WO2023019920A1 - 一种氮气发泡制备泡孔材料的方法 - Google Patents

一种氮气发泡制备泡孔材料的方法 Download PDF

Info

Publication number
WO2023019920A1
WO2023019920A1 PCT/CN2022/079783 CN2022079783W WO2023019920A1 WO 2023019920 A1 WO2023019920 A1 WO 2023019920A1 CN 2022079783 W CN2022079783 W CN 2022079783W WO 2023019920 A1 WO2023019920 A1 WO 2023019920A1
Authority
WO
WIPO (PCT)
Prior art keywords
foaming
nitrogen
polar liquid
preparing
preforms
Prior art date
Application number
PCT/CN2022/079783
Other languages
English (en)
French (fr)
Inventor
白朋
张振秀
Original Assignee
江苏大毛牛新材料有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 江苏大毛牛新材料有限公司 filed Critical 江苏大毛牛新材料有限公司
Priority to EP22729024.4A priority Critical patent/EP4389385A1/en
Priority to US17/773,853 priority patent/US20240174829A1/en
Priority to JP2022540863A priority patent/JP7455213B2/ja
Publication of WO2023019920A1 publication Critical patent/WO2023019920A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2331/04—Homopolymers or copolymers of vinyl acetate

Definitions

  • the present invention relates to the field of physical foaming, and more particularly, the present invention relates to C08J9/12.
  • Cellular materials are a type of polymer material with a large number of cells distributed inside the material.
  • the current foaming methods mainly include chemical foaming and physical foaming. Compared with chemical foaming, physical foaming does not undergo chemical changes, but only changes Physical state, conducive to environmental protection.
  • CN110343330A discloses a cross-linked polypropylene cellular material and a preparation method thereof, the cellular material includes the following raw materials, matrix resin, foaming agent, antioxidant, cell stabilizer and sensitizer; its preparation method includes Steps such as extrusion molding, radiation crosslinking, foaming agent impregnation, etc., use non-polluting carbon dioxide as foaming agent in the preparation process of the present invention; compared with traditional crosslinked polypropylene cellular materials, it does not cause secondary pollution and meets Green requirements.
  • the first aspect of the present invention provides a method for preparing cellular materials by nitrogen foaming, including: after the foaming matrix is cross-linked, a number of cross-linked preforms are obtained and added to the reactant containing polar liquid After adding nitrogen to the kettle for foaming, release the pressure, heat and foam to obtain the cellular material.
  • the present invention does not specifically limit the amount of the polar liquid, as long as the foaming matrix is completely submerged in the polar liquid.
  • the raw materials for preparing the foam matrix of the present invention include polymers, and the polymers are rubber and/or plastics, etc., without specific limitation, such as polyethylene, polypropylene, polytetrafluoroethylene, EPDM rubber, polyvinyl alcohol, polyamide, etc.
  • the raw materials for preparing the foam matrix in the present invention further include a crosslinking agent, and the crosslinking agent accounts for 1-5 wt% of the polymer.
  • the cross-linking agent can be selected from different cross-linking agents according to different functional groups of the polymer, such as peroxy cross-linking agent, isocyanate cross-linking agent, polyvinyl cross-linking agent, etc., which are not specifically limited.
  • peroxygen crosslinking agents include, but are not limited to, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl-(2-ethyl Hexyl) monoperoxycarbonate, 1,1-dipentylperoxycyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, peroxy-2- tert-butyl ethylhexyl carbonate, tert-butyl peroxyisononanoate.
  • isocyanate crosslinking agent examples include, but are not limited to, toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate.
  • polyvinyl crosslinkers include, but are not limited to, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate, dimethyl 1,4-Butanediol Acrylate, Triethylene Glycol Dimethacrylate.
  • the raw materials for preparing the foam matrix of the present invention also include an initiator, and the initiator accounts for 1 to 5 wt% of the polymer; such as a photoinitiator or a thermal initiator, etc., which are not specifically limited.
  • Examples include diphenylethanone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, benzophenone, 2,4-dihydroxybenzophenone, Michler’s ketone, peroxide Benzoyl, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-tert-valerate, azobisisobutyronitrile, and azobisisoheptanonitrile are not specifically limited.
  • the raw materials for the preparation of the foam matrix in the present invention may also include additives such as fillers, antioxidants, nucleating agents, and compatibilizers, which are not specifically limited.
  • the method for crosslinking the foamed matrix in the present invention is selected from one of thermal curing, ultraviolet curing and radiation curing. Not specifically limited. After the foaming matrix is cross-linked and molded, a cross-linked preform with a certain shape and size is obtained, which is used for foaming to obtain a cell material.
  • the functional group of the polar liquid in the present invention is selected from at least one of hydroxyl group, carbonyl group and ester group.
  • the polar liquid includes hydroxyl non-carbon compounds, such as water.
  • the polar liquid also includes hydroxyl carbon compounds, alkane compounds, such as alcohol, hydroxy acid, pentane, hexane and the like.
  • the present invention does not specifically limit the amount of hydroxyl non-carbon compounds used in polar liquids.
  • Examples include 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, 100wt%, such as 1-100wt%.
  • the present invention can improve the compatibility and saturation concentration of nitrogen and cross-linked preform by adding nitrogen foaming in the environment of polar liquid, so that higher foaming can be obtained under the condition of low polar liquid temperature. magnification and uniform cell structure.
  • the ratio of the distance between adjacent crosslinked preforms to the thickness of the crosslinked preform is (1.5 ⁇ 2):1.
  • a plurality of preforms can be added together for foaming with nitrogen, and a certain distance needs to be kept between the preforms.
  • the distance between the crosslinked preforms is the distance from the crosslinked preform A close to the crosslinked preform B to the crosslinked preform B, and the thickness of the crosslinked preform is that the crosslinked preform A is away from the crosslinked preform B
  • the surface A2 of the crosslinked preform A is the distance A1 from the surface of the crosslinked preform A close to the crosslinked preform B. If the distance between A1 and A2 is not constant, the maximum distance from A2 to A1 is taken as the thickness of the crosslinked preform.
  • the inventors found that in a polar liquid environment, compared with a general superfluid environment such as nitrogen, the distance between the cross-linked preforms needs to be reasonably selected, so that the cross-linked preforms can be better compatible with nitrogen-polar liquid The effect is to control the increase of the saturation and nucleation points in the preform, so as to avoid the large difference in the expansion ratio of the same batch of preforms after adding nitrogen, which will affect the subsequent foaming.
  • the inventors found that when adding nitrogen, the temperature of nitrogen added is controlled to be lower, and the temperature of polar liquid is higher. Through gas-liquid mass transfer, the compatibility and dispersion of nitrogen in polar liquid can be promoted, thereby further Promote the stability of nitrogen pre-expansion ratio.
  • the temperature difference between the softening point of the polymer of the present invention and the polar liquid is 20-30°C.
  • the temperature of the polar liquid in the present invention satisfies: the temperature of the polar liquid is greater than or equal to 40°C; and/or the temperature difference between the softening point of the polymer and the polar liquid is 20-30°C, the softening of the polymer provided by the present invention The point is greater than or equal to 60°C.
  • the softening point is measured according to ASTM D1525, which is the Vicat softening point.
  • the temperature difference in the present invention is the difference between the softening point temperature of the polymer and the temperature of the polar liquid, and the present invention does not specifically limit the temperature of the polar liquid, as long as the temperature of the polar liquid is lower than the softening point temperature of the polymer 20 ⁇ 30 °C can be.
  • the temperature for adding nitrogen is 30-40°C
  • the pressure for adding nitrogen is 10-20 MPa
  • the pressure release rate of the present invention is 3-4 MPa/s.
  • the present invention does not specifically limit the time of adding nitrogen to foam and the time of heating and foaming, which are controlled according to different polymers.
  • the temperature of heating and foaming in the present invention is 100-200° C., and the time is 0.5-3 hours.
  • the inventors found that when the high-pressure system is released by the method of rapid pressure release, it can promote the formation of a higher foaming ratio and at the same time obtain a suitable foaming channel, so that in the process of subsequent heating and further foaming, the foaming rate is promoted. Foaming is further carried out to obtain a uniform cellular material.
  • the present invention has the following beneficial effects:
  • inorganic foaming is foamed by soaking the high-pressure foaming agent into the polymer material for a long time.
  • the foaming is mainly related to the compatibility of the inorganic foaming agent and the polymer, and because the inorganic foaming agent and the The different properties of the polymer make it difficult for the inorganic foaming agent to enter the polymer and form good cells, so that the foaming ratio after adding nitrogen for foaming and after pressure release is low.
  • the inventors found that it is necessary to control the distance between adjacent crosslinked preforms and the thickness ratio of the preforms, as well as the temperature difference between the melting temperature of the polymer and the polar liquid, so as to promote the adjacent preforms
  • the product can be fully in contact with polar liquid, and through the system provided by the invention, pre-foaming can be carried out under the condition of low temperature difference, that is, the temperature of polar liquid is low, so as to promote the expansion ratio and cell uniformity.
  • Fig. 1 is the SEM figure of embodiment 1.
  • Fig. 2 is the SEM figure of embodiment 2.
  • Fig. 3 is the SEM figure of embodiment 3.
  • This example provides a method for preparing cellular materials by nitrogen foaming, including: after cross-linking the foaming matrix, several cross-linked preforms are obtained and put into a reaction kettle filled with water; after adding nitrogen gas to foam, release the pressure, heating and foaming to obtain the cellular material.
  • the distance between the adjacent crosslinked preforms and the thickness ratio of the crosslinked preforms are 2:1, the temperature difference between the softening point of the polymer and the polar liquid is 20°C, and the nitrogen foaming , the temperature for adding nitrogen is 40°C, the pressure for adding nitrogen is 20MPa, pressurize to 40MPa after holding the pressure for 1h, hold the pressure for 3h, the rate of pressure release is 4MPa/s, and the temperature for heating and foaming is 130 °C, the time is 1h.
  • the raw materials for the preparation of the foam matrix include polymers, cross-linking agents, and initiators.
  • the polymers are EVA (softening point: 70°C), 7320M purchased from Formosa Plastics, and the cross-linking agents are 1,1- Two-(t-butylperoxy)-3,3,5-trimethylcyclohexane, the initiator is azobisisobutyronitrile, the crosslinking agent accounts for 5wt% of the polymer, the initiator The agent accounted for 4 wt% of the polymer.
  • This example provides a method for preparing cellular materials by nitrogen foaming, including: after cross-linking the foaming matrix, several cross-linked preforms are obtained and put into a reaction kettle filled with water; after adding nitrogen gas to foam, release the pressure, heating and foaming to obtain the cellular material.
  • the distance between the adjacent crosslinked preforms and the thickness ratio of the crosslinked preforms are 1.5:1, the softening point of the polymer and the temperature difference of the polar liquid are 30°C, the nitrogen foaming , the temperature at which nitrogen is added is 30°C, the pressure at which nitrogen is added is 10MPa, after holding the pressure for 2 hours, pressurize to 30MPa, hold the pressure for 5 hours, the rate of pressure release is 3MPa/s, and the temperature of heating and foaming is 160 °C, the time is 0.8h.
  • the raw materials for the preparation of the foam matrix include polymers, cross-linking agents, and initiators.
  • the polymers are PP (softening point is 150° C.), purchased from Hyosung, South Korea’s B240P, and the cross-linking agents are tert-butyl -(2-Ethylhexyl) monoperoxycarbonate, the initiator is azobisisoheptanonitrile, the crosslinking agent accounts for 3wt% of the polymer, and the initiator accounts for 2wt% of the polymer.
  • This example provides a method for preparing cellular materials by nitrogen foaming, including: after cross-linking the foaming matrix, several cross-linked preforms are obtained and put into a reaction kettle filled with water; after adding nitrogen gas to foam, release the pressure, heating and foaming to obtain the cellular material.
  • the distance between the adjacent crosslinked preforms and the thickness ratio of the crosslinked preforms are 1.8:1, the softening point of the polymer and the temperature difference of the polar liquid are 25°C, the nitrogen foaming , the temperature at which nitrogen is added is 35°C, the pressure at which nitrogen is added is 15 MPa, and the pressure is maintained for 1.5 hours, then pressurized to 35 MPa, and the pressure is maintained for 4 hours, the rate of pressure release is 3.5 MPa/s, and the temperature The temperature is 150°C, and the time is 1h.
  • the preparation raw material of described foam matrix comprises polymer, cross-linking agent, initiator, and described polymer is PP (softening point is 150 °C), purchased from Daehan Petrochemical 5010, and described cross-linking agent is 1, 1-di-t-pentylperoxycyclohexane, the initiator is azobisisobutyronitrile, the crosslinking agent accounts for 3 wt% of the polymer, and the initiator accounts for 3 wt% of the polymer.
  • PP softening point is 150 °C
  • described cross-linking agent is 1, 1-di-t-pentylperoxycyclohexane
  • the initiator is azobisisobutyronitrile
  • the crosslinking agent accounts for 3 wt% of the polymer
  • the initiator accounts for 3 wt% of the polymer.
  • This example provides a method for preparing cellular materials by nitrogen foaming, including: after cross-linking the foaming matrix, several cross-linked preforms are obtained and put into a reaction kettle filled with water; after adding nitrogen gas to foam, release the pressure, heating and foaming to obtain the cellular material.
  • the distance between the adjacent crosslinked preforms and the thickness ratio of the crosslinked preforms are 1.8:1
  • the softening point of the polymer and the temperature difference of the polar liquid are 5°C
  • the nitrogen foaming the temperature at which nitrogen is added is 35°C
  • the pressure at which nitrogen is added is 15MPa
  • the pressure is maintained for 1.5 hours, then pressurized to 35MPa and maintained for 4 hours, the rate of pressure release is 3.5MPa/s
  • the temperature of heating and foaming The temperature is 150°C, and the time is 1h.
  • the preparation raw material of described foam matrix comprises polymer, cross-linking agent, initiator, and described polymer is PP (softening point is 150 °C), purchased from Daehan Petrochemical 5010, and described cross-linking agent is 1, 1-di-t-pentylperoxycyclohexane, the initiator is azobisisobutyronitrile, the crosslinking agent accounts for 3 wt% of the polymer, and the initiator accounts for 3 wt% of the polymer.
  • PP softening point is 150 °C
  • described cross-linking agent is 1, 1-di-t-pentylperoxycyclohexane
  • the initiator is azobisisobutyronitrile
  • the crosslinking agent accounts for 3 wt% of the polymer
  • the initiator accounts for 3 wt% of the polymer.
  • This example provides a method for preparing cellular materials by nitrogen foaming, including: after cross-linking the foaming matrix, several cross-linked preforms are obtained and put into a reaction kettle filled with water; after adding nitrogen gas to foam, release the pressure, heating and foaming to obtain the cellular material.
  • the distance between the adjacent crosslinked preforms and the thickness ratio of the crosslinked preforms are 1.8:1, the softening point of the polymer and the temperature difference of the polar liquid are 25°C, the nitrogen foaming , the temperature at which nitrogen is added is 35°C, the pressure at which nitrogen is added is 35MPa, the pressure is kept for 4.5h, the rate of pressure release is 3.5MPa/s, the temperature for heating and foaming is 150°C, and the time is 1h.
  • the preparation raw material of described foam matrix comprises polymer, cross-linking agent, initiator, and described polymer is PP (softening point is 150 °C), purchased from Daehan Petrochemical 5010, and described cross-linking agent is 1, 1-di-t-pentylperoxycyclohexane, the initiator is azobisisobutyronitrile, the crosslinking agent accounts for 3 wt% of the polymer, and the initiator accounts for 3 wt% of the polymer.
  • PP softening point is 150 °C
  • described cross-linking agent is 1, 1-di-t-pentylperoxycyclohexane
  • the initiator is azobisisobutyronitrile
  • the crosslinking agent accounts for 3 wt% of the polymer
  • the initiator accounts for 3 wt% of the polymer.
  • Pre-expansion ratio measure the thickness of the pre-foamed material and cross-linked product obtained after nitrogen foaming and pressure relief are L2 and L1 respectively, then it is the pre-expansion ratio L2/L1, and calculate the same batch of 10
  • Foaming ratio measure the thickness of the cellular material and the cross-linked product as L3 and L1 respectively, then the foaming ratio is L3/L1. Times, the results are shown in Table 1.
  • the preparation method of the cellular material provided by the present invention can improve the stability of foaming and the uniformity of cells by adding the foaming matrix into a polar liquid and soaking in a nitrogen environment, and then foaming. High expansion ratio and uniform cell material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Molding Of Porous Articles (AREA)

Abstract

本发明涉及物理发泡领域，更具体地，本发明涉及C08J9/12。包括：将发泡基体交联后，得到若干个交联预制品加入装有极性液体的反应釜中，加入氮气发泡后、泄压，加热发泡，得到所述泡孔材料。在极性液体体系中，发明人发现，需控制相邻交联预制品之间的距离和预制品的厚度比，以及聚合物熔融温度和极性液体的温度差，促进相邻预制品可充分和极性液体接触，且通过本发明提供的体系，可在温度差较低，也即极性液体的温度较低的条件下进行预发泡，促进发泡倍率和泡孔均匀。

Description

一种氮气发泡制备泡孔材料的方法 技术领域
本发明涉及物理发泡领域，更具体地，本发明涉及C08J9/12。
背景技术
泡孔材料为材料内部分布大量泡孔的一类聚合物材料，目前发泡的方法主要有化学发泡和物理发泡，相比于化学发泡，物理发泡不发生化学变化，而只是改变物理状态，有利于环境保护。
CN110343330A公开了一种交联聚丙烯泡孔材料及其制备方法，所述泡孔材料包括以下原料，基体树脂，发泡剂，抗氧剂，泡孔稳定剂以及敏化剂；其制备方法包括挤出成型、辐射交联、发泡剂浸渍等步骤，本发明制备过程中使用无污染的二氧化碳作为发泡剂；与传统的交联聚丙烯泡孔材料相比，不造成二次污染，符合绿色环保的要求。
但是目前的泡孔材料制备过程中存在发泡倍率不稳定、泡孔不均的问题，故需要提供一种新的制备方法，来提高发泡倍率的稳定和泡孔均匀性。
发明内容
为了解决上述问题，本发明第一个方面提供了一种氮气发泡制备泡孔材料的方法，包括：将发泡基体交联后，得到若干个交联预制品加入装有极性液体的反应釜中，加入氮气发泡后、泄压，加热发泡，得到所述泡孔材料。本发明不对极性液体的用量做具体限定，发泡基体完全浸没在极性液体中即可。
在一种实施方式中，本发明所述发泡基体的制备原料包括聚合物，所述聚合物为橡胶和/或塑料等，不做具体限定，如聚乙烯、聚丙烯、聚四氟乙烯、三元乙丙橡胶、聚乙烯醇、聚酰胺等。
在一种实施方式中，本发明所述发泡基体的制备原料还包括交联剂，所述交联剂占聚合物的1～5wt％。
所述交联剂根据聚合物的官能团不同，可选择不同的交联剂，如过氧交联剂、异氰酸酯交联剂、多乙烯基交联剂等，不做具体限定。
作为过氧交联剂的实例，包括但不限于，1,1-二-(叔丁基过氧)-3,3,5-三甲基环己烷、叔丁基-(2-乙基己基)单过氧碳酸酯、1,1-二特戊基过氧化环己烷、2,5- 二甲基-2,5-双(叔丁基过氧)己烷、过氧化-2-乙基己基碳酸叔丁酯、过氧化异壬酸叔丁酯。
作为异氰酸酯交联剂的实例，包括但不限于，甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯。
作为多乙烯基交联剂的实例，包括但不限于，三羟甲基丙烷三甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、三烯丙基异氰脲酸酯、二甲基丙烯酸1,4-丁二醇酯、二缩三乙二醇双甲基丙烯酸酯。
在一种实施方式中，本发明所述发泡基体的制备原料还包括引发剂，所述引发剂占聚合物的1～5wt％；如光引发剂或热引发剂等，不做具体限定，可列举的有，二苯基乙酮、α,α-二甲氧基-α-苯基苯乙酮、二苯甲酮、2,4-二羟基二苯甲酮、米蚩酮、过氧化苯甲酰、过氧化月桂酰、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、偶氮二异丁腈、偶氮二异庚腈，不做具体限定。
在一种实施方式中，本发明所述发泡基体的制备原料还可包括填料、抗氧剂、成核剂、相容剂等助剂，不做具体限定。
在一种实施方式中，本发明所述发泡基体交联的方法选自热固化、紫外固化、辐射固化中的一种。不做具体限定。发泡基体交联成型后，得到具有一定形状和大小的交联预制品，用于发泡，得到泡孔材料。
在一种实施方式中，本发明所述极性液体的官能团选自羟基、羰基、酯基中的至少一种。当官能团包括羟基时，所述极性液体包括羟基非碳化合物，如水，优选地，所述极性液体还包括羟基碳化合物、烷烃化合物，如醇、羟基酸、戊烷、己烷等。本发明不对羟基非碳化合物在极性液体中的用量做具体限定，可列举的有，1wt％、5wt％、10wt％、15wt％、20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％、85wt％、90wt％、95wt％、100wt％，如1～100wt％。
目前物理发泡过程中，为了提高物理发泡剂，如氮气进入交联预制品，并促进氮气在交联预制品中饱和浓度，一般需要在预制品软化点甚至熔点附近，并采用高压的氮气作用，但容易会出现大泡孔等问题，造成泡孔不均，甚至表面向内塌陷，且难以得到高发泡倍率的产品。而本发明通过采用在极性液体的环境中加入氮气发泡的方式，可改善氮气和交联预制品的相容性和饱和浓度，使得在低极 性液体温度条件下，可得到较高发泡倍率和均匀的泡孔结构。
在一种实施方式中，本发明所述相邻交联预制品之间的距离和交联预制品的厚度比为(1.5～2)：1。本发明可以将多个预制品共同加入氮气发泡，其中预制品之间需要保持一定的距离，若将相邻交联预制品分别叫做交联预制品A和交联预制品B，则相邻交联预制品之间的距离为交联预制品A接近交联预品B的面A1到交联预制品B的距离，交联预制品的厚度为交联预制品A远离交联预制品B的面A2，到交联预制品A接近交联预品B的面的距离A1，若A1和A2间的距离不是常数，则将A2到A1的最大距离作为交联预制品的厚度。
此外，发明人发现，在极性液体环境，相比于一般的氮气等超流体环境，需合理选择交联预制品之间的距离，从而使得交联预制品可更好和氮气-极性液体作用，控制预制品中的饱和度和成核点的增加，从而避免同批次预制品加氮气后发泡倍率相差较大，影响后续发泡。且发明人发现，当加入氮气的过程中，控制加入氮气的温度较低，极性液体的温度较高，通过气液传质，可促进氮气在极性液体中的相溶和分散，从而进一步促进氮气预发泡倍率的稳定。
在一种实施方式中，本发明所述聚合物的软化点和极性液体的温度差为20～30℃。本发明所述极性液体的温度满足：极性液体的温度大于等于40℃；和/或聚合物的软化点和极性液体的温度差为20～30℃，本发明提供的聚合物的软化点大于等于60℃。软化点根据ASTM D1525测试得到，为维卡软化点。本发明所述温度差为聚合物的软化点温度和极性液体的温度的差值，本发明不对极性液体的温度做具体限定，只需极性液体的温度比聚合物的软化点温度低20～30℃即可。
在一种实施方式中，本发明所述加入氮气发泡中，加入氮气的温度为30～40℃，加入氮气的压力为10～20MPa，保压1～2h后，加压至30～40MPa，保压3～5h。
在一种实施方式中，本发明所述泄压的速率为3～4MPa/s。
本发明不对加入氮气发泡的时间和加热发泡的时间做具体限定，根据不同的聚合物进行控制。在一种实施方式中，本发明所述加热发泡的温度为100～200℃，时间为0.5～3h。
此外，发明人发现，在加入氮气发泡的过程中，现在较低压力保压一段时间， 再在较高压力保压一段时间后，更有利于形成高的泡孔密度，促进发泡倍率的提高，避免大气泡的产生，这可能是因为现在较低压力，也即较低氮气在极性液体的浓度下保压时，可促进较低浓度氮气浸入聚合物并促进成核，形成合适的聚合物骨架，从而当压力增加，氮气在极性液体中溶解度增加的过程中，在高压带来的泡孔增加阻力增加，以及聚合物骨架和氮气成核位点的固定作用下，可促进更多氮气进入聚合物内部，形成均匀的成核位点，便于后续泄压后和加热发泡过程中利用过饱和氮气的发泡，避免大泡孔的形成。
且发明人发现，当采用快泄压的方式对高压体系进行泄压时，可促进形成更高发泡倍率的同时，得到合适的发泡孔道，从而当后续加热进一步发泡的过程中，促进发泡的进一步进行，得到均匀的泡孔材料。
本发明与现有技术相比具有以下有益效果：
(1)一般情况下无机发泡是通过将高压发泡剂长时间浸润聚合物材料进行发泡，发泡主要和无机发泡剂和聚合物的相容性有关，而因为无机发泡剂和聚合物性质不同，使得无机发泡剂很难进入聚合物内部，并形成好的泡孔，使得加入氮气发泡后、泄压后的发泡倍率较低，而本发明通过在包含水的极性液体体系下进行，使得无机发泡剂的浸润和无机发泡剂和水的相容，水和聚合物的相容，无机发泡剂和水的相容有关，发明人意外发现，可促进发泡剂浸入聚合物中，提高预发泡倍率。
(2)在极性液体体系中，发明人发现，需控制相邻交联预制品之间的距离和预制品的厚度比，以及聚合物熔融温度和极性液体的温度差，促进相邻预制品可充分和极性液体接触，且通过本发明提供的体系，可在温度差较低，也即极性液体的温度较低的条件下进行预发泡，促进发泡倍率和泡孔均匀。
(3)此外，通过控制加入氮气的压力和温度，以及和极性液体的温度差，在加入氮气和加压的过程中，可因为温度差等促进氮气溶解，并提高氮气的密度，从而进一步促进预发泡的稳定，从而促进最终发泡倍率的提高。
附图说明
图1为实施例1的SEM图。
图2为实施例2的SEM图。
图3为实施例3的SEM图。
具体实施方式
实施例
实施例1
本例提供一种氮气发泡制备泡孔材料的方法，包括：将发泡基体交联后，得到若干个交联预制品加入装有水的反应釜中，加入氮气发泡后、泄压，加热发泡，得到所述泡孔材料。所述相邻交联预制品之间的距离和交联预制品的厚度比为2：1，所述聚合物的软化点和极性液体的温度差为20℃，所述加入氮气发泡中，加入氮气的温度为40℃，加入氮气的压力为20MPa，保压1h后，加压至40MPa，保压3h，所述泄压的速率为4MPa/s，所述加热发泡的温度为130℃，时间为1h。所述发泡基体的制备原料包括聚合物、交联剂、引发剂，所述聚合物为EVA(软化点为70℃)，购自台塑的7320M，所述交联剂为1,1-二-(叔丁基过氧)-3,3,5-三甲基环己烷，所述引发剂为偶氮二异丁腈，所述交联剂占聚合物的5wt％，所述引发剂占聚合物的4wt％。
实施例2
本例提供一种氮气发泡制备泡孔材料的方法，包括：将发泡基体交联后，得到若干个交联预制品加入装有水的反应釜中，加入氮气发泡后、泄压，加热发泡，得到所述泡孔材料。所述相邻交联预制品之间的距离和交联预制品的厚度比为1.5：1，所述聚合物的软化点和极性液体的温度差为30℃，所述加入氮气发泡中，加入氮气的温度为30℃，加入氮气的压力为10MPa，保压2h后，加压至30MPa，保压5h，所述泄压的速率为3MPa/s，所述加热发泡的温度为160℃，时间为0.8h。所述发泡基体的制备原料包括聚合物、交联剂、引发剂，所述聚合物为PP(软化点为150℃)，购自韩国晓星的B240P，所述交联剂为叔丁基-(2-乙基己基)单过氧碳酸酯，所述引发剂为偶氮二异庚腈，所述交联剂占聚合物的3wt％，所述引发剂占聚合物的2wt％。
实施例3
本例提供一种氮气发泡制备泡孔材料的方法，包括：将发泡基体交联后，得到若干个交联预制品加入装有水的反应釜中，加入氮气发泡后、泄压，加热发泡，得到所述泡孔材料。所述相邻交联预制品之间的距离和交联预制品的厚度比为1.8：1，所述聚合物的软化点和极性液体的温度差为25℃，所述加入氮气发泡中， 加入氮气的温度为35℃，加入氮气的压力为15MPa，保压1.5h后，加压至35MPa，保压4h，所述泄压的速率为3.5MPa/s，所述加热发泡的温度为150℃，时间为1h。所述发泡基体的制备原料包括聚合物、交联剂、引发剂，所述聚合物为PP(软化点为150℃)，购自大韩油化的5010，所述交联剂为1,1-二特戊基过氧化环己烷，所述引发剂为偶氮二异丁腈，所述交联剂占聚合物的3wt％，所述引发剂占聚合物的3wt％。
实施例4
本例提供一种氮气发泡制备泡孔材料的方法，包括：将发泡基体交联后，得到若干个交联预制品加入装有水的反应釜中，加入氮气发泡后、泄压，加热发泡，得到所述泡孔材料。所述相邻交联预制品之间的距离和交联预制品的厚度比为1.8：1，所述聚合物的软化点和极性液体的温度差为5℃，所述加入氮气发泡中，加入氮气的温度为35℃，加入氮气的压力为15MPa，保压1.5h后，加压至35MPa，保压4h，所述泄压的速率为3.5MPa/s，所述加热发泡的温度为150℃，时间为1h。所述发泡基体的制备原料包括聚合物、交联剂、引发剂，所述聚合物为PP(软化点为150℃)，购自大韩油化的5010，所述交联剂为1,1-二特戊基过氧化环己烷，所述引发剂为偶氮二异丁腈，所述交联剂占聚合物的3wt％，所述引发剂占聚合物的3wt％。
实施例5
本例提供一种氮气发泡制备泡孔材料的方法，包括：将发泡基体交联后，得到若干个交联预制品加入装有水的反应釜中，加入氮气发泡后、泄压，加热发泡，得到所述泡孔材料。所述相邻交联预制品之间的距离和交联预制品的厚度比为1.8：1，所述聚合物的软化点和极性液体的温度差为25℃，所述加入氮气发泡中，加入氮气的温度为35℃，加入氮气的压力为35MPa，保压4.5h，所述泄压的速率为3.5MPa/s，加热发泡的温度为150℃，时间为1h。所述发泡基体的制备原料包括聚合物、交联剂、引发剂，所述聚合物为PP(软化点为150℃)，购自大韩油化的5010，所述交联剂为1,1-二特戊基过氧化环己烷，所述引发剂为偶氮二异丁腈，所述交联剂占聚合物的3wt％，所述引发剂占聚合物的3wt％。
性能评价
1、预发泡倍率：测量加入氮气发泡、泄压后得到的预泡孔材料和交联制品 的厚度分别为L2和L1，则为预发泡倍率L2/L1，计算同批次的10个交联预制品的平均预发泡倍率和发泡倍率的标准差。标准差在0.1倍以内为优，结果见表1。
2、发泡倍率：测量泡孔材料和交联制品的厚度分别为L3和L1，则发泡倍率为L3/L1。倍，结果见表1。
3、泡孔均匀性：用显微镜观察泡孔材料的截面泡孔均匀性，其中泡孔均匀，无大泡孔为优，其中实施例1～3的泡孔材料的SEM图如图1～3所示，可观察到泡孔均匀，结果见表1。
表1
Figure PCTCN2022079783-appb-000001
由测试结果可知，本发明提供的泡孔材料的制备方法，通过将发泡基体加入极性液体和氮气环境中浸渍后，进行发泡，可提高发泡的稳定性和泡孔均匀性，得到高发泡倍率和均匀的泡孔材料。
应理解，本文中描述的实施方式应仅在描述的意义上考虑且不用于限制的目的。各实施方式内的特征、优点或方面的描述应被认为可用于其它实施方式中的其它类似特征、优点或方面。

Claims (10)

  1. 一种氮气发泡制备泡孔材料的方法，其特征在于，包括：将发泡基体交联后，得到若干个交联预制品加入装有极性液体的反应釜中，加入氮气发泡后、泄压，加热发泡，得到所述泡孔材料。
  2. 根据权利要求1所述的氮气发泡制备泡孔材料的方法，其特征在于，所述发泡基体的制备原料包括聚合物，所述聚合物为橡胶和/或塑料。
  3. 根据权利要求1所述的氮气发泡制备泡孔材料的方法，其特征在于，所述发泡基体交联的方法选自热固化、紫外固化、辐射固化中的一种。
  4. 根据权利要求1所述的氮气发泡制备泡孔材料的方法，其特征在于，所述极性液体的官能团选自羟基、羰基、酯基中的至少一种。
  5. 根据权利要求4所述的氮气发泡制备泡孔材料的方法，其特征在于，当官能团包括羟基时，所述极性液体包括羟基非碳化合物。
  6. 根据权利要求5所述的氮气发泡制备泡孔材料的方法，其特征在于，所述极性液体还包括羟基碳化合物、烷烃化合物、脂肪酸中的至少一种。
  7. 根据权利要求1～6任意一项所述的氮气发泡制备泡孔材料的方法，其特征在于，相邻交联预制品之间的距离和交联预制品的厚度比为(1.5～2)：1。
  8. 根据权利要求1～6任意一项所述的氮气发泡制备泡孔材料的方法，其特征在于，所述聚合物的软化点和极性液体的温度差为20～30℃。
  9. 根据权利要求1～6任意一项所述的氮气发泡制备泡孔材料的方法，其特征在于，所述加入氮气发泡中，加入氮气的温度为30～40℃，加入氮气的压力为10～20MPa，保压1～2h后，加压至30～40MPa，保压3～5h。
  10. 根据权利要求1～6任意一项所述的氮气发泡制备泡孔材料的方法，其特征在于，所述泄压的速率为3～4MPa/s。
PCT/CN2022/079783 2021-08-16 2022-03-08 一种氮气发泡制备泡孔材料的方法 WO2023019920A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP22729024.4A EP4389385A1 (en) 2021-08-16 2022-03-08 Method for preparing cell material by nitrogen foaming
US17/773,853 US20240174829A1 (en) 2021-08-16 2022-03-08 A method for preparing foaming materials by nitrogen foaming
JP2022540863A JP7455213B2 (ja) 2021-08-16 2022-03-08 窒素発泡によって発泡材料を調製する方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110935419 2021-08-16
CN202110935419.6 2021-08-16

Publications (1)

Publication Number Publication Date
WO2023019920A1 true WO2023019920A1 (zh) 2023-02-23

Family

ID=85239437

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/079783 WO2023019920A1 (zh) 2021-08-16 2022-03-08 一种氮气发泡制备泡孔材料的方法

Country Status (4)

Country Link
US (1) US20240174829A1 (zh)
EP (1) EP4389385A1 (zh)
JP (1) JP7455213B2 (zh)
WO (1) WO2023019920A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106867228A (zh) * 2015-12-10 2017-06-20 福建新峰二维材料科技有限公司 一种改性热塑性聚氨酯弹性体发泡材料的制备方法
DE102016008038A1 (de) * 2016-07-01 2018-01-04 Promix Solutions Ag Verfahren zur Herstellung eines PET-Schaumkörpers
CN108047702A (zh) * 2018-01-26 2018-05-18 青岛科技大学 一种热塑性弹性体及其发泡材料
CN108102338A (zh) * 2018-01-26 2018-06-01 青岛科技大学 一种发泡鞋中底
CN110343330A (zh) 2019-05-24 2019-10-18 天津市大林新材料科技股份有限公司 一种交联聚丙烯发泡材料及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102229708B (zh) 2011-05-16 2013-06-05 四川大学 高发泡倍率高密度聚乙烯微孔发泡型材及其制备方法
JP5809895B2 (ja) 2011-09-13 2015-11-11 古河電気工業株式会社 ポリフェニレンサルファイド発泡体およびその製造方法
GB201409248D0 (en) 2014-05-23 2014-07-09 Zotefoams Plc Method for producing three dimensional foam articles
JP2019044123A (ja) 2017-09-06 2019-03-22 積水化成品工業株式会社 熱可塑性エラストマー発泡性粒子の製造方法及び発泡成形体の製造方法
CN112476929A (zh) 2020-09-27 2021-03-12 福建兴迅新材料科技有限公司 一种超临界流体低温二次发泡工艺

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106867228A (zh) * 2015-12-10 2017-06-20 福建新峰二维材料科技有限公司 一种改性热塑性聚氨酯弹性体发泡材料的制备方法
DE102016008038A1 (de) * 2016-07-01 2018-01-04 Promix Solutions Ag Verfahren zur Herstellung eines PET-Schaumkörpers
CN108047702A (zh) * 2018-01-26 2018-05-18 青岛科技大学 一种热塑性弹性体及其发泡材料
CN108102338A (zh) * 2018-01-26 2018-06-01 青岛科技大学 一种发泡鞋中底
CN110343330A (zh) 2019-05-24 2019-10-18 天津市大林新材料科技股份有限公司 一种交联聚丙烯发泡材料及其制备方法

Also Published As

Publication number Publication date
JP2023541496A (ja) 2023-10-03
EP4389385A1 (en) 2024-06-26
JP7455213B2 (ja) 2024-03-25
US20240174829A1 (en) 2024-05-30

Similar Documents

Publication Publication Date Title
WO2021077690A1 (zh) 可发泡聚丙烯组合物和发泡聚丙烯及其制备方法
CN101215394B (zh) 可降解环保型聚丙烯泡沫塑料及其制备方法
CN114341237B (zh) 聚丙烯系树脂发泡颗粒、其制造方法及聚丙烯系树脂发泡成型体
JP2009144096A (ja) ポリプロピレン系樹脂発泡粒子、及びその発泡粒子成形体
CN112759825B (zh) 纤维增强聚丙烯组合物和发泡聚丙烯复合材料及其制备方法
WO2021017579A1 (zh) 一种添加剂改性的聚丙烯发泡材料及其制备方法
WO2018094763A1 (zh) 一种酚酞基聚芳醚酮结构泡沫材料的制备方法
CN108084324B (zh) 一种高强度异型聚(甲基)丙烯酰亚胺泡沫的制备方法
WO2023019920A1 (zh) 一种氮气发泡制备泡孔材料的方法
CN107674233A (zh) 聚碳酸酯微孔发泡材料的制备方法
CN110054802A (zh) 一种制备等规聚丙烯微纳跨尺度泡孔结构材料的方法
CN110746633B (zh) 一种微孔聚甲基丙烯酰亚胺泡沫的制备方法
CN110216826B (zh) 具有取向孔洞的可用于压电材料的发泡聚丙烯及其制备法
CN111004456B (zh) 一种质轻高强耐热聚氯乙烯泡沫材料及其制备方法
CN113754806B (zh) 一种发泡聚苯乙烯的制备方法
JP2003313353A (ja) ポリプロピレン系樹脂発泡粒子
CN115850783A (zh) 低密度增韧聚丙烯发泡材料组合物以及低密度增韧聚丙烯发泡材料及其制备方法
JPH10292064A (ja) 変性プロピレン系樹脂発泡粒子
WO2023019919A1 (zh) 一种使用二氧化碳溶液发泡的工艺
CN111234385A (zh) 一种基于超临界二氧化碳的聚丙烯发泡材料及其制备方法
CN117734091A (zh) 一种高效制备高倍率热塑性弹性体泡沫的方法
CN112708258B (zh) 一种聚甲基丙烯酰亚胺泡沫、其制备方法及应用
CN111825877B (zh) 聚丙烯发泡材料及其制备方法
CN115960383B (zh) 一种制备物理发泡材料的方法
KR102327528B1 (ko) 경질 발포폼용 염화비닐계 중합체, 이의 제조방법 및 이를 포함하는 경질 발포폼

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 17773853

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2022540863

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22729024

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2022729024

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022729024

Country of ref document: EP

Effective date: 20240318