CN108623784A - 由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法 - Google Patents
由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法 Download PDFInfo
- Publication number
- CN108623784A CN108623784A CN201810195272.XA CN201810195272A CN108623784A CN 108623784 A CN108623784 A CN 108623784A CN 201810195272 A CN201810195272 A CN 201810195272A CN 108623784 A CN108623784 A CN 108623784A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- component
- degradation solution
- waste
- shoe
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7862—Nitrogen containing cyano groups or aldimine or ketimine groups
-
- 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
- C08J9/14—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 organic
- C08J9/141—Hydrocarbons
-
- 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
- C08J9/14—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 organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2410/00—Soles
-
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及聚氨酯材料领域,具体涉及到由废旧聚氨酯降解液制备聚氨酯原液及其制备方法。所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,包括A组分和B组分,所述A组分为聚酯多元醇、扩链剂、发泡剂、催化剂A和匀泡剂的混合物,所述B组分为异氰酸酯、聚酯多元醇和聚氨酯降解产物的预聚合反应的产物,所述预聚合反应中添加副反应阻止剂。所述制备方法包括A组分的制备和B组分的制备。本发明提供的技术方案通过使用废旧聚氨酯降解液解决了常规的低密度高硬度的聚氨酯鞋底成本高,不仅实现了废旧聚氨酯降解液的有效利用,同时有效降低了低密度高硬度聚氨酯鞋底的成本。
Description
技术领域
本发明涉及聚氨酯材料领域,具体涉及到由废旧聚氨酯降解液制备聚氨酯原液及其制备方法。
背景技术
聚氨酯作为新型多功能高分子材料,属于高科技、高性能、高附加值的产品,在材料工业中占有重要地位,已发展成为世界六大合成材料之一。聚氨酯鞋底呈微孔结构,是一种特殊的聚氨酯弹性体,具有强度高、耐磨、韧性好、耐折、穿着轻便舒适的特点,低密度和高硬度是聚氨酯鞋材供应商通常的要求之一,但是在降低密度的同时鞋底材料不可避免的会损害部分性能,密度过低会造成产品硬度下降、鞋底收缩变形、表面容易脱皮等一系列问题,市面上出售的一般普通聚氨酯鞋底液的解决方法是在鞋底原液的预聚体中添加大量的聚醚多元醇和多异氰酸酯,来防止收缩和提高硬度,聚醚和多异氰酸酯的价格居高不下大大提高了鞋底原液的成本。因此,如何低成本的制备低密度高硬度聚氨酯鞋底材料是鞋底行业的重要研究方向。
发明内容
本发明提供了一种由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法,用以解决常规的低密度高硬度的聚氨酯鞋底成本高的问题。
为了解决上述技术问题,本发明的技术方案是:所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,包括A组分和B组分,所述A组分为聚酯多元醇、扩链剂、发泡剂、催化剂A和匀泡剂的混合物,所述B组分为异氰酸酯、聚酯多元醇和聚氨酯降解产物的预聚合反应的产物,所述预聚合反应中添加副反应阻止剂。
可选地,所述A组分的活泼氢摩尔数与B组分的异氰酸根(-NCO)的摩尔数之比为100:99-101。
大量聚氨酯产品生产和应用的同时也产生了大量的废弃物,如聚氨酯生产的边角废料和废旧的聚氨酯软泡、硬泡及弹性体,对废旧聚氨酯进行回收利用,减少环境污染,具有重要意义。目前废旧聚氨酯的主流降解方法是醇解法,由于醇解法制备的降解多元醇中含有氨基甲酸酯基、醚基、酯基和大量的苯环等基团,粘度大,不易添加到聚氨酯的软泡和硬泡的组合料成分中,并且对制品的成型和物理机械性能造成不良影响,因而使其在聚氨酯硬泡和软泡领域的应用受到了限制。
可选地,所述A组分中各组分按重量份计配比为:
可选地,所述B组分中各组分按重量份计配比为:
异氰酸酯 100份
聚酯多元醇 5-30份
聚氨酯降解产物 5-30份。
可选地,所述聚氨酯降解产物的制备方法,包括如下步骤:将废旧聚氨酯、小分子二元醇和催化剂B加入到反应釜中,控制反应温度为180~230℃,反应时间3~5小时,除去小分子,出料,得到所述聚氨酯降解产物。
可选地,所述小分子二元醇选自乙二醇、丙二醇、二乙二醇和丁二醇中的一种或多种,所述催化剂B选自醋酸钾、醋酸锌、异辛酸钾、氢氧化钾、氢氧化钠、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、丁二胺和丙二胺中的一种或多种。
可选地,所述副反应阻止剂选自无机酸、有机酸或苯甲酰氯。
可选地,所述副反应阻止剂为磷酸。
可选地,所述聚氨酯降解产物的羟值为50~150mgKOH/g。
可选地,所述聚酯多元醇选自聚己二酸系聚酯多元醇和对苯二甲酸系聚酯多元醇的一种或多种;所述扩链剂选自1,4-丁二醇、乙二醇和一缩二乙二醇中的一种或多种;所述催化剂A选自二月桂酸二丁基锡、三乙烯二胺和四甲基二亚乙基三胺中的一种或多种;所述匀泡剂选自DC-193、DC-3042和DC-3043中的一种或多种;所述发泡剂选自水、氯氟烃和环戊烷中的一种或多种;所述异氰酸酯选自4,4-二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯和萘二异氰酸酯中的一种或多种。
可选地,所述异氰酸酯包括4,4-二苯基甲烷二异氰酸酯和碳化二亚胺改性二苯基甲烷二异氰酸酯,两者的重量比为95:5。
本发明还提供了上述由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备方法,包括如下步骤:
1)A组分的制备:将聚酯多元醇与扩链剂、发泡剂、催化剂A、匀泡剂加入反应釜,升温到50~80℃混合均匀,再冷却至35~40℃出料,获得A组份;
2)B组分的制备:将聚酯多元醇、聚氨酯降解产物、异氰酸酯和副反应阻止剂加入反应釜,于70~80℃条件下预聚合反应2~3h,获得B组份。
本发明提供的技术方案通过使用废旧聚氨酯降解液解决了常规的低密度高硬度的聚氨酯鞋底成本高,即在聚氨酯鞋底原液的预聚体中添加适量的废旧聚氨酯降解液替代原有的聚醚多元醇和部分多异氰酸酯组份,不仅实现了废旧聚氨酯降解液的有效利用,同时有效降低了低密度高硬度聚氨酯鞋底的成本。
具体实施方式
为了便于理解,下面结合实施例阐述由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法,应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。
实施例中使用的试剂或原材料如无特殊说明均为市售商品。
实施例1聚氨酯降解产物的制备方法
将500g聚氨酯冰箱硬泡分批加入到溶解了7.5g异辛酸钾的500g 1,4-丁二醇中,氮气保护下加热到180℃进行酯交换反应,反应时间3h,反应结束后去除小分子,得到羟值为90mgKOH/g,粘度为40000mPa·S(25℃)的聚氨酯降解产物。
实施例2聚氨酯降解产物的制备方法
将500g聚氨酯海绵软泡分批加入到溶解了5g氢氧化钠的400g乙二醇中,氮气保护下加热到190℃进行酯交换反应,反应时间3h,反应结束后去除小分子,得到羟值为120mgKOH/g,粘度为35000mPa·S(25℃)的聚氨酯降解产物。
实施例3聚氨酯降解产物的制备方法
将500g聚氨酯鞋底分批加入到溶解了10g二乙醇胺的450g二乙二醇中,氮气保护下加热到170℃进行酯交换反应,反应时间3h,反应结束后去除小分子,得到羟值为100mgKOH/g,粘度为45000mPa·S(25℃)的聚氨酯降解产物。
在以下所用实施例中使用下列组份:
聚酯多元醇1:数均分子量为2000的聚己二酸乙二醇二乙二醇酯多元醇,其中乙二醇和二乙二醇质量比为1:2。
聚酯多元醇2:数均分子量为1500的聚己二酸乙二醇二乙二醇酯多元醇,其中乙二醇和二乙二醇质量比为1:1。
聚酯多元醇3:数均分子量为2000的聚己二酸乙二醇丁二醇酯多元醇,其中乙二醇和丁二醇质量比为1:1。
聚酯多元醇4:数均分子量为1800的聚己二酸乙二醇二乙二醇三羟甲基丙烷酯多元醇,其中乙二醇、二乙二醇和三羟基甲烷质量比为5:5:1。
实施例4由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备
4.1 A组分原料:
4.2 B组分原料:
4.3制备过程
1)将A组分原料投入反应釜中,升温至60℃混合搅拌2小时,再冷却至40℃后出料,密封保存;
2)将B组分原料置于反应釜中,在氮气保护下升温至75℃,进行预聚合反应2.5小时,然后降温至45℃,游离的-NCO含量为22.5%,密封保存。
实施例5由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备
5.1 A组分原料:
5.2 B组分原料:
5.3制备过程
1)将A组分原料投入反应釜中,升温至60℃混合搅拌2小时,再冷却至40℃后出料,密封保存;
2)将B组分原料置于反应釜中,在氮气保护下升温至75℃,进行预聚合反应2.5小时,然后降温至45℃,游离-NCO含量为22.7%,密封保存。
实施例6由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备
6.1 A组分原料:
6.2 B组分原料:
6.3制备过程
1)将A组分原料投入反应釜中,升温至60℃混合搅拌2小时,再冷却至40℃后出料,密封保存;
2)将B组分原料置于反应釜中,在氮气保护下升温至75℃,进行预聚合反应2.5小时,然后降温至45℃,游离-NCO含量为19.1%,密封保存。
实施例7制样实验
将实施例4~6所制得的由废旧聚氨酯降解液制备聚氨酯鞋底原液分别在低压发泡机上进行试验,制成鞋底试样,具体为:
保持低压发泡机A料罐和B料罐的温度为40~50℃,通过自由泡试验确定发泡中心,(即A组分的活泼氢摩尔数与B组分的-NCO的摩尔数之比为100:99-101),通过低压发泡机将两组分充分混合,注入鞋底模具反应成型,脱模,熟化,得到制品。同时使用现有技术中低密度高硬度聚氨酯鞋底原液(A-9080G/B-6226)做对比试验,进行密度、硬度、尺寸稳定性和表皮外观进行测试,结果如下表1所示。
表1
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制。尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换,而这些修改或替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
1.一种由废旧聚氨酯降解液制备聚氨酯鞋底原液,其特征在于,包括A组分和B组分,所述A组分为聚酯多元醇、扩链剂、发泡剂、催化剂A和匀泡剂的混合物,所述B组分为异氰酸酯、聚酯多元醇和聚氨酯降解产物的预聚合反应的产物,所述预聚合反应中添加副反应阻止剂。
2.根据权利要求1所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,其特征在于,所述A组分的活泼氢摩尔数与B组分的异氰酸根摩尔数之比为100:99-101。
3.根据权利要求1所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,其特征在于,所述A组分中各组分按重量份计配比为:
4.根据权利要求1所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,其特征在于,所述B组分中各组分按重量份计配比为:
异氰酸酯 100份
聚酯多元醇 5-30份
聚氨酯降解产物 5-30份。
5.根据权利要求4所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,其特征在于,所述聚氨酯降解产物的制备方法,包括如下步骤:将废旧聚氨酯、小分子二元醇和催化剂B加入到反应釜中,控制反应温度为180~230℃,反应时间3~5小时,除去小分子,出料,得到所述聚氨酯降解产物。
6.根据权利要求5所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,其特征在于,所述小分子二元醇选自乙二醇、丙二醇、二乙二醇和丁二醇中的一种或多种,所述催化剂B选自醋酸钾、醋酸锌、异辛酸钾、氢氧化钾、氢氧化钠、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、丁二胺和丙二胺中的一种或多种。
7.根据权利要求1所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,其特征在于,所述副反应阻止剂选自无机酸、有机酸或苯甲酰氯。
8.根据权利要求1所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,其特征在于,所述聚氨酯降解产物的羟值为50~150mgKOH/g。
9.根据权利要求1所述由废旧聚氨酯降解液制备聚氨酯鞋底原液,其特征在于,所述聚酯多元醇选自聚己二酸系聚酯多元醇和对苯二甲酸系聚酯多元醇的一种或多种;所述扩链剂选自1,4-丁二醇、乙二醇和一缩二乙二醇中的一种或多种;所述催化剂A选自二月桂酸二丁基锡、三乙烯二胺和四甲基二亚乙基三胺中的一种或多种;所述匀泡剂选自DC-193、DC-3042和DC-3043中的一种或多种;所述发泡剂选自水、氯氟烃和环戊烷中的一种或多种;所述异氰酸酯选自4,4-二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯和萘二异氰酸酯中的一种或多种。
10.权利要求1-9任一所述由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备方法,其特征在于,包括如下步骤:
1)A组分的制备:将聚酯多元醇与扩链剂、发泡剂、催化剂A、匀泡剂加入反应釜,升温到50~80℃混合均匀,再冷却至35~40℃出料,获得A组份;
2)B组分的制备:将聚酯多元醇、聚氨酯降解产物、异氰酸酯和副反应阻止剂加入反应釜,于70~80℃条件下预聚合反应2~3h,获得B组份。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810195272.XA CN108623784B (zh) | 2018-03-09 | 2018-03-09 | 由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810195272.XA CN108623784B (zh) | 2018-03-09 | 2018-03-09 | 由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108623784A true CN108623784A (zh) | 2018-10-09 |
CN108623784B CN108623784B (zh) | 2021-04-27 |
Family
ID=63706163
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810195272.XA Active CN108623784B (zh) | 2018-03-09 | 2018-03-09 | 由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108623784B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110628205A (zh) * | 2019-09-05 | 2019-12-31 | 浙江温州轻工研究院 | 一种聚氨酯鞋底材料及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997027243A1 (en) * | 1996-01-25 | 1997-07-31 | Imperial Chemical Industries Plc | Process for hydrolysing polyurethane degradation products |
CN105693982A (zh) * | 2016-04-12 | 2016-06-22 | 广州聚天化工科技有限公司 | 一种基于聚氨酯降解产物制备的聚氨酯塑胶跑道乙组分及其制备方法和应用 |
CN105693993A (zh) * | 2016-04-12 | 2016-06-22 | 广州聚天化工科技有限公司 | 一种基于聚氨酯鞋垫降解产物的聚氨酯硬泡材料及其制备方法 |
CN107245162A (zh) * | 2017-07-21 | 2017-10-13 | 中山大学 | 一种聚氨酯降解方法及其降解产物在塑胶跑道乙组分中的应用 |
-
2018
- 2018-03-09 CN CN201810195272.XA patent/CN108623784B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997027243A1 (en) * | 1996-01-25 | 1997-07-31 | Imperial Chemical Industries Plc | Process for hydrolysing polyurethane degradation products |
CN105693982A (zh) * | 2016-04-12 | 2016-06-22 | 广州聚天化工科技有限公司 | 一种基于聚氨酯降解产物制备的聚氨酯塑胶跑道乙组分及其制备方法和应用 |
CN105693993A (zh) * | 2016-04-12 | 2016-06-22 | 广州聚天化工科技有限公司 | 一种基于聚氨酯鞋垫降解产物的聚氨酯硬泡材料及其制备方法 |
CN107245162A (zh) * | 2017-07-21 | 2017-10-13 | 中山大学 | 一种聚氨酯降解方法及其降解产物在塑胶跑道乙组分中的应用 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110628205A (zh) * | 2019-09-05 | 2019-12-31 | 浙江温州轻工研究院 | 一种聚氨酯鞋底材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN108623784B (zh) | 2021-04-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2134808C (en) | A process for the cfc-free production of cellular polyurethane molded parts | |
EP1726612B1 (en) | Carbon dioxide blown low density, flexible microcellular polyurethane elastomers | |
EP3470446A1 (en) | Rigid polyurethane foam system and application thereof | |
EP3664984B1 (en) | Isocyanate-functional polymer components and polyurethane articles formed from recycled polyurethane articles and associated methods for forming same | |
EP3935097B1 (en) | Polyol blends and their use in producing pur-pir foam-forming compositions | |
WO2019038289A1 (en) | RIGID POLYURETHANE FOAM SYSTEM AND CORRESPONDING APPLICATION | |
CA2557193A1 (en) | Process for making rigid polyurethane foams | |
CN108409934A (zh) | 高回弹耐低温聚氨酯鞋底原料及其制备方法 | |
CN101190973B (zh) | 塑性复合元件及其制造方法 | |
JP2781574B2 (ja) | ポリイソシアネート組成物、その製法及び発泡体の製法 | |
CN108623784A (zh) | 由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法 | |
CN108948320A (zh) | 一种用于制造聚氨酯鞋底材料的组合料 | |
CS223831B2 (en) | Method of making the cellular polyurethan elastomere | |
CN108997556A (zh) | 含有生物质粉末的聚氨酯原液及其制法和应用 | |
US20220227917A1 (en) | Low density polyurethane foam systems with high split tear | |
JP6259561B2 (ja) | クリーニングローラおよびクリーニングローラに使用されるポリウレタンフォームの製造方法 | |
CN103497297A (zh) | 一种基于聚碳酸1,3-丙二醇酯多元醇的聚氨酯材料 | |
TWI419906B (zh) | 多異氰酸酯基生質材料及其形成方法 | |
CN109251353A (zh) | Expancel DU:提高发泡聚氨酯物性的高效广谱助剂 | |
US11753516B2 (en) | HFO-containing compositions and methods of producing foams | |
US20040077740A1 (en) | Cellular polyurethane elastomers, a process for preparing these and their use | |
JP3780522B2 (ja) | 自動車シートクッション用軟質ポリウレタンフォームの製造方法 | |
US11767407B1 (en) | HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production | |
US5739207A (en) | Hexamethylene diisocyanate residue-based compositions as fillers for polyisocyanates | |
US5789497A (en) | Hexamethylene diisocyanate residue-based compositions as fillers for polyether polyols |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20210809 Address after: 215000 No. 3, GCL Middle Road, taicanggang Port Development Zone, Suzhou, Jiangsu Patentee after: XUCHUAN CHEMICAL (SUZHOU) Co.,Ltd. Address before: 198 Xinle Road, Dianshanhu Town, Kunshan City, Suzhou City, Jiangsu Province Patentee before: XUCHUAN CHEMICAL (KUNSHAN) Co.,Ltd. Patentee before: XUCHUAN CHEMICAL (SUZHOU) Co.,Ltd. |