CN105622783A - Preparation method of copolymer - Google Patents
Preparation method of copolymer Download PDFInfo
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- CN105622783A CN105622783A CN201410594179.8A CN201410594179A CN105622783A CN 105622783 A CN105622783 A CN 105622783A CN 201410594179 A CN201410594179 A CN 201410594179A CN 105622783 A CN105622783 A CN 105622783A
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Abstract
The invention discloses a preparation method of a copolymer. The method comprises the following steps: (1) dissolving an unsaturated copolymer in an organic solvent, and filling and draining and degassing; (2) adding a hydrogenation catalyst and a ligand, wherein the hydrogenation catalyst has the following general formula: (RmA)zRhXn; (3) filling hydrogen, stirring, and reacting at the reaction temperature of 0-30 DEG C and at hydrogen pressure of 0.05-15 Mpa for 1-120 min; (4) heating to 50-180 DEG C, keeping hydrogen pressure to 0.1-15 Mpa, and reacting for 1-20 h; and (5) removing an organic solvent in the reaction product obtained in the Step (4). By the method, application cost of the catalyst can be reduced, the reaction is easier to implement, hydrogenation reaction activity is high, hydrogenation degree of a hydrogenation product can be obviously raised, and the product has no obvious increase of gel content.
Description
Technical field
The present invention relates to copolymer field, in particular it relates to the preparation method of a kind of copolymer, the preparation method particularly relating to a kind of low gel, highly saturated nitrile rubber.
Background technology
Hydrogenated nitrile-butadiene rubber (HNBR) has the performances such as good oil resistant, heat-resisting, high temperature resistant, high pressure resistant, antioxidation, also there is very outstanding mechanical property simultaneously, be widely used in the fields such as automobile making, machining, metallurgical seal, petroleum industry.
For many years, the preparation of hydrogenated nitrile-butadiene rubber being constantly subjected to the concern of chemist, its focus is concentrated mainly on: how to use novel, cheap catalyst system to prepare the hydrogenated nitrile-butadiene rubber product of high saturation, low-gel content; How on existing catalyst system basis, constantly perfect by method, realize the selective hydrogenation to carbon-carbon double bond (C=C) more efficiently. Present stage, homogeneous phase solution hydrogenation method for hydrogenated nitrile-butadiene rubber, on the one hand, still mainly use rhodium metal organic complex catalyst, although the carbon-carbon double bond (C=C) in nitrile rubber is had very high hydrogenation selectivity and reactivity by rhodium metal organic complex catalyst, but the abundance that rhodium element is in the earth is less, expensive, and application cost is higher; On the other hand, the defects such as existing homogeneous phase solution hydrogenation method all also exists reaction temperature height, complicated operation always, energy consumption is high, hydrogenation reaction low and hydrogenation products the degree of hydrogenation of activity has much room for improvement.
Summary of the invention
The invention aims to overcome that catalyst application cost in art methods is high, not easily implement (reaction temperature height, complicated operation, energy consumption are high), defect that hydrogenation reaction low and hydrogenation products the degree of hydrogenation of activity has much room for improvement, it is provided that a kind of catalyst application cost is relatively low, be more easy to enforcement (reaction temperature is relatively low, simple to operate, energy consumption is low), the preparation method of the copolymer that degree of hydrogenation is improved significantly and hydrogenation products increases without obvious gel of hydrogenation reaction activity height, hydrogenation products.
The present inventor has been surprisingly found that under study for action, in the process preparing copolymer, is dissolved in organic solvent by unsaturated copolymer, fills after getting rid of gas, adds catalyst for hydrogenation (RmA)zRhXnAnd part, then first under low temperature (0-30 DEG C), hydrogenation reaction is carried out, hydrogenation reaction is carried out again under high temperature (50-180 DEG C), low temperature hydrogenation reaction is used with high-temperature hydrogenation reaction bonded, (reaction temperature is relatively low to make reaction be more easy to enforcement, simple to operate, energy consumption is low), the hydrogenation reaction activity of catalyst can not only be significantly improved, obtain response speed faster, shorten the response time, and the degree of hydrogenation of hydrogenation products can be significantly improved, and hydrogenation products increases without obvious gel, simultaneously, can also effectively reduce the preparation cost of high saturated copolymer.
Therefore, to achieve these goals, the preparation method that the invention provides a kind of copolymer, said method comprising the steps of:
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, fill and get rid of gas;
(2) adding catalyst for hydrogenation and part, described catalyst for hydrogenation has below general formula: (RmA)zRhXn, wherein, each R is independently selected from the aralkyl of the alkyl of C1-C8, the cycloalkyl of C4-C8, the aryl of C6-C15 or C7-C15; A is selected from phosphorus, arsenic, sulfur or sulfoxide radicals S=O; X is selected from hydrogen or anion; Z is 2,3 or 4; M is 2 or 3; N is 1,2 or 3;
(3) it is filled with hydrogen, stirring, react, the condition of described reaction includes: reaction temperature is 0-30 DEG C, and Hydrogen Vapor Pressure is 0.05-15Mpa, and the response time is 1-120 minute;
(4) being warming up to 50-180 DEG C, maintenance Hydrogen Vapor Pressure is 0.1-15Mpa, reacts 1-20 hour;
(5) organic solvent in the product that removal step (4) obtains.
The preparation method of the copolymer of the present invention, it is possible to increase the hydrogenation reaction activity of catalyst, it is thus achieved that response speed faster, shortens the response time, it is possible to significantly improve the degree of hydrogenation of hydrogenation products, and hydrogenation products relatively unsaturated copolymer increases without obvious gel. Meanwhile, the method has the advantages such as simple to operate, the response time is short, easy enforcement (reaction temperature is relatively low, simple to operate, energy consumption is low), it is possible to effectively reduce the preparation cost of high saturated copolymer.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The preparation method that the invention provides a kind of copolymer, the method comprises the following steps:
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, fill and get rid of gas;
(2) adding catalyst for hydrogenation and part, described catalyst for hydrogenation has below general formula: (RmA)zRhXn, wherein, each R is independently selected from the aralkyl of the alkyl of C1-C8, the cycloalkyl of C4-C8, the aryl of C6-C15 or C7-C15; A is selected from phosphorus, arsenic, sulfur or sulfoxide radicals S=O; X is selected from hydrogen or anion; Z is 2,3 or 4; M is 2 or 3; N is 1,2 or 3;
(3) it is filled with hydrogen, stirring, react, the condition of described reaction includes: reaction temperature is 0-30 DEG C, and Hydrogen Vapor Pressure is 0.05-15Mpa, and the response time is 1-120 minute;
(4) being warming up to 50-180 DEG C, maintenance Hydrogen Vapor Pressure is 0.1-15Mpa, reacts 1-20 hour;
(5) organic solvent in the product that removal step (4) obtains.
In the inventive method step (1), for the mass percentage concentration (namely the quality of unsaturated copolymer is divided by the quality sum of unsaturated copolymer Yu organic solvent) of unsaturated copolymer in glue, there is no particular limitation, can be concentration commonly used in the art, under preferable case, in glue, the mass percentage concentration of unsaturated copolymer is 2-15%, more preferably 4-12%.
In the inventive method step (1), for unsaturated copolymer, there is no particular limitation, can being the various unsaturated copolymers containing carbon-carbon double bond (C=C), it is preferable that in situation, unsaturated copolymer be bipolymer and/or terpolymer; Further preferably, bipolymer includes butadiene-acrylonitrile, butadiene-(methyl) acrylonitrile, 2-methyl isophthalic acid, 3-butadiene-acrylonitrile, 2-methyl isophthalic acid, one or more in 3-butadiene-(methyl) acrylonitrile and styrene butadiene styrene block copolymer (SBS), terpolymer includes one or more in butadiene-acrylonitrile-(methyl) acrylic acid, butadiene-(methyl) acrylonitrile-acrylic acid, butadiene-(methyl) acrylonitrile-(methyl) acrylic acid and butadiene-acrylonitrile-acrylic acid; More a step is preferably, and unsaturated copolymer is butadiene-acrylonitrile and/or butadiene-(methyl) acrylonitrile. When the mixture that unsaturated copolymer is butadiene-acrylonitrile and butadiene-(methyl) acrylonitrile, for the ratio not requirement that butadiene-acrylonitrile and butadiene-(methyl) acrylonitrile add, it is possible to for arbitrary proportion.
In the inventive method step (1), for organic solvent, there is no particular limitation, can be the various organic solvents that can dissolve unsaturated copolymer, catalyst for hydrogenation and part in this area, under preferable case, organic solvent is that aromatic hydrocarbons, aromatic hydrocarbons are by one or more in alkyl or the derivant of halogen substiuted, halogenated alkane, ketone and amide; It is further preferred that organic solvent is one or more in benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes, acetone, butanone and DMF.
In the inventive method step (2), in order to improve the hydrogenation reaction activity of catalyst for hydrogenation and increase the degree of hydrogenation of hydrogenation products, under preferable case, the addition of catalyst for hydrogenation is the 0.01-5% of unsaturated copolymer quality, more preferably 0.05-1%.
In the inventive method step (2), in order to increase the degree of hydrogenation of hydrogenation products, it is preferable that in situation, the addition of part is 1-20 times of catalyst for hydrogenation quality, more preferably 4-15 times.
In the inventive method step (2), in order to improve the hydrogenation reaction activity of catalyst for hydrogenation and increase the degree of hydrogenation of hydrogenation products, it is preferable that in situation, catalyst for hydrogenation is (PPh3)3RhCl. Catalyst for hydrogenation (RmA)zRhXnCan pass through commercially available.
In the inventive method step (2), in order to increase the degree of hydrogenation of hydrogenation products, it is preferable that in situation, part is one or more in the organic compound of organic phosphine, the organic pair of phosphine, organic cerium and nitrogenous, sulfur or oxygen; It is further preferred that part is organic phosphine; More a step is preferably, and part is triphenylphosphine.
For the organic compound of the organic phosphine in catalyst for hydrogenation and part, the organic pair of phosphine, organic cerium and nitrogenous, sulfur or oxygen, there is no particular limitation, it is possible to for the organic compound of various organic phosphines commonly used in the art, the organic pair of phosphine, organic cerium and nitrogenous, sulfur or oxygen.
In the inventive method step (3), the present inventor is further discovered that under study for action, the response time of low temperature hydrogenation reaction is long, the cyano group in hydrogenated nitrile-butadiene rubber can be caused to be reduced, thus causing that product structure and performance change, it is therefore preferable that in situation, the response time is 20-40 minute. In order to improve the hydrogenation reaction activity of catalyst for hydrogenation further and increase the degree of hydrogenation of hydrogenation products, it is further preferred that the condition of reaction includes: reaction temperature is 10-25 DEG C, and Hydrogen Vapor Pressure is 1-5Mpa, and the response time is 20-40 minute.
In the inventive method step (4), in order to increase the degree of hydrogenation of hydrogenation products further, it is preferable that in situation, being warming up to 80-150 DEG C, maintenance Hydrogen Vapor Pressure is 4-12Mpa, reacts 4-16 hour.
In the inventive method step (5), for the method for the organic solvent in the product that removal step (4) obtains, there is no particular limitation, the various methods can commonly used for those skilled in the art, such as can pass through the organic solvent in the product that the removal steps (4) such as ethanol cohesion, steam distillation obtain, thus obtaining hydrogenation products, then remove the solvent on the hydrogenation products obtained. For removing the method for the solvent on hydrogenation products, there is no particular limitation, the various methods can commonly used for those skilled in the art, it is preferable that in situation, the method removing solvent is vacuum drying, vacuum drying condition includes: temperature is 50-100 DEG C, and the time is 1-10 hour.
Embodiment
The present invention is further illustrated for below example, but and is not so limited the present invention.
In following example and comparative example, the assay method of degree of hydrogenation is bromine iodine method.
The assay method of gel content: weigh w1 gram of dry glue, add chlorobenzene, it is made into the solution of 1g/100mL, after dissolving 24 hours, 360 mesh filter screens that solution is poured into constant weight (w2 gram) filter, the dry constant weight of 360 mesh filter screens that will fill insoluble matter again, weight is designated as w3 gram, then gel content is: (w3-w2)/w1*106ppm��
Nmr analysis method is adopted to measure the cyano reduction rate in hydrogenated nitrile-butadiene rubber, method particularly includes: weigh w4 gram of dry glue, its cyano content is A mass % (known), dissolve with deuterochloroform, using styrene as interior mark, cinnamic addition is M1 mole, calculates, according to interior mark integral area, the cyano content obtaining being reduced in dry glue and is M2 mole, then the cyano reduction rate in hydrogenated nitrile-butadiene rubber is (M2*26)/(w4*A%).
Catalyst for hydrogenation (PPh3)3RhCl available from Acros.
Butadiene-propylene nitrile rubber is purchased from Lan Hua company, and the trade mark is N21L, and cyano content is 41 mass %.
Embodiment 1-14
The embodiments of the invention 1 14 preparation method for the copolymer of the present invention is described:
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, join in reactor, fill and get rid of gas;
(2) catalyst for hydrogenation and part are added;
(3) it is filled with hydrogen, stirring, react, the condition of reaction includes: reaction temperature is b DEG C, and Hydrogen Vapor Pressure is aMPa, and the response time is c minute;
(4) be warming up to e DEG C, maintenance Hydrogen Vapor Pressure be dMPa, react f hour;
(5) hydrogenation products by ethanol cohesion precipitate out, and at 60 DEG C vacuum drying 8 hours.
In embodiment 1-14, unsaturated copolymer is acrylonitrile butadiene rubber, and the gel content of acrylonitrile butadiene rubber is 304ppm, the quality of glue is 540g, gelatin concentration (i.e. the mass percentage concentration of unsaturated copolymer in glue), catalyst/unsaturated copolymer (i.e. the mass ratio of catalyst for hydrogenation and unsaturated copolymer), part/catalyst (i.e. the mass ratio of part and catalyst for hydrogenation), a-f and the degree of hydrogenation of hydrogenation products obtained, gel content, cyano reduction situation measurement result in Table 1.
Table 1
Comparative example 1-7
The condition of unsaturated copolymer, organic solvent, catalyst for hydrogenation and part in comparative example 1-4, gelatin concentration (i.e. the mass percentage concentration of unsaturated copolymer in glue), catalyst/unsaturated copolymer (i.e. catalyst for hydrogenation and the mass ratio of unsaturated copolymer), part/catalyst (i.e. the mass ratio of part and catalyst for hydrogenation) respectively with embodiment 2,8,10 and 11 identical, the difference is that, comparative example 1-4 method is reacted without low temperature hydrogenation. Comparative example 5 is compared with comparative example 1, the difference is that being extended by the response time f of comparative example 1. Comparative example 6 is compared with embodiment 2, the difference is that changing low temperature hydrogenation reaction into high-temperature hydrogenation reaction. In comparative example 1-6, gelatin concentration (i.e. the mass percentage concentration of unsaturated copolymer in glue), catalyst/unsaturated copolymer (i.e. the mass ratio of catalyst for hydrogenation and unsaturated copolymer), part/catalyst (i.e. the mass ratio of part and catalyst for hydrogenation), a-f and the degree of hydrogenation of hydrogenation products obtained, gel content, cyano reduction situation measurement result in Table 2.
Table 2
Comparative example 7
According to the method for embodiment 2, the difference is that, (1) adds catalyst for hydrogenation and part in a kettle., fills and gets rid of gas; (2) it is filled with hydrogen, stirring, react, the condition of reaction includes: reaction temperature is 15 DEG C, and Hydrogen Vapor Pressure is 3.0MPa, and the response time is 30 minutes; (3) unsaturated copolymer is dissolved in organic solvent, obtains glue, join in reactor; (4) be warming up to 130 DEG C, maintenance Hydrogen Vapor Pressure be 4.0MPa, react 8.0 hours; (5) hydrogenation products by ethanol cohesion precipitate out, and at 60 DEG C vacuum drying 8 hours. Wherein, the condition of unsaturated copolymer, organic solvent, catalyst for hydrogenation and part is with embodiment 2.
After measured, the degree of hydrogenation of hydrogenation products is 96.1%, and gel content is 753ppm.
By embodiment 2 compared with embodiment 5, when the temperature of step (3) low temperature hydrogenation reaction is 10-25 DEG C, it is possible to improve the degree of hydrogenation of hydrogenation products further.
By embodiment 2 compared with embodiment 9, when the time of step (3) low temperature hydrogenation reaction is 20-40 minute, it is possible to be effectively improved the degree of hydrogenation of hydrogenation products, hydrogenation products increases without obvious gel simultaneously; And when the time lengthening reacted by low temperature hydrogenation to 120 minute, cyano group in hydrogenated nitrile-butadiene rubber can be caused to be reduced, thus cause that product structure and performance change.
By embodiment 2 compared with embodiment 12, when organic solvent adopts chlorobenzene, it is possible to increase the degree of hydrogenation of hydrogenation products further.
By embodiment 2 compared with embodiment 13, when part adopts PPh3Time, it is possible to increase the degree of hydrogenation of hydrogenation products further.
By embodiment 2 compared with embodiment 14, when organic solvent adopts chlorobenzene and part to adopt PPh3Time, it is possible to increase the degree of hydrogenation of hydrogenation products further.
Embodiment 2 compared with comparative example 1 respectively, embodiment 8 compares with comparative example 2, embodiment 10 compares with comparative example 3, embodiment 11 compares with comparative example 4, known, (condition of reaction includes: reaction temperature is 0-30 DEG C to increase low temperature hydrogenation reaction before high-temperature hydrogenation reacts, Hydrogen Vapor Pressure is 0.05-15Mpa, response time is 1-120 minute) step, can effectively improve reaction rate, increase the degree of hydrogenation of hydrogenation products, and hydrogenation products increases without obvious gel.
By embodiment 2 compared with comparative example 5, if without low temperature hydrogenation reaction, (condition of reaction includes: reaction temperature is 0-30 DEG C before high-temperature hydrogenation reacts, Hydrogen Vapor Pressure is 0.05-15Mpa, response time is 1-120 minute) step, under the reaction condition that response time f is extended 2 hours, similar degree of hydrogenation could be obtained, illustrate that successively carrying out low temperature hydrogenation reaction reacts, with high-temperature hydrogenation, the reaction rate that can significantly improve hydrogenation reaction, being effectively improved the degree of hydrogenation of hydrogenation products, hydrogenation products increases without obvious gel simultaneously.
By embodiment 2 compared with comparative example 6, change low temperature hydrogenation reaction into high-temperature hydrogenation reaction, hydrogenation of net product degree there is no and improves effect, illustrate that successively carrying out low temperature hydrogenation reaction reacts, with high-temperature hydrogenation, the reaction rate that can significantly improve hydrogenation reaction, being effectively improved the degree of hydrogenation of hydrogenation products, hydrogenation products increases without obvious gel simultaneously.
By embodiment 2 compared with comparative example 7, change the charging sequence of glue and catalyst, low temperature hydrogenation reaction can be caused with high-temperature hydrogenation reacting phase to be combined the decline of hydrogenation effect, hydrogenation products has obvious gel to increase simultaneously.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the preparation method of a copolymer, it is characterised in that the method comprises the steps:
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, fill and get rid of gas;
(2) adding catalyst for hydrogenation and part, described catalyst for hydrogenation has below general formula: (RmA)zRhXn, wherein, each R is independently selected from the aralkyl of the alkyl of C1-C8, the cycloalkyl of C4-C8, the aryl of C6-C15 or C7-C15; A is selected from phosphorus, arsenic, sulfur or sulfoxide radicals S=O; X is selected from hydrogen or anion; Z is 2,3 or 4; M is 2 or 3; N is 1,2 or 3;
(3) it is filled with hydrogen, stirring, react, the condition of described reaction includes: reaction temperature is 0-30 DEG C, and Hydrogen Vapor Pressure is 0.05-15Mpa, and the response time is 1-120 minute;
(4) being warming up to 50-180 DEG C, maintenance Hydrogen Vapor Pressure is 0.1-15Mpa, reacts 1-20 hour;
(5) organic solvent in the product that removal step (4) obtains.
2. preparation method according to claim 1, wherein, in step (3), the condition of described reaction includes: reaction temperature is 10-25 DEG C, and Hydrogen Vapor Pressure is 1-5Mpa, and the response time is 20-40 minute.
3. preparation method according to claim 1, wherein, in step (4), is warming up to 80-150 DEG C, and maintenance Hydrogen Vapor Pressure is 4-12Mpa, reacts 4-16 hour.
4. the preparation method according to any one in claim 1-3, wherein, in step (1), in described glue, the mass percentage concentration of unsaturated copolymer is 2-15%.
5. the preparation method according to any one in claim 1-3, wherein, described unsaturated copolymer is bipolymer and/or terpolymer; Preferably, described bipolymer includes butadiene-acrylonitrile, butadiene-(methyl) acrylonitrile, 2-methyl isophthalic acid, 3-butadiene-acrylonitrile, 2-methyl isophthalic acid, one or more in 3-butadiene-(methyl) acrylonitrile and styrene butadiene styrene block copolymer (SBS), described terpolymer includes one or more in butadiene-acrylonitrile-(methyl) acrylic acid, butadiene-(methyl) acrylonitrile-acrylic acid, butadiene-(methyl) acrylonitrile-(methyl) acrylic acid and butadiene-acrylonitrile-acrylic acid; It is further preferred that described unsaturated copolymer is butadiene-acrylonitrile and/or butadiene-(methyl) acrylonitrile.
6. the preparation method according to any one in claim 1-3, wherein, described organic solvent is that aromatic hydrocarbons, aromatic hydrocarbons are by one or more in alkyl or the derivant of halogen substiuted, halogenated alkane, ketone and amide; Preferably, described organic solvent is one or more in benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes, acetone, butanone and DMF.
7. the preparation method according to any one in claim 1-3, wherein, in step (2), the addition of described catalyst for hydrogenation is the 0.01-5% of described unsaturated copolymer quality, it is preferred to 0.05-1%.
8. preparation method according to claim 7, wherein, the addition of described part is 1-20 times of described catalyst for hydrogenation quality, it is preferred to 4-15 times.
9. the preparation method according to any one in claim 1-3, wherein, described catalyst for hydrogenation is (PPh3)3RhCl��
10. the preparation method according to any one in claim 1-3, wherein, described part is one or more in the organic compound of organic phosphine, the organic pair of phosphine, organic cerium and nitrogenous, sulfur or oxygen; Preferably, described part is organic phosphine; It is further preferred that described part is triphenylphosphine.
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Cited By (1)
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| CN107200795A (en) * | 2016-03-16 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of method of hydrotreating of the polymer containing polar group |
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