CN111876107A - Epoxy polyurethane modified acrylic resin adhesive and preparation method and application thereof - Google Patents
Epoxy polyurethane modified acrylic resin adhesive and preparation method and application thereof Download PDFInfo
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- CN111876107A CN111876107A CN202010107054.3A CN202010107054A CN111876107A CN 111876107 A CN111876107 A CN 111876107A CN 202010107054 A CN202010107054 A CN 202010107054A CN 111876107 A CN111876107 A CN 111876107A
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, and provides an epoxy polyurethane modified acrylic resin adhesive and a preparation method thereof, aiming at solving the problem that the traditional single polyurethane or acrylic resin can not meet the requirements of various comprehensive properties of a reflective material, wherein the epoxy polyurethane modified acrylic resin adhesive comprises the following components in parts by weight: 20-40 parts of acrylate soft monomer, 1-15 parts of hard monomer, 1-5 parts of functional monomer, 0.2-2.0 parts of initiator, 50-70 parts of organic solvent and 2-10 parts of epoxy modified polyurethane prepolymer solution. The prepared adhesive has the characteristics of high adhesive force, washing resistance, dry cleaning resistance, elasticity, low cost, low temperature resistance, high reaction speed, high creep resistance and the like.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an epoxy polyurethane co-modified acrylic resin adhesive for a reflective material and a preparation method thereof.
Background
The reflecting material is generally made of acrylic resin as the compound adhesive, and polyurethane resin is also used as the compound adhesive. The existing acrylic resin is adopted, so that the cost is low, the curing is fast, but the problems of deviation of bead-grasping force, lack of low-temperature resistance, insufficient elasticity, good creep resistance and deviation of washing resistance and dry cleaning resistance exist; the product made of polyurethane resin has good water washing resistance, dry cleaning resistance, low temperature resistance and good elasticity, but has the conditions of higher cost, slower curing time and deviation of creep resistance. Therefore, when all properties of a reflective product are required to be considered, the characteristics of two adhesive resins need to be combined.
The traditional polyurethane modified acrylic acid generally adopts physical blending or introduces hydroxyethyl acrylate double bonds into polyurethane prepolymer, utilizes the double bonds in the hydroxyethyl acrylate to graft with acrylic monomer by free radical polymerization; by adopting a physical blending method, the glue is easy to layer, so that the uniformity is poor, and a plurality of performances cannot be met; by introducing double bond copolymerization, the prepolymer components cannot be added in a large proportion, and the comprehensive performance of the reflecting material cannot be better met.
Disclosure of Invention
In order to solve the problem that the traditional single polyurethane or acrylic resin can not meet the requirements of various comprehensive properties of a reflective material, the invention provides an epoxy polyurethane modified acrylic resin adhesive and a preparation method thereof, and the epoxy polyurethane modified acrylic resin adhesive has the characteristics of high adhesive force, washing resistance, dry cleaning resistance, elasticity, low cost, low temperature resistance, high reaction speed, good creep resistance and the like.
The invention is realized by the following technical scheme: the epoxy polyurethane modified acrylic resin adhesive comprises the following components in parts by weight:
the preparation method of the epoxy polyurethane modified acrylic resin adhesive comprises the following steps: putting an acrylate soft monomer, a hard monomer, a functional monomer, an epoxy modified polyurethane prepolymer solution, an organic solvent of 2/3-3/4 accounting for the total mass of the organic solvent and an initiator of 1/20-1/3 accounting for the total mass of the initiator into a reaction kettle, heating to 60-95 ℃, reacting for 1-2 hours, dissolving the rest of the initiator by using 0.5-10% of the total mass of the organic solvent, continuously dropwise adding the initiator into the reaction kettle for 3-5 hours, controlling the temperature to 75-85 ℃, preserving the heat for 2-3 hours, adding the rest of the organic solvent into the reaction kettle, cooling to 50-60 ℃, and discharging to obtain the epoxy polyurethane modified acrylate adhesive.
The reaction formula is shown as follows:
the acrylate soft monomer is selected from one or two of butyl acrylate, 2-ethylhexyl acrylate and lauryl methacrylate.
The hard monomer is selected from any one or two of methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate and vinyl versatate.
The functional monomer is selected from any one or more of acrylic acid, methacrylic acid, beta-acryloxypropionic acid and itaconic acid monobutyl ester; the acrylic acid has a hydrogen ion donor and can attack an epoxy group, and the adhesive force to the reflective glass bead can be improved by introducing strong polar groups such as a carbamate bond, the epoxy group and the like through the reaction of carboxyl and the epoxy group; rigid structures such as benzene rings are introduced, so that the cohesive strength and the temperature resistance of the adhesive are improved; the ether bond and the carbamate are introduced, so that the dry cleaning resistance can be improved.
The initiator is selected from any one or two of dibenzoyl peroxide, dilauroyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile.
The organic solvent is one or two of ethyl acetate and toluene.
The epoxy modified polyurethane prepolymer solution comprises the following components in parts by weight,
preferably, the sum of the parts by weight of polyester polyol, epoxy resin and isocyanate is equal to the part by weight of ethyl acetate.
The polyester polyol is selected from any one of poly (1, 4-butanediol adipate) glycol, poly (neopentyl glycol adipate) -1, 4-butanediol adipate glycol, poly (2-methyl propylene glycol adipate) -1, 4-butanediol succinate glycol, poly (neopentyl glycol isophthalate) glycol sebacate and poly (neopentyl glycol isophthalate); the polyester polyol is generally prepared by condensing (or transesterifying) organic dicarboxylic acid (anhydride or ester) and polyhydric alcohol (including glycol) or polymerizing lactone and the polyhydric alcohol, and has high cohesive strength and adhesive force and high strength and wear resistance because the molecule contains more polar groups such as ester groups, amino groups and the like.
The isocyanate is selected from any one or two of toluene diisocyanate and diphenylmethane diisocyanate. The diisocyanate has a functional group of-N ═ C ═ O, and the polyurethane material is prepared by polymerizing the diisocyanate and polyether polyol, so that the good application performance of the material is improved.
The epoxy resin is selected from one or more of commercially available E-12, E-20, E-44, E-39, E-51, hyperbranched epoxy resin and the like. The epoxy resin contains organic compounds of two or more than two epoxy groups, and is characterized in that the molecular chain contains active epoxy groups, the epoxy groups can be positioned at the tail end, in the middle or in a ring structure, and the epoxy resin has good physical and chemical properties, has excellent bonding strength to the surfaces of metal and non-metal materials, good dielectric properties, small deformation shrinkage, good dimensional stability of products, high hardness, good flexibility, and stability to alkali and most of solvents. Preferably, the epoxy resin adopts a conventional double-part A type, has certain strength and adhesive force, and the performance of each group is as follows:
the epoxy resin modified polyurethane prepolymer improves the bonding performance, and preferably, the preparation method of the epoxy modified polyurethane prepolymer solution comprises the following steps: mixing polyester polyol and epoxy resin, heating to 100-120 ℃, vacuumizing, dehydrating for 1-2 hours, cooling to 60-80 ℃, adding 2-10 parts of ethyl acetate and isocyanate, heating to 78-85 ℃, reacting for 2-3 hours, cooling, adding the rest of ethyl acetate, cooling to 50-60 ℃, discharging and cooling.
Epoxy resin modified polyurethane prepolymer, epoxy groups in the prepolymer react with carboxyl groups to be grafted on acrylic resin, and polyurethane units such as urethane bonds and the like are introduced, so that the polarity of the polymer is increased, the bonding fastness to metal and glass is increased, and a certain soft and hard blocks form microphase separation, so that the polymer has certain elasticity; although the ring-opening reaction of the epoxy resin can be carried out under an acidic condition, the activity is not very strong, the product can be only partially grafted, and part of the product is left, so that the grafting is not completely grafted, and a small part of prepolymer is remained, the molecular weight of the part is small, so that the epoxy resin can well penetrate and wet, and also has a good bonding effect.
The reaction schematic formula is shown as follows:
compared with the prior art, the invention has the beneficial effects that: the epoxy polyurethane modified acrylic resin adhesive has the comprehensive performances of high adhesion, washing resistance, dry cleaning resistance, elasticity, low cost, low temperature resistance, high reaction speed, good creep resistance and the like.
Polyurethane urethane bonds and epoxy groups are introduced, so that the adhesion to glass beads and aluminum foil and the dry-cleaning resistance are improved; the soft and hard segment block structure of polyurethane is introduced, so that the elasticity of the composite adhesive is improved; the high molecular weight characteristic of free radical synthesis of acrylate monomers is retained, a good creep resistance effect is achieved, and carboxyl groups and other groups are distributed in each molecular chain segment, so that the acrylate monomers and the isocyanate curing agent can react quickly to form a cross-linked network structure.
Detailed Description
The present invention is further illustrated by the following examples, in which the starting materials are either commercially available or prepared by conventional methods.
Example 1
(1) Taking 30 parts of poly neopentyl glycol adipate diol polyester polyol and 5 parts of epoxy resin E-12, heating to 110 ℃, vacuumizing (-0.1Mpa) for dehydration for 1 hour, cooling to 65 ℃, adding 10 parts of ethyl acetate and 4 parts of toluene diisocyanate, heating to 80 ℃, reacting for 3 hours, cooling, adding the rest 40 parts of ethyl acetate, cooling to 55 ℃, discharging and cooling for later use, and obtaining prepolymer 1.
(2) Adding 35 parts of butyl acrylate, 10 parts of vinyl acetate, 4 parts of acrylic acid, 5 parts of prepolymer 1, 45 parts of ethyl acetate and 0.2 part of dibenzoyl peroxide initiator into the bottom of a reaction kettle, heating to 83 ℃, reacting for 1 hour, dissolving the remaining 0.8 part of dibenzoyl peroxide initiator with 6 parts of toluene, continuously dropwise adding the solution into the reaction kettle for 4 hours, controlling the temperature to 80 ℃, preserving the temperature for 2.5 hours, adding 9 parts of ethyl acetate into the reaction system of the reaction kettle, cooling to 55 ℃, and discharging to obtain the epoxy polyurethane modified acrylate adhesive 1.
The epoxy urethane modified acrylate adhesive 1 has a solid content of 35% and a viscosity of 3500 mps.
Example 2
(1) Taking 25 parts of poly (neopentyl glycol isophthalate) polyester polyol sebacate and 8 parts of epoxy resin E-44, heating to 120 ℃, vacuumizing (-0.1Mpa) for dehydration for 1 hour, cooling to 70 ℃, adding 15 parts of ethyl acetate and 5 parts of diphenylmethane diisocyanate, heating to 80 ℃, reacting for 2 hours, starting cooling, adding the rest 35 parts of ethyl acetate, cooling to 60 ℃, discharging and cooling for later use, and obtaining prepolymer 2.
(2) Adding 25 parts of isooctyl acrylate, 7 parts of methyl methacrylate, 2 parts of methacrylic acid, 2 parts of beta-acryloxypropionic acid, 8 parts of prepolymer 2, 49 parts of ethyl acetate and 0.1 part of dilauroyl peroxide initiator into the bottom of a reaction kettle, heating to 83 ℃, reacting for 1 hour, dissolving the rest 1 part of dilauroyl peroxide initiator by using 4 parts of toluene, continuously dropwise adding into the reaction kettle for 5 hours, controlling the temperature to 83 ℃, keeping the temperature for 2.5 hours, adding 17 parts of ethyl acetate into the reaction system of the reaction kettle, cooling to 60 ℃, and discharging to obtain the epoxy polyurethane modified acrylate adhesive 2.
The epoxy urethane modified acrylate adhesive 2 has a solid content of 36% and a viscosity of 4000 mps.
Example 3
(1) Taking 40 parts of poly (neopentyl glycol isophthalate terephthalate) polyester polyol and 10 parts of epoxy resin E-21, heating to 100 ℃, vacuumizing (-0.1Mpa) for dehydration for 2 hours, cooling to 75 ℃, adding 8 parts of ethyl acetate and 8 parts of toluene diisocyanate, heating to 85 ℃, reacting for 3 hours, cooling, adding the rest 35 parts of ethyl acetate, cooling to 50 ℃, discharging and cooling for later use, and obtaining prepolymer 3.
(2) Adding 40 parts of lauryl methacrylate, 6 parts of vinyl acetate and 2 parts of vinyl versatate into the bottom of a reaction kettle, adding 3 parts of methacrylic acid, 5 parts of prepolymer 3, 35 parts of ethyl acetate and 0.3 part of azodiisobutyronitrile initiator, heating to 85 ℃, reacting for 1 hour, dissolving the rest 0.9 part of azodiisobutyronitrile initiator by using 1 part of ethyl acetate, continuously dropwise adding into the reaction kettle for 3 hours, controlling the temperature to 80 ℃, preserving the temperature for 2.5 hours, adding 14 parts of ethyl acetate into the reaction system of the reaction kettle, cooling to 50 ℃, and discharging to obtain the epoxy polyurethane modified acrylate adhesive 3.
The epoxy polyurethane modified acrylate adhesive 3 has the solid content of 35 percent and the viscosity of 3000 mps.
Comparative example
Using the epoxy urethane modified acrylate adhesives 1 to 3 prepared in examples 1 to 3, the commercially available acrylic resin system adhesive (802), and the polyurethane resin system adhesive (606), respectively, reflective fabrics were prepared by a conventional method, and performance tests were performed on the reflective fabrics, the test results are shown in tables 1 to 3:
TABLE 1
Table 2:
table 3:
from the above table, it can be seen that both polyurethane and acrylic have outstanding advantages in one aspect, but the epoxy urethane modified acrylate adhesive of the present invention has both acrylic and urethane properties.
| Acrylic resin | Polyurethane resin | Technical scheme of the invention | |
| Speed of curing | Fast-acting toy | Slow | Is quicker |
| Resistance to dry cleaning | Difference (D) | Good taste | Good taste |
| Creep resistance | Good taste | Difference (D) | Good taste |
| Elasticity | Difference (D) | Good taste | Good taste |
| Price | Is low in | Height of | Is lower than |
Claims (10)
1. The epoxy polyurethane modified acrylic resin adhesive is characterized by comprising the following components in parts by weight:
20-40 parts of acrylic ester soft monomer,
1 to 15 parts of a hard monomer,
1 to 5 parts of functional monomer,
0.2 to 2.0 parts of an initiator,
50-70 parts of an organic solvent,
2-10 parts of epoxy modified polyurethane prepolymer solution.
2. The epoxy polyurethane modified acrylic resin adhesive as claimed in claim 1, wherein the acrylic soft monomer is selected from one or two of butyl acrylate, 2-ethylhexyl acrylate and lauryl methacrylate.
3. The epoxy polyurethane modified acrylic resin adhesive of claim 1, wherein the hard monomer is selected from one or two of methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate and vinyl versatate.
4. The epoxy polyurethane modified acrylic resin adhesive according to claim 1, wherein the functional monomer is selected from any one or more of acrylic acid, methacrylic acid, beta-acryloxypropionic acid and monobutyl itaconate;
the initiator is selected from any one or two of dibenzoyl peroxide, dilauroyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile.
5. The epoxy polyurethane modified acrylic resin adhesive of claim 1, wherein the epoxy polyurethane modified polyurethane prepolymer solution comprises the following components in parts by weight,
20-40 parts of polyester polyol,
5 to 10 parts of epoxy resin,
1 to 10 parts of isocyanate,
40-60% of ethyl acetate.
6. The epoxy polyurethane modified acrylic resin adhesive of claim 5, wherein the sum of the parts by weight of the polyester polyol, the epoxy resin and the isocyanate is equal to the part by weight of the ethyl acetate.
7. The epoxy polyurethane modified acrylic resin adhesive of claim 5 or 6, wherein the polyester polyol is selected from any one of poly (1, 4-butylene adipate) glycol, poly (neopentyl glycol adipate) -1, 4-butylene glycol), poly (2-methylpropanediol-1, 4-butylene glycol adipate), poly (neopentyl glycol isophthalate) and poly (neopentyl glycol isophthalate);
the isocyanate is selected from any one or two of toluene diisocyanate and diphenylmethane diisocyanate.
8. The epoxy polyurethane modified acrylic resin adhesive according to claim 5 or 6, wherein the preparation method of the epoxy polyurethane modified prepolymer solution comprises the following steps: mixing polyester polyol and epoxy resin, heating to 100-120 ℃, vacuumizing, dehydrating for 1-2 hours, cooling to 60-80 ℃, adding 2-10 parts of ethyl acetate and isocyanate, heating to 78-85 ℃, reacting for 2-3 hours, cooling, adding the rest of ethyl acetate, cooling to 50-60 ℃, discharging and cooling.
9. The preparation method of the epoxy polyurethane modified acrylic resin adhesive according to any one of claims 1 to 8, wherein the preparation method comprises the following steps: putting an acrylate soft monomer, a hard monomer, a functional monomer, an epoxy modified polyurethane prepolymer solution, an organic solvent of 2/3-3/4 accounting for the total mass of the organic solvent and an initiator of 1/20-1/3 accounting for the total mass of the initiator into a reaction kettle, heating to 60-95 ℃, reacting for 1-2 hours, dissolving the rest of the initiator by using 0.5-10% of the total mass of the organic solvent, continuously dropwise adding the initiator into the reaction kettle for 3-5 hours, controlling the temperature to 75-85 ℃, preserving the heat for 2-3 hours, adding the rest of the organic solvent into the reaction kettle, cooling to 50-60 ℃, and discharging to obtain the epoxy polyurethane modified acrylate adhesive.
10. Use of the epoxy polyurethane modified acrylic adhesive according to any one of claims 1 to 8 in a reflective material.
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