CN116144172A - Polyamide 66 resin and preparation method thereof - Google Patents
Polyamide 66 resin and preparation method thereof Download PDFInfo
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- CN116144172A CN116144172A CN202111399076.2A CN202111399076A CN116144172A CN 116144172 A CN116144172 A CN 116144172A CN 202111399076 A CN202111399076 A CN 202111399076A CN 116144172 A CN116144172 A CN 116144172A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The invention provides a polyamide 66 resin and a preparation method thereof. The polyamide 66 resin comprises the following components in parts by weight: 66-100 parts of polyamide, 0.0002-0.01 part of stabilizer and 0.0005-0.005 part of lubricant; the polyamide 66 comprises the following raw material components in parts by weight: 115 parts of polyamide 66 salt, 0.0001 to 0.002 part of first catalyst and 0.00034 to 0.0014 part of second catalyst; the first catalyst is selected from any one or a combination of at least two of sodium bicarbonate, potassium bicarbonate or sodium carbonate; the second catalyst is selected from sodium hypophosphite and/or acetic acid. The polyamide 66 resin provided by the invention has better high temperature resistance, lubricity and fluidity.
Description
Technical Field
The invention belongs to the technical field of polyamide resin, and particularly relates to polyamide 66 resin and a preparation method thereof.
Background
Nylon 66 resin (polyamide 66 for short) is a widely used engineering plastic, and because the molecular chain of the nylon 66 resin contains amide groups (-CONH-) with stronger polarity, the structure of the PA66 is easy to crystallize due to the hydrogen bond formed between the groups, so that the nylon 66 resin has the characteristics of excellent mechanical property, self-lubricity, wide use temperature, good electrical insulation, good oil resistance, chemical stability, easy processing and the like, and is widely applied to the fields of automobile parts, mechanical parts, electronic appliances, adhesives, packaging materials and the like. However, nylon 66 has limited application due to its poor dimensional stability, high water absorption and poor high temperature resistance, and thus, how to obtain a polyamide 66 having excellent mechanical properties and excellent chemical properties has become a research focus.
CN101440215a discloses an ultra-high toughness polyamide 66 material, the ultra-high toughness polyamide 66 material is prepared from the following raw materials in parts by weight: 50-70% of nylon, 5-10% of compatilizer, 1-30% of styrene rubber, 10-30% of talcum powder and 0.1-1% of antioxidant; the compatilizer is an oligomer of grafting unsaturated acid or anhydride grafted by styrene rubber, and the grafting rate is 0.5-1%. The preparation method comprises the following steps: weighing the raw materials according to the weight percentage; mixing all the raw materials in a high-speed mixer for 5-8min; discharging; extruding and granulating the mixed raw materials in a screw machine, wherein the rotating speed of the screw machine is 180-600 rpm, and the temperature is 240-250 ℃. According to the technical scheme, the novel ultra-high toughness polyamide 66 material is prepared by adopting the novel compatilizer and matching with advanced formula design, and can be widely applied to the fields of automobiles, electronics, electrics, constructional engineering and the like.
CN102516761a discloses a hydrolysis-resistant alcoholysis nylon 66 composite material and a preparation method thereof. The hydrolysis-resistant alcoholysis nylon 66 composite material comprises, by weight, 51.8-84.5 parts of nylon resin, 15-40 parts of chopped glass fibers, 0.1-0.6 part of nucleating agent, 0.1-0.6 part of heat stabilizer, 0.1-1.0 part of alcoholysis-resistant auxiliary agent, 0.1-5 parts of barrier agent and 0.1-1.0 part of lubricant. The preparation method comprises the following steps: uniformly mixing the nylon 66 resin, the antioxidant, the hydrolysis inhibitor, the blocking agent, the nucleating agent and the lubricant which are dried in advance at a high speed; the mixture and the glass fiber are fed into a double-screw extruder for extrusion granulation. According to the technical scheme, various auxiliary agents are added into the glass fiber reinforced nylon 66 composite material to improve the crystallinity of the material, increase the stability of polyamide macromolecules in the processing and long-term use processes, improve the interfacial binding force between glass fibers and matrix resin and the like, and endow the glass fiber reinforced nylon 66 with good long-term glycol aqueous solution erosion resistance and long-term thermal oxygen stability.
CN101608065a discloses a halogen-free environment-friendly flame-retardant reinforced nylon 66 resin and a preparation method thereof, wherein the weight percentage content of polyamide 66 is 30.0-63.0%, and the weight percentage content of alkali-free long glass fiber is 20.0-35.0%; the composition also comprises the following components in percentage by weight: 2.0 to 10.0 percent of maleic anhydride grafting compatilizer, 0.5 to 3.0 percent of vinyl fluoride resin, 0.4 to 1.0 percent of hindered phenol antioxidant, 0.2 to 2.0 percent of pentaerythritol stearate, 0.2 to 1.0 percent of mixture of copper salt and halogen compound, and at most 16.0 percent of at least one of aluminum hypophosphite and melamine phosphate. In the technical scheme, the preparation method adopts a compatibilization technology and a blending technology, so that the bearable stress can be obviously improved, and the toughness of the alloy can be effectively improved; can also obviously improve the thermal stability, has higher heat distortion temperature and oxygen index, and improves the comprehensive mechanical property.
From the foregoing, it is known that the properties of the polyamide 66 are improved by using an auxiliary agent in most of the prior art, so that the polyamide 66 meets the use requirements of different fields, but the polymerization process of the polyamide 66 is not intensively studied. Therefore, how to obtain a polyamide 66 resin with excellent properties by controlling the polymerization process of the polyamide 66 and by using proper auxiliary agents has become a technical problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide polyamide 66 resin and a preparation method thereof. According to the invention, the polymerization process of the polyamide 66 is regulated and controlled through the matched use of the first catalyst and the second catalyst, and the polyamide 66 resin with good high temperature resistance and lubricity is prepared through the matched use of the stabilizer and the lubricant, so that the injection molding processability of the polyamide 66 resin is improved.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polyamide 66 resin, wherein the polyamide 66 resin comprises the following components in parts by weight:
66-100 parts of polyamide, 0.0002-0.01 part of stabilizer and 0.0005-0.005 part of lubricant;
the polyamide 66 comprises the following raw material components in parts by weight:
115 parts of polyamide 66 salt, 0.0001 to 0.002 part of first catalyst and 0.00034 to 0.0014 part of second catalyst;
the first catalyst is selected from any one or a combination of at least two of sodium bicarbonate, potassium bicarbonate or sodium carbonate;
the second catalyst is selected from sodium hypophosphite and/or acetic acid.
According to the invention, the polymerization process of the polyamide 66 is regulated and controlled by selecting a specific kind of catalyst and matching the first catalyst with the second catalyst, and the polyamide 66 resin with better high temperature resistance and lubricity is prepared by matching the stabilizer with the lubricant, so that the injection molding processability of the polyamide 66 resin is improved.
In the invention, the first catalyst is weak alkaline inorganic salt, and specifically any one or a combination of at least two of sodium bicarbonate, potassium bicarbonate or sodium carbonate is selected, and under the catalysis of the first catalyst, amide bonds are slowly hydrolyzed, so that the molecular chain of polyamide 66 is broken, the molecular weight of the polyamide 66 is reduced, and the aim of adjusting the molecular weight is fulfilled; the second catalyst is sodium hypophosphite and/or acetic acid, wherein the sodium hypophosphite is a weak acid compound, and can play a role in catalysis and tackifying in the polymerization process of polyamide 66, promote intermolecular dehydration and molecular chain growth, and the acetic acid can react with carboxyl to play a role in regulating and controlling the catalysis of the sodium hypophosphite.
In the present invention, the stabilizer may be 0.0002 parts, 0.0005 parts, 0.001 parts, 0.002 parts, 0.003 parts, 0.004 parts, 0.005 parts, 0.006 parts, 0.007 parts, 0.008 parts, 0.009 parts, or 0.01 parts, etc.
The lubricant may be 0.0005 parts, 0.001 parts, 0.0015 parts, 0.002 parts, 0.0025 parts, 0.003 parts, 0.0035 parts, 0.004 parts, 0.0045 parts, or 0.005 parts, etc.
The first catalyst may be 0.0001 part, 0.0002 part, 0.0004 part, 0.0008 part, 0.001 part, 0.0012 part, 0.0014 part, 0.0016 part, 0.0018 part, or 0.002 part, etc.
The weight part of the second catalyst may be 0.00034 part, 0.0004 part, 0.0005 part, 0.0006 part, 0.0007 part, 0.0008 part, 0.0009 part, 0.001 part, 0.0011 part, 0.0012 part, 0.0013 part, or 0.0014 part, etc.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
As a preferred technical scheme of the invention, the second catalyst is a combination of sodium hypophosphite and acetic acid.
Preferably, the sodium hypophosphite is 0.00004 to 0.0002 parts by weight, and for example, 0.00004 parts, 0.00006 parts, 0.00008 parts, 0.0001 parts, 0.00012 parts, 0.00014 parts, 0.00016 parts, 0.00018 parts, 0.0002 parts, or the like may be used.
Preferably, the weight part of the acetic acid is 0.0003 to 0.0012 part, for example, 0.0003 part, 0.0004 part, 0.0005 part, 0.0006 part, 0.0007 part, 0.0008 part, 0.0009 part, 0.001 part, 0.0011 part, 0.0012 part, or the like.
In the invention, the polyamide 66 resin prepared by selecting the combination of sodium hypophosphite and acetic acid as the second catalyst and controlling the weight parts of the sodium hypophosphite and the acetic acid within a specific range has better physical properties and processability. If sodium hypophosphite is used as the second catalyst, the catalysis effect of the sodium hypophosphite can lead to continuous growth of molecular chains in secondary heating, and finally the fluidity of the product is influenced, so that the processing is difficult; if acetic acid is used as the second catalyst, the polymerization rate is too slow, and even high polymers cannot be formed, which affects the product performance.
As a preferred embodiment of the present invention, the stabilizer is selected from copper salt stabilizers and/or hindered amine stabilizers.
Preferably, the copper salt stabilizer is selected from inorganic copper salt stabilizers and/or organic copper salt stabilizers.
Preferably, the inorganic copper salt stabilizer is selected from any one or a combination of at least two of copper acetate, copper iodide, copper bromide, copper nitrate, potassium iodide or potassium bromide.
Preferably, the organic copper salt stabilizer is selected from any one or a combination of at least two of a Bulgerman H3386 stabilizer, a Bulgerman H3336 stabilizer or a Bulgerman TP-H1606 stabilizer.
The manufacturer of the Bulgerman H3386 stabilizer, the Bulgerman H3336 stabilizer or the Bulgerman TP-H1606 stabilizer in the invention is Bulgerman in Germany.
Preferably, the hindered amine stabilizer is selected from any one or a combination of at least two of clariant TFB117, light stabilizer 5591, or light stabilizer 944.
It should be noted that, the manufacturer of the light stabilizer 5591 in the invention is a new chemistry; the manufacturer of the light stabilizer 944 is Beijing Tiangang.
Preferably, the stabilizer is a combination of a copper salt stabilizer and a hindered amine stabilizer.
Preferably, the weight part of the copper salt stabilizer is 0.0001 to 0.005 part, for example, 0.0001 part, 0.0005 part, 0.001 part, 0.0015 part, 0.002 part, 0.0025 part, 0.003 part, 0.0035 part, 0.004 part, 0.0045 part, or 0.005 part, etc.
Preferably, the hindered amine stabilizer is 0.0001 to 0.005 parts by weight, and for example, may be 0.0001 parts, 0.0005 parts, 0.001 parts, 0.0015 parts, 0.002 parts, 0.0025 parts, 0.003 parts, 0.0035 parts, 0.004 parts, 0.0045 parts, or 0.005 parts, etc.
In the invention, the combination of the copper salt stabilizer and the hindered amine stabilizer is selected as the stabilizer, the weight parts of the copper salt stabilizer and the hindered amine stabilizer are controlled within a specific range, and the polyamide 66 resin prepared through the synergistic interaction between the copper salt stabilizer and the hindered amine stabilizer has better high temperature resistance. If only a copper salt stabilizer or a hindered amine stabilizer is used, the prepared polyamide 66 resin has poor high temperature resistance.
As a preferred embodiment of the present invention, the lubricant is selected from any one or a combination of at least two of oleamide, erucamide, stearyl erucamide, aluminum stearate, aluminum distearate, zinc stearate, and magnesium stearate.
In a preferred embodiment of the present invention, the polyamide 66 resin further includes 0.0001 to 0.005 part of a fluidity improver, for example, 0.0001 part, 0.0002 part, 0.0003 part, 0.0005 part, 0.001 part, 0.0015 part, 0.002 part, 0.0025 part, 0.003 part, 0.0035 part, 0.004 part, 0.0045 part, 0.005 part, or the like.
Preferably, the fluidity improver is selected from any one or a combination of at least two of ethylene bisstearamide, hyperbranched polyamide polyester HyPer HPN202, montan wax or rice bran wax.
As a preferred technical scheme of the invention, the preparation method of the polyamide 66 comprises the following steps:
the first catalyst and the second catalyst are mixed with water to obtain a mixed solution, and then the mixed solution is mixed with a polyamide 66 salt to perform a polymerization reaction to obtain polyamide 66.
In a preferred embodiment of the present invention, the mass percentage of the first catalyst in the mixed solution is 5 to 15%, and may be, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%.
Preferably, the mass percentage of the second catalyst in the mixed solution is 5 to 20%, for example, 2%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, etc.
The second catalyst is preferably a combination of sodium hypophosphite and acetic acid, wherein the mass percentage of sodium hypophosphite in the mixed solution is 0.5 to 3% (for example, 0.5%, 1.5%, 2%, 2.5%, 3%, etc.), and the mass percentage of acetic acid in the mixed solution is 4 to 17% (for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, etc.).
As a preferred technical scheme of the invention, the specific method of the polymerization reaction is as follows:
concentrating the reaction system obtained by mixing the mixed solution and the polyamide 66 salt under 150-155 ℃ (for example, 150 ℃, 151 ℃, 152 ℃, 153 ℃, 154 ℃, 155 ℃ or the like) and 0.25MPa for 50-60 min (for example, 50min, 52min, 54min, 56min, 58min or 60min or the like), increasing the pressure to 1.75-1.85 MPa (for example, 1.75MPa, 1.77MPa, 1.79MPa, 1.81MPa, 1.83MPa or 1.85MPa or the like), maintaining the pressure for 50-60 min (for example, 50min, 52min, 54min, 56min, 58min or 60min or the like), and when the temperature of the reaction system reaches 265-267 ℃ (for example, 265 ℃, 266 ℃ or 267 ℃ or the like), the polymerization reaction is completed by depressurizing the reaction system to 0.2 to 0.6MPa (for example, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa or 0.6 MPa) within 40 to 60min (for example, 40min, 42min, 45min, 47min, 50min, 52min, 55min, 57min or 60min, etc.), evacuating the reaction system to-0.01 to-0.03 MPa (for example, -0.01MPa, 0.015MPa, -0.02MPa, -0.025MPa or-0.03 MPa, etc.), and then raising the pressure of the reaction system to 0.2 to 0.6MPa (for example, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa or 0.6MPa, etc.) when the temperature of the reaction system reaches 270 to 275 ℃ (for example, 271 ℃, 272 ℃, 274 ℃, 275 ℃ and the like).
It should be noted that the invention also includes a post-processing step, and the post-processing method is as follows: the polyamide 66 thus obtained was pelletized.
In a second aspect, the present invention provides a method for producing the polyamide 66 resin according to the first aspect, comprising the steps of:
the polyamide 66 resin is obtained by mixing the polyamide 66 with a stabilizer, a lubricant and optionally a fluidity improver by a screw extruder and then pelletizing.
As a preferable mode of the present invention, the operation temperature of the screw extruder is 265 to 330℃and may be 265, 270, 280, 290, 300, 310, 320 or 330℃for example.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the polymerization process of the polyamide 66 is regulated and controlled through the matched use of the first catalyst and the second catalyst, and the polyamide 66 resin with better high temperature resistance and lubricity is prepared through the matched use of the stabilizer, the lubricant and the flowability improver, so that the injection molding processability of the polyamide 66 resin is improved, and the tensile strength of the polyamide 66 resin can still be kept to be more than 80MPa and is 81.9-86.8 MPa after heat treatment for 72 hours at 180 ℃; the melt index is more than 87g/10min and is 87-93 g/10min; the relative viscosity can reach 2.66-2.67; the number of the demolding roots is 85-100, and the highest processing temperature is 280-285 ℃.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Some of the component sources in the examples and comparative examples are as follows:
hyperbranched polyamide polyester HyPer HPN202: wuhan hyperbranched resin technology Co., ltd;
montan wax: craien CaV102;
rice bran wax: a clariant RBW360;
light stabilizer 5591: chemistry of new and elegant;
bulgerman H3386 stabilizer: bulgerman, germany;
light stabilizer 944: beijing Tiangang.
Example 1
The embodiment provides a polyamide 66 resin and a preparation method thereof, wherein the polyamide 66 resin comprises the following components in parts by weight:
polyamide 66 100 parts, copper acetate 0.003 parts, colesen TFB117 stabilizer 0.002 parts, oleamide 0.002 parts and ethylene bis stearamide 0.001 parts;
the polyamide 66 comprises the following raw material components in parts by weight:
115 parts of polyamide 66 salt, 0.001 part of sodium bicarbonate, 0.0001 part of sodium hypophosphite and 0.001 part of acetic acid;
the preparation method of the polyamide 66 comprises the following steps:
mixing sodium bicarbonate, sodium hypophosphite, acetic acid and water to obtain a mixed solution, mixing the mixed solution with polyamide 66 salt, concentrating at 155 ℃ and 0.25MPa for 60min, then boosting to 1.75MPa, maintaining the pressure for 60min, decompressing the pressure of the reaction system to 0MPa when the temperature of the reaction system reaches 266 ℃ for 50min, vacuumizing the reaction system to-0.02 MPa within 10min, boosting to 0.4MPa when the temperature of the reaction system reaches 275 ℃, completing polymerization reaction, and granulating to obtain polyamide 66; wherein the mass percentage of the first catalyst in the mixed solution is 5%, the mass percentage of the sodium hypophosphite is 0.5%, and the mass percentage of the acetic acid is 5%.
The preparation method of the polyamide 66 resin comprises the following steps:
and mixing polyamide 66, copper acetate, a Craien TFB117 stabilizer, oleamide and ethylene bis-stearamide through a screw extruder, and granulating to obtain the polyamide 66 resin, wherein the working temperature of the screw extruder is 280 ℃.
Example 2
The embodiment provides a polyamide 66 resin and a preparation method thereof, wherein the polyamide 66 resin comprises the following components in parts by weight:
66 parts of polyamide 66, 0.0001 part of cuprous iodide, 0.0001 part of light stabilizer 5591, 0.0005 part of erucamide and 0.0001 part of hyperbranched polyamide polyester HyPer HPN 202;
the polyamide 66 comprises the following raw material components in parts by weight:
115 parts of polyamide 66 salt, 0.002 part of potassium bicarbonate, 0.0002 part of sodium hypophosphite and 0.0012 part of acetic acid;
the preparation method of the polyamide 66 comprises the following steps:
mixing potassium bicarbonate, sodium hypophosphite, acetic acid and water to obtain a mixed solution, mixing the mixed solution with polyamide 66 salt, concentrating at 150 ℃ and 0.25MPa for 55min, boosting to 1.80MPa, maintaining the pressure for 60min, decompressing the pressure of the reaction system to 0MPa when the temperature of the reaction system reaches 267 ℃ for 60min, vacuumizing the reaction system to-0.03 MPa within 3min, boosting to 0.4MPa when the temperature of the reaction system reaches 273 ℃, completing polymerization reaction, and granulating to obtain polyamide 66; wherein the mass percentage of the first catalyst in the mixed solution is 15%, the mass percentage of the sodium hypophosphite is 1.5%, and the mass percentage of the acetic acid is 9%.
The preparation method of the polyamide 66 resin comprises the following steps:
polyamide 66, cuprous iodide, light stabilizer 5591, erucamide and hyperbranched polyamide polyester HyPer HPN202 are mixed and granulated by a screw extruder, and the working temperature of the screw extruder is 290 ℃.
Example 3
The embodiment provides a polyamide 66 resin and a preparation method thereof, wherein the polyamide 66 resin comprises the following components in parts by weight:
66 parts of polyamide, 0.005 part of copper bromide, 0.005 part of light stabilizer 944 and 0.005 part of stearyl erucamide;
the polyamide 66 comprises the following raw material components in parts by weight:
115 parts of polyamide 66 salt, 0.0001 part of sodium carbonate, 0.00004 part of sodium hypophosphite and 0.0003 part of acetic acid;
the preparation method of the polyamide 66 comprises the following steps:
mixing sodium carbonate, sodium hypophosphite, acetic acid and water to obtain a mixed solution, mixing the mixed solution with polyamide 66 salt, concentrating at 150 ℃ and 0.25MPa for 60min, boosting to 1.85MPa, maintaining the pressure for 60min, decompressing the pressure of the reaction system to 0MPa within 40min when the temperature of the reaction system reaches 265 ℃, vacuumizing the reaction system to-0.01 MPa within 10min, boosting to 0.6MPa when the temperature of the reaction system reaches 275 ℃, completing polymerization reaction, and granulating to obtain polyamide 66; wherein the mass percentage of the first catalyst in the mixed solution is 5%, the mass percentage of the sodium hypophosphite is 2%, and the mass percentage of the acetic acid is 15%.
The preparation method of the polyamide 66 resin comprises the following steps:
polyamide 66, copper bromide, light stabilizer 944 and stearyl erucamide were mixed and pelletized by a screw extruder having an operating temperature of 320 c to obtain the polyamide 66 resin.
Example 4
The embodiment provides a polyamide 66 resin and a preparation method thereof, wherein the polyamide 66 resin comprises the following components in parts by weight:
100 parts of polyamide 66, 0.0008 part of Bulgerman H3386 stabilizer, 0.002 part of Corean TFB117 stabilizer, 0.001 part of aluminum stearate and 0.005 part of rice bran wax;
the polyamide 66 comprises the following raw material components in parts by weight:
115 parts of polyamide 66 salt, 0.0009 part of sodium bicarbonate, 0.00015 part of sodium hypophosphite and 0.001 part of acetic acid;
the preparation method of the polyamide 66 comprises the following steps:
mixing sodium bicarbonate, sodium hypophosphite, acetic acid and water to obtain a mixed solution, mixing the mixed solution with polyamide 66 salt, concentrating at 155 ℃ and 0.25MPa for 55min, boosting to 1.85MPa, maintaining the pressure for 60min, decompressing the pressure of the reaction system to 0MPa within 55min when the temperature of the reaction system reaches 267 ℃, vacuumizing the reaction system to-0.02 MPa within 6min, boosting to 0.3MPa when the temperature of the reaction system reaches 272 ℃, completing polymerization reaction, and granulating to obtain polyamide 66; wherein the mass percentage of the first catalyst in the mixed solution is 6%, the mass percentage of the sodium hypophosphite is 1%, and the mass percentage of the acetic acid is 6.67%.
The preparation method of the polyamide 66 resin comprises the following steps:
the polyamide 66 resin is obtained by mixing and granulating the polyamide 66, the Lv Geman H3386 stabilizer, the Kelain TFB117 stabilizer, the aluminum stearate and the rice bran wax through a screw extruder, wherein the working temperature of the screw extruder is 300 ℃.
Example 5
The present example provides a polyamide 66 resin and a method for producing the same, which are different from example 1 in that the raw material for producing the polyamide 66 does not contain sodium hypophosphite, the weight part of acetic acid is 0.0011 part, and other conditions are the same as in example 1.
Example 6
The present example provides a polyamide 66 resin and a method for producing the same, which are different from example 1 in that acetic acid is not contained in the raw material for producing polyamide 66, and sodium hypophosphite is 0.0011 parts by weight, and other conditions are the same as in example 1.
Example 7
This example provides a polyamide 66 resin and a method for producing the same, which are different from example 1 in that the polyamide 66 resin does not contain copper acetate, the weight part of the stabilizer, the colza TFB117, is 0.005 part, and the other conditions are the same as example 1.
Example 8
The present example provides a polyamide 66 resin and a method for preparing the same, which are different from example 1 in that the polyamide 66 resin does not contain a stabilizer of clahn TFB117, the weight part of copper acetate is 0.005 part, and other conditions are the same as in example 1.
Comparative example 1
This comparative example provides a polyamide 66 resin and a method for producing the same, which are different from example 1 in that the raw material for producing the polyamide 66 contains no sodium bicarbonate, and sodium hypophosphite and acetic acid are proportionally allocated to the parts by weight of sodium bicarbonate, with the other conditions being the same as example 1.
Comparative example 2
The comparative example provides a polyamide 66 resin and a method for producing the same, which are different from example 1 in that the raw material for producing the polyamide 66 does not contain sodium hypophosphite and acetic acid, the weight part of sodium bicarbonate is 0.0021 part, and other conditions are the same as example 1.
The properties of the polyamide 66 resin provided in the above examples and comparative examples were tested as follows:
tensile strength: the dumbbell-shaped tensile sample bar is prepared by using an injection molding machine, and is placed in a 180 ℃ oven for 72 hours, cooled for 24 hours at room temperature, and then tested for tensile strength by using a universal mechanical tester according to the standard of GB/T1040.1-2006 determination of tensile properties of plastics.
Melt index: the melt index of the sample was measured using a melt fingermeter under the test conditions of 275℃and a weight of 2.16kg according to the standard of GB-T3682-melt flow Rate measurement.
Relative viscosity: the relative viscosity of the samples was measured using a black-bone viscometer according to the standard of GB/T12006.1-2009 plastics polyamide part 1, viscosity number determination.
Lubricity: the ribbon is tested by using an injection molding machine, the ribbon mould is 1 mould 100, 5 x 150mm, the average demolding number of each ribbon is recorded, and the more the number is, the better the lubricity is.
Workability: when the injection molding machine is used for testing the injection molding ribbon, the highest processing temperature is recorded when the mold is full and has no edge overflow, and the lower the temperature is, the better the processing property is.
The results of the performance test of the polyamide 66 resins provided in the above examples and comparative examples are shown in table 1 below:
TABLE 1
As can be seen from the contents of Table 1, the polyamide 66 resin with better high temperature resistance and lubricity is prepared by selecting a specific catalyst and combining a first catalyst and a second catalyst, and simultaneously combining a copper salt stabilizer and a hindered amine stabilizer, so that the injection molding processability of the polyamide 66 resin is improved, and the tensile strength of the polyamide 66 resin can be still kept to be more than 80MPa and is 81.9-86.8 MPa after heat treatment for 72 hours at 180 ℃; the melt index is more than 87g/10min and is 87-93 g/10min; the relative viscosity can reach 2.66-2.67; the number of the demolding roots is 85-100, and the highest processing temperature is 280-285 ℃.
In comparison with example 1, if sodium hypophosphite is not contained in the catalyst system (example 5), the melt index and the relative viscosity of the prepared polyamide 66 resin are smaller and are 79g/10min and 2.51 respectively; if acetic acid is not contained in the catalyst system (example 6), the melt index of the polyamide 66 resin obtained is smaller than 65g/10min, the relative viscosity is excessively large of 2.75, and the maximum processing temperature is excessively high of 330 ℃. From this, the polyamide 66 resin prepared by selecting the combination of sodium hypophosphite and acetic acid as the second catalyst has excellent processability.
Compared with example 1, if the polyamide 66 resin does not contain a copper salt stabilizer (example 7), the prepared polyamide 66 resin has poorer high temperature resistance; if the polyamide 66 resin does not contain the hindered amine stabilizer (example 8), the prepared polyamide 66 resin has poor high temperature resistance and small tensile strength after heat treatment for 72 hours at 180 ℃. Therefore, the copper salt stabilizer and the hindered amine stabilizer have a synergistic effect, and the prepared polyamide 66 resin has excellent high temperature resistance through the combination of the copper salt stabilizer and the hindered amine stabilizer.
Compared with example 1, if the catalytic system does not contain sodium bicarbonate as a first catalyst (comparative example 1), the melt index of the prepared polyamide 66 resin is smaller than 70g/10min, and the highest processing temperature is 330 ℃; if the catalyst system does not contain sodium hypophosphite and acetic acid (comparative example 2), the melt index of the prepared polyamide 66 resin is 76g/10min, and the highest processing temperature is 320 ℃. From this, the polyamide 66 resin prepared by the combination of the first catalyst and the second catalyst has excellent processability.
In conclusion, the polyamide 66 resin prepared by selecting the specific catalyst, combining the first catalyst and the second catalyst, combining the copper salt stabilizer and the hindered amine stabilizer has better high temperature resistance, lubricity and fluidity,
The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The polyamide 66 resin is characterized by comprising the following components in parts by weight:
66-100 parts of polyamide, 0.0002-0.01 part of stabilizer and 0.0005-0.005 part of lubricant;
the polyamide 66 comprises the following raw material components in parts by weight:
115 parts of polyamide 66 salt, 0.0001 to 0.002 part of first catalyst and 0.00034 to 0.0014 part of second catalyst;
the first catalyst is selected from any one or a combination of at least two of sodium bicarbonate, potassium bicarbonate or sodium carbonate;
the second catalyst is selected from sodium hypophosphite and/or acetic acid.
2. The polyamide 66 resin of claim 1, wherein the second catalyst is a combination of sodium hypophosphite and acetic acid;
preferably, the weight part of the sodium hypophosphite is 0.00004-0.0002 part;
preferably, the weight portion of the acetic acid is 0.0003 to 0.0012 portion.
3. Polyamide 66 resin according to claim 1 or 2, characterized in that the stabilizer is selected from copper salt stabilizers and/or hindered amine stabilizers;
preferably, the copper salt stabilizer is selected from inorganic copper salt stabilizers and/or organic copper salt stabilizers;
preferably, the inorganic copper salt stabilizer is selected from any one or a combination of at least two of copper acetate, copper iodide, copper bromide, copper nitrate, potassium iodide or potassium bromide;
preferably, the organic copper salt stabilizer is selected from any one or a combination of at least two of a Bulgerman H3386 stabilizer, a Bulgerman H3336 stabilizer or a Bulgerman TP-H1606 stabilizer;
preferably, the hindered amine stabilizer is selected from any one or a combination of at least two of a colaen TFB117 stabilizer, a light stabilizer 5591, or a light stabilizer 944;
preferably, the stabilizer is a combination of a copper salt stabilizer and a hindered amine stabilizer;
preferably, the weight part of the copper salt stabilizer is 0.0001-0.005 part;
preferably, the hindered amine stabilizer is 0.0001 to 0.005 parts by weight.
4. A polyamide 66 resin according to any one of claims 1-3 wherein said lubricant is selected from any one or a combination of at least two of oleamide, erucamide, stearyl erucamide, aluminum stearate, aluminum distearate, zinc stearate or magnesium stearate.
5. The polyamide 66 resin according to any one of claims 1 to 4, wherein the polyamide 66 resin further comprises 0.0001 to 0.005 part of a fluidity improver;
preferably, the fluidity improver is selected from any one or a combination of at least two of ethylene bisstearamide, hyperbranched polyamide polyester HyPer HPN202, montan wax or rice bran wax.
6. The polyamide 66 resin according to any one of claims 1 to 5, wherein the polyamide 66 is prepared by the following method:
the first catalyst and the second catalyst are mixed with water to obtain a mixed solution, and then the mixed solution is mixed with a polyamide 66 salt to perform a polymerization reaction to obtain polyamide 66.
7. The polyamide 66 resin according to claim 6, wherein the mass percentage of the first catalyst in the mixed solution is 5-15%;
preferably, the mass percentage of the second catalyst in the mixed solution is 5% -20%.
8. Polyamide 66 according to claim 6 or 7, characterized in that the specific method of polymerization is as follows:
concentrating the reaction system after mixing the mixed solution and the polyamide 66 salt for 50-60 min at 150-155 ℃ and 0.25MPa, then boosting the pressure to 1.75-1.85 MPa, maintaining the pressure for 50-60 min, decompressing the pressure of the reaction system to 0MPa within 40-60 min after the temperature of the reaction system reaches 265-267 ℃, vacuumizing the reaction system to-0.01-0.03 MPa within 2-10 min, boosting the pressure to 0.2-0.6 MPa after the temperature of the reaction system reaches 270-275 ℃, and thus completing the polymerization reaction to obtain the polyamide 66.
9. A method for producing the polyamide 66 resin according to any one of claims 1 to 5, comprising the steps of:
the polyamide 66 resin is obtained by mixing the polyamide 66 with a stabilizer, a lubricant and optionally a fluidity improver by a screw extruder and then pelletizing.
10. The process according to claim 9, wherein the screw extruder is operated at a temperature of 265 to 320 ℃.
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| CN202111399076.2A CN116144172A (en) | 2021-11-19 | 2021-11-19 | Polyamide 66 resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111399076.2A CN116144172A (en) | 2021-11-19 | 2021-11-19 | Polyamide 66 resin and preparation method thereof |
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