A kind of preparation method of lightfast coating material
Technical field
The preparation method that the present invention relates to a kind of coating, particularly to a kind of performance preparation method close to solvent type light resistance acrylic resin coating.
Background technology
Being sprayed at external and internal wall, furniture, the coating on ironware surface and paint, all the time all directly or indirectly contacting with the mankind, poisonous, harmful coating also moment threatens the health of people.Field owing to using often contacts sunlight, and owing to containing a large amount of ultraviolet lights that colored objects is harmful, its wavelength about 290~460nm in sunray, these harmful ultraviolet lights, by redox chemically, make the change of coating generation color.
The acrylic resin of environment-friendly type is that disperse medium is replaced organic solvent by water, reduce the toxicity of acrylic resin, but the resinoid performance of gained water-and acrylate does not reach the performance of solvent-type acrylic esters resin, therefore it is limited to a certain extent in external and internal wall, furniture, the coating on ironware surface and the extensive use of paint.
The resinoid preparation of water-and acrylate needs add water soluble starter and emulsifying agent, these water soluble starters all can reduce the performance of acrylic resin, common water soluble starter is mainly persulfate, it is in the polymerization process of acrylic ester monomer, it is attached to the sulfite ion absorbed portion hydrone of polymer terminal, the seriality making acrylic resin institute film forming reduces, and reduces the mechanical property of acrylic resin.
Liposome is the self-assembly of lipid molecule (lipoid), is a kind of by the structure being coated with micro-aqueous phase in the middle of one or more lipid bilayer.Liposome can naturally occur, it is possible to synthetic.The bimolecular of different lipid compositions depends on various condition in aqueous phase and there is the change of " phase ", i.e. " phase transformation "." stiff " state of the cochain of phase transition temperature changes the motion to " flexible ", is improved the performance of acrylic resin by submissive strand.
Organic peroxy initiator is inexpensive and receive an acclaim with it, but the existence of impurity easily causes chain transfer reaction, and efficiency of initiation is greatly lowered, so that elicitation procedure poor reproducibility, causes unstable product quality.
Summary of the invention
It is desirable to provide the preparation method of a kind of lightfast coating material, technical problem to be solved: oil-soluble peroxide initiator is coated with by liposome, and photostabilized material is used in cladding, emulsifying agent that this cladding is polymerized as acrylic ester monomer and initiator, and select some compounds to suppress the chain transfer reaction owing to initiator causes, improve the service efficiency of initiator, the performance of prepared acrylic resin reaches or close to the performance of solvent-type acrylic esters resin, the light resistance of material also increases substantially.
Present invention employs techniques below scheme.
Technical scheme one
(1) take sphingomyelins 6g, peroxidating (2 ethyl hexanoic acid) tert-butyl ester 0.3g, pyridoxal 5-phosphate 0.2g, graphene oxide 0.02g, make it dissolve with 1,1-dichloroethanes 55ml, it is warmed up to 50 DEG C, stirring reaction 1h, add propionyl chloride 0.02g, stirring reaction 1h, forms liposome solutions;By liposome solutions on membrane evaporator, solvent is deviate from room temperature decompression distillation, forms liposomal body;
(2) in 250ml there-necked flask, water 60g, methacrylic acid 0.4g, above-mentioned (1) liposomal body 13g are added, reaction temperature is risen to 60 DEG C, mixing time 70min, add 2-hydroxypropyl acrylate 12.0g, adiphenine hydrochloride 0.3g and sodium borohydride 0.2g, emulsification times 60min, when temperature is raised to 70 DEG C of logical recirculation waters, insulation reaction 1h, add ammonia and adjust pH value 7, obtain lightfast coating material.
Technical scheme two
(1) take vincristine sulfate fat 6g, di-cyclohexylperoxy di-carbonate 0.2g, 4,4'-diphenyl-dimethanal 1.8g, CNT 0.07g, with 1,1-dichloroethanes 55ml makes it dissolve, and mix homogeneously is warmed up to 50 DEG C, stirring reaction 1h, add isobutyryl chloride 0.5g, stirring reaction 1h, form liposome solutions;By liposome solutions on membrane evaporator, solvent is deviate from room temperature decompression distillation, forms liposomal body;
(2) in 250ml there-necked flask, water 60g, methacrylic acid 0.4g, above-mentioned (1) liposomal body 16g are added, reaction temperature is risen to 60 DEG C, mixing time 70min, add hydroxyethyl methylacrylate 14.0g and meclofenoxane 0.3g, emulsification times 60min, when temperature is raised to 70 DEG C of logical recirculation waters, insulation reaction 2h, add ammonia and adjust pH value 7, obtain lightfast coating material.
The invention have the characteristics that:
(1) oil-soluble peroxidating class initiator is coated on the internal layer of liposome;
(2) utilize liposome to replace emulsifying agent used in traditional acrylic resin preparation, make the acrylic resin performance performance close to solvent type acrylic resin of aqueous;
(3) pyridoxal 5-phosphate, propionyl chloride, 4,4'-diphenyl-dimethanal, isobutyryl chloride, meclofenoxane etc. can reduce the impurity chain transfer reaction to peroxide initiator, improve the efficiency of initiator and make the stability of product quality improve, and improve water soluble acrylic acid esters resin performance so that it is close to organic solvent type acrylic resin.
(4) graphene oxide, CNT, tetradecenoic acid glyceride, Allantoin improve acrylic resin resistance to light of coating as photostabilized material.
Detailed description of the inventionThe present invention is further illustrated below in conjunction with example.
Example one
(1) sphingomyelins 6g, peroxidating (2 ethyl hexanoic acid) tert-butyl ester 0.3g, pyridoxal 5-phosphate 0.2g, graphene oxide 0.02g are taken, with 1,1-dichloroethanes 55ml makes it be dissolved in 100ml beaker, it is warmed up to 50 DEG C, stirring reaction 1h, add propionyl chloride 0.02g, stirring reaction 1h, form liposome solutions;By liposome solutions on membrane evaporator, solvent is deviate from room temperature decompression distillation, forms liposomal body;
(2) in 250ml there-necked flask, water 60g, methacrylic acid 0.4g, above-mentioned (1) liposomal body 13g are added, reaction temperature is risen to 60 DEG C, mixing time 70min, add 2-hydroxypropyl acrylate 12.0g, adiphenine hydrochloride 0.3g and sodium borohydride 0.2g, emulsification times 60min, when temperature is raised to 70 DEG C of logical recirculation waters, insulation reaction 1h, add ammonia and adjust pH value 7, obtain lightfast coating material.
Example two
(1) take vincristine sulfate fat 6g, di-cyclohexylperoxy di-carbonate 0.2g, 4,4'-diphenyl-dimethanal 1.8g, CNT 0.07g, with 1,1-dichloroethanes 55ml makes it be dissolved in 100ml beaker, and mix homogeneously is warmed up to 50 DEG C, stirring reaction 1h, add isobutyryl chloride 0.5g, stirring reaction 1h, form liposome solutions;By liposome solutions on membrane evaporator, solvent is deviate from room temperature decompression distillation, forms liposomal body;
(2) in 250ml there-necked flask, water 60g, methacrylic acid 0.4g, above-mentioned (1) liposomal body 16g are added, reaction temperature is risen to 60 DEG C, mixing time 70min, add hydroxyethyl methylacrylate 14.0g and meclofenoxane 0.3g, emulsification times 60min, when temperature is raised to 70 DEG C of logical recirculation waters, insulation reaction 2h, add ammonia and adjust pH value 7, obtain lightfast coating material.
Light resistance acrylic resin paint film prepared by example one to example two carries out performance test, and experimental data is as follows.
The gained film properties of table one acrylic resin
|
Market coating SB60 |
Example one |
Example two |
Elongation at break (%) |
160 |
150 |
145 |
Tensile strength (MPa) |
5.8 |
5.7 |
5.6 |
Abrasion resisting (level) |
4 |
3.5 |
4 |
Table one middle finger object detection method with reference to (Jiang Weiqi. leather finish physical and chemical inspection [M]. China Light Industry Press, 1999), coating gained film elongation at break of the present invention, tensile strength, abrasion resisting are close to solvent type acrylic resin.
For quantitative description acrylic resin resistance to light of coating energy, adopt spectrophotometer to detect, to obtain inverse difference △ E, describe the light resistance of acrylic resin.△ E represents color intensity of variation, and △ E is more big, and color change is more obvious.In general, △ E value is 0~1.5 slight change of genus;△ E value is that 1.5~3.0 genus can feel change;△ E value be 3.0~6.0 belong to significant changes (referring to Wang Fang, party's climax, Wang Liqin, the light degradation [J] of several organic historical relic's protection polymer coatings. Northwest University's journal, 2005,35 (5): 56 ~ 58).
The value of chromatism △ E change of acrylic resin paint film under the table two different irradiation under ultraviolet ray time
Time/min |
Market coating SB60 |
Example one |
Example two |
90 |
0.9 |
0.1 |
0.6 |
150 |
1.1 |
0.6 |
0.8 |
270 |
1.3 |
0.9 |
0.9 |
330 |
1.3 |
0.9 |
0.9 |
390 |
1.4 |
1.0 |
1.0 |
450 |
1.7 |
1.2 |
1.1 |
510 |
1.8 |
1.3 |
1.3 |
540 |
2.1 |
1.2 |
1.3 |
600 |
2.3 |
1.3 |
1.3 |
From table two it is found that example one to the acrylic resin film light resistance prepared by example two all in slight excursion, show good light resistance, and the light resistance acrylic resin coating on market be at more than 450min, belongs to and can feel change.