CN110117366B - Preparation of cationic amino modified epoxy silicone oil and preparation and application of polyacrylonitrile carbon fiber precursor oil agent - Google Patents
Preparation of cationic amino modified epoxy silicone oil and preparation and application of polyacrylonitrile carbon fiber precursor oil agent Download PDFInfo
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- 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
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- 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
- D06M15/652—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups comprising amino groups
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- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Abstract
The invention relates to a preparation method of self-assembled self-emulsified water-based cationic amino modified epoxy silicone oil and compounding and application of a polyacrylonitrile carbon fiber precursor oiling agent. Mixing certain amount of hydrophilic M1 and hydrophobic primary amine (R-NH) at room temperature2) Or a secondary diamine (R)1NH‑R‑NHR1) Putting the mixture into a reaction kettle, heating to 50-80 ℃ for melting or dissolving, adding a certain amount of epoxy resin and epoxy silicone oil, reacting for 2-6 hours at 90-115 ℃ in a nitrogen atmosphere, cooling to room temperature to obtain amino modified epoxy silicone oil (AMOA), and adding a salifying reagent into the reaction kettle for neutralization; and after stirring uniformly, adding a certain amount of water for emulsification to obtain the self-assembled self-emulsifying aqueous cationic amino modified epoxy silicone oil emulsion. AMOA is compounded with one or more of auxiliary silicone oil AMS1, AMS2 and AMS3, other additives and deionized water are added, and a polyacrylonitrile carbon fiber precursor oiling agent is prepared under stirring and is applied to a polyacrylonitrile carbon fiber production line.
Description
Technical Field
The invention relates to a key component of a polyacrylonitrile carbon fiber precursor oiling agent, a preparation method of cationic amino modified epoxy silicone oil and compounding with auxiliary silicone oil, in particular to a preparation technology of self-assembled self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil, a compounding method of a polyacrylonitrile carbon fiber precursor oiling agent and application in production of polyacrylonitrile carbon fiber precursors.
Background
In the background description of the US patent US20170284016A1, the oil agent is mainly epoxy modified silicone oil, amino modified silicone oil, polyether modified silicone oil and the compound thereof. The oil agent has the function of protecting polyacrylonitrile carbon fiber precursor from pre-oxidation at 200-400 ℃ in an air atmosphere and carbonization at an inert gas atmosphere, and the polyacrylonitrile carbon fiber precursor does not stick to a roller, and does not melt or merge filaments when the temperature reaches 1000 ℃ or above.
The oiling agent can protect and improve polyacrylonitrile carbon fiber precursor, and the precursor after oiling has antistatic, friction-resistant and filament-breaking functions in a series of processes such as drying, rolling and the like. The epoxy modified silicone oil is high temperature resistant, the amino modified silicone oil and polyacrylonitrile carbon fiber precursor have good adsorbability and increase the flexibility of the fiber material, and the polyether modified silicone oil has the characteristics of smoothness, softness, low surface tension, good hydrophilicity and moisture absorption, excellent antistatic performance and the like.
However, modified silicone oil agents, particularly amino-modified silicone oils, are unstable in a weakly acidic aqueous phase and are susceptible to decomposition crosslinking reaction, resulting in an increase in the viscosity of the oil emulsion. After oiling, polyacrylonitrile carbon fiber precursor is subjected to crosslinking reaction easily in the high-temperature drying process by using modified silicone oil, so that the viscosity of an oiling agent on the surface of the precursor is increased, the oiling agent is adhered to a roller, and the phenomena of fiber breakage and fuzz are caused.
The modified silicone oil can generate silicon dioxide in the pre-oxidation and carbonization processes of more than 200 ℃ and is discharged from an exhaust system, but the amino modified silicone oil and the epoxy modified silicone oil are subjected to a cross-linking reaction at high temperature and cannot be completely decomposed into silicon dioxide, and a large amount of modified silicone oil remains in carbon fibers, a pre-oxidation and carbonization furnace in the form of tar, so that the performance of the carbon fibers such as broken filaments and broken filaments is seriously influenced.
Polyether modified silicone oil is generally synthesized by addition reaction of polyethylene glycol monoallyl ether with hydrogen-containing silicone oil under a platinum catalyst, the efficiency of addition reaction of the hydrogen-containing silicone oil with the polyethylene glycol monoallyl ether decreases as the molecular weight of the polyethylene glycol monoallyl ether increases, and in addition, the platinum catalyst causes the color of the product to become grey, requiring the use of activated carbon for decolorization and filtration, and when the molecular weight of the hydrogen-containing silicone oil exceeds 3000, the viscosity of the product polyether modified silicone oil is very high, and it is difficult to filter and separate the decolorized activated carbon.
When epoxy modified silicone oil, amino modified silicone oil and polyether modified silicone oil with low polyether content are compounded, 20% of emulsifier is needed. The emulsifier is used for reducing the heat resistance of the oil agent, and on the other hand, the oil agent is easy to migrate along with the volatilization of water when the oil agent is formed on the surface of the polyacrylonitrile carbon fiber precursor, so that the film formation of the oil agent on the surface of the precursor is uneven. In addition, the oil emulsion prepared by using the emulsifier is easy to generate phase separation and has poor storage stability.
Aiming at the technical problems that the existing patent is difficult to implement and the production process of polyacrylonitrile carbon fiber precursors is difficult, the invention researches and develops self-assembly and self-emulsification cationic amino modified epoxy silicone oil, on one hand, an emulsifier is not needed, the size of the emulsion can be adjusted, and on the other hand, the storage stability of the modified silicone oil emulsion is good. Compared with similar oil agents abroad, the carbonized carbon fiber mechanical property is improved a little relatively.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of self-assembled self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil and the compounding and application of a polyacrylonitrile carbon fiber precursor oiling agent.
The invention aims to provide the self-assembly self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil emulsion prepared by the method, and the oleophylic and hydrophilic characteristics of the cationic amino modified epoxy silicone oil emulsion are changed by changing the molar ratio of hydrophilic polyether amine M1 (polyethylene glycol monomethyl ether shown in figure 1) to hydrophobic amine (octadecylamine shown in figure 1), so that the emulsion has the self-assembly self-emulsifying characteristic, the use of an emulsifier is avoided, and the storage stability of the oil emulsion is achieved; the particle size of the emulsion is controlled, and the oil solution emulsion is prevented from permeating into the polyacrylonitrile carbon fiber precursor, thereby preventing the formation of a graphitized structure during precursor carbonization.
The invention aims to provide the self-assembled self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil emulsion prepared by the method, and two molecular chain segments with large performance difference are linked in the same high molecular chain segment through the ring opening reaction of organic amine, epoxy resin and epoxy silicone oil. The epoxy resin such as bisphenol A epoxy resin has strong dipole-dipole intermolecular force among molecular chain segments, interaction and cohesion among the molecular chain segments of the cationic amino modified silicone oil polymer are enhanced, the particle size of the prepared oil emulsion is reduced along with the increase of the content of the bisphenol A epoxy resin, and conversely, the particle size of the prepared oil emulsion is increased, and the silicon content of the cationic amino modified epoxy silicone oil emulsion is changed, as shown in figure 2.
The invention aims to provide the self-assembled self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil emulsion prepared by the method, and the molecular weight of the cationic amino modified epoxy silicone oil is regulated and controlled by the molar ratio of organic amine to epoxy resin to epoxy silicone oil. The molecular weight is increased, the winding aggregation degree of polymer molecular chain segments is enhanced, and the particle size of the oil emulsion is reduced, as shown in Table 1.
The invention aims to provide the cationic amino modified epoxy silicone oil emulsion, which increases the film forming property and the adhesive force of modified silicone oil on the surface of polyacrylonitrile carbon fiber precursor through the hydrogen bond action between the nitrile group of the polyacrylonitrile carbon fiber precursor and the hydroxyl group of the modified silicone oil.
TABLE 1 cationic amino-modified silicone oil emulsion particle size varying with its molecular weight
The invention aims to provide a method for preparing a polyacrylonitrile carbon fiber precursor oiling agent by compounding cationic amino modified epoxy silicone oil emulsion, amino modified silicone oil, hydroxyl amino modified silicone oil and isocyanate modified polyether silicone oil. The oil agent has high heat resistance, the 5% thermal decomposition temperature is more than 350 ℃, and the temperature requirement (200-300 ℃) of the polyacrylonitrile carbon fiber precursor during pre-oxidation in air is met.
The invention aims to provide a method for preparing a polyacrylonitrile carbon fiber precursor oiling agent by compounding cationic amino modified epoxy silicone oil emulsion, amino modified silicone oil, hydroxyl amino modified silicone oil and isocyanate modified polyether silicone oil. The oil agent has the advantages of friction resistance, antistatic property and bundling property. Amino-modified silicone oil, hydroxy amino-modified silicone oil and isocyanate-modified polyether silicone oil, because the molecular chain segment contains amino (-NH)2) Hydroxyl (-OH) and carbamate (-NHCOO-) can form hydrogen bond with nitrile group (-CN) of polyacrylonitrile carbon fiber precursor, and the bonding force is large, thereby increasing the bundling property of the polyacrylonitrile carbon fiber precursor.
The invention aims to provide a method for preparing a polyacrylonitrile carbon fiber precursor oiling agent by compounding cationic amino modified epoxy silicone oil emulsion and amino modified silicone oil, which verifies that the oiling agent contains the amino modified silicone oil, and the polyacrylonitrile carbon fiber precursor is subjected to crosslinking reaction in the high-temperature drying process after oiling due to the instability of the amino modified silicone oil, so that the viscosity of the oiling agent on the surface of the precursor is increased, and the precursor is bonded with a drying roller and a conveying roller to cause filament breakage and broken filaments.
The invention aims to provide a polyacrylonitrile carbon fiber precursor oiling agent prepared by compounding one or two of cationic amino modified epoxy silicone oil emulsion, hydroxyl amino modified silicone oil and isocyanate modified polyether silicone oil by the method, wherein the oiling agent has the functions of bundling, lubricating and antistatic in the production process of polyacrylonitrile carbon fiber precursors. After the protofilament is carbonized, the mechanical property of the carbon fiber is equivalent to that of the used foreign oil agent, even slightly higher.
The purpose of the invention is realized by the following scheme: a preparation method of self-assembly self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil is characterized in that hydrophilic and hydrophobic groups are grafted to molecular structures of epoxy resin and epoxy silicone oil through an epoxy ring-opening reaction, and dimethyl silicone oil with high heat resistance is linked to a chain segment of the epoxy resin, so that the molecular weight is increased to a certain range, and the hydrophilic-hydrophobic characteristics of the amino modified epoxy silicone oil are changed, and the preparation method comprises the following steps:
(1) mixing certain amount of M1 with hydrophilicity and primary amine (R-NH) with hydrophobicity2) Or a secondary diamine (R)1NH-R-NHR1) Adding the mixture into a reaction kettle, and heating to 50-80 ℃ under nitrogen;
(2) adding epoxy resin and epoxy silicone oil, and controlling a certain proportion range;
(3) timing the reaction time when the temperature reaches the preset temperature, and cooling to room temperature after a certain time to obtain cationic amino modified epoxy silicone oil (AMOA);
(4) adding a pH regulator into the AMOA, adding water, and stirring to prepare a cationic amino modified epoxy silicone oil emulsion with the weight fraction of the amino modified epoxy silicone oil being 32%;
(5) adding a certain amount of one or more of auxiliary silicone oil AMS1, AMS2 and AMS3 into AMOA, adding a pH regulator and deionized water under stirring, and then adding other additives to prepare the aqueous polyacrylonitrile carbon fiber precursor silicone oil with the weight fraction of 32%.
M1 in the step (1) is amino-terminated polyether amine.
Preferably, the amino-terminated polyether amine is polyethylene glycol monoalkyl ether amine (R (OCH)2CH2)nNH2) Polypropylene glycol monoalkyl ether amine (R (OCH)2CH(CH3))nNH2) Or polyethylene glycol/propylene glycol copolymethylamine (R (OCH)2CH2）m1-(OCH2CH(CH3))m2NH2) And R is an alkyl group such as methyl, ethyl.
Preferably, the primary amine (R-NH) described in step (1)2) Or a secondary diamine (R)1NH-R-NHR1) Is primary or secondary monoamine.
Preferably, the monoprimary amine is aliphatic amine, specifically octadecylamine, dodecylamine, decamine, nonamine, octamine, heptamine, hexamine and/or aromatic amine such as aniline, methylaniline, naphthylamine and their combination, but not limited to the monoprimary amines listed in this patent.
The secondary diamine is one of N, N' -diethylethylenediamine, diethylenediamine (piperazine) and a combination thereof, but is not limited to the secondary diamines listed in the patent.
The epoxy resin in the step (2) is one of bisphenol a epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol a epoxy resin, novolac epoxy resin, brominated epoxy resin, aliphatic epoxy resin such as 1, 4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, epoxy-terminated polyacrylate and a combination thereof, but is not limited to the epoxy resin and the epoxy resin containing a bis-epoxy group listed in the patent.
The epoxy silicone oil in the step (2) is diepoxy end group dimethyl silicone oil, and the molecular structure is as follows:
the polyether amine M1 has the type M600 molecular weight of 600, the type M1000 molecular weight of 1000 and the type M2070 molecular weight of 2000, but is not limited to the types and molecular weight polyether amines listed in the patent.
The preset temperature in the step (3) is 80-120 ℃, and the optimal reaction temperature is selected to be 90-115 ℃ according to the reaction activity of amine.
The reaction time of the step (3) is 2-5 hours.
The pH regulator in the step (4) is formic acid and glacial acetic acid low-boiling-point organic acid.
The dosage of the pH regulator is the same as or not more than the total mole number of M1, primary amine (R-NH 2) or secondary diamine and the like.
The auxiliary silicone oil AMS1, AMS2 and AMS3 in the step (5) are respectively amino modified silicone oil, hydroxyl amino modified silicone oil and isocyanate modified polyether silicone oil.
Preferably, the amino-modified silicone oil is previously filed patent application No. 201811035932.4, publication No. 109180948 a.
Preferably, the hydroxyamino-modified silicone oil is previously patented, patent application No. 201910224377.8
Preferably, the isocyanate-modified polyether silicone oil is previously patented, patent application No. 201910360093.1
The invention provides self-assembled self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil, wherein the hydrophilicity and lipophilicity can be controlled, and the self-assembled self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil is prepared by any one of the methods, wherein the molar ratio of M1 to primary amine or secondary diamine is =1: 0-0: 1, and the optimal molar ratio is 0.8: 0.2-0.1: 0.9; the amino modified epoxy silicone oil of the invention has different hydrophilicity and lipophilicity and different molecular weight according to different molecular structures, and the particle size range of the silicone oil emulsion is more than 150nm.
The molar ratio of the epoxy resin to the epoxy silicone oil in the step (2) is (0-0.5): (1-0.5), and the optimal molar ratio is (0-0.25): (1-0.75), the heat resistance and the emulsion particle size of the cationic amino modified epoxy silicone oil are regulated and controlled to be more than 150nm by optimizing the type of the epoxy resin, the molecular weight of the epoxy silicone oil and the ratio of the epoxy resin to the epoxy silicone oil.
The inventionThe self-assembled self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil is provided, and the molecular weight can be controlled; the modified amino-modified epoxy silicone oil prepared by the method of any one of the preceding claims, wherein the molecular weight is calculated according to the equation: (n + 1) MWep+n*x%MM1+n(1- x %)MPA= MW, x% is the mole percentage content of M1 and primary or secondary amine, MWepIs the average molecular weight of epoxy resin and epoxy silicone oil, MM1Is M1 molecular weight, MPAThe molecular weight of primary amine or secondary diamine, n is the feeding molar ratio of epoxy resin, epoxy silicone oil and amine, and MW is the molecular weight of the modified epoxy resin. The MW of the series of amino modified epoxy silicone oil is controlled to be 5000-500000, and the optimal molecular weight is 10000-30000; the influence of the viscosity, the emulsion particle size, the operability and the film forming property on the surface of the polyacrylonitrile carbon fiber precursor is adjusted by optimizing the molecular weight of the amino modified epoxy silicone oil.
In the step (5), the compounding mass ratio of the cationic amino modified epoxy silicone oil to the auxiliary silicone oil (amino modified silicone oil, hydroxyl amino modified silicone oil and isocyanate modified polyether silicone oil) is 6: 4-9: 1, optimum range: 6.5: 3.5-8.5: 1.5.
The invention provides a preparation method of self-assembled self-emulsified amphiphilic water cationic amino modified epoxy silicone oil and a compound of polyacrylonitrile carbon fiber precursor oil, which is characterized in that hydrophilic and hydrophobic groups are grafted to molecular structures of epoxy resin and epoxy silicone oil through an epoxy ring-opening reaction, incompatible epoxy resin and epoxy silicone oil are linked together, the molecular weight of amino modified epoxy silicone oil is increased, and auxiliary modified silicone oil and other additive products, namely the polyacrylonitrile carbon fiber precursor oil, are added, and the preparation method comprises the following specific steps:
(1) mixing certain amount of hydrophilic M1 and hydrophobic monoamine (R-NH)2) Or a secondary diamine (R)1NH-R-NHR1) Adding into a reaction kettle, mixing in a certain amount of solvent, heating to dissolve or melt, adding a certain amount of epoxy resin such as bisphenol A epoxy resin and epoxy silicone oil at 50-80 deg.C, and mechanically stirring and protecting with nitrogen gasIn the reaction kettle;
(2) setting the reaction temperature at a certain temperature, and heating after the reaction temperature is stable;
(3) and when the temperature reaches the preset temperature, timing the reaction time, and cooling to room temperature after a certain time to obtain the amino modified epoxy silicone oil.
(4) Taking out the amino modified epoxy silicone oil, and adding a salifying reagent to adjust the pH value;
(5) and after stirring uniformly, adding a certain amount of water for emulsification to obtain the self-assembled self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil emulsion.
(6) Taking out a certain amount of amino modified epoxy silicone oil, adding one or more of amino modified silicone oil, hydroxyl amino modified silicone oil and isocyanate modified polyether silicone oil according to a certain proportion, stirring uniformly, adding a salifying reagent to adjust the pH, and adding a certain amount of water to emulsify to obtain the self-assembled self-emulsifying modified silicone oil compound oil agent.
(7) Adding an antistatic agent, a surfactant, an antioxidant, an antibacterial agent, a pH regulator and water into the modified silicone oil compound oil agent to prepare a polyacrylonitrile carbon fiber precursor oil agent finished product with the solid content of 32%.
M1 in the step (1) is polyether amine with terminal amino. The monoamine described in step (1) is an aliphatic amine such as octadecylamine, dodecylamine, decaamine, nonamine, octamine, heptamine, hexamine and/or in the presence of a suitable solvent
Or aromatic amines such as aniline, methylaniline, naphthylamine, and the like, and combinations thereof, but are not limited to the monoamines listed in this patent.
The diepoxy resin in step (1), such as bisphenol a epoxy resin, is one of E-51 type epoxy resin, 0164 type epoxy resin, polyglycidyl ether, bisphenol F epoxy resin 170, and the like, and combinations thereof, but is not limited to the epoxy resins listed in this patent.
The epoxy silicone oil in the step (1) is double-end epoxy dimethyl silicone oil (shown in claim 8).
The molecular weight of the polyether amine is 1000 in M1000 and 2000 in M2070.
And (2) setting the temperature at 80 ℃, slowly raising the temperature, and finally setting the temperature at 90-110 ℃.
The reaction time of the step (3) is 2-5 hours.
The salt forming agent in the step (4) is glacial acetic acid.
The water in the step (5) is deionized water.
Step (6) describes that a certain proportion is set at 80%: 20 percent, wherein the weight fraction of the amino modified epoxy silicone oil is 80 percent, and the amino modified epoxy silicone oil is used as a film forming agent. The other three modified silicone oils are used as auxiliary oil agents, the total amount is 20%, and the modified silicone oil has lubricating, bundling and antistatic effects. However, the film-forming agent oil and the auxiliary oil are not limited to the compounding ratio listed in the patent.
Step (7) describes that the additives are respectively:
the antistatic agent is nonionic propylene glycol, polyethylene glycol, polypropylene glycol, etc., the cationic type is quaternary ammonium salt such as tetrabutylammonium bromide, dodecyl dimethyl benzyl ammonium chloride, tetrabutyl phosphonium bromide, etc., and the dosage is 0.1-5%;
the surfactant is a fluorine-containing compound such as 3M FC-4430, VF-9120 of Shanghai Weiteng chemical engineering development Co., Ltd., Dynol 604 and surfynol 420 of American gas company, and the dosage is 0.05-0.1%;
the antioxidant is phenol compound such as antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate), 1076 (octadecyl beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate), 2, 6-di-tert-butyl-p-cresol (BHT), etc., phosphite ester, 0.1-0.5%;
the antibacterial agent is quaternary ammonium salt (dodecyl dimethyl benzyl ammonium chloride), imidazole, thiazole, isothiazole copper;
the pH regulator is formic acid or glacial acetic acid. The dosage of the glacial acetic acid is the same as or not more than the molar weight of amine substances such as M1 and the like.
A self-assembled self-emulsifying amphiphilic water-based cationic amino modified epoxy silicone oil is prepared by any one of the methods. The cationic amino modified epoxy silicone oil emulsion prepared by modifying epoxy silicone oil with high molar ratio hydrophobic amine (such as octadecylamine: methoxy polyetheramine with the molecular weight of 1000=0.9:01) is suitable for the main component of polyacrylonitrile carbon fiber precursor oiling agent.
By setting different reactant feeding ratios, the amino modified epoxy silicone oil series of the invention has different hydrophile-lipophile according to different molecular structures, and different molecular chain segment flexibilities can be respectively used for producing different polyacrylonitrile carbon fiber precursors.
The self-emulsifying method is adopted, so that the emulsion oiling machine has more advantages, namely, no need of an external emulsifier, no need of high-speed physical stirring, controllable emulsion particle size, narrow particle size distribution, good emulsion storage stability and high heat-resistant temperature, and can be applied to oiling polyacrylonitrile carbon fiber precursors. The invention has the advantages of low cost, small viscosity, good dispersibility, good film forming property, friction resistance, antistatic property and the like. The specific implementation method comprises the following steps:
performance testing in the following cases:
zeta potential laser particle size analyzer is adopted for particle size test
Storage stability test method (one):
the emulsion-sealed container was left at room temperature for more than six months, and the dispersion was observed for change. Good stability can be obtained without layering and solidification.
Storage stability test method (ii):
the emulsion was tested by high-speed centrifugation at 3000 rpm for 10 minutes, 20 minutes and 30 minutes, and the presence of sediment was observed.
Drawings
FIG. 1 is a reaction equation for synthesizing cationic amino-modified epoxy silicone oil;
FIG. 2 shows that the particle size of the cationic amino-modified epoxy silicone oil emulsion varies with the molar ratio of bisphenol A epoxy resin to epoxy silicone oil.
Detailed Description
Example 1:
30.78g of octadecylamine and 12.69g of polyetheramine (molecular weight is 1000) are mixed by using 50g N-methyl pyrrolidone (NMP), a sealing and condensing device is installed, nitrogen is introduced, the temperature is set to be 50 ℃, after the temperature reaches 50 ℃ and is stabilized for ten minutes, a water separator is added, the temperature is set to be 80 ℃, after the temperature is constant, 81.53g of epoxy silicone oil is added, the temperature is slowly increased to 110 ℃, the reaction is carried out for 2.5 hours, after the temperature is reduced to room temperature, 6.85g of glacial acetic acid is added, and 215g of water is added for emulsification. The cationic amino modified epoxy silicone oil emulsion has molecular weight of 5000, particle size of 622.59nm, silicone oil content of 32%, and no precipitation after storing 6 or 3000 rpm/30 min.
Example 2:
mixing 28.66g of octadecylamine and 11.82g of polyetheramine (molecular weight is 1000) by using 50g N-methylpyrrolidone (NMP), installing a sealing and condensing device, introducing nitrogen, setting the temperature at 50 ℃, adding a water separator after the temperature reaches 50 ℃ and is stabilized for ten minutes, setting the temperature at 80 ℃, adding 84.52g of epoxy silicone oil after the temperature is constant, slowly raising the temperature to 110 ℃, reacting for 2.5 hours, cooling to room temperature, adding 6.38g of glacial acetic acid, and adding 215g of water for emulsification. The cationic amino modified epoxy silicone oil emulsion has the molecular weight of 10000, the particle size of 193.97nm, the silicone oil content of 32 percent, and no precipitation after 6 or 3000 revolutions per 30 minutes of centrifugal rotation of the emulsion at room temperature.
Example 3:
27.60g of octadecylamine and 11.38g of polyetheramine (molecular weight is 1000) are mixed by using 50g N-methyl pyrrolidone (NMP), a sealing and condensing device is installed, nitrogen is introduced, the temperature is set to be 50 ℃, after the temperature reaches 50 ℃ and is stabilized for ten minutes, a water separator is added, the temperature is set to be 80 ℃, after the temperature is constant, 86.02g of epoxy silicone oil is added, the temperature is slowly increased to 110 ℃, the reaction is carried out for 2.5 hours, after the temperature is reduced to room temperature, 6.14g of glacial acetic acid is added, and 215g of water is added for emulsification. The cationic amino modified epoxy silicone oil emulsion has molecular weight of 20000, particle size of 173.42nm, silicone oil content of 32%, and no precipitation after storing 6 or 3000 r/30 min.
Example 4:
29.94g of octadecylamine and 19.60g of polyetheramine (molecular weight is 1000) are mixed by using 50g N-methyl pyrrolidone (NMP), a sealing and condensing device is installed, nitrogen is introduced, the temperature is set to 50 ℃, after the temperature reaches 50 ℃ and is stabilized for ten minutes, a water separator is added, the temperature is set to 80 ℃, after the temperature is constant, 67.64g of epoxy silicone oil and 7.82g of bisphenol A epoxy resin (epoxy equivalent weight is 185) are added, the temperature is slowly increased to 110 ℃, the reaction is carried out for 2.5 hours, after the temperature is reduced to room temperature, 7.06g of glacial acetic acid is added, and 215g of water is added for emulsification. The cationic amino modified epoxy silicone oil emulsion has molecular weight of 5000, particle size of 107.18nm, silicone oil content of 32%, and no precipitation after storing 6 or 3000 rpm/30 min.
Example 5:
mixing 30.93g of octadecylamine and 20.25g of polyetheramine (molecular weight is 1000) by using 50g N-methylpyrrolidone (NMP), installing a sealing and condensing device, introducing nitrogen, setting the temperature at 50 ℃, adding a water separator after the temperature reaches 50 ℃ and is stabilized for ten minutes, setting the temperature at 80 ℃, adding 61.60g of epoxy silicone oil and 12.21g of bisphenol A epoxy resin (epoxy equivalent 185) after the temperature is constant, slowly raising the temperature to 110 ℃, reacting for 2.5 hours, cooling to room temperature, adding 7.29g of glacial acetic acid, and adding 215g of water for emulsification. The cationic amino modified epoxy silicone oil emulsion has molecular weight of 5000, particle size of 87.86nm, silicone oil content of 32%, and no precipitation after storing 6 or 3000 rpm/30 min.
Example 6:
adding 4kg of cationic amino modified epoxy silicone oil (example 2) into a 25kg plastic barrel, adding 1kg of amino modified silicone oil (produced by Jilin Nanren New Material Co., Ltd.), 100PPM antioxidant 1010, 0.1% of antistatic agent dodecyl dimethyl benzyl ammonium chloride, 3M surfactant FC-44300.05%, lubricant (0.1% of modified mineral oil 6440, 0.3% of polyethylene glycol monooleate, Erwinikun USA), acetic acid to adjust the pH of the solution to 5-6, adding 12.7kg of deionized water under stirring, stirring at room temperature for 30 minutes, and filtering with a 300-mesh filter bag to obtain 32% solid content modified silicon carbon fiber protofilament oil solution. Diluting 32% oil solution with deionized water to 3.5%, applying to polyacrylonitrile carbon fiber precursor production line of Jilin carbon grain carbon fiber GmbH (as shown in Table 2 a), and comparing and using imported oil solution under the same conditions (as shown in Table 2d)
Example 7:
adding 4kg of cationic amino modified epoxy silicone oil (example 2) into a 25kg plastic barrel, adding 1kg of hydroxyl amino modified silicone oil (produced by Jilin Nanren New Material Co., Ltd.), 100PPM antioxidant 1010, 0.1% of antistatic agent dodecyl dimethyl benzyl ammonium chloride, 3M surfactant FC-44300.05%, lubricant (0.1% of modified mineral oil 6440, 0.3% of polyethylene glycol monooleate, Erwinikun USA), acetic acid to adjust the pH of the solution to 5-6, adding 12.7kg of deionized water under stirring, stirring for 30 minutes at room temperature, and filtering with a 300-mesh filter bag to obtain 32% solid content modified silicon carbon fiber protofilament oil solution. The oil solution with 32 percent of concentration is diluted to 3.5 percent by adding deionized water, and is applied to a polyacrylonitrile carbon fiber precursor production line of Jilin carbon valley carbon fiber GmbH (shown in a table 2 b).
Example 8: adding 4kg of cationic amino modified epoxy silicone oil produced by Jilin Qianren New Material Co., Ltd into a 25kg plastic barrel, adding 0.5kg of hydroxyl amino modified silicone oil produced by Jilin Qianren New Material Co., Ltd and 0.5kg of isocyanate modified polyether silicone oil, 100PPM antioxidant 1010, 0.1% of antistatic agent dodecyl dimethyl benzyl ammonium chloride, 0.05% of 3M surfactant FC-4430, lubricant (0.1% modified mineral oil 6440, 0.3% polyethylene glycol monooleate, American Erwining Kening), acetic acid adjusting solution pH 5-6, adding 12.7kg of deionized water under stirring, stirring at room temperature for 30 minutes, filtering with a 300-mesh filter bag to obtain 32% solid content modified silicon carbon fiber protofilament oil agent. The 32% oil agent is diluted to 3.5% by weight, and oil agent test is carried out on Jilin carbon-grain carbon fiber GmbH precursor production, and the foreign oil agent is compared under the same condition. The performance index of the oiled carbon fiber precursor is shown in table 2 c.
Example 9: the method comprises the steps of carrying out process adjustment on the oiled polyacrylonitrile carbon fiber precursors a, b, c and d (shown in table 2) on the basis of the Beijing university chemical industry carbon fiber and composite material institute T300-grade carbon fiber preparation process to set carbonization process parameters, wherein a sizing agent is provided by Jilin dried meat new material company Limited, and the properties of the carbon fibers are shown in table 3. Carbon fibers A, B, C and D correspond to polyacrylonitrile carbon fiber precursors a, b, c, and D (shown in table 2). Therefore, the oil agent has great influence on the performance of the final carbon fiber product.
TABLE 2 basic performance index of oiled polyacrylonitrile carbon fiber precursor
TABLE 3 basic performance index of carbonized carbon fiber from polyacrylonitrile carbon fiber precursor
The larger the number, the larger the amount of hairiness.
Claims (11)
1. The preparation method of the water-based polyacrylonitrile carbon fiber precursor silicone oil is characterized by comprising the following steps:
(1) adding hydrophilic amino-terminated polyether amine M1 and hydrophobic primary amine or secondary diamine into a reaction kettle, and heating to 50-80 ℃ under nitrogen, wherein the molar ratio of the amino-terminated polyether amine to the primary amine or the secondary diamine is (0.8: 0.2) - (0.1: 0.9);
(2) adding epoxy resin and epoxy silicone oil into a reaction kettle, wherein the epoxy resin is one or a combination of bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, novolac epoxy resin, brominated epoxy resin, 1, 4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether and double-end epoxy group polyacrylate, the epoxy silicone oil is diepoxy end group dimethyl silicone oil, and the molar ratio of the epoxy resin to the epoxy silicone oil is (0-0.5): (1-0.5);
(3) heating the reaction kettle to 80-120 ℃, reacting for 2-5 hours, and cooling the reaction kettle to room temperature to obtain self-assembled self-emulsified amphiphilic cationic amino modified epoxy silicone oil AMOA with the molecular weight MW of 5000-500000, wherein the particle size of emulsion particles in the emulsion obtained through the AMOA is more than 150 nm;
(4) adding auxiliary silicone oil, a pH regulator, water and other additives into the prepared AMOA, and stirring to obtain the water-based polyacrylonitrile carbon fiber precursor silicone oil, wherein the compounding mass ratio of the AMOA to the auxiliary silicone oil is 6: 4-9: 1, the auxiliary silicone oil is one or more of hydroxyl amino modified silicone oil or isocyanate modified polyether silicone oil; the structural formula of the hydroxyl amino modified silicone oil is as follows:
molecular weight is 350-; the structural formula of the isocyanate modified polyether silicone oil is as follows:
the molecular weight is 500-.
2. The method of claim 1, wherein the amine terminated polyether amine is polyethylene glycol monoalkyl ether amine R (OCH)2CH2)nNH2Polypropylene glycol monoalkyl ether amine R (OCH)2CH(CH3))nNH2Or polyethylene glycol propylene glycol copolyalkylamine R (OCH)2CH2）m1-(OCH2CH(CH3))m2NH2R is methyl or ethyl.
3. The method according to claim 1, wherein the primary monoamine is one or a combination of octadecylamine, dodecylamine, decylamine, nonadecylamine, octadecylamine, heptadecylamine, hexadecylamine, aniline, methylaniline and naphthylamine.
4. The method of claim 1, wherein the secondary diamine is one or a combination of N, N' -diethylethylenediamine, piperazine.
5. The method according to claim 1, wherein the molecular formula of the epoxy silicone oil in the step (2) is as follows:
6. the method of claim 1, wherein the polyetheramine M1 is one or a combination of M600 molecular weight 600, M1000 molecular weight 1000, and M2070 molecular weight 2000.
7. The preparation method according to claim 1, wherein the temperature of the reaction kettle in the step (3) is raised to 90-115 ℃.
8. The method according to claim 1, wherein the pH adjusting agent in the step (4) is one or both of formic acid and glacial acetic acid.
9. The method according to claim 1 or 8, wherein the amount of the pH adjusting agent is not more than M1, primary amine (R-NH)2) Or a secondary diamine (R)1NH-R-NHR1) Total moles of (a).
10. The method according to claim 1, wherein the AMOA molecular weight MW in the step (3) is 10000-30000.
11. The water-based polyacrylonitrile carbon fiber precursor silicone oil is characterized by being prepared according to the method of any one of claims 1 to 10.
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