CN111117548A - Thermoplastic polyurethane adhesive and preparation thereof - Google Patents
Thermoplastic polyurethane adhesive and preparation thereof Download PDFInfo
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- CN111117548A CN111117548A CN201811275083.XA CN201811275083A CN111117548A CN 111117548 A CN111117548 A CN 111117548A CN 201811275083 A CN201811275083 A CN 201811275083A CN 111117548 A CN111117548 A CN 111117548A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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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
- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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- 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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- 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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- 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
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a thermoplastic polyurethane adhesive and a preparation method thereof, wherein the thermoplastic polyurethane adhesive comprises the following components in parts by weight: 10-35 parts of isocyanate, 0-20 parts of aliphatic polyester diol, 50-85 parts of aromatic polyester diol, 1-10 parts of chain extender, 1-3 parts of fluorine-containing diol and 0.001-0.1 part of catalyst, wherein the fluorine-containing diol is 3,3, 3-trifluoro-1, 2-propanediol or 3-fluoro-1, 2-propanediol. The TPU adhesive is prepared by introducing isocyanate, aliphatic and aromatic polyester diol and fluorine-containing diol for copolymerization. The adhesive of the type has better improvement on the adhesive strength, the fluidity and the surface performance.
Description
Technical Field
The invention relates to thermoplastic polyurethane and a preparation method thereof.
Background
In recent years, Thermoplastic Polyurethane (TPU) materials have been developed very rapidly, and are increasingly applied to various fields of production and living by virtue of excellent properties and various processability. The thermoplastic polyurethane adhesive has the advantages of low VOC emission, environmental protection, excellent adhesion fastness, excellent washing resistance, wide hardness range, high peel strength, suitability for various processing temperature requirements, lasting elasticity and the like, and is widely applied to the fields of clothing, shoe industry, heat seal, printing, leather, artware or electronic products and the like. Patent CN106459360A uses a mixture of non-crystalline polyester polyol and polyester polyol of terephthalic acid to prepare a thermoplastic polyurethane adhesive with little change of viscosity for a long time after heating, and the adhesive can be used for bonding wood and shoes. Patent CN107739589A reports a low-melting-point thermoplastic polyurethane adhesive, which is obtained by polymerization reaction of polytetrahydrofuran ether, diphenylmethane diisocyanate and 1, 6-hexanediol, is used in the field of garment processing, and has excellent properties such as low processing temperature, excellent low temperature resistance, water washing resistance, high peel strength, high bonding strength and the like. In patent CN107406568A, polytetramethylene glycol succinate is used as polymer polyol to prepare high-melting-point quick-recrystallization thermoplastic polyurethane adhesive, and the crystallinity and the rebound resilience of the adhesive are excellent.
Currently, polyurethane adhesives are generally satisfactory for use in conventional substrate applications such as athletic shoes, trademarks, lettering films, leather, and screen printing. However, for a substrate with good waterproof and barrier properties, the peel strength of the conventional polyurethane adhesive during bonding cannot meet the requirements. Because the surface of the substrate of the type is subjected to the hydrophobic coating treatment, the surface tension is low, the general adhesive is difficult to spread on the surface of the substrate, and the peeling strength is poor.
Disclosure of Invention
The invention aims to provide a thermoplastic polyurethane adhesive and a preparation method thereof, which are used for overcoming the defects of the conventional TPU adhesive in the process of attaching a strong hydrophobic substrate.
The plastic polyurethane adhesive is composed of the following components in parts by weight:
preferably, the plastic polyurethane adhesive consists of the following components in parts by weight:
the isocyanate is one or more combinations of aliphatic isocyanate and aromatic isocyanate, such as 1, 6-Hexamethylene Diisocyanate (HDI), 4-dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), p-phenylene diisocyanate (PPDI);
preferably a mixture of aliphatic isocyanate and aromatic isocyanate, wherein the mass ratio of the aliphatic isocyanate to the aromatic isocyanate is 1: 0.5-3;
the aromatic polyester dihydric alcohol is polyester polyol with the number average molecular weight of 1000-4000 g/mol, which is prepared by polymerizing phthalic anhydride or m-phthalic anhydride and 1, 6-hexanediol;
the aliphatic polyester diol is one or more of polyester polyols with the number average molecular weight of 2000-5000 g/mol, which are prepared by polymerizing 1, 6-adipic acid and 1, 2-ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol or 1, 6-hexanediol;
the chain extender is one or a combination of more of 1, 2-Ethylene Glycol (EG), 1, 3-propylene glycol (PDO), 1, 4-Butanediol (BDO) and 1, 6-Hexanediol (HDO);
the fluorine-containing dihydric alcohol is 3,3, 3-trifluoro-1, 2-propanediol, 3-fluoro-1, 2-propanediol, preferably 3,3, 3-trifluoro-1, 2-propanediol;
the catalyst is a catalyst commonly used in the field, and includes an organotin catalyst, a potassium carboxylate catalyst, an organic heavy metal catalyst, a zinc carboxylate, a bismuth carboxylate, a titanate catalyst and the like, and can be specifically reported in a document of polyurethane elastomer handbook (Liu Thick Jun, chemical industry Press, second edition).
The method comprises the following steps:
(1) dispersing and mixing isocyanate, aromatic polyester diol, aliphatic polyester diol, a chain extender, fluorine-containing diol and a catalyst through a mixing head, then pouring the mixture into a double-screw reaction extruder, carrying out reaction extrusion, carrying out underwater granulation, dewatering, drying and curing to obtain thermoplastic polyurethane adhesive particles;
further, the temperature of the isocyanate component entering the mixing head is 90-140 ℃, preferably 100-140 ℃, and particularly preferably 100-130 ℃;
the temperature of the polyester glycol and the catalyst component entering the mixing head is 40-70 ℃, preferably 45-65 ℃, and preferably 50-65 ℃;
the temperature of the chain extender and the fluorine-containing diol component entering the mixing head is 40-70 ℃, preferably 45-65 ℃, and preferably 50-65 ℃;
the rotating speed of the extruder is 100-300 RPM;
the temperature of 1# to 7# section screw of the screw extruder is 100-200 ℃, preferably 115-190 ℃, and the temperature of 7# to 14# section screw is 200-120 ℃, preferably 190-130 ℃;
the melt pump is 180-220 ℃, and preferably 180-210 ℃;
the temperature of the die head is 180-220 ℃, and preferably 180-210 ℃;
enabling the prepolymer of the mixing head to enter a melt outlet from a feeding port, and extruding for 40-200 s, preferably 40-100 s;
the water temperature of the water circulation system in the underwater granulator is set to be 0-50 ℃, preferably 0-30 ℃, and particularly preferably 0-20 ℃.
The TPU adhesive is prepared by introducing isocyanate, aliphatic and aromatic polyester diol and fluorine-containing diol for copolymerization. The adhesive of the type has better improvement on the adhesive strength, the fluidity and the surface performance.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The raw material components are as follows according to the parts by weight:
isocyanate 17.3 parts
The isocyanate is a mixture of aliphatic isocyanate and aromatic isocyanate, and the mass ratio of the aliphatic isocyanate (HDI): aromatic isocyanate (MDI) ═ 1: 0.77;
(1) dispersing and mixing HDI, MDI, polyethylene glycol adipate glycol, poly (phthalic anhydride) hexanediol glycol, HDO, 3,3, 3-trifluoro-1, 2-propylene glycol and stannous octoate in a stirring mixing head, then pouring the mixture into a double-screw reaction extruder, carrying out reaction extrusion, carrying out underwater granulation, removing water, drying and curing to obtain the thermoplastic polyurethane adhesive particles;
the temperature of the isocyanate component entering the mixing head is 100 ℃;
the temperature of the polyester glycol and the catalyst component entering the mixing head is 50 ℃;
the temperature of the chain extender and the fluorine-containing diol component entering the mixing head is 60 ℃;
the rotating speed of the extruder is 300RPM, the temperature of the 1# to 7# section of screw rod of the screw extruder is 160 ℃, and the temperature of the 7# to 14# section of screw rod is 130 ℃; a melt pump 180 ℃; the die head temperature is 200 ℃; the prepolymer in the mixing head enters a melt outlet from a feeding port, and the extrusion time is 40 s; the water temperature of the water circulation system in the underwater pelletizer is set to 50 ℃.
Example 2
The raw material components are as follows according to the parts by weight:
isocyanate 15 parts
The isocyanate is a mixture of aliphatic isocyanate and aromatic isocyanate, and the mass ratio of the aliphatic isocyanate to the aromatic isocyanate is aliphatic isocyanate (H)12MDI): aromatic isocyanate (MDI) ═ 1: 1.83;
(1) h is to be12MDI, poly hexamethylene adipate glycol, poly hexamethylene phthalate glycol, BDO, 3,3, 3-trifluoro-1, 2-propylene glycol and stannous octoate are dispersed and mixed in a stirring mixing head, then the mixture is poured into a double-screw reaction extruder for reaction and extrusion, and the mixture is granulated under water, dewatered, dried and cured to obtain the thermoplastic polyurethane adhesive particles;
further, the temperature of the isocyanate component entering the mixing head is 100 ℃;
the temperature of the polyester glycol and the catalyst component entering the mixing head is 70 ℃;
the temperature of the chain extender and the fluorine-containing diol component entering the mixing head is 50 ℃;
the extruder speed was 100 RPM;
the temperature of 1# to 7# sections of screw rods of the screw extruder is 200 ℃, and the temperature of 7# to 14# sections of screw rods is 200 ℃;
a melt pump at 220 ℃;
the temperature of a die head is 180 ℃;
the prepolymer in the mixing head enters a melt outlet from a feeding port, and the extrusion time is 200s
The water temperature of the water circulation system in the underwater granulator is set to 0 ℃.
Example 3
The raw material components are as follows according to the parts by weight:
13.7 parts of isocyanate
The isocyanate is a mixture of aliphatic isocyanate and aromatic isocyanate, and the mass ratio of the aliphatic isocyanate to the aromatic isocyanate is aliphatic isocyanate (H)12MDI): aromatic isocyanate (TDI) ═ 1: 1.68;
(1) h is to be12Dispersing and mixing MDI, TDI, polyhexamethylene adipate glycol, poly-m-phthalic anhydride butanediol ester glycol, HDO, 3,3, 3-trifluoro-1, 2-propylene glycol and zinc isooctanoate in a stirring mixing head, then pouring into a double-screw reaction extruder, reacting and extruding, underwater granulating, dewatering, drying and curing to obtain the thermoplastic polyurethane adhesive particles;
further, the temperature of the isocyanate component entering the mixing head is 140 ℃;
the temperature of the polyester glycol and the catalyst component entering the mixing head is 70 ℃;
the temperature of the chain extender and the fluorine-containing diol component entering the mixing head is 40 ℃;
the extruder speed was 150 RPM;
the temperature of 1# to 7# sections of screw rods of the screw extruder is 100 ℃, and the temperature of 7# to 14# sections of screw rods is 200 ℃;
a melt pump at 220 ℃;
the temperature of a die head is 180 ℃;
the prepolymer in the mixing head enters a melt outlet from a feeding port, and the extrusion time is 200 s;
the water temperature of the water circulation system in the underwater pelletizer is set to be 30 ℃.
Example 4
The raw material components are as follows according to the parts by weight:
isocyanate 29.2 parts
The isocyanate is a mixture of aliphatic isocyanate and aromatic isocyanate, and the mass ratio of the aliphatic isocyanate (HDI): aromatic isocyanate (MDI) ═ 1: 0.47;
(1) dispersing and mixing HDI, MDI, polyhexamethylene adipate glycol, polyhexamethylene phthalate glycol, HDO, 3,3, 3-trifluoro-1, 2-propylene glycol and dibutyltin dilaurate in a stirring mixing head, then pouring the mixture into a double-screw reaction extruder, carrying out reaction extrusion, carrying out underwater granulation, removing water, drying and curing to obtain the thermoplastic polyurethane adhesive particles;
further, the temperature of the isocyanate component entering the mixing head is 90 ℃;
the temperature of the polyester glycol and the catalyst component entering the mixing head is 70 ℃;
the temperature of the chain extender and the fluorine-containing diol component entering the mixing head is 50 ℃;
the extruder speed was 200 RPM;
the temperature of 1# to 7# sections of screw rods of the screw extruder is 120 ℃, and the temperature of 7# to 14# sections of screw rods is 130 ℃;
a melt pump at 200 ℃;
the temperature of a die head is 180 ℃;
the prepolymer in the mixing head enters a melt outlet from a feeding port, and the extrusion time is 100 s;
the water temperature of the water circulation system in the underwater pelletizer is set to be 30 ℃.
Example 5
The raw material components are as follows according to the parts by weight:
isocyanate 20.4 parts
The isocyanate is a mixture of aliphatic isocyanate and aromatic isocyanate, and the mass ratio of the aliphatic isocyanate (HDI): aromatic isocyanate (MDI) ═ 1: 0.34;
(1) dispersing and mixing HDI, MDI, polyethylene glycol adipate glycol, polyethylene glycol phthalate glycol, PDO, 3,3, 3-trifluoro-1, 2-propylene glycol and stannous octoate in a stirring mixing head, then pouring the mixture into a double-screw reaction extruder, carrying out reaction extrusion, carrying out underwater granulation, removing water, drying and curing to obtain the thermoplastic polyurethane adhesive particles;
further, the temperature of the isocyanate component entering the mixing head is 100 ℃;
the temperature of the polyester glycol and the catalyst component entering the mixing head is 40 ℃;
the temperature of the chain extender and the fluorine-containing diol component entering the mixing head is 70 ℃;
the extruder speed was 100 RPM;
the temperature of 1# to 7# sections of screw rods of the screw extruder is 160 ℃, and the temperature of 7# to 14# sections of screw rods is 130 ℃;
a melt pump 210 ℃;
the die temperature is 220 ℃;
the prepolymer in the mixing head enters a melt outlet from a feeding port, and the extrusion time is 100 s;
the water temperature of the water circulation system in the underwater granulator is set to 0 ℃.
Example 6
The raw material components are as follows according to the parts by weight:
isocyanate 15.3 parts
The isocyanate is two kinds of aliphatic isocyanate and aromatic isocyanateA mixture of esters in the mass ratios of aliphatic isocyanate (HDI): aliphatic isocyanates (H)12MDI): aromatic isocyanate (MDI) ═ 3.3:6.2: 5.8;
(1) mixing MDI, HDI and H12MDI, polyethylene glycol adipate glycol, poly (m-phthalic anhydride) butanediol glycol, BDO, 3,3, 3-trifluoro-1, 2-propylene glycol and stannous octoate are dispersed and mixed in a stirring mixing head, then the mixture is poured into a double-screw reaction extruder for reaction and extrusion, and the thermoplastic polyurethane adhesive particles can be obtained after underwater granulation, dehydration, drying and curing;
further, the temperature of the isocyanate component entering the mixing head is 100 ℃;
the temperature of the polyester glycol and the catalyst component entering the mixing head is 60 ℃;
the temperature of the chain extender and the fluorine-containing diol component entering the mixing head is 65 ℃;
the extruder speed was 120 RPM;
the temperature of 1# to 7# sections of screw rods of the screw extruder is 160 ℃, and the temperature of 7# to 14# sections of screw rods is 130 ℃;
a melt pump 180 ℃;
the temperature of a die head is 180 ℃;
the prepolymer in the mixing head enters a melt outlet from a feeding port, and the extrusion time is 80 s;
the water temperature of the water circulation system in the underwater granulator is set to 0 ℃.
Example 7
The raw material components are as follows according to the parts by weight:
14.6 parts of isocyanate
The isocyanate is a mixture of two aliphatic isocyanates, and the mass ratio of the aliphatic isocyanate (HDI): aliphatic isocyanates (H)12MDI)＝1；
(1) HDI and H12Dispersing and mixing MDI, poly (hexamethylene glycol) phthalate, HDO, 3,3, 3-trifluoro-1, 2-propylene glycol and zinc isooctanoate in a stirring mixing head, then pouring the mixture into a double-screw reaction extruder for reaction and extrusion, carrying out underwater granulation, dewatering, drying and curing to obtain the thermoplastic polyurethane adhesive particles;
further, the temperature of the isocyanate component entering the mixing head is 100 ℃;
the temperature of the polyester glycol and the catalyst component entering the mixing head is 65 ℃;
the temperature of the chain extender and the fluorine-containing diol component entering the mixing head is 50 ℃;
the extruder speed was 300 RPM;
the temperature of 1# to 7# sections of screw rods of the screw extruder is 170 ℃, and the temperature of 7# to 14# sections of screw rods is 150 ℃;
a melt pump 210 ℃;
the die head temperature is 200 ℃;
enabling the prepolymer of the mixing head to enter a melt outlet from a feeding port, and extruding for 80s, preferably 40-100 s;
the water temperature of the water circulation system in the underwater pelletizer is set to be 30 ℃.
Comparative example 1
This comparative example is different from example 1 in that the aromatic polyester diol (polyhexamethylene phthalate diol) in the raw material list was replaced with the aliphatic polyester diol (polyethylene adipate diol), and the remaining raw materials and the amounts of raw materials and the preparation method and conditions were the same as in example 1.
Comparative example 2
This comparative example differs from example 3 in that the fluorine-containing diol (3,3, 3-trifluoro-1, 2-propanediol) in the raw material list was replaced with HDO, and the remaining raw materials and raw material amounts, and preparation methods and conditions were the same as in example 3.
The properties of the thermoplastic polyurethane adhesive prepared are shown in table 1 below, wherein:
table 1: examples 1 to 7, comparative examples 1 to 2 have the following properties:
from the performance test data (table 1) of the examples and comparative examples, it can be seen that:
*: after the waterproof cloth (nylon material subjected to waterproof treatment) is attached to the TPU adhesive, cutting the waterproof cloth into sample strips with the thickness of 25mm multiplied by 150mm, wherein the test speed is 100mm/min, and testing the average T-shaped stripping value of 5 groups of sample strips;
when the TPU adhesive prepared by the synergistic effect of the aromatic polyester glycol containing phthalic anhydride or isophthalic anhydride and the fluorine-containing micromolecule dihydric alcohol is applied to the substrate bonding of surface hydrophobic treatment, the excellent adhesive property is maintained, and the peel strength is as high as more than 70N.
Claims (9)
1. The thermoplastic polyurethane adhesive is characterized by comprising the following components in parts by weight:
the fluorine-containing dihydric alcohol is 3,3, 3-trifluoro-1, 2-propylene glycol or 3-fluoro-1, 2-propylene glycol.
2. The plastic polyurethane adhesive of claim 1, consisting of the following components in parts by weight:
3. the plastic polyurethane adhesive of claim 1 or 2, wherein the isocyanate is one or more combinations of aliphatic and aromatic isocyanates.
4. The plastic polyurethane adhesive of claim 3, wherein the isocyanate is one or more of 1, 6-Hexamethylene Diisocyanate (HDI), 4-dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), and p-phenylene diisocyanate (PPDI).
5. The plastic polyurethane adhesive as claimed in claim 4, wherein the isocyanate is a mixture of aliphatic isocyanate and aromatic isocyanate, and the mass ratio of aliphatic isocyanate to aromatic isocyanate is 1: 0.5-3.
6. The plastic polyurethane adhesive of claim 1 or 2, wherein the aromatic polyester diol is phthalic anhydride or isophthalic anhydride polymerized with 1, 6-hexanediol to produce a polyester polyol having a number average molecular weight of 1000 to 4000 g/mol;
the aliphatic polyester diol is one or more of polyester polyols with the number average molecular weight of 2000-5000 g/mol, which are prepared by polymerizing 1, 6-adipic acid and 1, 2-ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol or 1, 6-hexanediol.
7. The plastic polyurethane adhesive of claim 1 or 2, wherein the chain extender is one or more of 1, 2-Ethylene Glycol (EG), 1, 3-propylene glycol (PDO), 1, 4-Butanediol (BDO), 1, 6-Hexanediol (HDO); the catalyst comprises an organic tin catalyst, a potassium carboxylate catalyst, an organic heavy metal catalyst, zinc carboxylate, bismuth carboxylate and a titanate catalyst.
8. The method of preparing a plastic polyurethane adhesive according to any one of claims 1 to 7, comprising the steps of: dispersing and mixing isocyanate, aromatic polyester diol, aliphatic polyester diol, a chain extender, fluorine-containing diol and a catalyst through a mixing head, then pouring the mixture into a double-screw reaction extruder, carrying out reaction extrusion, carrying out underwater granulation, dewatering, drying and curing to obtain the thermoplastic polyurethane adhesive particles.
9. The process of claim 8 wherein the isocyanate component is introduced into the mixing head at a temperature of from 90 to 140 ℃;
the temperature of the polyester glycol and the catalyst component entering the mixing head is 40-70 ℃;
the temperature of the chain extender and the fluorine-containing diol component entering the mixing head is 40-70 ℃;
the rotating speed of the extruder is 100-300 RPM;
the temperature of 1# to 7# section of screw of the screw extruder is 100-200 ℃, and the temperature of 7# to 14# section of screw is 200-120 ℃;
a melt pump is used for 180-220 ℃;
the temperature of the die head is 180-220 ℃;
enabling the prepolymer of the mixing head to enter a melt outlet from a feeding port, and extruding for 40-200 s;
the water temperature of a water circulation system in the underwater granulator is set to be 0-50 ℃.
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| CN111690366A (en) * | 2020-07-28 | 2020-09-22 | 深圳市安伯斯科技有限公司 | Hybrid polyurethane resin glue and preparation method thereof |
| CN114316178A (en) * | 2021-12-14 | 2022-04-12 | 上海汇得科技股份有限公司 | Polyurethane resin for thermal transfer printing, preparation method thereof, working slurry and thermal transfer printing film |
| CN115521717A (en) * | 2022-10-11 | 2022-12-27 | 常州百佳年代薄膜科技股份有限公司 | Reactive co-extrusion adhesive film for heterojunction battery, preparation method and assembly thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690366A (en) * | 2020-07-28 | 2020-09-22 | 深圳市安伯斯科技有限公司 | Hybrid polyurethane resin glue and preparation method thereof |
| CN114316178A (en) * | 2021-12-14 | 2022-04-12 | 上海汇得科技股份有限公司 | Polyurethane resin for thermal transfer printing, preparation method thereof, working slurry and thermal transfer printing film |
| CN114316178B (en) * | 2021-12-14 | 2023-10-24 | 上海汇得科技股份有限公司 | Polyurethane resin for thermal transfer printing, preparation method thereof, working slurry and thermal transfer printing film |
| CN115521717A (en) * | 2022-10-11 | 2022-12-27 | 常州百佳年代薄膜科技股份有限公司 | Reactive co-extrusion adhesive film for heterojunction battery, preparation method and assembly thereof |
| CN115521717B (en) * | 2022-10-11 | 2024-01-26 | 常州百佳年代薄膜科技股份有限公司 | Reactive co-extrusion adhesive film for heterojunction battery, preparation method and assembly thereof |
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