CN110592942A - 一种提高天然纤维材料尺寸稳定性的试剂及其处理方法 - Google Patents
一种提高天然纤维材料尺寸稳定性的试剂及其处理方法 Download PDFInfo
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- CN110592942A CN110592942A CN201910890019.0A CN201910890019A CN110592942A CN 110592942 A CN110592942 A CN 110592942A CN 201910890019 A CN201910890019 A CN 201910890019A CN 110592942 A CN110592942 A CN 110592942A
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- natural fiber
- reagent
- fiber material
- polyphenol
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- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 3
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
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- JMGCAHRKIVCLFW-CNWXVVPTSA-N ellagitannin Chemical compound OC1=C(O)C(O)=CC(C(=O)O[C@H]2C3=C4C(=O)O[C@@H]2[C@@H]2[C@@H]5OC(=O)C6=CC(O)=C(O)C(O)=C6C6=C(O)C(O)=C(O)C=C6C(=O)OC[C@H]5OC(=O)C5=CC(O)=C(O)C(O)=C5C=5C(O)=C(O)C(O)=C(C=5C(=O)O2)C4=C(O)C(O)=C3O)=C1 JMGCAHRKIVCLFW-CNWXVVPTSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
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- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229950003776 protoporphyrin Drugs 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
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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
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
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- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/57—Sulfates or thiosulfates of elements of Groups 3 or 13 of the Periodic Table, e.g. alums
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- 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
- D06M13/10—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 oxygen
- D06M13/11—Compounds containing epoxy groups or precursors 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
- 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
- D06M13/10—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 oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/123—Polyaldehydes; Polyketones
-
- 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
- D06M13/10—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 oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
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- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
-
- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明涉及一种提高天然纤维材料尺寸稳定性的试剂及其处理方法,属于天然高分子材料技术领域。所述提高天然纤维材料尺寸稳定性的试剂包括A试剂和B试剂,其中,A试剂由100份水、3~25份植物多酚、0~15份醛类化合物组成;B试剂由100份水、1~30份金属盐、0~20份氨基化合物组成。本发明A试剂中的植物多酚和B试剂中的金属盐,在所述天然纤维材料的细胞内发生原位络合反应,形成“天然纤维‑植物多酚‑金属盐”动态多重牺牲键网络结构,在所述细胞的细胞壁内产生空间位阻,使其在吸湿和解吸过程中减小或不产生膨胀或收缩,从而达到提高天然纤维材料的尺寸稳定性的目的。
Description
技术领域
本发明涉及天然高分子材料技术领域,涉及一种提高天然纤维材料尺寸稳定性的试剂及其处理方法。
背景技术
环境材料已成为新材料领域的一个新的研究方向。在环境材料中,天然纤维材料扮演者越来越重要的角色。高性能天然纤维材料及其复合材料的研究、开发与应用已成为全球研究的热点。究其原因,是因为天然纤维材料具有许多突出的优点,来源丰富、价格低廉、可再生、可降解、高比性能等。但是它们也存在一些缺点:吸湿性高、尺寸稳定性差,质量不稳定等问题。而其根本原因是由于天然纤维材料中纤维素、半纤维素、淀粉、蛋白质等主要组成物质中含有大量的羟基(~OH)、羧基(~COOH)等基团,这些基团具有较强的吸湿性,当纤维中含水率高于周边环境的湿度时,会发生解吸,体积收缩;当纤维中含水率低于周边环境的湿度时,会发生吸湿,体积膨胀,从而导致尺寸不稳定,如:木、竹纤维干缩湿胀导致木、竹材料及制品开裂、变形;棉、麻、毛纤维的干缩湿胀导致纺织制品缩水;天然纤维材料尺寸不稳定严重制约了其应用。
发明内容
为解决现有技术中存在的问题,本发明提供一种提高天然纤维材料尺寸稳定性的试剂及其处理方法。所述试剂包括A试剂和B试剂,所述A试剂中的植物多酚和B试剂中的金属盐,在所述天然纤维材料的细胞内发生原位络合反应,形成“天然纤维-植物多酚-金属盐”动态多重牺牲键网络结构,在所述细胞的细胞壁内产生空间位阻,使其在吸湿和解吸过程中减小或不产生膨胀或收缩,从而达到提高尺寸稳定性的目的。
为了解决上述技术问题,本发明提供如下技术方案:
一方面,本发明提供一种提高天然纤维材料尺寸稳定性的试剂,包括A试剂和B试剂,其中,A试剂由以下质量份组分组成:100份水、3~25份植物多酚、0~15份醛类化合物;B试剂由以下质量份组分组成:100份水、1~30份金属盐、0~20份氨基化合物。
进一步的,所述植物多酚为聚棓酸酯类多酚和/或聚黄烷类多酚;所述棓酸酯类多酚包含至少有一个多元醇和多个酚羧酸,所述多元醇通过酯键与酚羧酸相连接;所述聚黄烷类多酚的分子量为500~3000,聚合物为2~10,单元之间以C~C键相连,分子骨架为C6·C3·C6结构,在两个酚香环(A环、B环)之间以一个三碳链(C~2,C~3,C~4)相连,其中一个碳原子与A环8a位置上的氧原子连接成吡喃环(C环)。
进一步的,所述醛类化合物为乙醛、乙二醛、戊二醛、甲醛的一种或多种混合物。
进一步的,所述金属盐为铁盐、铝盐、铜盐、锌盐的一种或多种。
进一步的,所述氨基化合物为尿素、酰胺、二甲胺、聚醚酰亚胺、聚赖氨酸的一种或多种。
进一步的,所述天然纤维材料包括木材、竹材、木纤维、竹纤维、棉纤维、麻纤维、毛纤维、蚕丝纤维及其原材料和/或制品。
另一方面,本发明提供一种提高天然纤维材料尺寸稳定性的处理方法,包括:
步骤1:准备适量天然纤维材料;
步骤2:把试剂A导入天然纤维材料,得到多酚天然纤维材料;
步骤3:把试剂B导入多酚天然纤维材料,得到多酚金属盐天然纤维材料;
步骤4:干燥多酚金属盐天然纤维材料,得到络合天然纤维材料。
进一步的,所述步骤2中,试剂A的添加量为天然纤维材料绝干质量的10~300%;所述步骤3中,试剂B的添加量为所述天然纤维材料绝干质量的5~200%。
进一步的,所述步骤4中,络合天然纤维材料含水率为3~16%。
进一步的,A试剂和B试剂导入时,采用加压浸渍导入,所述浸渍压力为0.1~3.5MPa,浸渍时间为5min~48h,浸渍温度为10℃-85℃。
在A试剂的导入过程中,天然纤维材料在水和醛类化合物的作用下,其细胞壁逐渐溶胀,所述植物多酚在压力作用下被逐渐地导入到所述天然纤维材料的表面、细胞壁、细胞腔和/或细胞间隙,所述多酚中的酚羟基与天然纤维材料中羟基(~OH)、羧基(~COOH)等亲水基团之间结合,产生多点氢键;所述植物多酚中的苯环与天然纤维材料中苯环、吡咯环等疏水基团之间结合,产生疏水键。
在A试剂的导入过程中,所述醛类化合物在压力的作用下,被逐渐地导入到所述多酚天然纤维材料的表面、细胞壁、细胞腔和/或细胞间隙中,在后续的干燥过程,与细胞壁纤维素中的醇羟基在热引发和金属盐的催化作用下,在细胞微反应器内发生反应,形成稳定的醚键。
在B试剂的导入过程中,所述金属盐在水和压力作用下,被逐渐地导入到所述多酚天然纤维材料的表面、细胞壁、细胞腔和/或细胞间隙中,并与植物多酚在细胞微反应器内发生原位络合反应,植物多酚中邻位二酚羟基与金属离子螯合,形成五元环络合物。
在干燥过程中,醛类化合物、氨基化合物与植物多酚在热引发和金属盐的催化作用下,在天然纤维材料细胞微反应器内发生了缩聚、加成反应,形成三维网状结构。
与现有技术相比,本发明具有以下有益效果:
本发明中,在天然纤维材料的细胞壁内引入植物多酚和金属盐,利用植物多酚的酚羟基与与天然纤维材料亲水基团:羟基(~OH)、羧基(~COOH)之间结合产生多点氢键结合,同时,邻位酚羟基与金属离子络合,将相邻的纤维素/半纤维素的分子链交联成网状结构,犹如在天然纤维材料的分子链支上了若干支架支撑,使其在吸湿或解吸时减小甚至不产生膨胀或收缩;在上述的基础上,在天然纤维材料的骨架内形成了大量的由氢键(植物多酚酚羟基和天然纤维材料中的羟基结合形成了多点氢键)和配位键(植物多酚酚环上的邻位羟基与金属盐络合形成了配位键)组成的多重牺牲键网络,此外,金属盐与水结合,使细胞壁内的水形成结晶水,从而使天然纤维材料密度增加,水与金属盐之间形成了氢键,在常温下,使木材中的结合水含量增加,提高了木材的塑性,从而提高了材料的稳定性。由于牺牲键键能小于共价键(纤维素、半纤维素、木质素以及蛋白质之间形成了共价键网络),当天然纤维材料受到内应力或外力作用时,牺牲键优先于共价键断裂。牺牲键不断地断裂和重构的动态作用,耗散了天然纤维材料体系内的大量能量,消除或削弱了内应力,保护了纤维素骨架共价键网络的完整。这为解决天然纤维材料的开裂问题提供了新方法。
本发明首先将把植物多酚导入天然纤维材料,使天然纤维材料发生了润胀;然后向其中导入金属盐,植物多酚与天然纤维材料中羟基(~OH)、羧基(~COOH)等亲水基团结合,形成多点氢键,同时,植物多酚与金属盐络合,将“天然纤维-植物多酚-金属盐”结合成一体,犹如在天然纤维的骨架分子中形成了若干支架支撑;然后,伴随的水分的蒸发和氧化反应,“天然纤维-植物多酚-金属盐”进一步交联和氧化,最终形成络合天然纤维材料。本发明“天然纤维-植物多酚-金属盐”动态多重牺牲键网络结构,支撑起纤维素、半纤维素、蛋白质等天然高分子,使其在吸湿或解吸时形成了空间位阻,减小甚至不产生膨胀或收缩,同时牺牲键不断地断裂和重构的动态作用,耗散了天然纤维材料体系内的大量能量,消除或削弱了内应力,保护了天然纤维材料骨架共价键网络的完整,从分子水平解决了天然纤维材料易开裂问题。
附图说明
图1为本发明实施例1试剂的紫外吸收光谱图;
图2为本发明实施例1中植物多酚与金属盐之间的络合化学结构式;
图3为本发明实施例3试剂的紫外吸收光谱图;
图4为本发明实施例4多酚木材的化学结构式;
图5为本发明实施例4未处理杨木、多酚杨木和络合杨木热重图;其中,1是未处理杨木,2是多酚杨木,3是络合杨木;
图6为本发明实施例4络合木材的化学结构式;
图7为本发明实施例5未处理竹集成材和络合竹集成材热重图;其中,1是未处理竹集成材,2是络合竹集成材;
图8为本发明实施例5络合竹材集成材化学式;
图9为本发明实施例6络合纤维化学结构式。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚,下面将结合具体实施例进行详细描述。
本发明中,所使用的材料及试剂未有特殊说明的,均可从商业途径得到。
实施例1
一种提高天然纤维材料尺寸稳定性的试剂,包括A试剂和B试剂,其中:
A试剂由以下质量份组分组成:100份水、3份单宁酸,所述单宁酸为2-多-O-棓酰基-1,3,4,6-四-O-棓酰基-β-D-葡萄糖,多棓酰基平均含有3个棓酰基,以缩合酚的形式存在,其结构其分子结构式为:
B试剂由以下质量份组分组成:100份水、1份硫酸亚铁。
将试剂A和试剂B按摩尔比1:1混合后,采用紫外吸收光谱仪分析(以单宁酸为参比),在330nm处出现了明显的吸收峰,如图1所示,说明单宁酸与金属盐发生了络合反应,形成了五元环配位键,如图2所示,其中,M为Fe,n为2。
实施例2
一种提高天然纤维材料尺寸稳定性的试剂,包括A试剂和B试剂,其中:
A试剂由以下质量份组分组成:100份水、25份鞣化单宁、20份戊二醛;所述鞣花单宁含有4个去氢二棓酰基和1个去氢二羟基二酚,二者通过糖核间连接键形式存在,其结构式为:
B试剂由以下质量份组分组成:100份水、15份硫酸铝。
将试剂A和试剂B按摩尔比1:2混合后,采用紫外吸收光谱仪分析(以单宁酸为参比),在330nm和393nm处出现了两个明显的吸收峰,如图3所示,说明鞣花单宁与金属盐发生了络合反应,形成了五元环配位键,并与戊二醛发生了聚合。
实施例3
一种提高天然纤维材料尺寸稳定性的试剂,包括A试剂和B试剂,其中,A试剂由以下质量份组分组成:100份水、15份黑荆树皮单宁、10份二甲胺;所述黑荆树皮单宁的A环为70%间苯二酚型的原刺槐定和25%原菲瑟定组成,B环为间苯三酚,平均分子量为1250,分子结构式为:
B试剂由以下质量份组分组成:100份水、1~30份硫酸铝钾、15份乙二醛。
混合后紫外吸收光谱图如图3所示,说明单宁酸与金属盐发生了络合反应.
实施例4
一种提高杨木锯材尺寸稳定性的处理方法,包括:
步骤1:准备适量杨木锯材,规格为1200×150×50mm;
步骤2:将杨木锯材置入至压力罐中,向其中添加实施例1的A试剂,试剂A的添加量为杨木锯材绝干质量的3倍;使得杨木锯材完全浸没在实施例1的试剂A中,逐步加压,浸渍时压力为0.5MPa,浸渍时间为24h,然后取出后干燥,得到单宁酸杨木锯材,化学结构式如图4所示;
步骤3:在多酚杨木锯材再次置入压力罐中,向其中添加实施例1的B试剂,试剂B的添加量为单宁酸杨木锯材绝干质量的3倍,使得单宁酸杨木锯材完全浸没在实施例1的试剂B中;逐步加压,浸渍时压力为0.3MPa,浸渍时间为24h,然后取出后干燥,得到单宁酸氯化铁杨木锯材;
步骤4:干燥单宁酸氯化铁杨木锯材至含水率为12%,得到络合杨木,化学结构式如图6所示。
处理前后杨木的物理力学性能如表1所示。从表1可以看出,经过处理后,木材的气干密度增加了13%;木材的径向和弦向干缩系数缩小了1倍以上;力学性能得到了显著的改善。经过热重分析结果显示,络合后的材料与原木和多酚木材相比,在103-220℃区间,有明显的失重,失重率占整体络合木的5.35,说明络合木材中结合水增加,如图5。
表1处理前、后杨木性能的比较
性能指标 | 未处理 | 络合处理 |
气干密度(g/cm<sup>3</sup>) | 0.45 | 0.51 |
径向干缩系数(%) | 0.13 | 0.06 |
弦向干缩系数(%) | 0.26 | 0.09 |
弯曲强度(MPa) | 64.3 | 73.6 |
弹性模量(GPa) | 6.45 | 8.71 |
压缩强度(MPa) | 35.6 | 44.7 |
拉伸强度(MPa) | 78.4 | 93.5 |
实施例5
一种提高竹集成材尺寸稳定性的处理方法,包括:
步骤1:准备适量竹集成材;
步骤2:将竹集成材置入液压压罐中,将实施例2中的A溶液稀释10倍;之后,将稀释后A试剂导入液压压力灌中,通过液压流量计测得导入竹集成材中试剂量为竹集成材质量的1.05倍;所述浸渍时压力为2.5MPa,浸渍时间为12h,然后取出,干燥,得到鞣化单宁竹集成材;
步骤3:在鞣化单宁竹集成材置入液压压罐中,向压力灌中导入实施例2的试剂B,通过液压流量计测得导入竹集成材中试剂量为竹集成材质量的0.80倍;所述浸渍压力为2.0MPa,浸渍时间为12h,得到鞣化单宁硫酸铜竹集成材;
步骤4:干燥鞣化单宁硫酸铜竹集成材至含水率为10%,得到络合竹集成材,化学结构式如图8所示。
处理前后竹材集成材的物理力学性能如表2所示。从表2可以看出,经过处理后,络合竹集成材的气干密度增加了9.6%;厚度和宽度方向干缩系数缩小了1倍以上;力学性能得到了显著的改善。经过热重分析结果显示,络合后的材料与竹集成材相比,在103-220℃区间,有明显的失重,说明络合竹集成材的结合水含量增加,其化学结构图如图7,纤维素和鞣花单宁与水之间形成了氢键;纤维素和单宁酸与甲醛发生了交联;多酚与金属盐之间形成了络合,金属盐与水分子形成了结晶水。
表2处理前、后竹集成材性能的比较
性能指标 | 未处理 | 络合处理 |
气干密度(g/cm<sup>3</sup>) | 0.62 | 0.68 |
厚度方向干缩系数(%) | 0.20 | 0.09 |
宽度方向干缩系数(%) | 0.12 | 0.04 |
弯曲强度(MPa) | 82 | 91 |
弹性模量(GPa) | 10567 | 11324 |
压缩强度(MPa) | 67 | 74 |
拉伸强度(MPa) | 104 | 112 |
实施例6
一种提高木纤维尺寸稳定性的处理方法,包括:
步骤1:准备适量木纤维;
步骤2:将木纤维加入实施例3的A试剂中,试剂A的添加量为纤维质量250%;使得木纤维浸没在实施例3的试剂A中,浸渍时压力为常压,浸渍时间为30min,然后取出干燥,得到黑荆树皮单宁/乙二醛木纤维;
步骤3:将黑荆树皮单宁/乙二醛木纤维加入实施例3的B试剂中,试剂B的添加量为纤维质量250%;使得木纤维浸没在实施例3的试剂B中,浸渍时压力为常压,浸渍时间为60min,然后取出干燥,得到硫酸铝钾黑荆树皮单宁/乙二醛木纤维;
步骤4:干燥硫酸铝钾黑荆树皮单宁/乙二醛木纤维至含水率为8%,得到络合木纤维,化学结构式如图9所示。
其化学结构图如图9,纤维素与水之间,纤维素与多酚之间、纤维素与水之间、多酚之间形成了氢键体系;纤维素和单宁酸与甲醛发生了交联;多酚与金属盐之间形成了络合,金属盐与水分子形成了结晶水。
综上可知,本发明通过“天然纤维-植物多酚-金属盐”动态多重牺牲键网络结构,支撑起纤维素、半纤维素、蛋白质等天然高分子,使其在吸湿或解吸时形成了空间位阻,减小甚至不产生膨胀或收缩,从分子水平解决了天然纤维材料易开裂问题。
以上所述是本发明的优选实施方式,对于本技术领域的普通技术人员来说,在不脱离本发明所述原理的前提下,作出若干改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种提高天然纤维材料尺寸稳定性的试剂,其特征在于,包括A试剂和B试剂,其中,A试剂由以下质量份组分组成:100份水、3~25份植物多酚、0~15份醛类化合物;B试剂由以下质量份组分组成:100份水、1~30份金属盐、0~20份氨基化合物。
2.根据权利要求1所述的提高天然纤维材料尺寸稳定性的试剂,其特征在于,所述植物多酚为聚棓酸酯类多酚和/或聚黄烷类多酚;所述棓酸酯类多酚包含至少有一个多元醇和多个酚羧酸,所述多元醇通过酯键与酚羧酸相连接;所述聚黄烷类多酚的分子量为500~3000,聚合物为2~10,单元之间以C~C键相连,分子骨架为C6·C3·C6结构,在两个酚香环(A环、B环)之间以一个三碳链(C~2,C~3,C~4)相连,其中一个碳原子与A环8a位置上的氧原子连接成吡喃环(C环)。
3.根据权利要求1所述的提高天然纤维材料尺寸稳定性的试剂,其特征在于,所述醛类化合物为乙醛、乙二醛、戊二醛、甲醛的一种或多种混合物。
4.根据权利要求3所述的提高天然纤维材料尺寸稳定性的试剂,其特征在于,所述金属盐为:铁盐、铝盐、铜盐、锌盐的一种或多种。
5.根据权利要求1所述的提高天然纤维材料尺寸稳定性的试剂,其特征在于,所述氨基化合物为尿素、酰胺、二甲胺、聚醚酰亚胺、聚赖氨酸的一种或多种。
6.根据权利要求1所述的提高天然纤维材料尺寸稳定性的试剂,其特征在于,所述天然纤维材料包括木材、竹材、木纤维、竹纤维、棉纤维、麻纤维、毛纤维、蚕丝纤维及其原材料和/或制品。
7.一种提高天然纤维材料尺寸稳定性的处理方法,其特征在于,包括:
步骤1:准备适量天然纤维材料;
步骤2:把试剂A导入天然纤维材料,得到多酚天然纤维材料;
步骤3:把试剂B导入多酚天然纤维材料,得到多酚金属盐天然纤维材料;
步骤4:干燥多酚金属盐天然纤维材料,得到络合天然纤维材料。
8.根据权利要求7所述的提高天然纤维材料尺寸稳定性的处理方法,其特征在于,所述步骤2中,试剂A的添加量为天然纤维材料绝干质量的10~300%;所述步骤3中,试剂B的添加量为所述天然纤维材料绝干质量的5~200%。
9.根据权利要求7所述的提高天然纤维材料尺寸稳定性的处理方法,其特征在于,所述步骤4中,所述络合天然纤维材料的含水率为3~16%。
10.根据权利要求7-9任一所述的提高天然纤维材料尺寸稳定性的处理方法,其特征在于,所述的A试剂和B试剂通过加压浸渍导入;所述浸渍压力为0.1~3.5MPa,浸渍时间为5min~48h,浸渍温度为10℃-85℃;
所述A试剂和B试剂按先后顺序导入到所述天然纤维材料的表面、细胞壁、细胞腔和/或细胞间隙中,并在天然纤维材料内发生原位络合反应,形成植物多酚金属盐络合物;所述金属盐与植物多酚酚通过配位键结合,所述植物多酚与天然纤维材料通过氢键结合。
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