Novel rosin modified phenolic resin and preparation method thereof
By using modifiers and reactants such as boric acid, methyl trimethoxysilane and epoxy chain extenders in rosin modified phenolic resin, the problem of too slow infiltration rate and too long curing time in traditional offset printing inks was solved. A new rosin modified phenolic resin with fast curing, good water resistance and anti-flying properties was prepared. It is suitable for a variety of offset printing inks and improves printing efficiency.
Patent Information
- Application Number
- CN202510126959.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-27
- Publication Date
- 2025-04-08
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The mineral oil used in traditional offset printing inks has potential impact on human health, while vegetable oil, as a substitute, requires a new rosin-modified phenolic resin to solve the problem of the slow penetration of vegetable oil into the paper and the curing time for too long, affecting printing efficiency.
Boric acid and methyl trimethoxysilane are used as modifiers, combined with epoxy chain extender and react with carboxyl groups in the precursor of the rosin-modified phenolic resin to form a new crosslinking point, enhancing the internal toughening properties and water resistance of the resin, and optimizing the condensation reaction process between phenols and aldehydes to produce a new rosin-modified phenolic resin with good solubility, medium and high viscosity and high gloss.
It has achieved rapid curing of new rosin-modified phenolic resin, excellent water resistance and ink resistance resistance, and is suitable for all types of single-sheet offset printing inks, cold-solid hot-solid offset printing inks and lithographic offset printing inks, improving printing efficiency.
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Figure BDA0005260136230000081
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of phenolic resins, and more specifically to a novel rosin-modified phenolic resin and a preparation method thereof. Background Art
[0002] Mineral oil hydrocarbons (MOH) is a mixture of hydrocarbons formed by the physical separation and chemical transformation of petroleum, mainly including linear, branched and cyclic saturated hydrocarbon mineral oils (MOSH) and benzene-ring-containing aromatic hydrocarbon mineral oils (MOAH). Traditional offset inks use mineral oil as a solvent, but mineral oil has potential effects on human health. For example, MOAH may be mutagenic and carcinogenic, and MOSH may accumulate in multiple tissues such as lymph nodes, spleen and liver. Vegetable oils do not have the above potential effects. Therefore, replacing traditional mineral oils with vegetable oils or their derivatives is an inevitable development trend of offset inks in the future.
[0003] Traditional offset ink contains 10% to 30% mineral oil. After the ink is transferred to the paper, the mineral oil will quickly penetrate into the pores of the paper. The ink loses solvent and turns from liquid phase to solid phase, forming penetration drying. In order to balance the penetration drying speed and ink gloss, offset ink containing mineral oil will choose highly soluble rosin-modified phenolic resin. However, the solubility of vegetable oil ink in rosin-modified phenolic resin is higher than that of traditional offset ink containing mineral oil. If the original high-soluble resin is still used, the speed of vegetable oil penetrating into the pores of the paper will slow down, the curing time will be longer, and the requirement of rapid flipping during printing will not be met, or it will take a long time to solidify before flipping, which will affect printing efficiency.
[0004] In the prior art, there are usually two processes for preparing rosin-modified phenolic resin:
[0005] (1) After the rosin is heated and dissolved, the required raw materials are added in sequence, firstly at 100-140°C for phenolic condensation reaction, and then the temperature is raised to 240-280°C for esterification reaction to produce rosin-modified phenolic resin, which is called the one-step process.
[0006] (2) Phenol and formaldehyde are first subjected to condensation reaction in the presence of a catalyst, then rosin is added for modification, and then polyols are added for esterification reaction to produce rosin-modified phenolic resin, which is called the two-step method. Regardless of the method used, the catalysts generally used in the phenol-formaldehyde condensation reaction are as follows: (1) alkali metal oxides or hydroxides, such as NaOH, KOH, CaO, Ca(OH)2, MgO, Mg(OH)2; (2) organic volatile alkaline compounds: ethanolamine, triethylamine, fatty amines, etc.
[0007] When using alkali metal oxides or hydroxides as catalysts, if the condensation reaction is not neutralized and washed with water, the catalyst will react with rosin to form rosin salt. If rosin salt is soluble in water, it will have a serious impact on the water resistance and emulsification of the ink; those that are insoluble in water (such as calcium abietic acid) are very difficult to dissolve in many solvents, and are also difficult to dissolve in vegetable oils and mineral oils, which is very unfavorable for synthesizing highly soluble products. If neutralization and washing are to be performed, the condensation reaction must be carried out in the presence of a solvent, which increases production costs and brings safety hazards, and also generates a large amount of wastewater, bringing environmental problems. At the same time, washing with water will cause a decrease in product yield and increase production costs. Summary of the invention
[0008] The invention provides a novel rosin-modified phenolic resin and a preparation method thereof. The prepared novel rosin-modified phenolic resin has good solubility, medium-high viscosity, high elastic structure, high gloss, good water resistance and good anti-ink flying property. It is suitable for various sheet-fed offset printing inks, cold-set and hot-set offset printing inks, and lithographic offset printing inks.
[0009] In a first aspect, the present invention provides a novel rosin-modified phenolic resin, the raw material components comprising:
[0010] The reactants are rosin, complex phenols, formaldehyde, catalyst, modifier and polyol, and epoxy chain extender is added to the reactants; the complex phenols include tert-octylphenol, tert-butylphenol and tert-butylphenol; the modifiers are boric acid and methyltrimethoxysilane.
[0011] Preferably, the mass ratio of boric acid to methyltrimethoxysilane in the modifier is 1:1-5.
[0012] Preferably, the epoxy chain extender is one or more of aliphatic epoxides, alicyclic epoxy compounds, epoxy functional polymers, polyethylene terephthalate and polybutylene terephthalate.
[0013] Preferably, the mass percentages of the composite phenols are 10-15% of p-tert-octylphenol, 5-7.2% of p-butylphenol, and 5-10% of p-tert-butylphenol.
[0014] Preferably, the mass percentages of the composite phenols are 12-15% of p-tert-octylphenol, 6.5-7.2% of p-butylphenol, and 8-10% of p-tert-butylphenol.
[0015] Preferably, the rosin is at least one of gum rosin, tall oil rosin and polymerized rosin; the gum rosin is horsetail rosin, wetland rosin, Yunnan rosin, South Asian rosin or South American rosin.
[0016] Preferably, the catalyst is one or more of sodium hydroxide, calcium hydroxide, sodium formate, sodium acetate, sodium oxalate, aqueous ammonia, diethylamine, triethylamine and hexamethylenetetramine.
[0017] Preferably, the mass ratio of boric acid to methyltrimethoxysilane in the modifier is 1:3.
[0018] Preferably, the polyol is one or more of ethylene glycol, propylene glycol, neopentyl glycol, glycerol, trimethylolpropane, and pentaerythritol.
[0019] In a second aspect, the present invention provides a method for preparing a novel rosin-modified phenolic resin, comprising the following steps:
[0020] (1) reacting rosin, polyols and a catalyst to obtain a rosin derivative;
[0021] (2) reacting the composite phenols with formaldehyde under the action of a catalyst to obtain a phenolic resin;
[0022] (3) adding the phenolic resin obtained in step (2) to the rosin derivative obtained in step (1), and then adding a modifier to obtain a novel rosin-modified phenolic resin.
[0023] Preferably, in step (1), the reaction temperature is 150-250° C. and the insulation time is 0.5-2 h.
[0024] Preferably, in step (2), the reaction temperature is 220-270°C.
[0025] In a third aspect, the present invention provides an application of a novel rosin-modified phenolic resin, and the application of the novel rosin-modified phenolic resin in ink.
[0026] In summary, the present invention has the following beneficial effects:
[0027] 1. In the present invention, boric acid and methyltrimethoxysilane are used as modifiers, phenol and formaldehyde are used as raw materials, and boron-modified phenolic resin and boron / silicon co-modified phenolic resin are prepared respectively. Boron and silicon atoms are connected to the phenolic resin molecular chain in the structures of BO, OBC, Si-OB, etc., which improves the heat resistance of the phenolic resin. Both BPF and B / SiPF can improve the flexural strength and high temperature stability of impregnated graphite.
[0028] 2. The epoxy chain extender of the present invention generates a hydroxyl group with the carboxyl group in the rosin-modified phenolic resin precursor, but the generated hydroxyl structure is subject to large steric hindrance, and the water resistance of the rosin-modified phenolic resin is improved. When the chain extender is an epoxy chain extender, it will react with the hydroxyl group in the rosin-modified phenolic resin precursor, the number of hydroxyl groups will decrease, the molecular weight will increase, and new cross-linking points will be formed, thereby enhancing the internal toughening performance of the phenolic resin, so that the water resistance of the rosin-modified phenolic resin is improved.
[0029] 3. The present invention uses phenols and aldehydes to condense in the presence of a catalyst to generate a soluble phenolic resin, and after reacting with the esterified synthetic product of rosin through a special process, an irregular reddish brown transparent solid resin is obtained. The obtained new rosin-modified phenolic resin has good solubility, medium-high viscosity, high elastic structure, high gloss, good water resistance and good anti-ink flying property. The new rosin-modified phenolic resin is suitable for various types of sheet-fed offset printing inks, cold-set and hot-set offset printing inks, lithographic offset printing inks, etc.
[0030] It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not intended to limit the scope of protection of the present invention. DETAILED DESCRIPTION
[0031] The present invention is further described in detail below in conjunction with the examples. It is particularly noted that if no specific conditions are specified in the following examples, the reactions are carried out according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following examples can be obtained from common commercial sources.
[0032] Example
[0033] Example 1
[0034] A novel rosin-modified phenolic resin, the raw material components include:
[0035] 950g of rosin, 280g of compound phenol, 565g of formaldehyde, 326g of catalyst, 450g of modifier and 265g of polyol reactants, 65g of epoxy chain extender is added to the reactants; the compound phenol includes 10% of tert-octylphenol, 5% of tert-butylphenol and 5% of tert-butylphenol; the modifier is a mixture of boric acid and methyltrimethoxysilane in a mass ratio of 1:1. The epoxy chain extender is KL-E4370, the rosin is horsetail rosin, the catalyst is triethylamine, and the polyol is pentaerythritol.
[0036] A method for preparing a novel rosin-modified phenolic resin comprises the following steps:
[0037] (1) reacting rosin, polyols and a catalyst to obtain a rosin derivative; the reaction temperature is 150° C. and the insulation time is 1 hour;
[0038] (2) reacting the composite phenols with formaldehyde under the action of a catalyst at a reaction temperature of 220° C. to obtain a phenolic resin;
[0039] (3) adding the phenolic resin obtained in step (2) to the rosin derivative obtained in step (1), and then adding a modifier to obtain a novel rosin-modified phenolic resin.
[0040] Example 2
[0041] A novel rosin-modified phenolic resin, the raw material components include:
[0042] 1200g of rosin, 310g of compound phenol, 520g of formaldehyde, 355g of catalyst, 425g of modifier and 286g of polyol reactants, 85g of epoxy chain extender is added to the reactants; the compound phenol includes 12% of tert-octylphenol, 6.5% of tert-butylphenol and 8% of tert-butylphenol; the modifier is a mixture of boric acid and methyltrimethoxysilane in a mass ratio of 1:3. The epoxy chain extender is KL-E4370, the rosin is horsetail rosin, the catalyst is triethylamine, and the polyol is pentaerythritol.
[0043] A method for preparing a novel rosin-modified phenolic resin comprises the following steps:
[0044] (1) reacting rosin, polyols and a catalyst to obtain a rosin derivative; the reaction temperature is 180° C. and the insulation time is 1 hour;
[0045] (2) reacting the composite phenols with formaldehyde under the action of a catalyst at a reaction temperature of 250° C. to obtain a phenolic resin;
[0046] (3) adding the phenolic resin obtained in step (2) to the rosin derivative obtained in step (1), and then adding a modifier to obtain a novel rosin-modified phenolic resin.
[0047] Example 3
[0048] A novel rosin-modified phenolic resin, the raw material components include:
[0049] 1052g of rosin, 275g of compound phenol, 505g of formaldehyde, 362g of catalyst, 469g of modifier and 265g of polyol reactants, 78g of epoxy chain extender added to the reactants; the compound phenol includes 15% of tert-octylphenol, 6% of tert-butylphenol and 8% of tert-butylphenol; the modifier is a mixture of boric acid and methyltrimethoxysilane in a mass ratio of 1:2. The epoxy chain extender is KL-E4370, the rosin is horsetail rosin, the catalyst is triethylamine, and the polyol is pentaerythritol.
[0050] A method for preparing a novel rosin-modified phenolic resin comprises the following steps:
[0051] (1) reacting rosin, polyols and a catalyst to obtain a rosin derivative; the reaction temperature is 200° C. and the heat preservation time is 1 hour;
[0052] (2) reacting the composite phenols with formaldehyde under the action of a catalyst at a reaction temperature of 250° C. to obtain a phenolic resin;
[0053] (3) adding the phenolic resin obtained in step (2) to the rosin derivative obtained in step (1), and then adding a modifier to obtain a novel rosin-modified phenolic resin.
[0054] Example 4
[0055] A novel rosin-modified phenolic resin, the raw material components include:
[0056] The reactants are 923g of rosin, 220g of compound phenol, 585g of formaldehyde, 312g of catalyst, 463g of modifier and 289g of polyol, and 82g of epoxy chain extender is added to the reactants; the compound phenol includes 13% of tert-octylphenol, 7% of tert-butylphenol and 12% of tert-butylphenol; the modifier is a mixture of boric acid and methyltrimethoxysilane in a mass ratio of 1:5. The epoxy chain extender is KL-E4370, the rosin is horsetail rosin, the catalyst is triethylamine, and the polyol is pentaerythritol.
[0057] A method for preparing a novel rosin-modified phenolic resin comprises the following steps:
[0058] (1) reacting rosin, polyols and a catalyst to obtain a rosin derivative; the reaction temperature is 190° C. and the heat preservation time is 1 hour;
[0059] (2) reacting the composite phenols with formaldehyde under the action of a catalyst at a reaction temperature of 230° C. to obtain a phenolic resin;
[0060] (3) adding the phenolic resin obtained in step (2) to the rosin derivative obtained in step (1), and then adding a modifier to obtain a novel rosin-modified phenolic resin.
[0061] Example 5
[0062] A novel rosin-modified phenolic resin, the raw material components include:
[0063] 1000g of rosin, 210g of compound phenol, 524g of formaldehyde, 350g of catalyst, 435g of modifier and 280g of polyol reactants, 72g of epoxy chain extender is added to the reactants; the compound phenol includes 14% of tert-octylphenol, 6.8% of tert-butylphenol and 10% of tert-butylphenol; the modifier is a mixture of boric acid and methyltrimethoxysilane in a mass ratio of 1:5. The epoxy chain extender is KL-E4370, the rosin is horsetail rosin, the catalyst is triethylamine, and the polyol is pentaerythritol.
[0064] A method for preparing a novel rosin-modified phenolic resin comprises the following steps:
[0065] (1) reacting rosin, polyols and a catalyst to obtain a rosin derivative; the reaction temperature is 200° C. and the heat preservation time is 1 hour;
[0066] (2) reacting the composite phenols with formaldehyde under the action of a catalyst at a reaction temperature of 270° C. to obtain a phenolic resin;
[0067] (3) adding the phenolic resin obtained in step (2) to the rosin derivative obtained in step (1), and then adding a modifier to obtain a novel rosin-modified phenolic resin.
[0068] Comparative Example 1
[0069] The preparation was carried out in the same manner as in Example 1, except that the modifiers boric acid and methyltrimethoxysilane were not added.
[0070] Comparative Example 2
[0071] The preparation was carried out in the same manner as in Example 1, except that the composite phenols p-tert-octylphenol, p-butylphenol and p-tert-butylphenol were not added.
[0072] Performance Testing:
[0073] The softening points of the novel rosin-modified phenolic resins prepared in Examples 1-5 and Comparative Examples 1-2 were tested using the ring and ball method.
[0074] The detection of the rotational viscosity of the new rosin-modified phenolic resin includes the following steps:
[0075] The resin and linseed oil were mixed in a mass ratio of 1:2, and then heated and dissolved at 200°C for 20 minutes. The viscosity was then measured using a NDJ-79 viscometer at a temperature of 25°C.
[0076] The test of n-heptane solubility of the new rosin-modified phenolic resin includes the following steps:
[0077] Place 2 grams of a 1:2 mixture of resin and linseed oil fired at 200°C in a 100ml beaker, control the temperature at 25°C, then add n-heptane dropwise while stirring until the No. 5 font on the newspaper underneath can no longer be read, and measure the amount of n-heptane added.
[0078] The detection of iron-cobalt color of new rosin-modified phenolic resin includes the following steps:
[0079] Pour the resin liquid into the sample tube and arrange it horizontally with the iron-cobalt colorimeter, compare through the side and take the closest color number.
[0080] The test results of the novel rosin-modified phenolic resins prepared in Examples 1-5 and Comparative Examples 1-2 are shown in Table 1 below.
[0081] Table 1
[0082]
[0083] As shown in Table 1, the novel rosin-modified phenolic resins prepared in Examples 1-5 have the characteristics of low solubility, high viscosity and high softening point. Compared with general high molecular weight and high solubility resins (n-heptane tolerance is higher than 5.0 mL / g) and high molecular weight and low solubility resins (n-heptane tolerance is lower than 5.0 mL / g), the novel rosin-modified phenolic resins are suitable for various types of sheet-fed offset printing inks, cold-set and hot-set offset printing inks, and lithographic offset printing inks. The prepared all-plant inks have fast fixation, excellent water resistance and excellent anti-ink flying performance.
[0084] The above is only an exemplary embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.
Claims
1. A novel rosin-modified phenolic resin, characterized in that: The raw material components include: The reactants are rosin, complex phenols, formaldehyde, catalyst, modifier and polyol, and epoxy chain extender is added to the reactants; the complex phenols include tert-octylphenol, tert-butylphenol and tert-butylphenol; the modifiers are boric acid and methyltrimethoxysilane.
2. The novel rosin-modified phenolic resin according to claim 1, characterized in that: The mass ratio of boric acid to methyltrimethoxysilane in the modifier is 1:1-5.
3. The novel rosin-modified phenolic resin according to claim 1, characterized in that: The epoxy chain extender is one or more of aliphatic epoxides, alicyclic epoxy compounds, epoxy functional polymers, polyethylene terephthalate, and polybutylene terephthalate.
4. The novel rosin-modified phenolic resin according to claim 1, characterized in that: The rosin is at least one of gum rosin, tall oil rosin and polymerized rosin; the gum rosin is horsetail rosin, wetland rosin, Yunnan rosin, South Asian rosin or South American rosin.
5. The novel rosin-modified phenolic resin according to claim 1, characterized in that: The catalyst is one or more of sodium hydroxide, calcium hydroxide, sodium formate, sodium acetate, sodium oxalate, ammonia water, diethylamine, triethylamine and hexamethylenetetramine.
6. The novel rosin-modified phenolic resin according to claim 1, characterized in that: The mass percentages of the composite phenols are 10-15% of p-tert-octylphenol, 5-7.2% of p-butylphenol and 5-10% of p-tert-butylphenol.
7. The novel rosin-modified phenolic resin according to claim 1, characterized in that: The polyol is one or more of ethylene glycol, propylene glycol, neopentyl glycol, glycerol, trimethylolpropane, and pentaerythritol.
8. The method for preparing the novel rosin-modified phenolic resin according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) reacting rosin, polyols and a catalyst to obtain a rosin derivative; (2) reacting the composite phenols with formaldehyde under the action of a catalyst to obtain a phenolic resin; (3) adding the phenolic resin obtained in step (2) to the rosin derivative obtained in step (1), and then adding a modifier to obtain a novel rosin-modified phenolic resin.
9. The method for preparing the novel rosin-modified phenolic resin according to claim 8, characterized in that: In step (1), the reaction temperature is 150-250° C. and the insulation time is 0.5-2 h; in step (2), the reaction temperature is 220-270° C.
10. The use of the novel rosin-modified phenolic resin according to claim 1, characterized in that: Application of the novel rosin-modified phenolic resin in ink.