CN100348637C - High-gloss and high temperature resistant silicon-acrylic polyurethane paint and method for preparing same - Google Patents
High-gloss and high temperature resistant silicon-acrylic polyurethane paint and method for preparing same Download PDFInfo
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- CN100348637C CN100348637C CNB2004100674087A CN200410067408A CN100348637C CN 100348637 C CN100348637 C CN 100348637C CN B2004100674087 A CNB2004100674087 A CN B2004100674087A CN 200410067408 A CN200410067408 A CN 200410067408A CN 100348637 C CN100348637 C CN 100348637C
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Abstract
The present invention relates to high-gloss and high temperature resistant silicon-acrylic polyurethane paint and a preparation method thereof. The present invention adopts octamethylcyclotetrasiloxane (D4) and vinylcyclotetrasiloxane (D4 <v>) as a monomer and hydroxy silicone oil as an end-capping agent; ring opening polymerization is carried out by catalysis of alkali catalyst to obtain hydroyl-terminated polydimethyl siloxane with ethenyl; then, free radical graft copolymerization is carried out among the obtained polydimethyl siloxane, methyl methacrylate, n-butyl acrylate and acrylate with hydroxy to obtain organosilicon acrylate resin with hydroxy; the organosilicon acrylate resin is then mixed with HDI trimer to obtain the high-gloss and high temperature resistant silicon-acrylic polyurethane paint of the present invention. The paint has the advantages of higher surface gloss, fine heat resistance and fine weatherability.
Description
Technical field
The present invention relates to a kind of high-gloss and high temperature resistant silicon-acrylic polyurethane paint and preparation method thereof.
Background technology
The acrylate polyurethane coating is an a kind of decorative surface and wear resistance coating preferably, uses comparatively general in building decoration and Industrial products.This is a kind of two-component coating, and a component is the polypropylene provided with hydroxyl group acid ester resin, and another component is the isocyanic ester performed polymer.From practical effect, the thermotolerance when polyacrylic ester is used as coating is not high.And the present employing tolylene diisocyanate (TDI) mostly of isocyanic ester performed polymer is a raw material, and easy brightness reversion variable color during as coating influences decorative effect.
Organosilicon polymer is that a class formation is special, half organic polymer of excellent performance.Its molecular backbone chain is the inorganic structure of Si-O key, and side group is an organic group, therefore has the dual performance of mineral compound and organic polymer concurrently.If any good thermotolerance, winter hardiness, water tolerance, weathering resistance etc., has toughness, snappiness and the plasticity-of organic polymer material simultaneously.In aromatic solvent and ketones solvent, good solubility is arranged.But the molecular chain of organosilicon polymer is submissiveer, and intermolecular reactive force is less, so physical strength is lower, and is relatively poor with the adhesivity of other object.
In recent years, more to the research of silicone-modified polyacrylate resin (abbreviation organosilicon acrylic resin), purpose is to improve the thermotolerance and the weathering resistance of polyacrylate resin.
With the silicone-modified polyacrylate resin random copolymerization and two kinds of method of modifying of graft copolymerization are arranged.Random copolymerization is about to carry out copolymerization after organosilane monomer and the acrylate monomer mixing.This method technology is simple, is applied in actual production.But in polymerization process, because two kinds of monomeric polymerization mechanism are all different with unexpectedly poly-rate, the multipolymer that obtains is actually two kinds of mixture of polymers, no chemical bond combination between the molecular chain.Because both chemical property differ greatly, two interphase interaction power are little, are easy to generate to be separated.Again because polysiloxane has very low surface energy, be easy to surface transport, cause it easily in the obvious enrichment of polymer surfaces, thereby destroyed the continuity of acrylic ester polymer phase, therefore, the organosilicon acrylic resin poor-performing that the random copolymerization modification obtains, the physical strength of filming of prepared coating is also lower.
Grafting, copolymerization and modification then is that the molecular chain with two kinds of polymkeric substance of organosilicon polymer and polyacrylate resin is connected by chemical bond.It is compatible that two kinds of polymkeric substance are forced to a certain extent, suppressed migration and the two alternate phase separations of polysiloxane segment to polymer surfaces to a great extent, and the over-all properties of polymkeric substance improves greatly.The preparation method of graft copolymerization organosilicon acrylic resin has two classes at present.One class is the polyacrylate resin that has hydroxyl or carboxyl on the first synthetic molecules chain, and the silicone resin of synthetic simultaneously terminal hydroxy group connects into graft copolymer with both reactions by functional group then.Another kind of is the organosilicon polymer of first anamorphic zone vinyl, by radical polymerization acrylate monomer is aggregated to then and forms graft copolymer on the organosilicon polymer.These two kinds of methods respectively have relative merits, and use is all arranged at present.
The present invention adopts the organosilicon polymer of first anamorphic zone vinyl, by radical polymerization acrylate monomer is aggregated to the method that forms graft copolymer on the organosilicon polymer then and prepares the organic silicon acrylic ester resin, at last with not containing phenyl ring, hexamethylene-diisocyanate (HDI) tripolymer that is not easy yellowing replaces traditional TDI tripolymer and organic silicon acrylic ester mixed with resin to prepare coating, has improved surface hardness, gloss and the thermotolerance of coating greatly.
Summary of the invention
The purpose of this invention is to provide a kind of high-gloss and high temperature resistant silicon-acrylic polyurethane paint.
Another object of the present invention provides the method for this coating of preparation.
In a first aspect of the present invention, high-gloss and high temperature resistant silicon-acrylic polyurethane paint of the present invention, by linking agent and organic silicon acrylic ester resin according to the hydroxyl mole number [HO] of the isocyano mole number [NCO] of linking agent and organic silicon acrylic ester resin than being to form in 0.8: 1～1: 1.4, wherein, the organic silicon acrylic ester resin is a polydimethylsiloxane 100 by component and weight proportion, methyl methacrylate 80～90, butyl acrylate 40～60, hydroxy acryl acid ester 5～10 carries out free radical grafting copolymerization and obtains, the employing weight proportion is 120～200 toluene during graft copolymerization, 120～200 N-BUTYL ACETATE is a mixed solvent, 0.5～1.5 initiator; The component and the weight proportion that prepare described polydimethylsiloxane are octamethylcyclotetrasiloxane (D
4) 100, vinyl cyclotetrasiloxane (D
4 v) 0.25～0.30, viscosity is the hydroxy silicon oil 0.05～0.1 of 40～60mPas, basic catalyst 0.3～0.5.
Better, having vinyl group pendant and terminal hydroxy group in the polydimethylsiloxane molecular structure of the present invention, this vinyl group pendant is used for and graft polymerization of acrylic ester, and this terminal hydroxy group is used for and the linking agent cross-linking reaction.Further, polydimethylsiloxane molecular weight of the present invention is 200,000～250,000.
The basic catalyst that uses among the present invention can be the known basic catalysts of those skilled in the art, is more preferably the Tetramethylammonium hydroxide silicon alkoxide.
Better, the initiator that uses among the present invention is Diisopropyl azodicarboxylate or dibenzoyl peroxide.
Better, have hydroxyl on the organic silicon acrylic ester resin side chain of the present invention, can with the linking agent cross-linking reaction.
Better, linking agent of the present invention is HDI tripolymer (hexamethylene-diisocyanate).
Better, hydroxy acryl acid ester of the present invention is senecioate-hydroxyl ethyl ester or methacrylic acid-beta-hydroxy ethyl ester.
High-gloss and high temperature resistant silicon-acrylic polyurethane paint time limit of service of the present invention is 8 hours.
In a second aspect of the present invention, high-gloss and high temperature resistant silicon-acrylic polyurethane paint of the present invention carries out in two steps,
The first step: the preparation of organic silicon acrylic ester resin: with octamethylcyclotetrasiloxane (D
4), vinyl cyclotetrasiloxane (D
4 v), hydroxy silicon oil and catalyzer Tetramethylammonium hydroxide silicon alkoxide weigh by prescription, adds in the three-necked flask, vacuumized 0.5～1 hour under 50～60 ℃, logical then nitrogen is warming up to 80～90 ℃, reacts 1～3 hour.Be warming up to 100～120 ℃, continue reaction 1～3 hour.Be warming up to more than 150～180 ℃ again and vacuumized 0.5～2 hour, gained polydimethylsiloxane molecular weight is 200,000～250,000, it is 0.5cm left and right sides particle that above-mentioned synthetic polydimethylsiloxane is cut into diameter, place three-necked flask, toluene and N-BUTYL ACETATE that adding is weighed by prescription, be stirred to described polydimethylsiloxane and all dissolve, be heated to 80 ℃; Methyl methacrylate, butyl acrylate and hydroxy acryl acid ester are mixed, and adding dibenzoyl peroxide, fully after the dissolving, slowly be added dropwise in the polydimethylsiloxane solution, the control dropping time is about 3 hours, again in 85 ℃ of insulations 1 hour, add remaining toluene and N-BUTYL ACETATE mixture again after adding, the after-filtration discharging stirs;
Second step: the preparation of high-gloss and high temperature resistant silicon-acrylic polyurethane paint: the hydroxyl mole number [HO] of measuring the organic silicon acrylic ester resin; And measure the trimerical isocyano mole number of HDI [NCO], with [NCO]: the ratio of [HO]=0.8: 1～1: 1.4 is mixed organic silicon acrylic ester with the HDI tripolymer, promptly get high-gloss and high temperature resistant silicon-acrylic polyurethane paint of the present invention.
The present invention has following advantage:
1. because organic silicon acrylic ester resin of the present invention has adopted thermotolerance and had excellent weather resistance in preparation organosilicon polymer, and form graft copolymer with acrylic ester copolymer, therefore thermotolerance and the weathering resistance with its prepared coating improves greatly, life-time service temperature＞150 ℃, short-term use temperature＞200 ℃, weathering resistance＞1000 hour.
2. because organic silicon acrylic ester resin of the present invention has adopted terminal hydroxy group organosilicon polymer and acrylate-functional monomer in preparation---senecioate-hydroxyl ethyl ester, contain hydroxyl in the resulting organic silicon acrylic ester resin, can carry out crosslinking reaction with the HDI tripolymer, so prepared coating has the good mechanical performance.
3. because coating of the present invention adopts the good HDI tripolymer of surface property as linking agent, the surface hardness height of gained coating, good luster (60 ° of gloss are greater than 70%) is difficult for yellowing.
Embodiment
Be described in further detail below in conjunction with example, the example of being lifted below being to be understood that does not comprise all the elements of the present invention just in order to explain the present invention:
Embodiment 1
Table 1 (polydimethylsiloxane preparation prescription) is consulted in the preparation of polydimethylsiloxane.At first, the polydimethylsiloxane prescription 1-1 by table 1 prepares polydimethylsiloxane.
Raw material in the prescription added be equipped with in the three-necked flask of agitator and condenser, vacuumized 0.5 hour under 60 ℃, logical then nitrogen is warming up to 80 ℃, reacts 3 hours.Be warming up to 110 ℃, continue reaction 3 hours.Be warming up to 180 ℃ and vacuumized 0.5 hour again.The molecular weight of products therefrom is 220,000.
Embodiment 2
Polydimethylsiloxane prescription 1-2 by table 1 prepares polydimethylsiloxane.The preparation method is identical with embodiment 1.The molecular weight of products therefrom is 23.5 ten thousand.
Embodiment 3
Polydimethylsiloxane prescription 1-3 by table 1 prepares polydimethylsiloxane.
Raw material in the prescription added be equipped with in the three-necked flask of agitator and condenser, vacuumized 0.5 hour under 60 ℃, logical then nitrogen is warming up to 90 ℃, reacts 3 hours.Be warming up to 120 ℃, continue reaction 2 hours.Be warming up to 150 ℃ and vacuumized 2.0 hours again.The molecular weight of products therefrom is 250,000.
Embodiment 4
Table 2 (organic silicon acrylic ester resins prescription) is consulted in the preparation of organic silicon acrylic ester resin.At first, the organic silicon acrylic ester resin formula 2-1 by table 2 prepares the organic silicon acrylic ester resin.
It is particle about 0.5cm that polydimethylsiloxane is cut into diameter, places the three-necked flask that agitator and condenser are housed, and adds the mixture of 100 parts of toluene and 100 parts of N-BUTYL ACETATEs, stirs more than 24 hours, all dissolves to polydimethylsiloxane.Be heated to 80 ℃.Methyl methacrylate, butyl acrylate and senecioate-hydroxyl ethyl ester is mixed, and adding dibenzoyl peroxide, fully after the dissolving, slowly be added dropwise in the polydimethylsiloxane solution, the control dropping time is about 3 hours, again in 85 ℃ of insulations 1 hour, add remaining toluene and N-BUTYL ACETATE mixture again after adding, the after-filtration discharging stirs.
Embodiment 5
Organic silicon acrylic ester resin formula 2-2 by table 2 prepares the organic silicon acrylic ester resin.The preparation method is identical with embodiment 4.
Embodiment 6
Organic silicon acrylic ester resin formula 2-3 by table 2 prepares the organic silicon acrylic ester resin.The preparation method is identical with embodiment 4.
Embodiment 7
Organic silicon acrylic ester resin formula 2-4 by table 2 prepares the organic silicon acrylic ester resin.The preparation method is identical with embodiment 4.
Embodiment 8
The organic silicon acrylic ester resin of embodiment 4～7 preparations is mixed with the HDI tripolymer, and ratio is all by [NCO]: [HO]=1: 1.2, promptly get high-gloss and high temperature resistant silicon-acrylic polyurethane paint of the present invention.Prepare in back 8 hours its brushing model, test performance at coating.The performance of four kinds of coating of gained is referring to table 3.
Table 1 polydimethylsiloxane preparation prescription (is 100 weight parts in octamethylcyclotetrasiloxane)
| Material name | Prescription 1-1 | Prescription 1-2 | Prescription 1-3 |
| Octamethylcyclotetrasiloxane (D 4) | 100 | 100 | 100 |
| Vinyl cyclotetrasiloxane (D 4 v) | 0.25 | 0.28 | 0.30 |
| Hydroxy silicon oil, viscosity 40～60mPas | 0.05 | 0.08 | 0.1 |
| The Tetramethylammonium hydroxide silicon alkoxide | 0.5 | 0.4 | 0.3 |
Table 2 organic silicon acrylic ester resins prescription (is 100 weight parts in polydimethylsiloxane)
| Material name | Prescription 2-1 | Prescription 2-2 | Prescription 2-3 | Prescription 2-4 |
| Polydimethylsiloxane (prescription 1-1) | 100 | 100 | - | - |
| Polydimethylsiloxane (prescription 1-2) | - | - | 100 | - |
| Polydimethylsiloxane (prescription 1-3) | - | - | - | 100 |
| Methyl methacrylate | 80 | 90 | 80 | 90 |
| Butyl acrylate | 50 | 40 | 60 | 40 |
| Senecioate-hydroxyl ethyl ester | 5 | 10 | 5 | - |
| Methacrylic acid-beta-hydroxy ethyl ester | - | - | - | 5.6 |
| Dibenzoyl peroxide | 0.5 | 1.5 | 1.0 | 1.0 |
| Toluene | 200 | 140 | 140 | 120 |
| N-BUTYL ACETATE | 120 | 180 | 180 | 200 |
The performance of table 3 high-gloss and high temperature resistant silicon-acrylic polyurethane paint of the present invention
| Test item | Prescription 1 | Prescription 2 | Prescription 3 | Prescription 4 |
| Outward appearance | Faint yellow clear liquid | Faint yellow clear liquid | Faint yellow clear liquid | Faint yellow clear liquid |
| Sticking power (cross-hatching)/% | 100 | 100 | 100 | 100 |
| Gloss (60 °) | 72 | 74 | 75 | 75 |
| Surface hardness (fork method) | 0.74 | 0.75 | 0.78 | 0.74 |
| The loss of gloss rate (150 ℃, 100h)/% | 4.1 | 4.5 | 3.9 | 4.1 |
| Rate of weight loss (150 ℃, 100h)/% | 14.5 | 13.8 | 14.2 | 14.0 |
| Coating weatherability (h)＞ | 1000 | 1000 | 1000 | 1000 |
By table 3 as seen, the high-gloss and high temperature resistant silicon-acrylic polyurethane paint by method preparation of the present invention has the described advantage of this specification sheets really.
Claims (10)
1. high-gloss and high temperature resistant silicon-acrylic polyurethane paint is to be made up of in 0.8: 1～1: 1.4 linking agent and organic silicon acrylic ester resin according to the hydroxyl mole ratio of the isocyano mole number of linking agent and organic silicon acrylic ester resin,
Wherein, the organic silicon acrylic ester resin is a polydimethylsiloxane 100 by component and weight proportion, methyl methacrylate 80～90, butyl acrylate 40～60, hydroxy acryl acid ester 5～10 carry out free radical grafting copolymerization and obtain, adopting weight proportion during graft copolymerization is that 120～200 toluene, 120～200 N-BUTYL ACETATE are mixed solvent, 0.5～1.5 initiator;
Preparing the component of described polydimethylsiloxane and weight proportion and be octamethylcyclotetrasiloxane 100, vinyl cyclotetrasiloxane 0.25～0.30, viscosity is the hydroxy silicon oil 0.05～0.1 of 40～60mPas, basic catalyst 0.3～0.5, each component is weighed by prescription during preparation, add in the container, vacuumize, lead to nitrogen, be warming up to 80～90 ℃, reacted 1～3 hour, be warming up to 100～120 ℃, continuation was reacted 1～3 hour, was warming up to more than 150～180 ℃ again and vacuumizes to get final product in 0.5～2 hour.
2. high-gloss and high temperature resistant silicon-acrylic polyurethane paint according to claim 1, it is characterized in that: have vinyl group pendant and terminal hydroxy group in the described polydimethylsiloxane molecular structure, this vinyl group pendant is used for and graft polymerization of acrylic ester, and this terminal hydroxy group is used for and the linking agent cross-linking reaction.
3. high-gloss and high temperature resistant silicon-acrylic polyurethane paint according to claim 2 is characterized in that: described polydimethylsiloxane molecular weight is 200,000～250,000.
4. high-gloss and high temperature resistant silicon-acrylic polyurethane paint according to claim 3 is characterized in that: described basic catalyst is the Tetramethylammonium hydroxide silicon alkoxide.
5. high-gloss and high temperature resistant silicon-acrylic polyurethane paint according to claim 4 is characterized in that: described initiator is Diisopropyl azodicarboxylate or dibenzoyl peroxide.
6. high-gloss and high temperature resistant silicon-acrylic polyurethane paint according to claim 5 is characterized in that: have hydroxyl on the described organic silicon acrylic ester resin side chain, can with the linking agent cross-linking reaction.
7. high-gloss and high temperature resistant silicon-acrylic polyurethane paint according to claim 6 is characterized in that: described linking agent is the hexamethylene-diisocyanate tripolymer.
8. high-gloss and high temperature resistant silicon-acrylic polyurethane paint according to claim 7 is characterized in that: described hydroxy acryl acid ester is senecioate-hydroxyl ethyl ester or methacrylic acid-beta-hydroxy ethyl ester.
9. high-gloss and high temperature resistant silicon-acrylic polyurethane paint according to claim 8 is characterized in that: its time limit of service is 8 hours.
10. the preparation method of the described high-gloss and high temperature resistant silicon-acrylic polyurethane paint of claim 1 comprises following two steps:
The first step: the preparation of organic silicon acrylic ester resin: with octamethylcyclotetrasiloxane, the vinyl cyclotetrasiloxane, hydroxy silicon oil and catalyzer Tetramethylammonium hydroxide silicon alkoxide are weighed by prescription, add in the three-necked flask, vacuumize, logical nitrogen, be warming up to 80～90 ℃, reacted 1～3 hour, be warming up to 100～120 ℃, continue reaction 1～3 hour, be warming up to more than 150～180 ℃ again and vacuumized 0.5～2 hour, above-mentioned synthetic polydimethylsiloxane is cut into particle, place three-necked flask, add part toluene and N-BUTYL ACETATE, extremely described polydimethylsiloxane all dissolves, and stirs simultaneously, is heated to 80 ℃; Methyl methacrylate, butyl acrylate and hydroxy acryl acid ester are mixed, and adding dibenzoyl peroxide, fully after the dissolving, slowly be added dropwise in the polydimethylsiloxane solution, the control dropping time is about 3 hours, again in 85 ℃ of insulations 1 hour, add remaining toluene and N-BUTYL ACETATE again after adding, the after-filtration discharging stirs;
Second step: the preparation of high-gloss and high temperature resistant silicon-acrylic polyurethane paint: the hydroxyl mole number of measuring the organic silicon acrylic ester resin; And the trimerical isocyano mole number of mensuration hexamethylene-diisocyanate, with the trimerical isocyano mole number of hexamethylene-diisocyanate: the ratio of the hydroxyl mole number of organic silicon acrylic ester resin=0.8: 1～1: 1.4 is mixed organic silicon acrylic ester with the hexamethylene-diisocyanate tripolymer, promptly get high-gloss and high temperature resistant silicon-acrylic polyurethane paint.
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