CN107163892B - Preparation method for producing polyester hot melt adhesive by using PET waste material - Google Patents
Preparation method for producing polyester hot melt adhesive by using PET waste material Download PDFInfo
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- CN107163892B CN107163892B CN201710558899.2A CN201710558899A CN107163892B CN 107163892 B CN107163892 B CN 107163892B CN 201710558899 A CN201710558899 A CN 201710558899A CN 107163892 B CN107163892 B CN 107163892B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a preparation method for producing polyester hot melt adhesive by utilizing PET waste materials, which comprises the following steps: esterification reaction: carrying out esterification reaction on dibasic acid, dihydric alcohol and a catalyst until no water is distilled off; alcoholysis and transesterification reactions: adding the PET waste and dihydric alcohol into an esterification kettle for alcoholysis and ester exchange reaction; and (3) polycondensation reaction: adding catalyst into the alcoholysis and ester exchange product to perform polycondensation reaction until reaching required melt index, and discharging. The invention utilizes the PET waste material to produce the polyester hot melt adhesive, greatly reduces the production cost, recycles the PET waste material, protects the environment, produces the product with good water resistance, and is particularly suitable for the hot melt adhesive for clothing.
Description
Technical Field
The invention belongs to the field of production of polyester hot melt adhesive, and particularly relates to a preparation method for producing polyester hot melt adhesive by using PET waste.
Background
The hot melt adhesive is a single-component, anhydrous, solvent-free adhesive which is solid at normal temperature. It acts on the surface of the adherend in a molten state and solidifies rapidly on cooling to form a glue joint. As an environmentally friendly adhesive, it has long been widely used in textile manufacturing for bonding between garment liners and face fabrics. The method not only reduces the cost and greatly improves the working efficiency, but also ensures that the clothes are durable, stiff and smooth.
Hot melt adhesives for textile use include polyethylene, polypropylene, EVA, polyvinyl chloride, polyester and polyamide, and the like. The hot melt adhesive for clothing has good washing resistance, namely good solvent resistance during dry washing and good water resistance during wet washing. A qualified hot-melt adhesive for clothes must ensure that the lining and the fabric are still tightly combined after the clothes are subjected to dry cleaning and wet cleaning for many times.
Among these known hot melt adhesives for clothing, polyolefin and polyvinyl chloride hot melt adhesives have poor adhesive strength to clothing materials, particularly to polyester fibers, and easily lose adhesiveness at high temperatures. EVA has poor washing resistance. Polyamide is the most widely used clothing hot melt adhesive at present, has excellent adhesive strength and good dry cleaning resistance, but does not necessarily have excellent water resistance. For example, the high-temperature water resistance of the common polyamide hot melt adhesive is not outstanding, and the original bonding strength of the common polyamide hot melt adhesive can be lost after hot water washing or steam ironing.
Polyesters are high molecular polymers made by the step-growth polycondensation reaction of dibasic acids and glycols. Polyesters are particularly suitable for use in hot melt adhesives because of their ease of crystallization and their high strength in the crystalline state. The polyester hot melt adhesive has the characteristics of good melt fluidity, high curing speed, high bonding strength, good flexibility and excellent water resistance. Therefore, polyester is one of the most commonly used hot melt adhesives for clothing at present. With regard to the production of garment liners alone, perhaps at least one million tons of polyester hot melt adhesives are required worldwide each year.
Because of the high melting point of the homopolymers of polyesters, copolyesters which are not all aromatic are generally used as polyester hotmelts. The main diacid monomers for preparing the copolyester are terephthalic acid or dimethyl terephthalate, isophthalic acid or dimethyl isophthalate and aliphatic diacids with 3-12 carbon atoms, such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid. The main diol monomer is a linear aliphatic diol having 2-10 carbon atoms, such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, decylene glycol, diethylene glycol, triethylene glycol, etc. The polyester hot melt adhesives disclosed in U.S. Pat. No. 3,436,302, U.S. Pat. No. 4,130,603, U.S. Pat. No. 4,252,940 German patent DE-A-3132059, German patent DE-A-4430048, Japanese patent JP54/153835, Chinese patent CN1760304, and Chinese patent publication CN101126006A1 all utilize the above monomers as the main raw materials.
Polyethylene terephthalate (PET) is one of the most common polyester polymers and is widely used in the production and manufacture of textiles, films, industrial fibers, bottled containers and packaging materials. However, during the production and use of PET and articles, large amounts of PET waste, 3-5% of the PET production, and also large amounts of PET waste containers, are produced. The polyester waste material has light weight, large volume and difficult natural decomposition, and must be treated in time to avoid environmental pollution. The utilization of PET waste as a secondary raw material to develop other products, such as polyester hot melt adhesives, is undoubtedly one of the most active waste treatment methods. However, because the melting point of PET is as high as 268 ℃, although the waste material contains two basic raw materials of polyester hot melt adhesive, namely terephthalic acid and ethylene glycol, the PET cannot be directly used as the hot melt adhesive, in particular to the hot melt adhesive for clothing with relatively lower melting point. Generally, the recovery of PET monomers is common.
Patent 200710187140 discloses a method for preparing hot melt adhesive from polyester waste. The method adopts the steps of carrying out alcoholysis on polyester waste, then carrying out esterification and finally carrying out polycondensation. In practical operation, the method has the disadvantages of difficult alcoholysis of polyester waste, large excess of diol required and long reaction time. Moreover, acetate needs to be added as an alcoholysis catalyst, which may affect the water resistance of the hot melt adhesive. These disadvantages are particularly pronounced, in particular when high-melting PET waste is used as starting material.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the defects of the prior art, the invention provides a preparation method for producing polyester hot melt adhesive by using PET waste.
The technical scheme is as follows: a preparation method for producing polyester hot melt adhesive by using PET waste comprises the following steps:
(1) esterification reaction: 10-45 parts of dibasic acid, 10-45 parts of dihydric alcohol and 0.02-0.2 part of catalyst are subjected to esterification reaction under the protection of nitrogen. The reaction temperature is 190 ℃ and 220 ℃, and the reaction time is 1-2h until no water is distilled off.
(2) Alcoholysis and transesterification reactions: and then adding 30-70 parts by weight of PET waste and 10-35 parts by weight of dihydric alcohol into the esterification reaction product, and carrying out alcoholysis reaction under the protection of nitrogen. The reaction temperature is 200-225 ℃, and the reaction time is 1-2h until the PET waste is completely depolymerized and no white particles exist.
(3) And (3) polycondensation reaction: adding 0.02-0.2 part by weight of catalyst into the product obtained by the alcoholysis and ester exchange reaction, carrying out polycondensation reaction for 1-3h at 230-260 ℃ and 80-100Pa vacuum degree until the required melt index is reached, and then discharging.
As an optimization: the PET waste is a recyclate of unfinished or PET articles in production and use.
As an optimization: the dibasic acid is one or more of isophthalic acid or aliphatic dibasic acid with 3-12 carbon atoms.
As an optimization: the aliphatic dibasic acid of 3-12 is malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dodecanedioic acid.
As an optimization: the dihydric alcohol is one or more of aliphatic dihydric alcohol with 2-10 carbon atoms and polyether dihydric alcohol with molecular weight of 200-2000 g/mol.
As an optimization: the aliphatic diol with 2-10 carbon atoms comprises ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, decanediol, ethylene glycol, triethylene glycol or 1, 6-cyclohexanedimethanol.
As an optimization: the polyether diol is polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
As an optimization: the molecular weight of the polyether diol is 400-1000 g/mol.
As an optimization: the catalyst is tetraethyl titanate or tetrabutyl titanate.
Has the advantages that: the invention utilizes the PET waste material to produce the polyester hot melt adhesive, so that the PET waste material can be recycled, and the environment is protected. The invention adopts the technology of firstly carrying out esterification and then depolymerizing the PET waste through alcoholysis and ester exchange reaction. Due to the existence of the esterification reaction product, the depolymerization process of the PET waste is facilitated, so that the reaction difficulty is reduced, the reaction time is shortened, the alcoholysis catalyst and a large amount of excessive dihydric alcohol are avoided, the production cost is reduced, the water resistance of the product is improved, and the method is particularly suitable for the hot melt adhesive for clothing.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Example 1
a. Esterification reaction: 5.1g of isophthalic acid, 22g of sebacic acid, 20g of butanediol, 7.5g of polyethylene glycol (molecular weight 400g/mol) and 0.03g of tetrabutyl titanate are introduced into a reaction flask equipped with a stirrer and a reflux condenser, and the temperature is controlled at 190 ℃ and 220 ℃ under nitrogen protection for 1 hour until no further water is distilled off.
b. Alcoholysis and transesterification reactions: 50g of PET waste and 15g of butanediol were added to the product of the esterification reaction described above. Under the protection of nitrogen, the temperature is controlled at 200 ℃ and 225 ℃, and the reaction is carried out for 1.5 hours until the PET waste is completely depolymerized and no white particles exist.
c. And (3) polycondensation reaction: 0.05g of tetrabutyl titanate is added in the reactants of the alcoholization and the ester exchange, the vacuum is slowly opened to be less than 100Pa, the temperature is controlled to be 230-260 ℃, and the polycondensation reaction is carried out. The reaction was allowed to proceed for 1.5 hours until the desired melt index was reached. And finally, filling nitrogen and discharging to obtain the polyester hot melt adhesive A.
The melting point of the polyester hot melt adhesive A was 125 ℃ as determined by DSC. The application test of the polyester cotton fabric on the bonding of the lining cloth shows that the polyester hot melt adhesive A has the initial peel strength of 12N/2.5cm, and the bonding layer does not crack after being washed by water at 60 ℃ for 2 hours.
Example 2
a. Esterification reaction: 5g of adipic acid, 25g of sebacic acid, 33g of butanediol and 0.03g of tetrabutyl titanate are added into a reaction flask provided with a stirrer and a reflux condenser, and the temperature is controlled at 200-220 ℃ under the protection of nitrogen, and the reaction is carried out for 1 hour until no further water is distilled off.
b. Alcoholysis and transesterification reactions: 70g of PET waste were added to the product of the esterification reaction with 12g of butanediol and 16g of diethylene glycol. And under the protection of nitrogen, controlling the temperature to be 200-225 ℃, and reacting for 1.5 hours until the PET waste is completely depolymerized without any white waste particles.
c. And (3) polycondensation reaction: and adding 0.05g of tetrabutyl titanate into the reactants for alcoholization and ester exchange, slowly opening the vacuum to be less than 100Pa, and controlling the temperature to be 230-260 ℃ to perform polycondensation reaction. The reaction was carried out for 2.5 hours until the desired melt index was reached. And finally, filling nitrogen and discharging to obtain the polyester hot melt adhesive B.
The melting point of the polyester hotmelt B was 122 ℃ as determined by DSC. The application test of the polyester cotton fabric on the bonding of the lining cloth shows that the polyester hot melt adhesive B has the initial peel strength of 10N/2.5cm, and the bonding layer does not crack after being washed by water at 60 ℃ for 2 hours.
. Example 3
a. Esterification reaction: 25g of isophthalic acid, 5g of sebacic acid, 31g of butanediol, 3g of polyethylene glycol (molecular weight 600g/mol) and 0.03g of tetrabutyl titanate are introduced into a reaction flask equipped with a stirrer and a reflux condenser, and the temperature is controlled at 200 ℃ and 220 ℃ under the protection of nitrogen, and the reaction is carried out for 1 hour until no further water is distilled off.
b. Alcoholysis and transesterification reactions: 40g of PET waste was added to 15g of 1, 6-cyclohexanedimethanol to the product of the esterification reaction. Under the protection of nitrogen, the temperature is controlled at 200 ℃ and 225 ℃, and the reaction is carried out for 1.5 hours until the PET waste is completely depolymerized and no white waste particles exist.
c. And (3) polycondensation reaction: 0.03g of tetrabutyl titanate is added in the reactants of the alcoholization and the ester exchange, the vacuum is slowly opened to be less than 100Pa, the temperature is controlled to be 230-260 ℃, and the polycondensation reaction is carried out. The reaction was allowed to proceed for 2 hours until the desired melt index was reached. And finally, filling nitrogen and discharging to obtain the polyester hot melt adhesive B.
The melting point of the polyester hot melt adhesive C was 118 ℃ as determined by DSC. The application test of the polyester cotton fabric on the lining cloth shows that the polyester hot melt adhesive C has the initial peel strength of 13N/2.5cm, and the adhesive layer does not crack after being washed for 2 hours at the temperature of 60 ℃.
Claims (5)
1. A preparation method for producing polyester hot melt adhesive by using PET waste is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) under the protection of nitrogen, 10-45 parts by weight of dibasic acid, 10-45 parts by weight of dihydric alcohol and 0.02-0.2 part by weight of catalyst are subjected to esterification reaction at 220 ℃ for 1-2h until no water is distilled off;
(2) under the same conditions, adding 30-70 parts by weight of PET waste and 10-35 parts by weight of dihydric alcohol into the esterification reaction product, and carrying out alcoholysis and ester exchange reaction at 225 ℃ of 200-;
(3) under the condition that the vacuum degree is 80-100Pa, 0.02-0.2 part by weight of catalyst is added into the products of the alcoholysis and ester exchange reaction, and the polycondensation reaction is carried out for 1-3h at the temperature of 230-; wherein:
the dibasic acid is isophthalic acid and/or aliphatic dibasic acid with 3-12 carbon atoms;
the dihydric alcohol is aliphatic dihydric alcohol with 2-10 carbon atoms and/or polyether dihydric alcohol with molecular weight of 200-2000 g/mol;
the catalyst is tetraethyl titanate or tetrabutyl titanate.
2. The preparation method for producing the polyester hot melt adhesive by using the PET wastes as claimed in claim 1, is characterized in that: the PET waste is a recyclate of unfinished or PET articles in production and use.
3. The preparation method for producing the polyester hot melt adhesive by using the PET wastes as claimed in claim 1, is characterized in that: the aliphatic dibasic acid is selected from one or more of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dodecanedioic acid.
4. The preparation method for producing the polyester hot melt adhesive by using the PET wastes as claimed in claim 1, is characterized in that: the aliphatic diol is one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, decanediol, diethylene glycol, triethylene glycol or 1, 6-cyclohexanedimethanol.
5. The preparation method for producing the polyester hot melt adhesive by using the PET wastes as claimed in claim 1, is characterized in that: the polyether diol is one or the combination of more than two of polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
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| CN108300394A (en) * | 2018-01-22 | 2018-07-20 | 储微微 | One kind is based on pet waste production polyester hot-melt adhesive and preparation method thereof |
| CN109134831A (en) * | 2018-07-28 | 2019-01-04 | 广东舜天新材料有限公司 | A kind of copolyesters preparation method of high yield |
| CN115938689A (en) * | 2023-01-06 | 2023-04-07 | 中天科技海缆股份有限公司 | Preparation method of high-voltage cable and high-voltage cable |
| TWI841251B (en) * | 2023-02-18 | 2024-05-01 | 國立清華大學 | Thermoplastic polyester elastomers derived from pet and their reaction method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353562A (en) * | 2007-07-25 | 2009-01-28 | 比亚迪股份有限公司 | Preparation of polyester hot-melt adhesive |
| CN101760163A (en) * | 2010-02-08 | 2010-06-30 | 启东市鑫鑫粘合剂有限公司 | Preparation method of producing polyester hot melt adhesive based on PET waste materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353562A (en) * | 2007-07-25 | 2009-01-28 | 比亚迪股份有限公司 | Preparation of polyester hot-melt adhesive |
| CN101760163A (en) * | 2010-02-08 | 2010-06-30 | 启东市鑫鑫粘合剂有限公司 | Preparation method of producing polyester hot melt adhesive based on PET waste materials |
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