CN111548720A - Bio-based single-component polyurethane waterproof coating and preparation method thereof - Google Patents
Bio-based single-component polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- CN111548720A CN111548720A CN202010528852.3A CN202010528852A CN111548720A CN 111548720 A CN111548720 A CN 111548720A CN 202010528852 A CN202010528852 A CN 202010528852A CN 111548720 A CN111548720 A CN 111548720A
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- 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
- C09D175/08—Polyurethanes from polyethers
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- 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
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- 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
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention relates to a bio-based single-component polyurethane waterproof coating and a preparation method thereof, wherein the waterproof coating comprises the following components: bio-based plasticizers, propylene glycol-based polyether polyols, glyceryl polyether polyols, talc, mica powder and modified aromatic isocyanates. The preparation method comprises the following steps: putting a bio-based plasticizer, mica powder, talcum powder, propylene glycol-based polyether polyol and glyceryl polyether polyol into a negative pressure reaction kettle, heating to 100-110 ℃, keeping the negative pressure at-0.09 to-0.1 Mpa for 0.5-1.5 hours; cooling to 65-75 ℃, closing the negative pressure, adding the modified aromatic isocyanate, heating to 70-80 ℃, and keeping stirring for 2-4 hours; adding polyamide wax and aromatic solvent oil; and defoaming to obtain the waterproof coating. The bio-based plasticizer in the waterproof coating disclosed by the invention can be used for increasing the flexibility, increasing the elongation, reducing the hardness and reducing the brittleness of the polyurethane waterproof coating.
Description
Technical Field
The invention relates to the field of polyurethane waterproof paint, in particular to bio-based single-component polyurethane waterproof paint and a preparation method thereof.
Background
The polyurethane waterproof paint is one kind of single component waterproof polyurethane paint prepared with isocyanate group-containing prepolymer prepared through addition polymerization of isocyanate, polyether, etc. and through mixing with catalyst, anhydrous assistant, anhydrous stuffing, solvent, etc.
Additives such as a plasticizer and the like are often required to be added into the waterproof coating in the prior art, so that the waterproof coating cannot be harmless to the environment and organisms. Short-chain chlorinated paraffin is commonly used as a plasticizer and a flame retardant in the polyurethane industry, and the usage amount of the short-chain chlorinated paraffin is very large in the whole industry. However, the short-chain chlorinated paraffin is a toxic substance and has strong toxicity to aquatic organisms. Phthalate-based substances (DEHP) are also frequently used as plasticizers, but are also toxic substances. Tar type waterproof paint has pungent smell, contains a large amount of volatile harmful toxicants, seriously pollutes and harms human health, and national construction prohibits the use of coal tar in polyurethane waterproof paint.
In order to improve the environmental protection property of the polyurethane waterproof coating, patent publication No. CN104403547 discloses an environmental protection type high performance polyurethane waterproof coating, in which bio-based soybean oil polyol is added in the waterproof coating, but the bio-based soybean oil polyol is only used as an organic solvent, and the plasticizer still adopts substances such as toxic chlorinated paraffin and the like.
Disclosure of Invention
Technical problem to be solved
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a polyurethane waterproof coating material with a bio-oil-based plasticizer, which solves the technical problem that the polyurethane waterproof coating material is toxic;
correspondingly, the invention also provides a preparation method of the polyurethane waterproof coating.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a bio-based single-component polyurethane waterproof coating comprises the following components: bio-based plasticizers, propylene glycol-based polyether polyols, glyceryl polyether polyols, talc, mica powder and modified aromatic isocyanates.
Further, the components are as follows according to the parts by weight: 10-30 parts of bio-based plasticizer, 5-12 parts of mica powder, 30-50 parts of talcum powder, 10-30 parts of propylene glycol-based polyether polyol, 15-20 parts of glyceryl polyether polyol and 10-20 parts of modified aromatic isocyanate.
Further, the components are as follows according to the parts by weight: 20 parts of bio-based plasticizer, 9 parts of mica powder, 40 parts of talcum powder, 20 parts of propylene glycol-based polyether polyol, 18 parts of glyceryl polyether polyol and 15 parts of modified aromatic isocyanate.
Further, the paint also comprises one or more than two of the following components: the components of the coating comprise a polymer, a.
Further, the paint also comprises one or more than two of the following components in parts by weight: 0.8-1.2 parts of poly-aminoacyl wax, 3-8 parts of methyl 3-methoxypropionate, 0.1-0.2 part of organic bismuth and 0.1-0.2 part of organic zinc.
Further, the bio-based plasticizer is a fatty acid methyl ester compound prepared from bio-derived oil.
Further, the fatty acid methyl ester compound is an epoxy fatty acid methyl ester compound; preferably, the carbon chain of the epoxy fatty acid methyl ester compound is l6-18 carbon atoms.
Further, the modified aromatic isocyanate comprises diphenylmethane diisocyanate or/and modified triphenylmethane triisocyanate.
The invention also provides a preparation method of the bio-based single-component polyurethane waterproof coating, which comprises the following steps of:
s1 includes bio-based plasticizer preparation:
after the biological grease and alcohol are subjected to ester exchange reaction, carrying out halogenation reaction to generate a bio-based plasticizer;
or
Extracting unsaturated fatty acid methyl ester from biological oil to prepare epoxy fatty acid methyl ester compound;
s2 includes high temperature vacuum dehydration: putting the obtained bio-based plasticizer, mica powder, talcum powder, propylene glycol-based polyether polyol and glyceryl polyether polyol into a negative pressure reaction kettle, starting stirring, heating to 100-110 ℃, setting the negative pressure to-0.09-0.1 Mpa, and keeping the negative pressure for 0.5-1.5 h to perform high-temperature vacuum dehydration;
s3 includes cooling and charging: cooling the inside of the negative pressure reaction kettle to 65-75 ℃, closing the negative pressure, adding the modified aromatic isocyanate, heating to 70-80 ℃, and keeping stirring for 2-4 hours;
s4 includes: adding polyamide wax and aromatic solvent oil;
s5 includes debubbling: and setting negative pressure of-0.03-0.05 mpa, and keeping for 5-15 min for defoaming to obtain the waterproof coating.
Further, it also includes the following steps: after the temperature is reduced and the materials are added in the step S3 and before the defoaming in the step S4, after the temperature in the negative pressure reaction kettle is naturally reduced to 55-65 ℃, the organic bismuth, the organic zinc catalyst and the 3-methoxy methyl propionate are added, and then the mixture is stirred for 10-20 min.
(III) advantageous effects
1. The waterproof coating disclosed by the invention is prepared by combining the bio-based plasticizer, the talcum powder and the modified aromatic isocyanate, does not contain toxic substances, can be applied to drinking water engineering, and can also be applied to common civil waterproof engineering. Compared with the existing waterproof coating, the waterproof coating has better hydrophobicity and can be suitable for special coatings; the waterproof coating has lower viscosity, and is convenient to construct without adding a diluent when in use.
2. Compared with the existing waterproof coating plasticizer and polyurethane, the bio-based plasticizer in the waterproof coating has better compatibility, so that the flexibility of the polyurethane waterproof coating is obviously improved, the elongation is increased, the hardness is reduced, and the brittleness is reduced.
3. According to the preparation method, firstly, the bio-based plasticizer and the talcum powder are subjected to high-temperature compatible dehydration to form a mixture, and then the modified isocyanate group in the mixture reacts with active hydrogen contained in the mixture to generate polyurethane group or polyurea to form a block polymer, so that the mechanical property and the environmental protection property of the coating are both best, and the bio-based single-component polyurethane waterproof coating is obtained.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention by way of specific embodiments thereof.
[ first embodiment ] to provide a toner
The embodiment of the invention provides a bio-based single-component polyurethane waterproof coating which comprises the following components of a bio-based plasticizer, propylene glycol-based polyether polyol, glyceryl polyether polyol, talcum powder, mica powder and modified aromatic isocyanate.
Bio-based plasticizer, talcum powder, mica powder and modified aromatic isocyanate.
The fireproof coating prepared by combining the bio-based plasticizer, the mica powder, the talcum powder and the modified aromatic isocyanate in the embodiment of the invention has the advantages of high tensile strength, high elongation at break, strong tearing strength, low-temperature bending property, water impermeability and good bonding force. The combination of propylene glycol based polyether polyols, glyceryl polyether polyols and bio-based plasticizing groups can enhance crosslinking.
Experiments show that: the combination of bio-based plasticizer, mica powder, talcum powder, propylene glycol based polyether polyol, glyceryl polyether polyol and modified aromatic isocyanate is adopted, and compared with the combination of plasticizers adopted in other waterproof coatings, the combination has better tensile strength.
Bio-based plasticizers, preferably vegetable oil plasticizers: can be produced by carrying out ester exchange reaction on natural oil and fat of biological raw materials such as soybean oil, palm oil, coconut oil, even animal oil and the like and alcohol, and then carrying out halogenation reaction; the natural oil exists mainly in the form of triacylglycerol. Alcohols, a large class of organic compounds, are compounds in which a hydrogen atom in a side chain of an aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon is substituted with a hydroxyl group, and the chlorination reaction generally refers to a reaction in which chlorine is introduced into the compound. Or the grease of the biological raw material is exchanged by methanol to form fatty acid methyl ester, and the fatty acid methyl ester is further processed into epoxy fatty acid methyl ester to be used as a plasticizer. Molecular formula C19H36O3The fatty acid methyl ester is prepared by reacting various straight chain fatty acids with methanol, and the carbon chain of the straight chain unsaturated fatty acid methyl ester is generally l6-18 carbons, and the structural formula of the straight chain unsaturated fatty acid methyl ester is as follows: r1One CH ═ CH-R2A COOCH: (wherein R is1And R2About 14-l 6). In the presence of H +, an organic acid (formic acid for example) is reacted with H +202The reaction generates peroxyformic acid, and the peroxyformic acid immediately reacts with unsaturated double bonds in the fatty acid methyl ester to generate epoxy fatty acid methyl ester.
Compared with other plasticizers, the vegetable-based plasticizer can effectively reduce the viscosity of the product, is convenient to mix, has good compatibility in a polyurethane system, and has better waterproof and hydrophobic functions and effects because the hydrophobicity of vegetable oil fatty acid ester and the compatibility of polyurethane are excellent. Compared with other plasticizers, the vegetable oil-based plasticizer has higher compatibility, the prepared product is more compact, the performance of the polyurethane waterproof coating can be improved, and particularly, the elongation of the polyurethane waterproof coating is improved, the hardness is reduced, and the brittleness is reduced. Vegetable oil plasticizers are compared to other plasticizers. High heating reduction and low oil absorption. The addition of the powder filler in the waterproof coating can be increased, a storage tank is not required to be heated for storage in production, energy is saved, the production cost is reduced, and the powder filler can be directly added into a reaction kettle without being heated in the production process. Compared with other plasticizers, the plant-based plasticizer has low viscosity at low temperature, is favorable for reducing the use of a solvent and improves the environmental protection property of the product. Compared with a short-chain chlorinated paraffin plasticizer, the vegetable oil-based plasticizer has lighter color and can be used for preparing colorful polyurethane waterproof coatings conveniently.
Compared with the plasticizer of the existing waterproof coating, the plant-based plasticizer applied to the waterproof coating has various advantages, and the addition amount of other functional components can be reduced, so that the manufacturing cost of the waterproof coating is greatly and indirectly reduced.
Preferably, the components are as follows according to parts by weight: 10-30 parts of bio-based plasticizer, 5-12 parts of mica powder, 30-50 parts of talcum powder, 10-30 parts of propylene glycol-based polyether polyol, 15-20 parts of glyceryl polyether polyol and 10-20 parts of modified aromatic isocyanate.
Preferably, the talcum powder is 1000 meshes talcum powder;
preferably, the mica powder is 2000-mesh mica powder;
preferably, the components are as follows according to parts by weight: the components are as follows by weight: 20 parts of bio-based plasticizer, 9 parts of mica powder, 40 parts of talcum powder, 20 parts of propylene glycol-based polyether polyol, 18 parts of glyceryl polyether polyol and 15 parts of modified aromatic isocyanate.
In order to improve the crosslinking strength between the waterproof coatings, the waterproof coating further comprises one or more than two of the following components: the components of the coating comprise a polymer, a.
Since the vegetable oil-based plasticizer affects the tear strength of the waterproof material compared to other plasticizers, the above-mentioned component is preferably: 1.2 parts of poly-aminoacyl wax, 5 parts of methyl 3-methoxypropionate, 0.1 part of organic bismuth and 0.1 part of organic zinc.
The waterproof coating material obtained has the best tensile strength only when the formula components and the corresponding weight parts are mixed, and the tensile strength of the waterproof coating material is reduced by simply replacing any component, so that the combination of any component and the vegetable oil-based plasticizer for the waterproof material has a synergistic effect on the tensile strength of the waterproof material.
The modified aromatic isocyanate is modified diphenylmethane diisocyanate or modified triphenylmethane triisocyanate;
the organobismuth catalyst is type BI 118.
The organic zinc catalyst is Zn1910 type
Further, the bio-based plasticizer is a fatty acid methyl ester compound prepared from bio-derived oil.
Further, the fatty acid methyl ester compound is an epoxy fatty acid methyl ester compound; preferably, the carbon chain of the epoxy fatty acid methyl ester compound is l6-18 carbon atoms.
Further, the modified aromatic isocyanate comprises diphenylmethane diisocyanate or/and modified triphenylmethane triisocyanate.
[ second embodiment ] to provide a medicine for treating diabetes
The embodiment of the invention also provides a preparation method of the bio-based single-component polyurethane waterproof coating, which comprises the following steps of:
s1 includes bio-based plasticizer preparation:
after the biological grease and alcohol are subjected to ester exchange reaction, carrying out halogenation reaction to generate a bio-based plasticizer;
or
Extracting unsaturated fatty acid methyl ester from biological oil to prepare epoxy fatty acid methyl ester compound;
the bio-based plasticizer prepared by the method has stronger tensile strength.
S2 includes high temperature vacuum dehydration: putting the obtained bio-based plasticizer, mica powder and talcum powder into a negative pressure reaction kettle, starting stirring, heating to 100-110 ℃, setting the negative pressure to-0.09-0.1 Mpa, and keeping the negative pressure for 0.5-1.5 h to perform high-temperature vacuum dehydration;
s3 includes cooling and charging: cooling the inside of the negative pressure reaction kettle to 65-75 ℃, closing the negative pressure, adding the modified aromatic isocyanate, heating to 70-80 ℃, and keeping stirring for 2-4 hours;
s4 includes: adding polyamide wax and aromatic solvent oil;
s5 includes debubbling: and setting negative pressure of-0.03-0.05 mpa, and keeping for 5-15 min for defoaming to obtain the waterproof coating.
Further, in step S2, propylene glycol-based polyether polyol and glycerin-based polyether polyol are also charged into the negative pressure reactor before stirring;
or/and
it also includes the following steps:
after the temperature is reduced and the materials are added in the step S3 and before the defoaming in the step S4, after the temperature in the negative pressure reaction kettle is naturally reduced to 55-65 ℃, the organic bismuth, the organic zinc catalyst and the 3-methoxy methyl propionate are added, and then the mixture is stirred for 10-20 min.
In this embodiment, since the reaction of the crosslinking functional group is more vigorous, the viscosity of the reaction system is too high, and in step S3, the viscosity of the crosslinking system of the bio-based plasticizer and other components is reduced by using a lower mixing temperature, so as to prolong the shelf life of the waterproof coating. And the polyamide wax and the aromatic hydrocarbon solvent oil must be added in step S4 in order to prevent the occurrence of easy precipitation due to the addition of the bio-based plasticizer. Preferably, the selected mica powder and the selected talcum powder are flaky powder, so that the occurrence of precipitation is further prevented.
In order to better understand the above technical solutions, exemplary embodiments of the present invention will be described in more detail below. While exemplary embodiments of the invention have been shown, it should be understood that the invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
The bio-based single-component polyurethane waterproof coating comprises the following components: 20 parts of bio-based plasticizer, 9 parts of mica powder, 40 parts of talcum powder, 15 parts of modified aromatic isocyanate, 1 part of polyurethane wax, 5 parts of methyl 3-methoxypropionate, 20 parts of propylene glycol-based polyether polyol, 18 parts of glyceryl polyether polyol, 0.15 part of organic bismuth and 0.15 part of organic zinc.
The preparation method comprises the following steps:
s1 high-temperature vacuum dehydration: propylene glycol-based polyether polyol, glyceryl polyether polyol,
Putting epoxy fatty acid methyl ester compounds, mica powder and talcum powder into a negative pressure reaction kettle, starting stirring, heating to 110 ℃, setting the negative pressure to be-0.09 Mpa, and keeping for 1h to perform high-temperature vacuum dehydration;
s2 cooling and feeding: cooling the inside of the negative pressure reaction kettle to 75 ℃, closing the negative pressure, adding diphenylmethane diisocyanate, heating to 70 ℃, and keeping stirring for 3 hours;
s3 adding rheological additives: adding polyamide wax and aromatic solvent oil;
s4, naturally cooling to 65 ℃ in the negative pressure reaction kettle, adding organic bismuth, organic zinc catalyst and 3-methoxy methyl propionate, and stirring for 10 min;
s5 includes debubbling: setting negative pressure of-0.04 mpa, and keeping for 10min for defoaming to obtain the waterproof coating.
Example 2
The bio-based single-component polyurethane waterproof coating comprises the following components: 10 parts of bio-based plasticizer, 8 parts of mica powder, 30 parts of talcum powder, 10 parts of diphenylmethane diisocyanate, 10 parts of modified triphenylmethane triisocyanate, 1 part of polyurethane wax, 3 parts of methyl 3-methoxypropionate, 30 parts of propylene glycol-based polyether polyol, 15 parts of glyceryl polyether polyol, 0.1 part of organic bismuth and 0.2 part of organic zinc.
The preparation method comprises the following steps:
s1 includes high temperature vacuum dehydration: putting epoxy fatty acid methyl ester compound, mica powder and talcum powder into a negative pressure reaction kettle, starting stirring, heating to 105 ℃, setting the negative pressure to-0.1 Mpa, and keeping the negative pressure for 0.5h to perform high-temperature vacuum dehydration;
s2 includes cooling and charging: cooling the inside of the negative pressure reaction kettle to 70 ℃, closing the negative pressure, adding diphenylmethane diisocyanate, heating to 80 ℃, and keeping stirring for 2 hours;
s3 includes: adding polyamide wax and aromatic solvent oil;
s4, naturally cooling to 60 ℃ in the negative pressure reaction kettle, adding the organic bismuth, the organic zinc catalyst and the 3-methoxy methyl propionate, and stirring for 20 min;
s5 propylene glycol-based polyether polyol, glyceryl polyether polyol;
s6 includes debubbling: setting negative pressure of-0.03 mpa, and keeping for 10min for defoaming to obtain the waterproof coating.
Example 3
The bio-based single-component polyurethane waterproof coating comprises the following components: 11 parts of bio-based plasticizer, 12 parts of mica powder, 40 parts of talcum powder, 5 parts of diphenylmethane diisocyanate, 6 parts of modified triphenylmethane triisocyanate, 1.2 parts of polyurethane wax, 5 parts of methyl 3-methoxypropionate, 11 parts of propylene glycol-based polyether polyol, 20 parts of glyceryl polyether polyol, 0.15 part of organic bismuth and 0.1 part of organic zinc.
The preparation method comprises the following steps:
s1 includes high temperature vacuum dehydration: putting epoxy fatty acid methyl ester compound, mica powder and talcum powder into a negative pressure reaction kettle, starting stirring, heating to 100 ℃, setting the negative pressure to-0.1 Mpa, and keeping for 1.5h to perform high-temperature vacuum dehydration;
s2 includes cooling and charging: cooling the inside of the negative pressure reaction kettle to 65 ℃, closing the negative pressure, adding diphenylmethane diisocyanate, heating to 75 ℃, and keeping stirring for 4 hours;
s3 includes: adding polyamide wax and aromatic solvent oil;
s4, naturally cooling to 55 ℃ in the negative pressure reaction kettle, adding organic bismuth, organic zinc catalyst and 3-methoxy methyl propionate, and stirring for 15 min;
s5 propylene glycol-based polyether polyol, glyceryl polyether polyol;
s6 includes debubbling: and setting negative pressure of-0.05 mpa, and keeping for 6min for defoaming to obtain the waterproof coating.
Comparative example 1
The other points are different from example 1 in that: the contained components and the modified diphenylmethane diisocyanate involved in the preparation method are replaced by modified triphenylmethane triisocyanate.
Comparative example 2
The other points are different from example 1 in that: the contained components and the plant-based plasticizer involved in the preparation method are replaced by the same parts by weight of modified diphenylmethane diisocyanate.
Comparative example 3
The other points are different from example 1 in that: the contained components and the methyl 3-methoxypropionate involved in the preparation method are replaced by the same weight parts of plant-based plasticizer.
Experimental data:
experiment I and mechanics detection
After the waterproof coatings obtained in examples 1 to 3 and comparative examples 1 to 3 of the present invention and the commercially available polyurethane waterproof coatings are cooled to room temperature, the tensile mechanical properties after coating are measured according to the GB/T19250-2013 type I standard, and the data shown in Table 1 are obtained:
inventive examples 1-3 were tested for tensile strength at break to give the results shown in table 1:
TABLE 1
| Sample(s) | Tensile Strength at Break TSb | Elongation at tear Eb |
| MPa | ％ | |
| Coating of example 1 | 4.012 | 693.794 |
| Coating of example 2 | 4.011 | 753.688 |
| Coating of example 3 | 4.105 | 690.838 |
| Coating on market | 2.875 | 583.901 |
| Coating of comparative example 1 | 3.811 | 712.881 |
| Coating of comparative example 2 | 2.789 | 601.358 |
| Coating of comparative example 3 | 3.127 | 638.743 |
The data in table 1 show that: the coatings obtained in examples 1 to 3 and 5 to 9 according to the present invention have stronger tensile strength and better tensile strength at break than those obtained in comparative examples 2 and 3 and the coatings on the market, and the modified diphenylmethane diisocyanate of the present invention and the plant-based plasticizer interact with the tensile properties of the waterproof coating, as can be seen from the data of example 1 and comparative examples 1 to 3.
2. Environmental protection Performance test
According to the JC/T1066-2008 method test, the detection of the embodiments 1-3 of the invention can pass the A-type standard requirements.
In addition, SCCPs are generally plasticizers, which are organic substances with durability, toxicity, bioaccumulation, and long-range migratory ability, are highly toxic to aquatic organisms, and have long-term negative effects on the aquatic environment. According to 11 months 2015, the european union committee issued directive (EU)2015/2030 that regulated mass fraction of SCCPs in articles to be less than 0.15%, and was prohibited if SCCPs less than 0.15% were declared as required by REACH regulations and were greater than or equal to 0.15%. In the 5 th month of 2017, stockholm convention on persistent organic pollutants (hereinafter, abbreviated as "convention"), the eighth meeting of convention on persistent organic pollutants (COP8) reviewed the risk profile and risk management evaluation of short-chain chlorinated paraffins (SCCPs) in the commission on examination of Persistent Organic Pollutants (POPRC), decided to add SCCPs to convention "annex a, and given specific exemptions, the convention was asked to gradually stop the production and use of SCCPs during the exemption period. The plant-based single-component polyurethane waterproof coating does not contain SCCPS and phthalate (DEHP).
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A bio-based single-component polyurethane waterproof coating is characterized by comprising the following components: bio-based plasticizers, propylene glycol-based polyether polyols, glyceryl polyether polyols, talc, mica powder and modified aromatic isocyanates.
2. The bio-based single-component polyurethane waterproof coating as claimed in claim 1, wherein the components are as follows by weight: 10-30 parts of bio-based plasticizer, 5-12 parts of mica powder, 30-50 parts of talcum powder, 10-30 parts of propylene glycol-based polyether polyol, 15-20 parts of glyceryl polyether polyol and 10-20 parts of modified aromatic isocyanate.
3. The bio-based mono-component polyurethane waterproof coating as claimed in claim 2, wherein the components are respectively as follows by weight: 20 parts of bio-based plasticizer, 9 parts of mica powder, 40 parts of talcum powder, 20 parts of propylene glycol-based polyether polyol, 18 parts of glyceryl polyether polyol and 15 parts of modified aromatic isocyanate.
4. The bio-based one-component polyurethane waterproof coating material according to claim 1, further comprising one or two or more of the following components: the components of the coating comprise a polymer, a.
5. The bio-based one-component polyurethane waterproof coating as claimed in claim 2, further comprising one or more of the following components in parts by weight: 0.8-1.2 parts of poly-aminoacyl wax, 3-8 parts of methyl 3-methoxypropionate, 0.1-0.2 part of organic bismuth and 0.1-0.2 part of organic zinc.
6. The bio-based one-component polyurethane waterproofing paint according to any one of claims 1 to 5, wherein: the bio-based plasticizer is a fatty acid methyl ester compound prepared from biological grease.
7. The bio-based one-component polyurethane waterproofing coating according to claim 6, wherein: the fatty acid methyl ester compound is an epoxy fatty acid methyl ester compound; preferably, the carbon chain of the epoxy fatty acid methyl ester compound is l6-18 carbon atoms.
8. The bio-based one-component polyurethane waterproofing coating according to claim 1, wherein: the modified aromatic isocyanate comprises diphenylmethane diisocyanate or/and modified triphenylmethane triisocyanate.
9. A method for preparing the bio-based one-component polyurethane waterproof coating material of claim 1, comprising the following steps performed in order:
s1 includes bio-based plasticizer preparation:
after the biological grease and alcohol are subjected to ester exchange reaction, carrying out halogenation reaction to generate a bio-based plasticizer;
or
Extracting unsaturated fatty acid methyl ester from biological oil to prepare epoxy fatty acid methyl ester compound;
s2 includes high temperature vacuum dehydration: putting the obtained bio-based plasticizer, mica powder, talcum powder, propylene glycol-based polyether polyol and glyceryl polyether polyol into a negative pressure reaction kettle, starting stirring, heating to 100-110 ℃, setting the negative pressure to-0.09-0.1 Mpa, and keeping the negative pressure for 0.5-1.5 h to perform high-temperature vacuum dehydration;
s3 includes cooling and charging: cooling the inside of the negative pressure reaction kettle to 65-75 ℃, closing the negative pressure, adding the modified aromatic isocyanate, heating to 70-80 ℃, and keeping stirring for 2-4 hours;
s4 includes: adding polyamide wax and aromatic solvent oil;
s5 includes debubbling: and setting negative pressure of-0.03-0.05 mpa, and keeping for 5-15 min for defoaming to obtain the waterproof coating.
10. The method for preparing bio-based one-component polyurethane waterproofing paint according to claim 9,
it is characterized by also comprising the following steps: after the temperature is reduced and the materials are added in the step S3 and before the defoaming in the step S4, after the temperature in the negative pressure reaction kettle is naturally reduced to 55-65 ℃, the organic bismuth, the organic zinc catalyst and the 3-methoxy methyl propionate are added, and then the mixture is stirred for 10-20 min.
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