CN104140480B - A kind of polystyrene Hydrogenation is for the method for poly-cyclohexyl. vinyl - Google Patents
A kind of polystyrene Hydrogenation is for the method for poly-cyclohexyl. vinyl Download PDFInfo
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Abstract
The present invention relates to a kind of polystyrene Hydrogenation method for poly-cyclohexyl. vinyl.The method includes: has with surface and runs through the SiO 2 hollow microsphere of macropore as carrier, with equi-volume impregnating or ion exchange load active component M, obtains the load hydrogenation catalyst that M load capacity is 1 10wt%；Dissolve 2 10g polystyrene with organic solvent and obtain glue, take the load hydrogenation catalyst accounting for polystyrene quality 10 50wt%, load hydrogenation catalyst and glue are joined in autoclave, by autoclave N2It is passed through hydrogen after emptying, carries out hydrogenation reaction；Load hydrogenation catalyst is reclaimed in glue centrifugation after hydrogenation reaction, is evaporated glue obtaining poly-cyclohexyl. vinyl.The polystyrene Hydrogenation with M/SHMs as catalyst that the present invention provides has the features such as catalyst activity height, hydrogenation efficiency height, reaction condition milder and cost are lower for the method for poly-cyclohexyl. vinyl.
Description
Technical field
The present invention relates to a kind of method that polystyrene catalytic hydrogenation prepares poly-cyclohexyl. vinyl, belong to hydrogenation of polymer and prepare
Speciality polymer field of material technology.
Background technology
Poly-cyclohexyl. vinyl (PVCH) is the high score of the function admirable prepared by being hydrogenated with the phenyl ring on PS chain
Sub-material.Owing to greatly improving its glass transition temperature (T after hydrogenationg), make this material have high temperature resistant, corrosion-resistant,
The advantages such as resistance to ozone, radiation hardness, thus it is widely used in functional digital disc substrate, anti-rotten material, nano material template
Etc. aspect.
Owing to aromatic ring in polystyrene (PS) to be hydrogenated with the hydrogenation difficulty than p-C=C-, traditional homogeneous catalyst (as
Wilkinson catalyst) it cannot be hydrogenated with, therefore the main method of PS hydrogenation is heterogeneous hydrogenation method.Open
The PS hydrogenation catalyst system sent out has Ni base catalyst (US Patent6417287B1), Pd base catalyst (Nakatani, H.;
Nitta,K.-H.;Uozumi,T.;Soga,K.,Preparation and Characterization of Hydrogenated
Syndiotactic Polystyene.Polymer1999,40,1623), Pt base catalyst (US Patent6399538), Rh base
Catalyst (Helbig, M.;Inoue,H.;Vogl,O.,Preparation and Characterization of Head-to-Head
Polymers.VIII.Head-to-Head Poly(vinyl cyclohexane).J.Polym.Sci.,Polym.Symp.1978,
63,329) etc..Owing to hydrogenation of polymer reaction system has gelatin viscosity height, polymer molecule spin dynamics diameter (RH)
The features such as greatly, diffusion rate is slow so that hydrogenation of polymer reaction exists the most different with little molecule hydrogenation reaction, highlights
Show that the pore passage structure of catalyst carrier plays vital effect to hydrogenation rate., Jie micro-for high-specific surface area
Hole carrier, such as activated carbon, mesoporous Al2O3And SiO2Carriers etc., its narrow duct makes PS molecule cannot be introduced into leading
Causing diffusion extremely difficult, so that major part active sites can not be fully utilized, and it is relatively low to ultimately result in hydrogenation efficiency；Right
In atresia or the super big hole carrier of low specific surface area, such as BaSO4Or CaCO3Deng, although PS molecule can quickly and its
Active sites haptoreaction in surface or macropore, but its low specific surface area causes active sites number very few, needs increase to urge
The reaction rate that agent consumption guarantee is certain, thus cause the cost of hydrogenation process to increase.Therefore, how load is eliminated
The body aperture impact on diffusion, had both ensured that polymer was fully contacted with active sites, had been provided that again sufficient amount of active sites,
Thus obtain high reaction rate, become the difficult point of polymer heterogeneous hydrogenation catalyst research exploitation.
1998, (Chang J-R, the Huang S-M.Pd/Al such as Chang2O3Catalysts for Selective Hydro-
genation of Polystyrene-block-polybutadiene-block-polystyrene Thermoplastic Elastomers[J].
Industrial&Engineering Chemistry Research,1998;37 (4): 1220-1227) Pd/Al is used2O3Catalyst
Polystyrene-polybutadiene-polystyrene is combined segmented polymer and has carried out selective hydrogenation, find with palladium
The catalyst prepared for palladium source, active component is the appearance aspect that eggshell type is distributed in catalyst, polymer molecule be not required to into
Enter and react to depths, catalyst duct, reduce the diffusion mass transfer impact on hydrogenation reaction to a certain extent, but owing to urging
Agent utilization rate of inner surface is the highest, and catalyst active center's number is less, and therefore catalyst activity is the highest.Nineteen ninety-five,
Dow Chemical (US Patent5612422) is with potassium silicate for silicon source, and Methanamide is stabilizer, is prepared for aperture and concentrates
It is distributed in the macro-pore SiO of 300-400nm2Carrier, specific surface area is 14.2m2/ g, pore volume is 1.37cm3/ g, loads 5%
Rh or Pd be active component, Hydrogen Vapor Pressure be 9.0MPa, temperature be 130 DEG C, the response time be the condition of 4h
Under, hydrogenation of polymer degree reaches more than 90%.This catalyst is with macro-pore SiO2For carrier, though weakening to a great extent
The impact of endoporus diffusion, but the specific surface area of catalyst is relatively low, be unfavorable for the dispersion of active substance and the raising of load capacity,
Thus decrease the number in active center；It addition, macro-pore SiO2Irregular profile and irregular pore passage structure are the most right
Polymer molecule being diffused with in duct necessarily affects, and causes reacting required condition harshness, and Catalytic Hydrogenation Properties also can be subject to
To impact.
In sum, how to improve the accessibility of PS molecule and catalyst activity position, make full use of the activity of catalyst
Center, becomes the key point of design PS heterogeneous hydrogenation catalyst.Existing PS heterogeneous hydrogenation catalyst is still deposited
The shortcomings such as the highest in catalysis activity, catalyst amount is excessive, and reaction condition is excessively harsh.Therefore, develop high activity,
The support type PS hydrogenation catalyst of high usage has important practical significance.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of polystyrene Hydrogenation for poly-cyclohexyl. vinyl
Method, run through the SiO 2 hollow microsphere (SHMs) of macropore by using surface to have, and using it as carrier loaded
Active metal can effectively eliminate endoporus as heterogeneous catalysis (load hydrogenation catalyst, M/SHMs), this catalyst
The impact of diffusion, and make full use of the active component in microsphere surfaces externally and internally and duct, thus real under the conditions of relatively mild
Existing PS deep hydrogenation prepares poly-cyclohexyl. vinyl.
For reaching above-mentioned purpose, the invention provides a kind of polystyrene Hydrogenation method for poly-cyclohexyl. vinyl, its bag
Include following steps:
Have with surface and run through the SiO 2 hollow microsphere of macropore as carrier, bear with equi-volume impregnating or ion exchange
Carry active component M, obtain the load hydrogenation catalyst that M load capacity is 1-10wt%；
Dissolve 2-10g polystyrene with the suitable organic solvent of 100mL and obtain glue, take and account for polystyrene quality 10-50wt%
Load hydrogenation catalyst, described load hydrogenation catalyst and glue are joined in autoclave, high pressure is anti-
Answer still N2Inputting hydrogen after emptying, then temperature be 100-170 DEG C, Hydrogen Vapor Pressure be 5-15MPa, response time
For 5-15h, the preferred 1200rpm of mixing speed 800-1500rpm() under conditions of, carry out hydrogenation reaction；
Load hydrogenation catalyst is reclaimed in glue centrifugation after hydrogenation reaction, then is evaporated being gathered to glue
Cyclohexyl. vinyl.
In the above-mentioned polystyrene Hydrogenation method for poly-cyclohexyl. vinyl, it is preferable that the method also includes with tetrahydrochysene furan
The step that the load hydrogenation catalyst reclaimed is washed by solvent of muttering.After washing, this load hydrogenation is catalyzed
Agent can be recycled and reused for the above-mentioned polystyrene Hydrogenation method for poly-cyclohexyl. vinyl.
In the above-mentioned polystyrene Hydrogenation method for poly-cyclohexyl. vinyl, it is preferable that surface has runs through the two of macropore
The particle diameter of silicon oxide tiny balloon (SHMs) be 5-30 μm, shell thickness be 0.5-2 μm, specific surface area be 30-150m2/g、
Pore volume is 0.4-2.0cm3/ g, the aperture running through macropore on its surface is 250-650nm.
In the above-mentioned polystyrene Hydrogenation method for poly-cyclohexyl. vinyl, it is preferable that active component M used
For Pd, Pt, Rh or Ni etc..
In the above-mentioned polystyrene Hydrogenation method for poly-cyclohexyl. vinyl, it is preferable that equi-volume impregnating uses solution
Concentration is the MCl of 0.06-0.16mol/LxHCl solution impregnate, x=2 or 3, ion exchange use concentration be
M (the NH of 0.03-0.08mol/L3)yClzAmmonia spirit carry out ion exchange, y=4 or 6, z=2.
In the above-mentioned polystyrene Hydrogenation method for poly-cyclohexyl. vinyl, it is preferable that the organic solvent used includes
The mixture of one or more in decahydronaphthalenes, oxolane, hexamethylene, methyl tertiary butyl ether(MTBE) and hexahydrotoluene etc..
It is highly preferred that above-mentioned organic solvent includes the mixture of one or more in decahydronaphthalenes, oxolane and hexamethylene etc..
In the above-mentioned polystyrene Hydrogenation method for poly-cyclohexyl. vinyl, it is preferable that the degree of hydrogenation of polystyrene is
More than 95%.
In the above-mentioned polystyrene Hydrogenation method for poly-cyclohexyl. vinyl, it is preferable that surface has runs through the two of macropore
Silicon oxide tiny balloon through the following steps that preparation:
The preparation of internal layer aqueous phase: 7-21g waterglass, 11-33g deionized water and 0.6-1.8g sodium polyacrylate are mixed,
Obtaining internal layer aqueous phase, wherein, the relative viscosity of described internal layer aqueous phase is 4.0-5.0, SiO in described waterglass2Content
For 26wt.%；
The preparation of oil phase: by 72mL normal hexane, 1.5g Tween80,1.5g Span80 mixing, obtain oil phase；
The preparation of outer water phase: mixed with 250mL deionized water by inorganic salt, obtaining concentration is outside 0.3-3mol/L
Layer aqueous phase；
Internal layer aqueous phase is mixed with oil phase, with rotating speed stirring and emulsifying 1min of 6000-14000rpm, forms water/oil systems；
Water/oil systems is mixed with outer water phase, under agitation in normal-temperature reaction 2h, be then passed through filter, go from
Sub-water and washing with alcohol, fully dried, prepare described surface and there is the SiO 2 hollow microsphere running through macropore.
According to specific embodiments of the present invention, during there is the SiO 2 hollow microsphere running through macropore in preparation,
The molecular weight of the sodium polyacrylate used can be 4000-30000, and the inorganic salt used can be NH4HCO3、
NH4Cl、NH4NO3Or (NH4)2SO4Deng, for internal layer aqueous phase viscosity control can by regulation deionized water,
Waterglass, the addition of sodium polyacrylate control.The macropore diameter of this tiny balloon can adjust within the range, should
Adjustment can realize by using the sodium polyacrylate of different molecular weight.
The process preparing the above-mentioned SiO 2 hollow microsphere having and running through macropore is with water glass solution and a certain amount of water
Soluble polymer (sodium polyacrylate) is internal layer aqueous phase, with normal hexane, Tween80 and Span80 as oil phase (OP), with nothing
Machine saline solution is outer water phase；First IWP Yu OP emulsifying under high velocity agitation is formed W/O system, then by upper
The system of stating joins in OWP, and the sodium silicate in IWP diffuses to OP interface and occurs hydrolysis condensation reaction to generate SiO2Shell
Layer；Meanwhile, the sodium polyacrylate in IWP, to external diffusion, is formed in silica shell and runs through macropore；Pass through
The relative viscosity of regulation IWP, can control the penetrability of macroporous structure；By changing the molecular weight of sodium polyacrylate,
Macropore diameter can be regulated.
Present invention also offers a kind of poly-cyclohexyl. vinyl, it is for poly-cyclohexyl. vinyl according to above-mentioned polystyrene Hydrogenation
Method prepare.
The catalyst carrier that above-mentioned polystyrene Hydrogenation provided by the present invention is used for the method for poly-cyclohexyl. vinyl
Have the SiO 2 hollow microsphere running through macropore for surface, the load active metal M loaded is evenly dispersed in microsphere
Inside surfaces externally and internally and duct, the specific surface area that carrier is bigger can ensure that catalyst has abundant active center, microsphere
The macropore that surface is enriched enables polymer molecule free diffusing and fills with the active component in microsphere surfaces externally and internally and endoporus
Tap is touched, and effectively eliminates the harmful effect of polymer molecule diffusion couple hydrogenation reaction performance in carrier duct, can
The purpose of PS deep hydrogenation is realized under the conditions of relatively mild.The polyphenyl with M/SHMs as catalyst that the present invention provides
Ethylene hydrogenation is prepared the method relatively traditional method of poly-cyclohexyl. vinyl and is had catalyst activity height, hydrogenation efficiency height, reaction bar
Part milder and the feature such as cost is lower.
Accompanying drawing explanation
Fig. 1 a and Fig. 1 b has the scanning of the SiO 2 hollow microsphere running through macropore by the surface that embodiment 1-5 is used
Electromicroscopic photograph；
The transmission electron microscope photo of the Pd/SHMs catalyst that Fig. 2 a is used by embodiment 1；
The Pd size of microcrystal scattergram of the Pd/SHMs catalyst that Fig. 2 b is used by embodiment 1；
Fig. 3 is PVCH Yu the PS infrared spectrogram prepared by embodiment 3；
Fig. 4 a be the surface in comparative example 1 be the stereoscan photograph of the SiO 2 hollow microsphere of smooth structure；
Fig. 4 b be the surface in comparative example 2 be the stereoscan photograph of the SiO 2 hollow microsphere of non-through macroporous structure.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing technology to the present invention
Scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
In embodiment, synthesize and raw materials used be SILVER REAGENT.The structure of the SHMs employed in embodiment such as Fig. 1 a and
Shown in scanning electron microscope (SEM) photo of Fig. 1 b, its mean diameter is that 15 μm, shell average thickness are 1 μm, compare table
Area is 120m2/ g, pore volume are 1.5cm3/ g, the average pore size running through macropore on its surface is 500nm.
In embodiment, SEM picture produces in Holland and obtains on FEI Quanta200F type field emission scanning electron microscope；
TEM picture produces JEM2100LaB6 type transmission electron microscope in Japan and obtains；Infrared spectrum produces in the U.S.
Record on Magna-IR560E.S.P type Fourier transform infrared (FT-IR) spectrogrph.
Embodiment 1
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
With PdCl2HCl solution be impregnation liquid, use equi-volume impregnating impregnate on SHMs, prepare
Active metal load capacity is the catalyst Pd/SHMs of 5wt.%；Transmission electron microscope (TEM) photo of this catalyst such as figure
Shown in 2a, Pd size of microcrystal is distributed as shown in Figure 2 b；
2g PS is dissolved in 100mL hexamethylene (80vol%) and obtains glue in the mixture of oxolane (20vol%)；
Take 0.5g Pd/SHMs and join in glue, high-pressure hydrogenation reactor carries out catalytic hydrogenation reaction, react bar
Part is: temperature 150 DEG C, Hydrogen Vapor Pressure 6MPa, response time 10h, stir speed (S.S.) 1200rpm；
After reaction terminates, it is centrifuged glue separating and recovering Pd/SHMs, sharp again after being then passed through oxolane washing
With, glue is evaporated, evaporates organic solvent therein and obtain the degree of hydrogenation of PVCH, PS and be shown in Table 1.
Embodiment 2
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
With Pd (NH3)4Cl2Ammonia spirit be impregnation liquid, use ion exchange to SHMs process, be prepared into
To the catalyst Pd/SHMs that active metal load capacity is 3wt.%；
3g PS is dissolved in 100mL decahydronaphthalenes solvent and obtains glue, take 0.8g Pd/SHMs and join in glue,
Carrying out catalytic hydrogenation reaction in high-pressure hydrogenation reactor, reaction condition is: temperature 140 DEG C, Hydrogen Vapor Pressure 8MPa,
Response time 8h, stir speed (S.S.) 1200rpm；
After reaction terminates, it is centrifuged glue separating and recovering Pd/SHMs, sharp again after being then passed through oxolane washing
With, glue is evaporated, evaporates organic solvent therein and obtain the degree of hydrogenation of PVCH, PS and be shown in Table 1.
Embodiment 3
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
With RhCl3HCl solution be impregnation liquid, use equi-volume impregnating impregnate on SHMs, prepare
Active metal load capacity is the catalyst Rh/SHMs of 8wt.%；
5g PS is dissolved in 100mL tetrahydrofuran solvent, takes 1g Rh/SHMs and join in glue, add at high pressure
Hydrogen reactor carries out catalytic hydrogenation reaction.Reaction condition is: temperature 120 DEG C, Hydrogen Vapor Pressure 10MPa, response time
10h, stir speed (S.S.) 1200rpm；
After reaction terminates, it is centrifuged glue separating and recovering Rh/SHMs, sharp again after being then passed through oxolane washing
With, glue is evaporated, evaporates organic solvent therein and obtain the degree of hydrogenation of PVCH, PS and be shown in Table 1.
PVCH Yu PS infrared spectrogram prepared by the present embodiment is as shown in Figure 3；As seen from Figure 3, hydrogenation is anti-
Ying Hou, PVCH infrared spectrum is positioned at 3027.3cm-1Place belongs to the vibration peak of-C-H on aromatic ring and is positioned at 1492.1cm-1
Place belongs to the vibration peak of-C=C-on aromatic ring and disappears, and is positioned at 2921.6cm-1And 2850.9cm-1Place belongs to-CH2Symmetrical and
Nonsymmetrical vibration peak strengthens.
Because polystyrene hydrogenation is the C--C single bond saturated for the double-bond hydrogenation on phenyl ring one-tenth hexamethylene, therefore catalytic hydrogenation
Rear infrared spectrum represents on the aromatic ring that phenyl ring exists the vibration peak of-C=C-in the vibration peak of-C-H and aromatic ring disappear, explanation
Phenyl ring is hydrogenated；-CH2Symmetrical and nonsymmetrical vibration peak strengthens, and illustrates to generate hexamethylene.Result shown in Fig. 3 can
With catalyst prepared by explanation the present embodiment, there is good hydrogenation effect, the degree of hydrogenation that comparison is high can be reached.
Embodiment 4
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
With Rh (NH3)5Cl3Ammonia spirit be impregnation liquid, use ion exchange to SHMs process, be prepared into
To the loaded catalyst Rh/SHMs that active metal load capacity is 2wt.%；
2g PS is dissolved in 100mL tetrahydrofuran solvent and obtains glue, take 1.0g Rh/SHMs and join in glue,
Carrying out catalytic hydrogenation reaction in high-pressure hydrogenation reactor, reaction condition is: temperature 80 DEG C, Hydrogen Vapor Pressure 6MPa, instead
8h between Ying Shi, stir speed (S.S.) 1200rpm；
After reaction terminates, it is centrifuged glue separating and recovering Rh/SHMs, sharp again after being then passed through oxolane washing
With, glue is evaporated, evaporates organic solvent therein and obtain the degree of hydrogenation of PVCH, PS and be shown in Table 1.
Embodiment 5
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
With Ni (NO3)2Solution is impregnation liquid, uses equi-volume impregnating to impregnate on SHMs, prepares activity
Content of metal is the loaded catalyst Ni/SHMs of 10%；
4g PS is dissolved in 100mL methyl cyclohexane alkane solvents and obtains glue, take 1.0g Ni/SHMs and join glue
In, high-pressure hydrogenation reactor carries out catalytic hydrogenation reaction, reaction condition is: temperature 170 DEG C, Hydrogen Vapor Pressure 8MPa,
Response time 10h, stir speed (S.S.) 1200rpm；
After reaction terminates, it is centrifuged glue separating and recovering Ni/SHMs, sharp again after being then passed through oxolane washing
With, glue is evaporated, evaporates organic solvent therein and obtain the degree of hydrogenation of PVCH, PS and be shown in Table 1.
Embodiment 6
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
Loaded catalyst Pd/SHMs after embodiment 1 reaction being terminated is reclaimed by centrifugation, then uses tetrahydrochysene
Furan washs 3 times, uses the reaction condition that embodiment 1 is identical, again adds it in reaction system, investigate it right
The Hydrogenation of PS, degree of hydrogenation is shown in Table 1.
Embodiment 7
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
Loaded catalyst Pd/SHMs after embodiment 2 reaction being terminated is reclaimed by centrifugation, then uses tetrahydrochysene
Furan washs 3 times, uses the reaction condition that embodiment 2 is identical, again adds it in reaction system, investigate it right
The Hydrogenation of PS, degree of hydrogenation is shown in Table 1.
Embodiment 8
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
Loaded catalyst Rh/SHMs after embodiment 3 reaction being terminated is reclaimed by centrifugation, then uses tetrahydrochysene
Furan washs 3 times, uses the reaction condition that embodiment 3 is identical, again adds it in reaction system, investigate it right
The Hydrogenation of PS, degree of hydrogenation is shown in Table 1.
Embodiment 9
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
Loaded catalyst Rh/SHMs after embodiment 4 reaction being terminated is reclaimed by centrifugation, then uses tetrahydrochysene
Furan washs 3 times, uses the reaction condition that embodiment 4 is identical, again adds it in reaction system, investigate it right
The Hydrogenation of PS, degree of hydrogenation is shown in Table 1.
Embodiment 10
Present embodiments providing a kind of PS Hydrogenation method for PVCH, it comprises the following steps:
Loaded catalyst Ni/SHMs after embodiment 5 reaction being terminated is reclaimed by centrifugation, uses oxolane
Wash 3 times, use the reaction condition that embodiment 5 is identical, again add it in reaction system, investigate it to PS
Hydrogenation, degree of hydrogenation is shown in Table 1.
Comparative example 1
This comparative example provides a kind of PS Hydrogenation method for PVCH, and it is that using a kind of is smooth structure with surface
SiO 2 hollow microsphere (existing without macropore, its SEM photograph is as shown in fig. 4 a) as the catalyst of carrier, survey
Its reactivity worth fixed, contrasts with embodiment 1.According to the PS method of hydrotreating in embodiment 1, reaction condition is constant,
The degree of hydrogenation of PS is 18% after completion of the reaction.
Comparative example 2
This comparative example provides a kind of PS Hydrogenation method for PVCH, and it is that using a kind of is that non-through is big with surface
The tiny balloon (its SEM photograph is as shown in Figure 4 b) of pore structure, as the catalyst of carrier, measures its reactivity worth,
Contrast with embodiment 1.According to the PS method of hydrotreating in embodiment 1, reaction condition is constant, after completion of the reaction PS
Degree of hydrogenation be 21%.
Table 1PS is hydrogenated with degree
| Embodiment | Degree of hydrogenation |
| 1 | 96.5% |
| 2 | 97.8% |
| 3 | 95.4% |
| 4 | 96.3% |
| 5 | 95.5% |
| 6 | 94.2% |
| 7 | 96.4% |
| 8 | 93.8% |
| 9 | 94.2% |
| 10 | 91.3% |
By the evaluation result shown in table 1 and comparative example 1,2 it can be seen that use surface to have the SHMs running through macroporous structure
The catalyst prepared for carrier has good PS hydrogenation activity, and first time and secondary PS degree of hydrogenation are all more than 90%.
Use surface without the SHMs of macroporous structure and non-through macroporous structure be the catalyst PS hydrogenation activity for preparing of carrier not
Height, degree of hydrogenation is respectively 18% and 21%.The polystyrene with M/SHMs as catalyst that this explanation present invention provides
Hydrogenation is for the advantage that method has catalyst activity height compared with traditional method, hydrogenation efficiency is high of poly-cyclohexyl. vinyl, meanwhile,
Preparation method provided by the present invention also has the features such as reaction condition gentleness, low cost.
Claims (8)
1. polystyrene Hydrogenation is for a method for poly-cyclohexyl. vinyl, and it comprises the following steps:
Have with surface and run through the SiO 2 hollow microsphere of macropore as carrier, bear with equi-volume impregnating or ion exchange
Carry active component M, obtain the load hydrogenation catalyst that M load capacity is 1-10wt.%；Wherein, described surface has
The particle diameter of the SiO 2 hollow microsphere running through macropore be 5-30 μm, shell thickness be that 0.5-2 μm, specific surface area are
30-150m2/ g, pore volume are 0.4-2.0cm3/ g, the aperture running through macropore on its surface is 250-650nm；
Dissolve 2-10g polystyrene with 100mL organic solvent and obtain glue, take and account for polystyrene quality 10-50wt.%
Load hydrogenation catalyst, joins in autoclave, by reaction under high pressure by described load hydrogenation catalyst and glue
Still N2Inputting hydrogen after emptying, then temperature be 100-170 DEG C, Hydrogen Vapor Pressure be 5-15MPa, the response time be
Under conditions of 5-15h, mixing speed 800-1500rpm, carry out hydrogenation reaction；
Load hydrogenation catalyst is reclaimed in glue centrifugation after hydrogenation reaction, then is evaporated being gathered to glue
Cyclohexyl. vinyl.
Polystyrene Hydrogenation the most according to claim 1 is for the method for poly-cyclohexyl. vinyl, wherein, the method
Also include the step load hydrogenation catalyst reclaimed washed with tetrahydrofuran solvent.
Polystyrene Hydrogenation the most according to claim 1 is for the method for poly-cyclohexyl. vinyl, wherein, described work
Property component M is Pd, Pt, Rh or Ni.
4. according to the polystyrene Hydrogenation described in claim 1 or 3 for the method for poly-cyclohexyl. vinyl, wherein, etc.
Volume impregnation method uses solution concentration to be the MCl of 0.06-0.16mol/LxHCl solution impregnate, x=2 or 3, from
M (the NH that sub-exchange process uses concentration to be 0.03-0.08mol/L3)yClzAmmonia spirit carry out ion exchange, y=4 or 6,
Z=2.
Polystyrene Hydrogenation the most according to claim 1 is for the method for poly-cyclohexyl. vinyl, wherein, described in have
Machine solvent includes one or more in decahydronaphthalenes, oxolane, hexamethylene, methyl tertiary butyl ether(MTBE) and hexahydrotoluene
Mixture.
The most according to claim 1 or 5, polystyrene Hydrogenation is for the method for poly-cyclohexyl. vinyl, wherein, and institute
State the mixture of one or more that organic solvent includes in decahydronaphthalenes, oxolane and hexamethylene.
Polystyrene Hydrogenation the most according to claim 1 is for the method for poly-cyclohexyl. vinyl, wherein, described poly-
Cinnamic degree of hydrogenation is more than 95%.
Polystyrene Hydrogenation the most according to claim 1 is for the method for poly-cyclohexyl. vinyl, wherein, described table
Mask have run through macropore SiO 2 hollow microsphere through the following steps that preparation:
The preparation of internal layer aqueous phase: 7-21g waterglass, 11-33g deionized water and 0.6-1.8g sodium polyacrylate are mixed,
Obtaining internal layer aqueous phase, wherein, the relative viscosity of described internal layer aqueous phase is 4.0-5.0, SiO in described waterglass2Content
For 26wt.%；
The preparation of oil phase: 72mL normal hexane, 1.5g Tween 80,1.5g Span 80 are mixed, obtains oil phase；
The preparation of outer water phase: mixed with 250mL deionized water by inorganic salt, obtaining concentration is outside 0.3-3mol/L
Layer aqueous phase；
Internal layer aqueous phase is mixed with oil phase, with rotating speed stirring and emulsifying 1min of 6000-14000rpm, forms water/oil systems；
Water/oil systems is mixed with outer water phase, under agitation in normal-temperature reaction 2h, be then passed through filter, go from
Sub-water and washing with alcohol, fully dried, prepare described surface and there is the SiO 2 hollow microsphere running through macropore.
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