CN109337012B - Preparation method of phenol modified copolymerized petroleum resin - Google Patents
Preparation method of phenol modified copolymerized petroleum resin Download PDFInfo
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- CN109337012B CN109337012B CN201811014230.8A CN201811014230A CN109337012B CN 109337012 B CN109337012 B CN 109337012B CN 201811014230 A CN201811014230 A CN 201811014230A CN 109337012 B CN109337012 B CN 109337012B
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- 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
- C08F8/00—Chemical modification by after-treatment
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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 a preparation method of phenol modified copolymerized petroleum resin, which comprises the following steps: mixing the C10 fraction A with a phenolic monomer and C5-C10 monoolefine to obtain a polymerization raw material B, adding a solvent into a reaction kettle with a stirrer, then simultaneously adding the polymerization raw material and a Friedel-Crafts catalyst, reacting to obtain a polymerization solution, and carrying out aftertreatment to obtain the phenol modified copolymerized petroleum resin. The modified copolymerized petroleum resin has light color, low leaching amount, stronger polymer polarity and good compatibility with ink, NBR rubber, CR rubber and the like, and is very suitable for the fields of rubber mixing, color printing and the like.
Description
Technical Field
The invention belongs to the field of petroleum resin, and particularly relates to a preparation method of phenol modified copolymerized petroleum resin.
Background
The petroleum resin is a solid or viscous liquid medium-low relative molecular weight polymer obtained by catalytic polymerization or free radical polymerization of byproducts C5, C9 fractions and the like of an ethylene device serving as main raw materials. The monomers and molecular structures constituting the resin can be roughly classified into aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, and the like.
The ethylene byproduct C10 fraction, namely C10 raffinate oil, is obtained by cracking naphthalene fraction and extracting naphthalene, wherein the naphthalene fraction contains Indene (Indene), Methyl Indene (Methyl-Indene), Methyl Styrene (Methyl-Styrene), naphthalene, Methyl naphthalene and other aromatic hydrocarbon monomers suitable for synthesis, and the aromatic hydrocarbon monomers all contain large conjugated electron cloud structures and are easy to copolymerize with certain monomers with electrophilic groups; in addition, the aromatic ring is also an ideal electrophilic substitution reaction substrate, and various polar groups are easily introduced to the aromatic ring for chemical modification.
Petroleum resins generally belong to the group of weakly polar resins, with aromatic petroleum resins being slightly more polar than aliphatic and cycloaliphatic resins. Some studies have been made to enhance the polarity of petroleum resins by introducing acid anhydrides, etc., such as JP1987212411, JP1992063822, JP1998195189, etc., to introduce carboxylic acid groups into the terminal groups of resin molecules to improve compatibility or oil resistance, etc., so that they are suitable for the fields of ink printing, coatings, electronics, etc. US4603186 provides a method for preparing a low intrinsic viscosity acrylonitrile-methyl methacrylate-methylstyrene/styrene-indene tetrapolymer, which is prepared to obtain a water-soluble resin with strong polarity. CN101649579 discloses a method for preparing a cationic polymer-based petroleum resin neutral sizing agent by using styrene, acrylate monomers, cationic monomers and the like as copolymerization raw materials and modifying with Maleic Anhydride (MAH). US5457175 discloses a low softening point terpene-phenol resin useful in the adhesive and ink fields.
How to improve the polarity of petroleum resin to improve the compatibility with ink pigments and polar rubbers such as nitrile rubber NBR, chloroprene rubber CR and the like, and improving the oil resistance, the wear resistance and the like are difficult points of the industry all the time, and the application of the resin in the fields of high-grade rubber modification, printing and the like is limited; meanwhile, color inks, rubber innertube, and the like require petroleum resins with extremely light color numbers and extremely low volatile contents.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of phenol modified copolymerized petroleum resin, the modified copolymerized petroleum resin prepared by the method has light color, low leaching amount, stronger polymer polarity and good compatibility with ink, NBR rubber, CR rubber and the like, and is very suitable for the fields of rubber mixing, color printing and the like.
The invention provides a preparation method of phenol modified copolymerized petroleum resin, which comprises the following steps:
(1) carrying out reduced pressure rectification on a raw material of an ethylene byproduct C10 to obtain a C10 fraction A with a boiling point of 160-210 ℃, and mixing the C10 fraction A with a phenolic monomer and C5-C10 monoolefine according to a mass ratio of 1 (0.01-0.3) to (0-0.5) to obtain a polymerization raw material B;
(2) adding a solvent accounting for 30-60 wt% of the total material into a reaction kettle with a stirrer, then simultaneously adding a polymerization raw material B and a Friedel-Crafts catalyst, reacting at-20-30 ℃ for 1.5-3 h, heating to 30-55 ℃, and reacting for 1-3 h while keeping the temperature to obtain a polymerization solution;
(3) washing the polymerization solution with alkali, and then washing to neutrality to obtain a resin solution (milky white to light yellow); then the resin liquid is rectified under reduced pressure to obtain the phenol modified copolymerized petroleum resin.
The components of the C10 fraction A in the step (1) comprise: 5-25 wt% of methyl styrene, 5-50 wt% of indene, 5-50 wt% of methyl indene, 0-2 wt% of dicyclopentadiene and the balance of saturated aromatic hydrocarbon components of C8-C10.
The phenolic monomer in the step (1) is one or more of phenol, cresol, hydroquinone, p-tert-butylphenol PTBP, 2-tert-butylcresol and benzenetriol.
The C5-C10 monoolefin in the step (1) is one of isoamylene, cyclopentene, 1-pentene, vinyl cyclohexene VCH, alpha-pinene, beta-pinene and limonene.
The solvent in the step (2) is one of tetrahydroindene, indane, hexahydroindane and tetrahydronaphthalene, or a saturated aromatic hydrocarbon mixture with a boiling point of 80-200 ℃, such as benzene, toluene, xylene and trimethylbenzene.
The Friedel-Crafts catalyst in the step (2) is one of gaseous boron trifluoride and boron trifluoride complex; the adding amount of the catalyst is 0.1-3 wt% of the total material.
The boron trifluoride complex is boron trifluoride diethyl etherate or boron trifluoride dibutyl ether.
The alkali washing in the step (3) is specifically alkali washing by using a 5 wt% NaOH aqueous solution at 30-90 ℃.
The process parameters of the vacuum rectification in the step (3) are as follows: the pressure is-0.085 to-0.095 MPa, and the temperature is 240 to 300 ℃.
The softening point of the phenol modified copolymerized petroleum resin in the step (3) is 80-130 ℃, the Gardner color number is less than or equal to 6#, and the hydroxyl equivalent (M)E) 200 to 8000g/eq and less than or equal to 2.0 wt% of volatile components.
Polymers can be classified as polar and non-polar, but the classification of such polymers is general and not easily defined; in general, nonpolar polymers are polymers whose dipole moment is zero, corresponding to dipole moments > 0 Cm being polar polymers. The petroleum resins prepared by the traditional process are all weak and extremely weakThe polar polymer has poor compatibility with polar rubber and printing ink according to a similar compatibility principle, so the invention provides a method for preparing the strong-polarity petroleum resin. The polarity of the polymer can be obtained by calculating dipole moment theory or measuring solubility parameters by a solution method, and the methods are complicated and are not beneficial to experiment and production; therefore, the hydroxyl equivalent (M) of the modified petroleum resin is measured in the inventionE) Denotes its polarity, MEA larger value indicates a weaker polarity of the corresponding polymer.
The elution amount of the rubber gasket is an important index for evaluating the tackifying modified resin, is closely related to the content of small molecular substances in the resin, and the elution performance of the tackifying modified resin is judged by measuring the volatile component of the modified petroleum resin at high temperature.
Advantageous effects
(1) According to the invention, the C10 component, the phenolic monomer and the monoolefine are subjected to catalytic reaction by a Friedel-Crafts catalyst to obtain the modified copolymerized petroleum resin with relatively high polarity, and the modified copolymerized petroleum resin has excellent compatibility with polar rubber, ink and the like;
(2) by adjusting the ratio of the modified monomer to the C10 polymerizable component in the raw materials, the softening point, color number and hydroxyl equivalent M of the resin can be adjusted as requiredEThe performance is equal, so that the material has wide application fields;
(3) the invention has simple and convenient process, and the prepared modified copolymerized petroleum resin has very low volatile component, excellent rubber anti-dissolution performance and is very suitable for being applied to the fields of rubber mixing, color printing and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The typical composition of the ethylene by-product C10 feed and the C10 fraction A obtained by vacuum distillation as described in the examples is as follows:
typical composition of C10 raw Material and fraction A, wt.%
| Components | C10 raw material | C10 fraction A |
| Styrene (meth) acrylic acid ester | 2.5 | 0.1 |
| Xylene | 3.0 | 2.0 |
| Methyl styrene | 13.0 | 18.0 |
| Trimethylbenzene | 7.0 | 15.0 |
| Dicyclopentadiene | 0.5 | 1.0 |
| Indene | 16.0 | 28.0 |
| Methyl indene | 18.0 | 35.0 |
| Naphthalene | 11.0 | 0.1 |
| The rest components | 29.0 | 0.8 |
Examples 1 to 6
Using C10 fraction A, p-tert-butylphenol PTBP and isoamylene as raw materials, indan as solvent and gaseous BF3The phenol modified petroleum resin was prepared for the catalyst, with the solvent accounting for 50 wt% of the total mass of the material and the catalyst amount accounting for 0.3 wt% of the total mass of the material.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Fraction A ratio of C10 | 1 | 1 | 1 | 1 | 1 | 1 |
| PTBP ratio | 0.05 | 0.05 | 0.1 | 0.1 | 0.2 | 0.2 |
| Isoamylene ratio | 0 | 0.25 | 0.25 | 0.5 | 0.25 | 0.5 |
| Yield, wt.% | 38.2 | 35.5 | 35.0 | 33.3 | 32.0 | 31.6 |
| Softening point, DEG C | 122.0 | 115.0 | 104.5 | 90.5 | 94.0 | 87.5 |
| Color number, # | 3 | 2 | 4 | 4 | 6 | 5 |
| ME，g/eq | 5715.47 | 5880.24 | 2721.30 | 2625.02 | 1043.59 | 1102.44 |
The reaction temperature is-10 ℃, the reaction time is 2h, the heat preservation temperature is 45 ℃, and the heat preservation time is 2 h; the resin liquid is rectified under reduced pressure at-0.085 MPa and 280 deg.C.
As can be seen from the above table, in the modified petroleum resin polymerization raw material ratio, as the PTBP content increases, the softening point of the resin decreases, and the hydroxyl equivalent METhe resin polarity increases with decreasing, but the resin color becomes darker. The content of isoamylene in the ingredients is increased, the softening point and the color number of the resin can be reduced, but for METhe influence is not great.
Example 7
Mixing C10 fraction A, phenol and vinyl cyclohexene VCH according to the mass ratio of 1:0.15:0.5 to obtain a polymerization raw material B, adding a mixed xylene solvent accounting for 40 wt% of the total material mass into a reaction kettle with a stirrer, then simultaneously adding the polymerization raw material B and a boron trifluoride diethyl etherate catalyst accounting for 1.2 wt% of the total material, reacting for 1.5h at 0 ℃, then heating to 50 ℃, and carrying out heat preservation reaction for 2h to obtain a polymerization liquid. The polymerization solution is washed by alkali with 5 wt% NaOH aqueous solution at the temperature of 70 ℃, and then washed by clean water to be neutralPerforming vacuum rectification on the resin liquid at-0.090 MPa and 290 ℃ to obtain a resin liquid with a softening point of 91.4 ℃, a Gardner color number of 5# and a hydroxyl equivalent (M)E) 1450.26g/eq and volatile matter less than or equal to 1.0 wt%.
Example 8
Mixing the C10 fraction A, benzenetriol and limonene according to the mass ratio of 1:0.3:0.4 to obtain a polymerization raw material B, adding a mixed xylene solvent accounting for 40 wt% of the total mass of the materials into a reaction kettle with a stirrer, then simultaneously adding the polymerization raw material B and a gaseous boron trifluoride catalyst accounting for 0.5 wt% of the total mass of the materials, reacting for 1.5h at 10 ℃, then heating to 55 ℃, and carrying out heat preservation reaction for 2h to obtain a polymerization liquid. The polymerization solution is alkali-washed by 5 wt% NaOH aqueous solution at the temperature of 90 ℃, then washed by clean water to be neutral to obtain light yellow resin solution, and then the resin solution is decompressed and rectified at the temperature of 280 ℃ under the pressure of-0.090 MPa to obtain the resin solution with the softening point of 88.8 ℃, the Gardner color number of 6# and the hydroxyl equivalent (M)E) 475.40g/eq and volatile matter less than or equal to 1.5 wt%.
Examples 9 to 12
Using C10 fraction A, p-tert-butylphenol PTBP and alpha-pinene as raw materials, hexahydroindane as solvent and gaseous BF3The phenol modified petroleum resin was prepared for the catalyst, with the solvent accounting for 50 wt% of the total mass of the material and the catalyst amount accounting for 0.3 wt% of the total mass of the material.
| Example 9 | Example 10 | Example 11 | Example 12 | |
| Fraction A ratio of C10 | 1 | 1 | 1 | 1 |
| PTBP ratio | 0.1 | 0.1 | 0.2 | 0.2 |
| Alpha-pinene ratio | 0.25 | 0.5 | 0.25 | 0.5 |
| Yield, wt.% | 36.0 | 34.7 | 30.8 | 28.8 |
| Softening point, DEG C | 107.4 | 93.6 | 97.5 | 82.0 |
| Color number, # | 4 | 4 | 5 | 5 |
| ME，g/eq | 2015.41 | 1948.66 | 878.95 | 789.10 |
The reaction temperature is-10 ℃, the reaction time is 2h, the heat preservation temperature is 45 ℃, and the heat preservation time is 2 h; the resin liquid is rectified under reduced pressure at-0.085 MPa and 280 deg.C.
As can be seen from the above table, when pinene is used as the monoolefin raw material, the resin softening point and color number adjusting effect are similar to those of C5 monoolefin, but the obtained modified copolymerized petroleum resin has obviously increased polarity strength and hydroxyl equivalent MERelatively decreases.
Example 13
After the catalyst is removed by alkali washing and water washing, the volatile content of the petroleum resin can be controlled by different rectification decompression conditions.
As can be seen from the above table, the volatile components of the petroleum resin can be reduced by reducing the pressure of the vacuum rectification and increasing the temperature; in order to control the smell of the resin, the volatile component is less than or equal to 2.0, and the rectification decompression operation parameters are preferably as follows: the pressure is-0.085 to-0.095 MPa, and the temperature is 240 to 300 ℃.
Claims (8)
1. A method for preparing a phenol-modified copolymerized petroleum resin, comprising:
(1) carrying out reduced pressure rectification on a raw material of an ethylene byproduct C10 to obtain a C10 fraction A with a boiling point of 160-210 ℃, and mixing the C10 fraction A with a phenolic monomer and alpha-pinene or limonene according to a mass ratio of 1 (0.01-0.3) to (0-0.5) to obtain a polymerization raw material B; wherein the addition amount of the alpha-pinene or the limonene is not 0;
(2) adding a solvent accounting for 30-60 wt% of the total material into a reaction kettle with a stirrer, then simultaneously adding a polymerization raw material B and a Friedel-Crafts catalyst, reacting at-20-30 ℃ for 1.5-3 h, heating to 30-55 ℃, and reacting for 1-3 h while keeping the temperature to obtain a polymerization solution;
(3) washing the polymerization solution with alkali, and then washing to neutrality to obtain a resin solution; then the resin liquid is rectified under reduced pressure to obtain the phenol modified copolymerized petroleum resin.
2. The method for producing a phenol-modified copolymerized petroleum resin according to claim 1, wherein: the components of the C10 fraction A in the step (1) comprise: 5-25 wt% of methyl styrene, 5-50 wt% of indene, 5-50 wt% of methyl indene, 0-2 wt% of dicyclopentadiene and the balance of saturated aromatic hydrocarbon components of C8-C10.
3. The method for producing a phenol-modified copolymerized petroleum resin according to claim 1, wherein: the phenolic monomer in the step (1) is one or more of phenol, cresol, hydroquinone, p-tert-butylphenol PTBP, 2-tert-butylcresol and benzenetriol.
4. The method for producing a phenol-modified copolymerized petroleum resin according to claim 1, wherein: the solvent in the step (2) is one of tetrahydroindene, indane, hexahydroindane and tetrahydronaphthalene, or a saturated aromatic hydrocarbon mixture with a boiling point of 80-200 ℃.
5. The method for producing a phenol-modified copolymerized petroleum resin according to claim 1, wherein: the Friedel-Crafts catalyst in the step (2) is one of gaseous boron trifluoride and boron trifluoride complex; the adding amount of the catalyst is 0.1-3 wt% of the total material.
6. The method for producing a phenol-modified copolymerized petroleum resin according to claim 5, wherein: the boron trifluoride complex is boron trifluoride diethyl etherate or boron trifluoride dibutyl ether.
7. The method for producing a phenol-modified copolymerized petroleum resin according to claim 1, wherein: the alkali washing in the step (3) is specifically alkali washing by using a 5 wt% NaOH aqueous solution at 30-90 ℃.
8. The method for producing a phenol-modified copolymerized petroleum resin according to claim 1, wherein: the process parameters of the vacuum rectification in the step (3) are as follows: the pressure is-0.085 to-0.095 MPa, and the temperature is 240 to 300 ℃.
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| CN112063100A (en) * | 2020-09-14 | 2020-12-11 | 江苏麒祥高新材料有限公司 | Modified resin liquid and preparation method thereof |
| CN114702611B (en) * | 2022-05-18 | 2024-01-02 | 江苏麒祥高新材料有限公司 | Anti-wet-skid resin and preparation method and application thereof |
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