1. The preparation method of the modified rosin phenolic resin is characterized by comprising the following steps:

s1 modification of rosin

Weighing rosin and dissolving the rosin in dichloromethane or tetrahydrofuran to obtain a solution A; weighing propyl zinc bromide and diisopropyl zinc, dissolving the propyl zinc bromide and the diisopropyl zinc bromide in anhydrous dichloromethane, stirring for 1-60min under the nitrogen protection atmosphere to obtain a solution B, mixing and stirring the solution A and the solution B uniformly to obtain a solution C, slowly adding an aromatic nitroso compound and 2-nitrosopyrimidine into the solution C under the nitrogen protection atmosphere and ice water bath conditions while stirring, continuously keeping the ice water bath and stirring for reaction for 20-24h after the addition is finished, adding petroleum ether or n-hexane after the reaction is finished, fully stirring, and separating and precipitating to obtain a rosin derivative;

wherein the aromatic nitroso compound is nitrosobenzene and alkylated derivatives thereof;

the mass ratio of the rosin to the propyl zinc bromide, the diisopropyl zinc, the aromatic nitroso compound and the 2-nitrosopyrimidine is 10.0: (5.7-5.8): (4.5-4.6): (2.0-2.5): (1.0-1.2);

s2 synthesis of phenolic pulp

Reacting alkylphenol with paraformaldehyde in the presence of an alkali catalyst to obtain alkylphenol formaldehyde resin slurry;

s3 preparation of rosin phenolic resin

Heating the rosin derivative to 240-255 ℃, adding a small amount of alkyl phenolic resin slurry for multiple times, carrying out heat preservation reaction for 1.5-2h to obtain a rosin phenolic condensation compound after the heat preservation reaction is finished, adding polyalcohol and an esterification catalyst, heating to 260-280 ℃, and carrying out heat preservation reaction for 1-2h to obtain the modified rosin phenolic resin.

2. The method for preparing a modified rosin phenol-formaldehyde resin according to claim 1, wherein in step S2, the weight ratio of the alkylphenol to the paraformaldehyde and the alkali catalyst is 1: (8-11): (0.002-0.004).

3. The method of claim 1, wherein in step S2, the alkylphenol is one or more selected from p-tert-butylphenol, p-tert-octylphenol, p-nonylphenol, and p-dodecylphenol.

4. The method according to claim 1, wherein in step S2, the base catalyst is triethylamine or an alkali metal hydroxide.

5. The method for preparing a modified rosin phenol resin according to claim 1, wherein in step S3, the weight ratio of the rosin derivative to the alkylphenol aldehyde resin syrup is (1.8-2): 2.

6. the method according to claim 1, wherein in step S3, the weight ratio of the rosin phenol aldehyde condensate to the polyol to the esterification catalyst is 100: (5-7): (0.01-0.02).

7. The method of claim 1, wherein in step S3, the polyol is one or more of 1, 4-butanediol, glycerol, and pentaerythritol.

8. The method for preparing modified rosin phenolic resin according to claim 1, wherein in step S3, the esterification catalyst is magnesium oxide and/or zinc oxide.

9. The method for preparing the modified rosin phenolic resin according to claim 1, wherein the rosin in step S1 is a pretreated rosin, and the preparation method is as follows:

weighing rosin, dissolving the rosin in dichloromethane or tetrahydrofuran, adding 4-dimethylaminopyridine, fully and uniformly stirring to obtain a solution D, heating to 50-60 ℃, dropwise adding thionyl chloride while stirring, heating to 75-85 ℃ after dropwise adding, stirring for reacting for 2-3 hours, adding dichloromethane or tetrahydrofuran with the same volume as a reaction system for diluting, dropwise adding alkyl diamine under the condition of ice-water bath, stirring for reacting for 1-2 hours, washing with an alkaline aqueous solution after the reaction is finished, and drying an organic phase and then evaporating the solvent to obtain the pretreated rosin;

wherein the weight ratio of the rosin to the 4-dimethylaminopyridine to the thionyl chloride to the alkyldiamine is 10: (0.05-0.07): (5-5.1): (2-2.3).

10. A modified rosin phenol resin characterized by being produced by the production method according to any one of claims 1 to 9.

Background

The inks are of a wide variety of types and vary in properties, and for offset inks, they are required to maintain colloidal properties under high shear conditions and to have fast drying characteristics, which requires the use of high quality binder resins for the inks. The binder is a liquid component in the ink, is a carrier of solid powder such as a coloring material, a filling material and the like, uniformly disperses the coloring material and the filling material in the carrier, enables the ink to have proper rheological property and drying property, and is a film-forming substance, and the pigment is firmly attached to the surface of a printing stock by film-forming through drying of the binder, so that the drying property and the film quality of the ink are determined by the binder.

The rosin modified phenolic resin is a high-grade ink binder component, is also the resin with the largest consumption in printing ink, and the performance of the rosin modified phenolic resin determines the quality grade of the ink, so that the preparation of the high-performance rosin modified phenolic resin becomes a key technology for producing the high-quality ink. With the development of the current printing industry, the printing speed is continuously improved, and the thermosetting offset printing ink is required to have the characteristics of high softening point, high viscosity and high heptane tolerance, but the general rosin modified phenolic resin has weakened solubility to mineral oil along with the increase of the softening point, and the heptane tolerance is reduced, so that the requirements of quick drying and high softening point of the thermosetting offset printing ink resin are difficult to meet.

How to improve the solution viscosity and mineral oil tolerance of the rosin modified phenolic resin is the key for improving the quality of the ink.

Disclosure of Invention

The invention provides a modified rosin phenolic resin and a preparation method thereof, aiming at the problem that the softening point and the accommodation degree of the rosin phenolic resin are difficult to be considered at the same time.

The purpose of the invention is realized by adopting the following technical scheme:

a preparation method of modified rosin phenolic resin comprises the following steps:

s1 modification of rosin

Weighing rosin and dissolving the rosin in dichloromethane or tetrahydrofuran to obtain a solution A; weighing propyl zinc bromide and diisopropyl zinc, dissolving the propyl zinc bromide and the diisopropyl zinc bromide in anhydrous dichloromethane, stirring for 1-60min under the nitrogen protection atmosphere to obtain a solution B, mixing and stirring the solution A and the solution B uniformly to obtain a solution C, slowly adding an aromatic nitroso compound and 2-nitrosopyrimidine into the solution C under the nitrogen protection atmosphere and ice water bath conditions while stirring, continuously keeping the ice water bath and stirring for reaction for 20-24h after the addition is finished, adding petroleum ether or n-hexane after the reaction is finished, fully stirring, and separating and precipitating to obtain a rosin derivative;

wherein the aromatic nitroso compound is nitrosobenzene and alkylated derivatives thereof;

the mass ratio of the rosin to the propyl zinc bromide, the diisopropyl zinc, the aromatic nitroso compound and the 2-nitrosopyrimidine is 10.0: (5.7-5.8): (4.5-4.6): (2.0-2.5): (1.0-1.2);

s2 synthesis of phenolic pulp

Reacting alkylphenol with paraformaldehyde in the presence of an alkali catalyst to obtain alkylphenol formaldehyde resin slurry;

s3 preparation of rosin phenolic resin

Heating the rosin derivative to 240-255 ℃, adding a small amount of alkyl phenolic resin slurry for multiple times, carrying out heat preservation reaction for 1.5-2h to obtain a rosin phenolic condensation compound after the heat preservation reaction is finished, adding polyalcohol and an esterification catalyst, heating to 260-280 ℃, and carrying out heat preservation reaction for 1-2h to obtain the modified rosin phenolic resin.

Preferably, in step S2, the weight ratio of the alkylphenol to the paraformaldehyde and the base catalyst is 1: (8-11): (0.002-0.004).

Preferably, in step S2, the alkylphenol is one or more of p-tert-butylphenol, p-tert-octylphenol, p-nonylphenol and p-dodecylphenol.

Preferably, in step S2, the base catalyst is triethylamine or alkali metal hydroxide.

Preferably, in step S3, the weight ratio of the rosin derivative to the alkylphenol aldehyde resin syrup is (1.8-2): 2.

preferably, in step S3, the weight ratio of the rosin phenol-formaldehyde condensate to the polyol and the esterification catalyst is 100: (5-7): (0.01-0.02).

Preferably, in step S3, the polyol is one or more of 1, 4-butanediol, glycerol, and pentaerythritol.

Preferably, in step S3, the esterification catalyst is magnesium oxide and/or zinc oxide.

Preferably, the rosin in step S1 is a pretreated rosin, and the preparation method thereof is:

weighing rosin, dissolving the rosin in dichloromethane or tetrahydrofuran, adding 4-dimethylaminopyridine, fully and uniformly stirring to obtain a solution D, heating to 50-60 ℃, dropwise adding thionyl chloride while stirring, heating to 75-85 ℃ after dropwise adding, stirring for reacting for 2-3 hours, adding dichloromethane or tetrahydrofuran with the same volume as a reaction system for diluting, dropwise adding alkyl diamine under the condition of ice-water bath, stirring for reacting for 1-2 hours, washing with an alkaline aqueous solution after the reaction is finished, and drying an organic phase and then evaporating the solvent to obtain the pretreated rosin;

wherein the weight ratio of the rosin to the 4-dimethylaminopyridine to the thionyl chloride to the alkyldiamine is 10: (0.05-0.07): (5-5.1): (2-2.3).

The invention also aims to provide a modified rosin phenolic resin prepared by the preparation method.

The invention has the beneficial effects that:

(1) the invention modifies rosin and then condenses with alkyl phenolic resin to obtain rosin phenolic resin with large accommodation degree, high softening point, low acid value and high viscosity, concretely, D-A addition activity of conjugated double bond of various diterpenoid resin acids in the rosin is utilized, nitroso double bond is taken as dienophile, diene addition is carried out under the condition of organic zinc catalyst, two ends of N ═ O group are respectively connected with conjugated diene carbon atom, aromatic group containing benzene ring or pyrimidine ring is introduced into resin acid, on one hand, the introduction of aromatic hydrocarbon matrix improves the softening point of the rosin and modified resin, and simultaneously improves the solubility of the rosin and modified resin in oily solvent, simultaneously, N-O bond formed by addition is easy to break, so that the rosin has amino and hydroxyl, the amino reduces the acid value of the modified resin, and the hydroxyl can form hydrogen bond structure with nitrogen atom on the pyrimidine ring, on the basis of avoiding increasing viscosity, the resin viscosity is improved, and the bonding and offset printing quality of the modified rosin phenolic resin is improved.

(2) The rosin modified phenolic resin is generally esterified by branched polyol and carboxyl to reduce the acid value of the rosin modified phenolic resin, and plays a role in crosslinking, but the carboxyl of the rosin is positioned on a tertiary carbon atom, so that the steric hindrance is large, and the polyol for crosslinking and esterification also has a branched structure, so that the reaction steric hindrance is further increased, the occurrence of esterification is not facilitated, and an esterification catalyst with higher activity is often needed; on the basis of utilizing amino to reduce the acid value, the method firstly uses alkyl diamine as a cross-linking agent through an acyl chlorination method, further reduces the acid value through carboxyl amidation, plays a role of primary cross-linking, further esterifies and cross-links through linear chain dihydric alcohol with low steric hindrance, reduces the steric hindrance of esterification, and simultaneously improves the cross-linking degree and the molecular weight.

Detailed Description

The invention is further described with reference to the following examples.

Example 1

The preparation method of the modified rosin phenolic resin comprises the following steps:

s1 modification of rosin

Weighing 100kg of rosin and dissolving the rosin in dichloromethane or tetrahydrofuran to obtain a solution A; weighing 57kg of propyl zinc bromide and 45kg of diisopropyl zinc, dissolving the propyl zinc bromide and the diisopropyl zinc in anhydrous dichloromethane, stirring for 10min under a nitrogen protective atmosphere to obtain a solution B, mixing and stirring the solution A and the solution B uniformly to obtain a solution C, stirring and slowly adding 22kg of nitrosobenzene and 10kg of 2-nitrosopyrimidine in the solution C under the nitrogen protective atmosphere and an ice water bath condition, keeping the temperature and stirring for reacting for 20h after the addition is finished, adding petroleum ether or n-hexane after the reaction is finished, fully stirring, and separating and precipitating to obtain a rosin derivative;

s2 synthesis of phenolic pulp

Placing 100kg of p-tert-octylphenol in a reaction kettle, heating until the p-tert-octylphenol is completely melted, adding 1000kg of paraformaldehyde and 0.3kg of triethylamine, heating to 95 ℃, carrying out heat preservation reaction until the Gauss viscosity of 80% isopropanol in the reaction kettle is T-U, so that the time is 2.5h, and cooling to 75 ℃ to obtain phenolic resin slurry for later use;

s3 preparation of rosin phenolic resin

Adding 200kg of rosin derivative into a reaction kettle, heating to 245 ℃, adding 200kg of phenolic resin slurry at a constant speed in batches within 4h, carrying out heat preservation reaction for 2h to obtain a rosin phenolic condensation compound, keeping the temperature of the rosin phenolic condensation compound at 245 ℃, adding 4 wt% of 1, 4-butanediol, 3 wt% of glycerol, 0.008 wt% of silicon dioxide and 0.012 wt% of magnesium oxide into the rosin phenolic condensation compound, heating to 265 ℃, and carrying out heat preservation reaction for 2h to obtain the modified rosin phenolic resin.

Example 2

The preparation method of the modified rosin phenolic resin comprises the following steps:

s0, pretreatment

Weighing 100kg of rosin, dissolving the rosin in dichloromethane or tetrahydrofuran, adding 0.6kg of 4-dimethylaminopyridine, fully and uniformly stirring to obtain a solution D, heating to 56 ℃, dropwise adding 50kg of thionyl chloride while stirring, heating to 80 ℃ after the dropwise addition is finished, stirring for reaction for 2 hours, adding dichloromethane or tetrahydrofuran with the same volume as that of a reaction system for dilution, dropwise adding 22kg of butanediamine under the ice-water bath condition, stirring for reaction for 2 hours, washing with an alkaline aqueous solution after the reaction is finished, and evaporating the solvent after an organic phase is dried to obtain the pretreated rosin;

s1 modification of rosin

Weighing the rosin prepared in the step S0, and dissolving the rosin in dichloromethane or tetrahydrofuran to obtain a solution A; weighing 57kg of propyl zinc bromide and 45kg of diisopropyl zinc, dissolving the propyl zinc bromide and the diisopropyl zinc in anhydrous dichloromethane, stirring for 10min under a nitrogen protective atmosphere to obtain a solution B, mixing and stirring the solution A and the solution B uniformly to obtain a solution C, stirring and slowly adding 22kg of nitrosobenzene and 10kg of 2-nitrosopyrimidine in the solution C under the nitrogen protective atmosphere and an ice water bath condition, keeping the temperature and stirring for reacting for 20h after the addition is finished, adding petroleum ether or n-hexane after the reaction is finished, fully stirring, and separating and precipitating to obtain a rosin derivative;

s2 synthesis of phenolic pulp

Placing 100kg of p-tert-octylphenol in a reaction kettle, heating until the p-tert-octylphenol is completely melted, adding 1000kg of paraformaldehyde and 0.3kg of triethylamine, heating to 95 ℃, carrying out heat preservation reaction until the Gauss viscosity of 80% isopropanol in the reaction kettle is T-U, so that the time is 2.5h, and cooling to 75 ℃ to obtain phenolic resin slurry for later use;

s3 preparation of rosin phenolic resin

Adding 200kg of rosin derivative into a reaction kettle, heating to 245 ℃, adding 200kg of phenolic resin slurry at a constant speed in batches within 4h, carrying out heat preservation reaction for 2h to obtain a rosin phenolic condensation compound, keeping the temperature of the rosin phenolic condensation compound at 245 ℃, adding 4 wt% of 1, 4-butanediol, 3 wt% of glycerol, 0.008 wt% of silicon dioxide and 0.012 wt% of magnesium oxide into the rosin phenolic condensation compound, heating to 265 ℃, and carrying out heat preservation reaction for 2h to obtain the modified rosin phenolic resin.

Comparative example 1

The preparation method of the modified rosin phenolic resin comprises the following steps:

s1 synthesis of phenolic pulp

Placing 100kg of p-tert-octylphenol in a reaction kettle, heating until the p-tert-octylphenol is completely melted, adding 1000kg of paraformaldehyde and 0.3kg of triethylamine, heating to 95 ℃, carrying out heat preservation reaction until the Gauss viscosity of 80% isopropanol in the reaction kettle is T-U, so that the time is 2.5h, and cooling to 75 ℃ to obtain phenolic resin slurry for later use;

s2 preparation of rosin phenolic resin

Adding 200kg of rosin into a reaction kettle, heating to 245 ℃, adding 200kg of the phenolic resin slurry at a constant speed in batches within 4h, carrying out heat preservation reaction for 2h to obtain a rosin phenolic condensation compound, keeping the temperature of the rosin phenolic condensation compound at 245 ℃, adding 4 wt% of 1, 4-butanediol, 3 wt% of glycerol, 0.008 wt% of silicon dioxide and 0.012 wt% of magnesium oxide into the rosin phenolic condensation compound, heating to 265 ℃, and carrying out heat preservation reaction for 2h to obtain the modified rosin phenolic resin.

Comparative example 2

A modified rosin phenol resin was prepared in the same manner as in example 1, wherein step S1 is:

weighing 100kg of rosin and dissolving the rosin in dichloromethane or tetrahydrofuran to obtain a solution A; weighing 57kg of propyl zinc bromide and 45kg of diisopropyl zinc, dissolving in anhydrous dichloromethane, stirring for 10min under a nitrogen protective atmosphere to obtain a solution B, mixing and stirring uniformly the solution A and the solution B to obtain a solution C, slowly adding 22kg of nitrosobenzene into the solution C under the conditions of the nitrogen protective atmosphere and an ice water bath while stirring, continuously keeping the temperature and stirring for reaction for 20h after the addition is finished, adding petroleum ether or n-hexane after the reaction is finished, fully stirring, and separating and precipitating to obtain the rosin derivative.

Examples of the experiments

The modified rosin phenol resins of examples 1-2 and comparative examples 1-2 were tested for their performance indexes, and the test results were as follows:

finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.