CN115627562B

CN115627562B - Spinning oil for polyboroazane fibers and application thereof

Info

Publication number: CN115627562B
Application number: CN202211629420.7A
Authority: CN
Inventors: 李茹; 齐学礼; 陈勇; 吕锋; 徐浩南; 王玉娇; 刘振
Original assignee: Shandong Industrial Ceramics Research and Design Institute Co Ltd
Current assignee: Shandong Industrial Ceramics Research and Design Institute Co Ltd
Priority date: 2022-12-19
Filing date: 2022-12-19
Publication date: 2023-03-21
Anticipated expiration: 2042-12-19
Also published as: CN115627562A

Abstract

The invention provides a spinning oil agent for polyboroazane fibers and application thereof, and belongs to the technical field of fiber surface treatment and ceramic fiber preparation. The spinning oil agent for the polyboroazane fiber is prepared by mixing the following raw materials: according to parts by weight, 0.01-30 parts of silicone oil, 1-50 parts of modified silicone oil, 0.03-40 parts of mineral oil, 0.02-10 parts of fatty salt, 0.01-10 parts of surfactant and 0.02-20 parts of antioxidant; the modified silicone oil is one or more of modified silicone oil in which part of methyl in the silicone oil is replaced by phenyl, modified silicone oil in which part of methyl in the silicone oil is replaced by hydrogen, and modified silicone oil in which part of methyl in the silicone oil is replaced by phenyl and hydrogen. The spinning oil for the polyboroazane fiber can be attached to the surface of the polyboroazane fiber for protection, the bundling property and the moisture resistance of the polyboroazane fiber are improved, and the problems of surface defects and the like caused by abrasion of the polyboroazane fiber due to the friction between the surface of the polyboroazane fiber and a bundling wheel and a roller in the production process, such as moisture absorption pulverization, adhesion and doubling are avoided.

Description

Spinning oil for polyboroazane fibers and application thereof

Technical Field

The invention relates to the technical field of fiber surface treatment and ceramic fiber preparation, in particular to a spinning oil agent for polyboroazane fibers and application thereof.

Background

The boron nitride fiber serving as a ceramic fiber has excellent high-temperature resistance, excellent dielectric property and good wave-transmitting property, is expected to meet the use requirements of an aircraft in high-speed and long-time flying environments on heat wave-transmitting materials, and is an excellent material for preparing a new-generation missile radome high-temperature-resistant low-ablation wave-transmitting material reinforcement.

The current preparation processes of boron nitride fibers mainly comprise two methods, namely an inorganic precursor conversion method and an organic precursor conversion method. The polyboroazane fiber is an important precursor fiber for preparing the boron nitride fiber by an organic precursor conversion method, and has the following problems: on one hand, the polyborosilazane fiber has large brittleness and low strength, and the friction between the surface of the polyborosilazane fiber and mechanical devices such as a cluster wheel, a roller and the like in the production process leads the polyborosilazane fiber to be worn to cause the surface of the polyborosilazane fiber to generate defects, thereby further reducing the strength; on the other hand, the polyboroazane fiber has large static electricity, fiber divergence in the spinning process, poor bundling property and unobvious boundary between fiber tows, thereby bringing troubles for continuous unwinding and application in the later period; on the other hand, polyborazine has extremely high activity, is sensitive to water and is easy to absorb moisture and pulverize. These problems affect the quality of the polyboroazane fibers and boron nitride fibers made from polyboroazane fibers. Therefore, when a polyborazine fiber is obtained by spinning, it is necessary to treat the polyborazine fiber with a spinning oil agent, to improve the bundling property and moisture resistance of the polyborazine fiber, and to reduce the hard friction between the polyborazine fiber and a mechanical device. However, the conventional spin finish is often used for protecting boron nitride precursor fibers (i.e., boron oxide fibers) in an inorganic precursor conversion method, and the spin finish suitable for boron oxide fibers is reactive with polyborazine and cannot be used for protecting polyborazine fibers, and development of a spin finish suitable for polyborazine fibers is a problem to be solved in the art.

Disclosure of Invention

In order to solve the problems, the invention provides a spinning oil for polyboroazane fibers and application thereof, which are suitable for protecting the polyboroazane fibers, can improve the bundling property and the moisture resistance of the polyboroazane fibers, and avoid the problems that the surface of the polyboroazane fibers is worn to cause the surface of the polyboroazane fibers to generate defects, the polyboroazane fibers absorb moisture and are pulverized, the polyboroazane fibers are adhered and doubled, and the quality of the polyboroazane fibers and the boron nitride fibers prepared from the polyboroazane fibers is further influenced, and the like.

In one aspect, the invention provides a spinning oil for polyboroazane fibers, which is prepared by mixing the following raw materials: according to the parts by weight, 0.01-30 parts of silicone oil, 1-50 parts of modified silicone oil, 0.03-40 parts of mineral oil, 0.02-10 parts of fatty salt, 0.01-10 parts of surfactant and 0.02-20 parts of antioxidant; the modified silicone oil is one or more of modified silicone oil A which replaces part of methyl in the silicone oil by phenyl, modified silicone oil B which replaces part of methyl in the silicone oil by hydrogen and modified silicone oil C which replaces part of methyl in the silicone oil by phenyl and hydrogen.

In the present invention, the "part" of the term "partial methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In some embodiments of the present invention, the viscosity of the modified silicone oil satisfies the following condition: the viscosity of the modified silicone oil at normal temperature is 0.1-100 mPas.

In some embodiments of the invention, the modified silicone oil A is selected from modified silicone oils A ₁ Modified silicone oil A ₂ Modified silicone oil A ₃ And modified silicone oil A ₄ One or more of; modified silicone oil A ₁ The molecular formula of (A) is:

wherein, a =1-18, b =1-8; modified silicone oil A ₂ The molecular formula of (A) is:

wherein, c =1-22, d =1-8; modified silicone oil A ₃ The molecular formula of (A) is:

wherein e =1-22, f =1-12; modified silicone oil A ₄ The molecular formula of (A) is:

wherein g =1-16, h =1-7, k =1-9.

In some embodiments of the invention, the modified silicone oil B is selected from modified silicone oil B ₁ Modified silicone oil B ₂ And modified silicone oil B ₃ One or more of (a); modified silicone oil B ₁ Of the formulaComprises the following steps:

wherein m =1-25; modified silicone oil B ₂ The molecular formula of (A) is:

wherein n =1-25; modified silicone oil B ₃ The molecular formula of (A) is:

wherein p =1-25.

In some embodiments of the invention, the modified silicone oil C is selected from modified silicone oil C ₁ Modified silicone oil C ₂ Modified silicone oil C ₃ And modified silicone oil C ₄ One or more of (a); modified silicone oil C ₁ The molecular formula of (A) is:

wherein q =1-18, r =1-8; modified silicone oil C ₂ The molecular formula of (1) is:

wherein s =1-18, t =1-8; modified silicone oil C ₃ The molecular formula of (A) is:

wherein w =1-22, x =1-12; modified silicone oil C ₄ The molecular formula of (A) is:

wherein y =1-22, z =1-12.

In some embodiments of the invention, the mineral oil is selected from C ₁₀ -C ₄₀ Alkane and/or C ₁₀ -C ₄₀ Cycloalkane of (a); the fatty salt is a higher fatty acid salt with 16-24 carbon atoms, and the higher fatty acid salt is selected from one or more of magnesium stearate, calcium stearate, boron stearate, magnesium palmitate, calcium palmitate and magnesium laurate; the surfactant is trisiloxane surfactantA sex agent; the antioxidant is selected from 2,6-di-tert-butyl-4-methylphenol, beta- (4-hydroxyphenyl-3,5-di-tert-butyl) n-octadecyl propionate and tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, N-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl]Hydrazine, 4,4' methylenebis (2,6-di-tert-butylphenol), N-1,6-hexylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]One or more of (a).

In some embodiments of the present invention, the spin finish for polyborazine fibers is prepared by mixing raw materials comprising: according to parts by weight, 0.01 part of silicone oil, 20 parts of modified silicone oil, 0.03 part of mineral oil, 0.02 part of fatty salt, 0.01 part of surfactant and 0.02 part of antioxidant.

On the other hand, the invention also provides application of the spin finish for the polyboroazane fiber, which is used for protecting the polyboroazane fiber by attaching the spin finish for the polyboroazane fiber to the polyboroazane fiber while obtaining the polyboroazane fiber through spinning.

In some embodiments of the present invention, the polyborazine fiber is attached to the polyborazine fiber with a spin finish by spraying or by roller coating with a spin finish for the polyborazine fiber.

In some embodiments of the present invention, the spin finish for the polyboroazane fiber attached to the polyboroazane fiber may be removed at a degreasing temperature ranging from room temperature to 100 ℃.

Compared with the prior art, the invention has the following beneficial effects:

the spinning oil for the polyboroazane fiber prepared by the method can be attached to the surface of the polyboroazane fiber to protect the polyboroazane fiber, the spinning oil for the polyboroazane fiber has no reaction or very small reactivity with the polyboroazane fiber, the polyboroazane fiber is not damaged, the static electricity is reduced after the polyboroazane fiber is oiled, the bundling property and the moisture resistance are improved, the problems that the polyboroazane fiber has less hairiness after oiling, the polyboroazane fiber is adhered and doubled, the friction between the surface of the polyboroazane fiber and a bundling wheel and a roller in the production process causes the abrasion of the polyboroazane fiber, and the like are solved, the polyboroazane fiber has less hairiness after oiling, the quality is good, the quality of the polyboroazane fiber prepared by the polyboroazane fiber is good, and the intensity of the boron nitride fiber is high.

The substitution amount of methyl in the modified silicone oil ensures that the viscosity of the modified silicone oil is 0.1-100mPa & s at normal temperature, the viscosity of the prepared spinning oil agent for the polyborazane fiber is low, and the smooth oiling of the polyborazane fiber can be ensured; according to the preparation method, the modified silicone oil A of partial methyl in phenyl-substituted silicone oil, the modified silicone oil B of partial methyl in hydrogen-substituted silicone oil, the modified silicone oil C of partial methyl in phenyl-substituted silicone oil and hydrogen-substituted silicone oil and the combination thereof are designed and researched, and the spinning oil agent for the polyboroazane fiber prepared from the modified silicone oil with the molecular formula limited by the invention hardly reacts with the polyboroazane fiber, so that the polyboroazane fiber can be well protected; the silicone oil, the mineral oil, the surfactant and the antioxidant have certain reactivity with the polyborazine fiber when used independently, but have little or no reaction when the modified silicone oil designed by the invention is used for preparing the spinning oil agent for the polyborazine fiber, so that the excellent performance brought by the spinning oil agent for the polyborazine fiber can be retained, the problem of reactivity is solved, and the polyborazine fiber can be effectively protected.

The spinning oil for the polyborosilazane fiber is applied to the polyborosilazane fiber obtained by spinning, the polyborosilazane fiber is oiled while being obtained by spinning, the polyborosilazane fiber is oiled immediately after being formed by spinning, static electricity is reduced, bundling property is improved, the polyborosilazane fiber is prevented from absorbing moisture and being pulverized, and the polyborosilazane fiber after being oiled can be stored for a long time for later use. In addition, when the boron nitride fiber needs to be prepared, the oiled polyborosilazane fiber can be degreased at room temperature to 100 ℃, the spinning oil for the polyborosilazane fiber can be completely removed, the smooth operation of later-stage boron nitride fiber preparation procedures (such as heat treatment procedures of non-melting treatment, nitriding treatment and the like) is not influenced, the problem that the ammonia gas is prevented from contacting with the surface of the polyborosilazane fiber due to the spinning oil for the polyborosilazane fiber during nitriding is solved, the high-quality boron nitride fiber can be prepared, the average tensile strength of the prepared boron nitride fiber is 650.31MPa-676.40MPa, the tensile strength is high, and the difference of the tensile strength of each part of the same boron nitride fiber is very small, so that the boron nitride fiber prepared by the method has uniform quality of each part, the defects of the oiled polyborosilazane fiber are few due to side reaction, and the quality of each part is uniform.

Drawings

In order to more clearly illustrate the technical solution in the embodiment of the present invention, the drawings required to be used in the embodiment of the present invention will be described below.

FIG. 1 is a graph comparing the tensile strength of boron nitride fibers made from polyborazine fibers greased in example 1 of the invention and boron nitride fibers made from unboiled polyborazine fibers as comparative example.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of various aspects of the present invention is provided with specific examples, which are only used for illustrating the present invention and do not limit the scope and spirit of the present invention.

Example 1:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: according to parts by weight, 0.01 part of silicone oil, 20 parts of modified silicone oil, 0.03 part of mineral oil, 0.02 part of fatty salt, 0.01 part of surfactant and 0.02 part of antioxidant; the modified silicone oil is modified silicone oil A which replaces part of methyl in the silicone oil by phenyl, modified silicone oil B which replaces part of methyl in the silicone oil by hydrogen, and modified silicone oil C which replaces part of methyl in the silicone oil by phenyl and hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 0.1 mPas.

In this example, modified silicone oil A was modified silicone oil A ₁ Modified silicone oil A ₂ Modified silicone oil A ₃ And modified silicone oil A ₄ 。

Modified silicone oil A ₁ The molecular formula of (1) is:

wherein, a =1, b =1; modified silicone oil A ₂ The molecular formula of (A) is:

wherein c =1,d =1; modified silicone oil A ₃ The molecular formula of (A) is:

wherein e =1, f =1; modified silicone oil A ₄ The molecular formula of (A) is:

wherein g =1,h =1,k =1.

In this example, modified silicone oil B was modified silicone oil B ₁ Modified silicone oil B ₂ And modified silicone oil B ₃ 。

Modified silicone oil B ₁ The molecular formula of (A) is:

wherein m =1; modified silicone oil B ₂ The molecular formula of (A) is:

wherein n =1; modified silicone oil B ₃ The molecular formula of (A) is:

wherein p =1.

In the present example, the modified silicone oil C was modified silicone oil C ₁ Modified silicone oil C ₂ Modified silicone oil C ₃ And modified silicone oil C ₄ 。

Modified silicone oil C ₁ The molecular formula of (A) is:

wherein q =1, r =1; modified silicone oil C ₂ The molecular formula of (A) is:

wherein s =1,t =1; modified silicone oil C ₃ The molecular formula of (A) is:

wherein w =1, x =1; modified silicone oil C ₄ The molecular formula of (A) is:

wherein y =1, z =1.

In this example, the mineral oil is C ₁₀ Alkane and C ₁₀ Cycloalkane of (a); the fatty salt is higher fatty acid salt with 16 carbon atoms, and the higher fatty acid salt is magnesium stearate, calcium stearate, boron stearate, magnesium palmitate, calcium palmitate or magnesium laurate; the surfactant is a trisiloxane surfactant; the antioxidant is 2,6-di-tert-butyl-4-methylphenol, beta- (4-hydroxyphenyl-3,5-di-tert-butyl) propionic acid n-octadecylCarbonic alcohol ester, tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, N-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl]Hydrazine, 4,4' methylenebis (2,6-di-tert-butylphenol) and N, N-1,6-hexylidene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]。

In this embodiment, the preparation method of the spin finish for polyboroazane fiber comprises the following steps: weighing silicone oil, modified silicone oil, mineral oil, fatty salt, a surfactant and an antioxidant in parts by weight; and uniformly mixing and stirring to obtain the spinning oil for the polyboroazane fiber.

The embodiment also provides an application of the spin finish for a polyborozane fiber in the embodiment, and the spin finish for a polyborozane fiber in the embodiment is attached to the polyborozane fiber when the polyborozane fiber is obtained by spinning, so as to protect the polyborozane fiber. In the present example, the specific manner of attaching the spin finish for a polyborazane fiber of the present example to a polyborazane fiber is spraying or roll coating with a roller coated with a spin finish for a polyborazine fiber. The polyborazine fiber oiled by the spinning oil for the polyborazine fiber of the embodiment has good clustering property, no adhesion and doubling between the polyborazine fibers, little hairiness of the polyborazine fiber after oiling, no phenomenon of moisture absorption and pulverization, and good quality of the polyborazine fiber after oiling.

In this embodiment, when the boron nitride fiber needs to be prepared, the oil can be removed from the applied polyborosilazane fiber attached to the polyborosilazane fiber with a spinning finish at room temperature in a protective atmosphere (e.g., nitrogen atmosphere), the polyborosilazane fiber can be completely removed with the spinning finish, and after the oil is removed, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 2:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: according to parts by weight, 30 parts of silicone oil, 50 parts of modified silicone oil, 40 parts of mineral oil, 10 parts of fatty salt, 10 parts of surfactant and 20 parts of antioxidant; the modified silicone oil is modified silicone oil A which replaces part of methyl in the silicone oil by phenyl, modified silicone oil B which replaces part of methyl in the silicone oil by hydrogen, and modified silicone oil C which replaces part of methyl in the silicone oil by phenyl and hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the modified silicone oil had a viscosity of 100 mPas at room temperature.

In this example, modified silicone oil A was modified silicone oil A ₁ Modified silicone oil A ₂ And modified silicone oil A ₃ 。

Modified silicone oil A ₁ The molecular formula of (A) is:

wherein, a =18, b =5; modified silicone oil A ₂ The molecular formula of (1) is:

wherein c =22,d =4; modified silicone oil A ₃ The molecular formula of (A) is:

wherein e =22, f =7.

In this example, modified silicone oil B was modified silicone oil B ₁ And modified silicone oil B ₂ 。

Modified silicone oil B ₁ The molecular formula of (A) is:

wherein m =25; modified silicone oil B ₂ The molecular formula of (A) is:

wherein n =20.

In the present example, the modified silicone oil C was modified silicone oil C ₁ Modified silicone oil C ₂ And modified Silicone oil C ₃ 。

Modified silicone oil C ₁ The molecular formula of (A) is:

wherein q =18, r =5; modified silicone oil C ₂ The molecular formula of (1) is:

wherein s =18, t =4; modified silicone oil C ₃ The molecular formula of (A) is:

wherein w =22, x =7.

In this example, the mineral oil is C ₄₀ Alkane and C ₄₀ Cycloalkane of (a); the fatty salt is higher fatty acid salt with 24 carbon atoms, and the higher fatty acid salt is magnesium stearate, calcium stearate, boron stearate, magnesium palmitate, calcium palmitate or magnesium laurate; the surfactant is a trisiloxane surfactant; the antioxidant is 2,6-di-tert-butyl-4-methylphenol, beta- (4-hydroxyphenyl-3,5-di-tert-butyl) propionic acid n-octadecyl ester, tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, N-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl]Hydrazine and 4,4' methylenebis (2,6-di-tert-butylphenol).

The present embodiment also provides an application of the spin finish for a polyborazine fiber of the present embodiment, and the spin finish for a polyborazine fiber of the present embodiment is attached to a polyborazine fiber while obtaining a polyborazine fiber by spinning, so as to protect the polyborazine fiber. In the present example, the specific manner of attaching the spin finish for a polyborazane fiber of the present example to a polyborazane fiber is spraying or roll coating with a roller coated with a spin finish for a polyborazine fiber. The polyborosilazane fiber oiled by the spinning oil for the polyborosilazane fiber of the embodiment has good bundling property, no adhesion and doubling between the polyborosilazane fibers, little hairiness of the polyborosilazane fiber after oiling, no phenomenon of moisture absorption and pulverization, and good quality of the polyborosilazane fiber after oiling.

In this embodiment, when the boron nitride fiber needs to be prepared, the applied polyborosilazane fiber attached to the polyborosilazane fiber can be degreased with a spinning oil agent under vacuum at a degreasing temperature of 100 ℃, the polyborosilazane fiber can be completely removed with the spinning oil agent, and after degreasing, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 3:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: according to parts by weight, 0.01 part of silicone oil, 1 part of modified silicone oil, 0.03 part of mineral oil, 0.02 part of fatty salt, 0.01 part of surfactant and 0.02 part of antioxidant; the modified silicone oil is modified silicone oil A which replaces part of methyl in the silicone oil by phenyl, modified silicone oil B which replaces part of methyl in the silicone oil by hydrogen, and modified silicone oil C which replaces part of methyl in the silicone oil by phenyl and hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of methyl groups substituted, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of methyl groups substituted, and therefore, the number of methyl groups substituted is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 5 mPas.

In this example, modified silicone oil A was modified silicone oil A ₂ And modified silicone oil A ₄ 。

Modified silicone oil A ₂ The molecular formula of (A) is:

wherein c =2,d =2; modified silicone oil A ₄ The molecular formula of (A) is:

wherein g =2,h =1,k =2.

In this example, modified silicone oil B was modified silicone oil B ₂ And modified silicone oil B ₃ 。

Modified silicone oil B ₂ The molecular formula of (A) is:

wherein n =2; modified silicone oil B ₃ The molecular formula of (A) is:

wherein p =3.

In the present example, the modified silicone oil C was modified silicone oil C ₂ And modified silicone oil C ₄ 。

Modified silicone oil C ₂ The molecular formula of (A) is:

wherein s =1, t =2; modified silicone oil C ₄ The molecular formula of (A) is:

wherein y =2, z =2.

In this example, the mineral oil is C ₁₀ An alkane of (a); the fatty salt is higher fatty acid salt with 16 carbon atoms, and the higher fatty acid salt is magnesium stearate, calcium stearate, boron stearate, magnesium palmitate or calcium palmitate; the surfactant is a trisiloxane surfactant; antioxidant agent2,6-di-tert-butyl-4-methylphenol, n-octadecyl beta- (4-hydroxyphenyl-3,5-di-tert-butyl) propionate, tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]Pentaerythritol ester and N, N-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl]A hydrazine.

The embodiment also provides an application of the spin finish for a polyborozane fiber in the embodiment, and the spin finish for a polyborozane fiber in the embodiment is attached to the polyborozane fiber when the polyborozane fiber is obtained by spinning, so as to protect the polyborozane fiber. In the present example, the specific manner of attaching the spin finish for a polyborazane fiber of the present example to a polyborazane fiber is spraying or roll coating with a roller coated with a spin finish for a polyborazine fiber. The polyborosilazane fiber oiled by the spinning oil for the polyborosilazane fiber of the embodiment has good bundling property, no adhesion and doubling between the polyborosilazane fibers, little hairiness of the polyborosilazane fiber after oiling, no phenomenon of moisture absorption and pulverization, and good quality of the polyborosilazane fiber after oiling.

In this embodiment, when the boron nitride fiber needs to be prepared, the applied polyborosilazane fiber attached to the polyborosilazane fiber can be degreased with a spinning oil agent under vacuum at a degreasing temperature of 30 ℃, the polyborosilazane fiber can be completely removed with the spinning oil agent, and after degreasing, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 4:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: 2 parts of silicone oil, 10 parts of modified silicone oil, 1 part of mineral oil, 2 parts of fatty salt, 1 part of surfactant and 2 parts of antioxidant; the modified silicone oil is modified silicone oil A which replaces part of methyl in the silicone oil by phenyl, modified silicone oil B which replaces part of methyl in the silicone oil by hydrogen, and modified silicone oil C which replaces part of methyl in the silicone oil by phenyl and hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of methyl groups substituted, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of methyl groups substituted, and therefore, the number of methyl groups substituted is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the modified silicone oil had a viscosity of 10 mPas at room temperature.

In this example, modified silicone oil A was modified silicone oil A ₁ 。

Modified silicone oil A ₁ The molecular formula of (A) is:

wherein a =4,b =2.

In this example, modified silicone oil B was modified silicone oil B ₃ 。

Modified silicone oil B ₃ The molecular formula of (A) is:

wherein p =4.

In the present example, the modified silicone oil C was modified silicone oil C ₁ 。

Modified silicone oil C ₁ The molecular formula of (A) is:

wherein q =3,r =2.

In this example, the mineral oil is C ₁₀ Cycloalkane of (a); the fatty salt is higher fatty acid salt with 24 carbon atoms, and the higher fatty acid salt is magnesium stearate, calcium stearate, boron stearate and magnesium palmitate; the surfactant is a trisiloxane surfactant; antioxidant agentIs 2,6-di-tert-butyl-4-methylphenol, n-octadecyl beta- (4-hydroxyphenyl-3,5-di-tert-butyl) propanoate and tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoate]Pentaerythritol esters.

In this embodiment, when the boron nitride fiber needs to be prepared, the oil of the applied polyborosilazane fiber attached to the polyborosilazane fiber can be removed with the spin finish in a protective atmosphere (e.g., nitrogen atmosphere) at an oil removal temperature of 35 ℃, the polyborosilazane fiber can be completely removed with the spin finish, and after the oil is removed, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 5:

the embodiment provides a spinning oil for polyborazine fiber, which is prepared by mixing the following raw materials: 5 parts of silicone oil, 18 parts of modified silicone oil, 7 parts of mineral oil, 3 parts of fatty salt, 2 parts of surfactant and 4 parts of antioxidant; the modified silicone oil is modified silicone oil A in which part of methyl groups in the silicone oil are replaced by phenyl groups, and modified silicone oil B in which part of methyl groups in the silicone oil are replaced by hydrogen groups.

In the present embodiment, the "part" of the term "part methyl group" means the number of methyl groups substituted, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of methyl groups substituted, and therefore, the number of methyl groups substituted is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the modified silicone oil had a viscosity of 25 mPas at room temperature.

Modified silicone oil A ₁ The molecular formula of (A) is:

wherein, a =6, b =4; modified silicone oil A ₂ The molecular formula of (A) is:

wherein, c =6,d =3; modified silicone oil A ₃ The molecular formula of (A) is:

wherein e =6, f =5; modified silicone oil A ₄ The molecular formula of (A) is:

wherein g =5,h =2,k =3.

Modified silicone oil B ₁ The molecular formula of (A) is:

wherein m =6; modified silicone oil B ₂ The molecular formula of (A) is:

wherein n =6; modified silicone oil B ₃ The molecular formula of (1) is:

wherein p =7.

In this example, the mineral oil is C ₄₀ An alkane of (a); the fatty salt is higher fatty acid salt with 18 carbon atoms, and the higher fatty acid salt is magnesium stearate, calcium stearate and boron stearate; the surfactant is a trisiloxane surfactant; the antioxidant is 2,6-di-tert-butyl-4-methylphenol and n-octadecyl beta- (4-hydroxyphenyl-3,5-di-tert-butyl) propionate.

In this embodiment, when the boron nitride fiber needs to be prepared, the applied oil of the polyboroazane fiber attached to the polyboroazane fiber can be completely removed with the spinning oil agent in vacuum at the oil removal temperature of 40 ℃, and after the oil removal, the polyboroazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so as to obtain the boron nitride fiber.

Example 6:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: according to parts by weight, 10 parts of silicone oil, 25 parts of modified silicone oil, 12 parts of mineral oil, 5 parts of fatty salt, 4 parts of surfactant and 7 parts of antioxidant; the modified silicone oil is modified silicone oil A in which part of methyl groups in the silicone oil are replaced by phenyl groups, and modified silicone oil B in which part of methyl groups in the silicone oil are replaced by hydrogen groups.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 40 mPas.

In this example, modified silicone oil A was modified silicone oil A ₂ Modified silicone oil A ₃ And modified silicone oil A ₄ 。

Modified silicone oil A ₂ The molecular formula of (A) is:

wherein c =8,d =3; modified silicone oil A ₃ The molecular formula of (A) is:

wherein e =8, f =5; modified silicone oil A ₄ The molecular formula of (1) is:

wherein g =8,h =3,k =6.

In this example, modified silicone oil B was modified silicone oil B ₁ And modified silicone oil B ₃ 。

Modified silicone oil B ₁ The molecular formula of (A) is:

wherein m =8; modified silicone oil B ₃ The molecular formula of (A) is:

wherein p =9.

In this example, the mineral oil is C ₄₀ Cycloalkane of (a); the fatty salt is higher fatty acid salt with carbon number of 20, and the higher fatty acid salt is magnesium stearate and calcium stearate; the surfactant is a trisiloxane surfactant; the antioxidant is 2,6-di-tert-butyl-4-methylphenol.

The present embodiment also provides an application of the spin finish for a polyborazine fiber of the present embodiment, and the spin finish for a polyborazine fiber of the present embodiment is attached to a polyborazine fiber while obtaining a polyborazine fiber by spinning, so as to protect the polyborazine fiber. In the present embodiment, the spin finish for a polyborazine fiber of the present embodiment is attached to a polyborazine fiber in a specific manner of spraying or roller coating with a spin finish for a polyborazine fiber. The polyborosilazane fiber oiled by the spinning oil for the polyborosilazane fiber of the embodiment has good bundling property, no adhesion and doubling between the polyborosilazane fibers, little hairiness of the polyborosilazane fiber after oiling, no phenomenon of moisture absorption and pulverization, and good quality of the polyborosilazane fiber after oiling.

In this embodiment, when the boron nitride fiber needs to be prepared, the applied polyborosilazane fiber attached to the polyborosilazane fiber can be degreased with a spinning oil agent under vacuum at a degreasing temperature of 50 ℃, the polyborosilazane fiber can be completely removed with the spinning oil agent, and after degreasing, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 7:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: according to parts by weight, 15 parts of silicone oil, 30 parts of modified silicone oil, 15 parts of mineral oil, 7 parts of fatty salt, 6 parts of surfactant and 10 parts of antioxidant; the modified silicone oil is modified silicone oil A in which part of methyl groups in the silicone oil are replaced by phenyl groups, and modified silicone oil B in which part of methyl groups in the silicone oil are replaced by hydrogen groups.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 45 mPas.

In this example, modified silicone oil A was modified silicone oil A ₁ And modified silicone oil A ₃ 。

Modified silicone oil A ₁ The molecular formula of (A) is:

wherein, a =9, b =5; modified silicone oil A ₃ The molecular formula of (1) is:

wherein e =10, f =5.

In this example, modified silicone oil B was modified silicone oil B ₂ 。

Modified silicone oil B ₂ The molecular formula of (A) is:

wherein n =10.

In this example, the mineral oil is C ₂₀ Cycloalkane of (a); the fatty salt is higher fatty acid salt with 22 carbon atoms, and the higher fatty acid salt is magnesium stearate; the surfactant is a trisiloxane surfactant; the antioxidant is beta- (4-hydroxyphenyl-3,5-di-tert-butyl) propionic acid n-octadecyl ester and tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol esters.

In this embodiment, when the boron nitride fiber needs to be prepared, the oil of the applied polyborosilazane fiber attached to the polyborosilazane fiber can be removed with the spin finish in a protective atmosphere (e.g., nitrogen atmosphere) at an oil removal temperature of 55 ℃, the polyborosilazane fiber can be completely removed with the spin finish, and after the oil is removed, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 8:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: according to parts by weight, 20 parts of silicone oil, 35 parts of modified silicone oil, 20 parts of mineral oil, 8 parts of fatty salt, 7 parts of surfactant and 12 parts of antioxidant; the modified silicone oil is modified silicone oil B which replaces part of methyl in the silicone oil by hydrogen and modified silicone oil C which replaces part of methyl in the silicone oil by phenyl and hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 50 mPas.

Modified silicone oil B ₁ The molecular formula of (A) is:

wherein m =14; modified silicone oil B ₂ The molecular formula of (A) is:

wherein n =13; modified silicone oil B ₃ The molecular formula of (A) is:

wherein p =13.

In the present example, the modified silicone oil C was modified silicone oil C ₁ And modified silicone oil C ₄ 。

Modified silicone oil C ₁ The molecular formula of (A) is:

wherein q =13, r =5; modified silicone oil C ₄ The molecular formula of (A) is:

wherein y =14,z =7.

In this example, the mineral oil is C ₂₁ Alkane and C ₂₅ Cycloalkane of (a); the fatty salt is higher fatty acid salt with 23 carbon atoms, and the higher fatty acid salt is calcium stearate and boron stearate; the surfactant is a trisiloxane surfactant; the antioxidant is 2,6-di-tert-butyl-4-methylphenol and tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol esters.

Example 9:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: 23 parts of silicone oil, 40 parts of modified silicone oil, 22 parts of mineral oil, 6 parts of fatty salt, 8 parts of surfactant and 14 parts of antioxidant; the modified silicone oil is modified silicone oil A which replaces part of methyl in the silicone oil by phenyl and modified silicone oil C which replaces part of methyl in the silicone oil by phenyl and hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 65 mPas.

In this example, modified silicone oil A was modified silicone oil A ₂ 。

Modified silicone oil A ₂ The molecular formula of (A) is:

wherein c =14,d =7.

In the present example, the modified silicone oil C was modified silicone oil C ₂ And modified silicone oil C ₃ 。

Modified silicone oil C ₂ The molecular formula of (A) is:

wherein s =14, t =7; modified silicone oil C ₃ The molecular formula of (A) is:

wherein w =15, x =7.

In this example, the mineral oil is C ₃₅ An alkane of (a); the fatty salt is higher fatty acid salt with carbon atom number of 17, and the higher fatty acid salt is boron stearate, magnesium palmitate and magnesium laurate; the surfactant is a trisiloxane surfactant; the antioxidant is 2,6-di-tert-butyl-4-methylphenol, N-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl]Hydrazine, 4,4' methylenebis (2,6-di-tert-butylphenol) and N, N-1,6-hexylidene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]。

In this embodiment, when the boron nitride fiber needs to be prepared, the applied polyborosilazane fiber attached to the polyborosilazane fiber can be degreased with a spinning oil agent under vacuum at a degreasing temperature of 65 ℃, the polyborosilazane fiber can be completely removed with the spinning oil agent, and after degreasing, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 10:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: 27 parts of silicone oil, 48 parts of modified silicone oil, 37 parts of mineral oil, 9 parts of fatty salt, 9 parts of surfactant and 17 parts of antioxidant in parts by weight; wherein the modified silicone oil is modified silicone oil A which substitutes part of methyl in the silicone oil by phenyl.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 80 mPas.

In this example, modified silicone oil A was modified silicone oil A ₄ 。

Modified silicone oil A ₄ The molecular formula of (A) is:

wherein g =16,h =6,k =8.

In this example, the mineral oil is C ₁₂ Alkane and C ₁₃ Cycloalkane of (a); the fatty salt is higher fatty acid salt with carbon number of 19, and the higher fatty acid salt is magnesium stearate and magnesium laurate; the surfactant is a trisiloxane surfactant; the antioxidant is beta- (4-hydroxyphenyl-3,5-di-tert-butyl) propionic acid n-octadecyl ester.

In this embodiment, the preparation method of the spin finish for polyborazine fiber includes the following steps: weighing silicone oil, modified silicone oil, mineral oil, fatty salt, a surfactant and an antioxidant in parts by weight; and uniformly mixing and stirring to obtain the spinning oil for the polyboroazane fiber.

In this embodiment, when the boron nitride fiber needs to be prepared, the oil of the applied polyborosilazane fiber attached to the polyborosilazane fiber can be removed with the spin finish in a protective atmosphere (e.g., nitrogen atmosphere) at an oil removal temperature of 70 ℃, the polyborosilazane fiber can be completely removed with the spin finish, and after the oil is removed, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 11:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: 2 parts of silicone oil, 38 parts of modified silicone oil, 3 parts of mineral oil, 1 part of fatty salt, 3 parts of surfactant and 1 part of antioxidant; wherein the modified silicone oil is modified silicone oil A which substitutes part of methyl in the silicone oil by phenyl.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 75 mPas.

In this example, modified silicone oil A was modified silicone oil A ₁ Modified silicone oil A ₃ And modified silicone oil A ₄ 。

Modified silicone oil A ₁ The molecular formula of (A) is:

wherein, a =14, b =8; modified silicone oil A ₃ The molecular formula of (A) is:

wherein e =17,f =12; modified silicone oil A ₄ The molecular formula of (A) is:

wherein g =12,h =7,k =9.

In this example, the mineral oil is C ₁₅ Cycloalkane of (a); the fatty salt is higher fatty acid salt with 18 carbon atoms, and the higher fatty acid salt is boron stearate; the surfactant is a trisiloxane surfactant; the antioxidant is N, N-1,6-hexylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]。

In this embodiment, when the boron nitride fiber needs to be prepared, the applied polyborosilazane fiber attached to the polyborosilazane fiber can be degreased with a spinning oil agent under vacuum at a degreasing temperature of 80 ℃, the polyborosilazane fiber can be completely removed with the spinning oil agent, and after degreasing, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 12:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: according to parts by weight, 0.1 part of silicone oil, 40 parts of modified silicone oil, 0.2 part of mineral oil, 0.1 part of fatty salt, 0.05 part of surfactant and 0.03 part of antioxidant; wherein the modified silicone oil is modified silicone oil B which replaces part of methyl in the silicone oil by hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 20 mPas.

Modified silicone oil B ₁ The molecular formula of (A) is:

wherein m =5; modified silicone oil B ₂ The molecular formula of (A) is:

wherein n =5.

In this example, the mineral oil is C ₁₄ Alkane and C ₂₅ Cycloalkane of (a); the fatty salt is higher fatty acid salt with 21 carbon atoms, and the higher fatty acid salt is magnesium palmitate, calcium palmitate or magnesium laurate; the surfactant is a trisiloxane surfactant; the antioxidant is tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and N, N-1,6-hexylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]。

The embodiment also provides an application of the spin finish for a polyborozane fiber in the embodiment, and the spin finish for a polyborozane fiber in the embodiment is attached to the polyborozane fiber when the polyborozane fiber is obtained by spinning, so as to protect the polyborozane fiber. In the present example, the specific manner of attaching the spin finish for a polyborazane fiber of the present example to a polyborazane fiber is spraying or roll coating with a roller coated with a spin finish for a polyborazine fiber. The polyborazine fiber oiled by the spinning oil for the polyborazine fiber of the embodiment has good bundling property, no adhesion and doubling between the polyborazine fibers, little hairiness of the polyborazine fiber after oiling, no phenomenon of moisture absorption and pulverization, and good quality of the polyborazine fiber after oiling.

In this embodiment, when the boron nitride fiber needs to be prepared, the applied oil of the polyborozane fiber attached to the polyborozane fiber can be completely removed with the spinning oil at 37 ℃ under vacuum, and after the oil is removed, the polyborozane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so as to obtain the boron nitride fiber.

Example 13:

the embodiment provides a spinning oil for polyborazine fiber, which is prepared by mixing the following raw materials: according to parts by weight, 0.01 part of silicone oil, 48 parts of modified silicone oil, 0.05 part of mineral oil, 0.02 part of fatty salt, 0.02 part of surfactant and 0.07 part of antioxidant; wherein the modified silicone oil is modified silicone oil B which replaces part of methyl in the silicone oil by hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the modified silicone oil has a viscosity of 2 mPas at room temperature.

In this example, modified silicone oil B was modified silicone oil B ₁ 。

Modified silicone oil B ₁ The molecular formula of (A) is:

wherein m =2.

In this example, the mineral oil is C ₃₇ An alkane of (a); the fatty salt is higher fatty acid salt with 16 carbon atoms, and the higher fatty acid salt is magnesium laurate; the surfactant is a trisiloxane surfactant; the antioxidant is 2N, N-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl]Hydrazine, 4,4' methylenebis (2,6-di-tert-butylphenol) and N, N-1,6-hexylidene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]。

In this embodiment, when the boron nitride fiber needs to be prepared, the oil of the applied polyborosilazane fiber attached to the polyborosilazane fiber can be removed with the spin finish in a protective atmosphere (e.g., nitrogen atmosphere) at an oil removal temperature of 48 ℃, the polyborosilazane fiber can be completely removed with the spin finish, and after the oil is removed, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 14:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: 3 parts of silicone oil, 50 parts of modified silicone oil, 1 part of mineral oil, 0.5 part of fatty salt, 3 parts of surfactant and 7 parts of antioxidant; wherein the modified silicone oil is modified silicone oil C which substitutes part of methyl in the silicone oil by phenyl and hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the viscosity of the modified silicone oil at room temperature was 17 mPas.

In the present example, the modified silicone oil C was modified silicone oil C ₃ And modified silicone oil C ₄ 。

Modified silicone oil C ₃ The molecular formula of (A) is:

wherein w =4, x =3; modified silicone oil C ₄ The molecular formula of (A) is:

wherein y =4, z =4.

In this example, the mineral oil is C ₃₂ An alkane of (a); the fatty salt is higher fatty acid salt with 21 carbon atoms, and the higher fatty acid salt is boron stearate, magnesium palmitate, calcium palmitate or magnesium laurate; the surfactant is a trisiloxane surfactant; the antioxidant is 2,6-di-tert-butyl-4-methylphenol and N, N-1,6-hexylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]。

In this embodiment, when the boron nitride fiber needs to be prepared, the applied polyborosilazane fiber attached to the polyborosilazane fiber can be degreased with a spinning oil agent under vacuum at a degreasing temperature of 56 ℃, the polyborosilazane fiber can be completely removed with the spinning oil agent, and after degreasing, the polyborosilazane fiber is subjected to heat treatment processes such as infusible treatment and nitriding treatment, so that the boron nitride fiber can be obtained.

Example 15:

the embodiment provides a spinning oil agent for polyboroazane fibers, which is prepared by mixing the following raw materials: according to parts by weight, 0.07 part of silicone oil, 49 parts of modified silicone oil, 0.04 part of mineral oil, 0.06 part of fatty salt, 0.6 part of surfactant and 0.09 part of antioxidant; wherein the modified silicone oil is modified silicone oil C which substitutes part of methyl in the silicone oil by phenyl and hydrogen.

In the present embodiment, the "part" of the term "part methyl group" means the number of substituted methyl groups, and the viscosity of the modified silicone oil at ordinary temperature differs depending on the number of substituted methyl groups, and therefore, the number of substituted methyl groups is generally expressed in terms of the viscosity of the modified silicone oil at ordinary temperature. In this example, the viscosity of the modified silicone oil satisfies the following conditions: the modified silicone oil had a viscosity of 52 mPas at room temperature.

In the present example, the modified silicone oil C was modified silicone oil C ₃ 。

Modified silicone oil C ₃ The molecular formula of (A) is:

wherein w =10, x =12.

In this example, the mineral oil is C ₄₀ Cycloalkane of (a); the fatty salt is higher fatty acid salt with 16 carbon atoms, and the higher fatty acid salt is magnesium stearate and magnesium laurate; the surfactant is a trisiloxane surfaceAn active agent; the antioxidant was 4,4' methylenebis (2,6-di-tert-butylphenol).

In the above examples 1 to 15, the polyborosilazane fiber obtained by spinning is 0.5k polyborosilazane fiber (that is, the polyborosilazane fiber obtained by spinning is a polyborosilazane fiber bundle including 500 filaments), the polyborosilazane fiber of each example is attached to different positions of the same polyborosilazane fiber by the spin finish when oiling the polyborosilazane fiber of examples 1 to 15, for example, the polyborosilazane fiber drawn by the spinning apparatus may be attached to the spin finish for the polyborosilazane fiber of example 1 from the beginning, the polyborosilazane fiber of example 1 is continuously drawn by the spin finish with the spin finish attached to the drawn polyborosilazane fiber, the polyborosilazane fiber of example 1 is marked after attaching a length, the polyborosilazane fiber drawn after marking is oiled by the spin finish attached to the drawn polyborosilazane fiber of example 2, the polyborosilazane fiber is continuously marked after attaching a length, the polyborosilazane fiber is marked after attaching a length, the steps are repeated until all the polyborazane fiber drawn by the polyborazane fiber of examples 1 to which the polyborazine fiber is oiled, and the polyborazine fiber of example 1 to which is not drawn is continuously oiled, and the polyborazine fiber is obtained. Thereafter, the polyboroazane fibers were cut from the marked positions to obtain 16-stage polyboroazane fibers, which were the polyboroazane fibers of examples 1 to 15, which were oiled with the spinning oil, and the undrawn polyboroazane fibers, which were comparative examples. The polyboroazane fibers obtained by degreasing the polyboroazane fibers of examples 1 to 15 with a spin finish and then subjecting the polyboroazane fibers to heat treatment such as nonmelting treatment and nitriding treatment, the 15-stage boron nitride fibers (corresponding to the polyboroazane fibers, which is also 0.5 k) corresponding to examples 1 to 15 were obtained, and the polyboroazane fibers obtained by subjecting the ungelled polyboroazane fibers to heat treatment such as nonmelting treatment and nitriding treatment, which corresponds to the boron nitride fibers (corresponding to the polyboroazane fibers, which is also 0.5 k) corresponding to the comparative examples. Starting from the ends of the 16 segments of boron nitride fibers, 8 segments were continuously cut out in each case at the same length, and each of the 8 samples was designated as corresponding to the 16 segments of boron nitride fibers, and the tensile strength test was carried out on each sample by GB3362-2017, and the experimental data are shown in Table 1 below.

TABLE 1 tensile Strength of boron nitride fibers prepared from polyborazine fibers of examples 1-15 oiled with spin finish and unboiled polyborazine fibers as comparative examples

As shown in table 1 above and fig. 1, among the boron nitride fibers obtained from the polyborazine fibers applied with the spin finish to the polyborazine fiber of example 1, samples 1 to 8 exhibited low fluctuation in tensile strength and small variability, indicating that the boron nitride fibers obtained from the polyborazine fibers applied with the spin finish to the polyborazine fiber of example 1 exhibited uniform quality at each site, and that the polyborazine fibers applied with the side reaction had few defects and uniform quality at each site; in the boron nitride fiber prepared from the polyboroazane fiber which is not oiled, the fluctuation of the tensile strength between 1 and 8 of the sample is extremely large, and the difference is extremely large, which shows that the mass difference of each part of the boron nitride fiber prepared from the polyboroazane fiber which is not oiled is large, the side surface reflects that the polyboroazane fiber which is not oiled has more defects and the quality of each part is uneven. In the same manner, as is clear from table 1, the boron nitride fibers obtained from the polyborono-alkane fibers of examples 2 to 15, which had been oiled with the spin finish, had uniform mass at each site as compared with the boron nitride fibers obtained from the ungathered polyborono-alkane fibers. The average tensile strength of the boron nitride fibers produced from the polyboroazane fibers of examples 1-15 oiled with the spin finish was significantly higher than the average tensile strength of the boron nitride fibers produced from the non-oiled polyboroazane fibers, and the tensile strength of each sample of the boron nitride fibers produced from the polyboroazane fibers of examples 1-15 oiled with the spin finish was substantially higher than the tensile strength of each sample of the boron nitride fibers produced from the non-oiled polyboroazane fibers.

The present invention has been described in conjunction with specific embodiments which are intended to be exemplary only and are not intended to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all modifications, variations or alterations that may occur to those skilled in the art without departing from the spirit of the invention. Therefore, various equivalent changes made according to the present invention still fall within the scope covered by the present invention.

Claims

1. The spinning oil for the polyboroazane fiber is characterized by being prepared by mixing the following raw materials:

according to the parts by weight, 0.01-30 parts of silicone oil, 1-50 parts of modified silicone oil, 0.03-40 parts of mineral oil, 0.02-10 parts of fatty salt, 0.01-10 parts of surfactant and 0.02-20 parts of antioxidant;

the modified silicone oil is one or more of modified silicone oil A for replacing part of methyl in the silicone oil by phenyl, modified silicone oil B for replacing part of methyl in the silicone oil by hydrogen and modified silicone oil C for replacing part of methyl in the silicone oil by phenyl and hydrogen;

the modified silicone oil A is selected from modified silicone oil A ₁ Modified silicone oil A ₂ Modified silicone oil A ₃ And modified silicone oil A ₄ One or more of; modified silicone oil A ₁ The molecular formula of (A) is:

wherein g =1-16,h =1-7,k =1-9;

the modified silicone oil B is selected from modified silicone oil B ₁ Modified silicone oil B ₂ And modified silicone oil B ₃ One or more of (a); modified silicone oil B ₁ The molecular formula of (A) is:

wherein m =1-25; modified silicone oil B ₂ The molecular formula of (1) is:

wherein n =1-25; modified silicone oil B ₃ Is divided intoThe subformula is:

wherein p =1-25;

the modified silicone oil C is selected from modified silicone oil C ₁ Modified silicone oil C ₂ Modified silicone oil C ₃ And modified silicone oil C ₄ One or more of; modified silicone oil C ₁ The molecular formula of (A) is:

wherein q =1-18, r =1-8; modified silicone oil C ₂ The molecular formula of (A) is:

wherein y =1-22, z =1-12;

the fatty salt is a higher fatty acid salt, and the higher fatty acid salt is selected from one or more of magnesium stearate, calcium stearate, boron stearate, magnesium palmitate, calcium palmitate and magnesium laurate; the surfactant is a trisiloxane surfactant.

2. The spin finish for polyboroazane fiber according to claim 1, wherein the viscosity of the modified silicone oil satisfies the following condition: the viscosity of the modified silicone oil at normal temperature is 0.1-100 mPas.

3. A spin finish for polyboroazane fibers according to claim 1, wherein the mineral oil is selected from C ₁₀ -C ₄₀ And/or C ₁₀ -C ₄₀ Cycloalkane of (a); the antioxidant is selected from 2,6-di-tert-butyl-4-methylphenol and beta- (4)N-octadecyl (E) -hydroxyphenyl-3,5-di-tert-butyl) propionate, tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]Pentaerythritol ester, N-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl]Hydrazine, 4,4' methylenebis (2,6-di-tert-butylphenol), N-1,6-hexylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]One or more of (a).

4. The spin finish for polyborazine fiber according to claim 1, wherein the spin finish for polyborazine fiber is prepared by mixing raw materials comprising: according to parts by weight, 0.01 part of silicone oil, 20 parts of modified silicone oil, 0.03 part of mineral oil, 0.02 part of fatty salt, 0.01 part of surfactant and 0.02 part of antioxidant.

5. Use of a spin finish for a polyborazine fiber according to any one of claims 1 to 4, wherein the polyborazine fiber is spun while the polyborazine fiber is adhered to the polyborazine fiber with a spin finish to protect the polyborazine fiber.

6. The use of a spin finish for polyborazine fiber as claimed in claim 5 wherein the polyborazine fiber spin finish is applied to the polyborazine fiber by spraying or by roller coating with a spin finish for polyborazine fiber.

7. The use of a spin finish for polyborazine fiber according to claim 5, wherein the spin finish for polyborazine fiber attached to the polyborazine fiber is removable at a degreasing temperature of from room temperature to 100 ℃.