CN104387525A - Imidazole modified copolymer as well as preparation method and application thereof - Google Patents
Imidazole modified copolymer as well as preparation method and application thereof Download PDFInfo
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- CN104387525A CN104387525A CN201410735755.6A CN201410735755A CN104387525A CN 104387525 A CN104387525 A CN 104387525A CN 201410735755 A CN201410735755 A CN 201410735755A CN 104387525 A CN104387525 A CN 104387525A
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Abstract
The invention provides an imidazole modified copolymer. The copolymer comprises polymerization units (A), (B) and (C) shown in the specification, wherein the quantities of the polymerization units (A), (B) and (C) in the copolymer are respectively x, y and z; x, y and z are respectively an integer from 100 to 1000; in the polymerization units (A), (B) and (C), groups R, R2, R4, R5 and R6 are respectively selected from hydrogen, C1-C20 alkyl and C6-C26 aryl independently; R1 is hydrogen or C1-C3 alkyl; R3 is C4-C10 alkyl. The invention also relates to a preparation method of the imidazole modified copolymer and a matting and curing agent which comprises the copolymer and is used for epoxy resin paints.
Description
Technical field
The present invention relates to paint additive field, more particularly, the present invention relates to can as the polymkeric substance of the solidifying agent of epoxypaint, and the preparation method and application of this polymkeric substance.
Background technology
Epoxy resin has good cohesiveness, erosion resistance, electrical property and mechanical property, is widely used in the fields such as sizing agent, matrix material, coating.As the epoxy resin average functionality of powder coating between 4 ~ 9.In the application of epoxy resin, solidifying agent occupies requisite critical role, and the solidifying agent for epoxy resin has amine, anhydrides, hydrazides class etc., and wherein imidazole and its derivants accounts for its important branch.
Conventional imidazoles epoxy curing agent has glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole etc.Compared with general epoxy curing agent, it is few that imidazole curing agent has consumption, and curing speed is fast, and cured article heat-drawn wire is high, the advantages such as good mechanical performance.But due to the high reactivity of imidazoles, therefore short with epoxy cure time, can bring adverse influence to the levelling property of powder coating, mixed working life is shorter, use the epoxy resin of this type of solidifying agent can not store as the single-component system long period.
In order to overcome the above-mentioned shortcoming of conventional imidazole curing agent with not enough, people urgently wish to carry out modification to imidazole and its derivants, synthesize new modified compound, thus extend set time while the advantage keeping pyrazoles solidifying agent.But, not yet report in prior art by the polymkeric substance of high molecular being connected with imidazoles thus obtaining the way of the imidazole curing agent of modification.
Summary of the invention
For above problem, the present invention is by being connected the 1-position of imidazoles with polymkeric substance long-chain, and provide novel solidifying agent, this solidifying agent maintains the advantage of conventional imidazole curing agent, overcome imidazole curing agent high reactivity, working life short shortcoming simultaneously, also there is excellent photoextinction.
According to a first aspect of the invention, provide a kind of imidazole modified multipolymer, this multipolymer comprises following polymerized unit A, B and C:
The polymerized unit (A) comprised in this multipolymer, the quantity of (B) and (C) are respectively x, y and z, and described x, y and z are respectively the integer of 20-8000; Preferred x, y and z are respectively the integer of 50-6000; More preferably x, y and z are respectively the integer of 100-1000;
In described polymerized unit (A), (B) and (C), radicals R, R
2, R
4, R
5and R
6separately be selected from hydrogen, C
1-C
20alkyl and C
6-C
26aryl; Preferred R, R
2, R
4, R
5and R
6separately be selected from hydrogen, C
1-C
15alkyl and C
6-C
20aryl; More preferably R, R
2, R
4, R
5and R
6separately be selected from hydrogen, C
1-C
8alkyl and C
6-C
12aryl;
R
1represent hydrogen or C
1-C
3alkyl;
R
3represent C
4-C
10alkyl.
According to an embodiment of the invention, the ratio of integer x, y and z is 0.3-25:1:0.5-30.
According to another implementation of the invention, described multipolymer is random copolymers, segmented copolymer, graft copolymer or alternating copolymer.
Second aspect of the present invention provides a kind of method being used for preparing imidazole modified multipolymer of the present invention, and the method comprises the following steps:
I () is under the condition that there is emulsifying agent and initiator, at the temperature of 50-100 DEG C, that make to replace or unsubstituted vinylformic acid or acrylate monomer A ', replace or unsubstituted acrylate monomer B ' and replace or unsubstituted glycidyl acrylate C ' there is emulsion polymerization, generate multipolymer intermediate;
(ii) drip the aqueous solution of substituted or unsubstituted imidazoles in the multipolymer intermediate then generated to step (i) at the temperature of 40-90 DEG C, modification is carried out to described multipolymer intermediate, forms described imidazole modified multipolymer;
Wherein, described replacement or unsubstituted vinylformic acid or acrylate monomer A ' form polymerized unit A after polymerization; Described replacement or unsubstituted acrylate monomer B ' forms polymerized unit B after polymerization; Described replacement or unsubstituted glycidyl acrylate C ' forms described polymerized unit C after polyreaction and modification.
According to an embodiment of the invention, described replacement or unsubstituted vinylformic acid or acrylate monomer A ' are selected from: two or more combination any of vinylformic acid, methyl acrylate, ethyl propenoate, propyl acrylate, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate and above-mentioned monomer;
Described replacement or unsubstituted acrylate monomer B ' is selected from: n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, the just own ester of vinylformic acid, isobornyl acrylate, n-BMA, the secondary butyl ester of methacrylic acid, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, Isooctyl methacrylate, the just own ester of methacrylic acid, two or more combination any of isobornyl methacrylate and above-mentioned monomer,
Described replacement or unsubstituted glycidyl acrylate C ' is selected from: the combination of glycidyl acrylate, glycidyl methacrylate and above-mentioned monomer.
According to another implementation of the invention, in described step (i), the ratio of select described monomer A according to the relative quantity of polymerized unit (A), (B) and (C) in described multipolymer ', monomers B ' and glycidyl acrylate C ', described emulsion polymerization continues to carry out 3-7 hour.
According to another implementation of the invention, in described step (i), the initiator used is selected from the mixing of any one or they in Diisopropyl azodicarboxylate, Potassium Persulphate, benzoyl peroxide, in the gross weight of used polymerization single polymerization monomer for benchmark, the consumption of described initiator is 0.1-0.5 % by weight.
According to another implementation of the invention, in described step (i), the emulsifying agent used is selected from the mixing of any one or they in sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium soap, sodium alkylarysulfonate, alkylphenol-polyethenoxy base ether, in the gross weight of used polymerization single polymerization monomer for benchmark, the consumption of described emulsifying agent is 1-6 % by weight.
According to another implementation of the invention, in described step (ii), described substituted or unsubstituted imidazoles is selected from the mixture of any one or they in glyoxal ethyline, 2-ethyl-4-methylimidazole and 2-phenylimidazole;
In described step (ii), described replacement or unsubstituted glycidyl acrylate C ' is 0.5-1.5 with the mol ratio of described substituted or unsubstituted imidazoles;
Described step (ii) continues to carry out 3-7 hour.
According to another implementation of the invention, after the reaction of step (ii) terminates, in reaction system, add acid, make the pH value of reaction system be 3-4, filtered and recycled product, and carry out drying treatment;
Described acid is selected from hydrochloric acid, sulfuric acid, nitric acid, the mixture of any one or they in acetic acid.
3rd aspect of the present invention relates to a kind of solidifying agent for epoxypaint, and described solidifying agent comprises imidazole modified multipolymer of the present invention.
Embodiment
" scope " disclosed herein is with the form of lower limit and the upper limit.One or more lower limit can be respectively, and one or more upper limit.Given range is limited by a selected lower limit and a upper limit.Selected lower limit and the upper limit define the border of special scope.All scopes that can carry out by this way limiting comprise and may be combined with, and namely any lower limit can be combined to form a scope with any upper limit.Such as, list the scope of 60-120 and 80-110 for special parameter, be interpreted as that the scope of 60-110 and 80-120 also expects.In addition, if the minimum extent value listed 1 and 2, and if list maximum range value 3,4 and 5, then the scope below can all expect: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, the breviary of any real combinings that numerical range " a-b " represents between a to b represents, wherein a and b is real number.Such as numerical range " 0-5 " represents the whole real numbers all listed between " 0-5 " herein, and the breviary of " 0-5 " just these combinations of values represents.
If do not particularly not pointed out, this specification sheets term " two kinds " used refers to " at least two kinds ".
In the present invention, if do not illustrated especially, all embodiments mentioned in this article and preferred implementation can be combined to form new technical scheme mutually.
In the present invention, if do not illustrated especially, all technical characteristics mentioned in this article and preferred feature can be combined to form new technical scheme mutually.
In the present invention, if do not illustrated especially, mentioned in this article sequentially can to carry out in steps, also can carry out at random, but preferably order is carried out.Such as, described method comprises step (a) and (b), represents that described method can comprise the step (a) and (b) of sequentially carrying out, also can comprise the step (b) and (a) of sequentially carrying out.Such as, describedly mention described method and also can comprise step (c), represent that step (c) random order can join described method, such as, described method can comprise step (a), (b) and (c), also step (a), (c) and (b) be can comprise, step (c), (a) and (b) etc. also can be comprised.
In the present invention, if do not illustrated especially, " comprising " mentioned in this article represents open, also can be closed.Such as, described " comprising " can represent other components that can also comprise and not list, and also can only comprise the component listed.
In multipolymer of the present invention, hydrogen atom and the glycidyl ether radical reaction that copolymer chain is connected of imidazoles 1-position, thus imidazolyl is connected with multipolymer.In this multipolymer, except the substituted or unsubstituted glycidyl acrylate polymerized unit C of described connection imidazolyl, also comprise polymerized unit A and B of two kinds of substituted or unsubstituted acrylate.
For above-mentioned polymerized unit, wherein radicals R, R
2and R
4can be hydrogen atom, C
1-C
20alkyl or C
6-C
26aryl; Preferred R, R
2and R
4can be hydrogen, C
1-C
15alkyl or C
6-C
20aryl; More preferably R, R
2and R
4can be hydrogen, C
1-C
8alkyl or C
6-C
12aryl; Most preferably R, R
2and R
4can be hydrogen, methyl or phenyl.R
1can be hydrogen or C
1-C
3alkyl, therefore polymerized unit A is by substituted or unsubstituted vinylformic acid or vinylformic acid C
1-C
3alkyl ester monomer A ' is formed.Of the present invention one preferred embodiment in, described monomer A ' two or more combination any of preferably vinylformic acid, methyl acrylate, ethyl propenoate, propyl acrylate, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate and above-mentioned monomer, but, also can use other substituted or unsubstituted vinylformic acid C
1-C
3alkyl ester monomer.
R
3represent C
4-C
10alkyl, therefore polymerized unit B is by substituted or unsubstituted vinylformic acid C
4-C
10alkyl ester monomer B ' is formed.Of the present invention one preferred embodiment in, described monomers B ' be preferably n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, the just own ester of vinylformic acid, isobornyl acrylate, n-BMA, the secondary butyl ester of methacrylic acid, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, Isooctyl methacrylate, the just own ester of methacrylic acid, two or more combination any of isobornyl methacrylate and above-mentioned monomer, but, also other substituted or unsubstituted vinylformic acid C can be used
4-C
10alkyl ester monomer.
Polymerized unit C is reacted by the hydrogen of glycidyl acrylate residue substituted or unsubstituted in multipolymer and pyridine 1-position and is formed.The glycidyl acrylate that the present invention can adopt preferably can be selected from the combination of glycidyl acrylate, glycidyl methacrylate and above-mentioned monomer.May be used for the mixture that pyridine of the present invention preferably includes any one or they in glyoxal ethyline, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
Multipolymer of the present invention can be random copolymers, segmented copolymer, graft copolymer or alternating copolymer, in other words, in described polymerized unit A, B, C any one or multiplely can to arrange with the form of stochastic distribution or ordered distribution in main polymer chain and the side chain that may exist.Of the present invention one preferred embodiment in, multipolymer of the present invention is random copolymers.Of the present invention another preferred embodiment in, multipolymer of the present invention is segmented copolymer, graft copolymer or alternating copolymer.The synthesis mode of described various different copolymer thing is well-known in the art, can by selecting the kind of various raw material, add opportunity and processing condition have been come.
In multipolymer of the present invention, the number of polymerized unit A, B, C of comprising in each polymerization long-chain is respectively x, y and z, and these parameters determine the polymerization degree of this multipolymer.In an embodiment of the invention, described x, y and z are respectively the integer of 20-8000, are preferably the integer of 50-6000, are more preferably the integer of 80-3000, most preferably are the integer of 100-1000.Of the present invention one preferred embodiment in, the ratio of x, y and z is x:y:z=0.3-25:1:0.5-30.Of the present invention one preferred embodiment in, the ratio of x, y and z is x:y:z=0.4-20:1:0.6-15; More preferably x:y:z=0.5-10:1:0.64-15; More preferably x:y:z=0.6-5:1:0.64-10.
Present invention also offers the method preparing above-mentioned multipolymer, the method comprises following two steps:
I (), under the condition that there is emulsifying agent and initiator, makes described acrylate monomer A ', B ' and glycidyl acrylate monomer C ' react the multipolymer intermediate being formed and comprise acrylic ester polymerization unit A, B and glycidyl acrylate polymerized unit;
(ii) in described reaction system, add imidazoles further, the glycidyl acrylate polymerized unit that comprises and imidazoles are reacted, form imidazole modified multipolymer of the present invention in described multipolymer intermediate.
Above-mentioned steps (i) is preferably carried out at the temperature of 50-100 DEG C and condition of normal pressure.The mol ratio of the polymerization single polymerization monomer added will determine the relative proportion of various polymerized unit in product, preferably, in step (i), the ratio of acrylate monomer A ', B ' and the glycidyl acrylate monomer C ' added is selected according to the relative quantity of polymerized unit (A), (B) and (C) in described multipolymer.In one preferred embodiment, the reaction in above-mentioned steps (i) continues to carry out 3-7 hour, and described duration of the reaction comprises the time added needed for raw material and the time kept after raw material adds.
The initiator used in step (i) can be any initiator being suitable for acrylic double bond polyreaction, the various initiators that such as Raolical polymerizable is conventional.In a preferred embodiment of the present invention, described initiator is selected from the mixing that used initiator is selected from any one or they in Diisopropyl azodicarboxylate, Potassium Persulphate, benzoyl peroxide, in the gross weight of used polymerization single polymerization monomer for benchmark, the consumption of described initiator is 0.1-0.5 % by weight.Of the present invention another preferred embodiment in, the emulsifying agent used is selected from the mixing of any one or they in sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium soap, sodium alkylarysulfonate, alkylphenol-polyethenoxy base ether, in the gross weight of used polymerization single polymerization monomer for benchmark, the consumption of described emulsifying agent is 1-6 % by weight.
Above-mentioned steps (ii) DEG C carries out 3-7 hour preferably at 40-90, and described duration of the reaction comprises the time added needed for imidazoles and the time kept after imidazoles adds.In this step, the glycidyl acrylate residue comprised in multipolymer intermediate is 0.5:1.5 with the mol ratio adding the imidazoles in reaction system, is preferably 0.8:1.2, is more preferably 0.9:1.1, is more preferably 0.95:1.05, most preferably be 1:1.Be appreciated that, when glycidyl acrylate residue is less than 1 with the mol ratio of the imidazoles added in reaction system time, in the multipolymer that reaction is obtained except comprising described polymerized unit A, B and C, also comprise glycidyl acrylate residue, the content of this residue depends on the ratio of used raw material and concrete reaction conditions.In a most preferred embodiment, the relation of the stoichiometric ratios such as the glycidyl acrylate residue comprised in multipolymer intermediate and the imidazoles added in reaction system are, is converted into polymerized unit C to make substantially all glycidyl acrylate residues all react with imidazoles.
In an embodiment of the invention, described imidazole modified multipolymer is made up of polymerized unit A, B and C, and does not comprise any other polymerized unit.In yet another embodiment of the present invention, described imidazole modified multipolymer is except comprising polymerized unit A, B and C, compatible other polymerized unit any with these three kinds of polymerized units can also be comprised, other polymerized unit described can be the glycidyl acrylate residue do not reacted with imidazoles, or formed by the following monomer added in reaction system, such as C
2-C
22alkene, such as ethene, propylene, butylene, amylene, hexene, heptene, nonene, decene, hendecene, myrcene, cetylene, vaccenic acid, eicosylene, two dodecylenes, divinyl, pentadiene, hexadiene, cyclopropylene, cyclobutene, cyclopentenes, tetrahydrobenzene, cyclopentadiene etc.; Acrylamide, Methacrylamide; Vinyl cyanide, methacrylonitrile; Alkynes; And the mixture of one or more monomers above-mentioned.Of the present invention one preferred embodiment in, to be used for the gross weight of all monomers forming described multipolymer for benchmark, the total amount of described other polymerized unit except polymerized unit A, B and C is less than 30 % by weight, preferably be less than 20 % by weight, be more preferably less than 10 % by weight, be more preferably less than 5 % by weight, be more preferably less than 2 % by weight, be more preferably less than 1 % by weight, be more preferably less than 0.5 % by weight, be more preferably less than 0.1 % by weight.
After the reaction of step (ii) terminates, in reaction system, add acid, the pH value of reaction system is adjusted to the scope of 3-4, filtered and recycled product, then drying treatment is carried out to product.The described acid being used for adjust ph can be the conventional any inorganic acid in this area or organic acid, as long as can not bring negative impact to reaction product, such as, can use hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, propionic acid etc.
Imidazole modified multipolymer of the present invention can be used as the solidifying agent of epoxypaint.In the gross weight of described epoxypaint for benchmark, content as the described imidazole modified multipolymer of solidifying agent can be 2-15 % by weight, preferred 8-12 % by weight, but those skilled in the art also can regulate the consumption of this solidifying agent as required.The component needed for other can be comprised in described epoxypaint, such as flow agent, bubble remover, sterilizing agent, mycocide, mould inhibitor, pigment, uv-absorbing agent, stablizer etc., those skilled in the art can select kind and the content of these components as required.
Next specifically describe the preferred embodiment of the present invention, but protection scope of the present invention is only defined by the claims, and is not limited in following embodiment in conjunction with the embodiments.
Embodiment
Below in an example, the E-12 epoxy resin using Anhui Meijia New Material Co., Ltd. to produce; 588 flow agents of the South Sea, Ningbo chemical production; The defoamer st-yrax of the South Sea, Ningbo chemical production; The NR760 titanium dioxide of the South Sea, Ningbo chemical production; The extinction barium that Qingdao east wind Chemical Co., Ltd. produces; The filler 44-HB that Guizhou Hua Jia company produces; The commodity that Jilin Petrochemical Company produces are called the alkylphenol polyoxyethylene of NP-10; Other synthesis material is analytical pure product, without process directly use further; The water used is deionized water.
Coating gloss is measured according to GB9754-1998; Coating shock strength is measured according to GB1732-93; Gel time is measured according to GB16995-1997.
Preparation example 1:
In this embodiment, use methyl methacrylate as monomer A ', use n-butyl acrylate as monomers B ', use glycidyl methacrylate as monomer C ', with A ': B ': the mol ratio synthetic copolymer intermediate of C '=3.9:1:6.2, its concrete reactions steps is as follows.
In the three neck round-bottomed flasks that mechanical stirrer, thermometer, reflux condensing tube, two opening connectors and constant pressure funnel are housed, add 65 grams of methyl methacrylates, 5 grams of butyl acrylates, 30 grams of glycidyl acrylates, 7 grams of mixed emulsifiers (stearic acid sodium salt: alkylphenol polyoxyethylene=7:3) and 100.0 grams of water, at room temperature stir 20 minutes, then formed emulsion is poured out 160.0 grams.Use water bath heating device that remaining emulsion is heated to 80 DEG C, then start in this reaction system, drip 2.0 grams of Diisopropyl azodicarboxylates and be dissolved in the solution of 50.0 grams of water formation and the above-mentioned emulsion poured out.This dropping process lasts 3 hours, Keep agitation in dropping process, remains on 80 DEG C by the temperature in flask.After dropwising, continue stirring 2 hours at 80 DEG C.
Preparation example 2
In this embodiment, use ethyl propenoate as monomer A ', use isobornyl methacrylate as monomers B ', use glycidyl acrylate as monomer C ', with A ': B ': the mol ratio synthetic copolymer intermediate of C '=0.89:1:1.04, its concrete reactions steps is as follows.
In the three neck round-bottomed flasks that mechanical stirrer, thermometer, reflux condensing tube, two opening connectors and constant pressure funnel are housed, add 20 grams of ethyl propenoates, 50 grams of isobornyl methacrylates, 30 grams of glycidyl methacrylate, 7 grams of mixed emulsifiers (stearic acid sodium salt: alkylphenol polyoxyethylene=7:3) and 200.0 grams of water, at room temperature stir 20 minutes, then formed emulsion is poured out 140.0 grams.Use water bath heating device that remaining emulsion is heated to 80 DEG C, then start in this reaction system, drip 1.0 grams of Diisopropyl azodicarboxylates and be dissolved in the solution of 50.0 grams of water formation and the above-mentioned emulsion poured out.This dropping process lasts 3 hours, Keep agitation in dropping process, remains on 80 DEG C by the temperature in flask.After dropwising, continue stirring 2 hours at 80 DEG C.
Preparation example 3
In this embodiment, use propyl acrylate as monomer A ', use Isooctyl acrylate monomer as monomers B ', use glycidyl methacrylate as monomer C ', with A ': B ': the mol ratio synthetic copolymer intermediate of C '=0.75:1:0.8, its concrete reactions steps is as follows.
In the three neck round-bottomed flasks that mechanical stirrer, thermometer, reflux condensing tube, two opening connectors and constant pressure funnel are housed, add 20 grams of β-dimethyl-aminoethylmethacrylates, 50 grams of Isooctyl acrylate monomers, 30 grams of glycidyl methacrylate, 7 grams of mixed emulsifiers (stearic acid sodium salt: alkylphenol polyoxyethylene=7:3) and 200.0 grams of water, at room temperature stir 20 minutes, then formed emulsion is poured out 340.0 grams.Use water bath heating device that remaining emulsion is heated to 80 DEG C, then start in this reaction system, drip 0.9 gram of Potassium Persulphate and be dissolved in the solution of 50.0 grams of water formation and the above-mentioned emulsion poured out.This dropping process lasts 3 hours, Keep agitation in dropping process, remains on 80 DEG C by the temperature in flask.After dropwising, continue stirring 2 hours at 80 DEG C.
Preparation example 4
In this embodiment, use methyl acrylate as monomer A ', use cyclohexyl acrylate as monomers B ', use glycidyl methacrylate as monomer C ', with A ': B ': the mol ratio synthetic copolymer intermediate of C '=0.6:1:0.64, its concrete reactions steps is as follows.
In the three neck round-bottomed flasks that mechanical stirrer, thermometer, reflux condensing tube, two opening connectors and constant pressure funnel are housed, add 16 grams of methyl acrylates, 54 grams of cyclohexyl acrylates, 30 grams of glycidyl methacrylate, 7 grams of mixed emulsifiers (stearic acid sodium salt: alkylphenol polyoxyethylene=7:3) and 200.0 grams of water, at room temperature stir 20 minutes, then formed emulsion is poured out 340.0 grams.Use water bath heating device that remaining emulsion is heated to 80 DEG C, then start in this reaction system, drip 1 gram of benzoyl peroxide and be dissolved in the solution of 50.0 grams of water formation and the above-mentioned emulsion poured out.This dropping process lasts 3 hours, Keep agitation in dropping process, remains on 80 DEG C by the temperature in flask.After dropwising, continue stirring 2 hours at 80 DEG C.
Embodiment 1
26.0 grams of glyoxal ethylines are dissolved in 200.0 grams of water, the reaction system of preparation example 1 are being heated to 75 ~ 85 DEG C, under agitation, within the time of 2 hours, the described imidazoles aqueous solution is added drop-wise to wherein, after dropwising, the temperature of reaction system is remained on 75-85 DEG C, stir 2 hours.After reaction terminates, the pH value adding the near system of hydrochloric acid of 1M is adjusted to 3 ~ 4, stirs half an hour, leaves standstill half an hour, solid collected by filtration product, and Air drying removing moisture, obtains white powder product.According to GB/T6040-2002, infrared spectra detection is carried out, at 674cm to this Product samples
-1and 682cm
-1place observes absorption peak; According to JY/T007/1996, superconducting pulse Fourier transform nuclear magnetic resonance detection is carried out to this Product samples in addition, observe the characteristic signal of imidazole ring, prove that glyoxal ethyline is connected on main polymer chain by above-mentioned sign, define the multipolymer of glyoxal ethyline modification.Be 89322 according to the number-average molecular weight that BG/T21864-2008 records this product by size exclusion chromatography.
Embodiment 2
31.2 grams of glyoxal ethylines are dissolved in 200.0 grams of water, the reaction system of preparation example 1 are being heated to 75 ~ 85 DEG C, under agitation, within the time of 2 hours, the described imidazoles aqueous solution is added drop-wise to wherein, after dropwising, the temperature of reaction system is remained on 75-85 DEG C, stir 2 hours.After reaction terminates, the pH value adding the near system of hydrochloric acid of 1M is adjusted to 3 ~ 4, stirs half an hour, leaves standstill half an hour, solid collected by filtration product, and Air drying removing moisture, obtains white powder product.Carry out infrared and nuclear-magnetism according to the mode identical with embodiment 1 to characterize, obtain substantially identical characterization result, prove that glyoxal ethyline is connected on main polymer chain, define the multipolymer of glyoxal ethyline modification.Be 89335 according to the number-average molecular weight that BG/T21864-2008 records this product by size exclusion chromatography.
Embodiment 3
39.0 grams of glyoxal ethylines are dissolved in 200.0 grams of water, the reaction system of preparation example 1 are being heated to 75 ~ 85 DEG C, under agitation, within the time of 2 hours, the described imidazoles aqueous solution is added drop-wise to wherein, after dropwising, the temperature of reaction system is remained on 75-85 DEG C, stir 2 hours.After reaction terminates, the pH value adding the near system of hydrochloric acid of 1M is adjusted to 3 ~ 4, stirs half an hour, leaves standstill half an hour, solid collected by filtration product, and Air drying removing moisture, obtains white powder product.Carry out infrared and nuclear-magnetism according to the mode identical with embodiment 1 to characterize, obtain substantially identical characterization result, prove that glyoxal ethyline is connected on main polymer chain, define the multipolymer of glyoxal ethyline modification.Be 89314 according to the number-average molecular weight that BG/T21864-2008 records this product by size exclusion chromatography.
Embodiment 4
34.9 grams of 2-ethyl-4-methylimidazoles are dissolved in 200.0 grams of water, the reaction system of preparation example 2 is being heated to 75 ~ 85 DEG C, under agitation, within the time of 2 hours, the described imidazoles aqueous solution is added drop-wise to wherein, after dropwising, the temperature of reaction system is remained on 75-85 DEG C, stirs 2 hours.After reaction terminates, the pH value adding the near system of sulfuric acid of 1M is adjusted to 3 ~ 4, stirs half an hour, leaves standstill half an hour, solid collected by filtration product, and Air drying removing moisture, obtains white powder product.According to GB/T6040-2002, infrared spectra detection is carried out, at 706cm to this Product samples
-1, 776cm
-1, 948cm
-1, 1106cm
-1, 1504cm
-1place observes absorption peak; According to JY/T007/1996, superconducting pulse Fourier transform nuclear magnetic resonance detection is carried out to this Product samples in addition, observe the characteristic signal of imidazole ring, prove that 2-ethyl-4-methylimidazole is connected on main polymer chain by above-mentioned sign, define the multipolymer of 2-ethyl-4-methylimidazole modification.Be 93527 according to the number-average molecular weight that BG/T21864-2008 records this product by size exclusion chromatography.
Embodiment 5
41.8 grams of 2-ethyl-4-methylimidazoles are dissolved in 200.0 grams of water, the reaction system of preparation example 2 is being heated to 75 ~ 85 DEG C, under agitation, within the time of 2 hours, the described imidazoles aqueous solution is added drop-wise to wherein, after dropwising, the temperature of reaction system is remained on 75-85 DEG C, stirs 2 hours.After reaction terminates, the pH value adding the near system of sulfuric acid of 1M is adjusted to 3 ~ 4, stirs half an hour, leaves standstill half an hour, solid collected by filtration product, and Air drying removing moisture, obtains white powder product.Carry out infrared and nuclear-magnetism according to the mode identical with embodiment 4 to characterize, obtain substantially identical characterization result, prove that 2-ethyl-4-methylimidazole is connected on main polymer chain, define the multipolymer of 2-ethyl-4-methylimidazole modification.Be 93530 according to the number-average molecular weight that BG/T21864-2008 records this product by size exclusion chromatography.
Embodiment 6
52.4 grams of 2-ethyl-4-methylimidazoles are dissolved in 200.0 grams of water, the reaction system of preparation example 3 is being heated to 75 ~ 85 DEG C, under agitation, within the time of 2 hours, the described imidazoles aqueous solution is added drop-wise to wherein, after dropwising, the temperature of reaction system is remained on 75-85 DEG C, stirs 2 hours.After reaction terminates, the pH value adding the near system of sulfuric acid of 1M is adjusted to 3 ~ 4, stirs half an hour, leaves standstill half an hour, solid collected by filtration product, and Air drying removing moisture, obtains white powder product.Carry out infrared and nuclear-magnetism according to the mode identical with embodiment 4 to characterize, obtain substantially identical characterization result, prove that 2-ethyl-4-methylimidazole is connected on main polymer chain, define the multipolymer of 2-ethyl-4-methylimidazole modification.Be 93254 according to the number-average molecular weight that BG/T21864-2008 records this product by size exclusion chromatography.
Embodiment 7
45.6 grams of 2-benzene imidazoles are dissolved in 200.0 grams of water, the reaction system of preparation example 3 are being heated to 75 ~ 85 DEG C, under agitation, within the time of 2 hours, the described imidazoles aqueous solution is added drop-wise to wherein, after dropwising, the temperature of reaction system is remained on 75-85 DEG C, stir 2 hours.After reaction terminates, the pH value adding the near system of sulfuric acid of 1M is adjusted to 3 ~ 4, stirs half an hour, leaves standstill half an hour, solid collected by filtration product, and Air drying removing moisture, obtains white powder product.According to GB/T6040-2002, infrared spectra detection is carried out, at 638cm to this Product samples
-1, 1028cm
-1, 1120cm
-1, 1504cm
-1place observes absorption peak; According to JY/T007/1996, superconducting pulse Fourier transform nuclear magnetic resonance detection is carried out to this Product samples in addition, observe the characteristic signal of imidazole ring, prove that 2-benzene imidazoles is connected on main polymer chain by above-mentioned sign, define the multipolymer that 2-benzene is imidazole modified.Be 86412 according to the number-average molecular weight that BG/T21864-2008 records this product by size exclusion chromatography.
Embodiment 8
54.8 grams of 2-benzene imidazoles are dissolved in 200.0 grams of water, the reaction system of preparation example 4 are being heated to 75 ~ 85 DEG C, under agitation, within the time of 2 hours, the described imidazoles aqueous solution is added drop-wise to wherein, after dropwising, the temperature of reaction system is remained on 75-85 DEG C, stir 2 hours.After reaction terminates, the pH value adding the near system of sulfuric acid of 1M is adjusted to 3 ~ 4, stirs half an hour, leaves standstill half an hour, solid collected by filtration product, and Air drying removing moisture, obtains pale yellow powder shape product.Carry out infrared and nuclear-magnetism according to the mode identical with embodiment 7 to characterize, obtain substantially identical characterization result, prove that 2-benzene imidazoles is connected on main polymer chain, define the multipolymer that 2-benzene is imidazole modified.Be 86488 according to the number-average molecular weight that BG/T21864-2008 records this product by size exclusion chromatography.
Embodiment 9
68.4 grams of 2-benzene imidazoles are dissolved in 200.0 grams of water, the reaction system of preparation example 4 are being heated to 75 ~ 85 DEG C, under agitation, within the time of 2 hours, the described imidazoles aqueous solution is added drop-wise to wherein, after dropwising, the temperature of reaction system is remained on 75-85 DEG C, stir 2 hours.After reaction terminates, the pH value adding the near system of nitric acid of 1M is adjusted to 3 ~ 4, stirs half an hour, leaves standstill half an hour, solid collected by filtration product, and Air drying removing moisture, obtains pale yellow powder shape product.Carry out infrared and nuclear-magnetism according to the mode identical with embodiment 7 to characterize, obtain substantially identical characterization result, prove that 2-benzene imidazoles is connected on main polymer chain, define the multipolymer that 2-benzene is imidazole modified.Be 86892 according to the number-average molecular weight that BG/T21864-2008 records this product by size exclusion chromatography.
Embodiment 10: coating property detects
In this embodiment, use the imidazole modified copolymer products of above embodiment 1-9 as solidifying agent, the epoxy resin (E-12) bought with business and other paint additive mix according to the consumption shown in following table 1, form epoxy powder coating.In table 1 below, E-12 is epoxy resin, and 288 is flow agents, and B is defoamer st-yrax, and NR760 is titanium dioxide, and 44-HB is filler.In addition; also use the glyoxal ethyline (writing 2MI in table) of 2 grams, the 2-phenylimidazole (being denoted as 2PI in table) of 2 grams and epoxy resin modification imidazoles (purchased from the GHM072 of the South Sea, Ningbo chemical company respectively; be denoted as GHM in table) as solidifying agent to prepare powder coating; it is as comparative example, lists composition and the performance of this comparative example in table 1 equally.
Specifically, the present invention uses the equipment shown in following table 2 to carry out coating preparation, coating formation and detection operation.
First, use electronic scales, according to the various components taken for preparing coating shown in following table 1, mixing in PVE plastics bag, then extruding in an extruder, forcing machine optimum configurations is as follows, wherein the temperature in the firstth district is 95 DEG C, and the temperature in the secondth district is 105 DEG C, and the temperature in the 3rd district is 60 DEG C, feed worm rotating speed is 350 revs/min, and extrusion screw rod rotating speed is 350 revs/min.Fetching portion extrude after material, put into electric crusher to pulverize, macrobead is screened out with 180 eye mesh screens after pulverizing, remaining powder uses electric spray gun by coating compound electrostatic spraying on aluminium plywood or iron plate, form the coated membrane (measuring with thickness gauge after baking) that thickness is 75 microns, the operating voltage of described electric spray gun is 0.5kV, and electric current is 60 microamperes, and air pressure is 3 kilograms.Then the sheet material with coated membrane is transferred in baking oven, toast 10 minutes at the temperature of 180 DEG C, form the cated test sheet material of tool.Use the glossiness of coating on glossometer, Coating impact instrument and gel instrument sheet material measurement, gelling property and impact resistance, evaluated the yellowness factor of coating by visual inspection, result gathers lists in table 1.
Coating composition (unit be gram) of table 1: embodiment of the present invention 1-9 and comparative example and performance
As can be seen from the experimental result that upper table 1 is listed, solidifying agent of the present invention effectively reduces the activity of imidazoles, achieves longer gel time, and has splendid eliminate optical property.
In addition, production technique of the present invention is extremely simple, as long as namely two steps can synthesize target product, is solvent in experimentation with water, harmful material is not had to produce, experimental temperature is no more than 100 DEG C, and reaction conditions is gentle, to pressure not requirement, raw material is all regular industrial raw material, easy acquisition, its production cost is lower, to equipment without particular requirement.
Table 2: coating preparation and measurement operate equipment used and correlation parameter
Claims (11)
1. an imidazole modified multipolymer, this multipolymer comprises following polymerized unit (A), (B) and (C):
The polymerized unit (A) comprised in this multipolymer, the quantity of (B) and (C) are respectively x, y and z, and described x, y and z are respectively the integer of 20-8000; Preferred x, y and z are respectively the integer of 50-6000; More preferably x, y and z are respectively the integer of 100-1000;
In described polymerized unit (A), (B) and (C), radicals R, R
2, R
4, R
5and R
6separately be selected from hydrogen, C
1-C
20alkyl and C
6-C
26aryl; Preferred R, R
2, R
4, R
5and R
6separately be selected from hydrogen, C
1-C
15alkyl and C
6-C
20aryl; More preferably R, R
2, R
4, R
5and R
6separately be selected from hydrogen, C
1-C
8alkyl and C
6-C
12aryl;
R
1represent hydrogen or C
1-C
3alkyl;
R
3represent C
4-C
10alkyl.
2. imidazole modified multipolymer according to claim 1, is characterized in that, the ratio of integer x, y and z is 0.3-25:1:0.5-30.
3. imidazole modified multipolymer according to claim 1, is characterized in that, described multipolymer is random copolymers, segmented copolymer, graft copolymer or alternating copolymer.
4. be used for preparing a method for imidazole modified multipolymer according to any one of claim 1-3, the method comprises the following steps:
I () is under the condition that there is emulsifying agent and initiator, that make to replace or unsubstituted vinylformic acid or acrylate monomer A ', replace or unsubstituted acrylate monomer B ' and replace or unsubstituted glycidyl acrylate C ' there is emulsion polymerization, generate multipolymer intermediate;
(ii) drip the aqueous solution of substituted or unsubstituted imidazoles in the multipolymer intermediate then generated to step (i), modification is carried out to described multipolymer intermediate, forms described imidazole modified multipolymer;
Wherein, described replacement or unsubstituted vinylformic acid or acrylate monomer A ' form polymerized unit A after polymerization; Described replacement or unsubstituted acrylate monomer B ' forms polymerized unit B after polymerization; Described replacement or unsubstituted glycidyl acrylate C ' forms described polymerized unit C after polyreaction and modification.
5. method according to claim 4, it is characterized in that, described replacement or unsubstituted vinylformic acid or acrylate monomer A ' are selected from: two or more combination any of vinylformic acid, methyl acrylate, ethyl propenoate, propyl acrylate, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate and above-mentioned monomer;
Described replacement or unsubstituted acrylate monomer B ' is selected from: n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, the just own ester of vinylformic acid, isobornyl acrylate, n-BMA, the secondary butyl ester of methacrylic acid, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, Isooctyl methacrylate, the just own ester of methacrylic acid, two or more combination any of isobornyl methacrylate and above-mentioned monomer,
Described replacement or unsubstituted glycidyl acrylate C ' is selected from: the combination of glycidyl acrylate, glycidyl methacrylate and above-mentioned monomer.
6. method according to claim 4, it is characterized in that, in described step (i), the ratio of select described monomer A according to the relative quantity of polymerized unit (A), (B) and (C) in described multipolymer ', monomers B ' and glycidyl acrylate C ', described emulsion polymerization continues to carry out 3-7 hour at the temperature of 50-100 DEG C.
7. method according to claim 4, it is characterized in that, in described step (i), the initiator used is selected from the mixing of any one or they in Diisopropyl azodicarboxylate, Potassium Persulphate, benzoyl peroxide, in the gross weight of used polymerization single polymerization monomer for benchmark, the consumption of described initiator is 0.1-0.5 % by weight.
8. method according to claim 4, it is characterized in that, in described step (i), the emulsifying agent used is selected from the mixing of any one or they in sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium soap, sodium alkylarysulfonate, alkylphenol-polyethenoxy base ether, in the gross weight of used polymerization single polymerization monomer for benchmark, the consumption of described emulsifying agent is 1-6 % by weight.
9. method according to claim 4, it is characterized in that, in described step (ii), described substituted or unsubstituted imidazoles is selected from the mixture of any one or they in glyoxal ethyline, 2-ethyl-4-methylimidazole and 2-phenylimidazole;
In described step (ii), described replacement or unsubstituted glycidyl acrylate C ' is 0.5-1.5 with the mol ratio of described substituted or unsubstituted imidazoles;
Described step (ii) continues to carry out 3-7 hour at the temperature of 40-90 DEG C.
10. method according to claim 4, is characterized in that, after the reaction of step (ii) terminates, in reaction system, adds acid, makes the pH value of reaction system be 3-4, filtered and recycled product, and carries out drying treatment;
Described acid is selected from hydrochloric acid, sulfuric acid, nitric acid, the mixture of any one or they in acetic acid.
11. 1 kinds of dulling and curing agents for epoxypaint, described dulling and curing agent comprises the imidazole modified multipolymer according to any one of claim 1-3.
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| CN105330765A (en) * | 2015-12-02 | 2016-02-17 | 江门盈骅光电科技有限公司 | Imidazole compound, preparation method and thermosetting composition containing imidazole compound |
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| WO2021156033A1 (en) | 2020-02-04 | 2021-08-12 | Tesa Se | High tg acrylate copolymers with nitrogen-containing aromatic heterocyclic group |
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