CN115505362B - Solvent-free polyurethane adhesive for composite low-surface-energy film and preparation method thereof - Google Patents
Solvent-free polyurethane adhesive for composite low-surface-energy film and preparation method thereof Download PDFInfo
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- CN115505362B CN115505362B CN202211346292.5A CN202211346292A CN115505362B CN 115505362 B CN115505362 B CN 115505362B CN 202211346292 A CN202211346292 A CN 202211346292A CN 115505362 B CN115505362 B CN 115505362B
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 73
- 229920000570 polyether Polymers 0.000 claims abstract description 73
- 229920005862 polyol Polymers 0.000 claims abstract description 65
- 150000003077 polyols Chemical class 0.000 claims abstract description 63
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 51
- 239000012948 isocyanate Substances 0.000 claims abstract description 32
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229920005903 polyol mixture Polymers 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 7
- 150000007519 polyprotic acids Polymers 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 41
- 239000000853 adhesive Substances 0.000 abstract description 39
- 230000002238 attenuated effect Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000005026 oriented polypropylene Substances 0.000 description 27
- 239000005025 cast polypropylene Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010410 layer Substances 0.000 description 10
- -1 polypropylene Polymers 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002313 adhesive film Substances 0.000 description 6
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 6
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000012939 laminating adhesive Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a solvent-free polyurethane adhesive for a composite low-surface-energy film and a preparation method thereof, wherein the adhesive consists of a component A and a component B; the component A is isocyanate-terminated prepolymer obtained by reacting isocyanate mixture with polyether polyol mixture, and the isocyanate mixture is prepared from 4,4 ， Diphenylmethane diisocyanate with 2,4 ， -diphenylmethane diisocyanate in a weight ratio of 1-2:1; the polyether polyol mixture is formed by mixing polyether polyols with average molecular weights of 300-500, 800-1500 and 1800-2500 according to the weight ratio of 1-2:3-4:1-2; the component B is formed by homogeneously mixing polyester polyol and low-molecular-weight polyether polyol; the molar ratio of isocyanate functional groups in the component A to hydroxyl functional groups in the component B is 1.3-1.5:1. The adhesive can compound OPP/CPP film, the T-shaped peeling strength after curing is 1.6-1.8N/15mm, and the peeling strength after 14 days is attenuated to be 1.2-1.4N/15mm.
Description
Technical Field
The invention relates to the field of polyurethane adhesives for composite flexible packages, in particular to a bi-component solvent-free polyurethane adhesive with high peel strength for OPP/CPP film structure composite and a preparation method thereof.
Background
With the vigorous development of economy, a large number of composite flexible packaging products are required to be used in daily life. The soft package compounding process is to bond plastic film, metal film, paper, etc. with different functions via adhesive to form two or more layers of film with composite structure. The composite structure film can simultaneously have beautiful appearance, barrier property, heat sealing property and other special performances which cannot be combined by the single-layer film, so that the composite structure film can adapt to the packaging requirements of various products and plays an increasingly important role in a plurality of fields.
The composite film of biaxially oriented polypropylene film (BOPP) and cast polypropylene film (CPP) is used in light packages such as foods and daily chemicals because of its high transparency, high gloss, good moisture resistance, excellent oil resistance and food hygiene. However, unlike polar materials such as PET and nylon, polypropylene (PP) films have a low surface free energy as a nonpolar material. The polyurethane resin adhesive contains a large number of polar groups, so that the polyurethane resin adhesive has high activity and cannot be well wetted and attached to the surface of a polypropylene film. Therefore, PP films are commonly subjected to corona treatment in the market to increase their surface free energy and thus the adhesion of the composite film. However, due to uneven corona effect, poor corona effect with time, and the like, the composite strength of the composite film is lower, the peeling strength of the composite film compounded for 1-3 days can barely meet the national standard requirement (the normal temperature T-shaped peeling strength of the polyurethane adhesive composite dry light packaging film is more than 0.6N/15 mm), the peeling strength can be attenuated with time, the peeling strength is attenuated to 0.1-0.3N/15 mm after 7 days, and the lower peeling strength has a great potential safety hazard for long-term storage of subsequent products.
Chinese patent application CN 110835513A discloses a solvent-free type bi-component polyurethane adhesive and a preparation method thereof, and the technology prepares an adhesive with good comprehensive performance by adopting polyoxypropylene polyol and bisphenol A-initiated polyether polyol and matching with organic isocyanate, and has excellent adhesion particularly to BOPP/CPP composite structures. But the peel strength of the cured product is about 0.8-0.9N/mm, and the product can not reach the national standard after being left for 7 days and 14 days until 60 days.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a solvent-free polyurethane adhesive for a composite low-surface-energy film and a preparation method thereof, so as to solve the technical problems in the prior art. The adhesive can compound the printing OPP with the thickness of 20-30 mu m with the CPP film, the T-shaped peeling strength after curing is 1.6-1.8N/15mm, and the peeling strength after 14 days is attenuated to be 1.2-1.4N/15mm. In addition, the product can still reach the national standard after being placed for 60 days.
The invention aims at realizing the following technical scheme:
a solvent-free polyurethane adhesive for a composite low-surface-energy film comprises a component A and a component B;
the component A is isocyanate-terminated prepolymer obtained by reacting an isocyanate mixture with a polyether polyol mixture, wherein the isocyanate mixture is prepared by mixing 4,4 '-diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate according to the weight ratio of 1-2:1; the polyether polyol mixture is formed by mixing polyether polyols with average molecular weights of 300-500, 800-1500 and 1800-2500 according to the weight ratio of 1-2:3-4:1-2;
the component B is formed by homogeneously mixing polyester polyol and low-molecular-weight polyether polyol;
the molar ratio of isocyanate functional groups in the component A to hydroxyl functional groups in the component B is 1.3-1.5:1.
The preparation method of the solvent-free polyurethane adhesive of the composite low-surface-energy film comprises the following steps:
and (3) respectively preparing a component A and a component B:
preparing a component A: adding the isocyanate mixture and the polyether polyol mixture into a container according to a preset weight ratio, heating to 80-90 ℃ for reaction for 3-4 hours, cooling, and discharging to obtain an isocyanate-terminated prepolymer serving as a component A; the isocyanate mixture is formed by mixing 4,4 '-diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate according to the weight ratio of 1-2:1; the polyether polyol mixture is formed by mixing polyether polyols with average molecular weights of 300-500, 800-1500 and 1800-2500 according to the weight ratio of 1-2:3-4:1-2;
preparation of a polyester polyol of component B: adding small molecular polybasic acid and small molecular polyol into a polyester kettle according to a preset weight ratio, adding an antioxidant and a catalyst, and reacting according to a conventional esterification condensation method to obtain the required polyester polyol;
and (3) preparing a component B: the prepared polyester polyol and polyether polyol with the molecular weight of 500-1000 are subjected to physical stirring according to a proportion to obtain a transparent and uniform component B;
preparing a solvent-free polyurethane adhesive: the prepared component A and the component B are mixed according to the mol ratio of 1.3-1.5:1 of isocyanate to hydroxyl, and the solvent-free polyurethane adhesive is obtained.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) In the component A, polyether polyols with average molecular weights of 300-500, 800-1500 and 1800-2500 are respectively mixed according to the weight ratio of 1-2:3-4:1-2 to form the polyether polyol mixture of the isocyanate prepolymer, so that the cured adhesive film has stronger cohesive force and better flexibility, and the adhesive has better viscoelasticity while the peeling strength is improved. Thus, through adjusting the proportion of polyether polyols with different average molecular weights, different high molecular chain segments can be generated when isocyanate prepolymer in the component A and hydroxyl in the component B are solidified, when the content of polyether polyol with the molecular weight of 300-500 is high, urethane bonds in the high molecular chain segments are increased, hard segments are increased, the acting force of hydrogen bonds and polar bonds in molecules is increased, the system viscosity is increased, the coating performance is influenced, when the content of polyether polyol with the molecular weight of 1800-2500 is high, the content of soft segments is high, the acting force of hydrogen bonds is reduced, the adhesive force between an adhesive and a base material is reduced, and the peeling strength is reduced.
(2) In the component A of the invention, the isocyanate mixture is formed by mixing 4, 4-diphenylmethane diisocyanate and 2, 4-diphenylmethane diisocyanate according to the proportion of 1-2:1, and the NCO group activity in the 4, 4-diphenylmethane diisocyanate is utilized to be larger, and the self-polymerization phenomenon can occur in the reaction process, so that the system viscosity is increased; and the polymer is white solid at normal temperature, and when the content is high, the prepolymer is slightly whitened, so that the transparency of the glue solution is poor; the lower content of 4, 4-diphenyl methane diisocyanate can affect the reactivity, and the invention can improve the transparency of the component A and the reaction efficiency by controlling the proportion of the 4, 4-diphenyl methane diisocyanate and the 2, 4-diphenyl methane diisocyanate.
(3) The molar ratio of isocyanate groups to hydroxyl groups in the component A and the component B is 1.3-1.5:1, so that the hydroxyl content is designed to be higher than that of a common solvent-free bi-component adhesive, a polymer chain segment after A, B component reaction curing is long enough and soft, and after the adhesive is placed for a period of time to be completely cured, the peeling strength attenuation rate of OPP and CPP is smaller and higher than the national standard.
The adhesive is solvent-free, has environmental protection, has smaller viscosity and is beneficial to coating operation. Has excellent adhesive property on the OPP/CPP composite structure and has great prospect in the field of light package laminating adhesives.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below; it will be apparent that the described embodiments are only some embodiments of the invention, but not all embodiments, which do not constitute limitations of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The terms that may be used herein will first be described as follows:
the term "and/or" is intended to mean that either or both may be implemented, e.g., X and/or Y are intended to include both the cases of "X" or "Y" and the cases of "X and Y".
The terms "comprises," "comprising," "includes," "including," "has," "having" or other similar referents are to be construed to cover a non-exclusive inclusion. For example: including a particular feature (e.g., a starting material, component, ingredient, carrier, formulation, material, dimension, part, means, mechanism, apparatus, step, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product or article of manufacture, etc.), should be construed as including not only a particular feature but also other features known in the art that are not explicitly recited.
The term "parts by weight" means a mass ratio relationship between a plurality of components, for example: if the X component is described as X weight parts and the Y component is described as Y weight parts, then the mass ratio of the X component to the Y component is expressed as x:y;1 part by weight may represent any mass, for example: 1 part by weight may be expressed as 1kg or 3.1415926 kg. The sum of the parts by weight of all the components is not necessarily 100 parts, and may be more than 100 parts, less than 100 parts, or 100 parts or equal. The parts, proportions and percentages described herein are by mass unless otherwise indicated.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as a range of values, the range is to be understood as specifically disclosing all ranges formed from any pair of upper and lower values within the range of values, regardless of whether ranges are explicitly recited; for example, if a numerical range of "2 to 8" is recited, that numerical range should be interpreted to include the ranges of "2 to 7", "2 to 6", "5 to 7", "3 to 4 and 6 to 7", "3 to 5 and 7", "2 and 5 to 7", and the like. Unless otherwise indicated, numerical ranges recited herein include both their endpoints and all integers and fractions within the numerical range.
The solvent-free polyurethane adhesive of the composite low surface energy film and the preparation method thereof are described in detail below. What is not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art. The specific conditions are not noted in the examples of the present invention and are carried out according to the conditions conventional in the art or suggested by the manufacturer. The reagents or apparatus used in the examples of the present invention were conventional products commercially available without the manufacturer's knowledge.
Solvent-free polyurethane adhesive of composite low surface energy film
The invention provides a solvent-free polyurethane adhesive for a composite low-surface-energy film, which consists of a component A and a component B;
the component A is isocyanate-terminated prepolymer obtained by reacting an isocyanate mixture with a polyether polyol mixture, wherein the isocyanate mixture is prepared by mixing 4,4 '-diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate according to the weight ratio of 1-2:1; the polyether polyol mixture is formed by mixing polyether polyols with average molecular weights of 300-500, 800-1500 and 1800-2500 according to the weight ratio of 1-2:3-4:1-2;
the component B is formed by homogeneously mixing polyester polyol and low-molecular-weight polyether polyol;
the molar ratio of isocyanate functional groups in the component A to hydroxyl functional groups in the component B is 1.3-1.5:1.
The isocyanate-terminated prepolymer obtained by reacting the isocyanate mixture of the component A with the polyether polyol mixture is obtained by polymerizing the isocyanate mixture and the polyether polyol mixture in a weight ratio of 5-6:4-5 at 80 ℃, and the NCO of the prepolymer is 12-15%.
The component B is physically mixed by polyester polyol and low molecular weight polyether polyol according to the weight ratio of 1:1-3, and is transparent and uniform liquid with the viscosity of 2000-4000mpa.s at 25 ℃. Lower viscosity facilitates uniform coating.
The average molecular weight of the polyester polyol in the component B is 800-1200. In a preferred embodiment, the polyester polyol is prepared from small molecule polybasic acid, small molecule polyol, 500ppm of antioxidant and 50ppm of catalyst, wherein the small molecule polyol and the small molecule polybasic acid are added according to the alkyd ratio range of 1.3-1.6, and the polyester polyol is prepared by conventional esterification condensation method. In a preferred embodiment, the small molecule polyacid is preferably one or more combinations of adipic acid and isophthalic acid;
the small molecule polyalcohol is one or more of 2-methyl-1, 3-propanediol, diethylene glycol, ethylene glycol, 1, 4-butanediol, glycerol and the like; preferably, 2-methyl-1, 3-propanediol is used, which is structurally similar to polypropylene molecules, and is advantageous for increasing the force between the adhesive and the polypropylene molecules. In addition, the proper amount of glycerol is added into the polyester polyol, so that the polyester polyol can be moderately crosslinked, and the viscosity of the polyester polyol can be increased.
The antioxidant is preferably triphenyl phosphite;
the catalyst is preferably tetra-n-butyl titanate.
Preferably, the polyether polyol in the component B has a molecular weight of 500 to 1000 and a hydroxyl value of 112 to 224mgKOH/g.
When the polyester polyol and the polyether polyol with small molecular weight are physically mixed and reacted with the isocyanate prepolymer in the component A, the curing speed is low, the adhesive layer after curing is sticky for one day, the ink layer on the OPP cannot be immediately transferred to the CPP, so that the peeling strength of the film just after curing is high, and the adhesive strength between the ink layer of the OPP and the CPP film needs to be reduced for the OPP film after printing, so that the separation of the OPP and the ink layer due to the high bonding strength is avoided, and the peeling strength is actually the adhesive force between the ink layer and the OPP, so that the measured actual peeling strength is low.
(II) a preparation method of the solvent-free polyurethane adhesive of the composite low-surface-energy film
The invention provides a preparation method of a solvent-free polyurethane adhesive for preparing a composite low-surface-energy film, which comprises the following steps:
and (3) respectively preparing a component A and a component B:
preparing a component A: adding the isocyanate mixture and the polyether polyol mixture into a container according to a preset weight ratio, heating to 80-90 ℃ for reaction for 3-4 hours, cooling, and discharging to obtain an isocyanate-terminated prepolymer serving as a component A; the isocyanate mixture is formed by mixing 4,4 '-diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate according to the weight ratio of 1-2:1; the polyether polyol mixture is formed by mixing polyether polyols with average molecular weights of 300-500, 800-1500 and 1800-2500 according to the weight ratio of 1-2:3-4:1-2;
preparation of a polyester polyol of component B: adding small molecular polybasic acid and small molecular polyol into a polyester kettle according to a preset weight ratio, adding an antioxidant and a catalyst, and reacting according to a conventional esterification condensation method to obtain the required polyester polyol;
and (3) preparing a component B: the prepared polyester polyol and polyether polyol with the molecular weight of 500-1000 are subjected to physical stirring according to a proportion to obtain a transparent and uniform component B;
in a preferred embodiment, the polyester polyol required for the B-component is prepared in the following manner: adding one or more of adipic acid or isophthalic acid and one or more of 2-methyl-1, 3-propanediol, diethylene glycol, ethylene glycol, 1, 4-butanediol and glycerol into a polyester kettle, adding 500ppm of antioxidant triphenyl phosphite and 50ppm of catalyst tetra-n-butyl titanate, and obtaining the polyester by an esterification polycondensation method commonly used in the field;
preparing a solvent-free polyurethane adhesive: the prepared component A and the component B are mixed according to the mol ratio of 1.3-1.5:1 of isocyanate to hydroxyl, and the solvent-free polyurethane adhesive is obtained.
In the component A of the method, the weight ratio of the isocyanate mixture to the polyether polyol mixture is 5-6:4-5, and the NCO of the prepolymer is 12-15%;
in the polyester polyol of the component B, the weight ratio of the small molecular polyacid to the small molecular polyol is X to Y;
in the component B, the weight ratio of the polyester polyol to the low molecular weight polyether polyol is 1:1-3.
(III) advantageous effects of the invention
Compared with the prior art, the solvent-free polyurethane adhesive of the composite low-surface-energy film and the preparation method thereof have the advantages that:
(1) The proportion of polyether polyols with different average molecular weights in the component A can be adjusted, so that different polymer chain segments can be generated during the curing reaction of isocyanate prepolymer in the component A and hydroxyl in the component B. When the content of the polyether polyol with the molecular weight of 300-500 is high, the urethane bonds in the high molecular chain segments are increased, and the hard segments are increased, so that the acting force of hydrogen bonds and polar bonds in the molecules is increased, the viscosity of the system is increased, and the coating performance is influenced. When the polyether polyol content of 1800-2500 molecular weight is high, the soft segment content is high, the hydrogen bond acting force is reduced, so that the adhesion force between the adhesive and the substrate is reduced, and the peeling strength is reduced. Therefore, the polyether polyols with the average molecular weights of 300-500, 800-1500 and 1800-2500 are respectively mixed according to the weight ratio of (1-2): (3-4): (1-2), so that the cured adhesive film has stronger cohesive force and better flexibility, and the adhesive has better viscoelasticity while the peeling strength is improved.
(2) The isocyanate in the component A adopts 4, 4-diphenyl methane diisocyanate and 2, 4-diphenyl methane diisocyanate to be mixed according to the proportion of (1-2): 1, and the self-polymerization phenomenon can occur in the reaction process because the NCO group in the 4, 4-diphenyl methane diisocyanate is relatively active, so that the system viscosity is increased. And the polymer is white solid at normal temperature, and when the content is high, the prepolymer is slightly whitened, so that the transparency of the glue solution is poor. And when the content of the 4, 4-diphenylmethane diisocyanate is low, the reactivity is affected, so that the transparency of the component A can be improved and the reaction efficiency can be improved by controlling the proportion of the 4, 4-diphenylmethane diisocyanate and the 2, 4-diphenylmethane diisocyanate.
(3) In order to improve the adhesion of the adhesive to OPP and CPP, the small molecular dihydric alcohol in 800-1200 polyester polyol is preferably 2-methyl-1, 3-propanediol, which has a similar molecular structure to polypropylene, and is beneficial to increasing the acting force between the adhesive and polypropylene molecules. In addition, the proper amount of glycerol is added into the polyester diol, so that the polyester polyol can be moderately crosslinked, and the viscosity of the polyester polyol can be increased.
(4) For the OPP film after printing, the viscosity of the adhesive between the ink layer of the OPP and the CPP film should be increased, and the bonding strength should be reduced, so that the separation of the OPP from the ink layer due to the too high bonding strength is avoided, and the tested peeling strength is actually the adhesion between the ink layer and the OPP, so that the measured actual peeling strength is lower. After the prepared polyester polyol and the polyether polyol with small molecular weight are physically mixed, when the polyester polyol reacts with the isocyanate prepolymer in the component A, the curing speed is low, the adhesive layer after curing for one day is sticky, the ink layer on the OPP can not be immediately transferred to the CPP, and therefore the peel strength of the film immediately after curing is high.
(5) The molar ratio of isocyanate groups to hydroxyl groups in the component A and the component B is regulated to be (1.3-1.5) 1, the hydroxyl group content is designed to be higher than that of the common solvent-free double-component adhesive, and the polymer chain segment after the component AB is reacted and solidified is long enough and soft. After the adhesive is placed for a period of time and is completely solidified, the peeling strength attenuation rate of OPP and CPP is smaller and higher than the national standard.
(6) The adhesive is solvent-free, has environmental protection, has smaller viscosity and is beneficial to coating operation. Has excellent adhesive property on the OPP/CPP composite structure and has great prospect in the field of light package laminating adhesives.
In summary, the adhesive of the embodiment of the invention can compound the printing OPP with the thickness of 20-30 mu m and the CPP film, the T-shaped peeling strength after curing is 1.6-1.8N/15mm, and the peeling strength after 14 days is attenuated to be 1.2-1.4N/15mm. In addition, the product can still reach the national standard after being placed for 60 days.
In order to clearly show the technical scheme and the technical effects, the solvent-free polyurethane adhesive of the composite low-surface-energy film and the preparation method thereof are described in detail in the following by using specific embodiments.
Example 1
Preparing a component A: firstly, adding 1.5 parts of polyether polyol with molecular weight of 300-500, 3.5 parts of polyether polyol with molecular weight of 800-1500 and 1 part of polyether polyol with molecular weight of 1800-2500 into a four-mouth bottle, then adding 5 parts of 4, 4-diphenylmethane diisocyanate and 2.5 parts of 2, 4-diphenylmethane diisocyanate, heating to 80 ℃ and stirring for 3 hours, wherein the NCO mass fraction of the obtained component A is 12-15%.
Preparation of the polyester polyol required for the B component: 3 parts of isophthalic acid, 5 parts of adipic acid, 3 parts of 2-methyl-1, 3-propanediol, 5 parts of diethylene glycol, 1 part of glycerol, 500ppm of antioxidant triphenyl phosphite and 50ppm of catalyst tetra-n-butyl titanate are added into a polyester kettle, and after condensation polymerization, polyester polyol with a hydroxyl value of 90-140mgKOH/g is obtained.
And (3) preparing a component B: the prepared polyester polyol and polyether polyol with molecular weight of 500-1000 are physically stirred according to the proportion of 1:3, so that the polyester polyol and the polyether polyol are uniformly mixed, are in a transparent state, and have viscosity of 2000-4000mpa.s at 25 ℃.
Preparing a solvent-free polyurethane adhesive: the NCO mass fraction of the component A and the hydroxyl value of the component B are measured, and then the component A and the component B are uniformly mixed according to the molar ratio of NCO to hydroxyl of 1.4:1.
Example 2
Preparing a component A: 1 part of polyether polyol with molecular weight of 300-500, 3 parts of polyether polyol with molecular weight of 800-1500 and 1.5 parts of polyether polyol with molecular weight of 1800-2500 are added into a four-mouth bottle, 4 parts of 4, 4-diphenylmethane diisocyanate and 4 parts of 2, 4-diphenylmethane diisocyanate are added, the temperature is raised to 80 ℃ and stirred for 3 hours, and the NCO mass fraction of the component A is 12-15%.
Preparation of the polyester polyol required for the B component: 3 parts of isophthalic acid, 5 parts of adipic acid, 10 parts of diethylene glycol, 1 part of glycerol, 500ppm of antioxidant triphenyl phosphite and 50ppm of catalyst tetra-n-butyl titanate are added into a polyester kettle, and after condensation polymerization, polyester polyol with a hydroxyl value of 90-140mgKOH/g is obtained.
And (3) preparing a component B: the prepared polyester polyol and polyether polyol with molecular weight of 500-1000 are physically stirred according to the proportion of 1:3, so that the polyester polyol and the polyether polyol are uniformly mixed, are in a transparent state, and have viscosity of 2000-4000mpa.s at 25 ℃.
Preparing a solvent-free polyurethane adhesive: the NCO mass fraction of the component A and the hydroxyl value of the component B are measured, and then the component A and the component B are uniformly mixed according to the molar ratio of NCO to hydroxyl of 1.4:1.
Example 3
Preparing a component A: firstly, adding 1.5 parts of polyether polyol with molecular weight of 300-500, 3.5 parts of polyether polyol with molecular weight of 800-1500 and 1 part of polyether polyol with molecular weight of 1800-2500 into a four-mouth bottle, then adding 5 parts of 4, 4-diphenylmethane diisocyanate and 2.5 parts of 2, 4-diphenylmethane diisocyanate, heating to 80 ℃ and stirring for 3 hours to obtain the component A with NCO mass fraction of 12-15%.
Preparation of the polyester polyol required for the B component: 20 parts of adipic acid, 7 parts of ethylene glycol, 8 parts of 2-methyl-1, 3-propanediol, 1 part of 1, 4-butanediol, 500ppm of antioxidant triphenyl phosphite and 50ppm of catalyst tetra-n-butyl titanate are added into a polyester kettle, and after condensation polymerization, polyester polyol with a hydroxyl value of 90-140mgKOH/g is obtained.
And (3) preparing a component B: the prepared polyester polyol and polyether polyol with molecular weight of 500-1000 are physically stirred according to the proportion of 1:3, so that the polyester polyol and the polyether polyol are uniformly mixed, are in a transparent state, and have viscosity of 2000-4000mpa.s at 25 ℃.
Preparing a solvent-free polyurethane adhesive: the NCO mass fraction of the component A and the hydroxyl value of the component B are measured, and then the component A and the component B are uniformly mixed according to the molar ratio of NCO to hydroxyl of 1.4:1.
Comparative example 1:
preparing a solvent-free polyurethane adhesive: the polyester polyol prepared in example 1 was uniformly mixed with polyether polyol having a molecular weight of 500 to 1000 in a ratio of 3:1 to obtain a B component. Then, the A component and the B component prepared in the example 1 are uniformly mixed according to the ratio of NCO to hydroxyl of 1.4:1 through actual measurement and calculation.
Comparative example 2:
preparing a solvent-free polyurethane adhesive: the polyester polyol prepared in example 1 was uniformly mixed with a polyether polyol having a molecular weight of 500 to 1000 in a ratio of 1:3 to obtain a B component. Then, the A component and the B component prepared in the example 1 are uniformly mixed according to the ratio of NCO to hydroxyl of 1.1:1 through actual measurement and calculation.
Comparative example 3:
preparing a solvent-free polyurethane adhesive: the polyester polyol prepared in example 1 was uniformly mixed with a polyether polyol having a molecular weight of 500 to 1000 in a ratio of 1:3 to obtain a B component. Then, the A component and the B component prepared in the example 1 are uniformly mixed according to the ratio of NCO to hydroxyl of 1.7:1 through actual measurement and calculation.
Comparative example 4:
the solvent-free adhesive YH752A/B for plastic structures, which is common in the market, is used, and the component A and the component B are uniformly mixed according to the ratio of 100:70 to obtain the bi-component adhesive.
Comparative example 5:
the solvent-free bi-component polyurethane laminating adhesive prepared in the Chinese patent application CN 110734732A is used for solving the problems of low strength and the like of the BOPP/CPP composite film.
Comparative example 6:
the bi-component polyurethane adhesive prepared in the Chinese patent application CN 110835513A is particularly excellent in adhesiveness to BOPP/CPP composite structures.
The two-component solvent-free polyurethane adhesives prepared in examples 1 to 3 and comparative examples 1 to 4 were compounded with 28 μm thick printed OPP and 25 μm thick CPP, respectively, and the T-peel strength of the OPP/CPP composite film after curing at 40℃for 24 hours and the T-peel strength after curing for 7 days and 14 days were measured according to BB/T0039-2013 Standard of commercial retail packaging bag. Comparative examples 5-6 are cited Chinese patent applications, wherein the composite curing process and test method are the same as the present invention, and have reference significance, and specific data results are shown in Table 1.
Table 1:
table 1 the results show that: in examples 1-3, the dual-component solvent-free polyurethane adhesive provided by the invention is adopted to compound a printed OPP film with the thickness of 20-30 mu m with a CPP film, and after curing for 24 hours at 40 ℃, the peeling strength can reach 1.6-1.8N/15mm, and at the moment, after peeling off the film, the glue is reversely adhered, but the transparency and the processing are not affected. After 7 days of standing, the peel strength increased, at which time the glue was slightly tacky and the printed layer on the OPP did not transfer. After the composite film is peeled off after the composite film is placed for 14 days, the glue is completely solidified, and the peeling strength is attenuated to be 1.2-1.4N/15mm, which is far higher than the peeling strength of the common solvent-free double-component polyurethane adhesive composite OPP/CPP.
It is understood that comparative examples 1-3 are not prior art, but are provided for the effect of the invention on performance of different combinations of components A, B, and that comparative example 1 has a 3:1 ratio of polyester polyol to polyether polyol of component B relative to example 1, resulting in less tackiness, more adequate cure, and greater peel strength of the cured film, but more peel strength decay after 14 days of standing. Comparative example 2 has an NCO to hydroxyl ratio of 1.1:1 relative to the AB component of example 1, with a higher hydroxyl component resulting in incomplete curing of the film, and after 14 days of standing, the film still has an improved peel strength but is still anti-adhesive. Comparative example 3 has an NCO to hydroxyl ratio of 1.7:1 relative to the AB component of example 1, which is a ratio of a common solvent-free two-component polyurethane adhesive, and the adhesive film is slightly sticky and has high peel strength, but the peel strength is reduced to below national standard after being placed for 14 days. Comparative example 4 is a solvent-free adhesive for a common plastic structure on the market, and the peel strength of the adhesive cannot reach the national standard after 14 days of attenuation. Comparative examples 5-6 are peel strength test data related to adhesives for BOPP/CPP composite films in the referenced chinese patent application.
As can be seen from examples 1-3 and comparative examples 1-6, the invention provides a solvent-free two-component polyurethane adhesive which is used for the problem that the bonding strength of OPP and CPP in the flexible package market is low, the peeling strength is reduced to below the national standard after being placed for 7 days in a compounding way, and when the solvent-free two-component polyurethane adhesive is used for compounding an OPP/CPP structure, the peeling strength is high after curing, the peeling strength is reduced to 1.2-1.4N/15mm after being cured completely for 14 days, and the T-type peeling strength of the composite packaging bag specified in the industry standard BB/T0039-2013 is higher than the requirement that the T-type peeling strength of the composite packaging bag is more than or equal to 0.6N/15 mm.
In summary, the solvent-free polyurethane adhesive of the present invention has excellent adhesion to low surface energy films, such as OPP/CPP films, and is composed of A, B two components, wherein the A component is an isocyanate prepolymer obtained by reacting isocyanate with several polyether polyols of different molecular weights. The component B is a homogeneous mixture of polyester polyol and polyether polyol, and the cured adhesive film has strength and flexibility by adjusting the proportion of the polyether polyols with different molecular weights in the component A; and secondly, adding a small molecular weight polyether polyol into the component B to ensure that the adhesive film just cured maintains a sticky property, thereby increasing the peeling strength between the OPP and the CPP film, and finally, regulating the molar ratio of NCO and hydroxyl of the component A and the component B to ensure that the molecular chain of the cured adhesive film is longer and softer, thereby reducing the attenuation rate of the peeling strength. The adhesive can compound OPP/CPP film, the T-shaped peeling strength after curing is 1.6-1.8N/15mm, and the peeling strength after 14 days is attenuated to be 1.2-1.4N/15mm.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims. The information disclosed in the background section herein is only for enhancement of understanding of the general background of the invention and is not to be taken as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Claims (7)
1. A solvent-free polyurethane adhesive of a composite low-surface-energy film is characterized by comprising a component A and a component B;
the component A is isocyanate obtained by reacting an isocyanate mixture and a polyether polyol mixture in a weight ratio of 5-6:4-5 at 80 DEG CAn acid ester-terminated prepolymer having an NCO of 12-15% and a viscosity of 6000-800mpa.s at 25 ℃, wherein the isocyanate mixture comprises 4,4 ， Diphenylmethane diisocyanate with 2,4 ， -diphenylmethane diisocyanate in a weight ratio of 1-2:1; the polyether polyol mixture is formed by mixing polyether polyols with average molecular weights of 300-500, 800-1500 and 1800-2500 according to the weight ratio of 1-2:3-4:1-2;
the component B is formed by homogeneously mixing polyester polyol and low-molecular-weight polyether polyol; the average molecular weight of the polyester polyol in the component B is 800-1200, the polyester polyol in the component B is prepared by taking small molecular polybasic acid, small molecular polyol, 300ppm of antioxidant and 50ppm of catalyst as raw materials, wherein the small molecular polyol and the small molecular polybasic acid are fed according to the alkyd ratio range of 1.3-1.6 and are obtained by a conventional esterification condensation method, and the small molecular polyol is one or a combination of 2-methyl-1, 3-propanediol, diethylene glycol, ethylene glycol, 1, 4-butanediol and glycerin;
the molar ratio of isocyanate functional groups in the component A to hydroxyl functional groups in the component B is 1.3-1.5:1.
2. The solvent-free polyurethane adhesive for composite low surface energy films according to claim 1, wherein the component B is formed by physically mixing polyester polyol and low molecular weight polyether polyol according to a weight ratio of 1:1-3.
3. The solvent-free polyurethane adhesive of the composite low surface energy film of claim 1, wherein the small molecule polyacid is one or more combinations of adipic acid and isophthalic acid;
the antioxidant is triphenyl phosphite;
the catalyst is tetra-n-butyl titanate.
4. The solvent-free polyurethane adhesive of the composite low surface energy film according to claim 1, wherein the polyether polyol in the B component has a molecular weight of 500 to 1000 and a hydroxyl value of 112 to 224mgKOH/g.
5. The solvent-free polyurethane adhesive of a composite low surface energy film according to claim 1 or 2, wherein the B component is a transparent uniform liquid with a viscosity of 2000 to 4000mpa.s at 25 ℃.
6. A method for preparing the solvent-free polyurethane adhesive of the composite low surface energy film according to any one of claims 1 to 5, comprising the steps of:
and (3) respectively preparing a component A and a component B:
preparing a component A: adding the isocyanate mixture and the polyether polyol mixture into a container according to a preset weight ratio, heating to 80-90 ℃ for reaction for 3-4 hours, cooling, and discharging to obtain an isocyanate-terminated prepolymer serving as a component A; the isocyanate mixture is composed of 4,4 ， Diphenylmethane diisocyanate with 2,4 ， -diphenylmethane diisocyanate in a weight ratio of 1-2:1; the polyether polyol mixture is formed by mixing polyether polyols with average molecular weights of 300-500, 800-1500 and 1800-2500 according to the weight ratio of 1-2:3-4:1-2;
preparation of a polyester polyol of component B: adding small molecular polybasic acid and small molecular polyol into a polyester kettle according to a preset weight ratio, adding an antioxidant and a catalyst, and reacting according to a conventional esterification condensation method to obtain the required polyester polyol;
and (3) preparing a component B: the prepared polyester polyol and polyether polyol with the molecular weight of 500-1000 are subjected to physical stirring according to a proportion to obtain a transparent and uniform component B;
preparing a solvent-free polyurethane adhesive: the prepared component A and the component B are mixed according to the mol ratio of 1.3-1.5:1 of isocyanate to hydroxyl, and the solvent-free polyurethane adhesive is obtained.
7. The method for preparing a solvent-free polyurethane adhesive for a composite low surface energy film according to claim 6, wherein the ratio of isocyanate mixture to polyether polyol mixture in the component A is 5-6:4-5, and the NCO of the prepolymer is 12-15%;
in the polyester polyol of the component B, the weight ratio of the small molecular polyacid to the small molecular polyol is X to Y;
in the component B, the weight ratio of the polyester polyol to the low molecular weight polyether polyol is 1:1-3.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503611A (en) * | 2009-03-10 | 2009-08-12 | 中山大学 | Solvent-free polyurethane adhesive for compound film |
| CN101597470A (en) * | 2008-06-03 | 2009-12-09 | 北京高盟燕山科技有限公司 | A kind of solvent free bi-component polyurethane adhesive and preparation method thereof |
| CN102174308A (en) * | 2011-01-01 | 2011-09-07 | 北京科聚化工新材料有限公司 | Polyether ester-based adhesive agent for solvent-free double-component polyurethane composite membrane and preparation method thereof |
| CN103215006A (en) * | 2013-03-19 | 2013-07-24 | 华南理工大学 | Low viscosity solvent-free polyurethane laminating adhesive and preparation method thereof |
| CN110734732A (en) * | 2019-11-07 | 2020-01-31 | 北京京都大成新材料科技有限公司 | Solvent-free bi-component polyurethane laminating adhesive and preparation method thereof |
| CN110804158A (en) * | 2019-11-27 | 2020-02-18 | 南通高盟新材料有限公司 | Double-head coating solvent-free polyurethane adhesive and preparation method thereof |
| CN112375535A (en) * | 2020-11-24 | 2021-02-19 | 上海都昱新材料科技有限公司 | Plastic-plastic composite polyurethane adhesive and preparation method thereof |
-
2022
- 2022-10-31 CN CN202211346292.5A patent/CN115505362B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597470A (en) * | 2008-06-03 | 2009-12-09 | 北京高盟燕山科技有限公司 | A kind of solvent free bi-component polyurethane adhesive and preparation method thereof |
| CN101503611A (en) * | 2009-03-10 | 2009-08-12 | 中山大学 | Solvent-free polyurethane adhesive for compound film |
| CN102174308A (en) * | 2011-01-01 | 2011-09-07 | 北京科聚化工新材料有限公司 | Polyether ester-based adhesive agent for solvent-free double-component polyurethane composite membrane and preparation method thereof |
| CN103215006A (en) * | 2013-03-19 | 2013-07-24 | 华南理工大学 | Low viscosity solvent-free polyurethane laminating adhesive and preparation method thereof |
| CN110734732A (en) * | 2019-11-07 | 2020-01-31 | 北京京都大成新材料科技有限公司 | Solvent-free bi-component polyurethane laminating adhesive and preparation method thereof |
| CN110804158A (en) * | 2019-11-27 | 2020-02-18 | 南通高盟新材料有限公司 | Double-head coating solvent-free polyurethane adhesive and preparation method thereof |
| CN112375535A (en) * | 2020-11-24 | 2021-02-19 | 上海都昱新材料科技有限公司 | Plastic-plastic composite polyurethane adhesive and preparation method thereof |
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