Rosin tackifying resin and preparation method thereof

Abstract

The invention belongs to the technical field of rosin, and particularly discloses rosin tackifying resin and a preparation method thereof.The preparation method comprises the following steps that 1, rosin resin is melted and heated till rosin is fully melted, modified titanium dioxide, polyethylene glycol diacrylate and a catalyst are added, and a precursor is obtained through a reaction; and (2) adding cardanol polyglycidyl ether epoxy phenolic resin into the precursor, and reacting to obtain the rosin tackifying resin. According to the rosin tackifying resin, rosin resin reacts with modified titanium dioxide and polyethylene glycol diacrylate and then reacts with cardanol polyglycidyl ether epoxy phenolic resin, and the rosin tackifying resin capable of effectively improving the initial adhesion and peel strength of glue is obtained.

Description

Technical Field

[0001] This invention relates to the field of rosin technology, and specifically to a rosin tackifying resin and its preparation method. Background Technology

[0002] Rosin-based tackifying resins use rosin as a base material, with resin acids as their core components, including monocarboxyl isomers with different double bond positions, such as rosin acid and rosinophilic acid. Due to the wide availability and low cost of raw materials, rosin-based tackifying resins are widely used in the adhesive industry.

[0003] However, traditional rosin resins have the following drawbacks: 1. Insufficient initial tack: Natural rosin molecules are relatively rigid and have poor wettability with the substrate, resulting in low initial bond strength; 2. Limited peel strength: The resin has a wide molecular weight distribution, with low molecular weight components easily migrating and high molecular weight components having poor flexibility, which affects cohesion.

[0004] Therefore, this application is submitted. Summary of the Invention

[0005] This invention provides a rosin tackifying resin and its preparation method. The rosin tackifying resin of this invention has excellent properties and can effectively improve the initial tack and peel strength of the adhesive, and has broad application prospects.

[0006] The present invention solves its technical problem by adopting the following technical solution: A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the rosin resin, heat it until the rosin is fully melted, add modified titanium dioxide, polyethylene glycol diacrylate and catalyst, react to obtain the precursor; (2) Cashew phenol polyglycidyl ether epoxy phenolic resin was added to the precursor and reacted to obtain rosin tackifying resin.

[0007] This invention reacts rosin resin with modified titanium dioxide and polyethylene glycol diacrylate, and then reacts it with cashew phenol polyglycidyl ether epoxy phenolic resin to obtain a rosin tackifying resin that can effectively improve the initial tack and peel strength of adhesives.

[0008] In this invention, a core-shell structure of titanium dioxide is incorporated. The core is titanium dioxide treated with a silane coupling agent, and the outer shell is a polydopamine coating layer. The polydopamine shell provides abundant phenolic hydroxyl groups, which form a hydrogen bond network with rosin carboxyl groups. The titanium dioxide core is embedded between rosin molecular chains through π-π interactions and crosslinks with cashew phenol polyglycidyl ether epoxy phenolic resin to construct a multi-interaction network, effectively improving the initial tack and peel strength of the adhesive.

[0009] In a preferred embodiment of the present invention, the mass ratio of rosin resin, modified titanium dioxide, polyethylene glycol diacrylate, and catalyst is 100:(8~15):(4~10):(0.5~1.2).

[0010] In a preferred embodiment of the present invention, the catalyst is p-toluenesulfonic acid.

[0011] As a preferred embodiment of the present invention, the reaction temperature in step (1) is 125~135℃ and the time is 4~10h.

[0012] In a preferred embodiment of the present invention, the mass ratio of cashew phenol polyglycidyl ether epoxy phenolic resin to the precursor is (3~6):100.

[0013] As a preferred embodiment of the present invention, the reaction temperature in step (2) is 125~135℃ and the time is 4~10h.

[0014] As a preferred embodiment of the present invention, the method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added and stirred until homogeneous. The pH was then adjusted to 8-9 using tris(hydroxymethyl)aminomethane hydrochloride buffer. The mixture was reacted, filtered, and dried to obtain modified titanium dioxide.

[0015] As a preferred embodiment of the present invention, the mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride is 1:(0.1~0.2):(0.01~0.02):(4~10):(0.4~0.6).

[0016] In a preferred embodiment of the present invention, the reaction temperature is 55~65℃ and the reaction time is 2~6h.

[0017] The present invention also provides a rosin tackifying resin, which is prepared by the preparation method described above.

[0018] The beneficial effects of the present invention are as follows: The present invention reacts rosin resin with modified titanium dioxide and polyethylene glycol diacrylate, and then reacts it with cashew phenol polyglycidyl ether epoxy phenolic resin to obtain a rosin tackifying resin that can effectively improve the initial tack and peel strength of the adhesive. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0021] In this invention, numerical ranges are involved. Unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe features or characteristics, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0022] In this invention, there are no particular limitations on the specific dispersion and stirring methods.

[0023] Unless otherwise specified, all reagents or instruments used in this invention are commercially available conventional products. Unless otherwise specified, the raw materials used in each comparative example and the parallel experiments of each embodiment are the same commercially available products.

[0024] Example 1 A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the primary resin rosin, heat it to 160°C until the rosin is fully melted, cool it down to 130°C, add modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid, and react at 130°C for 6 hours to obtain the precursor; the mass ratio of the rosin resin, modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid is 100:12:6:1.

[0025] (2) Cashew phenol polyglycidyl ether epoxy phenolic resin is added to the precursor and reacted at 130°C for 6 hours to obtain rosin tackifying resin. The mass ratio of cashew phenol polyglycidyl ether epoxy phenolic resin to precursor is 5:100.

[0026] The cashew phenol polyglycidyl ether epoxy phenolic resin is derived from Cardell, brand name Carlisle NC547.

[0027] The method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added, and the mixture was stirred at 200 rpm for 2 hours. The pH was then adjusted to 8.5 with tris(hydroxymethyl)aminomethane hydrochloride buffer, and the reaction was carried out at 58°C for 4 hours. The mixture was filtered and dried to obtain modified titanium dioxide. The mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride was 1:0.15:0.02:8:0.5.

[0028] Example 2 A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the primary resin rosin, heat it to 160°C until the rosin is fully melted, cool it down to 130°C, add modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid, and react at 130°C for 6 hours to obtain the precursor; the mass ratio of the rosin resin, modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid is 100:8:10:1.

[0029] (2) Cashew phenol polyglycidyl ether epoxy phenolic resin is added to the precursor and reacted at 130°C for 6 hours to obtain rosin tackifying resin. The mass ratio of cashew phenol polyglycidyl ether epoxy phenolic resin to precursor is 5:100.

[0030] The cashew phenol polyglycidyl ether epoxy phenolic resin is derived from Cardell, brand name Carlisle NC547.

[0031] The method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added, and the mixture was stirred at 200 rpm for 2 hours. The pH was then adjusted to 8.5 with tris(hydroxymethyl)aminomethane hydrochloride buffer, and the reaction was carried out at 58°C for 4 hours. The mixture was filtered and dried to obtain modified titanium dioxide. The mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride was 1:0.15:0.02:8:0.5.

[0032] Example 3 A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the primary resin rosin, heat it to 160°C until the rosin is fully melted, cool it down to 130°C, add modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid, and react at 130°C for 6 hours to obtain the precursor; the mass ratio of the rosin resin, modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid is 100:15:4:1.

[0033] (2) Cashew phenol polyglycidyl ether epoxy phenolic resin is added to the precursor and reacted at 130°C for 6 hours to obtain rosin tackifying resin. The mass ratio of cashew phenol polyglycidyl ether epoxy phenolic resin to precursor is 5:100.

[0034] The cashew phenol polyglycidyl ether epoxy phenolic resin is derived from Cardell, brand name Carlisle NC547.

[0035] The method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added, and the mixture was stirred at 200 rpm for 2 hours. The pH was then adjusted to 8.5 with tris(hydroxymethyl)aminomethane hydrochloride buffer, and the reaction was carried out at 58°C for 4 hours. The mixture was filtered and dried to obtain modified titanium dioxide. The mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride was 1:0.15:0.02:8:0.5.

[0036] Example 4 A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the primary resin rosin, heat it to 160°C until the rosin is fully melted, cool it down to 130°C, add modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid, and react at 130°C for 6 hours to obtain the precursor; the mass ratio of the rosin resin, modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid is 100:12:6:1.

[0037] (2) Cashew phenol polyglycidyl ether epoxy phenolic resin is added to the precursor and reacted at 130°C for 6 hours to obtain rosin tackifying resin. The mass ratio of cashew phenol polyglycidyl ether epoxy phenolic resin to precursor is 3:100.

[0038] The cashew phenol polyglycidyl ether epoxy phenolic resin is derived from Cardell, brand name Carlisle NC547.

[0039] The method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added, and the mixture was stirred at 200 rpm for 2 hours. The pH was then adjusted to 8.5 with tris(hydroxymethyl)aminomethane hydrochloride buffer, and the reaction was carried out at 58°C for 4 hours. The mixture was filtered and dried to obtain modified titanium dioxide. The mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride was 1:0.15:0.02:8:0.5.

[0040] Example 5 A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the primary resin rosin, heat it to 160°C until the rosin is fully melted, cool it down to 130°C, add modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid, and react at 130°C for 6 hours to obtain the precursor; the mass ratio of the rosin resin, modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid is 100:12:6:1.

[0041] (2) Cashew phenol polyglycidyl ether epoxy phenolic resin is added to the precursor and reacted at 130°C for 6 hours to obtain rosin tackifying resin. The mass ratio of cashew phenol polyglycidyl ether epoxy phenolic resin to precursor is 6:100.

[0042] The cashew phenol polyglycidyl ether epoxy phenolic resin is derived from Cardell, brand name Carlisle NC547.

[0043] The method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added, and the mixture was stirred at 200 rpm for 2 hours. The pH was then adjusted to 8.5 with tris(hydroxymethyl)aminomethane hydrochloride buffer, and the reaction was carried out at 58°C for 4 hours. The mixture was filtered and dried to obtain modified titanium dioxide. The mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride was 1:0.15:0.02:8:0.5.

[0044] Comparative Example 1

[0045] A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the primary resin rosin, heat it to 160°C until the rosin is fully melted, cool it down to 130°C, add modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid, and react at 130°C for 6 hours to obtain the precursor; the mass ratio of the rosin resin, titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid is 100:12:6:1.

[0046] (2) Cashew phenol polyglycidyl ether epoxy phenolic resin is added to the precursor and reacted at 130°C for 6 hours to obtain rosin tackifying resin. The mass ratio of cashew phenol polyglycidyl ether epoxy phenolic resin to precursor is 5:100.

[0047] The cashew phenol polyglycidyl ether epoxy phenolic resin is derived from Cardell, brand name Carlisle NC547.

[0048] Comparative Example 2

[0049] A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the primary resin rosin, heat it to 160°C until the rosin is fully melted, cool it down to 130°C, add modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid, and react at 130°C for 6 hours to obtain the precursor; the mass ratio of the rosin resin, modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid is 100:12:6:1.

[0050] (2) Cashew phenol polyglycidyl ether epoxy phenolic resin is added to the precursor and reacted at 130°C for 6 hours to obtain rosin tackifying resin. The mass ratio of cashew phenol polyglycidyl ether epoxy phenolic resin to precursor is 1:100.

[0051] The cashew phenol polyglycidyl ether epoxy phenolic resin is derived from Cardell, brand name Carlisle NC547.

[0052] The method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added, and the mixture was stirred at 200 rpm for 2 hours. The pH was then adjusted to 8.5 with tris(hydroxymethyl)aminomethane hydrochloride buffer, and the reaction was carried out at 58°C for 4 hours. The mixture was filtered and dried to obtain modified titanium dioxide. The mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride was 1:0.15:0.02:8:0.5.

[0053] Comparative Example 3

[0054] A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the primary resin rosin, heat it to 160°C until the rosin is fully melted, cool it down to 130°C, add modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid, and react at 130°C for 6 hours to obtain the precursor; the mass ratio of the rosin resin, modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid is 100:12:6:1.

[0055] (2) Cashew phenol polyglycidyl ether epoxy phenolic resin is added to the precursor and reacted at 130°C for 6 hours to obtain rosin tackifying resin. The mass ratio of cashew phenol polyglycidyl ether epoxy phenolic resin to precursor is 10:100.

[0056] The cashew phenol polyglycidyl ether epoxy phenolic resin is derived from Cardell, brand name Carlisle NC547.

[0057] The method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added, and the mixture was stirred at 200 rpm for 2 hours. The pH was then adjusted to 8.5 with tris(hydroxymethyl)aminomethane hydrochloride buffer, and the reaction was carried out at 58°C for 4 hours. The mixture was filtered and dried to obtain modified titanium dioxide. The mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride was 1:0.15:0.02:8:0.5.

[0058] Comparative Example 4

[0059] A method for preparing a rosin tackifying resin includes the following steps: (1) Melt the primary resin rosin, heat it to 160°C until the rosin is fully melted, cool it down to 130°C, add modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid, and react at 130°C for 6 hours to obtain the precursor; the mass ratio of the rosin resin, modified titanium dioxide, polyethylene glycol diacrylate and p-toluenesulfonic acid is 100:12:6:1.

[0060] (2) Cashew shell oil epoxy is added to the precursor and reacted at 130°C for 6 hours to obtain rosin tackifying resin. The mass ratio of cashew shell oil epoxy to precursor is 5:100.

[0061] The cashew shell oil epoxy is derived from Cardläne, brand name Cardläne NC-513.

[0062] The method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added, and the mixture was stirred at 200 rpm for 2 hours. The pH was then adjusted to 8.5 with tris(hydroxymethyl)aminomethane hydrochloride buffer, and the reaction was carried out at 58°C for 4 hours. The mixture was filtered and dried to obtain modified titanium dioxide. The mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride was 1:0.15:0.02:8:0.5.

[0063] Test case

[0064] Weigh out the following components by weight: 85 parts methyl acrylate, 15 parts hydroxyethyl acrylate, 1 part benzoyl peroxide, 0.1 part phenol, 100 parts solvent (ethyl acetate and toluene in a 1:1 weight ratio), 25 parts rosin tackifying resin, and 2 parts isocyanate, and prepare a pressure-sensitive adhesive for testing.

[0065] The ring-shaped initial tack was determined according to the standard (method A) of GB / T31125-2014.

[0066] The 180° peel strength between the adhesive tape and the stainless steel plate was determined according to the standard GB / T2792-2014.

[0067] Table 1

[0068] As can be seen from Table 1, the rosin tackifying resin described in this invention has excellent properties, can effectively improve the initial tack and peel strength of the adhesive, and has broad application prospects.

[0069] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a rosin tackifying resin, characterized in that, Includes the following steps: (1) Melt rosin resin, heat until rosin is fully melted, add modified titanium dioxide, polyethylene glycol diacrylate and catalyst, react to obtain precursor; (2) Cashew phenol polyglycidyl ether epoxy phenolic resin was added to the precursor and reacted to obtain rosin tackifying resin.

2. The method for preparing rosin tackifying resin according to claim 1, characterized in that, The mass ratio of the rosin resin, modified titanium dioxide, polyethylene glycol diacrylate, and catalyst is 100:(8~15):(4~10):(0.5~1.2).

3. The method for preparing rosin tackifying resin according to claim 1, characterized in that, The catalyst is p-toluenesulfonic acid.

4. The method for preparing rosin tackifying resin according to claim 1, characterized in that, The reaction temperature in step (1) is 125~135℃ and the time is 4~10h.

5. The method for preparing rosin tackifying resin according to claim 1, characterized in that, The mass ratio of the cashew phenol polyglycidyl ether epoxy phenolic resin to the precursor is (3~6):

100.

6. The method for preparing rosin tackifying resin according to claim 1, characterized in that, The reaction temperature in step (2) is 125~135℃ and the reaction time is 4~10h.

7. The method for preparing rosin tackifying resin according to claim 1, characterized in that, The method for preparing the modified titanium dioxide is as follows: Titanium dioxide, chitosan, and γ-aminopropyltriethoxysilane were added to water and stirred until homogeneous to obtain a mixture. Dopamine hydrochloride was added and stirred until homogeneous. The pH was then adjusted to 8-9 using tris(hydroxymethyl)aminomethane hydrochloride buffer. The mixture was reacted, filtered, and dried to obtain modified titanium dioxide.

8. The method for preparing rosin tackifying resin according to claim 7, characterized in that, The mass ratio of titanium dioxide, chitosan, γ-aminopropyltriethoxysilane, water, and dopamine hydrochloride is 1:(0.1~0.2):(0.01~0.02):(4~10):(0.4~0.6).

9. The method for preparing rosin tackifying resin according to claim 7, characterized in that, The reaction temperature is 55~65℃ and the time is 2~6h.

10. A rosin tackifying resin, characterized in that, It is prepared by any one of the preparation methods described in claims 1 to 9.

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