CN113087845B - Preparation method of long-chain olefin modified C9 petroleum resin - Google Patents
Preparation method of long-chain olefin modified C9 petroleum resin Download PDFInfo
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Abstract
The invention relates to the field of petroleum resin, and particularly discloses a preparation method of long-chain olefin modified C9 petroleum resin. Specifically, in the presence of a catalyst and an inert solvent and under an inert atmosphere, the C9 fraction and the long-chain olefin undergo a cationic polymerization reaction to obtain a crude product of the long-chain olefin modified C9 petroleum resin. The invention has mild polymerization conditions, utilizes the structural characteristics of long-chain olefin as long-chain monoolefin, has the property of chain transfer, and adjusts the molecular weight and the crosslinking degree of resin, thereby improving the molecular weight distribution of resin products, having the molecular weight distribution of 1.3-1.6, finally improving the compatibility with elastomers, and expanding the application range of the products in adhesives. The invention adopts long-chain olefin for product modification, and compared with the modification processes of piperylene, rosin and the like, the long-chain olefin has the advantages of low cost and price of raw materials and economic advantage; compared with the maleic anhydride modification process, the raw material long-chain olefin is liquid, so that the operation is easy, and the workload of workers is reduced; in addition, the long-chain olefin does not react with sodium hydroxide, so that the oily sewage is less generated, and the sewage treatment cost is reduced.
Description
Technical Field
The invention relates to the field of petroleum resin, in particular to a preparation method of long-chain olefin modified C9 petroleum resin.
Background
The C9 petroleum resin is prepared by polymerizing active components with double bonds such as methyl styrene, dicyclopentadiene, indene, methyl indene and the like in the ethylene byproduct C9 fraction by cationic polymerization reaction in the presence of a Lewis acid catalyst. The C9 petroleum resin is widely applied to the industries of paint, printing ink, adhesive and the like.
In recent years, the market demand of domestic petroleum resins is rapidly increasing, and particularly the annual demand of a large amount of petroleum resins used in various fields such as rubber processing, paint coating, printing ink, adhesive and the like is remarkably increased, but compared with petroleum resins produced abroad, the petroleum resins produced at home have single domestic variety and type, lower product quality level, more product cross-linking structure and large molecular weight distribution, seriously affect the compatibility of the products and Elastomers (EVA), and greatly restrict the application of the products in the adhesive.
At present, the modification method of C9 petroleum resin mainly comprises blending modification, modified monomers mainly comprise maleic anhydride, itaconic acid, amide, esters and the like, and the aim of improving the compatibility of the petroleum resin is achieved by introducing a new functional molecular chain. For example, CN20111011655.0 and CN1813008A introduce a method for preparing maleic anhydride grafted petroleum resin by heating and dissolving petroleum resin and maleic anhydride, the compatibility of the petroleum resin in an elastomer can be improved to a certain extent by using the method, but the molecular weight of the resin cannot be adjusted to reduce the cross-linking structure in the resin, the purpose of improving the viscosity of an adhesive cannot be achieved, in addition, the resin is easy to darken in the thermal polymerization process, the application of the product in sanitary products and environment-friendly products cannot be met, and the application range of the product is reduced.
CN200410056912.7 discloses a method for obtaining C9 petroleum resin by using maleic anhydride as a polymerization raw material and catalyzing C9 fractions with boron trifluoride diethyl etherate, but the maleic anhydride is easy to react with sodium hydroxide, so that not only is the ash content of the product influenced, but also oily wastewater is generated, and the sewage treatment cost is increased.
Zhang Kun et al disclose a method for modifying C9 petroleum resin with rosin in CN106967201, wang Bin et al disclose a method for improving compatibility of petroleum resin with tetrahydroindene modified C9 petroleum resin in CN107325228, but the modifier used in the method is expensive in raw material cost.
Disclosure of Invention
The invention provides a preparation method of long-chain olefin modified C9 petroleum resin, and the C9 petroleum resin prepared by the method has narrower molecular weight distribution and excellent compatibility with EVA.
The purpose of the invention is realized by the following technical scheme:
in the presence of a catalyst and an inert solvent and under an inert atmosphere, a C9 fraction and long-chain olefin undergo a cationic polymerization reaction to obtain a crude product of the long-chain olefin modified C9 petroleum resin.
The dosage of the long-chain olefin is 5-20% of the mass fraction of the C9 fraction.
The long-chain olefin is one or the combination of two of isomeric dodecene and isomeric hexadecene. The isomeric dodecene is tetrapropylene or trimerized isobutene. The isomeric hexadecene is a tetrameric isobutene body.
The catalyst is a Friedel-Crafts catalyst, and comprises boron trifluoride diethyl etherate or aluminum trichloride. The amount of the Friedel-Crafts catalyst is 0.2-1.5% of the mass fraction of the C9 fraction.
The using amount of the inert solvent is 20-200% of the mass fraction of the C9 fraction. The inert solvent is toluene, xylene or cyclohexane. The C9 fraction comprises the following components in percentage by mass: 10-40% of methyl styrene, 1-10% of dicyclopentadiene, 5-25% of indene and 15-45% of methyl indene.
The inert atmosphere is nitrogen, and other inert gases can also be used.
The reaction temperature of the cationic polymerization reaction is 10-50 ℃, and the reaction time is 1-6h.
The method also comprises the step of purifying the obtained crude long-chain olefin modified C9 petroleum resin, and specifically, after the obtained crude long-chain olefin modified C9 petroleum resin is subjected to alkali washing and water washing, the crude long-chain olefin modified C9 petroleum resin is subjected to reduced pressure distillation to obtain the purified long-chain olefin modified C9 petroleum resin. Wherein, the reduced pressure distillation pressure is-0.08 to-0.1 Mpa, and the distillation temperature is 220 to 250 ℃.
The alkali liquor for alkali washing is a sodium hydroxide or potassium hydroxide aqueous solution, the alkali liquor is an aqueous solution with the solid alkali content of 2-5% by mass fraction, and the molar weight of the solid alkali is larger than that of a Friedel-Crafts catalyst.
The invention also aims to provide the long-chain olefin modified C9 petroleum resin prepared by the preparation method, wherein the molecular weight distribution of the long-chain olefin modified C9 petroleum resin is 1.3-1.6.
The invention has the beneficial effects that:
(1) The invention has mild polymerization conditions, utilizes the structural characteristics of long-chain olefin as long-chain mono-olefin, has the property of chain transfer, and adjusts the molecular weight and the crosslinking degree of resin, thereby improving the molecular weight distribution of resin products, having the molecular weight distribution of 1.3-1.6, finally improving the compatibility with elastomers and expanding the application range of the products in adhesives.
(2) Compared with the maleic anhydride modification process, the long-chain olefin serving as the raw material is liquid, so that the operation is easy, and the workload of workers is reduced; in addition, the long-chain olefin does not react with sodium hydroxide, so that less oily sewage is generated, and the sewage treatment cost is reduced.
(3) The invention adopts long-chain olefin to modify products, compared with modification processes such as pentadiene, rosin and the like, the price of raw materials is low, and the invention has more obvious economic advantages.
Detailed Description
The following embodiments are given as examples of the present invention, and are not intended to limit the present invention in any way, and it will be understood by those skilled in the art that the present invention may be embodied in many forms without departing from the spirit and scope of the present invention.
The test method of each index in the invention comprises the following steps:
softening point: the measurement is carried out according to the ring and ball method specified in the GB/t2294-2019 standard.
Weight average molecular weight and molecular weight distribution: the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were determined by gel permeation chromatography analysis, and the molecular weight distribution was represented by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
Compatibility (cloud point): taking the weight of 1:1, respectively, mixing the resin with EVA with the content of 28%, heating until the mixture is clear, cooling, and observing the turbidity temperature. The lower the haze point temperature, the better the compatibility of the resin and the EVA.
In the present invention, all parts and percentages (%) are by mass unless otherwise specified.
In the invention, the long-chain olefin is one or the combination of two of isomeric dodecene and isomeric hexadecene. The isomeric dodecenes may be tetrapropylene or trimerized isobutylene. The isomeric hexadecene is an isobutylene tetramer.
Example 1
(1) Adding 100g of dimethylbenzene into a reaction kettle with a stirrer, adding 100g of C9 fraction and 5g of isododecene (tetrapropylene), controlling the temperature of reaction materials to be 20 ℃, slowly dropwise adding a boron trifluoride ether complex catalyst with 1.5 mass percent of C9 fraction into the reaction kettle at a constant speed within 10min, reacting for 3h, and using nitrogen for protection in the process to obtain dodecene modified C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 3 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then distilling the resin liquid under reduced pressure of-0.09 Mpa to 230 ℃ to remove oligomers to obtain the dodecene modified C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the other.
The softening point of the dodecene modified C9 petroleum resin is measured to be 128 ℃, the weight average molecular weight is 2875, the molecular weight distribution is 1.57, and the haze point is measured to be 145 ℃.
Example 2
(1) Adding 50g of dimethylbenzene into a reaction kettle with a stirrer, adding 100g of C9 fraction and 10g of isomeric dodecene (trimeric isobutylene), controlling the temperature of reaction materials to 10 ℃, slowly dropwise adding a boron trifluoride ether complex catalyst with 0.8 mass percent of C9 fraction into the reaction kettle at a constant speed within 10min, reacting for 3h, and protecting with nitrogen in the reaction process to obtain dodecene modified C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 3 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under the pressure of-0.1 Mpa to 240 ℃ to remove oligomers to obtain the dodecene modified C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the other.
The softening point of the dodecene modified C9 petroleum resin is 120 ℃, the weight average molecular weight is 2160, the molecular weight distribution is 1.38, and the fog point is 137 ℃.
Example 3
(1) Adding 100g of toluene into a reaction kettle with a stirrer, adding 100g of C9 fraction and 15g of isomeric hexadecene, controlling the temperature of reaction materials to 30 ℃, slowly dropwise adding a boron trifluoride ether complex catalyst with 0.8 mass percent of C9 fraction into the reaction kettle at a constant speed within 10min, reacting for 2h, and using nitrogen for protection in the reaction process to obtain the hexadecene modified C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with concentration of 5% to the reaction kettle to remove the catalyst, washing with distilled water to neutrality to obtain a light yellow clear resin solution, and then distilling under reduced pressure of-0.1 MPa to 235 ℃ to remove oligomers to obtain the hexadecene modified C9 petroleum resin.
The C9 fraction contained: 25% of methyl styrene, 3% of dicyclopentadiene, 20.5% of indene, 25.5% of methyl indene and 26% of the rest.
The softening point of the hexadecene modified C9 petroleum resin is 118 ℃, the weight-average molecular weight is 2057, the molecular weight distribution is 1.37, and the fog point is 127 ℃.
Example 4
(1) Adding 200g of toluene into a reaction kettle with a stirrer, adding 100g of C9 fraction and 10g of isomeric dodecene (trimeric isobutene), controlling the temperature of the reaction materials to 40 ℃, slowly adding an aluminum trichloride catalyst with 0.2 mass percent of C9 fraction into the reaction kettle, reacting for 6 hours, and using nitrogen for protection in the reaction process to obtain dodecene modified C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 2 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under-0.08 Mpa to 240 ℃ to remove oligomers to obtain the dodecene modified C9 petroleum resin.
The C9 fraction contained: 25% of methyl styrene, 3% of dicyclopentadiene, 20.5% of indene, 25.5% of methyl indene and 26% of the rest.
The softening point of the dodecene modified C9 petroleum resin is 123 ℃, the weight average molecular weight is 2257, the molecular weight distribution is 1.40, and the haze point is 146 ℃.
Comparative example 1
(1) Adding 100g of dimethylbenzene into a reaction kettle with a stirrer, then adding 100g of C9 fraction, controlling the temperature of reaction materials to be 20 ℃, slowly dropwise adding boron trifluoride diethyl etherate catalyst with 1.5% mass fraction of C9 fraction into the reaction kettle at a constant speed, reacting for 3 hours, and using nitrogen for protection in the process to obtain C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 5 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under the pressure of-0.1 Mpa to 230 ℃ to remove oligomers to obtain the C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the rest.
The C9 petroleum resin softening point was found to be 142 ℃, the weight average molecular weight was 4218, the molecular weight distribution was 2.21, and the haze point was 215 ℃.
Comparative example 2
(1) Adding 100g of dimethylbenzene into a reaction kettle with a stirrer, adding 100g of C9 fraction, controlling the temperature of reaction materials to be 10 ℃, slowly dripping boron trifluoride diethyl etherate complex catalyst with the mass fraction of 0.8% of reaction raw materials into the reaction kettle at a constant speed, reacting for 3 hours, and using nitrogen for protection in the reaction process to obtain C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 3 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under the pressure of-0.08 Mpa to 240 ℃ to remove oligomers to obtain the C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the other.
The softening point of the C9 petroleum resin was found to be 135 ℃, the weight average molecular weight was found to be 3860, the molecular weight distribution was found to be 2.16, and the haze point was found to be 202 ℃.
Comparative example 3
(1) Adding 100g of dimethylbenzene into a reaction kettle with a stirrer, adding 100g of C9 fraction, controlling the temperature of reaction materials to be 30 ℃, slowly dropwise adding a boron trifluoride diethyl etherate complex catalyst with 0.3% mass fraction of the C9 fraction into the reaction kettle at a constant speed, reacting for 2 hours, and protecting with nitrogen in the reaction process to obtain the C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 2 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under-0.09 Mpa to 220 ℃ to remove oligomers to obtain the C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the rest.
The C9 petroleum resin softening point was 137 ℃, the weight average molecular weight was 3957, the molecular weight distribution was 2.18, and the haze point was 208 ℃.
Claims (9)
1. A preparation method of long-chain olefin modified C9 petroleum resin is characterized in that in the presence of a catalyst and an inert solvent and under an inert atmosphere, C9 fraction and long-chain olefin undergo a cationic polymerization reaction to obtain a crude product of the long-chain olefin modified C9 petroleum resin; the dosage of the long-chain olefin is 5-20% of the mass fraction of the C9 fraction; the long-chain olefin is one or the combination of two of isomeric dodecene and isomeric hexadecene.
2. The method for preparing a long-chain olefin modified C9 petroleum resin according to claim 1, wherein the catalyst is a Friedel-Crafts catalyst and is used in an amount of 0.2 to 1.5% by mass of the C9 fraction.
3. The method for preparing a long-chain olefin modified C9 petroleum resin according to claim 2, wherein the Friedel-Crafts catalyst is boron trifluoride diethyl etherate or aluminum trichloride.
4. The method for preparing a long-chain olefin modified C9 petroleum resin as claimed in claim 1, wherein the amount of the inert solvent is 20-200% by mass of the C9 fraction.
5. The method for preparing a long-chain olefin modified C9 petroleum resin as claimed in claim 1, wherein the inert solvent is toluene, xylene or cyclohexane.
6. The method for producing a long-chain olefin-modified C9 petroleum resin according to claim 1, wherein the inert atmosphere is nitrogen.
7. The method for preparing a long-chain olefin modified C9 petroleum resin as claimed in claim 1, wherein the reaction temperature of the cationic polymerization is 10-50 ℃ and the reaction time is 1-6h.
8. The method for preparing a long-chain olefin modified C9 petroleum resin according to any one of claims 1 to 7, wherein the purified long-chain olefin modified C9 petroleum resin is obtained by subjecting the crude long-chain olefin modified C9 petroleum resin to alkali washing, water washing and reduced pressure distillation.
9. The long-chain olefin-modified C9 petroleum resin produced by the production process according to any one of claims 1 to 8, characterized in that it has a molecular weight distribution of 1.3 to 1.6.
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| CN115746187B (en) * | 2022-11-29 | 2023-11-14 | 广东新华粤树脂科技有限公司 | C9 petroleum resin modifier for adhesive, preparation method and application thereof |
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| JPS53146792A (en) * | 1977-05-27 | 1978-12-20 | Toyo Soda Mfg Co Ltd | Production of petroleum resin |
| CN100513528C (en) * | 2006-08-30 | 2009-07-15 | 中国石油兰州石油化工公司 | Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof |
| CN102643389B (en) * | 2011-02-22 | 2013-11-06 | 中国石油天然气股份有限公司 | Preparation method of high-softening-point petroleum resin |
| TW201402802A (en) * | 2012-07-05 | 2014-01-16 | Cpc Corp Taiwan | A method is provided for preparing hydrogenated C5 aliphatic petroleum resins by adopting C5 aliphatic petroleum resins as feed and was prepared by |
| CN105254808A (en) * | 2015-09-30 | 2016-01-20 | 宁波职业技术学院 | Method for preparing modified petroleum resin |
| CN105175634A (en) * | 2015-09-30 | 2015-12-23 | 宁波职业技术学院 | Preparation method of modified C5 petroleum resin |
| CN109280128A (en) * | 2018-09-21 | 2019-01-29 | 安徽同心化工有限公司 | A kind of C5 petroleum resin products and its controllable preparation method of molecular weight |
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