CN102911371A - Hyperbranched polyester modified acrylic resin and preparation method thereof - Google Patents
Hyperbranched polyester modified acrylic resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to hyperbranched polyester modified acrylic resin and a preparation method thereof. Firstly, a By-type polyhydroxylated compound is taken as nuclear molecules (wherein B represents hydroxyl, and the degree of functionality y of B is larger than of equal to 2), ABx-type polyhydroxy acid is taken as divergence molecules (wherein A represents carboxyl, B represents hydroxyl and x represents the degree of functionality of hydroxyl and is larger than or equal to 2), a polyester-type hyperbranched polymer with hydroxyl at the terminal is obtained through a vacuum fusion polycondensation method, and esterification reaction is performed on prepared hyperbranched polyester and acrylic resin with carboxyl in the presence of a water-carrying agent to obtain hyperbranched polyester modified acrylic resin. Acrylate with hyperbranched polyester introduced enriches a great amount of hydroxyl, and is taken as a cross-linking group to greatly reduce the curing time of a coating film; and at the same time, hyperbranched polyester has excellent performance of dendritic polymer, molecular chains are not easily twisted, and hyperbranched polyester modified acrylic resin with high solidity and low viscosity can be obtained. According to the invention, the source of raw materials is wide, the price of the raw materials is low, the synthetic method is simple, the controllability is good, and the production cost is low.
Description
Technical field
The present invention relates to a kind of acrylic resin and preparation method thereof, particularly a kind of hyper-branched polyester is acrylic resin modified and preparation method thereof.
Background technology
The acrylic resin synthetic technology is ripe, raw material is easy to get, films good combination property, is coating large usage quantity in the synthetic resins, the resin that purposes is wider.Traditional acrylic resin paint solid content is low, contains a large amount of volatile organic solvents (VOC), and pollution on the environment is serious.
Hyperbranched polymer is the highly branched polymkeric substance with 3 D stereo structure of a class, has the unexistent high resolution of general simple linear polymer, low viscosity, the characteristics such as high rheological variation and a large amount of functional end-groups obtain to use at functional areas such as rheologic additive, coating, softening agent, catalyzer, photoelectric material, nano materials.
Hyperbranched polymer is generally by AB
n(n＞=2) type monomer polycondensation forms (Kim, Y.H., Webster, the Macromolecules(macromole of O.W.), the 25th volume, 5561 (1992)).But AB
nThe type monomer generally needs investigator oneself synthetic, complicated process of preparation, and poor controllability, production cost is high, so that this synthetic method has certain limitation.
Summary of the invention
Hyper-branched polyester of the present invention is acrylic resin modified, comprises component (I) and component (II) forms by esterification, and wherein said component (I) is (i1) B
yType polyol and (i2) AB
xThe type polyhydroxy-acid forms by esterification, described component (II) is for containing (methyl) acrylic ester polymer of carboxyl, B representation hydroxy functional group wherein, its hydroxy functional group is counted y 〉=2, A representation carboxy functional group, functional group's number of x representation hydroxy and x 〉=2, mass ratio (i1)/(i2) are 0.05～0.1, and the mass ratio of component (I)/component (II) is 1:50～1:10.
(i1) B
yThe type polyol is selected from: ethylene glycol, propylene glycol, butyleneglycol, glycol ether, TriMethylolPropane(TMP), glycerol, triethylene glycol, 1,8-ethohexadiol or tetramethylolmethane and combination thereof.
(i2) AB
xPolyhydroxy-acid is selected from: dimethylol propionic acid, dimethylolpropionic acid or polyhydrony fatty acid, or the dihydroxylated acid and the combination thereof that are formed by equimolar phthalic anhydride, Pyroglutaric acid or Succinic anhydried and diisopropanolamine (DIPA) or diethanolamine reaction.
(methyl) acrylic ester polymer that component (II) contains carboxyl comprises at least two kinds of comonomers and is polymerized, comonomer one is selected from butyl acrylate, methyl methacrylate, methyl acrylate, ethyl propenoate and combination thereof, and comonomer two is selected from vinylformic acid, methacrylic acid and combination thereof.The molecular weight that component (II) contains (methyl) acrylic ester polymer of carboxyl is 5000-20000, and on average each acrylic resin molecule contains 1-10 carboxyl.
The manufacture method that hyper-branched polyester is acrylic resin modified, it comprises step:
(S1) with (i1) B
yType polyol and (i2) AB
xThe type polyhydroxy-acid adds catalyzer, carries out melt polycondensation reaction in 130 ℃ ~ 220 ℃ of temperature of reaction, vacuum tightness under 5KPa ~ 10Pa condition and obtains component (I), wherein B in 1 ~ 30 hour
yThe type polyol is core molecule, the B representation hydroxy, and its hydroxy functional group is counted y 〉=2, AB
xThe type polyhydroxy-acid is for dispersing molecule, and wherein A represents and contains a carboxyl functional group in the molecule, and hydroxy functional group and its hydroxy functional group that B represents in the molecule are counted x 〉=2, and the mass ratio of wherein said (i1)/(i2) is 0.05～0.1;
(S2) prepare (methyl) acrylic resin polymkeric substance that component (II) contains carboxyl by solution free radical polymerization;
(S3) component (II) for preparing in component (I) adding (S2) step for preparing in (S1) step is inner, add catalyzer, use the band aqua, to obtain hyper-branched polyester in 12-24 hour acrylic resin modified in reaction under the 140-220 ℃ of condition, and the mass ratio of wherein said component (I)/component (II) is 1:50～1:10.
Described step (S1) catalyzer, step (S3) catalyzer are acid organic catalyst independently of one another, be selected from have carboxyl, organic compound and the combination thereof of phosphate group, sulfonic acid group, sulfate group, catalyst levels is the 0.01%-5% of reactant total mass.
Described step (S1) catalyzer, step (S3) catalyzer are organotin catalysts independently of one another, are selected from n-caprylic acid tin (II), 2 ethyl hexanoic acid tin (II), tin laurate (II), dibutyltin oxide, diphenyl tin oxide, titanium dioxide dibutyl tin, dibutyltin diacetate, dibutyl tin laurate, two toxilic acid dibutyl tins, oxalic acid dioctyl tin and combination thereof.Catalyst levels is the 0.1-10% of reactant total mass.
The band aqua is dimethylbenzene, toluene or benzene.
The invention has the beneficial effects as follows: the acrylic resin modified viscosity of hyper-branched polyester is low, reduces the usage quantity of organic solvent, reduces organic solvent to the pollution level of environment; The acrylic resin modified great amount of hydroxy group that contains of hyper-branched polyester can reduce the set time of film forming as crosslinked group; The acrylic resin modified performance with dendritic macromole excellence of hyper-branched polyester, molecular chain is easy entanglement not, makes coating have good film forming properties; Prepare the acrylic resin modified raw material sources of hyper-branched polyester extensive, low price, synthetic method is simple, and controllability is good, and production cost is low.
Description of drawings
Fig. 1 is embodiment 1 acrylic resin and the acrylic resin modified infrared curve of hyper-branched polyester;
Fig. 2 is the acrylic resin modified gpc chromatogram of embodiment 1 hyper-branched polyester;
Fig. 3 is the acrylic resin modified thermogravimetric analysis figure of embodiment 1 hyper-branched polyester;
Fig. 4 is the acrylic resin modified thermal losses-time diagram of embodiment 1 hyper-branched polyester;
Fig. 5 is the solid content-viscogram of the acrylic resin modified solution of embodiment 1 hyper-branched polyester;
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
(1) with 0.7g to benzene methanesulfonic acid, 13.6g tetramethylolmethane and 53.54g dimethylol propionic acid (DMPA) mix, and at 160 ℃ of reaction 2.5h, vacuumize simultaneously (740mmHg), obtain the liquid of transparent little Huang; Add 107.28g DMPA in system, under the condition that vacuumizes (740mmHg), 160 ℃ of reactions until the acid number that records resin is poured out less than 10mg KOH/g, obtain hyper-branched polyester after the cooling again.
(2) condenser is being housed, add 80g dimethylbenzene in the four-hole boiling flask of agitator and thermometer, be warming up to 140 ± 2 ℃, the dropping funnel of then mixing solutions of 3g vinylformic acid, 28g butyl acrylate, 32g methyl methacrylate and 2g BPO and the positive Dodecyl Mercaptan composition of 1g chain-transfer agent evenly being packed into; Evenly splash in the four-hole boiling flask that dimethylbenzene is housed with 4 ~ 5h, then at 140 ± 2 ℃ of insulation 1h, add afterwards 0.35g initiator B PO and 14g dimethylbenzene, join in the four-hole boiling flask with dropping funnel, then continue behind 140 ± 2 ℃ of insulation 2h cooling discharge, obtain acrylic resin, molecular weight is 5000, and on average each acrylic resin molecule contains 5 carboxyls, called after P1.
(3) hyper-branched polyester with preparation in the step (1) adds in the part acrylic resin of preparation in the step (2), add the catalyzer dibutyl tin laurate, use band aqua dimethylbenzene, reaction is to not producing water under 140 ℃ of conditions, get hyper-branched polyester acrylic resin modified, called after P2, the mass ratio of the part acrylic resin that wherein prepares in the hyper-branched polyester/step (2) of preparation in the step (1) is 1:50.The acrylic resin modified infrared curve of acrylic resin and hyper-branched polyester is seen Fig. 1, and the P1 curve is the infrared curve of acrylic resin, and P2 is the acrylic resin modified infrared curve of hyper-branched polyester.Relatively P1 and P2 curve are at 3449cm
-1The position find that obvious hydroxyl stretching vibration peak is arranged among the P2.Can infer thus and contain a large amount of hydroxyls in the P2 resin, thereby prove the existence of hyperbranched group.
The acrylic resin modified gpc chromatogram of hyper-branched polyester is seen Fig. 2, and as can be seen from Figure 2 curve is " hump shape ", illustrates that the acrylic resin modified molecular weight distribution of hyper-branched polyester is reasonable, does not have large and especially little especially molecule.The properties that represents this type of acrylic resin is good, can not produce undesirable effect in actual applications.
The acrylic resin modified thermogravimetric analysis figure of hyper-branched polyester sees Fig. 3, as can be seen from Figure 3 under 220 ℃, the weight fraction of acrylate is 98.39%, and this illustrates under this temperature, the extent of thermal degradation that hyper-branched polyester is acrylic resin modified almost can be ignored.
Acrylic resin modified thermal losses-the time diagram of hyper-branched polyester is seen Fig. 4, as can be seen from Figure 4, reaches 4.5 hours 220 ℃ of lower heat hyper-branched polyesters are acrylic resin modified, and the thermal losses of resin only is 1.63%.
Solid content-the viscogram of the acrylic resin modified solution of hyper-branched polyester is seen Fig. 5, when the solid content of hyperbranched polyester acrylic ester (3wt.%) solution 50% when following, the viscosity of solution is lower than 560mPa.s, when solid content is lower than 79%, viscosity is lower than 650mPa.s, generally speaking, the soltion viscosity of acrylate with same molecular quality and solid content up to 1500mPa.s about, this is because the hyperbranched poly ester molecular structure is compact, have three-dimensional globosity, molecular chain is difficult for tangling.The introducing of hyper-branched polyester has obviously reduced the viscosity of system, is fit to be used as high solid coating.
Embodiment 2:
(1) with 0.7g to benzene methanesulfonic acid, 13.6g tetramethylolmethane and 53.64g dimethylol propionic acid (DMPA) mix, and at 160 ℃ of reaction 2.5h, vacuumize simultaneously (740mmHg), obtain the liquid of transparent little Huang; Add 107.28g DMPA in system, under the condition that vacuumizes (740mmHg), 160 ℃ of reactions until the acid number that records resin is poured out less than 10mg KOH/g, obtain hyper-branched polyester after the cooling again.
(2) to agitator, thermometer, add 70g dimethylbenzene in the four-hole boiling flask of dropping funnel and reflux condensing tube, with the 32g methyl methacrylate, the 28g butyl acrylate, 3g vinylformic acid, the positive Dodecyl Mercaptan of 2g BPO and 1g adds in the dropping funnel, under agitation condition, heating, the control temperature is at 120 ℃, when namely solvent reaches reflux state, in 4.0h, evenly drop in the reactor mix monomer and initiator, after mix monomer dropwises, append a small amount of initiator, again insulation reaction 1.0h, then be cooled to 50 ℃, discharging obtains white thick liquid, is acrylic resin, molecular weight is 10000, and on average each acrylic resin molecule contains 3 carboxyls.
(3) hyper-branched polyester with preparation in the step (1) adds in the part acrylic resin of preparation in the step (2), add the catalyzer dibutyl tin laurate, use band aqua dimethylbenzene, reaction is to not producing water under 160 ℃ of conditions, get hyper-branched polyester acrylic resin modified, the mass ratio of the part acrylic resin that wherein prepares in the hyper-branched polyester/step (2) of preparation in the step (1) is 1:20.
Embodiment 3:
(1) with 0.9g to benzene methanesulfonic acid, 13.6g tetramethylolmethane and 53.64g dimethylol propionic acid (DMPA) mix, and at 180 ℃ of reaction 2.5h, vacuumize simultaneously (740mmHg), obtain the liquid of transparent little Huang; Add 107.28g DMPA in system, under the condition that vacuumizes (740mmHg), 160 ℃ of reactions until the acid number that records resin is poured out less than 10mg KOH/g, obtain hyper-branched polyester after the cooling again.
(2) to agitator, thermometer, add 70g dimethylbenzene in the four-hole boiling flask of dropping funnel and reflux condensing tube, with the 32g methyl methacrylate, the 28g butyl acrylate, 3g vinylformic acid, the positive Dodecyl Mercaptan of 2g BPO and 1g adds in the dropping funnel, under agitation condition, heating, the control temperature is at 120 ℃, when namely solvent reaches reflux state, in 4.0h, evenly drop in the reactor mix monomer and initiator, after mix monomer dropwises, append a small amount of initiator, again insulation reaction 1.0h, then be cooled to 50 ℃, discharging obtains white thick liquid, is acrylic resin, molecular weight is 20000, and on average each acrylic resin molecule contains 2 carboxyls.
(3) to being hyper-branched polyester and the acrylic resin of 1:10 with adding mass ratio in the four-hole boiling flask of agitator, thermometer, water trap and reflux condensing tube, dibutyl tin laurate is as catalyzer, dimethylbenzene is as the band aqua, be heated to 180 ℃, react to water trap and no longer produce water, cooling, discharging.Obtain white or the transparent resin of little Huang, i.e. hyper-branched polyester modification acrylate.The hyper-branched polyester of preparation in the step (1) is added in the part acrylic resin of preparation in the step (2), add the catalyzer dibutyl tin laurate, use band aqua dimethylbenzene, reaction is to not producing water under 180 ℃ of conditions, get hyper-branched polyester acrylic resin modified, the mass ratio of the part acrylic resin that wherein prepares in the hyper-branched polyester/step (2) of preparation in the step (1) is 1:10.
The coating composition formula table
| Composition | 1 | 2 | 3 |
| The unmodified acrylic resin that step among the embodiment 1 (2) makes | 100 | 0 | 0 |
| The hyperbranched polyester acrylic ester of embodiment 1 | 0 | 100 | 0 |
| The hyperbranched polyester acrylic ester of |
0 | 0 | 100 |
| The methyl-etherified terpolycyantoamino-formaldehyde resin | 12 | 12 | 12 |
| Tosic acid | 0.5 | 0.5 | 0.5 |
Annotate: form deal and all represent with weight part
Coating composition performance table
Claims (11)
1. a hyper-branched polyester is acrylic resin modified, it is characterized in that, it comprises component (I) and component (II) forms by esterification, and wherein said component (I) is (i1) B
yType polyol and (i2) AB
xThe type polyhydroxy-acid forms by esterification, described component (II) is for containing (methyl) acrylic ester polymer of carboxyl, B representation hydroxy functional group wherein, its hydroxy functional group is counted y 〉=2, A representation carboxy functional group, functional group's number of x representation hydroxy and x 〉=2, mass ratio (i1)/(i2) are 0.05～0.1, and the mass ratio of component (I)/component (II) is 1:50～1:10.
2. hyper-branched polyester as claimed in claim 1 is acrylic resin modified, it is characterized in that, described (i1) B
yThe type polyol is selected from: ethylene glycol, propylene glycol, butyleneglycol, glycol ether, TriMethylolPropane(TMP), glycerol, 1,8-ethohexadiol, triethylene glycol or tetramethylolmethane and combination thereof.
3. hyper-branched polyester as claimed in claim 1 is acrylic resin modified, it is characterized in that, described (i2) AB
xThe type polyhydroxy-acid is selected from: dimethylol propionic acid, dimethylolpropionic acid or polyhydrony fatty acid, or the dihydroxylated acid and the combination thereof that are formed by equimolar phthalic anhydride, Pyroglutaric acid or Succinic anhydried and diisopropanolamine (DIPA) or diethanolamine reaction.
4. hyper-branched polyester as claimed in claim 1 is acrylic resin modified, it is characterized in that, (methyl) acrylic ester polymer that described component (II) contains carboxyl comprises at least two kinds of comonomers and is polymerized, comonomer one is selected from butyl acrylate, methyl methacrylate, methyl acrylate, ethyl propenoate and combination thereof, and comonomer two is selected from vinylformic acid, methacrylic acid and combination thereof.
5. hyper-branched polyester as claimed in claim 1 is acrylic resin modified, it is characterized in that, the molecular weight that described component (II) contains (methyl) acrylic ester polymer of carboxyl is 5000-20000, and on average each acrylic resin molecule contains 1-10 carboxyl.
6. preparation method that hyper-branched polyester claimed in claim 1 is acrylic resin modified, it comprises step:
(S1) with (i1) B
yType polyol and (i2) AB
xThe type polyhydroxy-acid adds catalyzer, carries out melt polycondensation reaction to the acid number of system in 130 ℃ ~ 220 ℃ of temperature of reaction, vacuum tightness under 5KPa ~ 10Pa condition and obtains component (I), wherein B less than 10mg KOH/g
yThe type polyol is core molecule, the B representation hydroxy, and its hydroxy functional group is counted y 〉=2, AB
xThe type polyhydroxy-acid is for dispersing molecule, and wherein A represents and contains a carboxyl functional group in the molecule, and hydroxy functional group and its hydroxy functional group that B represents in the molecule are counted x 〉=2, and the mass ratio of wherein said (i1)/(i2) is 0.05～0.1;
(S2) prepare (methyl) acrylic resin polymkeric substance that component (II) contains carboxyl by solution free radical polymerization;
(S3) component (II) of preparation in component (I) the adding step (S2) of preparation in the step (S1) is inner, add catalyzer, use the band aqua, to obtain hyper-branched polyester not acrylic resin modified to not producing water in reaction under the 140-220 ℃ of condition, and the mass ratio of wherein said component (I)/component (II) is 1:50～1:10.
7. the acrylic resin modified preparation method of hyper-branched polyester as claimed in claim 6, it is characterized in that, the catalyzer of the catalyzer of described step (S1), step (S3) is acid organic catalyst independently of one another, and catalyst levels is the 0.01%-5% of reactant total mass.
8. the acrylic resin modified preparation method of hyper-branched polyester as claimed in claim 7, it is characterized in that, the catalyzer of the catalyzer of described step (S1), step (S3) is selected from independently of one another: organic compound and combination thereof with carboxyl, phosphate group, sulfonic acid group, sulfate group.
9. the acrylic resin modified preparation method of hyper-branched polyester as claimed in claim 6, it is characterized in that, the catalyzer of the catalyzer of described step (S1), step (S3) is organotin catalysts independently of one another, and catalyst levels is the 0.1-10% of reactant total mass.
10. the acrylic resin modified preparation method of hyper-branched polyester as claimed in claim 9, it is characterized in that, the catalyzer of the catalyzer of described step (S1), step (S3) is selected from n-caprylic acid tin (II), 2 ethyl hexanoic acid tin (II), tin laurate (II), dibutyltin oxide, diphenyl tin oxide, titanium dioxide dibutyl tin, dibutyltin diacetate, dibutyl tin laurate, two toxilic acid dibutyl tins, oxalic acid dioctyl tin and combination thereof independently of one another.
11. the preparation method that hyper-branched polyester as claimed in claim 6 is acrylic resin modified is characterized in that, described band aqua is dimethylbenzene, toluene or benzene.
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