CN115536805A - Solvent-free polyurethane composition and preparation method thereof - Google Patents
Solvent-free polyurethane composition and preparation method thereof Download PDFInfo
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- CN115536805A CN115536805A CN202211182365.1A CN202211182365A CN115536805A CN 115536805 A CN115536805 A CN 115536805A CN 202211182365 A CN202211182365 A CN 202211182365A CN 115536805 A CN115536805 A CN 115536805A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
- C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a solvent-free polyurethane composition and a preparation method thereof, wherein the solvent-free polyurethane composition comprises a component A and a component B, wherein the component A is a polyurethane prepolymer and is prepared from the following components in parts by weight: 10-30 parts of modified special polyether polyol; 25-60 parts of isocyanate; 25-50 of polyester polyol I; the component B is prepared from the following components in parts by mass: 20-50 parts of modified special polyether polyol; 5-20 parts of isocyanate; 40-70 of second polyester polyol; 2-10 parts of micromolecular polyol; 0.3 to 5 portions of coupling agent. The solvent-free polyurethane composition has outstanding boiling resistance and boiling resistance, can resist boiling for 40 minutes at 100 ℃ and 40 minutes at 125 ℃, and has excellent transparency.
Description
Technical Field
The invention relates to a polyurethane composition, belongs to the field of preparation of high polymer materials, and particularly relates to a boiling and steaming resistant solvent-free polyurethane composition for flexible packaging aluminum foil lamination and a preparation method thereof.
Background
The boiling-resistant solvent-free polyurethane composition for the flexible packaging aluminum foil layer is a polyurethane material for the flexible packaging layer, and the solvent-free polyurethane material is an environment-friendly polyurethane material without any solvent.
The aluminum foil (AL) is a uniformly rolled aluminum product with a thickness of less than 0.20mm and a rectangular cross section. Because of its excellent properties, it is widely used for food, beverage, cigarette, medicine, household goods, etc., and is generally used as a packaging material thereof. The aluminum foil is a soft metal film, has the advantages of moisture resistance, air tightness, light shielding, abrasion resistance, fragrance retention, no toxicity, no odor and the like, and is easy to process various beautiful patterns and figures due to the elegant silvery luster, so that the aluminum foil is more popular with people. Particularly, after the aluminum foil and the plastic are compounded, the shielding performance of the aluminum foil and the heat sealing performance of the plastic are integrated, so that the shielding performance of the aluminum foil on water vapor, air, ultraviolet rays, bacteria and the like required by a packaging material is further improved, and the application market of the aluminum foil is greatly widened. The packed articles are completely isolated from outside light, moisture, gas and the like, so that the packed articles are well protected. Especially for the package of water boiling and steaming food, the material of the composite aluminum foil can ensure that the food does not deteriorate for more than one year. Moreover, the heating and unpacking are convenient, and are popular with consumers. However, the existing adhesive product has the defects of lower water boiling resistance and steaming resistance, layering after water boiling and steaming and the like in the field of water boiling and steaming containing aluminum foil structures.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a solvent-free polyurethane composition and a preparation method thereof, wherein the solvent-free polyurethane composition is environment-friendly and safe, has excellent boiling resistance and steaming resistance when being used for flexible packaging aluminum foil laminated films or bags, has excellent transparency, and can well solve the problems in the prior art.
The purpose of the invention is realized by the following technical scheme:
a solvent-free polyurethane composition is composed of a component A and a component B, wherein,
the component A is a polyurethane prepolymer and is prepared from the following components in parts by weight:
10-30 parts of modified special polyether polyol;
25-60 parts of isocyanate;
25-50 parts of polyester polyol I;
the component B is prepared from the following components in parts by mass:
20-50 parts of modified special polyether polyol;
preferably, in the composition, the modified special polyether polyols of the component A and the component B are polyether polyols with two or more functionality degrees, which are modified by nano materials, and the mass part of the nano materials in the polyether polyols is 1-5;
the nano material adopts nano silicon dioxide;
the polyether glycol with two or more functionalities is at least one of polypropylene glycol and polyglycerol, and the molecular weight of the polyether glycol is 300-1000.
Preferably, in the composition, the nano-silica is hydrophobic fumed silica.
Preferably, in the composition, the isocyanate in the component A and the isocyanate in the component B adopt a mixture of diphenylmethane-4, 4 '-diisocyanate, diphenylmethane-4, 4' -diisocyanate and diphenylmethane-2, 4 '-diisocyanate, and the weight ratio of 2,4' isomer in the mixture is more than or equal to 35%, at least one of polyether modified MDI, carbodiimide modified MDI, polymethylene polyphenyl polyisocyanate, isophorone diisocyanate, hexamethylene Diisocyanate (HDI) and HDI trimer;
the polyester polyol I of the component A and the polyester polyol II of the component B are both prepared by esterification and polycondensation of dibasic acid and polyhydric alcohol;
the small molecular polyol is at least one of triethylene glycol, dipropylene glycol, glycerol and trimethylolpropane;
the coupling agent is at least one of aminosilane, epoxy silane, phenyl silane, titanate coupling agent and aluminate coupling agent.
Preferably, in the composition, the dibasic acid is at least one of adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid and phthalic anhydride;
the polyhydric alcohol is at least one of 1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol and at least one of 2-methyl-1, 3-propanediol, 2-methyl-2, 4-pentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 2-propanediol and at least one of glycerol and trimethylolpropane.
Preferably, in the above composition, the component a further comprises:
the addition agent is 0.1 to 5 mass portions;
the component B also comprises:
0.01 to 5 portions of catalyst.
Preferably, in the composition, the auxiliary agent is at least one of phosphoric acid, benzoyl chloride, citric acid, tartaric acid and isocyanate silane;
the catalyst adopts at least one of an organic bismuth catalyst and an organic zinc catalyst.
The preparation method of the solvent-free polyurethane composition comprises the following steps:
preparing a component A: dehydrating the pre-prepared modified special polyether polyol and polyester polyol I at 110-120 ℃ for 1-2 hours in vacuum, reacting with isocyanate at 80-90 ℃ for 3 hours, and adding an auxiliary agent to prepare a component A;
preparing a component B: the prepared modified special polyether polyol and polyester polyol II are dehydrated for 1 to 2 hours in vacuum at the temperature of between 110 and 120 ℃, react with isocyanate for 3 hours at the temperature of between 80 and 90 ℃, and are added with a coupling agent, micromolecular polyol and a catalyst to prepare the component B.
Preferably, in the above preparation method, the modified special polyether polyol is prepared in the following manner:
and (3) placing the nano silicon dioxide and polyether polyol with two or more functionality degrees into a high-speed dispersion machine for dispersion, keeping the rotation speed of 1000 revolutions per minute for 5 to 10 minutes, increasing the rotation speed to 2000 revolutions per minute, keeping the rotation speed for 5 to 10 minutes, and stopping to obtain the modified special polyether polyol.
Compared with the prior art, the solvent-free polyurethane composition and the preparation method thereof have at least the following beneficial effects:
the solvent-free polyurethane composition has the advantages that the boiling resistance and good water resistance can be obviously improved due to the adoption of the modified special polyether polyol, the boiling resistance is also improved due to the addition of the coupling agent, and the temperature resistance is improved due to the independent addition of the micromolecule polyol, so that the solvent-free polyurethane composition has outstanding boiling resistance and steaming resistance, can resist boiling for 40 minutes at 100 ℃ and 40 minutes at 125 ℃, and has excellent transparency.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below; it is to be understood that the described embodiments are merely exemplary of the invention, and are not intended to limit the invention to the particular forms disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The terms that may be used herein are first described as follows:
the terms "comprising," "including," "containing," "having," or other similar terms of meaning should be construed as non-exclusive inclusions. For example: including a feature (e.g., material, component, ingredient, carrier, formulation, material, dimension, part, component, mechanism, device, process, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product, or article of manufacture), is to be construed as including not only the particular feature explicitly listed but also other features not explicitly listed as such which are known in the art.
The term "consisting of 823070 \8230composition" means to exclude any technical characteristic elements not explicitly listed. If used in a claim, the term shall render the claim closed except for the inclusion of the technical features that are expressly listed except for the conventional impurities associated therewith. If the term occurs in only one clause of the claims, it is defined only as specifically listed in that clause, and elements recited in other clauses are not excluded from the overall claims.
The term "parts by weight" is meant to indicate the relationship of mass proportions between the various components, for example: if the X component is described as X parts by weight and the Y component is described as Y parts by weight, the mass ratio of the X component to the Y component is represented 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 components is not necessarily 100 parts and may be greater than 100 parts, less than 100 parts or equal to 100 parts. Unless otherwise indicated, parts, ratios, and percentages described herein are by mass.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as ranges of values, the ranges of values should be understood to specifically disclose all ranges formed by any pair of upper values, lower values, or preferred values within the range, regardless of whether the ranges are explicitly recited; for example, if a numerical range of "2 to 8" is recited, then that numerical range should be interpreted to include ranges such as "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, the numerical ranges recited herein include both the endpoints thereof and all integers and fractions within the numerical range.
The low-density polyurethane hot melt adhesive and the preparation method thereof provided by the invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art. The examples of the present invention, in which specific conditions are not specified, were carried out according to the conventional conditions in the art or conditions suggested by the manufacturer. The reagents or instruments used in the examples of the present invention are not specified by manufacturers, and are all conventional products available by commercial purchase.
The embodiment of the invention provides a boiling and cooking resistant solvent-free polyurethane composition for a flexible package aluminum foil layer, which consists of a component A and a component B, wherein the component A is a polyurethane prepolymer and is prepared from the following components:
the modified special polyether polyol is used in the amount of 10-30 wt%,
25 to 60 mass portions of isocyanate,
25-50 parts by mass of first polyester polyol;
the component B is prepared from the following components:
the modified special polyether polyol is used in 20-50 wt%,
5 to 20 mass portions of isocyanate,
the second polyester polyol with the dosage of 40-70 parts by weight,
the dosage of the micromolecular polyalcohol is 2-10 parts by weight,
the dosage of the coupling agent is 0.3 to 5 mass portions.
Further, the component A also comprises: the addition agent is 0.1 to 5 mass portions;
the component B also comprises: the catalyst is 0.01-5 wt%.
In a preferred embodiment of the present invention, the modified special polyether polyol in the component A and the component B is polyether polyol with two or more functionalities modified by nano materials, and the weight ratio of the nano materials in the polyether polyol is 1-5%, preferably 1-3%.
The nano material is nano silicon dioxide, in particular to gas phase method silicon dioxide, in particular to hydrophobic gas phase silicon dioxide, and can be selected from Evonik silicon dioxide AEROSIL R972 and R974, cabot corporation CAB-O-
TS-620 and TS-610, wacker H15 and H20.
The polyether polyol with two or more functionalities is at least one of polypropylene glycol and polyglycerol, and the molecular weight of the polyether polyol is 300-1000, preferably 300-700.
In a preferred embodiment of the present invention, the isocyanate is at least one of diphenylmethane-4, 4' -diisocyanate (4, 4' -MDI), a mixture of diphenylmethane-4, 4' -diisocyanate and diphenylmethane-2, 4' -diisocyanate in which the 2,4' isomer weight ratio is 35% or more (liquefied MDI), polyether-modified MDI, carbodiimide-modified MDI, polymethylene polyphenyl polyisocyanate, isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), HDI trimer.
In a preferred embodiment of the invention, the polyester polyol I and the polyester polyol are both polyester polyols prepared by esterification and polycondensation of dibasic acid and polyhydric alcohol; wherein the dibasic acid is selected from: at least one of adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid, phthalic anhydride; the polyol is selected from: at least one of 1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, and at least one of 2-methyl-1, 3-propanediol, 2-methyl-2, 4-pentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 2-propanediol, and at least one of glycerol and trimethylolpropane.
Preferably, the first polyester polyol and the second polyester polyol are at least one selected from the group consisting of polycaprolactone diol and polycaprolactone triol.
In a preferred embodiment of the invention, the auxiliary agent is at least one of phosphoric acid, benzoyl chloride, citric acid, tartaric acid and isocyanatosilane.
In a preferred embodiment of the present invention, the small molecule polyol is at least one selected from triethylene glycol, dipropylene glycol, glycerol, and trimethylolpropane.
In a preferred embodiment of the present invention, the coupling agent is at least one selected from the group consisting of aminosilanes, epoxysilanes, phenylsilanes, titanate coupling agents, and aluminate coupling agents.
In a preferred embodiment of the invention, the catalyst is at least one of an organobismuth catalyst and an organozinc catalyst.
The embodiment of the invention also provides a preparation method of the boiling and steaming resistant solvent-free polyurethane composition for the flexible package aluminum foil layer, which comprises the following steps:
preparing modified special polyether polyol in advance: dispersing the nano silicon dioxide and polyether polyol in a high-speed dispersion machine at the rotating speed of 1000 rpm for 5-10 minutes, increasing the rotating speed to 2000 rpm, keeping the rotating speed for 5-10 minutes, and stopping to obtain the modified special polyether polyol;
preparing a component A: dehydrating the prepared modified special polyether polyol and polyester polyol I at 110-120 ℃ for 1-2 hours in vacuum, and reacting the dehydrated special polyether polyol and polyester polyol I with isocyanate at 80-90 ℃ for 3 hours to obtain a component A;
preparing a component B: the prepared modified special polyether polyol and polyester polyol II are dehydrated for 1 to 2 hours in vacuum at the temperature of between 110 and 120 ℃, react with isocyanate for 3 hours at the temperature of between 80 and 90 ℃, and are added with a coupling agent and micromolecular polyol to prepare a component B.
In the method, in the step of preparing the component A, after the component A reacts with isocyanate for 3 hours at the temperature of 80-90 ℃, the method also comprises the step of adding an auxiliary agent, and the component A is prepared by adding the auxiliary agent;
in the step of preparing the component B, a coupling agent and micromolecular polyalcohol are added, and a catalyst is also added at the same time to prepare the component B.
The prepared solvent-free polyurethane composition is applied to preparing flexible packaging aluminum foil laminated films/bags, and the main laminated structures are PET/AL/PA/PE, PET/AL/PA/CPP, PET/AL/PET/PE, PET/AL/PE, PET/AL/CPP and the like.
The boiling resistance of the solvent-free polyurethane composition of the invention is mainly realized by the following components:
(1) By adding the hydrophobic fumed silica, the boiling resistance is obviously improved.
(2) The polyether polyol adopts polypropylene glycol and polyglycerol with good water resistance.
(3) The boiling resistance can be improved by adding the coupling agent.
The boiling resistance is mainly realized by the following components:
(1) By adding the hydrophobic fumed silica, the boiling resistance is obviously improved.
(2) The polyester polyol adopts polycaprolactone diol and triol, and has good temperature resistance and water resistance.
(3) The polyester polyol is polyol with good temperature resistance and water resistance.
(4) The micromolecular polyalcohol is added independently, so that the temperature resistance is improved.
The transparency is mainly achieved by the following means:
(1) The preparation of the modified special polyether polyol is realized by adopting proper dosage of the hydrophobic fumed silica and a high-speed dispersion machine dispersion mode.
(2) Suitable structure and suitable molecular weight of the polyether polyol.
Example 1
The embodiment provides a solvent-free polyurethane composition, and a preparation method thereof comprises the following steps (the using amounts of the components are in parts by mass):
preparing modified special polyether polyol in advance: 2 parts of Yingchuang Evonik silicon dioxide AEROSIL R972 and 98 parts of polypropylene glycol (Mn = 400) are put into a high-speed dispersion machine for dispersion, the rotation speed is 1000 revolutions per minute and is kept for 8 minutes, and the rotation speed is increased to 2000 revolutions per minute and is kept for 8 minutes, so that the modified special polyether polyol is obtained;
preparing a first polyester polyol: adding 42 parts of adipic acid, 8 parts of isophthalic acid, 28 parts of 1, 4-butanediol, 15 parts of 2-methyl-1, 3-propanediol and 7 parts of glycerol into a reaction kettle, and performing esterification polycondensation reaction to generate polyester polyol I;
the polyester polyol II is polycaprolactone triol;
preparation of a component A: dehydrating 15 parts of modified special polyether polyol and 25 parts of polyester polyol I for 1 hour under the vacuum condition of 110-120 ℃, cooling to below 80 ℃, adding 18 parts of carbonized diimine modified MDI and 41 parts of liquefied MDI, and reacting for 3 hours to obtain a component A; preferably, 1 part of phosphoric acid can be added as an auxiliary agent in 3 hours of reaction to prepare a component A;
b, preparation of a component: firstly, dehydrating 33 parts of modified special polyether polyol and 50 parts of polyester polyol II for 1 hour under the vacuum condition of 110-120 ℃, cooling to the temperature below 80 ℃, adding 5 parts of carbonized diimine modified MDI and 5 parts of liquefied MDI, reacting for 3 hours at the temperature of 80-90 ℃, and adding 2 parts of aminosilane coupling agent and 4 parts of triethylene glycol to obtain a component B. Preferably, 1 part of an organozinc catalyst is added together with 2 parts of an aminosilane coupling agent and 4 parts of triethylene glycol.
Example 2
The embodiment provides a solvent-free polyurethane composition, and a preparation method thereof comprises the following steps (the use amounts of the components are in parts by mass):
preparing modified special polyether polyol in advance: 2 portions of Cabot CAB-O-
Placing TS-620 silicon dioxide and 98 parts of polypropylene glycol (Mn = 600) into a high-speed dispersion machine for dispersion, keeping the rotation speed for 8 minutes from 1000 revolutions per minute, and increasing the rotation speed to 2000 revolutions per minute for 8 minutes to obtain modified special polyether polyol;
preparing a first polyester polyol: adding 42 parts of adipic acid, 8 parts of terephthalic acid, 28 parts of 1, 6-hexanediol, 15 parts of diethylene glycol and 7 parts of glycerol into a reaction kettle, and performing esterification polycondensation to generate polyester polyol I;
the second polyester polyol is polycaprolactone triol;
preparation of a component A: firstly, dehydrating 15 parts of modified special polyether polyol and 25 parts of polyester polyol I for 1 hour under the vacuum condition of 110-120 ℃, cooling to the temperature below 80 ℃, adding 18 parts of 4,4' -MDI and 41 parts of liquefied MDI, and reacting for 3 hours to obtain a component A; preferably, 1 part of citric acid can be added as an auxiliary agent after the reaction is carried out for 3 hours to prepare a component A;
b, preparation of a component: firstly, dehydrating 33 parts of modified special polyether polyol and 50 parts of polyester polyol II for 1 hour under the vacuum condition of 110-120 ℃, cooling to the temperature below 80 ℃, adding 5 parts of carbonized diimine modified MDI and 5 parts of IPDI, reacting for 3 hours at 80-90 ℃, and adding 2 parts of epoxy silane coupling agent and 4 parts of glycerol to obtain a component B. Preferably, 1 part of an organozinc catalyst may be added along with 2 parts of the epoxysilane coupling agent and 3 parts of glycerol.
Example 3
The embodiment provides a solvent-free polyurethane composition, and a preparation method thereof comprises the following steps (the using amounts of the components are in parts by mass):
preparing a modified special polyether polyol in advance: 2 parts of Yingchuang Evonik silicon dioxide AEROSIL R974 and 98 parts of polyglycerol (Mn = 400) are placed into a high-speed dispersion machine for dispersion, the rotating speed is kept for 8 minutes from 1000 revolutions per minute, and the rotating speed is increased to 2000 revolutions per minute and kept for 8 minutes to obtain modified special polyether polyol;
preparing a first polyester polyol: firstly, adding 30 parts of adipic acid, 12 parts of sebacic acid, 8 parts of isophthalic acid, 28 parts of 2, 2-dimethyl-1, 3-propylene glycol, 15 parts of diethylene glycol and 7 parts of trimethylolpropane into a reaction kettle, and carrying out esterification polycondensation reaction to generate polyester polyol I;
the polyester polyol II is polycaprolactone diol;
preparation of a component A: firstly, dehydrating 15 parts of modified special polyether polyol and 25 parts of polyester polyol I for 1 hour under the vacuum condition of 110-120 ℃, cooling to the temperature below 80 ℃, adding 18 parts of polyether modified MDI and 41 parts of HDI, and reacting for 3 hours to obtain a component A; preferably, after reacting for 3 hours, 1 part of isocyanate silane can be added as an auxiliary agent to prepare a component A;
b, preparation of a component: firstly, dehydrating 33 parts of modified special polyether polyol and 50 parts of polyester polyol II for 1 hour under the vacuum condition of 110-120 ℃, cooling to the temperature below 80 ℃, adding 5 parts of polyether modified MDI and 5 parts of liquefied MDI, reacting for 3 hours at 80-90 ℃, and adding 2 parts of phenyl silane coupling agent, 1 part of organic zinc catalyst and 4 parts of dipropylene glycol to obtain a component B. Preferably, the component B is prepared by adding 1 part of organic zinc catalyst while adding 2 parts of phenyl silane coupling agent and 4 parts of dipropylene glycol.
The two-component solvent-free polyurethane composition synthesized in examples 1 to 3 was used as an adhesive, and the adhesive was prepared in a certain ratio to compound structures of PET/AL/PA/PE, PET/AL/PA/CPP, PET/AL/PET/PE, PET/AL/PE, PET/AL/CPP, etc., and the effects of PET/AL/PA/PE, PET/AL/PET/PE, PET/AL/PE resistant to 100 degrees, 40 minutes boiling, PET/AL/PA/CPP, PET/AL/CPP resistant to 125 degrees, 40 minutes boiling were examined, and the transparency and peel strength were tested.
(1) Evaluation of boiling resistance: the different structures have no obvious conditions of layering, glue layer falling and the like after being boiled for 40 minutes at the temperature of 100 ℃, all the structures have better transparency, and the boiling resistance results of the composite different structures of the examples 1-3 are shown in the following table 1:
TABLE 1 post-poaching Properties with different structures, peel Strength N/15mm
(2) Steaming resistance: the different structures have no obvious conditions of layering, glue layer falling off and the like after being cooked for 40 minutes at 125 ℃, all the structures have better transparency, and the results of the steaming resistance of the composite different structures of the examples 1 to 3 are shown in the table 2:
TABLE 2 post-cooking properties of different structures, peel strength N/15mm
The comparison shows that the flexible packaging aluminum foil laminated film/bag compounded by the solvent-free polyurethane composition has excellent boiling resistance and steaming resistance, and the peeling strength is still high after the composite structure PET/AL/PA/PE, PET/AL/PET/PE and PET/AL/PE are boiled for 40 minutes at 100 ℃; in addition, the structures such as PET/AL/PA/CPP, PET/AL/CPP and the like are resistant to cooking at 125 ℃ for 40 minutes, the delamination and the like do not occur, and the peeling strength is high, so that the double-component solvent-free polyurethane adhesive has the outstanding performances of resisting cooking at 125 ℃ for 40 minutes and water cooking at 100 ℃ for 40 minutes, and has excellent transparency.
The above description 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 that can be easily conceived by those skilled in the art within the technical scope of the present invention are also within 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 this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A solvent-free polyurethane composition is characterized by consisting of a component A and a component B, wherein,
the component A is a polyurethane prepolymer and is prepared from the following components in parts by weight:
10-30 parts of modified special polyether polyol;
25-60 parts of isocyanate;
25-50 parts of polyester polyol I;
the component B is prepared from the following components in parts by mass:
2. the solvent-free polyurethane composition of claim 1, wherein the modified special polyether polyols of the component a and the component B are polyether polyols with two or more functionalities modified by nano materials, and the mass fraction of the nano materials in the polyether polyols is 1-5;
the nano material adopts nano silicon dioxide;
the polyether polyol with two or more functionalities is at least one of polypropylene glycol and polyglycerol, and the molecular weight of the polyether polyol is 300-1000.
3. The solvent-free polyurethane composition of claim 2, wherein the nanosilica is hydrophobic fumed silica.
4. A solventless polyurethane composition according to any one of claims 1-3 wherein the isocyanates in both the a and B components are diphenylmethane-4, 4 '-diisocyanate, a mixture of diphenylmethane-4, 4' -diisocyanate and diphenylmethane-2, 4 '-diisocyanate having a 2,4' isomer weight ratio of 35% or more, at least one of polyether modified MDI, carbodiimide modified MDI, polymethylene polyphenyl polyisocyanate, isophorone diisocyanate, hexamethylene Diisocyanate (HDI), HDI trimer;
the polyester polyol I of the component A and the polyester polyol II of the component B are both prepared by esterification and polycondensation of dibasic acid and polyhydric alcohol;
the small molecular polyol is at least one of triethylene glycol, dipropylene glycol, glycerol and trimethylolpropane;
the coupling agent is at least one of aminosilane, epoxy silane, phenyl silane, titanate coupling agent and aluminate coupling agent.
5. The solvent-free polyurethane composition of claim 4, wherein the dibasic acid is at least one of adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid, phthalic anhydride;
the polyhydric alcohol is at least one of 1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol and at least one of 2-methyl-1, 3-propanediol, 2-methyl-2, 4-pentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 2-propanediol and at least one of glycerol and trimethylolpropane.
6. A solvent-free polyurethane composition according to any of claims 1 to 3, wherein the a-side further comprises:
the addition agent is 0.1 to 5 mass portions;
the component B also comprises:
0.01 to 5 percent of catalyst.
7. The solvent-free polyurethane composition of claim 5, wherein the auxiliary agent is at least one of phosphoric acid, benzoyl chloride, citric acid, tartaric acid, isocyanatosilane;
the catalyst adopts at least one of an organic bismuth catalyst and an organic zinc catalyst.
8. A method of preparing the solvent-free polyurethane composition of any of claims 1-7, comprising the steps of:
preparing a component A: carrying out vacuum dehydration on the prepared modified special polyether polyol and polyester polyol I at 110-120 ℃ for 1-2 hours, and reacting the special polyether polyol and the polyester polyol I with isocyanate at 80-90 ℃ for 3 hours to obtain a component A;
preparing a component B: the prepared modified special polyether polyol and polyester polyol II are dehydrated for 1 to 2 hours in vacuum at the temperature of between 110 and 120 ℃, react with isocyanate for 3 hours at the temperature of between 80 and 90 ℃, and are added with a coupling agent and micromolecular polyol to prepare a component B.
9. The method of claim 8 wherein the modified specialty polyether polyol is prepared by:
and (3) placing the nano silicon dioxide and polyether polyol with two or more functionality degrees into a high-speed dispersion machine for dispersion, keeping the rotation speed at 1000 revolutions per minute for 5 to 10 minutes, increasing the rotation speed to 2000 revolutions per minute, keeping the rotation speed for 5 to 10 minutes, and stopping to obtain the modified special polyether polyol.
10. The method for preparing the solvent-free polyurethane composition according to claim 8 or 9, wherein the step of preparing the component a further comprises a step of adding an auxiliary agent after reacting with isocyanate at 80 to 90 ℃ for 3 hours, wherein the component a is prepared by adding the auxiliary agent;
in the step of preparing the component B, a coupling agent and micromolecular polyol are added, and simultaneously, a catalyst is also added to prepare the component B.
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|---|---|---|---|---|
| CN116217876A (en) * | 2023-03-27 | 2023-06-06 | 南通高盟新材料有限公司 | High-barrier heat-resistant solvent-free polyurethane composite material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013043936A (en) * | 2011-08-24 | 2013-03-04 | Dic Corp | Resin composition for solventless adhesive and adhesive |
| CN102977837A (en) * | 2012-12-06 | 2013-03-20 | 南通高盟新材料有限公司 | Solventless double-component polyurethane adhesive and preparation method thereof |
| CN106675499A (en) * | 2016-12-19 | 2017-05-17 | 江苏力合粘合剂有限公司 | Solvent-free two-component polyurethane cooking adhesive and preparation method thereof |
| CN106986975A (en) * | 2017-05-11 | 2017-07-28 | 上海回天新材料有限公司 | A kind of preparation method of polyurethane laminating adhesive |
| CN112898948A (en) * | 2021-01-20 | 2021-06-04 | 广州机械科学研究院有限公司 | Single-component transparent organosilicon sealant and preparation method and application thereof |
| JP2021088184A (en) * | 2019-11-25 | 2021-06-10 | 東洋インキＳｃホールディングス株式会社 | Packaging material and package |
-
2022
- 2022-09-27 CN CN202211182365.1A patent/CN115536805A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013043936A (en) * | 2011-08-24 | 2013-03-04 | Dic Corp | Resin composition for solventless adhesive and adhesive |
| CN102977837A (en) * | 2012-12-06 | 2013-03-20 | 南通高盟新材料有限公司 | Solventless double-component polyurethane adhesive and preparation method thereof |
| CN106675499A (en) * | 2016-12-19 | 2017-05-17 | 江苏力合粘合剂有限公司 | Solvent-free two-component polyurethane cooking adhesive and preparation method thereof |
| CN106986975A (en) * | 2017-05-11 | 2017-07-28 | 上海回天新材料有限公司 | A kind of preparation method of polyurethane laminating adhesive |
| JP2021088184A (en) * | 2019-11-25 | 2021-06-10 | 東洋インキＳｃホールディングス株式会社 | Packaging material and package |
| CN112898948A (en) * | 2021-01-20 | 2021-06-04 | 广州机械科学研究院有限公司 | Single-component transparent organosilicon sealant and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116217876A (en) * | 2023-03-27 | 2023-06-06 | 南通高盟新材料有限公司 | High-barrier heat-resistant solvent-free polyurethane composite material and preparation method thereof |
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