CN106366247A - Method for preparing hot poly resin from C9 cold polymerized petroleum resin by-product - Google Patents
Method for preparing hot poly resin from C9 cold polymerized petroleum resin by-product Download PDFInfo
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- CN106366247A CN106366247A CN201610761278.XA CN201610761278A CN106366247A CN 106366247 A CN106366247 A CN 106366247A CN 201610761278 A CN201610761278 A CN 201610761278A CN 106366247 A CN106366247 A CN 106366247A
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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 invention discloses a method for preparing hot poly resin from C9 cold polymerized petroleum resin by-product. The method includes raw material pretreatment, polyreaction, and reduced pressure distillation. The step of raw material pretreatment uses as raw material a first time flashing oil and a second time flashing oil of the C9 cold polymerized petroleum resin by-product, mixed by a mass proportion of (0.5-1.5):1, then is used as the mixed raw material, for later use. The step of polyreaction is as follows:, after the mixed material is filled in a reactor with a stirring shaft, the reactor is tightly sealed, the nitrogen is replaced three times, then filled into the reactor and the pressure is raised to 0.7-2.5MPa, after being heated to 200-250 DEG C, reaction is carried out under a constant temperature for 4-10 hours, and the polymer solution is obtained. The step of reduced pressure distillation is as follows: the polymer solution is poured into a reactor, under the pressure of 0.08-0.095MPa the polymer solution is pressure reduced and distilled, until the fraction temperature rises to the highest then drops and no longer rises, the distilling is stopped, the polymer is poured out and cooled to obtain a product. The method is simple in process, green, energy saving, and environmentally friendly, and the quality of the obtained product is relatively high.
Description
Technical field
The present invention relates to Petropols preparing technical field, the cold poly- Petropols by-product hot polymerization resin of specifically a kind of c9
Preparation method.
Background technology
Petropols are originally for replacing Colophonium and its derivant to develop.But once appearance, have developed rapidly.Short
Decades in, there is the suitable level of production and yield.The country of especially industry prosperity in the world, petroleum resin products
Specification is many, and process units is on a grand scale.As Japan has nine companies to produce Petropols, production capacity reaches 1,000,000 tons/year.
The Exxon of the U.S., He Gelisi, solid special；The cdf company of France；Several main in the world oil such as ici company of Britain
Also there is Petropols process units in chemical company.The ground such as China Taiwan and South Korea also produces Petropols.China's research and life
Produce the unit of Petropols and producer is many, but small scale, production capacity is not high, and kind quantity is also well below some prosperity states abroad
Family.The raw material of Petropols is by-product c5 and c9 of cracker and benzene production equipment.The U.S. is to research and develop oil tree earliest
The country of fat, begins one's study for 1910, and the forties in 20th century, picoo company was first by its industrialization.After the sixties, the U.S.,
The Petropols industry of the states such as West Europe, Japan is rapidly developed.To the end of the eighties, U.S., day, English, Fa Deng state Petropols
Production capacity reaches 45.1 ten thousand tons/year, and wherein hydrogenated petroleum resin production capacity is 6.64 ten thousand tons/year.
In recent years, with technology update and the market competition needs, Petropols have developed into multi items, many
The trade mark, broad-spectrum feature synthetic resin.China started from 1964 to develop Petropols, successively built up some small-sized lifes
Produce device, but due to raw material and technical problem, slower development.Developing rapidly with China's Petrochemical, particularly ethylene
The raising year by year of production capacity, the quantity of cracking c9 fraction is continuously increased, and makes full use of this part resource to develop downstream product
Increasingly cause the attention of people.It is in the existing patent of existing Petropols, more to the report of c5 resin, c9 resin,
And the pressure hot polymerization with c9 cold poly resin by-product flash oil as raw material is little.In the middle of current oil resin art, oil
The by-product flash oil utilization orientation of resin is all often as tempered oil with freshening or hydrogenation, lacks the way down extending
Footpath, considerably increases the loss of energy consumption and unnecessary waste.Therefore, develop and the by-product of the development cold poly- Petropols of c9 dodges
Steam oil hot polymerization Petropols become when previous important subject, thus solving the comprehensive of China's oil resin by-products flash oil
Close Utilizing question, also extend the utilization of downstream sources simultaneously, be environmental protection, energy-conservation, innovate and contribute.
Content of the invention
It is an object of the invention to provide a kind of prepare the cold poly- oil tree of c9 being simple and convenient to operate and having better quality
The preparation method of fat by-product hot polymerization resin.
For achieving the above object, the following technical scheme of present invention offer:
The preparation method of the cold poly- Petropols by-product hot polymerization resin of c9, comprises the following steps:
1) pretreatment of raw material
The cold poly- Petropols of c9 production process can by be not engaged in or not exclusively participate in react component distillation go out, generally I
Be called full flashing, after full flashing, resin liquid carries out second distillation again, namely secondary flash, and full flashing is oily, secondary
The Main Ingredients and Appearance of flash oil contains macromole alkene component, a small amount of oligomer, and full flashing oil, the component of secondary flash oil have very
Big difference.Prepare Petropols for primary raw material and will carry out suitable ratio blending with full flashing oil, secondary flash oil, allow
Component comparatively facilitates polyreaction.
With the cold poly- Petropols by-product full flashing oil of c9, secondary flash oil as raw material, will be oily for full flashing and secondary
Flash oil (0.5～1.5) in mass ratio: as mixed material after 1 mixing, standby.
2) polyreaction
In the reactor with shaft, after mixed material is loaded, close reactor, after nitrogen displacement 3 times, then
It is filled with nitrogen boosting 0.7～2.5mpa, after being heated to 200～250 DEG C, isothermal reaction 4～10 hours, obtain polymer fluid.
3) vacuum distillation
Because mixed material is after polymerization, evaporate with the presence of the inactive ingredients having neither part nor lot in polyreaction.This unreacted reactant is such as
Insufficient removing, not only reduces resin softening point, and so that the performances such as thermostability and its color number of resin is significantly reduced, therefore select
Select distillation under vacuum to remove it.
Polymer fluid is poured in reactor, under -0.08～-0.095mpa pressure, polymer fluid is carried out with vacuum distillation, one
Directly steam and rise to maximum temperature to fraction temperature and decline again and no longer rising, stop distillation, pour out polymer, after cooling
To product.
As the further scheme of the present invention: described full flashing oil, secondary flash oil are mainly the cold poly resin of c9 and gather
Close the olefin component in vacuum -0.05～-0.08mpa, 100～160 DEG C of not reactions completely flashing off for the oil.
As the further scheme of the present invention: described full flashing oil, secondary flash oil are mainly the cold poly resin of c9 and gather
Close the olefin component in vacuum -0.08mpa, 110～160 DEG C of not reactions completely flashing off for the oil.
As the further scheme of the present invention: described full flashing oil, secondary flash oil 1:1 in mass ratio make after mixing
For mixed material.
As the further scheme of the present invention: described step 2) in, reactor is reactor.
As the further scheme of the present invention: described step 2) in, isothermal reaction 4～8 hours.
As the further scheme of the present invention: described step 2) in, it is filled with nitrogen boosting 1.0mpa, be heated to 230 DEG C
Afterwards, isothermal reaction 8 hours.
As the further scheme of the present invention: in described step 3), reactor is decompression flask.
As the further scheme of the present invention: in described step 3), the pressure of vacuum distillation is -0.09mpa.
As the further scheme of the present invention: in described step 3), the temperature stopping distillation is 290 DEG C.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention with the by-product of the cold poly- Petropols of c9 as primary raw material, no catalyst, no waste water, process is simple, operation letter
Single, the by-product of the cold poly- Petropols of c9 can be comprehensively utilized simultaneously, reaches green, energy-saving and environmental protection, comprehensive utilization of resources etc.
Purpose, obtained resin form and aspect are less than 13, and between 100～130 DEG C, active component conversion ratio is up to 80～90% to softening point,
Mean molecule quantity reaches more than 1000, can be widely applied to adhesive, paint industry.
Another feature of the present invention is: course of reaction need not add any catalyst, and the flash oil of hot polymerization can conduct
Preferably aromatic solvent naphtha raw material, two kinds of process synthesis utilize, and both can reduce resin cost, and can reduce the dirt to environment again
Dye.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of not making creative work, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, the preparation method of the cold poly- Petropols by-product hot polymerization resin of c9, comprise the following steps:
1) pretreatment of raw material
Raw material used by the present invention be Guangdong New Huayue Petrochemical Incorporated Company c9 cold poly- device by-product full flashing oil, two
Secondary flash oil (this full flashing oil, secondary flash oil be mainly c9 cold poly resin godied oil vacuum -0.08mpa, 110～
The olefin component of 160 DEG C of not reactions completely flashing off), and as mixed material after mixing by 1:1 ratio.
2) polyreaction
In the reactor with shaft, after mixed material is loaded, close reactor, after nitrogen displacement 3 times, then
It is filled with nitrogen boosting 0.7～2.5mpa, after being heated to 200～250 DEG C, isothermal reaction 4～10 hours, obtain polymer fluid.
3) vacuum distillation
Polymer fluid is poured in decompression flask, under -0.09mpa pressure, vacuum distillation is carried out to polymer fluid, steam fraction always
Temperature rises to maximum temperature and declines and till no longer rising, stop distillation, pours out polymer, obtains product after cooling.
In order to filter out the optimum process condition of the cold poly- Petropols by-product hot polymerization resin of c9, to step 2) in pressure
Power, temperature and response time carry out following value:
1st, when temperature be 230 DEG C, the response time be 8h when, different pressures 0.7mpa, 1.0mpa, 1.5mpa, 2.5mpa are to product
Yield impact, result is as shown in table 1；
2nd, when pressure be 1.0mpa, the response time be 8h when, 200 DEG C of different temperatures, 230 DEG C, 240 DEG C, 250 DEG C of receipts to product
Rate and the impact of color number, result is as shown in table 2；
3rd, when temperature be 230 DEG C, pressure be 1.0mpa when, the shadow of differential responses time 4h, 6h, 8h, 10h yield to product
Ring, result is as shown in table 3.
From table 1～3: reaction temperature reach 230 DEG C, reaction pressure 1.0mpa, response time 8h, the performance of product is
Excellent, it is 11 that yield reaches 55.6%, form and aspect.
The impact to yield for table 1 different pressures
The impact to yield and color number for the table 2 differential responses temperature
The impact to yield for the table 3 differential responses time
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, and do not carrying on the back
In the case of the spirit or essential attributes of the present invention, the present invention can be realized in other specific forms.Therefore, no matter from which
From the point of view of a bit, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention will by appended right
Ask rather than described above limits, it is intended that all changes that will fall in the implication and scope of the equivalency of claim
Include in the present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, not each embodiment only wraps
Containing an independent technical scheme, only for clarity, those skilled in the art should for this narrating mode of description
Using description as an entirety, the technical scheme in each embodiment can also form those skilled in the art through appropriately combined
Understandable other embodiment.
Claims (10)
- The preparation method of the cold poly- Petropols by-product hot polymerization resin of 1.c9 is it is characterised in that comprise the following steps:1) pretreatment of raw material: with the cold poly- Petropols by-product full flashing oil of c9, secondary flash oil as raw material, by full flashing Oil and secondary flash oil (0.5～1.5) in mass ratio: as mixed material after 1 mixing, standby；2) polyreaction: in the reactor with shaft, after mixed material is loaded, closed reactor, put with nitrogen After changing 3 times, it is then charged with nitrogen boosting 0.7～2.5mpa, after being heated to 200～250 DEG C, isothermal reaction 4～10 hours, obtain Polymer fluid；3) vacuum distillation: polymer fluid is poured in reactor, under -0.08～-0.095mpa pressure, polymer fluid is reduced pressure Distillation, steams always and rises to maximum temperature to fraction temperature and decline and no longer rising, stop distillation, pour out polymer, Product is obtained after cooling.
- 2. the preparation method of the cold poly- Petropols by-product hot polymerization resin of c9 according to claim 1 is it is characterised in that institute State full flashing oil, secondary flash oil be mainly c9 cold poly resin godied oil vacuum -0.05～-0.08mpa, 100～ The olefin component of 160 DEG C of not reactions completely flashing off.
- 3. the preparation method of the cold poly- Petropols by-product hot polymerization resin of c9 according to claim 2 is it is characterised in that institute The full flashing oil stated, secondary flash oil are mainly c9 cold poly resin godied oil in vacuum -0.08mpa, 110～160 DEG C of sudden strains of a muscle The olefin component of the not reaction completely steaming.
- 4. the preparation method of the cold poly- Petropols by-product hot polymerization resin of c9 according to claim 1 is it is characterised in that institute State full flashing oil, secondary flash oil 1:1 in mass ratio mixing after as mixed material.
- 5. the preparation method of the cold poly- Petropols by-product hot polymerization resin of c9 according to claim 1 is it is characterised in that institute The step 2 stated) in, reactor is reactor.
- 6. the preparation method of the cold poly- Petropols by-product hot polymerization resin of c9 according to claim 1 is it is characterised in that institute The step 2 stated) in, isothermal reaction 4～8 hours.
- 7. the preparation method of the cold poly- Petropols by-product hot polymerization resin of c9 according to claim 6 is it is characterised in that institute The step 2 stated) in, it is filled with nitrogen boosting 1.0mpa, after being heated to 230 DEG C, isothermal reaction 8 hours.
- 8. the preparation method of the cold poly- Petropols by-product hot polymerization resin of c9 according to claim 1 is it is characterised in that institute In the step 3) stated, reactor is decompression flask.
- 9. the preparation method of the cold poly- Petropols by-product hot polymerization resin of c9 according to claim 1 is it is characterised in that institute In the step 3) stated, the pressure of vacuum distillation is -0.09mpa.
- 10. the cold poly- Petropols by-product hot polymerization resin of c9 according to claim 1 preparation method it is characterised in that In described step 3), the temperature stopping distillation is 290 DEG C.
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| CN201610761278.XA CN106366247B (en) | 2016-08-31 | 2016-08-31 | The preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 |
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| CN201610761278.XA CN106366247B (en) | 2016-08-31 | 2016-08-31 | The preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 |
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| CN106366247B CN106366247B (en) | 2018-06-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4068062A (en) * | 1975-07-30 | 1978-01-10 | Exxon Research And Engineering Company | Polymerizing C5 and C6 olefins and diolefins with 3° hydrocarbyl halide to produce narrow molecular weight petroleum resins having low softening points |
| CN1948441A (en) * | 2006-10-08 | 2007-04-18 | 广东省茂名华粤集团有限公司 | Petroleum hydrocarbon cracking carbon nine cut fraction hydrogenation technology |
| WO2007060241A1 (en) * | 2005-11-28 | 2007-05-31 | Shell Internationale Research Maatschappij B.V. | Colourable binder composition |
| CN101062965A (en) * | 2007-05-28 | 2007-10-31 | 广东省茂名华粤集团有限公司 | Method for preparing petroleum resin by cracking C9 as raw material |
-
2016
- 2016-08-31 CN CN201610761278.XA patent/CN106366247B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4068062A (en) * | 1975-07-30 | 1978-01-10 | Exxon Research And Engineering Company | Polymerizing C5 and C6 olefins and diolefins with 3° hydrocarbyl halide to produce narrow molecular weight petroleum resins having low softening points |
| WO2007060241A1 (en) * | 2005-11-28 | 2007-05-31 | Shell Internationale Research Maatschappij B.V. | Colourable binder composition |
| CN1948441A (en) * | 2006-10-08 | 2007-04-18 | 广东省茂名华粤集团有限公司 | Petroleum hydrocarbon cracking carbon nine cut fraction hydrogenation technology |
| CN101062965A (en) * | 2007-05-28 | 2007-10-31 | 广东省茂名华粤集团有限公司 | Method for preparing petroleum resin by cracking C9 as raw material |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yang Shengru Inventor after: Liang Guoqiang Inventor after: Deng Guanliang Inventor after: He Weilian Inventor after: Liu Yang Inventor after: Zuo Hongliang Inventor before: Yang Shengru Inventor before: Deng Guanliang Inventor before: He Weilian |
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| COR | Change of bibliographic data | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 525000 Guangdong city in Maoming Province four City Road No. 18 Patentee after: GUANGDONG XINHUAYUE PETROCHEMICAL INCORPORATED Co. Address before: 525000 Guangdong city in Maoming Province four City Road No. 18 Patentee before: GUANGDONG XINHUAYUE PETROCHEMICAL INCORPORATED Co. |
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| CP01 | Change in the name or title of a patent holder | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of C9 cold polymerized petroleum resin by-product hot polymerized resin Effective date of registration: 20220720 Granted publication date: 20180626 Pledgee: Maoming Maonan sub branch of industrial and Commercial Bank of China Ltd. Pledgor: GUANGDONG XINHUAYUE PETROCHEMICAL INCORPORATED CO. Registration number: Y2022980010814 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |