CN111073480B - Organic silicon modified single-component polyurea waterproof coating and preparation method thereof - Google Patents
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
The invention discloses an organic silicon modified single-component polyurea waterproof coating and a preparation method thereof, wherein the organic silicon modified single-component polyurea waterproof coating comprises the following components in parts by weight: 12-24 parts of organic silicon double-end dihydric alcohol; 15-25 parts of organic silicon diamine; 4-8 parts of a plasticizer; 18-34 parts of pigment and filler; 6-9 parts of a solvent; 6-13 parts of diisocyanate; 0.1-1.5 parts of a chain extender; 2-4 parts of a blocked amine curing agent; 0.1-1 part of catalyst. The organic silicon modified single-component polyurea waterproof coating has excellent tensile strength, acid and alkali resistance, salt resistance, high water resistance and high elongation at break, has excellent hydrophobicity, weather resistance, ultraviolet resistance, water resistance and stain resistance of an organic siloxane material, and can meet the higher requirement on water resistance of an exposed application environment.
Description
Technical Field
The invention relates to the technical field of waterproof coatings, and particularly relates to an organic silicon modified single-component polyurea waterproof coating and a preparation method thereof.
Background
Along with the acceleration of urban construction pace, underground space utilization also increases along with it, makes many underground constructions be in simultaneously and shakes the interference environment, like large-scale underground shopping mall, parking area, subway, tunnel, consequently, leads to the condition that general waterproof coating just happens to coat fracture and peel off very easily to lose waterproof effect. The fact proves that the waterproof coating has strict performance requirements on large underground engineering in severe cold areas for long time due to structural deformation, settlement and the like. Because underground works are reinforced concrete structures buried underground, which are subjected to the pressure of underground water and the erosion of soil and corrosive media and mold in underground water for a long period of time, the waterproof materials used in underground works are subjected to much different and severe environmental influences than roofing materials.
Among a plurality of waterproof coatings, the two-component polyurea has the advantages of high performance, high tensile strength, high elongation at break, acid and alkali resistance, salt resistance and the like, so that the two-component polyurea becomes a preferred coating for protecting the surface of an underground building. However, the construction process is complex, concrete is required to be shot-blasted, puttied and subjected to base layer treatment, and then polyurea is sprayed, so that the construction performance has a great relationship with temperature and humidity, needle holes, bulging and separation are easy to occur when the treatment is not good, the construction is not suitable at the temperature of below 10 ℃, the cost price is more than twice of that of the common waterproof coating, and the large-area popularization is difficult.
In recent years, the American Setadel corporation, the American siberg corporation, the American cisternate corporation and the Sengstoco corporation have been spreading the single-component polyurea materials to the utmost. The single-component polyurea waterproof coating on the market is prepared by taking aliphatic isocyanate such as polyether polyol, IPDI and the like as main components and adding a blocked amine latent curing agent. It is solidified into a film after contacting with the water vapor in the air, and a flexible and firm seamless waterproof film is formed on the surface of a base layer. Solves the defects that the bi-component similar products are easy to generate pinholes and are not firmly bonded with a cement base layer, and has the original characteristics.
At present, compared with polyurethane waterproof coatings, the single-component polyurea coatings have more reasonable stress-strain characteristics and wider elastic regions, and the stress-strain curves of the two-component polyurea have narrow elastic regions, too large plastic regions and too fast curing time. Therefore, the one-component polyurea coating film has better and wider adaptability. However, the coating film of the single-component polyurea coating in the domestic market is easy to absorb water, so that the coating film is degraded or cracked, the waterproof performance and stain resistance of the polyurea waterproof material are poor, the weather resistance is general, and the multifunctional, all-weather and high-performance waterproof requirements of market demands cannot be met.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides the organic silicon modified single-component polyurea waterproof coating which has excellent tensile strength, acid and alkali resistance, salt resistance, high water resistance and high elongation at break, has excellent hydrophobicity, weather resistance, ultraviolet resistance, water resistance and stain resistance of an organic siloxane material, and can meet the higher requirement on water resistance of an exposed application environment.
The technical scheme adopted by the invention is as follows:
an organic silicon modified single-component polyurea waterproof coating comprises the following components in parts by weight:
preferably, the molecular weight of the organic silicon double-end dihydric alcohol is 1000-4000, and the structural formula is shown as the formula (1):
wherein R is1Is an alkyl group, and n is 8 to 50.
Preferably, the silicone di-terminal diol is Shanghai Tiger tech-2120, and/or tech-2140.
Preferably, the molecular weight of the organosilicon diamine is 1000-3000, and the structural formula is shown as a formula (2):
wherein R is2Is an alkyl group, and m is 10 to 40.
Preferably, the silicone diamine is Shanghai Tiger tech-2420.
Preferably, the plasticizer is at least one of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, trioctyl phosphate, citric acid ester and chlorinated paraffin plasticizer.
Preferably, the pigment and filler is one or more of carbon black, rutile type titanium dioxide, kaolin, fumed silica, heavy calcium, barium sulfate, magnesium oxide, calcium oxide, wollastonite, silicon micropowder and talcum powder.
Preferably, the solvent is one or more of toluene, xylene, trimethylbenzene, solvent oil, ethyl acetate, butyl acetate and propylene glycol methyl ether acetate.
Preferably, the diisocyanate is one or more of phorone isocyanate, 1,4 cyclohexyl diisocyanate, methylcyclohexyl diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, and the like.
Preferably, the chain extender is at least one of 4,4 '-methylene-bis (3-chloro-2, 6-diethylaniline), 4' -bis-sec-butylaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine and methylcyclohexanediamine.
Preferably, the blocked amine curing agent is one or more of 3-butyl-2- (1-ethylpentyl) oxazolidine, 3-hydroxyethyl-1, 3-oxazolidine, 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine, 2-phenyl-3-hydroxyethyl-1, 3-oxazolidine.
Preferably, the catalyst is at least one of an organic metal catalyst such as dibutyltin dilaurate, stannous octoate, lead isooctanoate and the like and/or a tertiary amine catalyst such as aliphatic amine, alicyclic amine, aromatic amine, alcamines and ammonium salt compounds thereof.
The preparation method of the organic silicon modified single-component polyurea waterproof coating comprises the following steps:
(1) adding organic silicon double-end dihydric alcohol, a plasticizer and pigment filler into a reaction container, and uniformly dispersing;
(2) transferring the dispersed slurry into a reaction kettle, stirring and heating to 100-110 ℃, and dehydrating for 2-3 hours under the relative vacuum degree of-0.08-0.1 MPa;
(3) reducing the temperature to 70-80 ℃, adding a solvent, gradually adding diisocyanate, stirring, adding a catalyst in an amount of 1/4-1/2, heating to 75-85 ℃, and reacting for 3-4 hours;
(4) controlling a certain dripping speed, gradually adding the organic silicon diamine, and reacting for 1 hour after the addition is finished;
(5) adding a chain extender, and reacting at 75-85 ℃ for 0.5-1 hour;
(6) cooling to 70-80 ℃, adding a blocked amine curing agent, and stirring for 0.5-1 hour;
(7) cooling to 50-60 ℃, adding the catalyst with the rest formula amount, and stirring for 0.5-1 hour;
(8) cooling to below 50 deg.C, introducing nitrogen for protection, and discharging.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the silicone diol, the silicone diamine and the aliphatic isocyanate are reacted to form the prepolymer, and a silicon-oxygen bond (Si-O-Si) chain segment structure with high heat resistance, weather-proof stability and hydrophobic effect is introduced, so that the advantages of excellent tensile strength, high elongation at break, acid and alkali resistance, salt resistance and the like of the traditional polyurea material are maintained, and the hydrophobicity, weather resistance, ultraviolet resistance, water resistance and stain resistance of the polyurea waterproof coating are greatly improved.
Detailed Description
In order that the nature of the invention may be better understood, a detailed description of the invention is provided below with reference to specific embodiments.
The following examples, comparative examples used the following sources of raw materials:
organosilicon diol at both ends: shanghai tag tech-2120 (molecular weight 2000);
organosilicon diamine: shanghai Tiger tech-2420 (molecular weight 2000);
polyether amine D2000: U.S. HUNTSMAN (HUNTSMAN) polyetheramine D2000 (molecular weight 2000).
Other raw materials which are not particularly described are all common commercial products.
Example 1
An organic silicon modified single-component polyurea waterproof coating comprises the following components in parts by weight:
the preparation process of the organic silicon modified single-component polyurea waterproof coating comprises the following steps:
(1) adding organic silicon double-end dihydric alcohol, a plasticizer and pigment filler into a reaction container, and uniformly dispersing;
(2) transferring the dispersed slurry into a reaction kettle, stirring and heating to 100-110 ℃, and dehydrating for 2-3 hours under the relative vacuum degree of-0.08-0.1 MPa;
(3) reducing the temperature to 70-80 ℃, adding a solvent, gradually adding diisocyanate, stirring, adding a catalyst in an amount of 1/4-1/2, heating to 75-85 ℃, and reacting for 3-4 hours;
(4) controlling a certain dripping speed, gradually adding the organic silicon diamine, and reacting for 1 hour after the addition is finished;
(5) adding a chain extender, and reacting at 75-85 ℃ for 0.5-1 hour;
(6) cooling to 70-80 ℃, adding a blocked amine curing agent, and stirring for 0.5-1 hour;
(7) cooling to 50-60 ℃, adding the catalyst with the rest formula amount, and stirring for 0.5-1 hour;
(8) cooling to below 50 deg.C, introducing nitrogen for protection, and discharging.
Example 2
An organic silicon modified single-component polyurea waterproof coating comprises the following components in parts by weight:
the preparation process of the organic silicon modified single-component polyurea waterproof coating is basically the same as that of the embodiment 1, and the details are not repeated here.
Example 3
An organic silicon modified single-component polyurea waterproof coating comprises the following components in parts by weight:
the preparation process of the organic silicon modified single-component polyurea waterproof coating is basically the same as that of the embodiment 1, and the details are not repeated here.
Example 4
An organic silicon modified single-component polyurea waterproof coating comprises the following components in parts by weight:
comparative example 1
A one-component polyurea waterproofing paint, the composition and preparation process of which are similar to those of example 1, except that polyether glycol DL-2000 is used instead of tech-2120 in example 1.
Comparative example 2
A one-component polyurea waterproofing paint, the composition and preparation process of which is similar to example 1, except that polyetheramine D2000 is used instead of the silicone diamine in example 1.
The performance of the one-component polyurea waterproof coatings prepared in the examples 1 to 4, the comparative example 1 and the comparative example 2 is tested according to JC/T2435-2018, the stain resistance is tested according to GB/T9780-2005, and the test performance is shown in Table 1.
TABLE 1
From the results shown in Table 1, it is understood that the prepolymers synthesized in examples 1 to 4 using the silicone polyol and the silicone polyamine are excellent in various properties of the product and excellent in stain resistance. Comparative example 1 where equal parts by mass of polyether polyol DL-2000 were used in place of silicone polyol tech-2120 in the formulation of comparative example 1 and equal parts by mass of polyetheramine D2000 were used in place of silicone polyol tech-2420 in the formulation of comparative example 2, it can be seen that the tensile strength, tear strength, etc. of the products of comparative examples 1, 2 differed significantly from comparative example 1. In terms of stain resistance, it can be seen that the use of polyether polyol or polyether polyamine results in deterioration of the stain resistance of the polyurea waterproof coating material and increase in water absorption. In other properties, particularly the strength retention rate and the elongation at break of the polyurea waterproof coating after 3000 hours of ultraviolet resistance are greatly reduced, so that the weather resistance, the water resistance and the stain resistance of the polyurea waterproof coating can be greatly improved by adopting the organic silicon polyol and the organic silicon polyamine to replace polyether polyol and polyether amine.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.
Claims (6)
1. The organic silicon modified single-component polyurea waterproof coating is characterized by comprising the following components in parts by weight:
12-24 parts of organic silicon double-end dihydric alcohol;
15-25 parts of organosilicon diamine;
4-8 parts of a plasticizer;
18-34 parts of pigment and filler;
6-9 parts of a solvent;
6-13 parts of diisocyanate;
0.1-1.5 parts by weight of a chain extender;
2-4 parts of a blocked amine curing agent;
0.1-1 part by weight of catalyst;
the organic silicon double-end dihydric alcohol is Shanghai Tiger tech-2120 and/or tech-2140;
the organic silicon diamine is Shanghai Tiger tech-2420.
2. The silicone-modified one-component polyurea waterproof coating according to claim 1, wherein the plasticizer is at least one of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, trioctyl phosphate, citric acid ester, and chlorinated paraffin plasticizer.
3. The organosilicon modified single-component polyurea waterproof coating according to claim 1, wherein the pigment and filler is one or more of carbon black, rutile titanium dioxide, kaolin, fumed silica, heavy calcium, barium sulfate, magnesium oxide, calcium oxide, wollastonite, silica micropowder and talcum powder.
4. The organosilicon modified single-component polyurea waterproof coating as claimed in claim 1, wherein the solvent is one or more of toluene, xylene, trimethylbenzene, solvent oil, ethyl acetate, butyl acetate and propylene glycol methyl ether acetate.
5. The organosilicon modified one-component polyurea waterproof coating according to claim 1, wherein the diisocyanate is one or more of isophorone diisocyanate, 1, 4-cyclohexyl diisocyanate, methylcyclohexyl diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate.
6. The preparation method of the organic silicon modified single-component polyurea waterproof coating material as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) adding organic silicon double-end dihydric alcohol, a plasticizer and pigment filler into a reaction container, and uniformly dispersing;
(2) transferring the dispersed slurry into a reaction kettle, stirring and heating to 100-110 ℃, and dehydrating for 2-3 hours under the relative vacuum degree of-0.08-0.1 MPa;
(3) reducing the temperature to 70-80 ℃, adding a solvent, gradually adding diisocyanate, stirring, adding a catalyst in an amount of 1/4-1/2, heating to 75-85 ℃, and reacting for 3-4 hours;
(4) controlling a certain dripping speed, gradually adding the organic silicon diamine, and reacting for 1 hour after the addition is finished;
(5) adding a chain extender, and reacting at 75-85 ℃ for 0.5-1 hour;
(6) cooling to 70-80 ℃, adding a blocked amine curing agent, and stirring for 0.5-1 hour;
(7) cooling to 50-60 ℃, adding the catalyst with the rest formula amount, and stirring for 0.5-1 hour;
(8) cooling to below 50 deg.C, introducing nitrogen for protection, and discharging.
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| CN114574080B (en) * | 2021-11-30 | 2022-09-13 | 科顺防水科技股份有限公司 | Single-component semi-polyurea waterproof coating and preparation method thereof |
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