CN112079958A - Preparation method of carbon-five copolymerized petroleum resin - Google Patents
Preparation method of carbon-five copolymerized petroleum resin Download PDFInfo
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- CN112079958A CN112079958A CN201910506165.9A CN201910506165A CN112079958A CN 112079958 A CN112079958 A CN 112079958A CN 201910506165 A CN201910506165 A CN 201910506165A CN 112079958 A CN112079958 A CN 112079958A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
- C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
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Abstract
The invention relates to the technical field of organic synthesis, in particular to a preparation method of carbon-five copolymerized petroleum resin. The method specifically comprises the following steps: c5 raw material pretreatment, polymerization, washing, atmospheric distillation, vacuum distillation and granulation. The carbon-five copolymerized petroleum resin prepared by the steps of the invention has the advantages of simple process, energy saving, controllable reaction, higher economic benefit and suitability for industrial production; the obtained product has light color, higher softening point and better compatibility.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of carbon-five copolymerized petroleum resin.
Background
Cationic polymerization of mixtures of unsaturated olefins is the theoretical basis for the manufacture of petroleum resins. The main active fractions participating in the cationic polymerization reaction in the C5 fraction include diolefins such as piperylene, isoprene and (di) cyclopentadiene, and monoolefins such as cyclopentene and methylbutene, which also participate in partial reaction. In terms of activity, the diolefins are greater than the monoolefins, and the order of activity is as follows: cyclopentadiene-isoprene-piperylene >1, 3-butadiene > 2-pentene > 2-methylbutene-1 > 1-pentene, cyclopentene. The C5 resin is the product of a multiple copolymerization reaction. The basic skeleton of the polymer molecular chain is composed of structural units formed by diolefin with higher content and more active reaction activity, and the monoolefine with lower reaction activity is partially embedded into the polymer chain. Generally, the synthesized product of raw materials with higher piperylene content and lower isoprene and (di) cyclopentadiene content has better quality. The high content of isoprene causes the solubility compatibility of petroleum resin to be poor and the molecular weight is not easy to control. Dicyclopentadiene mainly affects the hue and transparency of the resin. Cyclopentadiene in C5 generally forms a large amount of gel in the presence of a catalyst, deactivating the catalyst, terminating chain growth, decreasing resin yield, and the gel is black, deteriorating the hue of the resin.
The composition of the C5 feedstock directly affects the polymerization reaction and the quality of the resin product. The C5 petroleum resin directly prepared by using the untreated C5 raw material has lower softening point and color difference. The resins obtained from the hot polymer had a relatively high softening point but poor hue. When the content of DCPD in the raw material is high, the hue of the resin is also adversely affected and the resin is odorized.
Finally, improving the compatibility, viscosity increasing property and the like of the C5 petroleum resin with other polymers and expanding the application field of the C5 petroleum resin are one of the improvement purposes of the synthetic method of the C5 petroleum resin.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of carbon-five copolymerized petroleum resin, the method has simple process and low production cost, and the obtained petroleum resin has high yield, light hue, higher and adjustable softening point, controllable reaction, good compatibility and unexpected good effect. The specific scheme is as follows:
a preparation method of carbon five copolymerized petroleum resin comprises the following steps:
1) c5 raw material pretreatment: c5 raw material is thermally polymerized for 2-3 hours at 120 ℃, and the fraction of the thermally polymerized material is distilled to cut off less than 70 ℃ to be used as the polymerized material A; mixing the raw material A and styrene according to the mass ratio of 1: 0.05-0.25 to obtain a polymerization raw material B;
2) polymerization reaction: stirring and reacting a polymerization raw material B, an organic solvent and an aluminum trichloride complex catalyst at the temperature of 30-50 ℃ for 1-3 hours to obtain a polymerization solution, wherein the amount of the organic solvent is 30-50% of the mass of the raw material B, and the mass ratio of the aluminum trichloride complex catalyst to the polymerization raw material A is 1-3%;
3) washing: washing the polymerization solution obtained in the step 2) with alkali, and washing with clear water to neutrality;
4) atmospheric distillation: removing unreacted components and a solvent from the resin liquid obtained in the step 3) in a normal pressure distillation tower, wherein the temperature of a tower kettle is 100-200 ℃, and obtaining the resin liquid containing petroleum resin, oligomers and a small amount of solvent at the bottom of the tower;
5) reduced pressure distillation and granulation: and (3) distilling the resin liquid obtained in the step 4) in a scraper film evaporator under reduced pressure, heating to 220-300 ℃ and controlling the vacuum degree to 0.080-0.099 Mpa, and then granulating to obtain the copolycarbonate-penta petroleum resin.
Preferably, the raw material components of C5 are as follows: 1.30 wt% of 1, 3-butadiene, 2.12 wt% of 1, 4-pentadiene, 3.72 wt% of pentene-1, 5.47 wt% of 2-methyl-1-butene, 22.45 wt% of isoprene, 4.29 wt% of pentene-2, 2.86 wt% of 2-methyl-2-butene, 15.55 wt% of piperylene, 12.41 wt% of cyclopentadiene, 3.88 wt% of cyclopentene, 8.90 wt% of dicyclopentadiene, 1.10 wt% of rest dimer, and the rest is a mixture of aliphatic hydrocarbons of C4-C6; the dimer refers to a substance resulting from the polymerization of two olefin molecules.
The polymerization raw material A comprises the following components: 1.48 wt% of 1, 3-butadiene, 2.85 wt% of 1, 4-pentadiene, 5.00 wt% of pentene-1, 7.48 wt% of 2-methyl-1-butene, 27.04 wt% of isoprene, 5.67 wt% of pentene-2, 3.78 wt% of 2-methyl-2-butene, 18.76 wt% of piperylene, 0.63 wt% of cyclopentadiene, 4.82 wt% of cyclopentene, 0.78 wt% of dicyclopentadiene, and the balance of a mixture of aliphatic hydrocarbons of C4-C6.
Preferably, the mass ratio of the raw material A to the styrene in the step 1) is 1: 0.05-0.15.
Preferably, the organic solvent in step 2) is toluene or xylene.
Preferably, the reaction temperature in the step 2) is 30-40 ℃.
Preferably, the aluminum trichloride complex catalyst in the step 2) comprises the following components by mass: 20-50% of aluminum trichloride; 10-30% of ethylbenzene; 20-60% of dimethylbenzene; 1-10% of acetic anhydride.
Preferably, the aluminum trichloride complex catalyst in the step 2) comprises the following components by mass: 30-45% of aluminum trichloride; 15-20% of ethylbenzene; 30-50% of dimethylbenzene; 3-6% of acetic anhydride.
Preferably, the alkali used for the alkali washing in the step 3) is 5-10 wt% of NaOH solution or NH3And (4) OH solution.
Preferably, the alkali used in the alkali washing in the step 3) is 5-10 wt% of NaOH solution.
Preferably, the temperature of the tower kettle in the step 4) is 120-160 ℃; or the heating temperature in the step 5) is 260-290 ℃, and the vacuum degree is 0.096-0.098 Mpa.
The invention has the following beneficial effects:
(1) the preparation method has the advantages of simple process, energy conservation, controllable reaction, higher economic benefit and suitability for industrial production;
(2) the invention can prepare resin products with lighter color by using the aluminum trichloride complex catalyst, wherein the Gardner chroma is less than or equal to 4#, and the resin yield is more than or equal to 50%;
(3) the aim of adjusting the softening point is achieved by adjusting the mass ratio of the styrene to the decyclization C5 raw material, so that the softening point of the resin is adjusted within 65-95 ℃ as required;
(4) in the preparation process, benzene rings are introduced into the molecules of the carbon five petroleum resin, so that the polarity of aliphatic resin chain segments is enhanced, and the compatibility of the aliphatic resin with EVA, SIS, rubber and the like is improved.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
Pretreatment of raw materials
The decyclization C5 fraction is obtained by cracking C5 raw material, thermally polymerizing at 120 deg.C for 2-3 hours and distilling to cut off the fraction below 70 deg.C, the compositions of C5 raw material, thermally polymerizing A raw material and polymerizing B raw material are shown in tables 1, 2 and 3 respectively.
TABLE 1 analytical data for the C5 feedstock used in step 1)
TABLE 2 analytical data for typical thermal polymer materials
TABLE 3 analytical data for typical decyclization C5 material
Preparation of aluminium trichloride complex catalyst
50g of ethylbenzene, 120g of xylene and 10g of acetic anhydride were charged to the reaction vessel. Under the stirring state and the protection of nitrogen, adding 100g of anhydrous aluminum trichloride into a reaction kettle in batches at 90-100 ℃ until solid aluminum trichloride is completely dissolved, and discharging under the protection of nitrogen to obtain the aluminum trichloride complex catalyst.
Aluminum trichloride complex catalyst for preparing carbon-five copolymerized petroleum resin
The aluminum trichloride complex catalyst obtained above is adopted to carry out polymerization reaction, and the polymerization process is as follows: 500g of cyclopentadiene C5-removed fraction of less than 70 ℃, comonomer styrene and solvent benzene (the dosage of the solvent benzene is 50% of the cyclopentadiene C5-removed fraction of less than 70 ℃) are added into a polymerization kettle, aluminum trichloride complex catalyst is slowly added under stirring, the polymerization temperature is 30-50 ℃, the polymerization time is 1-3 hours, the polymerization solution is washed by alkali with 10 wt% of NaOH solution and washed by water for multiple times until the polymerization solution is neutral, then the distillation is carried out under normal pressure and reduced pressure, the distillate at the top of the tower is unreacted components, solvent and oligomer, and petroleum resin is obtained at the bottom of the kettle.
The analysis of the resins produced by the above process, with the shift in reaction temperature, catalyst and styrene amounts, gives the following results:
table 4 summary of the effects of aluminum trichloride complex catalyst on carbon five petroleum resin
Note: the catalyst (calculated by aluminum trichloride) and the styrene are used in percentage by mass of the addition amount of the C5 fraction.
The comparative example was carried out under otherwise unchanged polymerization conditions except that anhydrous aluminum trichloride was used instead of the complex catalyst of the present invention.
As can be seen from the test result data and comparative example test result data in Table 4, the resin product with adjustable softening point and light color can be prepared by using the aluminum trichloride complex catalyst, and the resin has high yield and unexpected good effect.
Although the embodiments of the present invention have been described in detail with reference to the examples, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the claims. Those skilled in the art can appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and the modified embodiments are also clearly included in the scope of the present invention.
Claims (10)
1. The preparation method of the carbon-five copolymerized petroleum resin is characterized by comprising the following steps of:
1) c5 raw material pretreatment: thermally polymerizing the C5 raw material at 115-125 ℃ for 2-3 hours, distilling the thermally polymerized material to cut a fraction of less than 70 ℃ to obtain a polymerized material A; mixing the raw material A and styrene according to the mass ratio of 1: 0.05-0.25 to obtain a polymerization raw material B;
2) polymerization reaction: stirring and reacting a polymerization raw material B, an organic solvent and an aluminum trichloride complex catalyst at the temperature of 30-50 ℃ for 1-3 hours to obtain a polymerization solution, wherein the amount of the organic solvent is 30-50% of the mass of the raw material B, and the mass ratio of the aluminum trichloride complex catalyst to the polymerization raw material A is 1-3%;
3) washing: washing the polymerization solution obtained in the step 2) with alkali, and washing with clear water to neutrality;
4) atmospheric distillation: removing unreacted components and a solvent from the resin liquid obtained in the step 3) in a normal pressure distillation tower, wherein the temperature of a tower kettle is 100-200 ℃, and a mixed liquid containing petroleum resin is obtained at the bottom of the tower;
5) reduced pressure distillation and granulation: and (3) distilling the resin liquid obtained in the step 4) in a scraper film evaporator under reduced pressure, heating to 220-300 ℃ and controlling the vacuum degree to 0.080-0.099 Mpa, and then granulating to obtain the copolycarbonate-penta petroleum resin.
2. The method for preparing the carbon-five copolymerized petroleum resin as claimed in claim 1, wherein the C5 raw material comprises the following components: 1.30 wt% of 1, 3-butadiene, 2.12 wt% of 1, 4-pentadiene, 3.72 wt% of pentene-1, 5.47 wt% of 2-methyl-1-butene, 22.45 wt% of isoprene, 4.29 wt% of pentene-2, 2.86 wt% of 2-methyl-2-butene, 15.55 wt% of piperylene, 12.41 wt% of cyclopentadiene, 3.88 wt% of cyclopentene, 8.90 wt% of dicyclopentadiene, 1.10 wt% of rest dimer, and the rest is a mixture of aliphatic hydrocarbons of C4-C6;
the polymerization raw material A comprises the following components: 1.48 wt% of 1, 3-butadiene, 2.85 wt% of 1, 4-pentadiene, 5.00 wt% of pentene-1, 7.48 wt% of 2-methyl-1-butene, 27.04 wt% of isoprene, 5.67 wt% of pentene-2, 3.78 wt% of 2-methyl-2-butene, 18.76 wt% of piperylene, 0.63 wt% of cyclopentadiene, 4.82 wt% of cyclopentene, 0.78 wt% of dicyclopentadiene, and the balance of a mixture of aliphatic hydrocarbons of C4-C6.
3. The method for preparing a carbon-five copolymerized petroleum resin according to claim 1, wherein the mass ratio of the raw material A to the styrene in the step 1) is 1: 0.05-0.15.
4. The method for preparing a carbon-five copolymerized petroleum resin according to claim 1, wherein the organic solvent in the step 2) is toluene or xylene.
5. The method for preparing a carbon-five copolymerized petroleum resin according to claim 1, wherein the reaction temperature in the step 2) is 30 to 40 ℃.
6. The method for preparing the carbon-five copolymerized petroleum resin according to claim 1, wherein the aluminum trichloride complex catalyst in the step 2) comprises the following components by mass: 20-50% of aluminum trichloride; 10-30% of ethylbenzene; 20-60% of dimethylbenzene; 1-10% of acetic anhydride.
7. The method for preparing the carbon-five copolymerized petroleum resin according to claim 1, wherein the aluminum trichloride complex catalyst in the step 2) comprises the following components by mass: 30-45% of aluminum trichloride; 15-20% of ethylbenzene; 30-50% of dimethylbenzene; 3-6% of acetic anhydride.
8. The method for preparing carbon-five copolymerized petroleum resin as claimed in claim 1, wherein the alkali used in the alkali washing in step 3) is 5-10 wt% NaOH solution or NH3And (4) OH solution.
9. The method for preparing carbon-five copolymerized petroleum resin according to claim 8, wherein the alkali used in the alkali washing in the step 3) is 5-10 wt% NaOH solution.
10. The method for preparing the carbon-five copolymerized petroleum resin as claimed in claim 1, wherein the temperature of the tower kettle in the step 4) is 120-160 ℃; or the heating temperature in the step 5) is 260-290 ℃, and the vacuum degree is 0.096-0.098 Mpa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812233A (en) * | 2021-01-08 | 2021-05-18 | 淄博鲁华泓锦新材料股份有限公司 | Continuous production process of carbon five-resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112812233A (en) * | 2021-01-08 | 2021-05-18 | 淄博鲁华泓锦新材料股份有限公司 | Continuous production process of carbon five-resin |
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Application publication date: 20201215 |