CN104045767B - The preparation method of a kind of indenes modification �� pinene resin - Google Patents
The preparation method of a kind of indenes modification �� pinene resin Download PDFInfo
- Publication number
- CN104045767B CN104045767B CN201410219088.6A CN201410219088A CN104045767B CN 104045767 B CN104045767 B CN 104045767B CN 201410219088 A CN201410219088 A CN 201410219088A CN 104045767 B CN104045767 B CN 104045767B
- Authority
- CN
- China
- Prior art keywords
- indenes
- pinene
- modification
- solvent
- preparation
- 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 - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to the preparation method of a kind of indenes modification �� pinene resin, comprise: solvent is dropped into reactor by (1), control temperature is at-50 DEG C��15 DEG C, after catalyzer and another part solvent are mixed, add reactor to stir, drip subsequently simultaneously and add ��-pinene and indenes mixture, react 1��6 hour, obtain reactive polymeric liquid; (2) reactive polymeric liquid is washed to pH=7, leave standstill, get upper oil phase, obtain resin liquid; (3) resin liquid is de-except partial solvent by underpressure distillation, the concentrated solution water vapour stripping that then will obtain, obtains indenes modification �� pinene resin. Technique of the present invention is simple, cost is low, by product is few, current cracking of ethylene by product C9 evaporates point the indenes section obtained through rectifying cutting and evaporates and point contain a large amount of indenes, and price is lower than the price of ��-pinene, the rosin products of the two copolymerization has higher economic benefit, is applicable to suitability for industrialized production, has a good application prospect.
Description
Technical field
The invention belongs to �� pinene resin field, in particular to the preparation method of a kind of indenes modification �� pinene resin.
Background technology
�� pinene resin has the performances such as excellent compatible, acid and alkali-resistance, anti-ageingization, thermally-stabilised, electrical isolation, the matrix being widely used as pressure sensitive adhesive, hotmelt and tackifier etc., and in the industry such as coating, rubber, plastics, printing, health and food product pack, ion exchange resin, potash fertilizer synergistic agent. This resinoid is the earliest with the synthesis of sulfuric acid catalysis turps, and 1933, Guefrefining company started pinene resin suitability for industrialized production. Patent US3479007, US3622550, US4016346, US4057682, US4113653, CN201210131568, CN201210130940, CN201210428245 describe the method utilizing ��-pinene synthesis pinene resin. Owing to resource and cost of labor limit, �� pinene resin is on the high side, constrains its development, fails these reproducibility natural resource are fully used, by ��-pinene and other monomer copolymerizations, reduction �� pinene resin production cost and raising added value are had great significance.
Indenes is extremely important industrial raw material, is mainly present in coal tar fraction and during petroleum cracking evaporates point, is a kind of important comonomer, it is possible to be used for changing the surface properties of polymkeric substance and thermal characteristics etc.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of indenes modification �� pinene resin, and the method technique is simple, and cost is low, and by product is few, has a good application prospect.
The preparation method of a kind of indenes modification �� pinene resin of the present invention, comprising:
(1) 30wt%��60wt% solvent is dropped into reactor, control temperature is at-50 DEG C��15 DEG C, after the solvent of the catalyzer of 0.1wt%��3wt% and 10wt%��20wt% is mixed, add reactor to stir, drip the indenes mixture of the ��-pinene adding 5wt%��50wt% and 5wt%��50wt% subsequently simultaneously, react 1��6 hour, obtain reactive polymeric liquid; Wherein, mass percent is all taking material total mass as benchmark;
(2) the reactive polymeric liquid of step (1) gained is washed to pH=7, leave standstill, after aqueous phase/oil phase layering, get upper oil phase, obtain resin liquid;
(3) resin liquid of step (2) gained is de-except partial solvent by underpressure distillation, the concentrated solution water vapour stripping that then will obtain, de-except remaining solvent and oligopolymer, obtain indenes modification �� pinene resin.
Solvent in described step (1) is toluene, benzene, dimethylbenzene, trimethylbenzene, acetone, monochloro methane, methylene dichloride, trichloromethane, normal hexane, hexanaphthene, methylcyclohexane, ethylcyclohexane, dimethyl cyclohexane, isohexane, Skellysolve A, pentamethylene, iso-pentane, methylcyclopentane, normal heptane, suberane, isoheptane, octane, cyclooctane or octane-iso.
Catalyzer in described step (1) is AlCl3��AlBr3��SbCl3��BF3��TiCl4��SnCl4��ZrCl4��AlCl3(C2H5)2O��BF3(C2H5)2O��BiCl3Or ZnCl2��
Indenes mixture in described step (1) comprises: 20wt%��99wt% indenes, 0wt%��10wt% naphthalene, and all the other are the hydrocarbon class of C8-C12.
Washing in described step (2) is specially successively through sodium hydroxide and the clear water washing of 1wt%��10wt%.
Stripping temperature in described step (3) is 230 DEG C��260 DEG C, and stripping time is 0.5��3 hour.
Useful effect
Technique of the present invention is simple, cost is low, by product is few, current cracking of ethylene by product C9 evaporates point the indenes section obtained through rectifying cutting and evaporates and point contain a large amount of indenes, and price is lower than the price of ��-pinene, the rosin products of the two copolymerization has higher economic benefit, is applicable to suitability for industrialized production, has a good application prospect.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further. Limit the scope of the invention it will be understood that these embodiments are only not used in for illustration of the present invention. In addition it will be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
60g toluene (analytical pure) is placed in the 500ml there-necked flask with whipping appts, is cooled to 2 DEG C, by 1gAlCl3After mixing with 20g toluene, slowly join in there-necked flask, by constant pressure funnel, by 70g ��-pinene (massfraction is 99wt%) and 70g indenes mixture, (massfraction is 99wt% simultaneously, all the other hydrocarbon classes being C8-C12) it is added drop-wise to there-necked flask, add rear isothermal reaction 2 hours, obtain reactive polymeric liquid. Then successively with the sodium hydroxide of 5wt% and clear water washing polymer fluid, to pH=7. Stratification, gets upper oil phase, carries out underpressure distillation, de-except after major part solvent, kettle base solution water vapour stripping 1 hour at 250 DEG C will be distilled, de-except remaining solvent and oligopolymer, obtain 132g copolymer resins, receipts rate is 94.3wt%, and the colourity of resin is 10#, and softening temperature is 128 DEG C.
Embodiment 2
50g toluene (analytical pure) is placed in the 500ml there-necked flask with whipping appts, is cooled to-25 DEG C, by 1gBF3(C2H5)2After O and 15g toluene mixes, slowly join in there-necked flask, 80g ��-pinene (massfraction is 99wt%) and 55g indenes mixture (consisting of: the hydrocarbon class of the indenes of 40wt%, the naphthalene of 5wt%, 55wt%C8-C12) are added drop-wise to there-necked flask by constant pressure funnel simultaneously, add rear isothermal reaction 3 hours, obtain reactive polymeric liquid. Then successively with the sodium hydroxide of 10wt% and clear water washing polymer fluid, to cleaning mixture pH=7. Stratification, gets upper oil phase, carries out underpressure distillation, de-except after major part solvent, kettle base solution water vapour stripping 2 hours at 260 DEG C will be distilled, de-except remaining solvent and oligopolymer, obtain 95.3g copolymer resins, receipts rate is 93.2wt%, and the colourity of resin is 8#, and softening temperature is 103 DEG C.
The every technical indicator detection method of the present invention is:
(1) mensuration of softening temperature: measure by the method for pitch softening point assay method ring and ball method (GB GB/T4507-1999).
(2) mensuration of colourity: measure by the method for epoxy resin color measurenent method Ghana's moral chromatmetry (GB GB/T222295-2008).
Claims (5)
1. a preparation method for indenes modification �� pinene resin, comprising:
(1) 30wt%��60wt% solvent is dropped into reactor, control temperature is at-50 DEG C��15 DEG C, after the solvent of the catalyzer of 0.1wt%��3wt% and 10wt%��20wt% is mixed, add reactor to stir, drip the indenes mixture of the ��-pinene adding 5wt%��50wt% and 5wt%��50wt% subsequently simultaneously, react 1��6 hour, obtain reactive polymeric liquid; Wherein, mass percent is all taking material total mass as benchmark;
(2) the reactive polymeric liquid of step (1) gained is washed to pH=7, leave standstill, after aqueous phase/oil phase layering, get upper oil phase, obtain resin liquid;
(3) resin liquid of step (2) gained is de-except partial solvent by underpressure distillation, the concentrated solution water vapour stripping that then will obtain, de-except remaining solvent and oligopolymer, obtain indenes modification �� pinene resin; Wherein, stripping temperature is 230 DEG C��260 DEG C, and stripping time is 0.5��3 hour.
2. the preparation method of a kind of indenes modification �� pinene resin according to claim 1, it is characterised in that: the solvent in described step (1) is toluene, benzene, dimethylbenzene, trimethylbenzene, acetone, monochloro methane, methylene dichloride, trichloromethane, normal hexane, hexanaphthene, methylcyclohexane, ethylcyclohexane, dimethyl cyclohexane, isohexane, Skellysolve A, pentamethylene, iso-pentane, methylcyclopentane, normal heptane, suberane, isoheptane, octane, cyclooctane or octane-iso.
3. the preparation method of a kind of indenes modification �� pinene resin according to claim 1, it is characterised in that: the catalyzer in described step (1) is AlCl3��AlBr3��SbCl3��BF3��TiCl4��SnCl4��ZrCl4��AlCl3(C2H5)2O��BF3(C2H5)2O��BiCl3Or ZnCl2��
4. the preparation method of a kind of indenes modification �� pinene resin according to claim 1, it is characterised in that: the indenes mixture in described step (1) comprises: 20wt%��99wt% indenes, 0wt%��10wt% naphthalene, and all the other are the hydrocarbon class of C8-C12.
5. the preparation method of a kind of indenes modification �� pinene resin according to claim 1, it is characterised in that: the washing in described step (2) is specially successively through sodium hydroxide and the clear water washing of 1wt%��10wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410219088.6A CN104045767B (en) | 2014-05-22 | 2014-05-22 | The preparation method of a kind of indenes modification �� pinene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410219088.6A CN104045767B (en) | 2014-05-22 | 2014-05-22 | The preparation method of a kind of indenes modification �� pinene resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104045767A CN104045767A (en) | 2014-09-17 |
| CN104045767B true CN104045767B (en) | 2016-06-01 |
Family
ID=51499199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410219088.6A Expired - Fee Related CN104045767B (en) | 2014-05-22 | 2014-05-22 | The preparation method of a kind of indenes modification �� pinene resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104045767B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2287535A (en) * | 1939-06-08 | 1942-06-23 | Armstrong Cork Co | Copolymerization of terpene hydrocarbons and coal tar hydrocarbons |
| CN101503495A (en) * | 2009-02-24 | 2009-08-12 | 宁波职业技术学院 | Preparation of alpha-pinene modified C5 hydrocarbon resin |
| CN101589100A (en) * | 2007-01-11 | 2009-11-25 | 株式会社普利司通 | Rubber combination and the tire that uses it |
| CN102633920A (en) * | 2012-05-02 | 2012-08-15 | 无锡信达胶脂材料有限公司 | Production method of terpene resin |
-
2014
- 2014-05-22 CN CN201410219088.6A patent/CN104045767B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2287535A (en) * | 1939-06-08 | 1942-06-23 | Armstrong Cork Co | Copolymerization of terpene hydrocarbons and coal tar hydrocarbons |
| CN101589100A (en) * | 2007-01-11 | 2009-11-25 | 株式会社普利司通 | Rubber combination and the tire that uses it |
| CN101503495A (en) * | 2009-02-24 | 2009-08-12 | 宁波职业技术学院 | Preparation of alpha-pinene modified C5 hydrocarbon resin |
| CN102633920A (en) * | 2012-05-02 | 2012-08-15 | 无锡信达胶脂材料有限公司 | Production method of terpene resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104045767A (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101503495B (en) | Preparation of alpha-pinene modified C5 hydrocarbon resin | |
| CN109337012A (en) | A kind of preparation method of phenol modified copolymer Petropols | |
| CN102757530A (en) | Preparation method of light-color cold polymerized C9 petroleum resin | |
| CN106543362A (en) | A kind of preparation method of C5/C10 copolymer resinses | |
| CN102690393B (en) | Copolymer containing functional group and prepared by C5 mixture and maleic anhydride, and preparation of copolymer | |
| WO2021232520A1 (en) | Method for preparing hydrogenated high aromatic hydrocarbon resin | |
| CN104045767B (en) | The preparation method of a kind of indenes modification �� pinene resin | |
| CN105418848B (en) | A kind of method that boron trifluoride catalysis prepares C5 Petropols | |
| CN100448906C (en) | Synthesis for copolymer of terminal amino and carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt | |
| CN103382238A (en) | Polymerization method for m-pentadiene petroleum resin | |
| CN101613438B (en) | Preparation method of piperylene modified DCPD petroleum resin | |
| CN103449955B (en) | Method for extracting triphen from coker naphtha | |
| CN102676195B (en) | Chemical modification method of coal pitch with unsaturated thermoplastic elastomer | |
| CN108219216B (en) | Abietyl modified C9 Petropols and its preparation method and application | |
| CN105566569A (en) | Hydroxyl coumarone resin and preparation method thereof | |
| CN106893056B (en) | A kind of modified dicyclopentadiene petroleum resin of s-B-S and preparation method | |
| CN109400806A (en) | A kind of light color C9 hot polymerization petroleum resin products and its preparation process | |
| CN202621171U (en) | Polymerization reaction kettle | |
| CN106146244A (en) | The preparation method of tire tread aromatic hydrocarbon resin | |
| CN103881027A (en) | Synthetic method for piperylene petroleum resin | |
| CN106699972B (en) | A kind of preparation method and its device of C5/C10 copolymer resins | |
| CN101041708A (en) | Method for synthesizing terminal amido SBS and application in modified pitch | |
| CN102702757A (en) | Modified asphalt waterproof coiled material and production process thereof | |
| CN103102449A (en) | Manufacturing method of piperylene petroleum resin | |
| CN106699973A (en) | Method for preparing low molecular weight C5/C10 copolymer 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160601 Termination date: 20170522 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |