CN117820742A - Preparation method of polyolefin pipe based on maleic anhydride grafted POE - Google Patents
Preparation method of polyolefin pipe based on maleic anhydride grafted POE Download PDFInfo
- Publication number
- CN117820742A CN117820742A CN202311813732.8A CN202311813732A CN117820742A CN 117820742 A CN117820742 A CN 117820742A CN 202311813732 A CN202311813732 A CN 202311813732A CN 117820742 A CN117820742 A CN 117820742A
- Authority
- CN
- China
- Prior art keywords
- poe
- maleic anhydride
- polyolefin
- raw materials
- anhydride grafted
- 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
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 63
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000001125 extrusion Methods 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000004595 color masterbatch Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- -1 polyethylene Polymers 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 3
- 239000004743 Polypropylene Substances 0.000 claims abstract description 3
- 229920000573 polyethylene Polymers 0.000 claims abstract description 3
- 229920001155 polypropylene Polymers 0.000 claims abstract description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 9
- 238000009472 formulation Methods 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- 230000002706 hydrostatic effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000009863 impact test Methods 0.000 description 5
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the technical field of polyolefin pipes, and discloses a preparation method of a polyolefin pipe based on maleic anhydride grafting POE, which comprises the following steps: s1: backup preparation of component raw materials; s2: preparing a maleic anhydride grafted POE product m-POE; s3: preparing the polyolefin pipe. The component raw materials in the step S1 are POE raw materials, maleic anhydride, an initiator, polyolefin raw materials and color master batch. The POE material may be replaced with polyethylene or polypropylene, but here, POE material is used. The specific preparation steps of the step S2 are as follows: s21: mixing and stirring POE raw materials, maleic anhydride and an initiator according to a formula proportion 1; s22: after S21 mixing and stirring are finished, the mixture is extruded by a double-screw granulator; s23: and S22, carrying out reaction extrusion, and granulating by a water ring to obtain a maleic anhydride grafted POE product m-POE. The pipe prepared by the invention does not burst under the test of 1000h hydrostatic pressure, and solves the problem that polyolefin pipe is easy to crack due to impact in low-temperature environment.
Description
Technical Field
The invention relates to the technical field of polyolefin pipes, in particular to a preparation method of a polyolefin pipe based on maleic anhydride grafting POE.
Background
Polyolefin pipe is widely used in cold and hot water pipeline system due to its light weight, low cost and good stability. However, under the low-temperature environment (the temperature is lower than-10 ℃), the polyolefin pipe can break after being impacted by certain external force, which seriously affects the transportation, construction and installation of the polyolefin pipe and is not beneficial to the popularization and use of the product at low temperature. Therefore, there is a need to develop a low temperature toughening technology that enables the pipe to maintain high strength toughness at low temperatures, withstand external impact at low temperatures, and ensure that the pipe can be installed and used at low temperatures.
Ethylene-octene copolymer (POE) has excellent low temperature toughness, ultraviolet light resistance and good compatibility with polyolefin, so that the ethylene-octene copolymer (POE) is widely applied to the field of plastic modification and plays a role in toughening. However, POE is a nonpolar material and has poor compatibility with polar color master batches, and therefore, it is necessary to graft-modify POE.
Thus, there is a need for a process for preparing polyolefin tubing based on maleic anhydride grafted POE.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a preparation method of a polyolefin pipe based on maleic anhydride grafting POE, which solves the problems in the prior art.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of a polyolefin pipe based on maleic anhydride grafted POE comprises the following steps:
s1: backup preparation of component raw materials;
s2: preparing a maleic anhydride grafted POE product m-POE;
s3: preparing the polyolefin pipe.
Preferably, the component raw materials in the step S1 are POE raw materials, maleic anhydride, an initiator, polyolefin raw materials and color master batches.
Preferably, the POE material is replaced by polyethylene or polypropylene, but the POE material is used herein.
Preferably, the specific preparation steps of the step S2 are as follows:
s21: mixing and stirring POE raw materials, maleic anhydride and an initiator according to a formula proportion 1;
s22: after S21 mixing and stirring are finished, the mixture is extruded by a double-screw granulator;
s23: and S22, carrying out reaction extrusion, and granulating by a water ring to obtain a maleic anhydride grafted POE product m-POE.
Preferably, the initiator is one or more of dicumyl peroxide, benzoyl peroxide and benzoyl peroxide.
Preferably, the formula 1 proportion in the step S21 is POE raw materials: maleic anhydride: initiator = 100:1.05 to 7.35:0.13 to 0.85.
Preferably, in the step S22, when the twin-screw granulator is used for extrusion, the extrusion temperature of the first section is 170-180 ℃, the extrusion temperature of the second section is 180-185 ℃, the extrusion temperature of the third section is 185-190 ℃, the die temperature is 185-190 ℃, the feeding speed is 80-130r/min, the motor rotation speed is 200-500r/min, and the granulating speed is 300-600r/min.
Preferably, the specific preparation steps of the step S3 are as follows:
s31: uniformly mixing polyolefin raw materials, m-POE and color master batch according to a formula proportion 2;
s32: and S31, mixing, and extruding and molding by using a single screw extruder to obtain the toughened polyolefin pipe.
Preferably, the proportion of formula 2 in step S31 is the polyolefin raw material: m-POE: masterbatch = 100:1.07 to 5.58:1.3 to 4.9.
Preferably, in the step S32, when the single screw extruder is used for extrusion, the extrusion temperature of the first section is 175-185 ℃, the extrusion temperature of the second section is 185-195 ℃, the extrusion temperature of the third section is 195-200 ℃, the die temperature is 200-210 ℃, and the rotating speed of the screw is 80-100r/min.
(III) beneficial effects
Compared with the prior art, the invention provides a preparation method of a polyolefin pipe based on maleic anhydride grafting POE, which has the following beneficial effects:
1. according to the invention, maleic anhydride is grafted and modified POE to obtain maleic anhydride modified POE (m-POE), and the m-POE is added into polyolefin pipes, so that a good toughening effect can be achieved.
2. The preparation method is simple and easy to implement, and the pipe can resist the impact of a drop hammer with the height of 1.5m and the weight of 5kg at the temperature of minus 15 ℃, and the pipe after the impact test is free from cracking;
3. the pipe prepared by the invention does not burst under the test of 1000h hydrostatic pressure, and the modification technology can solve the problem that the polyolefin pipe is easy to crack due to impact in a low-temperature environment.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
a preparation method of a polyolefin pipe based on maleic anhydride grafted POE comprises the following steps:
s1: backup preparation component raw materials: POE raw material, maleic anhydride, initiator, polyolefin raw material and color master;
s2: the preparation method of the maleic anhydride grafted POE product m-POE comprises the following specific preparation steps:
s21: POE starting material, maleic anhydride and initiator in the ratio 100:1.05:0.13, mixing and stirring;
s22: after S21 mixing and stirring are finished, the mixture is extruded by a double-screw granulator;
s23: after the reaction extrusion in the step S22, the maleic anhydride grafted POE product m-POE can be obtained after water ring granulation;
wherein, the initiator adopts dicumyl peroxide;
when the double-screw granulator is used for extrusion, the first section extrusion temperature is 175 ℃, the second section extrusion temperature is 180 ℃, the third section extrusion temperature is 185 ℃, the die temperature is 185 ℃, the feeding speed is 100r/min, the motor rotation speed is 300r/min, and the granulating speed is 450r/min;
s3: the preparation method of the polyolefin pipe comprises the following specific preparation steps:
s31: polyolefin raw material, m-POE and color masterbatch are mixed according to a proportion of 100:1.07:1.3, uniformly mixing;
s32: s31, after mixing, extruding and molding by using a single screw extruder to obtain a toughened polyolefin pipe;
wherein, when the single screw extruder extrudes, the extrusion temperature of the first section is 175 ℃, the extrusion temperature of the second section is 185 ℃, the extrusion temperature of the third section is 200 ℃, the die temperature is 200 ℃, and the rotating speed of the screw is 90r/min.
In conclusion, the toughened polyolefin pipe prepared by the invention has the breakage rate of 0 after being subjected to drop hammer impact test with the height of 5kg and 1.5m in the environment of-15 ℃; the 1000h hydrostatic test of the pipe is qualified, and other performances of the pipe meet the related requirements of GB/T18742.2-2017.
Embodiment two:
a preparation method of a polyolefin pipe based on maleic anhydride grafted POE comprises the following steps:
s1: backup preparation component raw materials: POE raw material, maleic anhydride, initiator, polyolefin raw material and color master;
s2: the preparation method of the maleic anhydride grafted POE product m-POE comprises the following specific preparation steps:
s21: POE starting material, maleic anhydride and initiator in the ratio 100:7.35: mixing and stirring 0.85;
s22: after S21 mixing and stirring are finished, the mixture is extruded by a double-screw granulator;
s23: after the reaction extrusion in the step S22, the maleic anhydride grafted POE product m-POE can be obtained after water ring granulation;
wherein, the initiator adopts dicumyl peroxide;
when the double-screw granulator is used for extrusion, the first section extrusion temperature is 175 ℃, the second section extrusion temperature is 180 ℃, the third section extrusion temperature is 185 ℃, the die temperature is 185 ℃, the feeding speed is 100r/min, the motor rotation speed is 300r/min, and the granulating speed is 450r/min;
s3: the preparation method of the polyolefin pipe comprises the following specific preparation steps:
s31: polyolefin raw material, m-POE and color masterbatch are mixed according to a proportion of 100:5.58:4.9, uniformly mixing;
s32: s31, after mixing, extruding and molding by using a single screw extruder to obtain a toughened polyolefin pipe;
wherein, when the single screw extruder extrudes, the extrusion temperature of the first section is 175 ℃, the extrusion temperature of the second section is 185 ℃, the extrusion temperature of the third section is 200 ℃, the die temperature is 200 ℃, and the rotating speed of the screw is 90r/min.
In conclusion, the toughened polyolefin pipe prepared by the invention has the breakage rate of 0 after being subjected to drop hammer impact test with the height of 5kg and 1.5m in the environment of-15 ℃; the 1000h hydrostatic test of the pipe is qualified, and other performances of the pipe meet the related requirements of GB/T18742.2-2017.
Embodiment III:
a preparation method of a polyolefin pipe based on maleic anhydride grafted POE comprises the following steps:
s1: backup preparation component raw materials: POE raw material, maleic anhydride, initiator, polyolefin raw material and color master;
s2: the preparation method of the maleic anhydride grafted POE product m-POE comprises the following specific preparation steps:
s21: POE starting material, maleic anhydride and initiator in the ratio 100:2:0.15, mixing and stirring;
s22: after S21 mixing and stirring are finished, the mixture is extruded by a double-screw granulator;
s23: after the reaction extrusion in the step S22, the maleic anhydride grafted POE product m-POE can be obtained after water ring granulation;
wherein, the initiator adopts dicumyl peroxide;
when the double-screw granulator is used for extrusion, the first section extrusion temperature is 175 ℃, the second section extrusion temperature is 180 ℃, the third section extrusion temperature is 185 ℃, the die temperature is 185 ℃, the feeding speed is 100r/min, the motor rotation speed is 300r/min, and the granulating speed is 450r/min;
s3: the preparation method of the polyolefin pipe comprises the following specific preparation steps:
s31: polyolefin raw material, m-POE and color masterbatch are mixed according to a proportion of 100:2:2.5, uniformly mixing;
s32: s31, after mixing, extruding and molding by using a single screw extruder to obtain a toughened polyolefin pipe;
wherein, when the single screw extruder extrudes, the extrusion temperature of the first section is 175 ℃, the extrusion temperature of the second section is 185 ℃, the extrusion temperature of the third section is 200 ℃, the die temperature is 200 ℃, and the rotating speed of the screw is 90r/min.
In conclusion, the toughened polyolefin pipe prepared by the invention has the breakage rate of 0 after being subjected to drop hammer impact test with the height of 5kg and 1.5m in the environment of-15 ℃; the 1000h hydrostatic test of the pipe is qualified, and other performances of the pipe meet the related requirements of GB/T18742.2-2017.
Example IV
A preparation method of a polyolefin pipe based on maleic anhydride grafted POE comprises the following steps:
s1: backup preparation component raw materials: POE raw material, maleic anhydride, initiator, polyolefin raw material and color master;
s2: the preparation method of the maleic anhydride grafted POE product m-POE comprises the following specific preparation steps:
s21: POE starting material, maleic anhydride and initiator in the ratio 100:3.5:0.35, mixing and stirring;
s22: after S21 mixing and stirring are finished, the mixture is extruded by a double-screw granulator;
s23: after the reaction extrusion in the step S22, the maleic anhydride grafted POE product m-POE can be obtained after water ring granulation;
wherein, the initiator adopts dicumyl peroxide;
when the double-screw granulator is used for extrusion, the first section extrusion temperature is 175 ℃, the second section extrusion temperature is 180 ℃, the third section extrusion temperature is 185 ℃, the die temperature is 185 ℃, the feeding speed is 100r/min, the motor rotation speed is 300r/min, and the granulating speed is 450r/min;
s3: the preparation method of the polyolefin pipe comprises the following specific preparation steps:
s31: polyolefin raw material, m-POE and color masterbatch are mixed according to a proportion of 100:3:3, uniformly mixing;
s32: s31, after mixing, extruding and molding by using a single screw extruder to obtain a toughened polyolefin pipe;
wherein, when the single screw extruder extrudes, the extrusion temperature of the first section is 175 ℃, the extrusion temperature of the second section is 185 ℃, the extrusion temperature of the third section is 200 ℃, the die temperature is 200 ℃, and the rotating speed of the screw is 90r/min.
In conclusion, the toughened polyolefin pipe prepared by the invention has the breakage rate of 0 after being subjected to drop hammer impact test with the height of 5kg and 1.5m in the environment of-15 ℃; the 1000h hydrostatic test of the pipe is qualified, and other performances of the pipe meet the relevant requirements of GB/T18742.2-2017:
although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the polyolefin pipe based on maleic anhydride grafted POE is characterized by comprising the following steps:
s1: backup preparation of component raw materials;
s2: preparing a maleic anhydride grafted POE product m-POE;
s3: preparing the polyolefin pipe.
2. The method for preparing the polyolefin pipe based on the maleic anhydride grafted POE, which is disclosed in claim 1, wherein the component raw materials in the step S1 are POE raw materials, maleic anhydride, an initiator, polyolefin raw materials and color master.
3. The process for the preparation of polyolefin pipes based on maleic anhydride grafted POE according to claim 2, characterized in that the POE raw materials are replaced by polyethylene or polypropylene, but here POE raw materials are used.
4. The method for preparing the polyolefin pipe based on the maleic anhydride grafted POE according to claim 1, wherein the specific preparation step of the step S2 is as follows:
s21: mixing and stirring POE raw materials, maleic anhydride and an initiator according to a formula proportion 1;
s22: after S21 mixing and stirring are finished, the mixture is extruded by a double-screw granulator;
s23: and S22, carrying out reaction extrusion, and granulating by a water ring to obtain a maleic anhydride grafted POE product m-POE.
5. The method for preparing the polyolefin pipe based on maleic anhydride grafted POE according to claim 4, wherein the initiator is one or more of dicumyl peroxide, benzoyl peroxide and benzoyl peroxide.
6. The method for preparing a polyolefin pipe based on maleic anhydride grafted POE according to claim 4, wherein the formulation 1 in step S21 is prepared from the following POE raw materials: maleic anhydride: initiator = 100:1.05 to 7.35:0.13 to 0.85.
7. The method for preparing polyolefin pipe based on maleic anhydride grafted POE according to claim 4, wherein in the step S22, the extrusion temperature of the first section is 170-180 ℃, the extrusion temperature of the second section is 180-185 ℃, the extrusion temperature of the third section is 185-190 ℃, the die temperature is 185-190 ℃, the feeding speed is 80-130r/min, the motor rotation speed is 200-500r/min, and the pelletizing speed is 300-600r/min.
8. The method for preparing the polyolefin pipe based on the maleic anhydride grafted POE according to claim 1, wherein the specific preparation step of the step S3 is as follows:
s31: uniformly mixing polyolefin raw materials, m-POE and color master batch according to a formula proportion 2;
s32: and S31, mixing, and extruding and molding by using a single screw extruder to obtain the toughened polyolefin pipe.
9. The method for preparing a polyolefin pipe based on maleic anhydride grafted POE according to claim 8, wherein the formula 2 ratio in step S31 is polyolefin raw material: m-POE: masterbatch = 100:1.07 to 5.58:1.3 to 4.9.
10. The method for preparing a polyolefin pipe based on maleic anhydride grafted POE according to claim 8, wherein the single screw extruder in the step S32 is used for extruding, the extrusion temperature of the first section is 175-185 ℃, the extrusion temperature of the second section is 185-195 ℃, the extrusion temperature of the third section is 195-200 ℃, the die temperature is 200-210 ℃, and the rotating speed of the screw is 80-100r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311813732.8A CN117820742A (en) | 2023-12-27 | 2023-12-27 | Preparation method of polyolefin pipe based on maleic anhydride grafted POE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311813732.8A CN117820742A (en) | 2023-12-27 | 2023-12-27 | Preparation method of polyolefin pipe based on maleic anhydride grafted POE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117820742A true CN117820742A (en) | 2024-04-05 |
Family
ID=90516437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311813732.8A Pending CN117820742A (en) | 2023-12-27 | 2023-12-27 | Preparation method of polyolefin pipe based on maleic anhydride grafted POE |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117820742A (en) |
-
2023
- 2023-12-27 CN CN202311813732.8A patent/CN117820742A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101423733B (en) | Method for preparing transparent hot melt adhesive for PP-R plastic-aluminum steady state tube | |
| CN102477202B (en) | Waste polypropylene modified thin-walled corrugated tube and manufacture method thereof | |
| CN110283412B (en) | Blending modified chlorinated polyvinyl chloride material and preparation method thereof | |
| CN101747600A (en) | Method for preparing polyethylene terephthalate (PET) blend | |
| CN102506241A (en) | Heat-insulation oxygen-blocking antibacterial high impact polypropylene tube and manufacturing method thereof | |
| CN101402711B (en) | Method for grafting maleic anhydride with ethylene propylene terpolymer | |
| CN117820742A (en) | Preparation method of polyolefin pipe based on maleic anhydride grafted POE | |
| CN112552595A (en) | High-strength high-toughness glass fiber reinforced polypropylene material and preparation method thereof | |
| CN101967241B (en) | Carbon black composition blending material and preparation method thereof | |
| CN108047573B (en) | Special material for PPR (polypropylene random) pipe and preparation method thereof | |
| CN112940153A (en) | Method for grafting modified polar monomer through high-molecular polymer reaction extrusion | |
| CN107286294B (en) | Compatilizer for PP/PS extrusion molding and preparation method thereof | |
| CN110194862A (en) | One kind being based on the fire-retardant PE CABLE MATERIALS of draft flowing deformation technology and its continuous preparation method | |
| CN112063031A (en) | HDPE steel strip spiral pipe and preparation method thereof | |
| CN113416359A (en) | Preparation method of low-temperature-resistant modified plastic | |
| CN116376172A (en) | Preparation method of low-temperature-resistant high-toughness PPR (Poly-p-phenylene) pipe | |
| CN105778836A (en) | Amorphous block copolymer-modified polyvinyl adhesive | |
| CN111320796A (en) | Preparation method and application of multi-component composite modifier | |
| CN110845786A (en) | EVA waterproof board and preparation method thereof | |
| CN104650440A (en) | Preparation method of nucleating agent modified polyethylene tube | |
| CN111825802A (en) | Ethylene oxide-octene copolymer composition and preparation method thereof | |
| CN115490949B (en) | PEXb tubular product with high shape memory function | |
| CN117986829B (en) | Environment-friendly degradable high-strength composite plastic packaging bag | |
| CN116948327B (en) | PVMK double-wall corrugated pipe for drain pipe and preparation method thereof | |
| CN113388072B (en) | Preparation method of efficient compatilizer for reclaimed materials (PE/PP) |
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 |