CN101787087B - Hydrogenation method of hydroxyl terminated butyl nitrile (HTBN) - Google Patents
Hydrogenation method of hydroxyl terminated butyl nitrile (HTBN) Download PDFInfo
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- CN101787087B CN101787087B CN2010101247395A CN201010124739A CN101787087B CN 101787087 B CN101787087 B CN 101787087B CN 2010101247395 A CN2010101247395 A CN 2010101247395A CN 201010124739 A CN201010124739 A CN 201010124739A CN 101787087 B CN101787087 B CN 101787087B
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- hydrogenation
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- paracril
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Abstract
The invention relates to a hydrogenation method of hydroxyl terminated butyl nitrile (HTBN), in particular to a hydrogenation method of liquid nitrile containing terminated hydroxyl. The method is characterized by comprising the following steps: reacting terminated hydroxyl and silane of an unsaturated polymer before hydrogenation to obtain an unsaturated polymer capped with tetramethylsilane, dissolving hydroxyl terminated butyl nitrile in a benzene solvent according to the mass concentration of 5-30%, adding in a hydrogenated kettle, and performing hydrogenation reaction for 2-20h, wherein the temperature is 65-165 DEG C, the pressure is 0.4-5.0 MPa, the rotation speed is 200-400r/min, and the dosage of a catalyst is 0.1-5%. The invention has the advantages that the hydrogenated polymer is a novel polymer, and the hydrogenation degree can be more than 98%.
Description
Technical field
The present invention relates to a kind of method of hydrotreating of new polymers-hydroxyl terminated butyl nitrile (HTBN), particularly unsaturated carbon-carbon double bond carries out the method that solution method is selected hydrogenation on the terminal hydroxy group molecular chain to containing.
Background technology
The unsaturated polymer of unsaturated polymer and nitrile group-containing (like perbutan) owing to contain carbon carbon unsaturated double-bond, thereby influences performances such as the thermotolerance of unsaturated polymer, anti-ozone on the molecular chain.Through shortening, generate saturated singly-bound, so both can keep the original performance of polymkeric substance, can improve its thermotolerance, anti-O again
3, SO
2Etc. performance, thereby make the polymkeric substance behind the hydrogenation have excellent comprehensive performances.This material is widely used under the exacting terms, such as oil-field development and automotive industry etc., thereby in the oil resistant low temperature resistant field, occupies an important position.
Report about the unsaturated polymer hydrogenation of unsaturated polymer and nitrile group-containing has been arranged at present a lot.USP 4581417 has been introduced a kind of hydroconversion condition, and wherein catalyzer is RhX (PPh
3)
3, catalyst levels is 0.05%-0.6% (weight by dry rubber, W
t%), the triphenyl phosphorus consumption is 2% (weight by dry rubber, W
t%), hydrogenation temperature is 100 ℃-145 ℃, and degree of hydrogenation can reach more than 90%.USP 3480659 has been introduced employing RhH (PPh
3)
3, unsaturated copolymer is carried out the homogeneous phase solution selective hydrogenation, degree of hydrogenation can reach more than 98%.USP 6084033 discloses a kind of Rh-Ru of employing bimetallic catalyst carries out solution hydrogenation to NBR method.In the method, Rh: Ru (mol ratio) is 3: 2, and hydrogen pressure is 1.4Mpa, and the reaction times is 4 hours, and degree of hydrogenation can reach more than 98%.Adopt noble metal hydrogenation catalyst, utilize the solution hydrogenation method, chemigum hydrogenation has been realized suitability for industrialized production.
For contain other polar groups (remove-bibliographical information of CN) nitrile rubber solution hydrogenation seldom, CN1422284A has introduced the hydrogenation to carboxylic paracril.This method adopts that to contain rhodium complex be catalyzer, to carboxylic chemigum hydrogenation, can reduce carbon-carbon double bond and does not influence carboxyl and itrile group.Through this hydrogenation mode, obtained a kind of polymkeric substance of novelty.This polymkeric substance has shown performance excellent under room temperature and high temperature.
The LNBR that contains terminal hydroxy group also is a kind of polymer-modified of paracril.Characteristics be molecular weight in the 5000-10000 scope, contain terminal hydroxy group.Be generally used for fields such as tackiness agent, softening agent.For this polymkeric substance, can be used as the softening agent of a variety of materials, can reduce the viscosity of material, improve processing characteristics, especially can improve the shortcoming of small molecules plasticizer exudation.But owing in molecular chain, contain carbon-carbon double bond, performances such as thermotolerance, anti-ozone can descend thereupon.Through hydrogenation, can improve performances such as the thermotolerance of this hydroxyl terminated butyl nitrile (HTBN) rubber, anti-ozone.Yet because the existence of terminal hydroxy group can make noble metal catalyst generation poisoning of catalyst, thereby can't realize the hydrogenation of hydroxyl terminated butyl nitrile (HTBN) rubber during hydrogenation.
Summary of the invention
The object of the present invention is to provide a kind of method of hydrotreating of realizing hydroxyl terminated butyl nitrile (HTBN) rubber.Characteristics are through end-blocking liquid hydroxyl paracril, under conditions such as certain catalyzer, temperature, pressure, realize solution method selection hydrogenation.Through improving processing condition (temperature, catalyst levels, pressure, time etc.), improve the degree of hydrogenation of polymkeric substance, thereby obtain degree of hydrogenation at the hydrogenation polymkeric substance more than 98%.
Above-mentioned and other purposes, feature and advantage of the present invention can obtain embodying in further elaboration of the present invention.
The objective of the invention is to realize through following method: elder generation is with the terminal hydroxy group and the silane effect of unsaturated polymer; Obtain containing the unsaturated polymer of TMS END CAPPED GROUP; Complex compound with rhodium-containing, ruthenium or ruthenium-rhodium is a catalyzer again, is solvent with the benzene class, under conditions such as certain temperature, pressure; End-blocking liquid hydroxyl butyronitrile is carried out selective hydrogenation, make this polymkeric substance have very high degree of hydrogenation.
Method of the present invention comprises following process step:
A kind of method of hydrotreating of hydroxyl terminated butyl nitrile (HTBN); At first get up with the hydroxyl protection of silane with hydroxyl terminated butyl nitrile (HTBN); Then end-blocking liquid hydroxyl butyronitrile is dissolved in the benzene kind solvent, carries out hydrogenation under catalyzer and the stirring condition being added with then, it is characterized in that earlier end-blocking liquid hydroxyl butyronitrile is dissolved in the benzene kind solvent by 5%～30% mass concentration; Join then in the hydrogenation still; At 65 ℃～165 ℃, pressure 0.4～5.0MPa, rotating speed is to carry out hydrogenation reaction under 200～400r/min, and in 2～20 hours reaction times, catalyst consumption is 0.1%～5% (in the hydroxyl terminated butyl nitrile (HTBN) weight after the protection).
The spendable noble metal catalyst of the present invention has triphenyl phosphorus halogenation rhodium, triphenyl phosphorus ruthenium halide, ruthenium-rhodium triphenyl phosphorus compound, and wherein halogen is C1, Br, I,, be preferably Cl.Catalyst levels is 0.1%～5% (in end-blocking liquid hydroxyl butyronitrile weight), is 0.2% better, is preferably 0.6～1.6%.
The spendable solvent of the present invention has chlorobenzene, bromobenzene, toluene, YLENE.When using the triphenyl phosphorus rhodium chloride, solvent is YLENE preferably.Strength of solution is 5%～30%, is preferably 5～20%.
The pressure that the present invention can react is 0.4～5.0MPa, is preferably 0.8～1.6MPa.The temperature of reaction can be 65 ℃～165 ℃, is preferably 85 ℃～145 ℃.Reaction times can be 2～20 hours, preferably 5～10 hours.
Hydrogenation multipolymer used in the present invention is by the hydroxyl terminated butyl nitrile (HTBN) behind the protected silane, and its molecular weight can be 5000-10000 (an osmometry mensuration).
The present invention adopts the hydroxyl terminated butyl nitrile (HTBN) after the homogeneous phase solution hydrogenation technology will be protected to carry out hydrotreatment, and not only degree of hydrogenation is high, and technology is simple.
Description of drawings
Shown in Figure 1 is the HNMR spectrogram of the hydroxyl terminated butyl nitrile (HTBN) before the hydrogenation behind the end-blocking,
Shown in Figure 2 is the HNMR spectrogram of the hydroxyl terminated butyl nitrile (HTBN) of (embodiment 1) after the hydrogenation behind the end-blocking.
Embodiment
Detail has been listed among the following embodiment.Following embodiment is used to further specify the present invention, rather than is used for limiting scope of the present invention.Except as otherwise noted, used per-cent all is based on weight.
Polymkeric substance adopts noble metal catalyst to carry out the general step of homogeneous phase solution hydrogenation:
Get a certain amount of hydroxyl terminated butyl nitrile (HTBN), adopt the method for existing protected silane hydroxyl, with the terminal hydroxy group on the hexamethyldisilazane protection nitrile (HTBN).A certain amount of end-blocking liquid hydroxyl butyronitrile is dissolved in benzene kind solvent, adds in the reaction kettle, under nitrogen atmosphere, catalyzer is joined reaction kettle; Under certain temperature of reaction and pressure condition, the hydrogenation certain hour stops heated and stirred; Be cooled to room temperature; Adopt the method for underpressure distillation that the solvent in the product is steamed, with the degree of hydrogenation of iodometric determination hydrogenation after product, with the infrared and structure nmr analysis product.
By the general step of above-mentioned hydrogenation, end-blocking liquid hydroxyl acrylonitrile-butadiene copolymer 7.5g (molecular weight is 7160, and the vinyl cyanide mass percentage content is 20%) is dissolved in the YLENE of 50ml; Be added in the hydrogenation reaction kettle of 100ml; Under nitrogen atmosphere, 0.06g triphenyl phosphorus rhodium chloride and 0.48g triphenyl phosphorus are joined in the reaction kettle, 100 ℃ of controlled temperature, the pressure of hydrogen are 1MPa; Reaction times is 8 hours, and the hydrogenation result sees table 1.
Comparative Examples 1
By above-mentioned method of hydrotreating, do not add catalyzer triphenyl phosphorus rhodium chloride, other is with embodiment 1, and the result sees table 1.
Table 1
| Experimental example | The % |
| Embodiment | |
| 1 | 94 |
| Comparative Examples 1 | 0 |
Embodiment 2
Change the amount of the end-blocking liquid hydroxyl butyronitrile among the embodiment 1 into 2.5g, 5g, 10g, other is with embodiment 1, and the result sees table 2.
Table 2
| The quality (g) of end-blocking liquid hydroxyl butyronitrile | The % hydrogenation degree |
| 2.5 | 89 |
| 5 | 92 |
| 10 | 75 |
Embodiment 3
Change the amount of the triphenyl phosphorus rhodium chloride among the embodiment 1 into 0.045g, 0.09g, 0.12g, other is with embodiment 1, and the result sees table 3.
Table 3
| The quality of triphenyl phosphorus rhodium chloride (g) | The % hydrogenation degree |
| 0.045 | 69 |
| 0.09 | 93 |
| 0.12 | 94 |
Embodiment 4
Change the reaction times among the embodiment 1 into 5h, 6h, 10h, other is with embodiment 1, and the result sees table 4.
Table 4
| Reaction times (h) | The % hydrogenation degree |
| 5 | 77 |
| 6 | 84 |
| 10 | 80 |
Embodiment 5
Change the temperature of reaction among the embodiment 1 into 85 ℃, 125 ℃, 145 ℃, other is with embodiment 1, and the result sees table 5.
Table 5
| Temperature of reaction (℃) | The % hydrogenation degree |
| 85 | 82 |
| 125 | 85 |
| 145 | 58 |
Embodiment 6
Change the reaction pressure among the embodiment 1 into 0.8MPa, 1.3MPa, 1.6MPa, other is with embodiment 1, and the result sees table 6.
Table 6
| Reaction pressure (MPa) | The % hydrogenation degree |
| ?0.8 | 66 |
| ?1.3 | 98 |
| ?1.6 | 99 |
Change the solvent among the embodiment 1 into chlorobenzene, bromobenzene, toluene, other is with embodiment 1, and the result sees table 7.
Table 7
| Solvent | The % hydrogenation degree |
| Chlorobenzene | 77 |
| Bromobenzene | 67 |
| Toluene | 81 |
Embodiment 8
Change the triphenyl phosphorus rhodium chloride among the embodiment 1 into the triphenyl phosphorus ruthenium chloride, ruthenium-rhodium triphenyl phosphorus compound, other is with embodiment 1, and the result sees table 8.
Table 8
| Catalyst type | The % hydrogenation degree |
| The triphenyl phosphorus ruthenium chloride | 65 |
| Ruthenium-rhodium triphenyl phosphorus compound | 78 |
Embodiment 9
Change the vinyl cyanide mass percentage content among the embodiment 1 into 15%, 25%, other is with embodiment 1, and the result sees table 9.
Table 9
| Vinyl cyanide mass percentage content in the polymkeric substance | The % hydrogenation degree |
| 15％ | 93 |
| 25％ | 91 |
Change the quality of the triphenyl phosphorus among the embodiment 1 into 0.36g, 0.6g, other is with embodiment 1, and the result sees table 10.
Table 10
| The quality of triphenyl phosphorus (g) | The % hydrogenation degree |
| ?0.36 | 92 |
| ?0.6 | 85 |
The hydrogenation embodiment of above hydroxyl terminated butyl nitrile (HTBN) is exemplary; The present invention is a method of a kind of new polymers-hydroxyl terminated butyl nitrile (HTBN) being selected hydrogenation, and characteristic is that unsaturated carbon-carbon double bond on the molecular chain is carried out a kind of process method that solution method is selected hydrogenation.Those skilled in the art can carry out suitable change to the method for hydroxyl terminated butyl nitrile (HTBN) hydrogenation of the present invention, such as changes the guard method of terminal hydroxy group, improves catalyst consumption, improves reaction pressure, changes solvent etc., all within the scope of the invention.
Claims (6)
1. the method for hydrotreating of a hydroxyl terminated butyl nitrile (HTBN) rubber; At first the hydroxyl with protected silane hydroxyl terminated butyl nitrile (HTBN) rubber obtains end-blocking liquid hydroxyl paracril; Then end-blocking liquid hydroxyl paracril is dissolved in the benzene kind solvent, carries out hydrogenation under catalyzer and the stirring condition being added with, it is characterized in that: end-blocking liquid hydroxyl paracril is dissolved in the benzene kind solvent by 5%～30% mass concentration; Join then in the hydrogenation still; Under 65 ℃～165 ℃, pressure 0.4～5.0MPa, rotating speed 200～400r/min, under protection of nitrogen gas, add catalyzer, when adding catalyzer; Add 6～10 times of triphenyl phosphorus and carry out hydrogenation reaction, 2～20 hours reaction times to catalyst quality; Wherein catalyst consumption is 0.2%～1.6% of an end-blocking liquid hydroxyl paracril weight, and the mass percentage content of vinyl cyanide is 15%～25% in the end-blocking liquid hydroxyl paracril.
2. method of hydrotreating according to claim 1; It is characterized in that catalyzer is triphenyl phosphorus halogenation rhodium, triphenyl phosphorus ruthenium halide or ruthenium-rhodium triphenyl phosphorus compound; Wherein halogen is Cl, Br or I, and described benzene kind solvent is chlorobenzene, bromobenzene, toluene or YLENE.
3. method of hydrotreating according to claim 2 is characterized in that benzene kind solvent is a YLENE.
4. method of hydrotreating according to claim 1, the mass concentration that it is characterized in that end-blocking liquid hydroxyl nitrile rubber solution is 5%～20%.
5. method of hydrotreating according to claim 1, the hydrogenation reaction temperature that it is characterized in that end-blocking liquid hydroxyl paracril are 85 ℃～145 ℃.
6. method of hydrotreating according to claim 1, the hydrogenation reaction pressure that it is characterized in that end-blocking liquid hydroxyl paracril is 0.4～1.6MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167774A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of acrylonitrile-butadiene rubber |
| CN1199051A (en) * | 1997-05-08 | 1998-11-18 | 南帝化学工业股份有限公司 | Unsaturated copolymer hydrogenating method and bimetal containing catalyst system therefor |
| CN101486775A (en) * | 2009-02-27 | 2009-07-22 | 北京化工大学 | Hydrogenation method for NBR Latex |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167774A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of acrylonitrile-butadiene rubber |
| CN1199051A (en) * | 1997-05-08 | 1998-11-18 | 南帝化学工业股份有限公司 | Unsaturated copolymer hydrogenating method and bimetal containing catalyst system therefor |
| CN101486775A (en) * | 2009-02-27 | 2009-07-22 | 北京化工大学 | Hydrogenation method for NBR Latex |
Non-Patent Citations (1)
| Title |
|---|
| 岳东梅等.液体丁腈橡胶的化学改性及应用.《高分子材料科学与工程》.2004,第20卷(第3期),第187-189页. * |
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