CN1341673A - Preparation of rosen modified mixed alkyl phenolic resin - Google Patents
Preparation of rosen modified mixed alkyl phenolic resin Download PDFInfo
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- CN1341673A CN1341673A CN 01131000 CN01131000A CN1341673A CN 1341673 A CN1341673 A CN 1341673A CN 01131000 CN01131000 CN 01131000 CN 01131000 A CN01131000 A CN 01131000A CN 1341673 A CN1341673 A CN 1341673A
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- mixed alkyl
- phenol
- rosin
- alkyl phenolic
- resin
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- Inks, Pencil-Leads, Or Crayons (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention belongs to the field of resin preparation technology that is a kind of connecting material to printing ink. It is obtained with processed by the following steps: arbitrarily mixing p-methyl hydroxybenzene, p-tert-butylphenol, p-tex-octylphenol and p-nonylphenol, making them produce reaction with formaldehyde to synthesize A-stage mixed alkyl phenolic resin, then using rosin to make modification and using polyhydric alcohol to make esterification. Said invention is easy to operate, safe, and its resin oil-solubility and fatty hydrocarbon solubility are good. Its colour is light and softening point is high. The printing ink made up by using said invented product does not skin, and possesses good printing property.
Description
One, technical field
The present invention introduces a kind of manufacturing technology for preparing the used resin of ink adhesive, more specifically to a kind of manufacture craft of rosen modified mixed alkyl phenolic resin.
Two, background technology
Existing history for many years such as the preparation of rosin modified phenol resol, Abietyl modified bisphenol A phenolic resin, Abietyl modified tert-butyl phenol resol etc., but with the printing ink that these resins are made, its glossiness, demulsification performance, drying, fixation performance and other printing performance all exist different separately defectives.Be prepared into Abietyl modified alkyl phenolic resin with containing the smaller alkylphenol of alkyl, oil soluble, the aliphatic hydrocarbon of this resin are poorly soluble, printing ink, the glossiness height made with it, but easy skinning, and printing back yellowing, the set time is too short, and printing performance is poor.Make Abietyl modified alkyl phenolic resin with containing the bigger alkylphenol of alkyl, the oil soluble of this resin, aliphatic hydrocarbon solvability are good, and the printing ink made from it, printing performance is good but glossiness is low, and the set time is oversize.Abietyl modifiedly in a word be used in the ink adhesive, influenced the printing effect and the speed of printing ink, can not satisfy the requirement of growing press by single alkylphenol synthetic resol.
Three, summary of the invention
By allocating phenol and the proportioning that contained alkyl varies in size, make the used rosen modified mixed alkyl phenolic resin of ink adhesive.Improve the performance of printing ink, the requirement of satisfying in press the printing ink different performance is the purpose that this resin synthetic method is provided.
The objective of the invention is to realize by following technical proposal: rosen modified mixed alkyl phenolic resin is that handle is to a tert.-butyl phenol, to monomethyl phenol, to a tert-octylphenol, to a nonylphenol, any two or more in these four kinds of phenol mixes mutually, under alkaline condition, synthesize first rank mixed alkyl resol liquid with formaldehyde reaction, carry out modification with rosin again, carry out fatization with polyvalent alcohol thereafter and make.
Its proportioning is:
First rank mixed alkyl resol liquid:
Mix phenol mole number sum: formaldehyde mole number=1: 1.5-2.5
Mix phenol weight sum: 96% caustic soda weight=1: 0.05-0.1
Rosen modified mixed alkyl phenolic resin:
Rosin weight: first rank mixed alkyl resol liquid weight=1: 0.4-0.8
Rosin weight: magnesium oxide or zinc oxide weight=1: 0.0002-0.001
The rosin mole number: glycerine or season the eleventh of the twelve Earthly Branches tetrol mole number=1: 1.1-1.5
A, mixed alkyl phenol and caustic soda are joined in the there-necked flask, heating and melting, molten back is opened and is stirred and cooling, under 50-60 ℃ condition, slowly adds formaldehyde, add the back at 60-70 ℃ of insulation reaction 3-5 hour, be cooled to 48-52 ℃ and neutralize, end when being neutralized to PH=5-6, stop stirring and left standstill 20 minutes with hydrochloric acid, water layer De Jia rank mixed alkyl resol liquid is abandoned in layering, organic layer washing twice;
B, rosin is joined in the there-necked flask, heating and melting, molten back is opened and is stirred.Under 180-200 ℃ condition, slowly add first rank mixed alkyl resol liquid, add the back 230 ℃ of insulation reaction one hour, add magnesium oxide or zinc oxide, stir, 210-250 ℃ slowly add glycerine or season the eleventh of the twelve Earthly Branches tetrol, thermal reacting for two hours under this temperature, being warming up to 265-275 ℃ of insulation reaction to reaction solution acid number ends during less than 20mgKOH/g, be decompressed to 300-400mmHg, steam low-boiling-point substance, get rosen modified mixed alkyl phenolic resin.
The beneficial effect that the present invention brings:
1, the resin of the present invention preparation, aliphatic hydrocarbon degree of holding, oil soluble is good, colourity is shallow, softening temperature is high.
2, molecular resin amount, viscosity, the acid number of the present invention's preparation are easy to control.
3, the printing ink of making is skinning not, do not return thick, the glossiness height, visco-elasticity, resistance to emulsion are good, set time, time of drying are moderate, the printing performance excellence.
4, the resin made from embodiment (1), (2), (3) is compared as follows with existing resin and corresponding ink performance:
Performance relatively
| Item name | Resin | Printing ink | |||||
| Normal heptane value (ml/2g) | Viscosity (mpas) | Glossiness | Resistance to emulsion (%) | Time of drying (hour) | The set time (branch) | Other | |
| Embodiment (1) resin | ????7.4 | ???6500 | ??78 | ????30-36 | ????6-7 | ??5-8 | Very |
| Embodiment (2) resin | ????5.8 | ???9200 | ??80 | ????30-36 | ????6-7 | ??5-8 | Excellent |
| Embodiment (3) resin | ????5.1 | ???7600 | ??81 | ????30-36 | ????6-7 | ??5-8 | Excellent |
| Abietyl modified sylvan urea formaldehyde | ????3.3 | ???3200 | ??80 | ????28-32 | ????3-4 | ??3-4 | Difference |
| Abietyl modified tert butyl phenolic resin | ????3.2 | ???8200 | ??82 | ????30-36 | ????4-5 | ??4-5 | Very |
| Abietyl modified bisphenol A phenolic resin | ????1.2 | ???14500 | ??82 | ????38-42 | ????3-4 | ??2-3 | Difference |
| Abietyl modified octyl phenol urea formaldehyde | ????9.1 | ???3500 | ??65 | ????39-45 | ????7-8 | ??9-10 | Very |
| Rosin Modified Nonyl Phenolic Resin | ????10.2 | ???3000 | ??60 | ????40-46 | ????8-9 | ??＞10 | Difference |
Four, the specific embodiment
Embodiment 1
To join to a tert-butyl phenol 34g, to a tert-octylphenol 100g, 15% caustic soda 60g in the there-necked flask of 500ml, heating and melting, open after molten and stir, be cooled to 60 ℃ and slowly drip 37% formaldehyde 141g, after adding 65 ℃ of insulation reaction 4 hours, be cooled to 50 ℃, hydrochloric acid with 10% neutralizes, end when being neutralized to PH=6, stop stirring and left standstill 20 minutes, twice of layering, organic layer washing, abandon water layer, get 216g first rank mixed alkyl phenolic resins liquid.
Rosin 400g is joined in the there-necked flask of 1000ml, heating and melting, open under the condition that is stirred in 180-182 ℃ after molten, slowly add first rank mixed alkyl phenolic resins liquid 216g, after adding 230 ℃ of insulation reaction one hour, add 0.2g zinc oxide, stir, slowly add glycerine 60g at 220 ℃, thermal reacting for two hours under this temperature is warming up to 265 ℃ of insulation reaction to reactant liquor acid number and ends during less than 20mgKOH/g, is decompressed to 300-400mmHg, steam low-boiling-point substance, get rosen modified mixed alkyl phenolic resin 542g. 162 ℃ of softening points, viscosity 6500mPaS, acid number 17mgKOH/g, normal heptane degree of holding 7.2ml/2g.
Embodiment 2:
Will be to a tert-butyl phenol 68g, to a nonyl phenol 65g, 15% caustic soda 53g joins in the there-necked flask of 500ml, heating and melting, molten rear the unlatching are stirred, be cooled to 50 ℃ and slowly drip 37% formaldehyde 140g, 60 ℃ of insulation reaction 3 hours, be cooled to 50 ℃ after adding, hydrochloric acid with 10% neutralizes, end when being neutralized to PH=5, stop stirring and left standstill 20 minutes, twice of layering, organic layer washing, abandon water layer, get 223g first rank mixed alkyl phenolic resins liquid.
Rosin 400g is joined in the there-necked flask of 1000ml, heating and melting, open after molten and stir, under 190 ℃ condition, slowly add first rank mixed alkyl phenolic resins liquid 223g, after adding 230 ℃ of insulation reaction one hour, add 0.2g magnesia, stir, slowly add season the eleventh of the twelve Earthly Branches tetrol 54g at 240 ℃, thermal reacting for two hours under this temperature is warming up to 270 ℃ of insulation reaction to reactant liquor acid number and ends during less than 20mgKOH/g, be decompressed to 300-400mmHg and steam low-boiling-point substance, get rosen modified mixed alkyl phenolic resin 530g. 170 ℃ of softening points, viscosity 9200mpaS, acid number 18mgKOH/g. Normal heptane degree of holding 5.8ml/2g.
Embodiment 3
Will be to monomethyl phenol 15g, to a tert-butyl phenol 56g, to a tert-octylphenol 44g, 15% caustic soda 60g joins in the there-necked flask of 500ml, 55 ℃ of slow formaldehyde 128g of 37% that drip are stirred, are cooled to heating and melting, molten rear the unlatching, after adding 70 ℃ of insulation reaction 5 hours, be cooled to 50 ℃, hydrochloric acid with 10% neutralizes, end when being neutralized to PH=6, stop stirring and left standstill 20 minutes, twice of layering, organic layer washing, abandon water layer, get 191g first rank mixed alkyl phenolic resins liquid.
Rosin 400g is joined in the there-necked flask of 1000ml, heating and melting, open after molten and stir, under 200 ℃ condition, slowly add first rank mixed alkyl phenolic resins liquid 191g, after adding 230 ℃ of insulation reaction one hour, add 0.3g magnesia, stir, slowly add glycerine 57g at 210 ℃, thermal reacting for two hours under this temperature is warming up to 268 ℃ of insulation reaction to reactant liquor acid number and ends during less than 20mgKOH/g, be decompressed to 300-400mmHg and steam low-boiling-point substance, get rosen modified mixed alkyl phenolic resin 518g.
Softening point: 160 ℃, viscosity: 7600mpaS, acid number: 18mgKOH/g. Normal heptane degree of holding: 5.1ml/2g.
Embodiment 4
Will be to a tert-butyl phenol 30g, to monomethyl phenol 10g, to a tert-octylphenol 40g, to a nonyl phenol 50g, 15% caustic soda 60g joins in the there-necked flask of 500ml, 50 ℃ of slow formaldehyde 130g of 37% that drip are stirred, are cooled to heating and melting, molten rear the unlatching, after adding 68 ℃ of insulation reaction 4.5 hours, be cooled to 50 ℃, the hydrochloric acid with 10% neutralizes, and ends when being neutralized to PH=6, stop stirring and left standstill 20 minutes, water layer is abandoned in layering, organic layer washing twice, gets 209g first rank mixed alkyl phenolic resins liquid.
Rosin 400g is joined in the there-necked flask of 1000ml, heating and melting, open after molten and stir, under 185 ℃ condition, slowly add first rank mixed alkyl phenolic resins liquid 209g, after adding 230 ℃ of insulation reaction one hour, add 0.3g zinc oxide, stir, slowly add season the eleventh of the twelve Earthly Branches tetrol 67g at 230 ℃, thermal reacting for two hours under this temperature is warming up to 275 ℃ of insulation reaction to reactant liquor acid number and ends during less than 20mgKOH/g, be decompressed to 300-400mmHg and steam low-boiling-point substance, get rosen modified mixed alkyl phenolic resin 552g.
Softening point: 168 ℃, viscosity: 8500mpaS, acid number: 17.5mgKOH/g. Normal heptane degree of holding: 8.3ml/2g.
Embodiment 5
First rank mixed alkyl phenolic resins liquid: rosen modified mixed alkyl phenolic resin:
To a tert-butyl phenol: 45g rosin: 400g
To monomethyl phenol: 54g first rank mixed alkyl phenolic resins liquid: 175g
15% caustic soda: 33g zinc oxide: 0.1g
37% formaldehyde: 130g season the eleventh of the twelve Earthly Branches tetrol: 50g
Must measure: 175g must measure: 507g
Preparation technology is with embodiment 1
Product index, softening point: 159 ℃
Viscosity: 4800mpas
Acid number: 16.4mgKOH/g
Normal heptane degree of holding: 4.3ml/2g
Embodiment 6
First rank mixed alkyl phenolic resins liquid: rosen modified mixed alkyl phenolic resin:
To monomethyl phenol: 35g rosin: 400g
To a tert-octylphenol: 100g first rank mixed alkyl phenolic resins liquid: 204g
15% caustic soda: 72g magnesia: 0.3g
37% formaldehyde: 110g season the eleventh of the twelve Earthly Branches tetrol: 59g
Must measure: 204g must measure: 540g
Preparation technology is with embodiment 2
Product index, softening point: 163 ℃
Viscosity: 8900mpas
Acid number: 18.5mgKOH/g
Normal heptane degree of holding: 6.8ml/2g
Embodiment 7 first rank mixed alkyl phenolic resins liquid: rosen modified mixed alkyl phenolic resin: to monomethyl phenol: 100g rosin: 400g is to a nonyl phenol: 38g first rank mixed alkyl phenolic resins liquid: 226g 15% caustic soda: 92g zinc oxide: 0.3g 37% formaldehyde: 122g glycerine: 53g must measure: 226g must measure: 526g preparation technology is with embodiment 1 product index, softening point: 165 ℃
Viscosity: 5800mpas
Acid number: 17.8mgKOH/g
Normal heptane degree of holding: 4.0ml/2g
Embodiment 8 first rank mixed alkyl phenolic resins liquid: rosen modified mixed alkyl phenolic resin: to a tert-octylphenol: 50g rosin: 400g is to a nonyl phenol: 125g first rank mixed alkyl phenolic resins liquid: 280g 15% caustic soda: 70g zinc oxide: 0.4g 37% formaldehyde: 155g glycerine: 45g must measure: 280g must measure: 570g preparation technology is with embodiment 1 product index, softening point: 159 ℃
Viscosity: 6000mpas
Acid number: 19.2mgKOH/g
Normal heptane degree of holding: 8.7ml/2g
Embodiment 9 first rank mixed alkyl phenolic resins liquid: rosen modified mixed alkyl phenolic resin: to a tert-butyl phenol: 15g rosin: 400g is to a tert-octylphenol: 68g first rank mixed alkyl phenolic resins liquid: 251g is to a nonyl phenol: 80g zinc oxide: 0.2g 15% caustic soda: 65g glycerine: 49g 37% formaldehyde: 130g must measure: 549g must measure: 251g preparation technology is with embodiment 1 product index, softening point: 162 ℃
Viscosity: 7800.mpas
Acid number: 19.5mgKOH/g
Normal heptane holds value: 7.4ml/2g
Embodiment 10 first rank mixed alkyl phenolic resins liquid: rosen modified mixed alkyl phenolic resin: to monomethyl phenol: 48g rosin 400g is to a tert-octylphenol: 20 first rank mixed alkyl phenolic resins liquid: 170g are to a nonyl phenol: 40g magnesia: 0.1g 15% caustic soda: 36g season the eleventh of the twelve Earthly Branches tetrol: 63g 37% formaldehyde: 85g must measure: 502g must measure: 170g preparation technology is with embodiment 2 product indexs, softening point: 148 ℃
Viscosity: 3000mpas
Normal heptane degree of holding: 10.5ml/2g
Acid number: 17.8mgKOH/g
Claims (3)
1, a kind of making method for preparing the used resin of ink adhesive, it is characterized in that: it is that handle is to a tert.-butyl phenol, to monomethyl phenol, to a tert-octylphenol, to a nonylphenol, any two or more in these four kinds of phenol mixes mutually, under alkaline condition with formaldehyde reaction, synthetic first rank mixed alkyl resol liquid, carry out modification with rosin again, carry out fatization with polyvalent alcohol thereafter and make;
2, a kind of making method for preparing the used resin of ink adhesive according to claim 1 is characterized in that; Proportioning raw materials is:
First rank mixed alkyl resol liquid:
Mix phenol mole number sum: formaldehyde mole number=1: 1.5-2.5
Mix phenol weight sum: 96% caustic soda weight=1: 0.05-0.1
Rosen modified mixed alkyl phenolic resin:
Rosin weight: first rank mixed alkyl resol liquid weight=1: 0.4-0.8
Rosin weight: magnesium oxide or zinc oxide weight=1: 0.0002-0.001
The rosin mole number: glycerine or season the eleventh of the twelve Earthly Branches tetrol mole number=1: 1.1-1.5
3, a kind of making method for preparing the used resin of ink adhesive according to claim 1 and 2 is characterized in that:
A, mixed alkyl phenol and caustic soda are joined in the there-necked flask, heating and melting, molten back is opened and is stirred and cooling, under 50-60 ℃ condition, slowly add formaldehyde, add the back at 60-70 ℃ of insulation reaction 3-5 hour, be cooled to 48-52 ℃ and neutralize, end when being neutralized to PH=5-6 with hydrochloric acid, stop stirring, leave standstill 20 minutes, layering, organic layer washing twice, abandon water layer De Jia rank mixed alkyl resol liquid;
B, rosin is joined in the there-necked flask, heating and melting, molten back is opened and is stirred.Under 180-200 ℃ condition, slowly add first rank mixed alkyl resol liquid, add the back 230 ℃ of insulation reaction one hour, add magnesium oxide or zinc oxide, stir, 210-250 ℃ slowly add glycerine or season the eleventh of the twelve Earthly Branches tetrol, thermal reacting for two hours under this temperature, being warming up to 265-275 ℃ of insulation reaction to reaction solution acid number ends during less than 20mgKOH/g, be decompressed to 300-400mmHg, steam low-boiling-point substance, get rosen modified mixed alkyl phenolic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011310006A CN1158320C (en) | 2001-08-30 | 2001-08-30 | Preparation of rosen modified mixed alkyl phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011310006A CN1158320C (en) | 2001-08-30 | 2001-08-30 | Preparation of rosen modified mixed alkyl phenolic resin |
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| Publication Number | Publication Date |
|---|---|
| CN1341673A true CN1341673A (en) | 2002-03-27 |
| CN1158320C CN1158320C (en) | 2004-07-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB011310006A Expired - Fee Related CN1158320C (en) | 2001-08-30 | 2001-08-30 | Preparation of rosen modified mixed alkyl phenolic resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532443A (en) * | 2011-12-27 | 2012-07-04 | 山东圣泉化工股份有限公司 | Phenolic resin and preparation method thereof |
| CN102911330A (en) * | 2012-10-16 | 2013-02-06 | 山西省应用化学研究所 | Vegetable oil modified rosin phenolic resin and preparation method thereof |
| CN103554401A (en) * | 2013-11-22 | 2014-02-05 | 天津市天宁树脂有限公司 | Formula and production method of phenolic resin for printing ink |
| CN104140510A (en) * | 2014-07-25 | 2014-11-12 | 广西众昌树脂有限公司 | Preparation method of rosin modified phenolic resin |
| CN110437400A (en) * | 2019-08-26 | 2019-11-12 | 刘伟俊 | A kind of environmental protection rosin modified phenolic resin and preparation method thereof |
-
2001
- 2001-08-30 CN CNB011310006A patent/CN1158320C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532443A (en) * | 2011-12-27 | 2012-07-04 | 山东圣泉化工股份有限公司 | Phenolic resin and preparation method thereof |
| CN102911330A (en) * | 2012-10-16 | 2013-02-06 | 山西省应用化学研究所 | Vegetable oil modified rosin phenolic resin and preparation method thereof |
| CN102911330B (en) * | 2012-10-16 | 2014-05-28 | 山西省应用化学研究所 | Vegetable oil modified rosin phenolic resin and preparation method thereof |
| CN103554401A (en) * | 2013-11-22 | 2014-02-05 | 天津市天宁树脂有限公司 | Formula and production method of phenolic resin for printing ink |
| CN103554401B (en) * | 2013-11-22 | 2015-08-26 | 天津市天宁树脂有限公司 | A kind of printing-ink phenolic resin formulations and production method thereof |
| CN104140510A (en) * | 2014-07-25 | 2014-11-12 | 广西众昌树脂有限公司 | Preparation method of rosin modified phenolic resin |
| CN110437400A (en) * | 2019-08-26 | 2019-11-12 | 刘伟俊 | A kind of environmental protection rosin modified phenolic resin and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1158320C (en) | 2004-07-21 |
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