CN101225283A - Infinite soluble pnenolic aldehyde modified rosin resin and production method thereof - Google Patents
Infinite soluble pnenolic aldehyde modified rosin resin and production method thereof Download PDFInfo
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Abstract
The invention discloses a complete miscibility phenolic aldehyde modified abietic resin, which can be fully dissolved in petroleum cyclane solvent. The synthetic method comprises the following process steps: (1) adding the alkylphenol, aldehyde and solvent into a reactor, heating, blending and reacting for 4 to 12 hours under the alternating action of acid base catalyst at 65 to 110 degrees C and obtaining the long chain resol; (2) adding the rosin into the reactor, heating and dissolving, and then adding the long chain resol in, reacting with the abietic acid for 5 to 16 hours ar 150 to 270 degrees C and then obtaining the complete miscibility phenolic aldehyde modified abietic resin after adding the polylol in to esterify first and dehydrate then or esterify first and modify then. The complete miscibility phenolic aldehyde modified abietic resin is of much significance for producing the ink which is good for the high speed printing machine.
Description
Technical field
The present invention relates to a kind of printing-ink raw material, particularly phenol aldehyde modified Gum Rosin and production method thereof.
Background technology
Along with the high speed development of China's printing industry, the printing-ink production technology is maked rapid progress, and kind is varied, and printing press requires more and more higher to the printing adaptability of printing ink.Till the present, the still phenol aldehyde modified Gum Rosin that the filmogen of oil-based ink mainly uses.Oil-based ink connects expects that the system that use is made up of phenol aldehyde modified rosin fat, vegetables oil, mineral oil still is the main flow that printing ink is produced.It is very different that the resin strip of different performance is given the characteristic of ink adhesive system, thereby makes printing ink form the printing adaptability energy with different characteristics.The universal problems of bringing a series of solutions of still needing of high-speed printer, as anti-emulsifying property and quick ink-water balance, the adaptability of printing ink under the high-shear, fast set, good transferring rate etc., printing press has become more diversified to the performance requriements of printing ink, the suitable property of ink printing has obtained new development, and wherein resin property improves the important effect of play more and more.
Last century the seventies, China begins to study phenol aldehyde modified Gum Rosin is synthetic, since at that time beginning, a lot of researchs are explored and have been used different phenols, carry out synthesis modification as phenol, dihydroxyphenyl propane, alkylphenol (single, or compound).Synthetic operational path and method have also been carried out diversified trial and research.The synthesis technique of rosin modified phenolic resin is a principal character with traditional synthesis technique still.The title that single stage method and two step method are wherein arranged.The characteristics of single stage method are; Earlier phenol, aldehyde are mixed the back direct reaction with rosin, the back adds the polyvalent alcohol esterification, and process form is simple, but controls such as follow-up each step intensification are had relatively high expectations; The characteristics of two step method are synthetic in advance phenolic condensation compound intermediates. react with rosin system again. and final low acid value, the high softening-point of forming after each specific step of reaction. have suitable molecular weight and certain deliquescent resin of mineral oil solvent.Resin high resolution and high visco-elasticity are to realize that offset litho printing ink adapts to the important ring that high speed printing, Dormant oils solvent take off development trend such as aromatization.Rosin modified phenolic resin is the matrix resin of offset litho printing ink, how to adapt to the printing demand of high-speed printer, is that rosin products is made the pending so far scientific and technological research topic in field.
In recent years, open source literature has been reported the method for some phenol aldehyde modified Gum Rosins, for example:
1, Chinese patent, application (patent) number: 03137280.5, title: Abietyl modified mixed alkylphenol phenolic resin and preparation method thereof, application (patent right) people: Research Inst., of Applied Chemistry, Shanxi Prov., summary: a kind of Abietyl modified mixed alkylphenol phenolic resin and preparation method thereof, be by right-tert-octylphenol, right-nonylphenol, dodecyl phenol and formaldehyde react the mixed alkylphenol phenolic resin condenses that obtains and prepare after Abietyl modified and polyvalent alcohol esterification under alkaline condition, wherein glycerine and the esterification of TriMethylolPropane(TMP) proceed step by step are adopted in the polyvalent alcohol esterification.The resol of the present invention's preparation is the softening temperature height not only, and visco-elasticity is good, and aliphatic hydrocarbon solubility property and oil soluble can be more excellent, and product color is shallow, and range of molecular weight distributions is narrow, is suitable for the manufacturing of high speed printing with extraordinary colored ink.
2, Chinese patent, application (patent) number: 93105520.2, the applying date: 1993.05.12, title: method application (patent right) people who makes rosin modified phenolic resin with rosin: Forest Products Industry Co., Longyan Prefecture, Fujian Prov., summary: the method that the present invention relates to directly make rosin modified phenolic resin with rosin.After being about to rosin fusion filtration, magnesium oxide and basic metal lithiumation thing with significant quantity are catalyzer, directly and phenol and formaldehyde consolute generation condensation, addition reaction, the mole ratio of phenol and formaldehyde is 1: 1.2～2.0, dehydration afterwards heats up, fractionate out byproduct turps, use glycerine esterification again, can get rosin products of light color, that softening temperature is high, oil soluble is good.Adopt present method can simplify manufacturing process, reduce the phenol consumption, thereby correspondingly increase the economic benefit of manufacturer.
3, Chinese patent, application (patent) number: 00800699.7, the applying date: 2000.05.02, title: the preparation method of phenol-modified rosin ester, phenol-modified rosin ester and uses thereof, application (patent right) people: Arakawa Chemical Industries, Ltd., address: Osaka, Japan, international application: PCT/JP00/02918 2000.5.2 international publication WO00/68289 day 2000.11.16 enters date: the 2000.12.27 of country summary: the invention provides a kind of method for preparing phenol-modified rosin ester, this method comprises rosin and phenol, the step of formaldehyde and polyol reaction, the method is characterized in that, with rosin or rosiny polyol ester and the volatile alkali catalyzer existence resol reaction of preparation down, the present invention provides the phenol-modified rosin ester with method for preparing in addition, and the present invention also provides the adhesive for printing ink of the rosin ester that contains this phenol modification, and the printing-ink that contains this adhesive for printing ink further is provided.
4, Chinese patent, application (patent) number: 93105515.6, the applying date: 1993.05.12, title: the manufacture method of light colour modified rosin phenolic aldehyde resin, application (patent right) people: Forest Products Industry Co., Longyan Prefecture, Fujian Prov., address: the East Road of ascending a height the Longyan, Fujian Province, summary: the method that the present invention relates to make the oily molten shape rosin phenolic resin of light color, promptly magnesium oxide and the basic metal lithiumation thing with significant quantity is catalyzer, and the mole ratio that makes phenol and formaldehyde is 1: 1.2～2.0, thereby make the product look number reach 89, save phenol about 30%.In addition, it is good that the light colour modified rosin phenolic aldehyde resin made from the inventive method is still had a softening temperature height, oil soluble, can be widely used in the industries such as paint, printing ink, cable, printing, rubber, plastics, tackiness agent.
5, Chinese patent, application (patent) number: 200410012161.9 applyings date: 2004.02.25, title: the manufacture method of mixed alkyl resol condenses, application (patent right) people: Geng Guoqing, address: No. 7, east northeast street, Yuci District road, Jinzhong City, Shanxi Province, summary: a kind of manufacture method of mixed alkyl resol condenses is the mixture of any two or three in p-tert-butylphenol, right-tert-octylphenol, right-three kinds of alkylphenols of nonylphenol and Paraformaldehyde 96 to be carried out condensation reaction prepare condenses in the aqueous solution of weakly alkaline catalyzer.This resin condensation thing can also react with rosin, makes rosen modified mixed alkyl phenolic resin.Substitute 37% formalin and use weak base with Paraformaldehyde 96 among the present invention, saved hydrochloric acid neutralization and washing twice processing step, reduced the discharging of phenolic wastewater, help environment protection, and improved production efficiency as catalyzer.
6, [autograph] senior printing ink synthetic [author] Han Li Ma Haiyan [mechanism] Fushun Research Inst. of Chem. Engineering ﹠ Design of Rosin Modified Nonyl Phenolic Resin, [periodical name] thermosetting resin .2006,21 (5) .-15-16[digests] employing two step method synthesis technique, with nonyl phenol and rosin and formaldehyde is main raw material, has synthesized rosin modified phenolic resin.The various reaction conditionss of synthetic are studied, determined best synthesis route.At first with nonyl phenol and the synthetic first rank of formaldehyde phenol formaldehyde condensation resin, best synthesis technique is: 65 ℃ of temperature of reaction, reaction times 6h; Phenolic aldehyde amount of substance ratio is 1: 2.4, and under zinc oxide and calcium acetate composite catalyzing, with polymerized rosin and rosin mixture modification, the polymerized rosin add-on is 10%, temperature of reaction 260-270 ℃, has realized dissolving viscosity and the balanced development of heptane degree of holding then.
7, building-up reactions [author] Shi Yuxiang [1] Wang Liqiu [2] [mechanism] [1] Fushun Research Inst. of Chem. Engineering ﹠ Design of [autograph] Abietyl modified nonyl phenol, formaldehyde resin, [periodical name] Liaoning chemical industry .2001,30 (3) .-99-102[digests] tell and be used by adding polymerized rosin and two kinds of catalyzer, solved the difficult problem that high heptane harm degree resin can cause low solution viscosity effectively, simultaneously, esterification degree and yield have been improved.And to the acid number of resin, viscosity, softening temperature and just more performance such as alkane tolerance carried out analytical test, finally obtained the pale rosin modification nonyl phenol urea formaldehyde product of low acid number, high softening-point, high viscosity, Gao Gengrong.
8, [mechanism] Heilongjiang Petrochemical Plant such as study on the synthesis [author] the fourth million eastern Zhang Guanghui of [autograph] single stage method Rosin Modified Nonyl Phenolic Resin, [periodical name] Speciality Petrochemicals progress .2001,2 (3) .-1-2, the 5[digest] synthesized Rosin Modified Nonyl Phenolic Resin in the indoor single stage method of experiment, investigate reaction upgrading pH value, the phenolic aldehyde mol ratio, the raw material nonyl phenol, add the influence of aldehyde speed and condensation soaking time to quality product, optimum synthesis condition is: the phenolic aldehyde mol ratio is 1: 23, and reaction medium pH value is 9, and nonyl phenol compares greater than 90: 10 the neighbour, the condensation soaking time is 3.5-4h, and the synthetic quality product meets or exceeds two-step process under this condition.
9, [autograph] catalyst levels and polyvalent alcohol are to rosin modified phenolic resin Effect on Performance [author] the Jiang Xiao plum Wang Wei people [mechanism] Hangzhou Bang Te printing ink stock company, [periodical name] Hangzhou chemical industry .2001,31 (2) .-22-25[digests] adopt glycerine, tetramethylolmethane to prepare in the technology of the rosin modified phenolic resin that printing-ink uses, catalyst consumption has a significant effect to the performance (as viscosity, consistency) of resin.The advantage of this technology is to have used weak base catalyst, rather than makees catalyzer with the big NaOH of alkalescence, and this experimental result shows the selection of raw catalyst, and loaded down with trivial details technology is oversimplified, and is easy to operate, and keeps the quality of synthetic resins.
Recognize from above-mentioned result for retrieval, open source literature has been reported the relevant content of research of more Abietyl modified phenolic resin, these documents propose under the effect of basic catalyst mostly, aldehyde and phenol compound are reacted, add the strong base catalyzer sodium hydroxide is arranged, basic metal lithiumation thing, the adding weakly alkaline catalyzer or the oxide catalyst that also have, for example zinc oxide and calcium acetate, magnesium oxide, but performance is good not enough when described Abietyl modified phenolic resin of above-mentioned document and mineral oil, the resin for printing ink solvability that the synthetic method that is proposed makes can not be satisfactory, from satisfying the requirement of high-quality high speed printing printing ink manufacturing to the resin quality distance arranged still.
Summary of the invention
The purpose of this invention is to provide a kind of can the phenol aldehyde modified Gum Rosin of complete miscibility in mineral oil (petroleum hydrocarbon solvent), manufacturing has special purposes to this resin to high speed printing printing ink.
Technical scheme of the present invention is achieved in that
The physics-chem characteristic of infinite soluble pnenolic aldehyde modified rosin resin is as follows:
1, resin can 100% dissolving in oil cycloalkane solvent (as common 200# mineral oil, 210# mineral oil, 270# mineral oil, 280# mineral oil and low aromatic hydrocarbons mineral oil).
2, resin is yellow solid at normal temperatures and pressures, and is transparent, water insoluble, 138 ℃-165 ℃ of softening temperatures (according to the phenol difference that adopts), and (resin and oleum lini 1: 2) drips normal heptane, the infinity of normal heptane value in the solution of resin and oleum lini.
3, resin does not precipitate when rising temperature for dissolving is cooled off again in the petroleum hydrocarbon solvent, and is non-crystallizable, haze-free.
Above-described infinite soluble pnenolic aldehyde modified rosin resin, its synthetic method comprises following processing step:
(1) alkylphenol, aldehyde, solvent being added the reactor intensification stirs, the mol ratio of alkylphenol and aldehyde is 1: 1.2～2.5, the amount that adds solvent is alkylphenol and aldehyde weight 0.1～1.0 times, under the acid base catalysator alternating action, reacted 4-12 hour, wherein an acidic catalyst reaction is 3-7 hour, alkaline catalysts reaction 1-5 hour, 60 ℃-110 ℃ of temperature of reaction (normal pressure) are reacted the resole condenses that can obtain long-chain through above-mentioned steps.
(2) add rosin in reactor, add the long-chain resole after the rising temperature for dissolving, the mass ratio of rosin and long-chain resole is 1～2: 1, and with sylvic acid reaction 5-16 hour, the back added the polyvalent alcohol esterification in 150 ℃-270 ℃.The mass content of polyvalent alcohol is the 0-10% of total material, and esterification temperature is 200 ℃-280 ℃, time 6-12 hour.
Through above-mentioned synthesis step, can obtain the infinite soluble pnenolic aldehyde modified rosin ester.
Above-described alkylphenol comprises p-tert-butylphenol, to tert-octylphenol, to nonyl phenol, dodecyl phenol;
Above-described aldehyde comprises formaldehyde, acetaldehyde, propionic aldehyde, furfural and Paraformaldehyde 96.
Above-described solvent is the petroleum-type solvent, for example cyclopropane, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane, dimethylbenzene etc. also can be the compound of the tape base group of these naphthenic hydrocarbon, for example methyl cyclopropane, ethyl cyclopentane, aryl rings butane etc.
Above-described alkaline catalysts comprises sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide or is the oxyhydroxide of alkalescence, aminated compounds is as quadrol, hexanediamine, aniline, triethylenediamine, dimethylcyclohexylamine, fatty amine, aromatic amine and alcamines catalyzer etc.Alkaline catalysts can make alkylphenol and aldehyde generate appropriate cancellated phenolic condensation compound in solvent, and the amount that alkaline catalysts adds is the 0.3-2% (in solid alkali) of alkylphenol quality.Alkaline catalysts adds can obtain appropriate cancellated resole.
Above-described an acidic catalyst comprises sulfuric acid, hydrochloric acid, acetic acid, oxalic acid or sulfonic acid etc.Acid catalysis helps the formation of long-chain compound, and the amount that acid catalyst adds is the 0.1-1% of alkylphenol quality.
The above can carry out acid catalysis earlier at the acid base catalysator alternating action, after carry out base catalysis, also can carry out base catalysis earlier, after carry out acid catalysis.
The polyvalent alcohol that the modified rosin resin of the above (2) step adds comprises methyl alcohol, ethanol, glycerine, Glycerol dimer, tetramethylolmethane, dipentaerythritol, ethylene glycol, sorbyl alcohol, TriMethylolPropane(TMP) etc.
The present invention is according to the different phenol aldehyde modified Gum Rosins that obtain different qualities of the molecular weight of alkylphenol and aldehyde, and for example, to the phenol aldehyde modified Gum Rosin that obtains with rosin, polyol reaction again behind special octyl phenol and the formaldehyde reaction, glossiness is higher, and rete is harder.The phenol aldehyde modified Gum Rosin that obtains with rosin, polyol reaction again behind dodecyl phenol and the polyformaldehyde reaction, gloss is soft, and toughness is better, can adapt to the printing-ink of making different characteristics and use.
The mechanism of the synthetic method of infinite soluble pnenolic aldehyde modified rosin resin of the present invention is as follows:
Conventional art only uses alkali or weak base to generate the mode of resol as catalyzer separately, so, may have to the more resole condenses of reticulated structure, and the present invention at acid base catalysator alternately down, can obtain more how long chain structure also is with the network-like resole condenses of appropriateness.The network-like resol of this long-chain is through just obtaining later the phenol aldehyde modified Gum Rosin of complete miscibility in mineral oil with rosin, polyvalent alcohol esterification and modification.The phenol aldehyde modified Gum Rosin of complete miscibility is because its high oil-soluable property, can be used as the auxiliary composition of macromolecular cpd and enter the ink vehicle system, expanded the degree of holding of ink adhesive system to greatest extent, thereby made the ink vehicle system present excellent flowability and transfer printing performance mineral oil.The lasting powerful extruding of high-shear state that forms when adapting to the high-speed printer operation for ink system and machinery makes printing ink remain good transitivity and printing adaptability contributes.
(macromole) compound of high structure, because its structure is big, molecular weight is big, the high-shear state that forms in the face of the high-speed printer operation time and the lasting powerful extruding of machinery are by printing ink keeps good fundamental property necessary; In the practice, for pursuing the adaptability of high speed printing, the synthetic method of phenol aldehyde modified Gum Rosin is more to be developed to bound macromolecule.The study on the synthesis of having ignored lower molecular weight, high resolution resin.And the result that general synthetic method causes, synthesizing of macromolecular compound will be cost with the oil soluble of sacrificing synthetics again.Marquis when this, the study on the synthesis of infinite soluble pnenolic aldehyde modified rosin resin has highlighted its meaning.Low structure (lower molecular weight) compound, because its structure is little, the oil soluble height can be used as in the auxiliary composition adding system of macromolecular cpd, thereby has changed the oil-soluble deficiency of system.We can say, infinite soluble pnenolic aldehyde modified rosin resin synthetic, the synthetic target different and pursue direction with the synthetic formation of the resin of (macromole) characteristics with high structure, but bring out the best in each other different way and reach the same goal.
The inventor thinks that succeeding in developing of infinite soluble pnenolic aldehyde modified rosin resin can widen the setting range of ink viscosity and viscosity, the flowability of printing ink is become be easy to adjust.How the unique effect that infinite soluble pnenolic aldehyde modified rosin resin is brought into play in ink system realizes that for the high speed printing ink resin connects the material system high resolution provides new optional approach.
Succeeding in developing of infinite soluble pnenolic aldehyde modified rosin resin pushed phenol aldehyde modified one of them direction of Gum Rosin study on the synthesis extremely to.Promptly from the direction of low structure (lower molecular weight) compound formation, the pursuing development that this synthetics is formed has arrived ultimate attainment,
In order fully to understand the performance of infinite soluble pnenolic aldehyde modified rosin resin of the present invention, we understand the difference part of infinite soluble pnenolic aldehyde modified rosin resin of the present invention and other phenol aldehyde modified Gum Rosin by following table 1.
Table 1, the physicochemical property of infinite soluble pnenolic aldehyde modified rosin resin and some compounds compare:
| Model | XY-40 | XY-R8 | XY-X10 | XY-S7 |
| Softening temperature | 152-162 | 145-158 | 140-150 | 138-148 |
| Viscosity | 38-45 | 20-25 | 7-12 | 7-9 |
| The normal heptane value | ≥50 | ≥100 | Molten entirely | ≥200 |
In the table, viscosity: gardner viscosity, unit line is to line/second.Portions of resin vegetables oil=1: 2
The normal heptane value: every milliliter/2 milligrams, softening temperature: ℃
XY-X10 is an infinite soluble pnenolic aldehyde modified rosin resin of the present invention in the last table.
XY-40, XY-R8, XY-S7 are the phenol aldehyde modified Gum Rosins of limited dissolved.
As can be seen from the table, molten entirely (molten entirely in hydrocarbon solution) and low viscous phenol aldehyde modified Gum Rosin promptly are infinite soluble pnenolic aldehyde modified rosin resins, and molten entirely promptly is the characteristics of this resin.
Embodiment
Embodiment 1
(1) with 1200 the gram to tert-octylphenol, acetaldehyde, the cyclopropane solvent adds the reactor intensification and stirs, mol ratio to tert-octylphenol and acetaldehyde is 1: 1.2～2.0, the amount that adds cyclopropane is 1.5～3.0 times to tert-octylphenol and acetaldehyde weight, use sulfuric acid reaction 2-6 hour earlier, the amount that 98% concentration sulfuric acid catalyst adds is the 0.1-1% of alkylphenol quality, used the sodium hydroxide alkali catalyst reaction then 1-3 hour, make it to generate the network-like resole of long-chain, 65 ℃-100 ℃ of temperature of reaction, the amount of the adding of sodium hydroxide catalyst is the 0.3-2% of alkylphenol quality in solid alkali.
(2) in reactor, add rosin 1200 grams, add the above-mentioned network-like resole of whole long-chains that obtains after the rising temperature for dissolving, in 150 ℃-270 ℃, reacted 5-16 hour with sylvic acid, the back adds ethylene glycol 200 grams, the esterification dehydration, esterification temperature is set at 200 ℃-280 ℃, time 6-12 hour, with 200 gram glycerin modifications, can obtain about 2000 grams of infinite soluble pnenolic aldehyde modified rosin ester again.
Embodiment 2
(1) with 1000 tert.-butyl phenol that restrain, formaldehyde, the tetramethylene solvent adds the reactor intensification and stirs, the mol ratio of tert.-butyl phenol and formaldehyde is 1: 1.2～2.0, the amount that adds tetramethylene is tert.-butyl phenol and formaldehyde weight 1.5～2.0 times, use sulfuric acid reaction 2-6 hour earlier, the amount that 98% concentration sulfuric acid catalyst adds is the 0.1-1% of alkylphenol quality, used the sodium hydroxide alkali catalyst reaction then 1-3 hour, make it to generate the network-like resole of long-chain, 65 ℃-100 ℃ of temperature of reaction, the amount of the adding of sodium hydroxide catalyst is the 0.3-2% of alkylphenol quality in solid alkali.
(2) in reactor, add rosin 800 grams, component progressively adds the above-mentioned network-like resole of whole long-chains that obtains after the rising temperature for dissolving, in 150 ℃-270 ℃, reacted 5-16 hour with sylvic acid, the back adds ethylene glycol 200 grams, the esterification dehydration, esterification temperature is set at 200 ℃-280 ℃, time 6-12 hour, can obtain infinite soluble pnenolic aldehyde modified rosin ester 2000 grams.
Embodiment 3
(1) with 1200 the gram to tert-octylphenol, Paraformaldehyde 96, xylene solvent adds the reactor intensification and stirs, mol ratio to tert-octylphenol and aldehyde is 1: 1.2～2.0, the amount that adds dimethylbenzene is 0.1～1.0 times to tert-octylphenol and polyoxymethylene weight, earlier with 95% sulfuric acid catalyst reaction 3-7 hour, 65 ℃-100 ℃ of temperature of reaction, the amount that sulfuric acid catalyst adds is the 0.2-1% of alkylphenol quality, and then with calcium hydroxide alkali reaction 2-6 hour, the concentration 10% of calcium hydroxide aqueous solution, add-on is to be the 5-10% of alkylphenol quality, makes it to generate the network-like resole of long-chain appropriateness;
(2) in reactor, add 1000 gram rosin, add the long-chain resole after the rising temperature for dissolving, in 150 ℃-270 ℃, reacted 5-16 hour with sylvic acid, the back adds 100 gram glycerine esterification dehydrations, esterification temperature is set at 200 ℃-280 ℃, time 6-12 hour, can obtain about 2000 gram infinite soluble pnenolic aldehyde modified rosin esters.
Embodiment 4
(1) with 1000 the gram to nonyl phenol, furfural, the suberane solvent adds the reactor intensification and stirs, mol ratio to nonyl phenol and furfural is 1: 1.2～2.0, the amount that adds suberane is 1.5～3.0 times to nonyl phenol and furfural weight, earlier with calcium hydroxide alkaline catalysts reaction 1-3 hour, 65 ℃-100 ℃ of temperature of reaction, calcium hydroxide catalyst concentration 10%, add-on is to be the 3-10% of alkylphenol quality, and then with hydrochloric acid reaction 2-6 hour, the concentration 30% of hydrochloric acid catalyst, the amount that adds is the 1-5% of alkylphenol quality, makes it to generate the network-like resole of long-chain;
(2) in reactor, add rosin, add the network-like resole of long-chain after the rising temperature for dissolving, in 150 ℃-270 ℃, reacted 5-16 hour with sylvic acid, the back adds 200 Keshan pears alcohol esterification dehydration, esterification temperature is set at 200 ℃-280 ℃, time 6-12 hour, with 200 gram tetramethylolmethane modifications, can obtain infinite soluble pnenolic aldehyde modified rosin ester 2000 grams again.
Embodiment 5
(1) with 1000 dodecyl phenol that restrain, Paraformaldehyde 96, cyclohexane solvent adds the reactor intensification and stirs, the mol ratio of dodecyl phenol and Paraformaldehyde 96 is 1: 1.2～2.0, the amount that adds hexanaphthene is 1.5～3.0 times to nonyl phenol and Paraformaldehyde 96 weight, earlier with hydrogen vulkacit H alkaline catalysts reaction 1-3 hour, make it to generate network-like resole, reacted 3-8 hour, 65 ℃-100 ℃ of temperature of reaction, the content of vulkacit H catalyzer is greater than 90%, add-on is to be the 0.5-5% of alkylphenol quality, and then with oxalic acid reaction 2-6 hour, the amount that the oxalic acid catalyzer adds is the 0.2-1% of alkylphenol quality, makes it to generate the network-like resole of long-chain;
(2) in reactor, add rosin, component adds the network-like resole of long-chain after the rising temperature for dissolving, in 150 ℃-270 ℃, reacted 5-16 hour with sylvic acid, the back adds 200 gram tetramethylolmethane esterification dehydrations, esterification temperature is set at 200 ℃-280 ℃, time 6-12 hour, glycol-modified with 200 grams again, can obtain infinite soluble pnenolic aldehyde modified rosin ester 2000 grams.
Embodiment 6
(1) dodecyl phenol, Paraformaldehyde 96, the cyclohexane solvent with 1000 grams adds reactor intensification stirring, mol ratio to dodecyl phenol and Paraformaldehyde 96 is 1: 1.2～2.0, the amount that adds hexanaphthene is 1.5～3.0 times to nonyl phenol and Paraformaldehyde 96 weight, use hydrochloric acid reaction 2-6 hour earlier, the amount that 30% hydrochloric acid catalyst adds is the 1-5% of alkylphenol quality, makes it to generate long catenate resole; 65 ℃-100 ℃ of temperature of reaction, vulkacit H catalyzer add-on is to be the 0.5-1% of alkylphenol quality, makes it to generate the network-like resole of long-chain;
(2) in reactor, add rosin, add the network-like resole of long-chain after the rising temperature for dissolving, in 150 ℃-270 ℃, reacted 5-16 hour with sylvic acid, again with 80 gram tetramethylolmethane modifications, esterification temperature is set at 200 ℃-280 ℃, time 6-12 hour, can obtain infinite soluble pnenolic aldehyde modified rosin ester 2000 grams.
Different process comparative analysis of the present invention
In alkylphenol, different phenol is to the special influence that is formed with in various degree seized with terror of product physics and chemistry.
In alkylphenol, the difference of different phenol molecular structures can cause the difference of resinous molecular structure, thereby it is special also different on seized with terror to be reflected at product physics and chemistry.Under the base catalysis condition, the data of the reaction of different phenol gained are different.
Table two
| Alkylphenol | P-tert-butylphenol | To tert-octylphenol | To nonyl phenol | Dodecyl phenol |
| Softening temperature | 155-165 | 142-152 | 140-150 | 138-148 |
| Viscosity | 15-25 | 7-15 | 7-12 | 6-9 |
| Normal heptane | ≥25 | ≥50 | ≥100 | ≥200 |
From table two as seen, the growth of alkyl chain in the alkylphenol contraposition, influence is directly proportional to synthetic resins.The normal heptane value is along with the growth of alkyl chain is increasing, and this is that molecular polarity is little because alkyl chain is big, and oil soluble is good, and the normal heptane value of product is just big; Alkyl chain is little, and molecular polarity is big, and the normal heptane value of product is just little.
After we changed this reaction process into soda acid by single base catalysis and replace catalysis, this difference had just become the difference of only remaining viscosity and softening temperature.
Table three,
| Alkylphenol | P-tert-butylphenol | To tert-octylphenol | To nonyl phenol | Dodecyl phenol |
| Softening temperature | 148-158 | 142-152 | 140-150 | 138-148 |
| Viscosity | 12-17 | 7-15 | 6-14 | 6-13 |
| Normal heptane | Molten entirely | Molten entirely | Molten entirely | Molten entirely |
So an acidic catalyst helps the formation of long-chain compound, basic catalyst then helps the formation of reticulated structure compound, and the present invention is to locate our needed synthetics behind both alternating actions.
Under the same reaction conditions, condensation temp has remarkable influence to quality product.
Table four
| Condensation temp | The condensation time | Softening temperature | Viscosity | The normal heptane value |
| 60-75 | 3-10 | 134 | 7 | 25 |
| 75-90 | 3-10 | 138 | 9 | 50 |
| 85-100 | 3-10 | 142 | 13 | 50 |
| 100-110 | 3-10 | 156 | 20 | 25 |
Different temperature of reaction is formed with direct influence to the products molecule structure.
Claims (9)
1. infinite soluble pnenolic aldehyde modified rosin resin is characterized in that having following physics-chem characteristic:
(1) resin can 100% dissolving in oil cycloalkane solvent.
(2) resin is the deep yellow solid at normal temperatures and pressures, and is transparent, water insoluble, softening temperature 138-165 ℃, and the infinity of normal heptane value.
(3) resin when cooling off, does not precipitate after oil cycloalkane solvent rising temperature for dissolving again, and is non-crystallizable, haze-free.
2. the production method of infinite soluble pnenolic aldehyde modified rosin resin as claimed in claim 1 is characterized in that: comprise following processing step:
(1) alkylphenol, aldehyde, petroleum-type solvent being added the reactor intensification stirs, the mol ratio of alkylphenol and aldehyde is 1: 1.2～2.5, the amount that adds solvent is alkylphenol and aldehyde weight 0.5～3.0 times, under the acid base catalysator alternating action, reacted 4-12 hour, wherein an acidic catalyst reaction is 3-7 hour, alkaline catalysts reaction 2-6 hour, 65 ℃-110 ℃ of temperature of reaction can obtain the long-chain resole through the above-mentioned steps reaction.
(2) in reactor, add rosin, add the long-chain resole after the rising temperature for dissolving, the mass ratio of rosin and long-chain resole is 1～2: 1, in 150 ℃-270 ℃, reacted 5-16 hour with sylvic acid, the back adds polyvalent alcohol esterification and modification, and the mass content of polyvalent alcohol is the 0-12% of total material, and esterification temperature is 200 ℃-280 ℃, time 6-12 hour, obtain the infinite soluble pnenolic aldehyde modified rosin ester.
3. the production method of infinite soluble pnenolic aldehyde modified rosin resin according to claim 2 is characterized in that: described alkylphenol comprises p-tert-butylphenol, to tert-octylphenol, to nonyl phenol or dodecyl phenol;
4. the production method of infinite soluble pnenolic aldehyde modified rosin resin according to claim 2, it is characterized in that: described aldehyde is formaldehyde, acetaldehyde, propionic aldehyde, furfural or Paraformaldehyde 96.
5. the production method of infinite soluble pnenolic aldehyde modified rosin resin according to claim 2, it is characterized in that: described solvent is the petroleum-type solvent, or the compound of the tape base of these naphthenic hydrocarbon group.
6. the production method of infinite soluble pnenolic aldehyde modified rosin resin according to claim 2, it is characterized in that: the alcohol of the adding of described modified rosin resin comprises methyl alcohol, ethanol, glycerine, Glycerol dimer, tetramethylolmethane, dipentaerythritol, ethylene glycol, glycerol, sorbyl alcohol or ethylene glycol.
7. the production method of infinite soluble pnenolic aldehyde modified rosin resin according to claim 2, it is characterized in that: described alkaline catalysts comprises sodium hydroxide, potassium hydroxide, calcium hydroxide, aminated compounds or is the oxyhydroxide of alkalescence that the amount that alkaline catalysts adds is the 0.3-2% of alkylphenol quality.
8. the production method of infinite soluble pnenolic aldehyde modified rosin resin according to claim 2, it is characterized in that: described an acidic catalyst comprises sulfuric acid, hydrochloric acid, organic and mineral acids such as acetic acid, oxalic acid or sulfonic acid, the amount that acid catalyst adds is the 0.1-1% of alkylphenol quality.
9. the production method of infinite soluble pnenolic aldehyde modified rosin resin according to claim 2 is characterized in that: described at the acid base catalysator alternating action, can carry out base catalysis earlier, after carry out acid catalysis, perhaps carry out acid catalysis earlier, after carry out base catalysis.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037668A (en) * | 2015-08-31 | 2015-11-11 | 桂林兴松林化有限责任公司 | Preparation method for rosin modified phenolic resin for ink |
| 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 |
| CN108048774A (en) * | 2017-12-31 | 2018-05-18 | 天长市飞龙金属制品有限公司 | A kind of metal surface hot dip coating method |
| CN113502031A (en) * | 2021-07-30 | 2021-10-15 | 上海菲诺利克新材料科技有限公司 | Thermoplastic phenolic resin and preparation method thereof |
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2008
- 2008-02-15 CN CN 200810073475 patent/CN101225283A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037668A (en) * | 2015-08-31 | 2015-11-11 | 桂林兴松林化有限责任公司 | Preparation method for rosin modified phenolic resin for ink |
| 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 |
| CN108048774A (en) * | 2017-12-31 | 2018-05-18 | 天长市飞龙金属制品有限公司 | A kind of metal surface hot dip coating method |
| CN108048774B (en) * | 2017-12-31 | 2020-07-10 | 天长市飞龙金属制品有限公司 | Metal surface hot dip plating method |
| CN113502031A (en) * | 2021-07-30 | 2021-10-15 | 上海菲诺利克新材料科技有限公司 | Thermoplastic phenolic resin and preparation method thereof |
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Application publication date: 20080723 |