阅读说明：本技术 一种对聚乙烯型整形外科植入元件表面快速改性的方法 (Method for quickly modifying surface of polyethylene type orthopedic implant element ) 是由 不公告发明人 于 2021-09-21 设计创作，主要内容包括：本发明涉及一种对聚乙烯型整形外科植入元件表面快速改性的方法,本发明的对聚乙烯型整形外科植入元件表面改性不使用其他材料包覆,也不使用任何强氧化剂和强酸,对于材料的改性选择性的将材料表层分子的亚甲基氧化成羰基和羟基等极性基团,增加材料与PMMA骨胶的粘附性,不会造成材料分子链断裂,不像现有技术使用的自由基引发剂那样会导致链段的交联或者降解,不影响聚合物的分子量分布,对材料的机械性能,热稳定性和安全性没有影响。(The invention relates to a method for quickly modifying the surface of a polyethylene orthopedic implant element, which is used for modifying the surface of the polyethylene orthopedic implant element without coating other materials and using any strong oxidant and strong acid, selectively oxidizes methylene of surface molecules of a material into polar groups such as carbonyl, hydroxyl and the like, increases the adhesion of the material and PMMA bone glue, does not cause the breakage of molecular chains of the material, does not cause the crosslinking or degradation of chain segments unlike a free radical initiator used in the prior art, does not influence the molecular weight distribution of a polymer, and does not influence the mechanical property, the thermal stability and the safety of the material.)

1. A method for quickly modifying the surface of a polyethylene type orthopedic implant component adopts the scheme that:

placing the polyethylene orthopedic implant element into a pressure-resistant reaction kettle, adding a solvent to immerse the polyethylene orthopedic implant element, adding an oxidation catalyst, stirring and mixing uniformly, then filling oxidizing gas into the reaction kettle, heating for reaction for 25-45min, cooling to room temperature after completion, taking out the polyethylene orthopedic implant element, washing with ethanol, and drying to complete the rapid surface modification of the polyethylene orthopedic implant element; the preparation method is characterized in that the oxidation catalyst is a fluorine-containing metal complex, and the preparation method comprises the following steps:

adding 1.96-2.58 parts by mass of 2,2, 2-trifluoroacetaldehyde, 20-30 parts by mass of pyrrole and 18-28 parts by mass of dichloromethane into a reaction kettle, uniformly stirring and mixing, adding 0.2-0.5 part by mass of boron trifluoride diethyl ether solution, controlling the temperature to be 25-35 ℃, stirring and reacting for 2-5 hours, quenching the catalyst by using 0.6-1 part by mass of triethylamine, adding 1.3-1.8 parts by mass of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, stirring and reacting for 30-60 minutes, and then completing the reaction to obtain a fluorine-containing cyclic ligand after purification; adding 0.5-1.2 parts of fluorine-containing cyclic ligand into 40-60 parts of N, N-dimethylformamide, stirring and mixing uniformly, adding 2.3-4.2 parts of metal acetate, controlling the temperature at 110 ℃ and stirring and reacting for 1-5h, and separating and purifying after the reaction is finished to obtain the fluorine-containing metal complex.

2. A method of rapidly modifying the surface of a polyethylene-based orthopaedic implant component according to claim 1, wherein: further, the metal acetate is lanthanum acetate or ruthenium acetate or cerium acetate or cobalt acetate.

3. A method of rapidly modifying the surface of a polyethylene-based orthopaedic implant component according to claim 1, wherein: further, the oxidation catalyst is used in an amount of 0.5 to 1.8g/m, calculated on the treatment area of the polyethylene type orthopedic implant component²。

4. A method of rapidly modifying the surface of a polyethylene-based orthopaedic implant component according to claim 1, wherein: further, the solvent is chloroform or dichloroethane or dichloromethane.

5. A method of rapidly modifying the surface of a polyethylene-based orthopaedic implant component according to claim 1, wherein: further, the oxidizing gas is oxygen with the mass portion of 45% -100%, and the rest is nitrogen.

6. A method of rapidly modifying the surface of a polyethylene-based orthopaedic implant component according to claim 1, wherein: further, the heating reaction temperature is 100-150 ℃.

7. A method of rapidly modifying the surface of a polyethylene-based orthopaedic implant component according to claim 1, wherein: further, the pressure of the oxidizing gas in the kettle is 0.1-5 MPa.

Technical Field

The invention relates to a method for quickly modifying the surface of a polyethylene type orthopedic implant element, belonging to the field of medical surgical materials.

Background

Polyethylene-based orthopaedic implant components are orthopaedic implant components made using ultra-high molecular weight polyethylene, such as tibial, patellar, acetabular, and acetabular components. Because the surface of polyethylene lacks active functional groups and has high crystallinity, the polyethylene has almost no polarity and is difficult to be mixed with other polar polymers, in the prior art, the polyethylene type plastic surgery implant component is firmly fixed on the bone of a patient through PMMA bone cement by mechanical fixation, the fixation effect is poor, and the hidden trouble of falling off is easy to appear.

CN105820363A discloses a surface modification method of a polyethylene plastic sheet, which comprises the following steps of coating an adhesive component on the polyethylene plastic sheet after plasma treatment, coating a modification component after heating treatment at 60-70 ℃ for 10-15 minutes, and standing for 28-35 hours at room temperature to 50 ℃ to complete the surface modification of the polyethylene plastic sheet; the bonding component is obtained by mixing an acrylate prepolymer, trimethylsiloxysilicate ester, diethyl phosphite, tetrazole and glycerol; the acrylate prepolymer is prepared from n-butyl acrylate and styrene; the modified component is prepared by mixing epoxy resin, an amine curing agent, hydroxylamine potassium, bisphenol A dianhydride and acetone. The polyethylene surface modification method adopted by the method not only has long process time, but also introduces amine curing agent or other substances, and is not suitable for surface modification of the implanted component of the plastic surgery.

In the prior art, surface modification is carried out by methods such as chemical reagent oxidation, plasma treatment, corona discharge treatment, photooxidation surface modification treatment or radiation grafting treatment. The surface roughness of the polyethylene element after the treatment is increased, and polar functional groups such as carboxyl, carbonyl or hydroxyl are introduced on the surface of the ultra-high molecular weight polyethylene fiber, so that the mechanical engagement and the chemical combination of the fiber and the polymer matrix material are enhanced. However, the above methods all have certain defects, for example, the attenuation rate of active groups of the polyethylene element after plasma treatment is relatively large, and the treatment method requires relatively high vacuum and requires the air pressure to be less than 40Pa, so that continuous industrial production is difficult to realize; the effect of corona discharge treatment on the polyethylene element is not obvious and is limited by the intermittent operation to a great extent, so that the realization of industrialization and continuity is difficult; the radiation grafting treatment of polyethylene elements, the intermittent operation of which limits the application thereof to a great extent, due to the fact that the fibres need to be irradiated for a certain time; the chemical reagent oxidized polyethylene element is easy to control and continuous production, but the use of potassium permanganate, potassium dichromate, nitric acid and other strong oxidants can cause the phenomena of material dyeing, heavy metal residue and material strength reduction, and is not suitable for surface modification of the implanted element in the plastic surgery.

Disclosure of Invention

The object of the present invention is to overcome the drawbacks of the prior art by providing a method for the rapid modification of the surface of polyethylene-based orthopaedic implant components, which overcomes the above-mentioned problems.

A method for quickly modifying the surface of a polyethylene type orthopedic implant component adopts the scheme that:

placing the polyethylene orthopedic implant element into a pressure-resistant reaction kettle, adding a solvent to immerse the polyethylene orthopedic implant element, adding an oxidation catalyst, stirring and mixing uniformly, then filling oxidizing gas into the reaction kettle, heating for reaction for 25-45min, cooling to room temperature after completion, taking out the polyethylene orthopedic implant element, washing with ethanol, and drying to complete the rapid surface modification of the polyethylene orthopedic implant element; the preparation method is characterized in that the oxidation catalyst is a fluorine-containing metal complex, and the preparation method comprises the following steps:

adding 1.96-2.58 parts by mass of 2,2, 2-trifluoroacetaldehyde, 20-30 parts by mass of pyrrole and 18-28 parts by mass of dichloromethane into a reaction kettle, uniformly stirring and mixing, adding 0.2-0.5 part by mass of boron trifluoride diethyl ether solution, controlling the temperature to be 25-35 ℃, stirring and reacting for 2-5 hours, quenching the catalyst by using 0.6-1 part by mass of triethylamine, adding 1.3-1.8 parts by mass of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, stirring and reacting for 30-60 minutes, and then completing the reaction to obtain a fluorine-containing cyclic ligand after purification; adding 0.5-1.2 parts of fluorine-containing cyclic ligand into 40-60 parts of N, N-dimethylformamide, stirring and mixing uniformly, adding 2.3-4.2 parts of metal acetate, controlling the temperature at 110 ℃ and stirring and reacting for 1-5h, and separating and purifying after the reaction is finished to obtain the fluorine-containing metal complex.

Further, the metal acetate is lanthanum acetate or ruthenium acetate or cerium acetate or cobalt acetate.

Further, the oxidation catalyst is used in an amount of 0.5 to 1.8g/m, calculated on the treatment area of the polyethylene type orthopedic implant component²。

Further, the solvent is chloroform or dichloroethane or dichloromethane.

Further, the oxidizing gas is oxygen with the mass portion of 45% -100%, and the rest is nitrogen.

Further, the heating reaction temperature is 100-150 ℃.

Further, the pressure of the oxidizing gas in the kettle is 0.1-5 MPa.

The invention creatively uses a fluorine-containing metal complex as a selective oxidation catalyst of C-H bonds, and the structure of the catalyst is shown in the attached figure 2 of the specification; under the catalysis of the catalyst, the process of the invention only uses oxygen which is a cheap and safe oxidant to complete the rapid oxidation modification of the surface of the polyethylene type orthopedic implant element, so that methylene on the surface of the polyethylene type orthopedic implant element is oxidized in a short time to generate polar functional groups such as carbonyl or hydroxyl, and the reaction principle is shown in the following chart:

the invention has the following beneficial effects: the surface modification of the polyethylene type orthopedic implant element is carried out without coating other materials or using any strong oxidant or strong acid, methylene of molecules on the surface layer of the material is selectively oxidized into polar groups such as carbonyl, hydroxyl and the like for the modification of the material, the adhesion of the material and PMMA bone glue is increased, the molecular chain of the material is not broken, the crosslinking or degradation of chain segments can not be caused unlike a free radical initiator used in the prior art, the molecular weight distribution of a polymer is not influenced, and the mechanical property, the thermal stability and the safety of the material are not influenced.

Drawings

FIG. 1: example 3 infrared spectra of the sample and high density polyethylene sheet;

FIG. 2: the structure of the fluorine-containing metal complex is shown schematically.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the examples of the present invention, a high-density polyethylene sheet having a thickness of 3mm was used as an experimental subject, subjected to surface modification treatment, and then the tensile strength and tensile shear strength of the modified material were measured. The greater the tensile strength, the better the surface modification effect.

And (3) testing the tensile test according to GB/T1040-2006, selecting II-shaped test samples as the tensile test samples according to the reference standard, forming the tensile test samples by adopting a hot punching method, wherein the tensile speed is 100 mm/min, and preparing 5 test samples in each group for testing. The tensile test equipment is a microcomputer controlled universal tester. The tensile shear strength is tested according to GB 7124-.

Example 1

Placing the ultrahigh-density polyethylene sheet into a pressure-resistant reaction kettle, adding a solvent to immerse the ultrahigh-density polyethylene sheet, then adding an oxidation catalyst, stirring and mixing uniformly, then filling oxidation gas into the reaction kettle, heating for reaction for 25min, cooling to room temperature after the reaction is finished, taking out the ultrahigh-density polyethylene sheet, washing with ethanol, and drying to finish the rapid surface modification of the ultrahigh-density polyethylene sheet; the preparation method is characterized in that the oxidation catalyst is a fluorine-containing metal complex, and the preparation method comprises the following steps:

adding 1.96kg of 2,2, 2-trifluoroacetaldehyde, 20kg of pyrrole and 18kg of dichloromethane into a reaction kettle, stirring and mixing uniformly, adding 0.2kg of boron trifluoride diethyl etherate solution, controlling the temperature to be 25 ℃, stirring and reacting for 2 hours, quenching the catalyst by using 0.6kg of triethylamine after the reaction is finished, adding 1.3kg of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, stirring and reacting for 30 minutes, finishing the reaction, and purifying to obtain a fluorine-containing cyclic ligand; adding 0.5kg of fluorine-containing cyclic ligand into 40kg of N, N-dimethylformamide, stirring and mixing uniformly, adding 2.3kg of metal acetate, controlling the temperature at 110 ℃, stirring and reacting for 1h, and separating and purifying to obtain the fluorine-containing metal complex.

Further, the metal acetate is lanthanum acetate.

Furthermore, the dosage of the oxidation catalyst is 0.5g/m calculated according to the disposal area of the ultra-high density polyethylene sheet²。

Further, the solvent is chloroform.

Further, the oxidizing gas is oxygen with the mass portion of 45%, and the rest is nitrogen.

Further, the heating reaction temperature is 100 ℃.

Further, the pressure of the oxidizing gas in the kettle is 0.1 MPa.

Example 2

Placing the ultrahigh-density polyethylene sheet into a pressure-resistant reaction kettle, adding a solvent to immerse the ultrahigh-density polyethylene sheet, then adding an oxidation catalyst, stirring and mixing uniformly, then filling oxidation gas into the reaction kettle, heating for reaction for 35min, cooling to room temperature after the reaction is finished, taking out the ultrahigh-density polyethylene sheet, washing with ethanol, and drying to finish the rapid surface modification of the ultrahigh-density polyethylene sheet; the preparation method is characterized in that the oxidation catalyst is a fluorine-containing metal complex, and the preparation method comprises the following steps:

adding 2.28kg of 2,2, 2-trifluoroacetaldehyde, 25kg of pyrrole and 24kg of dichloromethane into a reaction kettle, stirring and mixing uniformly, adding 0.4kg of boron trifluoride diethyl etherate solution, controlling the temperature to be 30 ℃, stirring and reacting for 3.5h, quenching the catalyst by using 0.8kg of triethylamine after the reaction is finished, adding 1.5kg of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, stirring and reacting for 45min, finishing the reaction, and purifying to obtain a fluorine-containing cyclic ligand; adding 0.9kg of fluorine-containing cyclic ligand into 50kg of N, N-dimethylformamide, stirring and mixing uniformly, adding 2.8kg of metal acetate, controlling the temperature at 120 ℃, stirring and reacting for 2.5h, and separating and purifying after the reaction is finished to obtain the fluorine-containing metal complex.

Further, the metal acetate is ruthenium acetate.

Furthermore, the dosage of the oxidation catalyst is 1.2g/m calculated according to the disposal area of the ultra-high density polyethylene sheet²。

Further, the solvent is dichloroethane.

Furthermore, the oxidizing gas is oxygen with the mass portion of 90%, and the rest is nitrogen.

Further, the heating reaction temperature is 130 ℃.

Further, the pressure of the oxidizing gas in the kettle is 2.5 MPa.

Example 3

Placing the ultrahigh-density polyethylene sheet into a pressure-resistant reaction kettle, adding a solvent to immerse the ultrahigh-density polyethylene sheet, then adding an oxidation catalyst, stirring and mixing uniformly, then filling oxidation gas into the reaction kettle, heating for reaction for 45min, cooling to room temperature after the reaction is finished, taking out the ultrahigh-density polyethylene sheet, washing with ethanol, and drying to finish the rapid surface modification of the ultrahigh-density polyethylene sheet; the preparation method is characterized in that the oxidation catalyst is a fluorine-containing metal complex, and the preparation method comprises the following steps:

adding 2.58kg of 2,2, 2-trifluoroacetaldehyde, 30kg of pyrrole and 28kg of dichloromethane into a reaction kettle, stirring and mixing uniformly, adding 0.5kg of boron trifluoride diethyl etherate solution, controlling the temperature to be 35 ℃, stirring and reacting for 5 hours, quenching the catalyst by using 1kg of triethylamine after the reaction is finished, adding 1.8kg of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, stirring and reacting for 60 minutes, finishing the reaction, and purifying to obtain a fluorine-containing cyclic ligand; adding 1.2kg of fluorine-containing cyclic ligand into 60kg of N, N-dimethylformamide, stirring and mixing uniformly, adding 4.2kg of metal acetate, controlling the temperature at 130 ℃, stirring and reacting for 5 hours, and separating and purifying to obtain the fluorine-containing metal complex.

Further, the metal acetate is cerium acetate.

Furthermore, the dosage of the oxidation catalyst is 1.8g/m calculated according to the disposal area of the ultra-high density polyethylene sheet²。

Further, the solvent is dichloromethane.

Further, the oxidizing gas is 100% oxygen in parts by weight, and the rest is nitrogen.

Further, the heating reaction temperature is 150 ℃.

Further, the pressure of the oxidizing gas in the kettle is 5 MPa.

Comparative example 1

The ultra-high density polyethylene sheet was not modified.

Comparative example 2

Placing the ultrahigh-density polyethylene sheet into a pressure-resistant reaction kettle, adding a solvent to immerse the ultrahigh-density polyethylene sheet, then adding an oxidation catalyst, stirring and mixing uniformly, then filling oxidation gas into the reaction kettle, heating for reaction for 25min, cooling to room temperature after the reaction is finished, taking out the ultrahigh-density polyethylene sheet, washing with ethanol, and drying to finish the rapid surface modification of the ultrahigh-density polyethylene sheet; the method is characterized in that the oxidation catalyst is lanthanum acetate.

Furthermore, the dosage of the oxidation catalyst is 0.5g/m calculated according to the disposal area of the ultra-high density polyethylene sheet²。

Further, the solvent is chloroform.

Further, the oxidizing gas is oxygen with the mass portion of 45%, and the rest is nitrogen.

Further, the heating reaction temperature is 100 ℃.

Further, the pressure of the oxidizing gas in the kettle is 0.1 MPa.

Comparative example 3

Placing the ultrahigh-density polyethylene sheet into a pressure-resistant reaction kettle, adding a solvent to immerse the ultrahigh-density polyethylene sheet, then adding an oxidation catalyst, stirring and mixing uniformly, then filling oxidation gas into the reaction kettle, heating for reaction for 25min, cooling to room temperature after the reaction is finished, taking out the ultrahigh-density polyethylene sheet, washing with ethanol, and drying to finish the rapid surface modification of the ultrahigh-density polyethylene sheet; the preparation method is characterized in that the oxidation catalyst is a metal complex and comprises the following steps:

adding 1.96kg of acetaldehyde, 20kg of pyrrole and 18kg of dichloromethane into a reaction kettle, uniformly stirring and mixing, adding 0.2kg of boron trifluoride diethyl etherate solution, controlling the temperature to be 25 ℃, stirring and reacting for 2 hours, quenching the catalyst by using 0.6kg of triethylamine after the reaction is finished, then adding 1.3kg of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, stirring and reacting for 30 minutes, finishing the reaction, and purifying to obtain a cyclic ligand; adding 0.5kg of cyclic ligand into 40kg of N, N-dimethylformamide, stirring and mixing uniformly, adding 2.3kg of metal acetate, controlling the temperature at 110 ℃, stirring and reacting for 1h, and separating and purifying to obtain the metal complex.

Further, the metal acetate is lanthanum acetate.

Furthermore, the dosage of the oxidation catalyst is 0.5g/m calculated according to the disposal area of the ultra-high density polyethylene sheet²。

Further, the solvent is chloroform.

Further, the oxidizing gas is oxygen with the mass portion of 45%, and the rest is nitrogen.

Further, the heating reaction temperature is 100 ℃.

Further, the pressure of the oxidizing gas in the kettle is 0.1 MPa.

Table: results of performance testing of high density polyethylene sheets prepared in different examples and comparative examples.

Numbering	Tensile shear Strength (MPa)	Tensile Strength (MPa)
			Example 1	15.82	23.41
Example 2	16.94	23.68
			Example 3	18.71	23.29
Comparative example 1	0.78	23.81
			Comparative example 2	6.82	23.57
Comparative example 3	11.47	23.71

The infrared spectrum measurement is carried out on the ultra-high density polyethylene sheet treated in the example 3, and the experimental result shows that: 1735cm in comparison to untreated ultra high density polyethylene sheet^-1And 1160cm^-1The infrared absorption peaks appear at wavenumbers, which are assigned to the characteristic absorptions of C = O (carbonyl) and-CH (-OH) - (tertiary alcohol), respectively, in the graft-segment PMA, as shown in the attached FIG. 1 of the description.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.