CN1928025A - Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof - Google Patents
Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof Download PDFInfo
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- CN1928025A CN1928025A CN 200610104529 CN200610104529A CN1928025A CN 1928025 A CN1928025 A CN 1928025A CN 200610104529 CN200610104529 CN 200610104529 CN 200610104529 A CN200610104529 A CN 200610104529A CN 1928025 A CN1928025 A CN 1928025A
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Abstract
The present invention relates to process of preparing C10, C15 and C20 olefin mixture prepolymer with ethylene cracking C5 fraction. The process includes the Diels-Alder reaction of ethylene cracking C5 fraction containing conjugated diolefin and mono-olefin at temperature of 140-300 deg.c and pressure of 1.0-12.0 MPa for 3-12 hr, cooling before discharging, and subsequent rectifying to eliminate unreacted C5 fraction to obtain C10, C15 and C20 olefin mixture prepolymer. The prepolymer of the present invention may be used in producing C5 petroleum resin with narrow molecular weight distribution, raised compatibility with other hot melt adhesive components SIS, SBS and EVA and extremely expanded use range. In the same time, the present invention raises the utilization rate of polymerisable olefin in C5 fraction effectively.
Description
Technical field
The invention belongs to petrochemical industry, relate to a kind of C with the cracking of ethylene by-product
5Fraction prepares the method for prepolymer, particularly a kind of C with the cracking of ethylene by-product
5The fraction preparation contains C
10, C
15, C
20The method of olefin prepolymer.The thermopolymer that obtains by this method can be used to produce C
5The series petroleum resin also can be produced the C with special application field
5Petroleum resin.
Background technology
Along with the development of petroleum resin technology, the fierceness of market competition and the demand of product innovation, the raw material of petroleum resin is by " coarse food grain " development to " flour and rice " direction.Want quality of production height, petroleum resin products that performance is good, must form by strict control raw material, common way is the rectifying condition of control raw material, adds a certain amount of active constituent that can improve product property etc. in raw material.
Cracking of ethylene by product C
5Fraction is to be used to produce C
5The best raw material of petroleum resin.The cracking stock difference that ethylene unit uses, the C of by-product
5Fractional composition has very big-difference.Because C
5The fraction complexity is formed often variation, and the character of petroleum resin products is also changed thereupon.Therefore before producing petroleum resin, in all sorts of ways to guarantee that the raw material composition is within allowed band.It is stable that a lot of companies adopt separation reliably, preprocessing means assurance resin to form, and the employing that has is added certain component and improved color and luster, improves productive rate, still adopts the C of above-mentioned preconditioning technique processing
5The petroleum resin poor-performing that fraction is produced, and feed stock conversion is low, and the raw material consumption of resin is higher.
At C
5Contain tens kinds of hydrocarbon hydrocarbon compounds in the fraction, isoprene is arranged, cyclopentadiene, dicyclopentadiene, diolefin and 1.4-pentadienes such as a-methyl bicycle pentadiene, along the 1.3-pentadiene, diolefins such as anti-1.3-pentadiene, also contain the 1-amylene, suitable-2 amylenes, anti--2 amylene, 2-methyl-1-butene alkene, the 2-methyl-2-butene, 3-methyl-1-butene, some monoolefines such as cyclopentenes, in addition also have some saturated alkane, as normal butane, neopentane, iso-pentane, pentamethylene, Skellysolve A, saturated alkane and benzene such as hexanaphthene, aromatic hydrocarbons such as toluene, wherein isoprene, cyclopentadiene, m-pentadiene, diolefins such as dicyclopentadiene can carry out Di Ersi (Diels) with alpha-olefin---Alder (Alder) reaction.At present, utilize the Diels-Alder principle to carry out the synthetic high quality C of pre-treatment
5The existing report of the technology of petroleum resin, but with C
5Fraction is that raw material carries out Diels-Alder to carry out the technology of raw materials pretreatment still unexposed.
Summary of the invention
The purpose of this invention is to provide a kind of C that is used to produce
5Petroleum resin contain C
10, C
15, C
20The prepolymer of alkene mixture, the present invention simultaneously also provides the preparation method of this prepolymer.
Preparation of the present invention contains C
10, C
15, C
20The method of alkene thermopolymer is to contain the cracking of ethylene C of diolefin, monoolefine
5Fraction carries out Diels-Alder and reacts cooling discharge after 3～12 hours 140～300 ℃ of temperature under pressure 1.0～12.0MPa, unreacted C is removed in rectifying
5Component must contain C
10, C
15, C
20The thermopolymer of alkene mixture.
The weight ratio of diolefin and monoolefine is 1: 0.5～1: 2.5 in the described cracking of ethylene C5 fraction.
Diolefin is at least a along in the 1.3-pentadiene, anti-1.3-pentadiene, cyclopentadiene, isoprene, 1.4-pentadiene, dicyclopentadiene, methyl bicycle pentadiene in the described cracking of ethylene C5 fraction.
Monoolefine is at least a in 3-methyl-1-butene, 1-amylene, suitable-2 amylenes, anti--the 2-amylene, 2-methyl-1-butene alkene, the 2-methyl-2-butene in the described cracking of ethylene C5 fraction.
The saturated alkane that also contains C5 fraction gross weight 10-90% in the described cracking of ethylene C5 fraction.
Described saturated alkane is at least a in neopentane, iso-pentane, pentamethylene, the Skellysolve A.
The present invention preparation contain C
10, C
15, C
20The prepolymer of alkene mixture mainly comprises the component of following weight ratio part:
C
10：70～99％，C
15：2～30％，C
20：0～1％。
The present invention preparation contain C
10, C
15, C
20The prepolymer of alkene mixture is as producing C
5The raw material of petroleum resin.
Effect of the present invention:
C used herein
5The diolefin and the monoolefine that contain enough participated in Diels-Alder reactions in the fraction, and the ratio control of diolefin and monoolefine is within reasonable range, corresponding temperature of reaction of control and reaction pressure in the Diels-Alder reaction are prepared into and contain C simultaneously
10, C
15, C
20The prepolymer of alkene mixture is further C
5The production of petroleum resin provides and has met the raw material that specific use properties requires, and improves C
5The yield of rare hydrocarbon in the fraction.
Facts have proved, be raw material with prepolymer of the present invention, carries out polyreaction under certain reaction temperature, certain reaction pressure, and the softening temperature of the petroleum resin products that obtains is 90～120 ℃; Viscosity is 180～250cp (180 ℃); Colourity is 8～10; Molecular weight is 650～750; Molecular weight distribution is 1.4～1.7.Because synthetic petroleum resin softening temperature is higher, viscosity is high, of light color, lower, the narrow molecular weight distribution of molecular weight, effectively improved the consistency of resin and other hot melt adhesive base material SIS, SBS, EVA, greatly expand the use range of petroleum resin, can be widely used in fields such as tackiness agent, coating, printing ink, pitch, rubber tyre.
Embodiment
Below by specific embodiment the present invention is further described.
Embodiment 1, in high temperature, autoclave, add C
5Raw material (C wherein
5Weight ratio part of each component is 4% 3-methyl-1-butene in the raw material; 6% 1-amylene; 8% cyclopentenes; 5% suitable-2 amylenes; 5% anti--2 amylenes; 8% 2-methyl-1-butene alkene; 3% 1.4-pentadiene; 2% suitable 1.3-pentadiene; 1.0% cyclopentadiene; 5% isoprene; 20% iso-pentane; 30% Skellysolve A; 3% benzene), be warming up to 170 ℃, react cooling discharge after 9 hours, unreacted C is removed in rectifying
5Component, the prepolymer that arrives (weight percent meter) composed as follows:
C
5：0.1％，C
10：88.4％，C
15：11.4％，C
20：0.1％。
Embodiment 2, with C
5Fraction raw material (C wherein
5Weight ratio part of each component is 3% 3-methyl-1-butene in the raw material; 4% 1-amylene; 8% cyclopentenes; 5% suitable-2 amylenes; 5% anti--2 amylenes; 8% 2-methyl-1-butene alkene; 3% 1.4-pentadiene; 4% suitable 1.3-pentadiene; 1.0% cyclopentadiene; 7% isoprene; 20% iso-pentane; 30% Skellysolve A; 2% benzene) join in high temperature, the autoclave, be warming up to 180 ℃, react cooling discharge after 9 hours, unreacted C is removed in rectifying
5Component, the prepolymer that arrives (weight percent meter) composed as follows:
C
5: 0.2%, C
10: 87.1%, C
15: 12.7%, C
20: trace
Embodiment 3, with C
5Fraction raw material (C wherein
5Weight ratio part of each component is 3% 3-methyl-1-butene in the raw material; 6% 1-amylene; 4% cyclopentenes; 4% suitable-2 amylenes; 5% anti--2 amylenes; 6% 2-methyl-1-butene alkene; 6% 1.4-pentadiene; 3% suitable 1.3-pentadiene; 1.0% cyclopentadiene; 7% isoprene; 30% iso-pentane; 35% Skellysolve A) join in high temperature, the autoclave, be warming up to 190 ℃, react cooling discharge after 9 hours, unreacted C is removed in rectifying
5Component, the prepolymer that arrives (weight percent meter) composed as follows:
C
5: 0.3%, C
10: 89.4%, C
15: 10.3%, C
20: trace
Embodiment 4, with C
5Fraction raw material (C wherein
5Weight ratio part of each component is 1% 3-methyl-1-butene in the raw material; 4% 1-amylene; 4% cyclopentenes; 3% suitable-2 amylenes; 4% anti--2 amylenes; 9% 2-methyl-1-butene alkene; 5% 2-methyl-2-butene, 3% 1.4-pentadiene; 1% suitable 1.3-pentadiene; 1% 1.3-pentadiene, 1.5% cyclopentadiene; 5% isoprene; 25% iso-pentane; 4% pentamethylene; 36% Skellysolve A) join in high temperature, the autoclave, be warming up to 220 ℃, react cooling discharge after 9 hours, unreacted C is removed in rectifying
5Component, the prepolymer that arrives (weight percent meter) composed as follows:
C
5: 0.1%, C
10: 90.4%, C
15: 9.5%, C
20: trace.
Claims (8)
1, a kind of with C
5The fraction preparation contains C
10, C
15, C
20The method of olefin prepolymer is to contain the cracking of ethylene C of diolefin, monoolefine
5Fraction carries out Diels-Alder and reacts cooling discharge after 3～12 hours 140～300 ℃ of temperature under pressure 1.0～12.0MPa, unreacted C is removed in rectifying
5Component must contain C
10, C
15, C
20The thermopolymer of alkene mixture.
2, contain C with the preparation of C5 fraction according to claim 1
10, C
15, C
20The method of olefin prepolymer is characterized in that: the weight ratio of diolefin and monoolefine is 1: 0.5～1: 2.5 in the described cracking of ethylene C5 fraction.
3, contain C with the preparation of C5 fraction as claimed in claim 1 or 2
10, C
15, C
20The method of olefin prepolymer is characterized in that: at least a for along in the 1.3-pentadiene, anti-1.3-pentadiene, cyclopentadiene, isoprene, 1.4-pentadiene, dicyclopentadiene, methyl bicycle pentadiene of diolefin in the described cracking of ethylene C5 fraction.
4, contain C with the preparation of C5 fraction as claimed in claim 1 or 2
10, C
15, C
20The method of olefin prepolymer is characterized in that: monoolefine is at least a in 3-methyl-1-butene, 1-amylene, suitable-2 amylenes, anti--the 2-amylene, 2-methyl-1-butene alkene, the 2-methyl-2-butene in the described cracking of ethylene C5 fraction.
5, as claim 1 or as described in contain C with C5 fraction preparation
10, C
15, C
20The method of olefin prepolymer is characterized in that: the saturated alkane that also contains C5 fraction gross weight 10-90% in the described cracking of ethylene C5 fraction.
6, as described in claim 5, contain C with the preparation of C5 fraction
10, C
15, C
20The method of olefin prepolymer is characterized in that: described saturated alkane is at least a in neopentane, iso-pentane, pentamethylene, the Skellysolve A.
7, according to claim 1 method preparation contain C
10, C
15, C
20The prepolymer of alkene mixture mainly comprises the component of following weight ratio part:
C
10：70～99％，C
15：2～30％，C
20：0～1％。
8, as described in claim 7, contain C
10, C
15, C
20The prepolymer of alkene mixture is as the raw material of producing the C5 petroleum resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101045293A CN100513528C (en) | 2006-08-30 | 2006-08-30 | Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101045293A CN100513528C (en) | 2006-08-30 | 2006-08-30 | Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1928025A true CN1928025A (en) | 2007-03-14 |
| CN100513528C CN100513528C (en) | 2009-07-15 |
Family
ID=37858161
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101045293A Active CN100513528C (en) | 2006-08-30 | 2006-08-30 | Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof |
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|---|---|
| CN (1) | CN100513528C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319030A (en) * | 2008-07-13 | 2008-12-10 | 中国石油兰州石油化工公司 | Method for synthesizing C5 petroleum resin by using composite catalytic system of catalyst-dispersion medium |
| CN101318871B (en) * | 2008-07-09 | 2011-03-23 | 中国石油兰州石油化工公司 | Method for reducing foreign solids generation of C5 material in hot polymerization process |
| CN102718924A (en) * | 2012-06-27 | 2012-10-10 | 浙江恒河石油化工股份有限公司 | Method for preparing C5/C9 copolymerized petroleum resin |
| CN103880998A (en) * | 2014-03-21 | 2014-06-25 | 李鹏露 | Additive for thermosetting asphalt mixture, and preparation method and application thereof |
| CN109912744A (en) * | 2019-03-26 | 2019-06-21 | 恒河材料科技股份有限公司 | A kind of preparation method of monomer modified C5 Petropols |
| CN110003388A (en) * | 2019-03-26 | 2019-07-12 | 恒河材料科技股份有限公司 | A kind of preparation method of hydrogenation modification C5 Petropols |
| CN110078847A (en) * | 2019-04-28 | 2019-08-02 | 恒河材料科技股份有限公司 | A kind of preparation method of high softening-point hydrogenated petroleum resin |
| CN113087845A (en) * | 2021-03-26 | 2021-07-09 | 广东新华粤树脂科技有限公司 | Preparation method of long-chain olefin modified C9 petroleum resin |
-
2006
- 2006-08-30 CN CNB2006101045293A patent/CN100513528C/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318871B (en) * | 2008-07-09 | 2011-03-23 | 中国石油兰州石油化工公司 | Method for reducing foreign solids generation of C5 material in hot polymerization process |
| CN101319030A (en) * | 2008-07-13 | 2008-12-10 | 中国石油兰州石油化工公司 | Method for synthesizing C5 petroleum resin by using composite catalytic system of catalyst-dispersion medium |
| CN101319030B (en) * | 2008-07-13 | 2015-03-04 | 中国石油兰州石油化工公司 | Method for synthesizing C5 petroleum resin by using composite catalytic system of catalyst-dispersion medium |
| CN102718924A (en) * | 2012-06-27 | 2012-10-10 | 浙江恒河石油化工股份有限公司 | Method for preparing C5/C9 copolymerized petroleum resin |
| CN103880998A (en) * | 2014-03-21 | 2014-06-25 | 李鹏露 | Additive for thermosetting asphalt mixture, and preparation method and application thereof |
| CN109912744A (en) * | 2019-03-26 | 2019-06-21 | 恒河材料科技股份有限公司 | A kind of preparation method of monomer modified C5 Petropols |
| CN110003388A (en) * | 2019-03-26 | 2019-07-12 | 恒河材料科技股份有限公司 | A kind of preparation method of hydrogenation modification C5 Petropols |
| CN110003388B (en) * | 2019-03-26 | 2021-09-07 | 恒河材料科技股份有限公司 | Preparation method of hydrogenated modified C5 petroleum resin |
| CN109912744B (en) * | 2019-03-26 | 2021-10-22 | 恒河材料科技股份有限公司 | Preparation method of monomer modified C5 petroleum resin |
| CN110078847A (en) * | 2019-04-28 | 2019-08-02 | 恒河材料科技股份有限公司 | A kind of preparation method of high softening-point hydrogenated petroleum resin |
| CN110078847B (en) * | 2019-04-28 | 2021-08-20 | 恒河材料科技股份有限公司 | Preparation method of high-softening-point hydrogenated petroleum resin |
| CN113087845A (en) * | 2021-03-26 | 2021-07-09 | 广东新华粤树脂科技有限公司 | Preparation method of long-chain olefin modified C9 petroleum resin |
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| Publication number | Publication date |
|---|---|
| CN100513528C (en) | 2009-07-15 |
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