CN116376499A - Moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol - Google Patents
Moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol Download PDFInfo
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- CN116376499A CN116376499A CN202310221352.9A CN202310221352A CN116376499A CN 116376499 A CN116376499 A CN 116376499A CN 202310221352 A CN202310221352 A CN 202310221352A CN 116376499 A CN116376499 A CN 116376499A
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- polyether polyol
- polyol
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- moisture
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- 229920005862 polyol Polymers 0.000 title claims abstract description 88
- 150000003077 polyols Chemical class 0.000 title claims abstract description 88
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 74
- 229920000570 polyether Polymers 0.000 title claims abstract description 74
- 239000004831 Hot glue Substances 0.000 title claims abstract description 53
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 49
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 49
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 238000013008 moisture curing Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 28
- 239000012948 isocyanate Substances 0.000 claims description 20
- 150000002513 isocyanates Chemical class 0.000 claims description 20
- 229920005906 polyester polyol Polymers 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000001723 curing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- -1 methylene, ethyl Chemical group 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 229920002125 Sokalan® Polymers 0.000 claims 1
- 239000006096 absorbing agent Substances 0.000 claims 1
- 229920006222 acrylic ester polymer Polymers 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 239000012943 hotmelt Substances 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 4
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- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 14
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- 239000000084 colloidal system Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 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 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 150000004658 ketimines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 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 description 2
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
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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
-
- 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
-
- 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
- C08G18/44—Polycarbonates
-
- 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
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Landscapes
- 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 discloses a moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol, and belongs to the technical field of adhesive synthesis. The invention provides a moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol, which is mainly prepared from the following raw materials in parts by weight: 65-95 parts of polyurethane prepolymer, 5-30 parts of modifier and 0.2-5 parts of auxiliary agent. The invention discloses a method for preparing a moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol, which has the characteristics of energy conservation, environmental protection, wide material selection, good compatibility, high adhesive force and the like, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of adhesive synthesis, and particularly relates to a moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol.
Background
The moisture-curing polyurethane hot melt adhesive is widely applied to the adhesion of materials such as metal, wood, paper, plastic and the like due to the advantages of environmental protection, high adhesion speed, high adhesion strength, wide application range of base materials, high cost performance and the like. Along with the continuous deep industrialization process in China, the moisture-curing polyurethane hot melt adhesive has wider application and larger usage, and according to incomplete statistics, the usage of the polyurethane hot melt adhesive in 2018 is increased by more than 40 percent compared with that in 2017, which is far higher than that of other hot melt adhesives or adhesive products, and the high-grade moisture-curing polyurethane hot melt adhesive can play an important role in the industrialization process in China.
At present, the moisture-curing polyurethane hot melt adhesive is prepared by mixing polyester polyol and polyether polyol, and the properties of each hot melt adhesive are adjusted according to different proportions of the polyester polyol and the polyether polyol. However, during the development process, it was found that the polyester polyol and the polyether polyol were incompatible, and the mixture of the two was in a milky-white non-transparent state, especially when mixed with the polyether polyol having a trifunctional or higher functionality, and the incompatibility of the two was very remarkable. The color of the hot melt adhesive is in a non-transparent state, and although the color of the hot melt adhesive has little correlation with the performance of the hot melt adhesive, the transparency of the hot melt adhesive directly influences the use experience of users, especially the visual appearance requirement in the actual use process.
Disclosure of Invention
Aiming at the problems of poor compatibility and poor mechanical property of the existing moisture-curing polyurethane hot melt adhesive, the research discovers that the polycarbonate polyether polyol has two functionalities of polycarbonate and polyether at the same time, and the compatibility of polycarbonate groups and polyester is very excellent, so that the moisture-curing polyurethane hot melt adhesive with good compatibility and mechanical property is obtained by using the characteristics of good compatibility of the polycarbonate polyether polyol, the polyester polyol and the polyether polyol as a surfactant.
The invention aims to provide a moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol, which has the advantages of good environmental protection and quick curing, can be widely used in the adhesion fields of furniture, woodworking, spinning, shoemaking, packaging, automobile traffic and the like, and is suitable for popularization and application.
It is an object of the present invention to provide a process for preparing moisture-curable polyurethane hot melt adhesives containing polycarbonate polyether polyols.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, a moisture-curable polyurethane hot melt adhesive containing a polycarbonate polyether polyol is provided, comprising the following raw materials in parts by weight: the polyurethane prepolymer is 65 to 95 parts by weight, for example 65 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, 86 parts by weight, 88 parts by weight, 90 parts by weight, 95 parts by weight, preferably 75 to 90 parts by weight; 5 to 30 parts by weight of a modifier, for example, 5 parts by weight, 7 parts by weight, 9 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, preferably 5 to 10 parts by weight; 0.2 to 5 parts by weight of auxiliary agents, for example 0.2 part by weight, 0.4 part by weight, 0.6 part by weight, 0.8 part by weight, 1.0 part by weight, 1.2 part by weight, 1.4 part by weight, 1.6 part by weight, 1.8 part by weight, 2.0 part by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight, 3.0 parts by weight, 3.2 parts by weight, 3.4 parts by weight, 3.6 parts by weight, 3.8 parts by weight, 4.0 parts by weight, 4.2 parts by weight, 4.4 parts by weight, 4.6 parts by weight, 4.8 parts by weight, 5.0 parts by weight, preferably 3 to 4 parts by weight.
The polyurethane prepolymer is obtained by reacting polyol with excessive isocyanate;
the polyol is selected from one of a combination of polyester polyol and polycarbonate polyether polyol, a combination of polyether polyol and polycarbonate polyether polyol, or a combination of polyester polyol, polyether polyol and polycarbonate polyether polyol;
wherein the polycarbonate polyether polyol accounts for not less than 3% of the mass of the mixture polyol.
The amounts of the polyester polyol and the polyether polyol may be adjusted according to actual needs, and the present invention is not limited.
The following details the raw materials:
polyurethane prepolymers
The polyurethane prepolymer is obtained by reacting a polyol with an excess of isocyanate.
The reaction of a specific polyol with an excess of isocyanate is: after dewatering and cooling the polyol, adding isocyanate and stirring to obtain polyurethane prepolymer;
preferably, the stirring is followed by a defoaming treatment.
Specifically, the water removal and temperature reduction of the polyol is to heat the polyol to 100-130 ℃ for vacuum water removal, the vacuum degree is-0.09 MPa to-0.1 MPa, and the vacuum holding time is more than 0.5 h; the water removal requirement is to detect that the water content is less than 500ppm.
The temperature is reduced to 40-100 ℃.
The stirring time is 0.5-1.2h, and the stirring speed is 100-500r/min.
The time for stirring the isocyanate may also be determined based on the theoretical NCO%.
Specifically, NCO% is the isocyanate content of 100g of the sample. Theoretical value NCO% = (moles of isocyanate-moles of hydroxyl-moles of water content x 2) x 42/total mass.
Wherein the bubble removal is performed in vacuum at 60-150 ℃.
Specifically, the defoaming treatment is to perform defoaming by vacuum.
Wherein the vacuum degree of the vacuum bubble removal is between-0.09 MPa and-0.1 MPa, and the vacuum time is more than 0.5 h.
Polycarbonate polyether polyol
The polycarbonate polyether polyol is a block copolymer of polycarbonate and polyether and can be represented by the following formula:
H-(-O-R 1 -O-CO-) m -(-O-R 2 -) n -OH。
wherein: r is R 1 And R is 2 Is alkyl, m and n are the number of molecules of the polycarbonate unit and the polyether unit contained in each molecule, respectively. The method can determine a plurality of technical indexes such as the state (solid state or liquid state at normal temperature) of the polycarbonate polyether polyol through the values of m and n, wherein the values of m and n are both larger than 1, and the specific values can be adjusted according to the actual requirements of products, and the method is not limited.
Preferably, R in the polycarbonate polyether polyol 1 Or R is 2 The number of carbon raw materials of (2) is not more than 5, preferably not more than 4. For example, methylene, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl or isopentyl. Wherein R is 1 And R is 2 May be the same or different.
Polyester polyol
The polyester polyol may be used alone or as a mixture of a crystalline polyester polyol and a noncrystalline polyester polyol. The polyester polyol used is not limited in kind and quantity, contains a large amount of ester bonds, can form hydrogen bonds with water, and has certain water absorption. Amorphous polyester polyols which contain certain pendant groups (e.g., methyl, ethyl, etc.) can theoretically result in hydrophobicity, but are negligible given that amorphous polyester polyols typically do not exceed 10% in content.
Polyether polyol
The polyether polyols are oligomers whose main chain contains ether bonds (-R-O-R-), and whose end groups or side groups contain more than 2 hydroxyl groups (-OH). Any one of those commonly used in the art may be employed, and the kind and amount of the polyester polyol used are not limited.
Isocyanate(s)
The isocyanate is an isocyanate-containing ester.
Preferably, the isocyanate is one or more of a diisocyanate or polyisocyanate.
Preferably, the isocyanate is a diisocyanate or a mixture of diisocyanates. Such as diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), naphthalene Diisocyanate (NDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI).
Modifying agent
The modifier may be any functional material known in the art that can be added to improve the properties of the polyurethane prepolymer (e.g., melt viscosity, tack, etc.).
Preferably, the modifier is one or more of vinyl acetate polymer, vinyl acetate-ethylene copolymer, acrylic polymer and copolymer thereof, thermoplastic polyurethane polymer.
Auxiliary agent
The auxiliary agent can be any material known in the art that can perform the effects of catalysis, leveling, antioxidation, curing, ultraviolet absorption and deodorization.
Preferably, the auxiliary agent is a mixture of various auxiliary agents such as a catalyst, a leveling agent, an antioxidant, a latent curing agent, an ultraviolet absorber, a deodorant and the like.
Preferably, the catalysts are T12 and DMDEE. Leveling agent BYK333. Antioxidants were 1010 and BHT. The latent curing agent is amine terminated polyether type.
The term "comprising" as used herein means that other materials may be included in addition to the above materials, and the term "comprising" as used herein may be replaced with "being closed" or "consisting of … …", etc.
In a second aspect, a method is provided for preparing a moisture-curable polyurethane hot melt adhesive comprising a polycarbonate polyether polyol, comprising the steps of:
s1, adding polyol into a container according to the raw material metering proportion, starting heating, starting stirring after the material temperature reaches 100-130 ℃, wherein the stirring speed is 200r/min, the vacuum is over 0.5h, the vacuum degree is between-0.09 MPa and-0.1 MPa, and stopping vacuum after the water content is detected to be less than 500ppm.
S2, stopping stirring, releasing vacuum, cooling to 80 ℃, adding isocyanate, stirring at 500r/min for 40min, and detecting NCO; detecting NCO% every 30-60min until NCO% reaches design theoretical value + -0.2%;
s3, adding a modifier and/or an auxiliary agent according to the raw material metering proportion, and stirring in vacuum for at least 30min at a stirring speed of 100r/min and a vacuum degree of between-0.09 MPa and-0.1 MPa; the materials are evenly mixed without bubbles, then the materials can be discharged, nitrogen is filled, and the materials are hermetically packaged and stored.
Preferably, in step S1, when the polyol is added into the container according to the raw material metering proportion, the modifier and the auxiliary agent are added. The moisture-curing polyurethane hot melt adhesive is obtained by adding the modifier and the auxiliary agent into polyurethane prepolymer, and the moisture-curing polyurethane hot melt adhesive can be obtained by adding the modifier and the auxiliary agent while preparing the polyurethane prepolymer. For example, the moisture-curable polyurethane hot melt adhesive of the present invention is obtained by adding a modifier and an auxiliary agent when a polyol is added, and then adding the modifier and the auxiliary agent after stirring, for example, after adding isocyanate.
The moisture-curing polyurethane hot melt adhesive provided by the invention has at least the following beneficial effects:
firstly, the moisture-curing polyurethane hot melt adhesive mainly comprises polyurethane prepolymer, modifier and auxiliary agent, and by adopting polycarbonate polyether polyol, the compatibility of the polyester polyol and the polyether polyol is increased, and the most obvious gain effect is that the appearance of the polyurethane hot melt adhesive is transparent light yellow liquid. The foreign matter mixing in and the quality problems such as uneven stirring can be identified.
And secondly, the polycarbonate polyether polyol is adopted, so that the moisture-curing polyurethane hot melt adhesive has the advantages of wider material selection, more living proportion, larger using amount of trifunctional polyether polyol, even the use of tetrafunctional polyether polyol and polyether polyol with more than tetrafunctional polyether polyol is possible, further, the initial adhesion strength and the final adhesion strength are effectively improved, and particularly, when the trifunctional polyether polyol or polyether polyol with more than trifunctional polyether polyol is adopted, the final adhesion strength improving effect is more obvious.
Finally, by adopting polycarbonate polyether polyol, according to different proportions, the polycarbonate contains a large amount of carbon-oxygen double bonds, and has the properties of excellent water resistance, ultraviolet resistance, aging resistance and the like. The polycarbonate polyether polyol used for the moisture-curing polyurethane hot melt adhesive has the advantages of environmental protection and high-efficiency curing speed, and the synthesized hot melt adhesive can be used in the adhesion fields of furniture, woodworking, spinning, shoemaking, packaging, automobile traffic and the like, and is suitable for popularization and application.
Drawings
FIG. 1 is a photograph of a hot melt adhesive prepared in example 1 of the present invention;
FIG. 2 is a photograph of the hot melt adhesive prepared in comparative example 1;
FIG. 3 is a photograph of the hot melt adhesive prepared in comparative example 2.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The starting materials are available from published commercial sources unless otherwise specified. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
Examples 1-3 and comparative examples 1-2
A preparation method of a moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol comprises the steps of mixing examples 1-3 and comparative examples 1-2 in a proportion shown in table 1;
TABLE 1 ingredients data sheet
The latent curing agent can be prepared and obtained according to Chinese patent document CN110698622A, namely a ketimine latent curing agent, a reactive polyurethane hot melt adhesive with the ketimine latent curing agent and a method disclosed in application.
The production method and the process are as follows:
1. sequentially adding raw material serial numbers 1, 2, 3, 5, 8, 9, 10 and 11 into a container according to the raw material metering proportion, starting heating, starting stirring after the temperature of the raw material reaches 100-130 ℃, wherein the stirring speed is 200r/min, the vacuum is over 0.5h, and the vacuum degree is between-0.09 MPa and-0.1 MPa. After the water content was detected to be less than 500ppm, the vacuum was stopped.
2. Stopping stirring, releasing vacuum, cooling to 80 ℃, adding raw material serial number 4, stirring at 500r/min for 40min, and detecting NCO; detecting NCO% every 30-60min until NCO% reaches design theoretical value + -0.2%;
3. adding raw material serial numbers 6 and 7 according to the raw material metering proportion, and stirring in vacuum for at least 30min, wherein the stirring speed is 100r/min, and the vacuum degree is between-0.09 MPa and-0.1 MPa; the materials are evenly mixed without bubbles, then the materials can be discharged, nitrogen is filled, and the materials are hermetically packaged and stored.
Table 2, experimental data for examples 1-3 and comparative examples 1-2
The hot melt adhesive prepared in example 1 is shown in fig. 1, the hot melt adhesive prepared in comparative example 1 is shown in fig. 2, and the hot melt adhesive prepared in comparative example 2 is shown in fig. 3.
From the results data of fig. 1-3 and table 2, it can be seen that:
1. examples 1 to 3 are the hot melt adhesive preparation methods provided by the invention, in which no polycarbonate polyether polyol and no polyether polyol are used in comparative example 1, and no polycarbonate polyether polyol and no latent curing agent are used in comparative example 2, and in which the above-mentioned examples and comparative examples are identical in terms of the amount of the polyester polyol, the polycarbonate polyether polyol, the polyether polyol and the latent curing agent, except for the amounts of the other components and the amounts, the colloid in comparative example 1 has an overall off-white color, is translucent (as shown in fig. 2), and is found to be poorly compatible; the comparative example 2 uses polyether polyol whose colloid has overall whiteness, opacity, and its white concentration is significantly higher than that of comparative example 2, and its compatibility is extremely poor. The hot melt adhesives prepared in examples 1-3 provided by the invention can all show transparent light yellow appearance, as shown in fig. 1, the hot melt adhesive colloid prepared in example 1 is transparent, almost has a cup bottom, has good compatibility, can solve the problem of miscibility of polyether polyol, can solve the problem of compatibility of a latent curing agent mainly composed of polyether polyamine, and has very remarkable effect compared with comparative examples 1 and 2.
2. In addition, when the amounts of the polyester polyol, the polycarbonate polyether polyol, the polyether polyol and the latent curing agent are adjusted only, the final tack shear strength of example 2 reaches 5.8, and the final tack shear strength of example 3 reaches 7.4, so that the final tack strength of the hot melt adhesive is improved to different degrees, and the hot melt adhesive has a remarkable effect.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the method disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points are referred to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol is prepared from the following raw materials in parts by weight:
65-95 parts of polyurethane prepolymer, 5-30 parts of modifier and 0.2-5 parts of auxiliary agent;
the polyurethane prepolymer is obtained by reacting polyol with excessive isocyanate;
the modifier is at least one selected from vinyl acetate polymer, vinyl acetate-ethylene copolymer, acrylic ester polymer and copolymer thereof and thermoplastic polyurethane polymer;
the auxiliary agent is at least one selected from catalysts, leveling agents, antioxidants, latent curing agents, ultraviolet absorbers and odor removing agents.
2. The moisture-curable polyurethane hot melt adhesive comprising a polycarbonate polyether polyol according to claim 1, wherein: the polyol is selected from one of a combination of polyester polyol and polycarbonate polyether polyol, a combination of polyether polyol and polycarbonate polyether polyol, or a combination of polyester polyol, polyether polyol and polycarbonate polyether polyol;
the proportion of the polycarbonate polyether polyol to the total mass of the polyol is not less than 3%;
the isocyanate is selected from any one of MDI, TDI, NDI, IPDI and HDI;
the reaction R value of the polyol and isocyanate is between 1.4 and 5.0 percent;
wherein the R value is the ratio of the moles of isocyanate groups to the moles of hydroxyl groups, i.e. r=nco/OH.
3. The moisture-curable polyurethane hot melt adhesive comprising a polycarbonate polyether polyol according to claim 2, wherein: the structural formula of the polycarbonate polyether polyol is shown as formula I:
H-(-O-R 1 -O-CO-) m -(-O-R 2 -) n -OH formula I
In the formula I, R 1 And R is 2 Are all selected from any one of C1-C5 alkyl groups; specifically selected from any one of C1-C4 alkyl; more specifically, any one of methylene, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl and isopentyl;
m is a polycarbonate unit contained in each molecule; m is more than or equal to 1;
n is the number of molecules of polyether units contained in each molecule; n is more than or equal to 1.
4. The moisture-curable polyurethane hot melt adhesive comprising a polycarbonate polyether polyol according to claim 1, wherein: the polyurethane prepolymer is obtained by reacting a polyol with an excess of isocyanate: after dewatering and cooling the polyol, adding isocyanate and stirring to obtain polyurethane prepolymer;
preferably, the isocyanate is added and stirred, and then the defoaming treatment is further included.
5. The moisture-curable polyurethane hot melt adhesive comprising a polycarbonate polyether polyol as described in claim 4, wherein: the polyol is heated to 100-130 ℃ for vacuum dehydration, the vacuum degree is-0.09 MPa to-0.1 MPa, and the vacuum holding time is more than 0.5 h;
the temperature is reduced to 40-100 ℃;
the stirring time is at least 30min, and the stirring speed is 100-500r/min.
6. The moisture-curable polyurethane hot melt adhesive comprising a polycarbonate polyether polyol according to claim 1, wherein: the modifier is at least one selected from vinyl acetate polymer, acrylic acid polymer and thermoplastic polyurethane polymer.
7. A process for preparing a moisture-curable polyurethane hot melt adhesive comprising a polycarbonate polyether polyol as defined in any one of claims 1 to 6, which is obtained by adding a modifier and an auxiliary agent in the preparation of a polyurethane prepolymer, comprising in particular:
s1, adding polyol into a container according to the raw material metering proportion, starting heating, starting stirring after the material temperature reaches 100-130 ℃, wherein the stirring speed is 200r/min, the vacuum is over 0.5h, the vacuum degree is between-0.09 MPa and-0.1 MPa, and stopping vacuum after the water content is detected to be less than 500ppm.
S2, stopping stirring, releasing vacuum, cooling to 80 ℃, adding isocyanate, stirring at 500r/min for 40min, and detecting NCO; detecting NCO% every 30-60min until NCO% reaches design theoretical value + -0.2%;
s3, adding a modifier and/or an auxiliary agent according to the raw material metering proportion, and stirring in vacuum for at least 30min at a stirring speed of 100r/min and a vacuum degree of between-0.09 MPa and-0.1 MPa; the materials are evenly mixed without bubbles, then the materials can be discharged, nitrogen is filled, and the materials are hermetically packaged and stored.
8. The method according to claim 7, wherein: and step S1, adding a modifier and/or an auxiliary agent when adding the polyol into the container according to the raw material metering proportion.
9. Use of a moisture-curable polyurethane hotmelt containing a polycarbonate polyether polyol as defined in any of claims 1 to 6 in bonding.
10. An adhesive product comprising the moisture-curable polyurethane hot melt adhesive comprising a polycarbonate polyether polyol as defined in any one of claims 1 to 6.
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| CN202310221352.9A CN116376499A (en) | 2023-03-09 | 2023-03-09 | Moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol |
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|---|---|---|---|
| CN202310221352.9A CN116376499A (en) | 2023-03-09 | 2023-03-09 | Moisture-curing polyurethane hot melt adhesive containing polycarbonate polyether polyol |
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| CN (1) | CN116376499A (en) |
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