CN105694018B - Method for preparing water-based MDI-modified polyester light-cured resin - Google Patents
Method for preparing water-based MDI-modified polyester light-cured resin Download PDFInfo
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- CN105694018B CN105694018B CN201410713346.6A CN201410713346A CN105694018B CN 105694018 B CN105694018 B CN 105694018B CN 201410713346 A CN201410713346 A CN 201410713346A CN 105694018 B CN105694018 B CN 105694018B
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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
Technical field
The present invention relates to a kind of preparation method of photocuring polyester resin, more particularly to a kind of aqueouss MDI modified poly ester
Light-cured resin, belongs to synthetic resin technical field.
Background technology
In recent years, environment-friendly type coating included that high solid and solventless coatings, water paint, powdery paints and photocuring were applied
Material obtains very fast development.Ultraviolet light polymerization has the advantages that fast reaction, ambient operation, low energy consumption and solvent-free of low pollution.
Aqueous photo-curing polyester has super branched molecule structure, and hyper-branched polyester is incorporated in UV curing systems, line style can be overcome
Some shortcomings of oligomer, such as film significant shrinkage, diluent are volatilized, toxicity is big etc.；Have in waterborne radiation curable coating and represent
Property one of aqueous photo-curing polyester coating, with gloss it is high, adhesive force is strong, richness is high, excellent impact resistance the features such as, because
This is widely used in protection and the decoration on metal and woodenware surface.
Aqueous hyperbranched polymer has highly branched molecular structure, with very narrow relative molecular mass distribution, with
Dendritic polymer has similar structure, as macromole has similar three-dimensional spherical cramped construction, hydrodynamics revolution half
Footpath is little, and the degree of branching is very high, intermolecular not easy entanglement, therefore viscosity is less with the increase change of relative molecular mass；And divide greatly
Subband has many functional end groups, has critically important impact to whole dissaving polymer, can be by controlling to terminal groups modification
The performance of dissaving polymer processed, such as vitrification point and the dissolubility in different solvents etc.；Therefore, aqueous photo-curing over-expense
Fluidized polymer has become the heat subject in polymer science.
Trimethylolpropane and 2,2 1 dihydromethyl propionic acids such as Tang Liming are that raw material, excessive maleic anhydride change
Property has synthesized photocuring dissaving polymer；Niu Jianting etc. is using double bond containing compounds such as acryloyl chloride, maleic anhydrides
Chemical modification is carried out to overspending compound, the functional hyperbranched compound that end group is double bond is obtained；The firm grade of virgin body is by over-expense
Fluidized polymer and glycidyl methacrylate are reacted, and introduce double bond, obtain can U V solidifications coating resin.
Wang Xiaoke etc. is modified to overspending compound and carrying out chemical end with TDI, be obtained the acryloyl group containing end, carboxyl light it is solid
Change aqueous hyperbranched polyester, then with NaOH and into salt, for emulsion polymerization, anionic self-emulsifying emulsions can be formed.But TDI
It is severe poisonous chemicals, chemical property is very active, volatility is high, when 25 DEG C, vapour pressure is 3.3Pa, saturated vapor concentration is 30 ×
10-6, with strong impulse abnormal smells from the patient and lacrimation, after suction, stimulate respiratory system, cause dry cough laryngalgia to suck for a long time micro-
Amount diisocyanate will cause headache bronchitis, and serious meeting causes death, and causes severe contamination to environment；International cancer
The in vitro tests that research institution (IARC) is carried out shows that TDI can cause the DNA Injury of people and chromosomal aberration grinding tooth
Zooblast gene mutation and Sister chromatid exohange, are suspect carcinogen matter.TDI resistances to ag(e)ing, are not suitable in room in addition
Outer use.
The content of the invention
Polyisocynate monomer of the present invention refers to 80%2,4'- methyl diphenylene diisocyanates and 20% using MDI-80
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, low cost, and colour retention is better than TDI.
In order to solve the problems, such as techniques as described above, the present invention takes technical scheme below：The present invention relates to a kind of aqueouss
MDI modified poly ester light-cured resins, by weight percentage, consisting of：The acrylic acid of hyper-branched polyester 1~3%, hydroxyl
Monomer 5~15%, MDI-8010~20%, dibutyl tin laurate 0.02~0.3%, cis-butenedioic anhydride 15~30%, N, N- diformazans
Base aniline 8~15%, sodium hydroxide 5~10%, deionized water 60~100%；Described hyper-branched polyester, by weight percentage
Meter, consisting of：2,2 1 dihydromethyl propionic acids 15~30%, trimethylolpropane 2~5%, p-methyl benzenesulfonic acid 0.1~
0.5%；The acrylic monomerss of described hydroxyl are acrylic acid -2- hydroxyl ethyl esters, 2-hydroxypropyl acrylate, acrylic acid -2- hydroxyl fourths
Ester.
A kind of preparation method of aqueouss MDI modified poly ester light-cured resin of present invention proposition, its preparation technology, including it is as follows
Step：
A, in a kettle., adds 2,2 one dihydromethyl propionic acids and trimethylolpropane by formula ratio, is passed through nitrogen guarantor
Shield, is warming up to 130 DEG C, adds the catalyst p-methyl benzenesulfonic acid of formula ratio, and nitrogen is closed after insulation reaction 4h, continues reaction 2h
Afterwards, 40 DEG C are cooled to, hyper-branched polyester is obtained, it is standby；
B, in a kettle., adds MDI-80 and catalyst dibutyltin dilaurylate by formula ratio, is warming up to 30~40
DEG C, the acrylic monomerss of the hydroxyl that Deca is measured, start sampling detection isocyanide acid number after reaction 0.5h under agitation, after
Sample once per 0.5h, when the half that isocyanide acid number is initial value is detected, by hyperbranched poly prepared by formula ratio addition step a
Ester, and 50~60 DEG C are warming up to, when continuation reaction to isocyanide acid number is less than 1%, 70~80 DEG C are warming up to, when isocyanide acid number cannot
When measuring, the next step is carried out；
C, in b step reactor the butanone for measuring is added to be dissolved, while adding the N of formula ratio, N- dimethyl
Aniline, is warmed up to 80 DEG C, 50% cis-butenedioic anhydride butanone solution of Deca, controls time for adding for 1h；After completion of dropping, often react 1h and start
Sampling detection system acid number, when half of the detection system acid number for initial value, is cooled to 50 DEG C；Add NaOH neutralization reactions
0.5h, adds deionized water (adjusting solid content to be 30~40%), and reduced vacuum extracts butanone out, and agitation and filtration packaging is obtained one kind
Milky aqueouss MDI modified poly ester light-cured resin.
Aqueouss MDI modified poly ester light-cured resin obtained in of the invention, excellent storage stability, cost performance are high；Light-initiated
In the presence of agent, film has excellent resistance to water, hardness, resistance to ag(e)ing and stain resistance, while also having glossiness high, resistance to
Mill property good, adhesive force is strong, richness is high, excellent impact resistance the features such as, be widely used in woodenware, metal, kirsite, aluminium alloy,
The surface emissivity application of the products such as magnesium alloy, plastics and protection.
Specific embodiment
Embodiment 1：
A, in a kettle., adds 27 part 2,2 one dihydromethyl propionic acids and 3 parts of trimethylolpropanes, is passed through nitrogen protection,
130 DEG C are warming up to, 0.2 part of p-methyl benzenesulfonic acid is added, nitrogen after insulation reaction 4h, is closed, after continuing reaction 2h, 40 is cooled to
DEG C, hyper-branched polyester is obtained, it is standby；
B, in a kettle., adds 20 parts of MDI-80 and 0.08 part of dibutyl tin laurates, is warming up to 30~40 DEG C,
The lower 9 parts of acrylic acid -2- hydroxyl ethyl ester monomers of Deca of stirring, start sampling detection isocyanide acid number, take per 0.5h later after reaction 0.5h
Sample once, when it is 16.0~16.5% for NCO to detect isocyanide acid number, adds 4 parts of the hyper-branched polyester of step a preparation, and rises
Temperature is warming up to 70~80 DEG C to 50~60 DEG C when continuation reaction to isocyanide acid number is less than 1%, when isocyanide acid number cannot be measured,
Carry out the next step；
C, in b step reactor add 5 parts of butanone to be stirred, after dissolving completely, add 12 parts of N, N- dimethyl benzenes
Amine, is warmed up to 80 DEG C, 40 parts of 50% cis-butenedioic anhydride butanone solution of Deca, controls time for adding for 1h；After completion of dropping, often react 1h and open
Begin sampling detection system acid number, when system acid number is 10~11mgKOH/g, is cooled to 50 DEG C；Add 8 parts of NaOH neutralization reactions
0.5h, adds 100 parts of deionized waters, reduced vacuum to extract butanone out, and it is 40% newborn that agitation and filtration packaging is obtained a kind of solid content
White water-borne MDI modified poly ester light-cured resins.
Embodiment 2：
A, hyper-branched polyester are with reference to having step a in example 1；
B, in a kettle., adds 15 parts of MDI-80 and 0.08 part of dibutyl tin laurates, is warming up to 30~40 DEG C,
The lower 7 parts of 2-hydroxypropyl acrylate monomers of Deca of stirring, start sampling detection isocyanide acid number, take per 0.5h later after reaction 0.5h
Sample once, when it is 16.0~16.5% for NCO to detect isocyanide acid number, adds 3 parts of the hyper-branched polyester of step a preparation, and rises
Temperature is warming up to 70~80 DEG C to 50~60 DEG C when continuation reaction to isocyanide acid number is less than 1%, when isocyanide acid number cannot be measured,
Carry out the next step；
C, in b step reactor add 4 parts of butanone to be stirred, after dissolving completely, add 10 parts of N, N- dimethyl benzenes
Amine, is warmed up to 80 DEG C, 30 parts of 50% cis-butenedioic anhydride butanone solution of Deca, controls time for adding for 1h；After completion of dropping, often react 1h and open
Begin sampling detection system acid number, when system acid number is 10~11mgKOH/g, is cooled to 50 DEG C；Add 6 parts of NaOH neutralization reactions
0.5h, adds 70 parts of deionized waters, reduced vacuum to extract butanone out, and it is 40% milky white that agitation and filtration packaging is obtained a kind of solid content
Color aqueouss MDI modified poly ester light-cured resin.
Embodiment 3：
Aqueouss MDI modified poly ester light-cured resin obtained in the embodiment of the present invention is configured to aqueouss UV varnish, formula is such as
Under：60~65 parts of aqueouss MDI modified poly ester light-cured resin, 5 parts of light trigger, 0.2 part of defoamer, 0.3 part of substrate wetting agents,
0.2 part of levelling agent, benefit deionized water to 100；Comparative example aqueouss TDI modified poly ester light-cured resin makes aqueouss by above-mentioned formula
UV varnish, carries out film performance contrast test, film radiation curing 10s, test result such as 1 institute of table according to relevant national standard
Show.
Table 1：Film performance test result
Although the present invention has been explained in detail and has been cited embodiment, for one of ordinary skill in the art, show
So can as specified above and make various schemes, modification and change, should be construed as being included within the scope of claim.
Claims (2)
1. a kind of aqueouss MDI modified poly ester light-cured resin, it is characterised in that：By weight percentage, consisting of：It is hyperbranched
The acrylic monomerss 5~15% of polyester 1~3%, hydroxyl, MDI-80 10~20%, dibutyl tin laurate 0.02~
0.3%th, cis-butenedioic anhydride 15~30%, N, accelerine 8~15%, sodium hydroxide 5~10%, deionized water 60~100%；Institute
The hyper-branched polyester stated, by weight percentage, consisting of：2,2 1 dihydromethyl propionic acids 15~30%, trimethylolpropane
2~5%, p-methyl benzenesulfonic acid 0.1~0.5%；The acrylic monomerss of described hydroxyl are acrylic acid -2- hydroxyl ethyl esters, propylene
Acid -2- hydroxypropyl acrylates, acrylic acid -2- hydroxy butyl esters.
2. a kind of preparation method of aqueouss MDI modified poly ester light-cured resin as claimed in claim 1, it is characterised in that：Institute
Preparation method is stated, is comprised the steps：
A, in a kettle., adds 2,2 one dihydromethyl propionic acids and trimethylolpropane by formula ratio, is passed through nitrogen protection, rises
Temperature adds the catalyst p-methyl benzenesulfonic acid of formula ratio to 130 DEG C, and nitrogen is closed after insulation reaction 4h, after continuing reaction 2h, cold
But to 40 DEG C, hyper-branched polyester is obtained, it is standby；
B, in a kettle., adds MDI-80 and catalyst dibutyltin dilaurylate by formula ratio, is warming up to 30~40 DEG C,
The acrylic monomerss of the hydroxyl that the lower Deca of stirring is measured, start sampling detection isocyanide acid number, often later after reaction 0.5h
0.5h is sampled once, when the half that isocyanide acid number is initial value is detected, adds the hyperbranched poly of step a preparation by formula ratio
Ester, and 50~60 DEG C are warming up to, when continuation reaction to isocyanide acid number is less than 1%, 70~80 DEG C are warming up to, when isocyanide acid number cannot
When measuring, the next step is carried out；
C, in b step reactor the butanone for measuring is added to be dissolved, while the DMA of formula ratio is added,
80 DEG C are warmed up to, 50% cis-butenedioic anhydride butanone solution of Deca controls time for adding for 1h；After completion of dropping, often react 1h and start sampling
Detection system acid number, when half of the detection system acid number for initial value, is cooled to 50 DEG C；NaOH neutralization reaction 0.5h are added,
Deionized water, reduced vacuum is added to extract butanone out, agitation and filtration packaging is obtained the milky that a kind of solid content is 30~40%
Aqueouss MDI modified poly ester light-cured resin.
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| CN108641515B (en) * | 2018-05-28 | 2020-10-27 | 湖南松井新材料股份有限公司 | High-adhesion primer coating |
| CN110669202A (en) * | 2019-10-18 | 2020-01-10 | 南雄市沃太化工有限公司 | Light-curable aqueous hyperbranched resin and preparation method thereof |
| CN113698563A (en) * | 2021-08-05 | 2021-11-26 | 明光科迪新材料有限公司 | Thioxanthone polyurethane modified epoxy acrylate LED (light-emitting diode) photocuring resin |
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| CN105482060A (en) * | 2015-12-25 | 2016-04-13 | 华南理工大学 | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof |
| CN105646816A (en) * | 2016-01-27 | 2016-06-08 | 平顶山正植科技有限公司 | Preparing method for persistent viscosity waterborne polyurethane dispersoid |
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| CN105482060A (en) * | 2015-12-25 | 2016-04-13 | 华南理工大学 | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof |
| CN105646816A (en) * | 2016-01-27 | 2016-06-08 | 平顶山正植科技有限公司 | Preparing method for persistent viscosity waterborne polyurethane dispersoid |
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