CN102443103A - 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; Preparing method for a kind of low colourity high softening-point dicyclopentadiene petroleum resin.
Background technology
Most petroleum resin products prepare through cationic polymerization; This polyreaction needs cationic catalyst to can be good at disperseing; Otherwise possibly produce gel and cause polymerization product performance heterogeneity; Post-reaction treatment technical process simultaneously is complicated, needs alkali cleaning neutralization, washing, underpressure distillation/stripping, drying and other steps just can obtain the finished product.The alkali cleaning washing not only need consume a large amount of water in last handling process; Bring environmental pollution problems, in the alkali cleaning water washing process, also possibly 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 NSC 7352 is 75～99% in the polymer raw; With alkane is solvent; To mix monoolefine is molecular weight regulator, through additional proportion, the hot polymerization temperature of reaction of solvent and monoolefine the softening temperature and the molecular weight of dicyclopentadiene petroleum resin is 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 NSC 7352, 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 NSC 7352 or NSC 7352 and vinylaromatic hydrocarbon hot polymerization to prepare petroleum resin, the solvent that wherein reacts as hot polymerization with straight-chain paraffin or aromatic hydrocarbon.This reaction need not add the Friedel-Crafts catalyzer, need not remove the technological process of catalyzer, simultaneously, if when needing the hydrogenation resin of light color more, 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 the requirement of some field to the high softening-point petroleum resin equally, and the transformation efficiency of polyreaction is not high simultaneously.The method for preparing dicyclopentadiene petroleum resin of US5379239 report is similar with US5502140; Utilize highly purified NSC 7352 or NSC 7352 and vinylaromatic hydrocarbon; With the straight-chain paraffin is solvent hot polymerization prepared in reaction dicyclopentadiene petroleum resin, and the petroleum resin products softening temperature that makes of this method has much room for improvement equally.
Summary of the invention
To the deficiency of 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 the dicyclopentadiene petroleum resin product that the polymerization yield is high, colourity is low, softening temperature is high, 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:
With the commercial grade NSC 7352 is raw material, is solvent with the perhydronaphthalene, under 180～300 ℃, 1.0～3.0MPa condition, and heat polymerization 6～20 hours; Hot polymerization reaction obtains dicyclopentadiene petroleum resin after remove unreacted monomer, solvent and oligopolymer after the underpressure distillation.The present invention can be through regulating the dicyclopentadiene petroleum resin that solvent and NSC 7352 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 a perhydronaphthalene, and the ratio of solvent and NSC 7352 is 1: 0.5～1: 5.
Concrete steps comprise:
1) reaction raw materials for preparing is pressed into by storage tank in the reaction kettle that has stirring with nitrogen, nitrogen replacement three times is to get rid of the influence of oxygen to the hot polymerization reaction;
2) open reaction kettle 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 NSC 7352 is: 1: 0.5～1: 3; Original pressure in the reaction kettle is 0.1～2.0MPa;
2) open reaction kettle 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 finds through experiment, selects suitable reaction solvent and NSC 7352 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 finds that through experiment 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 the appropriate reaction solvent and the rational proportion of NSC 7352 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.Dicyclopentadiene petroleum resin that in the hot polymerization reaction process, obtains and solvent have good consistency, make the polymerization process petroleum resin not have deposited phenomenon, and polymerization process is a homogeneous reaction system.Gained petroleum resin colourity low softening point is high, and the petroleum resin yield of this method is high simultaneously, calculates the resin yield with the monomeric amount of dicyclo amylene.
Embodiment
Specify the present invention with specific embodiment below, but embodiment does not limit the scope of the invention.
Embodiment 1:
Press in the reaction kettle in 5 risings, add 800g perhydronaphthalene, 1200g NSC 7352 (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 NSC 7352 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 reaction kettle in 5 risings, add 1200g perhydronaphthalene, 800g NSC 7352 (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 NSC 7352 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 reaction kettle in 5 risings, add 1000g perhydronaphthalene, 1000g NSC 7352 (purity＞87%), the confined reaction system; More than three times or three times, be warmed up to 275 ℃ of temperature of reaction with nitrogen replacement gradually, unreacted NSC 7352 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 are 8.3, product yield 91%.
Embodiment 4:
Press in the reaction kettle in 5 risings; Add 1000g perhydronaphthalene, 1000g NSC 7352 (purity＞87%), the confined reaction system is with nitrogen replacement more than three times or three times; Be warmed up to 240 ℃ of temperature of reaction gradually; Reaction under this temperature 2.0MPa after 20 hours underpressure distillation remove unreacted NSC 7352 monomer, reaction solvent and oligopolymer, 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 reaction kettle, add 600g perhydronaphthalene, 1400g NSC 7352 (purity＞87%), the confined reaction system in 5 risings; More than three times or three times, be warmed up to 255 ℃ of temperature of reaction with nitrogen replacement gradually, unreacted NSC 7352 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 reaction kettle in 5 risings, add 500g perhydronaphthalene, 1500g NSC 7352 (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 NSC 7352 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 reaction kettle in 5 risings; Add 800g solvent oil D40,1200g NSC 7352 (purity＞87%), the confined reaction system is with nitrogen replacement more than three times or three times; Be warmed up to 240 ℃ of temperature of reaction gradually; Reaction under this temperature 2.0MPa after 8 hours underpressure distillation remove unreacted NSC 7352 monomer, solvent oil D40 and oligopolymer, 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 reaction kettle, add 600g toluene, 1400g NSC 7352 (purity＞87%), the confined reaction system in 5 risings; More than three times or three times, be warmed up to 250 ℃ of temperature of reaction with nitrogen replacement gradually, unreacted NSC 7352 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 the foregoing description and comparative example, can find out; Through selecting suitable reaction solvent; Conditions such as the ratio of change NSC 7352 and reaction solvent, change hot polymerization temperature of reaction; The dicyclopentadiene petroleum resin that can prepare low colourity high softening-point is to satisfy the demand of different field to the 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:
With the NSC 7352 is raw material, is solvent with the perhydronaphthalene, under 180～300 ℃, 1.0～3.0MPa condition, and heat polymerization 6～20 hours; Hot polymerization reaction obtains dicyclopentadiene petroleum resin after remove unreacted monomer, solvent and oligopolymer after the underpressure distillation;
Solvent for use is a perhydronaphthalene, and the ratio of solvent and NSC 7352 is 1: 0.5～1: 5;
Concrete steps comprise:
1) reaction raw materials for preparing is pressed into by storage tank in the reaction kettle that has stirring with nitrogen, nitrogen replacement three times is to get rid of the influence of oxygen to the hot polymerization reaction;
2) open reaction kettle 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;
Through regulating the dicyclopentadiene petroleum resin that solvent and NSC 7352 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 NSC 7352 is: 1: 0.5～1: 3; Original pressure in the reaction kettle is 0.1～2.0MPa;
2) open reaction kettle 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788617A (en) * | 2015-04-09 | 2015-07-22 | 沈阳 | Method for reducing color number of cyclopentadiene petroleum resin |
| 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 |
| CN110204657A (en) * | 2019-06-18 | 2019-09-06 | 安徽同心新材料科技有限公司 | Light number a kind of, high softening-point C9 hot polymerization petroleum resin products and preparation process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61143413A (en) * | 1984-12-15 | 1986-07-01 | Maruzen Sekiyu Kagaku Kk | Production of dicyclopentadiene-based petroleum resin |
| 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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2011
- 2011-09-16 CN CN 201110274729 patent/CN102443103B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61143413A (en) * | 1984-12-15 | 1986-07-01 | Maruzen Sekiyu Kagaku Kk | Production of dicyclopentadiene-based petroleum resin |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788617A (en) * | 2015-04-09 | 2015-07-22 | 沈阳 | Method for reducing color number of cyclopentadiene petroleum resin |
| 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 |
| CN110204657A (en) * | 2019-06-18 | 2019-09-06 | 安徽同心新材料科技有限公司 | Light number a kind of, high softening-point C9 hot polymerization petroleum resin products and preparation process |
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