CN115181261B - Hyperbranched hydrophilizing agent, hydrophilically modified resin and preparation method thereof - Google Patents
Hyperbranched hydrophilizing agent, hydrophilically modified resin and preparation method thereof Download PDFInfo
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- CN115181261B CN115181261B CN202210883955.0A CN202210883955A CN115181261B CN 115181261 B CN115181261 B CN 115181261B CN 202210883955 A CN202210883955 A CN 202210883955A CN 115181261 B CN115181261 B CN 115181261B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
- C08G65/3356—Polymers modified by chemical after-treatment with organic compounds containing phosphorus having nitrogen in addition to phosphorus
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
Abstract
The invention provides a hyperbranched hydrophilic agent, hydrophilic modified resin and a preparation method thereof. The hyperbranched hydrophilic agent disclosed by the invention not only ensures that the hydrophilic agent can quickly migrate to the surface of the matrix resin, but also has stronger binding force with the matrix resin, and ensures the elution resistance of the matrix resin, so that the long-term stability of the hydrophilicity of the hydrophilically modified material is improved, and the hyperbranched hydrophilic agent can be applied to the fields of medical intervention catheters and the like, and can effectively improve the lubricity and reduce the potential safety risk.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a hyperbranched hydrophilic agent, a hydrophilic modified resin and a preparation method thereof.
Background
The vascular intervention technology is a technology for observing, diagnosing and treating the affected part of a patient by various catheters in vitro penetrating into the body, and represents a minimally invasive and noninvasive diagnosis method advocated by modern medicine, thereby greatly promoting the development of clinical medicine. In addition to the need for good blood compatibility and tissue compatibility, the lubricious nature of the surface of various catheters used in interventional procedures is also the most important property of vascular access catheters. The lubrication characteristic of the surface of the vascular interventional catheter can reduce the friction coefficient by 90% in a wet environment, so that the force of the intubation tube is reduced, the physiological pain of patients is reduced, and the tissue irritation and damage are avoided.
Obtaining high surface lubricity of interventional catheters by hydrophilic modification of the catheter material is the most common method. Currently, the hydrophilic modification method mainly comprises the following steps: surface hydrophilic treatment, hydrophilic substance blending, and the like.
The hydrophilic material blending treatment method is very simple and convenient, has low cost, and can increase the hygroscopicity and the water absorbability of the resin under the condition of basically keeping the original characteristics of the resin. The blended hydrophilic material utilizes it to contain a large amount of hydrophilic groups such as: carboxyl, amide, ethylene oxide, ionic bond, etc. improve the hydrophilicity of the resin surface of the interventional catheter, thereby improving the surface lubricity of the catheter. However, since the medical interventional catheter needs to stay in the human body for a period of time, whether the hydrophilic agent in the blending hydrophilic modification can be firmly fixed on the surface of the catheter and is not easy to be eluted by body fluid is one of the technical difficulties of the method.
The surface hydrophilic treatment is to carry out resin hydrophilic modification by using a small molecular surfactant, and the small molecular surfactant migrates to the surface of the resin because of partial compatibility in the hydrophobic resin, so that high hygroscopicity and lubricity are brought to the surface of the hydrophobic resin. However, in the biomedical field, the migration and precipitation of small hydrophilic molecules also present a potential threat to human health.
Disclosure of Invention
The invention aims to solve the technical problems of providing a hyperbranched hydrophilic agent, a hydrophilic modified resin and a preparation method thereof, and solves the problem that the hydrophilic agent is easy to separate from a resin material after hydrophilic modification is carried out on the resin material used in treatment in the prior art.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a hyperbranched hydrophilizing agent is prepared from acrylamide phosphate, amino-terminated polymer and monobasic long-chain aliphatic amine through reaction.
Preferably, the amino-terminated polymer is at least one of an amino-terminated polyether and an amino-terminated polyester;
preferably, the amino-terminated polymer is polyetheramine;
the mono long-chain fatty amine is at least one of C12-C24 long-chain fatty monoamine.
Preferably, the molecular weight of the amino-terminated polymer is 200-5000;
preferably, the molecular weight of the amino-terminated polymer is 200 to 1000.
Preferably, the molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1: (0.2-1): (0.01-0.5);
preferably, the molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1: (0.2-0.5): (0.05-0.2).
The invention also provides a preparation method of the hyperbranched hydrophilic agent, which comprises the following steps:
taking acrylamide phosphate, amino-terminated polymer and monobasic long-chain aliphatic amine, and reacting in a polar solvent for 4-24 hours at the temperature of 10-80 ℃ to obtain the catalyst.
Preferably, the polar solvent is at least one of methanol, ethanol, acetonitrile and water.
Preferably, the phosphoric acid acrylamide is obtained by the following method:
under the protection of inert gas, phosphorus oxychloride and an acid binding agent are dissolved in a solvent, and hydroxy acrylamide is added into the solvent to react for 1 to 4 hours at the temperature of-20 to 40 ℃ to obtain the catalyst.
Further preferably, the obtaining of the phosphoric acid acrylamide further comprises: and filtering the reacted solution, and spin-drying the solvent to obtain the acrylamide phosphate.
Preferably, the phosphoryl chloride is at least one of phosphorus oxychloride, ethyl dichlorophosphate and phenyl dichlorophosphate;
preferably, the hydroxy acrylamide is at least one of N-methylolacrylamide, N-hydroxyethyl acrylamide and N-hydroxypropyl acrylamide;
preferably, the acid-binding agent is an organic base.
Preferably, the organic base is at least one of triethylamine and pyridine.
Preferably, the solvent is at least one of dichloromethane, chloroform and tetrahydrofuran.
Preferably, the mole ratio of the phosphorus oxychloride to the acid binding agent is 1: (1-3.3);
the molar ratio of the hydroxyacrylamide to the phosphorus oxychloride is (1-3): 1.
the invention also provides a hydrophilic modified resin, which is obtained by reacting a matrix resin with the hyperbranched hydrophilic agent.
The invention also provides a preparation method of the hydrophilic modified resin, which comprises the following steps: and (3) taking matrix resin and the hyperbranched hydrophilic agent, uniformly mixing, and carrying out melt extrusion processing at 180-250 ℃ to obtain the hydrophilic modified resin.
The scheme of the invention at least comprises the following beneficial effects:
(1) The hyperbranched hydrophilic agent is obtained by reacting phosphoric acid acrylamide, amino-terminated polymer and monobasic long-chain fatty amine. The hyperbranched hydrophilic agent has smaller hydrodynamic radius, the migration rate of the hyperbranched hydrophilic agent in hydrophobic resin is not influenced by the large molecular weight of the hyperbranched hydrophilic agent, and the high migration rate of the hyperbranched hydrophilic agent in the resin can be ensured. Meanwhile, the surface of the three-dimensional space structure of the hyperbranched hydrophilic agent is provided with a large number of groups, so that strong interaction can be formed between the hyperbranched hydrophilic agent and the matrix resin, and the binding force of the hyperbranched hydrophilic agent on the surface of the hydrophobic resin is ensured, so that the hyperbranched hydrophilic agent is not easy to be eluted by body fluid of a human body. Therefore, the hydrophilic agent can be quickly migrated to the surface of the matrix resin, has stronger binding force with the matrix resin, and ensures the eluting resistance of the hydrophilic agent, so that the long-term stability of the hydrophilicity of the hydrophilically modified material is improved, and the hydrophilic agent can be effectively improved in lubricity and reduce potential safety risks when applied to the fields of medical interventional catheters and the like.
(2) The molecular weight of the amino-terminated polymer is 200-5000. The molecular weight of the amino-terminated polymer can influence the hydrophilic effect of the hyperbranched hydrophilic agent, and the higher the molecular weight of the amino-terminated polymer is, the worse the hydrophilic effect of the hyperbranched hydrophilic agent is; meanwhile, the molecular weight of the amino-terminated polymer is too small, the branching degree of the hyperbranched hydrophilic agent is too high, and the hydrophilicity is also reduced. In particular, when the molecular weight of the amino-terminated polymer is 200-1000, the obtained hyperbranched hydrophilic agent has optimal hydrophilic effect.
(3) The molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long-chain fat is 1: (0.2-1): (0.01-0.5). The charging proportion of the monobasic long-chain fatty amine has larger influence on the hydrophilicity of the final product, and the more the charging is, the worse the hydrophilicity of the hyperbranched hydrophilic agent is; meanwhile, the feeding ratio of the monobasic long-chain fatty amine is too low, and the obtained hyperbranched hydrophilic agent cannot provide the hydrophilicity required by the resin due to too large polarity. In particular, the molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1: (0.2-0.5): (0.05-0.2), the obtained hyperbranched hydrophilic agent is optimal in hydrophilic effect.
(4) According to the preparation method of the hyperbranched hydrophilic agent, the Michael addition reaction between the acrylamide and the amino is high in activity, the reaction process is mild, the complexity of the production process is avoided, and the production cost is reduced.
(5) The preparation method of the hyperbranched hydrophilic agent comprises the following steps: under the protection of inert gas, phosphorus oxychloride and an acid binding agent are dissolved in a solvent, and hydroxy acrylamide is added into the solvent to react for 1 to 4 hours at the temperature of-20 to 40 ℃ to obtain the catalyst. When the amino-terminated polymer is a monobasic amino-terminated polymer, the acrylamide phosphate can form a hyperbranched hydrophilic agent through the trifunctional hydroxy acrylamide, and the reaction temperature is higher and needs to reach 30-40 ℃ under the influence of steric hindrance effect.
(6) According to the preparation method of the hyperbranched hydrophilic agent, the molar ratio of the phosphoryl chloride to the acid binding agent is 1: (1-3.3); the molar ratio of the hydroxyacrylamide to the phosphorus oxychloride is (1-3): 1. the reaction molar ratio is regulated based on the functionality of phosphoryl chloride and hydroxy acrylamide, and ensures that the ratio of acyl chloride to hydroxy functional group in the reaction system is just or slightly lower than 1; deviation of the ratio can cause small molecule residues in the reaction system, influence the reaction process and reduce the yield. In contrast, the ratio of acyl chloride to hydroxyl functional group in the reaction system is adjusted to be higher than 1, and the reaction system is caused to have redundant hydrogen chloride although the influence on the final product is not great, so that the subsequent treatment step of acid removal is required to be added.
(7) The hydrophilic modified resin is obtained by reacting the hyperbranched hydrophilic agent with the matrix resin, and because the hyperbranched hydrophilic agent has the characteristic of three-dimensional space, the hyperbranched hydrophilic agent is easy to disperse in the matrix resin to form hydrophilic micro-areas, reduces aggregation of the hydrophilic agent, and can improve the dispersion of the hyperbranched hydrophilic agent in the matrix resin, thereby improving the persistence of the hydrophilic capability of the resin.
(8) According to the preparation method of the hydrophilic modified resin, the matrix resin and the hyperbranched hydrophilic agent are taken and uniformly mixed, and melt reaction is carried out to obtain the hydrophilic modified resin. The modification is realized by blending, the self characteristics of the resin are not changed greatly, and the obtained hydrophilic modified resin can still adopt a surface hydrophilic treatment technology to further carry out hydrophilic treatment on the resin, has good compatibility and can be used together with other hydrophilic technologies.
Detailed Description
The specific conditions not noted in the examples of the present invention were carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used are not marked for manufacturers, are conventional products which can be obtained through commercial purchase, and the implementation of the technical scheme and the realization of the technical effect of the invention are not influenced by raw materials of different manufacturers and models.
In order to ensure comparability of the hydrophilically modified resins prepared in each example of the present invention, polypropylene matrix resins were used as matrix resins in examples 1 to 9 of the present invention and comparative examples 1 to 2. The base resin of any kind and specification can be selected by those skilled in the art according to the actual situation, and for example, polyethylene resin, polyvinyl chloride resin, polystyrene resin, polycycloolefin resin, ABS resin, PC resin, etc. can also be used.
Example 1
The hyperbranched hydrophilic agent is prepared by reacting phosphoric acid acrylamide, amino-terminated polymer and monobasic long-chain aliphatic amine. Wherein the amino-terminated polymer is polyetheramine with a molecular weight of 200; the monobasic long-chain fatty amine is long-chain fatty monoamine of C18, and the monobasic long-chain fatty amine is octadecylamine.
The molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1:0.2:0.5.
the preparation method of the hyperbranched hydrophilic agent comprises the following steps:
(1) Under the protection of inert gas, phosphorus oxychloride and an acid binding agent are dissolved in a solvent, hydroxyl acrylamide is added into the solvent, and the reaction is carried out for 4 hours at the temperature of minus 20 ℃ to obtain phosphoric acid acrylamide; wherein the phosphorus oxychloride is phosphorus oxychloride; the hydroxy acrylamide is N-methylol acrylamide; the acid binding agent is organic base triethylamine; the solvent is dichloromethane. The mole ratio of the phosphorus oxychloride to the acid binding agent is 1:1, a step of; the molar ratio of the hydroxyacrylamide to the phosphorus oxychloride is 1:1.
(2) Taking acrylamide phosphate, amino-terminated polymer and monobasic long-chain fatty amine according to the selected dosage, and reacting in a polar solvent for 24 hours at 10 ℃ to obtain the hyperbranched hydrophilic agent. Wherein the polar solvent is methanol.
The hydrophilic modified resin of the embodiment is obtained by reacting a matrix resin with the hyperbranched hydrophilic agent. The preparation method of the hydrophilic modified resin comprises the following steps:
and uniformly mixing the matrix resin and the hyperbranched hydrophilic agent according to the weight ratio of 1:100, and carrying out melt extrusion processing at 180 ℃ to obtain the hydrophilic modified resin.
As a specific implementation manner of the embodiment, the melting reaction can be performed by melting extrusion granulation through a double-screw extruder at 180 ℃ and a screw rotating speed of 100rpm, and injection molding is performed.
Example 2
The hyperbranched hydrophilic agent is prepared by reacting phosphoric acid acrylamide, amino-terminated polymer and monobasic long-chain aliphatic amine. Wherein the amino-terminated polymer is polyetheramine with a molecular weight of 5000; the monobasic long-chain fatty amine is long-chain fatty monoamine of C12, and the monobasic long-chain fatty amine is dodecylamine.
The molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1:1:0.25.
the preparation method of the hyperbranched hydrophilic agent comprises the following steps:
(1) Under the protection of inert gas, phosphorus oxychloride and an acid binding agent are dissolved in a solvent, hydroxyl acrylamide is added into the solvent, the reaction is carried out for 2 hours at 30 ℃, and the solvent is dried after the solution after the reaction is filtered, so that the phosphoric acid acrylamide is obtained. Wherein the phosphoryl chloride is ethyl dichlorophosphate; the hydroxyl acrylamide is N-hydroxyethyl acrylamide; the acid binding agent is organic alkali pyridine; the solvent is chloroform. The mole ratio of the phosphorus oxychloride to the acid binding agent is 1:3.3; the molar ratio of the hydroxyacrylamide to the phosphorus oxychloride is 2:1.
(2) Taking acrylamide phosphate, amino-terminated polymer and monobasic long-chain fatty amine according to the selected dosage, and reacting in a polar solvent for 14h at 80 ℃ to obtain the product. Wherein the polar solvent is ethanol.
The hydrophilic modified resin of the embodiment is obtained by reacting a matrix resin with the hyperbranched hydrophilic agent. The preparation method of the hydrophilic modified resin comprises the following steps:
and uniformly mixing the matrix resin and the hyperbranched hydrophilic agent according to the weight ratio of 1:100, uniformly mixing, and carrying out melt extrusion processing at 210 ℃ to obtain the hydrophilic modified resin.
As a specific implementation manner of the embodiment, the melting reaction can be performed by melting extrusion granulation through a double-screw extruder at 210 ℃ and a screw rotating speed of 100rpm, and injection molding is performed.
Example 3
The hyperbranched hydrophilic agent is prepared by reacting phosphoric acid acrylamide, amino-terminated polymer and monobasic long-chain aliphatic amine. Wherein the amino-terminated polymer is amino-terminated polyester, and the molecular weight is 2600; the monobasic long-chain fatty amine is long-chain fatty monoamine of C24, and the monobasic long-chain fatty amine is tetracosamine.
The molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1:0.6:0.01.
the preparation method of the hyperbranched hydrophilic agent comprises the following steps:
(1) Under the protection of inert gas, phosphorus oxychloride and an acid binding agent are dissolved in a solvent, hydroxyl acrylamide is added into the solvent, the reaction is carried out for 1h at the temperature of 10 ℃, and the solvent is dried after the solution after the reaction is filtered, so that the phosphoric acid acrylamide is obtained. Wherein the phosphoryl chloride is phenyl dichlorophosphate; the hydroxy acrylamide is N-hydroxypropyl acrylamide; the acid binding agent is triethylamine. The solvent is tetrahydrofuran. The mole ratio of the phosphorus oxychloride to the acid binding agent is 1:2; the molar ratio of the hydroxyacrylamide to the phosphorus oxychloride is 3:1.
(2) Taking acrylamide phosphate, amino-terminated polymer and monobasic long-chain fatty amine according to the selected dosage, and reacting in a polar solvent for 4 hours at 45 ℃ to obtain the product. Wherein the polar solvent is acetonitrile.
The hydrophilic modified resin of the embodiment is obtained by reacting a matrix resin with the hyperbranched hydrophilic agent. The preparation method of the hydrophilic modified resin comprises the following steps:
and uniformly mixing the matrix resin and the hyperbranched hydrophilic agent according to the weight ratio of 1:100, and carrying out melt extrusion processing at the temperature of 250 ℃ to obtain the hydrophilic modified resin.
As a specific implementation manner of the embodiment, the melting reaction can be performed by melting extrusion granulation through a double-screw extruder at 250 ℃ and a screw rotating speed of 100rpm, and injection molding is performed.
Example 4
The hyperbranched hydrophilic agent is prepared by reacting phosphoric acid acrylamide, amino-terminated polymer and monobasic long-chain aliphatic amine. Wherein the amino-terminated polymer is monoamine-terminated polyether, the amino-terminated polymer is polyetheramine, and the molecular weight is 1000; the monobasic long-chain fatty amine is long-chain fatty monoamine of C18, and the monobasic long-chain fatty amine is octadecylamine.
The molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1:0.2:0.2.
the preparation method of the hyperbranched hydrophilic agent comprises the following steps:
(1) Under the protection of inert gas, phosphorus oxychloride and an acid binding agent are dissolved in a solvent, hydroxyl acrylamide is added into the solvent, the reaction is carried out for 4 hours at 40 ℃, and the solvent is dried after the solution after the reaction is filtered, so that the phosphoric acid acrylamide is obtained. Wherein the phosphorus oxychloride is phosphorus oxychloride; the hydroxy acrylamide is N-methylol acrylamide; the acid binding agent is organic base triethylamine. The solvent is dichloromethane. The mole ratio of the phosphorus oxychloride to the acid binding agent is 1:3.3; the molar ratio of the hydroxyacrylamide to the phosphorus oxychloride is 3:1.
(2) Taking acrylamide phosphate, amino-terminated polymer and monobasic long-chain fatty amine according to the selected dosage, and reacting in a polar solvent for 18h at 45 ℃ to obtain the modified polyacrylamide. Wherein the polar solvent is water.
The hydrophilic modified resin of the embodiment is obtained by reacting a matrix resin with the hyperbranched hydrophilic agent. The preparation method of the hydrophilic modified resin comprises the following steps:
and uniformly mixing the matrix resin and the hyperbranched hydrophilic agent according to the weight ratio of 1:100, and carrying out melt extrusion processing at 210 ℃ to obtain the hydrophilic modified resin.
As a specific implementation manner of the embodiment, the melting reaction can be performed by melting extrusion granulation through a double-screw extruder at 210 ℃ and a screw rotating speed of 100rpm, and injection molding is performed.
Example 5
The hyperbranched hydrophilic agent of this example was obtained using the same raw materials and preparation method as in example 4, with the only differences: phosphorus oxychloride was replaced with ethyl dichlorophosphate.
This example was prepared by the same method as in example 4 to obtain a hydrophilically modified resin.
Example 6
The hyperbranched hydrophilic agent of this example was obtained using the same raw materials and preparation method as in example 5, except that: the amino-terminated polymer is polyetheramine and has a molecular weight of 150.
This example was prepared by the same method as in example 5 to obtain a hydrophilically modified resin.
Example 7
The hyperbranched hydrophilic agent of this example was obtained using the same raw materials and preparation method as in example 5, except that: the molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1:0.2:0.005.
this example was prepared by the same method as in example 5 to obtain a hydrophilically modified resin.
Example 8
The hyperbranched hydrophilic agent of this example was obtained using the same raw materials and preparation method as in example 5, except that: the molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1:0.2:0.8.
this example was prepared by the same method as in example 5 to obtain a hydrophilically modified resin.
Example 9
The hyperbranched hydrophilic agent of this embodiment is obtained by using the same raw materials and preparation methods as in embodiment 5, except that the step (1) of the preparation method of the hyperbranched hydrophilic agent is specifically as follows:
under the protection of inert gas, phosphorus oxychloride and an acid binding agent are dissolved in a solvent, hydroxyl acrylamide is added into the solvent, the reaction is carried out for 4 hours at the temperature of minus 20 ℃, and the solvent is dried after the solution after the reaction is filtered, so that the phosphoric acid acrylamide is obtained.
This example was prepared by the same method as in example 5 to obtain a hydrophilically modified resin.
Comparative example 1
In this comparative example, a matrix resin was melt-extruded by a twin-screw extruder at 210℃and a screw speed of 100rpm to granulate, and injection molded.
Comparative example 2
In this comparative example, the same polyether amine as in example 5 was added as a linear hydrophilic polymer, the matrix resin and the polyether amine were uniformly mixed in a weight ratio of 1:100, and melt extrusion granulation was performed by a twin screw extruder at 210℃and a screw speed of 100rpm, and injection molding was performed.
Effect comparative example
In order to verify the technical effect of the hyperbranched hydrophilic agent, the following tests are carried out:
taking the hydrophilic modified resins prepared in examples 1-9 and comparative examples 1-2, forming into standard sample pieces according to the same size, and performing contact angle performance test by adopting a contact angle measuring instrument; then, each standard sample piece is placed in water at 40 ℃ for soaking for 1 hour, and after the surface is taken out and dried, the contact angle performance is tested again to verify the flushing resistance of the hyperbranched hydrophilic agent.
The results are as follows:
as can be seen from the comparison of comparative examples 1-2 and examples 1-9, the hyperbranched hydrophilic agent of the invention can reduce the contact angle of the matrix resin and improve the hydrophilicity of the resin surface. From a comparison of example 4 with example 5, the reaction of tri-functional phosphoric acid triacrylamide prepared with phosphorus oxychloride resulted in a hyperbranched hydrophilic agent with a lower hydrophilic effect than that obtained by the reaction of di-functional phosphoric acid diacrylamide, indicating that the choice of the ratio of reactant functionalities directly affects the final polymer hydrophilic effect. As can be seen from a comparison of example 6 with example 5, the amino-terminated polymer has too small a molecular weight, and the hyperbranched hydrophilic agent has too high branching degree and thus the hydrophilicity is also reduced. As can be seen from comparison of examples 5, 7 and 8, too much and too little of the feeding proportion of the monobasic long-chain fatty amine has a large influence on the hydrophilicity of the final product. As can be seen from the comparison of example 5 and example 9, the reaction temperature was too low, and the contact angle of the final product after being soaked in water was much reduced, and the final product was more easily eluted, and the washing resistance on the surface of the matrix resin was poor. Whereas example 5 is excellent in both hydrophilic effect and wash resistance.
It will be appreciated by those skilled in the art that the present invention can be carried out in other embodiments without departing from the spirit or essential characteristics thereof. Accordingly, the above disclosed embodiments are illustrative in all respects, and not exclusive. All changes that come within the scope of the invention or equivalents thereto are intended to be embraced therein.
Claims (10)
1. The hyperbranched hydrophilic agent is characterized by being prepared by reacting phosphoric acid acrylamide, amino-terminated polymer and monobasic long-chain aliphatic amine; the molar ratio of the phosphoric acid acrylamide to the amino-terminated polymer to the monobasic long chain fat is 1: (0.2-0.5): (0.05-0.2); the molecular weight of the amino-terminated polymer is 200-5000.
2. The hyperbranched hydrophilic agent of claim 1 wherein the amino-terminated polymer is at least one of an amino-terminated polyether, an amino-terminated polyester;
the mono long-chain fatty amine is at least one of C12-C24 long-chain fatty monoamine.
3. The hyperbranched hydrophilic agent of claim 2 wherein the amino-terminated polymer is a polyetheramine.
4. The hyperbranched hydrophilic agent according to claim 1 wherein,
the molecular weight of the amino-terminated polymer is 200-1000.
5. The preparation method of the hyperbranched hydrophilic agent is characterized by comprising the following steps of:
taking acrylamide phosphate, amino-terminated polymer and monobasic long-chain aliphatic amine, and reacting in a polar solvent for 4-24 hours at the temperature of 10-80 ℃ to obtain the catalyst.
6. The method for producing a hyperbranched hydrophilic agent according to claim 5, wherein the polar solvent is at least one of methanol, ethanol, acetonitrile, and water.
7. The method for preparing hyperbranched hydrophilic agents according to claim 5, wherein the phosphoric acid acrylamide is obtained by the following method:
under the protection of inert gas, phosphorus oxychloride and an acid binding agent are dissolved in a solvent, and hydroxy acrylamide is added into the solvent to react for 1 to 4 hours at the temperature of-20 to 40 ℃ to obtain the catalyst.
8. The method for preparing a hyperbranched hydrophilic agent according to claim 7, wherein the phosphorus oxychloride is at least one of phosphorus oxychloride, ethyl dichlorophosphate, phenyl dichlorophosphate;
the hydroxy acrylamide is at least one of N-methylol acrylamide, N-hydroxyethyl acrylamide and N-hydroxypropyl acrylamide;
the acid binding agent is organic alkali;
the solvent is at least one of dichloromethane, chloroform and tetrahydrofuran.
9. A hydrophilically modified resin, characterized in that it is obtained by reacting a matrix resin with a hyperbranched hydrophilic agent according to any one of claims 1 to 4.
10. A method for preparing a hydrophilically modified resin, comprising the steps of: uniformly mixing matrix resin and the hyperbranched hydrophilic agent according to any one of claims 1-4, and carrying out melt extrusion processing at 180-250 ℃ to obtain the hydrophilic modified resin.
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| CN202210883955.0A CN115181261B (en) | 2022-07-26 | 2022-07-26 | Hyperbranched hydrophilizing agent, hydrophilically modified resin and preparation method thereof |
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| CN107337767A (en) * | 2016-12-30 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of the water reducer of phosphorous acid groups |
| CN114605635A (en) * | 2022-04-13 | 2022-06-10 | 中国科学院宁波材料技术与工程研究所 | High-strength self-induction hyperbranched bonding material and green preparation method and application thereof |
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| US6673053B2 (en) * | 1999-05-07 | 2004-01-06 | Scimed Life Systems, Inc. | Hydrophilic lubricity coating for medical devices comprising an antiblock agent |
| BRPI0808105A2 (en) * | 2007-02-28 | 2014-06-17 | Dsm Ip Assets Bv | HYDROPHILIC COATING |
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| CN107337767A (en) * | 2016-12-30 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of the water reducer of phosphorous acid groups |
| CN114605635A (en) * | 2022-04-13 | 2022-06-10 | 中国科学院宁波材料技术与工程研究所 | High-strength self-induction hyperbranched bonding material and green preparation method and application thereof |
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