CN114940775B - Method for repairing acrylate polymer material - Google Patents
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- CN114940775B CN114940775B CN202210769809.5A CN202210769809A CN114940775B CN 114940775 B CN114940775 B CN 114940775B CN 202210769809 A CN202210769809 A CN 202210769809A CN 114940775 B CN114940775 B CN 114940775B
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C—CHEMISTRY; METALLURGY
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a repairing method of an acrylate polymer material, which comprises the following steps: (1) Coating a repair compound or a solution containing the repair compound on the surface of an acrylate polymer material to be repaired; and/or, (2) soaking the acrylate polymeric material to be repaired with a solution containing the repair compound; the repair compound is comprised of one or more cationic salts, wherein at least one cationic salt is a divalent cationic salt or a more divalent cationic salt. The repairing method has good repairing effect on the acrylate polymer material subjected to environments such as strong acid, strong alkali or high salt content, and the mechanical property and chemical property of the repaired acrylate polymer material can be recovered to the levels before degradation. The method has simple process, is friendly and safe to the environment and human body, and can be applied to material repair of electronic devices, mechanical equipment, building engineering or waterproof engineering.
Description
Technical Field
The invention relates to the technical field of material repair, in particular to a repair method of an acrylate polymer material.
Background
The acrylate polymer is one kind of high molecular polymer with acrylate as monomer and has main chain similar to polyacrylic acid and side chain of carboxylic acid cation salt. Most of the acrylate polymers have the advantages of high modulus, high rigidity, good heat resistance and insulativity and the like, and are widely applied to the fields of electronics, machinery, constructional engineering and the like. In the field of constructional engineering, the water conservancy and hydropower science institute and the Yangtze river academy of sciences in China are sequentially in the middle and later stages of 80 s, and an acrylic acid salt chemical grouting material is developed on the basis of the work of the former, and has the functions and principles that acrylic acid salt is polymerized into an acrylic acid salt gel polymer which is insoluble in water under a certain initiator, the anti-seepage and plugging effects are realized, and the material is also applied to projects such as Yangtze river three gorges.
However, while acrylate polymer materials are used in a variety of fields, there is little research on simple and environmentally friendly material repair methods. Taking magnesium acrylate waterproof material used in the field of constructional engineering as an example, the polymer of the material is insoluble in water and has good adhesive force after being sprayed to form a film, but when the material is subjected to environments such as strong acid, strong alkali or high salt content, the polymer material is degraded to a certain extent, and the waterproof capability of the material is seriously affected. At present, the problem can only be overcome by re-construction or other construction method changes, but the methods all require a great deal of manpower and material resources, which can lead to great increase of construction cost.
Therefore, it is necessary to provide a repairing method of the acrylate polymer material after construction, so that the repairing process is simpler, more convenient and more environment-friendly.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, it is a primary object of the present invention to provide a simple method for repairing an acrylate polymer material.
The invention achieves the aim and comprises the following technical proposal.
A method of repairing an acrylate polymeric material comprising the steps of:
(1) Coating a repair compound on the surface of the acrylate polymer material to be repaired; and/or the number of the groups of groups,
(2) Immersing or coating or spraying the acrylate polymer material to be repaired with a solution containing the repair compound;
the repair compound is comprised of one or more cationic salts, wherein at least one cationic salt is a divalent cationic salt or a more divalent cationic salt.
In some of these embodiments, the cation in the divalent cation salt or more than divalent cation salt is selected from the group consisting of: magnesium ion, calcium ion, aluminum ion, strontium ion, barium ion, scandium ion, yttrium ion, titanium ion, zirconium ion, vanadium ion, niobium ion, chromium ion, molybdenum ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, cadmium ion, mercury ion, gallium ion, indium ion, thallium ion, germanium ion, tin ion, lead ion, antimony ion, bismuth ion.
In some of these embodiments, the cation in the divalent cation salt or more than divalent cation salt is selected from the group consisting of: magnesium ion, calcium ion, aluminum ion, iron ion, cobalt ion, nickel ion, copper ion, and zinc ion.
In some of these embodiments, the repair compound consists of one or more cationic salts that are divalent and/or more than divalent.
In some of these embodiments, the cationic salt is selected from: magnesium sulfate, magnesium chloride, magnesium nitrate, calcium sulfate, calcium chloride, and calcium nitrate.
In some of these embodiments, the mass ratio of the repair compound to the acrylate polymeric material is from 0.0001 to 10000:1, preferably 0.1 to 100:1. the specific amount of the repairing compound is determined according to the damage (decomposition or degradation) degree of the acrylate polymer material to be repaired, if the damage is serious, the amount of the repairing compound can be more, if the repairing compound is only slightly damaged, and a good repairing effect can be obtained by using a small amount of the repairing compound.
In some of these embodiments, the solution containing the repair compound is an aqueous solution with water as a solvent.
In some of these embodiments, the mass concentration of the repair compound in the solution containing the repair compound is 0.00001% to 80%, preferably 1% to 60%, more preferably 15% to 30%.
In some of these embodiments, the acrylate polymer material is an acrylate polymer material that undergoes degradation or decomposition upon exposure to strong acid, strong base, and/or high salt environments.
In some of these embodiments, the acrylate polymeric material is selected from the group consisting of: magnesium acrylate polymer, calcium acrylate polymer, aluminum acrylate polymer, strontium acrylate polymer, barium acrylate polymer, scandium acrylate polymer, yttrium acrylate polymer, titanium acrylate polymer, zirconium acrylate polymer, vanadium acrylate polymer, niobium acrylate polymer, chromium acrylate polymer, molybdenum acrylate polymer, manganese acrylate polymer, iron acrylate polymer, cobalt acrylate polymer, nickel acrylate polymer, copper acrylate polymer, zinc acrylate polymer, cadmium acrylate polymer, mercury acrylate polymer, gallium acrylate polymer, indium acrylate polymer, thallium acrylate polymer, germanium acrylate polymer, tin salt polymer, lead acrylate polymer, antimony acrylate polymer, bismuth acrylate polymer.
In some of these embodiments, the repair process is operated at a temperature of-30 ℃ to 70 ℃, preferably 0 ℃ to 45 ℃, more preferably 25±5 ℃.
In some of these embodiments, the repair time of the repair method is from 0.1min to 24 hours, more preferably from 0.1min to 16 hours; the repair time refers to the reaction time after coating or the soaking time. The specific repair time is determined according to the damage (decomposition or degradation) degree of the acrylate polymer material to be repaired, and if the acrylate polymer material is only slightly damaged, the coating or soaking of a small amount of repair compound can achieve a good repair effect immediately; if the damage is serious, the repair time is prolonged, or the use amount of the repair compound is increased, so that the good repair effect can be obtained.
The repairing method of the acrylate polymer material has the following beneficial effects:
the repairing method provided by the invention has a good repairing effect on the acrylate polymer material subjected to environments such as strong acid, strong alkali or high salt content, and the mechanical property and chemical property of the repaired acrylate polymer material can be recovered to the levels before degradation, so that the defects of the prior art are overcome, the simple repairing of the acrylate polymer material is realized, and the repairing method can be applied to material repairing of electronic devices, mechanical equipment, constructional engineering or waterproof engineering. In addition, the material used in the method for repairing the acrylate polymer is a nontoxic and harmless substance, is friendly to the environment and human body, and is safe and environment-friendly.
Drawings
FIG. 1 is a photograph of the magnesium acrylate polymer before and after repair in example 1 of the present invention (a is before repair; b is in repair; c is after repair; d is magnesium acrylate polymer before undegraded).
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
In the present invention, the term "plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
The following are specific examples. The starting materials used in the examples below, unless otherwise specified, are all commercially available from conventional sources; the processes used, unless otherwise specified, are all conventional in the art. Room temperature refers to 25±5 ℃ unless otherwise specified below.
Example 1
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out, 0.5g of magnesium sulfate was coated on the surface of the test piece, and after 12 hours, performance test was performed on the test piece, and the test results are shown in table 2.
The tensile strength in Table 2 was measured at room temperature using an electronic universal tester, the gauge length of the test piece was specifically set to 10mm in the experimental test, and the clamp tensile rate was specifically set to 5 mm. Min in the experimental test -1 The test piece traits were obtained by visual inspection.
Example 2
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out, 0.5g of magnesium chloride was coated on the surface of the test piece, and after 12 hours, performance test was performed on the test piece, and the test results are shown in table 2.
Example 3
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution.
The soaked test piece was taken out, 0.5g of magnesium nitrate was coated on the surface of the test piece, and after 12 hours, performance test was performed on the test piece, and the test results are shown in table 2.
Example 4
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out, 0.5g of calcium sulfate was applied to the surface of the test piece, and after 12 hours, the test piece was subjected to performance test, and the test results are shown in table 2.
Example 5
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out, 0.5g of calcium chloride was applied to the surface of the test piece, and after 12 hours, the test piece was subjected to performance test, and the test results are shown in table 2.
Example 6
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out, 0.5g of calcium nitrate was applied to the surface of the test piece, and after 12 hours, the test piece was subjected to performance test, and the test results are shown in table 2.
Example 7
Magnesium chloride and calcium chloride were mixed in 20 parts: 80 parts by mass of the mixture to obtain a repairing mixture.
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out, 0.5g of the repair mixture was applied to the surface of the test piece, and after 12 hours, the test piece was subjected to performance test, and the test results are shown in table 2.
Example 8
Magnesium sulfate and calcium chloride were mixed in 50 parts: 50 parts by mass of the mixture are mixed to obtain a repairing mixture.
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out, 0.5g of the repair mixture was applied to the surface of the test piece, and after 12 hours, the test piece was subjected to performance test, and the test results are shown in table 2.
Example 9
20 parts by weight of magnesium chloride and 20 parts by weight of calcium chloride were dissolved in 100 parts by weight of distilled water to obtain a restoration mixture.
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. And taking out the soaked test piece, soaking the test piece in 20mL of repairing mixed solution, and performing performance test on the test piece after 12 hours, wherein the test result is shown in Table 2.
Example 10
20 parts by weight of calcium chloride was dissolved in 100 parts by weight of distilled water to obtain a restoration mixture.
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. And taking out the soaked test piece, soaking the test piece in 20mL of repairing mixed solution, and performing performance test on the test piece after 12 hours, wherein the test result is shown in Table 2.
Comparative example 1
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out and soaked in 20mL of distilled water again, and after 12 hours, performance test was performed on the test piece, and the test results are shown in table 2.
Comparative example 2
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out, 0.5g of sodium chloride was applied to the surface of the test piece, and after 12 hours, the test piece was subjected to performance test, and the test results are shown in table 2.
Comparative example 3
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. The soaked test piece was taken out, 0.5g of potassium sulfate was applied to the surface of the test piece, and after 12 hours, the test piece was subjected to performance test, and the test results are shown in table 2.
Comparative example 4
20 parts by weight of sodium sulfate was dissolved in 100 parts by weight of distilled water to obtain a restoration mixture.
Cutting the magnesium acrylate polymer into a test piece (1 g) with the thickness of 3mm and the length of 2cm multiplied by 1.5cm, soaking the test piece in sodium hydroxide aqueous solution (0.1 mol/L) for 8 hours, and expanding the volume of the soaked test piece into gel, thereby indicating that the magnesium acrylate polymer is degraded under the soaking of the sodium hydroxide aqueous solution. And taking out the soaked test piece, soaking the test piece in 20mL of repairing mixed solution, and performing performance test on the test piece after 12 hours, wherein the test result is shown in Table 2.
TABLE 1 repair Compounds or mixture compositions (parts by weight) and modes of use for examples 1-10 and comparative examples 1-4
TABLE 2 tensile Strength and shape of original test pieces, test pieces of examples 1 to 10 and comparative examples 1 to 4
As is clear from the results of Table 2, examples 1 to 10 were good in recovery of the properties of the acrylic polymer after the example recovery treatment (the recovery method of the acrylic polymer material according to the present invention) as compared with comparative examples 1 to 4, and were able to recover the tensile strength of the original test piece, whereas the properties of the acrylic polymer treated with comparative examples were not significantly changed, and the tensile strength was not significantly changed as compared with the test piece after the immersion. The method for repairing the acrylate polymer material has good repairing effect on the acrylate polymer damaged by alkali soaking.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method of repairing an acrylate polymeric material comprising the steps of:
(1) Coating a repair compound on the surface of the acrylate polymer material to be repaired; and/or the number of the groups of groups,
(2) Immersing or coating or spraying the acrylate polymer material to be repaired with a solution containing the repair compound;
the repair compound consists of one or more cationic salts, wherein at least one cationic salt is a divalent cationic salt or a more than divalent cationic salt;
the acrylate polymeric material is selected from: magnesium acrylate polymer, calcium acrylate polymer, aluminum acrylate polymer, strontium acrylate polymer, barium acrylate polymer, scandium acrylate polymer, yttrium acrylate polymer, titanium acrylate polymer, zirconium acrylate polymer, vanadium acrylate polymer, niobium acrylate polymer, chromium acrylate polymer, molybdenum acrylate polymer, manganese acrylate polymer, iron acrylate polymer, cobalt acrylate polymer, nickel acrylate polymer, copper acrylate polymer, zinc acrylate polymer, cadmium acrylate polymer, mercury acrylate polymer, gallium acrylate polymer, indium acrylate polymer, thallium acrylate polymer, germanium acrylate polymer, tin acrylate polymer, lead acrylate polymer, antimony acrylate polymer, bismuth acrylate polymer;
the acrylate polymer material to be repaired is an acrylate polymer material that undergoes degradation or decomposition after being subjected to a strong acid, strong base and/or high salt environment.
2. The method of claim 1, wherein the cation of the divalent cation salt or the more than divalent cation salt is selected from the group consisting of: magnesium ion, calcium ion, aluminum ion, strontium ion, barium ion, scandium ion, yttrium ion, titanium ion, zirconium ion, vanadium ion, niobium ion, chromium ion, molybdenum ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, cadmium ion, mercury ion, gallium ion, indium ion, thallium ion, germanium ion, tin ion, lead ion, antimony ion, bismuth ion.
3. The method of repairing an acrylic polymeric material according to claim 2, wherein the cation of the divalent cation salt or more than divalent cation salt is selected from the group consisting of: magnesium ion, calcium ion, aluminum ion, iron ion, cobalt ion, nickel ion, copper ion, and zinc ion.
4. A method of repairing an acrylate polymeric material according to any one of claims 1 to 3 wherein the repair compound consists of one or more cationic salts which are divalent and/or more than divalent.
5. The method of repairing an acrylic polymeric material according to claim 4, wherein said cationic salt is selected from the group consisting of: magnesium sulfate, magnesium chloride, magnesium nitrate, calcium sulfate, calcium chloride, and calcium nitrate.
6. A method of repairing an acrylic polymeric material according to any one of claims 1 to 3, wherein the mass ratio of the amount of the repairing compound to the acrylic polymeric material is from 0.0001 to 10000:1.
7. a method of repairing an acrylic polymeric material according to any one of claims 1 to 3 wherein said solution containing said repair compound is an aqueous solution with water as solvent.
8. A method of repairing an acrylic polymer material according to any one of claims 1 to 3, wherein the mass concentration of the repair compound in the solution containing the repair compound is 0.00001% to 80%.
9. The method of claim 8, wherein the concentration of the repair compound in the solution containing the repair compound is 1% to 60% by mass.
10. A method of repairing an acrylate polymer material according to any one of claims 1 to 3 wherein said acrylate polymer material is a magnesium acrylate polymer.
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| CN1098727A (en) * | 1993-04-23 | 1995-02-15 | 三菱油化株式会社 | High water absorbency polymer with enhanced gel-strength |
| CN1209831A (en) * | 1995-12-29 | 1999-03-03 | 普罗格特-甘布尔公司 | Hard-surface cleaning composition |
| JP2004124063A (en) * | 2002-08-02 | 2004-04-22 | Toagosei Co Ltd | Aqueous solution of water-stop material |
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| Complexes of poly(acrylic acid) with some divalent, tribalent and tetravalent metal ions;Rodolphe Roma-Luciow et al.;《European Polymer Journal》(第37期);第1741-1745页 * |
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