阅读说明：本技术 一种水溶性硅树脂及其应用 (Water-soluble silicone resin and application thereof ) 是由 罗洪杰 王诏田 张鸿帅 姜昊 于 2020-07-16 设计创作，主要内容包括：本发明实施例公开了一种水溶性硅树脂及其应用,属于上浆剂技术领域。一种水溶性硅树脂,以甲基三乙氧基硅烷或甲基三甲氧基硅烷为第一单体,KH-602为第二单体,水为引发剂和溶剂,HMDS为封端剂,在常温下聚合制成。本发明的水溶性硅树脂能有效提高玄武岩纤维在高温下的力学性能,对玄武岩纤维单纱进行了升温力学试验,结果表明,上浆玄武岩纤维在300℃时保持了65％以上的断裂力,在400℃时保持了49％以上的断裂力,满足工业应用要求。(The embodiment of the invention discloses water-soluble silicon resin and application thereof, belonging to the technical field of sizing agents. A water-soluble silicon resin is prepared from methyl triethoxy silane or methyl trimethoxy silane as the first monomer, KH-602 as the second monomer, water as initiator and solvent, and HMDS as end-capping agent through polymerizing at ordinary temp. The water-soluble silicone resin can effectively improve the mechanical property of basalt fiber at high temperature, and the heating mechanical test is carried out on basalt fiber single yarn, and the result shows that the sizing basalt fiber can keep more than 65% of breaking force at 300 ℃, can keep more than 49% of breaking force at 400 ℃ and meets the industrial application requirements.)

1. The water soluble silicon resin is prepared by using methyl triethoxysilane or methyl trimethoxysilane as a first monomer, N- (beta-aminoethyl) -3-aminopropyl methyl dimethoxysilane (KH-602) as a second monomer, water as an initiator and a solvent, and Hexamethyldisiloxane (HMDS) as an end-capping agent through polymerization at normal temperature.

2. The water-soluble silicone resin according to claim 1, wherein the molar ratio of the first monomer to the second monomer is 3 to 6:4 to 7.

3. The water-soluble silicone resin according to claim 1, wherein the ratio of the amount of water added (mL) to the number of moles (mol) of the first monomer is 666-2000: 1.

4. The water-soluble silicone resin according to claim 1, wherein HMDS is added in a molar amount of 1/12 to 1/6 of the molar amount of the first monomer.

5. The water-soluble silicone resin according to claim 1, wherein the first monomer and the second monomer are mixed and stirred uniformly, water is added dropwise, stirring is continued for 30-40 min after the addition, and HMDS is added, and the water is added to dilute the mixture into the water-soluble silicone resin with the concentration of 0.5-1.5%.

6. The water soluble silicone resin of claim 1 including but not limited to use in basalt fiber sizing agents.

Technical Field

The embodiment of the invention relates to the technical field of sizing agents, and particularly relates to water-soluble silicon resin and application thereof.

Background

Aerosol particles are harmful to human health, atmosphere, climate and marine surfaces and aerosol particle pollution is one of the most serious problems in modern industrial society. Through carrying out a large amount of researches on filtering and removing of dust particles in industrial flue gas, the results show that the bag filter has excellent separation efficiency (99.99%), good filter cake forming performance and low cost, can be cleaned and regenerated through pulse jet, and can be widely applied to industries such as boilers, incinerator systems, asphalt, cement, minerals, metallurgy, chemical engineering and the like.

Needle punched non-woven fabrics are one of the most widely used filter media for filter bags. In practical industrial applications, the filter bag is usually exposed to high temperature environment, and the high temperature needle punched fabric is made of polyphenylene sulfide (PPS), Polytetrafluoroethylene (PTFE), glass fiber, polyimide (p84) or composite fabric thereof, and is suitable for the temperature of 190 ℃ and 280 ℃. However, the industry has a higher desire for the application temperature of the filter bags, since a higher temperature of the filter system means lower cooling energy consumption, i.e. the higher the temperature of the bag filters, the more energy is saved.

The basalt fiber is a mineral fiber formed by melting volcanic rocks, has the main advantages of high mechanical property, fire resistance, heat resistance, chemical resistance, low cost, environmental protection, no toxicity and no health hazard, has close relationship between chemical components and structures and glass fiber, but lacks B₂O₃Containing a large amount of TiO₂、K₂O、MgO、Na₂O、Fe₂O₃And FeO, so that the basalt fiber has higher thermal resistance and better mechanical property at high temperature than the glass fiber. Therefore, it is considered that the needle-punched basalt fiber fabric can be made into a filter bag. However, the service temperature of the basalt fiber filter bag is still difficult to break through 300 ℃, and the most important reason is that the surface coating of the basalt fiber is decomposed above 300 ℃.

The fibers typically have a coating to protect and lubricate the fibers, reducing damage and yarn breakage during subsequent processing. Fiber sizing is an important process in the fiber processing process, and simultaneously, fiber sizing is one of the simplest and most economical methods for changing the surface property of fibers and improving the mechanical property of the fibers. At present, the heat-resistant sizing agent for basalt fibers is rarely researched, so that the thermal stability of the sizing agent is not matched with the use temperature of a basalt fiber filter bag. Therefore, it is necessary to find a heat-resistant sizing agent to increase the use temperature of basalt fabrics.

Polysiloxane is a polymer which takes repeated Si-O bonds as a main chain and directly connects organic groups on silicon atoms, has the advantages of strong adhesive force, high strength, small high-temperature weight loss, good film-forming property and the like, and is considered as a coating with good high-temperature resistance. Silicone resin sizing is less reported because most silicone resins are water insoluble resins.

Disclosure of Invention

In the industrial field, it is desired to increase the use temperature of filter bags. The needled basalt fiber fabric is a new material of a filter bag, but the use temperature of the needled basalt fiber fabric is still difficult to break through 300 ℃ due to the decomposition of a sizing agent. Therefore, the embodiment of the invention provides the water-soluble silicone resin and the application thereof, the water-soluble silicone resin is coated on the basalt fiber to improve the high-temperature mechanical property, the breaking force at 300 ℃ is maintained to be more than 76% and 3.8 times of that of the untreated fiber, and the breaking force at 400 ℃ is maintained to be more than 49% and 2.4 times of that of the untreated fiber.

In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:

according to the first aspect of the embodiments of the present invention, the embodiments of the present invention provide a water-soluble silicone resin, which is prepared by polymerizing methyltriethoxysilane or methyltrimethoxysilane as a first monomer, N- (β -aminoethyl) -3-aminopropylmethyldimethoxysilane (KH-602) as a second monomer, water as an initiator and a solvent, and Hexamethyldisiloxane (HMDS) as an end-capping agent at normal temperature.

Further, the molar ratio of the first monomer to the second monomer is 3-6: 4-7.

Further, the ratio of the amount of water added (mL) to the number of moles (mol) of the first monomer is 666 to 2000: 1.

Furthermore, the addition molar quantity of the HMDS is 1/12-1/6 of the molar quantity of the first monomer.

Further, after the first monomer and the second monomer are mixed and stirred uniformly, water is added dropwise, stirring is continued for 30-40 min after the addition is finished, HMDS is added, and the water is diluted into water-soluble silicone resin with the concentration of 0.5-1.5%.

The reaction equation of the water-soluble silicone resin is shown as (I):

according to a second aspect of embodiments of the present invention, embodiments of the present invention provide for the use of the water soluble silicone resins described above, including but not limited to, in basalt fiber sizing agents.

The embodiment of the invention has the following advantages:

in order to improve the mechanical property of the basalt fiber at high temperature, water-soluble silicone resin is prepared and coated on the surface of the basalt fiber. The conclusion is as follows:

1. the thermal stability of the silicone resin was investigated and the result showed that the thermal decomposition temperature of the silicone resin was above 370 ℃.

2. Surface topography studies indicate that silicone resin forms a uniform and dense layered structure for protecting the fiber surface.

3. The chemical bonding mode of the fiber is researched, and the result shows that the silicone resin and the surface of the fiber form chemical bonding;

4. dynamic contact angle research shows that the surface energy is increased after the silicon resin is sized, and the silicon resin layer can repair the defects on the fiber surface;

5. the silicone layer can effectively prevent fiber from cracking and brittleness, and the mechanical strength of the fiber at high temperature is improved. The basalt fiber single yarn is subjected to a temperature rise mechanical test, and the result shows that the sizing basalt fiber maintains over 65 percent of breaking force at 300 ℃ and over 49 percent of breaking force at 400 ℃, so that the industrial application requirements are met.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.

FIG. 1 shows the IR spectra of TBF-1, TBF-2, TBF-3 and TBF-4;

FIG. 2 shows TG curve (a) and DSC curve (b) of TBF-1, TBF-2, TBF-3 and TBF-4;

FIG. 3 is an SEM photograph of BF (a, b), TBF-1(c, d), TBF-2(e, f), TBF-3(g, h) and TBF-4(i, j);

FIG. 4 is an AFM image of BF (a), TBF-1(b), TBF-2(c), TBF-3(d), and TBF-4 (e);

FIG. 5 shows the roughness of BF, TBF-1, TBF-2, TBF-3 and TBF-4;

FIG. 6 is an XPS binding energy (B.E.) plot of BF and TBF pick unit orbits;

FIG. 7 is a comparison of force at break (a) and elongation at break (b) for BF, TBF-1, TBF-2, TBF-3 and TBF-4.

Detailed Description

The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.