Preparation method of polyvinyl chloride and polyacrylic acid modified bi-component waterborne polyurethane

Abstract

The invention provides a preparation method of polyvinyl chloride and polyacrylic acid modified bi-component waterborne polyurethane, and relates to the technical field of high polymer materials. The preparation method comprises the following steps: 1, preparing an acrylate modified polyvinyl chloride polyol emulsion; and 2, preparing the polyvinyl chloride and polyacrylic acid modified bi-component waterborne polyurethane. The polyvinyl chloride and polyacrylic acid modified bi-component waterborne polyurethane prepared by the invention has triple characteristics of polyvinyl chloride, polyacrylate and waterborne polyurethane. According to the present invention, the waterborne polyurethane has characteristics of high adhesive film glossiness, good water resistance, good alkali resistance, good acid resistance and good fire resistance, the problem of poor comprehensive performance of the current commercially available waterborne polyurethane is improved, the application method is simple, the application range is wide, and the waterborne polyurethane can be separately used, and can be directly compounded with the commercial polyurethane to use.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a method for preparing a two-component waterborne polyurethane modified by polyvinyl chloride and polyacrylic acid. Background Art

[0002] Two-component waterborne polyurethane (2K-WPU) is also called external cross-linked waterborne polyurethane, which is composed of a mixture of a waterborne polyol component and a polyisocyanate component. The waterborne polyol component is an important component of 2K-WPU, and its composition and structure have an important influence on 2K-WPU. According to different preparation methods, waterborne polyols can be divided into emulsion polyols and water dispersion polyols.

[0003] A large number of studies have shown that the structure of the polyol component has a great influence on the performance of 2K-WPU resin. Currently, the commonly used polyol components mainly include: acrylic polyols, polyester polyols, polyether polyols, polyurethane polyols, in addition to epoxy polyols, bio-based polyols, and hybrid polyols.

[0004] With the continuous emergence of new technologies and equipment, higher requirements are placed on the performance of two-component waterborne polyurethanes, and the development of two-component waterborne polyurethanes with excellent performance is imminent. The key to improving the performance of two-component waterborne polyurethanes lies in the development of waterborne polyols with different structures and properties, which is also the research focus and difficulty of the current polyurethane industry. Summary of the invention

[0005] 1. Technical issues to be resolved

[0006] In view of the deficiencies in the prior art, the present invention provides a method for preparing a two-component waterborne polyurethane modified with polyvinyl chloride and polyacrylic acid, which solves the technical problem that the existing two-component waterborne polyurethane has poor comprehensive performance.

[0007] (II) Technical solution

[0008] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0009] The preparation method of a two-component waterborne polyurethane modified with polyvinyl chloride and polyacrylic acid comprises the following steps:

[0010] Step 1: preparing acrylate-modified polyvinyl chloride polyol emulsion;

[0011] Step 2: Prepare a two-component waterborne polyurethane modified with polyvinyl chloride and polyacrylic acid.

[0012] Preferably, the acrylate-modified polyvinyl chloride polyol emulsion has a solid content of 45±1% and a particle size of 80-180 nm;

[0013] Its preparation method is:

[0014] Add deionized water, NaOH aqueous solution, emulsifier, ferrous sulfate, bleaching powder and EDTA into the polymerization kettle, stir evenly and then evacuate;

[0015] Add liquid vinyl chloride monomer, acrylate monomer and hydroxyl functional monomer at one time;

[0016] Raise the temperature to 58-62°C, add the pre-emulsified solution of acrylate monomer and hydroxyl functional monomer dropwise, and control the dropping time to 2-3h;

[0017] After the addition is completed, the temperature is kept for 1 hour, and the unreacted vinyl chloride monomer is removed and recovered by degassing and vacuuming;

[0018] Add tert-butyl hydroperoxide into the reactor, and add the aqueous solution of bleaching powder dropwise. The adding time is controlled at 0.5-1h. After the adding, keep warm for 0.5h.

[0019] Finally, the pH of the emulsion is adjusted to 7.5-8.5, and the temperature is lowered to below 40° C. to obtain an acrylate-modified polyvinyl chloride polyol emulsion.

[0020] Preferably, in the solid content of the acrylate-modified polyvinyl chloride polyol emulsion, the mass percentage of vinyl chloride monomer is 40%-60%, the mass percentage of acrylate monomer is 10%-30%, and the mass percentage of hydroxyl functional monomer is 10%-30%.

[0021] Preferably, the acrylate monomer added at one time accounts for 15%-20% of the total acrylate monomers, and the acrylate monomer added dropwise accounts for 80%-85% of the total acrylate monomers; the hydroxyl functional monomer added at one time accounts for 15%-30% of the total hydroxyl functional monomers, and the hydroxyl functional monomer added dropwise accounts for 70%-85% of the total hydroxyl functional monomers.

[0022] Preferably, the total amount of the emulsifier is 2%-4% of the solid content of the acrylate-modified polyvinyl chloride polyol latex.

[0023] Preferably, the emulsifier is a mixture of one or more of potassium laurate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, alkylphenol polyoxyethylene ether, polyoxyethylene alkyl ester, sodium cetyl betaine, and polyoxyethylene alkyl aryl ester.

[0024] Preferably, the acrylic acid ester monomer is a mixture of one or more of methyl methacrylate, butyl methacrylate, butyl acrylate, methyl acrylate, isooctyl acrylate, isopentyl acrylate, glycidyl acrylate, methacrylic acid, acrylic acid, acrylamide, and diallyl phthalate.

[0025] Preferably, the hydroxyl-functional monomer is a mixture of one or more of hydroxymethyl acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.

[0026] Preferably, the product of step 2 is obtained by mixing and reacting acrylate-modified polyvinyl chloride polyol, water-based polyol oligomer, water-based isocyanate and a catalyst.

[0027] Preferably, the water-based polyol oligomer is a mixture of one or more of polyethylene oxide (polyethylene glycol) glycol (PEG), polypropylene oxide (polypropylene glycol) glycol (PPG), polytetramethylene glycol (PTMEG), homopolymers or copolymers of the above monomers, diols or polyols, polyethylene adipate glycol ester glycol, polybutylene adipate glycol 1,4-diol ester glycol, and polyhexanediol adipate glycol ester glycol.

[0028] Preferably, the ratio of the acrylate-modified polyvinyl chloride polyol to the waterborne polyol oligomer is 9:1-1:9.

[0029] Preferably, the acrylate-modified polyvinyl chloride polyol emulsion, the water-based polyol oligomer and the water-based isocyanate are mixed in a ratio of n(-NCO):n(-OH)=(1.1:1)-(3:1), and diluted with water to obtain a two-component water-based polyurethane modified with polyvinyl chloride and polyacrylic acid having a solid content of 45%-55%.

[0030] Preferably, the catalyst is a mixture of one or more of stannous octoate, N,N-dimethylcyclohexylamine, dibutyltin dilaurate, and triethylenediamine.

[0031] (III) Beneficial effects

[0032] The invention provides a method for preparing a two-component waterborne polyurethane modified by polyvinyl chloride and polyacrylic acid.

[0033] Compared with the prior art, it has the following beneficial effects:

[0034] 1. The polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane prepared by the present invention has the triple characteristics of polyvinyl chloride, polyacrylate and waterborne polyurethane. The film has high gloss, good water resistance, alkali resistance, acid resistance and flame retardancy, and improves the problem of poor comprehensive performance of the currently commercially available waterborne polyurethane;

[0035] 2. The polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane prepared by the present invention has significantly lower cost than commercial polyurethane, and the application method of the present invention is simple and convenient, and the application range is wide. It can be used alone or directly compounded with commercial polyurethane. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0037] Figure 1 This is the particle size diagram of acrylate modified polyvinyl chloride polyol emulsion. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] The embodiment of the present application solves the technical problem of poor comprehensive performance of the existing two-component waterborne polyurethane by providing a method for preparing a two-component waterborne polyurethane modified by polyvinyl chloride and polyacrylic acid.

[0040] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods.

[0041] Embodiment 1:

[0042] The preparation method of polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane comprises the following steps:

[0043] Step 1: Preparation of acrylate-modified polyvinyl chloride polyol emulsion

[0044] Add deionized water, NaOH aqueous solution, potassium laurate, ferrous sulfate, bleaching powder and EDTA into the polymerization kettle, stir evenly and then evacuate;

[0045] Add liquid vinyl chloride monomer, part of acrylate monomer and hydroxyl functional monomer at one time;

[0046] Raise the temperature to 58-62°C, and drop the pre-emulsified solution of acrylic ester monomer and hydroxyl functional monomer. The dropping time is controlled within 2-3 hours.

[0047] After the addition is completed, the temperature is kept at room temperature for 1 hour, and the unreacted vinyl chloride monomer is removed and recovered by degassing and vacuuming; tert-butyl hydroperoxide is added to the reactor, and the aqueous solution of bleaching powder is added dropwise, and the addition time is controlled to be 0.5-1 hour. After the addition is completed, the temperature is kept at room temperature for 0.5 hour, and the post-stabilization treatment is completed;

[0048] Finally, the pH of the emulsion is adjusted to 7.5-8.5, and the temperature is lowered to below 40°C to obtain an acrylate-modified polyvinyl chloride polyol emulsion having a solid content of 45±1%. Figure 1 As shown, the particle size is 80-180nm.

[0049] Step 2: Preparation of two-component waterborne polyurethane modified with polyvinyl chloride and polyacrylic acid

[0050] Take 100g of acrylate-modified polyvinyl chloride polyol, then add 300g of commercial water-based polyol 2601 and 30g of Ultra 2547 water-based isocyanate crosslinker, and finally add 0.01g of triethylene diamine and stir evenly to obtain a two-component water-based polyurethane.

[0051] Embodiment 2 is different from Embodiment 1 in that:

[0052] 300 g of acrylate-modified polyvinyl chloride polyol was mixed with 100 g of commercial water-based polyol 2601, 96 g of Ultra 2547 water-based isocyanate crosslinker was added, and finally 0.01 g of triethylene diamine was added and stirred to obtain a two-component water-based polyurethane.

[0053] Embodiment 3 is different from Embodiment 1 in that:

[0054] 200 g of acrylate-modified polyvinyl chloride polyol and 200 g of commercial water-based polyol 2601 were mixed evenly, 140 g of Ultra 2547 water-based isocyanate crosslinker was added, and finally 0.01 g of triethylene diamine was added and stirred evenly to obtain a two-component water-based polyurethane.

[0055] In summary, compared with the prior art, the present invention has the following beneficial effects:

[0056] 1. The polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane prepared by the present invention has the triple characteristics of polyvinyl chloride, polyacrylate and waterborne polyurethane. The film has high gloss, good water resistance, alkali resistance, acid resistance and flame retardancy, and improves the problem of poor comprehensive performance of the currently commercially available waterborne polyurethane;

[0057] 2. The polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane prepared by the present invention has significantly lower cost than commercial polyurethane, and the application method of the present invention is simple and convenient, and the application range is wide. It can be used alone or directly compounded with commercial polyurethane.

[0058] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0059] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a two-component waterborne polyurethane modified with polyvinyl chloride and polyacrylic acid, characterized in that: The following steps are involved: Step 1: preparing acrylate-modified polyvinyl chloride polyol emulsion; Step 2: Prepare a two-component waterborne polyurethane modified with polyvinyl chloride and polyacrylic acid.

2. The method for preparing a two-component waterborne polyurethane modified with polyvinyl chloride and polyacrylic acid according to claim 1, characterized in that: The acrylate-modified polyvinyl chloride polyol emulsion has a solid content of 45±1% and a particle size of 80-180 nm; Its preparation method is: Add deionized water, NaOH aqueous solution, emulsifier, ferrous sulfate, bleaching powder and EDTA into the polymerization kettle, stir evenly and then evacuate; Add liquid vinyl chloride monomer, acrylate monomer and hydroxyl functional monomer at one time; Raise the temperature to 58-62°C, add the pre-emulsified solution of acrylate monomer and hydroxyl functional monomer dropwise, and control the dropping time to 2-3h; After the addition is completed, the temperature is kept for 1 hour, and the unreacted vinyl chloride monomer is removed and recovered by degassing and vacuuming; Add tert-butyl hydroperoxide into the reactor, and add the aqueous solution of bleaching powder dropwise. The adding time is controlled at 0.5-1h. After the adding, keep warm for 0.5h. Finally, the pH of the emulsion is adjusted to 7.5-8.5, and the temperature is lowered to below 40° C. to obtain an acrylate-modified polyvinyl chloride polyol emulsion.

3. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 2, characterized in that: The mass percentage of vinyl chloride monomer in the solid content of the acrylic ester modified polyvinyl chloride polyol emulsion is 40%-60%, the mass percentage of acrylic ester monomer is 10%-30%, and the mass percentage of hydroxyl functional monomer is 10%-30%.

4. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 2, characterized in that: The acrylate monomer added at one time accounts for 15%-20% of the total acrylate monomer, and the acrylate monomer added dropwise accounts for 80%-85% of the total acrylate monomer; the hydroxyl functional monomer added at one time accounts for 15%-30% of the total hydroxyl functional monomer, and the hydroxyl functional monomer added dropwise accounts for 70%-85% of the total hydroxyl functional monomer.

5. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 2, characterized in that: The total amount of the emulsifier is 2%-4% of the solid content of the acrylate-modified polyvinyl chloride polyol latex.

6. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 2, characterized in that: The emulsifier is a mixture of one or more of potassium laurate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, alkylphenol polyoxyethylene ether, polyoxyethylene alkyl ester, sodium cetyl betaine, and polyoxyethylene alkyl aryl ester.

7. The method for preparing a two-component waterborne polyurethane modified by polyvinyl chloride and polyacrylic acid as claimed in claim 2, characterized in that: The acrylic acid ester monomer is a mixture of one or more of methyl methacrylate, butyl methacrylate, butyl acrylate, methyl acrylate, isooctyl acrylate, isopentyl acrylate, glycidyl acrylate, methacrylic acid, acrylic acid, acrylamide, and diallyl phthalate.

8. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 2, characterized in that: The hydroxyl functional monomer is a mixture of one or more of hydroxymethyl acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate.

9. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 1, characterized in that: The product of step 2 is prepared by mixing and reacting acrylate-modified polyvinyl chloride polyol, water-based polyol oligomer, water-based isocyanate and a catalyst.

10. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 9, characterized in that: The water-based polyol oligomer is a mixture of one or more of polyethylene oxide (polyethylene glycol) glycol (PEG), polypropylene oxide (polypropylene glycol) glycol (PPG), polytetramethylene glycol (PTMEG), homopolymer or copolymer diol or polyol of the above monomers, polyethylene adipate glycol ester diol, polybutylene adipate 1,4-diol ester diol, and polyhexane adipate glycol ester diol.

11. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 9, characterized in that: The ratio of the acrylate-modified polyvinyl chloride polyol to the waterborne polyol oligomer is 9:1-1:

9.

12. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 9, characterized in that: The acrylate-modified polyvinyl chloride polyol emulsion, the water-based polyol oligomer and the water-based isocyanate are mixed in a ratio of n(-NCO):n(-OH)=(1.1:1)-(3:1), and diluted with water to obtain a two-component water-based polyurethane modified with polyvinyl chloride and polyacrylic acid and having a solid content of 45%-55%.

13. The method for preparing the polyvinyl chloride and polyacrylic acid modified two-component waterborne polyurethane according to claim 9, characterized in that: The catalyst is a mixture of one or more of stannous octoate, N,N-dimethylcyclohexylamine, dibutyltin dilaurate and triethylenediamine.

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