CN115322318B - 一种低成本环保可降解港宝及其制备方法 - Google Patents
一种低成本环保可降解港宝及其制备方法 Download PDFInfo
- Publication number
- CN115322318B CN115322318B CN202211034292.1A CN202211034292A CN115322318B CN 115322318 B CN115322318 B CN 115322318B CN 202211034292 A CN202211034292 A CN 202211034292A CN 115322318 B CN115322318 B CN 115322318B
- Authority
- CN
- China
- Prior art keywords
- low
- isophthalic acid
- harbor
- reaction
- diisocyanate
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920000728 polyester Polymers 0.000 claims abstract description 28
- 239000002699 waste material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000006136 alcoholysis reaction Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 20
- -1 polyethylene terephthalate-isophthalic acid copolymer Polymers 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims 1
- 229920005749 polyurethane resin Polymers 0.000 claims 1
- 239000004831 Hot glue Substances 0.000 abstract description 19
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 3
- 238000007493 shaping process Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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
- C08G18/28—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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
- A43B23/07—Linings therefor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid 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
- C08G18/4236—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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明属于港宝技术领域，公开了一种低成本环保可降解港宝及其制备方法，利用己二酸与乙二醇酯化制得聚己二酸乙二醇酯，然后将废弃聚对苯二甲酸乙二醇酯的醇解物和间苯二甲酸酯化缩聚合成一定分子量的聚对苯二甲酸乙二醇酯‑间苯二甲酸共聚物，将聚己二酸乙二醇酯和聚对苯二甲酸乙二醇酯‑间苯二甲酸共聚物共混后再与二异氰酸酯反应浇片制备得到热熔胶港宝。本发明制得的热熔胶港宝具有结晶温度高、冷却定型快、加工温度低等优点，低熔点的热熔胶港宝产品还具有优异的降解性能，并且使用乙二醇代替传统的丁二醇体系又具有明显的价格优势，回收再利用了废弃聚酯，符合绿色环保的理念。
Description
技术领域
本发明属于港宝技术领域，特别涉及一种低成本环保可降解港宝及其制备方法。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
热熔胶港宝作为一种新型的制鞋前后衬材料，由于具有操作温度低、开放时间长以及高粘结强度等特性而被广泛应用。目前，热熔胶港宝主要采用己二酸与丁二醇合成多元醇再与二异氰酸酯反应形成的热塑性聚氨酯(TPU)来制备，然而丁二醇居高不下的价格限制了其大规模应用。
聚酯材料在生产、加工和使用过程中，会产生大量的聚酯薄膜废料、废弃聚酯瓶等，这些废弃物难以自然降解，严重污染环境并造成了不可逆的经济损失。因此，将废弃的聚酯材料回收再利用，减少环境污染的同时也有利于降低碳排放。CN102675113A、CN113173856A等专利公开了一种醇解聚对苯二甲酸乙二醇酯(PET)制备对苯二甲酸乙二醇酯(BHET)的方法，但废弃聚酯醇解产物的高价值利用的问题仍有待解决。
发明内容
为了解决克服现有港宝成本过高，废弃聚酯浪费污染的问题，本发明提供了一种低成本环保可降解港宝及其制备方法。
为了实现上述目的，本发明采用如下技术方案：
本发明的第一个方面，提供了一种低成本环保可降解港宝的制备方法，包括：
将醋酸锌溶解在乙二醇中，然后加入废弃聚酯碎片，升温进行反应，反应完成后，洗涤、过滤、冷却，得到醇解产物；
将间苯二甲酸与所述醇解产物混合均匀，进行酯化反应，得到低分子量的共聚物，再加入钛酸酯或有机锡类催化剂进行真空缩聚，得到聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物；
将己二酸、乙二醇混合均匀，进行酯化反应，待出水减少后升温继续反应至不再出水，然后加入钛酸酯或有机锡类催化剂，进行酯交换反应，得到聚己二酸乙二醇酯；
将所述聚己二酸乙二醇酯与聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物共混均匀后与二异氰酸酯进行浇片反应，即得。
本发明通过对废弃聚酯醇解产物的再利用，来生产不饱和聚酯或聚氨酯，实现了废弃聚酯醇解产物的高价值利用。
本发明的第二个方面，提供了上述的方法制备的可降解港宝。
本发明的第三个方面，提供了上述的可降解港宝在制鞋领域中的应用。
本发明的有益效果
(1)本发明通过乙二醇醇解废弃聚酯得到醇解产物，减少废弃聚酯环境污染的同时又成功利用了其醇解产物，并且将废弃聚酯的醇解产物与间苯二甲酸酯化缩聚，合成了具有一定分子量的低熔点聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物。
(2)乙二醇系列港宝的结晶温度低，与结晶度高的聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物共混成功改善了其结晶成型慢的问题，并且添加了间苯二甲酸与醇解产物共聚，链段的规整性破坏，降低了产物的熔点，不影响热熔胶产品加工性能。
(3)本发明使用低成本的乙二醇代替成本更高的丁二醇，降低热熔胶港宝产品成本的同时有利于其更大范围的应用，此外，制备低熔点易加工的热熔胶港宝具有优异的可降解性能，符合绿色环保理念。
(4)本发明制备方法简单、实用性强，易于推广。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的说明。除非另有指明，本发明使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
一种低成本环保可降解港宝及其制备方法，包括：
(1)将废弃聚酯放入粉碎机中粉碎，然后将其洗涤干燥后得到聚酯碎片待用，将一定比例的乙二醇和醋酸锌加入反应釜中，在氮气保护下升温搅拌至醋酸锌完全溶解，然后加入上述聚酯碎片升温至190-230℃反应4-6h后倒出，洗涤并过滤后置于0℃左右环境中冷却结晶，得到醇解产物；
(2)将间苯二甲酸与过量的上述醇解产物在200℃进行2h的酯化反应合成低分子量的共聚物，加入80-100ppm钛酸酯或有机锡类催化剂后在260℃、-0.095Mpa真空度下缩聚成一定分子量的聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物。
(3)将己二酸、乙二醇加入反应釜中，在氮气保护下升温搅拌至180℃进行2h酯化反应，待出水减少后升温至220℃继续反应至不再出水，然后加入60-80ppm钛酸酯或有机锡类催化剂，抽真空至-0.095Mpa进行酯交换反应直至分子量达到要求，制得聚己二酸乙二醇酯(PEA)；
(4)将不同比例的PEA与聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物共混均匀后与二异氰酸酯进行浇片反应，得到热熔胶港宝。
在一些实施例中，步骤(1)中，所述废弃聚酯为聚对苯二甲酸乙二醇酯(PET)，对应的醇解产物为对苯二甲酸乙二醇酯(BHET)。
在一些实施例中，步骤(1)中，所述乙二醇用量为废弃聚酯质量的1.5～2倍，醋酸锌用量为废弃聚酯的0.3～0.5％。
在一些实施例中，废弃聚酯、乙二醇、醋酸锌进行反应的条件为升温至190-230℃反应4-6h，洗涤并过滤后置于0℃左右环境中冷却结晶。
在一些实施例中，所述间苯二甲酸与醇解产物进行酯化反应的条件为：200～210℃进行1.5～2h；
在一些实施例中，所述间苯二甲酸与醇解产物真空缩聚的条件为：于260～280℃、-0.095～0.085Mpa下反应。
在一些实施例中，步骤(2)中，所述聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物分子量为2000～3000。
在一些实施例中，步骤(3)中，所述PEA分子量为2000～6000。
在一些实施例中，步骤(4)中，所述二异氰酸酯为二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯中的至少一种。
在一些实施例中，步骤(4)中，所述二异氰酸酯中的-NCO与所述共混二醇的-OH的摩尔比(R值)为0.94～0.98：1。
下面结合具体的实施例，对本发明做进一步的详细说明，应该指出，所述具体实施例是对本发明的解释而不是限定。
如无特殊说明，下述各实施例、对比例中各原料加入的“份”均指质量份。
实施例1
(a)将废弃聚酯矿泉水瓶放入粉碎机中粉碎，然后将其洗涤干燥后得到1-3mm左右的聚酯碎片待用，将200份的乙二醇和0.4份醋酸锌加入反应釜中，在氮气保护下升温搅拌至醋酸锌完全溶解，然后加入上述100份聚酯碎片升温至196℃反应5h后倒出，洗涤并过滤后置于0℃左右环境中冷却结晶，得到醇解产物BHET。
(b)将摩尔比为1.4：1的BHET与间苯二甲酸在200℃进行2h的酯化反应合成低分子量的共聚物，加入80ppm钛酸四丁酯后在260℃、-0.095Mpa真空度下缩聚成2000分子量的聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物。
(c)将己二酸、乙二醇加入反应釜中，在氮气保护下升温搅拌至180℃进行2h酯化反应，待出水减少后升温至220℃继续反应至不出水，然后加入50ppm钛酸四丁酯，抽真空至-0.095Mpa进行酯交换反应，制得4000分子量的PEA。
(d)将质量比为8：2的PEA与聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物共混均匀后与二苯基甲烷二异氰酸酯进行浇片反应，得到热熔胶港宝，反应R值设为0.96。
实施例2
步骤(d)中PEA与聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物质量比为7：3，其余与实施例1相同。
实施例3
步骤(d)中PEA与聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物质量比为9：1，其余与实施例1相同。
实施例4
步骤(c)中制得PEA的分子量为2000，其余与实施例1相同。
实施例5
步骤(c)中制得PEA的分子量为6000，其余与实施例1相同。
对比例1
(a)将己二酸、乙二醇加入反应釜中，在氮气保护下升温搅拌至180℃进行2h酯化反应，待出水减少后升温至220℃继续反应至不出水，然后加入50ppm钛酸四丁酯，抽真空至-0.095Mpa进行酯交换反应，制得4000分子量的PEA。
(b)将PEA与二苯基甲烷二异氰酸酯进行浇片反应，得到热熔胶港宝，反应R值设为0.96。
以上各实施例、对比例所得热熔胶港宝与市售H290(美瑞新材料股份有限公司)的性能测试如下表1：
表1
由以上数据可见，本发明采用PEA和聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物与二苯基甲烷二异氰酸酯反应成功制备得到热熔胶港宝，通过调节PEA与聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物共混比例、PEA的分子量，得到结晶温度高、冷却定型快、流变温度较低的低成本环保可降解热熔胶港宝；相比于纯PEA与二异氰酸酯制备得到的热熔胶，本发明明显提升了其结晶温度，有利于实际加工定型；相比于价格较高的丁二醇体系的H290，本发明提供的基于乙二醇的热熔胶港宝又具有明显的价格优势，并且置于热水中的软化程度与H290相当，表明其能够在较低的温度下加工成型；此外，回收再利用了废弃聚酯，符合绿色环保的理念。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。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 (9)
1.一种低成本环保可降解港宝的制备方法，其特征在于，包括：
将醋酸锌溶解在乙二醇中，然后加入废弃聚酯碎片，升温进行反应，反应完成后，洗涤、过滤、冷却，得到醇解产物；
将间苯二甲酸与所述醇解产物混合均匀，进行酯化反应，得到低分子量的共聚物，再加入钛酸酯或有机锡类催化剂进行真空缩聚，得到聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物；所述间苯二甲酸与醇解产物的摩尔比为1:1.4；
将己二酸、乙二醇混合均匀，进行酯化反应，待出水减少后升温继续反应至不再出水，然后加入钛酸酯或有机锡类催化剂，进行酯交换反应，得到聚己二酸乙二醇酯；所述聚己二酸乙二醇酯分子量为2000～6000；
将所述聚己二酸乙二醇酯与聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物共混均匀后与二异氰酸酯进行浇片反应，即得；
所述聚己二酸乙二醇酯与聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物质量比为7:3～9:1。
2.如权利要求1所述的低成本环保可降解港宝的制备方法，其特征在于，所述废弃聚酯为聚对苯二甲酸乙二醇酯。
3.如权利要求1所述的低成本环保可降解港宝的制备方法，其特征在于，所述废弃聚酯、乙二醇、醋酸锌的质量比为1：1.5～2：0.003～0.005，
或，三者反应的条件为升温至190-230℃反应4-6h，洗涤并过滤后置于0℃左右环境中冷却结晶。
4.如权利要求1所述的低成本环保可降解港宝的制备方法，其特征在于，所述间苯二甲酸与醇解产物进行酯化反应的条件为：200～210℃进行1.5～2h；
或，所述真空缩聚的条件为：于260～280℃、-0.095～0.085Mpa下反应。
5.如权利要求1所述的低成本环保可降解港宝的制备方法，其特征在于，所述聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物分子量为2000～3000。
6.如权利要求1所述的低成本环保可降解港宝的制备方法，其特征在于，所述二异氰酸酯为二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯中的至少一种。
7.如权利要求1所述的低成本环保可降解港宝的制备方法，其特征在于，所述二异氰酸酯中的-NCO与聚己二酸乙二醇酯与聚对苯二甲酸乙二醇酯-间苯二甲酸共聚物的-OH的摩尔比为0.94～0.98：1。
8.权利要求1-7任一项所述的方法制备的可降解港宝。
9.权利要求8所述的可降解港宝在制鞋领域中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211034292.1A CN115322318B (zh) | 2022-08-26 | 2022-08-26 | 一种低成本环保可降解港宝及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211034292.1A CN115322318B (zh) | 2022-08-26 | 2022-08-26 | 一种低成本环保可降解港宝及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115322318A CN115322318A (zh) | 2022-11-11 |
| CN115322318B true CN115322318B (zh) | 2023-11-07 |
Family
ID=83927185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211034292.1A Active CN115322318B (zh) | 2022-08-26 | 2022-08-26 | 一种低成本环保可降解港宝及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115322318B (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760163A (zh) * | 2010-02-08 | 2010-06-30 | 启东市鑫鑫粘合剂有限公司 | 一种基于pet废料生产聚酯热熔胶的制备方法 |
| CN103289122A (zh) * | 2012-03-02 | 2013-09-11 | 江南大学 | 一种用乙二醇法解聚废弃聚酯纤维的生产方法 |
| CN105524259A (zh) * | 2014-10-23 | 2016-04-27 | 中国石油化工股份有限公司 | 一种聚酯弹性体及其制备方法 |
| CN107417897A (zh) * | 2017-05-25 | 2017-12-01 | 江南大学 | 一种乙二醇降解废弃涤纶面料制备水溶性聚酯的方法 |
| CN111234757A (zh) * | 2020-03-17 | 2020-06-05 | 北京华腾新材料股份有限公司 | 一种双组分无溶剂聚氨酯胶粘剂及其制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10336925B2 (en) * | 2015-09-08 | 2019-07-02 | Resinate Materials Group, Inc. | Polyester polyols for reactive hot-melt adhesives |
-
2022
- 2022-08-26 CN CN202211034292.1A patent/CN115322318B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760163A (zh) * | 2010-02-08 | 2010-06-30 | 启东市鑫鑫粘合剂有限公司 | 一种基于pet废料生产聚酯热熔胶的制备方法 |
| CN103289122A (zh) * | 2012-03-02 | 2013-09-11 | 江南大学 | 一种用乙二醇法解聚废弃聚酯纤维的生产方法 |
| CN105524259A (zh) * | 2014-10-23 | 2016-04-27 | 中国石油化工股份有限公司 | 一种聚酯弹性体及其制备方法 |
| CN107417897A (zh) * | 2017-05-25 | 2017-12-01 | 江南大学 | 一种乙二醇降解废弃涤纶面料制备水溶性聚酯的方法 |
| CN111234757A (zh) * | 2020-03-17 | 2020-06-05 | 北京华腾新材料股份有限公司 | 一种双组分无溶剂聚氨酯胶粘剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115322318A (zh) | 2022-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2480589B1 (en) | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof | |
| US7157139B2 (en) | Polymer manufacturing process | |
| CA2083281C (en) | Process for the production of high molecular weight polyester resins | |
| CN115322318B (zh) | 一种低成本环保可降解港宝及其制备方法 | |
| EP4001361A1 (en) | Polyester resin blend | |
| US6812319B2 (en) | Wholly aromatic polyester carbonate and process for production of same | |
| TWI828914B (zh) | 聚酯樹脂共混物及由其形成的製品 | |
| KR101121361B1 (ko) | 저 올리고머 함량을 갖는 1,4-사이클로헥산디메탄올이공중합된 폴리에스테르와 폴리카보네이트의 블렌드 및 그제조방법 | |
| TW202110939A (zh) | 聚酯樹脂共混物 | |
| KR20210039085A (ko) | 폴리에스테르 수지 혼합물 | |
| CN114380993B (zh) | 共聚物与其形成方法 | |
| JP2002053652A (ja) | 生分解性のリサイクルポリエステル樹脂およびその製造方法 | |
| CN115725059B (zh) | 共聚酯材料及其制备方法和应用 | |
| KR101159843B1 (ko) | 고상중합법을 이용한 공중합 폴리에스테르의 제조방법 | |
| CN118374057A (zh) | 废旧pet醇解及制pet共聚酯的方法 | |
| TW202415702A (zh) | 用於製備對苯二甲酸雙（二醇）酯寡聚物及聚酯樹脂的方法 | |
| TW202419514A (zh) | 包含對苯二甲酸雙（二醇）酯的聚酯樹脂及其製備方法 | |
| EP1115692B1 (en) | Production of improved polymers via the use of star cores | |
| CN117402330A (zh) | 一种pbat的制备方法 | |
| US20240336729A1 (en) | Extrusion blown resin having excellent extrusion processability and recyclable and composition comprising thereof | |
| CN115716909A (zh) | 一种高透明pbat可降解共聚酯及其制备方法 | |
| CN115785407A (zh) | 一种制备高性能高值化共聚酯的方法 | |
| CN116444955A (zh) | 一种生物可降解材料组合物及其制备方法 | |
| CN114207028A (zh) | 聚酯树脂混合物 | |
| CN117794977A (zh) | 聚酯共聚物的生产方法 |
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 |