阅读说明：本技术 一种有机硅-氟改性单组份聚氨酯防水涂料及其制备方法 (Organic silicon-fluorine modified single-component polyurethane waterproof coating and preparation method thereof ) 是由 亓帅 张小冬 孙德文 沈志明 卢立群 冉千平 刘加平 刘畅 李波 朱剑南 王中华 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种有机硅-氟改性单组份聚氨酯防水涂料及其制备方法。本发明所述聚氨酯防水涂料包括以下组分：异氰酸酯、端羟基聚醚二元醇、端羟基聚醚三元醇、有机硅烷封端剂、氟碳醇、增塑剂、溶剂、颜填料、催化剂及分散剂。本发明中所述有机硅-氟改性单组份聚氨酯防水涂料采用特定的有机硅、有机氟改性材料,对聚氨酯涂料改性,达到增强增韧目的；且有效地解决了有机硅-氟与传统聚氨酯树脂不相容的难题,该聚氨酯树脂含有有机硅烷和氟碳支链,能够使该聚氨酯树脂与建筑基材表面的羟基进行反应,从而具有很好的附着力,同时氟碳支链能够使该聚氨酯树脂具有疏水疏油的效果,耐候性大大提升。(The invention discloses an organosilicon-fluorine modified single-component polyurethane waterproof coating and a preparation method thereof. The polyurethane waterproof coating comprises the following components: isocyanate, hydroxyl-terminated polyether diol, hydroxyl-terminated polyether triol, an organosilane end-capping reagent, fluorocarbon alcohol, a plasticizer, a solvent, a pigment filler, a catalyst and a dispersing agent. The organic silicon-fluorine modified single-component polyurethane waterproof coating adopts specific organic silicon and organic fluorine modified materials to modify the polyurethane coating so as to achieve the purposes of strengthening and toughening; the polyurethane resin contains organic silane and fluorocarbon branched chain, and can react with hydroxyl on the surface of a building substrate, so that the polyurethane resin has good adhesive force, and meanwhile, the fluorocarbon branched chain can enable the polyurethane resin to have hydrophobic and oleophobic effects, and the weather resistance is greatly improved.)

1. The organic silicon-fluorine modified single-component polyurethane waterproof coating is characterized by comprising the following components in parts by weight:

the weight average molecular weight of the hydroxyl-terminated polyether glycol is 1000-4000;

the weight average molecular weight of the hydroxyl-terminated polyether triol is 3000-5000;

the organosilane blocking agent is alkoxy silane with amino, sulfydryl and carbamido functional groups, wherein the alkoxy is methoxy, ethoxy or propoxy, and the organosilane blocking agent at least contains one hydrolyzable alkoxy group;

the fluorocarbon alcohol is a straight-chain fluoroalcohol with the carbon number of 2-6 and no fluorine group on the carbon atom directly connected with the hydroxyl;

the plasticizer is an organic ester compound or chlorinated paraffin;

the solvent is any one of toluene, xylene, solvent oil, ethyl acetate and butyl acetate.

2. The organosilicon-fluorine modified one-component polyurethane waterproof paint according to claim 1, wherein the isocyanate is selected from any one of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI) and Hexamethylene Diisocyanate (HDI).

3. The silicone-fluorine modified one-component polyurethane waterproof coating as claimed in claim 1, wherein the hydroxyl-terminated polyether diol and the hydroxyl-terminated polyether triol are independently selected from any one of PPG polyether polyol, POP polymer polyether polyol and PTMG polytetrahydrofuran type polyol, and the hydroxyl value of each polyol is 40-180mg KOH/g.

4. The organosilicon-fluorine modified one-component polyurethane waterproof coating as claimed in claim 1, wherein the organosilane blocking agent is a silane coupling agent.

5. The organosilicon-fluorine modified one-component polyurethane waterproof coating of claim 4, wherein the silane coupling agent is selected from any one of KH-550, south Da-42, KH-602, KH-591, KH-592, KH-590, KH-582, KH-581 and KH-602.

6. The silicone-fluorine modified one-component polyurethane waterproof coating material according to claim 1, wherein the fluorocarbon alcohol is any one selected from trifluoroethanol, trifluoropropanol, tetrafluoropropanol, pentafluoropropanol, trifluorobutanol, tetrafluorobutanol, pentafluorobutanol, hexafluorobutanol, heptafluorobutanol, trifluoropentanol, tetrafluoropentanol, pentafluoropentanol, hexafluoropentanol, heptafluoropentanol, octafluoropentanol, nonafluoropentanol, trifluorohexanol, tetrafluorohexanol, pentafluorohexanol, hexafluorohexanol, heptafluorohexanol, octafluorohexanol, nonafluorohexanol, decafluorohexanol, and undecafluorohexanol.

7. The organosilicon-fluorine modified one-component polyurethane waterproof coating of claim 1, wherein the organic ester compound is selected from any one of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate and citric acid ester.

8. The organosilicon-fluorine modified single-component polyurethane waterproof paint of claim 1, wherein the pigment and filler is selected from one or more of carbon black, titanium dioxide, iron oxide red, kaolin, cement, heavy calcium, ultrafine calcium powder, barium sulfate, magnesium oxide, calcium oxide, wollastonite, silicon micropowder and talcum powder.

9. The organosilicon-fluorine modified one-component polyurethane waterproof paint of claim 1, wherein the catalyst is an organic metal catalyst selected from any one of dibutyltin dilaurate (T-12), stannous octoate and lead isooctanoate.

10. The preparation method of the organic silicon-fluorine modified single-component polyurethane waterproof coating material as claimed in any one of claims 1 to 9, characterized by comprising the following steps:

(1) adding hydroxyl-terminated polyether diol and hydroxyl-terminated polyether triol, a plasticizer and a pigment filler into a reaction vessel, stirring and heating to 100-120 ℃, and dehydrating for 2-3 hours under the vacuum degree of-0.08-0.1 MPa;

(2) reducing the temperature to 70-80 ℃, adding a dispersing agent and isocyanate, and reacting for 2-3 hours at the temperature of 75-85 ℃ under a stirring state;

(3) reducing the temperature to 50-60 ℃, adding an organosilane end-capping agent, heating to 70-80 ℃, reacting for 2-3 hours under a stirring state, then maintaining the temperature, adding fluorocarbon alcohol, and continuing stirring for 30-60 min;

(4) and (3) cooling to 50-60 ℃, adding a catalyst and a solvent, stirring for 30-60min, uniformly stirring, cooling to below 50 ℃, filling nitrogen for protection, and discharging to obtain the waterproof coating.

Technical Field

The invention belongs to the field of building waterproofing, and particularly relates to an organic silicon-fluorine modified single-component polyurethane waterproof coating and a preparation method thereof.

Background

The polyurethane waterproof paint is prepared with isocyanate group-containing prepolymer prepared through addition polymerization of isocyanate, polyether, etc. and through mixing with catalyst, anhydrous assistant, anhydrous stuffing, etc. The coating waterproof material is popularized and applied from the beginning of the 80 th of the 20 th century in China, is the most successful coating waterproof material used so far, and plays an important role in building waterproof application. The polyurethane waterproof coating is widely applied to projects such as tunnels, subways, high-speed rails, roofs, kitchens and toilets, and has a good waterproof effect. The polyurethane waterproof coating is divided into a single-component polyurethane waterproof coating and a multi-component polyurethane waterproof coating according to the composition and the curing mechanism of the polyurethane waterproof coating. As the multi-component polyurethane waterproof coating needs to be proportioned and mechanically stirred during field construction, foaming and inaccurate proportioning are introduced in the stirring process, and uneven stirring can affect the construction quality, so that waterproof quality accidents are caused at times; the single-component polyurethane waterproof coating is a single component, can be used immediately after being opened, does not need stirring, is reliable in construction, and is widely applied.

However, the traditional one-component polyurethane waterproof coating adopts aromatic isocyanate, and the curing mechanism is that a prepolymer containing-NCO end groups and moisture in a base layer or air are cured to form a film and CO is released₂Therefore, the traditional single-component polyurethane waterproof coating is easily interfered by the humidity of the construction environment in the construction process, the construction cannot be thick coated, and the cured coating film is easy to delaminate, not compact, bubble, pinhole and the like. In addition, the traditional single-component polyurethane has low strength, and if the single-component polyurethane is applied to an exposed type, the weather resistance cannot be ensured, and the construction performance is seriously influenced by cracking and the like caused by external force.

The invention is characterized in that linolenic acid glyceride synthesized by linolenic acid and glycerol and a modifier trimethylolpropane diallyl ether (TMPDE) are introduced, a reaction crosslinking mechanism of oxidizing alpha hydrogen on allyl ether to form peroxide free radical by absorbing oxygen in air replaces a crosslinking mechanism of isocyanate, and the paint is different from the traditional curing mechanism, does not release carbon dioxide gas and is beneficial to forming a compact polyurethane waterproof coating film; the patent CN 106634547B discloses a single-component exposed acrylic modified polyurethane waterproof coating and a preparation method thereof, the method adopts a chemical bonding mode to introduce acrylic ester into a polyurethane prepolymer structure, and then the acrylic modified polyurethane waterproof coating is prepared through free radical polymerization, and the acrylic modified polyurethane waterproof coating has good waterproof performance, excellent weather resistance and high brightness, and is suitable for construction of an exposed base surface. Although the single-component polyurethane waterproof coating disclosed by the invention makes a certain progress in the aspect of comprehensive performance improvement, the effect is far from expectation, particularly the tensile strength and the tearing strength respectively reach only 4MPa and 20N/mm at most, and the difference between the mechanical performance indexes (the tensile strength is more than or equal to 4MPa, and the tearing strength is more than or equal to 20N/mm) of the national standard II type polyurethane waterproof coating is obvious.

Disclosure of Invention

In order to overcome the defects of the existing single-component polyurethane waterproof coating, the invention provides the organosilicon-fluorine modified single-component polyurethane waterproof coating which has high strength, compact coating film, reliable construction and excellent physical property and weather resistance, and the preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme.

The invention provides an organosilicon-fluorine modified single-component polyurethane waterproof coating which comprises the following components in parts by weight:

the weight average molecular weight of the hydroxyl-terminated polyether glycol is 1000-4000;

the weight average molecular weight of the hydroxyl-terminated polyether triol is 3000-5000;

the isocyanate is selected from any one of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI) and Hexamethylene Diisocyanate (HDI).

The hydroxyl-terminated polyether diol and the hydroxyl-terminated polyether triol are independently selected from any one of PPG polyether polyol, POP polymer polyether polyol and PTMG polytetrahydrofuran polyol, and the hydroxyl value is preferably 40-180mg KOH/g.

The organosilane blocking agent is alkoxy silane with amino, sulfydryl and carbamido functional groups, wherein the alkoxy is methoxy, ethoxy or propoxy, and the organosilane blocking agent at least contains one hydrolyzable alkoxy group.

The organosilane blocking agent is preferably a silane coupling agent selected from any one of KH-550, Nanda-42, KH-602, KH-591, KH-592, KH-590, KH-582, KH-581 and KH-602.

The fluorocarbon alcohol is a linear fluorinated alcohol having 2 to 6 carbon atoms and no fluorine group on the carbon atom directly connected to the hydroxyl group, and is selected from any one of trifluoroethanol, trifluoropropanol, tetrafluoropropanol, pentafluoropropanol, trifluorobutanol, tetrafluorobutanol, pentafluorobutanol, hexafluorobutanol, heptafluorobutanol, trifluoropentanol, tetrafluoropentanol, pentafluoropentanol, hexafluoropentanol, heptafluoropentanol, octafluoropentanol, nonafluoropentanol, trifluorohexanol, tetrafluorohexanol, pentafluorohexanol, hexafluorohexanol, heptafluorohexanol, octafluorohexanol, nonafluorohexanol, decafluorohexanol, and undecafluorohexanol.

The plasticizer is an organic ester compound or chlorinated paraffin, wherein the organic ester compound is preferably any one of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate and citric acid ester.

The solvent is selected from any one of toluene, xylene, solvent oil, ethyl acetate and butyl acetate.

The pigment and filler of the invention is selected from one or a mixture of more of carbon black, titanium dioxide, iron oxide red, kaolin, cement, heavy calcium, superfine calcium powder, barium sulfate, magnesium oxide, calcium oxide, wollastonite, silica micropowder and talcum powder.

The catalyst is an organic metal catalyst and is selected from any one of dibutyltin dilaurate (T-12), stannous octoate and lead isooctanoate.

The dispersants of the present invention are those commonly used in the art for polyurethane products and are well known to those skilled in the art.

The invention also provides a preparation method of the organic silicon-fluorine modified single-component polyurethane waterproof coating, which comprises the following steps:

(1) adding hydroxyl-terminated polyether diol and hydroxyl-terminated polyether triol, a plasticizer and a pigment filler into a reaction vessel, stirring and heating to 100-120 ℃, and dehydrating for 2-3 hours under the vacuum degree of-0.08-0.1 MPa;

(2) reducing the temperature to 70-80 ℃, adding a dispersing agent and isocyanate, and reacting for 2-3 hours at the temperature of 75-85 ℃ under a stirring state;

(3) reducing the temperature to 50-60 ℃, adding an organosilane end-capping agent, heating to 70-80 ℃, reacting for 2-3 hours under a stirring state, then maintaining the temperature, adding fluorocarbon alcohol, and continuing stirring for 30-60 min;

(4) and (3) cooling to 50-60 ℃, adding a catalyst and a solvent, stirring for 30-60min, uniformly stirring, cooling to below 50 ℃, filling nitrogen for protection, and discharging to obtain the waterproof coating.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the fluorocarbon alcohol adopted in the invention belongs to a functional group with low surface activity, and has the properties of high hydrophobicity, chemical medium erosion resistance, ultraviolet aging resistance and the like. The organic silicon-fluorine modified single-component polyurethane waterproof coating adopts specific organic silicon and organic fluorine modified materials to modify the polyurethane coating so as to achieve the aim of strengthening and toughening, and can avoid the reaction of-NCO groups and moisture in the curing process without releasing CO₂Gas to form compact polyurethane waterproof coating, even if the coating is thickly coated or coated on a wet base surface, bubbles or pinholes are not formed on the surface of the coating, the coating is smooth and attractive, and the dependence of construction on the environment is reduced.

(2) According to the invention, an organic silicon-fluorine functional group obtained by the cross-linking reaction of organic silicon (an organic silane end-capping agent) and organic fluorine (fluorocarbon alcohol) is connected to a resin matrix (isocyanate) through a chemical bonding effect, so that the problem that the organic silicon-fluorine is incompatible with the traditional polyurethane resin is effectively solved, the polyurethane resin contains organic silane and fluorocarbon branched chains, the polyurethane resin can react with hydroxyl on the surface of a building substrate, and therefore, the polyurethane resin has good adhesive force, meanwhile, the fluorocarbon branched chains can enable the polyurethane resin to have hydrophobic and oleophobic effects, and the weather resistance is greatly improved.

(3) The preparation method provided by the invention is simple and feasible, the raw materials are easy to obtain, the preparation method is suitable for industrial production, and the prepared organic silicon-fluorine modified single-component polyurethane waterproof coating has good application and development prospects.

Detailed description of the preferred embodiments

The present invention is described in detail below by way of examples, which are illustrative only and do not represent a limitation on the scope of the invention, and one skilled in the art can modify the reactants and reaction process conditions, etc. within the scope of the invention in light of the disclosure herein. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Example 1

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

diphenylmethane diisocyanate (MDI)	12 portions of
		Polyether glycol (molecular weight 1000, PPG type)	25 portions of
Polyether triol (molecular weight 3000, PPG type)	7.5 parts of
		Organosilane blocking agent (containing amino group) KH-550	4 portions of
Trifluoroethanol	2 portions of
		Dioctyl phthalate (DOP)	7 portions of
Xylene	12 portions of
		Heavy calcium carbonate	29.9 parts
Carbon black	0.1 part
		Dibutyltin dilaurate (T-12)	0.2 part
Dispersing agent	0.3 part

The technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 25 weight parts of hydroxyl polyether glycol, 7.5 weight parts of trihydric alcohol, 7 weight parts of dioctyl phthalate (DOP), 29.9 weight parts of heavy calcium and 0.1 weight part of carbon black into a reaction vessel, stirring and heating to 100 ℃, and dehydrating for 2 hours under the vacuum degree of-0.08 to-0.1 MPa;

(2) cooling to 70 ℃, adding 0.3 part by weight of dispersant and 12 parts by weight of diphenylmethane diisocyanate (MDI), and reacting for 2 hours under the stirring state at 75 ℃;

(3) cooling to 50 deg.C, adding organic silane end capping agent (containing amino group) KH-5504 weight parts, heating to 70 deg.C, stirring, reacting for 2 hr, maintaining the temperature, adding 2 weight parts of trifluoroethanol, and stirring for 30 min;

(4) cooling to 50 ℃, adding organic tin catalyst T-120.2 weight parts and dimethylbenzene 12 weight parts, stirring for 30min, cooling to below 50 ℃, charging nitrogen for protection, and discharging.

Example 2

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

the technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 35 parts by weight of end hydroxyl polyether dihydric alcohol and 5 parts by weight of trihydric alcohol, 5 parts by weight of dioctyl phthalate (DOP), 15.9 parts by weight of heavy calcium and 0.1 part by weight of carbon black into a reaction vessel, stirring and heating to 120 ℃, and dehydrating for 3 hours under the vacuum degree of-0.1 MPa;

(2) cooling to 80 ℃, adding 0.3 part by weight of dispersant and 14 parts by weight of Toluene Diisocyanate (TDI), and reacting for 3 hours at 85 ℃ under a stirring state;

(3) reducing the temperature to 60 ℃, adding-425 parts by weight of organosilane end-capping agent (containing amino group), heating to 80 ℃, reacting for 3 hours under a stirring state, then maintaining the temperature, adding 4 parts by weight of trifluoropropanol, and continuing stirring for 60 min;

(4) cooling to 60 ℃, adding organic tin catalyst T-120.2 weight parts and xylene 15.5 weight parts, stirring for 60min, cooling to below 50 ℃, charging nitrogen for protection, and discharging.

Example 3

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

the technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 35 parts by weight of end hydroxyl polyether dihydric alcohol and 5.5 parts by weight of trihydric alcohol, 5 parts by weight of diisononyl phthalate (DLNP), 14.9 parts by weight of talcum powder and 0.1 part by weight of carbon black into a reaction vessel, stirring and heating to 120 ℃, and dehydrating for 3 hours under the vacuum degree of-0.1 MPa;

(2) cooling to 80 ℃, adding 0.2 part by weight of dispersant and 18 parts by weight of isophorone diisocyanate (IPDI), and reacting for 3 hours at 85 ℃ under a stirring state;

(3) cooling to 60 deg.C, adding organic silane end capping agent (containing amino group) KH-6025 weight parts, heating to 80 deg.C, stirring, reacting for 3 hr, maintaining the temperature, adding pentafluorobutanol 6 weight parts, and stirring for 60 min;

(4) cooling to 60 ℃, adding organic tin catalyst T-120.3 parts by weight and solvent oil 10 parts by weight, stirring for 60min, cooling to below 50 ℃, charging nitrogen for protection, and discharging.

Example 4

The raw material proportion of the imitation modified polyurethane waterproof coating is as follows:

hexamethylene Diisocyanate (HDI)	13 portions of
		Polyether glycol (molecular weight 4000, PPG type)	40 portions of
Polyether triol (molecular weight 3000, PPG type)	10 portions of
		Organosilane blocking agent (containing ureido) KH-591	3 portions of
Heptafluorohexanol	3 portions of
		Chlorinated paraffin	5 portions of
Xylene	10.5 portions
		Superfine calcium powder	14.9 portions
Carbon black	0.1 part
		Stannous octoate catalyst	0.4 portion of
Dispersing agent	0.1 part

The technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 40 parts by weight of end hydroxyl polyether dihydric alcohol and 10 parts by weight of trihydric alcohol, 5 parts by weight of chlorinated paraffin, 14.9 parts by weight of superfine calcium powder and 0.1 part by weight of carbon black into a reaction vessel, stirring and heating to 120 ℃, and dehydrating for 3 hours under the vacuum degree of-0.1 MPa;

(2) cooling to 80 ℃, adding 0.1 part by weight of dispersant and 13 parts by weight of Hexamethylene Diisocyanate (HDI), and reacting for 3 hours at 85 ℃ in a stirring state;

(3) cooling to 60 deg.C, adding KH-5913 weight parts of organosilane end-capping agent (containing ureido), heating to 80 deg.C, stirring, reacting for 3 hr, maintaining the temperature, adding 3 weight parts of heptafluorohexanol, and stirring for 60 min;

(4) cooling to 60 deg.C, adding stannous octoate catalyst 0.4 weight parts and xylene 10.5 weight parts, stirring for 60min, cooling to below 50 deg.C, introducing nitrogen for protection, and discharging.

Example 5

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

diphenylmethane diisocyanate (MDI)	20 portions of
		Polyether glycol (molecular weight 2000, PPG type)	30 portions of
Polyether triol (molecular weight 3000, POP type)	10 portions of
		Organosilane blocking agent (containing ureido) KH-592	5.5 parts of
Pentafluoropentanol	4 portions of
		Dioctyl phthalate (DOP)	5 portions of
Acetic acid butyl ester	10 portions of
		Barium sulfate	14.9 portions
Carbon black	0.1 part
		Lead isooctanoate catalyst	0.2 part
Dispersing agent	0.3 part

The technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 30 parts by weight of hydroxyl polyether dihydric alcohol and 10 parts by weight of trihydric alcohol, 5 parts by weight of dioctyl phthalate (DOP), 14.9 parts by weight of barium sulfate and 0.1 part by weight of carbon black into a reaction vessel, stirring and heating to 120 ℃, and dehydrating for 3 hours under the vacuum degree of-0.1 MPa;

(2) cooling to 80 ℃, adding 0.3 part by weight of dispersant and 20 parts by weight of diphenylmethane diisocyanate (MDI), and reacting for 3 hours at 85 ℃ under a stirring state;

(3) reducing the temperature to 60 ℃, adding KH-5925.5 weight parts of organosilane end-capping agent (containing ureido), heating to 80 ℃, reacting for 3 hours under a stirring state, then maintaining the temperature, adding 4 weight parts of penta-fluoropentanol, and continuously stirring for 60 minutes;

(4) cooling to 60 deg.C, adding lead isooctoate catalyst 0.2 weight parts and butyl acetate 10 weight parts, stirring for 60min, cooling to below 50 deg.C, introducing nitrogen for protection, and discharging.

Example 6

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

diphenylmethane diisocyanate (MDI)	17 portions of
		Polyether glycol (molecular weight 1000, PTMG type)	25 portions of
Polyether triol (molecular weight 3000, PPG type)	13 portions of
		Organosilane blocking agent (containing mercapto group) KH-590	5 portions of
Tetrafluorobutanol	5 portions of
		Chlorinated paraffin	5 portions of
Solvent oil	10 portions of
		Kaolin clay	19.4 parts of
Carbon black	0.1 part
		Dibutyltin dilaurate (T-12)	0.2 part
Dispersing agent	0.3 part

The technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 25 weight parts of hydroxyl polyether diol and 13 weight parts of triol, 5 weight parts of chlorinated paraffin, 19.4 weight parts of kaolin and 0.1 weight part of carbon black into a reaction vessel, stirring and heating to 100 ℃, and dehydrating for 2 hours under the vacuum degree of-0.08 to-0.1 MPa;

(2) cooling to 70 ℃, adding 0.3 weight part of dispersant and 17 weight parts of diphenylmethane diisocyanate (MDI), and reacting for 2 hours under the stirring state at 75 ℃;

(3) cooling to 50 deg.C, adding organic silane blocking agent (containing mercapto group) KH-5905 weight parts, heating to 70 deg.C, stirring, reacting for 2 hr, maintaining the temperature, adding 5 weight parts of tetrafluorobutanol, and stirring for 30 min;

(4) cooling to 50 ℃, adding organic tin catalyst T-120.2 parts by weight and solvent oil 10 parts by weight, stirring for 30min, cooling to below 50 ℃, charging nitrogen for protection, and discharging.

Example 7

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

the technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 29.5 parts by weight of hydroxyl polyether dihydric alcohol, 12.5 parts by weight of trihydric alcohol, 5 parts by weight of dioctyl phthalate (DOP), 15.4 parts by weight of wollastonite and 0.1 part by weight of carbon black into a reaction vessel, stirring and heating to 120 ℃, and dehydrating for 3 hours under the vacuum degree of-0.1 MPa;

(2) cooling to 80 ℃, adding 0.3 weight part of dispersant and 22 weight parts of Toluene Diisocyanate (TDI), and reacting for 3 hours at 85 ℃ under a stirring state;

(3) cooling to 60 deg.C, adding KH-5823 weight parts of organosilane blocking agent (containing mercapto), heating to 80 deg.C, stirring, reacting for 3 hr, maintaining the temperature, adding 2 weight parts of octafluorohexanol, and stirring for 60 min;

(4) cooling to 60 ℃, adding organic tin catalyst T-120.2 weight parts and ethyl acetate 10 weight parts, stirring for 60min, cooling to below 50 ℃, charging nitrogen for protection, and discharging.

Example 8

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

the technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 32.5 parts by weight of hydroxyl polyether dihydric alcohol, 6 parts by weight of trihydric alcohol, 5 parts by weight of citrate, 16.9 parts by weight of calcium oxide and 0.1 part by weight of iron oxide red into a reaction vessel, stirring and heating to 120 ℃, and dehydrating for 3 hours under the vacuum degree of-0.1 MPa;

(2) cooling to 80 ℃, adding 0.1 part by weight of dispersant and 14 parts by weight of Toluene Diisocyanate (TDI), and reacting for 3 hours at 85 ℃ under a stirring state;

(3) cooling to 60 deg.C, adding KH-5818 weight parts of organosilane blocking agent (containing mercapto), heating to 80 deg.C, stirring, reacting for 3 hr, maintaining the temperature, adding 7 weight parts of hexafluoropentanol, and stirring for 60 min;

(4) cooling to 60 deg.C, adding lead isooctoate catalyst 0.4 weight parts and xylene 10 weight parts, stirring for 60min, cooling to below 50 deg.C, introducing nitrogen for protection, and discharging.

Example 9

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

diphenylmethane diisocyanate (MDI)	14 portions of
		Polyether glycol (molecular weight 3000, POP type)	32.5 portions
Polyether triol (molecular weight 3000, PTMG type)	6 portions of
		Organosilane blocking agent (containing amine group) KH-602	8 portions of
Heptafluorohexanol	7 portions of
		Citric acid esters	5 portions of
Xylene	10 portions of
		Calcium oxide	16.9 portions
Titanium white powder	0.1 part
		Dibutyltin dilaurate (T-12)	0.4 portion of
Dispersing agent	0.1 part

The technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 32.5 parts by weight of hydroxyl polyether dihydric alcohol, 6 parts by weight of trihydric alcohol, 5 parts by weight of citrate, 16.9 parts by weight of calcium oxide and 0.1 part by weight of titanium dioxide into a reaction vessel, stirring and heating to 120 ℃, and dehydrating for 3 hours under the vacuum degree of-0.1 MPa;

(2) cooling to 80 ℃, adding 0.1 part by weight of dispersant and 14 parts by weight of diphenylmethane diisocyanate (MDI), and reacting for 3 hours at 85 ℃ under a stirring state;

(3) cooling to 60 deg.C, adding KH-6028 weight parts of organosilane blocking agent (containing amino group), heating to 80 deg.C, stirring, reacting for 3 hr, maintaining the temperature, adding 7 weight parts of heptafluorohexanol, and stirring for 60 min;

(4) cooling to 60 deg.C, adding 0.4 weight part of dibutyltin dilaurate (T-12) and 10 weight parts of xylene, stirring for 60min, cooling to below 50 deg.C, introducing nitrogen for protection, and discharging.

Comparative example 1

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

hexamethylene Diisocyanate (HDI)	13 portions of
		Polyether glycol (molecular weight 4000, PPG type)	40 portions of
Polyether triol (molecular weight 3000, PPG type)	10 portions of
		Organosilane blocking agent (containing ureido) KH-591	0 portion of
Heptafluorohexanol	3 portions of
		Chlorinated paraffin	5 portions of
Xylene	10.5 portions
		Superfine calcium powder	14.9 portions
Carbon black	0.1 part
		Stannous octoate catalyst	0.4 portion of
Dispersing agent	0.1 part

The technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 40 parts by weight of end hydroxyl polyether dihydric alcohol and 10 parts by weight of trihydric alcohol, 5 parts by weight of chlorinated paraffin, 14.9 parts by weight of superfine calcium powder and 0.1 part by weight of carbon black into a reaction vessel, stirring and heating to 120 ℃, and dehydrating for 3 hours under the vacuum degree of-0.1 MPa;

(2) cooling to 80 ℃, adding 0.1 part by weight of dispersant and 13 parts by weight of Hexamethylene Diisocyanate (HDI), and reacting for 3 hours at 85 ℃ in a stirring state;

(3) then, adding 3 parts by weight of heptafluorohexanol while maintaining the stirring state at 80 ℃, and continuing stirring for 60 min;

(4) cooling to 60 deg.C, adding stannous octoate catalyst 0.4 weight parts and xylene 10.5 weight parts, stirring for 60min, cooling to below 50 deg.C, introducing nitrogen for protection, and discharging.

Comparative example 2

The modified polyurethane waterproof coating comprises the following raw materials in proportion:

diphenylmethane diisocyanate (MDI)	12 portions of
		Polyether glycol (molecular weight 1000, PPG type)	25 portions of
Polyether triol (molecular weight 3000, PPG type)	7.5 parts of
		Organosilane blocking agent (containing amino group) KH-550	4 portions of
Trifluoroethanol	0 portion of
		Dioctyl phthalate (DOP)	7 portions of
Xylene	12 portions of
		Heavy calcium carbonate	29.9 parts
Carbon black	0.1 part
		Dibutyltin dilaurate (T-12)	0.2 part
Dispersing agent	0.3 part

The technical process of the modified polyurethane waterproof coating comprises the following steps:

(1) adding 25 weight parts of hydroxyl polyether glycol, 7.5 weight parts of trihydric alcohol, 7 weight parts of dioctyl phthalate (DOP), 29.9 weight parts of heavy calcium and 0.1 weight part of carbon black into a reaction vessel, stirring and heating to 100 ℃, and dehydrating for 2 hours under the vacuum degree of-0.08 to-0.1 MPa;

(2) cooling to 70 ℃, adding 0.3 part by weight of dispersant and 12 parts by weight of diphenylmethane diisocyanate (MDI), and reacting for 2 hours under the stirring state at 75 ℃;

(3) cooling to 50 ℃, adding an organosilane end-capping agent (containing amino) KH-5504 parts by weight, heating to 70 ℃, and reacting for 2.5 hours under a stirring state;

(4) cooling to 50 ℃, adding organic tin catalyst T-120.2 weight parts and dimethylbenzene 12 weight parts, stirring for 30min, cooling to below 50 ℃, charging nitrogen for protection, and discharging.

Comparative example 3

The polyurethane waterproof coating is purchased from a single-component polyurethane waterproof coating product DTPU-401 of Shanghai Dongda chemical Co. The performance test indexes of the samples of the examples and comparative examples of the present invention are as follows:

the mechanical properties of the organosilicon-fluorine modified single-component polyurethane waterproof coating obtained in the embodiments 1-9 meet the detection performance of a single-component polyurethane waterproof coating type II product in GB/T19250-2013 polyurethane waterproof coating. The coating is free from the interference of the humidity of the construction environment in the construction process, the cured coating is flat, compact and free of air bubbles, pinholes, delamination and other phenomena, the waterproof performance is excellent, the weather resistance is excellent, the coating is suitable for waterproofing of exposed parts of roofs, bridges, roads and the like, the decorative effect is good, and no finish paint is needed for protection. The mechanical properties of the comparative examples 1, 2 and 3 are far from the index requirements of the type II product of the single-component polyurethane waterproof coating in the GB/T19250-2013 polyurethane waterproof coating, and the defoaming effect per se is extremely poor and the weather resistance is insufficient.