CN104231118A - Hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber and preparation method thereof - Google Patents
Hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber and preparation method thereof Download PDFInfo
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- CN104231118A CN104231118A CN201410469630.3A CN201410469630A CN104231118A CN 104231118 A CN104231118 A CN 104231118A CN 201410469630 A CN201410469630 A CN 201410469630A CN 104231118 A CN104231118 A CN 104231118A
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Abstract
The invention provides hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber and a preparation method thereof. The preparation method of the hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber comprises the following steps: S1, taking and dissolving hydroxyl-terminated liquid nitrile-butadiene in an organic solvent to prepare a hydroxyl-terminated liquid nitrile-butadiene liquid; S2, adding a hydrazine hydrate aqueous liquid into the hydroxyl-terminated liquid nitrile-butadiene liquid, heating and stirring the mixed liquid; and S3, dropwise adding a mixture aqueous liquid of boric acid and hydrogen peroxide into the mixed liquid obtained in the step S2, cooling, standing and separating to obtain the hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber after the reaction is ended. According to the hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber and the preparation method thereof, an interface suspension system is adopted to carry out selective hydrogenation on the hydroxyl-terminated liquid nitrile-butadiene rubber; in the whole reaction, the mixed liquid of the hydrazine hydrate, the boric acid and the hydrogen peroxide is in an aqueous phase, the hydroxyl-terminated liquid nitrile-butadiene rubber liquid is in an oil phase, and the two phases are incompatible with each other to form the suspension system; under the action of the boric acid, the hydrazine in the aqueous phase reacts with the hydrogen peroxide to generate diimide; the diimide generates fast collision reaction with a carbon-carbon bond in an oil phase molecular chain on the two-phase interface, so that the carbon-carbon bond is saturated to obtain the hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber with high hydrogenation degree and low gel content.
Description
Technical field
The present invention relates to unsaturated polymer technical field, in particular to a kind of hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber and preparation method thereof.
Background technology
Unsaturated polymer, owing to there is carbon carbon unsaturated double-bond in its molecular chain, is easily subject to the attack of the factors such as light, ozone, heat, causes the resistance to ozone of its goods, resistance toheat poor, thus limit the application of product.By carrying out hydrogenation to unsaturated polymer, reducing the unsaturated double-bond in molecular chain, the resistance to ozone of polymkeric substance can be made, resistance toheat better improved, having widened the range of application of its goods.
For paracril, paracril is made up of divinyl and acrylonitrile compolymer, has excellent oil resistant, resistance to low temperature.But owing to there is unsaturated double-bond in molecular chain, cause the resistance to ozone of paracril, resistance toheat undesirable.Hydroxyl terminated butyl nitrile (HTBN) rubber is a kind of thick liquid of light yellow clear, also be the polymer-modified of a kind of paracril, its molecular weight ranges at 3000-10000, and has good cementability, oil-proofness and the performance such as low temperature resistant, is generally used for the field such as softening agent, tackiness agent.Equally, containing a large amount of carbon-carbon double bonds in the molecular chain of hydroxyl terminated butyl nitrile (HTBN) rubber, its ozone resistance, thermotolerance are not fine.Based on the problem of above-mentioned unsaturated polymer poor-performing, existing solution is mainly by carrying out hydrogenation reaction to it, and reduce the content of carbon-carbon double bond in molecular chain, make the ozone resistance of hydroxyl terminated butyl nitrile (HTBN) rubber, thermotolerance improves.
Solution hydrogenation method and the large class of latex hydrogenation method two is mainly divided at present for unsaturated polymer method of hydrotreating.Wherein, in solution hydrogenation method, adopt precious metal as catalyzer, under the condition of High Temperature High Pressure, carry out hydrogenation reaction.As disclosed a kind of hydrogenation conditions in US4581417, wherein RhX (PPh
3)
3for catalyzer and consumption is the 0.05%-0.6% (mass ratio) of dry glue, part triphenyl phosphorus consumption is 2% (mass ratio) of dry glue, and temperature of reaction is 100 DEG C-145 DEG C, and degree of hydrogenation can reach more than 90%.Although although this method can reach higher degree of hydrogenation, catalyzer needs preparation and use under the condition of isolated air, and technique is loaded down with trivial details, and the catalyzer adopted is expensive, and cost is high.
Although hydrazine derivative original position latex hydrogenation method reaction conditions is gentle, reaction unit simple and without noble metal catalyst, disadvantage is that gel content is high, limits its development and application.Although improve latex hydrogenation method in existing research, the high problem of hydrogenated products gel content cannot be solved all the time.As processed latex hydrogenation product with ozone, thus eliminating the crosslinked of hydrogenation products, namely being made the double bond chain rupture of multipolymer by ozone, making molecular weight and molecular weight.The wet product obtained by breakdown of emulsion can be dissolved in chloroform, but product is in drying process, and the end carboxyl, the terminal aldehyde group that are formed due to chain rupture place again can be cross-linked, thus make product carry out processing and utilization.
Summary of the invention
The present invention aims to provide a kind of hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber and preparation method thereof, and to solve, gel content existing in the method for hydrotreating of prior art is high, cost is high and the problem of complicated operation.
To achieve these goals, according to an aspect of the present invention, provide a kind of method utilizing interface suspension method to prepare hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber, comprise the following steps: step S1, get hydroxyl terminated butyl nitrile (HTBN) and be dissolved in organic solvent, be mixed with hydroxyl terminated butyl nitrile (HTBN) solution; Step S2, in hydroxyl terminated butyl nitrile (HTBN) solution, add hydrazine hydrate aqueous solution, be heated to temperature of reaction and constant temperature stirs; And step S3, to arrive after temperature of reaction, drip the mixture aqueous solution of boric acid and hydrogen peroxide in the mixed solution obtained in step S2, react rear cooling, leave standstill, separation, obtains hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber.
Further, the hydrogenation reaction of hydroxyl terminated butyl nitrile (HTBN) completes on oil-water two-phase interfaces.
Further, organic solvent is selected from one or more in toluene, dimethylbenzene and chlorobenzene.
Further, the acrylonitrile content in hydroxyl terminated butyl nitrile (HTBN) is 13wt%; The concentration of hydroxyl terminated butyl nitrile (HTBN) solution is 8wt%-40wt%.
Further, in the hydrazine hydrate aqueous solution added, the molar weight of hydrazine hydrate accounts for the 2.379-8.325 of carbon-carbon double bond molar weight in reaction system doubly.
Further, the molar weight of the boric acid added accounts for the 0.014-0.072 of hydrazine hydrate molar weight doubly, and the molar weight of the hydrogen peroxide added accounts for the 0.788-1.418 of hydrazine hydrate molar weight doubly.
Further, the molar weight of the boric acid added accounts for 0.029 times of hydrazine hydrate molar weight, and the molar weight of the hydrogen peroxide added accounts for 1.103 times of hydrazine hydrate molar weight.
Further, in step s 2, after adding hydrazine hydrate aqueous solution, being heated to 35 DEG C-70 DEG C in hydroxyl terminated butyl nitrile (HTBN) solution, constant temperature 2-10 hour is the reaction times; Preferably, be heated to 55 DEG C, constant temperature 6 hours.
Further, in step s3, the time for adding controlling the mixture aqueous solution of boric acid and hydrogen peroxide is 1 ~ 6 hour, is preferably 3 ~ 4 hours.
According to a further aspect in the invention, provide a kind of hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber, this hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber is prepared from for adopting any one method above-mentioned.
Applying technical scheme of the present invention, by being first dissolved in organic solvent by hydroxyl terminated butyl nitrile (HTBN), then adding hydrazine hydrate aqueous solution, and the mixture aqueous solution adding boric acid and hydrogen peroxide carries out catalysis and oxidizing reaction.The present invention has abandoned the solution method hydrogenation method that precious metal makes catalyzer, is also different from the latex hydrogenation method that emulsifying agent exists, but adopts a kind of interface suspension system to carry out selective hydrogenation to hydroxyl terminated butyl nitrile (HTBN).In whole reaction system, the mixing solutions of hydrazine hydrate, boric acid and hydrogen peroxide is in aqueous phase, hydroxyl terminated butyl nitrile (HTBN) solution is in oil phase, two-phase incompatibility, present a kind of suspension system, the hydrazine in aqueous phase generates imide with hydroperoxidation under boric acid catalysis effect, and the carbon-carbon double bond generation Fast Collision of imide in two-phase interface place and oil phase molecule chain is reacted and carbon-carbon double bond is reached capacity, under the effect of strong stirring, two-phase interface is constantly updated, and hydrogenation constantly carries out.Because hydrogenation occurs in the phase interface place of two dimension, and the concentration of interface unsaturated polymer is low, and the crosslinking reaction between molecular chain is difficult to occur, so the gel content of final product hydrogenation hydroxyl terminated butyl nitrile (HTBN) is very low, is even zero.
Instant invention overcomes that the cost existed in existing method of hydrotreating is high, complicated operation, the defect that especially gel content is high.Interface of the present invention suspension system gives this novel hydrogenation method following advantage: equipment is simple, and easy to operate, product is easily separated, and product is pure, and cost is cheap, and great advantage is that product degree of hydrogenation is high, and gel-free generates, and easily realizes industrialization continuous seepage.
Accompanying drawing explanation
The accompanying drawing forming a part of the present invention is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the nuclear-magnetism comparison diagram before and after the hydroxyl terminated butyl nitrile (HTBN) hydrogenation of preparation in embodiments of the invention 1.
Embodiment
Hereinafter also describe the present invention in detail with reference to accompanying drawing in conjunction with the embodiments.It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.
In order to the problem that the gel content existed when solving in prior art and prepare hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber is high, the invention provides a kind of preparation method of hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber.This preparation method comprises the following steps: step S1, get hydroxyl terminated butyl nitrile (HTBN) and be dissolved in organic solvent, is mixed with hydroxyl terminated butyl nitrile (HTBN) solution; Step S2, in hydroxyl terminated butyl nitrile (HTBN) solution, add hydrazine hydrate aqueous solution, be heated to temperature of reaction and constant temperature stirs; And step S3, to arrive after temperature of reaction, drip the mixture aqueous solution of boric acid and hydrogen peroxide in the mixed solution obtained in step S2, react rear cooling, leave standstill, separation, obtains hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber.The present invention has abandoned the solution hydrogenation method of precious metal as catalyzer, also the emulsion method hydrogenation method that emulsifying agent exists is different from, but adopt a kind of brand-new interface suspension system to carry out selective hydrogenation to hydroxyl terminated butyl nitrile (HTBN), namely whole hydrogenation process is formed on oil-water two-phase interfaces, by carrying out hydrogenation to carbon-carbon double bonds a large amount of on molecular chain, thus obtain the hydroxyl terminated butyl nitrile (HTBN) of hydrogenation.Instant invention overcomes that the cost existed in existing method of hydrotreating is high, complicated operation, the defect that especially gel content is high.Adopt interface suspension method, this interface suspension system gives this novel hydrogenation method following advantage: equipment is simple, easy to operate, product is easily separated, and product is pure, and cost is cheap, great advantage is that product degree of hydrogenation is high, and gel-free generates, and easily realizes industrialization continuous seepage.
Interface suspension method in the present invention refers to the existence of surfactant-free, and water-oil phase is incompatible.Hydrogenation occurs in two-phase interface place, and under the effect of strong stirring, interface is constantly updated, and hydrogenation constantly carries out.The present invention utilizes the mixing solutions of hydrazine hydrate, boric acid and hydrogen peroxide as aqueous phase, hydroxyl terminated butyl nitrile (HTBN) solution is as oil phase, thus formation oil-water two-phase interfaces, under the effect of strong stirring, the hydrogenation reaction of hydroxyl terminated butyl nitrile (HTBN) completes on oil-water two-phase interfaces.
Wherein, organic solvent is selected from one or more in toluene, dimethylbenzene and chlorobenzene.The present invention preferably but be not limited to above-mentioned organic solvent, as long as can dissolve hydroxyl terminated butyl nitrile (HTBN) and form uniform solution.
Consider the factors such as hydrogenation efficiency, hydrogenation cost and practical application, preferably, the acrylonitrile content in hydroxyl terminated butyl nitrile (HTBN) controls as 8wt%-27wt% by the present invention, controls the concentration of hydroxyl terminated butyl nitrile (HTBN) solution for 8wt%-40wt%.If acrylonitrile content is too high, virgin rubber synthesis cost is high and viscosity is excessive, there will be the problems such as hydrogenation cost is high, operational difficulty, hydrogenation efficiency are low.On the contrary, if acrylonitrile content is too low, the using value of oil-proofness will be lost.If the excessive concentration of hydroxyl terminated butyl nitrile (HTBN) solution, soltion viscosity is large, causes degree of hydrogenation not high, does not reach required degree of hydrogenation.If the concentration of hydroxyl terminated butyl nitrile (HTBN) solution is too low, reagent raw material availability can be caused low, cause the waste of reagent raw material, be unfavorable for scale operation.
Consider the factors such as hydrogenation cost and hydrogenation efficiency, in the hydrazine hydrate aqueous solution added, the molar weight of hydrazine hydrate accounts for the 2.379-8.325 of carbon-carbon double bond molar weight in reaction system doubly.Along with the increase of hydrazine hydrate consumption, the degree of hydrogenation of product first increases rear reduction, if the molar weight of the hydrazine hydrate added is too high, the degree of hydrogenation of product can be made to reduce and waste reagent raw material; If the molar weight of the hydrazine hydrate added is very few, the degree of hydrogenation of product is low, and then limits the application of hydrogenation products.
The Main Function of the boric acid added in the present invention is as catalyzer, catalysis hydrazine and hydroperoxidation generate activeconstituents imide, if it is too fast that the molar weight of the boric acid added too much can cause imide to produce, hydrogenation reaction is incomplete, hydrogenation efficiency reduces, very few there will be, waits a moment lacking of imide generation, and the degree of hydrogenation of product is low, all can not play the effect of catalysis preferably.Through considering, the molar weight of added boric acid is controlled 0.014-0.072 times for accounting for hydrazine hydrate molar weight by the present invention.In reaction mixture, add hydrogen peroxide is be used as oxygenant, if the molar weight of the hydrogen peroxide added is too much, can makes imide that reductibility is strong and hydroperoxidation, thus consume activeconstituents imide, the degree of hydrogenation of product is reduced.On the contrary, if the molar weight of the hydrogen peroxide added is very few, the imide of generation is few, and the degree of hydrogenation of product is low, and therefore, through considering, the molar weight of hydrogen peroxide is controlled 0.788-1.418 times for hydrazine hydrate molar weight by the present invention.Further preferably, the molar weight of the boric acid added accounts for 0.029 times of hydrazine hydrate molar weight, and the molar weight of the hydrogen peroxide added accounts for 1.103 times of hydrazine hydrate molar weight.
In the preferred embodiment of the present invention, in step s 2, add hydrazine hydrate aqueous solution in hydroxyl terminated butyl nitrile (HTBN) solution after, 35 DEG C-70 DEG C are heated to, constant temperature 2-10 hour.Heating temperature and constant temperature time control in above-mentioned scope by the present invention, mainly consider the factor such as hydrogenation efficiency and hydrogenation cost.If it is too high to be heated to temperature, the degree of hydrogenation of product can be reduced, and add cost.If temperature is too low, then the degree of hydrogenation of product is caused to reduce, hydrogenation weak effect.Constant temperature time is oversize or too short, degree of hydrogenation can be caused to reduce, and cause the wasting of resources.Further preferably, in step s 2, add hydrazine hydrate aqueous solution in hydroxyl terminated butyl nitrile (HTBN) solution after, 55 DEG C are heated to, constant temperature 6 hours.
Wherein, in step s3, the time for adding controlling the mixture aqueous solution of boric acid and hydrogen peroxide is 1 ~ 6 hour, is preferably 3 ~ 4 hours.If the excessive velocities dripped, the generation speed of activeconstituents imide is also fast, and imide can be consumed because there are other side reactions, causes it not react with carbon-carbon double bond fully, reduces the degree of hydrogenation of product.If the speed dripped is comparatively slow, produce activeconstituents imide comparatively slow, it is also slow that hydrogenation reaction is carried out, and extends the reaction times, add hydrogenation cost.
According to a further aspect in the invention, provide a kind of hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber, this hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber is prepared from for adopting any one method above-mentioned.Because whole hydrogenation process of the present invention completes on oil-water two-phase interfaces, be different from emulsion system hydrogenation, the product degree of hydrogenation of final preparation is high, and gel-free generates, and product is easily separated, and product is pure.
Excellent effect of the present invention is further illustrated below in conjunction with specific embodiment.
Boric acid (analytical pure); Hydrazine hydrate solution (mass concentration 80wt%); Superoxol (mass concentration 30wt%); Hydroxyl terminated butyl nitrile (HTBN) (HTBN), acrylonitrile content is 13wt%, makes solvent by hydroxyl terminated butyl nitrile (HTBN) wiring solution-forming with dimethylbenzene.
Embodiment 1
1) get hydroxyl terminated butyl nitrile (HTBN) to be dissolved in dimethylbenzene organic solvent, be mixed with hydroxyl terminated butyl nitrile (HTBN) (HTBN) solution that concentration is 16.7wt%, wherein, the acrylonitrile content in hydroxyl terminated butyl nitrile (HTBN) is 13wt%.In there-necked flask, add the above-mentioned HTBN solution 50ml prepared, then add the hydrazine hydrate solution 35ml that mass concentration is 80wt% again, then there-necked flask is placed in 55 DEG C of water-baths.
2) 1g boric acid being dissolved in 70ml mass concentration is in 30wt% superoxol, then gained mixing solutions is slowly instilled in there-necked flask, continuous stirring, hydrogenation starts and constant temperature continues 6h, reaction terminate rear cooling, leave standstill, be separated obtain hydrogenated products, i.e. hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber.Fig. 1 is the nucleus magnetic hydrogen spectrum figure before and after the hydroxyl terminated butyl nitrile (HTBN) hydrogenation in embodiment 1.
Comparative example 1
In there-necked flask, add solid content is 45% nitrile rubber 50ml, then adds hydrazine hydrate solution 35ml again, and by there-necked flask as in 55 DEG C of water-baths.Be dissolved in by 1g boric acid in 70ml superoxol, then slowly instilled in there-necked flask by gained mixing solutions, hydrogenation starts and constant temperature continues 6h, and reaction terminates rear cooling, leaves standstill, and obtains final product.The gel content of product is 39%, and the degree of hydrogenation being obtained product by nuclear-magnetism test is 73.2%.
Embodiment 2-3
Operation steps and the raw material adopted all in the same manner as in Example 1, difference is the mass concentration of HTBN solution, the mass concentration of the HTBN solution wherein adopted in embodiment 2 becomes 8wt%, and the mass concentration of the HTBN solution adopted in embodiment 3 becomes 40wt%.
Adopt dissolution method (solvent selects trichloromethane) to detect the gel content of the hydrogenated products obtained in embodiment 1-3, adopt the degree of hydrogenation of nuclear-magnetism test hydrogenated products, concrete numerical value is in table 1.
Table 1.HTBN strength of solution is on the impact of degree of hydrogenation and gel content
| Experimental example | Concentration/% | Degree of hydrogenation/% | Gel content/% |
| Embodiment 1 | 16.7 | 81.9 | 0 |
| Embodiment 2 | 8.0 | 92.6 | 0 |
| Embodiment 3 | 40.0 | 61.7 | 0 |
As can be seen from Table 1, the hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber adopting interface of the present invention suspension method to prepare has higher degree of hydrogenation, and gel-free.
Embodiment 4-5
Operation steps and the raw material adopted all identical with embodiment 1, difference is the add-on of hydrazine hydrate solution, wherein:
The volume of the hydrazine hydrate solution added in embodiment 4 is 20ml, and namely added molar weight accounts for 2.379 times of carbon-carbon double bond molar weight in reaction system.
The volume of the hydrazine hydrate solution added in embodiment 5 is 70ml, and namely added molar weight accounts for 8.325 times of carbon-carbon double bond molar weight in reaction system.
Adopt dissolution method (solvent selects trichloromethane) to detect the gel content of the hydrogenated products obtained in embodiment 1 and embodiment 6-11, adopt the degree of hydrogenation of nuclear-magnetism test hydrogenated products, concrete numerical value is in table 2.
Table 2. hydrazine hydrate consumption is on the impact of degree of hydrogenation and gel content
As can be seen from Table 2, the hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber adopting interface of the present invention suspension method to prepare has higher degree of hydrogenation, and gel-free.
Embodiment 6-7
Operation steps and the raw material adopted all identical with embodiment 1, difference is the add-on of superoxol, and the degree of hydrogenation of concrete add-on and final product and gel content are in table 3.
Table 3. hydrogen peroxide consumption is on the impact of degree of hydrogenation and gel content
As can be seen from Table 3, when the add-on of hydrogen peroxide is different, the hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber adopting interface of the present invention suspension method to prepare still has higher degree of hydrogenation, and gel-free.
Embodiment 8-9
Operation steps and the raw material adopted all identical with embodiment 1, difference is the add-on of boric acid solution, and the degree of hydrogenation of concrete add-on and final product and gel content are in table 4.
Table 4. boric acid consumption is on the impact of degree of hydrogenation and gel content
As can be seen from Table 4, when changing the consumption of boric acid, the hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber adopting interface of the present invention suspension method to prepare still has higher degree of hydrogenation, and gel-free.
Embodiment 10-11
Operation steps and the raw material adopted all identical with embodiment 1, difference is the add-on reducing or increase hydrazine hydrate solution, superoxol and boric acid in embodiment 1 in proportion, and other conditions are constant, and concrete numerical value and final product performance are in table 5.
The amount of table 5. hydrazine hydrate, hydrogen peroxide and boric acid changes the impact on degree of hydrogenation and gel content in proportion
| ? | Hydrazine hydrate/ml | Hydrogen peroxide/ml | Boric acid/g | Degree of hydrogenation/% | Gel content/% |
| Experimental example 1 | 35 | 70 | 1 | 81.9 | 0 |
| Experimental example 10 | 20 | 40 | 0.57 | 31.7 | 0 |
| Experimental example 11 | 60 | 120 | 1.71 | 98.3 | 0 |
Increase the add-on of hydrazine hydrate solution, superoxol and boric acid as can be seen from Table 5 in proportion, product degree of hydrogenation constantly increases, and gel-free produces.
Embodiment 12-13
Operation steps and the raw material adopted all identical with embodiment 1, difference be change the reaction times, other conditions are constant, and concrete numerical value and final product performance are in table 6.
Table 6 reaction times is on the impact of degree of hydrogenation and gel content
| Experiment numbers | Reaction times/h | Degree of hydrogenation/% | Gel content/% |
| Embodiment 1 | 6 | 81.9 | 0 |
| Embodiment 12 | 2 | 51.6 | 0 |
| Embodiment 13 | 10 | 85.2 | 0 |
Embodiment 14-15
Operation steps and the raw material adopted all identical with embodiment 1, difference be change the reaction times, other conditions are constant, and concrete numerical value and final product performance are in table 7.
Table 7. temperature of reaction is on the impact of degree of hydrogenation and gel content
| Experiment numbers | Temperature of reaction/DEG C | Degree of hydrogenation/% | Gel content/% |
| Embodiment 1 | 55 | 81.9 | 0 |
| Embodiment 14 | 35 | 72.4 | 0 |
| Embodiment 15 | 70 | 65.3 | 0 |
As can be seen from table 6 and table 7, when changing temperature of reaction and reaction times, higher product degree of hydrogenation can be obtained equally, and gel-free produces.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. utilize interface suspension method to prepare a method for hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber, it is characterized in that, comprise the following steps:
Step S1, get hydroxyl terminated butyl nitrile (HTBN) and be dissolved in organic solvent, be mixed with hydroxyl terminated butyl nitrile (HTBN) solution;
Step S2, in described hydroxyl terminated butyl nitrile (HTBN) solution, add hydrazine hydrate aqueous solution, be heated to temperature of reaction and constant temperature stirs; And
After step S3, arrival temperature of reaction, drip the mixture aqueous solution of boric acid and hydrogen peroxide in the mixed solution obtained in described step S2, hydrogenation starts, and has reacted rear cooling, leaves standstill, and is separated, obtains described hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber.
2. method according to claim 1, is characterized in that, the hydrogenation reaction of described hydroxyl terminated butyl nitrile (HTBN) completes on oil-water two-phase interfaces.
3. method according to claim 1, is characterized in that, described organic solvent be selected from toluene, dimethylbenzene and chlorobenzene one or more.
4. method according to claim 1, is characterized in that, the acrylonitrile content in described hydroxyl terminated butyl nitrile (HTBN) is 13wt%; The concentration of described hydroxyl terminated butyl nitrile (HTBN) solution is 8wt%-40wt%.
5. method according to claim 1, is characterized in that, in the described hydrazine hydrate aqueous solution added, the molar weight of hydrazine hydrate accounts for the 2.379-8.325 of carbon-carbon double bond molar weight in reaction system doubly.
6. method according to claim 1, is characterized in that, the molar weight of the described boric acid added accounts for the 0.014-0.072 of described hydrazine hydrate molar weight doubly, and the molar weight of the described hydrogen peroxide added accounts for the 0.788-1.418 of described hydrazine hydrate molar weight doubly.
7. method according to claim 6, is characterized in that, the molar weight of the described boric acid added accounts for 0.029 times of described hydrazine hydrate molar weight, and the molar weight of the described hydrogen peroxide added accounts for 1.103 times of described hydrazine hydrate molar weight.
8. method according to claim 1, is characterized in that, in described step S2, after adding described hydrazine hydrate aqueous solution, is heated to 35 DEG C-70 DEG C, constant temperature 2-10 hour in described hydroxyl terminated butyl nitrile (HTBN) solution; Preferably, be heated to 55 DEG C, constant temperature 6 hours.
9. method according to claim 1, is characterized in that, in described step S3, the time for adding controlling the mixture aqueous solution of described boric acid and hydrogen peroxide is 1 ~ 6 hour, is preferably 3 ~ 4 hours.
10. a hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber, is characterized in that, adopts the method according to any one of claim 1-9 to be prepared from.
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| CN106478924A (en) * | 2016-09-28 | 2017-03-08 | 北京化工大学 | A kind of hydrogenated butyronitrile type polyurethane of crosslinking |
| CN106700002A (en) * | 2016-12-23 | 2017-05-24 | 沈阳化工大学 | Phenolic foaming resin toughened with hydroxyl-terminated nitrile rubber |
| CN106866844A (en) * | 2017-03-06 | 2017-06-20 | 北京化工大学 | The method that emulsion method prepares hydrogenation natural gum |
| CN109400995A (en) * | 2018-09-28 | 2019-03-01 | 北京化工大学 | A kind of hydrorubber lotion and hyperfluorescence hydrogenated nitrile-butadiene rubber interpenetrating networks cross linking membrane |
| WO2022057848A1 (en) | 2020-09-16 | 2022-03-24 | 赞南科技(上海)有限公司 | Liquid hydrogenated nitrile-butadiene rubber, preparation method therefor and use thereof |
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| CN106478924A (en) * | 2016-09-28 | 2017-03-08 | 北京化工大学 | A kind of hydrogenated butyronitrile type polyurethane of crosslinking |
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| CN106866844A (en) * | 2017-03-06 | 2017-06-20 | 北京化工大学 | The method that emulsion method prepares hydrogenation natural gum |
| CN106866844B (en) * | 2017-03-06 | 2018-06-29 | 北京化工大学 | The method that emulsion method prepares hydrogenation natural gum |
| CN109400995A (en) * | 2018-09-28 | 2019-03-01 | 北京化工大学 | A kind of hydrorubber lotion and hyperfluorescence hydrogenated nitrile-butadiene rubber interpenetrating networks cross linking membrane |
| CN109400995B (en) * | 2018-09-28 | 2020-06-16 | 北京化工大学 | Hydrogenated rubber emulsion and strong-fluorescence hydrogenated nitrile-butadiene rubber interpenetrating network crosslinked film |
| WO2022057848A1 (en) | 2020-09-16 | 2022-03-24 | 赞南科技(上海)有限公司 | Liquid hydrogenated nitrile-butadiene rubber, preparation method therefor and use thereof |
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