is 100.0mmol, the 3rd component Al
2Et
3Cl
3Amount be 8.0mmol, the amount of the 4th component aluminum oxide is 20.5g, makes powder catalyst C
229.6g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer C that makes under nitrogen atmosphere
229.6g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 50 ℃ begin reaction, the particle diameter that adds simultaneously 72.4g be the talcum powder of 5-300nm as dispersion agent, reacted 1 hour, obtain polymerisate 941.8g through the aftertreatment drying.Calculate catalyzer C
2Catalytic activity is 9.42 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with comparative example 1.In polymerisate, the content of cis-1，4-polybutadiene is 95.0%.Because nanoparticle in product can't separate, calculate that in product, nanoparticle content is 7.5wt%.Can obviously observe products therefrom and be clamminess, particle adhesion becomes piece.
Contrast as can be known the catalyzer C of embodiment 3 with Comparative Examples 3 by embodiment 3
1Be comprised of first, second, third and fourth and BSA nanomete talc powder, BSA is as the part of catalyzer; And the catalyzer C of Comparative Examples 3
2Only formed by first, second, third and fourth component.Embodiment 3 carries out respectively the vapour phase polymerization of divinyl under identical condition with Comparative Examples 3, different is that Comparative Examples 3 adds talcum powder as dispersion agent in polymerization process.In embodiment 3 and Comparative Examples 3 gained polymerisates, talcous content is 7.5wt%.Can obviously observe, embodiment 3 products therefroms are not clamminess,, have good particle form; And Comparative Examples 3 products therefroms are clamminess, and particle adhesion becomes piece.The method in embodiment 3 that illustrates has played antiseized effect.Thereby as can be known, under the condition that inorganic particulate carbon black talcum powder is identical in product, adopt the method for the invention to carry out the vapour phase polymerization of catalyzer preparation and divinyl, can effectively prevent the adhesion of rubber, obtain comparatively desirable rubber grain.
Embodiment 4
(1) catalyzer preparation
Catalyzer is by Nd (P
204)
3, Al (Me)
2H, Al
2Et
3Cl
3, particle size range aluminum oxide and five kinds of components such as the nanoparticle talcum powder of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (P
204)
3Amount be 1.0mmol, second component Al (Me)
2The amount of H is 100.0mmol, the 3rd component Al
2Et
3Cl
3Amount be 8.0mmol, the amount of the 4th component aluminum oxide is 20.5g, the talcous amount of BSA is 80.0g, makes powder catalyst D
1109.3g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer D that makes under nitrogen protection
1109.3g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 50 ℃ were reacted 1 hour, and obtained polymerisate 935.0g through the aftertreatment drying.Calculate catalyzer D
1Catalytic activity is 9.36 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.9%.Because talcum powder in product can't separate, calculate that in product, talcum powder content is 8.3wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Comparative Examples 4
(1) catalyzer preparation
Catalyzer is by Nd (P
204)
3, Al (Me)
2H, Al
2Et
3Cl
3, four kinds of components such as the aluminum oxide of particle size range in 10-250 μ m form, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (P
204)
3Amount be 1.0mmol, second component Al (Me)
2The amount of H is 100.0mmol, the 3rd component Al
2Et
3Cl
3Amount be 8.0mmol, the amount of the 4th component aluminum oxide is 20.5g, makes powder catalyst D
229.1g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, first add the above-mentioned powder catalyzer D that makes under nitrogen protection
229.1g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 50 ℃ begin reaction, the particle diameter that adds simultaneously 80.0g be the talcum powder of 5-300nm as dispersion agent, reacted 1 hour, obtain polymerisate 934.7g through the aftertreatment drying.Calculate catalyzer D
2Catalytic activity is 9.36 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with comparative example 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.9%.Because talcum powder in product can't separate, calculate that in product, talcum powder content is 8.3wt%.Can obviously observe products therefrom and be clamminess, particle adhesion becomes piece.
Contrast as can be known the catalyzer D of embodiment 4 with Comparative Examples 4 by embodiment 4
1Be comprised of first, second, third and fourth and BSA nanomete talc powder, BSA is as the part of catalyzer; And the catalyzer D of Comparative Examples 4
2Only formed by first, second, third and fourth component.Embodiment 4 carries out respectively the vapour phase polymerization of divinyl under identical condition with Comparative Examples 4, different is that Comparative Examples 4 adds talcum powder as dispersion agent in polymerization process.In embodiment 4 and Comparative Examples 4 gained polymerisates, talcous content is 8.3wt%.Can obviously observe, embodiment 4 products therefroms are not clamminess, and have good particle form; And Comparative Examples 4 products therefroms are clamminess, and particle adhesion becomes piece.The method in embodiment 4 that illustrates has played antiseized effect.Thereby as can be known, under the condition that inorganic particulate talcum powder content is identical in product, adopt the method for the invention to carry out the vapour phase polymerization of catalyzer preparation and divinyl, can effectively prevent the adhesion of rubber, obtain comparatively desirable rubber grain.
Embodiment 5
(1) catalyzer preparation
Catalyzer is by Nd (naph)
3, Al (Me)
3, Al
2Me
3Cl
3, particle size range silicon-dioxide and five kinds of components such as the nanoparticle titanium dioxide of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (naph)
3Amount be 1.0mmol, second component Al (Me)
3Amount be 40.0mmol, the 3rd component Al
2Me
3Cl
3Amount be 5.0mmol, the amount of the 4th components silica is 50.0g, the amount of BSA titanium dioxide is 10.0g, makes powder catalyst E
174.3g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer E that makes under nitrogen protection
174.3g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 60 ℃ were reacted 1 hour, and obtained polymerisate 967.7g through the aftertreatment drying.Calculate catalyzer E
1Catalytic activity is 9.6 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.4%.Because titanium dioxide in product can't separate, calculate that in product, content of titanium dioxide is 1.04wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Comparative Examples 5
(1) catalyzer preparation
Catalyzer is by Nd (naph)
3, Al (Me)
3, Al
2Me
3Cl
3, four kinds of components such as the silicon-dioxide of particle size range in 10-250 μ m form, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (naph)
3Amount be 1.0mmol, second component Al (Me)
3Amount be 40.0mmol, the 3rd component Al
2Me
3Cl
3Amount be 5.0mmol, the amount of the 4th components silica is 50.0g, makes body of powder catalyzer E
264.1g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer E that makes under nitrogen atmosphere
2114.1g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 60 ℃ begin reaction, the particle diameter that adds simultaneously 10.0g be the titanium dioxide of 5-300nm as dispersion agent, reacted 1 hour, obtain polymerisate 967.1g through the aftertreatment drying.Calculate catalyzer E
2Catalytic activity be 9.6 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with comparative example 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.4%.Because titanium dioxide in product can't separate, calculate that in product, content of titanium dioxide is 1.04wt%.Can obviously observe products therefrom and be clamminess, particle adhesion becomes piece.
Contrast as can be known the catalyzer E of embodiment 5 with Comparative Examples 5 by embodiment 5
1Be comprised of first, second, third and fourth and BSA nano titanium oxide, BSA is as the part of catalyzer; And the catalyzer E of Comparative Examples 5
2Only formed by first, second, third and fourth component.Embodiment 5 carries out respectively the vapour phase polymerization of divinyl under identical condition with Comparative Examples 5, different is that Comparative Examples 5 adds titanium dioxide as dispersion agent in polymerization process.In embodiment 5 and Comparative Examples 5 gained polymerisates, the content of titanium dioxide is 1.04wt%.Can obviously observe, embodiment 5 products therefroms are not clamminess,, have good particle form; And Comparative Examples 5 products therefroms are clamminess, and particle adhesion becomes piece.The method in embodiment 5 that illustrates has played antiseized effect.Thereby as can be known, under the condition that the inorganic particulate content of titanium dioxide is identical in product, adopt the method for the invention to carry out the vapour phase polymerization of catalyzer preparation and divinyl, can effectively prevent the adhesion of rubber, obtain comparatively desirable rubber grain.
Embodiment 6
(1) catalyzer preparation
Catalyzer is by Nd (P
204)
3, Al (Me)
2H, Al
2Et
3Cl
3, the aluminum oxide of particle size range in 10-250 μ m
Five kinds of components such as the nanoparticle talcum powder with particle size range in 5-300nm form, and in catalyst preparation process, solvent for use is normal heptane, wherein the first component Nd (P
204)
3Amount be 1.0mmol, second component Al (Me)
2 HAmount be 100.0mmol, the 3rd component Al
2Et
3Cl
3Amount be 8.0mmol, the amount of the 4th component aluminum oxide is 20.5g, the talcous amount of BSA is 87.0g, makes powder catalyst F
1116.1g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer F that makes under nitrogen protection
1116.1g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 50 ℃ were reacted 1 hour, and obtained polymerisate 932.8g through the aftertreatment drying.Calculate catalyzer F
1Catalytic activity is 9.35 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 95.1%.Because talcum powder in product can't separate, calculate that in product, talcum powder content is 9.17wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Comparative Examples 6
(1) catalyzer preparation
Catalyzer is by Nd (P
204)
3, Al (Me)
2H, Al
2Et
3Cl
3, the aluminum oxide of particle size range in 10-250 μ m
Form Deng four kinds of components, in catalyst preparation process, solvent for use is normal heptane, wherein the first component Nd (P
204)
3Amount be 1.0mmol, second component Al (Me)
2The amount of H is 100.0mmol, the 3rd component Al
2Et
3Cl
3Amount be 8.0mmol, the amount of the 4th component aluminum oxide is 20.5g, makes powder catalyst F
229.3g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer F that makes under nitrogen atmosphere
229.3g, vacuumize and extract nitrogen, start stirring, pass into butadiene gas, under 0.1MPa pressure, 50 ℃ begin reaction, the particle diameter that adds simultaneously 87.0g be the talcum powder of 5-300nm as dispersion agent, reacted 1 hour, obtain polymerisate 932.5g through the aftertreatment drying.Calculate catalyzer F
2Catalytic activity is 9.35 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with comparative example 1.In polymerisate, the content of cis-1，4-polybutadiene is 95.1%.Because talcum powder in product can't separate, calculate that in product, talcum powder content is 9.17wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Contrast as can be known the catalyzer F of embodiment 6 with Comparative Examples 6 by embodiment 6
1Be comprised of first, second, third and fourth and BSA nanomete talc powder, BSA is as the part of catalyzer; And the catalyzer F of Comparative Examples 6
2Only formed by first, second, third and fourth component.Embodiment 6 carries out respectively the vapour phase polymerization of divinyl under identical condition with Comparative Examples 6, different is that Comparative Examples 6 adds talcum powder as dispersion agent in polymerization process.In embodiment 6 and Comparative Examples 6 gained polymerisates, talcous content is 9.17wt%.Can obviously observe, embodiment 6 products therefroms are not clamminess, and have good particle form; And Comparative Examples 6 products therefroms also are not clamminess, and have good particle form.The method in embodiment 6 and Comparative Examples 6 that illustrates has all played antiseized effect.Thereby as can be known, in product under the condition of inorganic particulate talcum powder content greater than 9wt%, adopt embodiment 6 and the described method of Comparative Examples 6 to carry out the vapour phase polymerization of catalyzer preparation and divinyl, all can effectively prevent the adhesion of rubber, obtain comparatively desirable rubber grain.
Embodiment 7
(1) catalyzer preparation
Catalyzer is by Nd (naph)
3, Al (i-Bu)
3, AlEtCl
2, particle size range silicon-dioxide and five kinds of components such as the nanoparticle carbon black of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is hexanaphthene, wherein the first component Nd (naph)
3Amount be 1.2mmol, second component Al (i-Bu)
3Amount be 96.0mmol, the 3rd component AlEtCl
2Amount be 7.2mmol, the amount of the 4th components silica is 2.4g, the amount of BSA carbon black is 7.2g, makes powder catalyst G 16.5g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer G16.5g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 70 ℃ were reacted 1 hour, and obtained polymerisate 2877.7g through the aftertreatment drying.Calculating catalyzer G catalytic activity is 2.4 * 10
6G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 93.4%.Because carbon black in product can't separate, calculate that in product, content of carbon black is 0.25wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 8
(1) catalyzer preparation
Catalyzer is by Nd (naph)
3, Al (i-Bu)
3, AlEtCl
2, particle size range silicon-dioxide and five kinds of components such as the nanoparticle carbon black of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is dimethylbenzene, wherein the first component Nd (naph)
3Amount be 1.2mmol, second component Al (i-Bu)
3Amount be 96.0mmol, the 3rd component AlEtCl
2Amount be 7.2mmol, the amount of the 4th components silica is 2.4g, the amount of BSA carbon black is 19.2g, makes powder catalyst H 28.3g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer H 28.3g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 70 ℃ were reacted 0.5 hour, and obtained polymerisate 1437.8g through the aftertreatment drying.Calculating catalyzer H catalytic activity is 2.35 * 10
6G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 93.4%.Because carbon black in product can't separate, calculate that in product, content of carbon black is 0.66wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 9
(1) catalyzer preparation
Catalyzer is by Nd (naph)
3, Al (i-Bu)
3, AlEtCl
2, particle size range silicon-dioxide and five kinds of components such as the nanoparticle carbon black of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is normal heptane, wherein the first component Nd (naph)
3Amount be 1.0mmol, second component Al (i-Bu)
3Amount be 20.0mmol, the 3rd component AlEtCl
2Amount be 6.0mmol, the amount of the 4th components silica is 200.0g, the amount of BSA carbon black is 1.0g, makes powder catalyst I 204.1g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyst I 204.1g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 60 ℃ were reacted 1 hour, and obtained polymerisate 1201.1g through the aftertreatment drying.Calculating the catalyst I catalytic activity is 1.2 * 10
6G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.2% because carbon black in product can't separate, and calculates that in product, content of carbon black is 0.1wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 10
(1) catalyzer preparation
Catalyzer is by Nd (OiPr)
3, MAO, t-BuCl, particle size range silicon-dioxide and five kinds of components such as the nanoparticle silicon-dioxide of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (OiPr)
3Amount be 1.2mmol, the amount of second component MAO is 50.0mmol, the amount of the 3rd component t-BuCl is 3.0mmol, the amount of the 4th components silica is 24g, the amount of BSA silicon-dioxide is 0.6g, makes powder catalyst J 29.0.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer J 29.0g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 40 ℃ were reacted 1 hour, and obtained polymerisate 124.3g through the aftertreatment drying.Calculating catalyzer J catalytic activity is 1.2 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 95.6%.Because silicon-dioxide in product can't separate, calculate that in product, dioxide-containing silica is 0.42wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 11
(1) catalyzer preparation
Catalyzer is by Nd (P
507)
3, Al (i-Bu)
2H, Al (i-Bu)
2Cl, particle size range aluminum oxide and five kinds of components such as the nanoparticle calcium carbonate of particle size range in 5-300nm in 10-250 μ m form, and in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (P
507)
3Amount be 1.2mmol, second component Al (i-Bu)
2The amount of H is 24.0mmol, the 3rd component Al (i-Bu)
2The amount of Cl is 12.0mmol, and the amount of the 4th component aluminum oxide is 4.8g, and the amount of BSA calcium carbonate is 2.4g, makes powder catalyst K 11.5g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer K 11.5g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 50 ℃ were reacted 1 hour, and obtained polymerisate 576.1g through the aftertreatment drying.Calculating catalyzer K catalytic activity is 4.8 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 95.1%.Because calcium carbonate in product can't separate, calculate that in product, calcium carbonate content is 0.42wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 12
(1) catalyzer preparation
Catalyzer is by Nd (P
204)
3, Al (Me)
2H, Al
2Et
3Cl
3, the aluminum oxide of particle size range in 10-250 μ m
Five kinds of components such as the nanoparticle antimonous oxide with particle size range in 5-300nm form, and in catalyst preparation process, solvent for use is ethylbenzene, wherein the first component Nd (P
204)
3Amount be 1.0mmol, second component Al (Me)
2The amount of H is 100.0mmol, the 3rd component Al
2Et
3Cl
3Amount be 8.0mmol, the amount of the 4th component aluminum oxide is 20.0g, the amount of BSA antimonous oxide is 6.4g, makes powder catalyst L 35.3g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer L 35.3g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 50 ℃ were reacted 1 hour, and obtained polymerisate 957.8g through the aftertreatment drying.Calculating catalyzer L catalytic activity is 9.6 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 95.0%.Because antimonous oxide in product can't separate, calculate that in product, antimonous oxide content is 0.67wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 13
(1) catalyzer preparation
Catalyzer is by Nd (naph)
3, Al (i-Bu)
3, AlEtCl
2, particle size range silicon-dioxide and five kinds of components such as the nanoparticle aluminium sesquioxide of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is normal hexane, wherein the first component Nd (naph)
3Amount be 1.0mmol, second component Al (i-Bu)
3Amount be 60.0mmol, the 3rd component AlEtCl
2Amount be 2.0mmol, the amount of the 4th components silica is 200.0g, the amount of BSA aluminium sesquioxide is 1.8g, makes powder catalyst M 207.1g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer M 207.1g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 70 ℃ were reacted 0.5 hour, and obtained polymerisate 1211.0g through the aftertreatment drying.The catalytic activity that calculates catalyzer M is 2.4 * 10
6G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 93.4%.Because aluminium sesquioxide in product can't separate, calculate that in product, aluminium sesquioxide content is 0.1wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 14
(1) catalyzer preparation
Catalyzer is by 2 ethyl hexanoic acid pr-nd enriched product, Al (i-Bu)
3, t-BuCl, particle size range silicon-dioxide and five kinds of components such as the nanoparticle polynite of particle size range in 5-300nm in 5-300 μ m form, in catalyst preparation process, solvent for use is normal heptane, wherein the amount of the first component 2 ethyl hexanoic acid pr-nd enriched product is 1.0mmol, second component Al (i-Bu)
3Amount be 60.0mmol, the amount of the 3rd component t-BuCl is 2.0mmol, the amount of the 4th components silica is 50.0g, the amount of BSA polynite is 7.0g, makes powder catalyst N 70.3g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyst n 70.3g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 60 ℃ were reacted 1 hour, and obtained polymerisate 1680.5g through the aftertreatment drying.The catalytic activity that calculates catalyst n is 1.68 * 10
6G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.3%.Because polynite in product can't separate, calculate that in product, polynite content is 0.42wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 15
(1) catalyzer preparation
Catalyzer is by Nd (P
204)
3, Al (i-Bu)
2H, AlEt
2Cl, particle size range silicon-dioxide and five kinds of components such as the nanoparticle calcium carbonate of particle size range in 5-350nm, carbon black in 10-250 μ m form, and in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (P
204)
3Amount be 1.2mmol, second component Al (i-Bu)
2The amount 48.0mmol of H, the 3rd component AlEt
2The amount of Cl is 7.2mmol, and the amount of the 4th components silica is 2.4g, and the amount of BSA calcium carbonate, carbon black is respectively 2.4g, makes powder catalyst O 15.3g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer O 15.3g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 50 ℃ were reacted 1 hour, and obtained polymerisate 578.5g through the aftertreatment drying.The catalytic activity that calculates catalyzer O is 4.8 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.9%.Because calcium carbonate, carbon black in product can't separate, calculate calcium carbonate in product, content of carbon black is 0.83wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 16
(1) catalyzer preparation
Catalyzer is by Nd (vers)
3, Al (i-Bu)
3, AlEtCl
2, particle size range carbon black and five kinds of components such as the nanoparticle titanium dioxide of particle size range in 5-300nm, calcium carbonate in 10-250 μ m form, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (naph)
3Amount be 1.2mmol, second component Al (i-Bu)
3Amount be 72.0mmol, the amount of the 3rd component AlEtCl2 is 3.6mmol, the amount of the 4th component carbon black is 4.8g, the amount of BSA titanium dioxide, calcium carbonate is respectively 1.0g, makes powder catalyst P 14.8g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyst P 14.8g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 40 ℃ were reacted 1 hour, and obtained polymerisate 115.7g through the aftertreatment drying.The catalytic activity that calculates catalyst P is 9.6 * 10
4G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 95.7%.Because titanium dioxide, calcium carbonate in product can't separate, calculate titanium dioxide in product, calcium carbonate content is 1.66wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 17
(1) catalyzer preparation
Catalyzer is by Nd (OiPr)
3, Al (i-Bu)
3, Al
2Et
3Cl
3, particle size range silicon-dioxide and five kinds of components such as the nanoparticle carbon black of particle size range in 5-300nm in 10-250 μ m form, in catalyst preparation process, solvent for use is toluene, wherein the first component Nd (OiPr)
3Amount be 1.0mmol, second component Al (i-Bu)
3Amount be 30.0mmol, the 3rd component Al
2Et
3Cl
3Amount be .1.0mmol, the amount of the 4th components silica is 50.0g, the amount of BSA carbon black is 125.0g, makes powder catalyst Q 196.1g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer Q 96.1g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 60 ℃ were reacted 1 hour, and obtained polymerisate 756.4g through the aftertreatment drying.The catalytic activity that calculates catalyzer Q is 7.48 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.0%.Because carbon black in product can't separate, calculate that in product, content of carbon black is 16.7wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 18
(1) catalyzer preparation
Under nitrogen atmosphere, add successively sequentially the first component rare earth compound Nd (naph) in container
31.2mmol, solvent normal hexane 50ml, second component promotor MAO 96.0mmol, the 3rd component AlEtCl
27.2mmol, silicon-dioxide (four component) 2.4g of particle size range in 10-250 μ m, extract solvent after stirring, add successively again solvent normal hexane, the BSA particle size range nanoparticle silicon-dioxide 2.4g in 5-300nm, extract solvent after stirring, obtain powder catalyst R 11.5g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer R 11.5g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 50 ℃ were reacted 1 hour, and obtained polymerisate 3026.9g through the aftertreatment drying.The catalytic activity that calculates catalyzer R is 2.52 * 10
6G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 97.5%.Because silicon-dioxide in product can't separate, calculate that in product, dioxide-containing silica is 0.1wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 19
(1) catalyzer preparation
Under nitrogen atmosphere, add successively the first component rare earth compound Nd (P in container
204)
3Amount be 1.0mmol, solvent toluene 50ml, second component promotor Al (Me)
2The amount of H is 100.0mmol, the 3rd component Al
2Et
3Cl
3Amount be that the amount of 8.0mmol, the aluminum oxide of particle size range in 10-250 μ m is 20.5g (the 4th component), extract solvent after stirring, adding successively solvent toluene, the talcous amount of the nanoparticle of BSA particle size range in 5-300nm is 80.0g again, extract solvent after stirring, obtain powder catalyst S 109.1g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyst S 109.1g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 50 ℃ were reacted 1 hour, and obtained polymerisate 1079.3g through the aftertreatment drying.The catalytic activity that calculates catalyst S is 1.08 * 10
6G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.9%.Because talcum powder in product can't separate, calculate that in product, talcum powder content is 7.2wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 20
(1) catalyzer preparation
Under nitrogen atmosphere, add successively the first component rare earth compound Nd (naph) in container
31.0mmol, solvent normal heptane 50ml, second component promotor Al (Me)
3Amount be 40.0mmol, the 3rd component Al
2Me
3Cl
3Amount be 5.0mmol, particle size range silicon-dioxide (the 4th component) 100.0g in 10-250 μ m, extract solvent after stirring, adding successively the amount of solvent normal heptane, the BSA particle size range nanoparticle titanium dioxide in 5-300nm is 1.0g again, extract solvent after stirring, obtain powder catalyst T 124.3g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer T 124.3g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 60 ℃ were reacted 1 hour, and obtained polymerisate 1071.8g through the aftertreatment drying.The catalytic activity that calculates catalyzer T is 1.07 * 10
6G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 94.4%.Because titanium dioxide in product can't separate, calculate that in product, content of titanium dioxide is 0.94wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 21
(1) catalyzer preparation
Under nitrogen atmosphere, add successively the first component rare earth compound Nd (naph) in container
31.2mmol, solvent hexanaphthene 50ml, second component promotor Al (i-Bu)
3Amount be 96.0mmol, the 3rd component AlEtCl
2Amount be that the amount of 7.2mmol, the silicon-dioxide of particle size range in 10-250 μ m is 2.4g (the 4th component), extract solvent after stirring, adding successively the amount of solvent hexanaphthene, the BSA particle size range nanoparticle carbon black in 5-300nm is 7.2g again, extract solvent after stirring, obtain powder catalyst U 16.5g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyzer U 16.5g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 70 ℃ were reacted 1 hour, and obtained polymerisate 3023.2g through the aftertreatment drying.The catalytic activity that calculates catalyzer U is 2.5 * 10
6G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 93.4%.Because carbon black in product can't separate, calculate that in product, content of carbon black is 0.24wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
Embodiment 22
(1) catalyzer preparation
Under nitrogen atmosphere, add successively the first component rare earth compound Nd (naph) in container
31.2mmol, solvent toluene 50ml, second component promotor Al (i-Bu)
3Amount be 72.0mmol, the 3rd component AlEtCl
2Amount be that the amount of 3.6mmol, the carbon black of particle size range in 10-250 μ m is 4.8g (the 4th component), extract solvent after stirring, add successively again nanoparticle titanium dioxide in 5-300nm of solvent toluene, BSA particle size range, the amount of calcium carbonate to be respectively 1.0g, extract solvent after stirring, obtain powder catalyst V 14.8g.
(2) butadiene gas-phase polymerization process
In the stirred reactor of purifying treatment, add the above-mentioned powder catalyst V 14.8g that makes under nitrogen protection, vacuumize and extract nitrogen; start stirring, pass into butadiene gas, under 0.1MPa pressure; 40 ℃ were reacted 1 hour, and obtained polymerisate 129.7g through the aftertreatment drying.The catalytic activity that calculates catalyst V is 1.07 * 10
5G ﹒ mol
-1﹒ h
-1Adopt the characterizing method assay products identical with embodiment 1.In polymerisate, the content of cis-1，4-polybutadiene is 95.7%.Because titanium dioxide, calcium carbonate in product can't separate, calculate titanium dioxide in product, calcium carbonate content is 1.5wt%.Can obviously observe products therefrom and not be clamminess, have good particle form.
By embodiment 1-22 as can be known, catalyzer is made of five kinds of components, by add the BSA nanoparticle in catalyst preparation process, can reach antiseized preferably effect when nanoparticle content is less.
In embodiment 1-17 catalyst preparation process, there is no specific order of addition(of ingredients).And embodiment 18-22 is in catalyst preparation process, according to certain order of addition(of ingredients), namely first to add successively the first component, solvent toluene, second component, the 3rd component, the 4th component in container, extract solvent after stirring, add successively again solvent toluene, BSA, extract solvent after stirring, obtain the catalyzer of the present invention of solid.Contrast as can be known by embodiment 1 and 18 contrasts, embodiment 4 and 19 contrasts, embodiment 6 and 20 contrasts, embodiment 7 and 21 contrasts, embodiment 16 and 22, the polymerisate that above-described embodiment makes is not clamminess, all played anti-adhesion effects preferably, and embodiment 18-22 increases than embodiment 1,4,6,7,16 by the activity of the catalyzer of the reinforced order gained of characteristics.
Comparative Examples 6 is to utilize first, second, third and fourth component to make catalyzer.In polymerization process, catalyst divinyl by preparation carries out vapour phase polymerization, introduce inorganic particulate as dispersion agent simultaneously in reactor, make its content in product〉9wt%, because dispersion agent can be scattered between rubber grain, play iris action, thereby play the effect that prevents that rubber is clamminess, obtain granular rubber.
But when dispersant dosage was less, the iris action between rubber grain died down, and anti-adhesion effects will descend greatly, did not even have antiseized effect.By Comparative Examples 1-5 as can be known, in product during content≤10 wt%, products therefrom is clamminess when inorganic particulate, and particle adhesion becomes piece.So, to be clamminess, be granular rubber in this polymerization technique and need be used relatively large dispersion agent.
Embodiment 1-5 has first, second, third and fourth identical component with the catalyzer of Comparative Examples 1-5, and different is that embodiment 1-5 has also introduced the BSA inorganic nano-particle in catalyst preparation process, makes it become the part of catalyzer, makes catalyzer.Embodiment 1-5 directly utilizes the gained catalyzer to carry out vapour phase polymerization and generates high cis-polybutadiene, and Comparative Examples 1-5 adds a certain amount of inorganic particulate as dispersion agent in the process of catalyst polymerizing butadiene.In the situation that in the polymerisate of embodiment 1-5 and Comparative Examples 1-5, the inorganic particulate massfraction is identical, embodiment 1-5 products therefrom is not clamminess, and particle form is good; And Comparative Examples 1-5 products therefrom is clamminess, and particle adhesion becomes piece.Explanation thus, embodiment 1-5 catalyzer used has played unforeseeable anti-adhesion effects.As seen, adopt catalyzer vapour phase polymerization of the present invention to prepare polyhutadiene, can still possess the irrealizable anti-adhesion effects of existing method in the situation that inorganic nano-particle content is low to moderate 0.1wt%, effectively prevent the adhesion of rubber, obtain desirable rubber grain.
Claims (10)
1. one kind is used for the catalyzer that vapour phase polymerization prepares high-cis-1，4-polybutadiene, it is characterized in that: the mixture that it is comprised of five components, wherein,
The first component is the rare earth compound of structure as shown in formula I,
In formula I, Ln is neodymium or pr-nd enriched product; R is alkoxyl group, carboxylic acid group, phosphate or phosphonate group;
Second component is any in aluminum alkyls, alkyl aluminium hydride, alkylaluminoxane;
The 3rd component is any in alkyl chloride, chlorination aluminum alkyls;
The 4th component is magnesium chloride, silicon-dioxide, carbon black or aluminum oxide;
BSA is nanoparticle, described nanoparticle be in nano silicon, nano carbon black, nano-aluminium oxide, nano titanium oxide, nanmeter antimong trioxide, nano-calcium carbonate, nanomete talc powder, nano imvite any or appoint several combinations;
The mol ratio of described the first component and second component is 1:20～100, the mol ratio of the first component and the 3rd component is 1:1～10, the mass ratio of the molar weight of the first component and the 4th component is 1:2000～200000, and the mass ratio of BSA and the 4th component is 1:0.125～200.
2. catalyzer according to claim 1, it is characterized in that: the C atomicity of the alkyl in described aluminum alkyls, alkyl aluminium hydride, alkylaluminoxane is 1-4.
3. catalyzer according to claim 1, it is characterized in that: the C atomicity of the alkyl in described alkyl chloride, chlorination aluminum alkyls is 1-4.
4. catalyzer according to claim 1, it is characterized in that: the particle diameter of described the 4th component is 10～250 μ m.
5. catalyzer according to claim 1, it is characterized in that: the particle diameter of described BSA is 5～300nm.
6. catalyzer according to claim 1, it is characterized in that: the C atomicity of the alkyl in described aluminum alkyls, alkyl aluminium hydride, alkylaluminoxane is 1-4, the C atomicity of the alkyl in described alkyl chloride, chlorination aluminum alkyls is 1-4, the particle diameter of described the 4th component is 10～250 μ m, and the particle diameter of described BSA is 5～300nm.
7. the preparation method of the catalyzer of any one in a claim 1 to 6, is characterized in that, comprises the following steps:
Under atmosphere of inert gases, first add the first component in container under 0～40 ℃ of condition, then add and to dissolve the first component, second component and can dissolve the solvent of the 3rd component again, then add successively sequentially second component, the 3rd component, the 4th component; Stir and extract solvent after the first component, second component and the 3rd component are dissolved fully; Add successively sequentially more described solvent, BSA; Extract described solvent after stirring, obtain pulverous described catalyzer.
8. preparation method according to claim 7, it is characterized in that: described solvent is saturated alkane or alkyl substituent aromatic compound.
9. preparation method according to claim 8, is characterized in that, described solvent is hexanaphthene, normal hexane, normal heptane, toluene, dimethylbenzene, ethylbenzene.
10. the method that right to use requires the catalyzer gas phase of any one in 1 to 6 to produce high-cis-1，4-polybutadiene rubber grain, is characterized in that: divinyl and described catalyzer are carried out gas phase polymerization more than 30 minutes under 40～70 ℃ of conditions.
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| CN103483481A (en) * | 2013-08-29 | 2014-01-01 | 浙江大学 | Polymerization system for preparing high-cis polybutadiene by gas-phase process and application thereof |
| CN103788271A (en) * | 2014-01-14 | 2014-05-14 | 浙江大学 | Catalyst for preparing medium vinyl polybutadiene by adopting gas phase method, and applications thereof |
| CN106220769A (en) * | 2016-08-28 | 2016-12-14 | 山东成泰化工有限公司 | A kind of EP rubbers carbon monoxide-olefin polymeric |
| CN106220766A (en) * | 2016-08-28 | 2016-12-14 | 山东成泰化工有限公司 | A kind of butadiene rubber carbon monoxide-olefin polymeric |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483481A (en) * | 2013-08-29 | 2014-01-01 | 浙江大学 | Polymerization system for preparing high-cis polybutadiene by gas-phase process and application thereof |
| CN103483481B (en) * | 2013-08-29 | 2016-03-02 | 浙江大学 | A kind of vapor phase process prepares polymerization system and the application thereof of high-cis polybutadiene |
| CN103788271A (en) * | 2014-01-14 | 2014-05-14 | 浙江大学 | Catalyst for preparing medium vinyl polybutadiene by adopting gas phase method, and applications thereof |
| CN106220769A (en) * | 2016-08-28 | 2016-12-14 | 山东成泰化工有限公司 | A kind of EP rubbers carbon monoxide-olefin polymeric |
| CN106220766A (en) * | 2016-08-28 | 2016-12-14 | 山东成泰化工有限公司 | A kind of butadiene rubber carbon monoxide-olefin polymeric |
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