CN115806650A - Method for purifying and preparing implant-grade polyether-ether-ketone by subcritical technology - Google Patents
Method for purifying and preparing implant-grade polyether-ether-ketone by subcritical technology Download PDFInfo
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 151
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000005516 engineering process Methods 0.000 title claims abstract description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000002253 acid Substances 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000013067 intermediate product Substances 0.000 claims abstract description 39
- 238000002791 soaking Methods 0.000 claims abstract description 36
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019253 formic acid Nutrition 0.000 claims abstract description 6
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 6
- 150000001413 amino acids Chemical class 0.000 claims abstract description 4
- 150000001261 hydroxy acids Chemical class 0.000 claims abstract description 4
- 235000011054 acetic acid Nutrition 0.000 claims abstract description 3
- 235000001014 amino acid Nutrition 0.000 claims abstract description 3
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims abstract 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 46
- 239000008103 glucose Substances 0.000 claims description 46
- 238000002513 implantation Methods 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 3
- 238000002360 preparation method Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 26
- 150000002500 ions Chemical class 0.000 abstract description 12
- 238000007872 degassing Methods 0.000 description 17
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
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- 239000002904 solvent Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229920006260 polyaryletherketone Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920001273 Polyhydroxy acid Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
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- 235000012054 meals Nutrition 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 230000000149 penetrating effect Effects 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to a method for purifying and preparing implantation-grade polyetheretherketone by a subcritical technology, which comprises the operation of soaking PEEK coarse powder in subcritical acid to obtain an intermediate product, and then soaking the intermediate product in subcritical pure water, wherein the acid is acetic acid, formic acid, oxalic acid, amino acid or hydroxy acid. The invention creatively utilizes heavy metal ions and CH under subcritical conditions 3 COO coordinates to form a stable water-soluble complex to remove heavy metal ions, and on the basis of not damaging the microporous structure of the polyether-ether-ketone coarse powder, the heavy metal ions in the polyether-ether-ketone can be effectively removed.
Description
Technical Field
The invention belongs to the technical field of polymer material synthesis, and relates to a method for purifying and preparing implant-grade polyether-ether-ketone by a subcritical technology.
Background
Polyetheretherketone (PEEK) has good physical and chemical properties, ray permeability, biocompatibility and mechanical properties matched with human bones, is used as a novel medical implant material to stand out in a plurality of medical materials, and is widely applied to the medical fields of wound, spine and craniomaxillofacial repair and the like.
The prior art discloses several PEEK purification processes, such as: in patent CN1640911A, N-methyl-2-pyrrolidone (NMP) and hexamethylphosphoric triamide (HMPA) are used as purification treatment agents, surfactants such as polyvinyl alcohol (PVA), polyethylene glycol (PEG) and the like are used as purification aids, and PEEK is subjected to post-treatment; CN102766257B adopts hydroxyethylidene diphosphonic acid water solution to treat PEEK; CN101602853B uses trichloroethane and ethylene glycol to purify polyaryletherketone; patent CN101486784B uses aqueous hydrochloric acid as a treating agent to treat PEEK particles. However, these PEEK purification processes can only remove light metal ions, such as Na, from PEEK + 、K + 、Ca 2+ 、F - 、Cl - 、Zn 2+ 、Mg 2+ And the like, but the removal capability of heavy metals (Ag, as, bi, cu, hg, mo, pb and Sn) (the heavy metals comprise metal simple substances, oxides, ions and the like) required in the implanted PEEK pharmaceutical industry standard (YY/T0660-2008) is limited, and the accumulated content of the heavy metals is 340-720 ppm according to the report of domestic and foreign production enterprises.
Subcritical is a condition where a substance is present, meaning that some substance exists in fluid form at a temperature above its boiling point but below its critical temperature and at a pressure below its critical pressure. Subcritical techniques can be used to extract various difficult-to-extract components from various solids. The subcritical state has "strong solubility". The subcritical technology is a new treatment technology, has the advantages of simple equipment, short treatment time, adjustability and no or little pollution to the solvent environment.
In patent CN103819663A, the crude polyaryletherketone product is soaked in subcritical water or supercritical water (350-400 ℃), and filtered to obtain purified polyaryletherketone, however, the temperature exceeds the melting point of polyetheretherketone (343 ℃), the microporous structure of polyetheretherketone coarse powder is destroyed, and the method cannot effectively remove heavy metals in polyetheretherketone.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for purifying and preparing implantation-grade polyether-ether-ketone by using a subcritical technology;
in order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a subcritical technological purification method for preparing implantation-grade polyetheretherketone comprises the steps of soaking PEEK coarse powder (pure PEEK coarse powder generally refers to industrial-grade sheet polyetheretherketone with the size of 2-5 mm) in subcritical acid to obtain an intermediate product, and soaking the intermediate product in subcritical pure water, wherein the acid is acetic acid, formic acid, oxalic acid, amino acid or hydroxy acid.
As a preferred technical scheme:
the method for purifying and preparing the implantation-grade polyetheretherketone by the subcritical technology is characterized in that the acid is degassed acetic acid; the pure water is degassed pure water.
In the method for purifying and preparing the implantation-grade polyetheretherketone by the subcritical technology, the subcritical acetic acid is acetic acid at the temperature of 117.9-321.6 ℃ and the pressure of 1 atm-5.78 MPa; the subcritical pure water is pure water at a temperature of 100 to 330 ℃ and a pressure of 1atm to 12.9 MPa.
The method for purifying and preparing the implant-grade polyetheretherketone by using the subcritical technology comprises the following steps of (1) purifying and preparing subcritical acetic acid at the temperature of 130-300 ℃ and the pressure of 0.144 kPa-4.18 MPa; the subcritical pure water is pure water at a temperature of 150 to 310 ℃ and a pressure of 0.48 to 9.86 MPa.
The method for purifying and preparing the implantation-grade polyetheretherketone by the subcritical technology comprises the following steps of preparing acetic acid in a subcritical state at the temperature of 250-290 ℃ and the pressure of 1.74-3.46 MPa; the subcritical pure water is pure water at a temperature of 250 to 290 ℃ and a pressure of 3.97 to 7.44 MPa.
The method for purifying and preparing the implantation-grade polyetheretherketone by the subcritical technology has the advantages that the average particle size of PEEK coarse powder is 15 mu m-5 mm, the melt index (400 ℃,2.16 kg) is 3-20 g/10min, and the porosity is 70-75%; the mass ratio of the PEEK coarse powder to the acid is 1; the mass ratio of the PEEK coarse powder to the pure water is 1; the time of each soaking treatment is 20 min-2 h.
In the method for purifying and preparing the implantation-grade polyetheretherketone by the subcritical technology, glucose is added into the subcritical acid while the PEEK coarse powder is placed into the subcritical acid; the adding amount of the glucose is 5 to 20 percent of the mass of the acid.
The method for purifying and preparing the implantation-grade polyetheretherketone by the subcritical technology comprises the following steps of putting the intermediate product into pure water in a subcritical state, and adding glucose into the pure water in the subcritical state; the adding amount of the glucose is 5-20% of the mass of the pure water.
A method for purifying and preparing implantation-grade polyetheretherketone by using the subcritical technology is described above, and the glucose is degassed glucose.
According to the method for purifying and preparing the implantation-grade polyetheretherketone by the subcritical technology, after the intermediate product is soaked in pure water in a subcritical state, the polyetheretherketone reaches a medical implantation-grade level, namely the content of heavy metals (Ag, as, bi, cd, cu, hg, mo, pb, sb and Sn) is less than 100ppm calculated As Pb, and the test of the United states pharmacopoeia 233 is carried out.
The principle of the invention is as follows:
after exposing the PEEK meal to subcritical acids (acetic, formic, oxalic, amino or hydroxy acids), the acids act as proton buffers providing stable H + Supplied to facilitate leaching of heavy metals and their ions, due to H + Can be rapidly consumed as the reaction proceeds, and can be coordinated with metal ions to promote the transfer of heavy metal ions from the solid phase to the aqueous phase. Due to the relatively large ionization equilibrium constant of the acid, in H + During the process of continuous consumption to attack metal and its oxide, the shift of equilibrium will provide H + Is continuously supplied. At the same time, the acid anion will form a stable complex with the metal cation by coordination, thereby promoting dissolution of the metal and its oxides. The valuable metal ion reacts with CH under subcritical condition 3 COO coordinates form a stable complex. Thus, the subcritical state contributes to a significant enhancement of the coordination between the metal cation and the acid anion. In the normal state of the process, the process is carried out,due to the surface tension of acid (water), the acid cannot efficiently enter the pores of the polyetheretherketone to be combined with metal ions to form a complex, or the water cannot efficiently enter the pores of the polyetheretherketone to carry the complex out.
The reduced metal ions will exhibit a higher solubility with the addition of glucose, thereby facilitating leaching of the metal into the aqueous phase. The superior leaching performance may be related to the reducibility of the aldehyde function in the glucose. The action of glucose as a reducing agent helps to improve the leaching effect.
During the reaction process, glucose is gradually oxidized into polyhydroxy acids, aldonic acids, tartaric acid, oxalic acid and formic acid, and finally, the polyhydroxy acids, the aldonic acids, the tartaric acid, the oxalic acid and the formic acid are completely converted into carbon dioxide and water. Most of the acid can coordinate strongly with the metal cation to form a stable and highly soluble metal-organic complex, which significantly facilitates leaching.
Heavy metal ion and CH under subcritical acid condition 3 COO coordination forms a stable water-soluble complex to be removed, subcritical water has the function of washing away residual acid, and because subcritical water has strong penetrating power and dissolution performance, residual water-soluble complex can be taken out, and the purpose of purification is achieved.
The invention creatively utilizes heavy metal ions and CH under subcritical conditions 3 COO coordinates to form a stable water-soluble complex to remove heavy metal ions, and the method for removing heavy metal ions by adopting a subcritical technology in the prior art is essentially different from the method for removing heavy metal ions by firstly removing organic matters on the surface of heavy metal and oxidizing heavy metal by using a subcritical water technology and then removing heavy metal ions by using metal replacement reaction or electrokinetic reaction.
Advantageous effects
(1) The method for purifying and preparing the implant-grade polyetheretherketone by the subcritical technology can effectively remove heavy metals in the polyetheretherketone on the basis of not damaging the microporous structure of polyetheretherketone coarse powder.
(2) Compared with the subcritical technology in the prior art, the method has the advantages of simple equipment, short treatment time and no or little pollution of the solvent to the environment.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The experimental procedures in the following examples, unless otherwise indicated, are conventional and are carried out according to the techniques or conditions described in the literature in the field or according to the instructions of the products. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specifications of the relevant substances in the examples and comparative examples are as follows:
pure water: the conductivity is less than 8 mu S/cm, the product is self-made and needs to be subjected to degassing treatment before use;
glucose: medical grade, requiring degassing treatment before use.
The detection method of the metal residue of the polyether-ether-ketone prepared in the examples and the comparative examples comprises the following steps: the test was performed with reference to the United states Pharmacopeia 233.
Example 1
A method for purifying and preparing implantation-grade polyether-ether-ketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (manufactured by Taketai far east Fine chemical Co., ltd., purity of 99.5%);
pure water: degassing pure water;
(2) Soaking PEEK coarse powder in acid at 250 deg.C and 1.74MPa for 60min to obtain intermediate product; wherein the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking the intermediate product prepared in the step (2) in pure water at the temperature of 250 ℃ and the pressure of 3.97MPa for 60min to obtain the medical implantation-grade polyether-ether-ketone; wherein the mass ratio of the PEEK coarse powder to the pure water is 1.
Comparative example 1
A method for purifying polyether-ether-ketone comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (manufactured by Taketai far east Fine chemical Co., ltd., purity of 99.5%);
pure water: degassing pure water;
(2) Soaking PEEK coarse powder in acid at 100 deg.C and normal pressure (one standard atmospheric pressure) for 60min to obtain intermediate product; wherein the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking the intermediate product prepared in the step (2) in pure water at 100 ℃ and normal pressure (one standard atmospheric pressure) for 60min; wherein the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 2
A method for purifying and preparing implantation-grade polyether-ether-ketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (manufactured by Taketai far east Fine chemical Co., ltd., purity of 99.5%);
pure water: degassing pure water;
(2) Soaking the PEEK coarse powder in acid at 270 ℃ and 2.32MPa for 60min to obtain an intermediate product; wherein the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking the intermediate product prepared in the step (2) in pure water at the temperature of 270 ℃ and the pressure of 5.5MPa for 60min to obtain the medical implantation-level polyether-ether-ketone; wherein the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 3
A method for purifying and preparing implant-grade polyetheretherketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (99.5% purity, manufactured by Yantai far east Fine chemical Co., ltd.);
pure water: degassing pure water;
(2) Soaking PEEK coarse powder in acid at 290 deg.C and 3.46MPa for 60min to obtain intermediate product; wherein the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 60min to obtain the medical implantation-level polyether-ether-ketone; wherein the mass ratio of the PEEK coarse powder to the pure water is 1.
Comparative example 2
A process for purifying polyetheretherketone substantially as in example 3, except that step (3) comprises: and (3) soaking the intermediate product prepared in the step (2) in pure water at the temperature of 100 ℃ and under the normal pressure (one standard atmospheric pressure) for 60min.
Comparative example 3
A process for purifying polyetheretherketone substantially as in example 3, except that step (2) comprises: soaking PEEK coarse powder in acid at 100 deg.C and normal pressure (one standard atmospheric pressure) for 60min to obtain intermediate product; wherein, the mass ratio of the PEEK coarse powder to the acid is 1.
Example 4
A method for purifying and preparing implantation-grade polyether-ether-ketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (99.5% purity, manufactured by Yantai far east Fine chemical Co., ltd.);
pure water: degassing pure water;
(2) Soaking the PEEK coarse powder in acid at 290 ℃ and 3.46MPa for 90min to obtain an intermediate product; wherein the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 90min to obtain the medical implantation-level polyether-ether-ketone; wherein the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 5
A method for purifying and preparing implantation-grade polyether-ether-ketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (99.5% purity, manufactured by Yantai far east Fine chemical Co., ltd.);
pure water: degassing pure water;
(2) Soaking the PEEK coarse powder in acid at 290 ℃ and 3.46MPa for 120min to obtain an intermediate product; wherein the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 120min to obtain the medical implantation-level polyether-ether-ketone; wherein the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 6
A method for purifying and preparing implant-grade polyetheretherketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (99.5% purity, manufactured by Yantai far east Fine chemical Co., ltd.);
glucose: de-aerated glucose;
pure water: degassing pure water;
(2) Soaking glucose and PEEK coarse powder in acid at 290 deg.C and 3.46MPa for 90min to obtain intermediate product; wherein, the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking glucose and the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 90min to obtain the medical implantation-level polyether-ether-ketone; wherein, the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 7
A method for purifying and preparing implant-grade polyetheretherketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (99.5% purity, manufactured by Yantai far east Fine chemical Co., ltd.);
glucose: de-aerated glucose;
pure water: degassing pure water;
(2) Soaking glucose and PEEK coarse powder in acid at 290 deg.C and 3.46MPa for 90min to obtain intermediate product; wherein, the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking glucose and the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 90min to obtain the medical implantation-level polyether-ether-ketone; wherein, the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 8
A method for purifying and preparing implantation-grade polyether-ether-ketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (manufactured by Taketai far east Fine chemical Co., ltd., purity of 99.5%);
glucose: degassing the glucose;
pure water: degassing pure water;
(2) Soaking glucose and PEEK coarse powder in acid at 290 deg.C and 3.46MPa for 90min to obtain intermediate product; wherein, the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking glucose and the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 90min to obtain the polyether-ether-ketone reaching the medical implantation level; wherein the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 9
A method for purifying and preparing implant-grade polyetheretherketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: degassed acetic acid (99.5% purity, manufactured by Yantai far east Fine chemical Co., ltd.);
glucose: de-aerated glucose;
pure water: degassing pure water;
(2) Soaking glucose and PEEK coarse powder in acid at 290 deg.C and 3.46MPa for 120min to obtain intermediate product; wherein, the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking glucose and the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 120min to obtain the medical implantation-level polyether-ether-ketone; wherein, the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 10
A method for purifying and preparing implant-grade polyetheretherketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: formic acid (manufacturer sahn chemical technology (shanghai) ltd, purity 99.5%);
glucose: degassing the glucose;
pure water: degassing pure water;
(2) Soaking glucose and PEEK coarse powder in acid at 215 deg.C and 2.43MPa for 30min to obtain intermediate product; wherein, the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking glucose and the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 30min to obtain the medical implantation-level polyether-ether-ketone; wherein, the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 11
A method for purifying and preparing implant-grade polyetheretherketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: oxalic acid (manufactured by saen chemical technology (shanghai) ltd., purity 98%);
glucose: de-aerated glucose;
pure water: degassing pure water;
(2) Soaking glucose and PEEK coarse powder in acid at 290 deg.C and 1.76MPa for 20min to obtain intermediate product; wherein, the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking glucose and the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 20min to obtain the medical implantation-level polyether-ether-ketone; wherein, the mass ratio of the PEEK coarse powder to the pure water is 1.
Example 12
A method for purifying and preparing implantation-grade polyether-ether-ketone by a subcritical technology comprises the following specific steps:
(1) Preparing raw materials:
PEEK coarse powder: the manufacturer is Shandong Junhao high performance polymer Co., ltd, and the mark is 5600P;
acid: amino acid (manufactured by Shandong Jingyun food ingredient Co., ltd., purity 98.5%);
glucose: de-aerated glucose;
pure water: degassing pure water;
(2) Soaking glucose and PEEK coarse powder in acid at 290 deg.C and 3.46MPa for 100min to obtain intermediate product; wherein, the mass ratio of the PEEK coarse powder to the acid is 1;
(3) Soaking glucose and the intermediate product prepared in the step (2) in pure water at 290 ℃ and 7.44MPa for 100min to obtain the medical implantation-level polyether-ether-ketone; wherein, the mass ratio of the PEEK coarse powder to the pure water is 1.
The polyether ether ketones obtained in the examples and comparative examples have the diphenyl sulfone residues and heavy metal residues shown in table 1 below (n.d. represents no detection, or below the detection limit of the instrument):
TABLE 1
It is seen from the data in table 1 that, in comparative example 1, there are still more residues of diphenyl sulfone and heavy metal of peek prepared in example 1, because acetic acid molecules are combined into a dimer (also called a di-associate) with a larger molecular volume through hydrogen bonds, and both the common acetic acid and the common pure water have larger surface tension, so that the acetic acid cannot efficiently enter the pores of peek to combine with metal ions to form a complex, and the pure water cannot efficiently enter the pores of peek to carry out the complex, therefore, the removal effect of diphenyl sulfone and heavy metal of the common acetic acid plus common pure water is worse than that of subcritical acetic acid plus subcritical water.
Compared with the polyether-ether-ketone prepared in the embodiment 3, the diphenyl sulfone and the heavy metal of the polyether-ether-ketone prepared in the embodiment 2 still have more residues, because most of the complex formed by combining acetic acid and metal ions (also called coordination reaction) is a multivalent ligand with larger molecular volume, and common pure water has large surface tension and cannot efficiently enter the pores of the polyether-ether-ketone to carry out the complex; therefore, the removal effect of diphenyl sulfone and heavy metals of subcritical acetic acid plus ordinary pure water is inferior to that of subcritical acetic acid plus subcritical water.
Compared with the polyether-ether-ketone prepared in the embodiment 3, the diphenyl sulfone and heavy metal of the polyether-ether-ketone prepared in the embodiment 3 still have more residues, because acetic acid molecules are combined into a dimer (also called a di-associate) with a larger molecular volume through hydrogen bonds, and the surface tension of common acetic acid is larger, so that the acetic acid cannot efficiently enter polyether-ether-ketone pores to be combined with metal ions to form a complex; therefore, the removal effect of diphenyl sulfone and heavy metals of ordinary acetic acid plus subcritical water is inferior to that of subcritical acetic acid plus subcritical water.
Meanwhile, the experimental results in the table also show that: the cleaner the solvent and the metal ions are removed along with the increase of the purification temperature or the prolonging of the purification time; the addition of glucose can further improve the removal efficiency of the solvent and metal ions; the method can effectively remove the solvent and metal ions in the PEEK, and the purified PEEK resin reaches the medical implantation level.
The present invention has been described in detail above. It will be apparent to those skilled in the art that the invention can be practiced within a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with reference to specific embodiments, it will be appreciated that the invention can be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.
Claims (10)
1. A subcritical technical purification preparation method of implantation grade polyetheretherketone is characterized by comprising the operation of soaking PEEK coarse powder in subcritical acid to obtain an intermediate product, and then soaking the intermediate product in subcritical pure water to obtain an intermediate product, wherein the acid is acetic acid, formic acid, oxalic acid, amino acid or hydroxy acid.
2. The method for purifying and preparing implantation-grade polyetheretherketone by using the subcritical technique according to claim 1, wherein the acid is degassed acetic acid; the pure water is degassed pure water.
3. The method for purifying and preparing implantation-grade polyetheretherketone by using the subcritical technology according to claim 2, wherein the acetic acid in the subcritical state is acetic acid at the temperature of 117.9-321.6 ℃ and the pressure of 1 atm-5.78 MPa; the subcritical pure water is pure water at a temperature of 100 to 330 ℃ and a pressure of 1atm to 12.9 MPa.
4. The method for purifying and preparing implantation-grade polyetheretherketone by using the subcritical technology according to claim 3, wherein the acetic acid in the subcritical state is acetic acid at a temperature of 130-300 ℃ and a pressure of 0.144 kPa-4.18 MPa; the subcritical pure water is pure water at a temperature of 150 to 310 ℃ and a pressure of 0.48 to 9.86 MPa.
5. The method for purifying and preparing implantation-grade polyetheretherketone by using the subcritical technology according to claim 4, wherein the acetic acid in the subcritical state is acetic acid at a temperature of 250-290 ℃ and a pressure of 1.74-3.46 MPa; the subcritical pure water is pure water at a temperature of 250 to 290 ℃ and a pressure of 3.97 to 7.44 MPa.
6. The method for purifying and preparing implantation-grade polyetheretherketone by using the subcritical technology according to claim 1, wherein the PEEK coarse powder has an average particle size of 15 μm-5 mm, a melt index of 3-20 g/10min and a porosity of 70-75%; the mass ratio of the PEEK coarse powder to the acid is 1; the mass ratio of the PEEK coarse powder to the pure water is 1; the time of each soaking treatment is 20 min-2 h.
7. The method for preparing the implantation-grade polyetheretherketone by subcritical technical purification according to claim 1, wherein glucose is added to the subcritical acid while the PEEK coarse powder is placed in the subcritical acid; the adding amount of the glucose is 5-20% of the mass of the acid.
8. The method for preparing polyetheretherketone by subcritical technical purification according to claim 1, wherein glucose is added to the pure water in the subcritical state while the intermediate product is placed in the pure water in the subcritical state; the adding amount of the glucose is 5 to 20 percent of the mass of the pure water.
9. The method for purifying and preparing implantation-grade polyetheretherketone by using the subcritical technique according to claim 7 or 8, wherein the glucose is degassed glucose.
10. The method for purifying and preparing implantation-grade polyetheretherketone by using the subcritical technology according to claim 1, wherein the polyetheretherketone reaches the medical implantation-grade level after the intermediate product is soaked in pure water in the subcritical state.
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Address after: 272200 Jining new material industrial park, Huji Town, Jinxiang County, Jining City, Shandong Province Applicant after: Shandong Junhao High Performance Polymer Co.,Ltd. Applicant after: Jiangsu Junhua Special Polymer Materials Co.,Ltd. Address before: 272200 Jining new material industrial park, Huji Town, Jinxiang County, Jining City, Shandong Province Applicant before: Shandong Junhao High Performance Polymer Co.,Ltd. Applicant before: JIANGSU JUNHUA HIGH PERFORMANCE SPECIALTY ENGINEERING PLASTICS (PEEK) PRODUCTS CO.,LTD. |
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