Carboxylic acid type ionic polymer as well as preparation method and application thereof

Abstract

The invention provides a carboxylic acid type ionic polymer and a preparation method and application thereof, and belongs to the technical field of ionic polymers, the preparation method comprises the following steps: (1) mixing an ethylene acrylic acid copolymer or an ethylene-methacrylic acid copolymer and a metal hydroxide aqueous solution, and introducing nitrogen for bubbling; and (2) carrying out nitrogen displacement, heating, reacting, cooling, adding a precipitant to generate a precipitate, and carrying out post-treatment to obtain the carboxylic acid type ionic polymer. The carboxylic acid type ionic polymer prepared by the preparation method provided by the invention is mild in reaction condition and easy to realize; water is used as a solvent, a byproduct is water, and the reaction process and results are harmless and environment-friendly; the essence of the preparation method is acid-base neutralization reaction, the atom utilization rate is high, and the processing cost is reduced; the method can be used for preparing various carboxylic acid type ionic polymers.

Description

Technical Field

[0001] The invention belongs to the technical field of ionic polymers and relates to a carboxylic acid type ionic polymer and a preparation method and application thereof. Background Art

[0002] Ionic polymers usually refer to a class of polymers that contain a small amount (molar fraction less than 15%) of suspended acid groups on the main chain of the macromolecule, and these suspended acid groups are partially or completely neutralized into salts. Ionic polymers can be divided into carboxylic acid ionic polymers, sulfonic acid ionic polymers, mercaptoethyl ionic polymers and phosphonic acid ionic polymers according to their ionized groups.

[0003] There are several methods for preparing carboxylic acid type ionomers: (1) copolymerizing olefin monomers such as ethylene, butadiene, styrene and methyl methacrylate with monomers containing carboxylic acid groups, and then reacting the resulting copolymers with metal oxides, hydroxides or acetates in solution or in a molten state to generate ionomers; (2) copolymerizing olefin monomers with acrylates or methacrylates, and then hydrolyzing or saponifying the resulting copolymers to convert some ester groups into acid groups or salt groups; (3) modifying high polymers containing double bonds with various reagents to generate carboxylic acid groups at the double bond sites, and then neutralizing with metal oxides. However, the above methods have the following disadvantages: method (1) has relatively high requirements for equipment, and it is currently difficult to achieve continuous large-scale production, and it is difficult to obtain colorless and transparent products; method (2) has many steps, poor atom economy, and often uses organic solvents (such as xylene), which consumes a lot of energy and causes a lot of pollution; method (3) is the common grafting modification, and it is difficult to obtain products with high acid content. Most grafting rates are between 1% and 2%, and the products have a strong smell and are yellowish in color.

[0004] For example, the following method is used in the prior art to prepare carboxylic acid ionomers: triethanolamine (or diethanolamine) is reacted with ethylene acrylic acid copolymer (EAA) or ethylene-methacrylic acid copolymer (EMAA) to form ion pairs, which are dissolved in aqueous solution, and then ion exchanged with a metal salt solution to generate a precipitate (i.e., a carboxylic acid ionomer). However, this method has the following defects: ① a large amount of triethanolamine is used, but it is not in the final product, the atom economy is too poor, and triethanolamine is relatively difficult to wash out; ② this preparation method is suitable for EAA with small steric hindrance, and the applicability of EMAA is poor.

[0005] Therefore, in the art, it is desired to develop a method for preparing a carboxylic acid type ionic polymer, which has high atomic utilization, is applicable to both EAA and EMAA, and has mild reaction conditions and is environmentally friendly. Summary of the invention

[0006] In view of the deficiencies of the prior art, the object of the present invention is to provide a carboxylic acid type ion polymer and a preparation method and application thereof. The preparation method provided by the present invention is used to prepare the carboxylic acid type ion polymer, which can improve the atom economy of the preparation of the ion polymer, reduce the processing cost, and the preparation process and results are more environmentally friendly and harmless, enriching the types and preparation processes of high-transmittance ion polymers, which is conducive to expanding the scope of application and industrialization.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a method for preparing a carboxylic acid type ion polymer, the preparation method comprising the following steps:

[0009] (1) mixing an ethylene acrylic acid copolymer or an ethylene-methacrylic acid copolymer and an aqueous solution of a metal hydroxide, and bubbling nitrogen gas therein;

[0010] (2) nitrogen replacement, followed by heating, reaction, cooling, and then adding a precipitant to generate precipitation, followed by post-treatment to obtain the carboxylic acid type ion polymer.

[0011] The preparation method provided by the present invention is used to prepare a carboxylic acid type ion polymer, and the reaction conditions are mild and easy to implement; water is used as a solvent, and the byproduct is water; the reaction process and results are harmless and environmentally friendly; the essence of the preparation method is an acid-base neutralization reaction, the atomic utilization rate is high, and the processing cost is reduced; and the method can be used to prepare a variety of carboxylic acid type ion polymers.

[0012] The reaction mechanism of the present invention is that EAA or EMAA reacts with metal hydroxide to form a negatively charged colloid, which forms a stable suspension in an aqueous solution (charges of the same kind repel each other and thus stably exist in the solution), and then a precipitant is added to break the suspension or a double decomposition reaction occurs to generate a precipitate, and the precipitate is the product.

[0013] Preferably, the acid content of the ethylene acrylic acid copolymer or ethylene-methacrylic acid copolymer in step (1) is ≥ 10 wt.%, such as 10 wt.%, 12 wt.%, 14 wt.%, 15 wt.%, etc.

[0014] Preferably, the metal hydroxide in step (1) comprises NaOH and / or KOH.

[0015] Preferably, in the aqueous solution of the metal hydroxide in step (1), the amount of water is 50-100 mL (for example, 50 mL, 60 mL, 70 mL, 80 mL, 90 mL, 100 mL, etc.), and the amount of the metal hydroxide is 1-3 g, for example, 1 g, 1.2 g, 1.4 g, 1.6 g, 1.8 g, 2 g, 2.2 g, 2.4 g, 2.6 g, 2.8 g, 3 g, etc.

[0016] Preferably, in step (1), based on 20 g of ethylene acrylic acid copolymer or ethylene-methacrylic acid copolymer, the amount of metal hydroxide used is 1-3 g, for example, 1 g, 1.2 g, 1.4 g, 1.6 g, 1.8 g, 2 g, 2.2 g, 2.4 g, 2.6 g, 2.8 g, 3 g, etc.

[0017] Preferably, the time for bubbling nitrogen in step (1) is 20-40 min, for example, 20 min, 25 min, 30 min, 35 min, 40 min, etc.

[0018] Preferably, when the reactant in step (1) is ethylene acrylic acid copolymer, the step (2) further includes a pressurization step before the heating. If the reactant in step (1) is ethylene-methacrylic acid copolymer, the pressurization step will result in a large number of bubbles being generated during the process, which makes subsequent treatment more troublesome.

[0019] Preferably, the pressurization is to be above 0.5 MPa, for example, 0.5 MPa, 0.6 MPa, 0.8 MPa, 1 MPa, etc.

[0020] Preferably, the heating in step (2) is to 90-180°C, for example, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, etc.

[0021] Preferably, the reaction time of step (2) is 0.5-1.5 hours, for example, 0.5 hours, 0.8 hours, 1 hour, 1.2 hours, 1.3 hours, 1.5 hours, etc.

[0022] Preferably, the cooling in step (2) is to a temperature below 60°C, for example, 60°C, 55°C, 50°C, 45°C, 40°C, 35°C, etc.

[0023] Preferably, the precipitant in step (2) comprises any one of methanol, ethanol, polyol, metal salt solution, acid solution or a combination of at least two thereof. It should be noted that the present invention does not specifically limit the amount of the precipitant, as long as it can fully precipitate the intermediate product.

[0024] Preferably, the polyol comprises glycerol and / or ethylene glycol.

[0025] Preferably, the metal salt solution includes any one of a sodium chloride aqueous solution, a zinc sulfate aqueous solution, and a copper sulfate aqueous solution, or a combination of at least two of them.

[0026] Preferably, the acid solution comprises any one of an aqueous formic acid solution, an alcoholic formic acid solution, an aqueous acetic acid solution, an alcoholic acetic acid solution (such as an ethyl acetate solution, etc.), or a combination of at least two of them.

[0027] Preferably, the post-treatment in step (2) includes filtration or centrifugal dehydration, washing and drying.

[0028] Preferably, the washing comprises washing with water.

[0029] Preferably, the drying temperature is 40-60°C, for example 40°C, 45°C, 50°C, 55°C, 60°C, etc., and the drying time is 8-18 hours, for example 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, etc.

[0030] As a preferred technical solution of the present invention, the preparation method comprises the following steps:

[0031] (1) mixing an ethylene acrylic acid copolymer or an ethylene-methacrylic acid copolymer and an aqueous solution of a metal hydroxide, and bubbling nitrogen therein for 20-40 minutes;

[0032] (2) nitrogen replacement, then heating to 90-180° C., reacting for 0.5-1.5 hours, cooling to below 60° C., then adding a precipitant to generate a precipitate, filtering or centrifugally dehydrating, washing, and drying to obtain the carboxylic acid type ion polymer.

[0033] In a second aspect, the present invention provides a carboxylic acid type ionic polymer, wherein the carboxylic acid type ionic polymer is prepared by the preparation method described in the first aspect.

[0034] In a third aspect, the present invention provides a use of the carboxylic acid type ion polymer as described in the second aspect in VSP skin packaging, condoms, golf balls, SGP laminated glass, perfume bottle caps, and polyethylene terephthalate (PET) modification.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The preparation method provided by the present invention is used to prepare a carboxylic acid type ion polymer, and the reaction conditions are mild and easy to implement; water is used as a solvent, and the byproduct is water, and the reaction process and results are harmless and environmentally friendly; the essence of the preparation method is an acid-base neutralization reaction, and the atomic utilization rate is high, which reduces the processing cost; it can be used to prepare a variety of carboxylic acid type ion polymers; and the performance of the carboxylic acid type ion polymer prepared by the preparation method of the present invention is equivalent to that of the carboxylic acid type ion polymer prepared by a conventional method. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is the infrared spectrum of the partially neutralized carboxylic acid type ion polymer obtained in Example 2. DETAILED DESCRIPTION

[0038] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0039] Example 1

[0040] In this embodiment, a completely neutralized carboxylic acid type ion polymer is provided, and the preparation method comprises the following steps:

[0041] ① Weigh 20 g of EAA 5980 (SK Company, South Korea) and add it to the reactor. Then dissolve 2.5 g of NaOH in 80 mL of deionized water to obtain a solution. Pour the solution into the reactor and bubble nitrogen for 30 min.

[0042] ② Nitrogen replacement, pressurized to 0.5MPa;

[0043] ③Heat to 100°C and react for 1 hour;

[0044] ④ Cool down to below 50°C and add sodium chloride solution (20g sodium chloride dissolved in 50mL deionized water);

[0045] ⑤Filter to obtain the precipitate, and wash it three times with water;

[0046] ⑥ Dry the precipitate at 60° C. overnight to obtain a white solid powder, that is, the completely neutralized carboxylic acid type ion polymer.

[0047] Example 2

[0048] In this embodiment, a partially neutralized carboxylic acid type ion polymer is provided, and the preparation method comprises the following steps:

[0049] ① Weigh 20g EAA 5980 (SK Company, South Korea) and add it into the reactor. Then dissolve 1.5g NaOH in 80mL deionized water to obtain a solution. Pour the solution into the reactor and bubble nitrogen for 30min.

[0050] ② Nitrogen replacement, pressurized to 0.5MPa;

[0051] ③Heat and raise the temperature to 140°C and react for 1 hour;

[0052] ④ Cool down to below 50°C and add sodium chloride solution (2 g sodium chloride dissolved in 40 mL deionized water);

[0053] ⑤Filter to obtain the precipitate, and wash it three times with water;

[0054] ⑥ Dry the precipitate at 50° C. overnight to obtain a white solid powder, that is, the partially neutralized carboxylic acid type ion polymer.

[0055] The infrared spectrum of the partially neutralized carboxylic acid type ion polymer obtained in this example is as follows: Figure 1 As shown, the manufacturer of the instrument used for infrared spectrum testing in the present invention is Bruker of Germany, and the model is INVENIO-S.

[0056] Example 3

[0057] In this embodiment, a zinc ionomer is provided, and a preparation method thereof comprises the following steps:

[0058] ① Weigh 20g EAA 5980 (SK Company, South Korea) and add it into the reactor. Then dissolve 1.5g NaOH in 80mL deionized water to obtain a solution. Pour the solution into the reactor and bubble nitrogen for 30min.

[0059] ② Nitrogen replacement, pressurized to 0.5MPa;

[0060] ③Heat and raise the temperature to 140°C and react for 1 hour;

[0061] ④ Cool down to below 50°C and add zinc sulfate solution (10 g zinc sulfate dissolved in 50 mL deionized water);

[0062] ⑤Filter to obtain the precipitate, and wash it three times with water;

[0063] ⑥ Dry the precipitate at 50° C. overnight to obtain a white solid powder, namely the zinc ion polymer.

[0064] Example 4

[0065] In this embodiment, a copper ion polymer is provided, and a preparation method thereof comprises the following steps:

[0066] ① Weigh 20g EAA 5980 (SK Company, South Korea) and add it into the reactor. Then dissolve 1.5g NaOH in 80mL deionized water to obtain a solution. Pour the solution into the reactor and bubble nitrogen for 30min.

[0067] ② Nitrogen replacement, pressurized to 0.5MPa;

[0068] ③Heat and raise the temperature to 140°C and react for 1 hour;

[0069] ④ Cool down to below 50°C and add copper sulfate solution (5 g copper sulfate dissolved in 50 mL deionized water);

[0070] ⑤Filter to obtain the precipitate, and wash it three times with water;

[0071] ⑥ Dry the precipitate at 50° C. overnight to obtain a blue solid powder, that is, the copper ion polymer.

[0072] Example 5

[0073] In this embodiment, a sodium ion polymer is provided, and a preparation method thereof comprises the following steps:

[0074] ① Weigh 20 g of EMAA960 (DuPont) and add it to the reactor, then dissolve 1.4 g of NaOH in 100 mL of deionized water to obtain a solution, pour the solution into the reactor, and introduce nitrogen bubbling for 30 min;

[0075] ② Nitrogen replacement;

[0076] ③Heat and raise the temperature to 140°C and react for 1 hour;

[0077] ④ Cool down to below 60°C and add ethanol solution of acetic acid (1.3 g acetic acid dissolved in 10 mL ethanol);

[0078] ⑤Filter to obtain the precipitate, and wash it three times with water;

[0079] ⑥ Dry the precipitate at 50° C. overnight to obtain a white solid powder, that is, the sodium ion polymer.

[0080] Comparative Example 1

[0081] In this comparative example, a partially neutralized carboxylic acid type ion polymer is provided, and the preparation method comprises the following steps:

[0082] ① Weigh 20g EAA 5980 (SK Company, South Korea) and add it into the reactor, then dissolve 1.5g NaOH in 80mL deionized water to obtain a solution, and pour the solution into the reactor;

[0083] ② Nitrogen replacement, pressurized to 0.5MPa;

[0084] ③Heat and raise the temperature to 140°C and react for 1 hour;

[0085] ④ Cool down to below 50°C and add sodium chloride solution (2 g sodium chloride dissolved in 40 mL deionized water);

[0086] ⑤Filter to obtain the precipitate, and wash it three times with water;

[0087] ⑥ Dry the precipitate at 50° C. overnight to obtain a light yellow solid powder, that is, the partially neutralized carboxylic acid type ion polymer.

[0088] Comparative Example 2

[0089] In this comparative example, a partially neutralized carboxylic acid type ion polymer is provided, and the preparation method comprises the following steps:

[0090] ① Weigh 20g EAA 5980 (SK Company, South Korea) and add it into the reactor. Then dissolve 1.5g NaOH in 80mL deionized water to obtain a solution. Pour the solution into the reactor and bubble nitrogen for 30min.

[0091] ② Nitrogen replacement, pressurized to 0.5MPa;

[0092] ③Heat and raise the temperature to 140°C and react for 1 hour;

[0093] ④ Add sodium chloride solution (2 g sodium chloride dissolved in 40 mL deionized water);

[0094] ⑤Filter to obtain the precipitate, and wash it three times with water;

[0095] ⑥ Dry the precipitate at 50° C. overnight to obtain a foamy white solid, that is, the partially neutralized carboxylic acid type ion polymer.

[0096] Comparative Example 3

[0097] In this comparative example, a carboxylic acid type ion polymer is provided, and the preparation method comprises the following steps:

[0098] ① Weigh 20g EAA 5980 (SK Company, South Korea) and add it into the reactor, then dissolve 16g triethanolamine in 80mL deionized water to obtain a solution, and pour the solution into the reactor;

[0099] ③Heat to 100°C and react for 1 hour;

[0100] ④ Cool down to room temperature and add sodium chloride solution (20g sodium chloride dissolved in 50mL deionized water);

[0101] ⑤Filter to obtain the precipitate, and wash it three times with water;

[0102] ⑥ Dry the precipitate at 60° C. overnight to obtain a light yellow solid powder, that is, the carboxylic acid type ion polymer.

[0103] The carboxylic acid type ion polymers provided in the examples and comparative examples were tested for performance, and the testing method was as follows:

[0104] (1) Light transmittance: Tested in accordance with GB / T 2410-2008, with a test sample thickness of 2 mm;

[0105] (2) Tensile strength: The test was conducted in accordance with GB / T 1040.3-2006. The sheets were pressed at 180°C, conditioned at 23°C and 50%, and then cut into 1BA type samples with a thickness of 2 mm and a width of 5 mm. The test was conducted at a tensile speed of 500 mm / min; the sensor was 5 KN; the number of samples was 5, and the average value was taken.

[0106] The performance test results are shown in Table 1.

[0107] Table 1

[0108] Light transmittance / % Tensile strength / MPa Appearance (160℃, 100MPa tableting) Example 1 90 26 Colorless and transparent Example 2 94 32 Colorless and transparent Example 3 91 29 Colorless and transparent Example 4 90 25 Blue transparent Example 5 94 33 Colorless and transparent Comparative Example 1 88 25 Yellow transparent Comparative Example 2 85 20 Colorless and transparent Comparative Example 3 92 30 Yellow transparent

[0109] As can be seen from Table 1, the performance of the carboxylic acid type ion polymer prepared by the preparation method of the present invention is comparable to that of the carboxylic acid type ion polymer prepared in Comparative Example 3. However, the preparation method provided by the present invention has mild reaction conditions and is easy to implement. Water is used as a solvent, and the by-product is water. The reaction process and results are harmless and environmentally friendly, and the atomic utilization rate is high.

[0110] Compared with Example 2, the preparation method provided in Comparative Example 1 did not involve nitrogen bubbling, and the obtained product was a light yellow solid powder.

[0111] Compared with Example 2, the preparation method provided in Comparative Example 2 does not include a cooling step, and sodium chloride solution is directly added after the reaction. The precipitation reaction is particularly uneven, and the precipitated product agglomerates into a ball in the shape of a foam plate, wrapped around the stirring paddle, and the tensile strength of the product is significantly reduced.

[0112] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the carboxylic acid type ion polymer and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a carboxylic acid type ion polymer, characterized in that: The preparation method comprises the following steps: (1) mixing an ethylene acrylic acid copolymer or an ethylene-methacrylic acid copolymer and an aqueous solution of a metal hydroxide, and bubbling nitrogen gas therein; (2) nitrogen replacement, followed by heating, reaction, cooling, and then adding a precipitant to generate precipitation, followed by post-treatment to obtain the carboxylic acid type ion polymer.

2. The preparation method according to claim 1, characterized in that: The metal hydroxide in step (1) comprises NaOH and / or KOH; In the aqueous solution of the metal hydroxide in step (1), the amount of the metal hydroxide is 1-3 g based on the amount of water being 50-100 mL; In step (1), based on 20 g of ethylene acrylic acid copolymer or ethylene-methacrylic acid copolymer, the amount of metal hydroxide used is 1-3 g.

3. The preparation method according to claim 1, characterized in that: The time for bubbling nitrogen in step (1) is 20-40 minutes.

4. The preparation method according to claim 1, characterized in that: When the reactant in step (1) is ethylene acrylic acid copolymer, step (2) further includes a step of pressurizing before heating; The pressurization is pressurization to 0.5 MPa or more.

5. The preparation method according to claim 1, characterized in that: The heating in step (2) is to 90-180° C. The reaction time of step (2) is 0.5-1.5 hours; The cooling in step (2) is to cool the temperature to below 60°C.

6. The preparation method according to claim 1, characterized in that: The precipitant in step (2) includes any one of methanol, ethanol, polyol, metal salt solution, acid solution or a combination of at least two thereof; The polyol includes glycerol and / or ethylene glycol; The metal salt solution includes any one of a sodium chloride aqueous solution, a zinc sulfate aqueous solution, and a copper sulfate aqueous solution, or a combination of at least two thereof; The acid solution includes any one of formic acid aqueous solution, formic acid alcohol solution, acetic acid aqueous solution, and acetic acid alcohol solution, or a combination of at least two thereof.

7. The preparation method according to claim 1, characterized in that: The post-treatment in step (2) includes filtering or centrifugal dehydration, washing, and drying; The washing comprises water washing; The drying temperature is 40-60° C. and the drying time is 8-18 hours.

8. A preparation method according to claim 1, characterized in that: The preparation method comprises the following steps: (1) mixing an ethylene acrylic acid copolymer or an ethylene-methacrylic acid copolymer and an aqueous solution of a metal hydroxide, and bubbling nitrogen therein for 20-40 minutes; (2) nitrogen replacement, then heating to 90-180° C., reacting for 0.5-1.5 hours, cooling to below 60° C., then adding a precipitant to generate a precipitate, filtering or centrifugally dehydrating, washing, and drying to obtain the carboxylic acid type ion polymer.

9. A carboxylic acid type ion polymer, characterized in that The carboxylic acid type ionic polymer is prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the carboxylic acid type ion polymer according to claim 9 in skin packaging, condoms, golf balls, laminated glass, perfume bottle caps, and polyethylene terephthalate modification.

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