CN1233680C - Phenol-formaldehyde resin by colophony modified with alkyl phenol being mixed and its preparation method - Google Patents
Phenol-formaldehyde resin by colophony modified with alkyl phenol being mixed and its preparation method Download PDFInfo
- Publication number
- CN1233680C CN1233680C CN 03137280 CN03137280A CN1233680C CN 1233680 C CN1233680 C CN 1233680C CN 03137280 CN03137280 CN 03137280 CN 03137280 A CN03137280 A CN 03137280A CN 1233680 C CN1233680 C CN 1233680C
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- alkylphenol phenolic
- mixed
- abietyl modified
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to rosin modified mixed alkylphenol phenolic resin and a preparation method thereof. The resin is prepared and obtained after the rosin modification and the polyatomic alcohol esterification of a condensation product of mixed alkylphenol phenolic resin, the condensation product is obtained through a reaction among 4-tert-octylphenol, 4-nonylphenol, dodecylphenol and formaldehyde under an alkaline condition, wherein the polyatomic alcohol esterification is carried out step by step by adopting glycerol and trimethylol propane. The phenolic resin prepared by the present invention has the advantages of high softening point, high viscoelasticity, superior aliphatic hydrocarbon solubility performance, superior oil solubility performance, light color of the product and narrow range of molecular weight distribution. The phenolic resin is suitable for the manufacture of special color ink for high-speed printing.
Description
One, technical field
The present invention relates to a kind of modified rosin resin, more specifically, the present invention relates to a kind of pale rosin modified phenolic resins that is suitable for printing-ink and the use of coating manufacturing.The invention still further relates to the preparation method of this resin.
Two, background technology
Rosin modified phenolic resin is one of printing-ink, the widely used resin of coating manufacturing, particularly important ink adhesive resin, and their quality is directly determining the use properties of printing ink, as 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, as rosin modified phenol resol, Abietyl modified bisphenol A phenolic resin, Abietyl modified right-tert-butyl phenol resol, Abietyl modified right-Te 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 energy, aliphatic hydrocarbon solubility property and the viscoelastic property.With the Abietyl modified alkylphenol phenolic resin that contains the preparation of the smaller alkylphenol of alkyl, oil soluble, lipolyse are poor, but the set time is short, the glossiness height; With the Abietyl modified alkylphenol phenolic resin that contains the preparation of the bigger alkylphenol of alkyl, though oil soluble, lipolyse 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 esterification under the comparatively high temps, 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 is subjected to the restriction of many index, viscosity can only be controlled at about 5000mPas, 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.
For this reason, we adopt the mixed phenol urea formaldehyde of multiple alkylphenol that rosin is carried out modification, have prepared rosen modified mixed alkyl phenolic resin (CN1341673A).This product is mixed mutually by any two or more in p-tert-butylphenol, right-methylphenol, right-tert-octylphenol, the right-nonylphenol, under alkaline condition with formaldehyde reaction, synthetic mixed alkyl resol prepares after Abietyl modified and polyvalent alcohol esterification again.The rosen modified mixed alkyl phenolic resin of above-mentioned prepared, product softening temperature height, aliphatic hydrocarbon solubility property, oil soluble are better, viscosity is big, viscoelastic property good, and functional gene is many, prepares at printing ink, coating to have obtained on the industry using widely, has better printing use properties.
Yet above-mentioned rosen modified mixed alkyl phenolic resin product also exists the some shortcomings part, is embodied in:
1, color of resin is darker, Jia Shi colorimetric number 〉=No. 11;
2, the aliphatic hydrocarbon solubility property is big not enough, normal heptane value≤7.5mL/2g;
Though the viscosity of 3 resins is big, molecular weight is big, the distribution range broad of molecular weight.
More than these deficiencies, make the application of rosen modified mixed alkyl phenolic resin be subjected to certain influence, particularly the application on light color inks and coating has been subjected to very big restriction.
Three, summary of the invention
The purpose of this invention is to provide a kind of Abietyl modified mixed alkylphenol phenolic resin that high speed printing printing ink uses that is suitable for, this resin is the softening temperature height not only, and visco-elasticity is good, and product color is shallow, oil soluble can be good.
The preparation method of above-mentioned rosin modified phenolic resin is provided, and is another goal of the invention of the present invention.
Abietyl modified mixed alkylphenol phenolic resin of the present invention is prepared after Abietyl modified and polyvalent alcohol esterification by the mixed alkylphenol phenolic resin condenses, wherein, the mixed alkylphenol phenolic resin condenses reacts acquisition by right-tert-octylphenol, mixture and formaldehyde right-nonylphenol, three kinds of alkylphenols of dodecyl phenol under alkaline condition, the amount of substance ratio of three kinds of alkylphenols consists of:
Right-tert-octylphenol 2～25
Right-nonylphenol 1～15
Dodecyl phenol 1～15
Different with general rosin modified phenolic resin is, the present invention has adopted glycerine and two kinds of polyvalent alcohols of TriMethylolPropane(TMP) that product is carried out the substep esterification, to replace original single polyvalent alcohol esterification, the amount of substance ratio of two kinds of polyvalent alcohols consists of glycerine: TriMethylolPropane(TMP)=0.5～6: 1.
The preparation method of the Abietyl modified mixed alkylphenol phenolic resin of the present invention is:
I, mixture right-tert-octylphenol, right-nonylphenol, three kinds of alkylphenols of dodecyl phenol carry out hybrid reaction with formaldehyde under alkaline condition, obtain the condenses of mixed alkylphenol phenolic resin.
II, the mixed alkylphenol phenolic resin condenses is joined in the fused rosin, carry out addition reaction.
III, in the presence of catalyzer, in the reaction product of II the substep add glycerine and TriMethylolPropane(TMP), carry out esterification stage by stage.
The present invention preparation method more specifically is:
I, right-tert-octylphenol, right-nonylphenol, dodecyl phenol are according to 2～25: 1～15: 1～15 amount of substance ratio mixes, obtain mixed alkyl phenol, add 10% NaOH solution again, its weight accounts for 20～100% of mixed alkyl phenol weight, behind the heating and melting, begin to drip 37% formaldehyde solution and carry out condensation reaction, formaldehyde solution is 1.8～3.5: 1 with the amount of substance ratio of mixed alkyl phenol consumption, and the control temperature of reaction system is 65～75 ℃ in the dropping process.After reaction finishes, extremely neutral with HCl solution conditioned reaction thing, and obtain the mixed alkylphenol phenolic resin condenses behind the washed reaction thing.
II, rosin is heated to fusion, according to mixed alkyl phenol: rosin=0.3～0.8: 1 amount of substance carries out addition reaction than add the mixed alkylphenol phenolic resin condenses in the rosin of fusion.
III, in the reaction product of II, add the composite catalyst account for rosin weight 0.02～0.3%, according to rosin: polyvalent alcohol=2.5～3.5: 1 amount of substance adds glycerine than substep and TriMethylolPropane(TMP) carries out esterification, temperature of reaction is controlled at 250～265 ℃, react after 4～6 hours, underpressure distillation, steam low-boiling-point substance, obtain Abietyl modified mixed alkylphenol phenolic resin product.
Composite catalyst wherein is made up of two kinds in zinc oxide, magnesium oxide, Lithium Oxide 98min mixing at least, can directly use, and also can re-use after the drying in the past earlier through phosphoric acid or oxalic acid treatment.
Oil soluble and aliphatic hydrocarbon solubility property and viscoelastic property that the present invention improves product by selecting different chain alkyl phenol to form.Select branched-chain alkyl phenol right-tert-octylphenol and straight chained alkyl phenol is right-nonylphenol, dodecyl phenol make up, when straight chained alkyl phenol proportion is big, can obtain the bigger product of heptane number, but product viscosity is on the low side, when branched-chain alkyl phenol large percentage, product viscosity is higher, but heptane number is on the low side.The amount of substance of regulating the three is than being right-tert-octylphenol: right-nonylphenol: dodecyl phenol=2～25: 1～15:, can obtain heptane number and viscosity needs-satisfying products simultaneously at 1～15 o'clock.
The temperature height that three kinds of alkylphenols and formaldehyde carry out condensation reaction also has very big influence for every performance index of product, for the reactive behavior that makes each alkylphenol all reaches maximum, must select suitable condensation temp.If condensation temp is lower than 65 ℃, the reactive behavior of alkylphenol is low, and active methylol group content is low in the condenses, makes the finished product viscosity on the low side, does not reach service requirements; Condensation temp is higher than 80 ℃, and then the alkylphenol reaction is violent, makes tripolymer and the increase of tetrameric ratio in the condenses, and active methylol group content reduces, and the finished product viscosity also can reduce.Select condensation temp between 65～75 ℃, to be advisable.
Under identical enzymatic synthesis condition.The ratio of alkylphenol and rosin consumption also has considerable influence to product performance, and the alkylphenol consumption is little, and the viscosity of product is low, and the printing-ink body bone of making is poor, and printing net-point is unintelligible; The alkylphenol consumption is big, the viscosity height of product, and acid number is not easy to lower, and is prone to the implode phenomenon, and the product oil soluble is poor, gel degree height, printing-ink viscosity, the viscosity made are excessive, can not use.Alkylphenol compares with 0.3～0.8 with the rosiny amount of substance: 1 is advisable.
The present invention adopts glycerine and two kinds of polyvalent alcohols of TriMethylolPropane(TMP) that rosin is carried out the substep esterification, purpose is to form unique starlike macromolecular structure, avoids using tetramethylolmethane esterification time space steric hindrance big, the esterification difficulty, resolve into the defective of big or small irregular material easily, obtain the product of excellent property.
When glycerine and TriMethylolPropane(TMP) are used for esterification simultaneously, its different ratios is very big to the product performance influence, when the amount of substance ratio of glycerine and TriMethylolPropane(TMP) is 0.5～6: in the time of 1, can obtain every indexs such as viscosity, heptane number and color and luster and all can meet the requirements of product.
When adopting glycerine and TriMethylolPropane(TMP) that rosin is carried out esterification, if esterification temperature is higher than 270 ℃, esterification rate is too fast, and esterification products chain rupture easily under this temperature, makes the viscosity of product on the low side, and color and luster is darker; If esterification temperature is lower than 240 ℃, then esterification is slower, and long reaction time, acid number are not easy to lower, and the product esterification is incomplete, and viscosity is low, and acid number is big.The length of esterification time is also influential to product performance, and esterification time is long, and product viscosity substantially no longer changes after increasing to certain value, and acid number is low; Esterification time is short, the viscosity height of product, and acid number is big, and oil soluble is poor.Esterification temperature is with 250～265 ℃, and 4～6 hours time was advisable.
The present invention adopts the catalyzer of the mixture of metal oxides such as zinc oxide, magnesium oxide, Lithium Oxide 98min as the polyvalent alcohol esterification, makes polyvalent alcohol can carry out esterification under lower temperature.This catalyst mixture uses after phosphoric acid or oxalic acid treatment and drying, can also further strengthen the catalytic activity of catalyzer.Use composite catalyst, avoided pyrolytic decomposition, the oxidation of product, the color and luster of the product of preparing is more shallow.
The present invention utilizes multiple chain alkyl phenol to be optimized combination, the substep esterification stage by stage of several polyvalent alcohols, and catalyzer selected and reaction conditions is optimized, the product of preparing not only has multiple functional group, and has unique more starlike molecular structure, the softening temperature height of product, visco-elasticity is good, has lighter color simultaneously, aliphatic hydrocarbon solvability, the characteristics that oily fusibleness is good, even molecular weight distribution.The suitable property of the ink printing of preparation, drying property, film forming properties all reach best, have Gao Guang, fast doing, and the characteristics that the body bone is good are suitable for the manufacturing of high speed printing with extraordinary colored ink, have satisfied the needs of part special ink and coating preparation.
Four, embodiment
Embodiment 1:
Take by weighing respectively 90g right-tert-octylphenol, 20g be right-nonylphenol, 5g dodecyl phenol and 81g10%NaOH solution adds in the 500mL there-necked flask, is heated to the material fusion.Open and stir, slowly drip 37% formaldehyde solution 89g, after dropwising, 70 ℃ of insulations 4 hours.Neutralize with 15%HCl solution, to the pH value be 6, stop to stir, leave standstill, treat material layering after, discard water layer, organic layer is washed twice again, obtain the condenses of 166g mixed alkylphenol phenolic resin.
400g rosin is joined in the 1000mL there-necked flask, and heating and melting is opened and is stirred, and slowly adds above-mentioned mixed alkylphenol phenolic resin condenses under 185 ℃ of temperature.Add the back 210 ℃ of insulations 1 hour, add 0.9g and handle and exsiccant zinc oxide-Lithium Oxide 98min composite catalyst, slowly add 32g glycerine, be incubated 2 hours at 230 ℃ through phosphoric acid, be warming up to 240 ℃, add the 9.5g TriMethylolPropane(TMP) again, be incubated 1 hour, be warming up to 255 ℃ of reactions, until the reaction solution acid number during less than 20mgKOH/g, be decompressed to 300～400mmHg, steam low-boiling-point substance, obtain the Abietyl modified mixed alkylphenol phenolic resin of 540g.165 ℃ of this product softening temperatures, viscosity 10500mPas, acid number 16mgKOH/g, normal heptane degree of holding 8.5mL/2g, No. 7, color and luster, Mn=8800, PDI=4.1.
Embodiment 2:
Take by weighing respectively 74g right-tert-octylphenol, 20g be right-nonylphenol, 10g dodecyl phenol and 90g 10%NaOH solution adds in the 500mL there-necked flask, is heated to the material fusion.Open and stir, drip 37% formaldehyde solution 99g, after dropwising, 68 ℃ of insulations 4 hours.Neutralize with 15%HCl solution, to the pH value be 6, stop to stir, leave standstill, branch vibration layer with organic layer washing twice, obtains the condenses of 172g mixed alkylphenol phenolic resin.
400g rosin is joined in the 1000mL there-necked flask, and heating and melting is opened and is stirred, and slowly adds above-mentioned mixed alkylphenol phenolic resin condenses under 190 ℃ of temperature.Add the back 200 ℃ of insulations 1 hour, add 0.5g through oxalic acid treatment and exsiccant zinc oxide-magnesium oxide composite catalyst, slowly add 34g glycerine, be incubated 2 hours at 220 ℃, be warming up to 230 ℃, add the 12g TriMethylolPropane(TMP) again, be incubated 1 hour, be warming up to 260 ℃ of reactions, until the reaction solution acid number during less than 20mgKOH/g, be decompressed to 300～400mmHg, steam low-boiling-point substance, obtain the Abietyl modified mixed alkylphenol phenolic resin of 508g.157 ℃ of this product softening temperatures, viscosity 9800mPas, acid number 17mgKOH/g, normal heptane degree of holding 9.0mL/2g, No. 8, color and luster, Mn=7400, PDI=3.2.
Embodiment 3:
Take by weighing respectively 76g right-tert-octylphenol, 5g be right-nonylphenol, 30g dodecyl phenol and 84g10%NaOH solution adds in the 500mL there-necked flask, is heated to the material fusion.Open and stir, drip 37% formaldehyde solution 95g, after dropwising, 72 ℃ of insulations 4 hours.Neutralize with 15%HCl solution, to the pH value be 6, stop to stir, leave standstill, branch vibration layer with organic layer washing twice, obtains the condenses of 210g mixed alkylphenol phenolic resin.
400g rosin is joined in the 1000mL there-necked flask, and heating and melting is opened and is stirred, and slowly adds the mixed alkylphenol phenolic resin condenses of above-mentioned preparation under 200 ℃ of temperature.Add the back 210 ℃ of insulations 1 hour, add 1.0g zinc oxide-Lithium Oxide 98min composite catalyst, slowly add 32g glycerine, be incubated 2 hours at 220 ℃, be warming up to 235 ℃, add the 13g TriMethylolPropane(TMP) again, be incubated 1 hour, be warming up to 258 ℃ of reactions, until the reaction solution acid number during less than 20mgKOH/g, be decompressed to 300～400mmHg, steam low-boiling-point substance, obtain the Abietyl modified mixed alkylphenol phenolic resin of 500g.165 ℃ of this product softening temperatures, viscosity 10000mPas, acid number 16mgKOH/g, normal heptane degree of holding 11.5mL/2g, No. 9, color and luster, Mn=8500, PDI=2.8.
Embodiment 4:
Take by weighing respectively 10g right-tert-octylphenol, 70g be right-nonylphenol, 40g dodecyl phenol and 56g10%NaOH solution adds in the 500mL there-necked flask, is heated to the material fusion.Open and stir, drip 37% formaldehyde solution 90g, after dropwising, 74 ℃ of insulations 4 hours.Neutralize with 15%HCl solution, to the pH value be 6, leave standstill, branch vibration layer with organic layer washing twice, obtains the condenses of 235g mixed alkylphenol phenolic resin.
400g rosin is joined in the 1000mL there-necked flask, and heating and melting is opened and is stirred, and slowly adds above-mentioned mixed alkylphenol phenolic resin condenses under 205 ℃ of temperature.Add the back 205 ℃ of insulations 1 hour, add 1.2g and handle and exsiccant zinc oxide-magnesium oxide composite catalyst, slowly add 38g glycerine, be incubated 2 hours, be warming up to 230 ℃, add the 9.6g TriMethylolPropane(TMP) again, be incubated 1 hour at 215 ℃ through phosphoric acid.Be warming up to 262 ℃ of reactions, during less than 20mgKOH/g, be decompressed to 300～400mmHg, steam low-boiling-point substance, obtain the Abietyl modified mixed alkylphenol phenolic resin of 562g until the reaction solution acid number.157 ℃ of this product softening temperatures, viscosity 6400mPas, acid number 17mgKOH/g, normal heptane degree of holding 13.0mL/2g, No. 8, color and luster, Mn=5800, PDI=3.6.
Embodiment 5:
Synthesis technique is with embodiment 2, various raw material consumptions:
Right-tert-octylphenol 95g is right-nonylphenol 30g
Dodecyl phenol 40g 10%NaOH solution 50g
37% formaldehyde solution 142g.
Obtain 246g mixed alkylphenol phenolic resin condenses.
The above-mentioned resin condensation thing of rosin 400g
Zinc oxide-magnesium oxide-Lithium Oxide 98min composite catalyst 0.1g
Glycerine 36g TriMethylolPropane(TMP) 16g
Obtain the Abietyl modified mixed alkylphenol phenolic resin product of 581g.
Product index: 175 ℃ of softening temperatures, viscosity 13000mPas, acid number 17mgKOH/g, normal heptane degree of holding 7.8mL/2g, No. 9, color and luster, Mn=6900, PDI=3.8.
Embodiment 6:
Synthesis technique is with embodiment 1, various raw material consumptions:
Right-tert-octylphenol 102g is right-nonylphenol 30g
Dodecyl phenol 13g 10%NaOH solution 50g
37% formaldehyde solution 151g.
Obtain 298g mixed alkylphenol phenolic resin condenses.
The above-mentioned resin condensation thing of rosin 400g
Zinc oxide-magnesium oxide composite catalyst 0.6g
Glycerine 30g TriMethylolPropane(TMP) 21g
Obtain the Abietyl modified mixed alkylphenol phenolic resin product of 587g.
Product index: 174 ℃ of softening temperatures, viscosity 14400mPas, acid number 20mgKOH/g, normal heptane degree of holding 7.5mL/2g, No. 8, color and luster, Mn=9000, PDI=4.2.
Claims (10)
1, Abietyl modified mixed alkylphenol phenolic resin, be to be prepared after Abietyl modified and polyvalent alcohol esterification by the mixed alkylphenol phenolic resin condenses, it is characterized in that: described mixed alkylphenol phenolic resin condenses is to react acquisition by right-tert-octylphenol, mixture and formaldehyde right-nonylphenol, three kinds of alkylphenols of dodecyl phenol under alkaline condition.
2, Abietyl modified mixed alkylphenol phenolic resin according to claim 1 is characterized in that: the amount of substance ratio of three kinds of alkylphenols consists of:
Right-tert-octylphenol 2～25
Right-nonylphenol 1～15
Dodecyl phenol 1～15
3, Abietyl modified mixed alkylphenol phenolic resin according to claim 1 is characterized in that: described polyvalent alcohol esterification is to adopt glycerine and the esterification of two kinds of polyvalent alcohol substeps of TriMethylolPropane(TMP).
4, Abietyl modified mixed alkylphenol phenolic resin according to claim 3 is characterized in that: the amount of substance ratio of two kinds of polyvalent alcohol consumptions of glycerine and TriMethylolPropane(TMP) is 0.5～6: 1.
5, the preparation method of Abietyl modified mixed alkylphenol phenolic resin is characterized in that being prepared by following steps:
I, mixture right-tert-octylphenol, right-nonylphenol, three kinds of alkylphenols of dodecyl phenol carry out hybrid reaction with formaldehyde under alkaline condition, obtain the condenses of mixed alkylphenol phenolic resin;
II, the mixed alkylphenol phenolic resin condenses joined carry out addition reaction in the fused rosin;
III, in the presence of catalyzer, in the reaction product of II the substep add glycerine and TriMethylolPropane(TMP), carry out esterification stage by stage.
6, the preparation method of Abietyl modified mixed alkylphenol phenolic resin according to claim 5 is characterized in that being prepared by following steps:
I, right-tert-octylphenol, right-nonylphenol, dodecyl phenol are according to 2～25: 1～15: 1～15 amount of substance ratio mixes, obtain mixed alkyl phenol, add 10% NaOH solution again, its weight accounts for 20～100% of mixed alkyl phenol weight, heating and melting, drip 37% formaldehyde solution, its amount of substance is equivalent to 1.8～3.5 times of mixed alkyl phenol amount of substance, carry out condensation reaction, it is extremely neutral with HCl solution conditioned reaction thing that reaction finishes the back, obtains the mixed alkylphenol phenolic resin condenses after the washing;
II, rosin is heated to fusion, according to mixed alkyl phenol: rosin=0.3～0.8: 1 amount of substance carries out addition reaction than add the mixed alkylphenol phenolic resin condenses in fused rosin;
III, in the reaction product of II, add the composite catalyst account for rosin weight 0.02～0.3%, according to rosin: polyvalent alcohol=2.5～3.5: 1 amount of substance adds glycerine than substep and TriMethylolPropane(TMP) carries out esterification, after reaction finishes, underpressure distillation steams low-boiling-point substance, obtains Abietyl modified mixed alkylphenol phenolic resin product.
7, the preparation method of Abietyl modified mixed alkylphenol phenolic resin according to claim 6 is characterized in that described composite catalyst is made up of two kinds in zinc oxide, magnesium oxide, Lithium Oxide 98min mixing at least.
8, the preparation method of Abietyl modified mixed alkylphenol phenolic resin according to claim 7 is characterized in that described composite catalyst is direct use, perhaps through phosphoric acid or oxalic acid treatment, and dry use later on.
9, the preparation method of Abietyl modified mixed alkylphenol phenolic resin according to claim 6, the temperature of reaction that it is characterized in that described condensation reaction is 65～75 ℃.
10, the preparation method of Abietyl modified mixed alkylphenol phenolic resin according to claim 6 is characterized in that described esterification is to react 4～6 hours under 250～265 ℃ of temperature condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137280 CN1233680C (en) | 2003-06-03 | 2003-06-03 | Phenol-formaldehyde resin by colophony modified with alkyl phenol being mixed and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137280 CN1233680C (en) | 2003-06-03 | 2003-06-03 | Phenol-formaldehyde resin by colophony modified with alkyl phenol being mixed and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1462759A CN1462759A (en) | 2003-12-24 |
| CN1233680C true CN1233680C (en) | 2005-12-28 |
Family
ID=29748537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03137280 Expired - Fee Related CN1233680C (en) | 2003-06-03 | 2003-06-03 | Phenol-formaldehyde resin by colophony modified with alkyl phenol being mixed and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1233680C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103080246A (en) * | 2010-11-26 | 2013-05-01 | 星光Pmc株式会社 | Process for manufacturing rosin-modified phenol resin for offset printing ink and process for manufacturing varnish for offset printing ink |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558476B (en) * | 2011-12-22 | 2013-06-26 | 桂林兴松林化有限责任公司 | Method for preparing bisphenol A rosin modified phenolic resin |
| CN105175666A (en) * | 2015-08-31 | 2015-12-23 | 桂林兴松林化有限责任公司 | Preparation method for rosin modified phenolic resin |
| CN105348459B (en) * | 2015-12-11 | 2017-08-25 | 华奇（中国）化工有限公司 | Abietyl modified resorcinol formaldehyde resin and its preparation method and application |
| CN106279588A (en) * | 2016-08-29 | 2017-01-04 | 广西梧州通轩林产化学有限公司 | The preparation method of coating rosin modified phenolic resin |
| CN109824841A (en) * | 2018-12-31 | 2019-05-31 | 泉州市东紫环保科技有限公司 | A kind of preparation method of the Abietyl modified urea-formaldehyde resin adhesive of methylol |
| CN110282811A (en) * | 2019-08-02 | 2019-09-27 | 山西省应用化学研究所(有限公司) | The processing method and equipment of rosin modified phenolic resin industrial wastewater |
| CN112442157B (en) * | 2019-09-05 | 2022-09-20 | 彤程化学（中国）有限公司 | Epoxy resin and rosin modified alkylphenol-formaldehyde resin and preparation method and application thereof |
| 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 |
-
2003
- 2003-06-03 CN CN 03137280 patent/CN1233680C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103080246A (en) * | 2010-11-26 | 2013-05-01 | 星光Pmc株式会社 | Process for manufacturing rosin-modified phenol resin for offset printing ink and process for manufacturing varnish for offset printing ink |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1462759A (en) | 2003-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1233680C (en) | Phenol-formaldehyde resin by colophony modified with alkyl phenol being mixed and its preparation method | |
| CN101100079B (en) | Core-shell type multifunctional composite wood precursor solution and its preparation method | |
| CN1667106A (en) | Vegetable oil with high epoxy value and its preparing method and use | |
| CN102586917A (en) | Method for preparing fluorescent anti-counterfeiting Lyocell fibers | |
| CN1075044C (en) | Glass fibre size composition, method using same, and resulting products | |
| CN1712466A (en) | Magnetic block printing ink | |
| CN102977301A (en) | Preparation method of rosin modified phenolic printing ink resin | |
| CN105001402A (en) | Preparation method of acrylic modified rosin ester polymer for high-end sheet-fed printing ink | |
| CN101041139A (en) | Catalyzer for regenerating the waste lubricant oil by hydrogenation and the preparing method | |
| CN113528133B (en) | Preparation method of brown coal-based white fluorescent carbon dots | |
| CN102585128A (en) | Preparation method of phenolic resin bonding agents for automobile felts | |
| CA2088885C (en) | Precure resistant thermoset resin for molded wood composites | |
| CN111944464B (en) | Modified phenolic resin adhesive and preparation method and application thereof | |
| CN1223620C (en) | Preparation process for mixed alkylphenol aldehyde resin condensation compound | |
| CN101974301B (en) | Preparation method of bio oil-phenol-methanal copolycondensation resin wood adhesive | |
| CN109487538B (en) | Reinforcing agent for carbon fiber sizing agent and preparation method thereof | |
| CN101381505B (en) | Synthetic resin produced by renewable resource and preparation method thereof | |
| CN1170861C (en) | Alkyl phenolic modified petroleum resin and its prepn. method | |
| CN1786080A (en) | Preparation process of benzodifuranone disperse red dye and product thereof | |
| CN109809742A (en) | A kind of cold mixing chromatic bitumen mixture and its preparation method and application | |
| CN101067016A (en) | Synthesis and usage of fast curing phenolic resin | |
| CN104164051A (en) | Toughening-type environmental protection phenolic resin and preparation method of its composite material | |
| CN1341673A (en) | Preparation of rosen modified mixed alkyl phenolic resin | |
| CN1760229A (en) | Preparing heat-resistant phenolic resins | |
| CN1958684A (en) | Lithographic plant rotary printing ink for books and periodicals prepared from resin of soybean oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20051228 |