CN101942070B - Phenolic resin for color offset printing ink and preparation method thereof - Google Patents
Phenolic resin for color offset printing ink and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a phenolic resin for color offset printing ink and a preparation method thereof. The method comprises the following steps: adding colophony into a reaction kettle, dissolving by heating, stirring, and heating to 100-110 DEG C; adding alkyl phenol, completely dissolving and evenly mixing by stirring, adding formaldehyde, defoaming agent and catalyst into the reaction kettle, heating to 145-148 DEG C, raising the pressure intensity to 0.4-0.5 Mpa, and reacting for 2-2.5 hours under constant temperature and constant pressure to obtain a colophony condensed intermediate; and adding mixed polyhydric alcohol, catalyst and defoaming agent into the reaction kettle for synthesizing the colophony condensed intermediate, heating to 240-260 DEG C, controlling the pressure intensity at 0.05-0.15 Mpa, and carrying out esterification reaction for 2-3 hours under constant temperature and constant pressure. The invention has the advantages of simple preparation technique, accessible raw materials, low investment, and no wastewater or exhaust emission, and realizes clean production; and the reactant conversion rate reaches 95%.
Description
Technical field
The present invention relates to the preparation method of fine chemical product coloured glue printing ink, coating connection material resol, the preparation method of particularly high performance coloured glue printing ink rosin modified phenolic resin and series product.
Background technology
The developmental level of the performance resins that the high-performance color flexographic ink is special-purpose is one of flourishing sign of countries and regions economic civilization of reflection.Connecting material is the fluid section in the printing ink, and the salient features of printing ink all depends on low-melting ink vehicle like flowability, viscosity, gloss, fastness, wear-resisting wiping, dryness and printing performance, and low-melting ink vehicle is called as the heart of printing ink.Connect material and mainly form, roughly be divided into natural resin, natural resin processed products and synthetic resins three major types by resin.Being applied to the high-performance color printing-ink in the market, to produce employed resin be to be main with phenol aldehyde modified Gum Rosin type, and this resinoid has environmental friendliness as connecting material, renewable and excellent properties becomes present main products.This modified resin gathers used phenols has alkylphenol, tertiary butyl phenol, phenol, sylvan etc.Rosin modified phenolic resin is used for the high-grade goods ink type has Rosin Modified Nonyl Phenolic Resin, resole condenses.Represent F7301 Article Number resin that resin dedicated KR-42404, K-1400, K-2300 Article Number resin and the Japanese firm that has U.S. Lauth OY to produce of the printing ink of world level produce etc., these resins all belong to the alkylphenol modified rosin resin.With the printing ink of these production of resins have Gao Guang, do soon, adhere to, the body bone reaches characteristics such as colour is bright-coloured well, can better satisfy top grades such as modern high low speed planography, colour and print the ink quality performance demands.Rosin modified phenolic resin technology is divided into single stage method and two step (multistep) methods at present.Single stage method is an example with the F7301 Article Number resin that Japanese firm produces, and main the utilization from the rosin of China's import is basic raw material, carries out condensation through adding alkylphenol and formaldehyde, through the dehydration esterification, makes rosin modified phenolic resin again.This preparing method's operational path is simpler, but the difficult control of the structure of the intermediate product first rank phenolic condensation compound of synthetic resins may influence the finished product resin purity or structure.Another approach is a two-step approach, obtains final product at first with alkylphenol and the synthetic first rank phenolic condensation compounds (or being called phenolic aldehyde slurry) of formaldehyde, and then with the rosin addition reaction through the polyvalent alcohol esterification.This technological reaction course is clear, and controllable product quality property is strong, but facility investment is more relatively.KR-42404, K-1400, K-2300 Article Number resin that U.S. Lauth OY produces, the ratio of raw material rosin, alkylphenol, polyvalent alcohol is relatively low, and cost is higher, and unknown concrete production process.
Summary of the invention
The objective of the invention is to overcome the problem that the off-set oil ink connecting material solvability that prior art produces is relatively poor, softening temperature is lower, viscosity is relatively poor exists with the not high defective prior art of molecular weight; Provide that a kind of raw material is easy to get, technology is simpler; Low, the excellent combination property of preparation cost; Reaction-ure conversion-age is high, coloured glue printing ink resol of no waste water and gas discharging and preparation method thereof.
The present invention is a raw material with rosin, alkylphenol, formaldehyde, preparation rosin condensation midbody under catalyzer and certain temperature and pressure effect; Through rosin condensation midbody and polyol blend, under certain temperature and pressure and catalyzer, carry out esterification, the preparation high-performance is used for the rosin modified phenolic resin of coloured glue printing ink.
The object of the invention is realized through following technical scheme:
A kind of preparation method of coloured glue printing ink resol may further comprise the steps:
(1) preparation rosin condensation midbody: rosin is added in the reaction kettle, and heating is dissolved and is stirred, and heats to 100-110 ℃; Add alkylphenol, be stirred to and dissolve fully and mix, formaldehyde, skimmer and catalyzer are added reaction kettle, heat to 145-148 ℃, pressure is brought up to 0.4-0.6Mpa, under constant temperature and pressure, reacts 2-2.5 hour, promptly obtains rosin condensation midbody;
Said formaldehyde: alkylphenol: the rosin mol ratio is 3-4: 1-1.5: 3.5-6;
Said catalyzer is an acidic catalyst or inorganic alkaline catalyst, and said an acidic catalyst is oxalic acid, toluenesulphonic acids, phosphorous acid or ortho phosphorous acid; Said inorganic alkaline catalyst is sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, Marinco H, calcium hydroxide, zinc oxide or Natural manganese dioxide; Said catalyst levels is the 0.1-0.2% of rosin weight;
Said skimmer is a dimethyl silicone oil, and consumption is the 0.0006-0.0008% of rosin weight;
Said alkylphenol is phenol, octyl phenol, NP, tertiary butyl phenol or 4-dodecylphenol;
(2) rosin modified phenolic resin preparation: the reaction kettle that polyol blend, catalyzer and skimmer is added the synthetic rosin condensation midbody of step (1); Be warmed up to 240-260 ℃; Pressure is controlled at 0.05-0.15Mpa; Agitator stirs, and constant temperature and pressure carried out esterification 2-3 hour, obtained the product rosin modified phenolic resin;
Described polyol blend is the mixture of the pure and mild second type of alcohol of the first kind; Wherein first kind alcohol is tetramethylolmethane; Second type of alcohol is USP Kosher and/or terepthaloyl moietie, and described polyol blend consumption is the 50-75% of rosin mole number, and wherein the mol ratio of the pure and mild second type of alcohol of the first kind is 1: 0.8-1;
Described catalyzer is an acidic catalyst, inorganic alkaline catalyst or organic basic catalyzer; Said an acidic catalyst is one or more in oxalic acid, toluenesulphonic acids, phosphorous acid and the ortho phosphorous acid; Inorganic alkaline catalyst is one or more in sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, Marinco H, calcium hydroxide, zinc oxide and the Natural manganese dioxide; Described organic basic catalyzer is one or both in hexamethylenetetramine, triethylamine and the diethylamine; Said catalyst levels is the 0.1-0.2% of rosin weight;
Described skimmer is a dimethyl silicone oil, and the skimmer consumption is the 0.0007-0.001% of rosin weight.
For further realizing the object of the invention, the formaldehyde of said step (1) is Paraformaldehyde 96 solid particulate and/or liquid formaldehyde.
It is 3-5 ℃/min that said step (1) heats to 100-110 ℃ heat-up rate.
It is 2-3 ℃/min that said step (1) heats to 145-148 ℃ heat-up rate.
It is 2.5-3.5 ℃/min that said step (2) is warmed up to 240-260 ℃ heat-up rate.
A kind of coloured glue printing ink resol is by method for preparing.
Compared with prior art, the present invention not only can produce the connection material that is applicable to different multicolor printings (low speed or high speed printing) printing ink, and production process is simple, operational safety, and have following advantage:
1. the inventive method can be accomplished the preparation of rosin modified phenolic resin and series product at a reaction kettle, has reduced facility investment.
2. the inventive method the first step temperature in the kettle when reaction kettle is prepared rosin condensation midbody is about 145-148 ℃; Need not the cooling of rosin condensation midbody can then be added polyol blend; Continue heating simultaneously temperature is brought up to 240-260 ℃, can reduce the energy consumption of operating process.
The inventive method preparation rosin condensation midbody and resol, employed catalyst selectivity is good, catalytic performance is high; This synthesis route is simple, and synthetic rosin condensation midbody productive rate reaches 95%, and the resol productive rate surpasses 90%.
4. preparation method of the present invention except the reaction creating pockets of air, through adding outside the extraction of skimmer deaeration and vacuum pump, does not have the discharging of by product and waste water and gas in the entire operation process, realizes cleaner production.
5. in reaction kettle, adopted rational heating and temperature control system, can make the interior difference temperature difference of entire reaction still, guaranteed rosin condensation midbody and resol quality product 0.5 ℃ of scope.
6. can be according to the performance of different colored printing inks; Adopt different catalysts or two kinds of catalyzer (comprising acidity or basic catalyst) compound; Different raw materials and ratio; Different operating conditions is prepared the rosin modified phenolic resin series product that have different performance rosin condensation midbody and have different performance, satisfies different colored printing inks and connects the material needs.
7. adopt pressing technology to prepare rosin condensation midbody, it is violent to add the pressure ratio synthesis under normal pressure, can shorten generated time by about 2 hours; The pressurization synthetic operation is steady, difficult generation rise still and close-burning phenomenon; Esterification pressure (0.05-0.15Mpa) helps the further condensation of phenolic aldehyde of not condensation a little more than normal pressure, has improved utilization ratio of raw materials.
Description of drawings
Fig. 1 is that colored used for offset ink resol prepares the device structure synoptic diagram.
Embodiment
Below in conjunction with embodiment the present invention is described further, but the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
As shown in Figure 1, colored used for offset ink resol prepares equipment and is mainly reaction kettle 1, is provided with whisking appliance 5 and well heater 20 in the reaction kettle 1, and reaction kettle 1 is connected with compressor 2 through pipeline 14; Reaction kettle 1 is connected with holding tank 19 through vacuum pump 17; Reaction kettle 1 is connected with tank 18 through cooling-water pump 3, and reaction kettle 1 also is connected with tank 18 through pipeline 11; Reaction kettle 1 is connected with storage tank 4 through pipeline 15; Reaction kettle 1 is connected with sampling line 12; Reaction kettle 1 is connected with exhaust-valve 16; Reaction kettle 1 also is connected with 13 with pipeline 6,7,8,9,10 respectively, is respectively applied for to add rosin, alkylphenol, catalyzer, formaldehyde, skimmer and polyvalent alcohol.Reaction kettle 1 jacketed refrigerating unit.
Embodiment 1
Application drawing 1 apparatus shown prepares colored used for offset ink resol and comprises the steps:
(1) drives exhaust-valve 16 and startup compressor 2, nitrogen was fed reaction kettle 1 cleaning reaction still about 15 minutes, close exhaust-valve 16 and compressor 2 through pipeline 14.Rosin is added reaction kettle 1 by pipeline 6, the raw material in the beginning reacting by heating still, and heat up gradually, heat-up rate is 3.5 ℃/min, heats to 110 ℃, the difference temperature head is controlled at 0.5 ℃ in the reaction kettle.Start whisking appliance 5 and stir, through pipeline 7 4-dodecylphenol is joined fused rosin reaction kettle 1 bottom, the mol ratio of rosin and 4-dodecylphenol is 3.8: 1; It is even to be stirred to the interior raw material of still, adds catalyst n aOH, Paraformaldehyde 96 (solid particulate) and skimmer dimethyl silicone oil respectively through pipeline 8,9,10; Catalyst consumption is 0.1% of a rosin weight, and the mol ratio of formaldehyde and 4-dodecylphenol is 4: 1, and the skimmer consumption is 0.0007% of a rosin weight.Then; Start the pressure raising 0.5Mpa (gauge pressure) of compressor 2 with reaction kettle 1, be warmed up to 146 ℃ simultaneously, heat-up rate is 3 ℃/min; Constant temperature and constant voltage building-up reactions are after 2 hours; Through pipeline 12 sampling analysis, prove that the 4-dodecylphenol transformation efficiency reaches more than 95% with regard to stopped reaction, obtains rosin condensation midbody.
(2) through exhaust-valve 16 pressure is reduced to 0.1Mpa (gauge pressure); Through pipeline 13 polyol blend is added to reaction kettle 1; Polyol blend is the mixture of USP Kosher and tetramethylolmethane; Wherein the mol ratio of USP Kosher and tetramethylolmethane is 1: 1, and the mol ratio of polyol blend and 4-dodecylphenol is 1: 2; Composite catalyst is added in the reaction kettle 1 through pipeline 8, and composite catalyst is that mol ratio is 1: 1 Natural manganese dioxide and a zinc oxide, and the consumption of composite catalyst is 0.1% of a rosin weight; The skimmer dimethyl silicone oil adds in the reaction kettle 1 through pipeline 10, and the skimmer consumption is 0.0008% of a rosin weight; With heat-up rate is that 3 ℃/min brings up to 260 ℃ with temperature; The difference temperature head is controlled at 0.5 ℃ in the reaction kettle; The constant temperature and pressure reaction began through sampling line 12 sampling analysis after 2 hours, when acid number (KOH)＜below the 20mg/g, all other quality index of sample meet following standard; Comprise: softening temperature＞175 ℃, viscosity＞17000mpas/20 ℃, color and luster (Gardner)≤10, normal heptane value＞8ml/g; Stopped reaction, (acid number of product is pressed GB2895282 and is measured, and softening temperature and color and luster are pressed the HG2-231-65 standard detection to make rosin modified phenolic resin #1; The resin that is determined as of viscosity mixes by 12: 1 volume ratios with oleum lini, is heated to 250 ℃ and dissolves, and is to be cooled to 35 ℃, and water temperature constant temperature is with NDJ-79 type rotary viscosity design determining; The normal heptane pH-value determination pH is: add 1g toluene with the above-mentioned viscosimetric analysis sample of every 2g, can hold normal heptane milliliter numerical table at 25 ℃ and show), stop heating; Startup vacuum pump 17 decompression vacuum pumpings (to-0.07Mpa) deaeration in 15 minutes; Foam is extracted into holding tank 19, stops to vacuumize, start cooling-water pump 3 and make product cool to 90 ℃ to jacket reactor 1 cooling-water pump through pipeline 11 from tank 18; Water coolant returns tank 18; Stop cooling, start compressor 2 and be forced into 0.02Mpa (gauge pressure), go out product to storage tank 4 through pipeline 15.Rosin modified phenolic resin #1 is mainly used in the connection material of high-grade coloured glue printing ink; Its performance index are following:
1. softening temperature:＞175 ℃
2. acid number (mgKOH/g)＜20
3. color and luster (Gardner)≤10
4. viscosity＞17000mpas/20 ℃
5. oil soluble: transparent no particle;
6. normal heptane value (ml/g)＞8
7. solvability in the benzene: clear
Molecular resin amount＞5,000 ten thousand.
Present embodiment makes the quality standard that colored used for offset ink resol #1 reaches the similar resin of Japanese firm (F7301 resin).
The price that adopts 1 ton of resol #1 expense of present embodiment method preparation and Japanese firm's like product import to such as
Table 1:
Table 1
Visible by table 1; The resol #1 price of the inventive method preparation is merely similar resin (F7301) price 57% from Japanese firm's import; This is because adopt the resol #1 of present technique invention in the preparation of Xinyi City, the rosin place of production, adopts local rosin raw material, has reduced transportation cost; And produce all basic raw materials of colored used for offset ink resol #1 and be the lower raw material of homemade commercially available price, it is lower to have reduced production cost.
With the equipment of Fig. 1, drive exhaust-valve 16 and compressor 2, through pipeline 14 nitrogen was fed reaction kettle 1 cleaning reaction still about 15 minutes, close exhaust-valve 16 and compressor 2.Rosin is added reaction kettle 1 by pipeline 6, the raw material in the beginning reacting by heating still, and heat up gradually; Heat-up rate is 4 ℃/min, heats to 100 ℃, and the difference temperature head is controlled at 0.5 ℃ in the reaction kettle; Start whisking appliance 5 and stir, with octyl phenol=(mol ratio) added Polycondensation Reactor and Esterification Reactor 1 through pipeline 7 with octyl phenol in 3.5: 1, it is also even to be stirred in the still material dissolution by rosin; Add catalyzer oxalic acid, Paraformaldehyde 96 (solid particulate) and skimmer dimethyl silicone oil respectively through pipeline 8,9,10, catalyst levels is 0.15% of a rosin weight, and the ratio of formaldehyde and octyl phenol is=3.8: 1 (mol ratio); The skimmer consumption is 0.0008% of a rosin weight, then, starts the pressure raising 0.6Mpa (gauge pressure) of compressor 2 with reaction kettle 1; Be warmed up to 145 ℃ simultaneously, heat-up rate is 2.5 ℃/min, and constant temperature and constant voltage building-up reactions are after 2.5 hours; Through pipeline 12 sampling analysis, prove that the 4-dodecylphenol transformation efficiency reaches more than 95% with regard to stopped reaction, obtains rosin condensation midbody.
Through exhaust-valve 16 pressure is reduced to 0.12Mpa (gauge pressure), through pipeline 13 by USP Kosher: tetramethylolmethane=mol ratio was added to reaction kettle 1 in 0.8: 1, and polyol blend (USP Kosher+tetramethylolmethane) is 1: 1.8 with the octyl phenol mol ratio; By the mol ratio of toluenesulphonic acids and ortho phosphorous acid is composite catalyst to be added to reaction kettle 1 through pipeline 8 in 1: 0.8, and catalyst levels is 0.15% of a rosin weight; The skimmer dimethyl silicone oil adds in the reaction kettle 1 through pipeline 10, and the skimmer consumption is 0.0009% of a rosin weight; With heat-up rate is that 3.5 ℃/min brings up to 255 ℃ with temperature; The difference temperature head is controlled at 0.5 ℃ in the reaction kettle; The constant temperature and pressure reaction began through sampling line 12 sampling analysis after 2.5 hours, when acid number (KOH)＜below the 20mg/g, all other quality index of sample meet following standard; Comprise: softening temperature＞172 ℃, viscosity＞15000mpas/20 ℃, the transparent no particle of oil soluble, normal heptane value＞7ml/g; Stopped reaction, (acid number of product is pressed GB2895282 and is measured, and softening temperature and color and luster are pressed the HG2-231-65 standard detection to make rosin modified phenolic resin #2; The resin that is determined as of viscosity mixes by 12: 1 volume ratios with oleum lini, is heated to 250 ℃ and dissolves, and is to be cooled to 35 ℃, and water temperature constant temperature is with NDJ-79 type rotary viscosity design determining; The normal heptane pH-value determination pH is: add 1g toluene with the above-mentioned viscosimetric analysis sample of every 2g, can hold normal heptane milliliter numerical table at 25 ℃ and show), stop heating; Startup vacuum pump 17 decompression vacuum pumpings (to-0.07Mpa) deaeration in 15 minutes; Foam is extracted into holding tank 19, stops to vacuumize, start cooling-water pump 3 and make product cool to 90 ℃ to jacket reactor 1 cooling-water pump through pipeline 11 from tank 18; Water coolant returns tank 18; Stop cooling, start compressor 2 and be forced into 0.02Mpa (gauge pressure), go out product to storage tank 4 through pipeline 15.Rosin modified phenolic resin #2 is mainly used in the material that is connected of newsprinting paper and advertisement coloured glue printing ink, and its performance index are following:
1. softening temperature＞172 ℃
2. acid number (mgKOH/g)＜20
3. color and luster (Gardner)≤10
4. viscosity＞15000mpas/20 ℃
5. oil soluble: transparent no particle;
6. normal heptane value (ml/g)＞7
7. solvability in the benzene: clear
Molecular resin amount＞6,000 ten thousand.
Product reaches the quality standard of the similar resin of U.S. Lauth OY.The price that adopts 1 ton of resol # 2 expense of the inventive method preparation and U.S. Lauth OY like product (KR-42404 resin) import is to such as table 2:
Table 2
Visible by table 2, the resol # 2 price of the inventive method preparation is merely similar resin (KR-42404 resin) price 56% from the import of U.S. Lauth OY.This is because adopt the resol # 2 of present technique invention in the preparation of Xinyi City, the rosin place of production; Adopt local rosin raw material; Reduced transportation cost; And produce all basic raw materials of colored used for offset ink resol # 2 and be the lower raw material of homemade commercially available price, it is lower to have reduced production cost.
With the equipment of Fig. 1, drive exhaust-valve 16 and compressor 2, through pipeline 14 nitrogen was fed reaction kettle 1 cleaning reaction still about 15 minutes, close exhaust-valve 16 and compressor 2.Rosin is added reaction kettle 1 by pipeline 6, the raw material in the beginning reacting by heating still, and heat up gradually; Heat-up rate is 4.5 ℃/min, heats to 105 ℃, and the difference temperature head is controlled at 0.5 ℃ in the reaction kettle; Start whisking appliance 5 and stir, with NP=(mol ratio) joined molten rosin Polycondensation Reactor and Esterification Reactor 1 through pipeline 7 with NP in 4: 1, it is also even to be stirred in the still material dissolution by rosin; Add catalyzer phosphorous acid, skimmer dimethyl silicone oil and formaldehyde (liquid) through pipeline 8,9,10, catalyst levels is 0.12% of a rosin weight, and the ratio of formaldehyde and NP is=3.5: 1 (mol ratio); The skimmer consumption is 0.0007% of a rosin weight, and liquid formaldehyde drips equably, after formaldehyde drips; Start the pressure raising 0.45Mpa (gauge pressure) of compressor 2 with reaction kettle 1, be warmed up to 148 ℃ simultaneously, heat-up rate is 3.5 ℃/min; About 2.2 hours of constant temperature and constant voltage building-up reactions; Through sampling line 12 sampling analysis, prove that the NP transformation efficiency reaches more than 95% with regard to stopped reaction, obtains product rosin condensation midbody.
To be reduced to 0.15Mpa (gauge pressure) by force through exhaust-valve 16; Through pipeline 13 by USP Kosher: tetramethylolmethane: the mol ratio of terepthaloyl moietie=1: 1: 0.8 is added to reaction kettle 1; Polyol blend (USP Kosher, tetramethylolmethane and terepthaloyl moietie) and NP mol ratio are 1: 2.1, are compound organic basic catalyst to be added to reaction kettle 1 through pipeline 8 in 1: 0.9 by the mol ratio of hexamethylene amine and triethylamine, and catalyst levels is 0.15% of a rosin weight; By froth breaking dosage is that 0.001% of rosin weight is passed through pipeline 10 adding reaction kettles 1; With heat-up rate is that 3.5 ℃/min brings up to 240 ℃ with temperature, and the difference temperature head is controlled at 0.5 ℃ in the reaction kettle, and the constant temperature and pressure esterification begins after 2 hours through sampling line 12 sampling analysis; As acid number (KOH)＜22mg/g; All other quality index of sample meet following standard, comprising: softening temperature＞167 ℃, viscosity＞10000mpas/20 ℃, the transparent no particle of oil soluble, normal heptane value＞5ml/g, stopped reaction; (acid number of product is pressed GB2895282 and is measured, and softening temperature and color and luster are pressed the HG2-231-65 standard detection to make rosin modified phenolic resin #3; The resin that is determined as of viscosity mixes by 12: 1 volume ratios with oleum lini, is heated to 250 ℃ and dissolves, and is to be cooled to 35 ℃, and water temperature constant temperature is with NDJ-79 type rotary viscosity design determining; The normal heptane pH-value determination pH is: add 1g toluene with the above-mentioned viscosimetric analysis sample of every 2g, can hold normal heptane milliliter numerical table at 25 ℃ and show), stop heating; Startup vacuum pump 17 decompression vacuum pumpings (to-0.07Mpa) deaeration in 15 minutes; Foam is extracted into holding tank 19, stops to vacuumize, start cooling-water pump 3 and make product cool to 90 ℃ to jacket reactor 1 cooling-water pump through pipeline 11 from tank 18; Water coolant returns tank 18; Stop cooling, start compressor 2 and be forced into 0.02Mpa (gauge pressure), go out product to storage tank 4 through pipeline 15.Rosin modified phenolic resin #3 is mainly used in the connection material of low speed or high speed plate color flexographic ink, and its performance index are following:
1. softening temperature＞167 ℃
2. acid number (mgKOH/g)＜22
3. color and luster (Gardner)≤10
4. viscosity＞10000mpas/20 ℃
5. oil soluble: transparent no particle;
6. normal heptane value (ml/g)＞5
7. solvability in the benzene: clear
Molecular resin amount＞4,000 ten thousand.
Product reaches the quality standard of the similar resin of U.S. Lauth OY.
Adopt the price contrast of 1 ton of resol # 3 expense of the inventive method preparation and U.S. Lauth OY import like product (K-2300 resin) as shown in table 3.Visible by table 3, the R5502 resol # 3 price of the inventive method preparation is merely similar resin (K-2300 resin) price 57.3% from the import of U.S. Lauth OY.This is because adopt the resol # 3 of present technique invention in the preparation of Xinyi City, the rosin place of production; Adopt local rosin raw material; Reduced transportation cost; And produce all basic raw materials of colored used for offset ink resol # 3 and be homemade relatively inexpensive raw material, it is lower to effectively reduce production cost.
Table 3
Claims (6)
1. the preparation method of a coloured glue printing ink resol is characterized in that may further comprise the steps:
(1) preparation rosin condensation midbody: rosin is added in the reaction kettle, and heating is dissolved and is stirred, and heats to 100-110 ℃; Add alkylphenol, be stirred to and dissolve fully and mix, formaldehyde, skimmer and catalyzer are added reaction kettle, heat to 145-148 ℃, pressure is brought up to 0.4-0.6Mpa, under constant temperature and pressure, reacts 2-2.5 hour, promptly obtains rosin condensation midbody;
Said formaldehyde: alkylphenol: the rosin mol ratio is 3-4: 1-1.5: 3.5-6;
Said catalyzer is an acidic catalyst or inorganic alkaline catalyst, and said an acidic catalyst is oxalic acid, toluenesulphonic acids, phosphorous acid or ortho phosphorous acid; Said inorganic alkaline catalyst is sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, Marinco H, calcium hydroxide, zinc oxide or Natural manganese dioxide; Said catalyst levels is the 0.1-0.2% of rosin weight;
Said skimmer is a dimethyl silicone oil, and consumption is the 0.0006-0.0008% of rosin weight;
Said alkylphenol is phenol, octyl phenol, NP, tertiary butyl phenol or 4-dodecylphenol;
(2) rosin modified phenolic resin preparation: the reaction kettle that polyol blend, catalyzer and skimmer is added the synthetic rosin condensation midbody of step (1); Be warmed up to 240-260 ℃; Pressure is controlled at 0.05-0.15Mpa; Agitator stirs, and constant temperature and pressure carried out esterification 2-3 hour, obtained the product rosin modified phenolic resin;
Described polyol blend is the mixture of the pure and mild second type of alcohol of the first kind; Wherein first kind alcohol is tetramethylolmethane; Second type of alcohol is USP Kosher and/or terepthaloyl moietie, and described polyol blend consumption is the 50-75% of rosin mole number, and wherein the mol ratio of the pure and mild second type of alcohol of the first kind is 1: 0.8-1;
Described catalyzer is an acidic catalyst, inorganic alkaline catalyst or organic basic catalyzer; Said an acidic catalyst is one or more in oxalic acid, toluenesulphonic acids, phosphorous acid and the ortho phosphorous acid; Inorganic alkaline catalyst is one or more in sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, Marinco H, calcium hydroxide, zinc oxide and the Natural manganese dioxide; Described organic basic catalyzer is one or both in hexamethylenetetramine, triethylamine and the diethylamine; Said catalyst levels is the 0.1-0.2% of rosin weight;
Described skimmer is a dimethyl silicone oil, and the skimmer consumption is the 0.0007-0.001% of rosin weight.
2. the preparation method of coloured glue printing ink resol according to claim 1 is characterized in that: the formaldehyde of said step (1) is Paraformaldehyde 96 solid particulate and/or liquid formaldehyde.
3. the preparation method of coloured glue printing ink resol according to claim 1 is characterized in that: it is 3-5 ℃/min that said step (1) heats to 100-110 ℃ heat-up rate.
4. the preparation method of coloured glue printing ink resol according to claim 1 is characterized in that: it is 2-3 ℃/min that said step (1) heats to 145-148 ℃ heat-up rate.
5. the preparation method of coloured glue printing ink resol according to claim 1 is characterized in that: it is 2.5-3.5 ℃/min that said step (2) is warmed up to 240-260 ℃ heat-up rate.
6. a coloured glue printing ink resol is characterized in that by the said method preparation of claim 1.
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|---|---|---|---|---|
| CN102977301B (en) * | 2012-12-07 | 2017-03-29 | 上海华谊（集团）公司 | A kind of preparation method of rosin modified phenolic ink resin |
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