CN115505326A - Dual-curing polyurethane floor coating and preparation method thereof - Google Patents
Dual-curing polyurethane floor coating and preparation method thereof Download PDFInfo
- Publication number
- CN115505326A CN115505326A CN202211432016.0A CN202211432016A CN115505326A CN 115505326 A CN115505326 A CN 115505326A CN 202211432016 A CN202211432016 A CN 202211432016A CN 115505326 A CN115505326 A CN 115505326A
- Authority
- CN
- China
- Prior art keywords
- component
- dual
- floor coating
- polyester polyol
- unsaturated double
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Floor Finish (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a dual-curing polyurethane floor coating and a preparation method thereof, belonging to the technical field of polyurethane floor coatings. The technical scheme is as follows: the coating comprises a component A and a component B, wherein the component A comprises 50-70 parts by weight of polyester polyol containing unsaturated double bonds, 30-50 parts by weight of inorganic filler, 1-3 parts by weight of photoinitiator and 0.2-0.4 part by weight of flatting agent; the B component is polyisocyanate, and preferably, the B component is polymethylene polyphenyl polyisocyanate. According to the invention, from the structure of polyester polyol, unsaturated double bonds are introduced on a polyester molecular chain, the polyester polyol for the floor coating is subjected to functional modification, and photo-initiated free radical polymerization is introduced on the basis of curing of two components, so that the cross-linked network structure of the system is increased, the defect that the polyester floor coating is not resistant to hydrolysis is overcome, the service life of the polyurethane floor is greatly prolonged, and the polyurethane floor coating is suitable for various indoor and outdoor places.
Description
Technical Field
The invention relates to the technical field of polyurethane floor coatings, in particular to a dual-curing polyurethane floor coating and a preparation method thereof.
Background
Along with the progress of society and the increasing promotion of living standard, people also gradually promote the aesthetic measure and the comfort level requirement of public environment, and terrace coating product receives market attention gradually and develops rapidly. The polyurethane terrace has the biggest characteristic that the flexibility can be adjusted, excellent crack bridging can be provided, and the polyurethane terrace also has excellent wear resistance, corrosion resistance and impact resistance, and is suitable for parking lots, playgrounds, various industrial and mining enterprise workshops and the like.
The polyester polyurethane terrace has excellent wear resistance and corrosion resistance, but has the biggest defect of poor hydrolysis resistance, and the service life of the terrace is shortened in an outdoor humid environment. Chinese patent CN113583223A uses polyfunctional castor oil and PET alcoholysis product as two-component polyurethane terrace. The castor oil is used as a main reaction system, the cost is reduced by adding the PET alcoholysis substance, and the utilization rate of the PET recovery bottle is improved. However, the service life of the terrace in outdoor environment can be greatly reduced by the introduced PET alcoholysis product, and in addition, the industrial production and popularization of the technical scheme have certain difficulty. Chinese patent CN113583223A uses castor oil modified polyester polyol to prepare water-soluble castor oil-based polyol, and prepares waterborne polyester polyol with good emulsifying property through exchange of castor oil and small molecular alcohol, and then applies the waterborne polyester polyol to a polyurethane terrace, but the castor oil modified polyester cannot solve the hydrolysis problem of polyester polyol in a humid environment.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the dual-curing polyurethane floor coating and the preparation method thereof overcome the defects of the prior art, and the dual-curing polyurethane floor coating is prepared by starting from a polyester polyol structure, introducing unsaturated double bonds on a polyester molecular chain, performing functional modification on the polyester polyol for the floor coating, introducing photo-initiated free radical polymerization on the basis of dual-component curing, increasing the cross-linked network structure of a system, overcoming the defect that the polyester floor coating is not resistant to hydrolysis, greatly prolonging the service life of the polyurethane floor, and being suitable for various indoor and outdoor places.
The technical scheme of the invention is as follows:
on one hand, the invention provides a dual-curing polyurethane floor coating, which comprises a component A and a component B, wherein the component A comprises 50-70 parts by weight of polyester polyol containing unsaturated double bonds, 30-50 parts by weight of inorganic filler, 1-3 parts by weight of photoinitiator and 0.2-0.4 part by weight of flatting agent; the component B is polyisocyanate.
Preferably, the mass ratio of the component A to the component B is 2-4.
Preferably, the unsaturated double bond-containing polyester polyol is prepared from aromatic dibasic acid, double bond-containing dibasic acid, unsaturated double bond-containing vegetable oil and fat and small molecular alcohol serving as raw materials through esterification-ester exchange reaction.
Preferably, the aromatic dibasic acid is one of phthalic anhydride, terephthalic acid and isophthalic acid; the double-bond-containing dibasic acid is one of maleic acid, maleic anhydride, itaconic acid and glutaconic acid.
Preferably, the double bond-containing dibasic acid is maleic acid.
Preferably, the vegetable oil containing unsaturated double bonds is one of tung oil, palm oil, oleic acid and soybean oil; the small molecular alcohol is one of diethylene glycol, triethylene glycol and dipropylene glycol.
Preferably, the small molecule alcohol is diethylene glycol.
Preferably, the molar ratio of the aromatic dibasic acid to the double-bond-containing dibasic acid is 3-5.
Preferably, when the polyester polyol containing unsaturated double bonds is prepared, the esterification reaction is carried out under the protection of nitrogen, and the temperature of the esterification reaction is 205-235 ℃; the vacuum degree of the ester exchange reaction is-0.097 to-0.1 MPa, and the temperature of the ester exchange reaction is 230 to 235 ℃.
Preferably, the hydroxyl value of the polyester polyol containing unsaturated double bonds is 150-300mgKOH/g, the acid value is less than or equal to 1.5mgKOH/g, and the viscosity (25 ℃) is less than or equal to 1500cps.
Preferably, the inorganic filler in the component A is one of kaolin, talcum powder and white carbon black; the initiator is benzophenone or alpha-hydroxy ketone; the component B is polymethylene polyphenyl polyisocyanate.
On the other hand, the invention also provides a preparation method of the dual-curing polyurethane floor coating, which comprises the steps of stirring and mixing the polyester polyol containing unsaturated double bonds, the inorganic filler, the photoinitiator and the flatting agent uniformly, then removing moisture and bubbles in vacuum at the temperature of 100-110 ℃, cooling and discharging to obtain the component A; and (3) under the room-temperature natural illumination condition, uniformly mixing the component A and the component B, and curing to obtain the dual-curing polyurethane floor coating.
The dual-curing polyurethane floor coating is prepared by reacting-OH in the component A with-NCO in the component B for curing, and polymerizing and curing the free radicals of unsaturated double bonds in the component A under the action of a photoinitiator, so that the dual-curing effect is realized. The curing mechanism is as follows:
compared with the prior art, the invention has the following beneficial effects:
1. on the basis of bi-component curing, unsaturated double bonds are introduced on a polyester molecular chain from a polyester polyol structure, the polyester polyol for the floor coating is subjected to functional modification, free radical polymerization of the double bonds is initiated under the irradiation of outdoor ultraviolet rays, the cross-linked network structure of the system is increased, the defect that the polyester type floor coating is not hydrolysis-resistant is overcome, the service life of the polyurethane floor is greatly prolonged, and the polyester type floor coating is suitable for various indoor and outdoor places.
2. The preparation method starts from a polyester polyol structure, introduces a high-content benzene ring structure into a polyester molecular chain, endows the terrace coating with higher hardness, increases the compatibility of the polyester polyol of the component A and the polymethylene polyphenyl polyisocyanate of the component B, and ensures that the prepared terrace coating has excellent color brightness.
3. The polyurethane floor coating prepared by the invention is a solvent-free bi-component system, avoids the solvent volatilization from causing environmental pollution and harm to human bodies in the construction process, is environment-friendly, and accords with the environmental protection concept.
4. In the polyurethane floor coating prepared by the invention, the component A has low viscosity and good fluidity, can be operated at normal temperature, is simple and easy to implement and is convenient for industrial production.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
The dual-curing polyurethane floor coating is prepared by the following method:
(1) Preparation of polyester polyols containing unsaturated double bonds
Putting 432g of phthalic anhydride, 68g of maleic acid, 525g of diethylene glycol and 1538g of tung oil into a four-mouth reaction bottle, and esterifying at 205 ℃ under normal pressure under the protection of nitrogen; then adding 50ppm tetrabutyl titanate catalyst, and carrying out ester exchange reaction for 6h under vacuum of-0.1 MPa and 235 ℃ to obtain unsaturated double bond-containing polyester polyol with the hydroxyl value of 150mgKOH/g, the acid value of 1.5mgKOH/g and the viscosity (25 ℃) of 1210 cps.
(2) Preparation of dual-curing polyurethane floor coating
And (2) component A: adding 50 parts of polyester polyol containing unsaturated double bonds, 50 parts of kaolin, 1 part of initiator benzophenone and 0.4 part of polyether modified silicone oil into a reaction bottle, uniformly stirring, heating to 105 ℃, removing water and bubbles under vacuum of-0.1 MPa, and then cooling and discharging to obtain a component A;
and B component: is a commercially available PM200 polyisocyanate.
And (2) mixing the component A and the component B according to the mass ratio of 4:1, spraying the mixture on the ground, curing and forming for 48 hours at room temperature under the natural illumination condition, and finally obtaining the dual-curing polyurethane terrace coating with the Shore hardness of 75D.
Example 2
The dual-curing polyurethane floor coating is prepared by the following method:
(1) Preparation of polyester polyols containing unsaturated double bonds
Putting 468g of terephthalic acid, 92g of itaconic acid, 530g of diethylene glycol and 1090g of tung oil into a four-mouth reaction bottle, and esterifying at 215 ℃ under normal pressure under the protection of nitrogen; then adding 50ppm tetrabutyl titanate catalyst, and carrying out ester exchange reaction for 5.5h at 233 ℃ under vacuum of-0.099 MPa to obtain unsaturated double bond-containing polyester polyol with the hydroxyl value of 175mgKOH/g, the acid value of 1.3mgKOH/g and the viscosity (25 ℃) of 1460 cps.
(2) Preparation of dual-curing polyurethane floor coating
And (2) component A: adding 60 parts of polyester polyol containing unsaturated double bonds, 40 parts of talcum powder, 1.5 parts of initiator alpha-hydroxy ketone and 0.3 part of polyether modified silicone oil into a reaction bottle, uniformly stirring, heating to 110 ℃, removing water and bubbles under vacuum of-0.1 MPa, and then cooling and discharging to obtain the component A.
And the component B comprises: is a commercial PM200 polyisocyanate.
Mixing the component A and the component B according to the mass ratio of 3.5:1, spraying the mixture on the ground, curing and forming for 48 hours at room temperature under the natural illumination condition, and finally obtaining the double-curing polyurethane terrace coating with the Shore hardness of 72D.
Example 3
The dual-curing polyurethane floor coating is prepared by the following method:
(1) Preparation of polyester polyols containing unsaturated double bonds
357g of phthalic anhydride, 78g of maleic anhydride, 864g of triethylene glycol and 866g of palm oil are put into a four-port reaction flask and esterified at 235 ℃ under normal pressure under the protection of nitrogen; then adding 50ppm tetrabutyl titanate catalyst, and carrying out ester exchange reaction for 6.5h at the temperature of 232 ℃ under vacuum of-0.097 MPa to obtain unsaturated double bond-containing polyester polyol with a hydroxyl value of 192mgKOH/g, an acid value of 0.9mgKOH/g and a viscosity (25 ℃) of 680 cps.
(2) Preparation of dual-curing polyurethane floor coating
The component A comprises: adding 60 parts of polyester polyol containing unsaturated double bonds, 40 parts of white carbon black, 2 parts of initiator benzophenone and 0.25 part of polyether modified silicone oil into a reaction bottle, uniformly stirring, heating to 102 ℃, removing water and bubbles under vacuum of-0.1 MPa, and then cooling and discharging to obtain the component A.
And B component: is a commercially available PM200 polyisocyanate.
Mixing the component A and the component B according to the mass ratio of 3:1, spraying the mixture on the ground, curing and forming for 48 hours at room temperature under the natural illumination condition, and finally obtaining the double-curing polyurethane terrace coating with the Shore hardness of 73D.
Example 4
The dual-curing polyurethane floor coating is prepared by the following method:
(1) Preparation of polyester polyols containing unsaturated double bonds
Putting 430g of isophthalic acid, 75g of glutaconic acid, 682g of dipropylene glycol and 1187g of oleic acid into a four-mouth reaction bottle, and esterifying at 225 ℃ under normal pressure under the protection of nitrogen; then adding 50ppm tetrabutyl titanate catalyst, and carrying out ester exchange reaction for 6.5h at 230 ℃ under vacuum of-0.097 MPa to obtain unsaturated double bond-containing polyester polyol with a hydroxyl value of 198mgKOH/g, an acid value of 0.5mgKOH/g and a viscosity (25 ℃) of 970 cps.
(2) Preparation of dual-curing polyurethane floor coating
The component A comprises: adding 70 parts of polyester polyol containing unsaturated double bonds, 30 parts of kaolin, 2.5 parts of initiator alpha-hydroxy ketone and 0.2 part of polyether modified silicone oil into a reaction bottle, uniformly stirring, heating to 108 ℃, removing water and bubbles under vacuum of-0.1 MPa, and then cooling and discharging to obtain the component A.
And B component: is a commercially available PM200 polyisocyanate.
Mixing the component A and the component B according to a mass ratio of 2:1, spraying the mixture on the ground, curing and forming for 48 hours at room temperature under the natural illumination condition, and finally obtaining the dual-curing polyurethane terrace coating with the Shore hardness of 70D.
Comparative example 1
The polyurethane floor coating is prepared by the following method:
(1) Preparation of polyester polyols containing unsaturated double bonds
Putting 450g of maleic acid, 580g of diethylene glycol and 1545g of tung oil into a four-mouth reaction bottle, and esterifying at 205 ℃ under normal pressure under the protection of nitrogen; then adding 50ppm tetrabutyl titanate catalyst, and carrying out ester exchange reaction for 6h under vacuum of-0.1 MPa and 235 ℃ to obtain unsaturated double bond-containing polyester polyol with the hydroxyl value of 151mgKOH/g, the acid value of 1.5mgKOH/g and the viscosity (25 ℃) of 970 cps.
(2) Preparation of dual-curing polyurethane floor coating
The component A comprises: adding 50 parts of polyester polyol containing unsaturated double bonds, 50 parts of kaolin, 1 part of initiator benzophenone and 0.4 part of polyether modified silicone oil into a reaction bottle, uniformly stirring, heating to 105 ℃, removing water and bubbles under vacuum of-0.1 MPa, and then cooling and discharging to obtain the component A.
And the component B comprises: is a commercial PM200 polyisocyanate.
Mixing the component A and the component B according to a mass ratio of 4:1, spraying the mixture on the ground, curing and forming for 48 hours at room temperature, and finally obtaining the polyurethane terrace coating with the Shore hardness of 68D.
Comparative example 2
The comparison document 2 differs from example 1 in that: comparative example 2 when the polyester polyol containing unsaturated double bonds is prepared, the photoinitiator is not added in the step (2), and the shore hardness of the finally prepared polyurethane terrace coating is 72D.
Comparative example 3
(1) Preparation of polyester polyols
Putting 432g of phthalic anhydride, 69g of succinic acid, 525g of diethylene glycol and 1538g of coconut oil into a four-port reaction bottle, and esterifying at 205 ℃ under normal pressure under the protection of nitrogen; then adding 50ppm tetrabutyl titanate catalyst, and carrying out ester exchange reaction for 6h under vacuum of-0.1 MPa and 235 ℃ to obtain polyester polyol with a hydroxyl value of 149mgKOH/g, an acid value of 1.4mgKOH/g and a viscosity (25 ℃) of 1190 cps.
(2) Preparation of polyurethane floor coating
The component A comprises: adding 50 parts of polyester polyol, 50 parts of kaolin, 1 part of initiator benzophenone and 0.4 part of polyether modified silicone oil into a reaction bottle, uniformly stirring, heating to 105 ℃, removing water and bubbles under vacuum of-0.1 MPa, and then cooling and discharging to obtain a component A;
and B component: is a commercial PM200 polyisocyanate.
Mixing the component A and the component B according to a mass ratio of 4:1, spraying the mixture on the ground, curing and forming for 48 hours at room temperature under the natural illumination condition, and finally obtaining the Shore hardness 71D of the dual-curing polyurethane floor coating.
Comparative example 4
The dual-curing polyurethane floor coating is prepared by the following method:
(1) Preparation of polyester polyols containing unsaturated double bonds
Putting 432g phthalic anhydride, 69g succinic acid, 525g diethylene glycol and 1538g tung oil into a four-mouth reaction bottle, and esterifying at 205 ℃ under normal pressure under the protection of nitrogen; then adding 50ppm tetrabutyl titanate catalyst, and carrying out ester exchange reaction for 6h under vacuum of-0.1 MPa and 235 ℃ to obtain unsaturated double bond-containing polyester polyol with the hydroxyl value of 151mgKOH/g, the acid value of 1.4mgKOH/g and the viscosity (25 ℃) of 1220 cps.
(2) Preparation of dual-curing polyurethane floor coating
And (2) component A: adding 50 parts of polyester polyol containing unsaturated double bonds, 50 parts of kaolin, 1 part of initiator benzophenone and 0.4 part of polyether modified silicone oil into a reaction bottle, uniformly stirring, heating to 105 ℃, removing water and bubbles under vacuum of-0.1 MPa, and then cooling and discharging to obtain a component A;
and the component B comprises: is a commercial PM200 polyisocyanate.
Mixing the component A and the component B according to a mass ratio of 4:1, spraying the mixture on the ground, curing and forming for 48 hours at room temperature under the natural illumination condition, and finally obtaining the Shore hardness 73D of the dual-curing polyurethane terrace coating.
Comparative example 5
The dual-curing polyurethane floor coating is prepared by the following method:
(1) Preparation of unsaturated double bond-containing polyester polyol:
putting 432g phthalic anhydride, 68g maleic acid, 525g diethylene glycol and 1538g coconut oil into a four-mouth reaction bottle, esterifying at 205 ℃ under normal pressure under the protection of nitrogen, then adding 50ppm tetrabutyl titanate catalyst, and carrying out ester exchange reaction for 6h under the conditions of vacuum-0.1 MPa and 235 ℃ to obtain unsaturated double bond-containing polyester polyol with the hydroxyl value of 151mgKOH/g, the acid value of 1.44mgKOH/g and the viscosity (25 ℃) of 1206 cps;
(2) Preparing a dual-curing polyurethane floor coating composition:
and (2) component A: adding 50 parts of polyester polyol containing unsaturated double bonds, 50 parts of kaolin, 1 part of initiator benzophenone and 0.4 part of polyether modified silicone oil into a reaction bottle, uniformly stirring, heating to 105 ℃, removing water and bubbles under vacuum of-0.1 MPa, and then cooling and discharging to obtain the component A.
And B component: is a commercial PM200 polyisocyanate.
And (2) mixing the component A and the component B according to the mass ratio of 4:1, spraying the mixture on the ground, curing and forming for 48 hours at room temperature under the natural illumination condition, and finally obtaining the Shore hardness 71D.
Comparative example 6
The dual-curing polyurethane floor coating is prepared by the following method:
(1) Preparation of polyester polyols containing unsaturated double bonds
Putting 432g phthalic anhydride, 68g maleic acid, 310g ethylene glycol and 1215g tung oil into a four-mouth reaction bottle, and esterifying at 205 ℃ under normal pressure under the protection of nitrogen; then adding 50ppm tetrabutyl titanate catalyst, and carrying out ester exchange reaction for 6h under vacuum-0.1 MPa and 235 ℃ to obtain unsaturated double bond-containing polyester polyol with the hydroxyl value of 150mgKOH/g, the acid value of 1.5mgKOH/g and the viscosity (25 ℃) of 2760 cps.
(2) Preparation of dual-curing polyurethane floor coating
The component A comprises: adding 50 parts of polyester polyol containing unsaturated double bonds, 50 parts of kaolin, 1 part of initiator benzophenone and 0.4 part of polyether modified silicone oil into a reaction bottle, uniformly stirring, heating to 105 ℃, removing water and bubbles under vacuum of-0.1 MPa, and then cooling and discharging to obtain a component A;
and B component: is a commercially available PM200 polyisocyanate.
And (2) mixing the component A and the component B according to the mass ratio of 4:1, the mixture is uniformly mixed, the influence of the filler in the receptor system is avoided, the viscosity of the system is higher, and the smoothness of the surface of a coating prepared by spraying the coating on the ground is poor and the construction requirement is not met.
The floor coatings prepared in examples 1 to 4 and comparative examples 1 to 5 were subjected to performance tests, and the test results are shown in tables 1 to 2.
TABLE 1
| Item | Example 1 | Example 2 | Example 3 | Example 4 |
| Appearance of coating film | The surface is bright and clean | The surface is bright and clean | The surface is bright and clean | The surface is bright and clean |
| Gel time/min | 47 | 55 | 52 | 58 |
| Shore hardness/D | 75 | 72 | 73 | 70 |
| Tensile strength/MPa | 4.8 | 4.4 | 4.6 | 4.5 |
| Resisting artificial weather aging for 1000h | No bubbling, no falling off and no crack | No bubbling, no falling off and no crack | No bubbling, no peeling off and no crack | No bubbling, no peeling off and no crack |
TABLE 2
| Item | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Appearance of coating film | The surface is bright and clean | Smooth surface and low brightness | The surface is bright and clean | The surface is bright and clean | The surface is bright and clean | The surface is bright and clean |
| Gel time/min | 47 | 48 | 52 | 55 | 54 | 53 |
| Shore hardness/D | 75 | 68 | 72 | 71 | 73 | 71 |
| Tensile strength/MPa | 4.8 | 4.1 | 3.5 | 4.4 | 4.0 | 3.8 |
| Resisting artificial weathering for 1000 hr | No bubbling, no falling off and no crack | No bubbling, no falling off, and cracks | Fall off | Falling off | Foaming and cracking | Blistering and cracking |
In tables 1-2, the weathering test was performed with reference to the national standard GB/T14522-2008 "fluorescent ultraviolet lamp for weathering test method of plastics, paints, and rubber materials for mechanical industry products".
As can be seen from tables 1 to 2, the terrace coating product prepared in comparative example 1 has low hardness because the polyester polyol prepared in comparative example 1 does not use an aromatic dibasic acid, and the prepared terrace coating has low hardness and low tensile strength because the polyester polyol of component a does not contain a rigid benzene ring structure. In addition, because the component B is polymethylene polyphenyl polyisocyanate, the conventional polyester polyol in the comparative example 1 has poor compatibility with the polymethylene polyphenyl polyisocyanate, so that a system is turbid after the component A and the component B are mixed, and the brightness of the prepared floor coating is poor. In embodiments 1-4 of the invention, aromatic dibasic acid containing a benzene ring structure is introduced into the polyester polyol of the component A, so that the compatibility of the component A and the component B is improved according to the principle of structural similarity, and the system is transparent after the component A and the component B are mixed, thereby improving the brightness of the floor coating.
In addition, as can be seen from tables 1-2, comparative example 2 adopts conventional two-component curing, and does not adopt a photocuring mechanism, so that the prepared terrace coating has low tensile strength; in a humid environment, the prepared terrace coating has poor weather resistance and is aged and peeled off due to poor hydrolysis resistance of the polyester polyol chain segment of the component A. In embodiments 1-4 of the present application, a photoinitiator is introduced to initiate radical polymerization of double bonds in the system, increase the cross-linking structure between molecular chains, and greatly improve the tensile strength and weather resistance of the floor coating. Comparative example 3 adopts saturated vegetable oil coconut oil to prepare polyester polyol, even if photoinitiator is added in the system, the polyester polyol system does not contain reactive unsaturated double bond, so that photocuring crosslinking can not be carried out, and the terrace coating can fall off in a humid environment due to the weather resistance of the polyester polyol. Comparative example 4 when preparing polyester polyol, unsaturated dibasic acid is not used, and the prepared floor coating adopts a dual curing mechanism, but because the non-grease chain segment part in the polyol molecular chain is not subjected to photocuring crosslinking, the weather resistance of the ester-containing chain segment in the polyester polyol is poor, so that the floor coating can generate cracks in a humid environment. Comparative example 5 adopts saturated vegetable oil coconut oil to prepare polyester polyol, and the prepared floor coating adopts a dual-curing mechanism, but because the grease chain segment part in the polyol molecular chain does not contain double bonds and can not be subjected to photocuring crosslinking, the ester chain and the grease chain segment in the polyester polyol molecular chain are easy to hydrolyze and break, so that the floor coating can crack in a humid environment. The comparative example 6 adopts ethylene glycol to prepare polyester polyol, and because the polyester polyol molecular chain prepared by the ethylene glycol has strong rigidity, strong crystallinity and poor low-temperature property, the polyester polyol of the system has poor fluidity due to the influence of crystallinity and does not meet the process requirements of the floor coating under the condition of being lower than 10 ℃.
Claims (10)
1. The dual-curing polyurethane floor coating is characterized by comprising a component A and a component B, wherein the component A comprises 50-70 parts by weight of polyester polyol containing unsaturated double bonds, 30-50 parts by weight of inorganic filler, 1-3 parts by weight of photoinitiator and 0.2-0.4 part by weight of flatting agent; the component B is polyisocyanate.
2. The dual cure polyurethane floor coating of claim 1, wherein the mass ratio of the component A to the component B is 2-4.
3. The dual-curing polyurethane floor coating of claim 1, wherein the polyester polyol containing unsaturated double bonds is prepared from aromatic dibasic acid, dibasic acid containing double bonds, vegetable oil containing unsaturated double bonds and small molecular alcohol as raw materials through esterification-ester exchange reaction.
4. The dual cure polyurethane floor coating of claim 3, wherein the aromatic diacid is one of phthalic anhydride, terephthalic acid, and isophthalic acid; the double-bond-containing dibasic acid is one of maleic acid, maleic anhydride, itaconic acid and glutaconic acid.
5. The dual-curing polyurethane terrace coating of claim 3, wherein the vegetable oil containing unsaturated double bonds is one of tung oil, palm oil, oleic acid and soybean oil; the small molecular alcohol is one of diethylene glycol, triethylene glycol and dipropylene glycol.
6. The dual-curing polyurethane floor coating of claim 3, wherein the molar ratio of the aromatic dibasic acid to the double-bond-containing dibasic acid is 3-5, the molar ratio of the small molecular alcohol to the total acid is 1.4-1.8, and the amount of the unsaturated double-bond-containing vegetable oil is 40-60% of the total mass of the unsaturated double-bond-containing polyester polyol.
7. The dual-curing polyurethane floor coating of claim 3, wherein, when preparing the polyester polyol containing unsaturated double bonds, the esterification reaction is carried out under the protection of nitrogen, and the temperature of the esterification reaction is 205-235 ℃; the vacuum degree of the ester exchange reaction is-0.097 to-0.1 MPa, and the temperature of the ester exchange reaction is 230 to 235 ℃.
8. The dual-curing polyurethane floor coating of claim 3, wherein the hydroxyl value of the polyester polyol containing unsaturated double bonds is 150-300mgKOH/g, the acid value is less than or equal to 1.5mgKOH/g, and the viscosity at 25 ℃ is less than or equal to 1500cps.
9. The dual cure polyurethane floor coating of claim 1, wherein the inorganic filler in component a is one of kaolin, talc and white carbon black; the initiator is benzophenone or alpha-hydroxy ketone; the component B is polymethylene polyphenyl polyisocyanate.
10. The preparation method of the dual curing polyurethane floor coating of any one of claims 1-9, characterized in that the polyester polyol containing unsaturated double bonds, inorganic filler, photoinitiator and leveling agent are stirred and mixed uniformly, then the moisture and air bubbles are removed in vacuum at 100-110 ℃, and the component A is prepared by cooling and discharging; and (3) under the condition of natural illumination at room temperature, uniformly mixing the component A and the component B, and curing to obtain the dual-curing polyurethane floor coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211432016.0A CN115505326B (en) | 2022-11-16 | 2022-11-16 | Double-curing polyurethane floor coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211432016.0A CN115505326B (en) | 2022-11-16 | 2022-11-16 | Double-curing polyurethane floor coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115505326A true CN115505326A (en) | 2022-12-23 |
| CN115505326B CN115505326B (en) | 2023-05-09 |
Family
ID=84513985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211432016.0A Active CN115505326B (en) | 2022-11-16 | 2022-11-16 | Double-curing polyurethane floor coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115505326B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117467396A (en) * | 2023-12-27 | 2024-01-30 | 山东一诺威聚氨酯股份有限公司 | High-performance aluminum plate adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188478A (en) * | 2016-07-26 | 2016-12-07 | 巨石集团有限公司 | A kind of modified polyurethane emulsion film former and its preparation method and application |
| CN110382584A (en) * | 2017-03-03 | 2019-10-25 | 瑞森内特材料集团有限公司 | It is sustainable, can the cured polyester polyol of energy and coating as made from it or rigid foam |
| CN110724249A (en) * | 2019-10-11 | 2020-01-24 | 万华化学集团股份有限公司 | Polyester polyol, preparation method and application |
| CN111234186A (en) * | 2020-01-14 | 2020-06-05 | 湖州欧美化学有限公司 | Polyester polyol for polyurethane adhesive, preparation method thereof and polyurethane adhesive |
-
2022
- 2022-11-16 CN CN202211432016.0A patent/CN115505326B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188478A (en) * | 2016-07-26 | 2016-12-07 | 巨石集团有限公司 | A kind of modified polyurethane emulsion film former and its preparation method and application |
| CN110382584A (en) * | 2017-03-03 | 2019-10-25 | 瑞森内特材料集团有限公司 | It is sustainable, can the cured polyester polyol of energy and coating as made from it or rigid foam |
| CN110724249A (en) * | 2019-10-11 | 2020-01-24 | 万华化学集团股份有限公司 | Polyester polyol, preparation method and application |
| CN111234186A (en) * | 2020-01-14 | 2020-06-05 | 湖州欧美化学有限公司 | Polyester polyol for polyurethane adhesive, preparation method thereof and polyurethane adhesive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117467396A (en) * | 2023-12-27 | 2024-01-30 | 山东一诺威聚氨酯股份有限公司 | High-performance aluminum plate adhesive and preparation method thereof |
| CN117467396B (en) * | 2023-12-27 | 2024-04-12 | 山东一诺威聚氨酯股份有限公司 | High-performance aluminum plate adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115505326B (en) | 2023-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2393866B1 (en) | Unsaturated polyester resin compositions containing 2,2,4,4-tetramethyl-1,3- cyclobutanediol and articles made therefrom | |
| CN102712820B (en) | Radiation-curable water-based paint compositions | |
| CN115505326B (en) | Double-curing polyurethane floor coating and preparation method thereof | |
| CN1134480C (en) | Unsaturated polyester resin and the use of it | |
| CN114133541B (en) | High-hydrolysis-resistance polyester polyol, preparation method thereof and application thereof in waterborne polyurethane resin | |
| KR20110097757A (en) | Aqueously dispersed polyester resin compositions | |
| CA1329810C (en) | Trimethylolheptanes and use thereof | |
| CN104292419A (en) | Preparation method of high-performance green and environment-friendly bi-component polyurethane modified unsaturated polyester for furniture coating | |
| CN111944415A (en) | Ultraviolet curing coating and preparation method and application thereof | |
| CN110325605B (en) | Ultraviolet light curing coating composition based on biological material | |
| CN113150245B (en) | Modified vinyl ester resin and preparation method thereof, toughened and modified vinyl ester resin with good air-drying property and preparation method and application thereof | |
| CN1675276A (en) | Urethane acrylate gel coat resin and method of making | |
| CN111574697B (en) | Modified unsaturated polyester resin and preparation method and application thereof | |
| EP3885386A1 (en) | Polyol formulation and polyurethane resin | |
| CN110218288B (en) | Silicon-modified zero-VOC (volatile organic compound) water-based polyester acrylic resin and preparation method thereof | |
| WO2009059706A1 (en) | Styrene-free unsaturated polyester resin composition | |
| CN111393621A (en) | Corrosion-resistant polyester resin and preparation method thereof | |
| CN110982367A (en) | Water-based 2K finishing paint and preparation process thereof | |
| CN116854866B (en) | MMA (methyl methacrylate) bi-component unsaturated polyester resin for road coating and preparation method thereof | |
| JP2002080545A (en) | Radically polymerizable resin composition | |
| JP2007112985A (en) | Radically curable resin composition | |
| JP4911921B2 (en) | Radical curable resin composition and method for curing the same | |
| AU2021267443B2 (en) | Gelcoat compositions for sanitised water pools | |
| CN114957634B (en) | Degradable polyester rubber and preparation method and application thereof | |
| CN114276514B (en) | Polyurethane-acrylic hybrid resin and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |