CN107502261B

CN107502261B - High-temperature-resistant anti-freezing resin adhesive for wooden products

Info

Publication number: CN107502261B
Application number: CN201710824891.6A
Authority: CN
Inventors: 申海利
Original assignee: Guangzhou Singky Chemical Tech Co ltd
Current assignee: Guangzhou Singky Chemical Tech Co ltd
Priority date: 2017-09-14
Filing date: 2017-09-14
Publication date: 2020-07-14
Anticipated expiration: 2037-09-14
Also published as: CN107502261A

Abstract

The invention relates to a high-temperature-resistant anti-freezing resin adhesive for a wooden product. The resin adhesive comprises a component A and a component B. The product A comprises the following components in parts by weight: 100-150 parts of resin shown as a polymer in a formula I, 10-15 parts of diluent, 2-5 parts of nano powder and 1-3 parts of auxiliary agent; the component B comprises the following components in parts by weight: 90-120 parts of curing agent, 1-2 parts of defoaming agent, 5-8 parts of nano powder and 1-3 parts of auxiliary agent. The resin adhesive is high temperature resistant and frost resistant.

Description

High-temperature-resistant anti-freezing resin adhesive for wooden products

Technical Field

The invention relates to a decorative material, in particular to a high-temperature-resistant anti-freezing resin adhesive for wooden products.

Background

The advent of epoxy adhesives was that in 1933, Schlack in germany initiated the synthesis of epoxy resins from bisphenol a, and in 1940, Casten in switzerland reported the production of diglycidyl ethers and esters, based on which Ciba corporation developed, and since 1946, mass production of epichlorohydrin began in the united states, and in the following years, commercial production of epoxy adhesives began. The industrial production of the resin with excellent performance is also put into the countries of western Rui Tu, former Soviet Union and Japan, etc. one after another. Epoxy adhesives have been developed after the application of epoxy resins to paints, and after the development of polyamide series curing agents and curing processes. Particularly, the epoxy resin has a series of excellent properties, such as: good adhesive property, excellent mechanical property, small curing shrinkage, good medium and heat resistance, good chemical stability and the like, thereby being developed quickly in industrial application.

Epoxy resins were commercialized in 1950 and began to be used in aluminum skin-balsa core sandwich structures for aircraft manufacture. In the early 60 s of the 26 th century, it began to be used in the repair and reinforcement of houses and hydraulic facilities in construction works. In 1963, the U.S. B-727 aircraft had specially bonded structures to be rivet welded with epoxy glue, thereby increasing the life of the aluminum skin. Epoxy structural adhesives are used in greater quantities in the machine manufacturing industry, machine repair and woodworking. In the 70 s of the 20 th century, various modified composite epoxy resin adhesives (such as epoxy-polysulfide, epoxy-organosilicon, epoxy-nylon, epoxy-butyronitrile, epoxy-phenolic aldehyde and the like) continuously appear, various novel curing agents are developed successively, so that the epoxy resin adhesives are developed in a new development period, and the application range is wider. No matter whether aviation, automobile, building, light industry, electron, etc

There is no epoxy adhesive present. After the 80 s in the 20 th century, the development of epoxy resin adhesives has been directed toward specialization, functionalization and high performance. The adhesive can be widely applied to the aviation industry, and can be used for bonding steel, wood, fabrics, porcelain and the like; even rubber and plastic have good bonding strength; the polyolefin plastic which is difficult to bond can be bonded into a glue joint with considerable strength by only processing the surface of the polyolefin plastic; for the materials with large performance difference (such as steel and concrete), the bonding can be smoothly carried out with large size difference (extremely thin and thick). This greatly facilitates the production and manufacture of all walks of life.

When the epoxy resin adhesive is used for bonding various objects, the stress distribution of the connecting part is uniform under the condition of reasonable joint design. When the release joint is stressed, the force is uniformly distributed on the whole bonding area. Because of this, it does not appear thermal stress, internal stress concentration in the material welding, perforating place like rivet welding, bolted connection, therefore its long service life, comprehensive strength is high, more antifatigue and lasting. If the steel plate is used for bonding a concrete beam with dynamic load, the concrete beam can bear 300 ten thousand times of fatigue dynamic load, and the surface joint is not damaged.

The quality of the bonding by using the epoxy resin adhesive is lighter than that of the traditional connecting process, which is particularly important for airplanes and astronavigation. In the aircraft manufacturing, the weight can be reduced by 20-30% due to the fact that the riveting is replaced by the bonding of the epoxy resin adhesive. In the manufacturing and installation of the large astronomical telescope, the weight can be reduced by 25 percent. When the epoxy resin adhesive is used for bonding an object, the epoxy resin adhesive has comprehensive good mechanical properties, not only is the bonding strength high, but also the performance of the adhesive layer is excellent. The tensile strength of the excellent epoxy resin adhesive can reach 35MPa, the compressive strength can reach 80MPa, the bending strength can reach 60MPa, and in addition, the excellent epoxy resin adhesive also has good water resistance, medium resistance and aging resistance. The epoxy resin adhesive has good strength of bonding substances, and also has multiple functions of sealing, leakage prevention, insulation, corrosion prevention and the like.

Since the advent of epoxy resin adhesives, many of the original deficiencies have been overcome, but the deficiencies still remain from the standpoint of the use requirements of users, mainly:

the impact strength and the peel strength of the epoxy resin adhesive on a glue joint are also low, so that the application of the epoxy resin adhesive in the mechanical manufacturing industry is greatly limited; meanwhile, the temperature resistance of the joint is also poor, the general glue can be used for a long time at about 150 ℃, and a few glue can reach 250 ℃ and 280 ℃, but the curing conditions are complex, and the further improvement is needed.

The glue joint quality of epoxy resin glue is affected by many factors, so that the product manufactured by glue control has large quality dispersity, usually the dispersity of glue joint strength is as high as 20% (15% for spot welding and only 8% for riveting), the design value is greatly reduced, and the application is restricted. In addition, the quality testing method is not perfect, and a non-destructive, reliable, visual and rapid quality testing method is rare. Although many of the recent practices of various non-destructive testing methods (e.g., ultrasonic) have also proven the reliability of epoxy adhesive applications, they have been unsatisfactory.

Research data of long-term endurance strength and aging resistance are still few, so that no clear answer is provided for the actual aging problem, and the popularization and application of the glue is limited.

Disclosure of Invention

Aiming at the defects in the prior art, one of the technical problems to be solved by the invention is to provide a high-temperature-resistant anti-freezing resin adhesive for wooden products.

At present, bisphenol A is generally used as a monomer for reaction of epoxy resin adhesives, and the related patent protection range is very wide. Without finding a structure with the same monomer having inconsistent 4, 4 'positions, the inventors introduced different groups at 4, 4' to obtain a modified epoxy adhesive with beneficial properties.

The utility model provides a high temperature resistant frost resistant resin glue for woodwork which characterized in that: the resin adhesive comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 100-150 parts of resin shown as a polymer in a formula I, 10-15 parts of diluent, 2-5 parts of nano powder and 1-3 parts of auxiliary agent; the component B comprises the following components in parts by weight: 90-120 parts of curing agent, 1-2 parts of defoaming agent, 5-8 parts of nano powder and 1-3 parts of auxiliary agent.

Preferably, the polymer of formula I is as follows:

wherein Ar is₁Independently selected from C_6-10Arylene, 5-10 membered heterocyclene, or 5-10 membered heteroarylene;

Ar₂independently selected from C_6-10Arylene, 5-10 membered heterocyclene, or 5-10 membered heteroarylene;

provided that Ar is₁And Ar₂Different, and not phenylene;

m of the polymer_w＝2.8～5.6×10³，M_n＝2.8～9.3×10²The molecular weight distribution coefficient is 6-10.

Preferably, Ar₁And Ar₂Independently selected from naphthylene, anthrylene, phenanthrylene, biphenylene, benzofuranylene.

Preferably, the component A consists of the following components in percentage by weight: resin 150 shown as a polymer in a formula I, a diluent 10, nano powder 2 and an auxiliary agent 1; the component B comprises the following components in parts by weight: curing agent 90, defoaming agent 1, nano powder 8 and auxiliary agent 1.

Preferably, the diluent is selected from acetone, ethanol, toluene, ethyl acetate, dimethylformamide; the nano powder is selected from aluminum oxide or silicon dioxide; the auxiliary agent is selected from ethylenediamine and diethylenetriamine; the antifoaming agent is selected from octanol; the curing agent is selected from PA or curing agent T31.

The invention also provides a polymer shown in the formula I, which is shown as follows:

provided that Ar is₁And Ar₂Different, and not phenylene;

Preferably, Ar₁And Ar₂Independently selected from the group consisting of naphthylene, anthrylene, phenanthrylene, biphenylene, and 2, 2-dimethylbenzofuranylene.

The polymers of formula I are useful in construction engineering.

The term "aryl" refers to monocyclic or bicyclic aromatic hydrocarbon groups having 6 to 12 carbon atoms in the ring portion, such as phenyl and naphthyl, each of which may be substituted.

The term "heteroaryl" refers to substituted and unsubstituted aromatic 5 or 6 membered monocyclic groups, 9-or 10-membered bicyclic groups, and 11 to 14 membered tricyclic groups having at least one heteroatom (O, S or N) in at least one ring, said heteroatom containing ring preferably having 1, 2 or 3 heteroatoms selected from O, S and N. The heteroatom-containing heteroaryl groups can contain one or two oxygen or sulfur atoms per ring and/or from 1 to 4 nitrogen atoms, provided that the total number of heteroatoms in each ring is 4 or less and each ring has at least one carbon atom. The fused rings completing the bicyclic and tricyclic groups may contain only carbon atoms and may be saturated, partially saturated, or unsaturated. The nitrogen and sulfur atoms may optionally be oxidized and the nitrogen atoms may optionally be quaternized. Bicyclic or tricyclic heteroaryl groups must include at least one fully aromatic ring, and the other fused rings may be aromatic or non-aromatic. The heteroaryl group may be attached at any available nitrogen or carbon atom of any ring. If the other ring is cycloalkyl or heterocyclic, it is additionally optionally substituted with ═ O (oxygen), as valency permits.

Examples

The invention is further illustrated by the following examples. It should be understood that the method described in the examples is only for illustrating the present invention and not for limiting the present invention, and that simple modifications of the preparation method of the present invention based on the concept of the present invention are within the scope of the claimed invention. All the starting materials and solvents used in the examples, unless otherwise specified, all the reagents and starting materials were used as usual commercial products.

Preparation of polymer of formula I example 1:

(1) adding 20g of anthraphenol and 15g of naphthol into a reaction vessel, adding 50 ml of acetone in an ice bath, stirring for dissolving, keeping the temperature of the system below 10 ℃, slowly dropwise adding 30 ml of concentrated sulfuric acid, reacting at room temperature for 3 hours, pouring the reaction solution into ice water, performing suction filtration, washing with water, and drying to obtain a white solid which is directly used for the next reaction without purification.

(2) And (2) adding 10g of the product obtained in the step (1) into a reaction container, adding 25g of epoxy chloropropane, and stirring for dissolving. Maintaining the temperature of the reaction system at about 60 ℃, slowly adding 15ml of 40 wt% sodium hydroxide solution, after finishing the dropwise addition, carrying out reflux reaction for 2h, and cooling to room temperature. Washing with distilled water and toluene for 3 times, and distilling under reduced pressure to obtain polymer (wherein Ar is₁Arthromethylenes, Ar₂Naphthylene).

M of the polymer_w＝3.1×10³，M_n＝4.4×10²The molecular weight distribution coefficient is 7, and part of the nuclear magnetic data is shown below.

¹H NMR(300MHz，DMSO)：8.32(m，CH，1H)，8.03(d，CH，1H)，7.87(d，CH，1H)，7.65(d，CH，1H)，7.37(s，CH，3H)，7.29(t，CH，1H)，6.76(d，CH，1H)，6.20(d，CH，1H).

Preparation of the Polymer of formula I example 2 (wherein Ar₁Naphthylene radical, Ar₂Biphenylene): m of the polymer_w＝4.8×10³，M_n＝7.0×10²Is divided intoThe quantum distribution coefficient was 6.8 and part of the nuclear magnetic data is shown below.

¹H NMR(300MHz，DMSO)：8.43(d，CH，2H)，8.33(d，CH，1H)，8.22(t，CH，2H)，7.90(d，CH，1H)，7.53(t，CH，1H)，7.46(m，CH，2H)，7.42(m，CH，2H)，7.20(t，CH，1H)，6.73(d，CH，1H)，6.11(d，CH，1H).

Preparation of the Polymer of formula I example 3 (wherein Ar₁Arthromethylenes, Ar₂2, 2-dimethylbenzofuranyl group): m of the polymer_w＝5.6×10³，M_n＝5.6×10²The molecular weight distribution coefficient is 10, and part of the nuclear magnetic data is shown below.

¹H NMR(300MHz，DMSO)：8.43(d，CH，2H)，8.22(t，CH，2H)，7.46(m，CH，2H)，7.42(m，CH，2H)，6.86(d，CH，1H)，6.73(d，CH，1H)，2.85(s，CH₂，2H)，1.47(s，CH₃，6H).

Preparation of the composition example 1:

the component A comprises: taking 150 g of resin shown in a polymer of a formula I (preparation example 1 of the polymer of the formula I), 10g of acetone, 2 g of aluminum oxide and 1 g of ethylenediamine; and B component: curing agent T3190 g, octanol 1 g, aluminum oxide 8 and ethylenediamine 1 g; mixing the component A and the component B, and fully stirring to form a homogeneous phase.

Preparation of the composition example 2:

the component A comprises: taking 120 g of resin shown in a polymer of a formula I (preparation example 2 of the polymer of the formula I), 10g of acetone, 2 g of silicon dioxide and 1 g of diethylenetriamine; and B component: curing agent T3190 g, octanol 1 g, silicon dioxide 8 and ethylenediamine 1 g; mixing the component A and the component B, and fully stirring to form a homogeneous phase.

Preparation of the composition example 3:

the component A comprises: taking 100 g of resin shown in a polymer of a formula I (preparation example 3 of the polymer of the formula I), 10g of ethanol, 2 g of aluminum oxide and 1 g of ethylenediamine; and B component: curing agent T31100 g, octanol 1 g, aluminum oxide 8 g and ethylenediamine 1 g; mixing the component A and the component B, and fully stirring to form a homogeneous phase.

Performance testing of the compositions:

the resin adhesive T-type peel strength test method comprises the following steps: an MPT-1101T-type peel tester (Jinnan Sick test technologies, Inc.) may be used.

The flexible material is preferably of a thickness to withstand the expected tensile forces, is of a uniform thickness, does not exceed 3mm, and is capable of withstanding peel bending angles without cracking. Sample size: the length is 200mm, and the width is 25 +/-0.5 mm. The surface of the sample is treated with an adhesive in a manner well known to those skilled in the art. The whole width of each adhered test piece is coated with glue, and the coating length is 150 mm. The method for obtaining the bonding surface with clear edge is to place a thin strip material (anti-sticking tape) at the end of the bonded material to be separated, so that the part of the test piece which does not need to be bonded is not stuck by the adhesive. The adhered test piece is bonded and cured according to the method recommended by the adhesive manufacturer. If the sample is prepared and pressurized, a uniform pressure should be applied across the adhesive joint, preferably up to 1 MPa. Preferably provided with timed depressurisation means. In order to obtain a uniform pressure distribution across the glued joint, the press plates should be parallel. If not, the press platen should be covered with a resilient gasket. The gasket has a thickness of 10mm and a hardness of about 45 degrees, and it is recommended that the applied pressure be 0.7 MPa. Another method for preparing the test specimens is to glue two suitably dimensioned sheets to form an enlarged test specimen and then to cut the test specimen from the enlarged test specimen, in which the influence of cutting heat and mechanical forces on the glue joint is minimized and the outermost 12mm of the enlarged test specimen parallel to the long side of the test specimen has to be removed. A wide strip portion. The average thickness of the adhesive layer of the sample was measured. The number of each lot was not less than five. Then the sample is placed at 0-4 ℃ for seven days. The non-glued ends of the flexible test piece are symmetrically clamped in the upper and lower holders. The clamping location cannot slip to ensure that the applied tension is evenly distributed across the width of the sample. The tester was started and the upper and lower grips were separated at a rate of 100. + -.10 mm/min. The test specimen had a peel length of at least 125mm and the recording device simultaneously plotted the peel load. And attention is paid to the form of failure, i.e., adhesive failure, cohesive failure, or adherend failure.

The tensile shear strength was measured according to GB/T7124-.

Claims

1. The utility model provides a high temperature resistant frost resistant resin glue for woodwork which characterized in that: the resin adhesive comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 100-150 parts of resin shown as a polymer in a formula I, 10-15 parts of diluent, 2-5 parts of nano powder and 1-3 parts of auxiliary agent; the component B comprises the following components in parts by weight: 90-120 parts of curing agent, 1-2 parts of defoaming agent, 5-8 parts of nano powder and 1-3 parts of auxiliary agent;

the polymer of formula I is shown below:

wherein Ar is₁Is an anthracenylene radical, Ar₂Is a-2, 2-dimethylbenzofuranyl group, M of said polymer_w＝5.6×10³，M_n＝5.6×10²The molecular weight distribution coefficient was 10.

2. The high temperature resistant antifreeze resin adhesive for wood products according to claim 1, wherein: the component A comprises the following components in parts by weight: resin 150 shown as a polymer in a formula I, a diluent 10, nano powder 2 and an auxiliary agent 1; the component B comprises the following components in parts by weight: curing agent 90, defoaming agent 1, nano powder 8 and auxiliary agent 1.

3. The high temperature resistant antifreeze resin adhesive for wood products according to claim 1, wherein: the diluent is selected from acetone, ethanol, toluene, ethyl acetate and dimethylformamide; the nano powder is selected from aluminum oxide or silicon dioxide; the auxiliary agent is selected from ethylenediamine and diethylenetriamine; the antifoaming agent is selected from octanol; the curing agent is selected from PA or curing agent T31.

4. A polymer of formula I, characterized by the following:

Ar₁is an anthracenylene radical, Ar₂Is a-2, 2-dimethylbenzofuranyl group, M of said polymer_w＝5.6×10³，M_n＝5.6×10²The molecular weight distribution coefficient was 10.

5. Use of the polymer according to claim 4 in construction engineering.