CN113603881A - Fluorinated polytetrahydrofuran diol and preparation method thereof, fluorinated polyurethane waterproof coating and composition thereof, and preparation method and application of fluorinated polyurethane waterproof coating - Google Patents
Fluorinated polytetrahydrofuran diol and preparation method thereof, fluorinated polyurethane waterproof coating and composition thereof, and preparation method and application of fluorinated polyurethane waterproof coating Download PDFInfo
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4607—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen having halogens
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
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- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
Abstract
The invention relates to the technical field of waterproof coatings, in particular to a fluorinated polytetrahydrofuran diol and a preparation method thereof, a fluorinated polyurethane waterproof coating and a composition, a preparation method and application thereof, wherein the coating composition contains the following components which are respectively independently stored or are mixed and stored: aliphatic polycarbonate diol, fluorinated polytetrahydrofuran diol, diisocyanate, plasticizer, chain extender, organic tin catalyst, latent curing agent, pigment filler and solvent, and optionally hexamethylene diisocyanate trimer. The fluorine-containing polyurethane waterproof coating provided by the invention can obviously improve the self-cleaning capability and the hydrophobic property of the coating, and has better waterproof and oil-proof functions and weather resistance.
Description
Technical Field
The invention relates to the technical field of waterproof coatings, and particularly relates to fluorinated polytetrahydrofuran diol and a preparation method thereof, a fluorinated polyurethane waterproof coating and a composition thereof, and a preparation method and application of the fluorinated polyurethane waterproof coating.
Background
The polyurethane waterproof paint is a synthetic high-molecular waterproof paint, has convenient construction and excellent performance, can form a continuous, elastic, seamless and integral waterproof layer after being cured at room temperature, has very wide application, and is suitable for various waterproof engineering systems such as roofs, basements, bridges, pools and the like.
With the rapid development of economy in China, more than moderate pollution appears in many cities, and common pollution comprises acid rain, haze, sand storm and the like. This presents a great problem for the daily cleaning of the external walls of buildings, and in order to be able to better solve these problems, some researchers have proposed self-cleaning coatings.
The self-cleaning coating comes from scientists and finds that the lotus leaf surface can not be wetted by water and can clean stains on the surface, thereby achieving the self-cleaning effect. Through microscopic observation of the lotus leaf surface, people find that the lotus leaf surface has micron-scale mastoid, nano-scale wax crystal substances are arranged on the mastoid, and the micro-nano-scale coarse structure can greatly improve the contact angle of water drops on the mastoid, so that the water drops are easy to roll off.
The self-cleaning coating is coated on the outer wall, and because the surface energy of the self-cleaning coating is low and the microstructure of the surface is rough, water and other pollutants are difficult to attach to the surface of the coating, or once the pollutants are attached, the pollutants are easily carried away by water flow washing, and a clean coating surface is left, so that the coating surface has an excellent self-cleaning effect.
The traditional polyurethane waterproof paint is poor in weather resistance and water resistance and easy to generate yellowing due to the fact that diisocyanate containing an aromatic ring structure is adopted for reaction, and therefore most of polyurethane waterproof paints are only applied to non-exposed parts.
For the above problems, for example, CN110951381A provides a high weather-resistant exposed one-component polyurethane waterproof coating, a siloxane bond (Si-O-Si) chain segment structure with high stability is introduced into a formed prepolymer, so that the weather resistance of the polyurethane waterproof coating is greatly improved, and the polyurethane waterproof coating has excellent weather resistance without adding an antioxidant, an ultraviolet absorber and other additives, and solves the problems that the traditional one-component polyurethane waterproof coating has poor weather resistance and is not suitable for being exposed. However, the coating provided by this document is susceptible to environmental pollution and is not easy to clean when exposed for use.
Therefore, it is necessary to develop a polyurethane waterproof coating material having excellent weather resistance and a self-cleaning function.
Disclosure of Invention
The invention aims to overcome the defects of poor weather resistance and self-cleaning capability of the existing coating.
The inventor of the invention finds in research that the fluorinated polytetrahydrofuran diol can be used for preparing the fluorine-containing polyurethane waterproof coating with excellent weather resistance and hydrophobic property, macromolecules of the fluorinated polytetrahydrofuran diol have fluorine-containing chain segments, the fluorine content of the prepared polyurethane is high, the fluorine-containing chain segments are easy to migrate to the surface and generate microphase separation because the fluoroalkyl groups in the polyurethane are positioned on the side chains of the polyurethane chain segments, and a rough nano structure is constructed on the surface of the coating, so that the fluorinated polyurethane waterproof coating has the advantages of hydrophobicity, anti-fouling and self-cleaning effects, and the prepared fluorine-containing polyurethane waterproof coating has excellent waterproof function and has a contact angle to water higher than 105 degrees. In view of the above, the inventors provide a solution to the present invention.
In order to achieve the above object, a first aspect of the present invention provides a fluorinated polytetrahydrofuran diol having a structure represented by formula (1),
wherein, in the formula (1), n is a positive integer, and n enables the weight average molecular weight of the fluorinated polytetrahydrofuran diol to be 1500-.
In a second aspect, the present invention provides a process for preparing a fluorinated polytetrahydrofuran diol as described in the first aspect, which comprises:
in the presence of an initiator, carrying out contact reaction on polytetrahydrofuran diol and hexafluoropropylene, wherein the weight ratio of the polytetrahydrofuran diol to the hexafluoropropylene is 1: 2-4, the structural formula of the polytetrahydrofuran diol is HO- [ CH2CH2CH2CH2O]m-H, wherein m is the same as n.
The third aspect of the present invention provides a fluorine-containing polyurethane waterproof coating composition, which contains the following components stored independently or in a mixture of two or more of them: aliphatic polycarbonate diol, fluorinated polytetrahydrofuran diol, diisocyanate, a plasticizer, a chain extender, an organic tin catalyst, a latent curing agent, a pigment filler and a solvent, and optionally contains hexamethylene diisocyanate trimer;
relative to 100 parts by weight of the coating composition, the content of the aliphatic polycarbonate diol is 15-27 parts by weight, the content of the fluorinated polytetrahydrofuran diol is 3-10 parts by weight, the content of the diisocyanate is 9-20 parts by weight, the content of the plasticizer is 3-7 parts by weight, the content of the chain extender is 1-2 parts by weight, the content of the organotin catalyst is 0.1-0.8 part by weight, the content of the latent curing agent is 1-2 parts by weight, the content of the pigment and filler is 17-45 parts by weight, the content of the solvent is 8-15 parts by weight, and the content of the hexamethylene diisocyanate trimer is 0-9 parts by weight;
wherein the fluorinated polytetrahydrofuran diol is the fluorinated polytetrahydrofuran diol of the first aspect.
The fourth aspect of the present invention provides a method for preparing a fluorine-containing polyurethane waterproof coating material, comprising:
(a) preparing fluorinated polytetrahydrofuran diol by the method of the second aspect;
(b) the components of the coating composition according to the third aspect are subjected to a first mixing.
The fifth aspect of the present invention provides the fluorine-containing polyurethane waterproof coating material prepared by the method described in the fourth aspect.
A sixth aspect of the present invention provides the use of the fluorine-containing polyurethane waterproof coating material according to the fifth aspect in waterproofing buildings.
Compared with the existing coating technology, the fluorine-containing polyurethane waterproof coating provided by the invention has at least the following advantages:
the fluorine-containing polyurethane waterproof coating provided by the invention has better self-cleaning capability, and has better waterproof and oil-proof functions and weather resistance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an infrared spectrum of fluorinated polytetrahydrofuran diol AA-1 prepared in preparation example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
It should be noted that, in various aspects of the present invention, the present invention is described only once in one aspect thereof without repeated description with respect to the same components in the aspects, and those skilled in the art should not be construed as limiting the present invention.
In the case where no explanation is given to the contrary, the room temperature in the present invention is 25. + -. 2 ℃.
As described above, the first aspect of the present invention provides a fluorinated polytetrahydrofuran diol having a structure represented by the formula (1),
wherein, in the formula (1), n is a positive integer, and n enables the weight average molecular weight of the fluorinated polytetrahydrofuran diol to be 1500-.
As previously mentioned, a second aspect of the present invention provides a process for the preparation of the fluorinated polytetrahydrofuran diol of the first aspect, which process comprises:
in the presence of an initiator, carrying out contact reaction on polytetrahydrofuran diol and hexafluoropropylene, wherein the weight ratio of the polytetrahydrofuran diol to the hexafluoropropylene is 1: 2-4, the structural formula of the polytetrahydrofuran diol is HO- [ CH2CH2CH2CH2O]m-H, wherein m is the same as n.
Preferably, the conditions of the contact reaction at least satisfy: the temperature is 80-100 ℃ and the time is 5-7 h.
Preferably, the initiator is selected from at least one of di-tert-butyl peroxide (DTBP), Azobisisobutyronitrile (AIBN), dibenzoyl peroxide (BPO).
According to a particularly preferred embodiment, the process for preparing the fluorinated polytetrahydrofuran diol of the aforementioned first aspect comprises the following steps:
freezing polytetrahydrofuran diol in an acetone/liquid nitrogen mixture, dehydrating for 120-150 min under vacuum, adding hexafluoropropylene and an initiator azobisisobutyronitrile, reacting for 5-7h at 80-100 ℃, cooling to room temperature, and purifying the product, wherein the weight ratio of the polytetrahydrofuran diol to the hexafluoropropylene is 1: 2-4.
Under the preferred embodiment, the inventors found that the prepared fluorinated polytetrahydrofuran diol can be used for preparing a fluorine-containing polyurethane waterproof coating material with excellent weather resistance and hydrophobic property.
As described above, the third aspect of the present invention provides a fluorine-containing polyurethane waterproof coating composition, which contains the following components stored independently or in a mixture of two or more of them: aliphatic polycarbonate diol, fluorinated polytetrahydrofuran diol, diisocyanate, a plasticizer, a chain extender, an organic tin catalyst, a latent curing agent, a pigment filler and a solvent, and optionally contains hexamethylene diisocyanate trimer;
relative to 100 parts by weight of the coating composition, the content of the aliphatic polycarbonate diol is 15-27 parts by weight, the content of the fluorinated polytetrahydrofuran diol is 3-10 parts by weight, the content of the diisocyanate is 9-20 parts by weight, the content of the plasticizer is 3-7 parts by weight, the content of the chain extender is 1-2 parts by weight, the content of the organotin catalyst is 0.1-0.8 part by weight, the content of the latent curing agent is 1-2 parts by weight, the content of the pigment and filler is 17-45 parts by weight, the content of the solvent is 8-15 parts by weight, and the content of the hexamethylene diisocyanate trimer is 0-9 parts by weight;
wherein the fluorinated polytetrahydrofuran diol is the fluorinated polytetrahydrofuran diol of the first aspect.
Preferably, the content of the aliphatic polycarbonate diol is 18 to 23 parts by weight, the content of the fluorinated polytetrahydrofuran diol is 5 to 10 parts by weight, the content of the diisocyanate is 10 to 15 parts by weight, the content of the plasticizer is 5 to 7 parts by weight, the content of the chain extender is 1 to 1.5 parts by weight, the content of the organotin catalyst is 0.3 to 0.6 part by weight, the content of the latent curing agent is 1 to 1.5 parts by weight, the content of the pigment and filler is 40 to 45 parts by weight, the content of the solvent is 10 to 12 parts by weight, and the content of the hexamethylene diisocyanate trimer is 2 to 5 parts by weight, relative to 100 parts by weight of the coating composition. Under the preferred embodiment, the inventors found that a fluorinated polyurethane waterproof coating having better weather resistance, hydrophobic property and self-cleaning ability can be obtained.
Preferably, the aliphatic polycarbonate diol is at least one selected from polypropylene carbonate diols.
Preferably, the polypropylene carbonate diol has a structure represented by formula (2),
wherein, in the formula (2), n 'is a positive integer, and n' is such that the weight average molecular weight of the polypropylene carbonate glycol is 2000-3000. More preferably, in formula (2), n' is 11 to 17.
Illustratively, the polypropylene carbonate diol may be polypropylene carbonate diol PPCD 222, polypropylene carbonate diol PPCD 221, polypropylene carbonate diol PPCD 231, polypropylene carbonate diol PPCD 232, all of which are available from fine chemical industries, dallingzhi, da, inc. Under the preferred embodiment, the inventors found that the present invention can obtain a fluorine-containing polyurethane waterproof coating material having better self-cleaning ability.
Preferably, the diisocyanate is selected from at least one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate.
Preferably, the plasticizer is at least one selected from the group consisting of chlorinated paraffin, trioctyl phosphate, polyester-based plasticizers, aliphatic dibasic acid ester-based plasticizers, and citrate-based plasticizers.
According to a particularly preferred embodiment, the diisocyanate is selected from at least one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate; the plasticizer is selected from at least one of chlorinated paraffin, trioctyl phosphate, polyester plasticizer, aliphatic dibasic acid ester plasticizer and citrate plasticizer.
Preferably, the chain extender is selected from at least one of trimethylolpropane, 1, 4-butanediol, ethylene glycol, propylene glycol, neopentyl glycol, and 1, 6-hexanediol.
Preferably, the organic tin catalyst is at least one of dibutyltin dilaurate, stannous octoate and environment-friendly non-butyl tin catalyst.
Preferably, the latent curing agent is selected from at least one of an imine-type latent curing agent and an oxazolidine-type latent curing agent. Illustratively, the imine latent curing agent is at least one of aldehyde amine latent curing agent and ketone amine latent curing agent, and the oxazolidine latent curing agent is at least one of 1, 3-oxazolidine and 2-isopropyl-1, 3-oxazolidine.
According to a particularly preferred embodiment, the chain extender is selected from at least one of trimethylolpropane, 1, 4-butanediol, ethylene glycol, propylene glycol, neopentyl glycol, 1, 6-hexanediol; the organic tin catalyst is at least one of dibutyltin dilaurate, stannous octoate and environment-friendly non-butyltin catalyst; the latent curing agent is at least one selected from an imine latent curing agent and an oxazolidine latent curing agent.
Preferably, the pigment and filler is selected from at least one of talcum powder, titanium dioxide and mica powder.
Preferably, the solvent is at least one selected from ethyl acetate, propylene glycol methyl ether acetate, butyl acetate, xylene and trimethylbenzene.
In order to obtain a fluorine-containing polyurethane waterproof coating material having better weather resistance, hydrophobic property and self-cleaning ability, as described above, the fourth aspect of the present invention provides a method for preparing a fluorine-containing polyurethane waterproof coating material, the method comprising:
(a) preparing fluorinated polytetrahydrofuran diol by the method of the second aspect;
(b) the components of the coating composition according to the third aspect are subjected to a first mixing.
Preferably, the operation of first mixing comprises the steps of:
(1) carrying out first contact reaction on each component in a composition A to obtain a product I, wherein the composition A contains aliphatic polycarbonate diol, fluorinated polytetrahydrofuran diol, a plasticizer and pigment and filler;
(2) carrying out second contact reaction on the product I and each component in a combination B to obtain a product II, wherein the combination B contains diisocyanate and a solvent, and optionally contains hexamethylene diisocyanate trimer;
(3) and carrying out a third contact reaction on the product II and each component in the combination C to obtain the fluorinated polyurethane waterproof coating, wherein the combination C contains a chain extender, an organic tin catalyst and a latent curing agent.
Preferably, in step (1), the conditions of the first contact reaction at least satisfy: the reaction temperature is 100-110 ℃, and the reaction time is 2-3 h.
Preferably, in step (2), the conditions of the second contact reaction at least satisfy: the reaction temperature is 90-95 ℃, and the reaction time is 2-3 h.
Preferably, in step (3), the conditions of the third contact reaction at least satisfy: the reaction temperature is 65-85 ℃, and the reaction time is 1.5-2.5 h.
According to a particularly preferred embodiment, the operation of first mixing comprises the following steps:
(1) dispersing aliphatic polycarbonate diol, fluorinated polytetrahydrofuran diol, a plasticizer, a pigment and filler, an optional dispersion stabilizer and an optional defoaming agent in a high-speed dispersion machine at 800-1200rpm for 4-6 min, and then adjusting the rotating speed to 1500-2000rpm for dispersing for 30-50 min; transferring the dispersed materials into a reaction container, stirring and heating to 110 ℃, and dehydrating for 2-3h under the relative vacuum degree of-0.08 MPa to-0.1 MPa;
(2) reducing the temperature to 90-95 ℃, adding 1/5-1/3 of solvent, then adding diisocyanate and optional hexamethylene diisocyanate trimer, stirring uniformly, and reacting for 2-3 h;
(3) adding a chain extender, and reacting for 0.5-1h at 75-85 ℃; then adding 1/4-1/2 dosage of organic tin catalyst, and continuing to react for 0.5 h; cooling to 65-70 deg.C, adding latent curing agent, and stirring for 0.5-1 h; and then adding the rest organic tin catalyst and solvent, charging nitrogen for protection and discharging to obtain the fluorine-containing polyurethane waterproof coating.
As described above, the fifth aspect of the present invention provides the fluorine-containing polyurethane waterproof coating material prepared by the method described in the fourth aspect.
As described above, the sixth aspect of the present invention provides the use of the fluorine-containing polyurethane waterproof coating material according to the fifth aspect in waterproofing a building.
The present invention will be described in detail below by way of examples.
In the following examples, unless otherwise specified, the laboratory instruments and raw materials are commercially available.
Laboratory apparatus
Rotary vane vacuum pump: 2XZ-2, Lechen instruments science and technology, Inc.;
electronic temperature-regulating electric heating jacket: DZTW, Tianjin Industriety laboratory instruments Co., Ltd;
the stirrer: 120W, Jiangyin Prohibit scientific research instruments ltd;
rotational viscometer: NDJ-9S, Shanghaineth instruments science and technology, Inc.;
a tensile testing machine: FR-103C, Shanghai Flori instruments science and technology, Inc.;
drawing the instrument for bonding strength: LBY-IV, Cangzhou Hengsheng great road instruments Inc.;
contact angle measuring instrument: SDC-200S, Dongguan sandingding precision instruments GmbH.
Raw materials
Aliphatic polycarbonate diol: PPCD 222, Fine chemical Co., Ltd, David Bay, Huizhou;
aliphatic polycarbonate diol: PPCD 221, Fine chemical Co., Ltd, David Bay, Huizhou;
aliphatic polycarbonate diol: PPCD 231, Fine chemical Co., Ltd, David Bay, Huizhou;
aliphatic polycarbonate diol: PPCD 232, Fine chemical Co., Ltd, David Bay, Huizhou;
fluorinated polytetrahydrofuran diol: prepared by the method described in the embodiment of the invention;
polytetrahydrofuran diol: HS589, shandonghao shun chemical ltd;
hexafluoropropylene: PFC-1216, Beijing Yuji science and technology development, Inc.;
initiator: azobisisobutyronitrile, analytical grade, with a purity of 98 mass%, Shanghai Arlatin Biotechnology Ltd;
plasticizer: chlorinated paraffin, 52#, toming chemical ltd, shanghai;
pigment and filler: titanium dioxide powder,
BLR-601, Lobori group, Inc.;
pigment and filler: talcum powder, HoushengTMSeries, 1250 mesh, san diei chemical ltd, mountain monkey;
solvent: propylene glycol methyl ether acetate, Shanghai Aladdin Biotechnology GmbH;
diisocyanate: the reaction product of isophorone diisocyanate (IPDI),
IPDI, Vanhua chemical group, Inc.;
hexamethylene diisocyanate trimer:
HDI, wanhua chemical group ltd;
chain extender: trimethylolpropane, Anhui pril advanced New materials, Inc.;
organotin catalyst: dibutyltin dilaurate, KR-101, Kary chemical technologies, Inc., Van.J.;
latent curing agent: an aldehyde amine type latent curing agent, JZ302, environmental protection materials Inc. of Guangzhou today.
The amounts of the components in the following examples are all expressed in parts by weight. Unless otherwise specified, the mass per weight part is 10 g.
In the following examples, the performance test methods involved are as follows:
1. mechanical Property test
The mechanical property is tested according to GB/T16777-.
2. Bond Strength Performance test
The bond strength performance was tested according to method A of GB/T16777-.
3. Stain resistance test of coating
The stain resistance of the coating is tested according to GB/T9780 plus 2013 'test method for stain resistance of coating of architectural coating', the standard is that the pollution source of the exterior wall coating is prepared by preparing ash, adding water to prepare suspension, attaching the suspension on a coating test board by a brushing method or a dipping method, then flushing the coating test board by water, and evaluating the stain resistance by measuring the change of the reflection coefficient before and after the coating stains or according to the color difference grade of a basic ash card.
4. Water contact Angle test
The water contact angle is tested by adopting a full-automatic water contact angle tester.
Preparation example 1
Fluorinated polytetrahydrofuran diol:
150g of polytetrahydrofuran diol are placed in a 500mL reaction vessel in a proportion of 1: 3, freezing in an acetone/liquid nitrogen mixture, dehydrating for 120min under vacuum, adding 300g of hexafluoropropylene and 2.5g of azobisisobutyronitrile (initiator), reacting for 6h at 90 ℃, cooling to room temperature, and purifying the product by reduced pressure distillation to obtain fluorinated polytetrahydrofuran diol AA-1;
detecting the prepared fluorinated polytetrahydrofuran diol AA-1 by infrared spectrum to obtain infrared spectrogram at 1190cm as shown in figure 1-1And 1287cm-1The strong characteristic absorption band can be attributed to the stretching vibration and absorption of C-F; 839cm-1And 680cm-1The spectral bands of (A) are respectively formed by CF3Stretching vibration and CF2Caused by deformation vibration of; 3467cm-1The absorption band at (A) is characteristic of O-H stretching; CH (CH)2The group is 1368cm-1、1430cm-1、2857cm-1、2940cm-1There are four peaks; furthermore, the C-O-C group of the polytetrahydrofuran diol is at 1106cm-1The absorption band of (B) is shifted to 1115cm-1And becomes weaker in the spectrum of the fluorinated polytetrahydrofuran diol due to the introduction of the electron-withdrawing fluoroalkyl group, resulting in a low color shift of the C-O-C group, indicating that the grafting reaction occurs on the carbon of the ether bond.
From the above analysis, it was confirmed that the substance produced was fluorinated polytetrahydrofuran diol, and the molecular weight thereof was 2000 by GPC.
Example 1
This example illustrates the preparation of a fluorine-containing polyurethane waterproof coating composition according to the present invention according to the formulation and process parameters shown in table 1, and according to the following method.
The method for preparing the fluorine-containing polyurethane waterproof coating comprises the following steps:
(1) dispersing aliphatic polycarbonate diol, fluorinated polytetrahydrofuran diol, a plasticizer, a pigment and filler, an optional dispersion stabilizer and an optional defoaming agent in a high-speed dispersion machine at 1000rpm for 5min, and then adjusting the rotating speed to 1800rpm for 40 min; transferring the dispersed materials into a reaction container, stirring and heating to 110 ℃, and dehydrating for 3h under the relative vacuum degree of-0.1 MPa;
(2) reducing the temperature to 95 ℃, adding 1/3 dosage of solvent, then adding diisocyanate and optional hexamethylene diisocyanate trimer, stirring uniformly, and reacting for 3 h;
(3) adding a chain extender, and reacting for 1h at 80 ℃; then adding 1/2 organic tin catalyst, continuing to react for 0.5 h; cooling to 70 ℃, adding the latent curing agent, and stirring for 1 h; and then adding the rest organic tin catalyst and solvent, charging nitrogen for protection and discharging to obtain the fluorine-containing polyurethane waterproof paint S1.
The remaining examples were carried out by the same procedure as in example 1, except that the fluorine-containing polyurethane waterproof coating composition formulation and the process parameters were different, unless otherwise specified, as shown in Table 1.
Comparative example 1
This comparative example was carried out using a procedure similar to that of example 1, except that: in the formula, polytetrahydrofuran diol with equal mass is adopted to replace fluorinated polytetrahydrofuran diol, and the specific reference is made to table 1.
TABLE 1
The performance of the fluorine-containing polyurethane waterproof coating obtained in each example was measured by the aforementioned test method, and the specific results are shown in table 2.
TABLE 2
From the results, the fluorine-containing polyurethane waterproof coating provided by the invention can obviously improve the self-cleaning capability and the hydrophobic property of the coating, and has better waterproof and oil-proof functions and weather resistance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A fluorinated polytetrahydrofuran diol characterized by having a structure represented by the formula (1),
wherein, in the formula (1), n is a positive integer, and n enables the weight average molecular weight of the fluorinated polytetrahydrofuran diol to be 1500-.
2. A process for the preparation of the fluorinated polytetrahydrofuran diol of claim 1, characterized in that it comprises:
in the presence of an initiator, carrying out contact reaction on polytetrahydrofuran diol and hexafluoropropylene, wherein the weight ratio of the polytetrahydrofuran diol to the hexafluoropropylene is 1: 2-4, the structural formula of the polytetrahydrofuran diol is HO- [ CH2CH2CH2CH2O]m-H, wherein m is the same as n.
3. The method of claim 2, wherein the conditions of the contact reaction at least satisfy: the temperature is 80-100 ℃, and the time is 5-7 h;
preferably, the initiator is selected from at least one of di-tert-butyl peroxide, azobisisobutyronitrile and dibenzoyl peroxide.
4. The waterproof coating composition of fluorine-containing polyurethane is characterized by comprising the following components which are stored independently or in a mixture of more than two of the components: aliphatic polycarbonate diol, fluorinated polytetrahydrofuran diol, diisocyanate, a plasticizer, a chain extender, an organic tin catalyst, a latent curing agent, a pigment filler and a solvent, and optionally contains hexamethylene diisocyanate trimer;
relative to 100 parts by weight of the coating composition, the content of the aliphatic polycarbonate diol is 15-27 parts by weight, the content of the fluorinated polytetrahydrofuran diol is 3-10 parts by weight, the content of the diisocyanate is 9-20 parts by weight, the content of the plasticizer is 3-7 parts by weight, the content of the chain extender is 1-2 parts by weight, the content of the organotin catalyst is 0.1-0.8 part by weight, the content of the latent curing agent is 1-2 parts by weight, the content of the pigment and filler is 17-45 parts by weight, the content of the solvent is 8-15 parts by weight, and the content of the hexamethylene diisocyanate trimer is 0-9 parts by weight;
wherein the fluorinated polytetrahydrofuran diol is the fluorinated polytetrahydrofuran diol of claim 1.
5. The coating composition according to claim 4, wherein the aliphatic polycarbonate diol is selected from at least one of polypropylene carbonate diol;
preferably, the polypropylene carbonate diol has a structure represented by formula (2),
wherein, in the formula (2), n 'is a positive integer, and n' is such that the weight average molecular weight of the polypropylene carbonate glycol is 2000-3000.
6. The coating composition according to claim 4 or 5, wherein the diisocyanate is selected from at least one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate; and/or
The plasticizer is selected from at least one of chlorinated paraffin, trioctyl phosphate, polyester plasticizer, aliphatic dibasic acid ester plasticizer and citrate plasticizer.
7. The coating composition according to any one of claims 4 to 6, wherein the chain extender is selected from at least one of trimethylolpropane, 1, 4-butanediol, ethylene glycol, propylene glycol, neopentyl glycol, 1, 6-hexanediol; and/or
The organic tin catalyst is at least one of dibutyltin dilaurate, stannous octoate and environment-friendly non-butyltin catalyst; and/or
The latent curing agent is at least one selected from an imine latent curing agent and an oxazolidine latent curing agent.
8. A method for preparing a fluorine-containing polyurethane waterproof coating material, characterized by comprising:
(a) preparing fluorinated polytetrahydrofuran diol by the process of claim 2 or 3;
(b) first mixing the components of the coating composition according to any one of claims 4 to 7.
9. The method of claim 8, wherein the first mixing operation comprises the steps of:
(1) carrying out first contact reaction on each component in a composition A to obtain a product I, wherein the composition A contains aliphatic polycarbonate diol, fluorinated polytetrahydrofuran diol, a plasticizer and pigment and filler;
(2) carrying out second contact reaction on the product I and each component in a combination B to obtain a product II, wherein the combination B contains diisocyanate and a solvent, and optionally contains hexamethylene diisocyanate trimer;
(3) and carrying out a third contact reaction on the product II and each component in the combination C to obtain the fluorinated polyurethane waterproof coating, wherein the combination C contains a chain extender, an organic tin catalyst and a latent curing agent.
10. The method of claim 9, wherein in step (1), the conditions of the first contact reaction at least satisfy: the reaction temperature is 100-110 ℃, and the reaction time is 2-3 h;
and/or, in step (2), the conditions of the second contact reaction at least satisfy: the reaction temperature is 90-95 ℃, and the reaction time is 2-3 h;
and/or, in step (3), the conditions of the third contact reaction at least satisfy: the reaction temperature is 65-85 ℃, and the reaction time is 1.5-2.5 h.
11. The fluorine-containing polyurethane waterproof coating material prepared by the method of any one of claims 8 to 10.
12. Use of the fluorine-containing polyurethane waterproof coating material according to claim 11 for waterproofing a building.
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