CN104059518A - Environment-friendly high-performance methyl methacrylate self-leveling coating, preparation method and application thereof - Google Patents
Environment-friendly high-performance methyl methacrylate self-leveling coating, preparation method and application thereof Download PDFInfo
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- CN104059518A CN104059518A CN201410013368.1A CN201410013368A CN104059518A CN 104059518 A CN104059518 A CN 104059518A CN 201410013368 A CN201410013368 A CN 201410013368A CN 104059518 A CN104059518 A CN 104059518A
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Abstract
The invention provides an environment-friendly high-performance methyl methacrylate self-leveling coating which includes an A component and a B component with a mass ratio of the A component to the B component being 1:1. The A component includes following components, by weight, 30-50 parts of a polyurethane prepolymer, 40-60 parts of an acrylic ester monomer, 0.01-0.05 parts of a polymerization inhibitor, 0.1-0.5 parts of a promoter and 0.3-1 part of a deoxidant; the B component includes following components, by weight, 30-50 parts of an polyurethane prepolymer, 40-60 parts of an acrylic ester monomer, 1-3 parts of an oxidizing agent and 0.01-0.05 parts of a polymerization inhibitor. The coating is simple in preparation technology and is mild in reaction conditions. Raw materials of the coating are easy to obtain. The coating is low in cost, is convenient to use, is high in wear resistance, flexibility, anti-permeability and is self-leveling. Convenience and intelligence in construction of the coating are improved. The coating is an excellent terrace material. Meanwhile, pollution of a solvent-type waterproof coating to the environment can be avoided.
Description
Technical field
The invention belongs to building material field, particularly a kind of environment-friendly type high performance methyl methacrylate self-leveling coating, also relates to the preparation method of this coating and the application in buildings waterproof.
Background technology
Along with the continuous reinforcement of energy-saving and emission-reduction and building environmental consciousness, environment-friendly type building waterproof paint has become the development trend that present material of construction is new, and research and development environment-friendly type novel material becomes the new direction of material of construction research.Meanwhile, along with the fresh target during national 11th Five-Year, new demand, high-speed railway, motorway and airport construction become the main project of nation-building, and this has just proposed very high requirement too to buildings waterproof.
Patent 102604507A has prepared a kind of polymethylmethacrylate composite coating, adopts reductive agent capsule to realize single-component packing, but has brought to packing instructions high (logical shielding gas) drawbacks such as condition of storage strict (isolation steam, moisture).
Patent 102140266A polymethylmethacrylawaterproof waterproof paint and preparation method thereof adopts polymethyl methacrylate as molding material as starting material, and 70-90 ℃ of reaction 1-6 hour, has brought energy consumption large, the defect of long reaction time.
Number of patent application CN101805532A invents a kind of bi-component methyl methacrylate waterproof paint, and it adopts the fillers such as aluminium hydroxide, barium sulfate, zinc oxide, is intended to increase the wear resistance of coating; Yet because needs increase multiple filler, the coating making can cause filling settlement in storage process, thereby have influence on stability in storage and the quality of coating.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, the object of the invention is to
Technical scheme: a kind of environment-friendly type high performance methyl methacrylate self-leveling coating provided by the invention, comprises that mass ratio is A component and the B component of 1:1; Described A component comprises the component of following weight part: polyurethane prepolymers 30-50 part, acrylic ester monomer 40-60 part, stopper 0.01-0.05 part, promotor 0.1-0.5 part, oxygen scavenger 0.3-1 part; Described B component comprises the component of following weight part: polyurethane prepolymers 30-50 part, acrylic ester monomer 40-60 part, oxygenant 1-3 part, stopper 0.01-0.05 part.
As preferably, described polyurethane prepolymers adopts following methods to make: after polyether glycol or polyester polyol and isocyanates substance reaction, then react with unsaturated acid hydroxyl Ester, obtain.
As further preferred, the mol ratio of described polyether glycol or polyester polyol, isocyanates material, unsaturated acid hydroxyl Ester is (1-5): (2-10): (1-10); The functionality of described polyether glycol is 2 or 3, and molecular weight is 2000-3000; The functionality of described polyester polyol is 2 or 3, and molecular weight is 2000-3000; Described isocyanates material is diphenylmethanediisocyanate, isophorone diisocyanate or tolylene diisocyanate; Described unsaturated acid hydroxyl Ester is Hydroxyethyl acrylate, Rocryl 410 or hydroxyethyl methacrylate monooctyl ester.
Preferred as another kind, described acrylic ester monomer comprises one or more of methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, methacrylic acid, butyl acrylate.
Preferred as another kind, described stopper is one or more of 2,6 ditertiary butyl p cresol, Resorcinol, para benzoquinone, toluhydroquinone, MEHQ;
Preferred as another kind, described promotor is the mixture of amine and organic transition metal salt, described amine is N, accelerine, N, N-dimethyl-p-toluidine or N, N-Diethyl Aniline, described organic transition metal salt is one or both in cobalt naphthenate and bismuth naphthenate, the mass ratio (0.5-1) of described amine and organic transition metal salt: (0.5-1);
Preferred as another kind, described oxygen scavenger is one or more of active wax, paraffin, polyethylene wax;
Preferred as another kind, described oxygenant is one or more of tertbutyl peroxide, benzoyl peroxide, methylethyl ketone peroxide, isopropyl benzene hydroperoxide.
The present invention also provides the preparation method of above-mentioned environment-friendly type high performance methyl methacrylate self-leveling coating, comprises the following steps:
(1) preparation of polyurethane prepolymers:
After polyether glycol, polyester polyol are dewatered respectively, with isocyanates substance reaction, temperature of reaction is 70-80 ℃, and the reaction times is 1-3h; Add unsaturated acid hydroxyl Ester, 50-60 ℃ of reaction 1-2h, obtains again;
(2) preparation of A component:
Polyurethane prepolymers, acrylic ester monomer, stopper, promotor, oxygen barrier agent are mixed, obtain A component; (3) B component preparation:
Polyurethane prepolymers, acrylic ester monomer, oxygenant, stopper are mixed, obtain B component.
The present invention also provides the application of above-mentioned environment-friendly type high performance methyl methacrylate self-leveling coating in buildings waterproof, is specially: A component is heated to 40-60 ℃, spraying after mixing with B component.
Beneficial effect: environment-friendly type high performance methyl methacrylate self-leveling coating preparation technology provided by the invention is simple, reaction conditions is gentle, raw material is easy to get, with low cost, easy to use, during construction, A combination and B component are directly mixed to spraying, operating efficiency is high, curing speed is fast, having constructed after 24 hours can open to traffic, convenient and swift, there is high abrasion, high flexibility, high impervious, the feature of Self-leveling, increased the convenience of its construction and intelligent, it is a kind of floor material of excellence, can avoid solvent-type waterproofing paint for the pollution of environment simultaneously, in addition, to have the soft monomer modified poly (methyl methacrylate) of high-flexibility, there is soft chain segment in its molecule segment in this coating, improved the defect that after polymethylmethacrylate coating is filmed, matter is crisp, snappiness is poor.
The component of this coating is not added filler, by cross-linking reaction, increases coating strength and wear resistance, simplifies production technique, can also avoid increasing the defect that filler causes unstable product quality simultaneously.
Preparation technology is simple for this coating, take acrylate as body, adopts the polymerization process that urethane is linking agent, in the situation that organic solvent-free exists, can make.
Embodiment
Embodiment 1
(1) polyurethane prepolymers preparation
| Material title | Amount of substance ratio |
| Diphenylmethanediisocyanate | 2 |
| Polyether glycol (2 functionality, molecular weight 2000) | 1 |
| Hydroxyethyl acrylate | 3 |
By after polyether glycol dehydration with diphenylmethanediisocyanate according to amount of substance than the reactor that drops into sealing together with 1:2, control temperature at 75 ℃, stirring reaction 2h; Be cooled to 55 ℃, add Hydroxyethyl acrylate, high-speed stirring reaction 1.5h, obtains polyurethane prepolymers;
(2) A component preparation
| Material title | Weight part |
| Polyurethane prepolymers | 39.49 |
| Methyl methacrylate | 60 |
| 2,6 ditertiary butyl p cresol | 0.01 |
| DMA | 0.1 |
| Cobalt naphthenate | 0.1 |
| Active wax | 0.3 |
At 50-60 ℃, above-mentioned substance is joined to reactor high-speed stirring 1h, be cooled to below 40 ℃, obtain component A.
(3) B component preparation
| Material title | Weight part |
| Base polyurethane prepolymer for use as | 60 |
| Methyl methacrylate | 30.99 |
| Butyl acrylate | 8.9 |
| 2,6 ditertiary butyl p cresol | 0.01 |
| Benzoyl peroxide | 0.1 |
Polyurethane prepolymers, acrylic ester monomer, oxygenant, stopper are mixed, obtain B component.
(4) use of environment-friendly type high performance polymethylmethacrylate self-leveling coating
A component is heated to 50 ℃,, according to mass ratio 1:1, by spray gun, mixes with B component, spraying film forming is used.
Performance characterization:
By filming of above-mentioned A, B component spraying film forming, according to standard GB/T16777-2008 < < Test methods for building waterproof coatings > > stretch, elongation at break, tear, low temperature flexibility, watertightness, hardness, wear resistance detect; Coating thickness 1.5 ± 0.2mm, result of study is as follows:
| Sequence number | Interventions Requested | Assay |
| 1 | Tensile strength (MPa) | 13.8 |
| 2 | Elongation at break (%) | 155 |
| 3 | Tear strength (N/mm) | 72 |
| 4 | Low temperature flexibility | -25 ℃ of flawlesses |
| 5 | Watertightness | 1.8MPa24h waterproof |
| 6 | Hardness (Shao A) | 90 |
| 7 | Wear resisting property/(750g/500r)/mg | 0.1 |
Embodiment 2
(1) polyurethane prepolymers preparation
| Material title | Amount of substance ratio |
| Isophorone diisocyanate | 2 |
| Polyether glycol (3 functionality, molecular weight 3000) | 1.5 |
| Rocryl 410 | 2 |
By after polyether glycol dehydration by with isophorone diisocyanate according to amount of substance than the reactor that drops into sealing together with 1.5:2, control temperature at 70 ℃, stirring reaction 3h; Be cooled to 60 ℃, add Rocryl 410, high-speed stirring 2h, obtains polyurethane prepolymers;
(2) A component preparation
| Material title | Weight part |
| Polyurethane prepolymers | 50 |
| Methyl methacrylate | 40 |
| Butyl acrylate | 8.48 |
| Resorcinol | 0.02 |
| N, N-Diethyl Aniline | 0.3 |
| Cobalt naphthenate | 0.2 |
| Paraffin | 1 |
At 50-60 ℃, above-mentioned substance is joined to reactor high-speed stirring 1h, be cooled to below 40 ℃, obtain component A.
(3) B component preparation
| Material title | Weight part |
| Base polyurethane prepolymer for use as | 55 |
| Methyl methacrylate | 35 |
| β-dimethyl-aminoethylmethacrylate | 5 |
| Butyl acrylate | 4.67 |
| MEHQ | 0.03 |
| Benzoyl peroxide | 0.3 |
Polyurethane prepolymers, acrylic ester monomer, oxygenant, stopper are mixed, obtain B component.
(4) use of environment-friendly type high performance polymethylmethacrylate self-leveling coating
A component is heated to 40 ℃,, according to mass ratio 1:1, by spray gun, mixes with B component, spraying film forming is used.
Performance characterization:
By filming of above-mentioned A, B component spraying film forming, according to standard GB/T16777-2008 < < Test methods for building waterproof coatings > > stretch, elongation at break, tear, low temperature flexibility, watertightness, hardness, wear resistance detect; Coating thickness 1.5 ± 0.2mm, result of study is as follows:
| Sequence number | Interventions Requested | Assay |
| 1 | Tensile strength (MPa) | 11.8 |
| 2 | Elongation at break (%) | 160 |
| 3 | Tear strength (N/mm) | 63 |
| 4 | Low temperature flexibility | -30 ℃ of flawlesses |
| 5 | Watertightness | 1.8MPa24h waterproof |
| 6 | Hardness (Shao A) | 80 |
| 7 | Wear resisting property/(750g/500r)/mg | 0.3 |
Embodiment 3
(1) polyurethane prepolymers preparation
| Material title | Amount of substance ratio |
| Tolylene diisocyanate | 5 |
| Polyester polyol (2 functionality, molecular weight 2000) | 3 |
| Hydroxyethyl methacrylate monooctyl ester | 6 |
By after polyester polyols dehydration of alcohols with tolylene diisocyanate according to amount of substance than the reactor that drops into sealing together with 5:3, control temperature at 80 ℃, stirring reaction 1h; Be cooled to 50 ℃, add hydroxyethyl methacrylate monooctyl ester, high-speed stirring 2h, obtains polyurethane prepolymers;
(2) A component preparation
| Material title | Weight part |
| Polyurethane prepolymers | 40 |
| Methyl methacrylate | 50 |
| Methacrylic acid | 9.05 |
| MEHQ | 0.05 |
| N, N-dimethyl-p-toluidine | 0.05 |
| Bismuth naphthenate salt | 0.05 |
| Polyethylene wax | 0.8 |
At 50-60 ℃, above-mentioned substance is joined to reactor high-speed stirring 1h, be cooled to below 40 ℃, obtain component A.
(3) B component preparation
| Material title | Weight part |
| Base polyurethane prepolymer for use as | 40 |
| Methyl methacrylate | 45 |
| Butyl acrylate | 14.65 |
| Toluhydroquinone | 0.05 |
| Isopropyl benzene hydroperoxide | 0.3 |
Polyurethane prepolymers, acrylic ester monomer, oxygenant, stopper are mixed, obtain B component.
(4) use of environment-friendly type high performance polymethylmethacrylate self-leveling coating
A component is heated to 60 ℃,, according to mass ratio 1:1, by spray gun, mixes with B component, spraying film forming is used.
Performance characterization:
By filming of above-mentioned A, B component spraying film forming, according to standard GB/T16777-2008 < < Test methods for building waterproof coatings > > stretch, elongation at break, tear, low temperature flexibility, watertightness, hardness, wear resistance detect; Coating thickness 1.5 ± 0.2mm, result of study is as follows:
| Sequence number | Interventions Requested | Assay |
| 1 | Tensile strength (MPa) | 12.3 |
| 2 | Elongation at break (%) | 150 |
| 3 | Tear strength (N/mm) | 72 |
| 4 | Low temperature flexibility | -25 ℃ of flawlesses |
| 5 | Watertightness | 1.8MPa24h waterproof |
| 6 | Hardness (Shao A) | 80 |
| 7 | Wear resisting property/(750g/500r)/mg | 0.2 |
Embodiment 4
(1) polyurethane prepolymers preparation
| Material title | Amount of substance ratio |
| Tolylene diisocyanate | 1 |
| Polyester polyol (3 functionality, molecular weight 3000) | 2 |
| Hydroxyethyl methacrylate monooctyl ester | 1 |
By after polyester polyols dehydration of alcohols with tolylene diisocyanate according to amount of substance than the reactor that drops into sealing together with 5:3, control temperature at 80 ℃, stirring reaction 1h; Be cooled to 50 ℃, add hydroxyethyl methacrylate monooctyl ester, high-speed stirring 2h, obtains polyurethane prepolymers;
(2) A component preparation
| Material title | Weight part |
| Polyurethane prepolymers | 30 |
| β-dimethyl-aminoethylmethacrylate | 60 |
| Para benzoquinone | 0.05 |
| N, N-dimethyl-p-toluidine | 0.05 |
| Bismuth naphthenate salt | 0.10 |
| Polyethylene wax | 0.8 |
Polyurethane prepolymers, acrylic ester monomer, oxygenant, stopper are mixed, obtain B component.
At 50-60 ℃, above-mentioned substance is joined to reactor high-speed stirring 1h, be cooled to below 40 ℃, obtain component A.
(3) B component preparation
| Material title | Weight part |
| Base polyurethane prepolymer for use as | 40 |
| Butyl methacrylate | 45 |
| Butyl acrylate | 14.65 |
| Resorcinol | 0.05 |
| Tertbutyl peroxide | 0.3 |
(4) use of environment-friendly type high performance polymethylmethacrylate self-leveling coating
A component is heated to 50 ℃,, according to mass ratio 1:1, by spray gun, mixes with B component, spraying film forming is used.
Performance characterization:
By filming of above-mentioned A, B component spraying film forming, according to standard GB/T16777-2008 < < Test methods for building waterproof coatings > > stretch, elongation at break, tear, low temperature flexibility, watertightness, hardness, wear resistance detect; Coating thickness 1.5 ± 0.2mm, result of study is as follows:
| Sequence number | Interventions Requested | Assay |
| 1 | Tensile strength (MPa) | 12.3 |
| 2 | Elongation at break (%) | 150 |
| 3 | Tear strength (N/mm) | 72 |
| 4 | Low temperature flexibility | -25 ℃ of flawlesses |
| 5 | Watertightness | 1.8MPa24h waterproof |
| 6 | Hardness (Shao A) | 80 |
| 7 | Wear resisting property/(750g/500r)/mg | 0.2 |
Embodiment 5
(1) polyurethane prepolymers preparation
| Material title | Amount of substance ratio |
| Tolylene diisocyanate | 5 |
| Polyester polyol (2 functionality, molecular weight 2000) | 10 |
| Hydroxyethyl methacrylate monooctyl ester | 10 |
By after polyester polyols dehydration of alcohols with tolylene diisocyanate according to amount of substance than the reactor that drops into sealing together with 5:3, control temperature at 80 ℃, stirring reaction 1h; Be cooled to 50 ℃, add hydroxyethyl methacrylate monooctyl ester, high-speed stirring 2h, obtains polyurethane prepolymers;
(2) A component preparation
| Material title | Weight part |
| Polyurethane prepolymers | 50 |
| Butyl methacrylate | 40 |
| Toluhydroquinone | 0.05 |
| N, N-dimethyl-p-toluidine | 0.10 |
| Bismuth naphthenate salt | 0.05 |
| Polyethylene wax | 0.8 |
At 50-60 ℃, above-mentioned substance is joined to reactor high-speed stirring 1h, be cooled to below 40 ℃, obtain component A.
(3) B component preparation
| Material title | Weight part |
| Base polyurethane prepolymer for use as | 40 |
| Methyl methacrylate | 45 |
| Butyl acrylate | 14.65 |
| Para benzoquinone | 0.05 |
| Methylethyl ketone peroxide | 0.3 |
Polyurethane prepolymers, acrylic ester monomer, oxygenant, stopper are mixed, obtain B component.
(4) use of environment-friendly type high performance polymethylmethacrylate self-leveling coating
A component is heated to 60 ℃,, according to mass ratio 1:1, by spray gun, mixes with B component, spraying film forming is used.
Performance characterization:
By filming of above-mentioned A, B component spraying film forming, according to standard GB/T16777-2008 < < Test methods for building waterproof coatings > > stretch, elongation at break, tear, low temperature flexibility, watertightness, hardness, wear resistance detect; Coating thickness 1.5 ± 0.2mm, result of study is as follows:
| Sequence number | Interventions Requested | Assay |
| 1 | Tensile strength (MPa) | 12.3 |
| 2 | Elongation at break (%) | 150 |
| 3 | Tear strength (N/mm) | 72 |
| 4 | Low temperature flexibility | -25 ℃ of flawlesses |
| 5 | Watertightness | 1.8MPa24h waterproof |
| 6 | Hardness (Shao A) | 80 |
| 7 | Wear resisting property/(750g/500r)/mg | 0.2 |
A kind of environment-friendly type high-wearing feature waterproof of preparing according to this scheme is mated formation with water-proof bond material, by rational molecule structure activity relationship design and functional group's type selecting, has realized wear resisting property, advantage that watertightness is outstanding, is a kind of good water-proof bond material.
Claims (10)
1. an environment-friendly type high performance methyl methacrylate self-leveling coating, is characterized in that: comprise that mass ratio is A component and the B component of 1:1; Described A component comprises the component of following weight part: polyurethane prepolymers 30-50 part, acrylic ester monomer 40-60 part, stopper 0.01-0.05 part, promotor 0.1-0.5 part, oxygen scavenger 0.3-1 part; Described B component comprises the component of following weight part: polyurethane prepolymers 30-50 part, acrylic ester monomer 40-60 part, oxygenant 1-3 part, stopper 0.01-0.05 part.
2. a kind of environment-friendly type high performance methyl methacrylate self-leveling coating according to claim 1, it is characterized in that: described polyurethane prepolymers adopts following methods to make: after polyether glycol or polyester polyol and isocyanates substance reaction, react with unsaturated acid hydroxyl Ester again, obtain.
3. a kind of environment-friendly type high performance methyl methacrylate self-leveling coating according to claim 2, is characterized in that: the mol ratio of described polyether glycol or polyester polyol, isocyanates material, unsaturated acid hydroxyl Ester is (1-5): (2-10): (1-10); The functionality of described polyether glycol is 2 or 3, and molecular weight is 2000-3000; The functionality of described polyester polyol is 2 or 3, and molecular weight is 2000-3000; Described isocyanates material is diphenylmethanediisocyanate, isophorone diisocyanate or tolylene diisocyanate; Described unsaturated acid hydroxyl Ester is Hydroxyethyl acrylate, Rocryl 410 or hydroxyethyl methacrylate monooctyl ester.
4. a kind of environment-friendly type high performance methyl methacrylate self-leveling coating according to claim 1, is characterized in that: described acrylic ester monomer comprises one or more of methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, methacrylic acid, butyl acrylate.
5. a kind of environment-friendly type high performance methyl methacrylate self-leveling coating according to claim 1, it is characterized in that: described stopper is one or more of 2,6 ditertiary butyl p cresol, Resorcinol, para benzoquinone, toluhydroquinone, MEHQ.
6. a kind of environment-friendly type high performance methyl methacrylate self-leveling coating according to claim 1, it is characterized in that: described promotor is the mixture of amine and organic transition metal salt, described amine is N, accelerine, N, N-dimethyl-p-toluidine or N, N-Diethyl Aniline, described organic transition metal salt is one or both in cobalt naphthenate and bismuth naphthenate, the mass ratio (0.5-1) of described amine and organic transition metal salt: (0.5-1).
7. a kind of environment-friendly type high performance methyl methacrylate self-leveling coating according to claim 1, is characterized in that: described oxygen scavenger is one or more of active wax, paraffin, polyethylene wax.
8. a kind of environment-friendly type high performance methyl methacrylate self-leveling coating according to claim 1, is characterized in that: described oxygenant is one or more of tertbutyl peroxide, benzoyl peroxide, methylethyl ketone peroxide, isopropyl benzene hydroperoxide.
9. a preparation method for the environment-friendly type high performance methyl methacrylate self-leveling coating described in claim 1 to 8 any one, is characterized in that: comprise the following steps:
(1) preparation of polyurethane prepolymers:
After polyether glycol, polyester polyol are dewatered respectively, with isocyanates substance reaction, temperature of reaction is 70-80 ℃, and the reaction times is 1-3h; Add unsaturated acid hydroxyl Ester, 50-60 ℃ of reaction 1-2h, obtains again; (2) preparation of A component:
Polyurethane prepolymers, acrylic ester monomer, stopper, promotor, oxygen barrier agent are mixed, obtain A component;
(3) B component preparation:
Polyurethane prepolymers, acrylic ester monomer, oxygenant, stopper are mixed, obtain B component.
10. the application of the environment-friendly type high performance methyl methacrylate self-leveling coating described in claim 1 to 8 any one in buildings waterproof, its feature is being: A component is heated to 40-60 ℃, spraying after mixing by spray gun with B component.
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