CN101659736A - Modification method of petroleum resin - Google Patents
Modification method of petroleum resin Download PDFInfo
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- CN101659736A CN101659736A CN200910192163A CN200910192163A CN101659736A CN 101659736 A CN101659736 A CN 101659736A CN 200910192163 A CN200910192163 A CN 200910192163A CN 200910192163 A CN200910192163 A CN 200910192163A CN 101659736 A CN101659736 A CN 101659736A
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- petroleum resin
- distillate
- petroleum
- polystyrene foam
- dicyclopentadiene
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Abstract
The invention discloses a modification method of petroleum resin, taking one or the mixture of more than one of C9 distillate, C5 distillate, dicyclopentadiene distillate, tarstyrene tar and other distillates full of unsaturation olefin as raw materials, wherein, C9 distillate, C5 distillate, dicyclopentadiene distillate and tarstyrene tar are the byproducts of petroleum cracking ethylene. The rawmaterials are polymerized and separated to obtain C9 petroleum resin, C5 petroleum resin, dicyclopentadiene petroleum resin, coumarone petroleum resin and various copolymerization petroleum resins; in the polymerized reaction, modifier which is waste polystyrene foam is added, and the mass ratio of polystyrene foam to petroleum resin is 1:(0.1-99); polymerized reaction is realized in that the mixture is stirred at the temperature of 30-150 DEG C for 0.5-1.5 hours, then temperature is increased to 180-280 DEG C to be kept for 1.5-2.5 hours, and pressure is controlled to be 0-1.5MPa. The invention uses waste polystyrene foam to serve as the modifier, which can save resources, protect environment and change waste into valuables. The invention can improve the softening point, hue and viscosity of original petroleum resin.
Description
Technical field
The present invention relates to a kind of method of modifying of petroleum resin, particularly relating to petroleum cracking system ethylene by-product---C9 cut, C 5 fraction, dicyclopentadiene cut, styrene tar and other cut that is rich in unsaturated olefin are raw material, with a kind of method of waste polystyrene foam modification C9 petroleum resin, C5 petroleum resin, dicyclopentadiene petroleum resin, coumarone petroleum resin and various copolymerized petroleum resins.
Background technology
Polystyrene foamed plastics is because characteristics such as its light weight, firm, shock-absorbing, the low moisture absorption, easy-formation and excellent water tolerance, heat insulating ability, price be low, is widely used in fields such as packing, insulation, waterproof, heat insulation, damping.PS mostly is disposable use, discards at occurring in nature can not rot to transform, and can not degrade voluntarily again and disappears, and has so both wasted valuable Nonrenewable resources, has caused the serious environmental pollution again.
The petroleum resin modified method of tradition is to use in a certain field at petroleum resin to carry out modification, purpose is to improve the service efficiency of petroleum resin in this field, as: is with the petroleum resin water soluble with maleic anhydride to petroleum resin modified purpose, improve the dispersing property of tree oil liposoluble water, so can improve the application of petroleum resin at drilling operation and cement manufacture field; With vinylformic acid petroleum resin modified purpose is provided the viscosity of petroleum resin, so can improve the service efficiency of petroleum resin in the sizing agent field; Or the like.The present invention is to improve the every overall target of petroleum resin with waste polystyrene foam to petroleum resin modified purpose, can reach the purpose of utilization of waste material again.
Summary of the invention
The purpose of this invention is to provide a kind of both recyclable waste that utilizes, again the method for modifying of the petroleum resin that can enhance product performance.
The method of modifying of a kind of petroleum resin provided by the invention, it is the C9 cut with petroleum cracking system ethylene by-product, C 5 fraction, the dicyclopentadiene cut, styrene tar and other are rich in that one or more mixture is a raw material in the cut of unsaturated olefin, through polymerization, separate and the C9 petroleum resin, the C5 petroleum resin, dicyclopentadiene petroleum resin, coumarone petroleum resin and various copolymerized petroleum resin, wherein in polyreaction, add properties-correcting agent, described properties-correcting agent is the depleted polystyrene foam, the weight ratio 1 of polystyrene foam and raw material wherein: (0.1～99), polyreaction is after stirring 0.5～1.5 hour under 30～150 ℃, be warming up to 180～280 ℃ again and kept 1.5～2.5 hours, pressure-controlling is at 0～1.5Mpa.
In polyreaction, also add initiator, the add-on of initiator accounts for 0.3～1% of raw material weight.
Described initiator is Diisopropyl azodicarboxylate, peroxidation two acyls or persulphate.
In the present invention, the boiling range section of ethylenic unsaturation hydrocarbon-fraction all can 60～230 ℃ of any scopes.
In separating step, rely on decompression add thermal distillation not polymeric component and low-molecular(weight)polymer separate, the not polymeric component in the material after the polymerization is separated, separation condition be vacuum tightness 0～-0.099Mpa, 120～320 ℃ of Heating temperatures.
In polyreaction, the reactor that reacts used is the withstand voltage high temperature resistant material of sealing, and alr mode is magnetic agitation or mechanical stirring.
The present invention adopts two temperature section stage feeding polymerizations, one section low temperature polymerization purpose is with macromole polystyrene and small molecules unsaturated olefin component initiated polymerization, and two sections high temperature polymerization purposes are the component polymerizations once more that part had neither part nor lot in polymeric component and copolymerization.
The present invention utilizes the depleted polystyrene foam to be properties-correcting agent, can economize on resources the protection environment; turn waste into wealth, employing the present invention can improve the softening temperature of protopetroleum resin, form and aspect and viscosity; the petroleum resin analysis indexes is as follows after the modification: softening temperature: 80～160 ℃, and form and aspect 10
#～18
#, potential of hydrogen (PH) is 5.5～7.5, ash content≤1%, and it can be applicable to fields such as coating, printing ink, sizing agent, rubber.
Embodiment
Embodiment 1
Depleted polystyrene foam 3kg is mixed the back to add in the reactor with raw material C9 cut 20kg; Adding initiator B PO then is 0.1kg, and polyreaction is after stirring 0.5～1.5 hour under 30～150 ℃, is warming up to 180～280 ℃ again to keep 1.5～2.5 hours, and pressure-controlling is at 0～1.5Mpa; Not polymeric component in the material after the polymerization is separated, separation condition be vacuum tightness 0～-0.099Mpa, 120～320 ℃ of Heating temperatures promptly obtain modified petroleum resin.
The resin softening point analytical procedure adopts coal-tar pitch softening point measurement method (GB2294-80), hue analysis sampling Gardner's colourity method (GB/T12007.1-89), solid coumarone-indene resin potential of hydrogen measuring method (GB4318-84) is adopted in the potential of hydrogen analysis, ash analysis sampling coal-tar pitch determination of ash method (GB2295-80).
The petroleum resin analysis indexes is as follows after the modification: softening temperature: 132 ℃, and form and aspect 10
#, potential of hydrogen (PH) is 6.8, ash content 0.3%.
Embodiment 2
Depleted polystyrene foam 4.5kg is mixed the back to add in the reactor with raw material C 5 fraction 40kg; Adding initiator B PO then is 0.2kg, and polyreaction is after stirring 0.5～1.5 hour under 30～150 ℃, is warming up to 180～280 ℃ again to keep 1.5～2.5 hours, and pressure-controlling is at 0～1.5Mpa; Not polymeric component in the material after the polymerization is separated, separation condition be vacuum tightness 0～-0.099Mpa, 120～320 ℃ of Heating temperatures promptly obtain modified petroleum resin.
Measuring method is identical with embodiment 1
The petroleum resin analysis indexes is as follows after the modification: softening temperature: 144 ℃, and form and aspect 15
#, potential of hydrogen (PH) is 7.3, ash content 0.6%.
Embodiment 3
Depleted polystyrene foam 3kg is mixed the back to add in the reactor with raw material DCPD cut 20kg; Adding initiator B PO then is 0.1kg, and polyreaction is after stirring 0.5～1.5 hour under 30～150 ℃, is warming up to 180～280 ℃ again to keep 1.5～2.5 hours, and pressure-controlling is at 0～1.5Mpa; Not polymeric component in the material after the polymerization is separated, separation condition be vacuum tightness 0～-0.099Mpa, 120～320 ℃ of Heating temperatures promptly obtain modified petroleum resin.
Measuring method is identical with embodiment 1.
The petroleum resin analysis indexes is as follows after the modification: softening temperature: 155 ℃, and form and aspect 8
#, potential of hydrogen (PH) is 6.5, ash content 0.21%.
Embodiment 4
Depleted polystyrene foam 6kg is mixed the back to add in the reactor with raw material C9 cut 30kg, C 5 fraction 20kg; Adding initiator B PO then is 0.3kg, and polyreaction is after stirring 0.5～1.5 hour under 30～150 ℃, is warming up to 180～280 ℃ again to keep 1.5～2.5 hours, and pressure-controlling is at 0～1.5Mpa; Not polymeric component in the material after the polymerization is separated, separation condition be vacuum tightness 0～-0.099Mpa, 120～320 ℃ of Heating temperatures promptly obtain modified petroleum resin.
Measuring method is identical with embodiment 1.
The petroleum resin analysis indexes is as follows after the modification: softening temperature: 130 ℃, and form and aspect 13
#, potential of hydrogen (PH) is 7.5, ash content 1%.
Claims (3)
1, a kind of method of modifying of petroleum resin, it is the C9 cut with petroleum cracking system ethylene by-product, C 5 fraction, the dicyclopentadiene cut, styrene tar and other are rich in that one or more mixture is a raw material in the cut of unsaturated olefin, through polymerization, separate and the C9 petroleum resin, the C5 petroleum resin, dicyclopentadiene petroleum resin, coumarone petroleum resin and various copolymerized petroleum resin, wherein in polyreaction, add properties-correcting agent, it is characterized in that described properties-correcting agent is the depleted polystyrene foam, wherein the mass ratio of polystyrene foam and petroleum resin is 1: (0.1～99), polyreaction is after stirring 0.5～1.5 hour under 30～150 ℃, be warming up to 180～280 ℃ again and kept 1.5～2.5 hours, pressure-controlling is at 0～1.5Mpa.
2, the method for modifying of a kind of petroleum resin according to claim 1 is characterized in that in polyreaction, also adds initiator, and the add-on of initiator accounts for 0.3～1% of raw material weight.
3, the method for modifying of a kind of petroleum resin according to claim 2 is characterized in that described initiator is Diisopropyl azodicarboxylate, peroxidation two acyls or persulphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910192163A CN101659736A (en) | 2009-09-04 | 2009-09-04 | Modification method of petroleum resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910192163A CN101659736A (en) | 2009-09-04 | 2009-09-04 | Modification method of petroleum resin |
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| CN101659736A true CN101659736A (en) | 2010-03-03 |
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| CN200910192163A Pending CN101659736A (en) | 2009-09-04 | 2009-09-04 | Modification method of petroleum resin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619121A (en) * | 2009-07-29 | 2010-01-06 | 宁波职业技术学院 | Method for preparing cracked C5 modified DCPD petroleum resin |
| CN101914184A (en) * | 2010-08-05 | 2010-12-15 | 奎屯达亿石油化工科技有限公司 | Ethylene tar resin granulation process and granulator |
| CN102690393A (en) * | 2012-05-04 | 2012-09-26 | 北京化工大学 | Copolymer containing functional group and prepared by C5 mixture and maleic anhydride, and preparation of copolymer |
| CN103484037A (en) * | 2013-09-11 | 2014-01-01 | 青岛天盾橡胶有限公司 | Formula of ntermediate adhesive suitable for remanufacturing mining giant tires |
| CN105542081A (en) * | 2015-12-25 | 2016-05-04 | 李道民 | Modified coumarone petroleum resin and preparation method thereof |
| CN105924579A (en) * | 2016-06-24 | 2016-09-07 | 李道民 | Production method of modified and tackified coumarone indene resin |
-
2009
- 2009-09-04 CN CN200910192163A patent/CN101659736A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619121A (en) * | 2009-07-29 | 2010-01-06 | 宁波职业技术学院 | Method for preparing cracked C5 modified DCPD petroleum resin |
| CN101619121B (en) * | 2009-07-29 | 2014-01-01 | 宁波职业技术学院 | Method for preparing cracked C5 modified DCPD petroleum resin |
| CN101914184A (en) * | 2010-08-05 | 2010-12-15 | 奎屯达亿石油化工科技有限公司 | Ethylene tar resin granulation process and granulator |
| CN101914184B (en) * | 2010-08-05 | 2013-06-19 | 奎屯达亿石油化工科技有限公司 | Ethylene tar resin granulation process and granulator |
| CN102690393A (en) * | 2012-05-04 | 2012-09-26 | 北京化工大学 | Copolymer containing functional group and prepared by C5 mixture and maleic anhydride, and preparation of copolymer |
| CN102690393B (en) * | 2012-05-04 | 2013-12-04 | 北京化工大学 | Copolymer containing functional group and prepared by C5 mixture and maleic anhydride, and preparation of copolymer |
| CN103484037A (en) * | 2013-09-11 | 2014-01-01 | 青岛天盾橡胶有限公司 | Formula of ntermediate adhesive suitable for remanufacturing mining giant tires |
| CN103484037B (en) * | 2013-09-11 | 2016-10-19 | 青岛天盾橡胶有限公司 | A kind of it is applicable to the intermediate rubber formula that giant mining tire remanufactures |
| CN105542081A (en) * | 2015-12-25 | 2016-05-04 | 李道民 | Modified coumarone petroleum resin and preparation method thereof |
| CN105924579A (en) * | 2016-06-24 | 2016-09-07 | 李道民 | Production method of modified and tackified coumarone indene resin |
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Open date: 20100303 |