CN111454552A - Polyglycolic acid modifier, composition, preparation method and application thereof - Google Patents
Polyglycolic acid modifier, composition, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyglycolic acid modifier and a preparation method and application thereof. The polyglycolic acid modifier comprises a component A and a component B, wherein the component A comprises: 1-15 parts of rare earth additive; the component B comprises: 0.1-3 parts of chain extender, 0.05-1 part of nucleating agent, 0.1-3 parts of initiator and 0.05-1 part of antioxidant. The polyglycolic acid modifier can improve the hydrophobicity and toughness of polyglycolic acid. The invention also discloses a polyglycolic acid composition and a preparation method thereof. The polyglycolic acid composition comprises 60 to 95 parts by weight of polyglycolic acid and 1.5 to 18 parts by weight of a polyglycolic acid modifier. The composition has good hydrophobicity and toughness.
Description
Technical Field
The invention relates to a polyglycolic acid modifier, a preparation method and application thereof, and also relates to a polyglycolic acid composition and a preparation method thereof.
Background
Polyglycolic acid (PGA for short), also called polyglycolic acid, is widely used as a degradable material. Since polyglycolic acid has a large number of hydroxyl groups and carboxyl groups on its surface, it tends to absorb water, has insufficient toughness, and is liable to be broken and cracked. Polyglycolic acid causes cracks in the matrix material after absorbing water, and when an external load is applied, the hygroscopicity of polyglycolic acid increases, and the rate of propagation of cracks increases. Therefore, the service time of the polyglycolic acid can be prolonged by increasing the hydrophobicity of the polyglycolic acid while increasing the toughness of the polyglycolic acid.
CN1768114A discloses a polyglycolic acid composition which is improved in moisture resistance stability and stretchability by adding a small amount of an aromatic polyester resin to a polyglycolic acid resin. CN101321829B discloses a polyglycolic acid composition, which is prepared by adding a carboxyl-capping agent and a hydrazine-based polymerization catalyst-inactivating agent to a polyglycolic acid resin to improve the water resistance of polyglycolic acid. CN101316877B discloses a method for controlling water resistance of polyglycolic acid resin, which is a method for controlling the amount of residual ethyl acetate in polyglycolic acid resin by adding a heat stabilizer. CN108079377A discloses a polyglycolic acid resin composite material, which contains polyglycolic acid resin, nano inorganic filler and reinforcing fiber. The composite material adopts nano inorganic filling material and reinforcing fiber to improve the mechanical property of the polyglycolic acid.
At present, reports on improvement of the hydrophobicity and mechanical properties of polyglycolic acid by using a rare earth polymer additive have not been found.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a polyglycolic acid modifier which can increase the hydrophobicity of polyglycolic acid and can enhance the toughness of polyglycolic acid. Further, the invention provides a preparation method of the polyglycolic acid modifier. Further, the present invention provides a use of the above modifier.
It is yet another object of the present invention to provide a polyglycolic acid composition having superior hydrophobicity and toughness. Further, the invention also provides a preparation method of the polyglycolic acid composition.
The technical purpose is achieved through the following technical scheme.
In one aspect, the present invention provides a polyglycolic acid modifier comprising:
component A
1-15 parts of rare earth additive;
component B
The rare earth additive is prepared by the following method: reacting a cationic surfactant with a rare earth salt compound to obtain an organic rare earth compound; reacting an organic rare earth compound with a coupling agent to obtain a rare earth auxiliary agent;
the cationic surfactant is a quaternary ammonium salt cationic surfactant containing C ═ C bonds, and the coupling agent is selected from one or more of silane coupling agents or titanate coupling agents.
The polyglycolic acid modifier according to the present invention, preferably, the cationic surfactant is selected from one or more of methacryloyloxyethyl dimethylhexadecylammonium bromide, hexadecyldimethylallylammonium chloride, p-vinylbenzyldimethyloctadecyl chloride, dimethyltetradecyl (2-acrylamidopropyl) ammonium bromide;
the rare earth element in the rare earth compound is selected from one or more of lanthanum or cerium;
the coupling agent is selected from one or more of KH550, KH560, KH570 and KH 602.
According to the polyglycolic acid modifier, the mass ratio of the cationic surfactant to the rare earth salt compound to the coupling agent is preferably (0.3-2) to (5-15) to (0.4-2).
According to the polyglycolic acid modifier of the present invention, preferably, the chain extender is selected from diisocyanate-based chain extenders;
the nucleating agent is selected from one or more of TMB-5, talcum powder/aluminum-based phosphate complex, 1,2,3, 4-butanetetracarboxylic acid, triallyl isonitrile uratate and phenyl zinc phosphate;
the initiator is selected from one or more of lysine triisocyanate, polyethylene glycol, lauric acid, glycerol and sorbitol;
the antioxidant is selected from one or more of antioxidant 9225, antioxidant 9215, antioxidant 168 and antioxidant 1010.
In another aspect, the present invention provides a method for preparing the polyglycolic acid modifier, comprising the steps of:
(1) reacting a cationic surfactant with a rare earth salt compound to obtain an organic rare earth compound; reacting an organic rare earth compound with a coupling agent to obtain a component A;
(2) mixing a chain extender, a nucleating agent, an initiator and an antioxidant to obtain a component B;
wherein, the step (1) comprises the following processes:
(a) mixing an organic acid and a cationic surfactant to form a mixed solution; adding rare earth carbonate into the mixed solution, reacting for 50-100 min at 40-60 ℃, then reacting for 1-3 h at 60-90 ℃ to obtain a reaction product, and drying the reaction product to obtain an organic rare earth compound;
(b) adding an organic rare earth compound into a coupling agent solution with the pH value of 3-6, and reacting for 0.5-3 h at the temperature of 30-80 ℃ to obtain a reaction product; and drying the reaction product to prepare powder to obtain the rare earth additive.
According to the production method of the present invention, preferably, in the process (a), the mixed solution is obtained by: mixing carboxylic acid and a cationic surfactant at 30-70 ℃, and then stirring for 20-50 min at 35-75 ℃;
in the process (b), the coupling agent solution is obtained by: and mixing the coupling agent and the alcohol solution to obtain a mixed solution, then adding carboxylic acid to adjust the pH of the mixed solution to 3-6, and stirring the mixed solution after the pH is adjusted for 300-700 min at the temperature of 30-80 ℃.
In a further aspect, the present invention provides the use of a polyglycolic acid modifier as described above for increasing the hydrophobicity and/or toughness of polyglycolic acid.
In another aspect, the present invention provides a polyglycolic acid composition comprising 60 to 95 parts by weight of polyglycolic acid and 1.5 to 18 parts by weight of the above-mentioned polyglycolic acid modifier.
In addition, the invention also provides a preparation method of the polyglycolic acid composition, which comprises the following steps:
(1') mixing polyglycolic acid and component A together in an internal mixer, and then granulating to obtain polyglycolic acid particles;
(2') blending polyglycolic acid particles with component B, and extruding through a twin-screw extruder to obtain a polyglycolic acid composition.
According to the preparation method provided by the invention, preferably, in the step (1'), the banburying temperature is 180-250 ℃, the banburying time is 5-20 min, and the screw rotating speed of a banbury mixer is 50-100 rpm;
and (2') extruding at the temperature of 180-250 ℃, wherein the screw rotating speed of the double-screw extruder is 20-70 rpm.
The organic rare earth compound prepared by the method has good hydrophobic association by utilizing good coordination capability of the rare earth element and the hydrophobicity of the cationic surfactant. The rare earth additive has dispersing and coupling effects through the modification of the coupling agent, the agglomeration of the rare earth additive in a high polymer material is reduced, the compatibility and the machining performance of the rare earth additive in polyglycolic acid resin are improved, and a soft segment for resisting crack expansion is provided for a polyglycolic acid matrix. The rare earth additive is matched with other components such as a chain extender and a nucleating agent to effectively improve the hydrophobicity and toughness of the polyglycolic acid.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
< polyglycolic acid-modifying agent >
The polyglycolic acid modifier of the present invention comprises component a and component B. The component A contains a rare earth additive; the component B comprises a chain extender, a nucleating agent, an initiator and an antioxidant.
In the component A, 1-15 parts by weight of rare earth additive is added; preferably 2 to 10 parts by weight; more preferably 2 to 6 parts by weight.
The rare earth additive is prepared by the following method: reacting a cationic surfactant with a rare earth salt compound to obtain an organic rare earth compound; reacting the organic rare earth compound with a coupling agent to obtain the rare earth additive.
In the present invention, the cationic surfactant is a quaternary ammonium salt type cationic surfactant containing C ═ C bonds; preferably a dimethyl quaternary ammonium salt type cationic surfactant containing a C ═ C bond; more preferably one or more of methacryloyloxyethyl dimethyl hexadecyl ammonium bromide, hexadecyl dimethyl allyl ammonium chloride, p-vinylbenzyl dimethyl octadecyl ammonium chloride and dimethyl tetradecyl (2-acrylamidopropyl) ammonium bromide; most preferably at least one of methacryloyloxyethyl dimethyl hexadecyl ammonium bromide, hexadecyl dimethyl allyl ammonium chloride and p-vinylbenzyl dimethyl octadecyl ammonium chloride. These cationic surfactants have good hydrophobic properties, are capable of associating with rare earth ions and are capable of reacting with coupling agents.
In the present invention, the coupling agent may be selected from one or more of a silane coupling agent or a titanate coupling agent. Examples of silane coupling agents include, but are not limited to, KH-550, KH-560, KH570, KH602, KH 750. Examples of titanate coupling agents include, but are not limited to, one or more of TMC-201, TMC-102, TMC-105, NDZ-102, NDZ-101. Preferably, the coupling agent is a silane coupling agent. More preferably, the coupling agent is selected from one or more of KH-550, KH-560 or KH-602. These coupling agents are able to better improve the toughness of polyglycolic acid.
In the present invention, the rare earth element in the rare earth salt compound may be selected from one or more of lanthanum or cerium. Preferably, the rare earth element is lanthanum. The rare earth salt compound can be rare earth acetate and rare earth carbonate. Examples of the rare earth salt-based compound include, but are not limited to, lanthanum carbonate, cerium carbonate, lanthanum acetate, and cerium acetate.
In the invention, the mass ratio of the cationic surfactant, the rare earth inorganic salt and the coupling agent can be (0.3-2): 5-15): 0.4-2; preferably (0.3-1.5): (7-13): (0.4-1.5); more preferably (0.7 to 1.5): (8 to 12): (0.5 to 1.2).
In the invention, the using amount of the chain extender is 0.1-3 parts by weight; preferably 0.3 to 2 parts by weight; more preferably 0.3 to 1.5 parts by weight. The chain extender may be a diisocyanate-based chain extender. Preferably, the chain extender is selected from one or more of hexamethylene diisocyanate, diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, isophorone diisocyanate. More preferably, the chain extender is selected from at least one of hexamethylene diisocyanate, diphenylmethane diisocyanate. The chain extender with proper dosage can improve the mechanical property of the polyglycolic acid.
In the invention, the nucleating agent is used in an amount of 0.05 to 1 part by weight; preferably 0.05 to 0.5 weight part; more preferably 0.1 to 0.4 parts by weight. The nucleating agent may be selected from one or more of TMB-5, talc/aluminium based phosphate complex, 1,2,3, 4-butanetetracarboxylic acid, triallyl isonitrile uratate, phenyl zinc phosphate. Preferably, the nucleating agent is selected from one or more of TMB-5, 1,2,3, 4-butanetetracarboxylic acid, triallyl isonitrile uratate. More preferably, the nucleating agent is selected from one of TMB-5, 1,2,3, 4-butanetetracarboxylic acid. This can improve the toughness of polyglycolic acid.
In the invention, the initiator is used in an amount of 0.1 to 3 parts by weight; preferably 0.1 to 2 parts by weight; more preferably 0.3 to 1.5 parts by weight. The initiator is one or more selected from lysine triisocyanate, polyethylene glycol, lauric acid, glycerol and sorbitol. Preferably, the initiator is selected from one or more of lysine triisocyanate, polyethylene glycol or sorbitol. More preferably, the initiator is selected from at least one of lysine triisocyanate and polyethylene glycol.
In the invention, the antioxidant is used in an amount of 0.05-1 part by weight; preferably 0.05 to 0.5 weight part; more preferably 0.1 to 0.4 parts by weight. The antioxidant can be one or more selected from antioxidant 9225, antioxidant 9215, antioxidant 168, and antioxidant 1010. Preferably, the antioxidant is at least one selected from the group consisting of antioxidant 9225, antioxidant 9215, and antioxidant 168. More preferably, the antioxidant is at least one selected from the group consisting of antioxidant 9225 and antioxidant 9215.
According to one embodiment of the invention, the polyglycolic acid modifier comprises:
component A
1-15 parts of rare earth additive;
component B
According to another embodiment of the present invention, a polyglycolic acid modifier comprises:
component A
2-10 parts of a rare earth additive;
component B
According to yet another embodiment of the present invention, a polyglycolic acid modifier comprises:
component A
2-6 parts of a rare earth additive;
component B
< method for producing polyglycolic acid modifier >
The preparation method of the polyglycolic acid modifier comprises the following steps:
(1) reacting a cationic surfactant with a rare earth salt compound to obtain an organic rare earth compound; reacting an organic rare earth compound with a coupling agent to obtain a component A;
(2) and mixing the chain extender, the nucleating agent, the initiator and the antioxidant to obtain a component B.
The cationic surfactant, rare earth salt compound, coupling agent, chain extender, nucleating agent, initiator, and antioxidant are selected and used as described above.
Specifically, the step (1) includes the following processes:
(a) mixing an organic acid and a cationic surfactant to form a mixed solution; adding rare earth carbonate into the mixed solution, firstly carrying out low-temperature reaction, then carrying out high-temperature reaction to obtain a reaction product, and drying the reaction product to obtain an organic rare earth compound;
(b) mixing a coupling agent with a solvent to form a coupling agent solution; and adding an organic rare earth compound into the coupling agent solution to obtain a reaction product, and drying the reaction product to prepare powder to obtain the rare earth auxiliary agent.
In the present invention, the organic acid may be an organic carboxylic acid; preferably an aliphatic organic carboxylic acid; more preferably acetic acid.
In the process (a), the low-temperature reaction temperature is 30-60 ℃; preferably 40-60 ℃; more preferably 45 to 60 ℃. The low-temperature reaction time is 50-100 min; preferably 50-80 min; more preferably 60-80 min. The high-temperature reaction temperature is 60-90 ℃; preferably 60-85 ℃; more preferably 65 to 80 ℃. The high-temperature reaction time is 1-3 h; preferably 1-2.5 h; more preferably 1-2 h.
The solvent in process (b) may be an alcohol solution; preferably a monohydric aliphatic alcohol; ethanol is more preferred.
The pH value of the coupling agent solution can be 3-6; preferably 4-6; more preferably 4 to 5.
The reaction temperature of the coupling agent and the organic rare earth compound can be 30-80 ℃; preferably 40-70 ℃; more preferably 40 to 60 ℃. The reaction time can be 0.5-3 h; preferably 0.5-2 h; more preferably 0.5 to 1.5 hours.
The mixed solution in the process (a) can be obtained by: mixing organic acid and cationic surfactant at 30-70 ℃, and then stirring for 20-50 min at 35-75 ℃. Preferably, the organic acid and the cationic surfactant are mixed at 40-60 ℃, and then stirred at 45-60 ℃ for 30-40 min.
The coupling agent solution in process (b) is obtained by the following method: and mixing the coupling agent and the solvent, then adding organic acid to adjust the pH of the mixed solution, and stirring the mixed solution after the pH adjustment for 300-700 min at the temperature of 30-80 ℃. Preferably, the coupling agent is mixed with the solvent, then the organic acid is added to adjust the pH of the mixed solution, and the mixed solution after pH adjustment is stirred for 400-600 min at 40-60 ℃.
< polyglycolic acid composition >
The polyglycolic acid composition of the present invention comprises polyglycolic acid and a polyglycolic acid modifier.
In the present invention, polyglycolic acid is used in an amount of 60 to 95 parts by weight, preferably 70 to 95 parts by weight, more preferably 80 to 90 parts by weight, which can achieve a further improved modification effect, and the number average molecular weight of polyglycolic acid may be 1 × 102～1×109Preferably 1 × 103～1×107More preferably 1 × 104～1×106. The specific gravity of the polyglycolic acid may be 0.3 to 5g/cm3(ii) a Preferably 0.8 to 3g/cm3(ii) a More preferably 0.8 to 2g/cm3。
The composition of the polyglycolic acid modifier is as described previously. The dosage of the polyglycolic acid modifier is 1.5-18 parts by weight; preferably 3 to 15 parts by weight; more preferably 3 to 10 parts by weight.
According to one embodiment of the present invention, a polyglycolic acid composition includes 60 to 95 parts by weight of polyglycolic acid and 1.5 to 18 parts by weight of a polyglycolic acid modifier.
According to another embodiment of the present invention, a polyglycolic acid composition includes 70 to 95 parts by weight of polyglycolic acid and 3 to 15 parts by weight of a polyglycolic acid modifier.
According to still another embodiment of the present invention, a polyglycolic acid composition includes 80 to 90 parts by weight of polyglycolic acid and 3 to 10 parts by weight of a polyglycolic acid modifier.
< use of polyglycolic acid modifier and Process for producing polyglycolic acid composition >
The present invention provides a use of the polyglycolic acid modifier for improving hydrophobicity and/or toughness of polyglycolic acid. The present invention also provides a method for producing the polyglycolic acid composition.
The preparation method and the application comprise the following specific steps:
(1') mixing polyglycolic acid and component A together in an internal mixer, and then granulating to obtain polyglycolic acid particles;
(2') blending polyglycolic acid particles with component B, and extruding through a twin-screw extruder to obtain a polyglycolic acid composition.
The preparation of component A and component B is as described above.
In the step (1'), banburying temperature can be 180-250 ℃; preferably 190-230 ℃; more preferably 200 to 220 ℃. The banburying time can be 5-20 min; preferably 5-15 min; more preferably 6 to 10 min. The rotating speed of the screw of the internal mixer can be 50-100 rpm; preferably 60-90 rpm; more preferably 60 to 80 rpm.
In the step (2'), the extrusion temperature can be 180-250 ℃; preferably 190-230 ℃; more preferably 200 to 220 ℃. The screw rotating speed of the double-screw extruder is 20-70 rpm; preferably 30-60 rpm; more preferably 30 to 50 rpm.
The test method is described below:
elongation at break: a universal tester is adopted for testing according to GB13022-91 test method for tensile property of plastic films.
Contact angle: the test was performed using a standard type contact angle tester.
The starting materials in the following examples are illustrated below:
polyglycolic acid: produced by Shanghai Mijing company, the specific weight is 1.24g/cm3The melt flow rate at 210 ℃ was 2.16kg/10min, and the number-average molecular weight was 100000.
Examples 1 to 3
Dissolving a cationic surfactant in acetic acid under the condition of 50 ℃ water bath, and stirring for 32min at 55 ℃ to form a mixed solution; slowly adding rare earth carbonate into the mixed solution, firstly reacting for 70min at 55 ℃, and then reacting for 1.5h at 70 ℃ to obtain a reactant; and drying the reactant at 60 ℃ for 3.5h to obtain the organic rare earth compound.
Mixing a coupling agent and an ethanol solvent to obtain a mixed solution, and then adding acetic acid to adjust the pH value of the mixed solution to 5; stirring the mixed solution after pH adjustment for 450min at 50 ℃ to obtain a coupling agent solution; slowly adding the organic rare earth compound into the coupling agent solution, reacting for 1h at 50 ℃, drying and grinding into powder to obtain the component A.
And mixing the nucleating agent, the chain extender, the initiator and the antioxidant to obtain the component B.
The specific materials and amounts used are shown in table 1.
TABLE 1
Example 4
(1) Mixing 87 parts by weight of polyglycolic acid and the component A prepared in example 1 together in an internal mixer, followed by granulation to obtain polyglycolic acid particles; the banburying temperature is 210 ℃, the banburying time is 8min, and the screw rotating speed of the banbury mixer is 70 rpm.
(2) Polyglycolic acid particles were blended with component B prepared in example 1 and extruded through a twin-screw extruder to obtain a polyglycolic acid composition. The extrusion temperature was 210 ℃ and the screw speed of the twin-screw extruder was 40 rpm. The properties of the polyglycolic acid composition are shown in table 2.
Example 5
(1) 86 parts by weight of polyglycolic acid and the component A prepared in example 2 were co-mixed and banburied in an internal mixer, followed by granulation to obtain polyglycolic acid particles; the banburying temperature is 210 ℃, the banburying time is 8min, and the screw rotating speed of the banbury mixer is 70 rpm.
(2) Polyglycolic acid particles were blended with the component B prepared in example 2 and extruded through a twin-screw extruder to obtain a polyglycolic acid composition. The extrusion temperature was 210 ℃ and the screw speed of the twin-screw extruder was 40 rpm. The properties of the polyglycolic acid composition are shown in table 2.
Example 6
(1) Mixing 90 parts by weight of polyglycolic acid and the component A prepared in example 3 together in an internal mixer, followed by granulation to obtain polyglycolic acid particles; the banburying temperature is 210 ℃, the banburying time is 8min, and the screw rotating speed of the banbury mixer is 70 rpm.
(2) Polyglycolic acid particles were blended with component B prepared in example 3 and extruded through a twin-screw extruder to obtain a polyglycolic acid composition. The extrusion temperature was 210 ℃ and the screw speed of the twin-screw extruder was 40 rpm. The properties of the polyglycolic acid composition are shown in table 2.
Comparative example
Polyglycolic acid purchased from Shanghai Pujing having a specific gravity of 1.24g/cm3The melt flow rate at 210 ℃ was 2.16kg/10min, and the number-average molecular weight was 100000. The properties of polyglycolic acid are shown in Table 2.
TABLE 2
| Elongation at Break (%) | Contact angle (°) | |
| Comparative example | 7.41 | 69.3±2.0 |
| Example 4 | 27.51 | 81.5±2.1 |
| Example 5 | 28.56 | 79.3±1.8 |
| Example 6 | 26.19 | 79.3±1.5 |
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. A polyglycolic acid modifier, comprising:
component A
1-15 parts of rare earth additive;
component B
The rare earth additive is prepared by the following method: reacting a cationic surfactant with a rare earth salt compound to obtain an organic rare earth compound; reacting an organic rare earth compound with a coupling agent to obtain a rare earth auxiliary agent;
the cationic surfactant is a quaternary ammonium salt cationic surfactant containing C ═ C bonds, and the coupling agent is selected from one or more of silane coupling agents or titanate coupling agents.
2. A polyglycolic acid modifier according to claim 1, characterized in that:
the cationic surfactant is selected from one or more of methacryloyloxyethyl dimethyl hexadecyl ammonium bromide, hexadecyl dimethyl allyl ammonium chloride, p-vinylbenzyl dimethyl octadecyl chloride and dimethyl tetradecyl (2-acrylamidopropyl) ammonium bromide;
the rare earth element in the rare earth compound is selected from one or more of lanthanum or cerium;
the coupling agent is selected from one or more of KH550, KH560, KH570 and KH 602.
3. The polyglycolic acid modifier according to claim 1, wherein the mass ratio of the cationic surfactant, the rare earth salt compound and the coupling agent is (0.3-2): (5-15): (0.4-2).
4. A polyglycolic acid modifier according to claim 1, characterized in that:
the chain extender is selected from diisocyanate chain extenders;
the nucleating agent is selected from one or more of TMB-5, talcum powder/aluminum-based phosphate complex, 1,2,3, 4-butanetetracarboxylic acid, triallyl isonitrile uratate and phenyl zinc phosphate;
the initiator is selected from one or more of lysine triisocyanate, polyethylene glycol, lauric acid, glycerol and sorbitol;
the antioxidant is selected from one or more of antioxidant 9225, antioxidant 9215, antioxidant 168 and antioxidant 1010.
5. The method for preparing a polyglycolic acid modifier according to any one of claims 1 to 4, comprising the steps of:
(1) reacting a cationic surfactant with a rare earth salt compound to obtain an organic rare earth compound; reacting an organic rare earth compound with a coupling agent to obtain a component A;
(2) mixing a chain extender, a nucleating agent, an initiator and an antioxidant to obtain a component B;
wherein, the step (1) comprises the following processes:
(a) mixing an organic acid and a cationic surfactant to form a mixed solution; adding rare earth carbonate into the mixed solution, reacting for 50-100 min at 40-60 ℃, then reacting for 1-3 h at 60-90 ℃ to obtain a reaction product, and drying the reaction product to obtain an organic rare earth compound;
(b) adding an organic rare earth compound into a coupling agent solution with the pH value of 3-6, and reacting for 0.5-3 h at the temperature of 30-80 ℃ to obtain a reaction product; and drying the reaction product to prepare powder to obtain the rare earth additive.
6. The method of claim 5, wherein:
in the process (a), the mixed solution is obtained by: mixing carboxylic acid and a cationic surfactant at 30-70 ℃, and then stirring for 20-50 min at 35-75 ℃;
in the process (b), the coupling agent solution is obtained by: and mixing the coupling agent and the alcohol solution to obtain a mixed solution, then adding carboxylic acid to adjust the pH of the mixed solution to 3-6, and stirring the mixed solution after the pH is adjusted at 30-80 ℃ for 300-700 min.
7. Use of a polyglycolic acid modifier according to any one of claims 1 to 4 for increasing hydrophobicity and/or toughness of polyglycolic acid.
8. A polyglycolic acid composition comprising 60 to 95 parts by weight of polyglycolic acid and 1.5 to 18 parts by weight of a polyglycolic acid modifier according to any one of claims 1 to 3.
9. A method of producing a polyglycolic acid composition according to claim 8, comprising the steps of:
(1') mixing polyglycolic acid and component A together in an internal mixer, and then granulating to obtain polyglycolic acid particles;
(2') blending polyglycolic acid particles with component B, and extruding through a twin-screw extruder to obtain a polyglycolic acid composition.
10. The method of claim 7, wherein:
step (1'), the banburying temperature is 180-250 ℃, the banburying time is 5-20 min, and the screw rotating speed of the banbury mixer is 50-100 rpm;
and (2') extruding at the temperature of 180-250 ℃, wherein the screw rotating speed of the double-screw extruder is 20-70 rpm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075332A (en) * | 2020-08-19 | 2022-02-22 | 国家能源投资集团有限责任公司 | Modified polyglycolic acid and preparation method and application thereof |
| CN115141615A (en) * | 2021-11-04 | 2022-10-04 | 中国石油化工股份有限公司 | Oil well fracturing temporary plugging agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030195135A1 (en) * | 2000-06-06 | 2003-10-16 | Dieter Boeckh | Use of cationically modified, particulate, hydrophobic polymers as an additive for rinsing, cleaning and impregnating agents for hard surfaces |
| CN107090151A (en) * | 2017-05-11 | 2017-08-25 | 江阴中达软塑新材料股份有限公司 | A kind of polyvinyl alcohol compositions with wider melt-processed window |
| CN108192250A (en) * | 2018-02-09 | 2018-06-22 | 怀化学院 | Shine polyvinyl alcohol material and preparation method thereof |
-
2020
- 2020-05-14 CN CN202010408106.0A patent/CN111454552B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030195135A1 (en) * | 2000-06-06 | 2003-10-16 | Dieter Boeckh | Use of cationically modified, particulate, hydrophobic polymers as an additive for rinsing, cleaning and impregnating agents for hard surfaces |
| CN107090151A (en) * | 2017-05-11 | 2017-08-25 | 江阴中达软塑新材料股份有限公司 | A kind of polyvinyl alcohol compositions with wider melt-processed window |
| CN108192250A (en) * | 2018-02-09 | 2018-06-22 | 怀化学院 | Shine polyvinyl alcohol material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075332A (en) * | 2020-08-19 | 2022-02-22 | 国家能源投资集团有限责任公司 | Modified polyglycolic acid and preparation method and application thereof |
| WO2022037319A1 (en) * | 2020-08-19 | 2022-02-24 | 国家能源投资集团有限责任公司 | Modified polyglycolic acid, preparation method therefor and use thereof |
| CN115141615A (en) * | 2021-11-04 | 2022-10-04 | 中国石油化工股份有限公司 | Oil well fracturing temporary plugging agent and preparation method and application thereof |
| CN115141615B (en) * | 2021-11-04 | 2023-11-03 | 中国石油化工股份有限公司 | Temporary plugging agent for oil well fracturing and preparation method and application thereof |
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