CN111117231A - Halogen-free polyamide 56 composition capable of resisting long-term aging of hot air and application thereof - Google Patents
Halogen-free polyamide 56 composition capable of resisting long-term aging of hot air and application thereof Download PDFInfo
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- CN111117231A CN111117231A CN201911415214.4A CN201911415214A CN111117231A CN 111117231 A CN111117231 A CN 111117231A CN 201911415214 A CN201911415214 A CN 201911415214A CN 111117231 A CN111117231 A CN 111117231A
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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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a halogen-free polyamide 56 composition capable of resisting long-term aging of hot air, which comprises the following raw materials in parts by weight: A. polyamide 56 resin; B. 10-50 parts of glass fiber; C. 0.1-0.5 part of composite antioxidant; D. 0-1 part of additive; wherein the sum of the weight parts of the raw materials A-D is 100 parts. The invention also discloses application of the halogen-free polyamide 56 composition for resisting long-term aging of hot air in extruded products and injection-molded products. According to the invention, the composite antioxidant containing no halogen and no metal copper is added into the polyamide 56 resin, so that the prepared material has long-term hot air aging resistance, and after aging in circulating air at 150 ℃ for 1000h, the retention rate of mechanical properties exceeds 80%, wherein the retention rate of notched impact strength of a cantilever beam is up to more than 90%.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a halogen-free polyamide 56 composition resistant to long-term aging by hot air and application thereof.
Background
Polyamides, commonly referred to as nylons, are polymers having amide linkages in the molecular backbone. It has been widely used in textile, automotive, electronic and electrical, packaging, sports products, etc. Polyamides are generally classified into two types, one is polyamides obtained by polycondensation of amino acids or ring-opening polymerization of lactams, and are also called AB-type polyamides; one is polyamide obtained by polycondensation of a dibasic acid and a diamine, also known as AABB type polyamide.
The conventional synthesis of polyamide requires obtaining polymerized monomers in large quantities from the petroleum industry, but with the consumption of petroleum resources and the increasing environmental problems brought by the consumption, the research of bio-based polyamide is carried out. The bio-based polyamide is prepared from raw materials of a biomass material, and mainly comprises bio-based amino acid, bio-based lactam, bio-based dibasic acid, bio-based diamine and the like.
The synthetic monomer pentanediamine of the polyamide 56 (hereinafter referred to as PA56) is from the fermentation of corn and straw, and is different from the traditional PA66, the PA56 naturally contains two different crystal forms, and the amide bond density is higher and the polarity is stronger. Compared with PA66, the glass fiber reinforced material prepared by using PA56 as a resin matrix can obtain the same outstanding mechanical properties, and in addition, the glass fiber reinforced PA56 material has lower fiber exposure and excellent part flatness.
The polyamide materials reinforced and modified by the glass fiber are mostly used for producing parts with higher environmental temperature, such as peripheral parts of an automobile engine, injection engine covers, engine radiators, engine water chambers, gearbox oil pans and the like, and connectors in contact with metal, and in order to resist long-term hot air baking, the technical personnel in the field are well known to utilize compound salts of copper halide and other halogenated alkali metal salts as long-acting antioxidants, and the effect is remarkable, but the material scheme containing the additives is not suitable for the field of electronic parts subjected to insert molding with metal, because the existence of the metal salts generates potential electrochemical corrosion on metal materials for conducting electricity, and finally the parts are totally failed.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a halogen-free polyamide 56 composition capable of resisting long-term aging in hot air and an application thereof, the invention adds a composite antioxidant which does not contain halogen and metal copper into polyamide 56 resin, so that the prepared material obtains the long-term performance of resisting long-term aging in hot air, and after the material is aged for 1000 hours in circulating air at 150 ℃, the retention rate of mechanical properties exceeds 80%, wherein the retention rate of notched izod impact strength is up to more than 90%.
The invention provides a halogen-free polyamide 56 composition capable of resisting long-term aging of hot air, which comprises the following raw materials in parts by weight:
A. polyamide 56 resin;
B. 10-50 parts of glass fiber;
C. 0.1-0.5 part of composite antioxidant;
D. 0-1 part of additive;
wherein the sum of the weight parts of the raw materials A-D is 100 parts.
Preferably, the complex antioxidant is a copper-free and halogen-free complex antioxidant.
Preferably, the composite antioxidant is a compound of hindered phenol antioxidants.
Preferably, the complex antioxidant is antioxidant H161 or antioxidant H20 from Bluegman, Germany.
The Bluegman company, Germany, is Br ü ggemann chemical Asia, Ltd.
Preferably, the relative viscosity of the polyamide 56 resin is 2.4 to 3.2.
Preferably, the relative viscosity of the polyamide 56 resin is 2.4 to 2.7.
The detection method of the relative viscosity comprises the following steps: the polyamide 56 resin is dissolved in a sulfuric acid solution with the mass fraction of 96% for detection, wherein the mass fraction of the polyamide 56 resin is 1%, and the detection method refers to the standard ISO 307.
The concentration of the terminal amino group of the polyamide 56 resin is not particularly required, the preferable concentration of the terminal amino group is more than or equal to 50mmol/KG, the preferable concentration of the terminal amino group is more than or equal to 60mmol/KG, and the more preferable concentration of the terminal amino group is more than or equal to 80 mmol/KG.
The polyamide 56 resin belongs to a semi-bio-based synthetic polymer, and is obtained by performing polycondensation reaction on pentanediamine (obtained by a biological fermentation method) and adipic acid (obtained by conventional chemical synthesis).
The synthesis process of the polyamide 56 resin is similar to that of the polyamide 66, and the specific method comprises the following steps: firstly, mixing 1, 5-pentanediamine and adipic acid according to a molar ratio of 1:1-1.05, adding an antioxidant, carrying out a salt forming reaction at a temperature of 10-130 ℃ and a pressure of 0.1-0.3MPa, pumping the solution into a tubular continuous reactor or a prepolymerization reaction kettle at a temperature of 230-290 ℃ and a pressure of 1-5MPa, and reacting for 30-300min to obtain a prepolymer. Further flash evaporating the obtained prepolymer to remove water, continuously pumping the dehydrated prepolymer into a polycondensation reactor, setting the reaction temperature at 250-300 ℃ under the protection of nitrogen, reacting for 30-200min to obtain polyamide 56, and extruding and granulating the melt thereof to obtain the final product, wherein the detailed synthesis steps can refer to patents CN105885038A, CN103145979A, CN104031263A and the like.
Preferably, the glass fibers are grade E alkali-free glass fibers.
Preferably, the glass fiber is treated by a surface sizing agent, and a film forming agent in the surface sizing agent is a polyurethane film forming agent.
Preferably, the polyurethane film former is a polyether polyurethane emulsion.
Preferably, the content of the film-forming agent in the surface sizing agent is not less than 25%.
The diameter of the glass fiber is not particularly limited, and is preferably 7 to 17 micrometers, more preferably 10 to 13 micrometers.
The length of the glass fiber is not particularly limited, and continuous uncut glass fiber filaments may be used, and cut glass chopped fibers may also be used, the chopped glass fibers preferably having a length of 2 to 5 mm.
The cross section of the glass fiber has no special requirement and can be round or rectangular. The rectangular cross section is vertical to the longitudinal direction of the fiber, the longest straight line distance in the rectangular cross section is a long axis, the shortest straight line distance in the rectangular cross section is a short axis, the length of the long axis and the short axis is 1.5-10:1, and the preferable ratio is 3-4: 1.
The surface sizing agent further comprises a coupling agent, such as: epoxy group-containing compounds, acrylic acid-containing compounds, polyurethane-containing compounds, and the like, and preferably, the coupling agent is a silane coupling agent-containing compound.
The general formula of the silane coupling agent is as follows:
(X-(CH2)n)k-Si-(O-(CmH2m+1)4-k；
wherein, X is amino, ethylene oxide, hydroxyl, etc.;
n is an integer from 2 to 10, preferably from 3 to 4;
m is an integer from 2 to 10, preferably from 3 to 4;
k is an integer from 1 to 3, preferably 1.
The silane coupling agent is used in an amount of 0.025 to 1%, preferably 0.05 to 0.5%, by weight of the glass fiber.
The invention can also comprise 0 to 0.5 weight percent of lubricant, wherein the lubricant is preferably carboxylate, fatty acid ester containing 10 to 44 methylene, fatty acid amide containing 10 to 44 methylene, olefin wax with the molecular weight of less than or equal to 3000g/mol, acidified olefin wax with the molecular weight of less than or equal to 3000g/mol, oxidized olefin wax with the molecular weight of less than or equal to 3000 g/mol; more preferably a fatty acid ester having 17 to 28 methylene groups, a fatty acid amide having 17 to 28 methylene groups, an olefin wax having a molecular weight of 3000g/mol or less, an acidified olefin wax having a molecular weight of 3000g/mol or less, and an oxidized olefin wax having a molecular weight of 3000g/mol or less.
The carboxylate is preferably at least one of an alkaline earth metal carboxylate, a zinc carboxylate salt and an aluminum carboxylate salt, more preferably at least one of an aluminum carboxylate salt and a magnesium carboxylate salt, and even more preferably at least one of magnesium stearate and aluminum distearate.
The carboxylic acid used in the synthesis of the fatty acid ester is a monocarboxylic acid or a dicarboxylic acid, and examples thereof include stearic acid, palmitic acid, lauric acid, margaric acid, and montanic acid.
The fatty alcohol used in the synthesis of the fatty acid ester is a monohydric or tetrahydric fatty alcohol, such as ethylene glycol, propylene glycol, and glycerol, preferably glycerol and pentaerythritol.
The fatty amine in the synthesis of the fatty acid amide may be a mono-to ternary fatty amine, for example, stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, etc., preferably ethylenediamine or hexamethylenediamine.
The fatty acid ester and the fatty acid amide can be used in combination in any proportion.
The olefin wax, the acidified olefin wax and the oxidized olefin wax are obtained by a series of cracking reactions, the molecular weight of the olefin wax, the acidified olefin wax and the oxidized olefin wax is greater than that of white oil and less than or equal to 3000g/mol, and the olefin wax is solid.
The acidified olefin WAX and the oxidized olefin WAX are obtained by further modifying the olefin WAX, and the common brands are oxidized WAX PED521 of Germany Kelaien and acidified WAX Hi-WAX 4202E of Mitsui chemical.
Such additives include, but are not limited to: at least one of an antioxidant, a lubricant, and a toner.
Nucleating agents useful in the present invention include, but are not limited to: kaolin, talcum powder, mica, wollastonite, solid and/or hollow glass microspheres, boron nitride, nano silicon dioxide, nano carbon black and an organic nucleating agent; organic nucleating agents such as: phenylphosphinate, polyamide oligomer.
The nucleating agent is preferably a polyamide oligomer, carbon black, or a combination of carbon black and other nucleating agents known in the art.
The polyamide oligomer is preferably polyamide 22; the particle diameter of the carbon black is preferably 10 to 100nm as measured in accordance with ASTM D-3849.
The toner of the present invention is not particularly limited, and common toner types include inorganic toner and organic toner, the inorganic toner includes titanium yellow, titanium dioxide, carbon black, etc., and the organic toner includes ultramarine blue, phthalocyanine blue, solvent yellow, solvent red, etc.
The invention also provides the application of the halogen-free polyamide 56 composition for resisting the long-term aging of hot air in extruded products and injection-molded products, such as engine covers, engine radiators, engine water chambers, engine oil pans and the like.
Any extrusion and injection molded article can be made using the present invention.
Has the advantages that:
the invention aims to provide a halogen-free polyamide 56 composition for resisting long-term aging of hot air, the invention adds a composite antioxidant containing no halogen and no metal copper into polyamide 56 resin, so that the prepared material obtains long-term performance of resisting long-term hot air aging, and after aging in circulating air at 150 ℃ for 1000h, the retention rate of mechanical properties exceeds 80%, wherein, the retention rate of notched Izod impact strength is as high as more than 90%.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
The starting materials used in examples E1-E6 and comparative example M of the present invention were as follows:
and (2) component A:
a1: PA56, designation 1270W, relative viscosity 2.7, terminal amino content 54meq/kg, purchased from Shanghai Kaiser Biotech Co., Ltd;
a2: PA56, designation 1270WHN, relative viscosity 2.7, terminal amino content 84meq/kg, available from Kyoeisha Biotechnology Co., Ltd;
and (B) component: alkali-free E-grade glass fiber, grade: ECS 301HP, available from Chongqing International composite materials corporation;
and (3) component C:
c1: antioxidant H161, available from Bluggeman, Germany;
c2: antioxidant H20, available from brugueman, germany;
c3: copper complex antioxidant, grade: h3336, available from brungelmann, germany;
and (3) component D: oxidized high-density polyethylene wax, grade: PED521, acid number 17mgKOH/g, was purchased from Claien specialty Chemicals, Inc., Germany.
The preparation methods of examples E1-E6 and comparative example M in the present invention are as follows: according to the proportion of each embodiment and comparative example, A, C, D is premixed, and then added into a first main hopper of a double-screw extruder produced by Nanjing Ruiya equipment Limited company with the screw diameter of 35mm, the length-diameter ratio of the screw is 48:1, the whole extruder is divided into 12 sections of barrels, a component B is fed from a second measuring feeding hopper which is arranged at the 8 th barrel, and the extrusion temperature is set as follows from a first area: 200-280 ℃, the head temperature is set to be 260 ℃, the screw rotating speed is set to be 300rpm, and the composition is obtained through melting plasticization, extrusion and grain cutting.
The resulting composition was dried and subsequently injection molded to give tensile bars according to ISO 527 standard, curved bars according to ISO178 standard and impact bars according to ISO 179 standard, the injection molding conditions being indicated in Table 1:
TABLE 1 injection parameters of the specimens
And detecting the performance of each sample strip, wherein the detection method comprises the following steps:
the notched impact strength of the material simply supported beam is measured according to the ISO 1791 eA standard.
The unnotched impact strength of the material simple beam is measured according to the ISO 1791 eU standard.
Aging conditions are as follows: taking a part of the sample strips, placing the sample strips in a blowing type oven, setting the temperature to be 150 ℃, taking out the sample strips after 1000 hours, immediately sealing and placing the sample strips in a drying dish, keeping the drying state, and testing the mechanical properties after aging after 24 hours.
The formulations and performance test results for examples E1-E6 and comparative example M are shown in Table 2:
TABLE 2 formulations and results of Performance testing of examples E1-E6 and comparative example M
As can be seen from the results in Table 2, comparative example M, which uses a halogen-containing copper complex antioxidant, gives a material with a retention of mechanical properties higher than 80% after aging test in hot air at 150 ℃ for 1000h, as is well known to those skilled in the art;
examples E1-E6 use copper-free and halogen-free complex antioxidants (antioxidant H161, antioxidant H20), the retention of the mechanical properties of the resulting materials after aging testing in hot air at 150 ℃ for 1000H is higher than 80%; also, it is appreciated that the retention of both flexural modulus and notched impact strength of the beam of examples E1-E6 after heat aging exceeds 90%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A polyamide 56 composition without halogen and capable of resisting long-term aging of hot air is characterized by comprising the following raw materials in parts by weight:
A. polyamide 56 resin;
B. 10-50 parts of glass fiber;
C. 0.1-0.5 part of composite antioxidant;
D. 0-1 part of additive;
wherein the sum of the weight parts of the raw materials A-D is 100 parts.
2. The halogen-free, hot air long term aging resistant polyamide 56 composition of claim 1 wherein the complex antioxidant is a copper-free and halogen-free complex antioxidant.
3. The halogen-free, hot air long term aging resistant polyamide 56 composition of claim 1 or 2, wherein the complex antioxidant is a complex of hindered phenolic antioxidants.
4. The halogen-free, hot air long term aging resistant polyamide 56 composition of any of claims 1-3, wherein the complex antioxidant is antioxidant H161 or antioxidant H20 from Bluegman, Germany.
5. The halogen-free, hot air long term aging resistant polyamide 56 composition of any of claims 1-4, wherein the polyamide 56 resin has a relative viscosity of 2.4 to 3.2; preferably, the relative viscosity of the polyamide 56 resin is 2.4 to 2.7.
6. The halogen-free, hot air long term aging resistant polyamide 56 composition of any of claims 1-5, wherein the glass fibers are grade E alkali free glass fibers.
7. The halogen-free polyamide 56 composition resistant to hot air long-term aging according to any of claims 1 to 6, wherein the glass fiber is treated with a surface treating agent, and the film-forming agent in the surface treating agent is a polyurethane film-forming agent.
8. The halogen-free, hot air long term aging resistant polyamide 56 composition of claim 7 wherein the polyurethane film former is a polyether polyurethane emulsion.
9. The halogen-free polyamide 56 composition resistant to hot air long term aging of claim 7 wherein the surface sizing contains not less than 25% film former.
10. Use of a halogen-free, hot air long term aging resistant polyamide 56 composition as claimed in any of claims 1 to 9 in extruded and injection moulded articles.
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| CN112724670A (en) * | 2020-12-29 | 2021-04-30 | 上海普利特复合材料股份有限公司 | High-strength and high-heat-resistance bio-based polyamide composition and preparation method thereof |
| CN113429781A (en) * | 2021-06-07 | 2021-09-24 | 南京聚隆科技股份有限公司 | Long glass fiber reinforced bio-based polyamide 56, alloy and preparation method thereof |
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