CN1179992C - Prep. of high softening point and high fusion viscosity pentadiene petroleum resin - Google Patents
Prep. of high softening point and high fusion viscosity pentadiene petroleum resin Download PDFInfo
- Publication number
- CN1179992C CN1179992C CNB021112606A CN02111260A CN1179992C CN 1179992 C CN1179992 C CN 1179992C CN B021112606 A CNB021112606 A CN B021112606A CN 02111260 A CN02111260 A CN 02111260A CN 1179992 C CN1179992 C CN 1179992C
- Authority
- CN
- China
- Prior art keywords
- pentadiene
- piperyene
- reaction
- resin
- petroleum resin
- 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.)
- Expired - Lifetime
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a preparation method for piperyene petroleum resin having the advantages of high softening point and high melting viscosity. A piperyene concentrated substance obtained by separating C5 which is a byproduct of cracking ethylene is used as a raw material, wherein the content of the piperyene is from 65 to 80 wt%, and benzene, toluene or xylene is used as a reaction solvent for polymerizing to prepare a piperyene petroleum resin product under the condition that aluminium trichloride which is used as a catalyst exists. The polymerization reaction is carried out in an airtight reactor, wherein polymerization temperature is from 40 to 80 DEG C, polymerization time is form 4 to 8 hours, and reaction raw materials are added to the reactor at uniform speed within the whole reaction time. The present invention has the advantages that the softening point of the obtained piperyene petroleum resin product is higher than 110 DEG C, melting viscosity is more than 500 cps so much as 800 cps. The piperyene petroleum resin product is especially suitable for come specific occasions, such as traffic paint used in tropical zones and adhesive used in high temperature environment.
Description
Technical field
The present invention relates to benzene, toluene or dimethylbenzene is reaction solvent, prepares the method for m-pentadiene petro-resin in the presence of the catalyzer aluminum chloride by cationoid polymerisation.
Background technology
From the carbon Wuyuan material of cracking of ethylene by-product, can obtain the m-pentadiene cut, can further obtain m-pentadiene petro-resin by cationoid polymerisation again by separation.With this petroleum resin products that prior art is produced, its softening temperature is generally below 105 ℃, and melt viscosity is then below 300cps (200 ℃, later on together).Yet, in some special application scenario, in the tackiness agent that uses in the traffic paint that uses as the torrid areas, the hot environment, often require this kind petroleum resin that higher softening temperature and melt viscosity are arranged, for example, softening temperature requires more than 110 ℃, and melt viscosity is preferably in more than the 500cps.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of high softening-point, high melt viscosity m-pentadiene petro-resin, this method is a raw material with the separating obtained m-pentadiene enriched substance of the carbon Five Classics of cracking of ethylene by-product, the m-pentadiene petro-resin product softening temperature that obtains is more than 110 ℃, melt viscosity even reaches 800cps more than 500 cps.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
The preparation method of a kind of high softening-point, high melt viscosity m-pentadiene petro-resin, this method is a raw material with the separating obtained m-pentadiene enriched substance of the carbon Five Classics of cracking of ethylene by-product, wherein m-pentadiene content is 65～80wt%, with benzene, toluene or dimethylbenzene is reaction solvent, polymerization makes the m-pentadiene petro-resin product in the presence of the catalyzer aluminum chloride, polyreaction is carried out in airtight reactor, polymerization temperature is 40～80 ℃, polymerization time is 4～8 hours, and described reaction raw materials at the uniform velocity added in the reactor in the entire reaction time.
Above-mentioned polymerization temperature is preferably 45～70 ℃; Polymerization time is preferably 6～8 hours; The weight ratio of solvent and raw material total amount can be 0.2～1: 1 usually, is preferably 0.6～1: 1; The consumption of catalyzer aluminum chloride can be preferably 0.8～2wt% for 0.8～3wt% of raw material total amount usually.
In the present invention, polyreaction is to adopt rhythmic reaction, it must be emphasized that polymerization reactor is airtight, and material adopts volume pump to feed in raw material, and reactor also has stirring and refrigerating unit usually.
Earlier catalyzer and solvent are mixed in reactor before feeding intake, according to the required reaction times polymer raw is added evenly then and carry out polyreaction in the reactor.Because this polyreaction belongs to a kind of cationic polymerization, its reaction process is almost finished in moment, and reinforced end can think that just reaction finishes.The product of polyreaction just obtains product after adopting conventional method to remove the processing of solvent and unreacted reactant, oligopolymer etc. again.
In general, two indexs of the softening temperature of petroleum resin and melt viscosity all with the polymerization degree, just polymericular weight is closely related, molecular weight is big more, softening temperature and melt viscosity are just high more.The contriver finds through after a large amount of tests, when adopting airtight reaction vessel, and suitably prolong polymerization send out seasonable between, and reaction raw materials is reinforced evenly in the time in entire reaction, can improve the polymerization degree greatly, obtain softening temperature more than 110 ℃, melt viscosity even reaches the high softening-point of 800cps, the m-pentadiene petro-resin of high melt viscosity more than 500cps.
Compared with prior art, advantage of the present invention is to be raw material with the separating obtained m-pentadiene enriched substance of the carbon Five Classics of cracking of ethylene by-product, just can obtain high softening-point and high melt viscosity m-pentadiene petro-resin by adjusting process condition suitably.
Embodiment
Below will describe details of the present invention by some embodiment, wherein yield is calculated as follows:
The testing method of softening temperature: ring and ball method, with reference to GB GB4507-84.The testing method of melt viscosity: adopt the melt viscosity instrument under 200 ℃, to record.The testing method of Gardner colourity: colorimetry, with reference to GB GB4317-84.
[embodiment 1～10]:
At a volume is 2500 liters, has the catalyzer aluminum chloride that adds 600 kilograms of solvent toluenes and aequum in the capping still of whipping appts and cooling jacket, stirs 5 minutes down at 30 ℃.According to the required reaction times, with the m-pentadiene raw material (m-pentadiene enriched substance that the carbon Five Classics of cracking of ethylene by-product separating obtained, composition see Table 1) of volume pump at entire reaction adding aequum in continuously and smoothly ground in the time.By the controlled chilling water flow velocity system temperature is controlled at and carries out polyreaction under the design temperature.The reinforced back that finishes adds an amount of 5wt%NaOH solution termination reaction.The pH value that reactant is washed until water lotion is neutral, to remove the catalyzer of oil phase.Oil phase material removes and desolvates and unreacted reactant, oligopolymer etc. through distillation and wet distillation, promptly obtains product.
Concrete reaction conditions sees Table 2, and the leading indicator of product sees Table 3.
Table 1.
| Composition | Content (%) |
| Pentamethylene | 2.84 |
| Cyclopentenes | 17.85 |
| M-pentadiene | 75.98 |
| Cyclopentadiene | 0.20 |
| Carbon six | 2.83 |
| Dicyclopentadiene | 0.30 |
Table 2.
| Reaction times (hr) | Temperature of reaction (℃) | Solvent/raw material total amount (weight ratio) | Catalyst levels (raw material total amount wt%) | |
| Embodiment 1 | 4 | 50 | 0.6 | 1.4 |
| Embodiment 2 | 4.5 | 50 | 0.6 | 1.2 |
| Embodiment 3 | 6 | 50 | 0.6 | 1.4 |
| Embodiment 4 | 6 | 45 | 0.5 | 2.0 |
| Embodiment 5 | 6 | 60 | 0.5 | 1.2 |
| Embodiment 6 | 5 | 60 | 0.5 | 1.3 |
| Embodiment 7 | 4 | 50 | 1 | 1.3 |
| Embodiment 8 | 6 | 50 | 0.5 | 1.0 |
| Embodiment 9 | 6 | 50 | 0.6 | 1.2 |
| Embodiment 10 | 7.5 | 68 | 0.6 | 0.8 |
Table 3.
| Yield (%) | Softening temperature (℃) | Melt viscosity (cps, 200 ℃) | Gardner colourity | |
| Embodiment 1 | 85 | 114 | 630 | 6 |
| Embodiment 2 | 83 | 111 | 660 | 5 |
| Embodiment 3 | 85 | 117 | 640 | 6 |
| Embodiment 4 | 84 | 112 | 680 | 5 |
| Embodiment 5 | 85 | 114 | 675 | 6 |
| Embodiment 6 | 85 | 115 | 690 | 6 |
| Embodiment 7 | 83.5 | 114 | 620 | 4 |
| Embodiment 8 | 82 | 110 | 610 | 4 |
| Embodiment 9 | 84 | 110 | 690 | 4 |
| Embodiment 10 | 86 | 124 | 820 | 5 |
Claims (5)
1, a kind of high softening-point, the preparation method of high melt viscosity m-pentadiene petro-resin, this method is a raw material with the separating obtained m-pentadiene enriched substance of the carbon Five Classics of cracking of ethylene by-product, wherein m-pentadiene content is 65～80wt%, with benzene, toluene or dimethylbenzene are reaction solvent, polymerization makes the m-pentadiene petro-resin product in the presence of the catalyzer aluminum chloride, polyreaction is carried out in airtight reactor, polymerization temperature is 40～80 ℃, polymerization time is 4～8 hours, the weight ratio of solvent and raw material total amount is 0.2～1: 1, the consumption of catalyzer aluminum chloride is 0.8～3wt% of raw material total amount, and described reaction raw materials at the uniform velocity adds in the reactor in the time in entire reaction.
2, the preparation method of high softening-point according to claim 1, high melt viscosity m-pentadiene petro-resin is characterized in that described polymerization temperature is 45～70 ℃.
3, the preparation method of high softening-point according to claim 1, high melt viscosity m-pentadiene petro-resin, it is characterized in that described polymerization time is 6～8 hours, described reaction raw materials adds in the reactor with uniform feed rate in the time in entire reaction.
4, the preparation method of high softening-point according to claim 1, high melt viscosity m-pentadiene petro-resin, the weight ratio that it is characterized in that described solvent and raw material total amount is 0.6～1: 1.
5, the preparation method of high softening-point according to claim 1, high melt viscosity m-pentadiene petro-resin, the consumption that it is characterized in that described catalyzer aluminum chloride is 0.8～2wt% of raw material total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021112606A CN1179992C (en) | 2002-04-04 | 2002-04-04 | Prep. of high softening point and high fusion viscosity pentadiene petroleum resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021112606A CN1179992C (en) | 2002-04-04 | 2002-04-04 | Prep. of high softening point and high fusion viscosity pentadiene petroleum resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1448417A CN1448417A (en) | 2003-10-15 |
| CN1179992C true CN1179992C (en) | 2004-12-15 |
Family
ID=28680515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021112606A Expired - Lifetime CN1179992C (en) | 2002-04-04 | 2002-04-04 | Prep. of high softening point and high fusion viscosity pentadiene petroleum resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1179992C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134797B (en) * | 2006-09-01 | 2010-05-12 | 上海江鸟实业有限公司 | Process for producing high-grade pentadiene petroleum resin |
| CN101497677B (en) * | 2008-12-11 | 2012-01-11 | 宁波职业技术学院 | Method for preparing C5 hydrocarbon resin from methyl tetrahydro benzoic anhydride production waste liquor |
| CN104277179B (en) * | 2014-09-24 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of method that free radical hot polymerization produces m-pentadiene petro-resin |
| CN106893034A (en) * | 2017-03-31 | 2017-06-27 | 安徽同心化工有限公司 | A kind of ethene m-pentadiene petro-resin and preparation method |
| CN108219068B (en) * | 2018-01-10 | 2024-04-05 | 安徽同心新材料科技有限公司 | High-performance polymer resin with controllable melt viscosity and preparation method thereof |
-
2002
- 2002-04-04 CN CNB021112606A patent/CN1179992C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1448417A (en) | 2003-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1274734C (en) | Unimodal radial block copolymer with functional group and its preparation method | |
| EP3434703B1 (en) | Method for industrial production of trans-butadiene-isoprene copolymer rubber and apparatus therefor | |
| CN102718924B (en) | Method for preparing C5/C9 copolymerized petroleum resin | |
| CN102746460B (en) | Method for preparing cold-polymerized indene resin with high softening point and light color | |
| CN107522806B (en) | Continuous polymerization method for preparing rare earth butadiene rubber | |
| CN1179992C (en) | Prep. of high softening point and high fusion viscosity pentadiene petroleum resin | |
| CN102643389B (en) | Preparation method for petroleum resin with high softening point | |
| CN103382238A (en) | Polymerization method for m-pentadiene petroleum resin | |
| JP2003513119A (en) | Production of highly reactive polyisobutene | |
| US20180016368A1 (en) | Process for continuous synthesis of a diene elastomer | |
| CN1114630C (en) | Process for preparing C5 monoolefin modified m-pentadiene petro-resin | |
| CN1229311C (en) | Process for producing alpha-olefin oligomer | |
| CN101497677B (en) | Method for preparing C5 hydrocarbon resin from methyl tetrahydro benzoic anhydride production waste liquor | |
| US4358574A (en) | Production of hydrocarbon resins and products resulting therefrom | |
| US4403080A (en) | Isomerization and polymerization of hydrocarbon resins | |
| CN112679297A (en) | Preparation method of high-purity dicyclopentadiene | |
| CN105175634A (en) | Preparation method of modified C5 petroleum resin | |
| CN109912744B (en) | Preparation method of monomer modified C5 petroleum resin | |
| CN102234342B (en) | Method for preparing rare earth catalyst applied to isoprene rubber production | |
| CN103881027A (en) | Synthetic method for piperylene petroleum resin | |
| CN111116775B (en) | Process and apparatus for producing low viscosity polyalphaolefin | |
| CN110452320B (en) | Process for preparing branched polyethylene | |
| CN1051566A (en) | The method of butadiene bulk polymerization and copolymerization | |
| CN1324874A (en) | Prepn. of cir-rich 1,4-polybutadine rubber for tyre | |
| CN112079958A (en) | Preparation method of carbon-five copolymerized petroleum resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20041215 |