CN102532446A - Preparation method of mixed phenolic rosin modified phenolic resin - Google Patents
Preparation method of mixed phenolic rosin modified phenolic resin Download PDFInfo
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- CN102532446A CN102532446A CN2011104324538A CN201110432453A CN102532446A CN 102532446 A CN102532446 A CN 102532446A CN 2011104324538 A CN2011104324538 A CN 2011104324538A CN 201110432453 A CN201110432453 A CN 201110432453A CN 102532446 A CN102532446 A CN 102532446A
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Abstract
The invention discloses a preparation method of mixed phenolic rosin modified phenolic resin. Under the alkaline conditions, p-tert-octyl phenol, p-nonylphenol and p-tert-butylphenol react with formaldehyde to obtain a mixed phenolic solvent type phenolic resin condensation product, and in the presence of a catalyst, the condensation product undergoes rosin modification and mixed polyalcohol esterification to form the phenolic resin. The mixed polyalcohol comprises glycerol and pentaerythritol. The prepared phenolic resin is high in softening point and good in viscosity, the miscibility of a solvent is good, the color is light, the molecular weight distribution is uniform, and the phenolic resin is suitable for manufacture of printing ink and is suitable for components of ink for offset printing or intaglio printing.
Description
Technical field
The present invention relates to a kind of preparation method of rosin phenolic resin, in particular, relate to a kind of preparation method of mixed phenol rosin modified phenolic resin.
Background technology
Rosin modified phenolic resin is mainly used in makes printing ink and coating; It cooperates the low-melting ink vehicle of processing printing ink with vegetables oil, Dormant oils solvent and other subsidiary material; Be one of printing-ink, the widely used resin of coating manufacturing; Particularly important ink adhesive is used resin, and their quality is directly determining the use properties of printing ink, like printability, drying property, film forming properties or the like.
For a long time; The ink adhesive resin mainly is the resol of Abietyl modified single alkyl, like rosin modified phenol resol, Abietyl modified bisphenol A phenolic resin, Abietyl modified to a tert-butyl phenol resol, Abietyl modified to special octyl phenol resol etc.These ink adhesives owing to only adopt the phenolic resin modified of single alkyl, also exist following defectives with resin:
1, the product function group is few; Can not take into account between oil soluble ability, aliphatic hydrocarbon solubility property and the viscoelastic property: with the Abietyl modified alkylphenol phenolic resin that contains the smaller alkylphenol preparation of alkyl; Oil soluble, lipolyse property are poor, but the set time is short, and glossiness is high; With the Abietyl modified alkylphenol phenolic resin that contains the preparation of the bigger alkylphenol of alkyl, though oil soluble, lipolyse property are good, the set time is long, and glossiness is low.
2, product color is darker: use conventional catalyst to prepare Abietyl modified alkylphenol phenolic resin, must be in cruelization under the comparatively high temps, and the easy high temperature oxidation variable color of product causes the color and luster of product darker, can not widen in the special inks such as being applied to white, yellow.
3, viscosity is not high enough: single alkylphenol prepares Abietyl modified alkyl phenolic resin, because reaction receives the restriction of many index, viscosity can only be controlled at about 5000mPa.s, and viscosity number is less than normal.
Owing to above reason; The Abietyl modified alkylphenol phenolic resin of single alkylphenol preparation is difficult in aspects such as drying property, printability, film forming properties, luminance brightness and all reaches best; Influence the printing effect and the speed of printing ink, can not satisfy growing press requirement.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of mixed phenol rosin modified phenolic resin; With right-tert-octylphenol, right-NP, p-tert-butylphenol under alkaline condition; Obtain mixed phenol solvent-borne type resol condenses with formolite reaction; Its condenses catalyzer in the presence of, after Abietyl modified and polyol blend esterification, make, wherein polyol blend comprises USP Kosher and tetramethylolmethane.
The preparation method of mixed phenol rosin modified phenolic resin of the present invention comprises the steps:
1), the YLENE of 90-150 weight part is dropped into reaction kettle, begin to heat up, add successively the 180-200 weight part to the p-tert-butylphenol of tert-octylphenol, 300-600 weight part, the NP of 20-50 weight part; Keep temperature in the kettle at 55-60 ℃, stirred 5-10 minute, add formaldehyde 180-200 weight part then; Add alkali lye 2-8 weight part, water 20-100 weight part more successively, be warming up to 90-95 ℃, carry out insulation reaction; Viscosity until reaction kettle internal reaction thing is 1.0-2.0 ten thousand mPa.s; Be cooled to 65-70 ℃, take out, obtain condensated liquid;
2), the rosin with the 1500-2000 weight part drops into reaction kettle; Be warming up to 175-185 ℃; Add the USP Kosher of 25-35 weight part, the tetramethylolmethane and the catalyzer 0.1-0.3 weight part of 140-190 weight part successively, continue to be warming up to 265-275 ℃, insulation reaction; Less than 20 o'clock, be cooled to 220-230 ℃ until the acid number of still internal reaction thing; 230-240 ℃ of the also insulation that heat up adds condensated liquid, and add-on is 1) 40-45% of the condensated liquid gross weight that obtains; Heat up then and be incubated 235-245 ℃, add condensated liquid, add-on is 1) 40-45% of the condensated liquid gross weight that obtains; Continue to heat up and be incubated 240-250 ℃, insulation adds 1) remaining condensated liquid; Be warming up to 270-280 ℃, insulation reaction when the acid number of still internal reaction thing is 15-20, is cooled to 230-250 ℃, takes the dish out of the pot, and obtains the mixed phenol rosin modified phenolic resin;
Described catalyzer is that mass concentration is the sulphuric acid soln of 10-15%.
In the aforesaid method:
Described alkali lye is the NaOH aqueous solution of 10-15% weight concentration.
Described formaldehyde is solid formaldehyde, and mass concentration is 92-96%.
In the step 1), the temperature rise rate that is warming up to 90-95 ℃ behind adding alkali lye and the water is 1.0 ℃/min.
Compared with prior art, the invention has the advantages that:
1, drop into alkali lye, water, add and finish, heat temperature raising is to 90-95 ℃, and this reaction is thermopositive reaction, and temperature is convenient to control, and formaldehyde and phenol are reacted as early as possible;
2, be controlled under the 230-250 ℃ of condition and add condensated liquid stage by stage, both can make the reacting balance that adds behind the condensated liquid, can prevent that also low-boiling point material from accelerating to cause splash because of volatilization;
3, not only softening temperature is high for the resol of the present invention preparation, and viscosity is good, and the compatibility of solvent is good, lighter color, even molecular weight distribution, be suitable for printing ink manufacturing, be applicable to flat board or gravure printing ink component.
Embodiment
The present invention will be described with embodiment below, but the present invention is not limited to these embodiment.
Embodiment 1
1), the YLENE of 90 weight parts is dropped into reaction kettle, begin to heat up, add successively 200 weight parts to the p-tert-butylphenol of tert-octylphenol, 400 weight parts, the NP of 30 weight parts; Keep temperature in the kettle at 55 ℃, stirred 10 minutes, add mass concentration then and be 92% formaldehyde 180 weight parts; Add alkali lye 4 weight parts, water 80 weight parts more successively, be warming up to 95 ℃, temperature rise rate is 1.0 ℃/min; Carrying out insulation reaction, is 1.8 ten thousand mPa.s until the viscosity of reaction kettle internal reaction thing, is cooled to 70 ℃; Take out, obtain condensated liquid;
2), the rosin with 2000 weight parts drops into reaction kettle; Be warming up to 175 ℃; The tetramethylolmethane and the mass concentration that add USP Kosher, 180 weight parts of 35 weight parts successively are 10% sulphuric acid soln 0.3 weight part, continue to be warming up to 265 ℃, insulation reaction; Less than 20 o'clock, be cooled to 220 ℃ until the acid number of still internal reaction thing; Heating up also is incubated 230 ℃, adds condensated liquid, and add-on is 1) the condensated liquid gross weight that obtains 40%; Heat up then and be incubated 235 ℃, add condensated liquid, add-on is 1) the condensated liquid gross weight that obtains 40%; Continue to heat up and be incubated 240 ℃, insulation adds 1) remaining condensated liquid; Be warming up to 270 ℃, insulation reaction is 19 until the acid number of still internal reaction thing, is cooled to 230 ℃, takes the dish out of the pot, and obtains the mixed phenol rosin modified phenolic resin.
Embodiment 2
1), the YLENE of 150 weight parts is dropped into reaction kettle, begin to heat up, add successively 180 weight parts to the p-tert-butylphenol of tert-octylphenol, 300 weight parts, the NP of 20 weight parts; Keep temperature in the kettle at 60 ℃, stirred 5 minutes, add mass concentration then and be 96% formaldehyde 200 weight parts; Add alkali lye 2 weight parts, water 100 weight parts more successively, be warming up to 90 ℃, temperature rise rate is 1.0 ℃/min; Carrying out insulation reaction, is 1.6 ten thousand mPa.s until the viscosity of reaction kettle internal reaction thing, is cooled to 70 ℃; Take out, obtain condensated liquid;
2), the rosin with 1800 weight parts drops into reaction kettle; Be warming up to 180 ℃; The tetramethylolmethane and the mass concentration that add USP Kosher, 140 weight parts of 25 weight parts successively are 15% sulphuric acid soln 0.1 weight part, continue to be warming up to 270 ℃, insulation reaction; Less than 20 o'clock, be cooled to 225 ℃ until the acid number of still internal reaction thing; Heating up also is incubated 235 ℃, adds condensated liquid, and add-on is 1) the condensated liquid gross weight that obtains 45%; Heat up then and be incubated 240 ℃, add condensated liquid, add-on is 1) the condensated liquid gross weight that obtains 45%; Continue to heat up and be incubated 245 ℃, insulation adds 1) remaining condensated liquid; Be warming up to 275 ℃, insulation reaction is 18 until the acid number of still internal reaction thing, is cooled to 240 ℃, takes the dish out of the pot, and obtains the mixed phenol rosin modified phenolic resin.
Embodiment 3
1), the YLENE of 120 weight parts is dropped into reaction kettle, begin to heat up, add successively 190 weight parts to the p-tert-butylphenol of tert-octylphenol, 500 weight parts, the NP of 50 weight parts; Keep temperature in the kettle at 60 ℃, stirred 10 minutes, add mass concentration then and be 94% formaldehyde 200 weight parts; Add alkali lye 8 weight parts, water 20 weight parts more successively, be warming up to 95 ℃, temperature rise rate is 1.0 ℃/min; Carrying out insulation reaction, is 1.9 ten thousand mPa.s until the viscosity of reaction kettle internal reaction thing, is cooled to 65 ℃; Take out, obtain condensated liquid;
2), the rosin with 1500 weight parts drops into reaction kettle; Be warming up to 185 ℃; The tetramethylolmethane and the mass concentration that add USP Kosher, 190 weight parts of 30 weight parts successively are 10% sulphuric acid soln 0.2 weight part, continue to be warming up to 275 ℃, insulation reaction; Less than 20 o'clock, be cooled to 230 ℃ until the acid number of still internal reaction thing; Heating up also is incubated 240 ℃, adds condensated liquid, and add-on is 1) the condensated liquid gross weight that obtains 40%; Heat up then and be incubated 245 ℃, add condensated liquid, add-on is 1) the condensated liquid gross weight that obtains 45%; Continue to heat up and be incubated 250 ℃, insulation adds 1) remaining condensated liquid; Be warming up to 280 ℃, insulation reaction is 19 until the acid number of still internal reaction thing, is cooled to 250 ℃, takes the dish out of the pot, and obtains the mixed phenol rosin modified phenolic resin.
Embodiment 4
1), the YLENE of 100 weight parts is dropped into reaction kettle, begin to heat up, add successively 200 weight parts to the p-tert-butylphenol of tert-octylphenol, 600 weight parts, the NP of 40 weight parts; Keep temperature in the kettle at 60 ℃, stirred 5 minutes, add mass concentration then and be 92% formaldehyde 180 weight parts; Add alkali lye 6 weight parts, water 60 weight parts more successively, be warming up to 90 ℃, temperature rise rate is 1.0 ℃/min; Carrying out insulation reaction, is 1.8 ten thousand mPa.s until the viscosity of reaction kettle internal reaction thing, is cooled to 65 ℃; Take out, obtain condensated liquid;
2), the rosin with 1800 weight parts drops into reaction kettle; Be warming up to 180 ℃; The tetramethylolmethane and the mass concentration that add USP Kosher, 160 weight parts of 25 weight parts successively are 15% sulphuric acid soln 0.1 weight part, continue to be warming up to 270 ℃, insulation reaction; Less than 20 o'clock, be cooled to 225 ℃ until the acid number of still internal reaction thing; Heating up also is incubated 235 ℃, adds condensated liquid, and add-on is 1) the condensated liquid gross weight that obtains 45%; Heat up then and be incubated 240 ℃, add condensated liquid, add-on is 1) the condensated liquid gross weight that obtains 45%; Continue to heat up and be incubated 245 ℃, insulation adds 1) remaining condensated liquid; Be warming up to 275 ℃, insulation reaction is 15 until the acid number of still internal reaction thing, is cooled to 240 ℃, takes the dish out of the pot, and obtains the mixed phenol rosin modified phenolic resin.
Embodiment 5
It is following that the resin of processing with embodiment 1,2,3 carries out performance with existing resin:
Performance relatively
Claims (4)
1. the preparation method of a mixed phenol rosin modified phenolic resin comprises the steps:
1), the YLENE of 90-150 weight part is dropped into reaction kettle, begin to heat up, add successively the 180-200 weight part to the p-tert-butylphenol of tert-octylphenol, 300-600 weight part, the NP of 20-50 weight part; Keep temperature in the kettle at 55-60 ℃, stirred 5-10 minute, add formaldehyde 180-200 weight part then; Add alkali lye 2-8 weight part, water 20-100 weight part more successively, be warming up to 90-95 ℃, carry out insulation reaction; Viscosity until reaction kettle internal reaction thing is 1.0-2.0 ten thousand mPa.s; Be cooled to 65-70 ℃, take out, obtain condensated liquid;
2), the rosin with the 1500-2000 weight part drops into reaction kettle; Be warming up to 175-185 ℃; Add the USP Kosher of 25-35 weight part, the tetramethylolmethane and the catalyzer 0.1-0.3 weight part of 140-190 weight part successively, continue to be warming up to 265-275 ℃, insulation reaction; Less than 20 o'clock, be cooled to 220-230 ℃ until the acid number of still internal reaction thing; 230-240 ℃ of the also insulation that heat up adds condensated liquid, and add-on is 1) 40-45% of the condensated liquid gross weight that obtains; Heat up then and be incubated 235-245 ℃, add condensated liquid, add-on is 1) 40-45% of the condensated liquid gross weight that obtains; Continue to heat up and be incubated 240-250 ℃, insulation adds 1) remaining condensated liquid; Be warming up to 270-280 ℃, insulation reaction when the acid number 15-20 of still internal reaction thing, is cooled to 230-250 ℃, takes the dish out of the pot, and obtains the mixed phenol rosin modified phenolic resin;
Described catalyzer is that mass concentration is the sulphuric acid soln of 10-15%.
2. the preparation method of mixed phenol rosin modified phenolic resin according to claim 1 is characterized in that: described alkali lye is selected from the NaOH aqueous solution of 10-15% weight concentration.
3. the preparation method of mixed phenol rosin modified phenolic resin according to claim 1 is characterized in that: described formaldehyde is solid formaldehyde, and mass concentration is 92-96%.
4. the preparation method of mixed phenol rosin modified phenolic resin according to claim 1 is characterized in that: in the described step 1), the temperature rise rate that is warming up to 90-95 ℃ behind adding alkali lye and the water is 1.0 ℃/min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772633A (en) * | 2012-10-22 | 2014-05-07 | 鹤壁百运佳印务有限公司 | Preparation method of high-glossiness resin for offset ink |
| CN104725775A (en) * | 2015-03-18 | 2015-06-24 | 桂林兴松林化有限责任公司 | Preparation method of nano silicon dioxide/rosin modified urea-formaldehyde resin |
| CN104693679B (en) * | 2015-03-18 | 2016-08-31 | 桂林兴松林化有限责任公司 | A kind of preparation method of nano silicon rosin modified phenolic resin |
| CN106146772A (en) * | 2015-04-17 | 2016-11-23 | 彤程化学（中国）有限公司 | A kind of preparation method of alkyl phenolic curing resin |
| CN113667076A (en) * | 2021-02-23 | 2021-11-19 | 广西藤县通轩立信化学有限公司 | Preparation method of phosphorus-modified rosin phenolic resin catalyzed by acid and then base |
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| CN1077461A (en) * | 1993-05-12 | 1993-10-20 | 福建省龙岩地区林产工业公司 | The manufacture method of light colour modified rosin phenolic aldehyde resin |
| CN101070372A (en) * | 2006-12-05 | 2007-11-14 | 福建师范大学 | Resin-modified method epoxy resin and preparing method |
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2011
- 2011-12-21 CN CN 201110432453 patent/CN102532446B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1077461A (en) * | 1993-05-12 | 1993-10-20 | 福建省龙岩地区林产工业公司 | The manufacture method of light colour modified rosin phenolic aldehyde resin |
| CN101070372A (en) * | 2006-12-05 | 2007-11-14 | 福建师范大学 | Resin-modified method epoxy resin and preparing method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772633A (en) * | 2012-10-22 | 2014-05-07 | 鹤壁百运佳印务有限公司 | Preparation method of high-glossiness resin for offset ink |
| CN103772633B (en) * | 2012-10-22 | 2016-04-20 | 鹤壁百运佳印务有限公司 | The preparation method of high gloss resin used for offset ink |
| CN104725775A (en) * | 2015-03-18 | 2015-06-24 | 桂林兴松林化有限责任公司 | Preparation method of nano silicon dioxide/rosin modified urea-formaldehyde resin |
| CN104693679B (en) * | 2015-03-18 | 2016-08-31 | 桂林兴松林化有限责任公司 | A kind of preparation method of nano silicon rosin modified phenolic resin |
| CN106146772A (en) * | 2015-04-17 | 2016-11-23 | 彤程化学（中国）有限公司 | A kind of preparation method of alkyl phenolic curing resin |
| CN113667076A (en) * | 2021-02-23 | 2021-11-19 | 广西藤县通轩立信化学有限公司 | Preparation method of phosphorus-modified rosin phenolic resin catalyzed by acid and then base |
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Effective date of registration: 20130903 Address after: 541306 Baili Industrial Development Zone, Xingan County, Guilin, the Guangxi Zhuang Autonomous Region Patentee after: Guilin Xingsong Forest Chemical Co., Ltd. Address before: 541306 Baili Industrial Development Zone, Xingan County, Guilin, the Guangxi Zhuang Autonomous Region Patentee before: Guilin Xingsong Forest Chemical Co., Ltd. Patentee before: Fan He |