CN114941243B - Special oiling agent for polyacrylonitrile-based carbon fiber and preparation method thereof - Google Patents
Special oiling agent for polyacrylonitrile-based carbon fiber and preparation method thereof Download PDFInfo
- Publication number
- CN114941243B CN114941243B CN202210268938.6A CN202210268938A CN114941243B CN 114941243 B CN114941243 B CN 114941243B CN 202210268938 A CN202210268938 A CN 202210268938A CN 114941243 B CN114941243 B CN 114941243B
- Authority
- CN
- China
- Prior art keywords
- modified polydimethylsiloxane
- parts
- epoxy
- mol
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/65—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a special oiling agent for polyacrylonitrile-based carbon fibers and a preparation method thereof. The oil agent consists of 10 parts of amino modified polydimethylsiloxane, 10-20 parts of epoxy modified polydimethylsiloxane, 5-10 parts of polyether modified polydimethylsiloxane, 5-10 parts of high-elasticity resin modified polydimethylsiloxane, 10-30 parts of emulsifier, 1-3 parts of antistatic agent, 1-2 parts of defoamer, 3-5 parts of organic solvent and 100-200 parts of desalted water. According to the invention, the epoxy modified polydimethylsiloxane with high molecular weight and the high-elasticity resin modified polydimethylsiloxane are introduced, so that the oiling agent can form a layer of uniform protective film with certain thickness on the surface of the monofilament in the fiber bundle more easily. The oil agent has good permeability when in use, can effectively wet the surface of the fiber, can improve the bundling property and the high temperature resistance of the fiber, can avoid the problem that the precursor oil agent sticks to rollers in a drying process section, reduces the generation of fiber breakage, and improves the quality of carbon fiber precursor.
Description
Technical Field
The invention belongs to the field of carbon fiber oiling agents, and relates to a polyacrylonitrile-based carbon fiber special oiling agent and a preparation method thereof.
Background
Polyacrylonitrile (PAN) -based carbon fiber has the excellent performances of light weight, high specific strength, high specific modulus, high temperature resistance, corrosion resistance, wear resistance, fatigue resistance, electric conduction, heat conduction and the like, and is widely applied to high-end fields of military industry, aviation, aerospace and the like. However, carbon fibers are brittle materials, and surface defects are a major factor limiting the tensile strength. Suitable oiling agents and reasonable oiling procedures are effective means for preventing the carbon fiber from generating surface defects.
The oiling agent has the main functions of forming a film with uniform thickness on the surface of the spun yarn after washing, effectively preventing or eliminating static electricity generated by friction, reducing friction coefficient, endowing the fiber with the characteristics of smoothness, softness and the like, and ensuring that the fiber has proper bundling property, drafting property, fiber splitting property, spinnability, oxidation resistance and heat resistance. Especially, during the preoxidation at 200-300 ℃, local thermal adhesion or thermal doubling between monofilaments is often caused due to heat release of the sharp cyclization reaction, and the local heat accumulation or overheating of the precursor tows is more seriously caused, so that the combustion phenomenon occurs. The oiling agent endows the filaments with good fiber separation performance, even if fission products are discharged, the filaments are not adhered and combined, and local overheating or burning phenomenon is not caused. After the pre-oxidation is finished, part of heat-resistant residues can continue to play a role in subsequent processing, and the heat-resistant residues are generally more than or equal to 20%. The low-temperature carbonization process still needs to play a role in protecting the surface of the fiber, but the oiling agent is required to be volatilized completely after carbonization at 800-900 ℃. The residual oil on the surface of the fiber can have negative influence on the mechanical properties of the composite material, because the residual oil can generate nonmetallic oxides with high hardness, high heat resistance and difficult removal under the high-temperature carbonization condition.
Chinese patent publication No. CN 10540144A discloses an oil agent prepared by emulsifying amino, epoxy and polyether modified silicone oil, however, the oil agent is difficult to form a uniform protective film on the surface of a monofilament in a fiber bundle, high-performance stable carbon fiber cannot be produced, and the emulsion or the conditions of yarn breakage and the like are caused.
In summary, the special oiling agent for the carbon fiber has much more severe requirements than the general spinning oiling agent, and the good oiling agent and oiling process are guarantees of the quality of the precursor fiber, and more importantly, the oiling agent has great influence on the subsequent preoxidation and carbonization processes, and even the positioning and quality of the final carbon fiber product.
Disclosure of Invention
The invention aims to provide a special oiling agent for polyacrylonitrile-based carbon fibers and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
the special oiling agent for the polyacrylonitrile-based carbon fiber comprises the following components in parts by weight:
10 parts of amino modified polydimethylsiloxane,
10 to 20 parts of epoxy modified polydimethylsiloxane,
5 to 10 parts of polyether modified polydimethylsiloxane,
5 to 10 parts of high-elasticity resin modified polydimethylsiloxane,
10-30 parts of an emulsifying agent,
1-3 parts of antistatic agent,
1-2 parts of defoaming agent,
3-5 parts of an organic solvent,
100-200 parts of desalted water.
In the invention, the amino modified polydimethylsiloxane can be side chain diamino modified or terminal amino modified polydimethylsiloxane, the modified group is one or more of primary amino, secondary amino, pyrazinyl and phenylamino, the amino content is 0.05-1.2 mmol/g, the viscosity at 25 ℃ is 20-40000 mpa.s, and the molecular weight is 5000-110000 g/mol.
Preferably, the amino-modified polydimethylsiloxane is amino-terminated modified polydimethylsiloxane, the modified group is primary amino or secondary amino, the amino content is 0.1-0.6 mmol/g, the viscosity at 25 ℃ is 1000-20000 mpa.s, and the molecular weight is 10000-80000 g/mol.
In the specific embodiment of the invention, the amino modified polydimethylsiloxane is terminal primary amino modified polydimethylsiloxane, the ammonia value is 0.5-0.6 mmol/g, and the molecular weight is 10000g/mol.
In the invention, the epoxy modified polydimethylsiloxane is side-chain epoxy modified polydimethylsiloxane or double-end epoxy modified polydimethylsiloxane. Wherein the main chain structure C of the side chain epoxy modified polydimethylsiloxane 2 H 6 SiO unit and side chain modified epoxy group CH (O) CH 2 The molar ratio of the units is (100-200) 1, and the molar ratio of the main chain structural units and the end epoxy groups of the double-end epoxy modified polydimethylsiloxane is (300-600) 1; the molecular weight of the epoxy modified polydimethylsiloxane is 20000-100000 g/mol.
Preferably, the backbone structure C of the side-chain epoxy-modified polydimethylsiloxane 2 H 6 SiO unit and side chain modified epoxy group CH (O) CH 2 The molar ratio of the units is (150-200): 1, and the molar ratio of the main chain structural units of the double-end epoxy modified polydimethylsiloxane to the end epoxy group units is (350-500): 1; the molecular weight of the epoxy modified polydimethylsiloxane is 20000-80000 g/mol.
In a specific embodiment of the present invention, epoxy-modified polydimethylsiloxane is employed as a pendantChain epoxy modified polydimethylsiloxane wherein backbone structure C 2 H 6 SiO unit and epoxy group CH (O) CH 2 The molar ratio of the units is 150:1, and the molecular weight is 20000-80000 g/mol.
In the present invention, the molecular weight of the polyether-modified polydimethylsiloxane is 1000 to 20000g/mol, preferably 8000 to 15000g/mol.
In the invention, the high-elasticity resin modified polydimethylsiloxane is formed by grafting high-activity polyurea elastic resin with a hard chain segment on the basis of an organosilicon soft chain segment, and the molecular weight of the high-elasticity resin modified polydimethylsiloxane is 10000-50000 g/mol.
In a specific embodiment of the present invention, the molecular weight of the highly elastic resin-modified polydimethylsiloxane employed was 18000g/mol.
In the invention, the emulsifier is the existing emulsifier which is conventionally used and is suitable for carbon fiber precursor oiling agents, and comprises, but is not limited to, isomeric alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan ester, alkyl alcohol amide and the like.
In the present invention, the antistatic agent is an existing conventionally used antistatic agent suitable for carbon fiber precursor oiling agents, including, but not limited to, polyethylene glycol fatty acid esters, polyoxyethylene laurate, dodecyl trimethyl ammonium chloride, sorbitan fatty acid esters, and the like.
In the invention, the defoamer is the conventional defoamer suitable for carbon fiber precursor oiling agents, including but not limited to fatty alcohol polyoxyethylene ether, isoamyl alcohol, diisobutyl methanol, modified polymethylsiloxane defoamer and the like.
In the invention, the organic solvent is the organic solvent which is conventionally used in the prior art and is suitable for carbon fiber precursor oiling agents, and comprises but is not limited to isopropanol, ethylene glycol monobutyl ether, dimethylformamide, acetic acid and the like.
The invention also provides a preparation method of the special oiling agent for the polyacrylonitrile-based carbon fiber, which comprises the following specific steps:
according to the proportion, firstly, amino modified polydimethylsiloxane, epoxy modified polydimethylsiloxane, polyether modified polydimethylsiloxane and high-elasticity resin modified polydimethylsiloxane are uniformly mixed, and then an emulsifier, an antistatic agent, a defoaming agent and an organic solvent are added into the uniformly mixed modified polydimethylsiloxane; or, firstly, amino modified polydimethylsiloxane, epoxy modified polydimethylsiloxane, polyether modified polydimethylsiloxane, high-elasticity resin modified polydimethylsiloxane, emulsifying agent, antistatic agent, defoaming agent and organic solvent are sequentially added, and then uniformly mixed; then adding desalted water slowly under stirring, stirring for 1-3 h, and regulating the pH to 6+/-1 to prepare the special oiling agent for the polyacrylonitrile-based carbon fiber.
The special oiling agent for the polyacrylonitrile-based carbon fiber prepared by the invention is a uniform and stable emulsion, and the average particle size is 200-500 nm.
Compared with the prior art, the invention has the following advantages:
according to the invention, the epoxy polydimethylsiloxane with high molecular weight and the high-elasticity resin modified polydimethylsiloxane are introduced, so that the prepared oiling agent is easier to form a layer of uniform protective film with certain thickness on the surface of the monofilaments in the fiber bundle compared with the oiling agent prepared by emulsifying the traditional amino modified polydimethylsiloxane, epoxy modified polydimethylsiloxane and polyether modified polydimethylsiloxane. The oil agent has good permeability when in use, can effectively wet the surface of the fiber, can improve the bundling property and the high temperature resistance of the fiber, can avoid the problem that the precursor oil agent sticks to rollers in a drying process section, and reduces the generation of fiber breakage. The oiling agent disclosed by the invention has important significance for improving the quality of carbon fiber precursors and improving the protection effect on the fiber surfaces in the oiling agent pre-oxidation and carbonization processes.
Detailed Description
The following is a further description of the invention and its technical solutions in conjunction with specific embodiments, so that those skilled in the art will further understand the invention, but should not be construed as limiting the invention. Simple modifications and substitutions of the method, steps or conditions of the invention without departing from the spirit of the invention are intended to be within the scope of the invention.
In the following examples, the highly elastic resin-modified polydimethylsiloxane used was purchased from Ningbo Ruo Highway New Material technologies Co., ltd. And the product name was novel resin-modified Songgao silicone oil RH-NB-6088-5/RH-NB-6088-3.
Example 1
Taking 10 parts by weight of terminal primary amino group modified polydimethylsiloxane with ammonia value of about 0.5-0.6 mmol/g and molecular weight of about 10000g/mol, taking main chain structure (C 2 H 6 SiO) unit with epoxy group [ CH (O) CH ] 2 The molar ratio of the units is about 150:1, 10 parts by weight of side chain epoxy modified polydimethylsiloxane with the molecular weight of about 20000g/mol are taken, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol are taken, 5 parts by weight of high-elasticity resin modified polydimethylsiloxane with the molecular weight of about 18000g/mol are taken, and 20 parts by weight of fatty alcohol polyoxyethylene ether are taken as an emulsifier. After the modified polydimethylsiloxane and the emulsifier were sufficiently mixed, 3 parts by weight of a polyoxyethylene laurate antistatic agent, 2 parts by weight of a modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropyl alcohol, and 100 parts by weight of desalted water were slowly added in a stirring and emulsifying state, and the pH was adjusted to about 6 with acetic acid to obtain an oil emulsion having a solid content of 32% and an average particle size distribution of 313 nm. The oil properties and the results of the evaluation and use on the production line are shown in Table 1.
Example 2
Taking 10 parts by weight of terminal primary amino group modified polydimethylsiloxane with ammonia value of about 0.5-0.6 mmol/g and molecular weight of about 10000g/mol, taking main chain structure (C 2 H 6 SiO) unit with epoxy group [ CH (O) CH ] 2 15 parts by weight of side chain epoxy modified polydimethylsiloxane with the molecular weight of 20000g/mol, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol, 5 parts by weight of high-elasticity resin modified polydimethylsiloxane with the molecular weight of 18000g/mol and 20 parts by weight of fatty alcohol polyoxyethylene ether serving as an emulsifier are taken according to the unit molar ratio of about 150:1. After the modified polydimethylsiloxane and the emulsifier are fully mixed, 3 parts by weight of polyoxyethylene laurate antistatic agent, 2 parts by weight of modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropanol and 100 parts by weight of desalted water are slowly added under stirring and emulsifying state, and the pH is regulated to about 6 by acetic acid to obtainTo an oil emulsion having a solids content of 34% and an average particle size distribution of 340 nm. The oil properties and the results of the evaluation and use on the production line are shown in Table 1.
Example 3
Taking 10 parts by weight of terminal primary amino group modified polydimethylsiloxane with ammonia value of about 0.5-0.6 mmol/g and molecular weight of about 10000g/mol, taking main chain structure (C 2 H 6 SiO) unit with epoxy group [ CH (O) CH ] 2 The molar ratio of the units is about 150:1, 20 parts by weight of side chain epoxy modified polydimethylsiloxane with the molecular weight of about 20000g/mol are taken, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol are taken, 5 parts by weight of high-elasticity resin modified polydimethylsiloxane with the molecular weight of about 18000g/mol are taken, and 20 parts by weight of fatty alcohol polyoxyethylene ether are taken as an emulsifier. After the modified polydimethylsiloxane and the emulsifier are fully mixed, 3 parts by weight of polyoxyethylene laurate antistatic agent, 2 parts by weight of modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropanol and 100 parts by weight of desalted water are slowly added under stirring and emulsifying conditions, and the pH is regulated to be about 6 by acetic acid, so that the oil emulsion with the solid content of 38% and the average particle size distribution of 386nm is obtained. The oil properties and the results of the evaluation and use on the production line are shown in Table 1.
Example 4
Taking 10 parts by weight of terminal primary amino group modified polydimethylsiloxane with ammonia value of about 0.5-0.6 mmol/g and molecular weight of about 10000g/mol, taking main chain structure (C 2 H 6 SiO) unit with epoxy group [ CH (O) CH ] 2 The molar ratio of the unit is about 150:1, 10 parts by weight of side chain epoxy modified polydimethylsiloxane with the molecular weight of about 50000g/mol are taken, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol are taken, 5 parts by weight of high-elasticity resin modified polydimethylsiloxane with the molecular weight of about 18000g/mol are taken, and 20 parts by weight of fatty alcohol polyoxyethylene ether are taken as an emulsifier. After the modified polydimethylsiloxane and the emulsifier are fully mixed, 3 parts by weight of polyoxyethylene laurate antistatic agent, 2 parts by weight of modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropanol and 100 parts by weight of desalted water are slowly added under stirring and emulsifying state, and the pH is regulated to be about 6 by acetic acid to obtain the solid content of 32 percent and the average particle size distribution of the solid content is obtained402nm oil emulsion. The oil properties and the results of the evaluation and use on the production line are shown in Table 1.
Example 5
Taking 10 parts by weight of terminal primary amino group modified polydimethylsiloxane with ammonia value of about 0.5-0.6 mmol/g and molecular weight of about 10000g/mol, taking main chain structure (C 2 H 6 SiO) unit with epoxy group [ CH (O) CH ] 2 The molar ratio of the unit is about 150:1, 10 parts by weight of side chain epoxy modified polydimethylsiloxane with the molecular weight of about 80000g/mol, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol, 5 parts by weight of high-elasticity resin modified polydimethylsiloxane with the molecular weight of about 18000g/mol and 20 parts by weight of fatty alcohol polyoxyethylene ether are taken as an emulsifier. After the modified polydimethylsiloxane and the emulsifier are fully mixed, 3 parts by weight of polyoxyethylene laurate antistatic agent, 2 parts by weight of modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropanol and 100 parts by weight of desalted water are slowly added under stirring and emulsifying conditions, and the pH is regulated to about 6 by acetic acid, so that the oil emulsion with the solid content of 33% and the average particle size distribution of 450nm is obtained. The oil properties and the results of the evaluation and use on the production line are shown in Table 1.
Example 6
Taking 10 parts by weight of terminal primary amino group modified polydimethylsiloxane with ammonia value of about 0.5-0.6 mmol/g and molecular weight of about 10000g/mol, taking main chain structure (C 2 H 6 SiO) unit with epoxy group [ CH (O) CH ] 2 The molar ratio of the unit is about 150:1, 10 parts by weight of side chain epoxy modified polydimethylsiloxane with the molecular weight of about 50000g/mol are taken, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol are taken, 10 parts by weight of high-elasticity resin modified polydimethylsiloxane with the molecular weight of about 18000g/mol are taken, and 20 parts by weight of fatty alcohol polyoxyethylene ether are taken as an emulsifier. After the modified polydimethylsiloxane and the emulsifier are fully mixed, 3 parts by weight of polyoxyethylene laurate antistatic agent, 2 parts by weight of modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropanol and 100 parts by weight of desalted water are slowly added under stirring and emulsifying conditions, and the pH is regulated to about 6 by acetic acid to obtain the oil emulsion with the solid content of 36% and the average particle size distribution of 416 nm. Oil properties and productionThe results of the on-line evaluation are shown in Table 1.
Comparative example 1
Taking 10 parts by weight of terminal primary amino group modified polydimethylsiloxane with ammonia value of about 0.5-0.6 mmol/g and molecular weight of about 10000g/mol, taking main chain structure (C 2 H 6 SiO) unit with epoxy group [ CH (O) CH ] 2 30 parts by weight of side chain epoxy modified polydimethylsiloxane with the molecular weight of about 50000g/mol, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol, 5 parts by weight of high-elasticity resin modified polydimethylsiloxane with the molecular weight of about 18000g/mol and 20 parts by weight of fatty alcohol polyoxyethylene ether serving as an emulsifier are taken according to the unit molar ratio of about 150:1. After the modified polydimethylsiloxane and the emulsifier were sufficiently mixed, 3 parts by weight of a polyoxyethylene laurate antistatic agent, 2 parts by weight of a modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropyl alcohol, and 100 parts by weight of desalted water were slowly added in a stirring and emulsifying state, and the pH was adjusted to about 6 with acetic acid to obtain an oil emulsion having a solid content of 41% and an average particle size distribution of 752 nm. The oil properties and the results of the evaluation and use on the production line are shown in Table 1.
Comparative example 2
Taking 10 parts by weight of terminal primary amino group modified polydimethylsiloxane with ammonia value of about 0.5-0.6 mmol/g and molecular weight of about 10000g/mol, taking main chain structure (C 2 H 6 SiO) unit with epoxy group [ CH (O) CH ] 2 The molar ratio of the units is about 150:1, 10 parts by weight of side chain epoxy modified polydimethylsiloxane with the molecular weight of about 50000g/mol is taken, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol is taken, and 20 parts by weight of fatty alcohol polyoxyethylene ether is taken as an emulsifier. After the modified polydimethylsiloxane and the emulsifier are fully mixed, 3 parts by weight of polyoxyethylene laurate antistatic agent, 2 parts by weight of modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropanol and 100 parts by weight of desalted water are slowly added under stirring and emulsifying conditions, and the pH is regulated to about 6 by acetic acid, so that the oil emulsion with the solid content of 30% and the average particle size distribution of 398nm is obtained. The oil properties and the results of the evaluation and use on the production line are shown in Table 1.
Comparative example 3
Take the ammonia value about10 parts by weight of terminal primary amino group modified polydimethylsiloxane having a molecular weight of about 10000g/mol and having a main chain structure (C) 2 H 6 SiO) unit with epoxy group [ CH (O) CH ] 2 The molar ratio of the unit is about 150:1, 10 parts by weight of side chain epoxy modified polydimethylsiloxane with the molecular weight of about 50000g/mol are taken, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol are taken, 15 parts by weight of high-elasticity resin modified polydimethylsiloxane with the molecular weight of about 18000g/mol are taken, and 20 parts by weight of fatty alcohol polyoxyethylene ether are taken as an emulsifier. After the modified polydimethylsiloxane and the emulsifier were sufficiently mixed, 3 parts by weight of a polyoxyethylene laurate antistatic agent, 2 parts by weight of a modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropyl alcohol, and 100 parts by weight of desalted water were slowly added in a stirred and emulsified state, and the pH was adjusted to about 6 to obtain an oil emulsion having a solid content of 39% and an average particle diameter distribution of 424 nm. The oil properties and the results of the evaluation and use on the production line are shown in Table 1.
Comparative example 4
Taking 10 parts by weight of primary amine radical modified polydimethylsiloxane with the molecular weight of 10000g/mol and the ammonia value of about 0.5-0.6 mmol/g, 5 parts by weight of polyether modified polydimethylsiloxane with the molecular weight of 8000g/mol, 5 parts by weight of high-elasticity resin modified polydimethylsiloxane with the molecular weight of about 18000g/mol and 20 parts by weight of fatty alcohol polyoxyethylene ether as an emulsifier. After the modified polydimethylsiloxane and the emulsifier were sufficiently mixed, 3 parts by weight of a polyoxyethylene laurate antistatic agent, 2 parts by weight of a modified polydimethylsiloxane type defoamer, 5 parts by weight of isopropyl alcohol, and 100 parts by weight of desalted water were slowly added in a stirred and emulsified state, and the pH was adjusted to about 6 to obtain an oil emulsion having a solid content of 27% and an average particle diameter distribution of 252 nm. The oil properties and the results of the evaluation and use on the production line are shown in Table 1.
Comparative example 5
All of the above examples and comparative examples were performed on 12K tows, and this comparative example produced example 4 on 24K tows.
As can be seen from Table 1, the epoxy-modified polydimethylsiloxane content of the oils of examples 1, 2, 3 and comparative example 1 was gradually increased (from 5 parts to 30 parts), and the average particle size distribution of the resulting oils was also gradually increased. This is because the high molecular weight epoxy-modified polydimethylsiloxane is difficult to thoroughly shear disperse during emulsification to form larger particle aggregates, and thus emulsion stability is poor, fiber strength is reduced, and ash content is increased. In comparative example 4, the emulsion was very layered and the running condition of the filaments was poor and the fiber strength was lowest because no epoxy modified polydimethylsiloxane was added to the finish. The epoxy-modified polydimethylsiloxane in the oils of examples 1, 4 and 5 had gradually increased molecular weight, which also resulted in an increase in the average particle size of the oils, but the oil prepared in example 4 had the best performance, the greatest fiber strength, and the best carbon hairiness.
The content of the highly elastic resin-modified polydimethylsiloxane in the oils of comparative example 2, examples 4, 6 and comparative example 3 was gradually increased, and when the content was 5 parts, the emulsion stability of the oils, the hairiness of the strands and the like, the carbon filament strength and the like were optimal. From the results of example 4 and comparative example 5, the oiling agent prepared by the invention is applicable to the production of 12K and 24K carbon fiber precursors at the same time, and has wide application range.
Claims (10)
1. The special oiling agent for the polyacrylonitrile-based carbon fiber is characterized by comprising the following components in parts by weight:
10 parts of amino modified polydimethylsiloxane,
10-20 parts of epoxy modified polydimethylsiloxane,
5-10 parts of polyether modified polydimethylsiloxane,
5-10 parts of high-elasticity resin modified polydimethylsiloxane,
10-30 parts of an emulsifying agent,
1-3 parts of an antistatic agent,
1-2 parts of a defoaming agent,
3-5 parts of an organic solvent,
100-200 parts of desalted water;
the epoxy modified polymerThe dimethyl siloxane is side chain epoxy modified dimethyl siloxane or double end epoxy modified dimethyl siloxane; wherein the main chain structure C of the side chain epoxy modified polydimethylsiloxane 2 H 6 SiO unit and side chain modified epoxy group CH (O) CH 2 The molar ratio of the units is (100-200) 1, and the molar ratio of the main chain structural units and the epoxy end groups of the double-end epoxy modified polydimethylsiloxane is (300-600) 1; the molecular weight of the epoxy modified polydimethylsiloxane is 20000-100000 g/mol;
the high-elasticity resin modified polydimethylsiloxane is formed by grafting high-activity polyurea elastic resin with a hard chain segment on the basis of an organosilicon soft chain segment, and the molecular weight of the high-elasticity resin modified polydimethylsiloxane is 10000-50000 g/mol.
2. The oil solution special for polyacrylonitrile-based carbon fiber according to claim 1, wherein the amino-modified polydimethylsiloxane is side chain diamino-modified or amino-terminated-modified polydimethylsiloxane, the modified groups are one or more of primary amino groups, secondary amino groups, oxazinyl groups and phenylamino groups, the amino content is 0.05-1.2 mmol/g, the viscosity at 25 ℃ is 20-40000 mpa.s, and the molecular weight is 5000-110000 g/mol.
3. The oil solution special for polyacrylonitrile-based carbon fiber according to claim 1, wherein the amino-modified polydimethylsiloxane is amino-terminated modified polydimethylsiloxane, the modified group is primary amino or secondary amino, the amino content is 0.1-0.6 mmol/g, the viscosity at 25 ℃ is 1000-20000 mpa.s, and the molecular weight is 10000-80000 g/mol.
4. The oil solution special for polyacrylonitrile-based carbon fiber according to claim 1, wherein the amino-modified polydimethylsiloxane is primary amine-terminated modified polydimethylsiloxane, the ammonia value is 0.5-0.6 mmol/g, and the molecular weight is 10000g/mol.
5. The oil solution for polyacrylonitrile-based carbon fiber as claimed in claim 1, which is characterized in thatIn the main chain structure C of the side chain epoxy modified polydimethylsiloxane 2 H 6 SiO unit and side chain modified epoxy group CH (O) CH 2 The molar ratio of the units is (150-200) 1, and the molar ratio of the main chain structural units and the epoxy end groups of the double-end epoxy modified polydimethylsiloxane is (350-500) 1; the molecular weight of the epoxy modified polydimethylsiloxane is 20000-80000 g/mol.
6. The oil solution for polyacrylonitrile-based carbon fiber as claimed in claim 1, wherein the epoxy-modified polydimethylsiloxane is a side chain epoxy-modified polydimethylsiloxane, wherein the main chain structure is C 2 H 6 SiO unit and epoxy group CH (O) CH 2 The molar ratio of the units is 150:1, and the molecular weight is 20000-80000 g/mol.
7. The oil solution special for polyacrylonitrile-based carbon fiber according to claim 1, wherein the molecular weight of the polyether modified polydimethylsiloxane is 1000-20000 g/mol.
8. The oil solution special for polyacrylonitrile-based carbon fiber according to claim 1, wherein the molecular weight of the polyether modified polydimethylsiloxane is 8000-15000 g/mol, and the molecular weight of the high-elasticity resin modified polydimethylsiloxane is 18000-g/mol.
9. The oil solution special for polyacrylonitrile-based carbon fiber according to claim 1, wherein the emulsifier is selected from the group consisting of isomeric alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan ester and alkyl alcohol amide; the antistatic agent is selected from polyethylene glycol fatty acid ester, polyoxyethylene laurate, dodecyl trimethyl ammonium chloride or sorbitan fatty acid ester; the defoaming agent is selected from fatty alcohol polyoxyethylene ether, isoamyl alcohol, diisobutyl methanol or modified polymethyl siloxane type defoaming agent; the organic solvent is selected from isopropanol, ethylene glycol monobutyl ether, dimethylformamide or acetic acid.
10. The preparation method of the special oiling agent for the polyacrylonitrile-based carbon fiber according to any one of claims 1 to 9, which is characterized by comprising the following specific steps:
according to the proportion, firstly, amino modified polydimethylsiloxane, epoxy modified polydimethylsiloxane, polyether modified polydimethylsiloxane and high-elasticity resin modified polydimethylsiloxane are uniformly mixed, and then an emulsifier, an antistatic agent, a defoaming agent and an organic solvent are added into the uniformly mixed modified polydimethylsiloxane; or, firstly, amino modified polydimethylsiloxane, epoxy modified polydimethylsiloxane, polyether modified polydimethylsiloxane, high-elasticity resin modified polydimethylsiloxane, emulsifying agent, antistatic agent, defoaming agent and organic solvent are sequentially added, and then uniformly mixed; and then adding desalted water slowly under stirring, stirring for 1-3 h, and regulating the pH to 6+/-1 to prepare the polyacrylonitrile-based carbon fiber special oiling agent with the particle size of 200-500 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210268938.6A CN114941243B (en) | 2022-03-18 | 2022-03-18 | Special oiling agent for polyacrylonitrile-based carbon fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210268938.6A CN114941243B (en) | 2022-03-18 | 2022-03-18 | Special oiling agent for polyacrylonitrile-based carbon fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114941243A CN114941243A (en) | 2022-08-26 |
| CN114941243B true CN114941243B (en) | 2023-05-26 |
Family
ID=82905774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210268938.6A Active CN114941243B (en) | 2022-03-18 | 2022-03-18 | Special oiling agent for polyacrylonitrile-based carbon fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114941243B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115679481B (en) * | 2022-09-08 | 2023-08-08 | 中复神鹰碳纤维股份有限公司 | Oiling agent for polyacrylonitrile carbon fiber precursor with low friction coefficient and preparation method thereof |
| CN115787147B (en) * | 2022-11-30 | 2024-05-17 | 上海丰泽源科技有限公司 | Oiling agent for polyacrylonitrile-based carbon fiber precursor and preparation method thereof |
| CN116657287B (en) * | 2023-07-14 | 2024-05-07 | 中复神鹰碳纤维股份有限公司 | High heat-resistant carbon fiber oiling agent and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4048230B2 (en) * | 2002-03-19 | 2008-02-20 | 東レ株式会社 | Precursor fiber for carbon fiber and method for producing the same |
| CN103031619B (en) * | 2011-09-30 | 2014-12-10 | 中国石油化工股份有限公司 | Small tows PAN-based carbon fiber precursor oiling agent |
| US8986647B2 (en) * | 2011-10-21 | 2015-03-24 | Wacker Chemical Corporation | Hydrophilic silicone copolymers useful in carbon fiber production |
| CN104179019A (en) * | 2014-08-25 | 2014-12-03 | 中复神鹰碳纤维有限责任公司 | Preparation method of carbon fiber precursor oil agent |
| CN107829306B (en) * | 2017-10-31 | 2020-04-10 | 中复神鹰碳纤维有限责任公司 | Coated carbon fiber precursor oiling agent and preparation method thereof |
| CN110042667B (en) * | 2019-05-09 | 2021-09-14 | 吉林乾仁新材料有限公司 | Preparation method of isocyanate modified polyether silicone oil nonionic emulsion, product and application thereof |
| CN110117366B (en) * | 2019-05-15 | 2021-09-14 | 吉林乾仁新材料有限公司 | Preparation of cationic amino modified epoxy silicone oil and preparation and application of polyacrylonitrile carbon fiber precursor oil agent |
-
2022
- 2022-03-18 CN CN202210268938.6A patent/CN114941243B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114941243A (en) | 2022-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114941243B (en) | Special oiling agent for polyacrylonitrile-based carbon fiber and preparation method thereof | |
| CN111139555B (en) | High-heat-resistance oil agent and preparation method of polyacrylonitrile carbon fiber thereof | |
| WO2023088399A1 (en) | Oiling agent for polyacrylonitrile carbon fiber precursors and preparation method therefor | |
| CN107829306B (en) | Coated carbon fiber precursor oiling agent and preparation method thereof | |
| CN102776786B (en) | Non-emulsion type pure oiling agent for high speed spinning of polyamide-6 filaments | |
| JPH0741677A (en) | Diorganopolysiloxane composition having excellent heat resistance | |
| JPH11217734A (en) | Carbon fiber and its production | |
| CN111501338B (en) | Efficient preparation process of DTY elasticizing auxiliary agent composite material | |
| CN114622417A (en) | Carbon fiber oil capable of quickly crosslinking to form film | |
| CN115679481A (en) | Oil agent for polyacrylonitrile carbon fiber precursor with low friction coefficient and preparation method thereof | |
| CN115679480A (en) | PAN (polyacrylonitrile) -based carbon fiber precursor oiling agent | |
| JP2007039866A (en) | Oil agent for carbon fiber precursor and carbon fiber precursor | |
| JP2009197358A (en) | Flame resistant polymer fiber bundle and method for producing flame resistant fiber bundle | |
| JP4305081B2 (en) | Oil for carbon fiber production and method for producing carbon fiber | |
| CN116288819B (en) | Bisphenol A main chain type benzoxazine polyether block modified carbon fiber oiling agent and preparation thereof | |
| CN116657286A (en) | Oil solution for ultrahigh-strength carbon fiber precursor and preparation method thereof | |
| CN115109260B (en) | Heat-resistant carbon fiber precursor oiling agent and preparation method thereof | |
| CN115613166B (en) | Benzoxazine modified carbon fiber oil agent and preparation method thereof | |
| JP2008202208A (en) | Precursor fiber for carbon fiber, carbon fiber and method for producing thereof | |
| JP4862226B2 (en) | Precursor fiber for carbon fiber and method for producing carbon fiber | |
| CN116657287B (en) | High heat-resistant carbon fiber oiling agent and preparation method thereof | |
| JPH05140821A (en) | Production of acrylic fiber for producing carbon fiber | |
| CN117513011A (en) | High-performance polyacrylonitrile carbon fiber precursor oiling agent and preparation method thereof | |
| CN114232139A (en) | Preparation method of carbon fiber oil for dry-jet wet-spun precursor | |
| JPS62231078A (en) | Production of acrylic precursor for producing carbon fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |