CN1058973C - Process for hydrogenation of acrylonitrile-butadiene rubber - Google Patents
Process for hydrogenation of acrylonitrile-butadiene rubber Download PDFInfo
- Publication number
- CN1058973C CN1058973C CN97103556A CN97103556A CN1058973C CN 1058973 C CN1058973 C CN 1058973C CN 97103556 A CN97103556 A CN 97103556A CN 97103556 A CN97103556 A CN 97103556A CN 1058973 C CN1058973 C CN 1058973C
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- CN
- China
- Prior art keywords
- hydrogenation
- temperature
- consumption
- catalyzer
- nbr
- Prior art date
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 7
- 229920000459 Nitrile rubber Polymers 0.000 title abstract description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000460 chlorine Substances 0.000 claims description 9
- 229920013649 Paracril Polymers 0.000 claims description 6
- 229920013644 Chemigum Polymers 0.000 claims description 5
- 229910052794 bromium Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000806 elastomer Substances 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a method for C-C double-bond selective hydrogenation of nitrile-butadiene rubber (NBR), which has the characteristics of catalyst efficiency improvement, catalyst consumption reduction and NBR lower-temperature hydrogenation. The present invention comprises the reaction conditions that the hydrogen pressure is from 6 to 15MPa, the hydrogenation temperature is higher than 70DEG C and lower than 100DEG C, the catalyst consumption is from 0.05 to 0.25 wt% (based on solid elastomer), the triphenylphosphine consumption is from 0.5 to 2 wt% (based on the solid elastomer), the C-C double-bond of the NBR is selectively hydrogenated, and the hydrogenation degree of the product is at least 90%. The obtained product has superior performance.
Description
The present invention relates to the method for a kind of paracril (NBR) hydrogenation.
Carbon double-bond hydrogenation technology in the existing paracril has many kinds, and typically for example: GB1558491 is disclosed, adopts (R
mB)
3R
hX
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 be 0.01～10% (weight by dry rubber, wt%), use excessive part, the part consumption be 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%, and (weight by dry rubber, wt%, triphenylphosphine consumption are 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 a kind of Application of Catalyst efficient that can improve is that catalyzer, part consumption are low, and temperature of reaction is low, and hydrogenation is effective, the chemigum hydrogenation processing method of hydrogenated products excellent property.
The objective of the invention is to realize by following method:
(weight by dry rubber wt%) after reacting 1～2 hour under 60 ℃～100 ℃ temperature, adds catalyzer again and carries out hydrogenation reaction at first to add 0.5～2% triphenyl in the glue of paracril.The catalyzer general formula is Rh (PR
3) nX, wherein R can be phenyl (Ph), methyl or ethyl (Et); N is 3 or 4; X is chlorine or bromine or hydrogen, and catalyst levels is 0.05～0.25% (weight by dry rubber wt%), preferably 0.05～0.2%, and its hydrogenation conditions is PH
2=5～15MPa, temperature is more than 70 ℃, is lower than 100 ℃.
The used paracril of hydrogenation can be an alternating copolymer among the present invention, can be random copolymers also, and vinyl cyanide in the multipolymer (AN) content is 10～50wt%, and solvent for use is a chlorobenzene.
Use chemigum hydrogenation method of the present invention, its advantage is to improve catalyst efficiency, make paracril under than low catalyst and part consumption and lesser temps, carry out hydrogenation reaction 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 done specifying.
Embodiment 1
With 30g NBR (AN=33%; ML
1+4 100 ℃=55) be dissolved in the 270g chlorobenzene, add reactor, treat that it all after the dissolving, at first adds the 0.3g triphenylphosphine, 70 ℃ down behind the reaction 2hr, add Rh (PPh again
3)
3Cl, 0.02g carry out hydrogenation under 95 ℃, 8.0MPa, it the results are shown in Table 1.
Embodiment 2
Use RhH (PPh
3)
4Be catalyzer, the triphenylphosphine add-on is 0.45g, behind 90 ℃ of following reaction 1hr, carries out the hydrogenation reaction reaction conditions with example 1, the results are shown in Table 1.
Embodiment 3
Catalyzer is Rh (PPh
3)
3Br, other condition of triphenylphosphine consumption 0.15g is carried out hydrogenation with embodiment 1, and reaction result sees Table 1.
Embodiment 4
Catalyzer is Rh (PEt
3)
3Cl, other condition of triphenylphosphine consumption 0.15g is carried out hydrogenation reaction with embodiment 1, the results are shown in Table 1.
Embodiment 5
Catalyzer Rh (PPh
3)
3Cl consumption 0.01g, 80 ℃ of temperature; Pressure 15MPa, other condition is carried out hydrogenation with embodiment 1, and reaction result sees Table 1.
Embodiment 6
Catalyzer Rh[P (CH
3)
3]
3Cl consumption 0.075g, 70 ℃ of temperature; Pressure 15MPa, other carries out hydrogenation with embodiment 1, and reaction result sees Table 1.
Embodiment 7
Catalyzer Rh (PPh
3)
3Cl consumption 0.03g, 95 ℃ of temperature; Pressure 5.0MPa, other carries out hydrogenation with embodiment 1, and reaction result sees Table 1.
Comparative example 1
30NBR, 270g chlorobenzene are added in the reactor, treat that it dissolves fully after, add the 0.3g triphenylphosphine again, 0.02gRh (PPh
3)
3Directly carry out hydrogenation under Cl, 100 ℃ of temperature, the pressure 8.0MPa, reaction result sees Table 1.
Comparative example 2
In the comparative example 2, except that 110 ℃ of catalyst levels 0.06g, triphenylphosphine consumption 0.6g, temperature, other condition is with comparative example 1, and it the results are shown in Table 1.
Comparative example 3
Removing catalyst levels is 0.129g, and the triphenylphosphine consumption is 0.45g, and other is with comparative example 1, and it the results are shown in Table 1.
Comparative example 4
Removing catalyst levels is 0.117g, and the triphenylphosphine consumption is 0.45g, and pressure is outside the 10.00MPa, and other the results are shown in Table 1 with comparative example 1.
Table 1
| Sequence number | Degree of hydrogenation (%) | Mooney viscosity (HL 1+4 100℃) |
| Embodiment 1 | 95 | 85 |
| Embodiment 2 | 97 | 85 |
| Embodiment 3 | 90 | 80 |
| Embodiment 4 | 91 | 80 |
| Embodiment 5 | 93 | 83 |
| Embodiment 6 | 97 | 85 |
| Embodiment 7 | 94 | 87 |
| Comparative example 1 | 70 | 80 |
| Comparative example 2 | 93 | 120 |
| Comparative example 3 | 96 | 130 |
| Comparative example 4 | 96 | 125 |
Claims (1)
1. the method for a chemigum hydrogenation, the general formula R h (PR of the catalyzer that is adopted
3) nX, wherein R is phenyl or methyl or ethyl; N is 3 or 4; X is chlorine or bromine or hydrogen.It is characterized in that adding earlier in the glue of paracril triphenylphosphine, the weight by dry rubber add-on is 0.5～2wt%, under 60～80 ℃ of temperature, reacted 1～2 hour, add catalyzer again, the weight by dry rubber add-on is that 0.05～0.25wt% carries out hydrogenation reaction, condition is 5～15MPa for the hydrogen dividing potential drop, and temperature is more than 70 ℃, is lower than 100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103556A CN1058973C (en) | 1997-04-22 | 1997-04-22 | Process for hydrogenation of acrylonitrile-butadiene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103556A CN1058973C (en) | 1997-04-22 | 1997-04-22 | Process for hydrogenation of acrylonitrile-butadiene rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1167774A CN1167774A (en) | 1997-12-17 |
| CN1058973C true CN1058973C (en) | 2000-11-29 |
Family
ID=5166726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97103556A Expired - Fee Related CN1058973C (en) | 1997-04-22 | 1997-04-22 | Process for hydrogenation of acrylonitrile-butadiene rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1058973C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787087B (en) * | 2010-03-12 | 2012-01-04 | 北京化工大学 | Hydrogenation method of hydroxyl terminated butyl nitrile (HTBN) |
| CN102336843B (en) * | 2011-06-30 | 2012-10-31 | 北京化工大学 | A Hydrogenation Process of Hydroxyl-terminated Liquid Butyronitrile |
| CN102335629A (en) * | 2011-07-21 | 2012-02-01 | 北京化工大学 | Preparation method of rhodium/ruthenium nanoparticle catalyst and application of rhodium/ruthenium nanoparticle catalyst in hydrogenation reaction |
| CN105622783B (en) * | 2014-10-29 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of preparation method of copolymer |
| CN107200796B (en) * | 2016-03-16 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of method of hydrotreating of ternary NBR latex |
| CN107200794B (en) * | 2016-03-16 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of method of hydrotreating of NBR latex |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4464515A (en) * | 1982-12-08 | 1984-08-07 | Polysar Limited | Polymer hydrogenation process |
| US4581417A (en) * | 1983-08-19 | 1986-04-08 | Bayer Aktiengesellschaft | Production of hydrogenated nitrile rubbers |
-
1997
- 1997-04-22 CN CN97103556A patent/CN1058973C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4464515A (en) * | 1982-12-08 | 1984-08-07 | Polysar Limited | Polymer hydrogenation process |
| US4581417A (en) * | 1983-08-19 | 1986-04-08 | Bayer Aktiengesellschaft | Production of hydrogenated nitrile rubbers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1167774A (en) | 1997-12-17 |
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