CN102443103B - Preparation method of low-chroma high-softening-point dicyclopentadiene petroleum resin - Google Patents
Preparation method of low-chroma high-softening-point dicyclopentadiene petroleum resin Download PDFInfo
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Abstract
The invention discloses a preparation method of low-chroma high-softening-point dicyclopentadiene petroleum resin. The method is characterized by comprising the following steps of: undergoing a thermal polymerization reaction under the condition that dicyclopentadiene is taken as a raw material, decahydronaphthalene is taken as a solvent, the ratio of the solvent to the dicyclopentadiene is 1:5, the temperature is 180-300 DEG C and the pressure is 1.0-3.0 MPa for 6-20 hours; and after the polymerization reaction, distilling under reduced pressure and removing unreacted monomers, solvents and low polymers to obtain the dicyclopentadiene petroleum resin.
Description
Technical field
The present invention relates to the petroleum resin technology of preparing; Preparation method for a kind of low colourity high softening-point dicyclopentadiene petroleum resin.
Background technology
Most petroleum resin products prepare by cationic polymerization, this polyreaction needs cationic catalyst to can be good at disperseing, otherwise may produce gel and cause polymerization product performance heterogeneity, post-reaction treatment technical process complexity needs alkali cleaning neutralization, washing, underpressure distillation/stripping, drying and other steps just can obtain the finished product simultaneously.The alkali cleaning washing not only needs to consume a large amount of water in last handling process, bring environmental pollution problems, in the alkali cleaning water washing process, also may have the emulsification situation simultaneously, make the catalyst removal difficulty strengthen, even remove not thorough, unfavorable to product performance and follow-up hydrogenation technology.
In general petroleum resin products, colourity can be deepened thereupon when obtaining than high softening-point, and darker colourity has limited the use of petroleum resin in some field, for the petroleum resin products that obtains low colourity need be carried out the hydrogenation modifying process process, but this technological process can reduce the softening temperature of petroleum resin again to a certain extent, and there is certain contradiction in both.
CN101555307A has announced a kind of preparation method of dicyclopentadiene petroleum resin, the content of dicyclopentadiene is 75～99% in the polymer raw, be solvent with alkane, be molecular weight regulator to mix monoolefine, by additional proportion, the hot polymerization temperature of reaction of solvent and monoolefine softening temperature and the molecular weight of dicyclopentadiene petroleum resin finely tuned.This method can be produced the rosin products of different demands, but the petroleum resin softening temperature of preparation when higher color darker, Ghana's colourity is greater than 8.0.
CN101613438A discloses a kind of preparation method who utilizes m-pentadiene modified dicyclopentadiene petroleum resin, regulates the ratio of m-pentadiene and dicyclopentadiene, is the Preparation of Catalyst petroleum resin with the aluminum trichloride (anhydrous).The colourity of gained resin is more shallow, but catalyzer remove the problem of remaining, and the softening temperature of gained petroleum resin declines to a great extent.
US5502140 discloses and has utilized dicyclopentadiene or dicyclopentadiene and vinylaromatic hydrocarbon hot polymerization to prepare petroleum resin, wherein the solvent that reacts as hot polymerization with straight-chain paraffin or aromatic hydrocarbon.This reaction does not need to add the Friedel-Crafts catalyzer, does not need to remove the technological process of catalyzer, simultaneously, if when needing lighter hydrogenation resin, does not have the introducing of catalyst for polymerization, can not produce the follow-up hydrogenation catalyzer and poison.But the dicyclopentadiene petroleum resin softening temperature of this method preparation is not high, can't satisfy some field equally to the requirement of high softening-point petroleum resin, and the transformation efficiency of polyreaction is not high simultaneously.The method for preparing dicyclopentadiene petroleum resin of US5379239 report is similar to US5502140, utilize highly purified dicyclopentadiene or dicyclopentadiene and vinylaromatic hydrocarbon, be solvent hot polymerization prepared in reaction dicyclopentadiene petroleum resin with the straight-chain paraffin, the petroleum resin products softening temperature that makes of this method has much room for improvement equally.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of preparation method of low colourity high softening-point dicyclopentadiene petroleum resin.Its objective is to obtain polymerization yield height, colourity is low, softening temperature is high dicyclopentadiene petroleum resin product, and have good economy and environmental benefit.Solve the dark and not high problem of softening temperature under the low or low colourity of softening temperature of existing dicyclopentadiene petroleum resin form and aspect.
The present invention is a kind of preparation method of low colourity high softening-point dicyclopentadiene petroleum resin, it is characterized in that:
Being raw material with the commercial grade dicyclopentadiene, is solvent with the perhydronaphthalene, under 180～300 ℃, 1.0～3.0MPa condition, and heat polymerization 6～20 hours; The hot polymerization reaction obtains dicyclopentadiene petroleum resin by removing unreacted monomer, solvent and oligopolymer after the underpressure distillation.The present invention can be by regulating the dicyclopentadiene petroleum resin that solvent and dicyclopentadiene ratio, temperature of reaction, reaction times prepare low colourity high softening-point, and the softening temperature of the dicyclopentadiene petroleum resin of preparation is at 110～250 ℃, and Ghana's colourity is less than 5.
Solvent for use is perhydronaphthalene, and the ratio of solvent and dicyclopentadiene is 1: 0.5～1: 5.
Concrete steps comprise:
1) reaction raw materials for preparing is pressed into by storage tank in the reactor that has stirring with nitrogen, nitrogen replacement three times is to get rid of oxygen to the influence of hot polymerization reaction;
2) open reactor and stir, under 180～300 ℃, 1.0～4.0MPa condition, heat polymerization 6～20 hours;
3) hot polymerization reaction finishes the back underpressure distillation and removes unreacted monomer, solvent and oligopolymer, and vacuum negative pressure is-0.01～-0.09MPa, only steam to dripless;
4) at vacuum drying oven in 120～180 ℃, vacuum-drying 5～12 hours drops to room temperature and gets dicyclopentadiene petroleum resin.
According to preparation method of the present invention, it is characterized in that: concrete steps are:
1) ratio of solvent and dicyclopentadiene is: 1: 0.5～1: 3; Original pressure in the reactor is 0.1～2.0MPa;
2) open reactor and stir, under 200～280 ℃, 1.0～3.0MPa condition, heat polymerization 6～12 hours;
3) hot polymerization reaction finishes the back underpressure distillation and removes unreacted monomer and solvent, and vacuum negative pressure is-0.05～-0.09MPa, only steam to dripless;
4) at vacuum drying oven in 140～180 ℃, vacuum-drying 5～10 hours drops to room temperature and gets dicyclopentadiene petroleum resin.
The present invention found through experiments, and selects suitable reaction solvent and dicyclopentadiene and solvent ratios to keep the performance of homogeneous reaction system and petroleum resin that material impact is arranged to polymerization process.
The present invention found through experiments, and polymeric reaction temperature and reaction times softening temperature and the colourity to the gained petroleum resin has direct relation.
The invention has the beneficial effects as follows: the present invention has selected appropriate reaction solvent and the rational proportion of dicyclopentadiene thereof, and polymeric reaction temperature and reaction times have been carried out rational control, the contriver finds that this petroleum resin preparation process is easy to implement, has environment friendly.The dicyclopentadiene petroleum resin that obtains in the hot polymerization reaction process and solvent have good consistency, make the polymerization process petroleum resin not have deposited phenomenon, and polymerization process is homogeneous reaction system.Gained petroleum resin colourity low softening point height, the petroleum resin yield height of this method calculates the resin yield with the amount of dicyclo amylene monomer simultaneously.
Embodiment
Describe the present invention in detail with specific embodiment below, but embodiment does not limit the scope of the invention.
Embodiment 1:
Press in the reactor in 5 risings, add 800g perhydronaphthalene, 1200g dicyclopentadiene (purity＞87%), the confined reaction system, more than three times or three times, be warmed up to 240 ℃ of temperature of reaction with nitrogen replacement gradually, unreacted dicyclopentadiene monomer, toluene and oligopolymer are removed in underpressure distillation after reacting 8 hours under this temperature 2.0MPa, 150 ℃ ,-the 0.1MPa negative pressure under dry 8 hours the dicyclopentadiene petroleum resin product, 143 ℃ of softening temperatures, Ghana's colourity are 4.1, product yield 87%.
Embodiment 2:
Press in the reactor in 5 risings, add 1200g perhydronaphthalene, 800g dicyclopentadiene (purity＞87%), the confined reaction system, more than three times or three times, be warmed up to 240 ℃ of temperature of reaction with nitrogen replacement gradually, unreacted dicyclopentadiene monomer, reaction solvent and oligopolymer are removed in underpressure distillation after reacting 8 hours under this temperature 2.0MPa, 150 ℃ ,-the 0.1MPa negative pressure under dry 8 hours the dicyclopentadiene petroleum resin product, 122 ℃ of softening temperatures, Ghana's colourity are 3.6, product yield 75%.
Embodiment 3:
Press in the reactor in 5 risings, add 1000g perhydronaphthalene, 1000g dicyclopentadiene (purity＞87%), the confined reaction system, with nitrogen replacement more than three times or three times, be warmed up to 275 ℃ of temperature of reaction gradually, unreacted dicyclopentadiene monomer, reaction solvent and oligopolymer are removed in underpressure distillation after reacting 8 hours under this temperature 2.0MPa, 150 ℃ ,-the 0.1MPa negative pressure under dry 8 hours the dicyclopentadiene petroleum resin product, 180 ℃ of softening temperatures, Ghana's colourity is 8.3, product yield 91%.
Embodiment 4:
Press in the reactor in 5 risings, add 1000g perhydronaphthalene, 1000g dicyclopentadiene (purity＞87%), the confined reaction system, with nitrogen replacement more than three times or three times, be warmed up to 240 ℃ of temperature of reaction gradually, unreacted dicyclopentadiene monomer, reaction solvent and oligopolymer are removed in underpressure distillation after reacting 20 hours under this temperature 2.0MPa, 150 ℃ ,-the 0.1MPa negative pressure under dry 8 hours the dicyclopentadiene petroleum resin product, 178 ℃ of softening temperatures, Ghana's colourity is 7.8, product yield 89%.
Embodiment 5:
Pressing in the reactor in 5 risings, add 600g perhydronaphthalene, 1400g dicyclopentadiene (purity＞87%), the confined reaction system, more than three times or three times, be warmed up to 255 ℃ of temperature of reaction with nitrogen replacement gradually, unreacted dicyclopentadiene monomer, perhydronaphthalene and oligopolymer are removed in underpressure distillation after reacting 8 hours under this temperature 2.0MPa, 150 ℃ ,-the 0.1MPa negative pressure under dry 8 hours the dicyclopentadiene petroleum resin product, 142 ℃ of softening temperatures, Ghana's colourity are 3.6, product yield 85%
Embodiment 6:
Press in the reactor in 5 risings, add 500g perhydronaphthalene, 1500g dicyclopentadiene (purity＞87%), the confined reaction system, more than three times or three times, be warmed up to 265 ℃ of temperature of reaction with nitrogen replacement gradually, unreacted dicyclopentadiene monomer, reaction solvent and oligopolymer are removed in underpressure distillation after reacting 8 hours under this temperature 2.0MPa, 150 ℃ ,-the 0.1MPa negative pressure under dry 8 hours the dicyclopentadiene petroleum resin product, 183 ℃ of softening temperatures, Ghana's colourity are 3.9, product yield 93%.
Comparative example 1:
Press in the reactor in 5 risings, add 800g solvent oil D40,1200g dicyclopentadiene (purity＞87%), the confined reaction system, with nitrogen replacement more than three times or three times, be warmed up to 240 ℃ of temperature of reaction gradually, unreacted dicyclopentadiene monomer, solvent oil D40 and oligopolymer are removed in underpressure distillation after reacting 8 hours under this temperature 2.0MPa, 150 ℃ ,-the 0.1MPa negative pressure under dry 8 hours the dicyclopentadiene petroleum resin product, 133 ℃ of softening temperatures, Ghana's colourity is 4.5, product yield 76%.
Comparative example 2:
Pressing in the reactor in 5 risings, add 600g toluene, 1400g dicyclopentadiene (purity＞87%), the confined reaction system, more than three times or three times, be warmed up to 250 ℃ of temperature of reaction with nitrogen replacement gradually, unreacted dicyclopentadiene monomer, reaction solvent and oligopolymer are removed in underpressure distillation after reacting 8 hours under this temperature 2.0MPa, 150 ℃ ,-the 0.1MPa negative pressure under dry 8 hours the dicyclopentadiene petroleum resin product, 147 ℃ of softening temperatures, Ghana's colourity are 7.6, product yield 83%.
From above-described embodiment and comparative example as can be seen, by selecting suitable reaction solvent, conditions such as the ratio of change dicyclopentadiene and reaction solvent, change hot polymerization temperature of reaction, the dicyclopentadiene petroleum resin that can prepare low colourity high softening-point is to satisfy different field to the demand of high softening-point petroleum resin.
Claims (2)
1. the preparation method of one kind low colourity high softening-point dicyclopentadiene petroleum resin is characterized in that:
Being raw material with the dicyclopentadiene, is solvent with the perhydronaphthalene, under 180～300 ℃, 1.0～3.0MPa condition, and heat polymerization 6～20 hours; The hot polymerization reaction obtains dicyclopentadiene petroleum resin by removing unreacted monomer, solvent and oligopolymer after the underpressure distillation;
Solvent for use is perhydronaphthalene, and the ratio of solvent and dicyclopentadiene is 1: 0.5～1: 5;
Concrete steps comprise:
1) reaction raw materials for preparing is pressed into by storage tank in the reactor that has stirring with nitrogen, nitrogen replacement three times is to get rid of oxygen to the influence of hot polymerization reaction;
2) open reactor and stir, under 180～300 ℃, 1.0～3.0MPa condition, heat polymerization 6～20 hours;
3) hot polymerization reaction finishes the back underpressure distillation and removes unreacted monomer, solvent and oligopolymer, and vacuum negative pressure is-0.01～-0.09MPa, only steam to dripless;
4) at vacuum drying oven in 120～180 ℃, vacuum-drying 5～12 hours drops to room temperature and gets dicyclopentadiene petroleum resin;
By regulating the dicyclopentadiene petroleum resin that solvent and dicyclopentadiene ratio, temperature of reaction, reaction times prepare low colourity high softening-point, the softening temperature of the dicyclopentadiene petroleum resin of preparation is at 110～250 ℃, and Ghana's colourity is less than 5.
2. according to the described preparation method of claim 1, it is characterized in that: concrete steps are:
1) ratio of solvent and dicyclopentadiene is: 1: 0.5～1: 3; Original pressure in the reactor is 0.1～2.0MPa;
2) open reactor and stir, under 200～280 ℃, 1.0～3.0MPa condition, heat polymerization 6～12 hours;
3) hot polymerization reaction finishes the back underpressure distillation and removes unreacted monomer and solvent, and vacuum negative pressure is-0.05～-0.09MPa, only steam to dripless;
4) at vacuum drying oven in 140～180 ℃, vacuum-drying 5～10 hours drops to room temperature and gets dicyclopentadiene petroleum resin.
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| CN104788617B (en) * | 2015-04-09 | 2018-06-22 | 沈阳 | A kind of method for reducing cyclopentadiene petroleum resin color number |
| CN106749918A (en) * | 2016-12-27 | 2017-05-31 | 宁波金海晨光化学股份有限公司 | The preparation method of dicyclopentadiene petroleum resin |
| CN110204657B (en) * | 2019-06-18 | 2022-07-19 | 安徽同心新材料科技有限公司 | Light-color C9 heat-polymerized petroleum resin product with high softening point and preparation process thereof |
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| US5410004A (en) * | 1994-01-24 | 1995-04-25 | Arizona Chemical Company | Thermal polymerization of dicyclopentadiene |
| CN101555307A (en) * | 2009-05-09 | 2009-10-14 | 中国石油兰州石油化工公司 | Method for synthesizing poly-dicyclopentadiene petroleum resin with adjustable molecular weight, distribution and softening point |
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