Rosin graft copolymer containing polyester cross-linking agent as well as preparation method and application of rosin graft copolymer

Abstract

The invention relates to the technical field of macromolecules, in particular to a rosin grafted copolymer containing a polyester cross-linking agent as well as a preparation method and application of the rosin grafted copolymer. The rosin grafted copolymer containing the polyester cross-linking agent is a cross-linking product obtained by carrying out cross-linking reaction on epoxy and rosin under the action of the polyester cross-linking agent. According to the invention, the polyester crosslinking agent is introduced into the rosin grafted copolymer structure, so that the rosin grafted copolymer can be fully crosslinked, the molecular weight and softening point of the polymer are improved, and the solvent resistance of the polymer is improved at the same time.

Description

Technical Field

[0001] The invention relates to the field of polymer technology, in particular to a rosin graft copolymer containing a polyester crosslinking agent and a preparation method and application thereof. Background Art

[0002] Polymerized rosin resin is a synthetic resin, belonging to a type of acrylic resin. Compared with natural rosin, polymerized rosin resin has higher activity, larger molecular weight, better film-forming properties, water resistance and yellowing resistance. Therefore, polymerized rosin resin has been widely used in the fields of ink, coating, adhesive, etc.

[0003] In the field of inks, polymerized rosin resin is suitable for solvent-based inks, water-based inks, and UV-curable inks, and can improve the comprehensive performance of inks in terms of stability, printing speed, and water resistance.

[0004] However, existing polymerized rosin resins have various problems such as poor fluidity, slow drying, dullness and poor solvent resistance. Summary of the invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a rosin graft copolymer containing a polyester crosslinking agent and a preparation method and application thereof, which has good fluidity, glossiness and solvent resistance.

[0006] The invention provides a rosin graft copolymer containing a polyester crosslinking agent, which is a crosslinked product of epoxy and rosin undergoing a crosslinking reaction under the action of the polyester crosslinking agent.

[0007] Optionally, the polyester crosslinking agent is a polymerization product of a polyol and a polyacid.

[0008] Optionally, the polyol includes one or more of neopentyl glycol, hydrogenated bisphenol A, 1,6-hexanediol, diethylene glycol, trimethylolpropane, pentaerythritol, ethylene glycol, 1,2-propylene glycol, and butanediol;

[0009] The polyacid includes one or more of phthalic anhydride, tetrahydrophthalic anhydride, adipic acid, and hexahydrophthalic anhydride.

[0010] Optionally, the mass ratio of the polyol to the polyacid is 0.1 to 5:1.

[0011] Optionally, the acid value of the polyester cross-linking agent is 50 to 250 mgKOH / g.

[0012] Optionally, the epoxy includes one or more of phenol-type novolac epoxy resin, bisphenol A epoxy resin, and bisphenol F epoxy resin.

[0013] Optionally, the rosin includes one or more of primary rosin, hydrogenated rosin, disproportionated rosin, and polymerized rosin.

[0014] Optionally, the mass ratio of the epoxy, rosin and polyester cross-linking agent is 1:0.1-5:0.01-5.

[0015] The present invention provides a method for preparing the above-mentioned rosin graft copolymer containing a polyester crosslinking agent, comprising the following steps:

[0016] Epoxy, rosin and polyester crosslinking agent are mixed, and crosslinking reaction is carried out under the action of an initiator to obtain a rosin graft copolymer containing a polyester crosslinking agent.

[0017] The invention provides an ink, comprising the above-mentioned rosin graft copolymer containing a polyester cross-linking agent.

[0018] Compared with the prior art, the present invention provides a rosin graft copolymer containing a polyester crosslinking agent, which is a crosslinked product of epoxy and rosin under the action of the polyester crosslinking agent. By introducing a polyester crosslinking agent into the structure of the rosin graft copolymer, the present invention can fully crosslink the rosin graft copolymer, increase the molecular weight and softening point of the polymer, and at the same time improve the solvent resistance of the polymer. DETAILED DESCRIPTION

[0019] The invention provides a rosin graft copolymer containing a polyester crosslinking agent, which is a crosslinked product of epoxy and rosin undergoing a crosslinking reaction under the action of the polyester crosslinking agent.

[0020] The invention introduces a polyester crosslinking agent into the structure of the rosin graft copolymer, so that the rosin graft copolymer can be fully crosslinked, the molecular weight and softening point of the polymer are increased, and the solvent resistance of the polymer is also increased.

[0021] Preferably, the polyester crosslinking agent is a polymerization product of a polyol and a polyacid.

[0022] The polyol preferably includes one or more of neopentyl glycol, hydrogenated bisphenol A, 1,6-hexanediol, diethylene glycol, trimethylolpropane, pentaerythritol, ethylene glycol, 1,2-propylene glycol, and butanediol.

[0023] In some specific embodiments of the present invention, the polyol includes neopentyl glycol and hydrogenated bisphenol A, or includes 1,6-hexanediol and diethylene glycol, or includes neopentyl glycol and trimethylolpropane, or includes neopentyl glycol and pentaerythritol.

[0024] The mass ratio of the neopentyl glycol to hydrogenated bisphenol A is preferably 1:(0.1-10), more preferably 1:(0.5-5), and even more preferably 1:(0.5-1.5).

[0025] The mass ratio of 1,6-hexanediol to diethylene glycol is preferably 1:(0.05-10), more preferably 1:(0.1-5), and further preferably 1:(0.2-1).

[0026] The mass ratio of the neopentyl glycol to trimethylolpropane is preferably 1:(0.05-10), more preferably 1:(0.1-5), and further preferably 1:(0.2-1).

[0027] The mass ratio of the neopentyl glycol to pentaerythritol is preferably 1:(0.01-10), more preferably 1:(0.01-1), and further preferably 1:(0.05-1).

[0028] The polyacid preferably includes one or more of phthalic anhydride, tetrahydrophthalic anhydride, adipic acid, and hexahydrophthalic anhydride.

[0029] In some specific embodiments of the present invention, the polyacid includes phthalic anhydride and tetrahydrophthalic anhydride, or includes phthalic anhydride and adipic acid.

[0030] The mass ratio of the phthalic anhydride to the tetrahydrophthalic anhydride is preferably 1:(0.5-10), more preferably 1:(1-5).

[0031] The mass ratio of the phthalic anhydride to the adipic acid is preferably 1:(0.05-10), and more preferably 1:(0.1-1).

[0032] Preferably, the mass ratio of the total amount of the polyol to the total amount of the polyacid is 0.1 to 5:1, more preferably 0.1 to 1:1, and further preferably 0.3 to 0.9:1.

[0033] Preferably, the acid value of the polyester cross-linking agent is 50 to 250 mgKOH / g.

[0034] The present invention has no particular limitation on the type of the epoxy, and may be an epoxy compound known to those skilled in the art for preparing rosin graft copolymers, preferably including one or more of phenol-type novolac epoxy resin, bisphenol A epoxy resin, and bisphenol F epoxy resin.

[0035] In some specific embodiments of the present invention, the epoxy is specifically NPPN-631 phenol novolac epoxy resin, NPEL-128 bisphenol A epoxy resin, NPEF-170 bisphenol F epoxy resin or NPES-904H bisphenol A epoxy resin.

[0036] The present invention has no particular limitation on the type of the rosin, which may be any rosin known to those skilled in the art for preparing rosin graft copolymers, preferably including one or more of primary rosin, hydrogenated rosin, disproportionated rosin, and polymerized rosin.

[0037] The mass ratio of the epoxy, rosin and polyester crosslinking agent is preferably 1:0.1-5:0.01-5, more preferably 1:0.1-3:0.05-3, and further preferably 1:0.3-2:0.05-2.

[0038] The present invention provides a method for preparing the above-mentioned rosin graft copolymer containing a polyester crosslinking agent, comprising the following steps:

[0039] Epoxy, rosin and polyester crosslinking agent are mixed, and crosslinking reaction is carried out under the action of an initiator to obtain a rosin graft copolymer containing a polyester crosslinking agent.

[0040] The temperature of the cross-linking reaction is preferably 180±2°C.

[0041] Preferably, the initiator of the reaction is selected from triphenylphosphine.

[0042] Preferably, the reaction is terminated when the acid value of the reaction system is less than 10 mgKOH / g.

[0043] The present invention has no particular limitation on the preparation method of the polyester crosslinking agent, and the preparation method can be obtained by mixing polyol and polyacid to carry out polymerization reaction.

[0044] The polymerization temperature is preferably 200±5°C.

[0045] The present invention provides the use of the rosin graft copolymer containing a polyester crosslinking agent as an ink dispersant.

[0046] The rosin graft copolymer containing a polyester crosslinking agent provided by the present invention has a moderate crosslinking network structure, a relatively high molecular weight and a softening point, and has good oil solubility, and can be used as a dispersant in ink.

[0047] Based on this, the present invention provides an ink, comprising the above-mentioned rosin graft copolymer containing a polyester cross-linking agent.

[0048] The test results show that after adding the above-mentioned rosin graft copolymer containing polyester cross-linking agent, the gloss, softening point and solvent resistance of the ink are significantly improved.

[0049] In order to further illustrate the present invention, the following is a detailed description in conjunction with the embodiments. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the invention.

[0050] All raw materials of the present invention have no particular limitation on their sources, and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0051] Examples 1-4

[0052] The dosage ratio of each raw material is shown in Table 1.

[0053] Preparation process: raise the system temperature to 150±5℃, add all diols, stir evenly, wait until the diols are completely melted, cool the system to 90±5℃, add dibasic acid, pass nitrogen, slowly heat the system to 200±5℃, keep warm, the column top temperature is always lower than 95℃ during the reaction, and gradually decrease until the column top temperature is lower than 50℃, and no water is distilled out. Keep the temperature constant, gradually reduce the pressure to further react and dehydrate, and finally keep the pressure constant at around 0.09 vacuum degree, measure the acid value every 2h until the acid value reaches the predetermined value, and obtain the polyester crosslinking agent.

[0054] Table 1 Amounts of raw materials used and acid values ​​in Examples 1-4

[0055]

[0056] Embodiment 5-8

[0057] The dosage ratio of each raw material is shown in Table 2.

[0058] Preparation process: put all materials into the reactor, pass nitrogen to deoxygenate, slowly heat the reactor to 100±2℃, and start stirring when the materials are completely melted. Gradually heat the reaction to 180±2℃ and keep warm. When the acid ester is <10mgKOH / g, the material can be discharged to obtain the rosin graft copolymer containing polyester crosslinking agent.

[0059] Table 2 Amounts of raw materials used and acid values ​​of Examples 5-8

[0060]

[0061] The gloss, softening point and butanone rubbing resistance of the prepared rosin graft copolymer were tested, and the structure is shown in Table 3.

[0062] Table 3 Performance test results of rosin graft copolymers prepared in Examples 5 to 8

[0063] Example 5 Example 6 Example 7 Example 8 Glossiness / ° 95 93 98 99 Softening point / ℃ 145 168 156 162 Butanone resistant wipe / 1kg 150 200 80 180

[0064] Among them, glossiness and butanone wiping resistance are the performance tests of inks by applying the above rosin graft copolymers to inks.

[0065] The ink formula is shown in Table 4 below:

[0066] Table 4 Ink formula

[0067]

[0068] Preparation method of ink: After manually stirring and mixing all materials evenly, grind them with a three-roll mill for about 10-15 minutes.

[0069] Comparative Example 1-2

[0070] The preparation process is the same as that of Examples 5-8. The proportion of each raw material is shown in Table 5. The glossiness, softening point and butanone-resistant wiping performance test results are shown in Table 6.

[0071] Table 5 Comparative Examples 1-2 Amounts of Raw Materials and Acid Values

[0072] Comparative Example 1 Mass / g Comparative Example 2 Mass / g NPEF-170 160.7 NPES-904H 356.7 Triphenylphosphine 1 Triphenylphosphine 1 First-grade rosin 339.4 First-grade rosin 143.5 Acid value / mgKOH / g 7.3 Acid value / mgKOH / g 8.4

[0073] Table 6 Performance test results of rosin graft copolymers prepared in Comparative Examples 1 to 2

[0074] Comparative Example 1 Comparative Example 2 Glossiness / ° 92 95 Softening point / ℃ 132 128 Butanone resistant wipe / 1kg 10 20

[0075] The above glossiness and butanone wiping resistance test methods are the same as those in Examples 5-8.

[0076] The above examples and comparative examples show that the introduction of a polyester-based crosslinking agent can improve the glossiness and softening point of the rosin graft copolymer, and at the same time improve the solvent resistance of the polymer.

[0077] The above embodiments are only used to help understand the method and core idea of ​​the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A rosin graft copolymer containing a polyester crosslinking agent, characterized in that: It is a cross-linked product of epoxy and rosin under the action of polyester cross-linking agent.

2. The rosin graft copolymer containing a polyester crosslinking agent according to claim 1, characterized in that: The polyester crosslinking agent is a polymerization product of polyol and polyacid.

3. The rosin graft copolymer containing a polyester crosslinking agent according to claim 2, characterized in that: The polyol includes one or more of neopentyl glycol, hydrogenated bisphenol A, 1,6-hexanediol, diethylene glycol, trimethylolpropane, pentaerythritol, ethylene glycol, 1,2-propylene glycol, and butanediol; The polyacid includes one or more of phthalic anhydride, tetrahydrophthalic anhydride, adipic acid, and hexahydrophthalic anhydride.

4. The rosin graft copolymer containing a polyester crosslinking agent according to claim 2, characterized in that: The mass ratio of the polyol to the polyacid is 0.1 to 5:

1.

5. The rosin graft copolymer containing a polyester crosslinking agent according to claim 1, characterized in that: The acid value of the polyester cross-linking agent is 50 to 250 mgKOH / g.

6. The rosin graft copolymer containing a polyester crosslinking agent according to claim 1, characterized in that: The epoxy includes one or more of phenol-type novolac epoxy resin, bisphenol A epoxy resin, and bisphenol F epoxy resin.

7. The rosin graft copolymer containing a polyester crosslinking agent according to claim 1, characterized in that: The rosin includes one or more of primary rosin, hydrogenated rosin, disproportionated rosin and polymerized rosin.

8. The rosin graft copolymer containing a polyester crosslinking agent according to claim 1, characterized in that: The mass ratio of the epoxy, rosin and polyester cross-linking agent is 1:0.1-5:0.01-5.

9. The method for preparing the rosin graft copolymer containing a polyester crosslinking agent according to any one of claims 1 to 8, comprising the following steps: Epoxy, rosin and polyester crosslinking agent are mixed, and crosslinking reaction is carried out under the action of an initiator to obtain a rosin graft copolymer containing a polyester crosslinking agent.

10. An ink comprising the rosin graft copolymer containing a polyester crosslinking agent according to any one of claims 1 to 8.

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