CN101555307A - Method for synthesizing poly-dicyclopentadiene petroleum resin with adjustable molecular weight, distribution and softening point - Google Patents
Method for synthesizing poly-dicyclopentadiene petroleum resin with adjustable molecular weight, distribution and softening point Download PDFInfo
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- CN101555307A CN101555307A CNA2009100226153A CN200910022615A CN101555307A CN 101555307 A CN101555307 A CN 101555307A CN A2009100226153 A CNA2009100226153 A CN A2009100226153A CN 200910022615 A CN200910022615 A CN 200910022615A CN 101555307 A CN101555307 A CN 101555307A
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Abstract
The invention provides a method for synthesizing poly-dicyclopentadiene petroleum resin with adjustable molecular weight, distribution and softening point, which takes commercial grade dicyclopentadiene as raw material, saturated alkane as solvent and mixed monoolefine as molecular weight regulator, and the commercial grade dicyclopentadiene, the saturated alkane and the mixed monoolefine have thermal polymerization for 1-8h under the condition of 160-300 DEG C and 0.1-4MPa; after that, the unreacted monomer and solvent are removed by reduced pressure distillation; finally, the poly-dicyclopentadiene petroleum resin is obtained. The method can regulate the indexes such as molecular weight, softening point and the like by adjusting the adding quantity solvent and mixed monoolefine according to the needs, so as to meet the requirements of different service performances. The poly-dicyclopentadiene petroleum resin prepared by the method has the molecular weight within the range of 200-1800, the molecular weight distribution within the range of 1.5-3.5 and the softening point within the temperature range of 60-180 DEG C, so as to be applicable to the industries such as paint, pressure-sensitive adhesive, hot-melt adhesive, printing ink, etc.
Description
Technical field
The invention belongs to the petrochemical technology field, the synthetic method that relates to a kind of poly-dicyclopentadiene petroleum resin, relate in particular to the synthetic method of a kind of molecular weight and distribution, poly-dicyclopentadiene petroleum resin that softening temperature is adjustable, be mainly used in industries such as can be used for coating, pressure-sensitive adhesive agent, hot-melting type caking agent, printing-ink.
Background technology
The synthetic method of industry PetroChina Company Limited. resin generally is to add a certain amount of cationic catalyst, reacts at a certain temperature, after reaction finishes again through processes such as alkali cleaning neutralization, washings, after underpressure distillation obtains rosin products.Some resin that is used for special dimension also needs through technologies such as hydrogenation decolourings, to reach desired use properties.
Traditional cationoid polymerisation arts demand cationic initiator must be through technologies such as alkali cleaning, washings after the polymerization, the technical process complexity, and contaminated wastewater is arranged, then facility investment is bigger if any adding hydrogen into resin technology.The poly-dicyclopentadiene petroleum resin product softening temperature that general direct heat polymerization obtains is higher, and color is darker relatively, and the use properties of product is relatively poor.
Usually the direct heat polymerization control method of producing the molecular weight of poly-dicyclopentadiene petroleum resin changes thermopolymerization temperature, reaction times etc. for adopting, but that its molecular weight varies with temperature is very big, can not finely tune indexs such as molecular weight, softening temperatures.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of molecular weight and distribution, poly-dicyclopentadiene petroleum resin that softening temperature is adjustable.
The synthetic method of poly-dicyclopentadiene petroleum resin of the present invention is to be raw material with the dicyclopentadiene, is solvent with the saturated alkane, is molecular weight regulator to mix monoolefine, under 160～300 ℃, the condition of 0.1～4MPa, and heat polymerization 1～8 hour; Thermopolymerization obtains poly-dicyclopentadiene petroleum resin after underpressure distillation removes unreacted monomer and solvent.
Described raw material is the commercial grade dicyclopentadiene, and wherein dicyclopentadiene content is 75～99%.
At least a in saturated straight chain alkane, branched paraffin, naphthenic hydrocarbon and the isomers thereof that described solvent saturated alkane is 5～12 carbon atoms is as pentane, pentamethylene, normal heptane, methylcyclopentane, octane-iso, iso-pentane, normal hexane etc.The add-on of solvent is 5～30%, preferred 10～20% of a described dicyclopentadiene raw material volume.
Described molecular weight regulator mixing monoolefine is to be mixed by at least two kinds of monoolefines that contain 5～8 carbon atoms, as instead-2-butylene, suitable-2-butylene, 3-methyl-1-butene, 1-amylene, cyclopentenes, suitable-2 amylenes, 2-methyl-1-butene alkene, 2-methyl-2-butene, 1.4-pentadiene, anti--2 amylenes, tetrahydrobenzene, 1-hexene, 2-methyl isophthalic acid-hexene, 1-heptene, 2-heptene, 2-methyl isophthalic acid-heptene, 1-octene, 2-octene etc.The add-on of molecular weight regulator is 1～20%, preferred 5～15% of a described dicyclopentadiene raw material volume.
The poly-dicyclopentadiene petroleum resin of the present invention preparation can be according to the difference of Application Areas, and product indexs such as its molecular weight and distribution, softening temperature are satisfied different needs by regulating solvent and conditions such as monoolefine additional proportion, heat polymerization temperature.
The molecular weight distribution of poly-dicyclopentadiene petroleum resin of the present invention can be regulated in 1.5～3.5 scopes, molecular weight can be regulated in 200～1800 scopes, softening temperature can be regulated in 60～180 ℃ of scopes, and the product look number is 5～No. 8 looks (Gardner's colourity).The poly-dicyclopentadiene petroleum resin product that makes can be used for industries such as coating, pressure-sensitive adhesive, hot-melting type caking agent, printing-ink.
Through a large amount of experimental results show that, the temperature of described heat polymerization is controlled at 210～270 ℃ scope interior (reaction pressure is produced voluntarily by reaction system), reaction times was controlled in 3～6 hours, and the performance of the poly-dicyclopentadiene petroleum resin of preparation is more superior.
The present invention compared with prior art has the following advantages:
1, the present invention adopts solvent and adds the heat polymerization that a spot of monoolefine carries out dicyclopentadiene petroleum resin, can obtain high-quality product under comparatively gentle reaction conditions; The heat polymerization time is short, can finish in 1～8 hour.
2, conditions such as the additional proportion of the present invention by regulating solvent and monoolefine, heat polymerization temperature are regulated the indexs such as molecular weight, softening temperature, colourity of poly-dicyclopentadiene petroleum resin, satisfy the requirement of its different use propertieies, and effectively reduce product colourity.
3, this technology of the present invention can be used for batch production or serialization production, compares with traditional cationoid polymerisation technology, need can not produce trade effluent with technologies such as the alkali cleaning of traditional cationoid polymerisation technology, washings, helps environmental protection.
4, thermopolymerization of the present invention can be used after wherein adding oxidation inhibitor after underpressure distillation separates the sold resin that obtains behind unreacted monomer and the solvent, can effectively reduce production costs and saves cost of investment.
5, the monoolefine of the present invention's adding has participated in polyreaction, has improved the use properties of product greatly.
6, production technique of the present invention is simple, and solvent that is adopted and monoolefine derive from Chemicals common on the market, and the reaction finish the back easily separated, can effectively reduce production costs.
Embodiment
The invention will be further described below by specific embodiment.
Embodiment 1:
Press in the reactor in 1 rising, the dicyclopentadiene that adds 50 milliliters of pentamethylene, 450ml (purity is 85%), add 30 milliliters of monoolefine mixture (3-methyl-1-butenes: 1-amylene: cyclopentenes volume ratio=1: 1: 1), closed reactor, after high pure nitrogen displacement 3～4 times, slowly be warming up to 240 ℃ of design temperatures, reacted 5 hours after underpressure distillation separates unreacted monomer and solvent, obtain the dicyclopentadiene petroleum resin product, 138 ℃ of softening temperatures, Gardner's colourity 5.5, molecular weight 466, molecular weight distribution 1.5, product yield are 85%.
Embodiment 2:
Press in the reactor in 1 rising, add 50 milliliters of mixed solvent (pentamethylene: octane-iso volume ratio=1: 1), the dicyclopentadiene of 450ml (purity is 85%), add 30 milliliters of monoolefine mixture (3-methyl-1-butenes: 1-amylene: cyclopentenes volume ratio=1: 1: 1), closed reactor, after high pure nitrogen displacement 3～4 times, slowly be warming up to 260 ℃ of design temperatures, reacted 5 hours after underpressure distillation separates unreacted monomer and solvent, obtain the dicyclopentadiene petroleum resin product, 124.5 ℃ of softening temperatures, Gardner's colourity 6.6, molecular weight 691, molecular weight distribution 2.1, product yield are 90%.
Embodiment 3,
Press 50 milliliters of hexanes of adding in the reactor in 1 rising, the dicyclopentadiene of 450ml (purity is 85%), add 50 milliliters of monoolefine mixtures (1-amylene: cyclopentenes: suitable-2 amylenes: 2-methyl-1-butene alkene volume ratio=1: 1: 1: 1), closed reactor, after high pure nitrogen displacement 3～4 times, slowly be warming up to 230 ℃ of design temperatures, reacted 4 hours after underpressure distillation separates unreacted monomer and solvent, obtain the dicyclopentadiene petroleum resin product, 120.4 ℃ of softening temperatures, Gardner's colourity 5.6, molecular weight 385, molecular weight distribution 2.25, product yield is 85%.
Embodiment 4,
Press in the reactor in 1 rising, add 50 milliliters of mixed solvent (hexanes: heptane: octane volume ratio=1: 1: 1), the dicyclopentadiene of 450ml (purity is 85%), add 50 milliliters of monoolefine mixtures (1-amylene: cyclopentenes: suitable-2 amylenes: 2-methyl-1-butene alkene volume ratio=1: 1: 1: 1), closed reactor, after high pure nitrogen displacement 3-4 time, slowly be warming up to 280 ℃ of design temperatures, reacted 8 hours after underpressure distillation separates unreacted monomer and solvent, obtain the dicyclopentadiene petroleum resin product, 180.4 ℃ of softening temperatures, Gardner's colourity 8.1, molecular weight 1271, molecular weight distribution 2.53, product yield are 90%.
Comparative example 1
Press in the reactor in 1 rising, directly add dicyclopentadiene (concentration is 85%) solution 500ml, closed reactor is after high pure nitrogen displacement 3-4 time, slowly be warming up to 250 ℃ of design temperatures, reacted 5 hours after underpressure distillation separates unreacted monomer and solvent, obtain the dicyclopentadiene petroleum resin product, 120.4 ℃ of softening temperatures, Gardner's colourity 7.5, molecular weight 714, molecular weight distribution 2.35, product yield is 89%.
Comparative example 2
Press in the reactor in 1 rising, add 50 milliliters of hexanes, add (purity is 85%) dicyclopentadiene 450ml, closed reactor, after high pure nitrogen displacement 3-4 time, slowly be warming up to 260 ℃ of design temperatures, reacted 5 hours after underpressure distillation separates unreacted monomer and solvent, obtain the dicyclopentadiene petroleum resin product, 142 ℃ of softening temperatures, Gardner's colourity 6.9, molecular weight 752, molecular weight distribution 2.94, product yield are 91%.
From the foregoing description and comparative example, as can be seen, by regulating conditions such as solvent and monoolefine additional proportion, change heat polymerization temperature, can regulate and prepare the poly-dicyclopentadiene petroleum resin of different softening point, molecular weight and molecular weight distribution, to satisfy of the different requirements of different application field to poly-dicyclopentadiene petroleum resin.
Claims (5)
1, a kind of synthetic method of poly-dicyclopentadiene petroleum resin is to be raw material with the dicyclopentadiene, is solvent with the saturated alkane, is molecular weight regulator to mix monoolefine, under 160～300 ℃, the condition of 0.1～4MPa, and heat polymerization 1～8 hour; Thermopolymerization obtains poly-dicyclopentadiene petroleum resin after underpressure distillation removes unreacted monomer and solvent.
2, the synthetic method of poly-dicyclopentadiene petroleum resin according to claim 1, it is characterized in that: described raw material dicyclopentadiene is the commercial grade dicyclopentadiene, wherein dicyclopentadiene content is 75～99%.
3, the synthetic method of poly-dicyclopentadiene petroleum resin according to claim 1, it is characterized in that: at least a in saturated straight chain alkane, branched paraffin, naphthenic hydrocarbon and the isomers thereof that described solvent saturated alkane is 5～12 each carbon atom, its add-on is 5～30% of a described dicyclopentadiene raw material volume.
4, the synthetic method of poly-dicyclopentadiene petroleum resin according to claim 1, it is characterized in that: described molecular weight regulator mixing monoolefine is mixed by at least two kinds of monoolefines that contain 5～8 carbon atoms, and its add-on is 1～20% of a described dicyclopentadiene raw material volume.
5, the synthetic method of poly-dicyclopentadiene petroleum resin according to claim 1, it is characterized in that: the temperature of described heat polymerization is 210～270 ℃, and reaction pressure is produced voluntarily by reaction system, the reaction times is 3～6 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443103A (en) * | 2011-09-16 | 2012-05-09 | 中国海洋石油总公司 | Preparation method of low-chroma high-softening-point dicyclopentadiene petroleum resin |
| CN103360546A (en) * | 2012-03-30 | 2013-10-23 | 青岛伊科思新材料股份有限公司 | Thermal polymerization method of meta-pentadiene petroleum resin |
| CN103724544A (en) * | 2013-12-25 | 2014-04-16 | 陈国兴 | Preparation method of hydrogenated dicyclopentadiene resin |
| CN107434839A (en) * | 2017-05-24 | 2017-12-05 | 淄博鲁华泓锦新材料股份有限公司 | A kind of method of copolymerized petroleum resin based on segmentation thermal polymerization production dicyclopentadiene |
| CN108329429A (en) * | 2018-03-07 | 2018-07-27 | 宁波金海晨光化学股份有限公司 | A kind of continuous method for preparing light dicyclopentadiene petroleum resin |
| CN113025149A (en) * | 2021-03-15 | 2021-06-25 | 上海东杰高分子材料有限公司 | High-molecular copolymer coating and preparation method thereof |
-
2009
- 2009-05-09 CN CNA2009100226153A patent/CN101555307A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443103A (en) * | 2011-09-16 | 2012-05-09 | 中国海洋石油总公司 | Preparation method of low-chroma high-softening-point dicyclopentadiene petroleum resin |
| CN103360546A (en) * | 2012-03-30 | 2013-10-23 | 青岛伊科思新材料股份有限公司 | Thermal polymerization method of meta-pentadiene petroleum resin |
| CN103724544A (en) * | 2013-12-25 | 2014-04-16 | 陈国兴 | Preparation method of hydrogenated dicyclopentadiene resin |
| CN103724544B (en) * | 2013-12-25 | 2016-03-09 | 陈国兴 | The preparation method of hydrogenation dcpd resin |
| CN107434839A (en) * | 2017-05-24 | 2017-12-05 | 淄博鲁华泓锦新材料股份有限公司 | A kind of method of copolymerized petroleum resin based on segmentation thermal polymerization production dicyclopentadiene |
| CN108329429A (en) * | 2018-03-07 | 2018-07-27 | 宁波金海晨光化学股份有限公司 | A kind of continuous method for preparing light dicyclopentadiene petroleum resin |
| CN108329429B (en) * | 2018-03-07 | 2020-08-21 | 宁波金海晨光化学股份有限公司 | Method for continuously preparing light-colored dicyclopentadiene petroleum resin |
| CN113025149A (en) * | 2021-03-15 | 2021-06-25 | 上海东杰高分子材料有限公司 | High-molecular copolymer coating and preparation method thereof |
| WO2022193321A1 (en) * | 2021-03-15 | 2022-09-22 | 上海东杰高分子材料有限公司 | High-molecular copolymer coating and preparation method therefor |
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