CN104558462A - Method for preparing rosin-modified phenolic resin - Google Patents

Abstract

The invention discloses a method for preparing a rosin-modified phenolic resin. The method comprises the following steps: heating and melting rosin or polymerized rosin or a mixture of rosin and polymerized rosin, after rosin or polymerized rosin or the mixture of rosin and polymerized rosin is completely molten, stirring, adding alkylphenol, cooling, adding paraformaldehyde and a catalyst in batches, reacting, adding pentaerythritol, heating, carrying out heat preservation for 6 hours, vacuumizing, cooling and discharging the material, wherein the molar ratio of alkylphenol to paraformaldehyde is (1: 2.30)-(1: 2.70); and the molar ratio of rosin or polymerized rosin or the mixture of rosin and polymerized rosin to alkylphenol is (1: 0.4)-(1: 0.5) and the catalyst accounts for 0.1%-0.15% of rosin or polymerized rosin or the mixture of rosin and polymerized rosin. By the method, the problems of difficulty in the control on the quality indicators of a condensation product and large amount of generated wastewater of the existing method for preparing rosin-modified phenolic resin can be solved.

Description

The preparation method of rosin modified phenolic resin

Technical field

The present invention relates to rosin deep process technology field, especially a kind of preparation method for rosin modified phenolic resin.

Background technology

Along with the development of China's economy, under the drive of the industries such as printing, journalism, packing and decorating, exploitation, ink industry is also developed rapidly; Meanwhile, along with Environmental Protection in China consciousness and the enhancing of Consciousness of food security, the specification of quality of people to all kinds of printed matter is more and more higher.Domestic and international market has also been put into effect serial policy and has been limited ink contamination problems, for adapting to the new demand both at home and abroad to ink, domestic ink enterprise develops environment-friendlyink ink one after another, as without benzene without ketone ink, water color ink, heavy metal flexographic ink up to standard, offset printing without aromatic hydrocarbons ink, offset printing soya-bean ink (low VOC) etc., the key that ink performance improves is the raising of its resin binder performance.Flexographic ink is occupied an leading position in the many ink kinds of China, and its annual production accounts for 50 ~ 60% of national ink ultimate production.Current resin used for offset ink is still based on rosin modified phenolic resin, but traditional rosin modified phenolic resin (phenol of use mainly contains phenol, xylenol, dihydroxyphenyl propane etc.) exists the shortcomings such as softening temperature is on the low side, solvability is poor, viscoelasticity is not good, the demand of high speed offset printing development cannot be met; And the performance of resin depends on the type of alkylphenol to a great extent, use the senior resol such as Abietyl modified tertiary butyl phenol, octyl phenol, nonyl phenol, 4-dodecylphenol to have higher viscosity, good solubility, substantially meet the requirement of high speed offset printing.

At present, the preparation technology of domestic rosin modified phenolic resin has two kinds, i.e. single stage method and two step method.

Single stage method, by alkylphenol, rosin melting, adds catalyzer (urotropine) and formaldehyde reacts, then esterification.Waste water in this technique is sloughed in vapour form, be easy to environmental protection treatment, but the phenol formaldehyde condensation occurred in molten rosin reaction is easily because temperature of reaction is high, dissolve uneven and produce a lot of side reaction, thus the detection of condensation product and the more difficult monitoring of Mass adjust-ment, not easily obtain stable rosin products.

Two step method first synthesizes your mixed alkyl of lithol resol, then with Abietyl modified and polyhydric alcohol; This method can obtain structure and the metastable phenol formaldehyde condensation oligopolymer of composition, each step of reaction is more easy to control, quality product is also comparatively stable, but this technique need neutralize through acid, and could react with rosin with after large water gaging repeatedly rinsing desalination, produce a large amount of phenolic wastewater thus, difficult treatment, big for environment pollution, and during the work consuming of pole.

Summary of the invention

Problem to be solved by this invention is to provide a kind of preparation method of rosin modified phenolic resin, to solve the more difficult monitoring of condensation product quality index of the preparation method of existing rosin modified phenolic resin, and the problem that the wastewater flow rate of generation is large.

In order to solve the problem, technical scheme of the present invention is: the preparation method of this rosin modified phenolic resin comprises the following steps: heated by the mixture of rosin or polymerized rosin or rosin and polymerized rosin and melt, stir after melting completely, alkylphenol is added 150 ~ 160 DEG C time, in 1 hour, add paraformaldehyde and catalyzer after being cooled to 118 ~ 143 DEG C in batches, insulation reaction is after 3 hours, be warming up to 225 ~ 230 DEG C of insulations 1 hour, add tetramethylolmethane, 270 ~ 275 DEG C of insulations are heated to after 6 hours with 2 hours, vacuumize, cooling discharge;

The mol ratio of described alkylphenol and described paraformaldehyde is 1:2.30 ~ 1:2.70;

The mixture of described rosin or polymerized rosin or rosin and polymerized rosin and the mol ratio of described alkylphenol are 1:0.4 ~ 1:0.5;

Described catalyzer accounts for 0.1% ~ 0.15% of the mixture of described rosin or polymerized rosin or rosin and polymerized rosin; Described catalyzer is zinc oxide or activated magnesia.

Owing to have employed technique scheme, the present invention compared with prior art has following beneficial effect:

The preparation method of this rosin modified phenolic resin with the mixture of rosin or polymerized rosin or rosin and polymerized rosin, paraformaldehyde, alkylphenol for main raw material, under zinc oxide or activated magnesia do the effect of catalyzer, adopt the rosin modified phenolic resin product that one-step synthesis method solvability is good, viscosity is high, be mainly used in high speed flexographic ink industry.Present method mainly comprises phenolic aldehyde addition reaction, the condensation of hydroxymethyl alkyl phenol, rosin and the condensation of hydroxymethyl alkyl phenol and the unit such as D ~ A addition reaction, polyhydric alcohol (polyvalent alcohol consumption is 1.10 ~ 1.20 times of carboxyl and hydroxyl equivalent in system) occurs, can effective control for product quality index, and the waste water produced is few.

Embodiment

Below in conjunction with embodiment, the invention will be further described:

Embodiment one:

To be crushed to particle diameter is about in the four-hole boiling flask of the stirring of 1cm rosin (acid number: 169mg/g) 700 grams input band, reflux exchanger, pass into nitrogen replacement, be heated to 150 ~ 160 DEG C of meltings, stirring is started after material melts completely, the p-tert-butylphenol 132.0 grams of 96% content is added at 150 ~ 160 DEG C, be cooled to 118 ~ 123 DEG C, in 1 hour, add the paraformaldehyde 73.5 grams of 93% content and 0.7 gram, zinc oxide in batches, 118 ~ 123 DEG C of insulation reaction 3 hours; Insulation terminates, and is warming up to 225 ~ 230 DEG C and after being incubated 1 hour, adds the tetramethylolmethane 67 grams of 98% content with 4 hours, be warming up to 270 ~ 275 DEG C with 2 hours, be incubated 6 hours, vacuumize 1 hour, be cooled to 230 ~ 240 DEG C, discharging, obtain rosin modified phenolic resin.Use rosin modified phenolic resin prepared by present method, its product appearance is transparent; Softening temperature (ring and ball method): 149.5 DEG C; Color (iron ~ cobalt colorimetric): 11+; Acid number: 22.3mg/g; Normal heptane value: 5.4ml/(25 DEG C 2g); Viscosity (resin: oleum lini=1:2,35 DEG C): 901 mpa.s; Solvability (with toluene 1:1): clear.Indices all meets salable product index.

Embodiment two:

To be crushed to particle diameter is about in the four-hole boiling flask of the stirring of 1cm rosin (acid number: 169mg/g) 700 grams input band, reflux exchanger, pass into nitrogen replacement, be heated to 150 ~ 160 DEG C of meltings, stirring is started after material melts completely, the p-tert-butylphenol 148.5 grams of 96% content is added at 150 ~ 160 DEG C, be cooled to 128 ~ 133 DEG C, what in 1 hour, add 93% content enters paraformaldehyde 76.5 grams and activated magnesia 0.7 gram in batches, 128 ~ 133 DEG C of insulation reaction 3 hours; Insulation terminates, and is warming up to 225 ~ 230 DEG C and after being incubated 1 hour, adds the tetramethylolmethane 69.8 grams of 98% content with 4 hours, be warming up to 270 ~ 275 DEG C with 2 hours, be incubated 6 hours, vacuumize 1 hour, be cooled to 230 ~ 240 DEG C, namely discharging obtains rosin modified phenolic resin.Use rosin modified phenolic resin prepared by present method, its product appearance is transparent; Softening temperature (ring and ball method): 156.8 DEG C; Color (iron ~ cobalt colorimetric): 11; Acid number: 22.3mg/g; Normal heptane value: 6.3ml/(25 DEG C 2g); Viscosity (resin: oleum lini=1:2,35 DEG C): 903 mpa.s; Solvability (with toluene 1:1): clear.Indices all meets salable product index.

Embodiment three:

To be crushed to particle diameter is about in the four-hole boiling flask of the stirring of 1cm rosin (acid number: 169mg/g) 700 grams input band, reflux exchanger, pass into nitrogen replacement, be heated to 150 ~ 160 DEG C of meltings, stirring is started after material melts completely, the p-tert-butylphenol 165 grams of 96% content is added at 150 ~ 160 DEG C, be cooled to 138 ~ 143 DEG C, in 1 hour, add the paraformaldehyde 91.8 grams of 93% content and 1.05 grams, zinc oxide in batches, 138 ~ 143 DEG C of insulation reaction 3 hours; Insulation terminates, and is warming up to 225 ~ 230 DEG C and after being incubated 1 hour, adds the tetramethylolmethane 69 grams of 98% content with 4 hours, be warming up to 270 ~ 275 DEG C with 2 hours, be incubated 6 hours, vacuumize 1 hour, be cooled to 230 ~ 240 DEG C, namely discharging obtains rosin modified phenolic resin.Use rosin modified phenolic resin prepared by present method, its product appearance is transparent; Softening temperature (ring and ball method): 156.0 DEG C; Color (iron ~ cobalt colorimetric): 11+; Acid number: 21.2mg/g; Normal heptane value: 7.4ml/(25 DEG C 2g); Viscosity (resin: oleum lini=1:2,35 DEG C): 945 mpa.s; Solvability (with toluene 1:1): clear.Indices all meets salable product index.

Embodiment four:

To be crushed to particle diameter is about in the four-hole boiling flask of the stirring of 1cm rosin (acid number: 169mg/g) 700 grams input band, reflux exchanger, pass into nitrogen replacement, be heated to 150 ~ 160 DEG C of meltings, stirring is started after material melts completely, the tert.-butyl phenol 165 grams to 96% content is added at 150 ~ 160 DEG C, be cooled to 118 ~ 123 DEG C, in 1 hour, add the paraformaldehyde 78.2 grams of 93% content and activated magnesia 0.7 gram in batches, 118 ~ 123 DEG C of insulation reaction 3 hours; Insulation terminates, and is warming up to 225 ~ 230 DEG C and after being incubated 1 hour, adds the tetramethylolmethane 63.4 grams of 98% content with 4 hours, be warming up to 270 ~ 275 DEG C with 2 hours, be incubated 6 hours, vacuumize 1 hour, be cooled to 230 ~ 240 DEG C, namely discharging obtains rosin modified phenolic resin.Use rosin modified phenolic resin prepared by present method, its product appearance is transparent; Softening temperature (ring and ball method): 156.0 DEG C; Color (iron ~ cobalt colorimetric): 10+; Acid number: 25.4mg/g; Normal heptane value: 7.1ml/(25 DEG C 2g); Viscosity (resin: oleum lini=1:2,35 DEG C): 892mpa.s; Solvability (with toluene 1:1): clear.Indices all meets salable product index.

Embodiment five:

To be crushed to particle diameter is about in the four-hole boiling flask of the stirring of 1cm rosin (acid number: 169mg/g) 700 grams input band, reflux exchanger, pass into nitrogen replacement, be heated to 150 ~ 160 DEG C of meltings, stirring is started after material melts completely, the p-tert-butylphenol 165 grams of 96% content is added at 150 ~ 160 DEG C, be cooled to 128 ~ 133 DEG C, in 1 hour, add the paraformaldehyde 85 grams of 93% content and activated magnesia 1.05 grams in batches, 128 ~ 133 DEG C of insulation reaction 3 hours; Insulation terminates, and is warming up to 225 ~ 230 DEG C and after being incubated 1 hour, adds the tetramethylolmethane 66.2 grams of 98% content with 4 hours, be warming up to 270 ~ 275 DEG C with 2 hours, be incubated 6 hours, vacuumize 1 hour, be cooled to 230 ~ 240 DEG C, namely discharging obtains rosin modified phenolic resin.Use rosin modified phenolic resin prepared by present method, its product appearance is transparent; Softening temperature (ring and ball method): 157.6 DEG C; Color (iron ~ cobalt colorimetric): 11; Acid number: 23.2mg/g; Normal heptane value: 6.0ml/(25 DEG C 2g); Viscosity (resin: oleum lini=1:2,35 DEG C): 1047mpa.s; Solvability (with toluene 1:1): clear.Indices all meets salable product index.

Claims (1)

1. the preparation method of a rosin modified phenolic resin, it is characterized in that: comprise the following steps: the mixture of rosin or polymerized rosin or rosin and polymerized rosin is heated and melts, stir after melting completely, alkylphenol is added 150 ~ 160 DEG C time, in 1 hour, add paraformaldehyde and catalyzer after being cooled to 118 ~ 143 DEG C in batches, insulation reaction is after 3 hours, be warming up to 225 ~ 230 DEG C of insulations 1 hour, add tetramethylolmethane, 270 ~ 275 DEG C of insulations are heated to after 6 hours with 2 hours, vacuumize, cooling discharge;

The mol ratio of described alkylphenol and described paraformaldehyde is 1:2.30 ~ 1:2.70;

The mixture of described rosin or polymerized rosin or rosin and polymerized rosin and the mol ratio of described alkylphenol are 1:0.4 ~ 1:0.5;

Described catalyzer accounts for 0.1% ~ 0.15% of the mixture of described rosin or polymerized rosin or rosin and polymerized rosin; Described catalyzer is zinc oxide or activated magnesia.