CN113861369A - Low-melting-point high-viscosity high-strength thermoplastic polyurethane elastomer material and preparation method thereof - Google Patents
Low-melting-point high-viscosity high-strength thermoplastic polyurethane elastomer material and preparation method thereof Download PDFInfo
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- CN113861369A CN113861369A CN202111086673.XA CN202111086673A CN113861369A CN 113861369 A CN113861369 A CN 113861369A CN 202111086673 A CN202111086673 A CN 202111086673A CN 113861369 A CN113861369 A CN 113861369A
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- thermoplastic polyurethane
- polyurethane elastomer
- elastomer material
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 45
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 45
- 229920001971 elastomer Polymers 0.000 title claims abstract description 35
- 239000000806 elastomer Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 30
- 230000008018 melting Effects 0.000 claims abstract description 23
- 239000012948 isocyanate Substances 0.000 claims abstract description 18
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 18
- -1 compound polyol Chemical class 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 7
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 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 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- 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 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000004831 Hot glue Substances 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 239000004744 fabric Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229920005586 poly(adipic acid) Polymers 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 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
- C08G18/65—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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
- C08G18/65—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
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a thermoplastic polyurethane elastomer material with low melting point, high viscosity and high strength and a preparation method thereof, belonging to the technical field of hot melt adhesives. The thermoplastic polyurethane elastomer material with low melting point, high viscosity and high strength comprises the following raw materials: compound polyol, diisocyanate, a chain extender and a catalyst; the number average molecular weight of the polymer polyol is 500-1000, and the functionality is 2.01-3; the R value (isocyanate mole number: hydroxyl mole number) of the whole system of the elastomer material is 0.7-1. The thermoplastic polyurethane elastomer material with low melting point, high viscosity and high strength has low melting point, high bonding strength and high mechanical strength; the invention also provides a simple and feasible preparation method.
Description
Technical Field
The invention relates to a thermoplastic polyurethane elastomer material with low melting point, high viscosity and high strength and a preparation method thereof, belonging to the technical field of hot melt adhesives.
Background
With the development of thermoplastic polyurethane elastomers, TPU is increasingly being applied to various aspects of production life by virtue of excellent properties and diverse processability, with TPU adhesives being one type of TPU application that has developed rapidly in recent years. The TPU structure contains both carbonyl and amino, and can interact with a plurality of polar groups to form hydrogen bonds, so that the TPU adhesive has excellent adsorption bonding force, and unique environmental protection advantages make the TPU adhesive occupy the key of numerous adhesives. According to the requirements of specific application fields, the TPU adhesive can be processed into films, net films, powder and other forms to be applied to industries such as clothing, shoe materials, automobiles, sanitary products, packaging, electronics and the like. The adhesive product has strict application requirements in the field of clothing, not only needs to maintain excellent adhesive strength, but also needs to be attached at a lower temperature and meet the washing requirement after attachment.
At present, the main problems of the adhesive products for clothing, including other types of adhesives, are that high-temperature-resistant fabrics cannot be damaged, and the bonded fabrics are ensured not to be degummed after being washed for many times. For the conventional fabrics in the market, particularly elastic fabrics, the development of products which can be laminated at low temperature, are resistant to washing, have high bonding strength and good strength still has obvious technical bottlenecks, and the expansion of the bonding agent in the field of fabric lamination is limited to a great extent.
CN 108070069 discloses a low-hardness high-resilience low-melting-point thermoplastic polyurethane elastomer, a preparation method and application thereof, but the mechanical strength of the thermoplastic elastomer prepared by the method is obviously as low as that of a conventional adhesive film, which means that the product has poor bonding strength and is not resistant to water washing.
CN 107739589 discloses a low-melting-point thermoplastic polyurethane adhesive and a preparation method thereof, and the product prepared by the method has poor adhesive force.
CN 111647382 discloses a method for preparing TPU adhesive, which has low melting point, but the method is complicated and requires multiple screw reactions.
CN 110903805 discloses a low-polarity high-resilience polyurethane hot melt adhesive, a preparation method and application thereof. The melting point of the hot melt adhesive prepared by the method is less than or equal to 135 ℃, the contrast melting point is still higher, and the product needs higher temperature for bonding in the using process.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a thermoplastic polyurethane elastomer material with low melting point, high viscosity and high strength, which not only has lower melting point, but also has higher adhesive strength and mechanical strength; the invention also provides a simple and feasible preparation method.
The thermoplastic polyurethane elastomer material with low melting point, high viscosity and high strength comprises the following raw materials: polymer polyol, diisocyanate, a chain extender and a catalyst;
the number average molecular weight of the polymer polyol is 500-1000, and the functionality is 2.01-3;
the R value (isocyanate mole number: hydroxyl mole number) of the whole system of the elastomer material is 0.7-1.
The polymer dihydric alcohol is one or two of polyester dihydric alcohol or polytetrahydrofuran polyhydric alcohol.
Preferably, the polyester diol is polycaprolactone, polybutylene sebacate diol, polybutylene adipate diol, polyhexamethylene adipate diol, 1, 4-polybutylene adipate diol, or polyethylene adipate diol.
Preferably, the diisocyanate is one or more of diphenylmethane diisocyanate (MDI-100), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), 4' -dicyclohexylmethane diisocyanate (HMDI), or Hexamethylene Diisocyanate (HDI).
Preferably, the chain extender is one or more of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol or 1, 8-octanediol.
Preferably, the catalyst is an organobismuth-based catalyst.
Preferably, the thermoplastic polyurethane elastomer material with low melting point, high viscosity and high strength comprises the following raw materials in parts by mass:
the hardness of the thermoplastic polyurethane elastomer is 60-80A, the tensile strength is greater than 30MPa, the melting point is less than 70-90 ℃, the product is attached at 90-100 ℃, and the bonding force is greater than 10N/mm.
The preparation method of the thermoplastic polyurethane elastomer material with low melting point, high viscosity and high strength comprises the following steps:
(1) mechanically stirring polymer polyol, a chain extender and a catalyst for 10-120r/min for 1-12 hours;
(2) adding the prepared polymer polyol and isocyanate into a double-screw extruder system through a feeding and filling system, and carrying out polymerization reaction at the temperature of 120-240 ℃, wherein the screw rotation speed is 150-;
(3) and (3) underwater granulating the molten polymer, drying the molten polymer by cold air (10-20 ℃) at the water temperature of 0-5 ℃ to obtain the thermoplastic polyurethane elastomer particles with low melting point, high viscosity and high strength.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, by using the polymer polyol with the functionality of 2.01-3, the R value (isocyanate mole number/hydroxyl mole number) of the whole system is controlled to be 0.7-1, chemical crosslinking is generated in the product system, the excessive hydroxyl number is ensured, the bonding effect of the whole system is improved, and the tearing force exceeds 10N/mm; the prepared material is ensured to have a lower melting point of 70-90 ℃, and the low-temperature bonding of 90-100 ℃ is realized;
(2) the polyurethane elastomer material prepared by the invention has excellent mechanical properties which are more than 30MPa, ensures that colloids such as product bonding woven fabric and the like are not damaged, and has super-strong washing resistance;
(3) the preparation method provided by the invention is a conventional one-step synthesis method, and is simple and feasible.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
The starting materials used in the examples are all commercially available, except where otherwise indicated.
Example 1
The raw materials and the parts by weight are as follows:
(1) mechanically stirring polyhexamethylene adipate glycol, polytetrahydrofuran polyol, a chain extender and a catalyst for 10r/min for 12 hours;
(2) adding the prepared polymer dihydric alcohol and isocyanate into a double-screw extruder system through a feeding and filling system, and carrying out polymerization reaction at 120 ℃ with the screw rotating speed of 150 r/min;
(3) and (3) underwater granulating the molten polymer, drying the molten polymer by cold air (10 ℃) at the water temperature of 5 ℃ to obtain the thermoplastic polyurethane elastomer particles with low melting point, high viscosity and high strength.
The product obtained in this example had an overall system R value (moles of isocyanate/moles of hydroxyl) of 0.896.
Example 2
(1) Mechanically stirring the poly adipic acid glycol ester dihydric alcohol, the poly adipic acid butanediol ester dihydric alcohol, BDO and a catalyst for 10r/min and stirring for 12 hours;
(2) adding the prepared polymer dihydric alcohol and isocyanate into a double-screw extruder system through a feeding and filling system, and carrying out polymerization reaction at 120 ℃ with the screw rotating speed of 150 r/min;
(3) and (3) underwater granulating the molten polymer, drying the molten polymer by cold air (20 ℃) at the water temperature of 1 ℃ to obtain the thermoplastic polyurethane elastomer particles with low melting point, high viscosity and high strength.
The product obtained in this example had an overall system R value (moles of isocyanate/moles of hydroxyl groups) of 0.97.
Example 3
The raw materials and the parts by weight are as follows:
(1) mechanically stirring polybutylene adipate glycol, HDO and a catalyst for 10r/min for 12 hours;
(2) adding the prepared polymer dihydric alcohol and isocyanate into a double-screw extruder system through a feeding and filling system, and carrying out polymerization reaction at 120 ℃ with the screw rotating speed of 150 r/min;
(3) and (3) underwater granulating the molten polymer, drying the molten polymer by cold air (15 ℃) at the water temperature of 1 ℃ to obtain the thermoplastic polyurethane elastomer particles with low melting point, high viscosity and high strength.
The product obtained in this example had an overall system R value (moles of isocyanate/moles of hydroxyl groups) of 0.72.
Example 4
The raw materials and the parts by weight are as follows:
(1) mechanically stirring polytetrahydrofuran polyol, polybutylene adipate glycol, BDO and a catalyst for 10r/min and 12 hours;
(2) adding the prepared polymer dihydric alcohol and isocyanate into a double-screw extruder system through a feeding and filling system, and carrying out polymerization reaction at 150 ℃ with the screw rotating speed of 250 r/min;
(3) and (3) underwater granulating the molten polymer, drying the molten polymer by cold air (15 ℃) at the water temperature of 1 ℃ to obtain the thermoplastic polyurethane elastomer particles with low melting point, high viscosity and high strength.
The product obtained in this example had an overall system R value (moles of isocyanate/moles of hydroxyl groups) of 0.85.
Comparative example 1
The raw materials and the parts by weight are as follows:
(1) mechanically stirring polyhexamethylene adipate glycol, polytetrahydrofuran polyol, BDO and a catalyst for 10r/min and stirring for 12 hours;
(2) adding the prepared polymer dihydric alcohol and isocyanate into a double-screw extruder system through a feeding and filling system, and carrying out polymerization reaction at 120 ℃ with the screw rotating speed of 150 r/min;
(3) and (3) underwater granulating the molten polymer, and drying the molten polymer by cold air (10 ℃) at the water temperature of 5 ℃ to obtain the thermoplastic polyurethane elastomer particles.
The product of this comparative example had an overall system R value (moles isocyanate/moles hydroxyl) of 0.97.
Comparative example 2
The raw materials and the parts by weight are as follows:
(1) mechanically stirring polybutylene adipate glycol, HDO and a catalyst for 10r/min for 12 hours;
(2) adding the prepared polymer dihydric alcohol and isocyanate into a double-screw extruder system through a feeding and filling system, and carrying out polymerization reaction at 120 ℃ with the screw rotating speed of 150 r/min;
(3) and (3) underwater granulating the molten polymer, and drying the molten polymer by cold air (10 ℃) at the water temperature of 5 ℃ to obtain the thermoplastic polyurethane elastomer particles.
The product of this comparative example had an overall system R value (moles isocyanate/moles hydroxyl) of 0.94.
And respectively carrying out performance tests on the obtained TPU, wherein the specific test method comprises the following steps:
outflow temperature: pass the Japan Shimadzu rheometer test.
Peel strength: preparing a film with the thickness of 0.1mm by using a casting machine for the product obtained in the embodiment, hot-pressing a TPU film between two pieces of denim cloth by using a hot-pressing machine, determining the bonding temperature to be 90 ℃, cutting the hot-pressed denim cloth into sample strips with the width of 25mm, wherein the stretching speed is 100mm/min, the peeling angle is 180, and the test result is the average value of 3 parallel sample strips.
Tensile strength and elongation: the test was carried out according to the method specified in the standard ASTM D412.
TABLE 1 Properties of the products obtained in the examples and comparative examples
As can be seen from the data in Table 1, the outflow temperature of the TPU prepared by the invention is less than 90 ℃, the excellent bonding of the TPU can be realized at 90 ℃, the peel strength is higher than 10N/mm, and the mechanical strength is obviously superior to that of the traditional hot melt adhesive film.
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (10)
1. A thermoplastic polyurethane elastomer material with low melting point, high viscosity and high strength is characterized in that:
the method comprises the following raw materials: polymer polyols, diisocyanates;
the polymer polyol has a number average molecular weight of 500-1000 and a functionality of 2.01-3;
molar isocyanate number of the whole system of the elastomer material: hydroxyl group mole number is 0.7-1.
2. The low-melting point high-viscosity high-strength thermoplastic polyurethane elastomer material according to claim 1, wherein: the polymer dihydric alcohol is one or two of polyester dihydric alcohol or polytetrahydrofuran polyhydric alcohol.
3. The low melt point high viscosity high strength thermoplastic polyurethane elastomer material of claim 2, wherein: the polyester type dihydric alcohol is polycaprolactone, polybutylene sebacate dihydric alcohol, polybutylene adipate dihydric alcohol, polyhexamethylene adipate-1, 4-butanediol ester dihydric alcohol or polyethylene glycol adipate dihydric alcohol.
4. The low-melting point high-viscosity high-strength thermoplastic polyurethane elastomer material according to claim 1, wherein: the diisocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate or hexamethylene diisocyanate.
5. The low-melting point high-viscosity high-strength thermoplastic polyurethane elastomer material according to claim 1, wherein: the raw materials also comprise a chain extender and a catalyst.
6. The low-melting point high-viscosity high-strength thermoplastic polyurethane elastomer material according to claim 5, wherein: the chain extender is one or more of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol or 1, 8-octanediol.
7. The low-melting point high-viscosity high-strength thermoplastic polyurethane elastomer material according to claim 5, wherein: the catalyst is an organic bismuth catalyst.
8. The low-melting point high-viscosity high-strength thermoplastic polyurethane elastomer material according to claim 5, wherein: the composite material comprises the following raw materials in parts by mass:
9. the low-melting point high-viscosity high-strength thermoplastic polyurethane elastomer material according to claim 1, wherein: the hardness of the thermoplastic polyurethane elastomer is 60-80A, the tensile strength is greater than 30MPa, the melting point is less than 70-90 ℃, the product is attached at 90-100 ℃, and the bonding force is greater than 10N/mm.
10. A method for preparing the low melting point high viscosity high strength thermoplastic polyurethane elastomer material according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
(1) mechanically stirring polymer polyol, a chain extender and a catalyst for 10-120r/min for 1-12 hours;
(2) adding the prepared polymer polyol and isocyanate into a double-screw extruder system through a feeding and filling system, and carrying out polymerization reaction at the temperature of 120-240 ℃, wherein the screw rotation speed is 150-;
(3) and (3) underwater granulating the molten polymer, and drying at the water temperature of 0-5 ℃ to obtain the low-melting-point high-viscosity high-strength thermoplastic polyurethane elastomer particles.
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