CN113694738A - 一种带抗凝血血液透析功能的超滤膜制备方法 - Google Patents
一种带抗凝血血液透析功能的超滤膜制备方法 Download PDFInfo
- Publication number
- CN113694738A CN113694738A CN202110070710.1A CN202110070710A CN113694738A CN 113694738 A CN113694738 A CN 113694738A CN 202110070710 A CN202110070710 A CN 202110070710A CN 113694738 A CN113694738 A CN 113694738A
- Authority
- CN
- China
- Prior art keywords
- membrane
- hemodialysis
- ultrafiltration membrane
- anticoagulation
- prepare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 238000001631 haemodialysis Methods 0.000 title claims abstract description 35
- 230000000322 hemodialysis Effects 0.000 title claims abstract description 35
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 22
- 230000010100 anticoagulation Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960002897 heparin Drugs 0.000 claims abstract description 15
- 229920000669 heparin Polymers 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000502 dialysis Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims abstract description 5
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001408 amides Chemical class 0.000 claims abstract description 4
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000012510 hollow fiber Substances 0.000 claims abstract description 4
- 239000003701 inert diluent Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 239000002562 thickening agent Substances 0.000 claims abstract description 4
- 235000021419 vinegar Nutrition 0.000 claims abstract description 4
- 239000000052 vinegar Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000023555 blood coagulation Effects 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000003053 toxin Substances 0.000 description 3
- 231100000765 toxin Toxicity 0.000 description 3
- 108700012359 toxins Proteins 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 208000009304 Acute Kidney Injury Diseases 0.000 description 1
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 208000033626 Renal failure acute Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 201000011040 acute kidney failure Diseases 0.000 description 1
- 208000012998 acute renal failure Diseases 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 230000036783 anaphylactic response Effects 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 208000020832 chronic kidney disease Diseases 0.000 description 1
- 208000022831 chronic renal failure syndrome Diseases 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000024203 complement activation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229920000973 polyvinylchloride carboxylated Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009256 replacement therapy Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Urology & Nephrology (AREA)
- Heart & Thoracic Surgery (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Vascular Medicine (AREA)
- Anesthesiology (AREA)
- Biomedical Technology (AREA)
- Hematology (AREA)
- Emergency Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- External Artificial Organs (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明公开了一种带抗凝血血液透析功能的超滤膜制备方法，具体操作步骤如下：S1：将过氧化氢加入到包含单烯属不饱和二羧酸酐基本结构单元的聚合物在惰性稀释剂中的悬浮液中反应，制备出不饱和过氧羧基聚合物，S2：将S1制备的共聚物与PVC(S‑70&S‑65)&PVP&PEG400等制膜聚合物共混乳化纺丝，S3：然后加入二甲基乙酰胺(DMAc)、增稠剂和氯醋，加热到58±5℃之间；搅拌配制制膜液，通过纺丝制成中空纤维式的血液透析膜，S4：在通过酰胺反应催化剂水按质量比为0.001—100:0.01—10:1000；在20—100℃温度下，反应0.1—500h制成肝素溶液，S5：充分置换溶剂后，再将血液透析膜浸泡于肝素的溶液中，将肝素接枝到透析膜表面，得到具有抗凝血血液透析功能的超滤膜。
Description
技术领域
本发明属于血液透析超滤膜技术领域，具体涉及一种带抗凝血血液透析功能的超滤膜制备方法。
背景技术
血液透析是治疗急慢性肾功能衰竭的有效替代疗法，临床应用的血液透析设备由透析机、水处理系统、透析液系统和透析器组成。其中，透析器的性能直接影响着透析效果，而血液透析膜是决定透析器性能的主要部分，是利用半透膜的原理，借助膜两侧的溶质梯度、渗透梯度和水压梯度，以达到清除毒素和体内潴留过多的水分，同时补充体内所需的物质，并维持电解质和酸碱平衡的目的的一种膜材料，目前，常用的血液透析膜有聚砜、聚甲基丙烯酸甲酯、聚醚砜、聚酰胺和聚丙烯腈。这些血液透析膜孔径较大，对水的通透性和超滤率高，对中大分子毒素的清除率高，还具有良好的力学性能、柔韧性和一定的生物相容性，但是其抗凝血性能不够理想，因其与人体的血液直接接触，在血液透析过程中，容易与血液中的各种成分发生生物或者化学反应，引起透析反应，常见的反应包括两种，一种是透析膜材料引起的过敏或凝血现象，另一种是补体激活效应。其中因膜材料引起的过敏和凝血现象较为常见，因膜材料的表面结构不同，引起血小板的聚集，发生血液凝固的现象。凝血现象的出现，导致透析效率降低，甚至会影响到透析者的生命安全。
发明内容
针对上述背景技术所提出的问题，本发明的目的是：旨在提供一种带抗凝血血液透析功能的超滤膜制备方法。
为实现上述技术目的，本发明采用的技术方案如下：
一种带抗凝血血液透析功能的超滤膜制备方法，其特征在于：具体操作步骤如下：
S1：将过氧化氢加入到包含单烯属不饱和二羧酸酐基本结构单元的聚合物在惰性稀释剂中的悬浮液中反应，制备出不饱和过氧羧基聚合物，采用原子转移自由基聚合，得到带自由羧基的共聚物；
S2：将S1制备的共聚物与PVC(S-70&S-65)&PVP&PEG400等制膜聚合物共混乳化纺丝，
S3：然后加入二甲基乙酰胺(DMAc)、增稠剂和氯醋，加热到58±5℃之间；搅拌配制制膜液，通过纺丝制成中空纤维式的血液透析膜；
S4：在通过酰胺反应催化剂水按质量比为0.001—100:0.01—10:1000；在20—100℃温度下，反应0.1—500h制成肝素溶液。
S5：充分置换溶剂后，再将血液透析膜浸泡于肝素的溶液中，将肝素接枝到透析膜表面，得到具有抗凝血血液透析功能的超滤膜。
进一步限定，所述所得的超滤膜用去离子水清洗。这样的结构设计便于洗去超滤膜表面未反应的肝素和催化剂。
进一步限定，所述通过过氧化氢的加入量来控制聚合物中过氧羧基的含量。这样的结构设计便于控制氧羧基的含量。
本发明的有益效果为：本发明先制成出带自由羧基的过氧羧基聚合物，然后将聚合物与PVC(S-70&S-65)&PVP&PEG400等制膜聚合物共混，纺丝，制备表面羧基化的PVC超滤血液透析膜。利用透析膜表面的羧基将肝素接枝到透析膜表面，改善透析膜的亲水性、生物相容性、通透性及抗凝血性能。本发明操作简便，有效地缓解了血液透析膜使用过程中的凝血问题。所制得的血液透析膜安全、表面亲水性明显改善，抗凝血能力显著提高且力学性能较其他血液透析膜大大提升。
具体实施方式
为了使本领域的技术人员可以更好地理解本发明，下面结合实施例对本发明技术方案进一步说明。
本发明的一种带抗凝血血液透析功能的超滤膜制备方法，其特征在于：具体操作步骤如下：
S1：将过氧化氢加入到包含单烯属不饱和二羧酸酐基本结构单元的聚合物在惰性稀释剂中的悬浮液中反应，制备出不饱和过氧羧基聚合物，采用原子转移自由基聚合，得到带自由羧基的共聚物；
S2：将S1制备的共聚物与PVC(S-70&S-65)&PVP&PEG400等制膜聚合物共混乳化纺丝，
S3：然后加入二甲基乙酰胺(DMAc)、增稠剂和氯醋，加热到58±5℃之间；搅拌配制制膜液，通过纺丝制成中空纤维式的血液透析膜；
S4：在通过酰胺反应催化剂水按质量比为0.001—100:0.01—10:1000；在20—100℃温度下，反应0.1—500h制成肝素溶液。
S5：充分置换溶剂后，再将血液透析膜浸泡于肝素的溶液中，将肝素接枝到透析膜表面，得到具有抗凝血血液透析功能的超滤膜。
优选所得的超滤膜用去离子水清洗。这样的结构设计便于洗去超滤膜表面未反应的肝素和催化剂。
优选通过过氧化氢的加入量来控制聚合物中过氧羧基的含量。这样的结构设计便于控制氧羧基的含量。
上述实施例仅示例性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。
Claims (3)
1.一种带抗凝血血液透析功能的超滤膜制备方法，其特征在于：具体操作步骤如下：
S1：将过氧化氢加入到包含单烯属不饱和二羧酸酐基本结构单元的聚合物在惰性稀释剂中的悬浮液中反应，制备出不饱和过氧羧基聚合物，采用原子转移自由基聚合，得到带自由羧基的共聚物；
S2：将S1制备的共聚物与PVC(S-70&S-65)&PVP&PEG400等制膜聚合物共混乳化纺丝；
S3：然后加入二甲基乙酰胺(DMAc)、增稠剂和氯醋，加热到58±5℃之间；搅拌配制制膜液，通过纺丝制成中空纤维式的血液透析膜；
S4：在通过酰胺反应催化剂水按质量比为0.001—100:0.01—10:1000；在20—100℃温度下，反应0.1—500h制成肝素溶液；
S5：充分置换溶剂后，再将血液透析膜浸泡于肝素的溶液中，将肝素接枝到透析膜表面，得到具有抗凝血血液透析功能的超滤膜。
2.根据权利要求1所述的一种带抗凝血血液透析功能的超滤膜制备方法，其特征在于：所述所得的超滤膜用去离子水清洗。
3.根据权利要求2所述的一种带抗凝血血液透析功能的超滤膜制备方法，其特征在于：所述通过过氧化氢的加入量来控制聚合物中过氧羧基的含量。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110070710.1A CN113694738A (zh) | 2021-01-19 | 2021-01-19 | 一种带抗凝血血液透析功能的超滤膜制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110070710.1A CN113694738A (zh) | 2021-01-19 | 2021-01-19 | 一种带抗凝血血液透析功能的超滤膜制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113694738A true CN113694738A (zh) | 2021-11-26 |
Family
ID=78647756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110070710.1A Pending CN113694738A (zh) | 2021-01-19 | 2021-01-19 | 一种带抗凝血血液透析功能的超滤膜制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113694738A (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102365304A (zh) * | 2009-04-02 | 2012-02-29 | 瓦克化学股份公司 | 基于聚乙烯醇的膜 |
| CN105311974A (zh) * | 2014-07-31 | 2016-02-10 | 中国科学院大连化学物理研究所 | 一种具有高抗凝血性能血液透析膜及其制备方法 |
-
2021
- 2021-01-19 CN CN202110070710.1A patent/CN113694738A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102365304A (zh) * | 2009-04-02 | 2012-02-29 | 瓦克化学股份公司 | 基于聚乙烯醇的膜 |
| CN105311974A (zh) * | 2014-07-31 | 2016-02-10 | 中国科学院大连化学物理研究所 | 一种具有高抗凝血性能血液透析膜及其制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5694298B2 (ja) | 改良された性能を有する膜の調製方法 | |
| Su et al. | Polyethersulfone hollow fiber membranes for hemodialysis | |
| NZ555302A (en) | Post treatment of microfiltration membranes with hyfrogen peroxide and a transition metal catalyst | |
| CN106310970B (zh) | 一种用于血液透析的改性聚偏氟乙烯中空纤维膜 | |
| CN106466562B (zh) | 抗凝血血液透析膜的制备方法 | |
| CN105521715B (zh) | 一种共混聚偏氟乙烯中空纤维膜及其制备方法 | |
| CN110743392B (zh) | 一种可用于血液透析且具有抗凝特性的pvdf中空纤维膜材料及其制备方法 | |
| CN105013355B (zh) | 类肝素化聚醚砜中空纤维膜及其制备方法与用途 | |
| CN109675134A (zh) | 一种血液透析器的抗凝改性方法及其应用 | |
| Zaman et al. | Recent advancement challenges with synthesis of biocompatible hemodialysis membranes | |
| US3799355A (en) | Dialysis membranes and manufacture | |
| CN113694738A (zh) | 一种带抗凝血血液透析功能的超滤膜制备方法 | |
| CN110756066B (zh) | 一种磺化柠檬酸壳聚糖改性聚砜血液透析膜及其制备方法 | |
| JPS6022901A (ja) | 選択透過性中空繊維 | |
| CN108970427B (zh) | 一种抗凝血血液透析膜及其制备方法 | |
| WO2000027447A1 (fr) | Epurateur de sang | |
| JP2000135421A (ja) | ポリスルホン系血液浄化膜 | |
| JP4352709B2 (ja) | ポリスルホン系半透膜およびそれを用いた人工腎臓 | |
| Seita et al. | Polyether‐segmented nylon hemodialysis membranes. I. Preparation and permeability characteristics of polyether‐segmented nylon 610 hemodialysis membrane | |
| JPS61293502A (ja) | 血液浄化用分離膜 | |
| CN114232129B (zh) | 聚醚砜纤维及其制备方法和用途 | |
| EP0097863A2 (en) | Mixing fluids by means of semipermeable membranes | |
| CN218356829U (zh) | 一种血液透析用体外循环连接管 | |
| JPH0582251B2 (zh) | ||
| JP2002224545A (ja) | 体外循環血液処理用分岐ポリエチレンオキシド−ポリスルホンブロック共重合体 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211126 |
|
| RJ01 | Rejection of invention patent application after publication |