Synthesis method of maleated rosin acrylate resin

Abstract

The invention relates to the technical field of polymer synthesis, in particular to a synthesis method of maleated rosin acrylate resin, which is prepared from the following raw materials in parts by weight: 37 to 54 parts of maleic anhydride, 46 to 77 parts of rosin, 39 to 62 parts of acrylate derivative, 5 to 15 parts of catalyst A, 3 to 10 parts of catalyst B, 0.5 to 2 parts of emulsifier, 0.5 to 1.5 parts of cross-linking agent, 0.3 to 0.8 part of initiator and 0.2 to 0.5 part of polymerization inhibitor. The resin prepared by the invention contains a rigid fused polyatomic alicyclic structure, has better heat resistance, does not yellow at high temperature, eliminates conjugated double bonds on the premise of not damaging a rosin structure, forms a six-membered intracyclic double bond structure with a relatively stable structure, effectively reduces the occurrence of side reactions, is beneficial to subsequent processing, and is suitable for industrial production. The double-bond structure of hydroxyethyl methylacrylate is used for polymerization, the reaction activity is high, the yield is effectively improved, the preparation method is simple in process, the reaction conditions are mild and controllable, the raw materials are environmentally friendly, easy to obtain and renewable, the product conversion rate is high, and the requirements of industrial large-scale production and application are met.

Description

Technical Field

[0001] The invention relates to the technical field of polymer synthesis, in particular to a method for synthesizing a maleic rosin acrylate resin. Background Art

[0002] Rosin and its derivatives are commonly used natural resins. Maleic rosin, also known as maleic anhydride rosin, is the product of the addition reaction between rosin and maleic anhydride (maleic anhydride). Because the addition reaction eliminates the conjugated double bonds and reduces the tendency to discolor due to oxidation, it can be used in the manufacture of light-colored oil-based resin paints. The rigid, fused, multi-component alicyclic structure of the rosin base provides high heat resistance and resists yellowing at high temperatures. Maleic acid-modified rosin ester resins can be blended with a variety of resins for use in screen printing inks, improving the system's heat resistance, hardness, and gloss. Synthetic resin is a high-molecular compound that can be used as both a product and a raw material for synthetic rubber. Resin acid, the main component of rosin, is a chemically active substance with two chemically reactive centers: carboxylic acid and double bonds. Through these two reactive centers, quarter-hour atoms or groups can be introduced to give the rosin the desired properties, achieving the purpose of modification, thereby changing the rational properties of the rosin, greatly expanding the application field of rosin and forming a wide variety of rosin derivatives. For example, maleated rosin acrylate resin has good high-temperature resistance and yellowing resistance. Today's maleated rosin acrylate resin has low synthesis efficiency, affecting the stability of the polymer, and the polymerization produces many side reactions, which will affect subsequent processing. Summary of the Invention

[0003] The present invention aims to provide a method for synthesizing a maleic rosin acrylate resin, so as to solve the problems mentioned in the above background art, such as low synthesis efficiency of maleic rosin acrylate resin, which affects the stability of the polymer, and a large number of side reactions generated during polymerization, which affect subsequent processing.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] A method for synthesizing a maleic rosin acrylate resin comprises the following raw materials in parts by weight: 37-54 parts of maleic anhydride, 46-77 parts of rosin, 39-62 parts of an acrylate derivative, 5-15 parts of a catalyst A, 3-10 parts of a catalyst B, 0.5-2 parts of an emulsifier, 0.5-1.5 parts of a cross-linking agent, 0.3-0.8 parts of an initiator, and 0.2-0.5 parts of a polymerization inhibitor. The synthesis method specifically comprises the following steps:

[0006] S10: Weigh the raw materials according to the above weight parts;

[0007] S20: Add rosin to a reactor, raise the temperature to 150-160° C., and stir continuously until the rosin is completely melted. Slowly add maleic anhydride and catalyst A while stirring. Adjust the temperature to 200±10° C., react for 5±0.5 h, and then cool to 40±5° C. to obtain maleic rosin.

[0008] S30: Take another reaction kettle, add the initiator and the maleic rosin prepared in step S10 into the reaction kettle, raise the temperature to 70±10°C under a sealed, reflux condenser and stirring state, add the acrylate derivative, catalyst B, emulsifier and polymerization inhibitor, and raise the temperature to 80-100°C;

[0009] S40: stirring continuously, adding an initiator dropwise during the stirring process, and then adding a crosslinking agent, and keeping the temperature to react for 2-3 hours to obtain a maleic rosin acrylate resin emulsion;

[0010] S50: Cooling the maleic rosin acrylate resin emulsion to obtain maleic rosin acrylate resin.

[0011] Preferably, the raw materials include the following parts by weight: 40 parts of maleic anhydride, 60 parts of rosin, 50 parts of acrylate derivatives, 10 parts of catalyst A, 5 parts of catalyst B, 1 part of emulsifier, 1 part of crosslinking agent, 0.5 parts of initiator and 0.3 parts of polymerization inhibitor.

[0012] Preferably, the raw materials include the following parts by weight: 50 parts of maleic anhydride, 70 parts of rosin, 60 parts of acrylate derivatives, 13 parts of catalyst A, 9 parts of catalyst B, 1.8 parts of emulsifier, 1.3 parts of crosslinking agent, 0.7 parts of initiator and 0.4 parts of polymerization inhibitor.

[0013] Preferably, the acrylate derivative is hydroxyethyl acrylate or hydroxypropyl acrylate.

[0014] Preferably, the catalyst A is aluminum chloride, boron trifluoride or bamboo charcoal sulfonated solid acid.

[0015] Preferably, the catalyst B is zinc oxide, aluminum chloride, p-toluenesulfonic acid or ion exchange resin.

[0016] Preferably, the emulsifier is a hydrogenated castor oil polyoxyethylene ether 40 / Span 60 complex.

[0017] Preferably, the cross-linking agent is polyethylene glycol diacrylate.

[0018] Preferably, the initiator is ammonium persulfate or a mixture of azobisisobutyronitrile and benzoyl peroxide.

[0019] Preferably, the polymerization inhibitor is hydroquinone, p-benzoquinone, methylhydroquinone or phenothiazine.

[0020] Compared with the prior art, the present invention has the following beneficial effects: the resin prepared by the synthesis method of the maleated rosin acrylate resin contains a rigid fused polycyclic alicyclic structure, has good heat resistance, and does not yellow at high temperatures; without destroying the rosin structure, the conjugated double bonds are eliminated to form a relatively stable six-membered ring double bond structure, while effectively reducing the occurrence of side reactions, which is beneficial to subsequent processing; the double bond structure of hydroxyethyl methacrylate is utilized for polymerization, the reaction activity is high, and the yield is effectively improved; the preparation method is simple, the reaction conditions are mild and controllable, the raw materials are environmentally friendly, easily available and renewable, and the product conversion rate is high, which meets the requirements of industrial large-scale production and application; and the natural structure of the maleated rosin, that is, the rigid fused polycyclic alicyclic structure, is utilized, and this structure ensures that the product has good heat resistance, does not yellow at high temperatures, and has excellent properties such as fast curing, low shrinkage, high gloss, good adhesion, high temperature resistance, and yellowing resistance. DETAILED DESCRIPTION

[0021] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0022] Example 1

[0023] A method for synthesizing a maleic rosin acrylate resin comprises the following raw materials in parts by weight: 54 parts of maleic anhydride, 77 parts of rosin, 62 parts of an acrylate derivative, 15 parts of a catalyst A, 10 parts of a catalyst B, 2 parts of an emulsifier, 1.5 parts of a cross-linking agent, 0.8 parts of an initiator, and 0.5 parts of a polymerization inhibitor. The synthesis method specifically comprises the following steps:

[0024] S10: Weigh the raw materials according to the above weight parts;

[0025] S20: Add rosin to the reactor, raise the temperature to 1160° C., stir continuously until the rosin is completely melted, and slowly add maleic anhydride and catalyst A while stirring. Adjust the temperature to 200° C., react for 5 hours, and then cool to 40° C. to obtain maleic rosin;

[0026] S30: Take another reactor, add the initiator and the maleic rosin prepared in step S10 into the reactor, raise the temperature to 70°C while sealing, reflux condensing and stirring, add the acrylate derivative, catalyst B, emulsifier and polymerization inhibitor, and raise the temperature to 90°C;

[0027] S40: stirring continuously, adding an initiator dropwise during the stirring process, and then adding a crosslinking agent, and keeping the temperature to react for 2 hours to obtain a maleic rosin acrylate resin emulsion;

[0028] S50: Cooling the maleic rosin acrylate resin emulsion to obtain maleic rosin acrylate resin.

[0029] In this embodiment, the acrylate derivative is hydroxypropyl acrylate, and the catalyst A is bamboo charcoal sulfonated solid acid.

[0030] Furthermore, the catalyst B is p-toluenesulfonic acid, and the emulsifier is a hydrogenated castor oil polyoxyethylene ether 40 / Span 60 complex.

[0031] Wherein, the cross-linking agent is polyethylene glycol diacrylate.

[0032] In addition, the initiator is a mixture of azobisisobutyronitrile and benzoyl peroxide, and the inhibitor is phenothiazine.

[0033] Example 2

[0034] A method for synthesizing a maleic rosin acrylate resin comprises the following raw materials in parts by weight: 40 parts of maleic anhydride, 60 parts of rosin, 50 parts of an acrylate derivative, 10 parts of a catalyst A, 5 parts of a catalyst B, 1 part of an emulsifier, 1 part of a cross-linking agent, 0.5 parts of an initiator, and 0.3 parts of a polymerization inhibitor. The synthesis method specifically comprises the following steps:

[0035] S10: Weigh the raw materials according to the above weight parts;

[0036] S20: Add rosin to the reactor, raise the temperature to 155° C., stir continuously until the rosin is completely melted, and slowly add maleic anhydride and catalyst A while stirring. Adjust the temperature to 200° C., react for 5 hours, and then cool to 40° C. to obtain maleic rosin;

[0037] S30: Take another reactor, add the initiator and the maleic rosin prepared in step S10 into the reactor, raise the temperature to 70°C while sealing, reflux condensing and stirring, add the acrylate derivative, catalyst B, emulsifier and polymerization inhibitor, and raise the temperature to 90°C;

[0038] S40: stirring continuously, adding an initiator dropwise during the stirring process, and then adding a crosslinking agent, and keeping the temperature to react for 3 hours to obtain a maleic rosin acrylate resin emulsion;

[0039] S50: Cooling the maleic rosin acrylate resin emulsion to obtain maleic rosin acrylate resin.

[0040] In this embodiment, the acrylate derivative is hydroxyethyl acrylate, and the catalyst A is bamboo charcoal sulfonated solid acid.

[0041] Furthermore, the catalyst B is zinc oxide, and the emulsifier is a hydrogenated castor oil polyoxyethylene ether 40 / Span 60 complex.

[0042] Wherein, the cross-linking agent is polyethylene glycol diacrylate.

[0043] In addition, the initiator is ammonium persulfate, and the inhibitor is hydroquinone.

[0044] Example 3

[0045] A method for synthesizing a maleic rosin acrylate resin comprises the following raw materials in parts by weight: 50 parts of maleic anhydride, 70 parts of rosin, 60 parts of an acrylate derivative, 13 parts of a catalyst A, 9 parts of a catalyst B, 1.8 parts of an emulsifier, 1.3 parts of a cross-linking agent, 0.7 parts of an initiator, and 0.4 parts of a polymerization inhibitor. The synthesis method specifically comprises the following steps:

[0046] S10: Weigh the raw materials according to the above weight parts;

[0047] S20: Add rosin to the reactor, raise the temperature to 150° C., stir continuously until the rosin is completely melted, and slowly add maleic anhydride and catalyst A while stirring. Adjust the temperature to 200° C., react for 5 hours, and then cool to 40° C. to obtain maleic rosin;

[0048] S30: Take another reactor, add the initiator and the maleic rosin prepared in step S10 into the reactor, raise the temperature to 70°C while sealing, reflux condensing and stirring, add the acrylate derivative, catalyst B, emulsifier and polymerization inhibitor, and raise the temperature to 80°C;

[0049] S40: stirring continuously, adding an initiator dropwise during the stirring process, and then adding a crosslinking agent, and keeping the temperature to react for 2 hours to obtain a maleic rosin acrylate resin emulsion;

[0050] S50: Cooling the maleic rosin acrylate resin emulsion to obtain maleic rosin acrylate resin.

[0051] In this embodiment, the acrylate derivative is hydroxypropyl acrylate, and the catalyst A is boron trifluoride.

[0052] Furthermore, the catalyst B is p-toluenesulfonic acid, and the emulsifier is a hydrogenated castor oil polyoxyethylene ether 40 / Span 60 complex.

[0053] Wherein, the cross-linking agent is polyethylene glycol diacrylate.

[0054] In addition, the initiator is ammonium persulfate, and the inhibitor is p-benzoquinone.

[0055] The resin prepared by the synthesis method of the maleated rosin acrylate resin contains a rigid fused multi-component alicyclic structure, has good heat resistance, and does not yellow at high temperatures. Without destroying the rosin structure, conjugated double bonds are eliminated to form a relatively stable six-membered ring double bond structure, effectively reducing the occurrence of side reactions and facilitating subsequent processing. The double bond structure of hydroxyethyl methacrylate is utilized for polymerization, resulting in high reaction activity and effectively improving the yield. The preparation method has a simple process, mild and controllable reaction conditions, and the raw materials are environmentally friendly, easily available and renewable, and the product conversion rate is high, meeting the requirements of industrial large-scale production and application. The natural structure of the maleated rosin, i.e., the rigid fused multi-component alicyclic structure, is utilized to ensure that the product has good heat resistance, does not yellow at high temperatures, and has the excellent properties of fast curing, low shrinkage, high gloss, good adhesion, high temperature resistance and yellowing resistance.

[0056] The above shows and describes the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely preferred examples of the present invention and are not intended to limit the present invention. Various changes and improvements may be made to the present invention without departing from the spirit and scope of the present invention. Such changes and improvements fall within the scope of the present invention. The scope of protection claimed in the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for synthesizing a maleic rosin acrylate resin, characterized in that: The invention comprises the following raw materials in parts by weight: 37-54 parts of maleic anhydride, 46-77 parts of rosin, 39-62 parts of acrylate derivatives, 5-15 parts of catalyst A, 3-10 parts of catalyst B, 0.5-2 parts of emulsifier, 0.5-1.5 parts of cross-linking agent, 0.3-0.8 parts of initiator and 0.2-0.5 parts of polymerization inhibitor. The synthesis method specifically comprises the following steps: S10: Weigh the raw materials according to the above weight parts; S20: Add rosin to a reactor, raise the temperature to 150-160° C., and stir continuously until the rosin is completely melted. Slowly add maleic anhydride and catalyst A while stirring. Adjust the temperature to 200±10° C., react for 5±0.5 h, and then cool to 40±5° C. to obtain maleic rosin. S30: Take another reaction kettle, add the initiator and the maleic rosin prepared in step S10 into the reaction kettle, raise the temperature to 70±10°C under a sealed, reflux condenser and stirring state, add the acrylate derivative, catalyst B, emulsifier and polymerization inhibitor, and raise the temperature to 80-100°C; S40: stirring continuously, adding an initiator dropwise during the stirring process, and then adding a crosslinking agent, and keeping the temperature to react for 2-3 hours to obtain a maleic rosin acrylate resin emulsion; S50: Cooling the maleic rosin acrylate resin emulsion to obtain maleic rosin acrylate resin.

2. The synthetic method of maleic rosin acrylate resin according to claim 1, wherein: The invention comprises the following raw materials in parts by weight: 40 parts of maleic anhydride, 60 parts of rosin, 50 parts of acrylate derivatives, 10 parts of catalyst A, 5 parts of catalyst B, 1 part of emulsifier, 1 part of crosslinking agent, 0.5 part of initiator and 0.3 part of polymerization inhibitor.

3. The synthetic method of maleated rosin acrylate resin according to claim 1, wherein: The invention comprises the following raw materials in parts by weight: 50 parts of maleic anhydride, 70 parts of rosin, 60 parts of acrylate derivative, 13 parts of catalyst A, 9 parts of catalyst B, 1.8 parts of emulsifier, 1.3 parts of crosslinking agent, 0.7 parts of initiator and 0.4 parts of polymerization inhibitor.

4. The synthetic method of maleated rosin acrylate resin according to claim 1, wherein: The acrylate derivative is hydroxyethyl acrylate or hydroxypropyl acrylate.

5. The synthetic method of maleated rosin acrylate resin according to claim 1, wherein: The catalyst A is aluminum trichloride, boron trifluoride or bamboo charcoal sulfonated solid acid.

6. The method for synthesizing the maleic rosin acrylate resin according to claim 1, wherein: The catalyst B is zinc oxide, aluminum chloride, p-toluenesulfonic acid or ion exchange resin.

7. The method for synthesizing the maleic rosin acrylate resin according to claim 1, wherein: The emulsifier is a hydrogenated castor oil polyoxyethylene ether 40 / Span 60 complex.

8. The method for synthesizing the maleic rosin acrylate resin according to claim 1, wherein: The cross-linking agent is polyethylene glycol diacrylate.

9. The method for synthesizing the maleic rosin acrylate resin according to claim 1, wherein: The initiator is ammonium persulfate or a mixture of azobisisobutyronitrile and benzoyl peroxide.

10. The method for synthesizing the maleic rosin acrylate resin according to claim 1, wherein: The polymerization inhibitor is hydroquinone, p-benzoquinone, methylhydroquinone or phenothiazine.