CN111286072B - 一种pu鞋底原液及其制备方法和相应的鞋底的制备方法 - Google Patents
一种pu鞋底原液及其制备方法和相应的鞋底的制备方法 Download PDFInfo
- Publication number
- CN111286072B CN111286072B CN202010090434.0A CN202010090434A CN111286072B CN 111286072 B CN111286072 B CN 111286072B CN 202010090434 A CN202010090434 A CN 202010090434A CN 111286072 B CN111286072 B CN 111286072B
- Authority
- CN
- China
- Prior art keywords
- component
- sole
- parts
- stock solution
- mold
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/02—Producing footwear made in one piece using a moulding technique, e.g. by injection moulding or casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/122—Soles
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular 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
- C08G18/4236—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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- 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
- C08G18/28—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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- 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
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- 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)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明提出了一种PU鞋底原液,包括A组分、B组分和C组分,其中:A组分:己二酸5‑10份;乙二醇5‑10份;MDI 25‑45份;B组分:微晶纤维素32‑37份;羟甲基纤维素12‑25份;发泡剂0.2‑0.5份;匀泡剂0.1‑0.3份;纯水1‑2份;C组分:乙二醇2‑5份;三乙烯二胺0.1‑0.2份。本发明采用纤维素作为聚酯‑醚多元醇材料水解稳定性好,常温下为液体,粘度低,发泡范围宽,便于操作,等优点,制得的PU鞋底原液撕裂强度大、拉伸强度大、拉伸率大的优良力学性能和聚醚型鞋底原液粘度低、耐水解的特性,具有很好的应用价值,制得的PU鞋底一体成型,外鞋底和内鞋底粘合力大,不易脱胶,实用性强。
Description
技术领域
本发明涉及高分子合成技术领域,具体涉及一种PU鞋底原液及其制备方法和相应的鞋底的制备方法。
背景技术
鞋底用聚氨酯树脂(polyurethane,PU),又称为聚氨酯鞋底原液,是制备聚氨酯鞋底的原料,其产量仅占所有聚氨酯产品的5%左右,但在鞋底材料中性能独特,发展迅速,成本不可取代的优秀材料。
目前用于PU鞋底用聚多元醇,主要有聚酯多元醇和聚醚多元醇两大类。聚酯型鞋底具有强度大,耐磨性好,与鞋面粘结性好等特性,占据了聚氨酯鞋底材料80%以上的市场份额。但是聚酯型鞋底材料也有其自身的缺点:耐水解性差,耐温性差,常温下是固体或高粘度液体,不便于操作等。聚醚型鞋底材料力学性能较聚酯型差,但由于其良好的耐水解稳定性,常温下为液体,粘度低,发泡范围宽,便于操作,经济性好,原料易得等特性,在聚氨酯鞋底材料中发展越来越快。
发明内容
本发明提供一种PU鞋底原液及其制备方法和相应的鞋底,其目的在于,提供一种PU鞋底原液,水解稳定性好,常温下为液体,粘度低,便于操作,经济性好,原料易得等优点,制得的PU鞋底一体成型,外鞋底和内鞋底粘合力大,不易脱胶,实用性强。
本发明提供一种PU鞋底原液,包括A组分、B组分和C组分,其中:
A组分:
己二酸5-10份;
乙二醇5-10份
MDI 25-45份;
B组分:
微晶纤维素32-37份;
羟甲基纤维素12-25份;
发泡剂0.2-0.5份;
匀泡剂0.1-0.3份;
水1-2份;
C组分:
乙二醇2-5份;
三乙烯二胺0.1-0.2份。
作为本发明进一步的改进,还包括D组分:抗黄剂5-10份、硬化剂2-5份。
作为本发明进一步的改进,所述发泡剂选自HCFC-141B或二氯甲烷中的一种;所述匀泡剂选自PU-1230、XHG-293、H420、DC190、PU-1253中的一种或几种混合。
作为本发明进一步的改进,所述抗黄剂选自抗黄剂L9322、抗黄剂UVK-CL、抗黄剂UVK-CL2、抗黄剂L-1268中的一种或几种混合;所述硬化剂为3,3’-二氯-4,4’-二氨基二苯基甲烷。
本发明进一步保护一种上述PU鞋底原液的制备方法,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至180-220℃反应2-3h,蒸出副产物水,降至75-85℃,加入MDI,搅拌反应1-2h,得到A组分;
S2.将微晶纤维素、羟甲基纤维素、发泡剂、匀泡剂、水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将A组分、B组分和C组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应3-5min开模,室温下自然熟化24h,得到PU鞋底原液。
本发明进一步保护一种上述PU鞋底原液的制备方法,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至180-220℃反应2-3h,蒸出副产物水,降至75-85℃,加入MDI,搅拌反应1-2h,得到A组分;
S2.将微晶纤维素、羟甲基纤维素、发泡剂、匀泡剂、水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将抗黄剂和硬化剂研细,混合均匀,得到D组分;
S5.将A组分、B组分、C组分和D组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应3-5min开模,室温下自然熟化24h,得到PU鞋底原液。
本发明进一步保护一种PU鞋底的制备方法,包括以下步骤:
S1.采用彩色粉和上述PU鞋底原液制成混合物,将所述混合物喷涂在浇注机的模具上,成型外鞋底;
S2.在模具的空腔内浇注发泡PU材料,加热得到成型的内鞋底,整个鞋底一体成型。
本发明进一步保护一种PU鞋底的制备方法,包括以下步骤:
S1.采用彩色粉和上述PU鞋底原液制成混合物,将所述混合物喷涂在浇注机的模具上,成型外鞋底;
S2.在模具的空腔内浇注发泡PU材料,加热得到成型的内鞋底,整个鞋底一体成型。
作为本发明进一步的改进,所述混合物的制备方法为将彩色粉与所述PU鞋底原液加热开炼机加热至200℃混合均匀;所述混合物以每分钟100mL的速度喷涂;步骤S2中所述加热温度为180-220℃。
本发明进一步保护如上述PU鞋底的制备方法制得的PU鞋底,所述外鞋底和内鞋底一体成型。
本发明具有如下有益效果:本发明采用纤维素作为聚酯-醚多元醇材料,兼具了聚酯多元醇的强度大,耐磨性好,与鞋面粘结性好等优点和聚醚多元醇的耐水解稳定性好,常温下为液体,粘度低,发泡范围宽,便于操作,经济性好,原料易得等优点,制得的PU鞋底原液撕裂强度大、拉伸强度大、拉伸率大的优良力学性能和聚醚型鞋底原液粘度低、耐水解的特性,具有很好的应用价值;
本发明制得的PU鞋底一体成型,外鞋底和内鞋底粘合力大,不易脱胶,实用性强。
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做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1PU鞋底原液的制备
原料组成(重量份):
A组分:
己二酸5份;
乙二醇5份
MDI 25份;
B组分:
微晶纤维素32份;
羟甲基纤维素12份;
发泡剂0.2份;所述发泡剂为二氯甲烷;
匀泡剂0.1份;所述匀泡剂为PU-1230;
纯水1份;
C组分:
乙二醇2份
三乙烯二胺0.1份。
PU鞋底原液的制备方法,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至180℃反应2h,蒸出副产物水,降至75℃,加入MDI,搅拌反应1h,得到A组分;
S2.将微晶纤维素、羟甲基纤维素、发泡剂、匀泡剂、纯水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将A组分、B组分和C组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应3min开模,室温下自然熟化24h,得到PU鞋底原液。
实施例2PU鞋底原液的制备
原料组成(重量份):
A组分:
己二酸10份;
乙二醇10份
MDI 45份;
B组分:
微晶纤维素37份;
羟甲基纤维素18份;
发泡剂0.5份;所述发泡剂为二氯甲烷;
匀泡剂0.3份;所述匀泡剂为PU-1230;
纯水2份;
C组分:
乙二醇5份
三乙烯二胺0.2份。
PU鞋底原液的制备方法,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至210℃反应3h,蒸出副产物水,降至82℃,加入MDI,搅拌反应2h,得到A组分;
S2.将微晶纤维素、羟甲基纤维素、发泡剂、匀泡剂、纯水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将A组分、B组分和C组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应4min开模,室温下自然熟化24h,得到PU鞋底原液。
实施例3PU鞋底原液的制备
原料组成(重量份):
A组分:
己二酸5份;
乙二醇5份
MDI 25份;
B组分:
微晶纤维素32份;
羟甲基纤维素20份;
发泡剂0.2份;所述发泡剂为二氯甲烷;
匀泡剂0.1份;所述匀泡剂为PU-1230;
纯水1份;
C组分:
乙二醇2份
三乙烯二胺0.1份;
D组分:
抗黄剂5份;抗黄剂为抗黄剂L9322;
硬化剂2份;硬化剂为3,3’-二氯-4,4’-二氨基二苯基甲烷。
PU鞋底原液的制备方法,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至190℃反应2h,蒸出副产物水,降至78℃,加入MDI,搅拌反应1h,得到A组分;
S2.将微晶纤维素、羟甲基纤维素、发泡剂、匀泡剂、纯水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将抗黄剂和硬化剂研细,混合均匀,得到D组分;
S5.将A组分、B组分、C组分和D组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应4min开模,室温下自然熟化24h,得到PU鞋底原液。
实施例4PU鞋底原液的制备
原料组成(重量份):
A组分:
己二酸10份;
乙二醇10份
MDI 45份;
B组分:
微晶纤维素37份;
羟甲基纤维素18份;
发泡剂0.5份;所述发泡剂为二氯甲烷;
匀泡剂0.3份;所述匀泡剂为PU-1230;
纯水2份;
C组分:
乙二醇5份
三乙烯二胺0.2份;
D组分:
抗黄剂10份;抗黄剂为抗黄剂L9322;
硬化剂5份;硬化剂为3,3’-二氯-4,4’-二氨基二苯基甲烷。
PU鞋底原液的制备方法,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至210℃反应3h,蒸出副产物水,降至82℃,加入MDI,搅拌反应2h,得到A组分;
S2.将微晶纤维素、羟甲基纤维素、发泡剂、匀泡剂、纯水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将抗黄剂和硬化剂研细,混合均匀,得到D组分;
S5.将A组分、B组分、C组分和D组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应4min开模,室温下自然熟化24h,得到PU鞋底原液。
对比例1PU鞋底原液的制备
与实施例4相比,未添加微晶纤维素,其他原料和制备方法一致。
原料组成(重量份):
A组分:
己二酸10份;
乙二醇10份
MDI 45份;
B组分:
羟甲基纤维素55份;
发泡剂0.5份;所述发泡剂为二氯甲烷;
匀泡剂0.3份;所述匀泡剂为PU-1230;
纯水2份;
C组分:
乙二醇5份
三乙烯二胺0.2份;
D组分:
抗黄剂10份;抗黄剂为抗黄剂L9322;
硬化剂5份;硬化剂为3,3’-二氯-4,4’-二氨基二苯基甲烷。
PU鞋底原液的制备方法,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至210℃反应3h,蒸出副产物水,降至82℃,加入MDI,搅拌反应2h,得到A组分;
S2.将羟甲基纤维素、发泡剂、匀泡剂、纯水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将抗黄剂和硬化剂研细,混合均匀,得到D组分;
S5.将A组分、B组分、C组分和D组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应4min开模,室温下自然熟化24h,得到PU鞋底原液。
对比例2
与实施例4相比,未添加羟甲基纤维素,其他原料和制备方法一致。
原料组成(重量份):
A组分:
己二酸10份;
乙二醇10份
MDI 45份;
B组分:
微晶纤维素55份;
发泡剂0.5份;所述发泡剂为二氯甲烷;
匀泡剂0.3份;所述匀泡剂为PU-1230;
纯水2份;
C组分:
乙二醇5份
三乙烯二胺0.2份;
D组分:
抗黄剂10份;抗黄剂为抗黄剂L9322;
硬化剂5份;硬化剂为3,3’-二氯-4,4’-二氨基二苯基甲烷。
PU鞋底原液的制备方法,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至210℃反应3h,蒸出副产物水,降至82℃,加入MDI,搅拌反应2h,得到A组分;
S2.将微晶纤维素、发泡剂、匀泡剂、纯水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将抗黄剂和硬化剂研细,混合均匀,得到D组分;
S5.将A组分、B组分、C组分和D组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应4min开模,室温下自然熟化24h,得到PU鞋底原液。
实施例5PU鞋底的制备
包括以下方法:
S1.采用彩色粉和实施例2制得PU鞋底原液制成混合物,混合物的制备方法为将彩色粉与所述PU鞋底原液加热开炼机加热至200℃混合均匀;所述混合物以每分钟100mL的速度喷涂;步骤S2中所述加热温度为180℃;将所述混合物喷涂在浇注机的模具上,成型外鞋底;
S2.在模具的空腔内浇注发泡PU材料,加热得到成型的内鞋底,整个鞋底一体成型。
实施例6PU鞋底的制备
包括以下步骤:
S1.采用彩色粉和实施例4制得的PU鞋底原液制成混合物,混合物的制备方法为将彩色粉与所述PU鞋底原液加热开炼机加热至200℃混合均匀;所述混合物以每分钟100mL的速度喷涂;步骤S2中所述加热温度为220℃;将所述混合物喷涂在浇注机的模具上,成型外鞋底;
S2.在模具的空腔内浇注发泡PU材料,加热得到成型的内鞋底,整个鞋底一体成型。
对比例3PU鞋底的制备
包括以下步骤:
S1.采用彩色粉和对比例1制得的PU鞋底原液制成混合物,混合物的制备方法为将彩色粉与所述PU鞋底原液加热开炼机加热至200℃混合均匀;所述混合物以每分钟100mL的速度喷涂;步骤S2中所述加热温度为220℃;将所述混合物喷涂在浇注机的模具上,成型外鞋底;
S2.在模具的空腔内浇注发泡PU材料,加热得到成型的内鞋底,整个鞋底一体成型。
对比例4PU鞋底的制备
包括以下步骤:
S1.采用彩色粉和对比例2制得的PU鞋底原液制成混合物,混合物的制备方法为将彩色粉与所述PU鞋底原液加热开炼机加热至200℃混合均匀;所述混合物以每分钟100mL的速度喷涂;步骤S2中所述加热温度为220℃;将所述混合物喷涂在浇注机的模具上,成型外鞋底;
S2.在模具的空腔内浇注发泡PU材料,加热得到成型的内鞋底,整个鞋底一体成型。
测试例1
将实施例5、6和对比例3、4制备的鞋底进行性能测试,结果见表1。
表1
由上表可知,本发明实施例5、6制备的PU鞋底与市售弹性鞋底进行对比,综合性能更优,表现为力学性能更好(耐磨)、密度更低(质量轻)、硬度更小(更软)。
对比例3采用对比例1制备的PU原液制备,对比例4采用对比例2制备的PU原液制备,其力学性能、密度和硬度性能大幅度下降,可见,微晶纤维素和羧甲基纤维素的添加,对于PU鞋底的性能具有明显的增强,具有协同增效的作用。
与现有技术相比,本发明采用纤维素作为聚酯-醚多元醇材料,兼具了聚酯多元醇的强度大,耐磨性好,与鞋面粘结性好等优点和聚醚多元醇的耐水解稳定性好,常温下为液体,粘度低,发泡范围宽,便于操作,经济性好,原料易得等优点,制得的PU鞋底原液撕裂强度大、拉伸强度大、拉伸率大的优良力学性能和聚醚型鞋底原液粘度低、耐水解的特性,具有很好的应用价值;
本发明制得的PU鞋底一体成型,外鞋底和内鞋底粘合力大,不易脱胶,实用性强。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种PU鞋底原液,其特征在于,包括A组分、B组分和C组分,以重量份计,其中:
A组分:
己二酸 5-10份;
乙二醇 5-10份
MDI 25-45份;
B组分:
微晶纤维素 32-37份;
羟甲基纤维素 12-25份;
发泡剂 0.2-0.5份;
匀泡剂 0.1-0.3份;
水 1-2份;
C组分:
乙二醇 2-5份;
三乙烯二胺 0.1-0.2份。
2.根据权利要求1所述一种PU鞋底原液,其特征在于,还包括以重量份计的D组分:抗黄剂5-10份、硬化剂2-5份。
3.根据权利要求1所述一种PU鞋底原液,其特征在于,所述发泡剂选自HCFC-141B或二氯甲烷中的一种;所述匀泡剂选自PU-1230、XHG-293、H420、DC190、PU-1253中的一种或几种混合。
4.根据权利要求2所述一种PU鞋底原液,其特征在于,所述抗黄剂选自抗黄剂L9322、抗黄剂UVK-CL、抗黄剂UVK-CL2、抗黄剂L-1268中的一种或几种混合;所述硬化剂为3,3’-二氯-4,4’-二氨基二苯基甲烷。
5.一种如权利要求1或3所述PU鞋底原液的制备方法,其特征在于,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至180-220℃反应2-3h,蒸出副产物水,降至75-85℃,加入MDI,搅拌反应1-2h,得到A组分;
S2.将微晶纤维素、羟甲基纤维素、发泡剂、匀泡剂、水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将A组分、B组分和C组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应3-5min开模,室温下自然熟化24h,得到PU鞋底原液。
6.一种如权利要求2或4所述PU鞋底原液的制备方法,其特征在于,包括以下步骤:
S1.按比例将己二酸与乙二醇混合加热至180-220℃反应2-3h,蒸出副产物水,降至75-85℃,加入MDI,搅拌反应1-2h,得到A组分;
S2.将微晶纤维素、羟甲基纤维素、发泡剂、匀泡剂、水按比例混合均匀,得到B组分;
S3.按比例将三乙烯二胺加入乙二醇中混合均匀,得到C组分;
S4.将抗黄剂和硬化剂研细,混合均匀,得到D组分;
S5.将A组分、B组分、C组分和D组分充分混合均匀,然后将其浇入到试片模具或鞋底模具中,熟化反应3-5min开模,室温下自然熟化24h,得到PU鞋底原液。
7.一种PU鞋底的制备方法,其特征在于,包括以下步骤:
S1.采用彩色粉和权利要求1或3所述PU鞋底原液制成混合物,将所述混合物喷涂在浇注机的模具上,成型外鞋底;
S2.在模具的空腔内浇注发泡PU材料,加热得到成型的内鞋底,整个鞋底一体成型。
8.一种PU鞋底的制备方法,其特征在于,包括以下步骤:
S1.采用彩色粉和权利要求2或4所述PU鞋底原液制成混合物,将所述混合物喷涂在浇注机的模具上,成型外鞋底;
S2.在模具的空腔内浇注发泡PU材料,加热得到成型的内鞋底,整个鞋底一体成型。
9.根据权利要求7或8所述PU鞋底的制备方法,其特征在于,所述混合物的制备方法为将彩色粉与所述PU鞋底原液开炼机加热至200℃混合均匀;所述混合物以每分钟100mL的速度喷涂;步骤S2中所述加热温度为180-220℃。
10.如权利要求7-9任一项权利要求所述PU鞋底的制备方法制得的PU鞋底,其特征在于,所述外鞋底和内鞋底一体成型。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010090434.0A CN111286072B (zh) | 2020-02-13 | 2020-02-13 | 一种pu鞋底原液及其制备方法和相应的鞋底的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010090434.0A CN111286072B (zh) | 2020-02-13 | 2020-02-13 | 一种pu鞋底原液及其制备方法和相应的鞋底的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111286072A CN111286072A (zh) | 2020-06-16 |
CN111286072B true CN111286072B (zh) | 2021-04-13 |
Family
ID=71025552
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010090434.0A Active CN111286072B (zh) | 2020-02-13 | 2020-02-13 | 一种pu鞋底原液及其制备方法和相应的鞋底的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111286072B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115141349A (zh) * | 2022-08-05 | 2022-10-04 | 杭州朴西生活家居有限公司 | 一种高回弹聚氨酯泡沫及其制备工艺 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103570908A (zh) * | 2012-07-19 | 2014-02-12 | 旭川化学(昆山)有限公司 | 一种聚氨酯鞋底材料原液 |
CN105461915A (zh) * | 2015-12-24 | 2016-04-06 | 山东一诺威新材料有限公司 | 微孔pu鞋底用聚酯-醚多元醇、其制法及其制备的pu鞋底原液和pu鞋底原液的制法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1358240A1 (en) * | 2000-12-27 | 2003-11-05 | World Properties, Inc. | Polyurethane foams and method of manafacture thereof |
-
2020
- 2020-02-13 CN CN202010090434.0A patent/CN111286072B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103570908A (zh) * | 2012-07-19 | 2014-02-12 | 旭川化学(昆山)有限公司 | 一种聚氨酯鞋底材料原液 |
CN105461915A (zh) * | 2015-12-24 | 2016-04-06 | 山东一诺威新材料有限公司 | 微孔pu鞋底用聚酯-醚多元醇、其制法及其制备的pu鞋底原液和pu鞋底原液的制法 |
Also Published As
Publication number | Publication date |
---|---|
CN111286072A (zh) | 2020-06-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104140520B (zh) | 一种超软质高弹性耐水解高剥离的湿式聚氨酯树脂及其制备方法 | |
CN106700029B (zh) | 聚氨酯鞋底用树脂及制备方法和应用 | |
CN103641980B (zh) | 耐水解热塑性聚氨酯弹性体及其制备方法 | |
EP3004247B1 (en) | Polyurethane composites comprising nanocrystalline cellulose and method for improving properties of polyurethanes thereof | |
CN111286072B (zh) | 一种pu鞋底原液及其制备方法和相应的鞋底的制备方法 | |
CN113185666B (zh) | 一种良好弹性鞋垫及制作工艺 | |
CN105504193B (zh) | 防潮环保三聚氰胺改性脲醛树脂胶粘剂及其制备方法 | |
CN111234763B (zh) | 一种轻质刨花板用的复配发泡胶黏剂 | |
CN102140158B (zh) | 一种二氧化碳共聚物多元醇为基础的聚氨酯材料及用途 | |
CN102079808A (zh) | 聚氨酯鞋用树脂 | |
CN111808267A (zh) | 一种无卤阻燃聚氨酯泡沫及其制备方法 | |
CN106674465B (zh) | 聚氨酯鞋底用树脂及制备方法和应用 | |
CN101503503A (zh) | 聚醚型聚氨酯鞋用仿木耐硫化材料的制备方法 | |
CN106810668B (zh) | 聚氨酯鞋底用树脂及制备方法和应用 | |
KR100971521B1 (ko) | 아미노수지를 포함하는 발포체용 폴리우레탄 수지 조성물 | |
CN111500055A (zh) | 一种低温柔型聚氨酯复合鞋材及制备方法 | |
CN107523039B (zh) | 聚氨酯鞋底及其制备方法 | |
EP3820925A1 (de) | Glasfaserverstärktes tpu | |
CN106674480A (zh) | Ndi改性mdi基聚氨酯微孔弹性体的制备方法 | |
KR101737764B1 (ko) | 바이오 폴리올을 사용한 미세기공형 폼시트용 폴리우레탄 수지조성물 | |
CN108178826A (zh) | 一种耐低温聚氨酯鞋材用树脂及其制备方法 | |
CN105732948A (zh) | 一种高固含量低模量镜面pu革用湿法树脂及其制备方法 | |
CN108383969A (zh) | 一种聚氨酯发泡鞋底及其制作方法 | |
CN111187464A (zh) | 一种epoe合成发泡高弹新型鞋底材料及其制备方法 | |
CN102675585A (zh) | 添加醇胺化合物的聚氨酯微孔弹性体及制备方法和应用 |
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 |