CN1167775A - Process for hydrogenation of NBR - Google Patents

Process for hydrogenation of NBR Download PDF

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Publication number
CN1167775A
CN1167775A CN 97103557 CN97103557A CN1167775A CN 1167775 A CN1167775 A CN 1167775A CN 97103557 CN97103557 CN 97103557 CN 97103557 A CN97103557 A CN 97103557A CN 1167775 A CN1167775 A CN 1167775A
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China
Prior art keywords
hydrogenation
nbr
condition
sio
weight
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CN 97103557
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Chinese (zh)
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CN1058974C (en
Inventor
刘志才
陈彩云
潘安成
苏玲
刘桂莲
王振华
王月霞
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CHEMICAL ENGINEERING RESEARCH INST LANZHOU CHEMICAL ENGINEERING CORP
China Petrochemical Corp
Sinopec Lanzhou Chemical Industry Co
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CHEMICAL ENGINEERING RESEARCH INST LANZHOU CHEMICAL ENGINEERING CORP
China Petrochemical Corp
Sinopec Lanzhou Chemical Industry Co
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Priority to CN97103557A priority Critical patent/CN1058974C/en
Publication of CN1167775A publication Critical patent/CN1167775A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation

Abstract

A C-C double-bond selective hydrogenation process for nitrile rubber (NBR) features that NBR is pretreated by Pb-Al2O3, Pd-SiO2, or Pd-diatomite and then hydrogenated, resulting in high catalytic efficiency, low amount of used catalyst (0.05-0,25 Wt%) and low temp (70-100 deg. C). The hydrogenated degree can reach 90% or more without or with less catalyst ligand, so the product has excellent properties.

Description

A kind of method of chemigum hydrogenation
The present invention relates to the method for a kind of paracril (NBR) hydrogenation.
Carbon-carbon double bond hydrogen addition technology in the existing paracril has many kinds, and typically for example: GB1558491 is disclosed, adopts (R mB) 3RhX nBe catalyzer, wherein R=C 1～C 8Alkyl, C 6～C 15Or C 7～C 15Aryl, B=P or As, X=Cl or Br, m=2 or 3, n=1 or 3, its consumption are 0.01～10% (weight by dry rubber, wt%) the excessive part of use, the part consumption is 5～25% (weight by dry rubber, wt%), temperature of reaction is 50～150 ℃, and catalyzer need remove.Also disclose a kind of chemigum hydrogenation technology in US4581417, its condition is: catalyzer is RhX (PPh 3) 3, its consumption is 0.05～0.6% (weight by dry rubber wt%), the triphenylphosphine consumption is that 2% (weight by dry rubber, wt%), hydrogenation temperature is 100～145 ℃.Can find out thus before technology otherwise than moderate moisture greater catalytic agent consumption, under the excess ligand condition NBR is selected hydrogenation, otherwise at comparatively high temps than low catalyst levels and add under a certain amount of part condition NBR is selected hydrogenation, the former catalyst levels is higher, catalyst utilization is low, the precious metal waste is serious, uneconomical, and too much catalyzer and part, product performance there is disadvantageous effect, latter's temperature is too high, and hydrogenated products produce crosslinked, influence processed and applied.
The purpose of this invention is to provide and a kind ofly can improve Application of Catalyst efficient, carry out hydrogenation under the catalyst ligand condition not adding under low catalyst levels and the lesser temps or add less, hydrogenation is effective, the chemigum hydrogenation processing method of hydrogenated products excellent property.
The objective of the invention is to realize by following method:
The butyronitrile glue is placed the Al that year Pd is housed 2O 3Or SiO 2Or in the diatomaceous still, under hydrogen atmosphere, carry out pre-treatment, treatment condition are to handle 2～3hr down in 50～100 ℃ in hydrogen atmosphere.Glue after the processing is higher than 70 ℃ in temperature, is lower than 100 ℃, carries out hydrogenation reaction under pressure 3～15MPa, and the catalyzer general formula that uses is Rh (BR m) nXi, wherein B=P or As; R=phenyl (Ph) or ethyl (Et) or methyl; M=2 or 3; N=3 or 4; X=Cl or Br; I=1 or 3; Catalyst levels is 0.05～0.25%, preferably 0.05～0.2% (weight by dry rubber, wt%), triphenyl see consumption be 0～2.0% (weight by dry rubber, wt%).
Can be alternating copolymer as the used NBR of hydrogen in the chemigum hydrogenation method of the present invention, can be random copolymers also, and vinyl cyanide in the multipolymer (AN) content is 10～50wt%, and in the hydrogenation catalyst, B is P preferably; R is phenyl preferably; I preferably 1; X is Cl preferably, used Al 2O 3Or SiO 2Or diatomite, its aperture is preferably 100～1000A; Specific surface is preferably 50～500m 2/ g; Carry the Pd amount and be preferably 0.1～3wt%.Behind the hydrogenation, C=C at least 90% is reduced in the paracril.
Use chemigum hydrogenation method of the present invention, its advantage is to make paracril at the low catalyst consumption, simultaneously under the lesser temps, do not add or add less under the condition of catalyst ligand and carry out hydrogenation well, have at least two keys of 90% to be reduced, need not to remove catalyzer, and the product performance that obtain behind the hydrogenation are good.Both made the preceding NBR mooney viscosity of hydrogenation very high, the product performance behind the hydrogenation still can guarantee.
Below by embodiment, effect of the present invention made specify.
Embodiment 1
With the 5g particle diameter is 2 * 3mm, and specific surface is 100m 2/ g, the aperture is the Al that is loaded with 2wt%Pd of 200A 2O 3Join 30g NBR (AN=33%ML 1/4 100 ℃=50) be dissolved in the 270g chlorobenzene solution, 80 ℃ of temperature to molten
Solution-treated 2hr, the glue after the processing adds reactor, adds Rh (PPh 3) 3The logical hydrogen of Cl carries out hydrogenation reaction, hydrogenation technique condition and the results are shown in Table 1.
Embodiment 2
With Rh (PPh 3) 3Cl changes Rh (PPh into 3) 3Other step of Br is carried out hydrogenation reaction with embodiment 1, hydrogenation technique condition and the results are shown in Table 1.
Embodiment 3
With the 5g particle diameter is 2 * 3mm, and specific surface is 200m 2/ g, the aperture is the SiO that is loaded with 1wt%Pd of 400 2Join in the chlorobenzene sol solution this glue is handled, treatment temp is 60 ℃, and other condition adds Rh (PPh with embodiment 1 3) 3Cl carries out hydrogenation reaction, hydrogenation technique condition and the results are shown in Table 1.
Embodiment 4 is with Rh (PPh 3) 3Cl changes Rh (PEt into 3) 3Other step of Cl is with embodiment 3: hydrogenation technique condition and the results are shown in Table 1.
Embodiment 5
With Rh (PPh 3) 3Cl changes Rh (PPh into 3) 3Cl 3Other step is with embodiment 3, hydrogenation technique condition and the results are shown in Table 1.
Embodiment 6
With the 5g particle diameter is 2 * 3mm, and specific surface is 30m 2/ g, the aperture is that the diatomite that is loaded with 0.5wt%Pd of 600 joins in the chlorobenzene sol solution this glue is handled under 100 ℃ of temperature, condition is used Rh (AsPh again with embodiment 1 3) 3Cl is that catalyzer carries out hydrogenation reaction, hydrogenation technique condition and the results are shown in Table 1.
Embodiment 7
With Rh (AsPh among the embodiment 6 3) 3Cl changes Rh[P (CH into 3) 3] 3Cl carries out hydrogenation reaction, and the hydrogenation technique condition sees Table 1.Table 1
Embodiment The pretreating reagent kind Catalyst type Catalyst concn (weight by dry rubber, wt%) Triphenylphosphine (g) P H2?(Mpa) ??T ?(℃) ????t ??(hr) Hydrogenation ratio (%)
????1 ????2 ??Pd-Al 2O 3 ??Rh(PPh 3) 3Cl ??Rh(PPh 3) 3Br ????0.06 ????0.25 ??0.45 ????0 ????8.0 ????5.6 ??95 ??70 ????10 ????10 ????95 ????93
??3 ??4 ??5 ??Pd-SiO 2 ??Rh(PPh 3) 3Cl ??Rh(PEt 3) 3Cl ??Rh(PPh 3) 3Cl 3 ????0.06 ????0.07 ????0.08 ???0.3 ????0 ????0 ????7.5 ????7.5 ????7.5 ??85 ??85 ??85 ????10 ????10 ????10 ????93 ????90 ????93
??6 ??7 Pd-diatomite ??Rh(AsPh 3) 3Cl ??Rh[P(CH 3) 3] 3Cl ????0.08 ????0.08 ???0.3 ????0 ????80 ????5.6 ??80 ??95 ????12 ????12 ????92 ????93
Embodiment 8,9,10
With 30g NBR (AN=33%ML 1+4 100 ℃=50) be dissolved in the 270g chlorobenzene, carry out pre-treatment by the pretreatment process of last embodiment 1 after, add reactor, add Rh (PPh 3) 3Cl carries out hydrogenation under differing temps, pressure, reaction result sees Table 2.
Table 2
Embodiment Catalyst levels (weight by dry rubber, wt%) ??P H2??(MPa) ????T ??(℃) Hydrogenation ratio (%) ML 1+4 100℃
????8 ????0.10 ????13.0 ????80 ????98 ????80
????9 ????0.15 ????8.5 ????95 ????97 ????83
????10 ????0.18 ????3.5 ????95 ????97 ????100
Comparative example 1,2,3,4,5
With 30g NBR (AN=33% ML 1+4 100 ℃=50) be dissolved in the 270g chlorobenzene, not treated adding reactor adds Rh (PPh 3) 3Cl changes hydroconversion condition and carries out hydrogenation reaction, its hydrogenation technique condition and the results are shown in Table 3.
Table 3
Comparative example Catalyst levels (weight by dry rubber, wt%) ?P H2(MPa) ????T ??(℃) Hydrogenation ratio (%) ML 1+4 100℃
??1 ????0.15 ????9.0 ??80 ????70 ????75
????2 ????0.15 ????8.5 ??100 ????80 ????80
????3 ????0.15 ????8.0 ??130 ????96 ????140
????4 ????0.43 ????8.0 ??100 ????96 ????130
????5 ????0.39 ????10.0 ??100 ????96 ????125

Claims (3)

1. the method for a chemigum hydrogenation, the general formula of the hydrogenation catalyst that is adopted is Rh (BR m) nXi, wherein B=P or As, R=phenyl or ethyl or methyl, m=2 or 3, n=3 or 4, X=Cl or Br, i=1 or 3 is characterized in that at first paracril liquid being placed the Al that carries Pd is housed 2O 3Or SiO 2Or handle in the diatomaceous still, pretreated condition is 50～100 ℃ of temperature, time 2～3hr, glue after the processing is higher than 70 ℃ in temperature again and is lower than 100 ℃, pressure is to carry out hydrogenation reaction under the condition of 3～15MPa, the hydrogenation catalyst consumption be 0.05～0.25% (weight by dry rubber, wt%), the triphenylphosphine consumption be 0～2.0% (weight by dry rubber, wt%).
2. chemigum hydrogenation method according to claim 1, used Al when it is characterized in that pre-treatment 2O 3Or SiO 2Or diatomite, its aperture is 100～1000A, specific surface is 50～500m 2/ g.
3. chemigum hydrogenation method according to claim 1 and 2, used Al when it is characterized in that pre-treatment 2O 3Or SiO 2Or year attached amount of diatomaceous palladium is 0.1～3wt%.
CN97103557A 1997-04-22 1997-04-22 Process for hydrogenation of NBR Expired - Fee Related CN1058974C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318493C (en) * 2001-06-12 2007-05-30 拜尔公司 Low molecular weight hydrogenated nitrile rubber
CN101954278A (en) * 2010-09-15 2011-01-26 郴州高鑫铂业有限公司 Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof
CN103418413A (en) * 2013-07-14 2013-12-04 北京化工大学 Preparation method and hydrogenation application of immobilized catalyst
CN104140479A (en) * 2013-05-08 2014-11-12 中国石油天然气股份有限公司 Hydrogenated butadiene-acrylonitrile rubber preparation method
CN105214653A (en) * 2015-08-28 2016-01-06 北京化工大学 A kind of preparation method of carbon nanotube loaded nanoparticle catalyst

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1220300A (en) * 1982-12-08 1987-04-07 Polysar Limited Polymer hydrogenation process
DE3329974A1 (en) * 1983-08-19 1985-02-28 Bayer Ag, 5090 Leverkusen MANUFACTURE OF HYDRATED NITRILE RUBBER

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318493C (en) * 2001-06-12 2007-05-30 拜尔公司 Low molecular weight hydrogenated nitrile rubber
CN101954278A (en) * 2010-09-15 2011-01-26 郴州高鑫铂业有限公司 Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof
CN104140479A (en) * 2013-05-08 2014-11-12 中国石油天然气股份有限公司 Hydrogenated butadiene-acrylonitrile rubber preparation method
CN104140479B (en) * 2013-05-08 2016-01-27 中国石油天然气股份有限公司 A kind of preparation method of hydrogenated nitrile-butadiene rubber
CN103418413A (en) * 2013-07-14 2013-12-04 北京化工大学 Preparation method and hydrogenation application of immobilized catalyst
CN103418413B (en) * 2013-07-14 2015-01-28 北京化工大学 Preparation method and hydrogenation application of immobilized catalyst
CN105214653A (en) * 2015-08-28 2016-01-06 北京化工大学 A kind of preparation method of carbon nanotube loaded nanoparticle catalyst
CN105214653B (en) * 2015-08-28 2018-09-21 北京化工大学 A kind of preparation method of carbon nanotube loaded nanoparticle catalyst

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