CN108017760A - The preparation method of DCPD hydrogenated petroleum resins - Google Patents
The preparation method of DCPD hydrogenated petroleum resins Download PDFInfo
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- CN108017760A CN108017760A CN201610966266.0A CN201610966266A CN108017760A CN 108017760 A CN108017760 A CN 108017760A CN 201610966266 A CN201610966266 A CN 201610966266A CN 108017760 A CN108017760 A CN 108017760A
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- 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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- 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
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
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Abstract
The present invention discloses a kind of preparation method of DCPD hydrogenated petroleum resins, before dicyclopentadiene feedstock polymerization, using the impurity in the method removing raw material of washing, filter is added in hydrogenation of petroleum resin reactor outlet, the colloid produced in removing hydrogenation process, at the same time by the method for backwash, the catalyst being attached in colloid recoil back hydrogenation reactor, recycling.The result shows that the present invention can effectively remove the impurity such as sulphur influential on hydrogenation catalyst, colloid, extend service life and the hydrogenation efficiency of catalyst for hydrogenation.
Description
Technical field
The present invention relates to a kind of production method that hydrogenated petroleum resin is prepared by DCPD.It is continuous in more particularly to a kind of industry
The method of hydrogenation production DCPD hydrogenated petroleum resins.
Background technology
It is also higher and higher to the quality requirement of Petropols with the continuous development in each field, wherein, adhesive and sealing
Agent application development, particularly transparent pressure sensitive adhesive tape, outdoor fluid sealant, disposable sanitary articles, medical adhesive tape, traffic paint with
And the application of the modifying agent of polyolefin is required for the good Petropols of lighter color, odorless and stability.At present, on international market
High-quality Petropols, colourity is less than 2#, and softening point is more than 100 DEG C, generally using hydrogenated petroleum resin technology, i.e. oil tree
Unsaturated hydrocarbons in Petropols, is changed into saturated hydrocarbons by the hydrogenated reaction of fat, improves the form and aspect of Petropols, smell and resistance to
The product of sign property.
The key of adding hydrogen into resin technology is catalyst and hydrogenation technique, and wherein catalyst is to impurity (gel, sulphur and some weights
Metal) sensitive, easy poisoning and deactivation, for this prior art such as US4384080A, US728569, CN105175633A,
CN104877077A, CN102746458A and CN201110060730.7 etc. mostly use Combined stone oleoresin hydrotreating side
Method, including sulfur removal technology and two-stage hydrogenation technique, first segment use activated clay, zinc oxide, iron oxide or alkali-earth metal modified
Ni-based resin eliminate the influence of poisonous substance, second segment reuses the noble metal catalyst of Pd, Rh even load type.
The prior art has certain effect, but practical operation, production cost and product stability (with for being hydrogenated with
Resin raw material fluctuation) etc. there is obvious deficiency, it is ineffective to gum-treated as hydrodesulfurization cost is higher；Absorption
Method loss of material is larger, solid waste is difficult to handle, group technology flow complexity, cost height etc..In addition for the poly- of dicyclopentadiene
Reaction is closed, existing autoclave and tower reactor is taken, oligomer colloid, Er Qieshuan is not only inevitably produced in polymer fluid
Cyclopentadiene can not react completely, they in hydrogenation reaction easily polymerization and coking, coking material be covered in catalyst surface and
It is deposited in duct, reduces the activity of catalyst.Therefore these unreacted components are also required to be handled before hydrogenation.
It can be seen from the above that asking for harmful substance (impurity such as gel and sulphur) is solved without simple effective method in the prior art
Topic, is both needed to that the resin after polymerization intricately handle just to can be used for hydrogenation reaction.
Since Petropols molecular weight is bigger, in chain and cyclic structure, polymer molecule is stretched in catalyst surface,
High spatial oil steric hindrance is formd, unsaturated bond hydrogenation reaction activation energy is high, reaction condition is become harsh, in order to obtain quality
Excellent product, hydrogenation reaction need to carry out under high temperature, high pressure.But the degraded of resin easily occurs under high pressure, makes resin soft
Changing point reduces, therefore the prior art such as CN200810084686.1 discloses slurry autoclave hydrogenation of petroleum resin technology of preparing,
In reaction kettle, using modified skeletal nickel catalyst, hydrogenated petroleum resin is prepared under conditions of pressure is 2.0-11.0MPa.
But its dedicated design of hydrogenation reaction equipment and the recycling of catalyst are extremely difficult；Japanese Huang Chuan chemical companies develop fountain
Hydrogenation technique, industrialization was realized in 1985.Its technical process is that grained catalyst is suspended on bubble cap plate, and use is special
Design solves the problems, such as some of highly viscous fluid flowing, so as to can obtain preferably being hydrogenated with effect under low pressure.This technique must
Adding hydrogen into resin must be separated with product and combined, design requirement is high, and equipment investment is big, is difficult to control.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of method of DCPD hydrogenated petroleum resins,
Its technical problems to be solved is to solve harmful poisonous substance by the processing of raw material and the design of hydrogenation technique (gel and sulphur etc. are miscellaneous
Matter) influence, polymer fluid is directly used in hydrogenation reaction, is obtained while extending catalyst life, reducing energy consumption and equipment investment
To good hydrogenated petroleum resin, and the stability of product quality can be kept, increase benefit.
It is the concrete scheme of the present invention below.
A kind of preparation method of DCPD hydrogenated petroleum resins, mainly includes the following steps that：
1) raw material DCPD removes the objectionable impurities such as sulphur, heavy metal in raw material by washing, and (water is with raw material DCPD's for water-oil factor
Mass ratio) be (1~3): 1, operating pressure is normal pressure, and washing temperature is room temperature, and washing material is discharged by washing column overhead；
2) enter reaction kettle after the DCPD raw materials after washing process obtained by step 1) are mixed with organic solvent to carry out
The mass ratio of heat polymerization, generation Petropols, DCPD and solvent is 1: (1~5), reaction temperature are 230~270 DEG C, instead
It is 1.0~3.0MPa to answer pressure, and the reaction time is 180~360min.
3) Petropols obtained by step 2) carry out hydrogenation reaction in a kettle under the action of skeletal nickel catalyst
Obtain thick hydrogenated petroleum resin, the molar ratio of Petropols and hydrogen is 1: (2~5), catalyst amount are the 0.5 of Petropols
~3.0wt%, reaction time are 120~300min, and reaction pressure is 4.0~10.0MPa, and reaction temperature is 170~250 DEG C；
4) the hydrogenation reaction material obtained by step 3), removes the gel produced in hydrogenation process through a filter, obtains
The mixture of Petropols and solvent, uses the backwashed strainer of reaction dissolvent during simultaneous reactions, will adsorb on strainer
Catalyst recoils to hydrogenation reaction kettle, and backwashing time is at intervals of 120~300min；
5) Petropols and solvent mixture obtained by step 4), through simple vacuum distillation recovered solvent, tower top obtains
Reaction dissolvent returns to polymer reactor, and tower reactor obtains the hydrogenated petroleum resin of high-quality.
Above-mentioned steps 1) mass ratio of the water and raw material DCPD is preferably (1.5~2.0): 1；
Above-mentioned steps 2) organic solvent is pentamethylene, any one of hexamethylene, benzene,toluene,xylene；
Above-mentioned steps 2) mass ratio of the DCPD raw materials and solvent is preferably 1: (1~2), reaction temperature are preferably 240
~260 DEG C, reaction pressure is preferably 1.5~2.0MPa, and the residence time is preferably 240~300min；
Above-mentioned steps 3) the catalyst nickel content is 40~80wt%, average pore size is 2.0~20.0 nanometers；
Above-mentioned steps 3) catalyst amount be preferably Petropols 1.0~2.0wt%, the reaction time is preferably
180~240min, reaction pressure are preferably 6.0~8.0MPa, and reaction temperature is preferably 200~220 DEG C；
Above-mentioned steps 2) organic solvent is preferably one kind in toluene and dimethylbenzene；
Above-mentioned steps 4) the backwashing time interval is preferably 180~240min.
In hydrogenation process, the gel for sulphur and some heavy metals and the polymerization process generation that raw band comes, which can all cause, to be added
The poisoning of hydrogen catalyst, therefore intricately processing need to be carried out to the resin after polymerization and just can be used for hydrogenation reaction.In the prior art,
General to use Combined stone oleoresin hydrotreating method, including sulfur removal technology and two-stage hydrogenation technique, first segment uses activity
Clay, zinc oxide, iron oxide or alkali-earth metal modified Ni-based resin eliminate the influence of poisonous substance, and second segment reuses Pd, Rh
The noble metal catalyst of even load type.Inventor it has been investigated that, can pass through simpler effective manner eliminate poisonous substance influence：
By simply washing the impurity that can be removed in raw material before polymerizable raw material, have an impact so as to reduce to follow-up hydrogenation catalyst
The impurity such as sulphur, extend service life and the hydrogenation efficiency of follow-up hydrogenation catalysts；Powdered modification is used in hydrogenation process
Raney nickel, the hydrogenated petroleum resin stablized at lower pressures with regard to good, product quality can be obtained, while tied in reaction
After beam by the way of backwash, colloid and recycling catalyst are removed.
The present invention changes the prior art in DCPD polymerisation post-treateds by carrying out washing process before polymerisation
The method of poisonous impurities in material, water enter water scrubber from water scrubber upper and lower part respectively with raw material DCPD, at normal temperatures and pressures,
Raw material is washed, the impurity such as sulphur, heavy metal in removing material, while exported in hydrogenation reaction and filtration apparatus is set, will
Colloid is filtered on strainer, and strainer is backwashed furthermore with reaction dissolvent, hydrogenation catalyst recoil back hydrogenation reactor, is solved
Hydrodesulfurization cost of having determined is higher, ineffective to gum-treated；Loss of material is larger, solid waste is difficult to handle, group technology stream
The defects of journey is complicated, of high cost., can the result shows that being washed to raw material and after hydrogenation reaction solution filtered and backwashed
The synthesis of hydrogenated petroleum resin is effectively carried out, simultaneous reactions are more complete, and colloid can be removed by simply filtering, so that
Simplify the process of processing resin colloid.Pass through the Petropols synthesis technique of the technological process of the present invention, hydrogenation catalyst service life
Be obviously prolonged, at the same the present invention only by increase by one simple water scrubber outside and filter, do not increase other process equipments,
Reduce the increased equipment investment because of removing poisonous impurities in existing process, have obvious advanced.
The beneficial effects of the present invention are：
1) by simply washing the objectionable impurities that can be removed in raw material before polymerizable raw material；
2) without the use of the catalyst such as palladium, platinum and the nickel of support type (hydrogenation needs higher pressure), and use powdered
Modification Raney nickel, the hydrogenated petroleum resin stablized at lower pressures with regard to that can obtain good, product quality, studies table
Bright, at the process conditions, for the conversion ratio of hydrogenation of petroleum resin up to more than 97%, softening point declines less than 5 DEG C.
3) colloid is removed in hydrogenation process by the backwash of circulating catalyst, extends follow-up hydrogenation reaction and urge
The service life of agent and hydrogenation efficiency.
4) resin polymerization liquid can be directly used for hydrogenation reaction without processing, effectively reduce energy consumption and equipment investment, increase effect
Benefit.
Below by specific embodiment, the invention will be further described, and resin yield involved in each embodiment calculates
Formula is as follows：
Brief description of the drawings
Fig. 1 is the process flow diagram of the preparation method of DCPD hydrogenated petroleum resins
Embodiment【1~10】
The technological process of embodiment 1~10 is shown in that Fig. 1, raw material W1 are the material rich in DCPD, it, which is mainly formed, is shown in Table 1, in fact
Apply in example, the process condition of water scrubber, polymer reactor and hydrogenation reactor is shown in Table 2, table 3 and table 4 respectively, and reaction terminates
Afterwards, weigh and analyze the indices (softening point, molecular weight distribution and bromine number etc.) of resin sample, the results are shown in Table 5.Using gel
Chromatography determination naval stores molecular weight distributing index (Mw/Mn), softening point is analyzed using ring and ball method GB/2294, using iodimetric titration
(SWB2301-62) Bromine Number analysis is carried out.
Table 1.
| Component | Content (wt.%) |
| CPD | 0.3 |
| DCPD | 84.0 |
| NB | 9.5 |
| It is other | 6.2 |
Table 2.
Table 3.
| Solvent | DCPD：Solvent | Reaction temperature/DEG C | Reaction pressure/Mpa | Residence time/min | |
| Embodiment 1 | Hexamethylene | 1∶4 | 230 | 1.0 | 360 |
| Embodiment 2 | Benzene | 1∶3 | 250 | 1.6 | 270 |
| Embodiment 3 | Toluene | 1∶1 | 240 | 1.5 | 330 |
| Embodiment 4 | Dimethylbenzene | 1∶1.2 | 245 | 1.6 | 290 |
| Embodiment 5 | Toluene | 1∶1.5 | 260 | 1.8 | 240 |
| Embodiment 6 | Dimethylbenzene | 1∶1.8 | 250 | 1.7 | 260 |
| Embodiment 7 | Toluene | 1∶1.6 | 245 | 1.6 | 280 |
| Embodiment 8 | Dimethylbenzene | 1∶2.0 | 255 | 1.9 | 250 |
| Embodiment 9 | Toluene | 1∶1.8 | 240 | 2.0 | 300 |
| Embodiment 10 | Pentamethylene | 1∶5 | 270 | 3.0 | 180 |
Table 4.
Table 5.
| Petropols yield/% | Profile exponent/(Mw/Mn) | Hydrogenation resin softening point/DEG C | Bromine number/(g/100g) | |
| Embodiment 1 | 80.8 | 1.35 | 104.3 | 2.5 |
| Embodiment 2 | 83.5 | 1.28 | 110.8 | 2.1 |
| Embodiment 3 | 82.8 | 1.29 | 113.6 | 2.0 |
| Embodiment 4 | 83.9 | 1.26 | 107.6 | 1.9 |
| Embodiment 5 | 83.2 | 1.33 | 114.2 | 1.8 |
| Embodiment 6 | 86.1 | 1.32 | 108.8 | 1.5 |
| Embodiment 7 | 83.5 | 1.30 | 111.3 | 2.1 |
| Embodiment 8 | 84.6 | 1.28 | 112.2 | 1.9 |
| Embodiment 9 | 82.5 | 1.31 | 115.0 | 1.6. |
| Embodiment 10 | 80.1 | 1.36 | 105.8 | 2.1 |
Claims (10)
1. a kind of preparation method of DCPD hydrogenated petroleum resins, it is characterised in that comprise the following steps：
1) raw material DCPD removes the objectionable impurities such as sulphur, heavy metal in raw material by washing, and the mass ratio of water and raw material DCPD are (1
~3): 1, operating pressure is normal pressure, and washing temperature is room temperature, and washing material is discharged by washing column overhead；
2) it is anti-to enter reaction kettle progress thermal polymerization after the DCPD after washing process obtained by step 1) is mixed with organic solvent
Answer, generation Petropols, the mass ratio of DCPD and solvent is 1: (1~5), reaction temperature are 230~270 DEG C, and reaction pressure is
1.0~3.0MPa, reaction time are 180~360min；
3) Petropols obtained by step 2) carry out hydrogenation reaction and obtain in a kettle under the action of skeletal nickel catalyst
The molar ratio of thick hydrogenated petroleum resin, Petropols and hydrogen be 1: (2~5), catalyst amount for Petropols 0.5~
3.0wt%, reaction time are 120~300min, and reaction pressure is 4.0~10.0MPa, and reaction temperature is 170~250 DEG C；
4) the hydrogenation reaction material obtained by step 3), removes the gel produced in hydrogenation process through a filter, obtains oil
The mixture of resin and solvent, uses the backwashed strainer of reaction dissolvent during simultaneous reactions, will adsorb the catalysis on strainer
Agent recoils to hydrogenation reaction kettle, and backwashing time is at intervals of 120~300min；
5) Petropols and the mixture of solvent obtained by step 4), through vacuum distillation recovered solvent, tower top obtains reacting molten
Agent returns to polymer reactor, and tower reactor obtains pure hydrogenated petroleum resin.
A kind of 2. preparation method of DCPD hydrogenated petroleum resins according to claim 1, it is characterised in that the step 1) water
Mass ratio with raw material DCPD is (1.5~2.0): 1.
3. a kind of preparation method of DCPD hydrogenated petroleum resins according to claim 1, it is characterised in that step 2) is described to be had
Solvent is any one of pentamethylene, hexamethylene, benzene,toluene,xylene.
4. the preparation method of DCPD hydrogenated petroleum resins according to claim 1, it is characterised in that the step 2) DCPD is former
The mass ratio of material and solvent is 1: (1~2).
5. a kind of preparation method of DCPD hydrogenated petroleum resins according to claim 1, it is characterised in that step 2) is described anti-
It is 240~260 DEG C to answer temperature, and reaction pressure is 1.5~2.0MPa, and the residence time is 240~300min.
6. a kind of preparation method of DCPD hydrogenated petroleum resins according to claim 1, it is characterised in that step 3) is described to urge
Agent nickel content is 40~80wt%, and average pore size is 2.0~20.0 nanometers.
7. a kind of preparation method of DCPD hydrogenated petroleum resins according to claim 1, it is characterised in that step 3) is described to urge
Agent dosage is 1.0~2.0wt% of Petropols.
8. a kind of preparation method of DCPD hydrogenated petroleum resins according to claim 1, it is characterised in that when step 3) is reacted
Between be 180~240min, reaction pressure is 6.0~8.0MPa, and reaction temperature is 200~220 DEG C.
A kind of 9. preparation method of DCPD hydrogenated petroleum resins according to claim 1 and claim 3, it is characterised in that institute
Organic solvent is stated as one kind in toluene and dimethylbenzene.
10. a kind of preparation method of DCPD hydrogenated petroleum resins according to claim 1, it is characterised in that step 4) is described anti-
Washing time is at intervals of 180~240min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585666A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | A preparing method of dicyclopentadiene hydrogenated petroleum resin |
| CN205495528U (en) * | 2016-03-31 | 2016-08-24 | 常州市新鸿医药化工技术有限公司 | High -pressure hydrogenation cauldron catalyst recovery system |
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2016
- 2016-10-28 CN CN201610966266.0A patent/CN108017760A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585666A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | A preparing method of dicyclopentadiene hydrogenated petroleum resin |
| CN205495528U (en) * | 2016-03-31 | 2016-08-24 | 常州市新鸿医药化工技术有限公司 | High -pressure hydrogenation cauldron catalyst recovery system |
Non-Patent Citations (1)
| Title |
|---|
| 潘炳力著: "《先进高分子材料摩擦学》", 31 August 2016, 国防工业出版社 * |
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