CN113087845A - 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 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. 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 and methyl indene in the by-product C9 fraction of ethylene by cationic polymerization reaction in the presence of Lewis acid catalyst. The C9 petroleum resin is widely used in 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 describe a method for preparing maleic anhydride grafted petroleum resin by heating and dissolving petroleum resin and maleic anhydride, the compatibility of 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 crosslinking structure in the resin, the purpose of improving the viscosity retention 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 hygienic products and environment-friendly products cannot be met, and the application range of the product is narrowed.
CN200410056912.7 discloses a method for obtaining C9 petroleum resin by using maleic anhydride as a polymerization raw material and catalyzing C9 fraction 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.
Zhankun et al discloses a method for modifying C9 petroleum resin with rosin in CN106967201, and Wang bin et al discloses a method for improving petroleum resin compatibility with C9 petroleum resin modified with tetrahydroindene in CN107325228, but the modifier used in the method has high cost of raw materials.
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:
a preparation method of long-chain olefin modified C9 petroleum resin comprises the step of carrying out cationic polymerization reaction on C9 fraction and long-chain olefin in the presence of a catalyst and an inert solvent and under an inert atmosphere 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 contains 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 be used.
The reaction temperature of the cationic polymerization reaction is 10-50 ℃, and the reaction time is 1-6 h.
The method also comprises the step of purifying the obtained crude long-chain olefin modified C9 petroleum resin, and specifically comprises the steps of performing alkali washing and water washing on the obtained crude long-chain olefin modified C9 petroleum resin, and performing 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 and 250 ℃.
The alkali liquor for alkali washing is an aqueous solution of sodium hydroxide or potassium hydroxide, 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 greater 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 oil-containing sewage is less generated, and the sewage treatment cost is reduced.
(3) Compared with the modification processes of piperylene, rosin and the like, the long-chain olefin is adopted for product modification, the raw material price is low, and the economic advantage is more obvious.
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): respectively taking the resin and EVA with the content of 28% according to the mass ratio of 1:1, mixing and 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 hexadecenes are isobutylene tetramers.
Example 1
(1) Adding 100g of dimethylbenzene into a reaction kettle with a stirrer, then adding 100g of C9 fraction and 5g of isododecene (tetrapropylene), controlling the temperature of reaction materials to 20 ℃, slowly dropwise adding a boron trifluoride diethyl etherate 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% 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-0.09 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 rest.
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 fog point is measured to be 145 ℃.
Example 2
(1) Adding 50g of dimethylbenzene into a reaction kettle with a stirrer, then 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% 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 rest.
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) 100g of toluene is added into a reaction kettle with a stirrer, 100g of C9 fraction and 15g of isomeric hexadecene are added, the temperature of reaction materials is controlled to be 30 ℃, boron trifluoride ether complex catalyst with 0.8 mass percent of C9 fraction is slowly dripped into the reaction kettle at a constant speed within 10min, the reaction is carried out for 2h, and nitrogen is used for protection in the reaction process, so that the hexadecene modified C9 petroleum resin liquid is obtained.
(2) Adding 100g of NaOH aqueous solution with the concentration of 5% 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 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 cloud 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 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 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 2% into a reaction kettle to remove a catalyst, washing the reaction kettle to be neutral by using 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 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 fog 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 20 ℃, slowly dropwise adding a boron trifluoride diethyl etherate complex catalyst with 1.5 mass percent 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 5% NaOH aqueous solution into a reaction kettle to remove the catalyst, washing with distilled water to be neutral 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 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, then adding 100g of C9 fraction, controlling the temperature of reaction materials to 10 ℃, slowly dropwise adding 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 protecting with nitrogen in the reaction process to obtain C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 3% into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by using 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 rest.
The C9 petroleum resin softening point was found to be 135 deg.C, the weight average molecular weight was 3860, the molecular weight distribution was 2.16, and the haze point was found to be 202 deg.C.
Comparative example 3
(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 30 ℃, slowly dropwise adding a boron trifluoride diethyl etherate complex catalyst with 0.3 mass percent of 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 2% NaOH aqueous solution into a reaction kettle to remove the catalyst, washing with distilled water to be neutral 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 has a softening point of 137 deg.C, a weight average molecular weight of 3957, a molecular weight distribution of 2.18, and a haze point of 208 deg.C.
Claims (10)
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.
2. The method for preparing long-chain olefin modified C9 petroleum resin according to claim 1, wherein the long-chain olefin is used in an amount of 5-20% by mass of the C9 fraction; the long-chain olefin is one or the combination of two of isomeric dodecene and isomeric hexadecene.
3. The method for preparing long-chain olefin modified C9 petroleum resin according to claim 1, wherein the catalyst is Friedel-Crafts catalyst and is used in an amount of 0.2-1.5% of the mass fraction of C9 fraction.
4. The method for preparing long-chain olefin modified C9 petroleum resin according to claim 3, wherein the Friedel-Crafts catalyst is boron trifluoride diethyl etherate or aluminum trichloride.
5. The method for preparing a long-chain olefin modified C9 petroleum resin as claimed in claim 1, wherein the inert solvent is used in an amount of 20-200% by mass of the C9 fraction.
6. The method for preparing long-chain olefin modified C9 petroleum resin according to claim 1, wherein the inert solvent is toluene, xylene or cyclohexane.
7. The method for preparing a long-chain olefin modified C9 petroleum resin according to claim 1, wherein the inert atmosphere is nitrogen.
8. The method for preparing long-chain olefin modified C9 petroleum resin according to claim 1, wherein the reaction temperature of the cationic polymerization is 10-50 ℃ and the reaction time is 1-6 h.
9. The method for preparing long-chain olefin modified C9 petroleum resin according to any one of claims 1 to 8, wherein the obtained crude long-chain olefin modified C9 petroleum resin is subjected to alkali washing, water washing and reduced pressure distillation to obtain purified long-chain olefin modified C9 petroleum resin.
10. The long-chain olefin-modified C9 petroleum resin prepared by the method according to any one of claims 1 to 9, having a molecular weight distribution of 1.3 to 1.6.
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Cited By (3)
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| CN114573752A (en) * | 2022-03-11 | 2022-06-03 | 广东新华粤石化集团股份公司 | Modified petroleum resin with narrow molecular weight distribution, preparation method and application |
| CN115746187A (en) * | 2022-11-29 | 2023-03-07 | 广东新华粤树脂科技有限公司 | C9 petroleum resin modifier for adhesive, preparation method and application thereof |
| CN117567684A (en) * | 2024-01-15 | 2024-02-20 | 上海希森材料科技有限公司 | Modified petroleum resin and preparation method thereof |
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| CN115746187A (en) * | 2022-11-29 | 2023-03-07 | 广东新华粤树脂科技有限公司 | C9 petroleum resin modifier for adhesive, preparation method and application thereof |
| 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 |
| CN117567684A (en) * | 2024-01-15 | 2024-02-20 | 上海希森材料科技有限公司 | Modified petroleum resin and preparation method thereof |
| CN117567684B (en) * | 2024-01-15 | 2024-03-22 | 上海希森材料科技有限公司 | Modified petroleum resin and preparation method thereof |
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