CN103421171B - Universal hyperbranched resin of mill base and preparation method thereof - Google Patents

Abstract

The invention discloses the universal hyperbranched resin of a kind of mill base, containing following component in the composition of raw materials of resin, the mass percent of each component is respectively: glycerine 1 ~ 30%; TriMethylolPropane(TMP) 1 ~ 20%; Tetramethylolmethane 1 ~ 8%; Neopentyl glycol 2.0 ~ 10%; Dimethylol propionic acid 1 ~ 40%; Phthalic anhydride 2 ~ 20% and/or cis-butenedioic anhydride 1 ~ 12%; Month silicic acid 10 ~ 50%; Phenylformic acid 1 ~ 10%; To lose lustre agent 0.05 ~ 0.2%; Oxidation inhibitor 0.05 ~ 0.2%; Dimethylbenzene 1 ~ 10%; To rare solvent 5 ~ 40%.This resin has good dispersion stabilization to pigment, and particularly for the charcoal blacks of more difficult dispersion, when using this resin as dispersion resin, the dispersion agent that only need add about 5% just can prepare the highly stable mill base of performance.Use this resin greatly can reduce the cost of mill base as mill base resins for universal use, increase economic efficiency.

Description

Universal hyperbranched resin of mill base and preparation method thereof

Technical field

Present method relates to synthetic resins field, is specifically related to coating mill base resins for universal use, particularly relates to universal hyperbranched resin of a kind of mill base and preparation method thereof.

Background technology

Mill base resins for universal use not only will have good compatibility, and requires to have good dispersion stabilization to pigment.

Mill base resins for universal use generally comprises aldehyde ketone resin, acrylic resin, polyester and Synolac, although these resins have good compatibility, some resin dispersion less stable, the standby mill base of some resin-made can make the degradation of paint film.As acrylic resin-based mill base can make mobility and the wettability of finish paint, and aldehyde ketone resin primary colours slurry can make the snappiness of paint film reduce, and polyester and Synolac primary colours slurry exist the slow defect of drying.

Mill base resins for universal use is widely used in the preparation of mill base owing to having good dispersion stabilization, mill base can be used for preparing colored paint, improves the decorative effect of paint film.The cost of colored paint directly depends on the dispersing property of resins for universal use, and the dispersing property of resins for universal use is good, and the consumption of dispersion agent is few, and the cost of colored paint is just low, otherwise the cost of colored paint is high.Therefore from this angle, the cost of colored paint depends primarily on the dispersing property of resins for universal use to pigment.Improve resins for universal use to the dispersing property of pigment, reduce the consumption of dispersion agent, the production cost reducing colored paint is imperative.

The production cost method reducing colored paint is a lot, and the viscosity as reduced general resin improves the dispersing property of resins for universal use itself, thus can reduce the consumption of dispersion agent.As reduced the consumption of phthalic anhydride in the synthesis of alcohol acids resins for universal use, obviously can reduce the viscosity of resin, although the content reducing phthalic anhydride can reduce viscosity, the hardness deliquescing of paint film, thus making the degradation of paint film, the performance requriements of paint film can not be met.

Summary of the invention

The object of the invention is to provide universal hyperbranched resin of a kind of mill base and preparation method thereof for the deficiencies in the prior art.

Another object of the present invention is the preparation method providing above-mentioned hyperbranched dispersion resin.

Above-mentioned purpose of the present invention is realized by following program:

Pigment is had to hyperbranched resin and the preparation method of high dispersive performance, it is as follows that its composition of raw materials calculates proportioning by mass percentage: glycerine 1 ~ 30%; TriMethylolPropane(TMP) 1 ~ 20%; Tetramethylolmethane 1 ~ 8%; Neopentyl glycol 2.0 ~ 10%; Dimethylol propionic acid 1 ~ 40%; Phthalic anhydride 2 ~ 20% and/or cis-butenedioic anhydride 1 ~ 12%; Month silicic acid 10 ~ 50%; Phenylformic acid 1 ~ 10%; To lose lustre agent 0.05 ~ 0.2%; Oxidation inhibitor 0.05 ~ 0.2%; Dimethylbenzene 1 ~ 10%; To rare solvent 5 ~ 40%.

Above-mentioned raw materials is commercially available prod, adopts technical grade just passable.

Described agent of losing lustre is Hypophosporous Acid, 50, phosphorous acid or phosphite.As sodium hypophosphite, triphenyl phosphite, Sodium Pyrosulfite etc.

Described oxidation inhibitor is phenolic compound or ester compound.As Resorcinol, two Lauryl Alcohol ester, two ten four carbon alcohols esters.

In above-mentioned raw materials formula, the present inventor studies discovery, in adopted polyvalent alcohol, when other condition is the same, the highest with the viscosity of the hyperbranched resin prepared by tetramethylolmethane, minimum with the viscosity of the hyperbranched resin prepared by Glycerin.In order to obtain suitable viscosity, a kind of polyvalent alcohol can be adopted separately, also can adopt the mixture of polyvalent alcohol.

In above-mentioned raw materials formula, phthalic anhydride and cis-butenedioic anhydride are used to the hardness improving resin, adopt the resin prepared by phthalic anhydride harder than the resin adopted prepared by cis-butenedioic anhydride, therefore can regulate the consumption of phthalic anhydride and cis-butenedioic anhydride in formula according to the hardness requirement of paint film.Two kinds of acid anhydrides can be used alone, also can be used in combination according to a certain percentage.

In above-mentioned raw materials formula, dimethylol propionic acid is as chainextender, and that is it plays to propagate and connects the effect in generation in the structure of resin, the quantity of functionality in resin, and the degree of branching of resin and the molecular weight of resin control by it.In formula, the consumption of dimethylol propionic acid is normally decided by the consumption of acid anhydrides and polyvalent alcohol.

In above-mentioned raw materials formula, the present inventor studies discovery, if the hyperbranched resin functionality utilizing above raw material to prepare is too high, that is terminal functionality is too much, and the viscosity of resin is very high, is unfavorable for the dispersion of pigment; The functionality of resin is too low, is also unfavorable for the dispersion of pigment.The sense number of degrees of resin are preferably 3 ~ 5.

In above-mentioned raw materials formula, the effect of dimethylbenzene is as reflux solvent during esterification, and in reaction process, take the micromolecular water in reaction system out of, makes reacting balance and carries out to desired direction.The present inventor studies discovery, in the preparation process of resin, dimethylbenzene also can not be used to dewater as reflux solvent, and use the water produced in vacuum removal reaction process.Dimethylbenzene is adopted to be reacting balance as the advantage of dehydrated solvent, easy to control; Shortcoming remains a small amount of dimethylbenzene in resin.

In above-mentioned raw materials formula, used is used to reduce whole resin system viscosity to the effect of rare solvent, easy construction, everyly usedly when prepared by Synolac all the present invention can be realized to rare solvent, normally organic solvent is selected to rare solvent, if arene organic solvent is (as toluene, dimethylbenzene etc.), lipid organic solvent is (as n-butyl acetate, isobutyl acetate), ether based organic solvent or organic solvent of ketone be (as 2-Butoxyethyl acetate, ethylene glycol monobutyl ether, isophorone etc.) etc.

When above-mentioned resin uses as mill base resins for universal use, need to add certain dispersion agent, wetting dispersing agent can make resin can well with the blending dispersion such as pigment or filler.Wetting dispersing agent those skilled in the art can be adopted to carry out time prepared by pigment printing paste any one wetting dispersing agent commonly used, as BYK-103BYK163BYK110 etc.The difference of the visual pigment of consumption of wetting dispersing agent and different, in mill base, to easily dispersible pigments such as general iron oxide yellow and titanium dioxides, the addition of wetting dispersing agent is 0 ~ 1%, and for difficult especially pigment disperseed such as carbon blacks, the addition of wetting dispersing agent is 1 ~ 5%.

The present invention adopts dimethylol propionic acid as chainextender to prepare hyperbranched resin, and this preparation method is simple, and can use at existing Synolac device.Prepared hyperbranched resin has unique dispersing property to pigment, particularly to charcoal blacks, without dispersion agent or dispersant dosage little time, just can prepare the stable mill base of excellent performance.

With current Baeyer RD181 resin-phase ratio on the market, the present invention has these excellent effect following:

The present invention opens the hyperbranched resin successfully producing excellent performance on original alkyd resin production equipment, this resin not only has good consistency, can with Synolac, nitro-resin and aminoresin etc. are compatible, and have unique dispersing property to pigment.

When this resin is used for mill base resins for universal use, when the consumption of dispersion agent is 2 ~ 5%, the good mill base of dispersion stabilization just can be prepared.And with the dispersion resin of market as mill base resins for universal use time, the addition of dispersion agent is generally 10 ~ 40%.Contrast can find, the mill base prepared by hyperbranched resin not only cost is low, and prepared mill base is without the appearance of loose colour color separation; Mill base has outstanding compatibility, can use in different systems; Be highly suitable for computer color matching system, the supply of material of polychrome kind, multiple batches of, short run can be completed fast.

Embodiment

Below in conjunction with specific embodiment, the present invention is described in detail.

Embodiment 1

The hyperbranched resin for disperse black carbon pigment of the present embodiment, its composition of raw materials, by mass percentage, is made up of following component:

Above-mentioned agent of losing lustre is Hypophosporous Acid, 50; Above-mentioned oxidation inhibitor is triphenyl phosphite; Above-mentioned is dimethylbenzene to rare solvent;

Its preparation method is as follows:

Step 1: after glycerine, tetramethylolmethane, TriMethylolPropane(TMP), dimethylol propionic acid, dimethylbenzene, lose lustre agent and oxidation inhibitor are put into reactor, in reactor, pass into nitrogen or argon gas simultaneously, and be warming up to 80 DEG C, start to stir, at 120 ~ 160 DEG C, react dehydration 6 hours simultaneously;

Step 2: when step 1 is cooled to less than 100 DEG C, drops into phthalic anhydride (cis-butenedioic anhydride), lauric acid, phenylformic acid and neopentyl glycol in reactor, is warming up to 180 ~ 220 DEG C of refuxing esterification dehydrations, insulation;

Step 3: be incubated and start sampling after 1 hour, to sample viscosity and acid number qualified, be cooled to less than 80 DEG C, add rare solvent, to rare hyperbranched resin solution obtaining required dispersed color.

The performance measurement result of prepared hyperbranched resin is as follows:

The performance of table 1 hyperbranched resin

Hyperbranched resin is as the Performance of mill base resins for universal use, and paste formula is as follows, and the RD181 resin in table is the market resin of Beyer Co., Ltd.

Table 2 paste formula

The joining of hyperbranched resin and polymeric polyisocyanate varnish paint Performance comparision as follows: polymeric polyisocyanate varnish is the commercial product of certain company.

Table 3 paint film property

+ represent and pass through

Found by the contrast of above-mentioned example, when hyperbranched resin uses as mill base resins for universal use, prepared mill base had both had good dispersion stabilization, had again good paint film property simultaneously.Than resins for universal use on the market, it can reduce the consumption of dispersion agent, thus reduces the cost of mill base.Illustrate that hyperbranched mill base resins for universal use of the present invention not only can resins for universal use outside subrogate country, the cost of mill base can be reduced simultaneously.

Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.

Claims (5)

1. the universal hyperbranched resin of mill base, its characteristic is, containing following component in the composition of raw materials of resin, the mass percent of each component is respectively: glycerine 2.53%; TriMethylolPropane(TMP) 3.62%; Tetramethylolmethane 3.18%; Neopentyl glycol 7.38%; Dimethylol propionic acid 15.29%; Phthalic anhydride 9.23% and/or cis-butenedioic anhydride 6.24%; Lauric acid 14.34%; Phenylformic acid 7.11%; To lose lustre agent 0.15%; Oxidation inhibitor 0.15%; Dimethylbenzene 3.49%; Letdown solvent dun 27.29%;

The preparation method of the universal hyperbranched resin of described mill base is as follows:

Step 1: after glycerine, tetramethylolmethane, TriMethylolPropane(TMP), dimethylol propionic acid, dimethylbenzene, lose lustre agent and oxidation inhibitor are put into reactor, in reactor, pass into nitrogen or argon gas simultaneously, and be warming up to 80 DEG C, start to stir, at 120 ~ 160 DEG C, react dehydration 6 hours simultaneously;

Step 2: when step 1 is cooled to less than 100 DEG C, drop into phthalic anhydride and/or cis-butenedioic anhydride, lauric acid in reactor, phenylformic acid and neopentyl glycol, is warming up to 180 ~ 220 DEG C of refuxing esterification dehydrations, insulation;

Step 3: be incubated and start sampling after 1 hour, to sample viscosity and acid number qualified, be cooled to less than 80 DEG C, add letdown solvent dun, latting drown obtains the hyperbranched resin solution of required dispersed color.

2. the universal hyperbranched resin of mill base according to claim 1, its characteristic is, described in agent of losing lustre be Hypophosporous Acid, 50, phosphorous acid or phosphite.

3. the universal hyperbranched resin of mill base according to claim 1, its characteristic is, described oxidation inhibitor is phenolic compound or ester compound.

4. the universal hyperbranched resin of mill base according to claim 1, its characteristic is, described letdown solvent dun is arene organic solvent or lipid organic solvent or ether based organic solvent or organic solvent of ketone.

5. a preparation method for the arbitrary described universal hyperbranched resin of mill base of Claims 1-4, its characteristic is, its preparation method is as follows:

Step 1: after glycerine, tetramethylolmethane, TriMethylolPropane(TMP), dimethylol propionic acid, dimethylbenzene, lose lustre agent and oxidation inhibitor are put into reactor, in reactor, pass into nitrogen or argon gas simultaneously, and be warming up to 80 DEG C, start to stir, at 120 ~ 160 DEG C, react dehydration 6 hours simultaneously;

Step 2: when step 1 is cooled to less than 100 DEG C, drop into phthalic anhydride and/or cis-butenedioic anhydride, lauric acid in reactor, phenylformic acid and neopentyl glycol, is warming up to 180 ~ 220 DEG C of refuxing esterification dehydrations, insulation;

Step 3: be incubated and start sampling after 1 hour, to sample viscosity and acid number qualified, be cooled to less than 80 DEG C, add letdown solvent dun, latting drown obtains the hyperbranched resin solution of required dispersed color.