CN102010481A - Preparation method of light-color pentadiene petroleum resins - Google Patents
Preparation method of light-color pentadiene petroleum resins Download PDFInfo
- Publication number
- CN102010481A CN102010481A CN 201010549279 CN201010549279A CN102010481A CN 102010481 A CN102010481 A CN 102010481A CN 201010549279 CN201010549279 CN 201010549279 CN 201010549279 A CN201010549279 A CN 201010549279A CN 102010481 A CN102010481 A CN 102010481A
- Authority
- CN
- China
- Prior art keywords
- pentadiene
- preparation
- polymerization
- lewis acid
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
The invention relates to a preparation method of light-color pentadiene petroleum resins. The method is characterized in that isoprene and dicyclopentadiene are separated from C5 which is the byproduct of ethylene pyrolysis, the obtained distillate the main component of which is pentadiene is taken as a raw material, the content of the pentadiene is 60-80wt%, and chain-shaped or annular saturated hydrocarbon is taken as a reaction agent. The method comprises the following process flows: a, thermal polymerization: carrying out thermal polymerization reaction for 4-10 hours at 220-280 DEG C under the pressure of 2-8 MPa by taking pentadiene as the raw material; b, catalytic polymerization: using an immobilized Lewis acid catalyst to carry out catalytic polymerization for 2-8 hours at 600-200 DEG C under the pressure of 0.1-0.8 MPa by taking materials subject to thermal polymerization as raw materials and toluene or xylene as a solvent; c, catalyst removal: removing the catalyst by deposition and filtering; d, separation: carrying out steam stripping to obtain the non-reacted reactant, solvent and oligomeric C5 resin under vacuum at 220-300 DEG C, wherein the residual is the pentadiene petroleum resin; and e, granulation.
Description
Technical field
The present invention relates to C5 fraction with the cracking of ethylene by-product after isolating isoprene, dicyclopentadiene, the distillate based on m-pentadiene of gained is a raw material, m-pentadiene content is 60～80wt%, with chain or cyclic stable hydrocarbon is reaction solvent, the method for the light degree m-pentadiene petro-resin of preparation behind thermopolymerization, catalyzed polymerization.
Background technology
Aliphatic petroleum resin is the big classifications of one in the petroleum resin, and it is to be prepared from through cationoid polymerisation by 20～80 ℃ of cuts (C5 fraction) that obtain in the petroleum cracking process of producing ethylene.Petroleum resin can be used for making tackiness agent, rubber, hot-melt coating, printing-ink, coating, earth material etc., and this resin also is used to other material of modification usually.
Usually to prepare raw materials used be to be that mixed olefins, these raw materials of main ingredient are also referred to as " carbon five monomers " usually with C 5 alkane, alkene and diolefine to petroleum resin, contain 1 in the raw material, 3-pentadiene (m-pentadiene), cyclopentenes, 2-methyl-2-butene, 2-methyl-2-amylene, polymerisable monomers such as isoprene, cyclopentadiene and dicyclopentadiene.Along with the development of carbon five isolation technique, other high value Chemicals synthesis material is made in isoprene, the separable purification of cyclopentadiene, and residue can be used as petroleum resin polymerization raw material production m-pentadiene petro-resin based on the C5 fraction oil of m-pentadiene.From the carbon Wuyuan material of cracking of ethylene by-product, can isolate isoprene, dicyclopentadiene, can obtain distillate, can further obtain m-pentadiene petro-resin by polyreaction again based on m-pentadiene.
CN1563127 discloses a kind of preparation method of m-pentadiene petro-resin, the m-pentadiene petro-resin that adopt catalyzed polymerization, remove catalyzer, synthesize, granulation process makes the softening temperature height, melt viscosity is high, with m-pentadiene, C5 is raw material, with C5 light oil is solvent, make catalyzer at 70 ℃～80 ℃ with aluminum chloride, catalyzed polymerization under pressure 1～2Kg condition removes the catalyzer aluminum chloride with sheet alkali under 150 ℃～160 ℃ conditions.
CN101134797 discloses a kind of process for producing high-grade pentadiene petroleum resin, with by aluminum chloride, the positively charged ion complex catalyst that main solvent and other solubility promoter hybrid reaction generate is done catalyst for polymerization, the recovery C 5 fraction is a polymer solvent, adopt the still formula to force adverse current outer circulation reactive mode, at 10～80 ℃, 0.03 under～0.40MPa the pressure, polyreaction 2～5 hours, polyreaction finishes the back and adds low boiling point solvent oil and contain highly basic, the alkaline aqueous solution of two kinds of components of nonionogenic tenside and the aqueous solution that contains nonionogenic tenside or contain water-soluble salt component obtain the softening temperature height to the reaction solution washing that neutralizes, form and aspect are low, the transparency height, melt viscosity is lower, the m-pentadiene petro-resin that thermotolerance and weathering resistance are good.
CN1448417 discloses the preparation method of a kind of high softening-point, high melt viscosity m-pentadiene petro-resin, with the separating obtained m-pentadiene enriched substance of the carbon Five Classics of cracking of ethylene by-product is raw material, with benzene, toluene or dimethylbenzene is reaction solvent, and polymerization makes the m-pentadiene petro-resin product in the presence of the catalyzer aluminum chloride.Polymerization temperature is 40～80 ℃, and polymerization time is 4～8 hours, and reaction raw materials at the uniform velocity adds in the reactor in the time in entire reaction.
Produce the m-pentadiene petro-resin preparation process from above-mentioned patent disclosure and existing industrial technology, adopt anhydrous AlCl more
3Make cationic polymerisation catalyst, again after the method that alkali cleaning, washing are handled or other removes catalyzer is handled, finally obtain the solidified m-pentadiene petro-resin through separation, granulation, Gardner (Gardner) colourity is generally at 4～7#, and softening temperature is generally below 110 ℃.Because the catalyzer that uses is aluminum chloride or boron trifluoride normally, there is following shortcoming in these homogeneous catalysts of use, and they are sneaked in the resin, often adopt alkali cleaning, water washing process to remove catalyzer, bring a large amount of waste water, cause environmental pollution.In addition, in subsequent separation process,, chlorion cause equipment corrosion serious because existing.
Summary of the invention
The present invention is a kind of preparation method of light degree m-pentadiene petro-resin, it is characterized in that: after this method is isolated isoprene, dicyclopentadiene with the carbon Five Classics of cracking of ethylene by-product, the distillate based on m-pentadiene of gained is a raw material, wherein m-pentadiene content is 60～80wt%, with chain or cyclic stable hydrocarbon is reaction solvent, has following technical process:
A. thermopolymerization is a raw material with the m-pentadiene, at 220～280 ℃, carries out heat polymerization under pressure 2～8MPa condition, polymerization time 4～10 hours;
B. catalyzed polymerization, with material after the thermopolymerization is raw material, with toluene or dimethylbenzene is reaction solvent, with immobilized lewis acid catalyst at 60～200 ℃, catalyzed polymerization under pressure 0.1～0.8MPa condition, the weight ratio of material is 0.5～5wt% after catalyzer and the thermopolymerization, and polymerization time is 2～8 hours;
C. remove catalyzer, take sedimentation solids removed by filtration catalyzer;
D. separate, at 220～300 ℃, stripping goes out not reactant, solvent and oligomeric carbon five resins under the vacuum condition, remains to be m-pentadiene petro-resin;
E. granulation.
According to preparation method of the present invention, it is characterized in that: the reaction conditions of described thermopolymerization is that temperature is 240～270 ℃, and pressure is 4～6MPa, and polymerization time is 5～8 hours.
According to preparation method of the present invention, it is characterized in that: in the catalyzed polymerization process, reaction conditions is that polymerization temperature is 60～180 ℃, and polymerization time is 3～6 hours, and the weight ratio of material is 1～3wt% after catalyzer and the thermopolymerization.
According to preparation method of the present invention, it is characterized in that; In the catalyzed polymerization process, the weight ratio of reaction solvent chain or cyclic stable hydrocarbon and raw material total amount is 0.2～1.
According to preparation method of the present invention, it is characterized in that; In the catalyzed polymerization process, described immobilized lewis acid catalyst consist of 5～30wt% Lewis acid, all the other are that macroporous silica gel is formed.
According to preparation method of the present invention, it is characterized in that; In the catalyzed polymerization process, described immobilized lewis acid catalyst preparation process is as follows: with AlCl
3Or BF
3Be Lewis acid, adopt the AlCl of distillation
3Or BF
3Steam and macroporous silica gel carrier fully act on, and make immobilized lewis acid catalyst, and N is used being higher than under 300 ℃ the temperature in reaction back
2Carrier gas purges, and removes unreacted AlCl
3Or BF
3
In the present invention, polyreaction adopts the rhythmic reaction mode to carry out, and it must be emphasized that polyreaction is airtight, especially in the polymerization catalyst process, must adopt nitrogen replacement to remove air, avoids causing polymerization petroleum resin products colourity to deepen.
Generally speaking, the control of the softening temperature of petroleum resin and colourity and polymerizing condition is closely related, and molecular weight is big more, and softening temperature is just high more; Degree of unsaturation and foreign matter content are low more in the resin, and resin colourity is shallow more.The contriver finds through after a large amount of tests, when adopting airtight reaction vessel, in certain polymerization time, adopts immobilized lewis acid catalyst, can obtain softening temperature more than 100 ℃, the m-pentadiene petro-resin of colourity＜5#.
Compared with prior art, advantage of the present invention is that the cut based on the separating obtained m-pentadiene of the C5 fraction of cracking of ethylene by-product is a raw material, adopt thermopolymerization, immobilized lewis acid catalyst to carry out catalyzed polymerization, just can obtain softening temperature height, the shallow m-pentadiene petro-resin of colourity by adjusting process condition suitably.The invention has the beneficial effects as follows, used immobilized lewis acid catalyst can recycle and be renewable, usually once compare with the non-loading type Lewis acid with catalyzer, reduced the waste treatment of used catalyst, in addition, the present invention does not need alkali cleaning, water washing process, does not have emulsion to produce, therefore do not produce environmental pollution, and avoided the etching problem of prior art follow-up equipment.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Wherein the m-pentadiene petro-resin yield is calculated as follows:
The m-pentadiene material quantity
The measuring method of softening temperature: ring and ball method, with reference to GB GB4507-84.
The measuring method of Gardner (Gardner) colourity: colorimetry, with reference to GB GB4317-84.
Embodiment 1
The macroporous silica gel Industrial products are put into autoclave, with a certain amount of anhydrous AlCl
3Put into crucible, crucible put into autoclave, charge into nitrogen, be warming up to 300 ℃ then, reacted 3 hours, then under 200～400 ℃, with the inflated with nitrogen method of replacement unreacted and be adsorbed in the AlCl of carrier surface
3Remove.Use AgNO
3Solution detects tail gas, promptly thinks up to no white precipitate to purge totally, makes required catalyzer.AlCl on the macroporous silica gel wherein
3Charge capacity is 5～30wt%.
Embodiment 2
2L has and adds 500g m-pentadiene raw material in the stainless steel autoclave of magnetic agitation (C5 fraction of cracking of ethylene by-product is main distillate through separating obtained m-pentadiene, form and see Table 1), closed reactor, carry out heat polymerization, control reaction temperature is 260 ℃, thermopolymerization pressure is 4.5MPa, and in 6 hours reaction times, material is stand-by after the removal thermopolymerization.Have the stainless steel autoclave adding cyclohexane solvent 100g of magnetic agitation again at another 2L, drop into the catalyzer of 8g embodiment 1 preparation, AlCl
3Charge capacity is 12wt%, stirs, and adds material after the 400g thermopolymerization again, and closed reactor adopts nitrogen replacement.Reacted 6 hours under 120 ℃ of temperature of reaction, reaction pressure 0.5MPa condition then, with polymer fluid and catalyzer filtering separation, under 0.098MPa, 260 ℃ were distilled 2 hours.The result is: m-pentadiene petro-resin yield 85wt%, 105 ℃ of softening temperatures, colourity 3#.
Embodiment 3～10
Adopt similar and step embodiment 2, concrete reaction conditions sees Table 2, and the leading indicator of product sees Table 3.
Table 1
| Component | Content, wt% |
| Pentamethylene | 2.84 |
| Cyclopentenes | 17.85 |
| Skellysolve A | 1.01 |
| M-pentadiene | 74.12 |
| Cyclopentadiene | 0.35 |
| Carbon six | 2.13 |
| Dicyclopentadiene | 0.23 |
| Other | 1.47 |
Table 2
Annotate: * 1: catalyst levels is the weight ratio of catalyzer and thermopolymerization material;
* 2: with the positive flow silane is reaction solvent;
* 3: select BF for use
3Be carried on the catalyzer that makes on the macroporous silica gel as Lewis acid, preparation process is similar to embodiment 1.
Table 3
| Yield, wt% | Softening temperature, ℃ | Gardner colourity, # | |
| Embodiment 3 | 85 | 105 | 3 |
| Embodiment 4 | 83 | 104 | 3 |
| Embodiment 5 | 86 | 109 | 3 |
| Embodiment 6 | 87 | 112 | 4 |
| Embodiment 7 | 82 | 111 | 3 |
| Embodiment 8 | 88 | 109 | 4 |
| Embodiment 9 | 88 | 102 | 3 |
| Embodiment 10 | 87 | 103 | 4 |
Claims (6)
1. the preparation method of a light degree m-pentadiene petro-resin, it is characterized in that: after this method is isolated isoprene, dicyclopentadiene with the carbon Five Classics of cracking of ethylene by-product, the distillate based on m-pentadiene of gained is a raw material, wherein m-pentadiene content is 60～80wt%, with chain or cyclic stable hydrocarbon is reaction solvent, has following technical process:
A. thermopolymerization is a raw material with the m-pentadiene, at 220～280 ℃, carries out heat polymerization under pressure 2～8MPa condition, polymerization time 4～10 hours;
B. catalyzed polymerization, with material after the thermopolymerization is raw material, with toluene or dimethylbenzene is reaction solvent, with immobilized lewis acid catalyst at 60～200 ℃, catalyzed polymerization under pressure 0.1～0.8MPa condition, the weight ratio of material is 0.5～5wt% after catalyzer and the thermopolymerization, and polymerization time is 2～8 hours;
C. remove catalyzer, take sedimentation solids removed by filtration catalyzer;
D. separate, at 220～300 ℃, stripping goes out not reactant, solvent and oligomeric carbon five resins under the vacuum condition, remains to be m-pentadiene petro-resin;
E. granulation.
2. preparation method according to claim 1 is characterized in that: the reaction conditions of described thermopolymerization is that temperature is 240～270 ℃, and pressure is 4～6MPa, and polymerization time is 5～8 hours.
3. preparation method according to claim 1 is characterized in that: in the catalyzed polymerization process, reaction conditions is that polymerization temperature is 60～180 ℃, and polymerization time is 3～6 hours, and the weight ratio of material is 1～3wt% after catalyzer and the thermopolymerization.
4. preparation method according to claim 1 is characterized in that; In the catalyzed polymerization process, the weight ratio of reaction solvent chain or cyclic stable hydrocarbon and raw material total amount is 0.2～1.
5. preparation method according to claim 1 is characterized in that; In the catalyzed polymerization process, described immobilized lewis acid catalyst consist of 5～30wt% Lewis acid, all the other are that macroporous silica gel is formed.
6. preparation method according to claim 1 is characterized in that; In the catalyzed polymerization process, described immobilized lewis acid catalyst preparation process is as follows: with AlCl
3Or BF
3Be Lewis acid, adopt the AlCl of distillation
3Or BF
3Steam and macroporous silica gel carrier fully act on, and make immobilized lewis acid catalyst, and N is used being higher than under 300 ℃ the temperature in reaction back
2Carrier gas purges, and removes unreacted AlCl
3Or BF
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010549279 CN102010481A (en) | 2010-11-18 | 2010-11-18 | Preparation method of light-color pentadiene petroleum resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010549279 CN102010481A (en) | 2010-11-18 | 2010-11-18 | Preparation method of light-color pentadiene petroleum resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102010481A true CN102010481A (en) | 2011-04-13 |
Family
ID=43840826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010549279 Pending CN102010481A (en) | 2010-11-18 | 2010-11-18 | Preparation method of light-color pentadiene petroleum resins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102010481A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382261A (en) * | 2011-08-22 | 2012-03-21 | 天津市兴源化工有限公司 | Preparation method for light-chroma aromatic petroleum resin |
| CN102702434A (en) * | 2012-06-07 | 2012-10-03 | 抚顺齐隆化工有限公司 | Method of two-stage continuous polymerization production of petroleum resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320648A (en) * | 2000-04-26 | 2001-11-07 | 上海石油化工股份有限公司 | Process for preparing C5 monoolefin modified m-pentadiene petro-resin |
| CN1563127A (en) * | 2004-03-23 | 2005-01-12 | 倪才国 | Method for preparing petroleum resin of piperyene |
| CN101134797A (en) * | 2006-09-01 | 2008-03-05 | 上海江鸟实业有限公司 | Process for producing high-grade pentadiene petroleum resin |
-
2010
- 2010-11-18 CN CN 201010549279 patent/CN102010481A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320648A (en) * | 2000-04-26 | 2001-11-07 | 上海石油化工股份有限公司 | Process for preparing C5 monoolefin modified m-pentadiene petro-resin |
| CN1563127A (en) * | 2004-03-23 | 2005-01-12 | 倪才国 | Method for preparing petroleum resin of piperyene |
| CN101134797A (en) * | 2006-09-01 | 2008-03-05 | 上海江鸟实业有限公司 | Process for producing high-grade pentadiene petroleum resin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382261A (en) * | 2011-08-22 | 2012-03-21 | 天津市兴源化工有限公司 | Preparation method for light-chroma aromatic petroleum resin |
| CN102382261B (en) * | 2011-08-22 | 2013-03-06 | 天津市兴源化工有限公司 | Preparation method for light-chroma aromatic petroleum resin |
| CN102702434A (en) * | 2012-06-07 | 2012-10-03 | 抚顺齐隆化工有限公司 | Method of two-stage continuous polymerization production of petroleum resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102297240B1 (en) | Method for producing hydrogenated petroleum resin | |
| CN101107274B (en) | Polymerization inhibitor for 1,3-butadiene and a method of inhibiting polymerization of 1,3-butadiene by imputing thereof | |
| CN103664472A (en) | Method for preparing high-purity dicyclopentadiene | |
| CN102816281A (en) | Method for preparing C5 petroleum resin for traffic paint | |
| CN101659733A (en) | Synthesis method of light chroma C9 petroleum resin | |
| CN111548246A (en) | Method for preparing high-purity dicyclopentadiene from cracking carbon nine fraction | |
| CN102382261B (en) | Preparation method for light-chroma aromatic petroleum resin | |
| CN102010481A (en) | Preparation method of light-color pentadiene petroleum resins | |
| CN102993386B (en) | Method for preparing modified C5 petroleum resin based on irradiation grafting | |
| CN104277179B (en) | A kind of method that free radical hot polymerization produces m-pentadiene petro-resin | |
| US2894937A (en) | Process for preparing petroleum resins ii | |
| CN110003266B (en) | Environment-friendly production method of high-quality 3-octanoyl thio-1-propyltriethoxysilane | |
| CN106540640B (en) | The commercial run and device of a kind of hydrogenation of petroleum resin process desulfurization, dechlorination | |
| CN113666802A (en) | Method for synthesizing and extracting and purifying 3-hexyne-2, 5-diol | |
| CN105315238A (en) | Production equipment of epoxypropane | |
| JPWO2014073230A1 (en) | Production method of polymer, polymer solution, and polymer | |
| CN107652317B (en) | Method for preparing alpha, omega-dichloro end-capped siloxane by cracking reaction of silicon rubber series substances | |
| CN101412787B (en) | Method for utilizing waste liquid from cyclopentadiene and methylcyclopentadiene production using C9 distillate | |
| CN107137948B (en) | Method for removing dicyclopentadiene from ethylene cracking carbon nine fraction | |
| CN1179992C (en) | Prep. of high softening point and high fusion viscosity pentadiene petroleum resin | |
| CN102351990A (en) | Method for preparing m-pentadiene petroleum resin | |
| CN101671224A (en) | Preparation method of high purity dicyclopentadiene | |
| KR20160036887A (en) | Method for the recovery of catalytic metal from polyketone | |
| CN217490835U (en) | Synthesizer of high-content rubber antioxidant RD | |
| CN114621046B (en) | Method for preparing high-purity dicyclopentadiene through ionic liquid catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110413 |