CN111690360A - Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof - Google Patents
Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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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
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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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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- C08G18/61—Polysiloxanes
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- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
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Abstract
The invention belongs to the field of polymer chemistry, and particularly relates to a reactive moisture-curing polyurethane hot melt adhesive and a preparation method thereof. The hot melt adhesive is prepared by reacting the following isocyanate component and isocyanate reactive component in parts by mass: the isocyanate component is: 15-35 parts by mass of isocyanate; the isocyanate-reactive component comprises: 30-55 parts by mass of at least one polyether polyol; 15-50 parts by mass of at least one polyester polyol; 0.01-10 parts by mass of at least one other hydroxy compound containing a long-chain aliphatic hydrocarbon; 0-3 parts by mass of hydroxyalkyl modified silicone oil. The reactive moisture-curing polyurethane hot melt adhesive disclosed by the invention has excellent moisture permeability, bonding strength, washing resistance and soft hand feeling; the preparation method has simple and convenient steps, effectively controls the occurrence of side reactions, and improves the quality and the production stability of final products.
Description
Technical Field
The invention belongs to the field of polymer chemistry, and particularly relates to a reactive moisture-curing polyurethane hot melt adhesive and a preparation method thereof.
Background
With the increasing living standard of human beings, the functional requirements of people on clothes are higher and higher, such as warm keeping, fashion, antibiosis, waterproof, moisture permeability, wind prevention and the like. The fabric with the waterproof and moisture permeable functions can reduce the stuffy feeling generated during sports, and is widely applied to the fields of sportswear, mountaineering wear, medical clothing, waterproof cloth, jacket, ski wear and the like.
A reactive moisture-curing polyurethane hot melt adhesive (PUR) is taken as one of environment-friendly adhesives and is widely applied to various fabric composite fabrics at present. If a general PUR product is adopted, the air and moisture permeability of the composite fabric can be greatly reduced, so researchers are dedicated to developing PUR products with high moisture permeability.
Chinese patent document CN108290993A discloses a preparation method of moisture-curing polyurethane hot melt adhesive: polyoxyethylene ether, aromatic polyester and crystalline polyester are used as the polyol component. The preparation method has the defect that the introduced polyoxyethylene ether and aromatic polyester polyol are not favorable for the washing resistance of the textile fabric.
Chinese patent document CN102167794A discloses a preparation method of polyurethane prepolymer: the polyalcohol is more than 75% of polytetramethylene glycol-ethylene glycol or polypropylene glycol, and the prepolymer prepared by the method has excellent moisture permeability and water washing resistance, but the polyether content is high, so the prepolymer is not favorable for the adhesive property of a final product.
Chinese patent document CN1341133A discloses a high moisture-permeable polyurethane hot melt adhesive with good hydrolysis resistance, which uses two polyether polyols as raw materials, one is polyoxyethylene-oxypropylene copolymer diol with low oxyethylene content (less than 40%), the other is low molecular weight polyalkylene glycol, and the polyester uses crystalline polyester polyol. The hot melt adhesive prepared by the method has good water washing resistance, but has poor moisture permeability due to low content of ethylene oxide, and meanwhile, the fabric has soft hand feeling due to the use of the low molecular weight polyol.
Therefore, the preparation of a reactive moisture-curing polyurethane hot melt adhesive with excellent moisture permeability, bonding strength, water washing resistance and soft hand feeling is urgently needed.
Disclosure of Invention
The invention aims to provide a reactive moisture-curing polyurethane hot melt adhesive which has excellent moisture permeability, bonding strength, water washing resistance and soft hand feeling.
The invention also aims to provide a preparation method of the reactive moisture-curing polyurethane hot melt adhesive, which can effectively control the occurrence of side reactions and improve the quality and production stability of final products.
The invention is realized by the following technical scheme:
in a first aspect, the invention provides a reactive moisture-curing polyurethane hot melt adhesive PUR prepared by reacting an isocyanate component and an isocyanate-reactive component in parts by mass:
the isocyanate component is:
15-35 parts by mass of isocyanate, preferably 20-30 parts by mass, such as 18 parts by mass, 23 parts by mass or 28 parts by mass;
the isocyanate-reactive component comprises:
30-55 parts by mass, preferably 40-50 parts by mass, such as 35 parts by mass, 43 parts by mass or 48 parts by mass of at least one polyether polyol;
15 to 50 parts by mass, preferably 20 to 40 parts by mass, for example 24 parts by mass, 27 parts by mass or 35 parts by mass of at least one polyester polyol;
0.01 to 10 parts by mass, preferably 0.5 to 5 parts by mass, such as 0.2 part by mass, 2.5 parts by mass, 4 parts by mass, 6 parts by mass or 8 parts by mass, of at least one other hydroxy compound containing a long-chain aliphatic hydrocarbon;
0 to 3 parts by mass, preferably 0.1 to 0.5 part by mass, for example 0.2 part by mass, 0.4 part by mass, 1.8 parts by mass or 2.6 parts by mass of a hydroxyalkyl-modified silicone oil;
preferably, the isocyanate-reactive component does not comprise a polyoxyethylene ether and/or a small molecule chain extender.
In a preferred embodiment, the isocyanate-reactive component does not comprise a polyoxyethylene ether. The polyoxyethylene ether is inferior to polyoxyethylene-oxypropylene copolyether in washing resistance and high in hygroscopicity, and thus is not favorable for the use stability of the PUR product in an open state.
In a preferred embodiment, the isocyanate-reactive component does not comprise a small molecule chain extender. The small molecular chain extender is used as a hard segment part of polyurethane after reaction, which is not favorable for the soft hand feeling of the fabric.
Preferably, in the above reactive moisture-curable polyurethane hot melt adhesive PUR, the other hydroxyl compound containing long-chain aliphatic hydrocarbon is a small molecular hydroxyl compound containing long-chain aliphatic hydrocarbon or a high molecular hydroxyl compound containing long-chain aliphatic hydrocarbon; and/or, the other hydroxyl compound containing the long-chain aliphatic hydrocarbon is a monohydroxy compound containing the long-chain aliphatic hydrocarbon or a polyhydroxy compound containing the long-chain aliphatic hydrocarbon; preferably, the other hydroxyl compound containing the long-chain aliphatic hydrocarbon is one or more selected from dodecanol, tetradecanol, hexadecanol, oleyl alcohol, stearyl alcohol, eicosanol, behenyl alcohol, tetracosanol, polyoxyethylene lauryl ether, polyoxyethylene cetyl alcohol, polyoxyethylene oleyl alcohol, polyoxyethylene stearyl alcohol, polyoxyethylene behenyl alcohol, polyoxyethylene oleic ether, polyoxyethylene stearic ether, dimer acid polyester diol, and the like. It has surprisingly been found that the addition of other hydroxy compounds containing long-chain aliphatic hydrocarbons significantly improves the adhesive properties of the product without adversely affecting the moisture permeability of the product.
Preferably, in the above reactive moisture-curing polyurethane hot melt adhesive PUR, the hydroxyalkyl modified silicone oil is selected from one or more of hydroxyethyl modified polydimethylsiloxane, hydroxypropyl modified polydimethylsiloxane, hydroxyisopropyl modified polydimethylsiloxane, hydroxybutyl modified polydimethylsiloxane, hydroxyhexyl modified polydimethylsiloxane, hydroxyl-terminated polyoxypropylene modified polydimethylsiloxane, hydroxyl-terminated polyoxyethylene oxypropylene modified polydimethylsiloxane; preferably, the hydroxyalkyl modified silicone oil is hydroxypropyl modified polydimethylsiloxane or hydroxyl terminated polyoxyethylene oxypropylene modified polydimethylsiloxane.
Preferably, in the above reactive moisture-curing polyurethane hot melt adhesive PUR, the polyether polyol is selected from one or more of polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene-oxypropylene copolymer and polytetrahydrofuran polyol; preferably, the polyether polyol is a polyoxyethylene-oxypropylene copolymer; more preferably, the content of the ethylene oxide group in the polyether polyol is 60-99 wt%, and the hydroxyl value is 20-300 mgKOH/g; still more preferably, the polyether polyol has an oxyethylene group content of 70 to 95 wt% and a hydroxyl value of 25 to 120 mgKOH/g. The polyether polyol selected by the invention has stronger hydrophilicity due to higher content of ethylene oxide, and can obviously improve the moisture permeability of the PUR.
Preferably, in the reactive moisture-curable polyurethane hot melt adhesive PUR, the polyester polyol is a mixture of crystalline polyester polyol a and amorphous polyester polyol B, wherein the molecular main chain of the crystalline polyester polyol a does not contain a side methyl group, and the hydroxyl value is 20 to 300mgKOH/g, preferably 30 to 120 mgKOH/g; the molecular main chain of the amorphous polyester polyol B contains side methyl, and the hydroxyl value is 20-300 mgKOH/g, preferably 30-120 mgKOH/g; preferably, the mass ratio of the crystalline polyester polyol A to the amorphous polyester polyol B is 0.1-5.0: 1, more preferably 1.0 to 2.5: 1, such as 1.2: 1 or 2.1: 1.
preferably, in the reactive moisture-curable polyurethane hot melt adhesive PUR, the crystalline polyester polyol a is obtained by reacting a dibasic acid a and a dihydric alcohol a, wherein the dihydric alcohol a is one or more selected from ethylene glycol, butanediol, hexanediol, octanediol and decanediol, and the dibasic acid a is one or more selected from adipic acid, suberic acid, sebacic acid and dodecanedioic acid; and/or the noncrystalline polyester polyol B is obtained by reacting dibasic acid B and dihydric alcohol B, wherein the dihydric alcohol B is dihydric alcohol with a side group, preferably dihydric alcohol with a side methyl group, more preferably one or more of 1, 2-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol and 3-methyl-1, 5-pentanediol, and still more preferably 2, 2-dimethyl-1, 3-propylene glycol; the dibasic acid B is one or more of adipic acid, suberic acid, sebacic acid, dodecyl diacid, phthalic acid, isophthalic acid and terephthalic acid.
The isocyanate component refers to a compound having an isocyanate group, and examples thereof include, but are not limited to, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), Hexamethylene Diisocyanate (HDI), methylcyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethyldimethylene diisocyanate (TMXDI), 1, 4-cyclohexane diisocyanate (CHDI), cyclohexanedimethylene diisocyanate (HXDI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), norbornane diisocyanate (NBDI), dimethylbiphenyl diisocyanate (TODI), and mixtures thereof, Methylcyclohexyl diisocyanate (HTDI), and the like, and polymers, modified products, and the like of such compounds, which may be used alone or in combination (above). The isocyanate component is preferably diphenylmethane diisocyanate.
Preferably, in the reactive moisture-curable polyurethane hot melt adhesive PUR, the molar ratio of the isocyanate group in the isocyanate component to the active hydrogen in the isocyanate-reactive component is 1.1 to 3.0: 1, preferably 1.5 to 1.8: 1, such as 1.2: 1,1.6: 1 or 2.0: 1.
the reactive moisture-curing polyurethane hot melt adhesive PUR according to the invention may optionally be supplemented with one or more auxiliaries known from the prior art.
Such adjuvants include, but are not limited to, catalysts, stabilizers, chain extenders, fillers, dyes, defoamers, thixotropic aids, plasticizers, coupling agents, adhesion promoters, leveling agents, and the like as are known in the art.
Catalysts refer to a class of compounds commonly used in the art for catalyzing the reaction of isocyanate groups with active hydrogen atoms, examples of which include, but are not limited to, stannous octoate, dibutyltin dilaurate, 2-dimorpholinodiethyl ether, triethylenediamine, triethanolamine, and the like.
The stabilizer is one or a combination of an antioxidant and a light stabilizer. The antioxidant is one or more of BHT, CHINOX1010, CHINOX 1076, CHINOX 1098, CHINOX 1024, CHINOX 245, CHINOX 1035 and CHINOX 1135; the light stabilizer is one or more of CHISORB 320, UV-1, UV-P, UV-292 and UV-329.
Coupling agents are well known in the art and include, but are not limited to, aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like.
Preferably, in the reactive moisture-curable polyurethane hot melt adhesive PUR, the reactive moisture-curable polyurethane hot melt adhesive further includes at least one of the following additives in parts by mass:
0-0.5 parts by mass of a stabilizer, such as 0.05, 0.1, 0.25 or 0.4 parts by mass;
0-0.5 parts by mass of a defoaming agent, such as 0.08, 0.15, 0.25 or 0.4 parts by mass;
0-0.5 parts by mass of a catalyst, such as 0.05, 0.12, 0.2 or 0.35 parts by mass;
0 to 5 parts by mass of a coupling agent, for example 0.05, 0.18, 0.25 or 0.4 parts by mass.
In a second aspect, the invention further provides a preparation method of the reactive moisture-curable polyurethane hot melt adhesive PUR, which comprises the following steps: mixing the selected isocyanate component, the isocyanate reactive component and the optional auxiliary agent in parts by mass for reaction, and obtaining the product after the reaction is finished.
Preferably, the above preparation method comprises the steps of: adding the isocyanate component in the selected mass part into a reactor, then adding the isocyanate reactive component in the selected mass part and optional auxiliary agents step by step, mixing and reacting, and obtaining the product after the reaction is finished.
More preferably, the above preparation method comprises the steps of:
(1) adding the selected isocyanate component in parts by mass into a reactor, and controlling the temperature in the reactor to be 60-80 ℃, for example, controlling the temperature in the reactor to be 60 ℃, 68 ℃, 72 ℃ or 80 ℃;
(2) adding a catalyst, a coupling agent, a stabilizer and a defoaming agent in selected parts by mass into the reactor;
(3) adding polyether polyol in selected parts by mass into the reactor, controlling the reaction temperature to be 70-80 ℃, for example, controlling the reaction temperature to be 72 ℃, 75 ℃ or 78 ℃, and stirring for reaction for 1-2 hours, for example, stirring for reaction for 1.5 hours or 1.8 hours;
(4) adding polyester polyol in selected parts by mass into the reactor, controlling the reaction temperature to be 70-80 ℃, for example, controlling the reaction temperature to be 72 ℃, 74 ℃ or 77 ℃, and stirring for reaction for 1-2 hours, for example, stirring for reaction for 1.2 hours or 1.8 hours;
(5) adding selected mass parts of other hydroxyl compounds containing long-chain aliphatic hydrocarbon and hydroxyalkyl modified silicone oil into the reactor, controlling the reaction temperature to be 70-80 ℃, such as 73 ℃, 75 ℃ or 78 ℃, and stirring for reaction for 1-6 hours, such as stirring for reaction for 1.5 hours, 2 hours, 3.5 hours or 4 hours;
(6) and when the NCO value in the reaction system reaches the theoretical NCO value of +/-0.3 wt%, uniformly stirring, discharging and packaging to obtain the product.
The preparation method of the reactive moisture-curing polyurethane hot melt adhesive PUR is obviously different from other patents. The preparation method commonly used in the art is to first add the isocyanate-reactive component in the reactor, after all mixing, then add the isocyanate component; the isocyanate component is firstly added into the reactor, and then different isocyanate reactive components are added step by step, so that the heat release during the reaction between the isocyanate and the isocyanate component can be effectively slowed down, the reaction temperature control is facilitated, the reaction byproducts can be effectively reduced, and the quality of the prepared product is more stable.
The preparation method can refer to the technical means commonly used in the field for specific processes, parameters, steps and operation modes which are not described, and the implementation of the invention is not influenced.
The reactive moisture-curable polyurethane hot melt adhesive PUR can be widely applied to bonding of various textile fabrics, and the fields of the reactive moisture-curable polyurethane hot melt adhesive PUR include but are not limited to bonding of polyester fabrics, nylon fabrics, blended fabrics, TPU films, PU films, PTFE films and the like, and the fabrics can be of non-waterproof grade or high-waterproof grade.
In the preparation method, the term "NCO content of the reaction system is +/-0.3 wt% of the theoretical value", and the term "NCO content of the reaction system is up to the theoretical value" means the NCO content of the mixture after the reactants are completely reacted in the step, and the data can be calculated according to the amount of the raw materials; "+ -. 0.3% by weight" means a range of plus or minus 0.3% by weight based on the theoretical NCO content of the reaction system.
In the preparation method, the components are added into the reactor slowly, in batches or at one time. The feeding mode is well known in the art, the invention preferably adopts slow feeding or batch feeding of raw materials, can control the reaction process and the reaction exothermy, is favorable for controlling the process parameters, and ensures that the product quality is more stable.
In the preparation method, the water content of the raw materials needs to be controlled below 0.05 wt%, even below 0.03 wt%, and the raw materials with too high water content can react with the isocyanate component, so that the viscosity of the product is higher. The method commonly used in the field is to select raw materials with water content meeting the requirement, or to perform water removal operation on the raw materials, for example, to remove water in the raw materials at high temperature of 80-120 ℃ under vacuum condition.
It should be noted that all the technical effects described in the present invention are the comprehensive effects of all the components and the mutual cooperation.
The technical scheme of the invention has the following advantages:
(1) the reactive moisture-curing polyurethane hot melt adhesive disclosed by the invention has excellent moisture permeability, bonding strength, water washing resistance and soft hand feeling.
(2) The preparation method of the reactive moisture-curing polyurethane hot melt adhesive has simple and convenient steps, effectively controls the occurrence of side reactions, and improves the quality and production stability of final products.
Detailed Description
The invention is further described with reference to the following examples, but is not intended to be limited thereto.
The examples and comparative examples are as follows:
isocyanate 1A: wannate MDI-100, diphenylmethane diisocyanate, Van der Chemie group Ltd;
polyether polyol 2A: a polyoxyethylene-oxypropylene copolymer, a glycol, wherein the oxyethylene content is 75% by weight, and the hydroxyl value is 30 mgKOH/g;
polyether polyol 2B: a polyoxyethylene-oxypropylene copolymer, a glycol, wherein the oxyethylene content is 90% by weight, and the hydroxyl value is 56 mgKOH/g;
polyether polyol 2C: a polyoxyethylene glycol having an oxyethylene content of 100% by weight and a hydroxyl value of 112 mgKOH/g;
polyether polyol 2D: a polyoxypropylene diol having an oxyethylene content of 0% by weight and a hydroxyl value of 280 mgKOH/g;
polyester polyol 3A: obtained by the reaction of dodecanedioic acid and hexanediol, and the hydroxyl value is 30 mgKOH/g;
polyester polyol 3B: WANTHANOL WHP-2024 prepared by reacting adipic acid with butanediol/ethylene glycol, and having a hydroxyl value of 56mgKOH/g, WANTHANOL CHEMICAL GROUP GmbH;
polyester polyol 3C: WANTHANOL WHP-104 obtained by reacting adipic acid with butanediol and having a hydroxyl value of 112mgKOH/g, WANTHANOL CHEMICAL GROUP GmbH;
polyester polyol 3D: WANTHANOL WHP-205 obtained by reacting adipic acid with 2, 2-dimethyl-1, 3-propanediol and having a hydroxyl value of 56mgKOH/g, Vanhua chemical group GmbH;
polyester polyol 3E: WANTHANOL WHP-105 prepared by reacting adipic acid with 2, 2-dimethyl-1, 3-propanediol and having a hydroxyl value of 112mgKOH/g, Vanhua chemical group GmbH;
polyester polyol 3F: obtained by the reaction of phthalic acid and 2, 2-dimethyl-1, 3-propanediol, the hydroxyl value of which is 112mgKOH/g, Vanhua chemical group GmbH;
long-chain aliphatic hydrocarbon-containing compound 4A: cetyl alcohol polyoxyethylene ether;
compound 4B containing long-chain aliphatic hydrocarbon: dimer acid polyester diol with a hydroxyl value of 56 mgKOH/g;
hydroxyalkyl-modified silicone oil 5A: hydroxypropyl modified polydimethylsiloxane;
antioxidant 1010: tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and double bond chemical industry.
Examples 1 to 4 and comparative example 1
The raw material ratios of examples 1 to 4 and comparative example 1 are shown in table 1.
TABLE 1 raw materials and their mass ratios of examples 1 to 4 and comparative example 1
| Raw materials (parts by mass) | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Isocyanate 1A | 24 | 20 | 20 | 27 | 28 |
| Polyether polyol 2A | 25 | ||||
| Polyether polyol 2B | 38 | 18 | 43 | 41 | |
| Polyether polyol 2C | 38 | ||||
| Polyether polyol 2D | 3 | 9 | 4 | ||
| Polyester polyol 3A | 2 | ||||
| Polyester polyol 3B | 20 | ||||
| Polyester polyol 3C | 20 | 20 | 12 | ||
| Polyester polyol 3D | 11.8 | 10 | |||
| Polyester polyol 3E | 14.5 | 14.5 | 10 | ||
| Polyester polyol 3F | 20 | ||||
| Compound 4A containing long-chain aliphatic hydrocarbon | 0.5 | 0.4 | 0.5 | ||
| Compound 4B containing long-chain aliphatic hydrocarbon | 5 | ||||
| Hydroxyalkyl modified silicone oil 5A | 0.2 | 0.1 | 0.5 | ||
| NCO(wt％) | 2.91 | 2.74 | 2.76 | 3.54 | 3.28 |
| NCO/OH molar ratio | 1.56 | 1.69 | 1.69 | 1.64 | 1.53 |
| Antioxidant 1010 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Catalyst 2, 2-dimorpholinyl diethyl ether | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
The preparation process of the reactive moisture-curing polyurethane hot melt adhesive PURs of examples 1 to 4 and comparative example 1 comprises the following steps: (1) dehydrating raw materials of polyether polyols 2A-2D and polyester polyols 3A-3F at 120 ℃ for 2 hours in vacuum to ensure that the water content is not more than 0.03 wt%; according to the proportion of the raw materials in the table 1, firstly, adding metered isocyanate into a four-neck flask, and setting the oil bath temperature to be 70 ℃; (2) then adding a metered antioxidant and a metered catalyst under a stirring state; (3) continuously adding metered polyether polyol, controlling the reaction temperature to be 75 ℃, and stirring for reaction for 1 h; (4) then adding metered polyester polyol, controlling the reaction temperature to be 75 ℃, and stirring for reaction for 1 h; (5) continuously adding other measured hydroxyl compounds containing long-chain aliphatic hydrocarbon and hydroxyalkyl modified silicone oil into the reactor, controlling the reaction temperature to be 80 ℃, and stirring for reaction for 4 hours; (6) and when the NCO value in the reaction system reaches the theoretical NCO value of +/-0.3 wt%, uniformly stirring, discharging and packaging to obtain the product.
Comparative example 2 is a commercially available moisture-permeable PUR product of a certain domestic company, numbered PU-1.
Examples of the experiments
Using the reactive moisture-curing polyurethane hot melt adhesive PUR samples prepared in examples 1 to 4 and comparative example 1, respectively, and the commercial product PU-1 of comparative example 2, a fabric and a TPU film were laminated, wherein the fabric was a 5-stage waterproof fabric, and the TPU film was a middle-permeable film (moisture permeability 8000 according to ASTM E96BW standard), composite post-cure was completed at a temperature of 23 ℃ and a humidity of 50% for 24 hours, and then the respective properties were tested in accordance with the following methods.
The water pressure resistance test method comprises the following steps: respectively fixing the prepared cloth film sample on a standard instrument according to ISO 811-2018 standard, pressurizing at constant speed until 3 water drops appear or the film is damaged, and recording the water pressure at the moment, namely the water pressure resistance value (mmH) of the sample2O)。
Moisture permeability test method: according to the ASTM E96BW standard, the inverted cup method is adopted, a cut cloth film sample prepared in the way that the cloth film sample is compounded and fixed in a certain area is fixed in a sample cup filled with purified water, then the sample cup is inverted on an inner rotating disc of a moisture-permeable instrument, the quality difference within a certain time difference is recorded,calculating the moisture permeability (g/m) of the sample by the secondary mass difference2∙24h)。
Washing resistance test method: respectively washing the prepared composite cloth film sample in a washing machine for 1h at the washing condition of 40 ℃; the total number of washes was 10. After washing 10 times, the cloth was tested again for water pressure resistance.
Water pressure retention after 10 water washes%: water resistance of the sample after 10 water washes/initial water resistance of the sample%.
Hand feeling: the prepared composite cloth film samples are uniformly placed in a constant temperature and humidity chamber (23 ℃ temperature and 50% humidity) respectively, and the average hand feeling of 5 persons is tested.
Specific test results are shown in table 2.
TABLE 2 test results of examples 1 to 4 and comparative examples 1 to 2
As is clear from Table 2, the PURs prepared in examples 1 to 4 were excellent in water pressure resistance, soft touch, moisture permeability and washing resistance after being used for fabric compounding, as compared with comparative examples 1 to 2.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The reactive moisture-curing polyurethane hot melt adhesive is characterized by being prepared by reacting an isocyanate component and an isocyanate reactive component in parts by mass as follows:
the isocyanate component is:
15-35 parts by mass of isocyanate, preferably 20-30 parts by mass;
the isocyanate-reactive component comprises:
30-55 parts by mass of at least one polyether polyol, preferably 40-50 parts by mass;
15-50 parts by mass of at least one polyester polyol, preferably 20-40 parts by mass;
0.01 to 10 parts by mass, preferably 0.5 to 5 parts by mass, of at least one other hydroxy compound containing a long-chain aliphatic hydrocarbon;
0-3 parts by mass of hydroxyalkyl modified silicone oil, preferably 0.1-0.5 part by mass;
preferably, the isocyanate-reactive component does not comprise a polyoxyethylene ether and/or a small molecule chain extender.
2. The reactive moisture-curing polyurethane hot melt adhesive according to claim 1, wherein the other hydroxyl compound containing long-chain aliphatic hydrocarbon is a small molecular hydroxyl compound containing long-chain aliphatic hydrocarbon or a high molecular hydroxyl compound containing long-chain aliphatic hydrocarbon; and/or, the other hydroxyl compound containing the long-chain aliphatic hydrocarbon is a monohydroxy compound containing the long-chain aliphatic hydrocarbon or a polyhydroxy compound containing the long-chain aliphatic hydrocarbon; preferably, the other hydroxyl compound containing long-chain aliphatic hydrocarbon is one or more selected from dodecanol, tetradecanol, hexadecanol, oleyl alcohol, stearyl alcohol, eicosanol, behenyl alcohol, tetracosanol, polyoxyethylene lauryl ether, polyoxyethylene cetyl alcohol, polyoxyethylene oleyl alcohol, polyoxyethylene stearyl alcohol, polyoxyethylene behenyl alcohol, polyoxyethylene oleic acid, polyoxyethylene stearic acid, and dimer acid polyester diol.
3. The reactive moisture-curing polyurethane hot melt adhesive according to claim 1 or 2, wherein the hydroxyalkyl-modified silicone oil is selected from one or more of hydroxyethyl-modified polydimethylsiloxane, hydroxypropyl-modified polydimethylsiloxane, hydroxyisopropyl-modified polydimethylsiloxane, hydroxybutyl-modified polydimethylsiloxane, hydroxyhexyl-modified polydimethylsiloxane, hydroxyl-terminated polyoxypropylene-based modified polydimethylsiloxane, hydroxyl-terminated polyoxyethylene-oxypropylene-modified polydimethylsiloxane; preferably, the hydroxyalkyl modified silicone oil is hydroxypropyl modified polydimethylsiloxane or hydroxyl terminated polyoxyethylene oxypropylene modified polydimethylsiloxane.
4. The reactive moisture-curing polyurethane hot melt adhesive according to any one of claims 1 to 3, characterized in that the polyether polyol is selected from one or more of polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene-oxypropylene copolymer and polytetrahydrofuran polyol; preferably, the polyether polyol is a polyoxyethylene-oxypropylene copolymer; more preferably, the content of the ethylene oxide group in the polyether polyol is 60-99 wt%, and the hydroxyl value is 20-300 mgKOH/g; still more preferably, the polyether polyol has an oxyethylene group content of 70 to 95 wt% and a hydroxyl value of 25 to 120 mgKOH/g.
5. The reactive moisture-curable polyurethane hot melt adhesive according to any one of claims 1 to 4, wherein the polyester polyol is a mixture of a crystalline polyester polyol A and an amorphous polyester polyol B, wherein the molecular main chain of the crystalline polyester polyol A does not contain a side methyl group, and the hydroxyl value is 20 to 300mgKOH/g, preferably 30 to 120 mgKOH/g; the molecular main chain of the amorphous polyester polyol B contains side methyl, and the hydroxyl value is 20-300 mgKOH/g, preferably 30-120 mgKOH/g; preferably, the mass ratio of the crystalline polyester polyol A to the amorphous polyester polyol B is 0.1-5.0: 1, more preferably 1.0 to 2.5: 1.
6. the reactive moisture-curing polyurethane hot melt adhesive according to claim 5,
the crystalline polyester polyol A is obtained by reacting dibasic acid A and dihydric alcohol A, wherein the dibasic alcohol A is selected from one or more of ethylene glycol, butanediol, hexanediol, octanediol and decanediol, and the dibasic acid A is selected from one or more of adipic acid, octanedioic acid, decanedioic acid and dodecanedioic acid; and/or the presence of a gas in the gas,
the non-crystalline polyester polyol B is obtained by reacting dibasic acid B and dihydric alcohol B, wherein the dihydric alcohol B is dihydric alcohol with a side group, preferably dihydric alcohol with a side methyl group, more preferably one or more of 1, 2-propylene glycol, 2-methyl-1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol and 3-methyl-1, 5-pentanediol, and still more preferably 2, 2-dimethyl-1, 3-propylene glycol; the dibasic acid B is one or more of adipic acid, suberic acid, sebacic acid, dodecyl diacid, phthalic acid, isophthalic acid and terephthalic acid.
7. The reactive moisture-curing polyurethane hot melt adhesive according to any one of claims 1 to 6, wherein the isocyanate is selected from one or more of toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, 1, 5-naphthalene diisocyanate NDI, hexamethylene diisocyanate HDI, methylcyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate IPDI, p-phenylene diisocyanate PPDI, p-phenylene diisocyanate XDI, tetramethyldimethylene diisocyanate TMXDI, 1, 4-cyclohexane diisocyanate CHDI, cyclohexanedimethylene diisocyanate HXDI, trimethyl-1, 6-hexamethylene diisocyanate TMHDI, norbornane diisocyanate NBDI, dimethylbiphenyl diisocyanate TODI and methylcyclohexyl diisocyanate HTDI, diphenylmethane diisocyanate is preferred.
8. The reactive moisture-curable polyurethane hot melt adhesive according to any one of claims 1 to 7, wherein the molar ratio of the isocyanate groups in the isocyanate component to the active hydrogen in the isocyanate-reactive component is 1.1 to 3.0: 1, preferably 1.5 to 1.8: 1.
9. the reactive moisture-curing polyurethane hot melt adhesive according to any one of claims 1 to 8, further comprising at least one of the following additives in parts by mass:
10. a method for preparing the reactive moisture-curing polyurethane hot melt adhesive according to any one of claims 1 to 9, which is characterized by comprising the following steps: mixing the selected isocyanate component, the isocyanate reactive component and the optional auxiliary agent in parts by mass for reaction, and obtaining the product after the reaction is finished;
preferably, the method comprises the following steps: firstly adding a selected mass part of isocyanate component into a reactor, then adding a selected mass part of isocyanate reactive component and an optional auxiliary agent step by step, mixing and reacting, and obtaining the product after the reaction is finished;
more preferably, the method comprises the following steps:
(1) adding the selected isocyanate component in parts by mass into a reactor, and controlling the temperature in the reactor to be 60-80 ℃;
(2) adding a catalyst, a coupling agent, a stabilizer and a defoaming agent in selected parts by mass into the reactor;
(3) adding polyether polyol in selected parts by mass into the reactor, controlling the reaction temperature to be 70-80 ℃, and stirring for reaction for 1-2 hours;
(4) adding polyester polyol with selected parts by mass into the reactor, controlling the reaction temperature to be 70-80 ℃, and stirring for reaction for 1-2 hours;
(5) adding selected parts by mass of other hydroxyl compounds containing long-chain aliphatic hydrocarbon and hydroxyalkyl modified silicone oil into the reactor, controlling the reaction temperature to be 70-80 ℃, and stirring for reaction for 1-6 hours;
(6) and when the NCO value in the reaction system reaches the theoretical NCO value of +/-0.3 wt%, uniformly stirring, discharging and packaging to obtain the product.
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