WO2023284583A1 - Résine polyamide à extrémité modifiée, son procédé de préparation, composition et produit moulé - Google Patents

Résine polyamide à extrémité modifiée, son procédé de préparation, composition et produit moulé Download PDF

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WO2023284583A1
WO2023284583A1 PCT/CN2022/103813 CN2022103813W WO2023284583A1 WO 2023284583 A1 WO2023284583 A1 WO 2023284583A1 CN 2022103813 W CN2022103813 W CN 2022103813W WO 2023284583 A1 WO2023284583 A1 WO 2023284583A1
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terminal
polyamide resin
modified polyamide
formula
weight
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PCT/CN2022/103813
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English (en)
Chinese (zh)
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左璞晶
徐凯
加藤公哉
横江牧人
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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 CN202280005910.1A priority Critical patent/CN116157472A/zh
Publication of WO2023284583A1 publication Critical patent/WO2023284583A1/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
    • C08G69/40—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

Definitions

  • the invention belongs to the field of polymer materials, and in particular relates to a terminal-modified polyamide resin, a preparation method, a composition and a molded product thereof.
  • Polyamide resins are widely used in various molded products such as fibers, various containers, films, electronic parts, automotive parts, and mechanical parts due to their excellent mechanical properties and heat resistance.
  • the filler is highly loaded to the resin.
  • the viscosity of the system increases sharply, which is prone to problems such as shear heat generation, deterioration of resin performance, and poor dispersion of fillers.
  • the polyamide resin has highly reactive carboxyl and amino end groups, it is easy for the filler and the end group of the polyamide resin to have a reaction during filling with some fillers that are easy to react with the above-mentioned end groups. Reaction leads to degradation of resin performance.
  • Patent Document 1 discloses a low-melt-viscosity terminal-modified polyamide resin having a specific terminal group structure, which reduces the melt viscosity of the polyamide resin by introducing a polyether structure into the terminal of the polyamide.
  • a polyamide resin with lower melt viscosity is obtained by further limiting the content of the polyether terminal structure, the molecular weight of the terminal-modified polyamide resin and other characteristics.
  • a monocarboxylic compound as an end-capping agent to control the molecular weight in addition to the monoamine polyether, the polymerization rate is further reduced.
  • Patent Document 1 International Patent Application Publication WO2015/182693
  • Patent Document 2 Publication of International Patent Application WO2018/101054
  • the object of the present invention is to solve the problems in the above-mentioned prior art, to provide a polyamide resin that can greatly shorten the polymerization time of the terminal modified polyamide resin, and can also suppress the volatilization of monomers (especially the volatilization of diamine monomers) during polymerization. ) to suppress the foaming of the polymerization product, thereby improving the preparation method of the end-modified polyamide resin of the pelletizing property of the polymer strand, and the end-modified polyamide resin capable of simultaneously satisfying excellent mechanical properties and processability.
  • the present invention consists of the following contents:
  • n ranges from 2 to 100
  • each R1 is the same or different, and is an alkylene group with 2 to 10 carbon atoms
  • R2 is an alkyl group with 1 to 30 carbon atoms
  • the compound for terminal modification represented by the formula I is added in an amount of 0.05-25 parts by weight, and the added amount of the boric acid compound is 0.005-1.0 parts by weight.
  • terminal-modifying compound shown in formula I and the boric acid compound can be added at any time before the end of the polymerization.
  • the boric acid compound is one or more selected from boric acid, borate, and organic boric acid compound.
  • the polyamide monomer is selected from diamines with 2 to 20 carbon atoms and diamines with 2 to 20 carbon atoms
  • the polyamide monomer is selected from diamines with 2 to 20 carbon atoms and diamines with 2 to 20 carbon atoms
  • dibasic acid combinations amino acids with 4 to 20 carbon atoms
  • lactams with 4 to 20 carbon atoms mixtures of the above polyamide monomers or their salts.
  • the molar ratio is in a relationship of not less than 1.010 and not more than 1.10.
  • a terminal-modified polyamide resin characterized in that: the terminal-modified polyamide resin has the terminal structure and boron element shown in formula II,
  • n ranges from 2 to 100
  • each R1 is the same or different, and is an alkylene group with 2 to 10 carbon atoms
  • R2 is an alkyl group with 1 to 30 carbon atoms
  • the content of the terminal structure represented by the formula II in the terminal-modified polyamide resin is 0.05-25wt% of the total weight of the terminal-modified polyamide resin,
  • the content of the boron element in the terminal-modified polyamide resin is 10-2000 ppm of the total weight of the terminal-modified polyamide resin.
  • n 16 to 100.
  • each R 1 is the same or different, and is -CH 2 -CH 2 -, -CH 2 At least one of -CH 2 -CH 2 -, -CH(CH 3 )-CH 2 -.
  • the terminal-modified polyamide resin according to the above-mentioned 8 characterized in that: the terminal-modified polyamide resin is prepared into a terminal-modified polyamide resin solution with a concentration of 0.01 g/ml by using 96 wt% sulfuric acid as a solvent , the relative viscosity ⁇ r measured at 25°C is 1.1 to 4.0.
  • the terminal-modified polyamide resin according to the above-mentioned 8 characterized in that the weight-average molecular weight Mw of the terminal-modified polyamide resin measured by gel permeation chromatography is in the range of 10,000-400,000.
  • terminal-modified polyamide resin according to the above-mentioned 8 characterized in that the amino group concentration in the terminal-modified polyamide resin is 105-400 mol/t.
  • the terminal-modified polyamide resin according to the above-mentioned 8 characterized in that: the carboxyl group concentration in the terminal-modified polyamide resin is 100 mol/t or less.
  • a terminal-modified polyamide resin composition comprising the terminal-modified polyamide resin according to any one of 8 to 16 above.
  • a molded article comprising the terminal-modified polyamide resin described in any one of 8 to 16 above or the terminal-modified polyamide resin composition described in 17 above.
  • the present invention by carrying out specific end-modified polyamide polymerization in the presence of a boric acid compound, while greatly shortening the polymerization time of the end-modified polyamide resin, by suppressing the volatilization of monomers during polymerization (especially diamine The volatilization of the monomer) to suppress the foaming of the polymerized product, so that the end-modified polyamide resin with excellent cutting performance of the extruded polymer strand can be obtained. Furthermore, the terminal-modified polyamide resin of the present invention can satisfy both excellent mechanical properties and processability.
  • n ranges from 2 to 100
  • each R1 is the same or different, and is an alkylene group with 2 to 10 carbon atoms
  • R2 is an alkyl group with 1 to 30 carbon atoms
  • the compound for terminal modification represented by the formula I is added in an amount of 0.05-25 parts by weight, and the added amount of the boric acid compound is 0.001-1.0 parts by weight.
  • the method for producing a terminal-modified polyamide resin of the present invention refers to a method of mixing a polyamide monomer, a terminal-modifying compound represented by formula I, and other components as required, and reacting them in the presence of a boric acid compound. .
  • the following methods can be exemplified: a method in which a polyamide monomer, a terminal modification compound represented by formula I, a boric acid compound, and other components as required are mixed in advance, and then condensed by heating; A method in which a compound for terminal modification represented by formula I and a boronic acid compound are added to react during polymerization of an amide monomer raw material, and the like. The above reaction is preferably carried out after further adding water.
  • the preparation method of the terminal-modified polyamide resin of the present invention may adopt a method of melt polymerization at a temperature above the melting point of the terminal-modified polyamide resin, or may adopt a temperature lower than the melting point of the terminal-modified polyamide resin.
  • the method of performing solid state polymerization at the temperature of the melting point of the resin may adopt a method of melt polymerization at a temperature above the melting point of the terminal-modified polyamide resin, or may adopt a temperature lower than the melting point of the terminal-modified polyamide resin.
  • diamines and dibasic acids can be used as polyamide monomers for polymerization, amino acids or lactams can also be used as monomers, and mixtures of these monomers or their salts can also be used. .
  • diamines and dibasic acids as monomers, at least one of dibasic acids with 2 to 20 carbon atoms and at least one of diamines with 2 to 20 carbon atoms are mentioned.
  • a sort of. When an amino acid or a lactam is used as a monomer, an amino acid having 4 to 20 carbon atoms or a lactam having 4 to 20 carbon atoms may be mentioned.
  • the above-mentioned monomers may be polymerized alone (homopolymer), or may be copolymerized in combination of two or more kinds (copolymer).
  • the above-mentioned diamine or dibasic acid may be additionally added in order to adjust the molar ratio of the total amino groups/carboxyl groups of the raw materials to be added.
  • amino acids include, but are not limited to, amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 4-aminomethylbenzoic acid.
  • lactams such as ⁇ -caprolactam, ⁇ -undecalactam or ⁇ -laurolactam.
  • diamines specifically, but not limited to, the following examples can be mentioned: ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octyldiamine, nonanediamine, decanediamine Amine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, Aliphatic diamines such as nonadecanediamine, eicosanediamine, 2-methyl-1,5-pentanediamine or 2-methyl-1,8-octanediamine; cyclohexanediamine or 4, Alicyclic diamines such as 4'-diaminodicyclohexylmethane and 4,4'-methylenebis(2-methylcyclohexylamine
  • dibasic acid specifically, but not limited to, the following examples can be mentioned: aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid or dodecanedioic acid; Phthalic acid, isophthalic acid, 2-chloro-1,4-benzenedicarboxylic acid, 2-methyl-1,4-benzenedicarboxylic acid or 5-methylisophthalic acid, 5-sodium sulfonate isophthalic acid Aromatic dicarboxylic acids such as dicarboxylic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Alkyl diesters and diacid chlorides derived from dibasic acids can also be exemplified as polyamide monomers.
  • aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid,
  • 6-aminocaproic acid 11-aminoundecanoic acid, 12-aminododecanoic acid, ⁇ -caprolactam, ⁇ -undecalactam, ⁇ -laurolactam, butylenediamine, pentanoic acid Diamine, hexamethylenediamine, decanediamine, undecanediamine, dodecanediamine, adipic acid, sebacic acid, dodecanedioic acid; more preferably ⁇ -caprolactam, butanediamine, hexamethylenediamine , adipic acid or sebacic acid.
  • the above-mentioned monomers can be used to make the main body of the polyamide molecular chain except the terminal structure formed by the terminal modification compound shown in formula I be a polyamide homopolymer or copolymer.
  • n 2-100.
  • adding the compound for terminal modification represented by formula I in the range of the amount added in the present invention will slow down the polymerization rate.
  • n is 4 or more, more preferably n is 8 or more, and most preferably n is 16 or more.
  • n is greater than 100, the heat resistance of the compound for terminal modification represented by formula I deteriorates.
  • n is 70 or less, more preferably n is 50 or less, most preferably n is 25 or less.
  • each R 1 is the same or different, and is an alkylene group having 2 to 10 carbon atoms.
  • R 1 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 - or -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - and the like.
  • R 1 is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms.
  • R 1 may be composed of different alkylene groups, preferably at least one of -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH(CH 3 )-CH 2 -.
  • R 2 is an alkyl group having 1 to 30 carbon atoms.
  • the number average molecular weight of the compound for terminal modification represented by the above formula I is preferably 750-10000.
  • the melt viscosity of the terminal-modified polyamide resin product can be further reduced. More preferably, it is 800 or more, and it is still more preferable that it is 900 or more.
  • the number average molecular weight 10000 or less the affinity with the main structural unit of a polyamide resin can be further improved. It is more preferably 5000 or less, still more preferably 2500 or less, and most preferably 1500 or less.
  • the compound for terminal modification represented by formula I examples include methoxypoly(ethylene glycol)amine, methoxypoly(1,3-propylene glycol)amine, methoxypoly(propylene glycol) amine, methoxy poly(1,4-butylene glycol) amine, methoxy poly(ethylene glycol) poly(propylene glycol) amine, etc.
  • a block polymerization structure may be formed, or a random copolymer structure may be formed.
  • two or more kinds of the above-mentioned compounds for terminal modification can be used.
  • the compound for terminal modification represented by formula I is added in an amount of 0.05-25 parts by weight based on 100 parts by weight of the polyamide monomer.
  • the melt viscosity of the terminal-modified polyamide can be further reduced by making the addition amount of the compound for terminal modification represented by formula I 0.05 parts by weight or more, preferably 1 part by weight or more, more preferably 1.5 parts by weight or more, even more preferably 2 parts by weight servings or more.
  • the addition amount of the compound for terminal modification shown in formula I be 25 parts by weight or less, an appropriate polymerization rate can be maintained, while the mechanical properties and crystallinity of the terminal-modified polyamide are maintained, preferably 15 parts by weight Parts or less, more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less.
  • the compound for terminal modification represented by the above formula I can be added at any time before the end of the polymerization. That is, the terminal modification compound represented by formula I can be added to the reaction system together with the polyamide monomer at the beginning of the polymerization, or can be added to the reaction system at any time during the polymerization.
  • a boric acid compound is also added.
  • the addition of the boric acid compound can not only increase the polymerization rate, but also suppress the foaming of the extruded polymer by suppressing the volatilization of monomers (especially the volatilization of diamine monomers) during polymerization.
  • the amount of the diamine in the reaction system is increased, so that the reaction with the carboxyl group can be carried out more effectively.
  • boric acid compound which may be boric acid, or other compounds derived from boric acid such as borate, organic boric acid compound, etc.
  • boric acid B(OH) 3
  • metaboric acid HBO 2
  • boric anhydride B 2 O 3
  • sodium tetraborate Na 2 B 4 O 7
  • organic boric acid compounds for example, alkylboronic acid (RB) in which the hydroxyl group (-OH) of boric acid is substituted by alkyl (-R) or aryl (-Ar) can be mentioned.
  • the group (-Ar) includes but not limited to phenyl, thienyl.
  • the above boric acid compounds may be used alone or in combination of two or more. Considering the compatibility of the added boric acid compound with the polyamide monomer and the water added during polymerization, boric acid, metaboric acid, boric anhydride, and borate are preferred, and boric acid is more preferred.
  • the amount of the boric acid compound added is 0.005-1.0 parts by weight based on 100 parts by weight of the polyamide monomer.
  • the addition amount of the boric acid compound 0.005 parts by weight or more and 1.0 parts by weight or less, foaming can be suppressed while ensuring the polymerization rate, preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, still more preferably 0.03 parts by weight or more.
  • the added amount of the boric acid compound is preferably not more than 0.5 parts by weight, more preferably not more than 0.1 parts by weight, and still more preferably not more than 0.05 parts by weight.
  • the above-mentioned boric acid compound may be added at any time before the end of the polymerization. That is, the boric acid compound may be added to the reaction system together with the polyamide monomer at the beginning of the polymerization, or may be added to the reaction system at any time during the polymerization. Among them, the boric acid compound is preferably added to the reaction system together with the polyamide monomer at the beginning of the polymerization.
  • the molar ratio of the total amino groups/total carboxyl groups of the polyamide monomers added and the terminal modification compounds shown in formula I is not particularly limited, considering the polymerization reaction speed , the molar ratio of the above-mentioned total amino groups/total carboxyl groups is preferably in the range of 0.9 to 1.1.
  • the molar ratio of the above-mentioned total amino groups/total carboxyl groups is preferably 1.010 or more, more preferably 1.020 or more, still more preferably 1.030 or more.
  • the molar ratio of the above-mentioned total amino groups/total carboxyl groups is preferably 1.10 or less, more preferably 1.050 or less, still more preferably 1.040 or less.
  • the molar ratio of total amino groups/total carboxyl groups is calculated using the amount of amino groups and carboxyl groups obtained by hydrolyzing amide groups.
  • the terminal-modified polyamide resin of the present invention based on 100 parts by weight of the polyamide monomer, it is preferable to further add 5 to 900 parts by weight of water.
  • the amount of water added is more preferably 10 parts by weight or more, and still more preferably 50 parts by weight or more.
  • the amount of water added is more preferably 200 parts by weight or less, and still more preferably 100 parts by weight or less.
  • additives can also be added as required, such as defoamers, flame retardants, antioxidant stabilizers, antibacterial additives, optical brighteners, Dyeable agents or other dyes, etc.
  • Adding a defoamer can further suppress the foaming during the polymerization process.
  • the defoamer can be selected from silicone-based defoamers, polyether and modified polyether defoamers, mineral oil defoamers, etc. Other types of defoamers.
  • the above-mentioned additives may be added at any time before the end of the polymerization. That is, the additive can be added to the reaction system together with the polyamide monomer at the beginning of the polymerization, or can be added at one time or in multiple times at any time during the polymerization.
  • the terminal-modified polyamide resin will be described in detail below.
  • the terminal modified polyamide resin of the present invention has the terminal structure and boron element shown in formula II,
  • n ranges from 2 to 100
  • each R1 is the same or different, and is an alkylene group with 2 to 10 carbon atoms
  • R2 is an alkyl group with 1 to 30 carbon atoms
  • the content of the terminal structure shown in the formula II in the terminal-modified polyamide resin is 0.05-25wt% of the total weight of the terminal-modified polyamide resin, so The content of the boron element in the terminal-modified polyamide resin is 10-2000 ppm of the total weight of the terminal-modified polyamide resin.
  • the polyamide main chain structure of terminal modified polyamide resin of the present invention can enumerate but not limited to following example: polycaprolactam (nylon 6), polyundecanolactam (nylon 11), polylaurolactam (nylon 12) , polyhexamethylene adipamide (nylon 66), polybutylene adipamide (nylon 46), polypentamethylene adipamide (nylon 56), polybutylene sebacamide (nylon 410), polybutylene adipamide (nylon 410), Pentamethylene sebacylamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecanediamide sebacamide (nylon 1010), polydodecyl Decamide (nylon 1012), polycaprolactam/polyhexamethylene adipamide copolymer (nylon 6/66), polym-xylylene adipamide (MXD6), polym
  • the polyamide main chain structure of the above-mentioned terminally modified polyamide resins is preferably polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene adipamide Pentamethylenediamide (Nylon 56), Polybutylene Sebacamide (Nylon 410), Polypentamethylene Sebacamide (Nylon 510), Polyhexamethylene Sebacamide (Nylon 610), Polyterephthalamide Nonanediamide (Nylon 9T) or Polydecanediamide Terephthalamide (Nylon 10T).
  • the main chain structure of the terminal-modified polyamide resin may be composed of one of the above-mentioned main chain structures alone, or may be composed of two or more of the above-mentioned main chain structures.
  • the main chain repeating units of the terminal-modified polyamide resin used in the present invention preferably 80 mol% or more are composed of structural units derived from the above-mentioned monomer raw materials (the number of repeating units of the polyamide main chain structure is 100 mol%) . In view of heat resistance and crystallinity, it is preferably 90 mol% or more, most preferably 100 mol%.
  • the end-modified polyamide resin of the present invention improves the mobility of the molecular chain as a whole by introducing the flexible polyether structure shown in formula II at the end of the polyamide, thereby reducing the melt viscosity, and at the same time, the crystallinity of the end-modified polyamide resin is improved. got hold.
  • n is 2-100. Like n in the above formula I, n is preferably 4 or more, more preferably 8 or more, and most preferably n is 16 or more. On the other hand, n is preferably 70 or less, more preferably n is 50 or less, most preferably n is 25 or less.
  • each R 1 is the same or different, and is an alkylene group having 2 to 10 carbon atoms, and R 2 is an alkyl group having 1 to 30 carbon atoms.
  • R 1 and R 2 in formula II can respectively include the same groups as exemplified by R 1 and R 2 in formula I above, and preferred groups are also described in R 1 and R 2 of formula I above same.
  • the content of the terminal structure represented by formula II is 0.05 to 25 wt% of the total weight of the terminal-modified polyamide resin.
  • the terminal structure The content of is preferably more than 0.1wt%, more preferably more than 0.5wt%, more preferably more than 1.5wt%, most preferably more than 2wt%;
  • the crystallinity and mechanical properties of the terminal-modified polyamide resin are better maintained, preferably less than 15 wt%, more preferably less than 10 wt%, even more preferably less than 5 wt%.
  • the content (wt%) of the terminal structure represented by the above-mentioned formula II relative to the terminal-modified polyamide resin is obtained by 1 H-NMR (nuclear magnetic spectrum) test.
  • the terminal-modified polyamide resin of the present invention also contains boron element, and the content of the boron element is 10-2000ppm of the total weight of the terminal-modified polyamide resin.
  • the boron element content is 20 ppm or more, more preferably 40 ppm or more, and still more preferably 60 ppm or more.
  • the boron element content is preferably 1000 ppm or less, more preferably 300 ppm or less, still more preferably 100 ppm or less.
  • the content of boron element in the end-modified polyamide resin is determined by ICP emission spectroscopic analysis method after adding sulfuric acid and nitric acid to the resin and heating and decomposing it under microwave irradiation.
  • the relative viscosity ⁇ r measured at 25° C. is preferably 1.1-4.0.
  • ⁇ r is less than 1.1, the toughness of the terminal-modified polyamide resin is poor. More preferably, ⁇ r is at least 1.6, still more preferably at least 1.7, and most preferably at least 1.8.
  • ⁇ r is higher than 4.0, the molecular weight of the terminal-modified polyamide resin is too high, resulting in higher melt viscosity and lower processability, more preferably ⁇ r is below 3.0, more preferably ⁇ r is below 2.5, and most preferably ⁇ r is below 2.5. Below 2.0.
  • the weight average molecular weight (Mw) of the terminal-modified polyamide resin in the present invention is preferably 10,000 or more. When the Mw reaches more than 10,000, the mechanical properties of the terminal-modified polyamide resin can be made to meet practical applications. Mw is more preferably 25,000 or more, still more preferably 30,000 or more, and most preferably 35,000 or more. In addition, Mw is preferably 400,000 or less. When Mw is 400,000 or less, the melt viscosity of the terminal-modified polyamide resin is low. Mw is more preferably 100,000 or less, still more preferably 70,000 or less, and most preferably 45,000 or less. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC).
  • the melting point (Tm) is preferably above 215°C, more preferably the melting point (Tm) of the terminal-modified polyamide resin is above 218°C.
  • Tm melting point
  • introducing a flexible structure into a polyamide resin through copolymerization will lower the melting point of the polyamide resin, but the present invention selectively introduces a polyether with a specific structure at the end of the resin, making it compatible with polyamides that do not contain a polyether terminal structure.
  • the decrease in the melting point of the polyamide resin introduced with polyether ends was kept to a minimum.
  • the melting point drop is preferably not more than 5°C, more preferably not more than 3°C.
  • the melting point of the polyamide resin described here is determined by a differential scanning calorimeter (DSC). Start to heat up from 20°C to a temperature 30°C higher than the temperature T0 of the endothermic peak that appears, keep the temperature at this temperature for 2 minutes, then cool down to 20°C at a cooling rate of 20°C/min and then again at 20°C/min The heating rate was increased to a temperature 30°C higher than T0, and the temperature of the endothermic peak that appeared during the second heating process was defined as the melting point (Tm).
  • DSC differential scanning calorimeter
  • the amino group concentration in the terminal-modified polyamide resin of the present invention is preferably not less than 105 mol/t and not more than 400 mol/t. By controlling the amino group concentration within the above preferred range, the mechanical strength required for practical applications can be maintained while preventing the molecular weight from being too high.
  • the amino group concentration is more preferably 150 mol/t or more, still more preferably 190 mol/t or more.
  • the amino group concentration is more preferably 300 mol/t or less, still more preferably 250 mol/t or less.
  • the concentration of carboxyl groups in the terminal-modified polyamide resin of the present invention is preferably below 100 mol/t.
  • carboxyl group concentration is below 100 mol/t, the cyclization reaction of the terminal adipic acid structural unit of the terminal-modified polyamide is suppressed, so that the decomposition of the terminal-modified polyamide resin is suppressed.
  • the carboxyl group concentration is more preferably 30 mol/t or less, still more preferably 15 mol/t or less.
  • the ratio of amino group concentration/carboxyl group concentration in the terminal-modified polyamide resin of the present invention is preferably 4.0 or more and 50 or less.
  • the ratio of amino group concentration/carboxyl group concentration is within the above range, the relative viscosity ⁇ r and weight average molecular weight Mw of the terminal-modified polyamide resin are within the above preferred ranges.
  • the ratio of amino group concentration/carboxyl group concentration is more preferably 10 or more and 40 or less.
  • terminal-modified polyamide resin composition of the present invention will be described in detail below.
  • the terminal-modified polyamide resin composition of the present invention refers to a compound compounded by further adding fillers, other types of polymers and various additives to the terminal-modified polyamide resin.
  • the end-modified polyamide resin composition of the present invention can also contain fillers, and the fillers can be enumerated but not limited to the following examples: glass fibers, carbon fibers, potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, aromatic Fibrous inorganic or organic fillers such as polyamide fiber, alumina fiber, silicon carbide fiber, ceramic fiber, graphite fiber, basalt fiber or metal fiber; wollastonite, zeolite, sericite, kaolin, mica, talc, clay, leaf wax Stone, bentonite, montmorillonite, asbestos, silicate, graphite, carbon black, silicon carbide, boron carbide, aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite Stone, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon nitrid
  • the above-mentioned non-fibrous inorganic fillers may be spherical, flake-shaped or other irregular shapes, and the above-mentioned fillers may also be hollow bodies.
  • the above-mentioned fillers may also be treated with coupling agents such as isocyanate compounds, organosilane compounds, organotitanate compounds, organoborane compounds, or epoxy compounds.
  • the above-mentioned montmorillonite may also be an organic montmorillonite obtained by exchanging interlaminar ions through an organic ammonium salt for cation exchange.
  • the above-mentioned fillers are preferably calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium hydroxide , aluminum hydroxide and other basic fillers.
  • the above-mentioned fillers are preferably fibrous inorganic fillers such as glass fibers, metal fibers, and carbon fibers.
  • the above-mentioned fillers can be added alone, or two or more kinds can be selected to be added in combination.
  • the content of the above-mentioned filler in the terminal-modified polyamide resin composition is preferably 5 to 80 wt% of the total weight of the terminal-modified polyamide resin composition, and the filler can be made Good dispersibility, improved mechanical properties and other properties (such as electrical conductivity, thermal conductivity, etc.), more preferably the amount of filler added is more than 40wt% of the total weight of the end-modified polyamide resin composition, more preferably more than 50wt%. On the other hand, the added amount of the filler is more preferably 70% by weight or less.
  • polystyrene resin composition examples include polyolefins such as polyethylene and polypropylene; polymers (or copolymers) obtained by polymerization of olefins and/or conjugated diene compounds material) and other modified polyolefins; polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN resin, polystyrene, except the terminal of the present invention Polyamide resins other than unmodified polyamide resins, etc.
  • polyolefins such as polyethylene and polypropylene
  • polyester polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN resin,
  • the above-mentioned other types of polymers in order to improve the impact resistance of the molded article obtained from the terminal-modified polyamide resin composition used in the present invention and reduce the shrinkage rate, it is preferable to use one obtained by polymerizing an olefin and/or a conjugated diene compound. Polymer (or copolymer) and other modified polyolefin and other impact agents.
  • the above-mentioned polymer can be exemplified but not limited to the following examples: vinyl copolymer, conjugated diene polymer or conjugated diene-aromatic vinyl copolymer and the like.
  • Ethylene copolymers refer to copolymers of ethylene and other monomers.
  • Other monomers copolymerized with ethylene include but are not limited to the following examples: ⁇ -olefins with more than 3 carbon atoms, non-conjugated dienes, vinyl acetate, vinyl alcohol, ⁇ , ⁇ -unsaturated carboxylic acids or derivatives thereof things. Two or more of the above-mentioned monomers may be selected and copolymerized with ethylene.
  • the ⁇ -olefins having 3 or more carbon atoms include, but are not limited to, the following examples: propylene, 1-butene, 1-pentene or 3-methyl-1-pentene, preferably propylene or 1-butene.
  • Non-conjugated diolefins can be cited 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 compounds such as norbornene, 5-(2-ethyl-2-butenyl)-2-norbornene or 5-methyl-5-vinylnorbornene; dicyclopentadiene, formazan tetrahydroindene, tetra
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acids include but are not limited to: acrylic acid, methacrylic acid, ethacrylic acid, 2-butenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or butyric acid Alkenic acid, etc.
  • Derivatives of ⁇ , ⁇ -unsaturated carboxylic acids include but are not limited to the following examples: alkyl esters, aryl esters, glycerides, acid anhydrides or imides of the above-mentioned ⁇ , ⁇ -unsaturated carboxylic acids.
  • the conjugated diene-based polymer refers to a polymer obtained by polymerizing at least one conjugated diene.
  • the conjugated dienes described here can be cited but not limited to the following examples: 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,-dimethyl -1,3-butadiene or 1,3-pentadiene, etc. Two or more kinds of the above-mentioned conjugated dienes may be selected and copolymerized.
  • the unsaturated bonds of the polymer can be partially or completely reduced by hydrogenation.
  • the conjugated diene-aromatic vinyl copolymer refers to a copolymer of conjugated diene and aromatic vinyl, which can be a block copolymer or a random copolymer.
  • the conjugated diene are the same as the above-mentioned raw materials for preparing the conjugated diene-based polymer, and 1,3-butadiene and isoprene are preferable.
  • aromatic vinyl include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, etc., preferably styrene.
  • unsaturated bonds other than the double bond of the aromatic ring in the conjugated diene-aromatic vinyl copolymer may be partially or completely reduced by hydrogenation.
  • the above-mentioned anti-impact agents specifically include: ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/1-hexene copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/5-ethylene Ethyl-2-norbornene copolymer, unhydrogenated or hydrogenated styrene/isoprene/styrene triblock copolymer, unhydrogenated or hydrogenated styrene/butadiene/styrene triblock copolymer, Ethylene/methacrylic acid copolymers or salts formed by part or all of the carboxylic acid groups in the copolymers with sodium, lithium, potassium, zinc or calcium, ethylene/methyl acrylate copolymers, ethylene/ethyl acrylate copolymers, ethylene/methacrylic acid copolymers, ethylene/methacrylic acid copo
  • the above-mentioned copolymers are preferably ethylene/methacrylic acid copolymers and salts formed by part or all of the carboxylic acid groups in the copolymers and sodium, lithium, potassium, zinc or calcium, ethylene/propylene-g-maleic anhydride copolymers, ethylene/ Butene-1-g-maleic anhydride copolymer.
  • the polymers other than the terminal-modified polyamide resin in the above-mentioned terminal-modified polyamide resin composition may be added alone, or two or more polymers may be selected and added in combination. Its addition amount is preferably more than 0wt%, 80wt% or less (taking the end-modified polyamide resin composition as 100wt%), by controlling the addition amount in the above-mentioned range, it is possible to make the end-modified polyamide resin composition melt. Mobility is better.
  • the added amount is more preferably 60 wt% or less, still more preferably 50 wt% or less.
  • the terminal-modified polyamide resin composition used in the present invention may further contain various additives.
  • antioxidants and heat stabilizers hindered phenols, hydroquinones, phosphites, phosphates and their substitution products, copper halides, iodine compounds, etc.
  • weather resistance agents resorcinol series, salicylic acid series, benzotriazole series, diphenyl ketone series or hindered amine series, etc.
  • release agent and lubricant fatty alcohol, fatty amide, fatty diamide or diurea or poly Vinyl wax, etc.
  • pigments calcium sulfide, phthalocyanine or carbon black, etc.
  • dyes aniline black, etc.
  • plasticizers n-octyl p-hydroxybenzoate or N-butylbenzenesulfonamide
  • antistatic agents Alkyl sulfate type anionic antistatic agent, 4th grade ammonium salt type cationic antistatic agent, nonionic antistatic
  • the terminal-modified polyamide resin of the present invention can be formed into a desired shape by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, or film forming. Molded articles obtained from the terminal-modified polyamide resin of the present invention and compositions containing the same can be applied to the following examples: resin molded articles such as electrical/electronic product parts, automobile parts, mechanical parts, clothing/industrial Fibers in the field of packaging, films in the field of electromagnetic recording, and metal joints, etc.
  • the end-modified polyamide resin obtained in each embodiment and comparative example was dissolved in deuterated concentrated sulfuric acid at a concentration of 50 mg/ml, and the 1 H- NMR nuclear magnetic test.
  • the peak corresponding to the hydrogen on the -CH 2 - adjacent to the oxygen of the ether bond on the terminal structure shown in the above formula II, and the hydrogen on the repeating unit of the polyamide main chain as the main component corresponds to
  • the content of the terminal structure shown in formula II in the terminal modified polyamide resin is calculated by calculating the peak area obtained by integrating each peak and the number of hydrogen atoms contained in each structure.
  • the heating rate of °C/min starts from 20 °C to a temperature 30 °C higher than the temperature T0 of the endothermic peak, and keeps the temperature at this temperature for 2 minutes, and then cools down to 20 °C at a cooling rate of 20 °C/min , keep the temperature at 20°C for 2min, then raise the temperature again at a heating rate of 20°C/min to a temperature 30°C higher than T0, and obtain the melting point T m .
  • T m is the temperature corresponding to the peak peak of the endothermic peak during the second heating process.
  • the end-modified polyamide resin or polyamide resin homopolymer obtained in each embodiment and comparative example was placed in a vacuum oven and dried at 80° C. for more than 12 hours, and then hot-pressed with a film press to form a film (film thickness 0.7mm) after being cut into discs with a diameter of 25mm, the melt viscosity was measured with a rotational rheometer (manufactured by Antonpas, MCR302, ⁇ 25 parallel plate) by the following method: under a nitrogen atmosphere, the above-mentioned sample was melted at 280° C.
  • the measured value of the complex viscosity at a frequency of 1 Hz was used as the melt viscosity.
  • nitrogen gas is introduced into the polymerization tank to pressurize to 0.05-0.1 MPa, and the polymer in the tank is discharged from the discharge valve at the bottom of the polymerization tank. Observe and record the state of the extruded polymer strands and pellets.
  • ⁇ There are holes inside the extruded polymer strands, and the surface is basically smooth, which can be pelletized but occasionally broken;
  • Hexamethylenediamine Aladdin Reagent (Shanghai) Co., Ltd.
  • Adipic acid Alfa Aesar

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  • Polyamides (AREA)

Abstract

La présente invention concerne une résine polyamide à extrémité modifiée et son procédé de fabrication. Dans le procédé de fabrication, la polymérisation est effectuée en présence d'un monomère de polyamide, d'un composé pour la modification d'extrémité représenté par la formule I, et d'un composé d'acide borique. X-(R1-O)n-R2 est la formule I, et dans la formule I, n est dans la plage de 2 à 100 ; chaque R1, identique ou différent, est un groupe alkylène ayant de 2 à 10 atomes de carbone ; R2 est un groupe alkyle ayant de 1 à 30 atomes de carbone ; et X est un ou plusieurs éléments choisis parmi NH2-, NH(CH3)-, HO-, HOOC-, O=C=N-. Sur la base du fait que le monomère de polyamide est de 100 parties en poids, la quantité d'addition du composé pour la modification d'extrémité représenté par la formule I est de 0,05 à 25 parties en poids, et la quantité d'addition du composé d'acide borique est de 0,005 à 1,0 partie en poids.
PCT/CN2022/103813 2021-07-13 2022-07-05 Résine polyamide à extrémité modifiée, son procédé de préparation, composition et produit moulé WO2023284583A1 (fr)

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