CN112979902A - Aqueous polyurethane adhesive composition, preparation method and application thereof - Google Patents
Aqueous polyurethane adhesive composition, preparation method and application thereof Download PDFInfo
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- CN112979902A CN112979902A CN202110412188.0A CN202110412188A CN112979902A CN 112979902 A CN112979902 A CN 112979902A CN 202110412188 A CN202110412188 A CN 202110412188A CN 112979902 A CN112979902 A CN 112979902A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a waterborne polyurethane adhesive composition, a preparation method and application thereof. The adhesive composition comprises an aqueous polyurethane dispersion and a compound shown as a formula (I). The adhesive has improved properties, improved hydrolysis resistance, heat resistance, peel strength, etc., and does not suffer from the disadvantages of adhesives known in the art, such as susceptibility to yellowing, difficulty in dispersion, etc. Has wide application prospect in the fields of automobiles, furniture, shoe materials and the like.
Description
Technical Field
The invention relates to a waterborne polyurethane adhesive composition, a preparation method and application thereof.
Background
The traditional solvent-based polyurethane adhesive has wide application and excellent performance, but does not meet the requirement of environmental protection, so that the development of the traditional solvent-based polyurethane adhesive is limited to a certain extent. In recent years, waterborne polyurethanes using water as a solvent have been rapidly developed. The aqueous polyurethane binder is a novel polyurethane system using water as a dispersion medium, and is also called water-dispersed polyurethane. At present, compared with solvent type polyurethane adhesives, although waterborne polyurethane has the advantages of safety, environmental protection, low volatile organic compounds and the like, the waterborne polyurethane still has a plurality of defects in the aspect of performance. Particularly, the waterborne polyurethane adopts polyester polyol as a soft segment, when the waterborne polyurethane is stored in a water phase environment or used in a high-temperature and humid environment, ester groups are easy to hydrolyze to generate carboxylic acid, and the carboxylic acid plays a catalytic role in the hydrolysis process, so that the molecular weight of the polyurethane is finally reduced, and the application performance of the product is also reduced.
The carbodiimide can react with carboxyl, and has the characteristics of environmental protection and low toxicity, so that the hydrolysis resistance of the waterborne polyurethane can be improved. A novel aqueous dispersion adhesive comprising a combination of an aqueous polyurethane dispersion and an aromatic carbodiimide is described in patent CN 102533199B. The composition can improve the heat distortion stability of the aqueous polyurethane adhesive, but problems are encountered in practical use. Compositions using aromatic carbodiimides are prone to undesirable discoloration when exposed to ultraviolet light and are limited in some applications where outdoor use has high color requirements. Aromatic carbodiimides are less reactive and require higher temperatures to function. The aromatic carbodiimide used in the patent is oily solid powder, has poor dispersibility in the aqueous polyurethane, needs to be additionally added with a wetting agent and a dispersing agent, and increases the difficulty of use.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide an adhesive based on an aqueous polyurethane dispersion having improved properties, improved resistance to hydrolysis, heat resistance, peel strength, etc., without the disadvantages of the adhesives known from the prior art, such as easy yellowing, difficult dispersion, etc. Has wide application prospect in the fields of automobiles, furniture, shoe materials and the like.
The invention provides an aqueous polyurethane adhesive composition, which comprises an aqueous polyurethane dispersion and a compound shown as a formula (I),
wherein R is1Is a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms; r2A residue obtained by removing a hydrogen atom from an active hydrogen-containing hydrophilic compound; n is 1 to 10; the hydrophilic compound containing active hydrogen is polymethoxy monohydric alcohol, polymethoxy dihydric alcohol, polymethoxy monoamine, polymethoxy diamine, sulfonic acid hydroxyalkyl ester, sulfonic acid aminoalkyl ester, monohydroxy carboxylic acid or dihydroxy carboxylic acid, and the molecular weight of the hydrophilic compound containing active hydrogen is less than 1000 g/mol.
In one embodiment of the present invention, in the compound represented by the formula (I), R is1The divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms in (b) may be a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms; for example, a divalent aliphatic hydrocarbon group having 6 carbon atoms; and for example- (CH)2)6-。
In one embodiment of the present invention, in the compound represented by the formula (I), R is1The divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms in (b) may be a divalent alicyclic hydrocarbon group having 5 to 13 carbon atoms; for example, a divalent alicyclic hydrocarbon group having 9 to 13 carbon atoms; also for example
In one embodiment of the present invention, in the compound represented by formula (I), the active hydrogen-containing hydrophilic compound is a polymethoxy monohydric alcohol or polymethoxy dihydric alcohol, such as polyethylene glycol monomethyl ether or polypropylene glycol monomethyl ether.
In a certain scheme of the invention, in the compound shown in the formula (I), the molecular weight of the active hydrogen-containing hydrophilic compound may be less than 1000g/mol, for example, 100 to 1000g/mol, and for example, 400 g/mol.
In one embodiment of the present invention, in the compound represented by formula (I), n is generally an integer, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
In one embodiment of the present invention, in the compound represented by the formula (I), R is1Can be a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms (e.g.
)；R2Can be the residue of polyethylene glycol monomethyl ether after hydrogen atoms are removed; n can be 3-7 (e.g., 3, 5, or 7).
In one embodiment of the present invention, the compound represented by formula (I) may have the following structure:
wherein n and R2As described in any aspect of the invention.
In one embodiment of the present invention, the compound represented by formula (I) may have the following structure:
in the compound shown as the formula (B), R2The compound is a residue of polyethylene glycol monomethyl ether after hydrogen atoms are removed, and the molecular weight of the polyethylene glycol monomethyl ether is 400 g/mol;
in the compound shown as the formula (C), R2The compound is a residue of polyethylene glycol monomethyl ether after hydrogen atoms are removed, and the molecular weight of the polyethylene glycol monomethyl ether is 400 g/mol;
in the compound shown as the formula (D), R2The compound is a residue of polyethylene glycol monomethyl ether after hydrogen atoms are removed, and the molecular weight of the polyethylene glycol monomethyl ether is 400 g/mol;
in the compound shown as the formula (E), R2After removal of hydrogen atoms for methoxypolyethylene glycolsA residue of polyethylene glycol monomethyl ether having a molecular weight of 400 g/mol;
in the compound shown as the formula (F), R2Is residue of polypropylene glycol monomethyl ether after hydrogen atoms are removed, and the molecular weight of the polypropylene glycol monomethyl ether is 400 g/mol;
in the compound shown as the formula (G), R2The molecular weight of the polyethylene glycol monomethyl ether is 400g/mol, and the residue is the residue of the polyethylene glycol monomethyl ether after hydrogen atoms are removed.
In one embodiment of the invention, the mass ratio of the aqueous polyurethane dispersion to the compound represented by the formula (I) can be (22.5-497.5): 1; for example (22.5-497.5) 1; also for example 22.5:1, 47.5:1, 122.5:1, 247.5:1 or 497.5: 1.
In one embodiment of the present invention, the content of the compound represented by formula (I) may be a content conventionally used in such adhesives in the art. The content of the compound shown in the formula (I) preferably in the invention can be 0.04-4 wt%; for example, from 0.2% to 4% by weight; also for example 0.2 wt%, 0.4 wt%, 0.8 wt%, 2 wt% or 4 wt%; the wt% refers to the percentage of the compound shown in the formula (I) in the total mass of the waterborne polyurethane adhesive composition.
In one embodiment of the present invention, the compound represented by formula (I) may be present in the form of an aqueous dispersion. In the aqueous dispersion of the compound shown in the formula (I), the mass ratio of the compound shown in the formula (I) to water can be (0.25-4) to 1; e.g., (0.25-1.5) 1; and for example 2: 3.
In one embodiment of the invention, the aqueous dispersion of the compound of formula (I) may be present in an amount conventionally used in such adhesives in the art. The content of the aqueous dispersion of the compound shown in the formula (I) in the invention can be 0.1-10 wt%; for example, from 0.5% to 5% by weight; also for example 0.5 wt%, 1 wt%, 2 wt%, 5 wt% or 10 wt%; the wt% refers to the percentage of the water dispersion of the compound shown in the formula (I) in the total mass of the waterborne polyurethane adhesive composition.
In a certain aspect of the present invention, the aqueous polyurethane dispersion may include a soft segment polyol structure of one or more of a polyester polyol, a polyether polyol, and a polyolefin polyol; such as polyester polyols.
In one embodiment of the present invention, the aqueous polyurethane dispersion may include a hard segment diisocyanate structure of one or more of aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate; such as aliphatic and/or cycloaliphatic diisocyanates.
In a certain aspect of the present invention, the aqueous polyurethane dispersion may be cationic polyurethane, anionic polyurethane, nonionic polyurethane; for example, anionic polyurethanes, preferably carboxylate-modified and/or sulfonate-modified polyurethanes (e.g., commercially available Dispercoll U53).
In one aspect of the invention, the aqueous polyurethane adhesive composition does not contain a wetting agent and/or a dispersant.
In one embodiment of the present invention, the compound represented by formula (I) can be prepared by a method conventional in the art; for example, the compound shown in the formula (I) is prepared by the following preparation method:
step i, carrying out polycondensation reaction on the compound shown as the formula (2) under the condition of a catalyst to obtain a compound shown as the formula (3); and
step ii, carrying out end-capping reaction on the compound shown as the formula (3) to obtain a compound shown as a formula (I), wherein an end-capping reagent in the end-capping reaction is R2H；
Wherein each group is as defined above.
In a certain embodiment of the present invention, in the preparation method of the compound represented by formula (I), in step I, the catalyst may be a catalyst conventional in such reactions in the art, and is preferably an organic phosphorus compound; for example, one or more of 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 1-methyl-3-chloro-2-phospholene-1-oxide; as another example, 3-methyl-1-phenyl-2-phospholene-1-oxide.
In a certain embodiment of the present invention, in the preparation method of the compound represented by formula (I), in step I, the amount of the catalyst can be the amount of the catalyst conventional in such reactions in the art, such as 200-10000 ppm; further for example 2000 ppm; ppm means parts per million by mass of the catalyst relative to the compound represented by the formula (2).
In a certain embodiment of the present invention, in the preparation method of the compound represented by formula (I), in step I, the temperature of the polycondensation reaction may be a temperature conventional in the art, such as 120-200 ℃; for example, 135-.
In one embodiment of the present invention, in the preparation method of the compound represented by formula (I), in step I, the time of the polycondensation reaction can be monitored by a conventional test method in the art. The time of the polycondensation reaction can be 5 to 24 hours; for example 5 hours, 6 hours, 8 hours, 12 hours or 24 hours.
In a certain embodiment of the invention, in the preparation method of the compound represented by the formula (I), in the step I, the polycondensation reaction is preferably performed under the protection of an inert gas; the inert gas may be nitrogen.
In a certain embodiment of the present invention, in the preparation method of the compound represented by formula (I), in step I, the polycondensation reaction may be performed under stirring conditions.
In a certain embodiment of the present invention, in the preparation method of the compound represented by the formula (I), in the step ii, the molar ratio of the end-capping agent to the compound represented by the formula (3) may be (2-2.2): 1; such as 2: 1.
In a certain embodiment of the present invention, in the preparation method of the compound represented by formula (I), in step ii, the temperature of the end-capping reaction may be a temperature conventional in the art for such a reaction, for example, 80 to 140 ℃; for example, 120 deg.c.
In a certain aspect of the present invention, when the compound represented by the formula (I) is the compound represented by the formula (B) described above, the compound represented by the formula (B) may be prepared by the following preparation method:
step i, carrying out polycondensation reaction on hexamethylene diisocyanate at 160 ℃ for 6 hours under the condition of a catalyst to obtain a carbodiimide prepolymer with the polymerization degree of 3; the catalyst is 3-methyl-1-phenyl-2-phospholene-1-oxide, and the dosage of the catalyst is 2000 ppm; and
step ii, carrying out end-capping reaction on the carbodiimide prepolymer obtained in the step i at 120 ℃ for 2 hours until the content of-NCO residue is 0, and obtaining a compound shown as a formula (B); the end-capping reagent is polyethylene glycol monomethyl ether (for example, the molecular weight is 400g/mol), and the molar ratio of the end-capping reagent to the carbodiimide prepolymer is 2: 1.
In a certain aspect of the present invention, when the compound represented by the formula (I) is the compound represented by the formula (C) described above, the compound represented by the formula (C) may be prepared by the following preparation method:
step i, under the condition of a catalyst, performing polycondensation reaction on dicyclohexylmethane diisocyanate at 160 ℃ for 12 hours to obtain a carbodiimide prepolymer with the polymerization degree of 3; the catalyst is 3-methyl-1-phenyl-2-phospholene-1-oxide, and the dosage of the catalyst can be 2000 ppm; and
step ii, carrying out end-capping reaction on the carbodiimide prepolymer obtained in the step i at 120 ℃ for 2 hours until the content of-NCO residue is 0, and obtaining a compound shown as a formula (C); the end-capping reagent is polyethylene glycol monomethyl ether (for example, the molecular weight is 400g/mol), and the molar ratio of the end-capping reagent to the carbodiimide prepolymer is 2: 1.
In a certain aspect of the present invention, when the compound represented by the formula (I) is the compound represented by the formula (D) described above, the compound represented by the formula (D) may be prepared by the following preparation method:
step i, carrying out polycondensation reaction on dicyclohexylmethane diisocyanate at 160 ℃ for 15 hours under the condition of a catalyst to obtain a carbodiimide prepolymer with the polymerization degree of 5; the catalyst is 3-methyl-1-phenyl-2-phospholene-1-oxide, and the dosage of the catalyst can be 2000 ppm; and
step ii, carrying out end-capping reaction on the carbodiimide prepolymer obtained in the step i at 120 ℃ for 2 hours until the content of-NCO residue is 0, and obtaining a compound shown as a formula (D); the end-capping reagent is polyethylene glycol monomethyl ether (for example, the molecular weight is 400g/mol), and the molar ratio of the end-capping reagent to the carbodiimide prepolymer is 2: 1.
In a certain aspect of the present invention, when the compound represented by the formula (I) is the compound represented by the formula (E) described above, the compound represented by the formula (E) may be prepared by the following preparation method:
step i, carrying out polycondensation reaction on dicyclohexylmethane diisocyanate at 160 ℃ for 18 hours under the condition of a catalyst to obtain a carbodiimide prepolymer with the polymerization degree of 7; the catalyst is 3-methyl-1-phenyl-2-phospholene-1-oxide, and the dosage of the catalyst can be 2000 ppm; and
step ii, carrying out end-capping reaction on the carbodiimide prepolymer obtained in the step i at 120 ℃ for 2 hours until the content of-NCO residue is 0, and obtaining a compound shown as a formula (E); the end-capping reagent is polyethylene glycol monomethyl ether (for example, the molecular weight is 400g/mol), and the molar ratio of the end-capping reagent to the carbodiimide prepolymer is 2: 1.
In a certain aspect of the present invention, when the compound represented by the formula (I) is the compound represented by the formula (F) described above, the compound represented by the formula (F) may be prepared by the following preparation method:
step i, under the condition of a catalyst, performing polycondensation reaction on dicyclohexylmethane diisocyanate at 160 ℃ for 12 hours to obtain a carbodiimide prepolymer with the polymerization degree of 3; the catalyst is 3-methyl-1-phenyl-2-phospholene-1-oxide, and the dosage of the catalyst can be 2000 ppm; and
step ii, carrying out end-capping reaction on the carbodiimide prepolymer obtained in the step i at 120 ℃ for 2 hours until the content of-NCO residue is 0, and obtaining a compound shown as a formula (F); the end-capping reagent is polypropylene glycol monomethyl ether (for example, the molecular weight is 400g/mol), and the molar ratio of the end-capping reagent to the carbodiimide prepolymer is 2: 1.
In a certain aspect of the present invention, when the compound represented by the formula (I) is the compound represented by the formula (G) described above, the compound represented by the formula (G) may be prepared by the following preparation method:
step i, carrying out polycondensation reaction on dicyclohexylmethane diisocyanate at 135 ℃ for 10 hours under the condition of a catalyst to obtain a carbodiimide prepolymer with the polymerization degree of 3; the catalyst is 3-methyl-1-phenyl-2-phospholene-1-oxide, and the dosage of the catalyst can be 2000 ppm; and
step ii, carrying out end-capping reaction on the carbodiimide prepolymer obtained in the step i at 120 ℃ for 2 hours until the content of-NCO residue is 0, and obtaining a compound shown as a formula (G); the end-capping reagent is polyethylene glycol monomethyl ether (for example, the molecular weight is 400g/mol), and the molar ratio of the end-capping reagent to the carbodiimide prepolymer is 2: 1.
The present invention also provides a method for preparing the aqueous polyurethane adhesive composition, which comprises the following steps: and (2) mixing the compound shown as the formula (I) with the aqueous polyurethane dispersion to obtain the aqueous polyurethane adhesive composition.
The invention also provides application of the aqueous polyurethane adhesive composition as an adhesive in the manufacture of automobiles, furniture and shoe materials.
In the present invention, the term "divalent aliphatic hydrocarbon group" means a straight-chain or branched alkylene, alkenylene or alkynylene group, such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-ethyltrimethylene, 1-methyltetramethylene, vinylene, propenylene, ethynylene, and the like.
In the present invention, the term "divalent alicyclic hydrocarbon group" means a divalent cyclic hydrocarbon group having properties similar to those of an aliphatic group, such as cycloalkylene, cycloalkenylene, or cycloalkynylene.
In the present invention, the term "residue of an active hydrogen-containing hydrophilic compound from which a hydrogen atom has been removed" means a residue of the active hydrogen-containing hydrophilic compound from which a hydrogen contained in a functional group has been removed. For example, polyethylene glycol monomethyl etherThe residue after removal of a hydrogen atom may have the structure
The residue of polypropylene glycol monomethyl ether from which a hydrogen atom has been removed may have the structure
Wherein x and y can be determined from the molecular weight of the polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the aqueous polyurethane adhesive composition of the invention can improve the performances of hydrolysis resistance, heat resistance, peeling strength and the like on the basis of the original performances.
(2) The carbodiimide in the invention is aliphatic or alicyclic carbodiimide which is modified by hydrophile, has better dispersion performance and is not easy to yellow when used outdoors.
(3) The aqueous polyurethane adhesive composition is safe and environment-friendly, has easily obtained raw materials, and has wide application prospect.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The main raw materials and compound sources referred to in the following examples are as follows:
aqueous polyurethane dispersion: dispercoll U53, an anionic polyurethane dispersion with 40% solids content, suitable for use in heat-activated adhesive formulations, available from kochia.
Defoaming agent: BYK-024 available from Pico Chemicals.
Wetting agent: AEROSOL OT-75 available from Cyanid.
Carbodiimide compound a and aqueous dispersion thereof: a carbodiimide based on 2, 4-toluene diisocyanate and having a degree of polymerization of 3, which is prepared by the following steps:
1000g of 2, 4-Toluene Diisocyanate (TDI) was added into a 5L three-necked flask, nitrogen gas was introduced for protection, 2g of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) was added, and the mixture was reacted at 130 ℃ for 6 hours to obtain carbodiimide compound A (810g) having a polymerization degree of about 3 and a molecular weight of 600 g/mol.
9g of wetting agent AEROSOL OT-75 and 10g of defoamer BYK-024 are added into 1065g of water and mixed evenly. The resulting carbodiimide compound was added to the resulting carbodiimide compound with stirring and dissolved sufficiently to obtain an aqueous dispersion of carbodiimide compound A having a solid content of 40%.
Carbodiimide compound B and aqueous dispersion thereof: a polyethylene glycol monomethyl ether (MPEG-400) terminated carbodiimide based on hexamethylene diisocyanate and having a degree of polymerization of 3, the preparation method thereof is as follows:
1000g of Hexamethylene Diisocyanate (HDI) was charged into a 5L three-necked flask, and 2g of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) was introduced under nitrogen protection to react at 160 ℃ for 6 hours to obtain a carbodiimide prepolymer (804g) having a degree of polymerization of about 3. The temperature of the system is reduced to 120 ℃, 1191g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g/mol) is added, the reaction is carried out for 2 hours, and the NCO value of the system is reduced to 0, thereby obtaining 1995g of polycarbodiimide compound B, the molecular weight is 1340 g/mol.
2992g of deionized water was added to the polycarbodiimide compound B while stirring and dissolved sufficiently to obtain a carbodiimide compound B aqueous dispersion having a solid content of 40%.
Carbodiimide compound C and aqueous dispersion thereof: a polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g/mol) terminated carbodiimide with a degree of polymerization of 3 based on dicyclohexylmethane diisocyanate is prepared by the following steps:
1000g of dicyclohexylmethane diisocyanate (HMDI) was added into a 5L three-necked flask, nitrogen gas was introduced for protection, 2g of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) was added, and the mixture was reacted at 160 ℃ for 12 hours to obtain 874g of a carbodiimide prepolymer having a degree of polymerization of about 3. The temperature of the system is reduced to 120 ℃, 763g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g/mol) is added, the reaction lasts for 2 hours, the NCO value of the system is reduced to 0, and 1637g of polycarbodiimide compound C with molecular weight 1716g/mol is obtained.
2455g of deionized water was added to the polycarbodiimide compound C while stirring, and the solution was sufficiently dissolved to obtain a carbodiimide compound C aqueous dispersion having a solid content of 40%.
Carbodiimide compound D and aqueous dispersion thereof: a polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g/mol) terminated carbodiimide with a degree of polymerization of 5 based on dicyclohexylmethane diisocyanate is prepared by the following steps:
1000g of dicyclohexylmethane diisocyanate (HMDI) was added into a 5L three-necked flask, nitrogen gas was introduced for protection, 2g of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) was added, and the mixture was reacted at 160 ℃ for 15 hours to obtain a carbodiimide prepolymer (860g) having a degree of polymerization of about 5. The temperature of the system is reduced to 120 ℃, 509g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g/mol) is added, the reaction lasts for 2 hours, the NCO value of the system is reduced to 0, and 1369g of polycarbodiimide compound D with the molecular weight of 2152g/mol is obtained.
2054g of deionized water was added to the polycarbodiimide compound D while stirring, and the mixture was sufficiently dissolved to obtain an aqueous dispersion of the carbodiimide compound D having a solid content of 40%.
Carbodiimide compound E and aqueous dispersion thereof: a polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g/mol) terminated carbodiimide with a degree of polymerization of 7 based on dicyclohexylmethane diisocyanate is prepared by the following steps:
1000g of dicyclohexylmethane diisocyanate (HMDI) is added into a 5L three-neck flask, nitrogen is introduced for protection, 2g of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) is added, and the reaction is carried out for 18 hours at 160 ℃ to obtain a carbodiimide prepolymer (853g) with the polymerization degree of about 7. The temperature of the system is reduced to 120 ℃, 382g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g/mol) is added, the reaction is carried out for 2 hours, the NCO value of the system is reduced to 0, and 1235g of polycarbodiimide compound E with molecular weight 2588g/mol is obtained.
1852g of deionized water was added to the polycarbodiimide compound E while stirring and dissolved sufficiently to obtain an aqueous dispersion of the carbodiimide compound E having a solid content of 40%.
Carbodiimide compound F and aqueous dispersion thereof: a polypropylene glycol monomethyl ether (MPPG-400, molecular weight 400g/mol) terminated carbodiimide with a degree of polymerization of 3 based on dicyclohexylmethane diisocyanate is prepared by the following steps:
1000g of dicyclohexylmethane diisocyanate (HMDI) was added into a 5L three-necked flask, nitrogen gas was introduced for protection, 2g of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) was added, and the mixture was reacted at 160 ℃ for 12 hours to obtain 874g of a carbodiimide prepolymer having a degree of polymerization of about 3. Reducing the temperature of the system to 120 ℃, adding 763g of polypropylene glycol monomethyl ether (MPPG-400, molecular weight 400g/mol), reacting for 2 hours, and reducing the NCO value of the system to 0 to obtain 1637g of polycarbodiimide compound F, wherein the structure is as follows: the molecular weight is 1716.
2455g of deionized water was added to the polycarbodiimide compound F while stirring, and the resulting solution was dissolved sufficiently to obtain an aqueous dispersion of the carbodiimide compound F having a solid content of 40%.
Carbodiimide compound G and aqueous dispersion thereof: a kind of carbodiimide which is based on isophorone diisocyanate and has a degree of polymerization of 3 and is terminated by polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g/mol), and the preparation method is as follows:
1000g of isophorone diisocyanate (IPDI) is added into a 5L three-neck flask, nitrogen is introduced for protection, 2g of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) is added, and the reaction is carried out for 10 hours at 135 ℃ to obtain carbodiimide prepolymer (851g) with the polymerization degree of about 3. The temperature of the system is reduced to 120 ℃, 900G of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400G/mol) is added, the reaction is carried out for 2 hours, the NCO value of the system is reduced to 0, 1751G of polycarbodiimide compound G is obtained, and the molecular weight is 1556G/mol.
2626G of deionized water was added to the above polycarbodiimide compound G while stirring, and the resulting solution was sufficiently dissolved to obtain an aqueous dispersion of the carbodiimide compound G having a solid content of 40%.
Preparation of aqueous polyurethane adhesive compositions
Example 1:
1 part by mass of an aqueous dispersion of carbodiimide compound B (0.4 part by mass of carbodiimide compound B) and 99 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Example 2:
0.5 parts by mass of an aqueous dispersion of the carbodiimide compound C (0.2 parts by mass of the carbodiimide compound C) and 99.5 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Example 3:
1 part by mass of an aqueous dispersion of the carbodiimide compound C (0.4 part by mass of the carbodiimide compound C) and 99 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Example 4:
2 parts by mass of an aqueous dispersion of the carbodiimide compound C (0.8 part by mass of the carbodiimide compound C) and 98 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Example 5
5 parts by mass of an aqueous dispersion of the carbodiimide compound C (2 parts by mass of the carbodiimide compound C) and 95 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Example 6
10 parts by mass of an aqueous dispersion of the carbodiimide compound C (4 parts by mass of the carbodiimide compound C) and 90 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Example 7:
1 part by mass of an aqueous dispersion of the carbodiimide compound D (0.4 part by mass of the carbodiimide compound D) and 99 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Example 8:
1 part by mass of an aqueous dispersion of the carbodiimide compound E (0.4 part by mass of the carbodiimide compound E) and 99 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Example 9:
1 part by mass of an aqueous dispersion of the carbodiimide compound F (0.4 part by mass of the carbodiimide compound F) and 99 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Example 10:
1 part by mass of an aqueous dispersion of a carbodiimide compound G (0.4 part by mass of the carbodiimide compound G) and 99 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Comparative example 1
1 part by mass of an aqueous dispersion of a carbodiimide compound A (0.4 part by mass of the carbodiimide compound A) and 99 parts by mass of Dispercoll U53 were mixed together and sufficiently stirred uniformly.
Effects of the embodiment
The adhesive compositions of examples 1 to 10 and comparative example 1 were used for peel strength test, hydrolysis resistance test, heat resistance test and yellowing performance test. On the other hand, the aqueous polyurethane adhesive compositions prepared in examples 1 to 10 and comparative example 1 were uniformly applied on the surface of a 150 × 25mm rubber strip which had been treated with a polishing and applying treatment agent, and then activated and dried at 60 ℃, and then pressed and bonded, and then stored at room temperature for 3 days to ensure that the curing reaction was complete.
And (3) testing the peel strength: after the sample is prepared, the temperature is adjusted for 48 hours under the conditions of 23 +/-2 ℃ and the relative humidity of 50% +/-5%, and the test is carried out according to GB/T532 'determination of bonding strength of vulcanized rubber or thermoplastic rubber and fabrics', and the peel strength of the sample strip is tested, wherein the peel speed is 50 mm/min.
And (3) hydrolysis resistance test: after the sample is prepared, the sample is adjusted for 48 hours under the conditions that the temperature is 23 +/-2 ℃ and the relative humidity is 50 +/-5 percent, the sample is placed in a constant temperature and humidity cabinet with the temperature of 70 +/-2 ℃ and the relative humidity of 95 +/-5 percent and aged for 24 hours and then taken out, the sample is adjusted for 24 hours under the conditions that the temperature is 23 +/-2 ℃ and the relative humidity is 50 +/-5 percent, the test is carried out according to GB/T532 'determination of bonding strength of vulcanized rubber or thermoplastic rubber and fabrics', the peeling strength of a sample strip is tested, and the peeling speed is 50 mm/min. The higher the peel strength after aging, the better the hydrolysis resistance of the test specimens.
And (3) testing heat resistance: after the sample is prepared, the temperature is adjusted for 48 hours under the conditions that the temperature is 23 +/-2 ℃ and the relative humidity is 50% +/-5%, the sample is placed in an oven at the temperature of 80 ℃, the upper end of the sample is fixed, a weight of 1kg is hung at the lower end of the sample, and the stripping length of the glue layer within 30min is recorded. The shorter the peel length, the better the heat resistance of the sample.
And (4) testing the yellowing performance: the prepared waterborne polyurethane adhesive composition is poured into a tetrafluoro mold according to the same mass, dried for 12 hours at 60 ℃, and stored for 3 days at room temperature to ensure that the curing reaction is complete. The formed sample piece was taken out of the mold, irradiated with xenon lamp at 60 ℃ and 50% humidity for 120 hours, and tested for yellowness index YI. The higher the yellowness index, the more yellowing the sample is.
The test results are shown in table 1.
TABLE 1
The initial peel strength of the adhesive after carbodiimide addition was significantly improved compared to the blank (containing only Dispercoll U53) (comparative example 1, examples 1-10). The peel strength of the adhesive after addition of the hydrophilic modified aliphatic or alicyclic carbodiimide (examples 1, 3, 7, 8, 10) was higher than that of the adhesive after addition of the aromatic carbodiimide (comparative example 1) at the same addition amount.
After humid heat aging, the adhesive had significantly improved peel strength and maintained a higher maintenance rate after carbodiimide addition than the blank (comparative example 1, examples 1-10). The peel strength after wet heat aging of the adhesive after addition of the hydrophilic modified aliphatic or alicyclic carbodiimide (examples 1, 3, 7, 8, 10) was higher than that of the adhesive after addition of the aromatic carbodiimide (comparative example 1) at the same addition amount.
The heat resistance test results show that the heat resistance of the adhesive is significantly improved and the peel length is greatly shortened after the carbodiimide is added compared to the blank group (comparative example 1, examples 1-10). The heat resistance of the adhesive after addition of the hydrophilic modified aliphatic or alicyclic carbodiimide (examples 1, 3, 7, 8, 10) was superior to that of the adhesive after addition of the aromatic carbodiimide (comparative example 1) at the same addition amount.
After light aging, the coupons with the addition of the aromatic carbodiimide (comparative example 1) turned significantly yellow, while the coupons with the addition of the hydrophilically modified aliphatic or alicyclic carbodiimides (examples 1-10) did not change color significantly.
The carbodiimide compound C has different performance-improving effects on the aqueous polyurethane adhesive when added in different amounts. With increasing amounts of additives (examples 2, 3, 4, 5, and 6), the properties such as peel strength, hydrolysis resistance, and heat resistance tend to increase and then decrease.
For the same synthetic monomer dicyclohexylmethane diisocyanate, the carbodiimide compounds with different polymerization degrees have different performance improvement effects on the aqueous polyurethane adhesive. With the increase in the degree of polymerization (examples 3, 7, and 8), the properties such as peel strength, hydrolysis resistance, and heat resistance tend to increase and then decrease.
With respect to the same synthetic monomer dicyclohexylmethane diisocyanate, the same degree of polymerization 3, carbodiimide compound C (example 3) using polyethylene glycol monomethyl ether (MPEG-400) as a hydrophilic end-capping agent was superior in application effect to carbodiimide compound F (example 9) using polypropylene glycol monomethyl ether (MPPG-400) as a hydrophilic end-capping agent.
The carbodiimide compounds prepared from different synthetic monomers have different performance improving effects on the waterborne polyurethane adhesive. Overall, isophorone diisocyanate (IPDI) (example 10) outperforms dicyclohexylmethane diisocyanate (HMDI) (example 3) outperforms Hexamethylene Diisocyanate (HDI) (example 1).
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (10)
1. An aqueous polyurethane adhesive composition is characterized by comprising an aqueous polyurethane dispersion and a compound shown as a formula (I),
wherein R is1Is a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms; r2A residue obtained by removing a hydrogen atom from an active hydrogen-containing hydrophilic compound; n is 1 to 10; the hydrophilic compound containing active hydrogen is polymethoxy monohydric alcohol, polymethoxy dihydric alcohol, polymethoxy monoamine, polymethoxy diamine, sulfonic acid hydroxyalkyl ester, sulfonic acid aminoalkyl ester, monohydroxy carboxylic acid or dihydroxy carboxylic acid, and the molecular weight of the hydrophilic compound containing active hydrogen is less than 1000 g/mol.
2. The aqueous polyurethane adhesive composition of claim 1, wherein R is1Is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 13 carbon atoms;
and/or the hydrophilic compound containing active hydrogen is polymethoxy monohydric alcohol or polymethoxy dihydric alcohol;
and/or the molecular weight of the active hydrogen-containing hydrophilic compound is 100-1000 g/mol.
3. The aqueous polyurethane adhesive composition of claim 2, wherein R is1Is a divalent aliphatic hydrocarbon group having 6 carbon atoms or a divalent alicyclic hydrocarbon group having 9 to 13 carbon atoms;
and/or the hydrophilic compound containing active hydrogen is polyethylene glycol monomethyl ether or polypropylene glycol monomethyl ether;
and/or the molecular weight of the hydrophilic compound containing active hydrogen is 400 g/mol.
4. The aqueous polyurethane adhesive composition of claim 3, wherein R is1Is- (CH)2)6-、
5. The aqueous polyurethane adhesive composition of claim 1, wherein the compound of formula (I) is present in the form of an aqueous dispersion;
and/or the mass ratio of the aqueous polyurethane dispersion to the compound shown in the formula (I) is (22.5-497.5): 1;
and/or the content of the compound shown in the formula (I) is 0.04 wt% -4 wt%, wherein wt% refers to the percentage of the compound shown in the formula (I) in the total mass of the waterborne polyurethane adhesive composition;
and/or the aqueous polyurethane dispersion comprises a soft segment polyol structure of one or more of polyester polyol, polyether polyol and polyolefin polyol;
and/or the hard segment diisocyanate structure contained in the aqueous polyurethane dispersion is one or more of aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate;
and/or the aqueous polyurethane dispersion is one or more of cationic polyurethane, anionic polyurethane and nonionic polyurethane;
and/or the aqueous polyurethane adhesive composition does not contain a wetting agent and/or a dispersant.
6. The aqueous polyurethane adhesive composition of claim 5,
when the compound shown in the formula (I) exists in the form of aqueous dispersion, the mass ratio of the compound shown in the formula (I) to water in the aqueous dispersion of the compound shown in the formula (I) is (0.25-4): 1; e.g., (0.25-1.5) 1; as another example 2: 3;
and/or, when the compound shown in the formula (I) exists in the form of aqueous dispersion, the content of the aqueous dispersion of the compound shown in the formula (I) is 0.1-10 wt%; for example, from 0.5% to 5% by weight; also for example 0.5 wt%, 1 wt%, 2 wt%, 5 wt% or 10 wt%; the wt% refers to the percentage of the water dispersion of the compound shown in the formula (I) in the total mass of the waterborne polyurethane adhesive composition;
and/or the mass ratio of the aqueous polyurethane dispersion to the compound shown in the formula (I) is (22.5-497.5): 1; yet another example is 22.5:1, 47.5:1, 122.5:1, 247.5:1, or 497.5: 1;
and/or the content of the compound shown in the formula (I) is 0.2-4 wt%; for example 0.2 wt%, 0.4 wt%, 0.8 wt%, 2 wt% or 4 wt%;
and/or the aqueous polyurethane dispersion is carboxylate modified polyurethane and/or sulfonate modified polyurethane; such as commercially available DispercollU 53.
7. The aqueous polyurethane adhesive composition according to any one of claims 1 to 6, wherein the compound of formula (I) is prepared by the following preparation method:
step i, carrying out polycondensation reaction on the compound shown as the formula (2) under the condition of a catalyst to obtain a compound shown as the formula (3); and
step ii, carrying out end-capping reaction on the compound shown as the formula (3) to obtain a compound shown as a formula (I), wherein an end-capping reagent in the end-capping reaction is R2H，
Wherein R is1、R2And n is as defined in any one of claims 1 to 6.
8. The aqueous polyurethane adhesive composition of claim 7,
in the step i, the catalyst is an organic phosphorus compound; for example, one or more of 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 1-methyl-3-chloro-2-phospholene-1-oxide;
and/or, in the step i, the dosage of the catalyst is 200-10000 ppm; for example 2000ppm, ppm means mass parts per million of the catalyst relative to the compound represented by the formula (2);
and/or, in the step i, the temperature of the polycondensation reaction is 120-200 ℃; for example, 135 ℃ and 160 ℃;
and/or in the step i, the time of the polycondensation reaction is 5-24 hours; e.g., 5 hours, 6 hours, 8 hours, 12 hours, or 24 hours;
and/or, in the step ii, the molar ratio of the end-capping reagent to the compound shown in the formula (3) is (2-2.2): 1; for example 2: 1;
and/or, in step ii, the temperature of the end-capping reaction is 80-140 ℃; for example 120 ℃;
and/or, in the step ii, the end capping reaction time is 1-3 hours; for example 2 hours.
9. A method of making the aqueous polyurethane adhesive composition of any one of claims 1-8, comprising the steps of: and (2) mixing the compound shown as the formula (I) with the aqueous polyurethane dispersion to obtain the aqueous polyurethane adhesive composition.
10. Use of an aqueous polyurethane adhesive composition according to any one of claims 1 to 8 as an adhesive in the manufacture of automobiles, furniture, footwear.
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| JP2019085511A (en) * | 2017-11-08 | 2019-06-06 | 三井化学株式会社 | Coating composition and laminate |
| CN110099965A (en) * | 2016-12-27 | 2019-08-06 | 日清纺化学株式会社 | The preparation method of carboxylic aqueous resin composition, formed body and polycarbodiimide compound |
| CN112625202A (en) * | 2019-12-26 | 2021-04-09 | 上海朗亿功能材料有限公司 | Polycarbodiimide crosslinking agent, preparation method and application thereof, and composition containing polycarbodiimide crosslinking agent |
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| US20060194939A1 (en) * | 2002-02-13 | 2006-08-31 | Basf Aktiengesellschaft | Aqueous dispersions consisting of polycarbodiimides |
| CN107099019A (en) * | 2010-04-01 | 2017-08-29 | 科思创德国股份有限公司 | Carbodiimidation method |
| CN110099965A (en) * | 2016-12-27 | 2019-08-06 | 日清纺化学株式会社 | The preparation method of carboxylic aqueous resin composition, formed body and polycarbodiimide compound |
| JP2019085511A (en) * | 2017-11-08 | 2019-06-06 | 三井化学株式会社 | Coating composition and laminate |
| CN112625202A (en) * | 2019-12-26 | 2021-04-09 | 上海朗亿功能材料有限公司 | Polycarbodiimide crosslinking agent, preparation method and application thereof, and composition containing polycarbodiimide crosslinking agent |
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