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CN-122011366-A - Polyamide resin and polyamide composition

CN122011366ACN 122011366 ACN122011366 ACN 122011366ACN-122011366-A

Abstract

The present invention relates to a polyamide resin and a polyamide composition, the polyamide resin comprising units derived from diamine monomers and dicarboxylic acid monomers, 0 to 100mol%, excluding 0mol% and 100mol% of 1, 6-hexamethylenediamine based on the molar amount of all diamine monomers, 0.01 to 5mol% of 1, 2-cyclohexanediamine based on the molar amount of all diamine monomers, and the trans isomer content of the 1, 2-cyclohexanediamine being not less than 70% of the total molar amount of 1, 2-cyclohexanediamine. Compared with the prior art, the polyamide resin prepared by the invention has improved fluidity and heat resistance.

Inventors

  • LI WENDA
  • TAO RUOYUAN

Assignees

  • 中石油(上海)新材料研究院有限公司
  • 中国石油天然气股份有限公司

Dates

Publication Date
20260512
Application Date
20241111

Claims (10)

  1. 1. A polyamide resin, characterized in that the polyamide resin comprises the following components: Units derived from diamine monomers and dicarboxylic acid monomers; 0 to 100 mole% excluding 0 mole% and 100 mole% of 1, 6-hexamethylenediamine, based on the molar amount of the total diamine monomer; 0.01 to 5 mole% of 1, 2-cyclohexanediamine, based on the molar amount of total diamine monomers; The content of trans isomer of 1, 2-cyclohexanediamine is not less than 70% of the total molar amount of 1, 2-cyclohexanediamine.
  2. 2. A polyamide resin as claimed in claim 1, wherein, the diamine monomer is selected from 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1, 14-tetradecanediamine, 1, 16-hexadecanediamine, 1, 18-octadecanediamine, 1-butyl-1, 2-ethylenediamine, 1-dimethyl-1, 4-butanediamine, 1-ethyl-1, 4-butanediamine, 1, 2-dimethyl-1, 4-butanediamine, 1, 3-dimethyl-1, 4-butanediamine, 1, 4-dimethyl-1, 4-butanediamine, 2, 3-dimethyl-1, 4-butanediamine 2-methyl-1, 5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2, 5-dimethyl-1, 6-hexanediamine, 2, 4-dimethyl-1, 6-hexanediamine, 3-dimethyl-1, 6-hexanediamine, 2, 4-trimethyl-1, 6-hexanediamine, 2, 4-diethyl-1, 6-hexanediamine, 2-dimethyl-1, 7-heptanediamine, 2, 3-dimethyl-1, 7-heptanediamine, 2, 4-dimethyl-1, 7-heptanediamine, 2, 5-dimethyl-1, 7-heptanediamine, 2-methyl-1, 8-octanediamine, 3-methyl-1, 8-octanediamine, 4-methyl-1, 8-octanediamine, 1, 3-dimethyl-1, 8-octanediamine, 1, 4-dimethyl-1, 8-octanediamine, 2, 4-dimethyl-1, 8-octanediamine, 3, 4-dimethyl-1, 8-octanediamine, 4, 5-dimethyl-1, 8-octanediamine, 2-dimethyl-1, 8-octanediamine, 3-dimethyl-1, 8-octanediamine, 4-dimethyl-1, 8-octanediamine, 5-methyl-1, 9-nonanediamine.
  3. 3. A polyamide resin according to claim 1, wherein said dicarboxylic acid monomer is one or more selected from the group consisting of aromatic diacids and aliphatic diacids.
  4. 4. A polyamide resin according to claim 3, wherein said aromatic diacid is selected from one or more of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid.
  5. 5. A polyamide resin according to claim 3, wherein the aliphatic diacid is selected from one or more of oxalic acid, malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 2-methyl suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, 1, 12-dodecanedioic acid, 1, 13-tridecanedioic acid, 1, 14-tetradecanedioic acid, cyclohexanedicarboxylic acid.
  6. 6. A polyamide resin according to claim 1, characterized in that the polyamide resin has a crystallization enthalpy of at least 20J/g by differential scanning calorimetry, measured at a heat up and heat down rate of 20 ℃ per minute according to ISO 11357-1/3 standard.
  7. 7. A polyamide resin according to claim 1, characterized in that the polyamide resin has a relative viscosity of more than 1.80 when measured in a polyamide solution having a concentration of 10mg/mL in concentrated sulfuric acid having a concentration of 98% at a temperature of 25 ℃.
  8. 8. A polyamide resin according to claim 1, wherein 0.5 to 3 mole% of 1, 2-cyclohexanediamine, based on the molar amount of all diamine monomers.
  9. 9. A polyamide resin according to claim 1, wherein the trans isomer content of 1, 2-cyclohexanediamine is not less than 80% of the total molar amount of 1, 2-cyclohexanediamine.
  10. 10. A polyamide composition comprising the polyamide resin according to any one of claims 1 to 9, said polyamide composition comprising the following components: 30-95wt% of polyamide resin, 0-70wt% of glass fiber and 0-50wt% of additive, wherein the sum of the mass percentages of the polyamide resin, the glass fiber and the additive is 100%.

Description

Polyamide resin and polyamide composition Technical Field The invention belongs to the technical field of high polymer materials, and relates to polyamide resin and a polyamide composition. Background Polyamide represented by polyamide 6 (PA 6) and polyamide 66 (PA 66) is one of five engineering plastics in China, and has the advantages of excellent mechanical property, good shock resistance, small friction coefficient, wear resistance, self-lubricity, shock absorption and the like, and is widely applied to the fields of spinning, automobiles, mechanical manufacturing, electronic appliances and the like. With the recent progress of Surface Mount Technology (SMT), the requirements for heat resistance of polyamide materials are increasing year by year in the field of electronic and electric appliances requiring reflow soldering heat resistance and in the years for peripheral materials of fuel car engines. On the other hand, in many fields of application of polyamides, particularly various molded articles in the field of electronic appliances, there is a systematic trend toward miniaturization and microminiaturization, which also puts higher demands on the flowability of polyamides. The alicyclic compound, especially the alicyclic compound with larger steric hindrance, is used for the polymerization monomer of copolyamide, mainly plays the roles of reducing the crystallinity and the crystal size of polyamide and improving the amorphous state content, and is one of important monomers for preparing the transparent appearance polyamide material. For example CN102076770a discloses a partially crystalline transparent polyamide comprising 10-40 mole% based on the total diamine of bis (4-amino-3-methylcyclohexyl) methane and/or bis (4-aminocyclohexyl) methane. However, the introduction of alicyclic monomers tends to bring about a decrease in crystallinity and melting temperature while increasing the glass transition temperature of copolyamide, and the decrease in heat resistance of the material makes it limited in application to temperature resistant conditions, especially in high temperature environments. For example, CN104619777a discloses a copolyamide containing more than 25mol% of 1, 4-cyclohexanedicarboxylic acid based on the total amount of copolyamide, which is sufficiently crystallized upon mold forming at 80 ℃ and has mold contamination optimizing properties. However, as is clear from the description of the relative crystallinity used in the examples, the material exhibits a cold crystallization peak at a temperature rise in a Differential Scanning Calorimetry (DSC) test, and the cold crystallization peak is often an indication of imperfect crystallization of the material, and it can be judged that the introduction of alicyclic diacid results in a significant decrease in the crystallization degree of the material. For another example, CN112341618a discloses a copolyamide comprising hexamethylenediamine and 1, 3-bis (aminomethyl) cyclohexane, wherein the proportion of 1, 3-bis (aminomethyl) cyclohexane is 12.5 to 22mol% based on the total amount of copolyamide, which copolyamide has an improved high-gloss good surface after molding. However, the introduction of alicyclic monomers significantly lowers the melting and crystallization temperatures, especially in the range of 30 to 50℃which is clearly disadvantageous for the heat resistance of the polyamide. The decrease in crystallinity and melting temperature of the copolyamide caused by the alicyclic monomer can be balanced by adjusting the content of other monomers, for example, CN105308096A discloses a PA6T/6I copolyamide containing from 7.5 to 12.5mol% isophorone diamine based on the total amount of the copolyamide. The introduction of isophorone diamine increases the glass transition temperature of the material, but results in a significant decrease in crystallinity and melting temperature, which patent counteracts the decrease in crystallinity and melting temperature by increasing the proportion of terephthalic acid in the diacid component of the feed, thereby obtaining a semi-aromatic copolyamide with improved properties. The patent does not disclose the flowability of copolyamide, and since there are up to four methyl/methylene groups which do not participate in the reaction in the cyclohexane in the chemical structure of isophorone diamine, a large resistance will be caused in the process of molecular chain movement, and it can be judged that isophorone diamine will cause the reduction of the flowability of the material. Disclosure of Invention The object of the present invention is to provide a polyamide resin and a polyamide composition which overcome at least one of the drawbacks of the prior art described above, and to provide a polyamide resin having improved flowability and improved heat resistance as compared with the prior art. The aim of the invention can be achieved by the following technical scheme: One of the technical schemes of the inven