CN104672399B - Preparation method of novel acrylic acid modified resin for aqueous two-component polyurethane adhesive - Google Patents
Preparation method of novel acrylic acid modified resin for aqueous two-component polyurethane adhesive Download PDFInfo
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Abstract
The invention belongs to the field of adhesives, and relates to a preparation method of novel acrylic modified resin for a water-based two-component polyurethane adhesive. Directly selecting high molecular resin or synthesizing the high molecular resin by using raw materials, then adding a solvent, modifying by using vinyl or acrylic acid and ester monomers thereof at a certain temperature or under an initiator, and respectively reacting by using organic amine and acid substances to obtain the acrylic acid modified resin for the aqueous two-component polyurethane adhesive. The acrylic modified resin obtained by the method is directly used or matched with an isocyanate-containing component after chain extension to obtain a polyurethane adhesive, and isocyanate groups contained in the adhesive preferentially react with active groups on the resin in an aqueous environment and stably exist in the aqueous environment; and has lower VOC content than solvent-based polyurethane adhesives; the defects of peeling from a base material, film foaming, poor bonding, material defects and the like of the common waterborne polyurethane adhesive after bonding are also eliminated; the cost of the polyurethane adhesive is reduced.
Description
Technical Field
The invention relates to a preparation method of novel acrylic modified resin for a water-based two-component polyurethane adhesive, belonging to the field of adhesives.
Background
The polyurethane adhesive refers to an adhesive containing urethane bonds or isocyanate groups in base material molecules. The polyurethane adhesive contains isocyanate and urethane groups with strong polarity and chemical activity, and has excellent chemical adhesive force and firm adhesion with porous materials containing active hydrogen, such as wood, leather, paper, ceramic and the like, and smooth surface materials such as metal, glass, rubber, plastic and the like. Because isocyanate groups are very active, the isocyanate groups can react with compounds containing active hydrogen, such as alcohol, acid, amine and water, and react according to a certain equivalent weight, the reaction of isocyanate and water generates carbon dioxide, so that the loss of isocyanate is caused, the isocyanate which reacts with a base material or an adhesive base material is reduced, the bonding performance is reduced or even fails, the content of moisture and substances containing active hydrogen, such as alcohol amines and phenols, in various raw materials and diluents of the general polyurethane adhesive is strictly controlled, and the large fluctuation of the bonding performance is often caused in high-humidity weather, such as southern plum rain season, and unnecessary loss is caused.
The polyurethane adhesive used in China at present is mainly a solvent-type double-component polyurethane adhesive, contains a large amount of esters, ketones, benzenes and free isocyanate, is harmful to human health and destroys ecological environment. In order to avoid volatilization of a large amount of organic solvents, researchers developed waterborne polyurethane coatings; generally, the content of VOC is greatly reduced in the aqueous polyurethane, but due to unstable performance, isocyanate reacts with water to generate carbon dioxide gas, and the isocyanate is easy to gel, peel off from a base material, blister and the like due to careless construction operation. The price of the water-based two-component polyurethane adhesive is high, so the current water-based two-component polyurethane adhesive has certain limitation in application.
Disclosure of Invention
The waterborne acrylic modified resin and the polyurethane adhesive which can be used for the waterborne two-component polyurethane adhesive are prepared, water can be used as a diluent, and the resin is matched with an isocyanate-containing curing agent component to prepare the waterborne polyurethane adhesive when in use, so that the VOC content of the waterborne acrylic modified resin and the polyurethane adhesive is lower than that of a common solvent-based polyurethane adhesive; the defects of base material peeling, foaming and the like easily occurring in the bonding process of the common water-based double-component polyurethane adhesive are also solved; but also reduces the cost of the aqueous two-component polyurethane adhesive.
A water-based two-component polyurethane adhesive is composed of A, B components, wherein the A component is acrylic acid modified resin, the molecular weight range of the resin is 1600-30000, preferably 2000-16000, and can be diluted by water or organic solvent, the B component is a substance containing polyisocyanate, including TDI, MDI, HDI, PAPI, and other isocyanate, reaction products of the isocyanate and poly-methylol propane (or glycerol) and dimer trimer polymer thereof, the component is used as a curing agent for reaction, and can be diluted by organic solvent in a certain proportion to the concentration of 60-80% before use.
The component A is acrylic acid modified resin and is synthesized by the following raw materials in percentage by weight: 0-80 parts of high molecular resin, 0-60 parts of solvent, 10-90 parts of vinyl or acrylic acid and ester monomers thereof, 0-8 parts of initiator, 0.1-20 parts of organic amine and 0-20 parts of acid substances.
The preferable scheme of various raw materials in the formula is as follows: 0-50 parts of high molecular resin, 10-60 parts of solvent, 20-80 parts of vinyl or acrylic acid and ester monomers thereof, 0.1-8 parts of initiator, 0.1-10 parts of organic amine and 0.1-10 parts of acid substances.
The polymer resin is selected from one or more of polyester resin, alkyd resin, epoxy resin and phenolic resin.
The polymer resin is selected from polyester or alkyd resin, and the monomers selected in the synthesis process comprise: adipic acid, maleic anhydride, terephthalic acid, isophthalic acid, trimellitic anhydride, trimethylolpropane, neopentyl glycol, dimethylolpropionic acid, ricinoleic acid, soya-oleic acid, coconut oil acid and one or more of synthetic fatty acids.
The solvent is one or more selected from ethylene glycol monobutyl ether, propylene glycol methyl ether acetate, butanol or alcohol ester twelve, N-methyl pyrrolidone and diethylene glycol butyl ether.
The vinyl or acrylic acid and ester monomers thereof are selected from one or more of styrene, acrylic acid, methacrylic acid, butyl methacrylate, methyl methacrylate, butyl acrylate, glycidyl (meth) acrylate, 1, 2-epoxy-4-vinylcyclohexane, lauryl methacrylate, isobornyl methacrylate, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
The initiator is selected from one or more of dibenzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, azobisisoheptonitrile, cyclohexanone peroxide, tert-butyl hydroperoxide, cumyl peroxide, hydrogen peroxide, persulfate, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, 2 '-azobis (2-methyl-4-carboxybutyronitrile) and 2, 2' -azobis (2-cyanopropane-1-sulfonate).
The organic amine is one or more of diethylenetriamine, triethylene tetramine, monomethyl ethanolamine, diethanolamine and 2-amino-2-methyl-1-propanol.
The acid substance is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, citric acid, formic acid, acetic acid and lactic acid.
The preparation method of the acrylic acid modified resin for the two-component polyurethane adhesive comprises the following steps:
(1) adding or synthesizing 0-80 parts by weight of polymer resin, adding polybasic acid and polyalcohol into a reactor, heating to 240 ℃ at the kettle temperature and 90-100 ℃ at the column temperature, reacting to obtain water, measuring the water amount, and controlling the acid value to be less than 5 mgKOH/g.
(2) Adding 0-60 parts by weight of solvent into a three-necked bottle, and heating to 60-150 ℃;
(3) dripping 10-90 parts of mixture of vinyl or acrylic acid and its esters and initiator at 60-150 deg.C under stirring for 2-6hr, and keeping the temperature at 60-150 deg.C for 2-4 hr.
(4) Cooling to 50-90 deg.C, adding 0.1-20 parts of organic amine, stirring, and keeping the temperature for 0.5-3 hr;
(5) adding 0-20 parts of acid substances under the condition of heat preservation, and stirring for 0.5-2hr to obtain the acrylic modified resin for the two-component polyurethane adhesive.
The prepared resin is taken according to the amount of isocyanate/hydroxyl substances and 0.9-0.99, 0-0.15 of glycerol/glycol is added, isocyanate such as TDI, MDI, HDI, PAPI and the like is added, and the reflux chain extension reaction is carried out for 3-5 hours at the temperature of 80-105 ℃ to obtain the component A, or the prepared acrylic modified resin can be directly used as the component A.
The component B is a polyisocyanate curing agent. Alternative polyisocyanate curing agents include: polyisocyanate monomers such as TDI, HDI, MDI and IPDI, and dimers, trimers and polymers thereof, and those formed by reacting the above-mentioned isocyanate dimers, trimers and polyhydroxymethylpropanes (e.g., trimethylolpropane, glycerol, etc.).
The invention has the beneficial effects that: the water-based acrylic modified resin which is one of the main film forming materials can be compatible with solvent type isocyanate for use, so that the solvent type isocyanate is dispersed in water, but does not react with water to generate gas to form bubbles and reduce the performance of a coating film, and the defects of interlayer stripping, foaming and the like generated in the construction process are solved; the problems that the double-component polyurethane adhesive has high VOC content, unstable component performance and bonding performance influenced by external hydroxyl-containing substances are solved; as a high-molecular film forming material of the adhesive, the VOC discharge capacity of the adhesive is greatly reduced, the stability of the adhesive is enhanced, the defect of air bubbles in a glue layer is fundamentally solved, the defect of the material is effectively inhibited, the construction difficulty is reduced, and the cost of the polyurethane adhesive is reduced.
Detailed Description
Preparation of acrylic acid modified resin
Example 1
TABLE 1 Table for feeding of selected polybasic acids and polyhydric alcohols for partial polyester synthesis
TABLE 2 acrylic copolymer monomer initiator feeding table
a. Adding the monomers except the coconut oil acid in the table 1 into a four-mouth bottle with a stirrer, a thermometer and a rectifying column, controlling the temperature of the kettle to be not more than 230 ℃, controlling the temperature of the column to be 95-100 ℃, weighing the water after reacting for 2-4hr, measuring the acid value to be less than 5mgKOH/g, adding the coconut oil acid, continuing to react for 1-1.5hr, measuring the acid value to be less than 5mgKOH/g, and cooling to 100 ℃.
b. Adding 150g of propylene glycol methyl ether and 80g of ethylene glycol monobutyl ether, and controlling the temperature to 90-100 ℃;
c. uniformly mixing monomers such as Methyl Methacrylate (MMA), Butyl Acrylate (BA), Lauryl Methacrylate (LMA), Glycidyl Methacrylate (GMA), isobornyl methacrylate (IBOMA) and the like and Azobisisobutyronitrile (AIBN) at 90-100 ℃, dropwise adding into a four-mouth bottle for 2-2.5hr, supplementing 3g of AIBN after dropwise adding is finished, and keeping the temperature for 3 hr;
c. keeping the temperature for 3hr, cooling to 50 deg.C, adding 41g triethylene tetramine, and keeping the temperature for 2 hr;
d. adding 52g of formic acid for neutralization to obtain the acrylic acid modified resin for the aqueous two-component polyurethane adhesive.
Example 2
TABLE 3 Table for feeding of selected polybasic acids and polyhydric alcohols for partial polyester synthesis
TABLE 4 acrylic copolymer monomer initiator feeding table
a. Adding the monomers except the soya-bean oil acid in the table 1 into a four-mouth bottle with a stirrer, a thermometer and a rectifying column, controlling the kettle temperature to be not more than 230 ℃, the column temperature to be 95-100 ℃, weighing the water after reacting for 2-4hr, measuring the acid value to be less than 5mgKOH/g, adding the soya-bean oil acid, continuing to react for 1-1.5hr, measuring the acid value to be less than 5mgKOH/g, and cooling to 100 ℃.
b. Uniformly mixing monomers such as Methyl Methacrylate (MMA), Butyl Acrylate (BA), Butyl Methacrylate (BMA), Glycidyl Methacrylate (GMA), isobornyl methacrylate (IBOMA) and the like and Benzoyl Peroxide (BPO) at 100 ℃, dropwise adding into a four-mouth bottle for 2-2.5 hours, supplementing 3g of BPO after dropwise adding is finished, and preserving heat for 3 hours;
c. keeping the temperature for 3hr, cooling to 50 deg.C, adding 122g diethanolamine, and keeping the temperature for 2 hr;
d. adding 65g of acetic acid for neutralization to obtain the acrylic acid modified resin for the aqueous two-component polyurethane adhesive.
Example 3
TABLE 5 Table for feeding of selected polybasic acids and polyhydric alcohols for partial polyester synthesis
TABLE 6 acrylic copolymer monomer initiator feeding table
a. Adding the monomers except the soya-bean oil acid in the table 1 into a four-mouth bottle with a stirrer, a thermometer and a rectifying column, controlling the kettle temperature to be not more than 230 ℃, controlling the column temperature to be 95-100 ℃, weighing the water after reacting for 2-4hr, measuring the acid value to be less than 5mgKOH/g, adding the soya-bean oil acid, continuing to react for 1-1.5hr, measuring the acid value to be less than 5mgKOH/g, and cooling to 110 ℃.
b. Uniformly mixing monomers such as Methyl Methacrylate (MMA), Butyl Acrylate (BA), Lauryl Methacrylate (LMA), Glycidyl Methacrylate (GMA), isobornyl methacrylate (IBOMA) and the like and tert-butyl peroxybenzoate (TBPB) at 110 ℃, dropwise adding into a three-neck flask for 2-2.5hr, supplementing 3g of TBPB after dropwise adding is finished, and keeping the temperature for 3 hr;
c. maintaining the temperature for 3hr, cooling to 50 deg.C, adding 54g diethanolamine and 9.3g AMP-95 (2-amino-2-methyl-1-propanol), and maintaining the temperature for 2 hr;
d. adding 78.6g of lactic acid for neutralization to obtain the acrylic acid modified resin for the aqueous two-component polyurethane adhesive material.
Example 4
TABLE 7 acrylic copolymer monomer initiator feeding Table
a. Adding 650g of propylene glycol methyl ether and 150g of ethylene glycol butyl ether into a three-necked bottle with a stirring thermometer, and heating to 120 ℃;
b. uniformly mixing monomers such as Methyl Methacrylate (MMA), Butyl Acrylate (BA), Lauryl Methacrylate (LMA), Glycidyl Methacrylate (GMA), isobornyl methacrylate (IBOMA) and the like and tert-butyl peroxybenzoate (TBPB) at 120 ℃, dropwise adding into a three-neck flask for 2-2.5hr, supplementing 3g of TBPB after dropwise adding is finished, and keeping the temperature for 3 hr;
c. keeping the temperature for 3hr, cooling to 50 deg.C, adding 75g monomethyl ethanolamine, and keeping the temperature for 2 hr;
d. adding 46g of formic acid for neutralization to obtain the acrylic acid modified resin for the aqueous two-component polyurethane adhesive.
Example 5
TABLE 8 acrylic copolymer monomer initiator feed Table
a. Adding propylene glycol methyl ether into a three-mouth bottle with stirring and a thermometer, and heating to 90 ℃;
b. uniformly mixing monomers such as alkyl (meth) acrylate, styrene (St), Butyl Acrylate (BA), Lauryl Methacrylate (LMA), Glycidyl Methacrylate (GMA) and isobornyl methacrylate (IBOMA) with tert-butyl peroxybenzoate (TBPB) at 90 ℃, dropwise adding into a three-neck flask for 2-2.5hr, and keeping the temperature for 3hr after dropwise adding;
c. keeping the temperature for 3hr, cooling to 50 deg.C, adding 23g of monomethyl ethanolamine, and keeping the temperature for 2 hr;
d. adding 14g of formic acid for neutralization to obtain the acrylic acid modified resin for the aqueous two-component polyurethane adhesive.
The neutralized resin can be easily dispersed in water.
Preparation of aqueous two-component polyurethane adhesive
Reacting acrylic acid modified resin or the acrylic acid modified resin and polyisocyanate monomer according to the ratio of 1:0.9-0.99 to obtain a resin component with a larger molecular weight as a component A; the curing agent containing polyisocyanate is diluted to 60-80% concentration by using diluent such as propylene glycol methyl ether acetate or N-methyl pyrrolidone, etc. as component B.
Mixing A, B components at ratio of 100:5-50, stirring, adding 10-120% water at the above ratio, adjusting to proper viscosity, and cementing. The shelf life of the adhesive is 3-6hr, and the viscosity slightly rises. Hot air drying to remove water and organic solvent, gluing, curing at 40-60 deg.C for 50hr, or heating for rapid curing at 90 deg.C for 20min to obtain good gluing strength.
Claims (2)
1. A preparation method of novel acrylic acid modified resin for a water-based two-component polyurethane adhesive comprises the following steps:
(1) adding 12.76g of maleic anhydride, 53g of adipic acid, 115g of isophthalic acid, 20g of trimethylolpropane and 137g of neopentyl glycol into a four-mouth bottle with a stirring, thermometer and rectifying column, controlling the kettle temperature to be not more than 230 ℃, the column temperature to be 95-100 ℃, weighing the water after reacting for 2-4hr, measuring the acid value to be less than 5mgKOH/g, adding 122g of coconut oil, continuing to react for 1-1.5hr, measuring the acid value to be less than 5mgKOH/g, and cooling to 100 ℃;
(2) adding 150g of propylene glycol methyl ether and 80g of ethylene glycol monobutyl ether, and controlling the temperature to 90-100 ℃;
(3) uniformly mixing 56g of Methyl Methacrylate (MMA), 35g of Butyl Acrylate (BA), 22g of Lauryl Methacrylate (LMA), 84g of Glycidyl Methacrylate (GMA), 22g of isobornyl methacrylate (IBOMA) monomer and 15g of Azobisisobutyronitrile (AIBN) at 90-100 ℃, dropwise adding into a four-mouth bottle for 2-2.5hr, after dropwise adding, supplementing 3g of AIBN, and keeping the temperature for 3 hr;
(4) keeping the temperature for 3hr, cooling to 50 deg.C, adding 41g triethylene tetramine, and keeping the temperature for 2 hr;
(5) adding 52g of formic acid for neutralization to obtain the acrylic acid modified resin for the aqueous two-component polyurethane adhesive.
2. A preparation method of a two-component polyurethane adhesive is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the acrylic modified resin prepared according to claim 1 with polyisocyanate monomers in an isocyanate/hydroxyl mass ratio of 0.9 to 0.99: 1 to obtain a resin component with larger molecular weight as a component A; using propylene glycol methyl ether acetate or N-methyl pyrrolidone as a diluent to dilute the curing agent containing the polyisocyanate substance to the concentration of 60-80 percent as a component B;
(2) a, B is prepared by mixing the two components at a ratio of 100:5-50, stirring, adding water to adjust to appropriate viscosity, and cementing.
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| CN105348487B (en) * | 2015-12-16 | 2018-03-20 | 江南大学 | A kind of preparation method of castor oil acidic group UV curable water-borne resins |
| CN109081902B (en) * | 2017-06-14 | 2020-11-24 | 万华化学集团股份有限公司 | Artificial board adhesive without aldehyde addition and artificial board without aldehyde addition manufactured by using same |
| CN111454423B (en) * | 2020-04-29 | 2022-01-11 | 东莞市冠力胶业有限公司 | Water-based vacuum plastic and preparation method thereof |
| CN112625637A (en) * | 2020-12-10 | 2021-04-09 | 福建国邦新材料有限公司 | Single-component solvent-free polyurethane adhesive and preparation method thereof |
| CN114989436B (en) * | 2022-05-30 | 2023-04-28 | 浙江鹏孚隆新材料有限公司 | Water-based polyester modified organic silicon resin, preparation method and application thereof |
| CN116082597A (en) * | 2022-12-05 | 2023-05-09 | 广州境好新材料有限公司 | Polyurethane-acrylic ester-alkyd aqueous dispersion, preparation method and application thereof |
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| CN102643622A (en) * | 2012-04-10 | 2012-08-22 | 苏州福斯特光伏材料有限公司 | Solvent type double-component polyurethane adhesive and preparation method thereof |
| CN103554379A (en) * | 2013-10-29 | 2014-02-05 | 西北永新涂料有限公司 | Aqueous acrylic acid-modified alkyd resin and preparation method thereof |
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| CN102643622A (en) * | 2012-04-10 | 2012-08-22 | 苏州福斯特光伏材料有限公司 | Solvent type double-component polyurethane adhesive and preparation method thereof |
| CN103554379A (en) * | 2013-10-29 | 2014-02-05 | 西北永新涂料有限公司 | Aqueous acrylic acid-modified alkyd resin and preparation method thereof |
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