CN113801617B - Liquid reactive polyurethane adhesive - Google Patents
Liquid reactive polyurethane adhesive Download PDFInfo
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- CN113801617B CN113801617B CN202010527524.1A CN202010527524A CN113801617B CN 113801617 B CN113801617 B CN 113801617B CN 202010527524 A CN202010527524 A CN 202010527524A CN 113801617 B CN113801617 B CN 113801617B
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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
- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
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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
- C08G18/48—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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention provides a liquid reaction type polyurethane adhesive, which comprises a polyurethane prepolymer, wherein the polyurethane prepolymer is blocked by isocyanate groups and is obtained by a polymerization reaction, and a reaction monomer of the polymerization reaction comprises polyisocyanate, polyol, a stabilizer, a catalyst and hydrophobic filler. The functionality of the polyisocyanate is 2.4 to 3, the molecular weight of the polyol is 1000 to 8000, and the polyol has hydrolysis resistance, the stabilizer has a structure shown in a formula (I), the catalyst has a structure shown in a formula (II), and each symbol in the formula (I) and the formula (II) is defined in the specification. Therefore, the liquid reactive polyurethane adhesive has good adhesive strength and no toxicity through different components and formulas, and is favorable for serving as an adhesive for structural woodwork.
Description
Technical Field
The present invention relates to a liquid reactive polyurethane adhesive, and more particularly to a liquid reactive polyurethane adhesive for structural woodworking.
Background
The conventional laminated wood (GLT or Gllam) is called as "laminated wood" in which the fiber directions (wood direction) of sawn boards or small angle wood are parallel to each other and laminated and Glued in the thickness, width and length directions. However, the manufacturing process of the laminated wood mainly includes drying the integrated unit after the raw wood is made into a sawn board (integrated unit), sizing the integrated unit (fixed width and fixed thickness), longitudinally connecting or widely connecting and splicing the integrated unit, grading the integrated unit, coating an adhesive, then integrating, refitting and the like, wherein the type of the selected adhesive can be selected according to the use environment.
Phenol/resorcinol/formaldehyde resin (PRF) and melamine/urea/formaldehyde resin (MUF) have been used as adhesives for laminated materials in the conventional industry, but the raw materials thereof contain formaldehyde, which is toxic and non-environmentally friendly, and other common adhesives, such as PVAc white glue and hot melt adhesive, cannot meet the strict structural safety standards.
In view of the above, there is still a need for an adhesive that has good adhesive strength and non-toxic properties, and can meet various building safety standards and be a new environmental building material.
Disclosure of Invention
An object of the present invention is to provide a liquid reactive polyurethane adhesive which has good adhesive strength and weather resistance, and does not require any volatile organic solvent, thereby achieving the purpose of environmental protection.
One embodiment of the present invention provides a liquid reactive polyurethane adhesive, which comprises a polyurethane prepolymer. The polyurethane prepolymer is end-capped with isocyanate group and is obtained by a polymerization reaction, and the reaction monomer of the polymerization reaction comprises polyisocyanate, polyol, a stabilizer, a catalyst and a hydrophobic filler. Wherein the functionality of the polyisocyanate is 2.4 to 3, the molecular weight of the polyol is 1000 to 8000, and hydrolysis resistance is provided. The stabilizer has a structure shown in a formula (I):
wherein R is 1 、R 2 、R 3 Are each independently a hydrogen atom or a monovalent organic group. The catalyst has a structure shown in a formula (II):
wherein R is 4 And R 5 Are each independently a hydrogen atom or an alkyl group, n 1 And n 2 Are each independently an integer from 2 to 4.
The liquid reaction type polyurethane adhesive according to the previous embodiment, wherein the polyisocyanate is selected from aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate or a mixture thereof.
The liquid reactive polyurethane adhesive according to the previous embodiment, wherein the polyol is selected from polycarbonate polyol, polyether polyol or a mixture thereof.
The liquid reactive polyurethane adhesive according to the previous embodiment, wherein the hydrophobic filler is selected from hydrophobic calcium carbonate, hydrophobic silica, hydrophobic talc, hydrophobic clay, or a mixture thereof.
In the liquid reactive polyurethane adhesive according to the above embodiment, the reactive monomer of the polyurethane prepolymer may further include a polyamine, and the molecular weight of the polyamine may be 1000 to 8000.
The liquid reaction type polyurethane adhesive according to the previous embodiment, wherein the polyisocyanate may be contained in an amount of 40 to 70 parts by weight, the polyol may be contained in an amount of 30 to 60 parts by weight, the stabilizer may be contained in an amount of 0.01 to 3 parts by weight, the catalyst may be contained in an amount of 0.01 to 3 parts by weight, and the hydrophobic filler may be contained in an amount of 0.5 to 5 parts by weight, based on 100 parts by weight of the total weight of the reactive monomers.
The liquid reactive polyurethane adhesive according to the previous embodiment, wherein the total content of the polyol and the polyamine may be 30 to 60 parts by weight based on 100 parts by weight of the total weight of the reactive monomers.
In the liquid reactive polyurethane adhesive according to the above embodiment, the reactive monomer of the polyurethane prepolymer may further include an additive, and the additive may be an antioxidant.
Therefore, the liquid reaction type polyurethane adhesive has good adhesive strength and no toxicity through different components and formulas, and is favorable for serving as an adhesive for structural woodwork.
Detailed Description
Embodiments of the invention are discussed in more detail below. However, this embodiment may be an application of various inventive concepts, which may be embodied within various specific ranges. The particular embodiments are illustrative only and not limiting to the scope of the disclosure.
In the present invention, the range represented by "one numerical value to another numerical value" is a general expression avoiding all numerical values in the range from being enumerated in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification. For example, a range of "0.1wt% to 1wt%" encompasses a range of "0.5wt% to 0.8wt%", regardless of whether other values are recited in the specification.
< liquid reactive polyurethane adhesive >
The invention provides a liquid reaction type polyurethane adhesive, which comprises a polyurethane prepolymer. The polyurethane prepolymer is end-capped by isocyanate group and is obtained by a polymerization reaction, and a reaction monomer of the polymerization reaction comprises polyisocyanate, polyol, a stabilizer, a catalyst and hydrophobic filler. The content of the polyisocyanate may be 40 to 70 parts by weight, the content of the polyol may be 30 to 60 parts by weight, the content of the stabilizer may be 0.01 to 3 parts by weight, the content of the catalyst may be 0.01 to 3 parts by weight, and the content of the hydrophobic filler may be 0.5 to 5 parts by weight, based on 100 parts by weight of the total weight of the reactive monomers. In addition, the reaction monomer of the polyurethane prepolymer of the present invention may further include a polyamine, and the total content of the polyol and the polyamine may be 30 parts by weight to 60 parts by weight, based on 100 parts by weight of the total weight of the reaction monomers.
The functionality of the polyisocyanate in the reactive monomers of the polyurethane prepolymer is from 2.4 to 3. The polyisocyanate may be selected from aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates or mixtures thereof. For example, the polyisocyanate may be, but is not limited to, one or a mixture of more than one of hexamethylene diisocyanate Trimer (HDI Trimer), hexamethylene diisocyanate Biuret (HDI Biuret), polymethylene polyphenyl polyisocyanate (PAPI).
The polyurethane prepolymer may contain only polyol or polyol and polyamine, wherein the polyol and polyamine have molecular weight of 1000-8000 and hydrolysis resistance. The polyol may be selected from polycarbonate polyols, polyether polyols, or mixtures thereof. For example, the polyol may be, but is not limited to, one or a mixture of more than one of a polyoxypropylene polyol, a polyoxyethylene polyol, a polyoxypropylene-oxyethylene copolyol, a polytetrahydrofuran polyol, a polycarbonate-polyoxypropylene polyol. The polyamine may be, but not limited to, one or a mixture of more than one of polyoxypropylene polyamine, polyoxyethylene polyamine, and polyoxypropylene-oxyethylene copolymer polyamine.
In the reaction monomers of the polyurethane prepolymer, the stabilizer has a structure shown as the formula (I):
wherein R is 1 、R 2 、R 3 Are each independently a hydrogen atom or a monovalent organic group. The monovalent organic group may be a hydroxyl group, a nitrile group, a nitro group, a substituted or unsubstituted amine group, an amide group, a hydrazine group, a hydrazone group, a substituted or unsubstituted C 1 ～C 60 Alkyl, substituted or unsubstituted C 2 ～C 60 Alkenyl of (a), substituted or unsubstituted C 2 ～C 60 Alkynyl, substituted or unsubstituted C 1 ～C 60 Alkoxy, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkenyl group of (a), substituted or unsubstituted C 3 ～C 10 Heterocycloalkyl, substituted or unsubstituted C 3 ～C 10 Heterocycloalkenyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 6 ～C 30 Aryloxy group of (1), substituted or unsubstituted C 6 ～C 30 Arylthio group of (A), substituted or unsubstituted C 2 ～C 30 A substituted or unsubstituted aldehyde group or a substituted or unsubstituted silane group. The term "substituted" means that at least one hydrogen atom may be substituted with a deuterium atom, a halogen atom or a monovalent organic group (hereinafter, the deuterium atom, halogen atom or monovalent organic group substituting for the hydrogen atom is referred to as a substituent) as described in the above paragraph with respect to the monovalent organic group, and further, when at least a hydrogen atom is substituted, the kind of the substituent may be the same or different. Common substituents include, but are not limited to, C 1 ～C 60 Alkyl of (C) 6 ～C 30 Aryl or C of 2 ～C 30 The heteroaryl group of (a).
In the reaction monomers of the polyurethane prepolymer, the catalyst has a structure shown in a formula (II):
wherein R is 4 And R 5 Are each independently a hydrogen atom or an alkyl group, n 1 And n 2 Are each independently an integer from 2 to 4. For example, the catalyst of formula (II) may be, but is not limited to, a catalyst having a structure represented by any one of formula (II-1) and formula (II-2), wherein the catalyst of formula (II-1) is 2, 2-dimorpholinodiethyl ether, and the catalyst of formula (II-2) is bis [2- (2, 6-dimethylmorpholinyl) ethyl) ether.
In the reactive monomers of the polymer prepolymer, the hydrophobic filler may be selected from hydrophobic calcium carbonate, hydrophobic silica, hydrophobic talc, hydrophobic clay, or mixtures thereof. In addition, the reactive monomer of the polymer prepolymer may further comprise an additive, and the additive may be an antioxidant.
< examples and comparative examples >
The polyisocyanates used in the examples/comparative examples and their isocyanate group contents are shown in table one. In Table I, polyisocyanate (Iso-1) is a trimer of a low-viscosity solvent-free aliphatic polyisocyanate: (
N3600) available from Covestro, polyisocyanate (Iso-2) being a trimer of a low viscosity solvent-free aliphatic polyisocyanate (DURANATE) TM TPA-100) purchased from AsahikaSEI, and the polyisocyanate (Iso-3) is diphenylmethane diisocyanate (MILLIONATE NM), which is purchased from TOSOH.
The polyols/polyamines used in the examples/comparative examples and their hydroxyl/amine values and molecular weights are shown in table two. In Table two, the polyol (Poly-1) is a polycarbonate-polyether copolymer diol (C1)
CPX-2520-56) available from aramco, polyol (Poly-2) is polycarbonate Diol (DURANOL) TM T5652) from AsahikaSEI, polyol (Poly-3) is a low monofunctional, highly reactive polyether diol (C: (C)
4220N) which was purchased from Covestro, polyol (Poly-4)Is a low monofunctional polyether copolymer diol (VARANOL 1000 LM) available from DOW and the polyamine (Poly-5) is a polyoxypropylene diamine: (VARANOL 1000 LM)
D-4000) which was purchased from Huntsman, polyol (Poly-6) was Poly (1, 4-butylene adipate) diol (P-2420) which was purchased from Nissner chemical, and polyol (Poly-7) was Poly (ethylene adipate) 1, 4-butylene glycol diol (P-2720) which was purchased from Nissner chemical.
The stabilizers used in the examples/comparative examples and their structural formulas are shown in table three. In Table III, stabilizer (Add-1) was N-ethyl-p-toluenesulfonamide, stabilizer (Add-2) was N- (2-hydroxypropyl) benzenesulfonamide, and stabilizer (Add-3) was N-butylbenzenesulfonamide, all of which were purchased from Merck KGaA.
Examples/comparative examples the hydrophobic filler (Add-4) used was a fatty acid surface-treated light calcium carbonate (calcium carbonate)
CCR-S) purchased from Shiraishi-Omya GmbH, while the hydrophobic filler (Add-5) is a hydrophobic silica (A) (C)
R972) purchased from EVONIK.
Example/comparative example 2, 2-Dimorpholinodiethyl ether (Add-6) was used as the catalyst
DMDEE), which was purchased from Huntsman.
The additive (Add-7) used in examples/comparative examples was pentaerythrityl tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate (B)
1010 Purchased from BASF).
< preparation of liquid reactive polyurethane adhesive >
The liquid reactive polyurethane adhesives of examples 1 to 4 of the present invention were prepared according to the components and weight ratio of table four. Firstly, accurately weighing polyol/polyamine, a stabilizer, a hydrophobic filler, a catalyst and an additive according to the content of the fourth component, putting the polyol/polyamine, the stabilizer, the hydrophobic filler, the catalyst and the additive into a reaction container, heating to 115-120 ℃, carrying out vacuum dehydration for 1.5 hours, then cooling to 55-60 ℃, adding polyisocyanate according to the content of the fourth component, heating to 80-85 ℃, reacting for 2 hours, testing NCO%, cooling to 55-60 ℃ after compliance, and packaging to obtain a polyurethane prepolymer, namely the liquid reaction polyurethane adhesive.
The liquid reactive polyurethane adhesives of comparative examples 1 to 6 of the present invention were prepared according to the composition and weight ratio of table five. The remaining steps are the same as in examples 1 to 4.
< evaluation measurement method >
Measurement of viscosity: the obtained liquid reactive polyurethane adhesive was oven-set at 25 ℃ and then measured for viscosity by a rotary viscometer (Brookfield viscometer) according to the standard method of ASTM 2196.
Determination of the isocyanate group content (NCO%): di-n-butylamine (dibutyl amine) was dissolved in dimethylformamide (dimethyl formamide) to react with isocyanate groups (-NCO) in the liquid reactive polyurethane adhesive, and the excess di-n-butylamine was titrated with hydrochloric acid standard solution (hydrochloric acid) to determine the isocyanate group content in the sample, in wt%.
Determination of the molar ratio of isocyanate groups to hydroxyl groups of the polyol (NCO/OH): and (3) detecting the OH value of each polyalcohol by an acid-base titration method, and calculating the mole number of OH according to a formula. The isocyanate group content is converted to a number of moles, and the number of moles of the isocyanate group is divided by the number of moles of OH to obtain a ratio of the number of moles of the isocyanate group to the number of moles of the hydroxyl group of the polyol.
And (3) testing the gel opening rate by soaking: after the liquid reactive polyurethane adhesive is attached to a structural carpenter, the carpenter is immersed in room temperature water (10 ℃ to 25 ℃) for 24 hours, and then is left to dry (70 ℃) for 24 hours.
Boiling water test of the gel opening rate: after the liquid reactive polyurethane adhesive is attached to a structural carpenter, the carpenter is immersed in boiled water (100 ℃) for 4 hours, then immersed in room-temperature water (10 ℃ to 25 ℃) for 1 hour, and finally placed and dried (70 ℃) for 24 hours.
And (3) testing the gel opening rate by pressurization and decompression: after the liquid reaction type polyurethane adhesive is attached to a structural carpenter, the structural carpenter is immersed into room temperature water (10 ℃ to 25 ℃) at the pressure of 0.085MPa for 5 minutes, then the pressure is changed to 0.51MPa for 1 hour, and after secondary circulation, the structural carpenter is placed and dried (70 ℃) for 24 hours.
The operation time is as follows: the time from the very beginning of the application of glue to the final complete pressing.
Pressurizing time: the time from the start of pressurization to the release of pressure.
Viscosity stability: the mixture was left at ambient temperature of 70 ℃ for 5 days and the viscosity was measured with a rotary viscometer (Brookfield viscometer).
When the liquid reaction type polyurethane adhesive is used for carrying out a bonding test under different environments with structural woodworkers, the glue opening rate is required to be less than 5%, the operation time is required to be less than 10 minutes, the pressurization time is required to be less than 25 minutes, and the viscosity stability of the liquid reaction type polyurethane adhesive is required to be less than 35000cps to meet the standard. Additionally, the substrate of the structural carpentry may be juniper, redwood, cedar, or radial wood.
The liquid reaction type polyurethane adhesives of examples 1 to 4 were subjected to the above-described evaluation measurement method, and the results are recorded in table six.
The liquid reaction type polyurethane adhesives of comparative examples 1 to 6 were subjected to the above-described evaluation measurement method, and the results are recorded in table seven.
From the results of the above tables four to seven, the following analyses were made for the differences between examples 1 to 4 and comparative examples 1 to 6.
The functionality of the polyisocyanate in the comparative example 1 is equal to 2, and when the polyisocyanate used in the present case is used for a bonding test with a structural carpenter, the adhesive splitting rate is far more than 5% due to insufficient crosslinking of the adhesive under the environments of immersion, boiling water and pressurization and decompression, so that the polyisocyanate cannot be applied to structural carpenter bonding.
The polyols of comparative examples 2 and 3 are polyester polyols, which have no hydrolysis resistance and are liable to cause physical deterioration due to hydrolysis, and the liquid reactive polyurethane adhesive of comparative example 2 has too high crystallinity, and the prepolymer thereof is solid at room temperature and has no tackiness, and thus cannot be subjected to a bonding test with a structural carpenter. However, the crystallinity of the polyol in the liquid reactive polyurethane adhesive of comparative example 3 is low, the prepolymer can still flow at normal temperature, but when the adhesive is tested by a structural carpenter, the adhesive release rate is much greater than 5% under the environment of soaking, boiling water and pressurization and decompression, and the adhesive cannot be applied to the structural carpenter adhesion.
Comparative example 4, which is not added with a stabilizer, has poor viscosity stability when stored in a high temperature environment, and the poor stability cannot ensure that the product is delivered to the client and still meets the specification within the shelf life, so that the product cannot be a commercial product.
In comparative example 5, no hydrophobic filler was added, and when the adhesive was tested in conjunction with structural carpentry, the adhesive layer was shrunk and creeped in boiling water and under pressure and pressure, and the adhesive-breaking rate was much greater than 5%, which was not applicable to structural carpentry.
In comparative example 6, no catalyst is added, and the operation time and the pressurization time are too long when the bonding test is performed with a structural carpenter, so that the overall process time is too long, and the use requirement of a client is not met.
In summary, it can be seen that the liquid reactive polyurethane adhesive without the stabilizer, hydrophobic filler, and catalyst of the present invention and with the polyisocyanate and polyol of the present invention can not be applied to structural woodworking. Therefore, when the liquid reactive polyurethane adhesives of embodiments 1 to 4 of the present invention are bonded to structural carpentry, the adhesive release rate is less than 5% at different temperatures and pressures, which means that the adhesive strength is high and the weather resistance is good, and the liquid reactive polyurethane adhesives are liquid adhesives, which do not need to be compounded and have good workability. In addition, compared with the traditional structural carpentry adhesive, the gluing amount of the liquid reactive polyurethane adhesive is 140-220 g/m 2 Lower than that of the traditional structure for carpentersThe adhesive has no formaldehyde and solvent, meets VOC emission standard and various building safety standard tests, is suitable for being applied to structural woodwork adhesives, and becomes a new generation of environment-friendly building materials.
Although the present invention has been described with reference to particular embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (12)
1. A liquid reactive polyurethane adhesive comprising:
a polyurethane prepolymer, wherein the polyurethane prepolymer is terminated with isocyanate groups and is obtained by polymerization reaction, and the reaction monomers of the polymerization reaction comprise:
a polyisocyanate having a functionality of 2.4 to 3;
a polyol having a molecular weight of 1000 to 8000 and having hydrolysis resistance;
a stabilizer having a structure according to formula (I):
wherein R is 1 、R 2 、R 3 Are each independently a hydrogen atom or a monovalent organic group;
a catalyst having a structure as shown in formula (II):
wherein R is 4 And R 5 Are each independently a hydrogen atom or an alkyl group, n 1 And n 2 Are each independently an integer from 2 to 4; and
a hydrophobic filler.
2. The liquid reactive polyurethane adhesive of claim 1, wherein the polyisocyanate is selected from the group consisting of aromatic polyisocyanate, aliphatic polyisocyanate, cycloaliphatic polyisocyanate, and mixtures thereof.
3. The liquid reactive polyurethane adhesive of claim 1, wherein the polyol is selected from polycarbonate polyol, polyether polyol or a mixture thereof.
4. The liquid reactive polyurethane adhesive of claim 1, wherein the hydrophobic filler is selected from hydrophobic calcium carbonate, hydrophobic silica, hydrophobic talc, hydrophobic clay, or a mixture thereof.
5. The liquid reactive polyurethane adhesive of claim 1, wherein the reactive monomer of the polyurethane prepolymer further comprises a polyamine having a molecular weight of 1000 to 8000.
6. The liquid reactive polyurethane adhesive according to claim 1, wherein the polyisocyanate is contained in an amount of 40 to 70 parts by weight, based on 100 parts by weight of the total reaction monomers.
7. The liquid reactive polyurethane adhesive according to claim 1, wherein the polyol is contained in an amount of 30 to 60 parts by weight, based on 100 parts by weight of the total reaction monomers.
8. The liquid reactive polyurethane adhesive according to claim 5, wherein the total content of the polyol and the polyamine is 30 to 60 parts by weight based on 100 parts by weight of the total reaction monomers.
9. The liquid reactive polyurethane adhesive according to claim 1, wherein the stabilizer is contained in an amount of 0.01 to 3 parts by weight, based on 100 parts by weight of the total reaction monomers.
10. The liquid reactive polyurethane adhesive according to claim 1, wherein the catalyst is contained in an amount of 0.01 to 3 parts by weight, based on 100 parts by weight of the total weight of the reactive monomers.
11. The liquid reactive polyurethane adhesive according to claim 1, wherein the hydrophobic filler is contained in an amount of 0.5 to 5 parts by weight, based on 100 parts by weight of the total reaction monomers.
12. The liquid reactive polyurethane adhesive according to claim 1, wherein the reactive monomer of the polyurethane prepolymer further comprises an additive, and the additive is an antioxidant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6309507B1 (en) * | 1999-03-01 | 2001-10-30 | Nippon Polyurethane Industry Co., Ltd. | Polyisocyanate curing agent for laminate adhesive laminate adhesive comprising the same and its use |
| CN1871185A (en) * | 2003-10-31 | 2006-11-29 | 伊利诺斯器械工程公司 | Polyurethane adhesive for masonry construction |
| JP5011933B2 (en) * | 2005-11-21 | 2012-08-29 | Ｄｉｃ株式会社 | Moisture-cure polyurethane hot-melt adhesive for wet veneer and cosmetic product using the same |
| US10626212B2 (en) * | 2015-07-06 | 2020-04-21 | Dow Global Technologies Llc | Polyurethane prepolymers |
| CN110551474A (en) * | 2018-06-01 | 2019-12-10 | 日胜化工股份有限公司 | Solvent-free polyurethane adhesive, composite film material and preparation method of composite film material |
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