CN101967213A - Preparation method of carboxyl-contained polyacrylic ester with low molecular weight - Google Patents
Preparation method of carboxyl-contained polyacrylic ester with low molecular weight Download PDFInfo
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Abstract
The invention relates to a preparation method of carboxyl-contained polyacrylic ester with low molecular weight, belonging to the field of light-curing low polymers. The low polymer side chain contains carboxyls, has low molecular weight and high reaction speed and conversion rate as well as obviously enhanced absorption capability to a substrate by the carboxyl content in the structure. The preparation method of the low polymer comprises the following steps of: copolymerizing solution free radicals of one or more of (methyl) acrylic acid and (methyl) acrylic alkyl acrylate to obtain a main chain including pure C-C bonds; and then, introducing the side chain with light reaction activity through a condensation reaction of functional groups, wherein monomers participating in the condensation reaction include glycidyl methacrylate, heahydroxy-ethyl acrylate, and the like. The invention controls the molecular weight and the molecular weight distribution of the low polymer by selecting the monomers and controlling the content of acrylic acid and the dosages of an initiator and a chain transfer agent and controls the content of carboxyl groups by controlling the esterification rate to prepare the polyacrylic ester low polymer with excellent performance. The process has the advantages of simple and convenient operation and easy industrial production.
Description
Technical field:
The present invention relates to UV light-cured type acrylate resin.Belong to photocuring oligopolymer field.
Background technology
UV-curing technology has " 5E " advantage, that is: Efficient (efficiently), Enabling (wide adaptability), Economical (economy), Energy Saving (energy-conservation) and Environmental Friendly (environmental friendliness) are widely used in fields such as coating, printing ink, tackiness agent, plate making, stereolithography and precision sizing.The ultraviolet light polymerization system is mainly by oligopolymer, reactive thinner, and light trigger and other auxiliary agent are formed, and wherein oligopolymer accounts for the 50-80% of whole prescription, has determined the Main physical and the chemical property of cured film, is of paramount importance integral part.
The polyacrylic ester acrylic resin is a kind of less oligopolymer of studying, but it is an important kind of photocuring prepolymer, have following major advantage: 1. main chain does not have phenyl ring, the molecular chain kindliness is bigger, intermolecular tap density is big, hardness of film is higher behind the curing cross-linked, has similar enamelled outward appearance.2. molecular side chain has a large amount of ester groups, gives appearance of film plentiful, slick characteristic.3. main chain is the C-C singly-bound entirely, does not have tangible absorption band in the ultraviolet wavelength scope, the ultraviolet-resistant performance excellence of resin, thus give the good ageing-resistant performance of filming.
Adopt progressively polymerization different mostly with other kind quasi-oligomer, the main chain of polyacrylic ester acrylic resin adopts the method for two key chain polymerizations to synthesize, because the monomeric variation of reactivity ratio of monomer is very big to product result's influence, and reaction is comparatively violent, heat release is many, wayward, tend to cause molecular weight of product and dispersed the increase.Molecular weight increases then viscosity and increases, and polymolecularity greatly then makes every degradation, thus generally can not use as the main body oligopolymer, but use as some matching components or property regulation component.Hindered its range of application greatly.
Therefore, adopt the method for the chain-transfer agent that adds to control molecular weight among the present invention, polymolecularity is then adjusted by choosing suitable monomers kind, proportioning and adjusting polymeric reaction conditions.Target of the present invention designs exactly, synthetic series reaction speed is fast, transformation efficiency is high, molecular weight is low, the polyacrylic ester acrylic resin oligopolymer of excellent performance.Particularly select by monomer, introduce some carboxyls in oligomer structure, this will bring certain benefit to the character that strengthens its base material adhesive ability.
Summary of the invention
The purpose of this invention is to provide in a kind of structure and contain carboxyl, molecular weight is low, speed of reaction is fast, transformation efficiency is high, solidifies polyacrylic ester acrylic resin oligopolymer of back excellent performance and preparation method thereof.This oligopolymer can be used as matrix resin and uses, and owing to containing carboxyl in the structure its adhesive ability to base material is obviously strengthened because viscosity is low.
The object of the present invention is achieved like this: by " two-step approach " the synthetic low-molecular-weight polyacrylic ester acrylate that contains carboxyl functional group.Described origoester acrylate is made up of main chain and side chain two portions.Main chain is pure C-C, by vinylformic acid and acrylic double bond copolymerization and get.Side chain is a segment of introducing optical active group by the condensation reaction of functional group.
The first step adopts synthetic (methyl) acrylate copolymer that has carboxyl functional group of the method for solution free radical polymerization.The comonomer of described acrylate copolymer is made up of two portions:
1. (methyl) alkyl acrylate monomer, its structure can be used general formula (I) expression:
Wherein: R1 is hydrogen atom or methyl, and R2 is that carbonatoms is 1～18 alkyl.Specifically, comprise n-butyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer (claiming 2-EHA again) dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, (methyl) methyl acrylate, ethyl propenoate, the methacrylic dodecyl gallate, tridecyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems, isodecyl acrylate etc.
2. functional monomer.In the acrylic or methacrylic acid one or both.Its structure is shown in (II):
Wherein, R1 is hydrogen atom or methyl.
The actual conditions of the first step copolyreaction is as follows: initiator is a kind of in azo-bis-isobutyl cyanide (AIBN) or the dibenzoyl peroxide (BPO), and the total amount that initiator adds is 0.25%～5% (molar fraction) of monomer total amount.Chain-transfer agent is a fats mercaptan, is octyl mercaptan, a kind of in the positive Dodecyl Mercaptan, and the total amount that chain-transfer agent adds is monomeric 0～4% (molar fraction).Copolymerization temperature is 50 ℃～100 ℃.The solvent that adopts in the polymerization is an organic solvent, for aromatic hydrocarbon based, and the ester class, the mixture of one or more in alcohols and the ketone specifically comprises ethyl acetate, toluene, pimelinketone etc.
Second step was adopted the condensation reaction of functional group, had the condensation monomer that has light reaction in (methyl) acrylate copolymer of carboxyl in the grafting in the reaction product of the first step.Can be glycidyl methacrylate (GMA), (methyl) Hydroxyethyl acrylate, a kind of in (methyl) Propylene glycol monoacrylate.Its structure is respectively:
Lower molecular weight has the preparation method of the polyacrylic ester acrylate of carboxyl, it is characterized in that step is as follows:
The first step causes comonomer by radical initiator and obtains acrylate copolymer by solution polymerization;
Comonomer is a kind of of (methyl) alkyl acrylate monomer and acrylic or methacrylic acid, and acrylic or methacrylic acid mole number accounts for 5%～100% of monomer total amount; Initiator is a kind of in azo-bis-isobutyl cyanide or the dibenzoyl peroxide, and the total mole number that initiator adds is monomeric 0.25%～5%; Chain-transfer agent is a fats mercaptan, and the total mole number that chain-transfer agent adds is monomeric 0.5～4%; Copolymerization temperature is 50 ℃～100 ℃;
The solvent that adopts in the polymerization is an organic solvent, for aromatic hydrocarbon based, and ester class, the mixture of one or more in alcohols and the ketone; Reaction end is determined by measuring infrared spectra, is treated 1650cm
-1And 810cm
-1Place's acrylic double bond absorption peak disappears, and reaction finishes;
With being dissolved in acetone after the oven dry of the first step product, be titrating solution with the KOH ethanolic soln, with phenolphthalein indicator, measure acid number;
Second step was on the carboxylic group of the first step reaction product, by introducing optical active group with the monomeric esterification of condensation;
The condensation monomer is a kind of in glycidyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or the Rocryl 410, according to acid number that the first step is surveyed, monomeric add-on of condensation and acid number mol ratio are 1: 1, catalyzer is Tetrabutyl amonium bromide or tetrabutylammonium chloride, and add-on is the 0.5wt%～5wt% of condensation monomer weight; Stopper is a Resorcinol, and add-on is the 0.2wt%～5wt% of condensation monomer weight; Solvent adopts organic solvent toluene, and reaction is 1-5 hour under 111 ℃～124 ℃ temperature; The lower molecular weight that obtains different number-average molecular weights has the polyacrylic ester acrylate Mn=400-4000 of carboxyl.
The present invention introduces carboxyl by vinylformic acid with different acrylate monomer copolymerization.The selection by different reactivity ratio monomeric species and the adding of chain-transfer agent realize the control to molecular weight and molecular weight distribution.By regulating the transformation efficiency that the comonomer proportioning improves the acroleic acid esterification reaction, promptly improve two key density in the oligopolymer, and then improve photocuring reaction speed.Because esterification impossible 100% transforms, so must contain carboxyl in the oligopolymer, this raising to sticking power has very great help.The theoretical foundation that can realize the low-molecular-weight oligomer preparation has following several: 1. comonomer is of a great variety, and have different reactivity ratios between the different monomers, so therefore select different monomers will obtain the oligopolymer of a series of different number-average molecular weights. can realize the control of molecular weight and distribution thereof by the proportioning of different monomers.2. the adding of chain-transfer agent can improve the molecular chain transfer constant greatly, thereby improves chain termination speed, obtains low-molecular-weight oligopolymer.
Embodiment:
Following embodiment can illustrate further characteristics of the present invention, but not limited by these examples.
Molecular weight and molecular weight distribution are recorded by the GPC that waters company produces, and weight-average molecular weight is measured by the polystyrene standard conversion and obtained.The sample concentration of GPC test is 2mg/mL, and the sample import volume is 50 μ mL, and 30 ℃ of temperature under the condition of flow velocity 1mL/min, are measured by the tetrahydrofuran (THF) dissolving.
During the cured film property detection, adopt line rod spreader will prepare resin and be coated on the tinplate sheet of 100mm * 50mm * 2mm, thickness is about 60 μ m.Under high voltage mercury lamp, shine certain hour, film-forming, cured film is tested according to GB: pencil hardness adopts GB/T6739-1996 to test; Snappiness adopts GB 1731-1979 to test; Glossiness adopts GB9754-88 to test; Sticking power adopts GB/1720-1979 paint film adhesion assay method to test.
Embodiment 1:
The first step, prolong is being housed, agitator, the adding mol ratio is 1: 1: 1 vinylformic acid (AA), methyl acrylate (MA), an ethyl propenoate (BA) in the reactor of heating unit, adding is the initiator A IBN of monomer total amount 1mol%, be the positive Dodecyl Mercaptan of chain-transfer agent [S] of monomer total amount 0.5mol%, add solvent toluene, be heated with stirring to 50 ℃ all reactants are all dissolved, reheat to 73 ℃, react after one hour, begin to measure infrared spectra, treat 1650cm
-1And 810cm
-1Place's acrylic double bond absorption peak disappears, i.e. reaction finishes.
Measure the molecular weight (Mn) and the molecular weight distribution (PDI) of product, the result is as shown in table 1.
Second step with being dissolved in acetone after the product oven dry, was a titrating solution with the KOH ethanolic soln, was indicator with phenolphthalein, measured acid number.Then according to the survey acid esters, in four-hole bottle, add and 1: 1 glycidyl methacrylate of acid number mol ratio (GMA), add the catalyzer Tetrabutyl amonium bromide that accounts for glycidyl methacrylate weight 1wt%, account for glycidyl methacrylate weight 0.2wt% hydroquinone of polymerization retarder, be warming up to 111 ℃ of reactions 1 hour, fixed time test acid number in the reaction process when acid number no longer continuation decline in half an hour, and occurs 1650cm respectively in infrared spectra
-1And 810cm
-1During the C=C at place pair of key charateristic avsorption band, reaction finishes.
Use the 1%NaOH aqueous solution, washing is washed once with the NaCl saturated aqueous solution to neutral again at twice, and dry back underpressure distillation removes desolvates and residual monomer, obtains product.Measure acid number, esterification yield calculates with the acid number before and after the reaction.Conversion rate of esterification sees Table 1.
The 3rd step, the test of cured film character.Prepared carboxylic polyacrylic ester acrylic resin and reactive thinner TMPTA are pressed in mass ratio adding in 7: 3 beaker, add 0.5wt% light trigger 1173, dispersed with stirring is even, be coated on the tinplate under the irradiation of the UV-light of 30mW, make its completely solidified film forming, and carry out the mechanical and physical performance test according to corresponding national standards.Test result sees Table 1.
Embodiment 2～example 3, with embodiment 1, just the consumption of chain-transfer agent changes, and changes 2%, 4% respectively into.
Embodiment 4:
The first step, prolong is being housed, agitator, the adding mol ratio is 1: 2 vinylformic acid (AA) and an ethyl propenoate (EA) in the reactor of heating unit, adding is the initiator A IBN of monomer total amount 0.25mol%, be the positive Dodecyl Mercaptan of chain-transfer agent [S] of monomer total amount 3.0mol%, add solvent toluene, be heated with stirring to 50 ℃ of all reactants and all dissolve, reheat to 73 ℃, react after one hour, begin to measure infrared spectra, treat 1650cm
-1And 810cm
-1Place's acrylic double bond absorption peak disappears, i.e. reaction finishes.
Measure the molecular weight (Mn) and the molecular weight distribution (PDI) of product, the result is as shown in table 1.
Second step with being dissolved in acetone after the product oven dry, was a titrating solution with the KOH ethanolic soln, was indicator with phenolphthalein, measured acid number.Then according to the survey acid esters, in four-hole bottle, add and 1: 1 Hydroxyethyl acrylate of acid number mol ratio, add the catalyzer tetrabutylammonium chloride that accounts for Hydroxyethyl acrylate weight 0.5wt%, account for the hydroquinone of polymerization retarder of Hydroxyethyl acrylate weight 5wt%, be warming up to 124 ℃ of reactions 1 hour, fixed time test acid number in the reaction process when acid number no longer continuation decline in half an hour, and occurs 1650cm respectively in infrared spectra
-1And 810cm
-1During the C=C at place pair of key charateristic avsorption band, reaction finishes.
The 3rd step is with embodiment 1.
Embodiment 5～6, and with embodiment 4, just the amount of initiator changes, and changes 1.5,5% respectively into.
Embodiment 7
The first step is being equipped with prolong, agitator, add vinylformic acid (AA) and methyl acrylate (MA) in the reactor of heating unit, wherein the vinylformic acid mole number accounts for 5% of total moles monomer, and adding is the initiator A IBN of monomer total amount 1mol%, is the positive Dodecyl Mercaptan of chain-transfer agent [S] of monomer total amount 2.5mol%, add solvent toluene, be heated with stirring to 50 ℃ of all reactants and all dissolve, reheat to 73 ℃ reacts after one hour, begin to measure infrared spectra, treat 1650cm
-1And 810cm
-1Place's acrylic double bond absorption peak disappears, i.e. reaction finishes.
Measure the molecular weight (Mn) and the molecular weight distribution (PDI) of product, the result is as shown in table 1.
Second step with being dissolved in acetone after the product oven dry, was a titrating solution with the KOH ethanolic soln, was indicator with phenolphthalein, measured acid number.Then according to the survey acid esters, in four-hole bottle, add and 1: 1 Rocryl 410 of acid number mol ratio, account for the catalyzer Tetrabutyl amonium bromide of Rocryl 410 weight 5wt%, account for the hydroquinone of polymerization retarder of Rocryl 410 weight 0.2wt%, be warming up to 111 ℃ of reactions 5 hours, fixed time test acid number in the reaction process when acid number no longer continuation decline in half an hour, and occurs 1650cm respectively in infrared spectra
-1And 810cm
-1During the C=C at place pair of key charateristic avsorption band, reaction finishes.
The 3rd step is with embodiment 1.
Embodiment 8～9, and with embodiment 7, just vinylformic acid accounts for monomeric ratio and changes, and is respectively 50%, 100%
Embodiment 10,
The first step, prolong is being housed, agitator, the adding mol ratio is 1: 1 vinylformic acid (AA) and a methyl acrylate (MA) in the reactor of heating unit, adding is the initiator B PO of monomer total amount 1mol%, be the chain-transfer agent octyl mercaptan of monomer total amount 2.0mol%, add solvent toluene, be heated with stirring to 50 ℃ of all reactants and all dissolve, reheat to 100 ℃, react after one hour, begin to measure infrared spectra, treat 1650cm
-1And 810cm
-1Place's acrylic double bond absorption peak disappears, i.e. reaction finishes.
Measure the molecular weight (Mn) and the molecular weight distribution (PDI) of product, the result is as shown in table 1.
Second step with being dissolved in acetone after the product oven dry, was a titrating solution with the KOH ethanolic soln, was indicator with phenolphthalein, measured acid number.Then according to the survey acid esters, add and 1: 1 hydroxyethyl methylacrylate of acid number mol ratio, account for the catalyzer Tetrabutyl amonium bromide of hydroxyethyl methylacrylate weight 1wt%, account for the hydroquinone of polymerization retarder of hydroxyethyl methylacrylate weight 0.2wt%, be warming up to 111 ℃ of reactions 3 hours, fixed time test acid number in the reaction process when acid number no longer continuation decline in half an hour, and occurs 1650cm respectively in infrared spectra
-1And 810cm
-1During the C=C at place pair of key charateristic avsorption band, reaction finishes.
The 3rd step is with embodiment 1.
Embodiment 11,
The first step, prolong is being housed, agitator, the adding mol ratio is 1: 1 methacrylic acid (MAA) and a methyl methacrylate (MMA) in the reactor of heating unit, adding is the initiator B PO of monomer total amount 1mol%, be the chain-transfer agent octyl mercaptan of monomer total amount 2.0mol%, add solvent toluene, be heated with stirring to 50 ℃ of all reactants and all dissolve, reheat to 100 ℃, react after one hour, begin to measure infrared spectra, treat 1650cm
-1And 810cm
-1Place's acrylic double bond absorption peak disappears, i.e. reaction finishes.
Measure the molecular weight (Mn) and the molecular weight distribution (PDI) of product, the result is as shown in table 1.
Second step with being dissolved in acetone after the product oven dry, was a titrating solution with the KOH ethanolic soln, was indicator with phenolphthalein, measured acid number.Then according to the survey acid esters, add and 1: 1 Propylene glycol monoacrylate of acid number mol ratio, add the catalyzer Tetrabutyl amonium bromide that accounts for Propylene glycol monoacrylate 1wt%, account for the hydroquinone of polymerization retarder of Propylene glycol monoacrylate 0.2wt%, be warming up to 124 ℃ of reactions 1 hour, fixed time test acid number in the reaction process when acid number no longer continuation decline in half an hour, and occurs 1650cm respectively in infrared spectra
-1And 810cm
-1During the C=C at place pair of key charateristic avsorption band, reaction finishes.
The 3rd step is with embodiment 1.
Table 1 polymerization formula and polymer property
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| AA | 1 | 1 | 1 | 1 | 1 | 1 |
| MA | 1 | 1 | 1 | - | - | - |
| EA | 1 | 1 | 1 | 2 | 2 | 2 |
| Initiator | 1％ | 1％ | 1％ | 0.25％ | 1.5％ | 5％ |
| Chain-transfer agent | 0.5％ | 2％ | 4％ | 3.0％ | 3.0％ | 3.0％ |
| Mn | 1434 | 1321 | 1139 | 1323 | 1310 | 1159 |
| PDI | 2.31 | 2.10 | 1.94 | 1.83 | 1.75 | 1.76 |
| Esterification yield | 78％ | 82％ | 83％ | 77％ | 78％ | 80％ |
| Hardness | 2H | 2H | 2H | 2B | 2B | 2B |
| Glossiness | 58Gs | 58Gs | 62Gs | 61Gs | 62Gs | 63Gs |
| Snappiness | 4 grades | 5 grades | 5 grades | 6 grades | 6 grades | 6 grades |
| Sticking power | 85％ | 83％ | 80％ | 85％ | 89％ | 80％ |
Continuous table 1
Claims (1)
1. lower molecular weight has the preparation method of the polyacrylic ester acrylate of carboxyl, it is characterized in that step is as follows:
The first step causes comonomer by radical initiator and obtains acrylate copolymer by solution polymerization;
Comonomer is a kind of of (methyl) alkyl acrylate monomer and acrylic or methacrylic acid, and acrylic or methacrylic acid mole number accounts for 5%～100% of monomer total amount; Initiator is a kind of in azo-bis-isobutyl cyanide or the dibenzoyl peroxide, and the total mole number that initiator adds is monomeric 0.25%～5%; Chain-transfer agent is a fats mercaptan, and the total mole number that chain-transfer agent adds is monomeric 0.5～4%; Copolymerization temperature is 50 ℃～100 ℃;
The solvent that adopts in the polymerization is an organic solvent, for aromatic hydrocarbon based, and ester class, the mixture of one or more in alcohols and the ketone; Reaction end is determined by measuring infrared spectra, is treated 1650cm
-1And 810cm
-1Place's acrylic double bond absorption peak disappears, and reaction finishes;
With being dissolved in acetone after the oven dry of the first step product, be titrating solution with the KOH ethanolic soln, with phenolphthalein indicator, measure acid number;
Second step was on the carboxylic group of the first step reaction product, by introducing optical active group with the monomeric esterification of condensation;
The condensation monomer is a kind of in glycidyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or the Rocryl 410, according to acid number that the first step is surveyed, monomeric add-on of condensation and acid number mol ratio are 1: 1, catalyzer is Tetrabutyl amonium bromide or tetrabutylammonium chloride, and add-on is the 0.5wt%～5wt% of condensation monomer weight; Stopper is a Resorcinol, and add-on is the 0.2wt%～5wt% of condensation monomer weight; Solvent adopts organic solvent toluene, and reaction is 1-5 hour under 111 ℃～124 ℃ temperature; The lower molecular weight that obtains different number-average molecular weights has the polyacrylic ester acrylate Mn=400-4000 of carboxyl.
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| CN102391398A (en) * | 2011-08-31 | 2012-03-28 | 武汉理工大学 | Alkali soluble photosensitive modified polyacrylic acid prepolymer and preparation method thereof |
| CN106589335A (en) * | 2016-12-23 | 2017-04-26 | 宁波慧谷特种纤维科技有限公司 | Aromatic polyester photosensitive coating composition and aromatic polyester protective coating prepared by aromatic polyester photosensitive coating composition |
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| CN102286300A (en) * | 2011-08-30 | 2011-12-21 | 山西华顿实业有限公司 | Metal corrosion inhibitor and preparation method thereof |
| CN102286300B (en) * | 2011-08-30 | 2013-10-23 | 山西华顿实业有限公司 | Metal corrosion inhibitor and preparation method thereof |
| CN102391398A (en) * | 2011-08-31 | 2012-03-28 | 武汉理工大学 | Alkali soluble photosensitive modified polyacrylic acid prepolymer and preparation method thereof |
| CN102391398B (en) * | 2011-08-31 | 2013-07-17 | 武汉理工大学 | Alkali soluble photosensitive modified polyacrylic acid prepolymer and preparation method thereof |
| CN106749864A (en) * | 2016-11-24 | 2017-05-31 | 华南理工大学 | A kind of water polyacrylic acid resin of UV solidifications and preparation method and application |
| CN106589335A (en) * | 2016-12-23 | 2017-04-26 | 宁波慧谷特种纤维科技有限公司 | Aromatic polyester photosensitive coating composition and aromatic polyester protective coating prepared by aromatic polyester photosensitive coating composition |
| CN106589335B (en) * | 2016-12-23 | 2019-05-31 | 宁波海格拉新材料科技有限公司 | A kind of polyarylate Photoactivatable coating composition and polyarylate protective coating prepared therefrom |
| CN109517183A (en) * | 2018-11-23 | 2019-03-26 | 湖南师范大学 | Heterozygous epoxy acrylate modified side chain polyacrylic resin and synthetic method |
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| CN113736034A (en) * | 2021-08-25 | 2021-12-03 | 武汉三源特种建材有限责任公司 | Nanometer type super-long slump retaining polycarboxylate superplasticizer and preparation method thereof |
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