CN104031202B - Polyacrylic acid ink resin and preparation method thereof - Google Patents
Polyacrylic acid ink resin and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to printing-ink field, be specifically related to printing polyacrylic acid ink resin and preparation method thereof. the present invention is by (methyl) acrylic acid, (methyl) acrylate, vinyl monomer, active function monomer, helper component, molecular weight regulator and initator mix and obtain reaction mass in head tank, then reaction mass being pumped into inside is equipped with in the tubular reactor of static mixing device, under HTHP, adopt continuous bulk polymerization method to be prepared polyacrylic acid ink resin, the technique of continuous bulk polymerization adopting has effectively suppressed gel in bulk polymerisation process, the generation of implode reaction, ensure the controllability of the molecular weight of polyacrylic acid ink resin, the polyacrylic acid ink resin that to have prepared number-average molecular weight be 10000～70000. polyacrylic acid ink resin of the present invention has good solvent release and printing adaptability.
Description
Technical field
The invention belongs to printing-ink field, be specifically related to printing polyacrylic acid ink resin and preparation thereofMethod.
Background technology
In recent years, along with the variation of packing instructions and the development of packing technique, each as packaging materialPlanting plastic sheeting arises at the historic moment. Owing to decorating or surface protection, plastic film for wrapping needs conventionallyPrint. Plastic gravure ink is the coloured material for plastics package printing.
In recent years,, there is valency in the ester dissolubility occurring on market, the polyurethane plastics gravure ink of alcohol dissolubilityLattice are high, to problems such as pigment wetting bad dispersibility, affected promoting the use of of this series products.
Given this, research staff is more and more for the exploitation of the acrylic ink resin of alcohol dissolubility, for example,Chinese patent CN101747475B discloses a kind of employing acrylate, tertiary ethylene carbonate, vinyl acetateThe synthetic resin for alcohol-soluble printing ink of the preparation such as ester. This resin, for gravure printing ink, has peopleBody, environmental hazard are little, the features such as raw material is conveniently easy to get, preparation cost is low, pigment wetting good dispersion.Chinese patent CN102241795A discloses a kind of employing methacrylate, acrylate, active official's energyOne of the preparation such as single group body, tertiary carbonic acid glycidyl ester, cationic functional monomer, rosin addition polymerPlant alcohol soluble acrylic thermoplastic resin.
But market practice shows, such acrylic ink resin that solvent method is produced has solvent releaseThe defects such as poor, dissolvent residual is high, have had a strong impact on promoting the use of of such ink resin. Therefore develop toolThere is the polyacrylic acid ink resin of good solvent release property significant.
Propose to prepare acrylic acid by mass polymerization from the A.W.Hanson of Dow Chemical in 1956 solidSince body resin, people are devoted to the research of polymerisation in bulk always. Due to conventional solid propenoic acid resinBe at normal temperatures and pressures solid-state, when pyroreaction, monomer is again gaseous state, so can only be at the bar of HTHPUnder part, react, reaction condition has proposed strict demand to consersion unit. Afterwards, abroad someone proposedAdopt the water-soluble solid acrylic resin of suspension polymerization for the preparation of water color ink, but suspension polymerisationNeed to introduce the reaction raw materials such as protection glue, product need to carry out post processing to remove impurity, raising purity,Hardness and gloss; Simultaneously molecular resin amount profile exponent is higher, so that ink viscosity is bigger than normal, on market extremelyThe modern product that adopts this explained hereafter of seldom seeing.
Rhom and Hass has proposed employing tube method and has prepared this type of water soluble acrylic resin, but so far veryFew employing. US Patent No. 4529787 has proposed a kind of mode that adopts continuous stirring and has entered in reactorRow is prepared the method for the solid propenoic acid resin of the low and even molecular weight distribution of molecular weight, in the time stirring, needsInstalling coil pipe is to solve the emission problem of reaction heat, thus control molecular weight distribution, and equipment requirement is strict.
Chinese patent CN1279693A discloses a kind of employing tubular reactor and has prepared low Tg admittedlyThe method of body acrylate. Made resin weight average molecular weight is 10000 or lower, main as being coated withThe additive of resin system for material and casting.
Chinese patent CN1146579C discloses one, and to add a small amount of dipropylene glycol methyl ether and water be solvent,The method of carrying out accurate body continuous polymerization in a controllable temperature reactor. Made water-soluble phenylethene/propyleneAcid resin is mainly used in water-based ink, paint and coating. But the ink tree that adopts this formula to prepareFat has serious printability problem.
Chinese patent CN100560622C discloses a kind of employing continuous bulk polymerization legal systemThe method of 6000～9000 solid propenoic acid resin, this resin is mainly used in water color ink, as mill baseGrinding distribution resin and the protection resin of acrylic emulsion polymerization.
Summary of the invention
One of object of the present invention is to overcome the defect that the made polyacrylic acid ink resin of current solvent method exists,Thereby provide a kind of polyacrylic acid ink resin with good solvent release property, good printability.
Two of object of the present invention is to provide a kind of continuous bulk polymerization legal system that adopts and sets for polyacrylic acid inkThe method of fat.
Polyacrylic acid ink resin of the present invention is that the reaction mass being obtained after mixing by following raw material carries outAfter continuous bulk polymerization, obtain, taking the gross weight of reaction mass as benchmark, each raw material components accounts for reactantThe ratio of the gross weight of material is:
Described (methyl) acrylic acid is selected from one or both the mixing in acrylic acid, methacrylic acidThing.
Described (methyl) acrylate be selected from (methyl) methyl acrylate, (methyl) ethyl acrylate,(methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl)Acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) propyleneAcid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid benzeneEster, (methyl) benzyl acrylate, (methyl) acrylic acid ethyoxyl methyl esters, (methyl) acrylic acid methoxyl groupEthyl ester, (methyl) acrylic acid propoxyl group ethyl ester, (methyl) acrylic acid butoxyethyl, (methyl) propyleneThe mixture of one or more in acid ethyoxyl propyl ester, (methyl) isobornyl acrylate.
Described vinyl monomer be selected from propionate, vinyl butyrate, trimethylace tonitric vinyl acetate,2 ethyl hexanoic acid vinyl acetate, vinyl laurate, styrene, methyl styrene, tertiary ethylene carbonate, 4-The mixture of one or more in hydroxy butyl vinyl ether.
Described active function monomer is selected from maleic acid, itaconic acid, maleic anhydride, (methyl) acrylic acid-2-Hydroxy methacrylate, (methyl) 2-hydroxypropyl acrylate, acrylamide, acrylonitrile, dimethylaminoethyl acrylate methylOne or more in amino ethyl ester, allyl glycidyl ether, (methyl) glycidyl acrylateMixture.
Described helper component is selected from rosin, newtrex, abalyn, ester gum, rosin twoGlycol ester, pentalyn, rosin phenolic resin, rosin terpene phenolic resin, terpene resin,Polyketone resin, Petropols, gum dammar, phenolic resins, polyethers, polyester, polyurethane, polyamide,Cellulose, polyvinylpyrrolidone, epoxy resin, polyvinyl formal, polyvinyl butyral resin,Melamine resin, alkyd resins, ethylene-vinyl acetate resin, polyphenylene oxide, polysulfones, poly-carbonic acidThe mixture of one or more in ester, Lauxite.
Described molecular weight regulator be selected from isopropyl alcohol, n-butanol, isobutanol, ethylene glycol, propane diols,Mercaptoethanol, mercaprol, Mercaptobutanol, sulfydryl hexanol, TGA, 3-mercaptopropionic acid, 3-sulfydrylThe mixture of one or more in butyl propionate, tertiary lauryl mercaptan, AMS dimer.
Described initator is selected from azodiisobutyronitrile, ABVN, diacetyl peroxide, peroxideChange two lauroyl, benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide, peroxidating twoTertiary pentyl, TBHP, benzoyl peroxide formic acid tertiary butyl ester, tert-butyl hydroperoxide laurateIn one or more mixture.
The preparation method of polyacrylic acid ink resin of the present invention: by (methyl) acrylic acid, (methyl) thirdOlefin(e) acid ester, vinyl monomer, active function monomer, helper component, molecular weight regulator and initator existIn head tank, mix and obtain reaction mass, then reaction mass is pumped into inside static mixing dress is housedIn the tubular reactor of putting, carry out continuous bulk polymerization; In the time carrying out continuous bulk polymerization, tubular reactorTemperature be 100～300 DEG C, pressure is 0.5～4MPa, when the stop of reaction mass in tubular reactorBetween be 2～40 minutes; After product discharging, through extracting, granulation, obtain polyacrylic acid ink resin;Wherein: taking the gross weight of reaction mass as benchmark, (methyl) acrylic acid accounts for the gross weight of reaction mass1～20%, (methyl) acrylate account for reaction mass gross weight 30～70%, vinyl monomer accounts for insteadAnswer material gross weight 20～40%, active function monomer account for reaction mass gross weight 1～30%, auxiliaryHelp component account for reaction mass gross weight 2～15%, molecular weight regulator accounts for the gross weight of reaction mass0.5～20%, initator account for reaction mass gross weight 0.01～4%.
The number-average molecular weight of described polyacrylic acid ink resin is 10000～70000.
The present invention adopts continuous bulk polymerization method to be prepared polyacrylic acid ink resin under HTHP,The technique of continuous bulk polymerization adopting has effectively suppressed sending out of gel in bulk polymerisation process, implode reactionRaw, ensure the controllability of the molecular weight of polyacrylic acid ink resin, prepare number-average molecular weight and be10000～70000 polyacrylic acid ink resin. Polyacrylic acid ink resin of the present invention has good moltenAgent release property and printing adaptability, thus ensure that made gravure printing ink has good solvent and dischargesProperty, glossiness and printability.
Below by specific embodiment, the present invention is described in further detail, but should not be understood as the present inventionThe restriction of protection domain, all based on above-mentioned technological thought, utilize ordinary skill knowledge and strong handAmendment, replacement, change that section is made all belong to scope of the present invention. Adopt gel permeation chromatography, to gatherStyrene is the number-average molecular weight that reference material is measured product.
Detailed description of the invention
Embodiment 1
By the methacrylic acid of 1 kilogram, 41 kilograms methyl methacrylate, 40 kilograms styrene,The maleic acid of 1 kilogram, the rosin of 15 kilograms, the isopropyl alcohol of 1 kilogram, the azodiisobutyronitrile of 1 kilogram existIn head tank, mix and obtain reaction mass, then reaction mass is pumped into inside static mixing dress is housedIn the tubular reactor of putting, carry out continuous bulk polymerization; In the time carrying out continuous bulk polymerization, tubular reactorTemperature be 100 DEG C, pressure is 0.5MPa, the time of staying of reaction mass in tubular reactor is 40Minute; After product discharging, through extracting, granulation, make number-average molecular weight and be 70000 polypropyleneAcid ink resin.
Embodiment 2
By the acrylic acid of 10 kilograms, the methacrylic acid of 10 kilograms, the butyl acrylate, 18 of 12 kilogramsKilogram acrylic acid pentyl ester, the vinyl butyrate of 21 kilograms, the methyl styrene, 10 kilograms of 9 kilogramsItaconic acid, the acrylonitrile of 5.5 kilograms, the rosin phenolic resin of 1 kilogram, the epoxy resin, 0.3 of 1 kilogramKilogram propane diols, the TGA of 0.2 kilogram, the benzoyl peroxide of 0.5 kilogram, the mistake of 1.5 kilogramsOxidation diisopropylbenzene (DIPB) mixes and obtains reaction mass in head tank, then reaction mass is pumped into insideBe equipped with in the tubular reactor of static mixing device and carry out continuous bulk polymerization; Carrying out continuous bulk polymerizationTime, the temperature of tubular reactor is 300 DEG C, and pressure is 4MPa, and reaction mass is in tubular reactorThe time of staying is 2 minutes; After product discharging, through extracting, granulation, making number-average molecular weight is 10000Polyacrylic acid ink resin.
Embodiment 3
By the acrylic acid of 7 kilograms, the methacrylic acid of 3.5 kilograms, the isobutyl acrylate, 40 of 10 kilogramsKilogram nonyl methacrylate, the vinyl laurate of 5 kilograms, the tertiary ethylene carbonate, 5 of 15 kilogramsKilogram 2-Hydroxy ethyl acrylate, the acrylamide of 7 kilograms, the cellulose of 1 kilogram, 2 kilograms poly-Carbonic ester, the sulfydryl hexanol of 0.1 kilogram, the 3-mercaptopropionic acid of 0.4 kilogram, the peroxidating diethyl of 2.5 kilogramsAcyl, the tert-butyl hydroperoxide laurate of 1.5 kilograms mix and obtain reaction mass in head tank, soAfter reaction mass is pumped into inside be equipped with and in the tubular reactor of static mixing device, carry out continuous bulk polymerization;In the time carrying out continuous bulk polymerization, the temperature of tubular reactor is 200 DEG C, and pressure is 3.5MPa, reactionThe time of staying of material in tubular reactor is 30 minutes; After product discharging, through extracting, granulation,Make number-average molecular weight and be 50000 polyacrylic acid ink resin.
Embodiment 4
By the acrylic acid of 1 kilogram, the methacrylic acid of 0.24 kilogram, the acrylic acid ester in the ninth of the ten Heavenly Stems, 16 of 14 kilogramsKilogram acrylic acid methoxyl group ethyl ester, the methyl styrene of 8 kilograms, the 4-hydroxyl butyl vinyl of 12 kilogramsEther, the allyl glycidyl ether of 5 kilograms, the GMA, 4 kilograms of 25 kilogramsPetropols, the Lauxite of 4.5 kilograms, the 3-mercaptopropionic acid butyl ester of 7 kilograms, the uncle ten of 3.25 kilogramsDialkyl group mercaptan, the diacetyl peroxide of 0.005 kilogram, peroxidating two tertiary pentyls of 0.005 kilogram are enteringIn batch can, mix and obtain reaction mass, then reaction mass is pumped into inside static mixing device is housedTubular reactor in carry out continuous bulk polymerization; In the time carrying out continuous bulk polymerization, tubular reactorTemperature is 180 DEG C, and pressure is 2.25MPa, and the time of staying of reaction mass in tubular reactor is 25Minute; After product discharging, through extracting, granulation, make number-average molecular weight and be 40000 polypropyleneAcid ink resin.
Embodiment 5
By the methacrylic acid of 1 kilogram, the isobutyl acrylate of 20 kilograms, the methacrylic acid of 50 kilogramsPhenyl ester, the 4-hydroxy butyl vinyl ether of 20 kilograms, the maleic anhydride of 0.4 kilogram, the methyl-prop of 0.6 kilogramOlefin(e) acid dimethylaminoethyl, the flexalyn of 1 kilogram, the polyester of 4.495 kilograms, 0.2 kilogram differentButanols, the mercaprol of 0.3 kilogram, the dilauroyl peroxide of 0.5 kilogram, the peroxidating of 1.505 kilogramsDiisopropylbenzene (DIPB) mixes and obtains reaction mass in head tank, then reaction mass is pumped into inside and is equipped withIn the tubular reactor of static mixing device, carry out continuous bulk polymerization; In the time carrying out continuous bulk polymerization,The temperature of tubular reactor is 280 DEG C, and pressure is 1.6MPa, reaction mass stopping in tubular reactorStaying the time is 32 minutes; After product discharging, through extracting, granulation, making number-average molecular weight is 57000Polyacrylic acid ink resin.
Embodiment 6
By the acrylic acid of 3 kilograms, the methacrylic acid of 7 kilograms, ethyl acrylate, 35 public affairs of 10 kilogramsThe acrylic acid methoxyl group ethyl ester of jin, the 2 ethyl hexanoic acid vinyl acetate of 13 kilograms, the styrene, 0.3 of 7 kilogramsKilogram 2-hydroxypropyl acrylate, 0.7 kilogram allyl glycidyl ether, 1 kilogram terpene resin,The gum dammar of 2 kilograms, the mercaptoethanol of 4 kilograms, the AMS dimer, 0.4 of 16 kilogramsKilogram dilauroyl peroxide, the benzoyl peroxide formic acid tertiary butyl ester of 0.6 kilogram in head tank, mix allThe even reaction mass that obtains, then pumps into inside by reaction mass and is equipped with the tubular reactor of static mixing deviceIn carry out continuous bulk polymerization; In the time carrying out continuous bulk polymerization, the temperature of tubular reactor is 260 DEG C,Pressure is 2.5MPa, and the time of staying of reaction mass in tubular reactor is 21 minutes; Product goes outAfter material, through extracting, granulation, make number-average molecular weight and be 43000 polyacrylic acid ink resin.
Claims (9)
1. a polyacrylic acid ink resin, is characterized in that, described polyacrylic acid ink resin be by belowRaw material obtains after after mixing, the reaction mass that obtains carries out continuous bulk polymerization, total with reaction massWeight is benchmark, and the ratio that each raw material components accounts for reaction mass gross weight is:
Described vinyl monomer be selected from propionate, vinyl butyrate, trimethylace tonitric vinyl acetate,2 ethyl hexanoic acid vinyl acetate, vinyl laurate, styrene, methyl styrene, tertiary ethylene carbonate, 4-The mixture of one or more in hydroxy butyl vinyl ether;
Described helper component is selected from rosin, newtrex, abalyn, ester gum, rosin twoGlycol ester, pentalyn, rosin phenolic resin, rosin terpene phenolic resin, terpene resin,Polyketone resin, Petropols, gum dammar, phenolic resins, polyethers, polyester, polyurethane, polyamide,Cellulose, polyvinylpyrrolidone, epoxy resin, polyvinyl formal, polyvinyl butyral resin,Melamine resin, ethylene-vinyl acetate resin, polyphenylene oxide, polysulfones, Merlon, urea aldehyde treeThe mixture of one or more in fat.
2. polyacrylic acid ink resin according to claim 1, is characterized in that: described polyacrylic acidThe number-average molecular weight of ink resin is 10000～70000.
3. polyacrylic acid ink resin according to claim 1, is characterized in that: described (methyl)Acrylic acid is selected from one or both the mixture in acrylic acid, methacrylic acid.
4. polyacrylic acid ink resin according to claim 1, is characterized in that: described (methyl)Acrylate is selected from (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid thirdEster, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid pentyl ester, (firstBase) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl)Decyl acrylate, (methyl) dodecylacrylate, (methyl) phenyl acrylate, (methyl) propyleneAcid benzyl ester, (methyl) acrylic acid ethyoxyl methyl esters, (methyl) acrylic acid methoxyl group ethyl ester, (methyl) thirdOlefin(e) acid propoxyl group ethyl ester, (methyl) acrylic acid butoxyethyl, (methyl) acrylic acid ethyoxyl propyl ester, (firstBase) one or more mixture in isobornyl acrylate.
5. polyacrylic acid ink resin according to claim 1, is characterized in that: described active functionMonomer is selected from maleic acid, itaconic acid, maleic anhydride, (methyl) 2-Hydroxy ethyl acrylate, (methyl)2-hydroxypropyl acrylate, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, pi-allylThe mixture of one or more in glycidol ether, (methyl) glycidyl acrylate.
6. polyacrylic acid ink resin according to claim 1, is characterized in that: described polyester is alcoholAcid resin.
7. polyacrylic acid ink resin according to claim 1, is characterized in that: described molecular weight is adjustedJoint agent be selected from isopropyl alcohol, n-butanol, isobutanol, ethylene glycol, propane diols, mercaptoethanol, mercaprol,Mercaptobutanol, sulfydryl hexanol, TGA, 3-mercaptopropionic acid, 3-mercaptopropionic acid butyl ester, tertiary dodecylThe mixture of one or more in mercaptan, AMS dimer.
8. polyacrylic acid ink resin according to claim 1, is characterized in that: described initator choosingFrom azodiisobutyronitrile, ABVN, diacetyl peroxide, dilauroyl peroxide, peroxidatingBenzoyl, cumyl peroxide, di-t-butyl peroxide, peroxidating two tertiary pentyls, t-butyl peroxyMixing of one or more in change hydrogen, benzoyl peroxide formic acid tertiary butyl ester, tert-butyl hydroperoxide laurateCompound.
9. a preparation method for the polyacrylic acid ink resin described in claim 1～8 any one, its spyLevy and be: by (methyl) acrylic acid, (methyl) acrylate, vinyl monomer, active function monomer,Helper component, molecular weight regulator and initator mix and obtain reaction mass in head tank, thenReaction mass is pumped into inside to be equipped with and in the tubular reactor of static mixing device, to carry out continuous bulk polymerization;In the time carrying out continuous bulk polymerization, the temperature of tubular reactor is 100～300 DEG C, and pressure is 0.5～4MPa,The time of staying of reaction mass in tubular reactor is 2～40 minutes; After product discharging, through extracting,Granulation, obtains polyacrylic acid ink resin; Wherein: taking the gross weight of reaction mass as benchmark, (methyl)Acrylic acid account for reaction mass gross weight 1～20%, (methyl) acrylate accounts for the gross weight of reaction mass30～70%, vinyl monomer account for reaction mass gross weight 20～40%, active function monomer accounts for insteadAnswer material gross weight 1～30%, helper component account for reaction mass gross weight 2～15%, molecular weightConditioning agent account for reaction mass gross weight 0.5～20%, initator accounts for the gross weight of reaction mass0.01～4％。
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| CN108671867A (en) * | 2018-06-06 | 2018-10-19 | 博立尔化工（扬州）有限公司 | A kind of device and method thereof preparing solid propenoic acid resin |
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| CN108671867A (en) * | 2018-06-06 | 2018-10-19 | 博立尔化工（扬州）有限公司 | A kind of device and method thereof preparing solid propenoic acid resin |
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