CN106366247B - The preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 - Google Patents
The preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 Download PDFInfo
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- CN106366247B CN106366247B CN201610761278.XA CN201610761278A CN106366247B CN 106366247 B CN106366247 B CN 106366247B CN 201610761278 A CN201610761278 A CN 201610761278A CN 106366247 B CN106366247 B CN 106366247B
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- 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 kind of preparation method of the cold poly- Petropols by-product hot polymerization resins of C9, including：1）Pretreatment of raw material：Using the cold poly- Petropols by-product full flashing oil of C9, secondary flash oil as raw material, in mass ratio（0.5~1.5）：It is spare as mixed raw material after 1 mixing；2）Polymerisation：In the reactor with agitating shaft, after mixed raw material is loaded, reactor has been closed, after being replaced 3 times with nitrogen, has been then charged with nitrogen 0.7~2.5MPa of boosting, after being heated to 200~250 DEG C, isothermal reaction 4~10 hours obtains polymer fluid；3）Vacuum distillation：Polymer fluid is poured into reactor, polymer fluid is evaporated under reduced pressure under 0.08~0.095MPa pressure, steams always and declines again and no longer rise to only to fraction temperature rise to maximum temperature, stop distillation, pour out polymer, cool down to obtain product.Present invention process is simple, green, energy-saving and environmental protection, and obtained product quality is higher.
Description
Technical field
The present invention relates to Petropols preparing technical field, specifically a kind of cold poly- Petropols by-product hot polymerization resins of C9
Preparation method.
Background technology
Petropols are originally to replace rosin and its derivative to develop.But it once appearance, have developed rapidly.Short
Decades in, with comparable production level and yield.The especially country of industry prosperity in the world, petroleum resin products
Specification is more, and process units is on a grand scale.If Japan has nine companies to produce Petropols, production capacity reaches 1,000,000 tons/year.
The Exxon in the U.S., is consolidated specifically He Gelisi；The CDF companies of France；The main several oil in the world such as ICI companies of Britain
Also there is Petropols process units in chemical company.The ground such as China Taiwan and South Korea also produce Petropols.China is studied and life
Unit and the producer for producing Petropols are many, but small scale, and production capacity is not high, and kind quantity is also well below external certain flourishing states
Family.The raw material of Petropols is the by-product C5 and C9 of cracker and benzene production equipment.The U.S. is earliest research and development oil tree
The country of fat begins one's study for 1910, and the 1940s, Picoo companies were industrialized first.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 states 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 continuously improve and the needs of market competition, Petropols have developed into multi items, more
The trade mark, widely used functional synthetic resin.China developed Petropols since 1964, successively built up some small-sized lifes
Device is produced, but due to raw material and technical problem, is developed slowly.With the rapid development of China's Petrochemical, particularly ethylene
The raising year by year of production capacity, the quantity of pyrolysis c9 fraction are continuously increased, this part resource is made full use of to develop downstream product
It increasingly attracts people's attention.It is more to the report of C5 resins, C9 resins in existing Petropols have patent,
It is and seldom as the pressure hot polymerization of raw material using the cold poly resin by-product flash oils of C9.In current oil resin art, oil
The by-product flash oil utilization orientation of resin is all often with freshening or hydrogen is added to lack the way extended down as tempered oil
Diameter considerably increases the loss of energy consumption and unnecessary waste.Therefore, the by-product for developing and developing the cold poly- Petropols of C9 dodges
Steam oil hot polymerization Petropols become when previous important subject, so as to solve the comprehensive of China's oil resin by-products flash oil
Utilizing question is closed, while also extends the utilization of downstream sources, is contributed for environmentally friendly, energy saving, innovation.
Invention content
The purpose of the present invention is to provide a kind of cold poly- oil trees of C9 for preparing and being simple and convenient to operate and with better quality
The preparation method of fat by-product hot polymerization resin.
To achieve the above object, the present invention provides following technical solution：
The preparation method of the cold poly- Petropols by-product hot polymerization resins of C9, includes the following steps：
1）Pretreatment of raw material
The cold poly- Petropols of C9 can go out the component distillation for being not engaged in or not exclusively participating in reaction in production process, lead to
Often we are called full flashing, and resin liquid carries out second distillation namely secondary flash again after full flashing, full flashing oil,
The main ingredient of secondary flash oil contains macromolecular alkene component, a small amount of oligomer, and full flashing is oily, the component of secondary flash oil
It is very different.Appropriate ratio tune is carried out so that full flashing is oily, secondary flash oil prepares Petropols as primary raw material
It closes, component is allowed to comparatively facilitate polymerisation.
Using 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 is in mass ratio（0.5~1.5）：It is spare as mixed raw material after 1 mixing.
2）Polymerisation
In the reactor with agitating shaft, after mixed raw material is loaded, reactor has been closed, after being replaced 3 times with nitrogen,
Nitrogen 0.7~2.5MPa of boosting is then charged with, after being heated to 200~250 DEG C, isothermal reaction 4~10 hours obtains polymer fluid.
3）Vacuum distillation
Since mixed raw material is after polymerization, evaporate with the presence of the inactive ingredients for having neither part nor lot in polymerisation.This unreacted
For example insufficient removing of object, not only reduces resin softening point, but also the performances such as heat resistance and its color number for making resin significantly reduce, because
This selection distillation under vacuum removes it.
Polymer fluid is poured into reactor, polymer fluid is evaporated under reduced pressure under -0.08~-0.095MPa pressure, one
Straight steam declines and no longer rises to only to fraction temperature rise to maximum temperature again, stops distillation, pours out polymer, after cooling
To product.
As further embodiment of the present invention：The full flashing is oily, secondary flash oil is mainly that the cold poly resins of C9 are gathered
Close the olefin component do not reacted completely that oil is flashed off in vacuum degree -0.05~-0.08MPa, 100~160 DEG C.
As further embodiment of the present invention：The full flashing is oily, secondary flash oil is mainly that the cold poly resins of C9 are gathered
Close the olefin component do not reacted completely that oil is flashed off in vacuum degree -0.08MPa, 110~160 DEG C.
As further embodiment of the present invention：The full flashing is oily, secondary flash oil in mass ratio 1：Make after 1 mixing
For mixed raw material.
As further embodiment of the present invention：The step 2）In, reactor is reaction kettle.
As further embodiment of the present invention：The step 2）In, isothermal reaction 4~8 hours.
As further embodiment of the present invention：The step 2）In, nitrogen boosting 1.0MPa is filled with, is heated to 230 DEG C
Afterwards, isothermal reaction 8 hours.
As further embodiment of the present invention：The step 3）In, reactor is decompression flask.
As further embodiment of the present invention：The step 3）In, the pressure of vacuum distillation is -0.09MPa.
As further embodiment of the present invention：The step 3）In, the temperature for stopping distillation is 290 DEG C.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention is using the by-product of the cold poly- Petropols of C9 as primary raw material, no catalyst, without waste water, simple for process, behaviour
Make simply, while the by-product of the cold poly- Petropols of C9 can be comprehensively utilized, reach green, energy-saving and environmental protection, resource comprehensive profit
With the purpose of, obtained resin form and aspect are less than 13, softening point between 100~130 DEG C, active component high conversion rate up to 80~
90%, average molecular weight reaches more than 1000, can be widely applied to adhesive, paint industry.
Another feature of the present invention is：Reaction process need not add any catalyst, and the flash oil of hot polymerization can conduct
Preferable aromatic solvent naphtha raw material, two kinds of process synthesis utilize, and can not only reduce resin cost, but also can reduce the dirt to environment
Dye.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical solution in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art's all other embodiments obtained without 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 resins of C9 includes the following steps：
1）Pretreatment of raw material
Raw material used in the present invention is the cold poly- device by-product full flashings of Guangdong New Huayue Petrochemical Incorporated Company C9
Oil, secondary flash oil（Full flashing oil, secondary flash oil be mainly the cold poly resin godied oils of C9 vacuum degree -0.08MPa,
110~160 DEG C of olefin components do not reacted completely flashed off）, and by 1：Mixed raw material is used as after the mixing of 1 ratio.
2）Polymerisation
In the reaction kettle with agitating shaft, after mixed raw material is loaded, reaction kettle has been closed, after being replaced 3 times with nitrogen,
Nitrogen 0.7~2.5MPa of boosting is then charged with, after being heated to 200~250 DEG C, isothermal reaction 4~10 hours obtains polymer fluid.
3）Vacuum distillation
Polymer fluid is poured into decompression flask, polymer fluid is evaporated under reduced pressure under -0.09MPa pressure, steams arrive always
Fraction temperature rise to maximum temperature declines and no longer rises to only again, stops distillation, pours out polymer, produced after cooling
Product.
In order to filter out the optimum process condition of the cold poly- Petropols by-product hot polymerization resins of C9, to step 2）In pressure
Power, temperature and reaction time carry out following value：
1st, when temperature is 230 DEG C, the reaction time is 8h, different pressures 0.7MPa, 1.0MPa, 1.5MPa, 2.5MPa couple
The influence of the yield of product, the results are shown in Table 1；
2nd, when pressure is 1.0MPa, the reaction time is 8h, 200 DEG C of different temperatures, 230 DEG C, 240 DEG C, 250 DEG C to product
Yield and color number influence, the results are shown in Table 2；
3rd, when temperature is 230 DEG C, pressure is 1.0MPa, differential responses time 4h, 6h, 8h, 10h are to the yield of product
It influences, the results are shown in Table 3.
From table 1~3：Reaction temperature reach 230 DEG C, reaction pressure 1.0MPa, reaction time 8h, the performance of product is most
Excellent, yield reaches 55.6%, form and aspect 11.
Influence of 1 different pressures of table to yield
Influence of the 2 differential responses temperature of table to yield and color number
Influence of the 3 differential responses time of table to yield
It is obvious to a person skilled in the art that the present invention is not limited to the details of above-mentioned exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requirement rather than above description limit, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in each embodiment can also be properly combined, forms those skilled in the art
The other embodiment being appreciated that.
Claims (10)
- The preparation method of the cold poly- Petropols by-product hot polymerization resins of 1.C9, which is characterized in that include the following steps：1）Pretreatment of raw material：Using 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 are in mass ratio（0.5~1.5）：It is spare as mixed raw material after 1 mixing；2）Polymerisation：In the reactor with agitating shaft, after mixed raw material is loaded, reactor is closed, has been put with nitrogen After changing 3 times, nitrogen 0.7~2.5MPa of boosting is then charged with, after being heated to 200~250 DEG C, isothermal reaction 4~10 hours obtains Polymer fluid；3）Vacuum distillation：Polymer fluid is poured into reactor, polymer fluid is depressurized under -0.08~-0.095MPa pressure Distillation steams and declines again and no longer rise to only to fraction temperature rise to maximum temperature, stops distillation, pour out polymer always, Product is obtained after cooling.
- 2. the preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 according to claim 1, which is characterized in that institute Full flashing oil, the secondary flash oil stated be mainly the cold poly- Petropols godied oils of C9 vacuum degree -0.05~-0.08MPa, 100~160 DEG C of olefin components do not reacted completely flashed off.
- 3. the preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 according to claim 2, which is characterized in that institute Full flashing oil, the secondary flash oil stated are mainly the cold poly- Petropols godied oils of C9 in vacuum degree -0.08MPa, 110~160 The olefin component do not reacted completely DEG C flashed off.
- 4. the preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 according to claim 1, which is characterized in that institute Full flashing oil, the secondary flash oil in mass ratio 1 stated：Mixed raw material is used as after 1 mixing.
- 5. the preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 according to claim 1, which is characterized in that institute The step 2 stated）In, reactor is reaction kettle.
- 6. the preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 according to claim 1, which is characterized 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 resins of C9 according to claim 6, which is characterized 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 resins of C9 according to claim 1, which is characterized in that institute The step 3 stated）In, reactor is decompression flask.
- 9. the preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 according to claim 1, which is characterized in that institute The step 3 stated）In, the pressure of vacuum distillation is -0.09MPa.
- 10. the preparation method of the cold poly- Petropols by-product hot polymerization resins of C9 according to claim 1, which is characterized in that The step 3）In, the temperature for stopping distillation is 290 DEG C.
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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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Legal Events
| 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 |