CN109575188B - Preparation method of maleic anhydride modified terpene resin - Google Patents
Preparation method of maleic anhydride modified terpene resin Download PDFInfo
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- CN109575188B CN109575188B CN201811443137.9A CN201811443137A CN109575188B CN 109575188 B CN109575188 B CN 109575188B CN 201811443137 A CN201811443137 A CN 201811443137A CN 109575188 B CN109575188 B CN 109575188B
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- maleic anhydride
- terpene resin
- modified terpene
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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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
Abstract
The invention discloses a preparation method of maleic anhydride modified terpene resin, which comprises the following steps: (1) adding 3-carene, maleic anhydride and a catalyst B into a reaction kettle, heating to 50-100 ℃ under a stirring state, and stirring and reacting for 1 hour at a constant temperature to obtain a maleic anhydride modified substance M; (2) adding the catalyst A into a solvent, uniformly mixing, dripping the maleic anhydride modified substance M at the low temperature of-15 to-5 ℃, keeping the low-temperature polymerization reaction, and sequentially performing hydrolysis, water washing and distillation on the obtained reaction product to obtain the maleic anhydride modified terpene resin. The preparation method of the maleic anhydride modified terpene resin adopts the byproduct of turpentine oil after vacuum reduced pressure fractionation as the raw material, replaces expensive pinene in the prior art, and greatly reduces the raw material cost for synthesizing the terpene resin.
Description
Technical Field
The invention relates to preparation of terpene resin, in particular to a preparation method of maleic anhydride modified terpene resin.
Background
The 3-carene is one of byproducts of turpentine distillation, and the effective utilization of the turpentine is restricted due to the special position of a double bond, so that the use value of the turpentine is greatly influenced, and the 3-carene is always treated as low-grade residual oil. The research on the synthesis of terpene resin by using the double bond of 3-carene is still in the way and cannot be broken through.
The terpene resin is a thermoplastic block copolymer which has the advantages of light color, low odor, high hardness, high adhesive force, good oxidation resistance, good thermal stability, good compatibility and solubility and the like, particularly has excellent compatibility, weather resistance and tackifying effect in hot sol of EVA SIS system, SBS system and the like, and is a good thickener. At present, terpene resin is resin secreted from trees of the genus pinus, called turpentine, and can be extracted from trees of the genus pinus. From the chemical composition point of view, rosin is mainly a solution of solid resin acid dissolved in terpenes. At present, the terpene resin is produced by using toluene as solvent and catalyst for low-temperature polymerization, and the product after low-temperature polymerization is hydrolyzed, washed and distilled to synthesize the solid terpene resin. Since the price of pinene with higher purity is expensive, the production cost of terpene resin is higher, and the price of terpene resin products is always high.
Disclosure of Invention
The invention aims to provide a preparation method of maleic anhydride modified terpene resin, which aims to solve the problem that the existing synthetic terpene resin is single in raw material and short in raw material, expand the use application of a turpentine byproduct 3-carene and improve the use value of the 3-carene.
The purpose of the invention is realized by the following technical scheme: a preparation method of maleic anhydride modified terpene resin comprises the following steps:
(1) adding 3-carene, maleic anhydride and a catalyst B into a reaction kettle, heating to 50-100 ℃ under a stirring state, and stirring and reacting for 1 hour at a constant temperature to obtain a maleic anhydride modified substance M;
(2) adding the catalyst A into a solvent, uniformly mixing, slowly dropwise adding the maleic anhydride modified substance M at a low temperature of-15 to-5 ℃ for low-temperature polymerization reaction, and sequentially performing hydrolysis, water washing and distillation on the obtained reaction product to obtain the maleic anhydride modified terpene resin.
Further, in the step (1), the catalyst B is one or a combination of more of anhydrous zinc chloride, anhydrous stannic chloride and anhydrous aluminum trichloride.
Further, in the step (1), the mass ratio of the 3-carene, the maleic anhydride and the catalyst B is as follows: 0.5-1.5: 1: 0.015-0.025.
Further, in the step (2), the solvent is toluene; the mass ratio of the solvent to the maleic anhydride modifier M is 0.8-1.8: 1.
Further, in the step (2), the catalyst A is one or a mixture of anhydrous aluminum trichloride and boron trifluoride diethyl etherate; the mass ratio of the catalyst A to the maleic anhydride modifier M is 0.04-0.08: 1.
Further, in the step (2), the temperature of the low-temperature polymerization reaction is-15 ℃ to-5 ℃, and the time of the low-temperature polymerization reaction after the dropping of the maleic anhydride modifier M is completed is 4-8 hours.
Further, in the step (2), the time for dripping the maleic anhydride modifier M is 1-2 hours.
Further, in the step (2), the mass ratio of the solvent to the maleic anhydride modifier M is 1.1-1.3: 1.
Further, in the step (2), the mass ratio of the catalyst A to the maleic anhydride modifier M is 0.06: 1.
Further, in the step (1), the 3-carene is a product of turpentine oil subjected to vacuum reduced pressure fractionation, and the content is more than or equal to 90%.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the maleic anhydride modified terpene resin adopts the byproduct of turpentine oil after vacuum reduced pressure fractionation as the raw material, replaces expensive pinene in the prior art, and greatly reduces the raw material cost for synthesizing the terpene resin.
2. The invention discloses and proposes that maleic anhydride is used for modifying 3-carene, so that the double bond of the 3-carene is transferred to improve the activity of the 3-carene, an active double bond is provided for a polymerization reaction, the technical barrier of synthesizing terpene resin by the 3-carene is broken, a new using path is developed for the turpentine byproduct 3-carene, the 3-carene is more fully utilized, and the using value of the 3-carene is improved.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the following embodiments, but the present invention is not limited thereto.
Example 1
Adding 50g of 90.8% 3-carene, 100g of maleic anhydride and 2.5g of anhydrous zinc chloride into a reaction kettle, heating to 50 ℃ under the stirring state, and stirring and reacting for 1 hour at the constant temperature of 50 ℃ to obtain a maleic anhydride modified substance M. Then adding 8g of anhydrous aluminum trichloride into 180g of toluene, uniformly mixing, cooling to-15 ℃, slowly dropwise adding 100g of maleic anhydride modifier M, finishing dropwise adding within 1 hour, keeping the temperature at-15 ℃, stirring and reacting for 8 hours, and finishing the low-temperature polymerization reaction. Adding 200g of 5% hydrochloric acid aqueous solution into a reaction product, heating to 90 ℃ for hydrolysis for 0.5 hour, after hydrolysis, draining the lower layer of acid water layer by layer, washing the upper layer of solution with hot water at 85 ℃ for three times until the water layer is neutral, then settling, layering, taking an oil layer, and carrying out the working procedures of atmospheric distillation for recovering the solvent and reduced pressure jet-extraction for distilling the oligomer to obtain 38.5g of the synthetic maleic anhydride modified terpene resin. The raw material 3-carene is the product of vacuum reduced pressure fractionation of turpentine.
Example 2
Adding 500g of 95.2% 3-carene, 500g of maleic anhydride and 10g of anhydrous stannic chloride into a reaction kettle, heating to 70 ℃ under a stirring state, and stirring and reacting for 1 hour at a constant temperature of 70 ℃ to obtain a maleic anhydride modified substance M. Then 60g of anhydrous boron trifluoride diethyl etherate is added into 1300g of toluene to be uniformly mixed, 1000g of maleic anhydride modifier M is slowly dripped when the temperature is reduced to minus 10 ℃, dripping is finished within 1.5 hours, and then the mixture is kept at minus 10 ℃ and stirred to react for 6 hours to complete low-temperature polymerization reaction. Adding 2000g of 5% hydrochloric acid aqueous solution into the reaction product, heating to 90 ℃ for hydrolysis for 0.5 hour, after hydrolysis, discharging lower layer of acid water layer by layer, washing the upper layer of solution with 85 ℃ hot water for three times until the water layer is neutral, then settling, taking an oil layer after layer separation, and carrying out the working procedures of recovering the solvent by atmospheric distillation and distilling off oligomers by reduced pressure spraying to obtain 376g of the synthesized maleic anhydride modified terpene resin. The raw material 3-carene is the product of vacuum reduced pressure fractionation of turpentine.
Example 3
Adding 1500g of 95.8% 3-carene, 1000g of maleic anhydride, 9g of anhydrous aluminum trichloride and 6g of anhydrous stannic chloride into a reaction kettle, heating to 100 ℃ under a stirring state, and stirring and reacting for 1 hour at a constant temperature of 100 ℃ to obtain a maleic anhydride modified substance M. Then adding 80g of anhydrous aluminum trichloride and 20g of anhydrous boron trifluoride diethyl etherate into 2000g of toluene, uniformly mixing, cooling to-5 ℃, slowly dropwise adding 2500g of maleic anhydride modifier M, finishing dropwise adding within 2 hours, keeping the temperature at-5 ℃, stirring and reacting for 4 hours, and finishing the low-temperature polymerization reaction. 4000g of 5% hydrochloric acid aqueous solution is added into a reaction product, the reaction product is heated to 90 ℃ for hydrolysis for 0.5 hour, after the hydrolysis is finished, lower-layer acid water is drained layer by layer, an upper-layer solution is washed with hot water at 85 ℃ for three times until a water layer is neutral, then the reaction product is settled and layered, an oil layer is taken, and the working procedures of recovering a solvent by normal pressure distillation and distilling and steaming out oligomers by reduced pressure spray extraction are carried out, so that 1136g of the synthetic maleic anhydride modified terpene resin is obtained. The raw material 3-carene is the product of vacuum reduced pressure fractionation of turpentine.
The above examples are some embodiments of the present invention, and are not intended to limit the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the principles of the invention.
Claims (9)
1. The preparation method of the maleic anhydride modified terpene resin is characterized by comprising the following steps:
(1) adding 3-carene, maleic anhydride and a catalyst B into a reaction kettle, heating to 50-100 ℃ under a stirring state, and stirring and reacting for 1 hour at a constant temperature to obtain a maleic anhydride modified substance M;
(2) adding a catalyst A into a solvent, uniformly mixing, dripping the maleic anhydride modified substance M obtained in the step (1) at a low temperature of-15 to-5 ℃, keeping a low-temperature polymerization reaction, and sequentially performing hydrolysis, washing and distillation on the obtained reaction product to obtain maleic anhydride modified terpene resin;
the catalyst A is one or a mixture of two of anhydrous aluminum trichloride and boron trifluoride diethyl etherate;
the catalyst B is one or a combination of more of anhydrous zinc chloride, anhydrous stannic chloride and anhydrous aluminum trichloride.
2. The method for producing a maleic anhydride-modified terpene resin according to claim 1, wherein: in the step (1), the mass ratio of the 3-carene, the maleic anhydride and the catalyst B is as follows: 0.5-1.5: 1: 0.015-0.025.
3. The method for producing a maleic anhydride-modified terpene resin according to claim 2, wherein: in the step (2), the solvent is toluene; the mass ratio of the solvent to the maleic anhydride modifier M is 0.8-1.8: 1.
4. The method for producing a maleic anhydride-modified terpene resin according to claim 1 or 3, wherein: in the step (2), the mass ratio of the solvent to the maleic anhydride modifier M is 1.1-1.3: 1.
5. The method for producing a maleic anhydride-modified terpene resin according to claim 1 or 3, wherein: in the step (2), the mass ratio of the catalyst A to the maleic anhydride modifier M is 0.04-0.08: 1.
6. The method for producing a maleic anhydride-modified terpene resin according to claim 5, wherein: in the step (2), the mass ratio of the catalyst A to the maleic anhydride modifier M is 0.06: 1.
7. The method for producing a maleic anhydride-modified terpene resin according to claim 1, wherein: in the step (2), the temperature of the low-temperature polymerization reaction is-15 ℃ to-5 ℃, and the time of the low-temperature polymerization reaction is 4 to 8 hours after the maleic anhydride modifier M is dropwise added.
8. The method for producing a maleic anhydride-modified terpene resin according to claim 1 or 7, wherein: in the step (2), the time for dripping the maleic anhydride modifier M is 1-2 hours.
9. The method for producing a maleic anhydride-modified terpene resin according to claim 1, wherein: in the step (1), the 3-carene is a product of turpentine oil subjected to vacuum reduced pressure fractionation, and the content is more than or equal to 90%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118819A (en) * | 1991-04-03 | 1992-06-02 | Union Camp Corporation | Process for the preparation of delta-3-carene diadducts |
| CN1748013A (en) * | 2003-02-06 | 2006-03-15 | 阿利桑那化学公司 | Terpene resin- and hydrocarbon resin-based surfactants and acqueous disperson of tacifier resins |
| CN102826995A (en) * | 2012-09-07 | 2012-12-19 | 中国林业科学研究院林产化学工业研究所 | Low-viscosity turpentine-based monoterpene vinyl ester resin monomer and preparation method and application thereof |
| CN104892847A (en) * | 2015-05-19 | 2015-09-09 | 广西民族大学 | A terpenyl maleimide hyperdispersant and a preparing method thereof |
-
2018
- 2018-11-29 CN CN201811443137.9A patent/CN109575188B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118819A (en) * | 1991-04-03 | 1992-06-02 | Union Camp Corporation | Process for the preparation of delta-3-carene diadducts |
| CN1748013A (en) * | 2003-02-06 | 2006-03-15 | 阿利桑那化学公司 | Terpene resin- and hydrocarbon resin-based surfactants and acqueous disperson of tacifier resins |
| CN102826995A (en) * | 2012-09-07 | 2012-12-19 | 中国林业科学研究院林产化学工业研究所 | Low-viscosity turpentine-based monoterpene vinyl ester resin monomer and preparation method and application thereof |
| CN104892847A (en) * | 2015-05-19 | 2015-09-09 | 广西民族大学 | A terpenyl maleimide hyperdispersant and a preparing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 松油醇副产松油烯与马来酸酐加成反应条件研究;王桂英 等;《化工生产与技术》;20100228;第17卷(第1期);29-32 * |
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