阅读说明：本技术 一种含有环氧基团的笼状倍半硅氧烷交联剂的制备方法 (Preparation method of cage-like silsesquioxane cross-linking agent containing epoxy group ) 是由 张求慧 杨国超 黄新鑫 于 2019-11-14 设计创作，主要内容包括：本发明涉及一种含有环氧基团的笼状倍半硅氧烷交联剂的制备方法。为了更好地解决大豆蛋白胶黏剂的强度问题,耐水性差,易燃等问题,提出了采用添加含有环氧基团的笼状聚倍半硅氧烷改善大豆蛋白胶黏剂的强度、阻燃性能,提高大豆蛋白胶黏剂的应用效果。该发明以γ-(2,3-环氧丙氧)丙基三甲氧基硅烷(KH560)为主体,利用水解—缩合的反应原理制备含有环氧基团支链的笼状倍半硅氧烷。在紫外光照射下,将KH560乙醇溶液中进行水解反应脱去甲醇形成含有硅羟基的硅醇。将制得的硅醇在弱碱性的氨水中进行高温缩合反应,最终旋蒸、清洗、旋蒸得到含有环氧基团的笼状倍半硅氧烷交联剂。(The invention relates to a preparation method of a cage-shaped silsesquioxane cross-linking agent containing epoxy groups. In order to better solve the problems of strength, poor water resistance, flammability and the like of the soybean protein adhesive, the method for improving the strength and the flame retardant property of the soybean protein adhesive by adding the cage-shaped polysilsesquioxane containing epoxy groups is provided, and the application effect of the soybean protein adhesive is improved. The invention takes gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) as a main body, and prepares the cage-shaped silsesquioxane containing epoxy group branched chains by utilizing the reaction principle of hydrolysis-condensation. Under the irradiation of ultraviolet light, KH560 ethanol solution is hydrolyzed to remove methanol, thus forming silanol containing silicon hydroxyl. And (3) carrying out high-temperature condensation reaction on the prepared silanol in alkalescent ammonia water, and finally carrying out rotary evaporation, cleaning and rotary evaporation to obtain the cage-shaped silsesquioxane cross-linking agent containing the epoxy group.)

1. A preparation method of a cage-shaped silsesquioxane cross-linking agent containing epoxy groups comprises the following steps:

1) adding 5-50 g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) and 230ml of deionized water into a three-neck flask, and stirring vigorously for 5 minutes at room temperature;

2) adding 50-150 ml of absolute ethyl alcohol into the mixed solution, and continuously stirring for five minutes at room temperature;

3) placing the solution prepared in the step 2) under ultraviolet light with the wavelength of 360nm for irradiating for 4-6 hours, and stirring vigorously;

4) carrying out reduced pressure distillation on the solution prepared in the step 3), wherein the vacuum degree is-0.1 MPa, the temperature is 50-80 ℃, and distilling is carried out until no liquid flows out;

5) pouring the viscous substance prepared in the step 4) into a three-neck flask, adding 200ml of ammonia water, heating to 80 ℃, refluxing, and continuously reacting for 10 hours;

6) carrying out reduced pressure distillation on the solution prepared in the step 5), wherein the vacuum degree is-0.1 MPa, the temperature is 50-70 ℃, and distilling is carried out until no liquid flows out;

7) washing the viscous substance prepared in the step 6) by using acetone, and then carrying out reduced pressure distillation, wherein the vacuum degree is-0.1 MPa, the temperature is 50-70 ℃, and the distillation is carried out until no liquid flows out;

8) repeating the step 7) once, and then carrying out freeze drying at the temperature of-40 ℃.

Technical Field

The invention relates to a preparation method of an organic-inorganic hybrid cross-linking agent, in particular to a method for improving the water resistance and the flame retardance of a soybean protein adhesive.

Background

At present, the quantity of natural forest wood is sharply reduced in the global scope, the demand of human beings on wood products is continuously increased, and in order to solve the demand of human beings on wood products, the method for preparing various artificial boards based on fast growing wood becomes an effective solution. However, most adhesives used for preparing the artificial boards at present contain hazardous chemical substances such as formaldehyde, VOC and the like. The hazardous volatile gas released by the adhesive in the using process can cause great harm to human bodies. The soybean-based protein adhesive taking soybean products such as soybean protein isolate, soybean meal and the like as main materials has environmental protection, economy and safety, and can be used as a green adhesive for preparing artificial boards to replace aldehydes adhesives, so that the release of harmful gases is avoided. At present, because the soybean protein is hydrophilic groups, a large amount of binding water and free water are combined, most of protein structures are connected by hydrogen bonds, and the hydrogen bonds are hydrophilic groups and are easy to absorb water, so that the bio-based adhesive has the defects of poor water resistance, low strength and flammability, is easy to crack, warp and adhere when used for manufacturing artificial boards, and has the problems of unqualified fire safety and the like. In order to overcome the problems of poor water resistance, low strength and flammability of soybean protein, acid-base modification, grafting modification, acylation modification, carbamide guanidine hydrochloride modification, enzymatic modification and the like are proposed by researchers at present. The soybean protein is modified by strong acid and strong alkali, so that hydrogen bonds are strengthened, the strength of the adhesive is strengthened, and the water resistance of the relative adhesive is obviously reduced. The method of modifying the soybean protein adhesive by acetylation has the characteristic of poor water resistance although the strength of the adhesive can be enhanced. The urea guanidine hydrochloride modified soy protein adhesive can effectively improve the dry and wet strength of the adhesive, but ammonia gas with pungent smell is released in the using process, so that the normal use of the plywood is seriously influenced; the soybean protein adhesive can be modified by the enzyme method under a mild environment, the hydrolysis degree of protein can be controlled, even the breaking position of peptide bonds can be controlled, however, the modification treatment process conditions of the enzyme are high, and the activity cannot be lost easily. The soybean protein adhesive prepared by graft modification can form a large molecular weight net structure, and the connection of different functional groups enables the molecular structure to be criss-cross, so that the strength and the water resistance of the adhesive can be effectively improved; however, graft modification has the disadvantage of poor flame retardancy.

In order to better solve the problems of strength, poor water resistance, flammability and the like of the soybean protein adhesive, the method for improving the strength and the flame retardant property of the soybean protein adhesive by adding the cage-shaped polysilsesquioxane containing epoxy groups is provided, and the application effect of the soybean protein adhesive is improved. Polysilsesquioxane containing a cage-shaped structure is prepared by utilizing a siloxane hydrolysis condensation reaction containing a carbon chain, contains an inorganic inner core and an organic branched chain with reaction activity, and the crosslinking property of soybean protein can be improved by adding the cage-shaped polysilsesquioxane to form a high-crosslinked polymeric macromolecular protein adhesive material.

Disclosure of Invention

The invention provides a preparation method of a cage-shaped silsesquioxane cross-linking agent containing epoxy groups, which takes gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) as a main body and utilizes the hydrolysis-condensation reaction principle to prepare the cage-shaped silsesquioxane containing epoxy group branched chains. Under the irradiation of ultraviolet light, KH560 is put into ethanol solution for hydrolysis reaction to remove methanol and form silanol containing silicon hydroxyl. And (3) carrying out high-temperature condensation reaction on the prepared silanol in alkalescent ammonia water, and finally carrying out rotary evaporation, flow cleaning and rotary evaporation to obtain the cage-shaped silsesquioxane cross-linking agent containing the epoxy group.

The technical problem solved by the invention is realized by adopting the following technical scheme:

1) adding 5-50 g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) and 230ml of deionized water into a three-neck flask, and stirring vigorously for 5 minutes at room temperature;

2) adding 50-150 ml of absolute ethyl alcohol into the mixed solution, and continuously stirring for five minutes at room temperature;

3) placing the solution prepared in the step 2) under ultraviolet light with the wavelength of 360nm for irradiating for 4-6 hours, and stirring vigorously;

4) carrying out reduced pressure distillation on the solution prepared in the step 3), wherein the vacuum degree is-0.1 MPa, the temperature is 50-80 ℃, and distilling is carried out until no liquid flows out;

5) pouring the viscous substance prepared in the step 4) into a three-neck flask, adding 200ml of ammonia water, heating to 80 ℃, refluxing, and continuously reacting for 10 hours;

6) carrying out reduced pressure distillation on the solution prepared in the step 5), wherein the vacuum degree is-0.1 MPa, the temperature is 50-70 ℃, and distilling is carried out until no liquid flows out;

7) washing the viscous substance prepared in the step 6) by using acetone, and then carrying out reduced pressure distillation, wherein the vacuum degree is-0.1 MPa, the temperature is 50-70 ℃, and the distillation is carried out until no liquid flows out;

8) repeating the step 7) once, and freeze-drying at-40 deg.C

Detailed Description

The invention provides a preparation method of a cage-shaped silsesquioxane cross-linking agent containing epoxy groups, which comprises the following steps.

1) Adding 5-50 g of KH560 and 230ml of deionized water into a three-neck flask at the same time, and violently stirring for 5 minutes at room temperature;

2) adding 50-150 ml of absolute ethyl alcohol into the mixed solution, and continuously stirring for five minutes at room temperature;

3) placing the solution prepared in the step 2) in ultraviolet light with the wavelength of 360nm for irradiation for 4-6 hours, and stirring vigorously;

4) carrying out reduced pressure distillation on the solution prepared in the step 3), wherein the vacuum degree is-0.1 MPa, the temperature is 50-80 ℃, and distilling is carried out until no liquid flows out;

5) pouring the viscous substance prepared in the step 4) into a three-neck flask, adding 200ml of ammonia water, heating to 80 ℃, refluxing, and continuously reacting for 10 hours;

6) carrying out reduced pressure distillation on the solution prepared in the step 5), wherein the vacuum degree is-0.1 MPa, the temperature is 50-70 ℃, and distilling is carried out until no liquid flows out;

7) washing the viscous substance prepared in the step 6) by using acetone, and then carrying out reduced pressure distillation, wherein the vacuum degree is-0.1 MPa, the temperature is 50-70 ℃, and the distillation is carried out until no liquid flows out;

8) repeating the step 7) once, and freeze-drying at-40 deg.C

The method for preparing the caged silsesquioxane cross-linking agent containing the epoxy group, which is provided by the invention, comprises the steps of adding 31.8g of KH560 and 230ml of deionized water into a three-neck flask, and stirring vigorously for 5 minutes at room temperature; adding 100ml of absolute ethyl alcohol into the mixed solution, and continuously stirring for five minutes at room temperature; placing the solution prepared in the step under ultraviolet light with the wavelength of 360nm for irradiating for 5 hours, and stirring vigorously; carrying out reduced pressure distillation on the solution prepared in the step until no liquid flows out, wherein the vacuum degree is-0.1 MPa and the temperature is 70 ℃; pouring the viscous substance prepared in the step into a three-neck flask, adding 200ml of ammonia water, heating to 80 ℃, refluxing, and continuously reacting for 10 hours; distilling the solution obtained in the above steps under reduced pressure at a vacuum degree of-0.1 MPa and a temperature of 60 ℃ until no liquid flows out; washing the viscous substance prepared by the steps by using acetone, and then carrying out reduced pressure distillation at the vacuum degree of-0.1 MPa and the temperature of 60 ℃ until no liquid flows out; repeating the above steps once, and freeze-drying at-40 deg.C.

The above is merely a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto. It will be appreciated by those skilled in the art that the present invention is not limited by the embodiments described above, which are presented in the description to illustrate the principles of the invention. Various changes and modifications may be made to the invention without departing from the spirit and scope of the invention, and such changes and modifications are intended to be within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.