CN106470808A - 经处理的多孔材料 - Google Patents
经处理的多孔材料 Download PDFInfo
- Publication number
- CN106470808A CN106470808A CN201580033576.0A CN201580033576A CN106470808A CN 106470808 A CN106470808 A CN 106470808A CN 201580033576 A CN201580033576 A CN 201580033576A CN 106470808 A CN106470808 A CN 106470808A
- Authority
- CN
- China
- Prior art keywords
- cellulosic material
- polymer
- arrives
- alkyl
- modifying agent
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
- B27K3/153—Without in-situ polymerisation, condensation, or cross-linking reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
- B27K3/0292—Processes; Apparatus involving an additional treatment during or after impregnation for improving fixation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/20—Compounds of alkali metals or ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/36—Aliphatic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
- D21H17/43—Carboxyl groups or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/20—Removing fungi, molds or insects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/70—Hydrophobation treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
- C08L23/0876—Neutralised polymers, i.e. ionomers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
Abstract
本公开描述了经处理的纤维素材料,其包含:具有限定多个孔的多孔结构的纤维素材料,孔的至少一部分含有处理剂,所述处理剂包含:包含烯烃‑羧酸共聚物的聚合物;以及包含季化合物的改性剂。
Description
背景技术
多孔材料(如纤维素材料)需加保护以防止霉变、昆虫侵袭、腐烂以及浸水,从而有助于保持纤维素材料的物理特性。这种纤维素材料的一个实例为木材。已知多种处理剂和保存方法可保存纤维素材料。
现代保存方法通常涉及用处理剂压力处理纤维素材料。压力处理通常使得处理剂渗入纤维素材料的整个多孔结构中。处理剂通常为一种经选择以赋予纤维素材料所期望物理特性的化合物。举例来说,提高纤维素材料硬度、增加纤维素材料耐水性以及改进纤维素材料尺寸稳定性的处理剂是令人感兴趣的。木材在水中的吸收能力多达其重量的100%,从而引起木材膨胀,在经由蒸发而发生水损失之后,引起木材收缩。这个水吸收/蒸发过程是不均匀的且在木材中产生内应力,导致裂开、翘曲、弓形、弯曲、扭曲、卷曲等。另外,水可充当使纤维素材料降解的生物体(诸如昆虫或真菌)的路径。驱赶昆虫或使真菌/霉菌形成降到最低或改善纤维素材料的整体耐久性的处理剂是令人感兴趣的。另外,处理剂可改进抗风性、抗紫外辐射、高温和低温下的稳定性、抗害虫性、抗霉性、耐火性以及可能影响纤维素材料物理特性的其它问题。
白蚁是造成木材损坏的最显著昆虫类群中的一种。为了减轻白蚁损坏,已采用使用自然耐久的木材种类、防腐处理和经工程改造的木制品。然而,由于耐久木材的有限可供使用性、防腐剂提供功效所需的高百分比重量增加和工程化木材的“非天然”外观,对改进的抗蚁性技术的需求为合乎需要的。对木材提供抗蚁性和尺寸稳定性的技术为高度合乎需要的。
用于处理木材的一种化合物为季铵化合物,在本文中被称作季化合物。已知季化合物增加木材的抗昆虫和抗真菌性。还已知季化合物从木材解离,并且可为皮肤和呼吸刺激物并引起对水生系统的损害。季化合物的另一个缺点为它们可表现为表面活性剂并且使木材曝露于雨,更容易地吸取湿气。
经改进的纤维素材料处理剂是所期望的。具体来说,防止季化合物从纤维素材料解离同时仍然维持良好抗昆虫和抗真菌性的处理剂是期望的。此外,当使用季化合物时改进的尺寸稳定性是期望的。
发明内容
本公开描述了经处理的纤维素材料,其包含:具有限定多个孔的多孔结构的纤维素材料,孔的至少一部分含有处理剂,所述处理剂包含:包含烯烃-羧酸共聚物的聚合物;以及包含季化合物的改性剂。
本公开另外描述了用于制备经处理的纤维素材料的方法,其包含:提供纤维素材料;包含用包含聚合物的水分散液浸渍纤维素材料的第一处理方案,聚合物包含烯烃-羧酸共聚物;以及包含用改性剂浸渍纤维素材料的第二处理方案,改性剂包含季化合物。
具体实施方式
“经处理的纤维素材料”为一种已用处理剂处理以改性纤维素材料特性的纤维素材料。经处理剂改性的特性包括(但不限于)增强的疏水性、尺寸稳定性、抗真菌性、抗霉性、抗昆虫性、硬度、表面外观、UV稳定性、防火性以及可涂布性。通过降低水吸收和蒸发速率来增强纤维素材料的疏水性能够提供其它辅助益处,如尺寸稳定性,从而降低膨胀以及收缩的内应力。
“处理剂”为当与纤维素材料组合时使纤维素材料特性改性的物质。在一种情况下,处理剂包含聚合物和改性剂。将处理剂施加到纤维素材料中。一种将处理剂施加到纤维素材料的方法是通过使用压力处理的浸渍。在一种情况下,聚合物作为分散液的一部分施加到纤维素材料中。已知施加处理剂的其它方法,如刷涂、涂布、喷涂、浸涂、浸泡以及挤压。一旦施加,则处理剂将渗入纤维素材料的至少一部分孔中。
“处理剂”为当与纤维素材料结合时改性纤维素材料特性的物质。在一种情况下,处理剂包含聚合物和改性剂。将处理剂施加到纤维素材料中。一种将处理剂施加到纤维素材料的方法是通过使用压力处理的浸渍。已知施加处理剂的其它方法,如刷涂、涂布、喷涂、浸涂、浸泡以及挤压。一旦施加,则处理剂将渗入纤维素材料的至少一部分孔中。
如本文所使用,聚合物是指由一种或多种类型的单体形成的分子。聚合物优选为共聚物或共聚物与聚合物的混合物。如本文所用,共聚物可是指交替共聚物、周期共聚物、统计共聚物、无规共聚物、嵌段共聚物、接枝共聚物或如所知的其它共聚物。如本文所使用,共聚物是指通过合并两个或更多个单体形成的聚合物。共聚物实例包括二元共聚物、三元共聚物、四元共聚物以及其它更高次元共聚物。在一种情况下,聚合物包含烯烃-羧酸共聚物。在一种情况下,所述烯烃-羧酸共聚物包含选自包含以下的群组的呈聚合形式的单体:乙烯、丙烯、1-丁烯、3-甲基-1-丁烯、4-甲基-1-戊烯、3-甲基-1-戊烯、1-庚烯、1-己烯、1-辛烯、1-癸烯、1-十二碳烯、丁二烯、苯乙烯、(甲基)丙烯酸、顺丁烯二酸、顺丁烯二酸酐或其混合物。在一种情况下,苯乙烯丙烯酸分散液是合适的,例如可购自陶氏化学公司(The DowChemical Company)的OrotanTM CA-2005。存在于混合物中的其它合适聚合物及/或共聚物包括弹性体、塑料以及纤维。
在某些实施例中,聚合物包含极性烯烃聚合物,其具有极性基团作为共聚单体或接枝单体。如本文所使用,极性烯烃聚合物为含有一个或多个极性基团的烯烃(共)聚合物。在例示性实施例中,聚合物可例如包含一种或多种极性聚烯烃,其具有共聚单体或接枝单体形式的极性基团。极性基团的实例包括羧酸、羧酸酐、羧酸酯、羧酸盐以及羧酸酰胺。例示性极性聚烯烃包括(但不限于)乙烯/丙烯酸(EAA)和乙烯/甲基丙烯酸(EMAA)共聚物,如以商标PRIMACORTM(可商购自陶氏化学公司)、NUCRELTM(可商购自杜邦公司(E.I.DuPont deNemours))和ESCORTM(可商购自埃克森美孚化学公司(ExxonMobil Chemical Company))可用的共聚物。例示性共聚物也包括乙烯/顺丁烯二酸酐共聚物,如可以AMPLIFYTM GR商标商购自陶氏化学公司的那些。例示性共聚物进一步包括乙烯/顺丁烯二酸酐以及丙烯/顺丁烯二酸酐共聚物,如可以LICOCENETM商标商购自科莱恩国际有限公司(ClariantInternational Ltd.)的那些。其它例示性基础聚合物包括(但不限于)乙烯/乙酸乙烯酯共聚物、乙烯/丙烯酸乙酯(EEA)共聚物、乙烯/甲基丙烯酸甲酯(EMMA)共聚物以及乙烯丙烯酸丁酯(EBA)共聚物。
其它烯烃-羧酸共聚物也可以用作聚合物。具有酯或酸酐官能团的共聚物可以转化成羧酸,或聚合物也可以通过本领域技术人员已知的方法对官能羧酸盐进行化学改性而得到。也可以修饰聚合物以形成其它官能团,如酯或酰胺等。本领域的普通技术人员将认识到,也可以使用多种其它适用的聚合物。
在一个实施例中,基础聚合物可例如包含选自由以下组成的群组的极性聚烯烃:乙烯/丙烯酸(EAA)共聚物、乙烯/甲基丙烯酸共聚物(EMAA)及其组合。在一种情况下,聚合物包含单独或与其它聚合物或共聚物混合的乙烯/(甲基)丙烯酸共聚物。
如本文所使用,在如丙烯酸酯的另一术语之前使用的术语“(甲基)”是指丙烯酸酯与甲基丙烯酸酯。举例来说,术语“(甲基)丙烯酸酯”是指丙烯酸酯或甲基丙烯酸酯;术语“(甲基)丙烯酸类”是指丙烯酸类或甲基丙烯酸类;且术语“(甲基)丙烯酸”是指丙烯酸或甲基丙烯酸。
在一种情况下,聚合物为水性分散液的组成部分。在一种情况下,分散液为包含聚合物、水以及一种或多种有机溶剂的介质。制备水性分散液使得分散液中的悬浮颗粒尺寸适于穿过纤维素材料孔以便分布于整个纤维素材料中。在一种情况下,分散液也包含一种或多种添加剂。在一种情况下,存在于水性分散液中的任何固体保持于稳定悬浮液中并且可通过分散液输送到纤维素材料的孔中。在一种情况下,分散液的固体含量为1重量%到75重量%。在一种情况下,有机溶剂为氧化溶剂、烃溶剂、卤化溶剂或其组合。
聚合物的羧酸部分用中和剂至少部分地中和以形成稳定水性分散液。如本文所用,中和剂为其中与羧酸的反应可潜在地引起盐形成的任何材料。在一种情况下,中和剂选自碱金属的氢氧化物、氨或其有机衍生物(包括胺)。在一种情况下,中和剂为强碱或弱碱。举例来说,中和剂可以为氢氧化钠、氢氧化钾或氨或胺,如单乙醇胺(MEA)、三乙醇胺(TEA)、二乙基乙醇胺(DEEA)或二甲基氨基乙醇(DMEA)。稳定分散液为适于穿过纤维素材料的孔的分散液。中和剂中和聚合物的至少一部分羧酸基。如本文所用,羧酸基团的中和是指其中使羧酸基团的氢转移的任何反应。在一种情况下,聚合物中5摩尔%到100摩尔%的羧酸基团通过中和剂中和。在另一情况下,10摩尔%到80摩尔%的羧酸基团通过中和剂中和。在又另一情况下,20摩尔%到70摩尔%的羧酸基团通过中和剂中和。
改性剂为当与聚合物组合提高纤维素材料的疏水性、尺寸稳定性和抗昆虫性的物质。在一种情况下,改性剂为包含季铵阳离子和阴离子的季铵化合物,并且在本文中被称作季化合物。合适的改性剂包括季铵化合物。合适的季铵化合物的实例包括(但不限于)具有式R1R2R3R4N+X的那些,其中R1、R2、R3和R4独立地为碳取代基,其为直链、支化、环状或其任何组合饱和或不饱和的,并且X为阴离子。在R1、R2、R3和R4中的碳原子数的总和大体上在约8到50的范围内。R1、R2、R3和R4可为烷基、烯基、炔基、环烷基、芳基或这些的任何组合,并且阴离子X可为氯离子、溴离子、碘离子、硼酸根、碳酸根、碳酸氢根、亚硝酸根,或羧酸根如乙酸根、月桂酸根或硬脂酸根。合适的改性剂的实例包括三甲基大豆烷基氯化铵,或烷基三甲基氯化铵/溴化铵(其中烷基可为C12、C16、C18、C12、椰油基、棕榈酰基(palmacyl)),或二烷基二甲基氯化铵/溴化铵(其中烷基可为C8、C10、C12、C16、C18、氢化牛脂)或烷基二甲基苯甲基氯化铵/溴化铵(其中烷基可为C12、C14、C16、C18、椰油基)或其混合物。
将处理剂与纤维素材料结合。在一种情况下,如本文所述,处理剂通过压力处理引入纤维素材料中。在另一情况下,处理剂通过本领域中已知的其它技术引入纤维素材料中,例如刷涂、涂布、浸涂、浸泡、喷涂以及挤压。处理剂变得浸渍于纤维素材料的至少一部分孔中,并且因此增加了纤维素材料的重量。在一种情况下,聚合物使纤维素材料的重量增加了1%到80%(如将纤维素材料干燥之后所计算)。在一种情况下,处理剂(聚合物与改性剂的组合)使纤维素材料的重量增加了5%到大于100%(如将纤维素材料干燥之后所计算)。
在一种情况下,处理剂包含一种或多种添加剂。添加剂可以作为分散液的一部分、作为改性剂的一部分包括,或可以从其中分别包括。已知使经处理纤维素材料增添特性的添加剂是合适的,如阻燃剂、分散剂及和/或染料。举例来说,添加剂可以为有机化合物、金属化合物或有机金属化合物。在一种情况下,添加剂为一种改进聚合物润湿于或渗透于木材中的材料,例如在分散液中稳定的溶剂或表面活性剂(阴离子、阳离子或非离子型)。添加剂的实例包括溶剂、填充剂、增稠剂、乳化剂、分散剂、缓冲剂、颜料、渗透剂、抗静电剂、气味物质、腐蚀抑制剂、防腐剂、渗硅剂、流变改性剂、抗沉降剂、抗氧化剂、其它交联剂(例如二元醇和多元醇)、光学增亮剂、蜡、聚结剂、杀生物剂以及消泡剂。这种蜡可包括石油蜡、石蜡、天然蜡,或合成蜡,如聚乙烯蜡或氧化聚乙烯蜡、蜂蜡、或散蜡。此外,处理剂可与木材防腐剂结合使用,所述木材防腐剂含有例如铜-氨、铜-胺、铜-氨-胺络合物、季铵化合物或其它体系。举例来说,处理剂可与碱性铜-季铵(ACQ)防腐剂体系使用。处理剂还可与使用锌盐或含硼化合物的木材防腐技术一起使用。任选地,可将其它添加剂(如杀虫剂、杀白蚁剂、杀真菌剂以及杀霉菌剂)添加到处理剂中。在一种情况下,添加剂作为分散液的一部分包括并且与其形成稳定悬浮液。在一种情况下,将一种或多种表面活性剂添加到分散液中。在一种情况下,选择使聚合物在纤维素材料表面的胶凝减少的表面活性剂。在一种情况下,选择使浸渍于纤维素材料中的聚合物的量增加的表面活性剂。举例来说,合适的表面活性剂可以为非离子、阴离子或阳离子型。非离子表面活性剂的实例包括:烷氧基化醇、烷氧基化烷基酚、脂肪酸酯、胺和酰胺衍生物、烷基聚葡糖苷、环氧乙烷/环氧丙烷共聚物、多元醇以及烷氧基化多元醇。举例来说,非离子型表面活性剂为可购自陶氏化学公司的TERGITOLTM L-62。阴离子表面活性剂的实例包括:烷基硫酸盐、烷基醚硫酸盐、硫酸化烷醇酰胺、α烯烃磺酸盐、木质素磺酸盐、磺基丁二酸盐、脂肪酸盐以及磷酸酯。阳离子表面活性剂的实例包括烷基三甲基铵盐。
在一种情况下,通过压力处理将纤维素材料制备为经处理纤维素材料。用于压力处理纤维素材料的压力可高于大气压或低于大气压。在一种情况下,压力低于环境压力,例如0.0001MPa到0.09MPa(0.75mmHg到675mmHg)。在另一情况下,压力大于环境压力,例如0.1MPa到1.7MPa(750mmHg到12750mmHg)。据设想,本领域中已知的压力处理方法适用于用处理剂浸渍纤维素材料。
在一种情况下,经处理的纤维素材料根据至少第一处理方案和第二处理方案制备。在一种情况下,第一处理方案包含用聚合物浸渍纤维素材料。第一处理方案包含以下步骤中的一项或多项:(a)使纤维素材料在容器中沉积;(b)使容器在真空下保持5到60分钟;(c)将聚合物引入容器中;(d)将容器加压到1.03MPa维持5到60分钟;(e)排放过量聚合物;(f)任选地通过真空去除过量聚合物;和(g)将纤维素材料在20℃到60℃下空气干燥24到48小时。在一种情况下,聚合物为水分散液的一部分。
在一种情况下,第一处理方案的产物随后根据第二处理方案制备,所述第二处理方案用改性剂浸渍纤维素材料。第二处理方案包含以下步骤中的一项或多项:(a)使根据第一处理方案制备的纤维素材料在容器中沉积;(b)将改性剂引入容器中;(c)将容器维持在真空或增加的压力下5到60分钟;(d)任选地通过真空去除过量改性剂;和(e)将纤维素材料在60℃下空气干燥24到48小时。
若干个干燥步骤可在一系列温度下进行,从而空气干燥步骤的持续时间与温度成比例。合适的空气干燥温度在室温(约20℃)和180℃之间。干燥可以在空气中、在氮气中或其它合适的气氛中进行。
利用水浸测试,根据美国木材保护协会标准(American Wood ProtectionAssociation Standard)E4至11程序(《经压缩处理木材的防水性标准测试方法(StandardMethod of Testing Water Repellency of Pressure Treated Wood)》)测定经处理纤维素材料的防水性。水浸测试包括:首先,提供包含如本文所述制备的经处理的纤维素材料的经处理薄片,与包含根据本文所述第一处理方案处理(但其中分散液用蒸馏水替换)的纤维素材料的对照薄片;第二,测量经处理薄片和对照薄片两者的切向尺寸,以得到初始切向尺寸(T1)(其中切向尺寸垂直于纤维素材料的颗粒方向);第三,将经处理薄片和对照薄片两者都放入维持在65±3%相对湿度和21℃±3℃的调节室中,直到实现恒重;第四,将经处理薄片和对照薄片两者都浸渍于24℃±3℃的蒸馏水中30分钟;和第四,从水中移出后,测量经处理薄片和对照薄片两者的切向尺寸,以得到后切向尺寸(T2)。
DoN是指聚合物中的羧酸官能团的中和度。
各单独薄片(经处理薄片与对照薄片两者)的膨胀百分比(S)如下计算:
在本文的每个实例中,对照薄片的膨胀百分比为4.7%。
防水效率(WRE)用于测定为经处理纤维素材料提高防水特性的处理剂的有效性。WRE计算为:
S1是指未处理薄片的膨胀百分比;S2是指经处理薄片的膨胀百分比。根据E4-11,对于大部分户外应用来说,75%的最小WRE为优选的。未经任何处理的原始木材的WRE为0%。
根据肖氏(硬度计)测试,使用D型硬度计(30°锥体,1.40mm直径,2.54mm延长,44.48N弹簧力)测定经处理的纤维素材料的硬度。使用D型硬度计,通过将纤维素材料放置于硬平坦表面上来测定硬度,且硬度计的压脚是利用抵抗纤维素材料的给定弹簧力按压。在与纤维素材料接触的一秒内,记录硬度计上的量表的硬度值。每个纤维素材料的样品进行至少五次硬度测试。在本文中报告的硬度值为对给定纤维素材料进行的测试的平均值。未处理薄片的硬度值为40。
通过制备两组每组八个样品确定经处理的木材的抗白蚁性,第一组样品包含根据特定处理范围制备的木材的八个薄片(测试样品),第二组样品包含未处理的木材的八个薄片(对照样品)。样品中的每个通过首先将样品在49℃下干燥24小时制备。然后称量样品。将白蚁的两个群落(黄胸散白蚁,每个群落重复四次处理,每次重复100个职蚁)放入保持在28℃和60%相对湿度下的Conviron生长箱(CG72型)中,并且保持七天。在七天之后,通过将样品的消耗和测试样品的白蚁死亡与对照样品比较观察木材抗白蚁性。在其中在第一个七天之后白蚁的生存保持高的情况下,样品和白蚁返回到Conviron维持另外七天,并且随后评估。
以下实例说明本公开的某些方面,但本公开的范围不限于以下实例。
如本领域中已知,以下实例中的分散液通过将聚合物与给定量的碱组合于120℃下的加压混合容器中来制得(例如,合适的分散液可以根据陶氏化学公司的“PRIMACOR共聚物的水性分散液的制备”来制备)。在实例中的所有真空操作都是在-0.00399MPa到-0.00267Mpa的范围内。实例中的所有真空操作都是在0.00399MPa到0.00267Mpa的范围内。
实例1
松木薄片(南方黄松,4cm×2cm×0.5cm)通过砝码(在此使用环)保持在帕尔(Parr)反应器的底部。将反应器压力设定成真空维持30分钟。将包含20重量%Primacor5980的80mL的分散液(具有MEA的50%DoN,8.21pH,117nm的粒度)和80重量%水引入到反应器。然后在氮气下将反应器压力设定成1.03MPa维持60分钟。然后将薄片放入烘箱中并且在60℃下空气干燥48小时。薄片通过砝码保持于反应器底部。用足够的三甲基大豆烷基氯化铵溶液(在异丙醇和水中的50%活性剂,Davies HLB 20.8,以Arquad SV-50由阿克苏诺贝尔(Akzonobel)出售)填充反应器以浸没薄片。反应器压力设定为真空维持60分钟。然后将薄片放入烘箱中且在60℃下空气干燥48小时,由此提供经处理的薄片。薄片的第一段和对照薄片各自根据E4-11程序处理。薄片的第一段的溶胀百分比为1.5%;薄片的第一段的WRE为66.67%。经处理的薄片的硬度使用D型硬度计测量为37.6。抗白蚁性测试:对照样品消耗为70.63mg,而测试样品消耗为1.72mg。
实例示出,当纤维素材料含有包括聚合物和改性剂两者的处理剂时,获得有利的WRE结果。然而,其中纤维素材料尚未通过聚合物和改性剂两者处理,未获得有利的WRE结果。实例另外示出与未处理的木材相比经处理的纤维素材料呈现改进的抗白蚁性。
Claims (15)
1.一种经处理的纤维素材料,其包含:
具有限定多个孔的多孔结构的纤维素材料,所述孔中的至少一部分含有处理剂,所述处理剂包含:
包含烯烃-羧酸共聚物的聚合物;以及
包含季化合物的改性剂。
2.根据权利要求1所述的经处理的纤维素材料,其中所述共聚物的所述羧酸基的至少一部分被中和。
3.根据权利要求1到权利要求2中任一项所述的经处理的纤维素材料,其中所述烯烃-羧酸共聚物包含选自包含以下各项的群组的呈聚合形式的单体:乙烯、丙烯、1-丁烯、3-甲基-1-丁烯、4-甲基-1-戊烯、3-甲基-1-戊烯、1-庚烯、1-己烯、1-辛烯、1-癸烯、1-十二碳烯、丁二烯、苯乙烯或其混合物。
4.根据权利要求1到权利要求3中任一项所述的经处理的纤维素材料,其中所述烯烃-羧酸共聚物包含选自包含以下各项的群组的呈聚合形式的羧酸单体或酸酐单体:丙烯酸、马来酸顺丁烯二酸酐或其混合物。
5.根据权利要求1到权利要求4中任一项所述的经处理的纤维素材料,其中所述聚合物包含除了所述烯烃-羧酸共聚物之外的一种或多种聚合物的混合物。
6.根据权利要求1到权利要求5中任一项所述的经处理的纤维素材料,其中所述改性剂包含式R1R2R3R4N+X的季铵化合物,其中每个R1、R2、R3和R4独立地为烷基、烯基、炔基、环烷基、芳基或这些的任何组合,并且所述阴离子X为氯离子、溴离子、碘离子、硼酸根、碳酸根、碳酸氢根、亚硝酸根或羧酸根,如乙酸根、月桂酸根或硬脂酸根或其组合。
7.根据权利要求1到权利要求6中任一项所述的经处理的纤维素材料,其中所述改性剂为具有C12-C18烷基的烷基三甲基氯化铵、二癸基二甲基氯化铵、具有C8-C14烷基的二烷基二甲基氯化铵、烷基二甲基苯甲基氯化铵,或具有C12-C18烷基的烷基苯甲基二甲基铵或其混合物。
8.根据权利要求1到权利要求7中任一项所述的经处理的纤维素材料,其中所述改性剂为三甲基大豆烷基氯化铵。
9.根据权利要求1到权利要求8中任一项所述的经处理的纤维素材料,其中所述改性剂通过所述聚合物至少部分保持在所述纤维素材料中。
10.根据权利要求1到权利要求9中任一项所述的经处理的纤维素材料,其中所述聚合物为乙烯-丙烯酸共聚物。
11.根据权利要求1到权利要求10中任一项所述的经处理的纤维素材料,其中所述经处理的纤维素材料通过如下制备:(1)用包含所述聚合物的水性分散液浸渍所述纤维素材料,和(2)用所述改性剂浸渍所述纤维素材料。
12.根据权利要求1到权利要求11中任一项所述的经处理的纤维素材料,其中所述处理剂另外包含一种或多种添加剂。
13.一种制备经处理纤维素材料的方法,其包含:
(a)提供纤维素材料;
(b)包含用包含聚合物的水性分散液浸渍所述纤维素材料的第一处理方案,所述聚合物包含烯烃-羧酸共聚物;以及
(c)包含用改性剂浸渍所述纤维素材料的第二处理方案,所述改性剂包含季化合物。
14.根据权利要求13所述的方法,其中所述第一处理方案的所述浸渍在高于或低于环境的压力下进行。
15.根据权利要求13到权利要求14中任一项所述的方法,其中所述改性剂为三甲基大豆烷基氯化铵、二癸基二甲基氯化铵或其混合物。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201462018946P | 2014-06-30 | 2014-06-30 | |
US62/018946 | 2014-06-30 | ||
PCT/US2015/038471 WO2016003996A1 (en) | 2014-06-30 | 2015-06-30 | Treated porous material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106470808A true CN106470808A (zh) | 2017-03-01 |
Family
ID=53541964
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201580033576.0A Pending CN106470808A (zh) | 2014-06-30 | 2015-06-30 | 经处理的多孔材料 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10201909B2 (zh) |
EP (1) | EP3160698A1 (zh) |
JP (1) | JP6523344B2 (zh) |
CN (1) | CN106470808A (zh) |
AU (1) | AU2015284279B2 (zh) |
WO (1) | WO2016003996A1 (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3105773A (en) * | 1959-10-28 | 1963-10-01 | American Cyanamid Co | Preservation of cellulosic materials |
CN1207786A (zh) * | 1995-12-05 | 1999-02-10 | 陶氏化学公司 | 对纤维材料进行外部施胶的方法 |
CN1263489A (zh) * | 1997-01-16 | 2000-08-16 | 伦萨公司 | 木材防水和防腐组合物 |
CN101562972A (zh) * | 2006-12-20 | 2009-10-21 | 雅宝公司 | 具有保护木材结构的新作用方式的季铵化合物 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3024283A (en) * | 1958-04-01 | 1962-03-06 | Armour & Co | Production of quaternary ammonium compounds |
US3389109A (en) * | 1965-07-26 | 1968-06-18 | Dow Chemical Co | Method for preparing aqueous dispersions of ethylene copolymers |
US4445688A (en) * | 1978-04-04 | 1984-05-01 | Amf Incorporated | Bowling pin having an ionomer resin cladding |
CA1146704A (en) * | 1981-02-05 | 1983-05-24 | Neil G. Richardson | Wood treatment composition |
DE3639063A1 (de) | 1986-11-14 | 1988-05-19 | Wolman Gmbh Dr | Holzschutzmittel |
DE3711680A1 (de) * | 1987-04-07 | 1988-10-27 | Hoechst Ag | Waessrige biozide kationische kunststoffdispersionen und deren verwendung als fungizide, bakterizide und algizide ausruestungsmittel |
AU7680991A (en) | 1990-10-12 | 1992-05-20 | Dow Chemical Company, The | Antimicrobial hydrogels |
ZA943999B (en) | 1993-06-09 | 1995-02-03 | Lonza Ag | Quaternary ammonium and waterproofing/preservative compositions |
US5993604A (en) * | 1995-12-05 | 1999-11-30 | The Dow Chemical Company | Internally sized articles and method for making same |
US6953501B2 (en) * | 2001-08-10 | 2005-10-11 | Inventions & Discoveries, Llc | Wood treatment composition and method of use |
JP3866668B2 (ja) * | 2002-02-28 | 2007-01-10 | 三洋化成工業株式会社 | 木材用防腐剤 |
JP4226348B2 (ja) * | 2003-01-31 | 2009-02-18 | 三洋化成工業株式会社 | 防蟻剤組成物 |
US20070167407A1 (en) | 2005-12-20 | 2007-07-19 | Albemarle Corporation | Quaternary ammonium borate compositions and substrate preservative solutions containing them |
CN102990741A (zh) * | 2011-09-09 | 2013-03-27 | 赵强 | 一种木材防腐剂 |
CN103568088B (zh) * | 2013-11-11 | 2016-02-03 | 中南林业科技大学 | 甲基丙烯酸甲酯在木材中本体聚合制备玻璃化木材的方法 |
-
2015
- 2015-06-30 CN CN201580033576.0A patent/CN106470808A/zh active Pending
- 2015-06-30 WO PCT/US2015/038471 patent/WO2016003996A1/en active Application Filing
- 2015-06-30 EP EP15736762.4A patent/EP3160698A1/en not_active Withdrawn
- 2015-06-30 AU AU2015284279A patent/AU2015284279B2/en not_active Ceased
- 2015-06-30 JP JP2016573984A patent/JP6523344B2/ja not_active Expired - Fee Related
- 2015-06-30 US US15/315,234 patent/US10201909B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3105773A (en) * | 1959-10-28 | 1963-10-01 | American Cyanamid Co | Preservation of cellulosic materials |
CN1207786A (zh) * | 1995-12-05 | 1999-02-10 | 陶氏化学公司 | 对纤维材料进行外部施胶的方法 |
CN1263489A (zh) * | 1997-01-16 | 2000-08-16 | 伦萨公司 | 木材防水和防腐组合物 |
CN101562972A (zh) * | 2006-12-20 | 2009-10-21 | 雅宝公司 | 具有保护木材结构的新作用方式的季铵化合物 |
Also Published As
Publication number | Publication date |
---|---|
AU2015284279B2 (en) | 2019-04-04 |
US20170129131A1 (en) | 2017-05-11 |
JP2017519662A (ja) | 2017-07-20 |
WO2016003996A1 (en) | 2016-01-07 |
AU2015284279A1 (en) | 2017-02-02 |
EP3160698A1 (en) | 2017-05-03 |
US10201909B2 (en) | 2019-02-12 |
JP6523344B2 (ja) | 2019-05-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106470810A (zh) | 经处理多孔材料 | |
AU2016285430A1 (en) | Treated porous material | |
CN106470808A (zh) | 经处理的多孔材料 | |
CN106573389B (zh) | 经处理的多孔材料 | |
CN106457599B (zh) | 经处理的多孔材料 | |
CN107000245A (zh) | 经处理的多孔材料 | |
AU2015284278B2 (en) | Treated porous material | |
CN107000244A (zh) | 经过处理的多孔材料 | |
EP3160700B1 (en) | Treated porous material | |
CN109963695A (zh) | 经处理多孔材料 |
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 | ||
AD01 | Patent right deemed abandoned | ||
AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20200110 |