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CN117701223B - Solvent-free double-component polyurethane adhesive and preparation method and application thereof - Google Patents

Solvent-free double-component polyurethane adhesive and preparation method and application thereof Download PDF

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Publication number
CN117701223B
CN117701223B CN202311822206.8A CN202311822206A CN117701223B CN 117701223 B CN117701223 B CN 117701223B CN 202311822206 A CN202311822206 A CN 202311822206A CN 117701223 B CN117701223 B CN 117701223B
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China
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component
polyurethane adhesive
polyol
polyether polyol
polyether
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CN117701223A (en
Inventor
许磊
夏锋
张大华
孙玉芹
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XUCHUAN CHEMICAL (SUZHOU) CO Ltd
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XUCHUAN CHEMICAL (SUZHOU) CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a solvent-free double-component polyurethane adhesive and a preparation method and application thereof, wherein the solvent-free double-component polyurethane adhesive comprises a component A and a component B, raw materials of the component A comprise polyether polyol A, polyether polyol B and isocyanate, raw materials of the component B comprise polyether modified polyester polyol and a silane coupling agent, and the polyether modified polyester polyol is obtained by reacting small-molecule polybasic acid, small-molecule polybasic acid and polyether polyol C; the specific component A and the specific component B are selected for matching, so that the obtained double-component polyurethane adhesive has excellent comprehensive performance, and can simultaneously meet the requirements of strong ink matching, good aluminizing effect, good elasticity, high bonding strength, boiling resistance, good low temperature resistance and low friction coefficient, and the double-component polyurethane adhesive is used as a laminating adhesive to effectively solve the problem of frequent replacement of the laminating adhesive in a flexible packaging compound factory.

Description

Solvent-free double-component polyurethane adhesive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a solvent-free double-component polyurethane adhesive, and a preparation method and application thereof.
Background
At present, laminating adhesives adopted in the flexible packaging industry comprise two types of solvent-free polyurethane adhesives and solvent-based polyurethane adhesives, wherein the solvent-based polyurethane adhesives account for more than 60% of market share. The solvent type polyurethane adhesive is simple and convenient to operate, contains solvents such as ethyl acetate and the like, has strong volatility, is harmful to human bodies, pollutes the atmospheric environment, has potential safety hazards when in use, is an environment-friendly adhesive because the solvent-free polyurethane laminating adhesive does not use solvents, and is used by more and more flexible package compound factories.
The solvent-free polyurethane laminating adhesive is divided into two types of double-component polyurethane laminating adhesive and single-component polyurethane laminating adhesive; the single-component polyurethane laminating adhesive is generally used for paper-plastic compounding, and the solvent-free double-component polyurethane laminating adhesive is generally used for compounding plastic, aluminum-plastic and aluminum-plated materials. Solvent-free double-component polyurethane laminating adhesives are gradually replacing solvent-based double-component polyurethane laminating adhesives, which is also the future development direction of flexible package laminating adhesives.
In general, flexible packaging compounding factories use a large variety of inks, and the compounding process cannot affect the requirements of packaging on printing. This requires that the solvent-free polyurethane laminating adhesive does not dissolve ink in films printed with various inks, and does not have defects such as white spots in appearance. For example, CN113667444A discloses a solvent-free double-component polyurethane adhesive and a preparation method and application thereof, wherein the adhesive comprises a component A and a component B, wherein the raw materials of the component A comprise branched polyester polyol, polyether polyol, dehydrated castor oil and polyisocyanate, the raw materials of the component B comprise modified polyester polyol and an adhesion promoter, and the modified polyester polyol is prepared from small molecular dicarboxylic anhydride, small molecular linear diol, small molecular branched diol, dehydrated castor oil and a modifier. When the adhesive is applied to the composite OPP/VMPET/PE, the composite inner layer film has a low friction coefficient, and the addition of dehydrated castor oil obviously improves the matching property of the adhesive and the printing ink on the composite surface layer film, but also brings the defects of darker color, castor oil smell and higher cost. The adhesive does not relate to the properties of steaming resistance, bonding strength, low temperature resistance and the like.
However, when the flexible package compound factory is used for preparing the bag, the bag has different purposes and different requirements on laminating adhesive; if the aluminized film is required to be not transferred, reinforced aluminized or chemical aluminum is generally adopted, the bonding strength of the aluminized film is tested after compounding, aluminized transfer is reduced as much as possible, and the strength after compounding is required to be larger than 1.2N/15mm and is not qualified if the strength is lower than 0.6N/15 mm; for another example, PET/AL/PA/RCPP is used in retort pouches, requiring solvent-free polyurethane film adhesive to be high strength, retort, elastic, and low temperature resistant. If the bonding strength is not high, the film and the film (or aluminum foil) are easy to open, and great loss is brought; the steaming resistance is poor, and the bag is glued once steamed, so that great loss is caused; the elasticity is poor or the low temperature resistance is poor, the bag is easy to be damaged during low-temperature storage, and great loss and quality compensation can be brought.
At present, in the market of flexible packaging materials, there is few solvent-free polyurethane laminating adhesives which can meet the requirements at the same time and also meet the composite requirements of different structures, and the solvent-free polyurethane laminating adhesives with different functions are required to be replaced aiming at the composite films with different structures, so that the replacement frequency of the solvent-free polyurethane laminating adhesives is high, and the production efficiency is greatly influenced.
Because of the need for developing a general solvent-free two-component polyurethane adhesive which can simultaneously meet the requirements of high ink matching property, good elasticity, high bonding strength, boiling resistance, good low temperature resistance and low friction coefficient and can be used as an aluminizing material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the solvent-free double-component polyurethane adhesive, and the preparation method and the application thereof, wherein the solvent-free double-component polyurethane adhesive has excellent steaming performance, good ink matching performance, and can meet the requirements of high bonding strength, good low temperature resistance and low friction coefficient, is widely applicable to various film materials, can greatly reduce the replacement frequency of the solvent-free polyurethane laminating adhesive, improve the production efficiency and ensure the quality stability of products.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a solvent-free two-component polyurethane adhesive comprising a component A and a component B;
the raw materials of the component A comprise polyether polyol A, polyether polyol B and isocyanate;
the raw materials of the component B comprise polyether modified polyester polyol and a silane coupling agent, and the polyether modified polyester polyol is obtained by reacting small molecule polybasic acid, small molecule polyol and polyether polyol C.
The solvent-free double-component polyurethane adhesive provided by the invention comprises the component A and the component B, wherein the component A is obtained by selecting two polyether polyols to match, and the component B is prepared by adopting the polyester modified polyol and the silane coupling agent to match, so that the solvent-free double-component polyurethane adhesive has excellent cooking performance and good ink matching property, can meet the requirements of high bonding strength, good low temperature resistance and low friction coefficient, has wide application to various film materials, can be used for bonding of soft package composites as solvent-free polyurethane laminating adhesives, can greatly reduce the replacement frequency of the solvent-free polyurethane laminating adhesives, improves the production efficiency, and ensures the quality stability of products.
Preferably, the raw materials of the component A comprise the following components in percentage by mass:
20-40% of polyether polyol A;
5-20% of polyether polyol B;
Isocyanate balance.
Wherein the mass percent of the polyether polyol A can be 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36% or 38%, etc.
The polyether polyol B may be 7%, 9%, 11%, 13%, 15%, 17%, 19%, or the like.
Preferably, the polyether polyol a has a number average molecular weight of 1000 to 2000, such as 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, etc.
Preferably, the polyether polyol a has a functionality of 2.
Preferably, the polyether polyol B has a number average molecular weight of 400 to 1000, such as 500, 600, 700, 800 or 900, etc.
Preferably, the polyether polyol B has a functionality of 3.
Preferably, the isocyanate comprises any one or a combination of at least two of MDI-50, MDI-100, liquefied MDI, HDI, HDI trimer, IPDI or H 12 MDI, more preferably MDI-50 and/or liquefied MDI, even more preferably MDI-50 and liquefied MDI, and the proportion of MDI-50 is higher than 70%.
Preferably, the mass ratio of the polyether modified polyester polyol to the silane coupling agent is 100 (0.3-1.2), such as 100:0.4, 100:0.5, 100:0.6, 100:0.7, 100:0.8, 100:0.9, 100:1 or 100:1.1, etc.
Preferably, the silane coupling agent comprises any one or a combination of at least two of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane (such as silane coupling agent KH-560), gamma-glycidoxypropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N-B (aminoethyl) -gamma-aminopropyl triethoxysilane, benzyl triethoxysilane or benzyl trimethoxysilane.
Preferably, the polyether polyol C is contained in the raw material of the polyether modified polyester polyol in an amount of 10 to 20% by mass, for example, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 19% by mass, etc.
Preferably, the polyether polyol C has a number average molecular weight of 400 to 1000, such as 500, 600, 700, 800 or 900, etc.
Preferably, the polyether polyol C has a functionality of 2.
Preferably, the small molecule polyacid comprises any one or a combination of at least two of adipic acid, sebacic acid, phthalic anhydride, terephthalic acid, isophthalic acid, or azelaic acid.
Preferably, the small molecule polyol comprises any one or a combination of at least two of ethylene glycol, diethylene glycol, ethylbutylpropanediol, 1, 3-butanediol, 1, 4-butanediol, methylpropanediol, 1, 6-hexanediol, neopentyl glycol, glycerol or trimethylol propane.
Preferably, the preparation method of the polyether modified polyester polyol comprises the following steps: in an inert gas environment, adding polyether polyol C, small molecular polyacid and small molecular polyol into a reaction kettle with a distillation tower, dehydrating at 150-210 ℃ (such as 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃ and the like), controlling the temperature at the top of the distillation tower to 98-102 ℃ (such as 99 ℃, 100 ℃ or 101 ℃ and the like), keeping the temperature for 0.5-1.5 h (such as 0.7h, 0.9h, 1.1h or 1.3h and the like), then reacting at 150-210 ℃ (such as 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃ and the like) for 3-6 h (such as 3.5h, 4h, 4.5h, 5h or 5.5h and the like), adding a catalyst, raising the temperature to 230-240 ℃ (such as 232 ℃,234 ℃, 236 ℃ or 238 ℃ and the like), and carrying out vacuum dealcoholization for 2-5 h (such as 2.5h, 3h, 3.5h, 4h or 4.5h and the like.
Preferably, the polyether modified polyester polyol has a hydroxyl value of 190 to 210mgKOH/g, for example, 192mgKOH/g, 194mgKOH/g, 196mgKOH/g, 198mgKOH/g, 200mgKOH/g, 202mgKOH/g, 204mgKOH/g, 206mgKOH/g, 208mgKOH/g, or the like.
Preferably, the polyether modified polyester polyol has an acid value of 0.8mgKOH/g or less, for example, 0.7mgKOH/g, 0.6mgKOH/g, 0.5mgKOH/g, 0.4mgKOH/g, 0.3mgKOH/g, 0.2mgKOH/g, or the like.
Preferably, the catalyst comprises one or two of isopropyl titanate, tetrabutyl titanate or organotin, more preferably isopropyl titanate, which is derived from Shanghai Aba Ding Shiji company
Preferably, the molar ratio of isocyanate groups in the A component to hydroxyl groups in the B component is (1.4-2.2): 1, e.g., 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, or 2.1:1, etc.
In a second aspect, the present invention provides a method for preparing the two-component polyurethane adhesive according to the first aspect, wherein the preparation method comprises the preparation of the component A and the preparation of the component B;
The preparation of the component A comprises the following steps: reacting polyether polyol A, polyether polyol B and isocyanate to obtain a component A;
the preparation of the component B comprises the following steps: and mixing polyether modified polyester polyol and a silane coupling agent to obtain the component B.
Preferably, the preparation method of the component A specifically comprises the following steps: putting polyether polyol A and polyether polyol B into a reaction kettle, and reacting for 3 hours at 100-105 ℃ (for example, 101.5 ℃, 102 ℃, 102.5 ℃, 103 ℃, 103.5 ℃, 104 ℃ or 104.5 ℃ and the like), dehydrating at a vacuum degree of more than-0.092 MPa, requiring less than 500ppm of water, then reducing the temperature to below 55 ℃, adding isocyanate, and reacting at 70-90 ℃ (for example, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃ or 88 ℃ and the like) to obtain the end NCO group polyurethane prepolymer, namely the component A.
Preferably, the preparation method of the component B comprises the following steps: the polyether-modified polyester polyol and the silane coupling agent are mixed at 50 to 60 ℃ (e.g., 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ or the like) to obtain the component B.
In a third aspect, the present invention provides the use of a two-component polyurethane adhesive according to the first aspect in flexible package bonding.
Preferably, the flexible package material comprises any one or a combination of at least two of PET, OPP, PA, aluminum foil, VMPET, VMOPP, VMCPP, CPP, RCPP, PE, or PVDC.
Compared with the prior art, the invention has the following beneficial effects:
The solvent-free double-component polyurethane adhesive comprises a component A and a component B, wherein the raw materials of the component A comprise polyether polyol A, polyether polyol B and isocyanate, the raw materials of the component B comprise polyether modified polyester polyol and a silane coupling agent, and the polyether modified polyester polyol is obtained by reacting small-molecule polybasic acid, small-molecule polyol and polyether polyol C; the specific component A and the specific component B are selected for matching, so that the obtained double-component polyurethane adhesive has excellent comprehensive performance, can simultaneously meet the requirements of strong ink matching, good aluminizing effect, good elasticity, high bonding strength, boiling resistance, good low temperature resistance and low friction coefficient, and can be used as laminating adhesive, thereby effectively solving the problem of frequent replacement of laminating adhesive model in a flexible packaging compound factory and greatly improving the production efficiency and quality stability.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation example 1
A polyether modified polyester polyol A, its preparation method includes: under nitrogen environment, 173.5kg of polyether polyol DL-400 (with the number average molecular weight of 400), 125.5kg of ethylene glycol, 275.8kg of diethylene glycol, 401.2kg of adipic acid and 24kg of isophthalic acid are added into a reaction kettle with a distillation tower, dehydration is carried out at about 190 ℃, the temperature at the top of the distillation tower is controlled to be 98-102 ℃, the temperature is kept for 1h, then the reaction is carried out for 3h at 220 ℃, 0.04kg of isopropyl titanate is added, the temperature is raised to 240 ℃, and vacuumizing and dealcoholization are carried out for 4h, so as to obtain the polyether modified polyester polyol with the hydroxyl value of 209.2mgKOH/g and the acid value of 0.3 mgKOH/g.
Preparation example 2
A preparation method of polyether modified polyester polyol B comprises the following steps: in a nitrogen environment, 158.8kg of polyether polyol DL-400 (with the number average molecular weight of 400), 280.5kg of diethylene glycol, 165.3kg of neopentyl glycol, 363.3kg of adipic acid and 32.1kg of sebacic acid are added into a reaction kettle with a distillation tower, dehydration is carried out at about 185 ℃, the temperature at the top of the distillation tower is controlled to be 98-102 ℃, the temperature is kept for 1h, then the reaction is carried out for 3h at 220 ℃, 0.03kg of isopropyl titanate is added, the temperature is increased to 230 ℃, and vacuum-pumping dealcoholization is carried out for 3.5h, so as to obtain the polyether modified polyester polyol with the hydroxyl value of 203.5mgKOH/g and the acid value of 0.4 mgKOH/g.
Preparation example 3
A preparation method of polyether modified polyester polyol C comprises the following steps: in a nitrogen environment, 196.4kg of polyether polyol DL-1000 (with the number average molecular weight of 1000), 43.5kg of hexanediol, 304.5kg of diethylene glycol, 16.4kg of trimethylolpropane, 330kg of adipic acid and 32.6kg of isophthalic acid are added into a reaction kettle with a distillation tower, dehydration is carried out at about 195 ℃, the temperature at the top of the distillation tower is controlled to be 98-102 ℃, the temperature is kept for 1h, then the reaction is carried out at 220 ℃ for 3h, 0.04kg of isopropyl titanate is added, the temperature is increased to 230-240 ℃, and the vacuum is pumped for dealcoholization for 5h, thus obtaining the polyether modified polyester polyol with the hydroxyl value of 192.4mgKOH/g and the acid value of 0.2 mgKOH/g.
Preparation example 4
A polyether-modified polyester polyol D was different from preparation example 1 in that the amount of polyether polyol DL-400 was 70kg, and the other components, amounts and preparation methods were the same as those of preparation example 1.
Preparation example 5
A polyether-modified polyester polyol D was different from preparation example 1 in that the amount of polyether polyol DL-400 was 250kg, and the other components, amounts and preparation methods were the same as those of preparation example 1.
Example 1
A solvent-free double-component polyurethane adhesive comprises a component A and a component B in a weight ratio of 100:67;
The preparation method of the component A comprises the following steps: 250kg of polyether polyol DL-2000 (with a number average molecular weight of 2000 and a functionality of 2) and 110kg of polyether polyol MN-700 (with a number average molecular weight of 700 and a functionality of 3) are added into a reaction kettle, dehydrated at a high temperature in vacuum until the water content is less than 0.05%, then 570kg of MDI-50 and 70kg of pure MDI-100 (Wanhua chemical MDI-100) are added at 55 ℃, reacted for 3 hours at 75 ℃, the mass percent of the test NCO groups is 18.5%, and the mixture is cooled to 45 ℃ and discharged to obtain the component A;
The preparation method of the component B comprises the following steps: 995kg of polyether modified polyester polyol A (preparation example 1) and 5kg of silane coupling agent KH-560 are put into a reaction kettle, stirred uniformly at 60 ℃, cooled to below 45 ℃ and discharged, so that the component B is obtained.
Example 2
A solvent-free double-component polyurethane adhesive comprises a component A and a component B in a weight ratio of 100:66;
The preparation method of the component A comprises the following steps: 220kg of polyether polyol DL-1000 (with the number average molecular weight of 1000 and the functionality of 2) and 140kg of polyether polyol MN-1000 (with the number average molecular weight of 1000 and the functionality of 3) are added into a reaction kettle, dehydrated at a high temperature in vacuum until the water content is less than 0.05%, then 580kg of MDI-50 and 60kg of liquefied MDI-100 (Wanhua liquefied W1631) are added at 55 ℃, the reaction is carried out for 3 hours at 77 ℃, the mass percent of the test NCO groups is 17.5%, the temperature is reduced to 45 ℃ and the material is discharged, so that the component A is obtained;
The preparation method of the component B comprises the following steps: 994kg of polyether modified polyester polyol B (preparation example 2) and 6kg of silane coupling agent KH-560 are put into a reaction kettle, stirred uniformly at 60 ℃, cooled to below 45 ℃ and discharged, so that the component B is obtained.
Example 3
A solvent-free double-component polyurethane adhesive comprises a component A and a component B in a weight ratio of 100:66;
The preparation method of the component A comprises the following steps: adding 315kg of polyether polyol DL-2000 (with the number average molecular weight of 2000 and the functionality of 2) and 100kg of polyether polyol MN-1000 (with the number average molecular weight of 1000 and the functionality of 3) into a reaction kettle, dehydrating at a high temperature in vacuum until the water content is less than 0.05%, adding 535kg of MDI-50 and 50kg of liquefied MDI (Wanhua liquefied W1631) at 55 ℃, reacting for 3 hours at 78 ℃, testing the mass percent of NCO groups to be 16.8%, and cooling to 45 ℃ and discharging to obtain the component A;
The preparation method of the component B comprises the following steps: 993kg of polyether modified polyester polyol C (preparation example 3) and 7kg of silane coupling agent KH-560 are put into a reaction kettle, stirred uniformly at 60 ℃, cooled to below 45 ℃ and discharged, so that the component B is obtained.
Example 4
A solvent-free two-component polyurethane adhesive is different from example 1 in that the amount of polyether polyol DL-2000 is 130kg, the amount of polyether polyol MN-700 is 230kg, and other components, amounts and preparation methods are the same as those of example 1.
Example 5
A solvent-free two-component polyurethane adhesive is different from example 1 in that the amount of polyether polyol DL-2000 is 320kg, the amount of polyether polyol MN-700 is 40kg, and other components, amounts and preparation methods are the same as those of example 1.
Example 6
A solvent-free two-component polyurethane adhesive is different from example 1 in that polyether modified polyester polyol D obtained in preparation example 4 is used for replacing polyether modified polyester polyol A provided in preparation example 1, and other components, amounts and preparation methods are the same as those in example 1.
Example 7
A solvent-free two-component polyurethane adhesive is different from example 1 in that polyether modified polyester polyol E obtained in preparation example 5 is used for replacing polyether modified polyester polyol A provided in preparation example 1, and other components, amounts and preparation methods are the same as those in example 1.
Comparative example 1
A solvent-free two-component polyurethane adhesive is different from example 1 in that no polyether polyol DL-2000 is added, the addition amount of polyether polyol MN-700 is 360kg, and other components, amounts and preparation methods are the same as those of example 1.
Comparative example 2
A solvent-free two-component polyurethane adhesive is different from example 1 in that no polyether polyol MN-700 is added, the adding amount of polyether polyol DL-2000 is 360kg, and other components, the using amount and the preparation method are the same as those of example 1.
Comparative example 3
A solvent-free two-component polyurethane adhesive is different from example 1 in that a silane coupling agent KH-560 is not added, and other components, amounts and preparation methods are the same as in example 1.
Performance test:
In the following test, the test method adopted is as follows:
(1) Ink matching: observing the appearance of the solvent-free double-component polyurethane adhesive, and judging whether the definition of the ink is good or not and whether handwriting blurring and lace phenomena occur or not;
(2) Coefficient of friction: according to GB/T10006-2021 standard test;
(3) Adhesive strength: cutting strips with the width of 15mm and the length of more than 10cm, and testing the strips on a tensile testing machine, wherein the testing standard is GB/T8808-1988;
(4) Boiling and retort resistance: testing according to GB/T10004-2008 standard;
(5) Elasticity: at 23 ℃, a 50% humidity standard laboratory, comparing and judging the hand feeling condition according to the hand feeling of the tested synthetic leather;
(6) Low temperature resistance: placing the mixture in a low-temperature incubator for more than 24 hours, and placing the mixture at room temperature for 4 hours to observe whether the appearance is separated, cracked and abnormal;
(7) Aluminizing transfer condition: and (3) testing the peeling strength according to BB/T0030-2019 standard, and observing whether the aluminized layer is transferred to another film or not after testing.
1. Ink compatibility and coefficient of friction test
Alcohol ester soluble ink of six ink companies are selected, wherein the manufacturers are respectively cercis ink limited company, zhejiang Yongzhi chemical industry limited company, hang Hua ink stock limited company, guangdong Tianlong ink group stock limited company, new eastern ink limited company and Wenzhou Yingke ink limited company;
The inks from the above manufacturers were used to print on OPP, and OPP and PE (thickness: 3.5 filaments) were printed by compounding the solvent-free two-component polyurethane adhesives provided in examples 1 to 7 and comparative examples 1 to 3, and the ink matching properties and friction coefficients were tested, and the data are shown in Table 1 below:
TABLE 1
2. Elasticity, adhesive strength, boiling resistance, low temperature resistance test
PET, aluminum foil and PA, RCPP, OPP, VMPET, PE are adopted, the solvent-free two-component polyurethane adhesives provided in examples 1-7 and comparative examples 1-3 are used for compounding PET/aluminum foil/PA/RCPP, OPP/VMPET/PE and PET/aluminum foil/PA/RCPP, the adhesive strength, boiling resistance, elasticity and low temperature resistance are tested, and the OPP/VMPET/PE is used for testing the adhesive strength of an aluminized layer and observing aluminized transfer conditions. Wherein, the bonding strength is tested for PET/aluminum foil layer, aluminum foil layer/PA, PA/RCPP layer, OPP/VMPET layer, and the results are shown in Table 2 below;
TABLE 2
From the data in tables 1 and 2, it can be seen that:
The solvent-free two-component polyurethane adhesives provided in examples 1-7 have good performance in terms of ink matching and friction coefficient; the aluminum plastic has good bonding strength in the aspects of water boiling and cooking; in the aspect of aluminizing materials, the aluminizing transfer has small influence, large peel strength and basically no transfer condition; the test requirements can be met in terms of low temperature resistance and elasticity, the design expectations are basically met, and the technical standard of the general solvent-free two-component polyurethane adhesive can be reached;
The solvent-free two-component polyurethane adhesive provided in comparative examples 1-3 has relatively low bonding strength in terms of water boiling and steaming of aluminum plastic; in the case of aluminizing materials, the aluminizing transfer effect is large, the peel strength is relatively small, and the performance is general in terms of low temperature resistance and elasticity.
The applicant states that the present invention is described by way of the above examples as a solvent-free two-component polyurethane adhesive, and a method for preparing and using the same, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (12)

1. The solvent-free two-component polyurethane adhesive is characterized by comprising a component A and a component B;
The raw materials of the component A comprise the following components in percentage by mass:
20-40% of polyether polyol A;
7-20% of polyether polyol B;
Isocyanate balance;
the raw materials of the component B are polyether modified polyester polyol and a silane coupling agent, and the polyether modified polyester polyol is obtained by reacting small molecule polybasic acid, small molecule polyol and polyether polyol C;
The mass ratio of the polyether modified polyester polyol to the silane coupling agent is 100 (0.3-1.2);
The mass percentage of polyether polyol C in the raw materials of the polyether modified polyester polyol is 10-20%;
The number average molecular weight of the polyether polyol A is 1000-2000;
The functionality of the polyether polyol a is 2;
the number average molecular weight of the polyether polyol B is 400-1000;
the functionality of the polyether polyol B is 3.
2. The two-component polyurethane adhesive of claim 1, wherein the isocyanate comprises any one or a combination of at least two of MDI-50, MDI-100, liquefied MDI, HDI, HDI trimer, IPDI, or H 12 MDI.
3. The two-component polyurethane adhesive of claim 1, wherein the silane coupling agent comprises any one or a combination of at least two of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane, benzyl triethoxysilane, or benzyl trimethoxysilane.
4. The two-component polyurethane adhesive of claim 1, wherein the polyether polyol C has a number average molecular weight of 400-1000.
5. The two-component polyurethane adhesive of claim 1, wherein the polyether polyol C has a functionality of 2.
6. The two-component polyurethane adhesive of claim 1, wherein the small molecule polyacid comprises any one or a combination of at least two of adipic acid, sebacic acid, terephthalic acid, isophthalic acid, or azelaic acid.
7. The two-component polyurethane adhesive of claim 1, wherein the small molecule polyol comprises any one or a combination of at least two of ethylene glycol, diethylene glycol, ethylbutylpropanediol, 1, 3-butanediol, 1, 4-butanediol, methylpropanediol, 1, 6-hexanediol, neopentyl glycol, glycerol, or trimethylolpropane.
8. The two-component polyurethane adhesive according to claim 1, wherein the molar ratio of isocyanate groups in the component A to hydroxyl groups in the component B is (1.4-2.2): 1.
9. A method for preparing the two-component polyurethane adhesive according to any one of claims 1 to 8, wherein the preparation method comprises preparation of a component a and preparation of a component B;
The preparation of the component A comprises the following steps: reacting polyether polyol A, polyether polyol B and isocyanate to obtain a component A;
the preparation of the component B comprises the following steps: and mixing polyether modified polyester polyol and a silane coupling agent to obtain the component B.
10. Use of the two-component polyurethane adhesive according to any one of claims 1 to 8 in flexible package bonding.
11. The use of claim 10, wherein the flexible packaging material comprises any one or a combination of at least two of PET, OPP, PA, aluminum foil, CPP, PE, or PVDC.
12. The use according to claim 11, wherein the PET is VMPET;
The OPP is VMOPP;
The CPP is VMCPP and/or RCPP.
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CN108148536A (en) * 2017-12-20 2018-06-12 上海康达化工新材料股份有限公司 A kind of media-resistant polyurethane laminating adhesive and its preparation method and application
CN115521749A (en) * 2022-10-17 2022-12-27 山东逸飞新材料有限公司 Bi-component solvent-free steaming-resistant polyurethane composite adhesive and preparation method thereof

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EP3959282A4 (en) * 2019-04-24 2022-11-23 Henkel AG & Co. KGaA Two-component solvent free polyurethane laminating adhesive composition
CN112063352B (en) * 2020-09-08 2023-04-11 湖北回天新材料(宜城)有限公司 Low-odor solvent-free bi-component polyurethane adhesive and preparation method and application thereof

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CN108148536A (en) * 2017-12-20 2018-06-12 上海康达化工新材料股份有限公司 A kind of media-resistant polyurethane laminating adhesive and its preparation method and application
CN115521749A (en) * 2022-10-17 2022-12-27 山东逸飞新材料有限公司 Bi-component solvent-free steaming-resistant polyurethane composite adhesive and preparation method thereof

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