WO2018068705A1 - Polyamide, son procédé de préparation et adaptateur métallique - Google Patents

Polyamide, son procédé de préparation et adaptateur métallique Download PDF

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Publication number
WO2018068705A1
WO2018068705A1 PCT/CN2017/105546 CN2017105546W WO2018068705A1 WO 2018068705 A1 WO2018068705 A1 WO 2018068705A1 CN 2017105546 W CN2017105546 W CN 2017105546W WO 2018068705 A1 WO2018068705 A1 WO 2018068705A1
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Prior art keywords
polyamide resin
aliphatic polyamide
less
chain
chain aliphatic
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PCT/CN2017/105546
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English (en)
Chinese (zh)
Inventor
左璞晶
宋婷婷
陈斌
加藤公哉
大久保拓郎
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东丽先端材料研究开发（中国）有限公司
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Priority to CN201780057035.0A priority Critical patent/CN109715705B/zh
Priority to JP2019514788A priority patent/JP2019530766A/ja
Publication of WO2018068705A1 publication Critical patent/WO2018068705A1/fr

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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
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • 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
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • 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

Definitions

  • the invention belongs to the field of polymer materials, and particularly relates to a chain aliphatic polyamide resin containing a polyether diamine block and a preparation method thereof.
  • Polyamide resins are widely used in various molded articles such as fibers, various containers, films, electronic components, automotive parts, and machine parts because of their excellent mechanical properties and heat resistance.
  • branching of the polyamide resin is a common method (Chinese Patent Application Nos. CN101939358A, CN101421336A, CN1108329C, CN102203187A).
  • the branched structure reduces the crystallization and mechanical properties of the polyamide resin.
  • Japanese Patent Application Publication No. JPA1986163935 discloses a polyamide resin having improved mechanical properties and moldability, the polyamide resin having an alkyl group having 6 to 22 carbon atoms and a relative viscosity of 2.5 to 6.
  • the melt viscosity of the polyamide resin obtained by this method is still high, and there is still a problem that the molding processability is insufficient for the demand for miniaturization, complication, thinning, and weight reduction of the molded article which has been increasing in recent years.
  • Chinese patent application CN101426833A discloses a copolymer comprising alternating polyamide resin block PA and polyether block PE, which copolymer has improved optical and mechanical properties.
  • thermoplastic elastomer which can be obtained by reactive coupling of a polyamide prepolymer having a hydroxyl end group and an isocyanate terminated polyether prepolymer.
  • the polyether amide block copolymer described in the above patent has a high melt viscosity, and the problem of insufficient moldability is still present.
  • problems such as a decrease in the melting point of the polyamide homopolymer, a lower melting crystallization temperature, a slow curing speed during injection molding, and a long molding cycle.
  • Chinese patent application CN105400187A discloses a thermoplastic polyamide and an amine terminated a highly flowable thermoplastic polyamide resin composition of polyether, but in the composition most of the amine-terminated polyether is present in a state in which it is not chemically bonded to the polyamide, although the amine-terminated polyether present in the above state exists
  • the melt viscosity of the polyamide resin composition can be lowered to some extent, but the effect is not remarkable.
  • the above-mentioned polyamide resin composition also has a drawback that the surface amine-terminated polyether of the molded article is easily precipitated.
  • the international patent application publication WO 2015/182693 discloses a low melt viscosity terminally modified polyamide resin having a specific end group structure. Although the introduction of the polyether structure to the end of the polyamide greatly reduces the melt viscosity of the polyamide resin, it takes a long time to increase the degree of polymerization due to the capping action of the monoamine-based polyether on the active end of the polyamide, resulting in production. low efficiency.
  • the international patent application publication WO 2012/111636 discloses a semi-aromatic polyamide elastomer containing a polyether diamine block.
  • a semi-aromatic polyamide elastomer having good heat resistance, crystallinity, and flexibility is obtained by introducing a polyether diamine block, but a tensile modulus exists in comparison with a corresponding semi-aromatic polyamide homopolymer. The problem of a significant drop in mechanical properties.
  • metal/plastic hybrid composite combines the high strength of metal with the light weight of plastic, while meeting the mechanical strength requirements and lightweight requirements of automotive structural components.
  • the metal member and the plastic are bonded together by mechanical riveting and adhesive bonding to form a hybrid composite material.
  • the plastic component and the metal component need to be processed separately, and then joined by riveting, gluing or the like. Together form the finished part.
  • the international patent application publication WO 2015/022955 discloses a composite of a thermoplastic resin and a metal, which may be a polyether copolymer modified polyamide elastomer or a thermoplastic resin composition composed of a water-absorbing thermoplastic resin and a metal hydroxide. Things.
  • the mechanical properties of polyamide elastomers are significantly reduced compared to polyamide homopolymers.
  • the polyamide elastomer has a lower glass transition temperature than the polyamide homopolymer, and the curing speed is slower at the time of injection molding, and the molding cycle is lengthened. At the same time, the polyamide elastomer has poor adhesion to metals.
  • Chinese Patent Application Publication No. CN105479659A discloses a composite of a plastic material and a metal material comprising a polyether block amide. Although the plastic material and the metal have excellent bonding strength and provide a certain degree of sealing property, due to the polyether block amide The content of the polyether structure is high, and the mechanical properties of the polyether block amide are degraded compared with the polyamide homopolymer, and the bonding property of the polyether block amide with the metal is insufficient.
  • the present invention contains a flexible polyether diamine block having a specific molecular weight in a molecular chain of a chain aliphatic polyamide to achieve the purpose of lowering the melt viscosity and improving the molding processability, and contains the same as the corresponding homopolymer.
  • the thermal properties of the polyether diamine block chain aliphatic polyamide resin are maintained, and the deterioration of mechanical properties is also controlled to a minimum.
  • the polymerization time required in the preparation method of the polyamide resin is also reduced.
  • the thermoplastic resin composition containing the polyamide resin of the present invention has also been found to have excellent metal bondability.
  • the invention consists of the following:
  • a chain aliphatic polyamide resin comprising a polyether diamine block, the polyether diamine block having a structure as shown in Formula I,
  • a, b, and c are positive numbers, and R 1 , R 2 , and R 3 are the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms;
  • the number average molecular weight of the segment is 500 or more and less than 1500 and the content of the polyether diamine block in the chain aliphatic polyamide resin is 0.5% by weight or more and 15% by weight or less based on the total weight of the chain aliphatic polyamide;
  • the aliphatic aliphatic polyamide resin is formulated into a chain aliphatic polyamide resin solution having a concentration of 0.01 g/ml using 96 wt% sulfuric acid as a solvent, the relative viscosity ⁇ r measured at 25 ° C is 1.1 or more and 4.0 or less.
  • the following alkyl groups are examples of the following alkyl groups.
  • R 6 is an alkyl group having 1 or more and 30 or less carbon atoms, an alkyl group substituted with an aryl group, an aryl group or an alkyl group substituted with an alkyl group.
  • the joint strength with metal aluminum measured at min is 10 MPa or more.
  • a method for preparing a chain aliphatic polyamide resin which comprises polymerizing one or more of an aminocarboxylic acid, a lactam or a dibasic acid/diamine as a monomer to prepare a chain aliphatic polyamide resin
  • a polyether diamine as shown in formula IV
  • d, e, and f are each a same or different positive number, and R 7 , R 8 , and R 9 are each the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms;
  • the polyether diamine has a molecular weight of 500 or more and less than 1,500 and the polyether diamine is added in an amount of 0.5% by weight or more and 15% by weight or less based on the total weight of the aminocarboxylic acid, lactam or dibasic acid/diamine monomer. .
  • n is an integer of 2 or more and 100 or less
  • R 10 is an alkylene group having 2 or more and 10 or less carbon atoms
  • R 11 is an alkyl group having 1 or more and 30 or less carbon atoms
  • R 12 or R 13 are the same or different alkylene groups having 1 or more and 20 or less carbon atoms.
  • R 14 is an alkyl group or an aryl-substituted alkyl group, an aryl group or an alkyl-substituted aryl group having 1 or more and 30 or less carbon atoms
  • R 15 or R 16 are the same or different alkylene groups having 1 or more and 20 or less carbon atoms.
  • thermoplastic resin composition contains the chain aliphatic polyamide resin according to any one of the above 1 to 5.
  • the chain aliphatic polyamide resin of the present invention contains a polyether diamine block, and the structure of the polyether diamine block is as shown in Formula I,
  • a, b, and c are positive numbers, and R 1 , R 2 , and R 3 are the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms;
  • the number average molecular weight of the segment is 500 or more and less than 1500 and the content of the polyether diamine block in the chain aliphatic polyamide resin is 0.5% by weight or more and 15% by weight or less based on the total weight of the chain aliphatic polyamide resin;
  • the chain aliphatic polyamide resin is formulated into a chain aliphatic polyamide resin solution having a concentration of 0.01 g/ml using 96 wt% sulfuric acid as a solvent, the relative viscosity ⁇ r measured at 25 ° C is 1.1 or more and 4.0 or less.
  • the chain aliphatic polyamide resin of the present invention has a polyether diamine block as shown in the above formula I at least in a part of the molecular chain.
  • the chain aliphatic polyamide resin described herein is preferably a polyamide resin having an aromatic component content of 20% by weight or less, more preferably a polyamide resin having an aromatic component content of 10% by weight or less and a branched structure content of 0.04% by weight or less. .
  • the structure represented by Formula I contains an ether bond, it is highly mobile and has a strong affinity with an amide bond.
  • the flexibility of the polyamide molecule is improved, so that the molecular mobility of the polyamide is greatly increased, thereby lowering the melt viscosity and improving the molding processability. .
  • a, b, and c are preferably positive numbers within a range of 1 or more and 31 or less each of the same or different, and when any one of the values a, b, and c exceeds 31, the melt viscosity lowering effect is deteriorated. At the same time, the heat resistance of the polyether diamine block structure is also deteriorated; and when any of the values of a, b, and c is less than 1, the crystallinity of the polyamide resin is largely impaired.
  • a, b, and c satisfy the following conditions: 2 ⁇ a + c ⁇ 10 and 1.5 ⁇ b ⁇ 31. Further preferably, 3 ⁇ a + c ⁇ 8 and 7 ⁇ b ⁇ 15; still more preferably 5 ⁇ a + c ⁇ 7 and 10 ⁇ b ⁇ 14.
  • a+c and b herein mean an average value.
  • R 1 , R 2 and R 3 are each the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms. Considering the stability of the polyether diamine block structure and the interaction between the molecular chains and the complexation between the molecular chains, it is preferred that R 1 , R 2 and R 3 are alkyl groups having 1 or more and 10 or less carbon atoms. .
  • R 1 , R 2 , and R 3 are alkyl groups, the smaller the number of carbon atoms in R 1 , R 2 , and R 3 , the higher the affinity with the main structural unit of the polyamide, and the polyether 2
  • the amine block is less likely to form a condensed state, and it is preferable that R 1 , R 2 and R 3 are an alkyl group having 1 or more and 5 or less carbon atoms, and more preferably R 1 , R 2 and R 3 are 1 or more carbon atoms. Further, an alkyl group of 2 or less is most preferably a methyl group at the same time as R 1 , R 2 and R 3 .
  • the polyether diamine block represented by the above formula I has a number average molecular weight of 500 or more and less than 1,500.
  • the number average molecular weight of the polyether diamine block is 550 or more, and it is more preferable that the number average molecular weight of the polyether diamine block is 850 or more.
  • the polyether diamine block has a number average molecular weight of 1200 Further, it is more preferable that the number average molecular weight of the polyether diamine block is 1100 or less.
  • the polyether diamine block represented by Formula I in the chain aliphatic polyamide resin of the present invention is contained in the chain aliphatic polyamide resin in an amount of 0.5% by weight or more and 15% by weight or less (based on the weight of the chain aliphatic polyamide resin) 100 wt%, the same below), by making the polyether diamine block of the formula I having a mass content of 0.5% by weight or more, the purpose of lowering the melt viscosity and improving the moldability can be achieved.
  • the content of the polyether diamine block in the chain aliphatic polyamide resin is preferably 1% by weight or more, more preferably 1.5% by weight or more, still more preferably 2% by weight or more; on the other hand, by the polymerization of Formula I
  • the mass ratio of the ether diamine block is 15% by weight or less
  • the crystallinity and mechanical properties of the chain aliphatic polyamide resin can be more preferably maintained, and it is preferably 11% by weight or less, further preferably 6% by weight or less, and still more preferably 4.5 wt% or less.
  • the content (wt%) of the polyether diamine block represented by the above formula I with respect to the chain aliphatic polyamide resin was obtained by 1H-NMR (nuclear magnetic resonance) test.
  • the relative viscosity ⁇ r measured at 25 ° C is preferably 1.1 or more and 4.0 or less.
  • ⁇ r is less than 1.1, the mechanical properties of the composition are poor.
  • ⁇ r is 1.2 or more, and further preferably 1.4 or more.
  • ⁇ r is more than 4, the molecular weight is too high, and thus the melt viscosity is too high, and the moldability is too poor, and ⁇ r is preferably 3 or less.
  • the polyamide resin composition contains a filler described later in an amount of 1% by mass or more, the filler should be removed to a state where the mass content is less than 1%, and then the viscosity is measured.
  • the chain aliphatic polyamide resin of the present invention may contain, in addition to the polyether diamine block, a block of another structure such as a polyolefin block, a polyester block or the like. However, in consideration of the melt viscosity lowering effect and the retention of crystallinity, it is preferred that the chain aliphatic polyamide resin does not contain a block having another structure except for the polyether diamine block.
  • the block of the other structure referred to herein means a polymer block other than the polyether diamine block having the number of repeating units of 8 or more.
  • the terminal group of the chain aliphatic polyamide resin of the present invention is not particularly required, and may be a reactive terminal group such as an amino group or a carboxyl group, or may be another non-reactive terminal group.
  • a terminal group represented by Formula II is preferable as a non-reactive terminal group.
  • the affinity of the polyether end to the polyamide main chain is preferably high, and -Y- is preferably -NH-.
  • m in the above formula II is less than 2, the effect of lowering the melt viscosity and maintaining the crystallinity is inferior, and the moldability and crystallinity are insufficient.
  • m is preferably 4 or more, further preferably m is 8 or more, and most preferably m is 10 or more.
  • m is more than 100, the end group structure is inferior in heat resistance.
  • m is preferably 70 or less, more preferably m is 35 or less, and most preferably m is 25 or less.
  • R 4 is the same or different and is an alkylene group having 2 or more and 10 or less carbon atoms.
  • R 4 may specifically be -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH(CH 3 )-CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 - , -CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, and the like.
  • R 4 groups may be composed of different alkylene groups, most preferably -CH 2 -CH 2 - and -CH(CH 3 )-CH 2 -.
  • R 5 is an alkyl group having 1 or more and 30 or less carbon atoms.
  • the smaller the number of carbon atoms in R 5 the higher the affinity with the main structural unit of the polyamide resin. Therefore, R 5 is preferably an alkyl group having 1 or more and 20 or less carbon atoms, and more preferably 1 carbon atom.
  • the alkyl group of the above 10 or less is more preferably an alkyl group having 1 or more and 5 or less carbon atoms, and most preferably a methyl group.
  • the chain aliphatic polyamide resin of the present invention preferably contains a terminal group represented by Formula II at least at a terminal of a part of the polyamide molecular chain, and the terminal group has a content of 0.005 mmol or more in 1 g of the chain aliphatic polyamide resin.
  • the content of the terminal group represented by the formula II in 1 g of the chain-like aliphatic polyamide resin is controlled to be 0.005 mmol or less, the molecular weight of the polyamide resin is increased slowly during melt retention, thereby improving melting.
  • the melt viscosity of the polyamide resin can be further lowered to further improve the moldability, and is preferably 0.01 mmol/g or more, more preferably 0.02 mmol/g or more, and still more preferably 0.03 mmol/g or more.
  • the content of the terminal group represented by Formula II in 1 g of the chain aliphatic polyamide resin to 0.1 mmol or less, the molecular weight of the chain aliphatic polyamide resin can be made easier.
  • the progress is preferably 0.08 mmol/g or less, more preferably 0.07 mmol/g or less, and most preferably 0.06 mmol/g or less.
  • the content of the terminal group represented by the above formula II with respect to the polyamide resin was obtained by a 1H-NMR (nuclear magnetic resonance) test.
  • Melt retention stability by melting the polyamide resin under a nitrogen atmosphere at a melting point of Tm + 40 ° C for 1 hour, and measuring its weight average molecular weight (Mw) by GPC, and calculating its Mw increase relative to the melt retention. Rate, expressed as a percentage.
  • the Mw increase rate is preferably 60% or less, more preferably 40% or less, still more preferably 20% or less.
  • the other is preferably a terminal group as shown in Formula III
  • R 6 is preferably an alkane having 1 or more and 20 or less carbon atoms. Base or phenyl.
  • the chain aliphatic polyamide resin of the present invention preferably contains a terminal group represented by Formula III at least at a terminal of a part of the polyamide molecular chain, and the terminal group has a content of 0.005 mmol or more in 1 g of the chain aliphatic polyamide resin.
  • the content of the terminal group represented by Formula III in 1 g of the chain-like aliphatic polyamide resin is controlled to 0.005 mmol or less, the molecular weight of the polyamide resin is increased slowly during melt retention, thereby improving melting.
  • the retention stability is preferably 0.01 mmol/g or more, more preferably 0.02 mmol/g or more, still more preferably 0.03 mmol/g or more; on the other hand, the terminal group represented by Formula III is aggregated at 1 g of the chain aliphatic group.
  • the content of the amide resin is controlled to 0.1 mmol or less, the molecular weight of the chain aliphatic polyamide resin can be more easily carried out, and it is preferably 0.08 mmol/g or less, more preferably 0.07 mmol/g or less, and most preferably 0.06 mmol/ g below.
  • the content of the terminal group represented by the above formula III with respect to the polyamide resin (mmol/g) was obtained by 1H-NMR (nuclear magnetic resonance) test.
  • the weight average molecular weight (Mw) of the chain aliphatic polyamide resin of the present invention is preferably 10,000 or more. When the Mw reaches 10,000 or more, the mechanical properties can be further improved. Mw is further preferably 20,000 or more, and still more preferably 30,000 or more. Further, Mw is preferably 400,000 or less. When the Mw is 400,000 or less, the melt viscosity is low and the formability is good. Mw is more preferably 300,000 or less, still more preferably 250,000 or less.
  • the weight average molecular weight (Mw) can be determined by gel permeation chromatography (GPC).
  • the present invention is intended to obtain a chain-like aliphatic polyamide resin having good heat resistance. Therefore, the melting point (Tm) of the chain aliphatic polyamide resin is preferably 215 ° C or higher, and further preferably the melting point of the chain aliphatic polyamide resin ( Tm) is above 218 °C.
  • the invention adopts the structure and number average of the polyether diamine block The above definition of the amount and content allows the decrease in the melting point and the crystallization temperature of the chain aliphatic polyamide resin after the introduction of the polyether diamine block to the minimum.
  • the melting point of the chain aliphatic polyamide resin containing the polyether diamine block is not more than 5 ° C, and preferably the melting point is not more than 3 ° C, as compared with the melting point of the corresponding chain aliphatic polyamide homopolymer. Meanwhile, the melting crystallization temperature of the chain aliphatic polyamide resin containing the polyether diamine block is not more than 5 ° C, preferably the melting crystallization temperature, compared with the melting crystallization temperature of the corresponding chain aliphatic polyamide homopolymer. The drop does not exceed 3 °C.
  • the melting point and melt crystallization temperature of the polyamide resin described herein are determined by differential scanning calorimetry (DSC): the polyamide resin is accurately weighed 5 to 7 mg, and the temperature is raised at a temperature rising rate of 20 ° C/min under a nitrogen atmosphere. At 20 ° C, the temperature is raised to a temperature 30 ° C higher than the peak temperature T0 of the endothermic peak, and the temperature is kept at this temperature for 2 min, and then the temperature is lowered to 20 ° C at a temperature drop rate of 20 ° C / min, during the above-mentioned cooling process.
  • DSC differential scanning calorimetry
  • the temperature corresponding to the peak tip of the exothermic peak appearing is defined as the melting crystallization temperature (Tc), and thereafter is again raised to a temperature 30 ° C higher than T0 at a temperature increase rate of 20 ° C/min, during the second heating process.
  • the temperature corresponding to the peak tip of the endothermic peak appearing is defined as the melting point (Tm).
  • the main component of the chain aliphatic polyamide resin of the present invention may be exemplified by, but not limited to, the following examples: polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene diamine (nylon) 46), polyhexamethylene pentane diamine (nylon 56), polysebacyl diamine (nylon 410), polysebacyl pentane diamine (nylon 510), polyphthalamide (nylon 610) Polydodecyl hexamethylenediamine (nylon 612) and a copolymer of the above polymers.
  • polycaprolactam nylon 6
  • polyhexamethylene adipamide nylon 66
  • polyhexamethylene diamine nylon 46
  • polyhexamethylene pentane diamine nylon 56
  • polysebacyl diamine nylon 410
  • polysebacyl pentane diamine polyphthalamide
  • polyphthalamide poly
  • polycaprolactam nylon 6
  • polyhexamethylene adipamide nylon 66
  • polyhexamethylene pentane diamine nylon 56
  • polysebacyl diamine nylon 410
  • polydidecyl pentylene Diamine nylon 510
  • polydecamethylenediamine nylon 610
  • polycaprolactam/polyhexamethylene adipamide nylon 6/66
  • a method for producing a chain aliphatic polyamide resin containing a polyether diamine block described later may be exemplified by amino acid,
  • the ratio of the lactam or the dicarboxylic acid/diamine as the monomer starting material and the polyether diamine of the formula IV to the preferred total amino group amount [NH 2 ] and the total carboxyl group amount [COOH] described later [ The ratio of NH 2 ]/[COOH] was carried out.
  • the starting material is a lactam
  • an amount of the amino groups [NH 2] or carboxy groups [COOH] is the amount of the amino-lactam hydrolysis [NH 2] or carboxy groups [COOH].
  • a method for producing a chain aliphatic polyamide resin containing a polyether diamine block described later, which is a raw material may be mentioned.
  • the ratio of the preferred total amino group amount [NH 2 ] and the total carboxyl group amount [COOH] of the amino acid, lactam, dicarboxylic acid and diamine and the polyether diamine of the formula IV to the following [NH 2 ] /[COOH] is used for the ratio.
  • the starting material is a lactam
  • an amount of the amino groups [NH 2] or carboxy groups [COOH] is the amount of the amino-lactam hydrolysis [NH 2] or carboxy groups [COOH].
  • melt viscosity ratio as shown in the following formula VII is also defined in the present invention:
  • Melt viscosity ratio (%) ⁇ (melt viscosity of chain aliphatic polyamide resin containing polyether diamine block) / (having the same molecular weight as chain aliphatic polyamide resin containing polyether diamine block but Melt viscosity of the chain aliphatic polyamide resin not containing the polyether diamine block) ⁇ ⁇ 100 (%) (formula VII).
  • the chain aliphatic polyamide resin containing a polyether diamine block refers to a polyamide resin containing a polyether diamine block of the formula I in the chain aliphatic polyamide resin of the present invention.
  • the melt viscosity ratio as defined in the formula VII of the present invention is preferably 80% or less, more preferably 60% or less, still more preferably 50% or less.
  • the melt viscosity ratio referred to herein is an index which achieves an effect of lowering the melt viscosity by introducing a polyether diamine block into a molecular chain of a chain aliphatic polyamide resin. When the melt viscosity ratio is within the above range, the molding processability can be improved.
  • the chain aliphatic polyamide resin having the same molecular weight but not containing the polyether diamine block as the chain aliphatic polyamide resin containing the polyether diamine block means that the Mw contains the polyether A chain-like aliphatic polyamide resin containing no polyether diamine block in a range of 95% or more and 105% or less of the chain aliphatic polyamide resin Mw of the diamine block.
  • the closer the Mw of the chain aliphatic polyamide resin not containing the polyether diamine block to the chain aliphatic polyamide resin Mw containing the polyether diamine block the better.
  • the preferred range of Mw of the chain aliphatic polyamide resin not containing the polyether diamine block is 100% of the chain aliphatic polyamide resin Mw containing the polyether diamine block.
  • the melt viscosity can be obtained by a rotary rheometer test.
  • the means to obtain the melt viscosity ratio in the above range for example, a method in which the polyether diamine represented by the above formula I is within the above preferred range can be exemplified.
  • the chain-like aliphatic polyamide resin of the present invention has a high metal bonding strength, and preferably has a chain-like aliphatic polyamide resin having a tensile shear strength of 10 MPa or more bonded to the metal aluminum, and more preferably has a tensile shear strength of 15 MPa or more.
  • a chain aliphatic polyamide resin having a tensile shear strength of 20 MPa or more is most preferable.
  • the tensile shear strength of the chain-like aliphatic polyamide resin bonded to the metal described herein was measured according to ISO 19095, and was tested at a tensile speed of 5 mm/min.
  • the above-mentioned joined body is molded at a mold temperature of 120 ° C
  • the above-mentioned metal aluminum is defined as an aluminum sheet A6061 which has been subjected to an NMT surface treatment method of Dacheng Chemical or a similar surface treatment method, and the surface of the metal surface subjected to the above surface treatment is electronically scanned. Microscopic observation, there is an average pore diameter of 10 or more and 100 nm or less The tiny holes.
  • the chain-like aliphatic polyamide resin of the present invention has excellent adhesion to a metal, when a thermoplastic resin composition containing the chain-like aliphatic polyamide resin of the present invention is used, it is possible to obtain a metal-bonding property. Joint body.
  • the chain aliphatic polyamide resin of the present invention may, but not limited to, the following production method: a raw material as a main component of the chain aliphatic polyamide resin is in the presence of a polyether diamine as described in the following formula IV A method of copolymerization.
  • the method of copolymerization may be exemplified by one or more of a raw material such as an aminocarboxylic acid, a lactam, or a dibasic acid/diamine as a main component of the chain aliphatic polyamide resin.
  • a polyether diamine as shown in Formula IV is added,
  • d, e, and f are a positive number, and R 7 , R 8 , and R 9 are each the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms; and the polyether diamine
  • the molecular weight is 500 or more and less than 1,500 and the polyether diamine is added in an amount of 0.5% by weight or more and 15% by weight or less based on the total weight of the aminocarboxylic acid, lactam or dibasic acid/diamine monomer.
  • d, e, and f are positive numbers in the range of 1 or more and 31 or less, and when any of d, e, and f values exceeds 31, the effect of reducing the melt viscosity may be poor, and at the same time, the polyether 2
  • the amine block structure is also inferior in heat resistance; and when any of the d, e, and f values is less than 1, the crystallinity damage to the polyamide resin may be large.
  • d, e, and f satisfy the following conditions: 2 ⁇ d + f ⁇ 10 and 1.5 ⁇ e ⁇ 31.
  • d+f and e herein mean an average value.
  • R 7 , R 8 and R 9 are each the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms; in view of the stability of the polyether diamine block structure, R 7 and R 8 and R 9 are preferably an alkyl group having 1 or more and 10 or less carbon atoms.
  • R 7 , R 8 and R 9 are alkyl groups, the smaller the number of carbon atoms in R 7 , R 8 and R 9 , the higher the affinity with the main structural unit of the polyamide resin, and preferably R 7 , R 8 and R 9 are an alkyl group having 1 or more and 5 or less carbon atoms, and more preferably R 7 , R 8 and R 9 are an alkyl group having 1 or more and 2 or less carbon atoms, and most preferably R 7 or R 8 and R 9 are both methyl.
  • the number average molecular weight of the polyether diamine represented by the above formula IV is preferably 500 or more and less than 1,500, and when the number average molecular weight is less than 500, the crystallinity of the polyamide resin is greatly inhibited.
  • the crystallinity is preferably 550 or more, and the number average molecular weight of the polyether diamine is preferably 580 or more.
  • the number average molecular weight of the polyether diamine is preferably 1200 or less, and more preferably the number average molecular weight of the polyether diamine is 1100 or less.
  • the polyether diamine represented by the formula IV in the method for producing the chain aliphatic polyamide resin of the present invention is preferably added in an amount of 0.5 wt% of the total weight of the aminocarboxylic acid, lactam or dibasic acid/diamine monomer. % or more and 15% by weight or less (100% by weight based on the total weight of the aminocarboxylic acid, lactam or dibasic acid/diamine monomer, the same applies hereinafter).
  • the addition amount of the polyether diamine represented by Formula IV is 0.5% by weight or more, the melt viscosity of the obtained polyamide product is lowered, and the molding process type is improved.
  • the polyether diamine represented by Formula IV is added in an amount of 15 wt% or less, the obtained polyamide product crystallinity Can be maintained. It is more preferably 11% by weight or less, still more preferably 6% by weight or less, and most preferably 4.5% by weight or less.
  • the polyether diamine represented by the above formula IV may specifically be exemplified by, but not limited to, the following polyether diamines: RE-900, RT-1000, One or more of ED-900 (commercial products from Huntsman) may be selected in combination of two or more kinds of polyether diamines such as those exemplified above.
  • the polyether diamine represented by the above formula IV may be added simultaneously with one or more of an aminocarboxylic acid, a lactam, or a dibasic acid/diamine before the start of polymerization, or may be polymerized after the start of polymerization. Add it at any time during the process.
  • a polymerization accelerator may be added as necessary.
  • the polymerization accelerator is preferably an inorganic phosphorus compound such as phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid or an alkali metal salt or an alkaline earth metal salt of the above phosphoric acid, and more preferably sodium phosphite or sodium hypophosphite.
  • the amount of use of the polymerization accelerator is preferably 0.001 part by weight or more and 1 part by weight or less (the weight of the raw material for preparing the polyamide resin other than the polyether diamine having the structure represented by the above formula IV is 100 parts by weight).
  • the obtained polyamide can be obtained by controlling the addition amount of the polymerization accelerator to the above range of 0.001 part by weight or more and 1 part by weight or less.
  • the mechanical properties and molding processability of the resin are well balanced.
  • the polyether diamine is preferably controlled in a range of 0.95 or more and 1.05 or less in a ratio of a preferred total amount of amino groups [NH 2 ] and a total amount of carboxyl groups [COOH] [NH 2 ]/[COOH] described later.
  • a preferred range of NH 2 ]/[COOH] is 0.98 or more and 1.02 or less, and more preferably 0.99 or more and 1.01 or less.
  • an amount of the amino groups [NH 2] or carboxy groups [COOH] is the amount of the amino-lactam hydrolysis [NH 2] or carboxy groups [COOH].
  • n is an integer of 2 or more and 100 or less
  • R 10 is the same or different, and is an alkylene group having 2 or more and 10 or less carbon atoms
  • R 11 is an alkyl group having 1 or more and 30 or less carbon atoms.
  • R 12 or R 13 are the same or different alkylene groups having 1 or more and 20 or less carbon atoms.
  • n in the above formula V is less than 2, the effect of lowering the melt viscosity and maintaining the crystallinity is inferior, and the improvement in moldability is limited.
  • n is 4 or more, further preferably 8 or more, and most preferably 10 or more.
  • n is more than 100, the end group structure is inferior in heat resistance.
  • n is 70 or less, further preferably 35 or less, and most preferably 25 or less.
  • R 10 is the same or different and is an alkylene group having 2 or more and 10 or less carbon atoms, and in view of affinity with a main structural unit of the polyamide resin, a subatomic ratio of 2 or more and 6 or less is preferable.
  • the alkyl group is more preferably an alkylene group having 2 or more and 4 or less carbon atoms.
  • R 10 examples include -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH(CH 3 )-CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 - , -CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, and the like.
  • R 10 groups may be composed of different alkylene groups, preferably -CH 2 -CH 2 - and -CH(CH 3 )-CH 2 -.
  • R 11 is an alkyl group having 1 or more and 30 or less carbon atoms.
  • the smaller the number of carbon atoms in R 11 the higher the affinity with the main structural unit of the polyamide resin. Therefore, R 11 is preferably an alkyl group having 1 or more and 20 or less carbon atoms, and more preferably 1 carbon atom.
  • the alkyl group of the above 10 or less is more preferably an alkyl group having 1 or more and 5 or less carbon atoms, and most preferably a methyl group.
  • the compound represented by the above formula V may specifically be exemplified by, but not limited to, the following examples: M-600, M-1000, M-2005, M-2070 and so on.
  • R 14 is an alkyl group or an aryl-substituted alkyl group, an aryl group or an alkyl-substituted aryl group having 1 or more and 30 or less carbon atoms
  • R 15 or R 16 are the same or different alkylene groups having 1 or more and 20 or less carbon atoms.
  • R 14 preferably has 1 or more carbon atoms.
  • the compound represented by the above formula VI may specifically be exemplified by, but not limited to, the following examples: methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, and the like.
  • An aliphatic monoamine such as propylamine or dibutylamine; an alicyclic monoamine such as cyclohexylamine or dicyclohexylamine; or an aromatic monoamine such as aniline, toluidine, diphenylamine or naphthylamine.
  • the compound represented by the above monoamine type VI may be used singly or in combination of two or more.
  • the compound represented by the above formula VI may specifically be exemplified by, but not limited to, the following examples: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, and fourteen.
  • Aliphatic monobasic acids such as alkanoic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; alicyclic monobasic acids such as cyclohexanoic acid; benzoic acid, toluic acid, ⁇ -naphthoic acid, ⁇ -naphthoic acid An aromatic monobasic acid such as methylnaphthoic acid or phenylacetic acid. Among them, acetic acid is preferred.
  • the compound of the above monobasic acid type VI may be used singly or in combination of two or more.
  • the chain aliphatic polyamide of the present invention is a chain aliphatic polyamide resin prepared by using an amino acid, a lactam, or a diacid and a diamine as a main raw material, and contains the block structure represented by the above formula I.
  • the following examples can be exemplified as the monomer raw material constituting the main structural unit of the main chain of the chain aliphatic polyamide resin.
  • amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or 4-aminomethylbenzoic acid
  • lactams such as ⁇ -caprolactam or ⁇ -laurolactam
  • the corresponding alkyl diester and diacid chloride of the dicarboxylic acid can also be exemplified as the monomer raw material constituting the chain aliphatic polyamide main chain structure.
  • the chain aliphatic polyamide resin in the present invention may be a chain aliphatic polyamide homopolymer prepared from a monomer raw material such as the above, or a chain aliphatic polyamide copolymer.
  • the chain aliphatic polyamide resin may be a polyamide resin or may be composed of two or more polyamide resins.
  • the specific structure of the chain aliphatic polyamide resin is not particularly limited, but in view of heat resistance and crystallinity, it is preferred that 80 mol% or more of the chain aliphatic polyamide main chain repeating unit is the monomer raw material exemplified above.
  • the composition of the structural unit is more preferably 90 mol% or more, and most preferably 100 mol%.
  • a filler, a polymer of another type, and various additives may be added to form a chain-like aliphatic polyamide resin composition in a range not impairing the advantageous effects of the present invention. use.
  • the filler may be a filler for a general resin, and the addition of the filler may further improve the strength, rigidity, heat resistance and dimensional stability of the molded article obtained from the chain aliphatic polyamide resin.
  • the filler may be exemplified by, but not limited to, the following examples: glass fiber, carbon fiber, titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber , fibrous or inorganic fillers such as gypsum fibers or metal fibers; wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, asbestos, silicate, alumina, Silica, magnesia, zirconia, titania, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide
  • the filler may be hollow, and the filler may be treated with a coupling agent such as an isocyanate compound, an organosilane compound, an organic titanate compound, an organoborane compound or an epoxy compound.
  • a coupling agent such as an isocyanate compound, an organosilane compound, an organic titanate compound, an organoborane compound or an epoxy compound.
  • the above montmorillonite may also be an organic montmorillonite obtained by cation exchange of interlamellar ions through an organic ammonium salt.
  • the above filler is preferably a fibrous inorganic filler, and more preferably glass fiber or carbon fiber.
  • the content of the above filler in the chain aliphatic polyamide resin composition obtained after compounding is preferably When the amount of the filler added is 5% by weight or more, the shrinkage ratio of the resin composition is reduced, and dimensional stability is good, and when used as a metal-bonding resin composition, when the filler is added in an amount of 5 wt% or more and 80 wt% or less Since the shrinkage ratio of the resin composition is reduced, the resin composition infiltrated into the fine pores of the surface-treated metal surface is melted, and the interfacial peeling of the resin composition from the metal is suppressed, thereby bonding the resin composition and the metal.
  • the filler is added in an amount of 10% by weight or more, more preferably 20% by weight or more, and most preferably 30% by weight or more based on the total weight of the resin composition.
  • the amount of the filler added is 80% by weight or less, the melt of the resin composition has good fluidity, more preferably 60% by weight or less, still more preferably 50% by weight or less.
  • polymers to be added may be exemplified by, but not limited to, polyolefins such as polyethylene or polypropylene; modified polyolefins such as copolymers obtained by polymerizing olefins and/or conjugated diene compounds; and polyesters; Polyamide resin other than polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN resin, polystyrene, or chain aliphatic polyamide resin of the present invention .
  • the above polymers may be added in combination of two or more kinds.
  • the addition amount of the other kind of polymer is preferably 0% by weight or more and 80% by weight or less (100% by weight of the resin composition obtained after compounding), and by controlling the added amount to the above range, a chain aliphatic group can be obtained.
  • the low melt viscosity properties of polyamides are better reflected. It is further preferably 60% by weight or less, and still more preferably 50% by weight or less.
  • the above-mentioned other kinds of polymers are preferably polymers (or copolymers) obtained by polymerizing an olefin and/or a conjugated diene compound.
  • An impact agent such as a modified polyolefin.
  • the polymer may, but not limited to, the following examples: an ethylene-based copolymer, a conjugated diene-based polymer, or a conjugated diene-aromatic ethylene copolymer.
  • the ethylene-based copolymer means a copolymer of ethylene and another monomer.
  • Other monomers copolymerized with ethylene may, but not limited to, the following examples: an ⁇ -olefin having 3 or more carbon atoms, a non-conjugated diene, vinyl acetate, vinyl alcohol, an ⁇ , ⁇ -unsaturated acid or a derivative thereof. Two or more kinds of the above monomers may be copolymerized with ethylene.
  • the ⁇ -olefin having 3 or more carbon atoms may, but not limited to, the following examples: propylene, 1-butene, 1-pentene, or 3-methyl-1-pentene, preferably propylene or 1-butene.
  • the non-conjugated diene may be exemplified by, but not limited to, the following examples: 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5 -propenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-butenyl-2-norbornene, 5-(2-methyl-2-butenyl)-2 - norbornene, 5-(2-ethyl-2-butenyl)-2-norbornene, or norbornene compound such as 5-methyl-5-vinylnorbornene; dicyclopentadiene, Methyltetrahydroanthracene, tetrahydroanthracene, 1,5-cyclooctadiene, 1,4-hexadiene, 6-Methyl-1,5-heptadiene, or 11-tridecadiene, etc.,
  • the ⁇ , ⁇ -unsaturated acid may be exemplified by, but not limited to, the following examples: acrylic acid, methacrylic acid, ethacrylic acid, 2-butenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, or butyl Oleic acid and the like.
  • the derivative of the ⁇ , ⁇ -unsaturated carboxylic acid may, but not limited to, the following examples: an alkyl ester, an aryl ester, a glyceride, an acid anhydride, or an imide of the above ⁇ , ⁇ -unsaturated carboxylic acid.
  • the conjugated diene polymer refers to a polymer obtained by polymerizing at least one conjugated diene.
  • the conjugated diene described herein may be exemplified by, but not limited to, the following examples: 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl Base-1,3-butadiene, or 1,3-pentadiene, and the like.
  • the conjugated diene may be copolymerized in two or more types. Additionally, the unsaturated bonds of the polymer can be partially or completely reduced by hydrogenation.
  • the conjugated diene-aromatic ethylene copolymer refers to a copolymer of a conjugated diene and an aromatic ethylene, and may be a block copolymer or a random copolymer.
  • Examples of the conjugated diene may be the same as those of the above-mentioned conjugated diene-based polymer, and 1,3-butadiene and isoprene are preferable.
  • the aromatic vinyl may, for example, be styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, or vinylnaphthalene, etc., preferably styrene.
  • the unsaturated bond other than the double bond other than the aromatic ring of the conjugated diene-aromatic ethylene copolymer may be partially or completely reduced by hydrogenation.
  • the impact agent include an ethylene/propylene copolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/propylene/dicyclopentadiene copolymer, and an ethylene/propylene/5-Asian Base-2-norbornene copolymer, unhydrogenated or hydrogenated styrene/isoprene/styrene triblock copolymer, unhydrogenated or hydrogenated styrene/butadiene/styrene triblock a salt of a part or all of a carboxylic acid group of a copolymer, an ethylene/methacrylic acid copolymer or a copolymer with sodium, lithium, potassium, zinc or calcium, an ethylene/methyl acrylate copolymer, an ethylene/ethyl acrylate copolymer , ethylene/methyl methacrylate copolymer, ethylene/ethy
  • the above copolymer is preferably an ethylene/methacrylic acid copolymer and a salt of a part or all of a carboxylic acid group of the copolymer with sodium, lithium, potassium, zinc or calcium, an ethylene/propylene-g-maleic anhydride copolymer, ethylene. /butene-1-g-maleic anhydride copolymer.
  • antioxidants or heat stabilizers hindered phenols, hydroquinones, phosphorous acid or substituted products thereof, copper halides, iodine compounds, etc.
  • weathering agents resorcinol, Salicylic acid, benzotriazole, diphenyl ketone, or hindered amines, mold release agents and lubricants (fatty alcohols, aliphatic amides, aliphatic diamides, or diureas or poly Ethylene wax, etc., pigment (calcium sulfide, phthalocyanine, or carbon black, etc.), dye (aniline black, etc.), plasticizer (n-octyl p-hydroxybenzoate, or N-butylbenzenesulfonamide), antistatic Agent (alkyl sulfate type anionic antistatic agent, 4-stage ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate or trimethylg
  • the chain aliphatic polyamide resin of the present invention can be obtained into a desired shape by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, or film forming.
  • the molded article obtained from the chain aliphatic polyamide resin of the present invention and the composition containing the chain aliphatic polyamide resin can be applied to the following examples: resin molded articles such as electric/electronic product parts, automobile parts, mechanical parts, and the like. /Industry and other fibers, films such as packaging/electromagnetic recording, and metal joints.
  • Polyether diamine block content represented by Formula I The polyamide resin having the polyether diamine block of the above formula I obtained in each of the Examples and Comparative Examples was dissolved at a concentration of 50 mg/ml. In the deuterated concentrated sulfuric acid, a 1H-NMR nuclear magnetic test was performed using Japanese electronic JEOL ECX 400P under the condition of 256 scans.
  • the content of the polyether diamine block in the polyamide resin is calculated by the peak area obtained by integrating each peak and the number of hydrogen atoms contained in each structure.
  • End group content represented by Formula II The polyamide resin having the terminal group represented by the above formula II obtained in each of the examples and the comparative examples was dissolved in deuterated concentrated sulfuric acid at a concentration of 50 mg/ml, and was scanned.
  • the 1H-NMR nuclear magnetic test was carried out using Japanese electronic JEOL ECX 400P under the conditions of 256 times.
  • the peaks are integrated by The peak area obtained and the number of hydrogen atoms contained in each structure were calculated to obtain the terminal group content of the formula II in the polyamide resin.
  • the polyamide resin obtained in each of the examples and the comparative examples was accurately weighed 5 to 7 mg by a differential scanning calorimeter (DSC Q100) of TA Corporation, and started at 20 ° C at a heating rate of 20 ° C / min under a nitrogen atmosphere.
  • DSC Q100 differential scanning calorimeter
  • Tc is the temperature corresponding to the peak tip of the exothermic peak during the cooling process
  • ⁇ Hc is the peak area of the exothermic peak during the cooling process.
  • T m is the endothermic heat during the second temperature rise
  • ⁇ H m is the peak area of the endothermic peak during the second temperature rise.
  • the polyamide resin obtained in each of the examples and the comparative examples was dried in a vacuum oven at 80 ° C for 12 hours or more, and then formed into a film having a diameter of 25 mm by hot pressing with a laminator (film thickness: 0.7 mm).
  • the melt viscosity was measured by the following method using a rotary rheometer (manufactured by Antonpas, MCR302, ⁇ 25 parallel plate): the sample was melted at 260 ° C for 5 minutes, the parallel plate pitch was 0.5 mm, and the vibration mode was measured under a nitrogen atmosphere. The frequency was 0.5 to 6.88 Hz, and 50 points (0.5 minutes) and an amplitude of 1% were measured.
  • the complex viscosity measurement at a frequency of 1.02 Hz was used as the melt viscosity.
  • the spline size is Type IV in ASTM D638, and the tensile modulus is tested by Shimadzu AG--IS 1KN.
  • the test temperature is 23 ° C
  • the humidity is 50% RH
  • the tensile speed is 10 mm/min
  • the clamp spacing is 60 mm.
  • the tensile modulus results are taken as the average of the five spline test results.
  • the injection molding conditions for the spline are as follows:
  • Injection temperature 250 ° C (Examples 1 to 16, Comparative Examples 1 to 9, 12 to 17)
  • the molded spline used for the above tensile modulus test was placed in a constant temperature and humidity chamber at a temperature of 60 ° C and a relative humidity of 90% RH for 1000 hours.
  • the metal piece was placed in a cavity, and after the mold was held for 1 minute, the melt of the thermoplastic resin composition was metered and injected into the mold. After the melt is cooled and solidified, the mold is opened to obtain a joined body.
  • the bond between resin and metal is characterized by tensile shear strength.
  • the test is tested according to ISO 19095.
  • the spline size is the specified size in ISO 19095 shown in Figure 1.
  • the joint area is 0.5 cm2.
  • the Shimadzu AG-IS 1KN test is used.
  • the tensile shear strength results are taken as the average of the five spline test results.
  • Sebacic acid Hebei Kaide Biomaterial Co., Ltd.
  • the heater set temperature was lowered to 260 ° C, and the pressure in the autoclave was gradually decreased from 1.75 MPa to normal pressure within 1 hour (the temperature in the autoclave was 260 ° C when the pressure was reached).
  • a nitrogen gas stream was introduced into the autoclave, and melt polymerization was carried out for 10 minutes under a nitrogen stream (up to a temperature of 263 ° C) to obtain a nylon 610 containing a polyether diamine block.
  • the nylon 610 obtained by the above method had a relative viscosity of 1.73 and a melt viscosity of 16 Pa ⁇ s.
  • the nylon 610 obtained by the above method is pelletized, placed in a Soxhlet extractor, and the unreacted polyether diamine is removed with methanol, and the content of the polyether diamine block is determined by nuclear magnetic resonance spectroscopy (1H-NMR). 5.1wt%. Other physical properties are shown in Table 1.
  • Example 1 The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 1 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 1.
  • Table 1 The properties of the obtained nylon 610 are shown in Table 1.
  • Example 1-3 Compared with Comparative Example 1, it can be seen that the melt viscosity of nylon 610 containing 5.1 wt% of the polyether diamine block is only the polyether diamine block-free nylon 610 having the same weight average molecular weight.
  • the homopolymer has a melt viscosity of 8 to 9%, and there is no difference in crystallinity and mechanical properties.
  • Comparative Example 2 when the number average molecular weight of the polyether diamine block is less than 500, the crystallization temperature of the polyamide resin The degree, melting point and mechanical properties were all significantly decreased, while the number average molecular weight of the polyether diamine block in Comparative Example 3 was more than 1,500, and the melt viscosity decreased not significantly.
  • Example 2 The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 2 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 2.
  • Table 2 The properties of the obtained nylon 610 are shown in Table 2.
  • Example 2 and Examples 4-6 maintained the same crystallinity and mechanical properties as Comparative Example 1 as compared with Comparative Example 5 having a higher polyether diamine block content (20 wt%).
  • Example 3 The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 3 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 3.
  • the properties of the obtained nylon 610 are shown in Table 3.
  • Example 2 By comparing Example 2 and Comparative Example 6-8, the melt viscosity reduction effect of Example 2 was better than that of the polyether block containing other structures.
  • Example 4 The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 4 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 4.
  • the properties of the obtained nylon 610 are shown in Table 4.
  • the heater set temperature was lowered to 260 ° C, and the pressure in the autoclave was gradually reduced from 1 MPa to normal pressure within 1 hour (the temperature in the autoclave was 260 ° C when the pressure was reached).
  • a nitrogen gas stream was introduced into the autoclave, and melt polymerization was carried out for 10 minutes under a nitrogen stream (up to a temperature of 263 ° C) to obtain a nylon 6 containing a polyether diamine block.
  • the obtained nylon 6 was pelletized, placed in a Soxhlet extractor, and unreacted caprolactam and polyether diamine were removed by methanol, and the relative viscosity was 1.77, and the melt viscosity was 18 Pa ⁇ s.
  • the content of the polyether diamine block was 5.6 wt% by nuclear magnetic resonance spectroscopy (1H-NMR). Other physical properties are shown in Table 5.
  • Example 11 The other operations were the same as in Example 11 except that the raw materials were changed as shown in Table 5 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 5. The properties of the obtained nylon 6 are shown in Table 5.
  • the heater set temperature was lowered to 280 ° C, and the pressure in the autoclave was gradually reduced from 1.75 MPa to normal pressure within 1 hour (the temperature in the autoclave was 275 ° C when the pressure was reached).
  • a nitrogen stream was introduced into the kettle, and melt polymerization was carried out for 10 minutes under a nitrogen stream (up to a temperature of 282 ° C) to obtain a nylon 66 containing a polyether diamine block.
  • the nylon 66 obtained by the above method had a relative viscosity of 1.99 and a melt viscosity of 22 Pa ⁇ s.
  • the nylon 66 obtained by the above method was pelletized, placed in a Soxhlet extractor, and the unreacted polyether diamine was removed with methanol, and the content of the polyether diamine block was determined by nuclear magnetic resonance spectroscopy (1H-NMR). 5.1wt%. Other physical properties are shown in Table 5.
  • the nylon MXD10 containing a polyether diamine block was obtained by dropping to atmospheric pressure.
  • the nylon MXD10 obtained by the above method had a relative viscosity of 1.81 and a melt viscosity of 150 Pa ⁇ s.
  • the nylon MXD10 obtained by the above method is pelletized, placed in a Soxhlet extractor, and the unreacted polyether diamine is removed with methanol, and the content of the polyether diamine block is determined by nuclear magnetic resonance spectroscopy (1H-NMR). 5.1wt%. Other physical properties are shown in Table 5.
  • Example 14 The other operations were the same as in Example 14 except that the raw materials were changed as shown in Table 5.
  • the properties of the obtained nylon 66 are shown in Table 5.
  • Example 11-13 the melt viscosity was significantly lowered as compared with the nylon 6 homopolymer in Comparative Example 9.
  • Example 14 the melt viscosity was also significantly lowered as compared with the nylon 66 homopolymer in Comparative Example 12.
  • Comparative Example 10 and Comparative Example 11 the semi-aromatic nylon MXD10 containing the polyether diamine block had a lower melt viscosity reduction effect in Comparative Example 10 than the corresponding semi-aromatic nylon homopolymer, and at the same time mechanically The performance is significantly reduced.
  • Example 11 The other operations were the same as in Example 11 except that the raw materials were changed as shown in Table 6 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 6. The properties of the obtained nylon 6 are shown in Table 6.
  • Example 6 The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 6 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 6.
  • the properties of the obtained nylon 610 are shown in Table 6.
  • Example 7 The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 7 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 7.
  • Table 7 The properties of the obtained nylon 610 are shown in Table 7.
  • the surface-treated metal sheet (NMT treatment, Shenzhen Baoyuanjin Co., Ltd.) was placed in a ST10S2V (NISSEI) injection molding machine mold, and the injection molding machine completed the measurement of the polyether diamine block obtained in Example 13.
  • Nylon 6 and a nylon 6 melt were injected into the mold for a cooling time of 15 s, and the mold was opened to obtain a joined body having a screw temperature of 260 ° C and a mold temperature of 120 ° C.
  • the joined body obtained by the above method was subjected to metal bonding performance test at a tensile speed of 5 mm/min in accordance with ISO 19095, and the results are shown in Table 8.
  • the performance of the resulting joined body was as shown in Table 8, except that the resin used for the injection molding or the mold temperature during the injection molding was changed as shown in Table 8.
  • the surface-treated metal sheet (NMT treatment, Shenzhen Baoyuanjin Co., Ltd.) was placed in the ST10S2V (NISSEI) injection molding machine mold, and the injection molding machine completed the measurement of the commercial polyamide elastomer (PEBAX 5533SP01, manufactured by Arkema, melting After the viscosity of 42 Pa ⁇ s), the resin melt was injected into the mold for a cooling time of 15 s.
  • the screw temperature was 260 ° C and the mold temperature was 120 ° C. At a mold temperature of 120 ° C, the polyamide elastomer cannot be solidified in a mold, and is deformed during demolding, so that a joined body cannot be obtained.

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Abstract

La présente invention concerne une résine de polyamide aliphatique à chaîne ayant des performances d'usinage de formation remarquables, des performances thermiques et mécaniques exceptionnelles, et son procédé de préparation. Les principales caractéristiques de la résine de polyamide aliphatique à chaîne selon l'invention sont les suivantes : la résine de polyamide aliphatique à chaîne ayant des séquences de polyéthènoxyamine, la structure de chaque séquence de polyéthènoxyamine est représentée par la formule I, a, b et c dans la formule I sont des valeurs positives identiques ou différentes, R1, R2 et R3 sont des groupes alkyle identiques ou différents et le nombre d'atomes d'hydrogène ou de carbone les constituant est supérieur à 1 et inférieur à 10; le poids moléculaire moyen en nombre de la séquence de polyéthènoxyamine est supérieur à 500 et inférieur à 1 500, et la teneur de la séquence de polyéthènoxyamines dans la résine de polyamide aliphatique à chaîne est supérieure à 0,5 % en poids et inférieure à 15 % en poids du poids total de la résine de polyamide aliphatique à chaîne; lorsque la résine de polyamide aliphatique à chaîne est transformée en une solution de résine de polyamide aliphatique à chaîne dont la teneur est 0,01 g/ml en utilisant de l'acide sulfurique à 96 % en poids comme solvant, la viscosité relative ηr mesurée à 25 °C est supérieure à 1,1 et inférieure à 4,0.
PCT/CN2017/105546 2016-10-11 2017-10-10 Polyamide, son procédé de préparation et adaptateur métallique WO2018068705A1 (fr)

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CN111592755B (zh) * 2019-02-21 2022-07-19 上海凯赛生物技术股份有限公司 一种增强生物基聚酰胺56组合物及其制备方法
CN111285993B (zh) * 2020-03-09 2022-01-28 江苏科技大学 一种高流动聚酰胺6弹性体的制备方法
CN115044033B (zh) * 2022-06-23 2023-04-28 湖南工业大学 一种半芳香族聚酰胺树脂及其制备方法
CN115260751B (zh) * 2022-09-27 2023-01-13 广东永鑫华新型材料有限公司 一种挤出级超韧尼龙的制备方法

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