CN101497749B - Surface modified nano silicon dioxide and acrylic resin coating containing the same - Google Patents
Surface modified nano silicon dioxide and acrylic resin coating containing the same Download PDFInfo
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- CN101497749B CN101497749B CN2009100965348A CN200910096534A CN101497749B CN 101497749 B CN101497749 B CN 101497749B CN 2009100965348 A CN2009100965348 A CN 2009100965348A CN 200910096534 A CN200910096534 A CN 200910096534A CN 101497749 B CN101497749 B CN 101497749B
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Abstract
The invention discloses a nano-silicon dioxide which is functionalized by acrylic ester and modified on surface by perfluoro alkoxy, a method for preparing the nano-silicon dioxide, and an acrylic resin coating containing the nano-silicon dioxide. The acrylic resin coating containing the nano-silicon dioxide also contains single-functional acrylic ester, acrylic ester containing at least two acrylic ester groups, alcoholic solvent and evocating agent. The acrylic resin coating containing fluorine and silicon can be quickly solidified, and the coating film hereby formed has excellent oil resistance, water resistance, weather resistance, pollution resistance, surface hardness and surface gloss.
Description
Technical field
The fluoroacrylic resin coating that the present invention relates to surface modified nano silicon and contain this nano silicon.
Background technology
Acrylate resin/nanometer silica composite is the important composition of high-performance coating, and filming of forming thus has good hardness and scratch resistance.For making the organic components such as acrylate resin in nano silicon and the coating reach good consistency, earlier nano silicon is carried out surface chemical modification usually, as acrylic ester functionalized.The surface chemical modification of nano silicon normally utilizes esterification or the condensation reaction of its surperficial hydroxy functional group to carry out.For example, CN1978553 discloses nano silicon of surface grafting organic functional molecular and preparation method thereof.On the other hand, fluorine resin or have low surface energy, high thermostability and chemicalstability usually through the material after the fluorochemicals modification.But; Because the direct blend of fluorine resin or fluorochemicals and vinyl resin and nano silicon is difficult to effective realization; Therefore, in the prior art, the characteristic of fluorochemicals and the characteristic of nano silicon can not produce synergistic effect in the coating based on vinyl resin.
Summary of the invention
The present invention anchors to nano-silica surface through chemical process with perfluoro alkoxy group, and simultaneously the surface silicon alcoholic extract hydroxyl group of nano silicon is carried out acrylic ester functionalizedly, and a kind of novel surface modified manometer silicon dioxide is provided.
The present invention also provides the preparation method of above-mentioned surface modified nano silicon.
The present invention also provides a kind of siliceous fluoroacrylic resin coating; Promptly; Above-mentioned surface modified nano silicon is added in the acrylic resin paint; Make this coating have nano silicon and fluorine-containing organic group effect concurrently, give film good hardness, oil resistant water tolerance and resistance to soiling.Further, coating compatibility of the present invention can be adjusted according to actual needs.
A kind of surface modified nano silicon carries out acrylic ester functionalizedly making with the perfluoro alkoxy modified-reaction to the surface silicon alcoholic extract hydroxyl group of nano silicon through compd A and compd B;
Wherein,
The general structure of described compd A is:
In the formula: R
1Be H or CH
3
The general structure of described compd B is:
In the formula: X is S or NH
R
fGeneral structure be:
In the formula: n=1,2 or 3
Behind the modified-reaction, through being covalently bound to the R on the described surface modified nano silicon
fThe mol ratio of group and acrylate group is 1: 1～1: 20.Look compatible the situation of coating component and to the oil resistant water tolerance of filming and the different demands of surface hardness, this mol ratio can be done suitable adjustment.As require to film and have high Waterproofing/oilproofing performance and surface hardness, then can in the preparation process, suitably improve the feed ratio of compd B, make to be covalently bound to the R on the surface modified nano silicon
fThe relative quantity of group is higher; If but R
fThe relative quantity of group is too high, then possibly cause the consistency of surface modified nano silicon and acrylate resin coating too poor.
Prepare above-mentioned reaction synoptic diagram through acrylic ester functionalized and perfluoro alkoxy group surface modified nano silicon referring to accompanying drawing 1; Concrete preparation process is following: place container to mix successively nano silicon, organic solvent, water, compd A and compd B; Wherein, the weight ratio of nano silicon, compd A and compd B is (20～30): (5～15): (2～10); Adding hydrochloric acid soln again, to regulate pH value be 4～5, is warmed up to 70～80 ℃ and stirs down, reacts after 3～4 hours, cools off promptly to get the product jelly that is creamy white.
Wherein,
Choose commercially available nano silicon, preferably adopting grain diameter is the nano silicon of 5～25nm, possibly cause mixing inhomogeneous too small with surface-area because the particle of nano silicon is excessive.
Organic solvent is at least a in Virahol, terepthaloyl moietie, USP Kosher, the ethylene glycol monomethyl ether.
The general structure of compd A is:
In the formula: R
1Be H or CH
3
Compd A can directly adopt commercially available commodity, also can make through the number of chemical method of routine is synthetic, and one of concrete preparation scheme is listed below: adopt (methyl) allyl acrylate and alkoxyl silicone hydrogen to carry out addition reaction, with H
2PtCl
6/ i-PrOH is a catalyzer, is stopper with the 2,5 di tert butyl hydroquinone, is reflected at 50～60 ℃ and carries out.
The general structure of compd B is:
In the formula: X is S or NH
R
fGeneral structure be:
In the formula: n=1,2 or 3;
Compd B can be made according to following reaction formula by Compound C and Compound D:
Compound D Compound C compd B
R in the Compound C
fWith R in the compd B
fDefinition identical.X is identical with the definition of X in the compd B in the Compound D.
Among the present invention, Compound C is available from Zhejiang Juhua Group Co..
Compound D is 3-mercaptopropyl trimethoxysilane or 3-aminopropyl trimethoxysilane.Compound D also can use other organoalkoxysilane analogue to substitute, as: 3-mercaptopropyltriethoxysilane or 3-aminopropyl triethoxysilane etc.
The detailed process of preparation compd B is following:
Equimolar Compound C and Compound D are mixed and with little solvent (like anhydrous diethyl ether) dilution, slowly reacted 2-3 hour under the reflux conditions, and steaming desolventizes, and obtains compd B, and product is a colourless transparent liquid.
A kind of siliceous fluoroacrylic resin coating consists of: above-mentioned surface modified nano silicon of the present invention, single functionality (methyl) propenoate, the propenoate that contains at least 2 acrylate groups, alcoholic solvent and initiator.
In parts by weight, siliceous fluoroacrylic resin system component is:
2～20 parts of surface modified nano silicons of the present invention
20～80 parts of single functionality (methyl) propenoate
5～20 parts of propenoate that contain at least 2 acrylate groups
2～20 parts of alcoholic solvents
2～10 parts of initiators;
Preferably, siliceous fluoroacrylic resin system component is following: (in parts by weight)
5～15 parts of surface modified nano silicons of the present invention
40～80 parts of single functionality (methyl) propenoate
5～15 parts of propenoate that contain at least 2 acrylate groups
5～10 parts of alcoholic solvents
2～5 parts of initiators.
Among the present invention; Single functionality (methyl) propenoate is the main diluting effect that rises in system; It also plays a leading role to the dissolving of light trigger and to the snappiness of cured film; Be preferably at least a in (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) ethyl acrylate, (methyl) isodecyl acrylate, the single functionality aliphatic urethane acrylate (for example can select Gencure PUA550/565/569/5126/5127/5129 for use), further be preferably at least a in isodecyl acrylate, the single functionality aliphatic urethane acrylate (for example can select Gencure PUA569 for use).
Among the present invention; The propenoate that contains at least 2 acrylate groups is preferably the propenoate that contains 2 or 3 acrylate groups, as: at least a in tri (propylene glycol) diacrylate, Viscoat 295, bisphenol A epoxide resin diacrylate (for example can select EBECRYL 600, the EBECRYL 605 of Belgian UCB. S.A. (BE) Bruxelles Belgium for use), aromatic urethane diacrylate (for example can select the EBECRYL 210 of Belgian UCB. S.A. (BE) Bruxelles Belgium for use), aliphatic urethane diacrylate (for example can select the EBECRYL 270 of Belgian UCB. S.A. (BE) Bruxelles Belgium for use), the Viscoat 295; Further be preferably at least a in tri (propylene glycol) diacrylate, the Viscoat 295.
Among the present invention, alcoholic solvent is at least a in Virahol, terepthaloyl moietie, USP Kosher, the ethylene glycol monomethyl ether, and its content is looked consistency and the coating construction requirement of coating each component and decided.
Among the present invention; Initiator is general various commercially available initiator; The commercially available free radical photo-initiation of preferred employing; As: 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholinyl phenyl) butanone (Irgacure 369), 1-hydroxy-cyclohexyl phenyl ketone (Irgacure 184) or 2-hydroxy-2-methyl-1-phenyl-1-acetone (Darocur 1173), preferred Irgacure 184.Above initiator is Ciba production.
After nano silicon, single functionality acrylate monomer, the propenoate that contains at least 2 acrylate groups, alcoholic solvent and the initiator of above-mentioned surface-treated of the present invention mixed in proportion, use conventional method can obtain fluorine-containing siliceous acrylic resin paint of the present invention.
Fluorine-containing siliceous acrylic resin paint of the present invention can form behind heating, ultraviolet irradiation or electron beam irradiation fast setting has filming of excellent oil resistant water tolerance, resistance to soiling and surface hardness and surface of good glossiness.
Description of drawings
Fig. 1 is the reaction synoptic diagram of preparation surface modified nano silicon.Wherein, R
1Be H or CH
3X is S or NH; R
fGeneral structure is:
In the formula: n=1,2 or 3.
Embodiment
Below, specify content of the present invention through embodiment, but the present invention is not limited thereto.
Embodiment 1:
With 0.5 mole of molecular formula be:
Compound C (manufacturer: Zhejiang Juhua Group Co.) and 0.5 mole 3-mercaptopropyl trimethoxysilane (Compound D) be mixed in the round-bottomed flask; And with a small amount of anhydrous diethyl ether dilution; Slowly reacting 2 hours under the reflux conditions, steaming desolventizes, and obtains molecular formula to be:
Compd B, product is a colourless transparent liquid.
Count by weight; Be that (manufacturer: Zhejiang ten thousand scape Materials Co., Ltd) 23 parts, 21 parts of Virahols, 9 parts in water, 10 parts, 4 parts compd Bs that obtained by above-mentioned steps of 3-(methacryloxypropyl) propyl trimethoxy silicane (compd A) are put into there-necked flask for the silicon-dioxide of 5～25nm with particle diameter successively; Add dilute hydrochloric acid solution again and regulate pH=4～5; Stir down at 75 ℃, react after 3 hours, cooling; Obtain acrylic ester functionalized and perfluoro alkoxy surface modified nano silicon, the product jelly that is creamy white.
In parts by weight, get 5 parts of above-mentioned surface modified nano silicons, 40 parts of isodecyl acrylates, 30 parts of single functionality aliphatic urethane acrylates (PUA569), 15 parts of Viscoat 295s, 5 parts of Virahols, 5 parts of Irgacure 184.After above-mentioned component mixed, obtain siliceous fluoroacrylic resin coating.
This coating is coated on the dull and stereotyped slide glass coat-thickness 130-150 μ m, ultraviolet irradiation (wavelength 254nm, power 240mW/cm
2), irradiation time 20s forms siliceous fluoroacrylic resin and films.
Embodiment 2:
With 3-mercaptopropyl trimethoxysilane (Compound D) in 3-aminopropyl triethoxysilane (Compound D) alternate embodiment 1, other condition is all identical with embodiment 1, obtains molecular formula to be:
Compd B and corresponding acrylic ester functionalized and perfluoro alkoxy surface modified nano silicon.
According to preparing siliceous fluoroacrylic resin coating and illumination curing, form siliceous fluoroacrylic resin and film with embodiment 1 identical method.
Embodiment 3:
With 3-mercaptopropyl trimethoxysilane (Compound D) in 3-aminopropyl trimethoxysilane (Compound D) alternate embodiment 1, other condition is all identical with embodiment 1, prepares molecular formula to be:
Compd B and corresponding acrylic ester functionalized and perfluoro alkoxy surface modified nano silicon.
According to preparing siliceous fluoroacrylic resin coating and illumination curing, form siliceous fluoroacrylic resin and film with embodiment 1 identical method.
Embodiment 4:
With 0.5 mole molecular formula do
Compound C (manufacturer: Zhejiang Juhua Group Co.) and 0.5 mole 3-mercaptopropyl trimethoxysilane (Compound D) be mixed in the round-bottomed flask; And with a small amount of anhydrous diethyl ether dilution; Slowly reacting 2 hours under the reflux conditions, steaming desolventizes, and obtains molecular formula to be:
Compd B, product is a colourless transparent liquid.
Count by weight; Be that (manufacturer: Zhejiang ten thousand scape Materials Co., Ltd) 20 parts, 21 parts of Virahols, 9 parts in water, 12 parts and 5 parts compd Bs that obtained by abovementioned steps of 3-(methacryloxypropyl) propyl trimethoxy silicane (compd A) are put into there-necked flask for the silicon-dioxide of 5～25nm with particle diameter successively; Add dilute hydrochloric acid solution again and regulate pH=4～5; Stir down at 75 ℃, react after 3 hours, cooling; Obtain acrylic ester functionalized and perfluoro alkoxy surface modified nano silicon, the product jelly that is creamy white.
According to preparing siliceous fluoroacrylic resin coating and illumination curing, form siliceous fluoroacrylic resin and film with embodiment 1 identical method.
Embodiment 5:
According to preparing acrylic ester functionalized and the perfluoro alkoxy surface modified nano silicon with embodiment 4 identical methods.
In parts by weight, get 10 parts of resulting surface modified nano silicons, 40 parts of isodecyl acrylates, 30 parts of single functionality aliphatic urethane acrylates (PUA569), 10 parts of aliphatic urethane diacrylates (EBECRYL 270), 5 parts of Viscoat 295s, 5 parts of Virahols, 5 parts of Irgacure 184.After above-mentioned component mixed, obtain siliceous fluoroacrylic resin coating.
This coating is coated on the sheet glass coat-thickness 130～150 μ m, ultraviolet irradiation (wavelength 254nm, power 240mW/cm
2), irradiation time 20s forms siliceous fluoroacrylic resin and films.
Embodiment 6:
According to preparing acrylic ester functionalized and the perfluoro alkoxy surface modified nano silicon with embodiment 4 identical methods.
In parts by weight, get 5 parts of resulting surface modified nano silicons, 40 parts of isodecyl acrylates, 35 parts of single functionality aliphatic urethane acrylates (PUA569), 10 parts of aliphatic urethane diacrylates (EBECRYL 270), 5 parts of tri (propylene glycol) diacrylates, 5 parts of Virahols, 5 parts of Irgacure 184.After above-mentioned component mixed, obtain siliceous fluoroacrylic resin coating.
This coating is coated on the sheet glass coat-thickness 130～150 μ m, ultraviolet irradiation (wavelength 254nm, power 240mW/cm
2), irradiation time 20s forms siliceous fluoroacrylic resin and films.
According to following method the performance of filming that coating of the present invention forms is tested.
Water tolerance: water characterizes at the contact angle of film coated surface, and contact angle determination is carried out on the CTS-200 contact angle instrument.
Solvent resistance: have 10 * 2.5cm slide glass of filming to immerse N one side, at room temperature soak 1 hour in dinethylformamide (DMF) solvent after, observe changing conditions such as coating damage, surface luster.Pass judgment on based on criterion: A) no abnormal; B) surface gloss descends; C) swelling of paint coating.
Hardness: characterize with pencil hardness, based on GB/T6739-1996
The result of following table 1 for according to the method described above embodiment 1～6 being carried out performance test, the result shows: this is filmed and has excellent oil resistant water tolerance and surface hardness.
Table 1
| Pencil hardness | Water contact angle (°) | Solvent resistance (DMF) | |
| Embodiment 1 | 4H | 102 | ?A |
| Embodiment 2 | 4H | 100 | ?B |
| Embodiment 3 | 4H | 98 | ?B |
| Embodiment 4 | 4H | 90 | ?B |
| Embodiment 5 | 4H | 115 | ?A |
| Embodiment 6 | 3H | 90 | ?B |
Claims (10)
1. surface modified nano silicon is characterized in that: through compd A and compd B the surface silicon alcoholic extract hydroxyl group of nano silicon is carried out acrylic ester functionalizedly making with the perfluoro alkoxy modified-reaction; Wherein,
The general structure of described compd A is:
In the formula: R
1Be H or CH
3
The general structure of described compd B is:
In the formula: X is S or NH
R
fGeneral structure be:
In the formula: n=1,2 or 3
R on the described surface modified nano silicon
fThe mol ratio of group and acrylate group is 1: 1～1: 20.
2. the preparation method of surface modified nano silicon as claimed in claim 1 comprises:
Place container to mix successively nano silicon, organic solvent, water, compd A and compd B, adding hydrochloric acid soln adjusting pH value again is 4～5, is warmed up to 70～80 ℃ and stirs down, reacts after 3～4 hours, and cooling promptly gets; Wherein,
The general structure of described compd A is:
In the formula: R
1Be H or CH
3
The general structure of described compd B is:
In the formula: X is S or NH
R
fGeneral structure be:
In the formula: n=1,2 or 3
The weight ratio of described nano silicon, compd A and compd B is (20～30): (5～15): (2～10);
Described organic solvent is at least a in Virahol, terepthaloyl moietie, USP Kosher, the ethylene glycol monomethyl ether.
3. preparation method as claimed in claim 2 is characterized in that: the grain diameter of described nano silicon is 5～25nm.
4. siliceous fluoroacrylic resin coating is characterized in that: composed of the following components, and in parts by weight,
5. siliceous fluoroacrylic resin coating according to claim 4 is characterized in that: described single functionality (methyl) propenoate is at least a in (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) ethyl acrylate, (methyl) isodecyl acrylate, the single functionality aliphatic urethane acrylate.
6. siliceous fluoroacrylic resin coating according to claim 5 is characterized in that: described single functionality (methyl) propenoate is at least a in isodecyl acrylate, the single functionality aliphatic urethane acrylate.
7. siliceous fluoroacrylic resin coating according to claim 4 is characterized in that: the described propenoate that contains at least 2 acrylate groups is the propenoate that contains 2 or 3 acrylate groups.
8. siliceous fluoroacrylic resin coating according to claim 7 is characterized in that: the described propenoate that contains at least 2 acrylate groups is at least a in tri (propylene glycol) diacrylate, bisphenol A epoxide resin diacrylate, aromatic urethane diacrylate, aliphatic urethane diacrylate, the Viscoat 295.
9. siliceous fluoroacrylic resin coating according to claim 8 is characterized in that: the described propenoate that contains at least 2 acrylate groups is at least a in tri (propylene glycol) diacrylate, the Viscoat 295.
10. siliceous fluoroacrylic resin coating according to claim 4 is characterized in that: described alcoholic solvent is at least a in Virahol, terepthaloyl moietie, USP Kosher, the ethylene glycol monomethyl ether.
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