CN116063971A - Moisture-curing polyurethane adhesive and preparation method and application thereof - Google Patents

Moisture-curing polyurethane adhesive and preparation method and application thereof Download PDF

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CN116063971A
CN116063971A CN202310047008.2A CN202310047008A CN116063971A CN 116063971 A CN116063971 A CN 116063971A CN 202310047008 A CN202310047008 A CN 202310047008A CN 116063971 A CN116063971 A CN 116063971A
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moisture
polyurethane adhesive
curing
polycaprolactone
polyol
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李因文
田泽鑫
李兴建
马建峰
徐守芳
李法强
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Linyi University
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Linyi University
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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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001—Use of materials characterised by their function or physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/046—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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    • 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
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    • 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
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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
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
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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
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    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy 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
    • C08G18/40—High-molecular-weight compounds
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    • C08G18/4829—Polyethers containing at least three hydroxy 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • 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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    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
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Abstract

The invention discloses a moisture-curing polyurethane adhesive and a preparation method and application thereof, and belongs to the technical field of functional polymer materials. The invention prepares polyurethane prepolymer by polymerizing the combination of polypropylene polyol and polycaprolactone polyol with isocyanate, and then obtains moisture-curing polyurethane adhesive by reacting with components such as curing accelerator, filler, dehydrating agent, pigment, defoamer and the like. The polyurethane adhesive can rapidly initiate curing reaction by only using trace water vapor in air and shows excellent mechanical strength in a short time, and meanwhile, the introduction of polycaprolactone polyol endows good biocompatibility and degradability, thereby laying a good foundation for subsequent recycling; in addition, the polyurethane adhesive disclosed by the invention is simple in production process and long in product storage time, can meet the requirements of medical and other emergency repair and reinforcement fields by optimally controlling the types and proportions of polyether polyol, isocyanate monomers, curing accelerators, pigment fillers and auxiliary agents, and has a wide application prospect.

Description

Moisture-curing polyurethane adhesive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a moisture-curing polyurethane adhesive and a preparation method and application thereof.
Background
The polyurethane adhesive, namely PU adhesive, contains a plurality of polar groups such as carbamate groups, ester groups, ether groups and the like in the molecular structure, and can form hydrogen bonds with hydrogen-containing polar groups on materials to be bonded, so that the polyurethane adhesive has very firm bonding performance and is widely applied to bonding of metals, wood, fibers, plastics and the like. The single-component moisture-curing polyurethane adhesive is a type of adhesive which achieves the bonding purpose by utilizing the reaction of free active isocyanate groups in the polymer and water vapor in the atmosphere or active hydrogen atoms in a bonding substrate, and the reaction medium is mainly water and does not need heating or other energy, so that the problem of volatile organic compounds does not exist, and the adhesive has better wear resistance, thermal stability, hardness and chemical stability after curing.
At present, the single-component moisture-curing polyurethane adhesive is widely applied to various fields of industrial and agricultural production and life, wherein the application in the medical field is taken as an example, and gypsum bandages are mostly adopted for reinforcing treatment of fracture patients to help the bone healing of the patients. Although the gypsum has low price and sufficient source, the gypsum has the defects of high density, air impermeability, low X-ray transmittance, easy breakage and the like, and is easy to cause secondary infection and brings trouble to treatment. The current mainstream technology is to impregnate the softened glass fiber knitted fabric with thermosetting resin meeting the performance requirement to prepare a medical glass fiber bandage, wherein the common thermosetting resin comprises epoxy resin, unsaturated resin and polyurethane adhesive, and the epoxy resin adhesive needs to be added with a curing agent or a cross-linking agent during curing and needs to be heated to promote the cross-linking reaction, so that the curing speed is low and the curing speed is not in accordance with the requirements of glass fiber bandage coating; the unsaturated resin adhesive can be cured at room temperature without adding a curing agent or a cross-linking agent, but has longer curing time and low bonding strength, and does not meet the requirements of glass fiber bandage coating. Therefore, the polyurethane adhesive is selected to impregnate the glass fiber, and the polyurethane adhesive which is used for coating the glass fiber and meets the technical requirements is developed by adjusting the content of components, changing the process formula, the temperature, the humidity and the like. However, the existing moisture-curing polyurethane adhesives still have many defects, such as slow curing rate, long complete curing time of the adhesive film, low mechanical strength after curing and hardening, and the like, which limit the further popularization and application of the glass fiber bandages coated with the moisture-curing polyurethane adhesives. CN201910211039.0 discloses a polyurethane resin composite material for medical bandage coating, the production process is relatively complex, the strength after curing is measured by soaking in water, the difference from the practical application condition is large, the mechanical property after curing and hardening is still to be further improved, and in addition, the degradability of the polyurethane resin composite material for bandage coating is not involved.
Disclosure of Invention
In order to solve the defects in the prior art, the primary aim of the invention is to provide a novel moisture-curing polyurethane adhesive, and simultaneously the invention also provides a preparation method of the novel moisture-curing polyurethane adhesive.
Meanwhile, another object of the invention is to provide an application of the novel moisture-curing polyurethane adhesive, in particular to a method for coating the moisture-curing polyurethane adhesive on glass fibers, and the novel moisture-curing polyurethane adhesive is applied to the medical field of orthopedic multi-part fixation, orthopedic appliances for orthopedic surgery, artificial limb auxiliary appliances, supporting tools and local protective brackets for burn department and other emergency repair and reinforcement fields.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the moisture-curing polyurethane adhesive is prepared from the following raw materials in parts by weight: 85-90 parts of polyurethane prepolymer component, 1-3 parts of curing accelerator, 1-5 parts of filler, 1-3 parts of dehydrating agent, 2-4 parts of pigment and 1-3 parts of defoamer.
Further, the polyurethane prepolymer component is obtained by utilizing the polymerization reaction of active hydroxyl OH of polyether polyol and active isocyanate functional group NCO in isocyanate monomer, and the specific preparation steps are as follows: adding polyether polyol into a reaction kettle, introducing nitrogen, heating to 110 ℃, dehydrating in vacuum for 1h, adding isocyanate monomer, stirring for 2-3h, ending the reaction, cooling to room temperature, and discharging to obtain the polyurethane prepolymer component.
Still further, the polyether polyols are polycaprolactone polyol PCL and polypropylene polyol.
The polypropylene polyol is one of polypropylene glycol PPG600, polypropylene glycol PPG800, polypropylene triol N303 and polypropylene triol N306.
The polycaprolactone polyol PCL has the structure of a general formula (I):
Figure BDA0004055969440000021
in the polycaprolactone polyol PCL shown in the formula I, R is a molecular skeleton segment of polyol (ethylene glycol, glycerol, trimethylolpropane and pentaerythritol);
the molecular weight (Mw) of the polycaprolactone polyol PCL shown in the formula I is 400-800, the repeating unit (x) of the polycaprolactone PCL chain segment is 1-5, and the hydroxyl functionality (y) is 2-4.
The polycaprolactone polyol PCL is one of glycol-based polycaprolactone diol, glycerol-based polycaprolactone triol, trimethylol propane-based polycaprolactone triol and pentaerythritol-based polycaprolactone tetrol.
Further, the mass ratio of polypropylene polyol to polycaprolactone polyol in the polyether polyol is (3-4): (1-2).
Further, the isocyanate monomer is one or more of diphenylmethane diisocyanate MDI, polymethylene polyphenyl isocyanate PAPI, toluene diisocyanate TDI, isophorone diisocyanate IPDI and dicyclohexylmethane diisocyanate HMDI.
Further, the mass ratio of the polyether polyol to the isocyanate monomer is (4-5): (5-6).
Further, the curing accelerator is one or more of dimorpholinodiethyl ether and dibutyl tin dilaurate; the filler is one or more of nanoscale white carbon black, calcium oxide and zinc oxide, the pigment is one or more of oily phthalocyanine blue, phthalocyanine green, carbon black and iron oxide red color paste, and the dehydrating agent is one or more of methanesulfonic acid, maleic anhydride, itaconic anhydride and molecular sieve.
Further, the defoamer refers to an organosilicon defoamer.
The preparation method of the moisture-curing polyurethane adhesive comprises the following preparation steps: adding polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then respectively adding a filler, a pigment, a dehydrating agent and a defoaming agent, uniformly stirring for 0.5h, adding a curing accelerator, continuously reacting for 0.5h, thus obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
The application of the moisture-curing polyurethane adhesive is specifically that the moisture-curing polyurethane adhesive is coated on glass fibers and is applied to the medical field of orthopedic multi-part fixation, orthopedic tools for orthopedic surgery, prosthetic auxiliary tools, supporting tools and local protective brackets for burn department and other emergency repair and reinforcement fields.
Advantageous effects
(1) The novel moisture-curing polyurethane adhesive disclosed by the invention adopts the reaction of the combined polyether polyol and the isocyanate monomer, so that excellent adhesive performance is provided, meanwhile, the quick-initiating curing reaction can be realized by utilizing trace water vapor in the air, and the novel moisture-curing polyurethane adhesive has excellent mechanical strength within a short time of 3-5 minutes.
(2) The introduction of polycaprolactone polyol in the invention endows the moisture-curing polyurethane adhesive with good biocompatibility and degradability, and lays a good foundation for subsequent recycling;
(3) The novel moisture-curing polyurethane adhesive has the advantages of simple production process and long storage time, can be used in the medical field by optimally controlling the types and the proportions of polyether polyol, isocyanate monomer, curing accelerator, pigment, filler and auxiliary agent, and has wide application prospect in other related emergency repair and reinforcement fields.
Drawings
FIG. 1 is a structural formula of polycaprolactone polyol PCL according to the present invention: (a) is glycol-based polycaprolactone diol, (b) is glycerol-based polycaprolactone triol, (c) is trimethylol propane-based polycaprolactone triol, and (d) is pentaerythritol-based polycaprolactone tetrol;
FIG. 2 is a synthetic route for example 1 to prepare polyurethane prepolymers from ethylene glycol based polycaprolactone diol, polypropylene glycol PPG600, and diphenylmethane diisocyanate MDI.
FIG. 3 is a glass fiber bandage without the moisture-curable polyurethane adhesive of the present invention;
FIG. 4 is a glass fiber bandage coated with a moisture-curable polyurethane adhesive according to the present invention;
FIG. 5 is a graph showing contact angles of glass fibers before (a) and after (b) coating the moisture-curable polyurethane adhesive of the present invention;
fig. 6 is a diagram showing the action mechanism of the moisture-curable polyurethane adhesive coated glass fiber according to the present invention.
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of glycol polycaprolactone diol (Mw is approximately equal to 400) and 40kg of polypropylene diol (PPG 600, mw is approximately equal to 600) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is finished after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 2
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: adding 20kg of glycerol-based polycaprolactone triol (Mw is approximately equal to 600) and 40kg of polypropylene glycol (PPG 600, mw is approximately equal to 600) into a reaction kettle, introducing nitrogen, heating to 110 ℃, dehydrating for 1h in vacuum, adding 80kg of diphenylmethane diisocyanate (MDI), stirring for 3h, ending the reaction, cooling to room temperature, and discharging to obtain the polyurethane prepolymer component.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 3
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: adding 20kg of trimethylol propyl polycaprolactone triol (Mw is approximately equal to 600) and 40kg of polypropylene glycol (PPG 600, mw is approximately equal to 600) into a reaction kettle, introducing nitrogen, heating to 110 ℃, dehydrating for 1h in vacuum, adding 80kg of diphenylmethane diisocyanate (MDI), stirring for 3h, ending the reaction, cooling to room temperature, and discharging to obtain the polyurethane prepolymer component.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 4
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of pentaerythritol-based polycaprolactone tetraol (Mw is approximately equal to 800) and 40kg of polypropylene glycol (PPG 600, mw is approximately equal to 600) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is finished after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 5
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of glycol polycaprolactone diol (Mw is approximately equal to 400) and 40kg of polypropylene triol (N303, mw is approximately equal to 300) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 6
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of glycol polycaprolactone diol (Mw is approximately equal to 400) and 40kg of polypropylene triol (N306, mw is approximately equal to 600) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 7
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of glycol polycaprolactone diol (Mw is approximately equal to 400) and 40kg of polypropylene diol (PPG 800, mw is approximately equal to 800) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is finished after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 8
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 25kg of glycol polycaprolactone diol (Mw is approximately equal to 400) and 35kg of polypropylene triol (N303, mw is approximately equal to 300) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 9
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 30kg of glycol polycaprolactone diol (Mw is approximately equal to 400) and 30kg of polypropylene triol (N306, mw is approximately equal to 600) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 10
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 25kg of glycol polycaprolactone diol (Mw is approximately equal to 400) and 35kg of polypropylene triol (N303, mw is approximately equal to 300) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 85kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 11
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 25kg of glycerol alcohol-based polycaprolactone triol (Mw is approximately equal to 800) and 35kg of polypropylene triol (N303, mw is approximately equal to 300) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 12
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of pentaerythritol-based polycaprolactone tetraol (Mw is approximately equal to 600) and 40kg of polypropylene glycol (PPG 600, mw is approximately equal to 600) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 85kg of diphenylmethane diisocyanate (MDI) is added, the reaction is finished after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 13
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of pentaerythritol-based polycaprolactone tetraol (Mw is approximately equal to 800) and 40kg of polypropylene glycol (PPG 800, mw is approximately equal to 800) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 85kg of diphenylmethane diisocyanate (MDI) is added, the reaction is finished after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: according to the weight portions, 90kg of polyurethane prepolymer components are added into a reaction kettle, nitrogen is introduced and the temperature is raised to 50-60 ℃, then 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer are respectively added, the mixture is stirred uniformly for 0.5h, 2kg of dimorpholinodiethyl ether is added, the reaction is continued for 0.5h, and the moisture-curing polyurethane adhesive is obtained, and the moisture-curing polyurethane adhesive is stored in a sealing way.
Example 14
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 25kg of pentaerythritol-based polycaprolactone tetraol (Mw is approximately equal to 800) and 35kg of polypropylene triol (N303, mw is approximately equal to 300) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 85kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 15
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of glycol polycaprolactone diol (Mw is approximately equal to 600) and 40kg of polypropylene triol (N303, mw is approximately equal to 300) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 16
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of glycol polycaprolactone diol (Mw is approximately equal to 800) and 40kg of polypropylene triol (N306, mw is approximately equal to 600) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 17
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 30kg of glycol polycaprolactone diol (Mw is approximately equal to 400) and 30kg of polypropylene triol (N306, mw is approximately equal to 600) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2.5kg of maleic anhydride and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 1.5kg of dibutyltin dilaurate, continuing to react for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 18
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 25kg of glycol polycaprolactone diol (Mw is approximately equal to 400) and 35kg of polypropylene triol (N303, mw is approximately equal to 300) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 85kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then respectively adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer, uniformly stirring for 0.5h, adding 3kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 19
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of glycol polycaprolactone dihydric alcohol (Mw is approximately equal to 800) and 40kg of polypropylene triol (N306, mw is approximately equal to 600) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 2.0kg of calcium oxide, 2.5kg of carbon black, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2.0kg of dibutyltin dilaurate, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Example 20
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 25kg of pentaerythritol-based polycaprolactone tetraol (Mw is approximately equal to 800) and 35kg of polypropylene triol (N303, mw is approximately equal to 300) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 85kg of diphenylmethane diisocyanate (MDI) is added, the reaction is completed after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 85kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then respectively adding 5kg of white carbon black, 3.0kg of phthalocyanine blue, 2.5kg of methanesulfonic acid and 2.5kg of organic silicon defoamer, uniformly stirring for 0.5h, adding 2.0kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Comparative example 1
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 60kg of glycol polycaprolactone dihydric alcohol (Mw is approximately equal to 400) is added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is finished after stirring for 3h, the reaction is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Comparative example 2
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 60kg of polypropylene glycol (Mw is approximately equal to 600) is added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is finished after 3h of stirring reaction, the reaction kettle is cooled to room temperature, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Comparative example 3
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: 20kg of polypropylene glycol (Mw is approximately equal to 600) and 40kg of polypropylene triol (N303, mw is approximately equal to 300) are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 110 ℃, vacuum dehydration is carried out for 1h, 80kg of diphenylmethane diisocyanate (MDI) is added, the reaction is finished after stirring for 3h, cooling to room temperature is carried out, and the polyurethane prepolymer component is obtained after discharging.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Comparative example 4
The preparation method of the moisture-curing polyurethane adhesive comprises the following steps:
(1) Preparation of polyurethane prepolymer component: adding 20kg of polypropylene glycol (Mw is approximately equal to 600) and 40kg of polypropylene triol (N306, mw is approximately equal to 600) into a reaction kettle, introducing nitrogen, heating to 110 ℃, vacuum dehydrating for 1h, adding 80kg of diphenylmethane diisocyanate (MDI), stirring for 3h, ending the reaction, cooling to room temperature, discharging, and obtaining the polyurethane prepolymer component.
(2) Preparation of a moisture-curing polyurethane adhesive: adding 90kg of polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then adding 1.5kg of white carbon black, 2.5kg of phthalocyanine blue, 2kg of methanesulfonic acid and 2kg of organic silicon defoamer respectively, uniformly stirring for 0.5h, adding 2kg of dimorpholinodiethyl ether, continuously reacting for 0.5h, and obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
Performance testing
The performance test of the moisture-curing polyurethane adhesive refers to the standard of medical dressing rescue bandages (YY/T1467-2016). (1) storage stability: the novel moisture-curing polyurethane adhesive is placed for 6 months, and the viscosity change condition of the novel moisture-curing polyurethane adhesive is observed. (2) viscosity measurement: the viscosity of the moisture-curable polyurethane adhesive was measured with a rotational viscometer (NDJ-8) and the measurement was performed rapidly under room temperature drying conditions. (3) cure time test: and (3) coating a proper amount of moisture-curing polyurethane adhesive on the glass fiber, then scraping the glass fiber completely by a scraper, recording the time (min) for eliminating the viscosity on the surface of the adhesive layer by a stopwatch, and judging the standard to be non-sticky. (4) contact angle test: the static contact angle (theta) of the moisture-curing polyurethane adhesive before and after coating the glass fiber surface is measured by using a hanging drop method by taking blank glass fiber as a control, and then the wettability of the coating is evaluated by using the static contact angle (theta). (5) mechanical strength test: and taking blank glass fibers as a control, taking a moisture-cured polyurethane adhesive and a completely cured glass fiber bandage as a sample, and measuring the tensile strength and the breaking strength by using an electronic universal tester. The specific results are shown in Table 1:
TABLE 1 novel moisture curable polyurethane adhesive Properties according to the invention
Figure BDA0004055969440000121
The results show that the embodiment of the invention introduces more flexible polycaprolactone polyol segments compared with comparative examples 3 and 4, so that the prepared moisture-curing polyurethane adhesive has moderate viscosity and is more beneficial to subsequent industrialized coating application. When the adhesive is used for coating glass fibers, the glass fiber bandage without the moisture-curing polyurethane adhesive is very soft in texture, but the moisture-curing polyurethane adhesive prepared by the invention can be quickly cured and formed after being coated, and the curing reaction can be initiated by only using a trace amount of water vapor in the air, and the adhesive has excellent mechanical strength in a short time of 3-5 minutes. The polyurethane adhesive is characterized in that the residual isocyanate groups in the polyurethane adhesive are solidified with glass fiber bandages or water vapor in the air, and meanwhile, the moisture-solidified polyurethane adhesive structure contains not only rigid benzene rings and urethane bonds, but also polycaprolactone polyol chain segments with better toughness, so that the glass fibers are endowed with excellent strength, hardness and toughness by virtue of the unique soft and hard segment molecular structure. Contact angle measurements further showed that the moisture curable polyurethane adhesive coated on the glass fibers cured and hardened, well combined with the glass fibers to form an interpenetrating polymer-glass fiber network structure. In addition, the polycaprolactone polyol with good biocompatibility and degradability introduced in the invention also lays a good foundation for recycling the subsequent coated and peeled fiber.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.

Claims (10)

1. The moisture-curing polyurethane adhesive is characterized by comprising the following raw materials in parts by weight: 85-90 parts of polyurethane prepolymer component, 1-3 parts of curing accelerator, 1-5 parts of filler, 1-3 parts of dehydrating agent, 2-4 parts of pigment and 1-3 parts of defoamer.
2. The moisture-curable polyurethane adhesive according to claim 1, wherein the polyurethane prepolymer component is obtained by polymerization reaction of active hydroxyl groups of polyether polyol and active isocyanate functional groups in isocyanate monomers, and the preparation method comprises the following steps: adding polyether polyol into a reaction kettle, introducing nitrogen, heating to 110 ℃, dehydrating in vacuum for 1h, adding isocyanate monomer, stirring for 2-3h, ending the reaction, cooling to room temperature, and discharging to obtain the polyurethane prepolymer component.
3. The moisture-curable polyurethane adhesive of claim 2, wherein the polyether polyols are polycaprolactone polyols and polypropylene polyols; the polypropylene polyol is one of polypropylene glycol PPG600, polypropylene glycol PPG800, polypropylene triol N303 and polypropylene triol N306; the polycaprolactone polyol has the structure of general formula (I):
Figure FDA0004055969430000011
in the polycaprolactone polyol shown in the formula I, R is a molecular skeleton segment of the polyol; the molecular weight of the polycaprolactone polyol shown in the formula I is 400-800, the repeating unit x of the polycaprolactone chain segment is 1-5, and the hydroxyl functionality y is 2-4.
4. The moisture-curable polyurethane adhesive of claim 3, wherein the polycaprolactone polyol is one of ethylene glycol based polycaprolactone diol, glycerol based polycaprolactone triol, trimethylol propane based polycaprolactone triol, pentaerythritol based polycaprolactone tetrol.
5. The moisture-curable polyurethane adhesive according to claim 3, wherein the mass ratio of polypropylene polyol to polycaprolactone polyol in the polyether polyol is (3-4): (1-2).
6. The moisture-curable polyurethane adhesive of claim 2, wherein the isocyanate monomer is one or more of diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate.
7. The moisture-curable polyurethane adhesive according to claim 2, wherein the mass ratio of the polyether polyol to the isocyanate monomer is (4 to 5): (5-6).
8. The moisture-curable polyurethane adhesive according to claim 1, wherein the curing accelerator is one or more of dimorpholinodiethyl ether and dibutyltin dilaurate; the filler is one or more of nanoscale white carbon black, calcium oxide and zinc oxide, the pigment is one or more of oily phthalocyanine blue, phthalocyanine green, carbon black and iron oxide red color paste, and the dehydrating agent is one or more of methanesulfonic acid, maleic anhydride, itaconic anhydride and molecular sieve.
9. A method for preparing the moisture-curable polyurethane adhesive according to any one of claims 1 to 8, comprising the steps of: adding polyurethane prepolymer components into a reaction kettle, introducing nitrogen, heating to 50-60 ℃, then respectively adding a filler, a pigment, a dehydrating agent and a defoaming agent, uniformly stirring for 0.5h, adding a curing accelerator, continuously reacting for 0.5h, thus obtaining the moisture-curing polyurethane adhesive, and sealing and preserving.
10. Use of a moisture-curable polyurethane adhesive according to any one of claims 1 to 8, in particular for application of moisture-curable polyurethane adhesives to glass fibers and in the medical and other emergency repair and reinforcement fields of orthopedic multi-part fixation, orthopedic appliances, prosthetic aids and support tools, local protective stents for burn-in surgery.
CN202310047008.2A 2023-01-31 2023-01-31 Moisture-curing polyurethane adhesive and preparation method and application thereof Pending CN116063971A (en)

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