CN105694018A - Method for preparing water-based MDI-modified polyester light-cured resin - Google Patents

Abstract

The invention relates to a method for preparing water-based MDI-modified polyester light-cured resin which is composed of 1-3% of hyperbranched polyester, 5-15% of a hydroxyl-containing acrylic monomer, 10-20% of MDI-80, 0.02-0.3% of dibutyltin dilaurate, 15-30% of maleic anhydride, 8-15% of N,N-dimethylaniline, 5-10% of sodium hydroxide, and 60-100% of deionized water. The hyperbranched polyester is synthesized from DMPA and TMP under an action of a catalyst; the prepared water-based MDI-modified polyester light-cured resin is good in storage stability and high in cost performance ratio; under the action of a photoinitiator, a coating film has excellent water resistance, hardness, aging resistance and contamination resistance, also has the characteristics of high glossiness, good abrasion resistance, strong adhesion power, high fullness, good impact resistance and the like, and is widely used in surface radiation coating and protection of woodware, metals, zinc alloys, aluminum alloys, magnesium alloys, plastics and other products.

Description

A kind of preparation method of aqueous MDI modified poly ester light-cured resin

Technical field

The preparation method that the present invention relates to a kind of photocuring polyester resin, refers more particularly to a kind of aqueous MDI modified poly ester light-cured resin, belongs to synthetic resin technical field。

Background technology

In recent years, environment-friendly type coating included high solid and solventless coatings, water paint, powdery paints and the photocureable coating very fast development of acquirement。Ultraviolet light polymerization has the advantages such as fast reaction, ambient operation, low energy consumption and solvent-free of low pollution。Aqueous photo-curing polyester has super branched molecule structure, is incorporated into by hyper-branched polyester in UV curing system, it is possible to overcome some shortcomings of linear oligomer, and such as film significant shrinkage, diluent volatilizees, toxicity is big；Aqueous photo-curing polyester coating one of representative in waterborne radiation curable coating, has gloss height, a feature such as adhesive force is strong, richness is high, excellent impact resistance, is therefore widely used in protection and the decoration on metal and woodenware surface。

Aqueous hyperbranched polymer has highly branched molecular structure, there is very narrow relative molecular mass distribution, similar structure is had with dendritic polymer, owing to macromole has the cramped construction that similar three-dimensional is spherical, the hydrodynamics radius of gyration is little, the degree of branching is significantly high, intermolecular not easy entanglement, and therefore viscosity changes less with the increase of relative molecular mass；And macromole is with many functional end group, and whole dissaving polymer is had critically important impact, it is possible to by terminal groups modification being controlled the performance of dissaving polymer, such as vitrification point and the dissolubility etc. in different solvents；Therefore, aqueous photo-curing dissaving polymer has become the heat subject in polymer science。

Tang Liming etc. are that raw material, excessive maleic anhydride modified have synthesized photocuring dissaving polymer with trimethylolpropane and 2,2 1 dihydromethyl propionic acids；Niu Jianting etc. utilize the double bond containing compound such as acryloyl chloride, maleic anhydride that hyperbranched compound is carried out chemical modification, obtain the functional hyperbranched compound that end group is double bond；The virgin firm grade of body, by reacting with glycidyl methacrylate at dissaving polymer, introduces double bond, obtains the coating resin of UV-curable。

Hyperbranched compound is carried out chemical end with TDI and modifiies by Wang Xiaoke etc., prepares the aqueous hyperbranched polyester of photocuring containing end acryloyl group, carboxyl, then with in NaOH with become salt, for emulsion polymerization, anionic self-emulsifying emulsions can be formed。But TDI is severe poisonous chemicals, chemical property is very active, and volatility is high, and when 25 DEG C, vapour pressure is 3.3Pa, and saturated vapor concentration is 30 × 10^-6, there is strong impulse abnormal smells from the patient and lacrimation, after suction, stimulate respiratory system, cause the long-term trace diisocyanate that sucks of dry cough laryngalgia will cause headache bronchitis, serious meeting causes death, and environment is caused severe contamination；The in vitro tests that international cancer research institution (IARC) carries out shows, TDI can cause the DNA Injury of people and chromosomal aberration rodent cells gene mutation and Sister chromatid exohange, for suspect carcinogen matter。Additionally TDI resistance to ag(e)ing, is not suitable in outdoor application。

Summary of the invention

Polyisocynate monomer of the present invention adopts MDI-80 to refer to 80%2,4'-methyl diphenylene diisocyanate and 20%4,4'-mixtures of diisocyanates and diphenylmethane, because MDI-80 can be only generated single quinone chromophoric group under light illumination, and the toxicity of MDI-80 is relatively low, cost is low, and colour retention is better than TDI。

In order to solve techniques as described above problem, the present invention takes techniques below scheme: the present invention relates to a kind of aqueous MDI modified poly ester light-cured resin, by weight percentage, it consists of: hyper-branched polyester 1～3%, the acrylic monomers 5～15% of hydroxyl, MDI-8010～20%, dibutyl tin laurate 0.02～0.3%, cis-butenedioic anhydride 15～30%, DMA 8～15%, sodium hydroxide 5～10%, deionized water 60～100%；Described hyper-branched polyester, by weight percentage, it consists of: 2,2 one dihydromethyl propionic acids 15～30%, trimethylolpropane 2～5%, p-methyl benzenesulfonic acid 0.1～0.5%；The acrylic monomers of described hydroxyl is acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, acrylic acid-2-hydroxy butyl ester。

The preparation method that the present invention proposes a kind of aqueous MDI modified poly ester light-cured resin, its preparation technology, comprise the steps:

A, in a kettle., adds 2,2 one dihydromethyl propionic acid and trimethylolpropanes by formula ratio, passes into nitrogen protection; it is warming up to 130 DEG C, adds the catalyst p-methyl benzenesulfonic acid of formula ratio, after insulation reaction 4h, close nitrogen, after continuing reaction 2h; it is cooled to 40 DEG C, prepares hyper-branched polyester, standby；

B, in a kettle., MDI-80 and catalyst dibutyltin dilaurylate is added by formula ratio, it is warming up to 30～40 DEG C, under agitation drip the acrylic monomers of the hydroxyl measured, sampling detection isocyanide acid number is started after reaction 0.5h, every 0.5h samples once later, when detecting the half that isocyanide acid number is initial value, the step a hyper-branched polyester prepared is added by formula ratio, and be warming up to 50～60 DEG C, continue reaction to isocyanide acid number less than 1% time, be warming up to 70～80 DEG C, when isocyanide acid number cannot be measured, carry out the next step；

C, adding the butanone measured dissolve in b step reactor, be simultaneously introduced the DMA of formula ratio, be warmed up to 80 DEG C, drip 50% cis-butenedioic anhydride butanone solution, control time for adding is 1h；After dropwising, often reaction 1h starts to sample detection system acid number, when the half that detection system acid number is initial value, is cooled to 50 DEG C；Adding in NaOH and reaction 0.5h, add deionized water (adjusting solid content is 30～40%), reduced vacuum extracts butanone out, and namely agitation and filtration packaging prepares a kind of milky aqueous MDI modified poly ester light-cured resin。

The aqueous MDI modified poly ester light-cured resin that the present invention prepares, excellent storage stability, cost performance is high；Under the effect of light trigger, film has the resistance to water of excellence, hardness, resistance to ag(e)ing and stain resistance; also there is glossiness height simultaneously, the feature such as wearability is good, adhesive force is strong, richness is high, excellent impact resistance, be widely used in surface emissivity application and the protection of the goods such as woodenware, metal, kirsite, aluminium alloy, magnesium alloy, plastics。

Detailed description of the invention

Embodiment 1:

A, in a kettle., adds 27 part of 2,2 dihydromethyl propionic acid and 3 parts of trimethylolpropanes, passes into nitrogen protection; it is warming up to 130 DEG C, adds 0.2 part of p-methyl benzenesulfonic acid, after insulation reaction 4h, close nitrogen, after continuing reaction 2h; it is cooled to 40 DEG C, prepares hyper-branched polyester, standby；

B, in a kettle., add 20 parts of MDI-80 and 0.08 part of dibutyl tin laurate, it is warming up to 30～40 DEG C, under agitation 9 parts of acrylic acid-2-hydroxyl acetate monomer of dropping, sampling detection isocyanide acid number is started after reaction 0.5h, every 0.5h samples once later, when detecting isocyanide acid number and be NCO being 16.0～16.5%, add the step a hyper-branched polyester 4 parts prepared, and be warming up to 50～60 DEG C, continue reaction to isocyanide acid number less than 1% time, be warming up to 70～80 DEG C, when isocyanide acid number cannot be measured, carry out the next step；

C, adding 5 parts of butanone be stirred in b step reactor, dissolve after completely, add 12 parts of DMAs, be warmed up to 80 DEG C, drip 50% cis-butenedioic anhydride butanone solution 40 parts, control time for adding is 1h；After dropwising, often reaction 1h starts to sample detection system acid number, when system acid number is 10～11mgKOH/g, is cooled to 50 DEG C；Adding in 8 parts of NaOH and reaction 0.5h, add 100 parts of deionized waters, reduced vacuum extracts butanone out, and namely agitation and filtration packaging prepares a kind of solid content is 40% milky aqueous MDI modified poly ester light-cured resin。

Embodiment 2:

A, hyper-branched polyester are with reference to a in steps in example 1；

B, in a kettle., add 15 parts of MDI-80 and 0.08 part of dibutyl tin laurate, it is warming up to 30～40 DEG C, under agitation 7 parts of 2-hydroxypropyl acrylate monomers of dropping, sampling detection isocyanide acid number is started after reaction 0.5h, every 0.5h samples once later, when detecting isocyanide acid number and be NCO being 16.0～16.5%, add the step a hyper-branched polyester 3 parts prepared, and be warming up to 50～60 DEG C, continue reaction to isocyanide acid number less than 1% time, be warming up to 70～80 DEG C, when isocyanide acid number cannot be measured, carry out the next step；

C, adding 4 parts of butanone be stirred in b step reactor, dissolve after completely, add 10 parts of DMAs, be warmed up to 80 DEG C, drip 50% cis-butenedioic anhydride butanone solution 30 parts, control time for adding is 1h；After dropwising, often reaction 1h starts to sample detection system acid number, when system acid number is 10～11mgKOH/g, is cooled to 50 DEG C；Adding in 6 parts of NaOH and reaction 0.5h, add 70 parts of deionized waters, reduced vacuum extracts butanone out, and namely agitation and filtration packaging prepares a kind of solid content is 40% milky aqueous MDI modified poly ester light-cured resin。

Embodiment 3:

The aqueous MDI modified poly ester light-cured resin that the embodiment of the present invention is prepared is configured to aqueous UV varnish, formula is as follows: aqueous MDI modified poly ester light-cured resin 60～65 parts, light trigger 5 parts, and defoamer 0.2 part, substrate wetting agents 0.3 part, levelling agent 0.2 part, benefit deionized water are to 100；Comparative example aqueous TDI modified poly ester light-cured resin makes aqueous UV varnish by above-mentioned formula, carries out film performance contrast test according to relevant national standard, and film radiation curing 10s, test result is as shown in table 1。

Table 1: film performance test result

Although the present invention has been explained in detail and has quoted as proof embodiment, but for those of ordinary skill in the art, it is clear that can various schemes, amendment and change that make as specified above, should be construed as being included within scope of the claims。

Claims (2)

1. an aqueous MDI modified poly ester light-cured resin, it is characterized in that: by weight percentage, it consists of: hyper-branched polyester 1～3%, the acrylic monomers 5～15% of hydroxyl, MDI-8010～20%, dibutyl tin laurate 0.02～0.3%, cis-butenedioic anhydride 15～30%, DMA 8～15%, sodium hydroxide 5～10%, deionized water 60～100%；Described hyper-branched polyester, by weight percentage, it consists of: 2,2 one dihydromethyl propionic acids 15～30%, trimethylolpropane 2～5%, p-methyl benzenesulfonic acid 0.1～0.5%；The acrylic monomers of described hydroxyl is acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, acrylic acid-2-hydroxy butyl ester。

2. the preparation method of an aqueous MDI modified poly ester light-cured resin as claimed in claim 1, it is characterised in that: described preparation method, comprise the steps:

A, in a kettle., adds 2,2 one dihydromethyl propionic acid and trimethylolpropanes by formula ratio, passes into nitrogen protection; it is warming up to 130 DEG C, adds the catalyst p-methyl benzenesulfonic acid of formula ratio, after insulation reaction 4h, close nitrogen, after continuing reaction 2h; it is cooled to 40 DEG C, prepares hyper-branched polyester, standby；

B, in a kettle., MDI-80 and catalyst dibutyltin dilaurylate is added by formula ratio, it is warming up to 30～40 DEG C, under agitation drip the acrylic monomers of the hydroxyl measured, sampling detection isocyanide acid number is started after reaction 0.5h, every 0.5h samples once later, when detecting the half that isocyanide acid number is initial value, the step a hyper-branched polyester prepared is added by formula ratio, and be warming up to 50～60 DEG C, continue reaction to isocyanide acid number less than 1% time, be warming up to 70～80 DEG C, when isocyanide acid number cannot be measured, carry out the next step；

C, adding the butanone measured dissolve in b step reactor, be simultaneously introduced the DMA of formula ratio, be warmed up to 80 DEG C, drip 50% cis-butenedioic anhydride butanone solution, control time for adding is 1h；After dropwising, often reaction 1h starts to sample detection system acid number, when the half that detection system acid number is initial value, is cooled to 50 DEG C；Adding in NaOH and reaction 0.5h, add deionized water (adjusting solid content is 30～40%), reduced vacuum extracts butanone out, and namely agitation and filtration packaging prepares a kind of milky aqueous MDI modified poly ester light-cured resin。