CN110452654B - Single-component water-based polyurethane adhesive for automobile roof and preparation method thereof - Google Patents
Single-component water-based polyurethane adhesive for automobile roof and preparation method thereof Download PDFInfo
- Publication number
- CN110452654B CN110452654B CN201910796221.7A CN201910796221A CN110452654B CN 110452654 B CN110452654 B CN 110452654B CN 201910796221 A CN201910796221 A CN 201910796221A CN 110452654 B CN110452654 B CN 110452654B
- Authority
- CN
- China
- Prior art keywords
- parts
- acetone
- adhesive
- chain extender
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G18/58—Epoxy resins
-
- 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
- C08G18/65—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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
-
- 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
Abstract
The invention discloses a single-component waterborne polyurethane adhesive for an automobile roof, which comprises the following raw materials in parts by weight: 20-60 parts of polyether polyol with the hydroxyl value of 20-70 mgKOH/g, 50-80 parts of polyester polyol with the hydroxyl value of 30-120 mgKOH/g, 20-70 parts of isocyanate, 3-10 parts of dimethylolpropionic acid, 5-10 parts of primary chain extender, 2-8 parts of triethylamine, 1-8 parts of secondary chain extender, 1-10 parts of epoxy resin, 20-50 parts of acetone and 200-300 parts of water. The invention also discloses a preparation method of the adhesive. The waterborne polyurethane adhesive has better adhesive property; the high-temperature and high-humidity environment with the temperature of 65 +/-2 ℃ and 85 +/-2 percent is resisted; the appearance is not changed when the product is heated to 130 ℃, and the product has better heating resistance; the automobile roof is soaked in normal-temperature water for 48 hours, has no change in appearance, has good water resistance, can meet the use requirements of the automobile roof, and is simple in preparation process.
Description
Technical Field
The invention relates to a water-based polyurethane adhesive and a preparation method thereof, in particular to a single-component water-based polyurethane adhesive for an automobile roof and a preparation method thereof.
Background
Compared with a solvent type polyurethane adhesive, the water-based adhesive has high sanitation and safety performance and does not have solvent residue; water is used as a solvent, and the water does not pollute the environment after being volatilized into the air, so that the water is environment-friendly; the adhesive has higher initial adhesion to different materials; the working environment is improved, the pollution is reduced, the working strength is reduced, and the fire hazard is avoided; the sizing process is simple and convenient and easy to operate; the water-based adhesive has small smell and low toxicity, and meets the requirements of laws and regulations. The waterborne polyurethane adhesive is one of waterborne adhesives, has the advantages of excellent wear resistance, chemical corrosion resistance, good flexibility, good adhesive force, high gloss and the like, and has the characteristics of low content of volatile organic solvent, no toxicity, incombustibility, no peculiar smell, no pollution to the environment, no health hazard to operators and the like.
The aqueous polyurethane automotive interior adhesive can be applied to interior parts of parts such as automobile roofs, carpets, ground mats, instrument panels, door inner panels and the like, the parts are usually formed by compounding multiple layers of non-metal materials in the manufacturing process, and connecting materials in the parts can be bonded by an aqueous polyurethane adhesive or used as surface treatment materials. However, the single-component polyurethane water-based adhesive is rarely used in the automobile roof, mainly because the existing single-component polyurethane water-based adhesive has poor adhesive property and harsh production process conditions, and the automobile roof has high requirements on high temperature resistance and humidity resistance of the adhesive.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems, the invention provides a single-component waterborne polyurethane adhesive which has good bonding performance, high temperature resistance and damp and heat resistance and is used for an automobile ceiling. The invention also aims to provide a preparation method of the adhesive.
The technical scheme is as follows: the single-component waterborne polyurethane adhesive for the automobile roof comprises the following raw materials in parts by weight: 20-60 parts of polyether polyol with the hydroxyl value of 20-70 mgKOH/g, 50-80 parts of polyester polyol with the hydroxyl value of 30-120 mgKOH/g, 20-70 parts of isocyanate, 3-10 parts of dimethylolpropionic acid DMPA, 5-10 parts of primary chain extender, 2-8 parts of triethylamine, 1-8 parts of secondary chain extender, 1-10 parts of epoxy resin, 20-50 parts of acetone and 200-300 parts of water.
Preferably, the polyether polyol contains 5 to 20 mass percent of ethylene oxide, and the content of the ethylene oxide has great influence on the reactivity and the performance of the polyether polyol, and the range is optimal.
Preferably, the starter of the polyester polyol is sebacic acid, isophthalic acid, ethylene glycol or neopentyl glycol.
Preferably, the isocyanate is selected from at least one of toluene diisocyanate TDI and diphenylmethane diisocyanate MDI.
Preferably, the primary chain extender is one or two selected from ethylene glycol, 1, 4-butanediol BDO and trimethylolpropane TMP.
Preferably, the secondary chain extender is selected from one of ethylenediamine, propylenediamine or polyetheramine.
Preferably, the epoxy value of the epoxy resin is 0.2-0.7, and the epoxy value in the range can enable the adhesive to have a better crosslinking degree.
The method for preparing the adhesive comprises the following steps:
(1) carrying out vacuum dehydration treatment on polyether polyol, polyester polyol and epoxy resin at 110-120 ℃, and cooling to 55-65 ℃;
(2) adding isocyanate into the step (1), and carrying out prepolymerization reaction for 60-120 min at 50-80 ℃ to generate a prepolymer;
(3) adding dimethylolpropionic acid into the step (2), reacting at 50-80 ℃ for 60-100 min, adding a primary chain extender, then adding one third of acetone by weight, reacting at 50-80 ℃ for 60-100 min, then adding one third of acetone by weight, and continuing to react for 60-100 min;
(4) cooling the reaction system in the step (3) to 40-60 ℃, adding a secondary chain extender, adding the remaining one third of acetone in parts by weight, stirring for 20-50 min, and adding triethylamine;
(5) and (4) removing acetone in the system obtained in the step (4) to obtain the water-based polyurethane adhesive.
In the steps (3) and (4), the addition amount of acetone is one third of the total weight part, so that the moderate viscosity of the adhesive can be ensured, and the used solvent amount is small.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the initial peel strength of the waterborne polyurethane adhesive prepared by the invention is as high as 5.89N/cm, the final peel strength is as high as 24.59N/cm, and the molecular weight of the adhesive is improved due to the addition of epoxy resin for ring-opening crosslinking in a system, so that the waterborne polyurethane adhesive has better adhesive property; the process of chain extension for the first time and chain extension for the second time is adopted in the preparation of the adhesive, the whole reaction system is stable, the molecular weight distribution of the obtained adhesive is uniform, and the adhesive can resist high-temperature and high-humidity environments of 65 +/-2 ℃ and 85 +/-2%; because the polyester polyol has better hydrophobicity and high glass transition temperature, and the preparation process of chain extension for the first time and chain extension for the second time is adopted, the molecular weight distribution range of the adhesive is narrower, the appearance of the adhesive is unchanged when the adhesive is heated to 130 ℃, the adhesive has better heating resistance, the appearance is unchanged after the adhesive is soaked in normal-temperature water for 48 hours, and the adhesive has better water resistance.
Drawings
FIG. 1 is an infrared spectrum of a polyester polyol;
FIG. 2 is an infrared spectrum of a polyurethane prepolymer.
Detailed Description
The invention is further described below with reference to the figures and examples.
The waterborne polyurethane adhesive comprises the following raw materials in parts by weight: 20-60 parts of polyether polyol with the hydroxyl value of 20-70 mgKOH/g, 50-80 parts of polyester polyol with the hydroxyl value of 30-120 mgKOH/g, 20-70 parts of isocyanate, 3-10 parts of dimethylolpropionic acid, 5-10 parts of primary chain extender, 2-8 parts of triethylamine, 1-8 parts of secondary chain extender, 1-10 parts of epoxy resin, 20-50 parts of acetone and 200-300 parts of water.
Example 1
The raw materials comprise: 30 parts of polyether polyol (polypropylene glycol PPG-2000, the difunctional, the contained ethylene oxide EO percent is 15 percent, and the hydroxyl value is 56mgKOH/g), 70 parts of polyester polyol (polybutylene adipate glycol PBA-2000, the difunctional, the hydroxyl value is 56mgKOH/g), 36.74 parts of toluene diisocyanate, 7.7 parts of dimethylolpropionic acid, 8.01 parts of primary chain extender (7.24 parts of 1, 4-butanediol and 0.77 part of trimethylolpropane), 5.81 parts of triethylamine, 5.25 parts of secondary chain extender propylene diamine, 78 parts of epoxy resin E-512.0 (the epoxy value is 0.51), 23.1 parts of acetone and 240 parts of water.
The raw materials adopted by the invention can be purchased from the market.
The preparation method comprises the following steps:
(1) and (3) dehydrating: adding polyether polyol PPG-200030 g, polyester polyol PBA-200070 g and epoxy resin E-512.0 g into a three-neck flask, dehydrating for 1h under the condition of 110-120 ℃, and then cooling to about 60 ℃;
(2) prepolymerization reaction: dropwise adding TDI-8036.74 g of toluene diisocyanate into the system in the step (1), controlling the dropwise adding time within 30min, wherein the reaction is an exothermic reaction, controlling the temperature to be about 60 ℃ in the dropwise adding process, heating to 70 ℃ after dropwise adding is finished, preserving heat for reacting for 90min, sampling after the reaction is finished, carrying out infrared spectrum detection, and measuring a hydroxyl characteristic peak to ensure complete reaction;
(3) primary chain extension: adding 7.7g of dimethylolpropionic acid DMPA into the system in the step (2), reacting for 60min at a heat preservation temperature of 70 ℃, then dropwise adding 7.24g of mixed solution of 1, 4-butanediol BDO and 0.77g of trimethylolpropane TMP, finishing dropwise adding within 60min, adding 7.7g of acetone after dropwise adding, reacting for 60min at a heat preservation temperature of 70 ℃, then adding 7.7g of acetone, and continuing to react for 60min, wherein the acetone can be properly added by observing the viscosity of the reaction system in the process of dropwise adding the chain extender;
(4) and (3) secondary chain extension: cooling the system in the step (3) to 60 ℃, adding 5.25g of propane diamine, adding 7.7g of acetone according to the stirring condition of the system, stirring for 30min, slowly adding a triethylamine aqueous solution (5.81g of triethylamine is dissolved in 240g of water), neutralizing the triethylamine aqueous solution to 100%, and dispersing at a high speed;
(5) vacuum desolventizing: and (4) heating the system in the step (4) to 65 ℃, carrying out vacuum dehydration and desolventizing, paying attention to the acetone smell in the system in the desolventizing process, and if the acetone smell is still remained after the water part is removed, adding 50g of water to continuously remove the acetone until the system is almost odorless. Then water is added to prepare 40% glue solution.
Example 2
The raw materials comprise: 40 parts of polyether polyol (polypropylene glycol PPG-3000, the difunctional degree, EO percent and hydroxyl value are 7 percent and 37.4mgKOH/g), 60 parts of polyester polyol (polybutylene adipate glycol PBA-1000, the difunctional degree and the hydroxyl value are 112mgKOH/g), 52.81 parts of diphenylmethane diisocyanate, 10.0 parts of dimethylolpropionic acid, 5.65 parts of primary chain extender (4.88 parts of ethylene glycol and 0.77 part of trimethylolpropane), 7.54 parts of triethylamine, 5.53 parts of secondary chain extender ethylenediamine, E-442.0 parts of epoxy resin (0.44 of epoxy value), 23.1 parts of acetone and 264 parts of water.
The raw materials adopted by the invention can be purchased from the market.
The preparation method comprises the following steps:
(1) and (3) dehydrating: adding polyether polyol PPG-300040 g, polyester polyol PBA-100060g and epoxy resin E-442.0 g into a three-neck flask, dehydrating for 1h under the condition of 110-120 ℃, and then cooling to about 60 ℃;
(2) prepolymerization reaction: dropwise adding MDI-5052.81 g of diphenylmethane diisocyanate into the system in the step (1), controlling the dropwise adding time within 30min, wherein the reaction is an exothermic reaction, controlling the temperature to be about 60 ℃ in the dropwise adding process, heating to 70 ℃ after the dropwise adding is finished, carrying out heat preservation reaction for 90min to obtain a polyurethane prepolymer, sampling after the reaction is finished, carrying out infrared spectrum detection, and determining a hydroxyl characteristic peak to ensure complete reaction; FIG. 1 is an infrared spectrum of polyester polyol at 3500cm-1Has hydroxyl absorption peak, and FIG. 2 is infrared spectrogram of 3500cm of polyurethane prepolymer-1The absorption peak of hydroxyl group disappears at 2750cm-1An NCO-group absorption peak appears, which indicates that hydroxyl is consumed, and a polyurethane prepolymer is generated;
(3) primary chain extension: adding 10.0g of dimethylolpropionic acid DMPA into the system in the step (2), reacting for 60min at a heat preservation temperature of 70 ℃, then dropwise adding mixed solution of 4.88g of ethylene glycol EG and 0.77g of trimethylolpropane TMP, completing dropwise adding within 60min, adding 7.7g of acetone after completing dropwise adding, reacting for 60min at a heat preservation temperature of 70 ℃, then adding 7.7g of acetone, and continuing to react for 60min, wherein the acetone can be properly added by observing the viscosity of the reaction system in the process of dropwise adding the chain extender;
(4) and (3) secondary chain extension: cooling the system in the step (3) to 60 ℃, adding 5.53g of ethylenediamine, adding 7.7g of acetone according to the stirring condition of the system, stirring for 30min, slowly adding a triethylamine aqueous solution (7.54g of triethylamine is dissolved in 264g of water), neutralizing the triethylamine aqueous solution to 100%, and dispersing at a high speed;
(5) vacuum desolventizing: and (4) heating the system in the step (4) to 65 ℃, carrying out vacuum dehydration and desolventizing, paying attention to the acetone smell in the system in the desolventizing process, and if the acetone smell is still remained after the water part is removed, adding 50g of water to continuously remove the acetone until the system is almost odorless. Then water is added to prepare 40% glue solution.
Example 3
The raw materials comprise: 30 parts of polyether polyol (polypropylene glycol PPG-1000, the difunctional, the contained ethylene oxide EO percent is 10 percent, and the hydroxyl value is 112mgKOH/g), 70 parts of polyester polyol (polybutylene adipate glycol PBA-2000, the difunctional, the hydroxyl value is 56mgKOH/g), 43.42 parts of toluene diisocyanate, 7.7 parts of dimethylolpropionic acid, 5.65 parts of primary chain extender (4.88 parts of ethylene glycol and 0.77 part of trimethylolpropane), 5.25 parts of triethylamine, 1.68 parts of secondary chain extender propylene diamine, 511.0 parts of epoxy resin E (0.51 of epoxy value), 23.1 parts of acetone and 240 parts of water.
The raw materials adopted by the invention can be purchased from the market.
The preparation method comprises the following steps:
(1) and (3) dehydrating: adding polyether polyol PPG-100030 g, polyester polyol PBA-200070 g and epoxy resin E-511.0 g into a three-neck flask, dehydrating for 1h under the condition of 110-120 ℃, and then cooling to about 60 ℃;
(2) prepolymerization reaction: dropwise adding TDI-8043.42 g of toluene diisocyanate into the system in the step (1), controlling the dropwise adding time within 30min, wherein the reaction is an exothermic reaction, controlling the temperature to be about 60 ℃ in the dropwise adding process, heating to 70 ℃ after dropwise adding is finished, preserving heat for reacting for 90min, sampling after the reaction is finished, carrying out infrared spectrum detection, and measuring a hydroxyl characteristic peak to ensure complete reaction;
(3) primary chain extension: adding 7.7g of dimethylolpropionic acid DMPA into the system in the step (2), reacting for 60min at a temperature of 70 ℃, then dropwise adding a mixed solution of 4.88g of ethylene glycol and 0.77g of trimethylolpropane TMP, completing dropwise adding within 60min, adding 7.7g of acetone after completing dropwise adding, reacting for 60min at a temperature of 70 ℃, then adding 7.7g of acetone, and continuing to react for 60min, wherein the acetone can be properly added by observing the viscosity of the reaction system in the process of dropwise adding the chain extender;
(4) and (3) secondary chain extension: cooling the system in the step (3) to 60 ℃, adding 1.68g of propane diamine, adding 7.7g of acetone according to the stirring condition of the system, stirring for 30min, slowly adding a triethylamine aqueous solution (5.25g of triethylamine is dissolved in 240g of water), neutralizing the triethylamine aqueous solution to 100%, and dispersing at a high speed;
(5) vacuum desolventizing: and (4) heating the system in the step (4) to 65 ℃, carrying out vacuum dehydration and desolventizing, paying attention to the acetone smell in the system in the desolventizing process, and if the acetone smell is still remained after the water part is removed, adding 50g of water to continuously remove the acetone until the system is almost odorless. Then water is added to prepare 40% glue solution.
Comparative example 1
The raw material composition does not contain epoxy resin E-44, and other components and preparation method are the same as example 2.
Comparative example 2
The raw materials of the composition of dimethylolpropionic acid 12.0 parts, triethylamine 9.05 parts, other components and preparation method are the same as example 2.
Comparative example 3
The composition of the raw materials was the same as that of example 2.
The preparation method comprises the following steps:
(1) and (3) dehydrating: adding polyether polyol PPG-300040 g, polyester polyol PBA-100060g, epoxy resin E-442.0 g, dimethylolpropionic acid DMPA 10.0g, ethylene glycol EG 4.88g and trimethylolpropane TMP0.77g into a three-neck flask, dehydrating for 1h under the condition of 110-120 ℃, and then cooling to about 60 ℃;
(2) prepolymerization reaction: dropwise adding MDI-5052.81 g of diphenylmethane diisocyanate into the system in the step (1), controlling the dropwise adding time within 30min, wherein the reaction is an exothermic reaction, controlling the temperature to be about 60 ℃ in the dropwise adding process, heating to 70 ℃ after the dropwise adding is finished, and carrying out heat preservation reaction for 90min to obtain a polyurethane prepolymer;
(3) chain extension: cooling the system in the step (2) to 60 ℃, adding 5.53g of ethylenediamine, adding 7.7g of acetone according to the stirring condition of the system, stirring for 30min, slowly adding a triethylamine aqueous solution (7.54g of triethylamine is dissolved in 264g of water), neutralizing the triethylamine aqueous solution to 100%, and dispersing at a high speed;
(4) vacuum desolventizing: and (3) heating the system in the step (3) to 65 ℃, carrying out vacuum dehydration and desolventizing, paying attention to the acetone smell in the system in the desolventizing process, and if the acetone smell is still remained in the water part, adding 50g of water to continuously remove the acetone till the system is almost odorless. Then water is added to prepare 40% glue solution.
The properties of the aqueous polyurethane adhesives prepared in examples and comparative examples and commercially available aqueous polyurethane adhesives, including solid content, adhesive property, high temperature and high humidity resistance, heat resistance and water resistance, were compared, and the results of the measurements are shown in Table 1. The measurement of the bonding performance is reflected by the peel strength, and the measurement of the initial peel strength is that firstly the waterborne polyurethane adhesive is coated on a PVC film, the PVC film is baked at 60 ℃ and then placed at normal temperature for 1h, and then the test is carried out according to GB-T2791-; the final peel strength was determined by first coating a waterborne polyurethane adhesive on a PVC film, baking at 60 ℃ and then standing at room temperature for 24 hours, and then testing according to GB-T2791-1995. The heat resistance is measured by placing the sheet in a constant temperature and humidity box with the temperature of 130 ℃ and the temperature of 50% for 2h, observing the appearance, measuring the initial peel strength and the final peel strength, and if the appearance is not damaged and degummed and the deviation is within 10%, the high temperature resistance test is passed. The water resistance is measured by immersing in water at 40 ℃ for 48 hours, observing the appearance, and measuring the initial peel strength and the final peel strength, and if the appearance is not damaged and degummed and the deviation is within 20%, the water resistance test is passed.
TABLE 1 Properties of the aqueous polyurethane adhesives prepared and marketed by the examples and comparative examples
The waterborne polyurethane adhesive prepared by the invention has better high temperature and high humidity resistance (65 +/-2 ℃ and 85 +/-2%), has no change in appearance when heated to 130 ℃, and has better heating resistance; the adhesive has good water resistance and good bonding performance after being soaked in normal temperature water for 48 hours, the initial peel strength of the adhesive in the best embodiment 2 is up to 5.89N/cm, the final peel strength is up to 24.59N/cm, and the adhesive can be used for automobile roofs.
Comparing example 2 with comparative example 1, the initial peel strength and final peel strength of the waterborne polyurethane adhesive of example 2 are obviously higher than those of comparative example 1, because the epoxy resin is added in the examples, the waterborne polyurethane adhesive has better cohesiveness, and the ring is opened in a system for crosslinking, so that the molecular weight of the prepared adhesive is improved, and the adhesive property of the adhesive can be effectively improved. Comparing example 2 with comparative example 2, the dimethylolpropionic acid in comparative example 2 is 12 parts, which is greater than the maximum 10 parts defined by the content of the invention, and with the increase of the dimethylolpropionic acid content, the hydrophilic groups in the system are increased, so that the hydrophilicity is improved, the adhesive is easy to absorb water, the hydrolysis resistance is poor, and therefore, the adhesive in comparative example 2 cannot pass the high temperature and high humidity resistance test and the water resistance test. Comparing example 2 with comparative example 3, in comparative example 3, when the adhesive is prepared, the polyester polyol, the polyether polyol and the cross-linking agent are mixed together to perform a prepolymerization reaction, and then a chain extension reaction is performed, compared with the primary chain extension and the secondary chain extension reaction in example 2, although the preparation process in comparative example 2 is simplified, the system reaction is too fast, the molecular weight distribution of the adhesive is not uniform, and the high temperature and high humidity resistance of the adhesive is affected.
The two commercially available single-component waterborne polyurethane adhesives are respectively subjected to corresponding performance tests, so that the commercially available product 1 cannot pass a high-temperature high-humidity resistance test and a water resistance test, and the commercially available product 2 cannot pass the water resistance test.
Claims (2)
1. The preparation method of the single-component waterborne polyurethane adhesive for the automobile ceiling is characterized in that the adhesive comprises the following raw materials in parts by weight: 40 parts of polyether polyol, 60 parts of polyester polyol, 52.81 parts of isocyanate, 10 parts of dimethylolpropionic acid, 5.65 parts of primary chain extender, 7.54 parts of triethylamine, 5.53 parts of secondary chain extender, 2.0 parts of epoxy resin, 23.1 parts of acetone and 264 parts of water; wherein the polyether polyol is polypropylene glycol PPG-3000, has difunctional, contains 7 mass percent of ethylene oxide and has a hydroxyl value of 37.4 mgKOH/g; the polyester polyol is polybutylene adipate glycol PBA-1000, and has the bifunctional degree and the hydroxyl value of 112 mgKOH/g; the isocyanate is diphenylmethane diisocyanate; the primary chain extender is 4.88 parts of ethylene glycol and 0.77 part of trimethylolpropane; the secondary chain extender is ethylenediamine; the epoxy resin is E-44, and the epoxy value is 0.44;
the method comprises the following steps:
(1) dehydrating polyether polyol, polyester polyol and epoxy resin in vacuum and then cooling;
(2) adding isocyanate into the step (1) to perform prepolymerization reaction to generate a prepolymer;
(3) adding dimethylolpropionic acid into the step (2) for reaction, adding a primary chain extender, then adding one third of acetone by weight for reaction, and then adding one third of acetone by weight for continuous reaction;
(4) cooling the reaction system in the step (3), adding a secondary chain extender, adding the remaining one third of acetone in parts by weight, stirring, and adding triethylamine;
(5) and (4) removing acetone in the system obtained in the step (4) to obtain the water-based polyurethane adhesive.
2. The preparation method according to claim 1, wherein the step (1) is vacuum dehydration at 110-120 ℃, and the temperature is reduced to 55-65 ℃; the step (2) is carried out prepolymerization reaction for 60-120 min at 50-80 ℃; reacting at 50-80 ℃ for 60-100 min after dimethylolpropionic acid is added in the step (3), adding one third of acetone by weight for reacting at 50-80 ℃ for 60-100 min, and adding one third of acetone by weight for continuously reacting for 60-100 min; and (4) cooling the reaction system in the step (4) to 40-60 ℃, and stirring for 20-50 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910796221.7A CN110452654B (en) | 2019-08-27 | 2019-08-27 | Single-component water-based polyurethane adhesive for automobile roof and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910796221.7A CN110452654B (en) | 2019-08-27 | 2019-08-27 | Single-component water-based polyurethane adhesive for automobile roof and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110452654A CN110452654A (en) | 2019-11-15 |
| CN110452654B true CN110452654B (en) | 2021-10-12 |
Family
ID=68489412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910796221.7A Active CN110452654B (en) | 2019-08-27 | 2019-08-27 | Single-component water-based polyurethane adhesive for automobile roof and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110452654B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909650A (en) * | 2020-07-03 | 2020-11-10 | 江苏龙蟠科技股份有限公司 | Moisture-curing polyurethane hot melt adhesive and preparation method thereof |
| CN111748309B (en) * | 2020-07-09 | 2021-11-26 | 漳州市锐普化工有限公司 | High-temperature-and-humidity-resistant environment-friendly adhesive and preparation method thereof |
| CN113861831A (en) * | 2021-10-21 | 2021-12-31 | 海南必凯水性新材料有限公司 | Protective coating special for vehicle paint and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696259A (en) * | 2009-10-09 | 2010-04-21 | 宜兴市光辉胶粘剂有限公司 | Method for preparing composite water-based polyurethane |
| CN105062403A (en) * | 2015-08-26 | 2015-11-18 | 山东天庆科技发展有限公司 | Synthetic leather binding agent and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4137660A1 (en) * | 1991-11-15 | 1993-05-19 | Basf Ag | AQUEOUS POLYURETHANE DISPERSIONS |
-
2019
- 2019-08-27 CN CN201910796221.7A patent/CN110452654B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696259A (en) * | 2009-10-09 | 2010-04-21 | 宜兴市光辉胶粘剂有限公司 | Method for preparing composite water-based polyurethane |
| CN105062403A (en) * | 2015-08-26 | 2015-11-18 | 山东天庆科技发展有限公司 | Synthetic leather binding agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110452654A (en) | 2019-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110452654B (en) | Single-component water-based polyurethane adhesive for automobile roof and preparation method thereof | |
| CN105153387B (en) | A kind of polyurethane amino resins modified water-based alkyd resin and preparation and application | |
| CN110229301B (en) | Preparation method and application of waterborne polyurethane resin synthetic leather | |
| NO337215B1 (en) | wood compound | |
| JPH1053636A (en) | Anionic aqueous polyurethane dispersion | |
| CN110835401A (en) | Waterborne polyurethane surface layer resin and preparation method thereof | |
| CN106928428B (en) | Aqueous polyurethane emulsion and preparation method thereof | |
| CN110105912A (en) | Water-based polyurethane adhesive for automobile interiors and preparation method thereof | |
| CN113025184A (en) | High-adhesion waterborne polyurethane coating resin and preparation method thereof | |
| CN114045025A (en) | SIS derivative modified waterborne polyurethane-epoxy resin and preparation method thereof | |
| WO2001098392A1 (en) | Preparation of aqueous urethane resin composition | |
| CN113980225A (en) | Hydroxypropyl distarch phosphate modified waterborne polyurethane resin and preparation method thereof | |
| CN106661186A (en) | Aqueous polyurethane - vinyl polymer hybrid dispersions | |
| CN112358598B (en) | Waterborne polyurethane surface layer resin for synthetic leather and preparation method thereof | |
| CN112080185A (en) | Waterborne polyurethane industrial paint and preparation method thereof | |
| CN111826113A (en) | Paper-plastic film-coated moisture curing reaction type polyurethane hot melt adhesive and preparation method thereof | |
| CN114736596B (en) | Quick-drying type single-component polyurethane waterproof coating and preparation method thereof | |
| CN112778959B (en) | High-strength damp-heat resistant bi-component PU adhesive and preparation method thereof | |
| CN112521581B (en) | Waterborne polyurethane surface layer resin for synthetic leather and preparation method and application thereof | |
| CN113788925A (en) | Waterborne polyurethane resin and preparation method and application thereof | |
| CN113462339B (en) | Preparation method of sebum and sweat resistant moisture-curing polyurethane hot melt adhesive | |
| KR101218180B1 (en) | Composition for aqueous 2K polyurethane coating on flexible platic substrates | |
| KR102130377B1 (en) | Aqueous type surface treating agent excellent in anti-sunscreen property and method for producing the same | |
| CN114213618A (en) | Hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin and preparation method thereof | |
| CN114409852A (en) | Acrylic acid modified aqueous polyurethane dispersion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |