CN113549364B - Water-based environment-friendly unsaturated polyester putty for rail transit vehicles and preparation method thereof - Google Patents
Water-based environment-friendly unsaturated polyester putty for rail transit vehicles and preparation method thereof Download PDFInfo
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- CN113549364B CN113549364B CN202111028199.5A CN202111028199A CN113549364B CN 113549364 B CN113549364 B CN 113549364B CN 202111028199 A CN202111028199 A CN 202111028199A CN 113549364 B CN113549364 B CN 113549364B
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Abstract
The invention discloses aqueous environment-friendly unsaturated polyester putty for rail transit vehicles and a preparation method thereof, and relates to the technical field of coatings. The water-based environment-friendly unsaturated polyester putty prepared by the method has the advantages of no crusting on the appearance, no stirring or hard block opening, easy coating and scraping, no curling phenomenon, and other indexes superior to the industrial standard.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to water-based environment-friendly unsaturated polyester putty for rail transit vehicles and a preparation method thereof.
Background
According to the current requirements on the prevention and treatment of the ecological environmental pollution of the coating, the rail transit coating gradually and comprehensively realizes the water-based property. At present, partial water-based primer, intermediate coat and finish coat in the rail transit coating are realized, and the water-based unsaturated polyester putty is not realized.
Products such as conventional unsaturated polyester putty (putty) must be based on unsaturated polyester resins. This binder contains 30-40% of the conventional monomers usually used for styrene.
The current environmental protection improvement direction mainly focuses on improvement of monomers, adopts environment-friendly and nonirritating high-boiling-point active monomers such as acrylate monomers, but is still an oily system, and the aim of water-based preparation is difficult to realize. And the solvent resistance of the water-based epoxy primer is poorer than that of the oil-based epoxy primer, and the problems of bottom biting and poor interlayer adhesion are easy to occur when the solvent-based traditional putty is applied. Therefore, the high-performance environment-friendly and zero-VOC aqueous environment-friendly unsaturated polyester putty product matched with aqueous industrial paint is urgently expected to appear in the field of rail transit.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the water-based environment-friendly unsaturated polyester putty. The putty uses a water-based acrylic acid modified unsaturated polyester resin dispersoid and an aliphatic polyurethane acrylate dispersoid as main base materials, uses deionized water as a diluent to replace traditional active diluents such as styrene and the like, and endows the putty with excellent dryness, adhesive force and environmental protection genes; the oil-to-water resin is creatively applied to the putty, and the phenomenon of oxygen inhibition is avoided in the dry curing process; the use of the composite drier ensures the drying requirement of baking the putty at 60 ℃ for 2h under extreme conditions of low temperature, high humidity and the like or the self-drying polishing requirement at night; the compatibility of the composite stabilizer can ensure the construction time of the putty, so that the putty is particularly suitable for large-area construction of high-speed railway rolling stocks; the water-based environment-friendly unsaturated polyester putty has the advantages of no pungent smell, strong adhesive force, good dryness, long service time, good flexibility and good impact resistance, is suitable for large-area construction, and the product quality reaches the requirements of Q/CRRC 546.1-2018 putty technical conditions for high-speed rail locomotives.
The technical scheme adopted by the invention for realizing the purpose is as follows: the component A of the formula comprises the following components in percentage by weight:
the component B comprises the following components in percentage by weight:
the preparation method of the waterborne acrylic modified unsaturated polyester resin dispersion comprises the following steps:
firstly, adding propylene glycol, diethylene glycol, maleic anhydride, phthalic anhydride, antioxidant BHT and hydroquinone according to the formula ratio, gradually heating to 140 ℃ until the solid is basically molten, then heating to 180 ℃ and 185 ℃, carrying out heat preservation reaction, and pumping water for 20min under the vacuum pressure control of-0.07 MPa when the acid value is less than 40 mg/Kg; cooling to 70-80 deg.C, adding xylene, and proceeding to the next step;
introducing nitrogen for protection, adding a mixed monomer of acrylic acid, butyl acrylate and methyl methacrylate, heating to 70-80 ℃, keeping the temperature for 6 hours, extracting xylene for 20-30 minutes, and adding triethylamine for neutralization;
thirdly, adding deionized water, dispersing uniformly at a high speed, cooling to 40 ℃, filtering and packaging.
The acrylic acid mixed monomer is grafted to the polyester, the monomer is grafted on an alpha hydrogen bond or a carbon-carbon double bond, and a proper double bond is reserved, so that a curable activation center can be provided, and the hardness and curing speed of the water-based unsaturated polyester putty are effectively improved.
The specific raw materials of the waterborne aliphatic polyurethane acrylate dispersoid in the invention are prepared from the following raw materials in parts by weight: 15-35 parts of aliphatic diisocyanate (HDI), 5-8 parts of polytetrahydrofuran glycol (PTMEG), 10-25 parts of polyethylene glycol (PEG600), 0.5-1 part of dibutyl dilaurate, 10-25 parts of pentaerythritol triacrylate (PETA), 30-40 parts of acetone and 0.6-2 parts of triethylamine.
The preparation method of the aqueous aliphatic polyurethane acrylate dispersion comprises the following steps:
firstly, adding polytetrahydrofuran diol, polyethylene glycol, dibutyl dilaurate and part of acetone into a reaction kettle, introducing nitrogen for protection, heating to 38-45 ℃, stirring and dropwise adding aliphatic diisocyanate (HDI), dropwise adding after about 35-45 minutes, keeping the temperature for 40-60 minutes, and tracking and measuring the content of-NCO by using di-n-butylamine in the process;
supplementing residual acetone, adding pentaerythritol triacrylate, heating to 58-62 ℃, preserving heat for 60-80 minutes, and cooling to 40 ℃;
adding triethylamine and deionized water, and dispersing uniformly at a high speed;
fourthly, distilling for 5 to 8 hours under reduced pressure, filtering and packaging;
the novel aqueous dispersion resin is developed through synthesis, the pollution of traditional active diluents such as styrene and the like to the environment is thoroughly solved by using deionized water, and the zero VOC emission in the putty construction and drying process is realized.
Further, the functional monomer is one or a mixture of more than two of vinyl toluene, DVE-3, acrylamide and acrylonitrile;
one or two mixtures of waterborne dispersants BYK190, BYK192, TEGO755W, TEGO750W, OMG1252 and Zhanxin 6208;
the water-based antifoaming agent is a mixture of two of BYK021, DF660, TEGO810, TEGO910, DF7015 and W0507;
the aqueous thixotropic agent can be two or three of fumed silica, organic bentonite, LUVOGEL W2N, EXILVA F01-V;
the composite stabilizer can be any two or more than two of hydroquinone, p-tert-butyl catechol, chloranil, diphenoquinone and p-hydroxyanisole;
the composite drier is a mixture of two or more than two of 12-mercapto dodecyl phosphoric acid, 2-mercapto-1-methylimidazole, pentaerythritol tetramercapto propionate, pentaerythritol tetramercapto acetate, copper naphthenate, cobalt isooctanoate and cerium isooctanoate;
the adhesion force enhancing monomer is one or a mixture of two of methacryloxypropyl triisopropoxysilane, methacryloxypropyl methyldimethoxysilane, 3- (acryloxy) methyldimethoxysilane and methacrylic acid propyl triethoxysilane;
the functional filler is nano spherical silicon micro powder;
the plasticizer is a mixture of environmentally-friendly synthetic vegetable ester and DOTP.
The invention also aims to provide a preparation method of the water-based environment-friendly unsaturated polyester putty, which comprises the following steps: the method specifically comprises the following steps:
(1) putting the aqueous acrylic acid modified unsaturated polyester resin dispersoid, part of the aqueous dispersant, part of the aqueous defoamer and titanium dioxide into a high-speed dispersion machine, and uniformly mixing under the condition of 1000-1200r/min to obtain uniform slurry-coarse suspension without obvious particles;
(2) sanding the coarse suspension liquid by a grinder to obtain titanium white slurry, wherein the fineness is controlled below 30 um;
(3) adding the aqueous aliphatic polyurethane acrylate dispersoid, the functional monomer, the adhesion force enhancing monomer, barium sulfate, the aqueous thixotropic agent, part of the aqueous dispersant, part of the aqueous defoamer, the composite drier, the composite stabilizer, the talcum powder and the functional filler into the titanium white slurry according to the formula ratio, stirring and dispersing at a high speed until uniform paste with proper consistency is formed, and obtaining the aqueous environment-friendly unsaturated polyester putty component A;
(4) dispersing the antioxidant colorant and part of the plasticizer in a formula amount at a high speed through a three-roller machine, controlling the fineness below 20um, adding the color paste into the benzoyl peroxide and part of the plasticizer in the formula amount, dispersing at a low speed to obtain a pre-dispersion body, and then adding the fumed silica in the formula amount into the pre-dispersion body, and dispersing at a high speed to form a uniform paste body with proper consistency, thus obtaining the component B of the water-based environment-friendly unsaturated polyester putty;
(5) the use method of the water-based environment-friendly unsaturated polyester putty comprises the following steps: mixing the prepared component A and component B according to the ratio of 100: 3-5 weight ratio, and mixing uniformly to obtain the high-performance primer material water-based environment-friendly unsaturated polyester putty suitable for high-speed rails, locomotives and subways.
Compared with the prior art, the invention has the beneficial effects that:
(1) the water-based environment-friendly unsaturated polyester putty prepared by the method has the advantages that the appearance of the putty is free from crusting, stirring and hard lump opening, the putty is easy to smear and generate a curling phenomenon, the consistency is about 10cm and is superior to the industrial standard, the working life (min) of the two-component coating is more than 40 and is superior to that required by the industrial standard for not less than 30min, the color and the appearance surface of the putty film are smooth, the putty film is free from particles, cracks and bubbles, the putty film is easy to polish, is not sticky with sand paper, has no obvious white points, and other indexes are superior to the industrial standard.
(2) The product is free of dangerous chemical styrene, and is regulated according to the industry regulations: the products (the closed cup flash point is less than or equal to 60 ℃) such as synthetic resin, paint, auxiliary materials, coating and the like containing flammable solvents are managed according to dangerous chemicals, and the water-based environment-friendly unsaturated polyester putty takes deionized water as a diluent and does not belong to dangerous chemicals, so that the safety of the products in the processes of production, storage, transportation and construction is greatly improved.
(3) The content of Volatile Organic Compounds (VOC) of the product is zero, and is lower than the limit value that the VOC of the coating is less than or equal to 80g/L in the environmental protection certification standard of the highest standard of the current industry; it does not contain heavy metals such as mercury, lead, chromium and the like.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a process flow diagram of the production process of the water-based environment-friendly polyester putty.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are further described in detail below by way of examples with reference to the accompanying drawings. In the specification, the same or similar reference numerals denote the same or similar components. The following description of the embodiments of the present invention with reference to the accompanying drawings is intended to explain the general inventive concept of the present invention and should not be construed as limiting the invention.
Furthermore, in the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the disclosure. It may be evident, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are shown in schematic form in order to simplify the drawing.
Example 1
The embodiment provides water-based environment-friendly unsaturated polyester putty for rail transit vehicles, which comprises a component A and a component B, wherein the formula of the component A comprises the following components: 32 parts of water-based acrylic acid modified unsaturated polyester resin, 12 parts of water-based aliphatic polyurethane acrylate dispersoid, 6 parts of functional monomer, 1.2 parts of titanium dioxide, 4 parts of barium sulfate, 0.8 part of water-based dispersant, 0.8 part of water-based defoamer, 2 parts of water-based thixotropic agent, 20 parts of talcum powder, 1.8 parts of composite drier, 1.5 parts of composite stabilizer, 5 parts of adhesion enhancing monomer and 5 parts of functional filler.
The formula of the component B is as follows: 3 parts of antioxidant colorant, 40 parts of benzoyl peroxide, 0.4 part of fumed silica and 12 parts of plasticizer.
Referring to fig. 1, the embodiment provides a preparation method of an aqueous environment-friendly unsaturated polyester putty for rail transit vehicles, which comprises the following steps:
(1) putting the water-based acrylic acid modified unsaturated polyester resin and the titanium dioxide with the formula ratio into a high-speed dispersion machine, and uniformly mixing under the condition of 1000-1200r/min to obtain uniform slurry-coarse suspension without obvious particles;
(2) conveying the coarse suspension to a grinder to grind the coarse suspension until the fineness is less than or equal to 20 micrometers, and obtaining titanium white slurry;
(3) conveying titanium white slurry into a dispersion cylinder, adding aqueous aliphatic polyurethane acrylate dispersoid, functional monomer, titanium dioxide 1, barium sulfate, aqueous dispersant, aqueous defoamer, aqueous thixotropic agent, talcum powder, composite drier, composite stabilizer, adhesion-enhancing monomer and functional filler according to the mass ratio of the component A in the formula, and stirring and dispersing at high speed until uniform paste with proper consistency is formed, thereby obtaining the component A of the aqueous environment-friendly unsaturated polyester putty;
(4) and (2) dispersing the antioxidant colorant and part of the plasticizer through a three-roll machine at a high speed according to the formula amount of the component B in the formula, controlling the fineness to be below 20 mu m, adding the color paste into benzoyl peroxide and part of the plasticizer in the formula amount, dispersing at a low speed to obtain a pre-dispersion body, and then adding fumed silica in the pre-dispersion body in the formula amount, and dispersing at a high speed to form a uniform paste body with proper consistency to obtain the component B of the water-based environment-friendly unsaturated polyester putty.
(5) The use method of the water-based environment-friendly unsaturated polyester putty comprises the following steps: mixing the prepared component A and component B according to the ratio of 100: 3-5 weight ratio, and mixing uniformly to obtain the high-performance primer material water-based environment-friendly unsaturated polyester putty suitable for high-speed railway locomotives.
Example 2
The difference between this example and example 1 is the ratio of the component A, the ratio of the component B and the preparation method and process of the component A, B are the same as those of example 1.
The formula of the component A is as follows: 38 parts of waterborne acrylic modified unsaturated polyester resin, 8 parts of waterborne aliphatic polyurethane acrylate dispersoid, 6 parts of functional monomer, 1.2 parts of titanium dioxide, 6 parts of barium sulfate, 1.0 part of waterborne dispersant, 0.8 part of waterborne defoamer, 2.5 parts of waterborne thixotropic agent, 25 parts of talcum powder, 2.0 parts of composite drier, 1.8 parts of composite stabilizer, 5 parts of adhesion enhancing monomer and 6 parts of functional filler.
Example 3
The difference between this example and example 1 is the ratio of the component A, the ratio of the component B and the preparation method and process of the component A, B are the same as those of example 1.
The formula of the component A is as follows: 40 parts of water-based acrylic acid modified unsaturated polyester resin, 10 parts of water-based aliphatic polyurethane acrylate dispersoid, 6 parts of functional monomer, 1.5 parts of titanium dioxide, 8 parts of barium sulfate, 1.0 part of water-based dispersant, 1.0 part of water-based defoamer, 4 parts of water-based thixotropic agent, 28 parts of talcum powder, 2.0 parts of composite drier, 1.8 parts of composite stabilizer, 6 parts of adhesion enhancing monomer and 8 parts of functional filler.
The following table shows the detection results of the waterborne environment-friendly unsaturated polyester putty obtained in example 1:
the above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The water-based environment-friendly unsaturated polyester putty for rail transit vehicles is characterized by comprising a component A and a component B, wherein the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
the aqueous acrylic acid modified unsaturated polyester resin dispersoid adopts acrylic acid, butyl acrylate and methyl methacrylate modifiers and deionized water as a diluent;
the obtained water-based environment-friendly unsaturated polyester putty has the consistency of 9-12cm, the adhesive force of less than 1, the adhesive force of more than 4Mpa by a pulling method and the impact property of more than 15 kg.cm;
the functional monomer is one or a mixture of more than two of vinyl toluene, DVE-3, acrylamide and acrylonitrile;
the aqueous acrylic acid modified unsaturated polyester resin dispersoid is prepared from the following raw materials in parts by weight:
18-22 parts of propylene glycol, 4-15 parts of diethylene glycol, 14-21 parts of maleic anhydride, 11-18 parts of phthalic anhydride, 0.01-0.2 part of antioxidant, 0.05-0.2 part of hydroquinone, 5-10 parts of acrylic acid, butyl acrylate and methyl methacrylate mixed monomer, 0.05-0.15 part of benzoyl peroxide, 15-22 parts of dimethylbenzene and 40-50 parts of deionized water;
the preparation of the aqueous acrylic modified unsaturated polyester resin dispersion comprises the following steps:
firstly, adding propylene glycol, diethylene glycol, maleic anhydride, phthalic anhydride, antioxidant BHT and hydroquinone according to the formula ratio, gradually heating to 140 ℃ until solid is molten, then heating to 180 ℃ and 185 ℃, carrying out heat preservation reaction, controlling the vacuum pressure to be-0.07 MPa, pumping water for 20min when the acid value is less than 40mg/Kg, cooling to 70-80 ℃, adding dimethylbenzene, and entering the next step;
introducing nitrogen for protection, adding mixed monomers of acrylic acid, butyl acrylate and methyl methacrylate and benzoyl peroxide, heating to 70-80 ℃, keeping the temperature for 6 hours, extracting xylene for 20-30 minutes, and adding triethylamine for neutralization;
thirdly, adding deionized water, dispersing uniformly at a high speed, cooling to 40 ℃, filtering and packaging;
the aqueous aliphatic polyurethane acrylate dispersion is prepared from the following raw materials in parts by weight: 15-35 parts of aliphatic diisocyanate, 5-8 parts of polytetrahydrofuran glycol, 10-25 parts of polyethylene glycol, 0.5-1 part of dibutyl dilaurate, 10-25 parts of pentaerythritol triacrylate, 30-40 parts of acetone and 0.6-2 parts of triethylamine;
the preparation of the aqueous aliphatic polyurethane acrylate dispersion comprises the following steps:
firstly, adding polytetrahydrofuran diol, polyethylene glycol, dibutyl dilaurate and part of acetone into a reaction kettle, introducing nitrogen for protection, heating to 38-45 ℃, stirring and dropwise adding aliphatic diisocyanate, keeping the temperature for 40-60 minutes after dropwise adding, and tracking and determining the-NCO content by using di-n-butylamine in the process;
② supplementing residual acetone, adding pentaerythritol triacrylate, heating to 58-62 ℃, keeping the temperature for 60-80 minutes, and cooling to 40 ℃;
adding triethylamine and deionized water, and dispersing uniformly at a high speed;
fourthly, reduced pressure distillation is carried out for 5 to 8 hours, and filtration and packaging are carried out.
2. The water-based environment-friendly unsaturated polyester putty as claimed in claim 1, wherein the weight ratio of the mixed monomers of acrylic acid, butyl acrylate and methyl methacrylate is 1:12: 12.
3. The water-based environment-friendly unsaturated polyester putty as claimed in claim 1, characterized in that the water-based dispersant is one or two mixtures of BYK190, BYK192, TEGO755W, TEGO750W, OMG1252 and Zhanxin 6208;
the water-based defoaming agent is a mixture of two of BYK021, DF660, TEGO810, TEGO910, DF7015 and W0507;
the aqueous thixotropic agent is a mixture of two or three of fumed silica, organic bentonite and LUVOGEL W2N;
the composite stabilizer is any two or a mixture of more than two of hydroquinone, p-tert-butyl catechol, chloranil, diphenoquinone and p-hydroxyanisole;
the composite drier is a mixture of two or more than two of 12-mercapto dodecyl phosphoric acid, 2-mercapto-1-methylimidazole, pentaerythritol tetramercapto propionate, pentaerythritol tetramercapto acetate, copper naphthenate, cobalt isooctanoate and cerium isooctanoate;
the adhesion force enhancing monomer is one or a mixture of two of methacryloxypropyl triisopropoxysilane, methacryloxypropyl methyldimethoxysilane and 3- (acryloyloxy) methyldimethoxysilane;
the plasticizer is a mixture of environmentally-friendly synthetic vegetable ester and DOTP.
4. A method for preparing the water-based environment-friendly unsaturated polyester putty for rail transit vehicles as defined in any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) putting the aqueous acrylic acid modified unsaturated polyester resin dispersoid, part of the aqueous dispersant, part of the aqueous defoamer and titanium dioxide into a high-speed dispersion machine, and uniformly mixing under the condition of 1000-1200r/min to obtain a coarse suspension of uniform slurry without obvious particles;
(2) sanding the coarse suspension liquid by a grinder to obtain titanium white slurry, wherein the fineness is controlled below 30 um;
(3) adding the aqueous aliphatic polyurethane acrylate dispersoid, the functional monomer, the adhesion force enhancing monomer, barium sulfate, the aqueous thixotropic agent, part of the aqueous dispersant, part of the aqueous defoamer, the composite drier, the composite stabilizer, the talcum powder and the nano spherical silicon micro powder into the titanium white slurry according to the formula ratio, stirring and dispersing at a high speed until uniform paste with proper consistency is formed, and obtaining the aqueous environment-friendly unsaturated polyester putty component A;
(4) dispersing the antioxidant colorant and part of the plasticizer in a formula amount at a high speed through a three-roller machine, controlling the fineness below 20um, adding the color paste into the benzoyl peroxide and part of the plasticizer in the formula amount, dispersing at a low speed to obtain a pre-dispersion body, and then adding the fumed silica in the formula amount into the pre-dispersion body, and dispersing at a high speed to form a uniform paste body with proper consistency, thus obtaining the component B of the water-based environment-friendly unsaturated polyester putty;
(5) the use method of the water-based environment-friendly unsaturated polyester putty comprises the following steps: mixing the prepared component A and component B according to the ratio of 100: 3-5 weight ratio, and mixing uniformly to obtain the high-performance primer material water-based environment-friendly unsaturated polyester putty suitable for rail transit.
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