阅读说明：本技术 一种泡沫塑料用粘接助剂、制备方法及应用 (Bonding auxiliary agent for foamed plastic, preparation method and application ) 是由 张勇 余启勇 潘广镇 刘光亚 吕多军 龚祥明 刘辉 赵严 吴恒 于 2021-09-03 设计创作，主要内容包括：本发明公开了一种泡沫塑料用粘接助剂、制备方法及应用,该粘接助剂由由小分子多元胺改性的异氰酸酯与单氨基硅烷偶联剂反应制得；制备方法为：将小分子多元胺溶解在有机溶剂中形成稀释液；将稀释液在20℃以下的惰性氛围下滴加到异氰酸酯中搅拌反应30-60min,接着升温到60-70℃,搅拌30-60min,反应结束,降温至20℃以下,继续将单氨基硅烷偶联剂分批次加入到混合液中,搅拌反应20-60 min,接着升温至60-70℃,搅拌反应1-2 h即得到所述的泡沫塑料用粘接助剂。该粘接助剂使泡沫塑料的粘接性能更加稳定,且一个粘接助剂分子中较多的硅氧烷结构,因此,其在改性使用时用最少的添加量即能获得最佳的性能,降低了改性成本。(The invention discloses an adhesive auxiliary agent for foamed plastic, a preparation method and application thereof, wherein the adhesive auxiliary agent is prepared by reacting micromolecular polyamine modified isocyanate with a monoamino silane coupling agent; the preparation method comprises the following steps: dissolving small molecular polyamine in an organic solvent to form a diluent; dropwise adding the diluent into isocyanate in an inert atmosphere below 20 ℃, stirring and reacting for 30-60min, then heating to 60-70 ℃, stirring for 30-60min, cooling to below 20 ℃ after the reaction is finished, continuously adding the mono-aminosilane coupling agent into the mixed solution in batches, stirring and reacting for 20-60 min, then heating to 60-70 ℃, and stirring and reacting for 1-2 h to obtain the bonding auxiliary agent for the foamed plastic. The bonding auxiliary agent enables the bonding performance of the foam plastic to be more stable, and more siloxane structures exist in one bonding auxiliary agent molecule, so that the best performance can be obtained by using the minimum adding amount during modification, and the modification cost is reduced.)

1. The bonding auxiliary agent for the foam plastic is characterized by being prepared by reacting micromolecular polyamine modified isocyanate with a monoamino silane coupling agent.

2. An adhesion promoter for foam according to claim 1, characterized in that: the mol ratio of the small molecular polyamine, the isocyanate and the monoamino silane coupling agent is 1: (3-5): (2-4).

3. A method for preparing the bonding auxiliary agent for the foam plastic as claimed in claim 1, which comprises the following steps:

dissolving small molecular polyamine in an organic solvent to form a diluent;

dropwise adding the diluent in the step (1) into isocyanate under an inert atmosphere of below 20 ℃, stirring and reacting for 30-60min, then heating to 60-70 ℃, and stirring for 30-60 min;

and (3) after the reaction in the step (2) is finished, cooling to below 20 ℃, continuously adding the mono-amino silane coupling agent into the mixed solution in the step (2) in batches, stirring and reacting for 20-60 min, then heating to 60-70 ℃, and stirring and reacting for 1-2 h to obtain the bonding auxiliary agent for the foamed plastic.

4. The method for producing a bonding assistant for foam according to claim 3, wherein: the mass ratio of the micromolecular polyamine to the organic solvent is 1: (1-2).

5. The method for producing a bonding assistant for foam according to claim 3, wherein: the micromolecular polyamine is one or more of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.

6. The method for producing a bonding assistant for foam according to claim 3, wherein: the monoamino silane coupling agent is one or more of bis (3-trimethoxysilylpropyl) amine, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane and N-phenyl-gamma-aminopropyltrimethoxysilane.

7. The method for producing a bonding assistant for foam according to claim 3, wherein: the isocyanate is one or more of 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene-2, 4-diisocyanate (TDI), and Xylylene Diisocyanate (XDI).

8. The method for producing a bonding assistant for foam according to claim 3, wherein: the organic solvent is butyl acetate, ethyl acetate, butanone, toluene or dimethyl carbonate.

9. Use of the bonding assistant for foam according to claim 1 in foam, wherein: the addition amount of the bonding auxiliary agent for the foam plastic accounts for 0.5-3% of the total weight of the foam plastic.

10. The use of an adhesion promoter for foam according to claim 9, wherein: the foamed plastic is polyurethane foam, phenolic foam, epoxy resin foam or unsaturated polyester resin foam.

Technical Field

The invention belongs to the technical field of preparation of bonding aids, and particularly relates to a bonding aid for foam plastics, a preparation method and application thereof.

Background

Generally, the adhesion performance of the existing foam and certain materials without active hydrogen, such as glass, aluminum and the like, is poor, and the market generally adopts a method of directly adding a coupling agent or a method of treating a substrate in advance to improve the adhesion performance. However, since the silane coupling agent is added directly, the molecular weight of the silane coupling agent is relatively small and the amount of siloxane contained in each molecule is at most 6, and if a good adhesion effect is to be achieved, a relatively large amount of the silane coupling agent is often added, which results in a high modification cost. If the base material is pretreated by the treating agent, the field operation is troublesome and the construction is inconvenient.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: overcomes the defects in the prior art, and provides an adhesive auxiliary agent for foam plastics, a preparation method and application thereof.

The technical scheme adopted by the invention for solving the technical problem is as follows:

the bonding auxiliary agent for the foamed plastic is prepared by reacting micromolecular polyamine modified isocyanate with a monoamino silane coupling agent.

Preferably, the mole ratio of the small-molecule polyamine to the isocyanate to the monoamino silane coupling agent is 1: (3-5): (2-4).

The preparation method of the bonding auxiliary agent for the foamed plastic comprises the following steps:

(1) dissolving small molecular polyamine in an organic solvent to form a diluent;

(2) dropwise adding the diluent in the step (1) into isocyanate under an inert atmosphere of below 20 ℃, stirring and reacting for 30-60min, then heating to 60-70 ℃, and stirring for 30-60 min;

(3) and (3) after the reaction in the step (2) is finished, cooling to below 20 ℃, continuously adding the silane coupling agent into the mixed solution in the step (2) in batches, stirring and reacting for 20-60 min, then heating to 60-70 ℃, and stirring and reacting for 1-2 h to obtain the bonding auxiliary agent for the foamed plastic.

Preferably, the mass ratio of the small molecular polyamine to the organic solvent is 1: (1-2).

Preferably, the small molecular polyamine is one or more of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.

Preferably, the monoamino silane coupling agent is one or more of bis (3-trimethoxysilylpropyl) amine, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane and N-phenyl-gamma-aminopropyltrimethoxysilane.

Preferably, the isocyanate is one or more of 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene-2, 4-diisocyanate (TDI), and Xylylene Diisocyanate (XDI).

Preferably, the organic solvent is butyl acetate, ethyl acetate, butanone, toluene or dimethyl carbonate.

The bonding auxiliary agent for the foamed plastic is applied to the foamed plastic, and the addition amount of the bonding auxiliary agent for the foamed plastic accounts for 0.5-3% of the total weight of the foamed plastic.

Preferably, the foam is a polyurethane foam, a phenolic foam, an epoxy resin foam or an unsaturated polyester resin foam.

The invention has the following positive beneficial effects:

according to the invention, the bonding auxiliary agent containing isocyanate groups, a large number of siloxane groups and a large number of carbamido groups in molecules is prepared by reacting small molecular polyamine, isocyanate and a monoamino silane coupling agent, wherein the large number of carbamido groups have the characteristics of high polarity, strong cohesive force and good adhesiveness, the siloxane groups have good bonding performance, and the more the siloxane groups are, the better the bonding performance is, so that the bonding auxiliary agent disclosed by the invention has excellent bonding performance.

Meanwhile, when the isocyanate is modified by adopting the micromolecular polyamine, the modified product contains a large amount of carbamido and has stable molecular structure.

When the adhesive is used for modifying the adhesive property of the foam plastic, a part of a foam main chain is formed by the reaction of isocyanate groups in molecules and active hydrogen in a foam plastic raw liquid, and the foam plastic main chain contains a molecular structure of an adhesive auxiliary agent, so that the adhesive auxiliary agent enables the adhesive property of the foam plastic to be more stable, and a plurality of siloxane structures are contained in one adhesive auxiliary agent molecule, so that the adhesive can obtain the optimal property by using the minimum adding amount during modification, and the modification cost is reduced.

Detailed Description

The technical solutions of the present invention will be further described in detail and clearly in the following with reference to specific examples, but the scope of the present invention is not limited thereto.

Example 1:

a preparation method of an adhesive auxiliary agent for foam plastics comprises the following specific steps:

(1) performing dehydration treatment on diethylenetriamine before reaction, and dissolving diethylenetriamine in butyl acetate at the temperature of lower than 20 ℃ to form a diluent;

(2) dropwise adding the diluent in the step (1) into 1, 6-Hexamethylene Diisocyanate (HDI) in an inert atmosphere, wherein the dropwise adding temperature is lower than 20 ℃, after dropwise adding reaction for 20 min, raising the reaction temperature to 60 ℃, and continuously stirring and reacting for 30min, wherein the stirring speed is 300 r/min;

(3) and (3) after the reaction in the step (2) is finished, cooling to below 20 ℃, continuously adding bis (3-trimethoxysilylpropyl) amine into the mixed solution in the step (2) in batches, keeping the rotating speed unchanged, stirring for reaction for 25 min, then heating to 60 ℃, and continuously stirring for reaction for 1 h to obtain the bonding auxiliary agent.

Wherein the molar ratio of diethylenetriamine, 1, 6-Hexamethylene Diisocyanate (HDI) and bis (3-trimethoxysilylpropyl) amine is 1:3: 2; the mass ratio of diethylenetriamine to butyl acetate is 1: 1.

example 2

A preparation method of an adhesive auxiliary agent for foam plastic comprises the following steps:

(1) carrying out dehydration treatment on triethylene tetramine before reaction, and dissolving triethylene tetramine in ethyl acetate at the temperature of lower than 20 ℃ to form a diluent;

(2) dropwise adding the diluent in the step (1) into isophorone diisocyanate (IPDI) in an inert atmosphere, wherein the dropwise adding temperature is lower than 20 ℃, and after dropwise adding reaction for 30min, raising the reaction temperature to 65 ℃; stirring and reacting for 40min at the rotation speed of 200 r/min

(3) And (3) after the reaction in the step (2) is finished, cooling to below 20 ℃, continuously adding the gamma-aminopropyltriethoxysilane into the mixed liquid in the step (2) in batches, keeping the rotating speed unchanged, stirring for reaction for 30min, then heating to 65 ℃, and stirring for reaction for 1.5 h to obtain the bonding auxiliary agent.

Wherein the molar ratio of triethylene tetramine, IPDI and gamma-aminopropyl triethoxysilane is 1: 4: 3; the mass ratio of triethylene tetramine to ethyl acetate is 1: 1.

example 3

A preparation method of an adhesive auxiliary agent for foam plastic comprises the following steps:

(1) carrying out dehydration treatment before reaction of tetraethylenepentamine, and dissolving the tetraethylenepentamine in toluene at the temperature lower than 20 ℃ to form a diluent;

(2) dropwise adding the diluent in the step (1) into toluene-2, 4-diisocyanate (TDI) under an inert atmosphere, wherein the dropwise adding temperature is lower than 20 ℃, after dropwise adding reaction for 40min, raising the reaction temperature to 70 ℃, and continuously stirring and reacting for 50 min;

(3) and (3) after the reaction in the step (2) is finished, cooling to below 20 ℃, continuously adding the N-phenyl-gamma-aminopropyltrimethoxysilane into the mixed liquid in the step (2) in batches, keeping the rotating speed unchanged, stirring for reacting for 45 min, then heating to 70 ℃, and stirring for reacting for 2 h to obtain the bonding auxiliary agent.

Wherein the mol ratio of tetraethylenepentamine, toluene-2, 4-diisocyanate (TDI) and N-phenyl-gamma-aminopropyltrimethoxysilane is 1: 5: 4; the mass ratio of tetraethylenepentamine to toluene is 1: 1.5.

example 4

A preparation method of an adhesive auxiliary agent for foam plastic comprises the following steps:

(1) performing dehydration treatment on diethylenetriamine before reaction, and dissolving the diethylenetriamine in dimethyl carbonate at the temperature of lower than 20 ℃ to form a diluent;

(2) dropwise adding the diluent in the step (1) into Xylylene Diisocyanate (XDI) in an inert atmosphere, wherein the dropwise adding temperature is lower than 20 ℃, after dropwise adding reaction for 40min, raising the reaction temperature to 70 ℃, and stirring for reaction for 60min, wherein the stirring speed is 300 r/min;

(3) and (3) after the reaction in the step (2) is finished, cooling to below 20 ℃, continuously adding the gamma-aminopropyltrimethoxysilane into the mixed liquid in the step (2) in batches, keeping the rotating speed unchanged, stirring and reacting for 60min, then heating to 70 ℃, and stirring and reacting for 2 h to obtain the bonding auxiliary agent.

Wherein the molar ratio of diethylenetriamine, XDI and gamma-aminopropyltrimethoxysilane is 1:3: 2; the mass ratio of diethylenetriamine to dimethyl carbonate is 1: 1.

example 5

A preparation method of an adhesive auxiliary agent for foam plastic comprises the following steps:

(1) performing dehydration treatment on diethylenetriamine before reaction, and dissolving the diethylenetriamine in butanone at the temperature lower than 20 ℃ to form a diluent;

(2) dropwise adding the diluent in the step (1) into isophorone diisocyanate (IPDI) in an inert atmosphere, wherein the dropwise adding temperature is lower than 20 ℃, after dropwise adding reaction for 50min, raising the reaction temperature to 70 ℃, and carrying out stirring reaction for 60min at the stirring rotation speed of 400 r/min;

(3) and (3) after the reaction in the step (2) is finished, cooling to below 20 ℃, continuously adding bis (3-trimethoxysilylpropyl) amine into the mixed solution in the step (2) in batches, stirring and reacting for 60min, then heating to 70 ℃, and keeping the rotating speed unchanged, stirring and reacting for 2 h to obtain the bonding auxiliary agent.

Wherein the molar ratio of diethylenetriamine, IPDI and bis (3-trimethoxysilylpropyl) amine is 1:3: 2; the mass ratio of diethylenetriamine to butanone is 1: 2.

application case 1:

the bonding aids prepared in the above examples 1 to 5 were applied to polyurethane foam according to the following addition methods, respectively, specifically:

(1) polyether, a foam stabilizer, a catalyst and a foaming agent are mixed according to a mass ratio of 96.0: 4: 0.02: 0.2, mixing evenly to prepare a component A; the polyether is YD304, the catalyst is dibutyltin dilaurate, and the foaming agent is water;

(2) uniformly mixing the bonding auxiliary agent and the isocyanate-containing polymer, and removing the solvent in the mixture to finally prepare a component B, wherein the mass ratio of the bonding auxiliary agent to the isocyanate-containing polymer is 5.0: 95.0;

(3) the component A and the component B are uniformly mixed according to the weight ratio of 1:1 and then foamed into polyurethane foam.

The application cases of the polyurethane foam modified by the bonding auxiliary agents prepared in examples 1 to 5 according to the modification method of the application case 1 are respectively marked as application cases 1 to 1; application cases 1-2; application cases 1-3; application cases 1-4; application cases 1-5.

Application case 2:

the phenolic resin foam is modified by the bonding auxiliary agent prepared in the example 1, and the modification method specifically comprises the following steps: the expandable phenolic resin is uniformly mixed with the bonding auxiliary agent prepared in the embodiment 1 according to the mass ratio of 100:3:3:2.5 under the condition of normal temperature under the condition that n-pentane is used as a foaming agent and polysorbate 80 is used as an emulsifier, the mixture is kept at the temperature of 90 ℃ for 2 hours, then the temperature is continuously increased to 170 ℃ and kept at the temperature for 4 hours, and finally the expandable phenolic resin is foamed and molded.

Application case 3:

the modification method of the bonding assistant prepared in the above example 1 to the epoxy resin foam is as follows:

the E51 type epoxy resin is mixed with the bonding auxiliary agent prepared in the example 1 under the conditions that dicyandiamide is used as a curing agent, UR300 is used as a urea promoter, and Expancel 461DU40 is used as a foaming microsphere according to the mass ratio of 100:11:3: 5: 2.5, mixing uniformly at normal temperature, keeping the temperature at 150 ℃ for 50min, and finally foaming and molding.

Application case 4:

the bonding assistant prepared in the above example 1 modifies the unsaturated polyester resin foam by the following specific modification method:

the 196 type unsaturated polyester resin and the bonding auxiliary agent prepared in the example 1 are mixed according to the mass ratio of 100:0.4: 4: 2.5, mixing uniformly at normal temperature, keeping the temperature at 125 ℃ for 50min, and finally foaming and molding.

Comparative example 1:

this example is a comparative example of application 1, and differs from application 1 in that: the polyurethane foam B component is not added with the bonding auxiliary agent prepared in the examples 1-5, namely the B component is 100 parts of isocyanate-containing polymer; the rest is the same as application case 1.

Comparative example 2:

this example is a comparative example of application case 2, and differs from application case 2 in that: the phenolic resin foam raw material component is not added with the bonding auxiliary agent prepared in the example 1; the rest is the same as application case 2.

Comparative example 3:

this example is a comparative example of application case 3, and differs from application case 3 in that: the bonding aid prepared in example 1 was not added to the epoxy resin foam raw material components; the rest is the same as application case 3.

Comparative example 4:

this example was a comparative example of application case 4, and differs from application case 4 in that: the bonding auxiliary agent prepared in example 1 was not added to the unsaturated polyester resin foam raw material components; the rest is the same as application case 4.

The foams prepared in the above application examples 1 to 4 and the foams prepared in comparative examples 1 to 4 were respectively tested for adhesion properties, and the results of the adhesion properties are shown in tables 1 and 2.

TABLE 1

	Adhesive Strength (MPa)	Form of destruction
			Application cases 1-1	7.3	3% surface destruction
Application cases 1-2	7.7	2% surface destruction
			Application cases 1 to 3	7.2	3% surface brokenBad
Application cases 1 to 4	7.9	4% surface destruction
			Application cases 1 to 5	7.5	3% surface destruction
Application case 2	8.7	3% surface destruction
			Application case 3	6.9	2% surface destruction
Application case 4	6.4	4% surface destruction

TABLE 2

	Adhesive Strength (MPa)	Form of destruction
			Comparative example 1	2.3	70% surface damage
Comparative example 2	3.2	69% surface damage
			Comparative example 3	2.0	67% surface breakdown
Comparative example 4	1.8	70% surface damage

As can be seen from tables 1 and 2: compared with the foam plastics which are not modified by the bonding auxiliary agents prepared in the embodiments 1 to 5, the modified foam plastics prepared in the application cases 1 to 4 have greatly improved bonding performance, 2 to 3 times of bonding strength when the modified foam plastics are not modified, and greatly reduced damage degree of the surface of the base material, thereby achieving the purpose of modification.