[go: up one dir, main page]

CN117904897A - 一种纸浆造纸助剂制备方法 - Google Patents

一种纸浆造纸助剂制备方法 Download PDF

Info

Publication number
CN117904897A
CN117904897A CN202310584384.5A CN202310584384A CN117904897A CN 117904897 A CN117904897 A CN 117904897A CN 202310584384 A CN202310584384 A CN 202310584384A CN 117904897 A CN117904897 A CN 117904897A
Authority
CN
China
Prior art keywords
auxiliary agent
pulp
reacting
dosage
strengthening
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
Application number
CN202310584384.5A
Other languages
English (en)
Inventor
王欢
章松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Champion Chemicals Yangzhou Co ltd
Original Assignee
Champion Chemicals Yangzhou Co ltd
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 Champion Chemicals Yangzhou Co ltd filed Critical Champion Chemicals Yangzhou Co ltd
Priority to CN202310584384.5A priority Critical patent/CN117904897A/zh
Publication of CN117904897A publication Critical patent/CN117904897A/zh
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/36Hydroxylated esters of higher fatty acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67Unsaturated compounds having active hydrogen
    • C08G18/6705Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07Nitrogen-containing compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11Halides
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/25Cellulose
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/28Starch
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57Polyureas; Polyurethanes
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63Inorganic compounds
    • D21H17/65Acid compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63Inorganic compounds
    • D21H17/66Salts, e.g. alums
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/16Sizing or water-repelling agents
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/18Reinforcing agents
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/64Paper recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Abstract

本发明公开了一种纸浆造纸助剂制备方法,以玉米淀粉和纤维素为原料,加入丙烯酰胺和甲基丙烯酰氧乙基三甲基氯化铵,在引发剂的作用下,聚合接枝,将玉米淀粉和纤维素接枝复合,得到复合乳液,将强化助剂加入复合乳液中,使得强化助剂上的异氰酸酯基与复合乳液中的羟基或氨基发生反应后,加入己二酸二酰肼混合均匀,制得纸浆造纸助剂;强化助剂为超支化结构,且分支链上具有有机硅链段,侧链含有长氟链和碳链,使得强化助剂具有很好的疏水效果,且疏水基团中的酮羰基能够与己二酸二酰肼中的酰肼基团交联进而在纸张表面形成致密的疏水膜,与纤维素和淀粉配合进一步提升的纸张的力学性能。

Description

一种纸浆造纸助剂制备方法
技术领域
本发明涉及造纸技术领域,具体涉及一种纸浆造纸助剂制备方法。
背景技术
随着造纸工业的不断发展,纸的用途已从书写、印刷等文化生活方面,发展到人类生活的各个领域。纸和纸板不仅是人类文化与信息的载体,也是工业、农业、科学、生活和卫生等方面的重要材料;它与工农业生产以及国民经济各个部门都有密切的联系,成为人类社会物质文明与精神文明的基础。造纸湿部化学口堤论述造纸浆料中各组分如纤维、水、料、化学助剂等在造纸机网部滤水、留着、成形以及白水循环过程中产生的相互间反应与作用规律的一门学科。国内外的造纸实践经验证明,各种化学助剂在造纸生产过程中的应用能起到事半功倍的作用,因此越来越得到各造纸生产厂家的青睐,造纸湿部化学的理论和应用得到了迅速发展。
发明内容
本发明的目的在于提供一种纸浆造纸助剂制备方法,解决了现阶段纸张强度低且耐水性差的问题。
本发明的目的可以通过以下技术方案实现:
一种纸浆造纸助剂制备方法,具体包括如下步骤:
步骤S1:将玉米淀粉和纤维素分散在去离子水中,加入丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚,在转速为200-300r/mi n,温度为80-90℃的条件下,搅拌并加入过硫酸铵,进行反应3-5h,制得复合乳液;
步骤S2:将复合乳液在转速为150-200r/mi n,温度为60-70℃的条件下,搅拌并加入强化助剂和二月桂酸二丁基锡,进行反应4-6h后,加入己二酸二酰肼混合均匀,制得纸浆造纸助剂。
进一步,步骤S1所述的玉米淀粉、纤维素、去离子水、丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚的用量比为1.5g:1g:10mL:0.6g:0.13g:0.01g。
进一步,步骤S2所述的复合乳液和强化助剂的用量比为25mL:2g,二月桂酸二丁基锡的用量为强化助剂质量的4-6%,己二酸二酰肼的用量为1-3%。
进一步,所述的强化助剂由如下步骤制成:
将改性单体和蓖麻油混合,在转速为300-500r/mi n,温度为60-70℃的条件下,搅拌并加入二苯基甲烷二异氰酸酯,进行反应5-10mi n后,升温至80-85℃,继续反应1-1.5h,制得强化助剂。
进一步,所述的改性单体、蓖麻油和二苯基甲烷二异氰酸酯的摩尔比为n:2n+1:4n+2,n为大于0的自然数。
进一步,所述的改性单体由如下步骤制成:
步骤A1:将十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和去离子水混合均匀,在转速为200-300r/mi n,温度为25-30℃的条件下,搅拌20-30mi n后,加入四氢呋喃和浓硫酸,升温至55-65℃,保温5-10mi n,加入1,1,3,3-四甲基二硅氧烷,进行反应3-5h,制得中间体1;
步骤A2:将丙烯酸、二乙醇胺、1-羟基苯并三唑和四氢呋喃混合均匀,在转速为200-300r/mi n,温度为30-40℃的条件下,进行反应3-5h,制得中间体2,将中间体2、环氧氯丙烷、苄基三甲基溴化铵和甲苯混合均匀,在转速为150-200r/mi n,温度为100-105℃的条件下,进行反应3-5h后,降温至70-75℃,加入氢氧化钠溶液,进行反应5-7h,制得中间体3;
步骤A3:将中间体3、中间体1和甲苯混合均匀,通入氮气保护,在转速为200-300r/mi n,温度为50-60℃的条件下,搅拌并加入氯铂酸,进行反应6-8h后,升温至100-110℃,加入乙酰丙酸和三苯基膦,进行反应1-1.5h,升温至120-125℃,进行反应至酸值小于10mg/g,制得改性单体。
进一步,步骤A1所述的十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷、去离子水和1,1,3,3-四甲基二硅氧烷的用量比为2mmo l:3mmo l:5mmo l:5mL:3mmo l,浓硫酸的用量为十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和1,1,3,3-四甲基二硅氧烷质量和的3-5%。
进一步,步骤A2所述的丙烯酸、二乙醇胺、1-羟基苯并三唑的摩尔比为1:1:1.1,中间体1、环氧氯丙烷和氢氧化钠的摩尔比为1:2:3,氢氧化钠溶液的质量分数为30%,苄基三甲基溴化铵的用量为中间体1和环氧氯丙烷质量和2%。
进一步,步骤A3所述的中间体3、中间体1和乙酰丙酸的摩尔比为2:1:4,氯铂酸的用量为中间体1和中间体3质量和的0.01‰,三苯基膦的用量为乙酰丙酸质量0.01‰。
本发明的有益效果:本发明制备的一种纸浆造纸助剂以玉米淀粉和纤维素为原料,加入丙烯酰胺和甲基丙烯酰氧乙基三甲基氯化铵,在引发剂的作用下,聚合接枝,将玉米淀粉和纤维素接枝复合,得到复合乳液,将强化助剂加入复合乳液中,使得强化助剂上的异氰酸酯基与复合乳液中的羟基或氨基发生反应后,加入己二酸二酰肼混合均匀,制得纸浆造纸助剂,强化助剂由改性单体、蓖麻油和二苯基甲烷二异氰酸酯反应,通过用量控制,形成聚氨酯预聚体,制得强化助剂,改性单体十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷和二甲基二氯硅烷为原料水解,再与1,1,3,3-四甲基二硅氧烷聚合,形成S i-H键封端的中间体1,将丙烯酸和二乙醇胺在1-羟基苯并三唑的作用下,使得丙烯酸上的羧基与二乙醇胺上的亚胺脱水缩合,制得中间体2,将中间体2和环氧氯丙烷反应,使得中间体2上的醇羟基与环氧氯丙烷上的环氧基反应后,再在氢氧化钠溶液的作用下闭环,制得中间体3,将中间体3和中间体1反应,使得中间体3上的双键和中间体1上的S i-H键反应后,加入乙酰丙酸和三苯基膦,乙酰乙酸上的羧基在三苯基膦的作用下会与环氧基反应,产生醇羟基,制得改性单体,强化助剂为超支化结构,且分支链上具有有机硅链段,侧链含有长氟链和碳链,使得强化助剂具有很好的疏水效果,而纤维素和淀粉上又含有大量亲水基团,且含有阳离子,当造纸助剂使用时由于阳离子的存在,使得造纸助剂带有正电荷,能够通过静电作用与带有负电荷的纸浆纤维结合,使得疏水基团向纸外定向排列,且疏水基团中的酮羰基能够与己二酸二酰肼中的酰肼基团交联进而在纸张表面形成致密的疏水膜,与纤维素和淀粉配合进一步提升的纸张的力学性能。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
一种纸浆造纸助剂制备方法,具体包括如下步骤:
步骤S1:将玉米淀粉和纤维素分散在去离子水中,加入丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚,在转速为200r/mi n,温度为80℃的条件下,搅拌并加入过硫酸铵,进行反应3h,制得复合乳液;
步骤S2:将复合乳液在转速为150r/mi n,温度为60℃的条件下,搅拌并加入强化助剂和二月桂酸二丁基锡,进行反应4h后,加入己二酸二酰肼混合均匀,制得纸浆造纸助剂。
步骤S1所述的玉米淀粉、纤维素、去离子水、丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚的用量比为1.5g:1g:10mL:0.6g:0.13g:0.01g。
步骤S2所述的复合乳液和强化助剂的用量比为25mL:2g,二月桂酸二丁基锡的用量为强化助剂质量的4%,己二酸二酰肼的用量为1%。
所述的强化助剂由如下步骤制成:
将改性单体和蓖麻油混合,在转速为300r/mi n,温度为60℃的条件下,搅拌并加入二苯基甲烷二异氰酸酯,进行反应5mi n后,升温至80℃,继续反应1h,制得强化助剂。
所述的改性单体、蓖麻油和二苯基甲烷二异氰酸酯的摩尔比为1:3:6。
所述的改性单体由如下步骤制成:
步骤A1:将十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和去离子水混合均匀,在转速为200r/mi n,温度为25℃的条件下,搅拌20mi n后,加入四氢呋喃和浓硫酸,升温至55℃,保温5mi n,加入1,1,3,3-四甲基二硅氧烷,进行反应3h,制得中间体1;
步骤A2:将丙烯酸、二乙醇胺、1-羟基苯并三唑和四氢呋喃混合均匀,在转速为200r/mi n,温度为30℃的条件下,进行反应3h,制得中间体2,将中间体2、环氧氯丙烷、苄基三甲基溴化铵和甲苯混合均匀,在转速为150r/mi n,温度为100℃的条件下,进行反应3h后,降温至70℃,加入氢氧化钠溶液,进行反应5h,制得中间体3;
步骤A3:将中间体3、中间体1和甲苯混合均匀,通入氮气保护,在转速为200r/min,温度为50℃的条件下,搅拌并加入氯铂酸,进行反应6h后,升温至100℃,加入乙酰丙酸和三苯基膦,进行反应1h,升温至120℃,进行反应至酸值小于10mg/g,制得改性单体。
步骤A1所述的十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷、去离子水和1,1,3,3-四甲基二硅氧烷的用量比为2mmo l:3mmo l:5mmo l:5mL:3mmol,浓硫酸的用量为十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和1,1,3,3-四甲基二硅氧烷质量和的3%。
步骤A2所述的丙烯酸、二乙醇胺、1-羟基苯并三唑的摩尔比为1:1:1.1,中间体1、环氧氯丙烷和氢氧化钠的摩尔比为1:2:3,氢氧化钠溶液的质量分数为30%,苄基三甲基溴化铵的用量为中间体1和环氧氯丙烷质量和2%。
步骤A3所述的中间体3、中间体1和乙酰丙酸的摩尔比为2:1:4,氯铂酸的用量为中间体1和中间体3质量和的0.01‰,三苯基膦的用量为乙酰丙酸质量0.01‰。
实施例2
一种纸浆造纸助剂制备方法,具体包括如下步骤:
步骤S1:将玉米淀粉和纤维素分散在去离子水中,加入丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚,在转速为200r/mi n,温度为85℃的条件下,搅拌并加入过硫酸铵,进行反应4h,制得复合乳液;
步骤S2:将复合乳液在转速为150r/mi n,温度为65℃的条件下,搅拌并加入强化助剂和二月桂酸二丁基锡,进行反应5h后,加入己二酸二酰肼混合均匀,制得纸浆造纸助剂。
步骤S1所述的玉米淀粉、纤维素、去离子水、丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚的用量比为1.5g:1g:10mL:0.6g:0.13g:0.01g。
步骤S2所述的复合乳液和强化助剂的用量比为25mL:2g,二月桂酸二丁基锡的用量为强化助剂质量的5%,己二酸二酰肼的用量为2%。
所述的强化助剂由如下步骤制成:
将改性单体和蓖麻油混合,在转速为300r/mi n,温度为65℃的条件下,搅拌并加入二苯基甲烷二异氰酸酯,进行反应8mi n后,升温至83℃,继续反应1.5h,制得强化助剂。
所述的改性单体、蓖麻油和二苯基甲烷二异氰酸酯的摩尔比为2:5:10。
所述的改性单体由如下步骤制成:
步骤A1:将十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和去离子水混合均匀,在转速为200r/mi n,温度为30℃的条件下,搅拌25mi n后,加入四氢呋喃和浓硫酸,升温至60℃,保温8mi n,加入1,1,3,3-四甲基二硅氧烷,进行反应4h,制得中间体1;
步骤A2:将丙烯酸、二乙醇胺、1-羟基苯并三唑和四氢呋喃混合均匀,在转速为200r/mi n,温度为35℃的条件下,进行反应4h,制得中间体2,将中间体2、环氧氯丙烷、苄基三甲基溴化铵和甲苯混合均匀,在转速为150r/mi n,温度为100℃的条件下,进行反应4h后,降温至73℃,加入氢氧化钠溶液,进行反应6h,制得中间体3;
步骤A3:将中间体3、中间体1和甲苯混合均匀,通入氮气保护,在转速为200r/min,温度为55℃的条件下,搅拌并加入氯铂酸,进行反应7h后,升温至105℃,加入乙酰丙酸和三苯基膦,进行反应1.3h,升温至123℃,进行反应至酸值小于10mg/g,制得改性单体。
步骤A1所述的十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷、去离子水和1,1,3,3-四甲基二硅氧烷的用量比为2mmo l:3mmo l:5mmo l:5mL:3mmol,浓硫酸的用量为十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和1,1,3,3-四甲基二硅氧烷质量和的4%。
步骤A2所述的丙烯酸、二乙醇胺、1-羟基苯并三唑的摩尔比为1:1:1.1,中间体1、环氧氯丙烷和氢氧化钠的摩尔比为1:2:3,氢氧化钠溶液的质量分数为30%,苄基三甲基溴化铵的用量为中间体1和环氧氯丙烷质量和2%。
步骤A3所述的中间体3、中间体1和乙酰丙酸的摩尔比为2:1:4,氯铂酸的用量为中间体1和中间体3质量和的0.01‰,三苯基膦的用量为乙酰丙酸质量0.01‰。
实施例3
一种纸浆造纸助剂制备方法,具体包括如下步骤:
步骤S1:将玉米淀粉和纤维素分散在去离子水中,加入丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚,在转速为300r/mi n,温度为90℃的条件下,搅拌并加入过硫酸铵,进行反应5h,制得复合乳液;
步骤S2:将复合乳液在转速为200r/mi n,温度为70℃的条件下,搅拌并加入强化助剂和二月桂酸二丁基锡,进行反应6h后,加入己二酸二酰肼混合均匀,制得纸浆造纸助剂。
步骤S1所述的玉米淀粉、纤维素、去离子水、丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚的用量比为1.5g:1g:10mL:0.6g:0.13g:0.01g。
步骤S2所述的复合乳液和强化助剂的用量比为25mL:2g,二月桂酸二丁基锡的用量为强化助剂质量的6%,己二酸二酰肼的用量为3%。
所述的强化助剂由如下步骤制成:
将改性单体和蓖麻油混合,在转速为500r/mi n,温度为70℃的条件下,搅拌并加入二苯基甲烷二异氰酸酯,进行反应10mi n后,升温至85℃,继续反应1.5h,制得强化助剂。
所述的改性单体、蓖麻油和二苯基甲烷二异氰酸酯的摩尔比为3:7:14。
所述的改性单体由如下步骤制成:
步骤A1:将十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和去离子水混合均匀,在转速为300r/mi n,温度为30℃的条件下,搅拌30mi n后,加入四氢呋喃和浓硫酸,升温至65℃,保温10mi n,加入1,1,3,3-四甲基二硅氧烷,进行反应5h,制得中间体1;
步骤A2:将丙烯酸、二乙醇胺、1-羟基苯并三唑和四氢呋喃混合均匀,在转速为300r/mi n,温度为40℃的条件下,进行反应5h,制得中间体2,将中间体2、环氧氯丙烷、苄基三甲基溴化铵和甲苯混合均匀,在转速为200r/mi n,温度为105℃的条件下,进行反应5h后,降温至75℃,加入氢氧化钠溶液,进行反应7h,制得中间体3;
步骤A3:将中间体3、中间体1和甲苯混合均匀,通入氮气保护,在转速为300r/min,温度为60℃的条件下,搅拌并加入氯铂酸,进行反应8h后,升温至110℃,加入乙酰丙酸和三苯基膦,进行反应1.5h,升温至125℃,进行反应至酸值小于10mg/g,制得改性单体。
步骤A1所述的十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷、去离子水和1,1,3,3-四甲基二硅氧烷的用量比为2mmo l:3mmo l:5mmo l:5mL:3mmol,浓硫酸的用量为十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和1,1,3,3-四甲基二硅氧烷质量和的3-5%。
步骤A2所述的丙烯酸、二乙醇胺、1-羟基苯并三唑的摩尔比为1:1:1.1,中间体1、环氧氯丙烷和氢氧化钠的摩尔比为1:2:3,氢氧化钠溶液的质量分数为30%,苄基三甲基溴化铵的用量为中间体1和环氧氯丙烷质量和2%。
步骤A3所述的中间体3、中间体1和乙酰丙酸的摩尔比为2:1:4,氯铂酸的用量为中间体1和中间体3质量和的0.01‰,三苯基膦的用量为乙酰丙酸质量0.01‰。
对比例1
本对比例与实施例1相比,用中间体2代替中间体3,将中间体2、中间体1和甲苯混合均匀,通入氮气保护,在转速为200r/mi n,温度为50℃的条件下,搅拌并加入氯铂酸,进行反应6h,得到的反应产物代替改性单体。
对比例2
本对比例与实施例1相比,用丙烯醇代替中间体3,将丙烯醇、中间体1和甲苯混合均匀,通入氮气保护,在转速为200r/mi n,温度为50℃的条件下,搅拌并加入氯铂酸,进行反应6h,得到的反应产物代替改性单体。
将绝干纸浆用蒸馏水配成质量分数为0.5%的浆料,疏解1mi n,分别加入实施例1-3和对比例1-2制得的助剂,助剂的加入量为绝干纸浆的1%,混合均匀后,用纸样抄取器上抄取定量为160g/m2的纸片,制得试样。
依照GB/T4652-2008的标准,将纸张于温度为23℃,相对湿度为50%下恒温恒湿4h,裁成12.5cm×1.27cm的样条,于DYSY-1压缩实验仪上测定纸张的环压指数。
依照GB/T4652-2008的标准,将纸张于温度为23℃,相对湿度为50%下恒温恒湿4h,裁成18cm×1.5cm的样条,于WZL-300卧式电脑拉力仪上测定职场的抗张指数。
将纸张依照I SO5637:1989的标准检测吸水值,检测结果如下。
由上表可知实施例1-3制得的纸浆造纸助剂处理的纸张的环压指数为8.95-9.01N·m/g,抗张指数为60.12-60.25N·m/g,吸水值为20.6-21.3g/m2,表明本发明能够增强纸张力学性能,并增强防水效果。
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。

Claims (9)

1.一种纸浆造纸助剂制备方法,其特征在于:具体包括如下步骤:
步骤S1:将玉米淀粉和纤维素分散在去离子水中,加入丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚,搅拌并加入过硫酸铵,进行反应,制得复合乳液;
步骤S2:将复合乳液搅拌并加入强化助剂和二月桂酸二丁基锡,进行反应后,加入己二酸二酰肼混合均匀,制得纸浆造纸助剂。
2.根据权利要求1所述的一种纸浆造纸助剂制备方法,其特征在于:步骤S1所述的玉米淀粉、纤维素、去离子水、丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵和丙二醇甲醚的用量比为1.5g:1g:10mL:0.6g:0.13g:0.01g。
3.根据权利要求1所述的一种纸浆造纸助剂制备方法,其特征在于:步骤S2所述的复合乳液和强化助剂的用量比为25mL:2g,二月桂酸二丁基锡的用量为强化助剂质量的4-6%,己二酸二酰肼的用量为1-3%。
4.根据权利要求1所述的一种纸浆造纸助剂制备方法,其特征在于:所述的强化助剂由如下步骤制成:
将改性单体和蓖麻油混合搅拌并加入二苯基甲烷二异氰酸酯,进行反应后,升温继续反应,制得强化助剂。
5.根据权利要求4所述的一种纸浆造纸助剂制备方法,其特征在于:所述的改性单体、蓖麻油和二苯基甲烷二异氰酸酯的摩尔比为n:2n+1:4n+2,n为大于0的自然数。
6.根据权利要求1所述的一种纸浆造纸助剂制备方法,其特征在于:所述的改性单体由如下步骤制成:
步骤A1:将十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和去离子水混合搅拌后,加入四氢呋喃和浓硫酸,升温保温,加入1,1,3,3-四甲基二硅氧烷,进行反应,制得中间体1;
步骤A2:将丙烯酸、二乙醇胺、1-羟基苯并三唑和四氢呋喃混合反应,制得中间体2,将中间体2、环氧氯丙烷、苄基三甲基溴化铵和甲苯混合反应后,降温并加入氢氧化钠溶液,进行反应,制得中间体3;
步骤A3:将中间体3、中间体1和甲苯混合搅拌并加入氯铂酸,进行反应后,升温并加入乙酰丙酸和三苯基膦,进行反应,继续升温进行反应至酸值小于10mg/g,制得改性单体。
7.根据权利要求6所述的一种纸浆造纸助剂制备方法,其特征在于:步骤A1所述的十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷、去离子水和1,1,3,3-四甲基二硅氧烷的用量比为2mmol:3mmol:5mmol:5mL:3mmol,浓硫酸的用量为十二烷基二甲氧基硅烷、全氟辛基甲基二甲氧基硅烷、二甲基二氯硅烷和1,1,3,3-四甲基二硅氧烷质量和的3-5%。
8.根据权利要求6所述的一种纸浆造纸助剂制备方法,其特征在于:步骤A2所述的丙烯酸、二乙醇胺、1-羟基苯并三唑的摩尔比为1:1:1.1,中间体1、环氧氯丙烷和氢氧化钠的摩尔比为1:2:3,氢氧化钠溶液的质量分数为30%,苄基三甲基溴化铵的用量为中间体1和环氧氯丙烷质量和2%。
9.根据权利要求6所述的一种纸浆造纸助剂制备方法,其特征在于:步骤A3所述的中间体3、中间体1和乙酰丙酸的摩尔比为2:1:4,氯铂酸的用量为中间体1和中间体3质量和的0.01‰,三苯基膦的用量为乙酰丙酸质量0.01‰。
CN202310584384.5A 2023-05-23 2023-05-23 一种纸浆造纸助剂制备方法 Pending CN117904897A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310584384.5A CN117904897A (zh) 2023-05-23 2023-05-23 一种纸浆造纸助剂制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310584384.5A CN117904897A (zh) 2023-05-23 2023-05-23 一种纸浆造纸助剂制备方法

Publications (1)

Publication Number Publication Date
CN117904897A true CN117904897A (zh) 2024-04-19

Family

ID=90686657

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310584384.5A Pending CN117904897A (zh) 2023-05-23 2023-05-23 一种纸浆造纸助剂制备方法

Country Status (1)

Country Link
CN (1) CN117904897A (zh)

Similar Documents

Publication Publication Date Title
CN103524696B (zh) 一种硅烷改性的磺酸型水性聚氨酯乳液及其制备方法
DE2019758C3 (de) Verfahren zur Herstellung von Epoxypolyaddukten
CN103059770B (zh) 淀粉胶粘剂、其制备方法及应用
CN103497307A (zh) 季铵型阳离子聚氨酯基聚醚嵌段亲水性有机硅柔软剂超微乳液的制备方法及其产品
CN107163301A (zh) 一种高吸水树脂及其制备方法和应用
CN115142299B (zh) 一种无塑涂布环保包装材料
CN102230301B (zh) 阳离子苯丙类表面施胶剂的制备方法
CN117904897A (zh) 一种纸浆造纸助剂制备方法
CN113527719B (zh) 一种基于废铬革屑的高强度纳米复合三网络水凝胶的制备方法
CA1128546A (en) Acrylamide or methacrylamide alkoxypropyl quaternary compounds
CN105086736A (zh) 一种门板保护剂的制备方法
CN110655632B (zh) 一种淀粉基水性聚氨酯乳液的制备及其在包装纸中的应用
CN108330739A (zh) 一种用缩水甘油醚改性胶原蛋白制备的造纸施胶剂及其制备方法
CN103865469A (zh) 蒙脱土改性醇溶型聚氨酯胶黏剂的制备方法
CN112695565B (zh) 一种天然环保湿强剂的制备方法
CA1047692A (en) Amine-epichlorohydrin polymeric compositions
DE1570296A1 (de) Verfahren zur Herstellung wasserloeslicher Derivate von Polyalkyleniminen
CN113774715B (zh) 一种无机-有机杂化材料改性的聚合物施胶增强剂的制备方法
CN1637038A (zh) 高沸醇木质素环氧树脂的制备方法
CN115928501A (zh) 一种抗菌包装纸及其制备方法
CN115012248A (zh) 一种新型造纸用增强剂及其制备方法及其应用
CN112376279B (zh) 一种用于生产玻璃纤维连续毡浸润剂的制备方法
CN117355502A (zh) 由可再生二甲氨基乙醇获得生物源单体的方法
CN113480707A (zh) 芳纶纤维水溶性环氧树脂表面上浆剂及其制备和应用
CN118126508B (zh) 超疏水、高比强度环保纤维板材及生产工艺

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