CN1288017A - Alkyl phenolic modified petroleum resin and its prepn. method - Google Patents
Alkyl phenolic modified petroleum resin and its prepn. method Download PDFInfo
- Publication number
- CN1288017A CN1288017A CN 00129199 CN00129199A CN1288017A CN 1288017 A CN1288017 A CN 1288017A CN 00129199 CN00129199 CN 00129199 CN 00129199 A CN00129199 A CN 00129199A CN 1288017 A CN1288017 A CN 1288017A
- Authority
- CN
- China
- Prior art keywords
- petroleum resin
- resin
- add
- degrees centigrade
- modified petroleum
- 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.)
- Granted
Links
Abstract
The present invention relates to the manufacturing technology of printing ink connecting resin. It uses by-preduct C5 fraction and C9 fraction from cracking process of producing ethylene and flax oil as raw material to synthesize petroleum resin A which is modified by maleic anhydride and caprylic acid to obtain modified petroleum resin B, uses para-tert octyl phenol and formaldehyde to synthesize alkyl phenol formaldehyde resin liquid C, uses alkyl phenol formaldehyde resin liquid C to condense with modified petroleum resin B to form the invented product. The said resin condense with modified petroleum resin B to form the invented product. The said resin possesses high softening point, high viscosity light colour and high solubility in high boiling point solvent and drying oil, and the printing ink made with said resin is good in viscoelasticity, thixotropy and antiemulsification.
Description
The invention belongs to a kind of manufacturing technology of forming the required resin of ink adhesive, more specifically to a kind of alkyl phenolic modified petroleum resin and manufacture craft.
Along with the development of printing industry, the raising of print speed requires printing ink to possess following characteristic: 1, good thixotropy; 2, moderate set and rate of drying; 3, You Yi glossiness; 4, good resistance to emulsion; 5, good attachment fastness and shock resistance.For this resin that just requires to form ink adhesive of quality that guarantees printing ink should have following characteristic: 1, have certain polarity, visco-elasticity; 2, be soluble in the high boiling solvent; 3, be soluble in the siccative oil.According to US4385149, US4401791 and clear 4-63822 patent report, the resin of making of these three kinds of schemes exists the difficult control of manufacture craft, cost is higher, printing ink thixotropy, pigment wetting performance that solubility property is poor in high boiling solvent and siccative oil, visco-elasticity is low, make are poor, the not high deficiency of glossiness has hindered the development of press.
The alkyl phenolic modified petroleum resin and the manufacture craft that the object of the present invention is to provide that a kind of cost of manufacture is low, technology is controlled well, good solubility is arranged in high boiling solvent and siccative oil, visco-elasticity, the printing ink made have good thixotropy, higher gloss degree.
The objective of the invention is to realize by following technical proposal: alkyl phenolic modified petroleum resin is by petroleum cracking system ethylene by-product C
5Fraction and C
9Fraction and oleum lini are raw material synthesizing petroleum resin A, get modified petroleum resin B with MALEIC ANHYDRIDE, octanol modified petroleum resin A, with right-special octyl phenol and formaldehyde two step method synthesis of alkyl resol liquid C, make with alkyl phenolic resin liquid C condensation and modification petroleum resin B.
Its proportioning (weight %) is:
Petroleum resin A: modified petroleum resin B:
C
9Fraction: 40-55 petroleum resin A:85-90
C
5Fraction: 30-45 MALEIC ANHYDRIDE: 2-6
Oleum lini: 10-20 octanol: 5-10
Alkyl phenolic resin liquid C: alkyl phenolic modified petroleum resin:
Right-special octyl phenol: 39.4 modification stone common house centipede resin B: 70-80
6N hydrochloric acid: 1.1 rosin: 15-25
37% formaldehyde: 30.5 zinc oxide: 0.05-0.5
96% caustic soda: 1.4 glycerine: 1-5
Toluene: 27.6 modified petroleum resin B: alkyl phenolic resin liquid C
=1：0.1-0.6
Manufacture craft is as follows:
A, with C
5Fraction, C
9Fraction and oleum lini are put into to stir in the autoclave and are warming up to 250-280 degree centigrade, pressure 0.35-0.6MPa, reacted 2-5 hour, carry out underpressure distillation afterwards, steam unreacted reactant, be not decompressed to when the 0.08Mpa tower top temperature degree centigrade has overhead product by 120 degrees centigrade of steamings to 150 and end, steam rate 10-20% gets petroleum resin A;
B, petroleum resin A is put into the fusion that heats up in the there-necked flask, and be warming up to 180 degrees centigrade and add MALEIC ANHYDRIDE while stirring, at 180-200 degree centigrade of insulation reaction 1-2 hour, then add octanol, 180-200 degree centigrade of insulation 1-2 hour, discharging got modified petroleum resin B;
C, right-special octyl phenol and toluene are joined in the there-necked flask behind the heating and melting, adding hydrochloric acid adds while stirring at 50 degrees centigrade and was warming up to 80 degrees centigrade of insulation reaction 3 hours after formaldehyde adds, be cooled to 50 degrees centigrade of adding caustic soda, reaction solutions and be alkalescence adding formaldehyde, add the back 60-65 degree centigrade of insulation reaction 4 hours, being cooled to 50-55 degree centigrade is that 30% hydrochloric acid neutralizes and ends when reaching the pH value for 5-6 with concentration, add toluene and stirred 10 minutes, the standing demix organic layer washes with water once to be abandoned water layer and gets alkyl phenolic resin liquid C;
D, modified petroleum resin B and rosin are added in the there-necked flask, under 150-160 degree centigrade condition, carry out fusion, adding zinc oxide after the fusion stirs, add the basic liquid phenolic resin C of burning down at 180-200 degree centigrade, add the back at 200 degrees centigrade of insulation reaction 1-3 hours, be warming up to 210 degrees centigrade and add glycerine, add intensification, steam moisture content in 220-240 degree centigrade of insulation decompression in 2-4 hour and get alkyl phenolic modified petroleum resin.
The beneficial effect that the present invention brings:
1, synthetic this resin raw material cost that is easy to get is low;
2, the softening temperature height, viscosity is big, colourity is shallow, solubility property is good in high boiling solvent and siccative oil;
3, easily-controlled operation;
4, make printing ink, visco-elasticity, thixotropy, demulsification performance is good, glossiness is high, set time, time of drying are moderate.
Cost is (raw materials cost) relatively:
| The present invention | 10000 yuan/ton |
| US4385149 | 23000 yuan/ton |
| US4401791 | 15000 yuan/ton |
| Clear 4-63822 | 18000 yuan/ton |
Ink performance compares:
| Resin | Glossiness | Time of drying (hour) | Resistance to emulsion (%) | The set time (branch) | Thixotropy |
| The present invention | ?64-68 | ?6-8 | ?30-38 | ?5-8 | Excellent |
| US4385149 | ?44-60 | ?3-4.5 | ?0 | ?5-8 | ?- |
| US4401791 | ?48-56 | ?- | ?- | ?16.8-17.2 | ?- |
Embodiment 1:
With the 450g boiling range 140-190 degree centigrade C
5Fraction, 600g boiling range are 140-230 degree centigrade C
9Fraction, the 150g oleum lini is put in the autoclave of 5 liters and is stirred, be warming up to 250 degrees centigrade, pressure is 0.4MPa, reacts 2 hours, carry out underpressure distillation afterwards, steam unreacted reactant, be not decompressed to when the 0.08Mpa tower top temperature degree centigrade has overhead product by 120 degrees centigrade of steamings to 150 and end, petroleum resin A1080g, softening temperature is 78 degrees centigrade, acid number 1.4mgKOH/g.
Petroleum resin A1080g put in 2000 milliliters the there-necked flask, the intensification fusion also is warming up to the 180 MALEIC ANHYDRIDE 25.4g that add while stirring Celsius, 180 degrees centigrade of insulation reaction 2 hours, then add octanol 63.5g, got modified petroleum resin B1168.9g in 2 hours 190 degrees centigrade of insulations, softening temperature is 79 degrees centigrade, acid number 23mgKOH/g.
Right-special octyl phenol 600g and 150g toluene joined the hydrochloric acid 17g that adds 6N in 2000 milliliters the there-necked flask behind the heating and melting, add 37% formaldehyde 195g while stirring at 50 degrees centigrade, be warming up to 80 degrees centigrade after adding, insulation reaction 3 hours, be cooled to the caustic soda 21.3g of 50 degrees centigrade of addings 96%, reaction solution is the formaldehyde 269.5g of alkalescence adding 37%, adds the back 63
± 2Degree centigrade insulation reaction 4 hours is cooled to 53
± 2Degree centigrade, be that 30% hydrochloric acid neutralizes and ends when reaching the pH value for 5-6 with concentration, add toluene 270.3g, stir 10 minutes standing demix organic layers and wash with water and once abandon water layer and get alkyl phenolic resin liquid C1450g.
Modified petroleum resin B1168.9g and rosin 250.5g added in 2000 milliliters the there-necked flask, under 150-160 degree centigrade condition, carry out fusion, adding zinc oxide 0.8g after the fusion stirs, add alkyl phenolic resin liquid C117g at 180 degrees centigrade, add the back 200 degrees centigrade of insulations 1 hour, be warming up to 210 degrees centigrade, add glycerine 16.7g, add and be warming up to 220 degrees centigrade of insulations 4 hours, decompression steams moisture content and gets alkyl phenolic modified petroleum resin 1510g, 153 degrees centigrade of softening temperatures, viscosity 14000MPaS, acid number 17mgKOH/g.
Embodiment 2:
With the 475g boiling range is the C of 140-190
5Fraction, 6009 boiling ranges are 140-230 degree centigrade C
9Fraction, 187.5g putting into to stir in the autoclave of 5 liters, oleum lini is warming up to 270 degrees centigrade, pressure is 0.5MPa, reacted 3 hours, and carried out underpressure distillation afterwards, steam unreacted reactant, be not decompressed to when the 0.08Mpa tower top temperature degree centigrade has overhead product by 120 degrees centigrade of steamings to 150 and end, get petroleum resin A1073g, 88 degrees centigrade of softening temperatures, acid number 0.9mgKOH/g.
Petroleum resin A1073g is fed into the fusion that heats up in 2000 milliliters the there-necked flask, and be warming up to 180 degrees centigrade and add MALEIC ANHYDRIDE 49.3g while stirring, 190 degrees centigrade of insulations 2 hours, then add octanol 86.3g, get modified petroleum resin B1208.7g in 200 degrees centigrade of insulations discharging in 1 hour, 91 degrees centigrade of softening temperatures, acid number 26mgKOH/g.
The alkyl phenolic resin liquid C goods of embodiment 1
Modified petroleum resin B1208.7g and rosin 322.3g are joined in 2000 milliliters of there-necked flasks, under 150-160 degree centigrade condition, carry out fusion, adding zinc oxide 4.8g after the fusion stirs, add alkyl phenolic resin liquid C484g at 190 degrees centigrade, add the back 200 degrees centigrade of insulations 2 hours, be warming up to 210 degrees centigrade, add glycerine 48.3g, add and be warming up to 230 degrees centigrade of insulations decompression in 3 hours and steam moisture content and get alkyl phenolic modified petroleum resin 1895g, 158 degrees centigrade of softening temperatures, viscosity 16000MPaS, acid number 23mgKOH/g.
Embodiment 3:
With the 491g boiling range 140-190 degree centigrade C
5Fraction, 600 boiling ranges are 140-230 degree centigrade C
9Fraction, 218g oleum lini are put into to stir in the autoclave of 5 liters and are warming up to 280 degrees centigrade, pressure is 0.6MPa, reacted 5 hours, carry out underpressure distillation afterwards, steam unreacted reactant, be not decompressed to when the 0.08Mpa tower top temperature degree centigrade has overhead product by 120 degrees centigrade of steamings to 150 and end, petroleum resin A1047g, softening temperature is 98 degrees centigrade, acid number 0.7mgKOH/g.
Petroleum resin A1047g put in 2000 milliliters the there-necked flask, the intensification fusion also is warming up to 180 degrees centigrade, add MALEIC ANHYDRIDE 69.8g while stirring, 200 degrees centigrade of insulations 1 hour, then add octanol 116g, 180 degrees centigrade of insulations 2 hours, discharging got modified petroleum resin B1232.8g, 88 degrees centigrade of softening temperatures, acid number 28mgKOH/g.
The alkyl phenolic resin liquid C goods of embodiment 1.
Modified petroleum resin B1232.8g and rosin 385.3g are joined in 2000 milliliters of there-necked flasks, under 150-160 degree centigrade condition, carry out fusion, adding zinc oxide 7.7g after the fusion stirs, add alkyl phenolic resin liquid C739g at 200 degrees centigrade, add the back 200 degrees centigrade of insulation reaction 3 hours, be warming up to 210 degrees centigrade and add glycerine 77.1g, add intensification at 240 degrees centigrade, being incubated decompression in 2 hours steams moisture content and gets alkyl phenolic modified petroleum resin 2176g, 148 degrees centigrade of softening temperatures, viscosity 15000MPaS, acid number 24mgKOH/g.
Claims (3)
1, a kind of making method of forming the ink adhesive resin is characterized in that: it is with petroleum cracking system ethylene by-product C
5Fraction, C
9Fraction and oleum lini are raw material synthesizing petroleum resin A, get modified petroleum resin B with MALEIC ANHYDRIDE, octanol modified petroleum resin A, with right-special octyl phenol and formaldehyde two step method synthesis of alkyl resol liquid C, make with alkyl phenolic resin liquid C condensation and modification petroleum resin B.
2, a kind of making method of forming the ink adhesive resin according to claim 1, it is characterized in that: proportioning raw materials (weight %) is:
Petroleum resin A: modified petroleum resin B:
C
9Fraction: 40-55 petroleum resin A:85-90
C
5Fraction: 30-45 MALEIC ANHYDRIDE: 2-6
Oleum lini: 10-20 octanol: 5-10
Alkyl phenolic resin liquid C: alkyl phenolic modified petroleum resin:
Right-special octyl phenol: 39.4 modified petroleum resin B:70-80
6N hydrochloric acid: 1.1 rosin: 15-25
37% formaldehyde: 30.5 zinc oxide: 0.05-0.5
96% caustic soda: 1.4 glycerine: 1-5
Toluene: 27.6 modified petroleum resin B: alkyl phenolic resin liquid C
=1：0.1-0.6
3, a kind of making method of forming the ink adhesive resin according to claim 1 and 2 is characterized in that:
A, with C
5Fraction, C
9Fraction and oleum lini are put into to stir in the autoclave and are warming up to 250-280 degree centigrade, pressure 0.35-0.6MPa, react and carried out underpressure distillation in 2-5 hour afterwards, steam unreacted reactant, be not decompressed to when the 0.08mMPa tower top temperature degree centigrade has overhead product by 120 degrees centigrade of steamings to 150 and end, steam rate 10-20% gets petroleum resin A;
B, petroleum resin A is put into the fusion that heats up in the there-necked flask, and be warming up to 180 degrees centigrade and add MALEIC ANHYDRIDE while stirring, then added octanol at 180-200 degree centigrade of insulation reaction 1-2 hour, 180-200 degree centigrade of insulation 1-2 hour, discharging got modified petroleum resin B;
C, right-special octyl phenol and toluene are joined in the there-necked flask behind the heating and melting, add hydrochloric acid and add formaldehyde while stirring at 50 degrees centigrade, be warming up to 80 degrees centigrade of insulation reaction after adding 3 hours, be cooled to 50 degrees centigrade and add caustic soda, reaction solution is alkalescence and adds formaldehyde, add the back 60-65 degree centigrade of insulation reaction 4 hours, being cooled to 50-55 degree centigrade is that 30% hydrochloric acid neutralizes and ends when reaching the pH value for 5-6 with concentration, add toluene and stirred 10 minutes, the standing demix organic layer washes with water once to be abandoned water layer and gets alkyl phenolic resin liquid C;
D, modified petroleum resin B and rosin are added in the there-necked flask, under 150-160 degree centigrade condition, carry out fusion, adding zinc oxide after the fusion stirs, add molten basic liquid phenolic resin C down at 180-200 degree centigrade, add the back at 200 degrees centigrade of insulation reaction 1-3 hours, be warming up to 210 degrees centigrade and add glycerine, add intensification, 220-240 degree centigrade of insulation 2-4 hour, decompression steamed moisture content and gets alkyl phenolic modified petroleum resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001291998A CN1170861C (en) | 2000-10-13 | 2000-10-13 | Alkyl phenolic modified petroleum resin and its prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001291998A CN1170861C (en) | 2000-10-13 | 2000-10-13 | Alkyl phenolic modified petroleum resin and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1288017A true CN1288017A (en) | 2001-03-21 |
| CN1170861C CN1170861C (en) | 2004-10-13 |
Family
ID=4593369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001291998A Expired - Fee Related CN1170861C (en) | 2000-10-13 | 2000-10-13 | Alkyl phenolic modified petroleum resin and its prepn. method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1170861C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314751C (en) * | 2004-05-21 | 2007-05-09 | 中国印钞造币总公司 | Gelling high acid value phenol-formaldehyde resin oil |
| CN1325525C (en) * | 2004-08-20 | 2007-07-11 | 中国石油天然气集团公司 | C5,C9 copolymerized petroleum resin preparation method |
| CN106883416A (en) * | 2015-12-16 | 2017-06-23 | 华奇（中国）化工有限公司 | C9 resin modified phenol formaldehyde resins and its preparation method and application |
| CN106967201A (en) * | 2016-12-29 | 2017-07-21 | 彤程化学（中国）有限公司 | A kind of Abietyl modified C9 Petropols and its preparation method and application |
| CN108219216A (en) * | 2017-12-25 | 2018-06-29 | 彤程化学（中国）有限公司 | Abietyl modified C9 Petropols and its preparation method and application |
| CN111333797A (en) * | 2020-03-04 | 2020-06-26 | 山东阳谷华泰化工股份有限公司 | Maleic anhydride modified p-tert-butyl phenol formaldehyde resin and synthetic method thereof |
| CN113943559A (en) * | 2021-12-21 | 2022-01-18 | 山东得顺源石油科技有限公司 | Micro-nano viscosity-reducing plugging agent for oil-based drilling fluid and preparation method thereof |
-
2000
- 2000-10-13 CN CNB001291998A patent/CN1170861C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314751C (en) * | 2004-05-21 | 2007-05-09 | 中国印钞造币总公司 | Gelling high acid value phenol-formaldehyde resin oil |
| CN1325525C (en) * | 2004-08-20 | 2007-07-11 | 中国石油天然气集团公司 | C5,C9 copolymerized petroleum resin preparation method |
| CN106883416A (en) * | 2015-12-16 | 2017-06-23 | 华奇（中国）化工有限公司 | C9 resin modified phenol formaldehyde resins and its preparation method and application |
| CN106967201A (en) * | 2016-12-29 | 2017-07-21 | 彤程化学（中国）有限公司 | A kind of Abietyl modified C9 Petropols and its preparation method and application |
| CN106967201B (en) * | 2016-12-29 | 2018-11-02 | 彤程化学（中国）有限公司 | A kind of Abietyl modified C9 Petropols and its preparation method and application |
| CN108219216A (en) * | 2017-12-25 | 2018-06-29 | 彤程化学（中国）有限公司 | Abietyl modified C9 Petropols and its preparation method and application |
| CN108219216B (en) * | 2017-12-25 | 2019-09-13 | 彤程化学（中国）有限公司 | Abietyl modified C9 Petropols and its preparation method and application |
| CN111333797A (en) * | 2020-03-04 | 2020-06-26 | 山东阳谷华泰化工股份有限公司 | Maleic anhydride modified p-tert-butyl phenol formaldehyde resin and synthetic method thereof |
| CN111333797B (en) * | 2020-03-04 | 2023-02-10 | 山东阳谷华泰化工股份有限公司 | Maleic anhydride modified p-tert-butyl phenol formaldehyde resin and synthetic method thereof |
| CN113943559A (en) * | 2021-12-21 | 2022-01-18 | 山东得顺源石油科技有限公司 | Micro-nano viscosity-reducing plugging agent for oil-based drilling fluid and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1170861C (en) | 2004-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101338013B (en) | Improved process for producing alkylphenols thermoplastic resin | |
| Ma et al. | An approach to improve the application of acid-insoluble lignin from rice hull in phenol–formaldehyde resin | |
| Abdollahi et al. | Poly (ε-caprolactone) chains grafted from lignin, hydroxymethylated lignin and silica/lignin hybrid macroinitiators: synthesis and characterization of lignin-based thermoplastic copolymers | |
| CN106800645B (en) | A kind of synthetic method of air-drying property unsaturated polyester (UP) | |
| CN1170861C (en) | Alkyl phenolic modified petroleum resin and its prepn. method | |
| CN109912805A (en) | A kind of modified resin with tear resistance, preparation method and applications | |
| CN112280459B (en) | Flame-retardant vegetable oil-based waterborne polyurethane coating and preparation method thereof | |
| CN104774552B (en) | A kind of soluble polyurethane heat insulation reflecting coating and preparation method thereof | |
| CN113667106A (en) | Ultraviolet-cured itaconic acid-based polyester resin and preparation method thereof | |
| US3870664A (en) | Resinous reaction product of a sucrose partial ester, a cyclic dicarboxylic acid anhydride and a diepoxide | |
| CN115418884B (en) | Preparation method of degradable waterproof high-strength recyclable paper plastic and recycling method thereof | |
| CN113817226B (en) | Polymer composite material additive and application thereof | |
| CN110845954A (en) | Water-based surface treating agent with flame-retardant effect for synthetic leather and preparation method thereof | |
| CN101818026A (en) | Method for preparing oligomeric rosin by taking slash pine rosin as raw material | |
| CN115850658A (en) | Preparation method of ultraviolet-curing flame-retardant epoxy acrylate and ultraviolet-curing coating | |
| CN101225283A (en) | Infinite soluble pnenolic aldehyde modified rosin resin and production method thereof | |
| CN114507324A (en) | Water-based acrylic acid modified alkyd hybrid resin, preparation method thereof, paint and application | |
| PL80608B1 (en) | ||
| CN113929968A (en) | Resveratrol-based flame retardant and preparation method and application thereof | |
| CN111808292A (en) | Birch alcohol-based hydrolysis-resistant flame-retardant polyester polyol and preparation method thereof | |
| US5559197A (en) | Modified phenolic resin toughened by phenoxy resin | |
| CN108424511B (en) | Method for preparing water-based polyester resin by using printing and dyeing slurry residues and application | |
| CN107686544B (en) | Method for synthesizing alkylphenol formaldehyde vulcanized resin by organic base catalysis | |
| CN116102942B (en) | Anticorrosive high-temperature-resistant waterborne polyurethane coating and preparation method thereof | |
| US3032533A (en) | Process for producing phenol-modified coumarone-indene type resins |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |