CN114031793B - Polyamide composition and preparation method and application thereof - Google Patents

Polyamide composition and preparation method and application thereof Download PDF

Info

Publication number
CN114031793B
CN114031793B CN202111255009.3A CN202111255009A CN114031793B CN 114031793 B CN114031793 B CN 114031793B CN 202111255009 A CN202111255009 A CN 202111255009A CN 114031793 B CN114031793 B CN 114031793B
Authority
CN
China
Prior art keywords
cyclodextrin
ion
polyamide composition
parts
ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111255009.3A
Other languages
Chinese (zh)
Other versions
CN114031793A (en
Inventor
林洁龙
张超
张永
肖军华
刘纪庆
叶士兵
安朋
王飞
邱志强
付大炯
吴鹏
许建稳
夏建盟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Jiangsu Kingfa New Material Co Ltd
Original Assignee
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Jiangsu Kingfa New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kingfa Science and Technology Co Ltd, Shanghai Kingfa Science and Technology Co Ltd, Jiangsu Kingfa New Material Co Ltd filed Critical Kingfa Science and Technology Co Ltd
Priority to CN202111255009.3A priority Critical patent/CN114031793B/en
Publication of CN114031793A publication Critical patent/CN114031793A/en
Application granted granted Critical
Publication of CN114031793B publication Critical patent/CN114031793B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/16—Cyclodextrin; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/168—Zinc halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/262—Alkali metal carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a polyamide composition, which comprises the following components in parts by weight: 100 parts of polyamide resin; 10-40 parts of flame retardant; 0.01-10 parts of irradiation cross-linking agent; 0.1-2 parts of cyclodextrin or a derivative thereof; 0.1-1.5 parts of metal salt; the polyamide composition has a cross-linked structure among polyamide molecules. According to the invention, a certain amount of cyclodextrin or a derivative thereof is added into the irradiation crosslinking polyamide resin system, so that the fluidity of the composition can be obviously improved, and the anti-creeping stability after multiple melt processing is ensured. Meanwhile, the metal salt improves the defect of thermal decomposition and precipitation of cyclodextrin or derivatives thereof.

Description

Polyamide composition and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyamide composition, a preparation method and application thereof.
Background
The irradiation crosslinking is a technical means for initiating crosslinking reaction between polymer long chains by utilizing various types of radiation, and an irradiation source can select electron beams, gamma rays, neutron beams, particle beams and the like according to polymer types and performance requirements. For polyamide materials, irradiation crosslinking agents typically required to be used are triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), methyltriallyl isocyanurate (TMAIC). The polyamide resin composition after irradiation crosslinking can have good anti-creeping properties. However, since the resin matrix of the crosslinked polyamide composition has an irregular crosslinking phenomenon, the leakage preventing property after the melt processing is affected.
The prior art generally improves melt flow by adding inorganic fillers. However, when applied to some light and thin components with low density and high flexibility, it is difficult to use the above method.
Disclosure of Invention
The purpose of the present invention is to provide a polyamide composition which has excellent leakage-proof electrical stability and melt processability.
It is another object of the present invention to provide a process for preparing the above polyamide composition.
The invention is realized by the following technical scheme:
A polyamide composition comprises the following components in parts by weight:
100 parts of polyamide resin;
10-40 parts of flame retardant;
0.01-10 parts of irradiation cross-linking agent;
0.1-2 parts of cyclodextrin or a derivative thereof;
0.05-1.5 parts of metal salt;
the polyamide molecules in the polyamide composition have a cross-linked structure;
The flame retardant is a brominated flame retardant/flame retardant synergist compound system;
the metal ion of the metal salt is at least one of lithium ion, sodium ion, potassium ion, calcium ion, zinc ion or copper ion, and the anion paired with the metal ion is at least one of halogen ion, carbonate ion, nitrate ion, sulfate ion or acetate ion.
For the purposes of CTI stability and precipitation improvement, preferably, the cyclodextrin or its derivative is 0.2-0.9 part and the metal salt is 0.1-0.6 part; more preferably, the cyclodextrin or its derivative has a content of 0.3-0.6 part and a metal salt content of 0.15-0.4 part.
The irradiation crosslinking agent is at least one selected from triallyl cyanurate, triallyl isocyanurate, methyl triallyl isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate or dipropylene glycol diacrylate.
The cyclodextrin or the derivative thereof is at least one selected from beta-cyclodextrin, gamma-cyclodextrin, hydroxypropyl-beta-cyclodextrin, sulfobutyl ether-beta-cyclodextrin, disaccharide-beta-cyclodextrin, methyl-beta-cyclodextrin and hydroxyethyl-beta-cyclodextrin;
preferably, the cyclodextrin or derivative thereof is selected from the group consisting of beta-cyclodextrin. Preferred cyclodextrins have better resistance to precipitation.
The brominated flame retardant is selected from brominated polystyrene, polybrominated styrene, brominated polyphenylene ether, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromobiphenyl, hexabromobiphenyl oxide, octabromobiphenyl oxide, decabromobiphenyl oxide, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2, 3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether) tetrabromobisphenol A derivative, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2, 3-dibromopropyl ether) tetrabromobisphenol S derivative, tetrabromophthalic anhydride at least one of tetrabromophthalimide, ethylene bis-tetrabromophthalimide, tetrabromophthalic anhydride derivative, hexabromocyclododecane, decabromodiphenyl ether, decabromodiphenyl ethane, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylene bis-tribromophenyl ether, ethylene bis-pentabromophenyl ether, tetradecyl bromopropylenol, brominated polycarbonate, brominated epoxy resin, poly-pentabromobenzyl methacrylate, brominated polyphenylene ether, poly-2, 6-dibromophenyl ether, octabromonaphthalene, pentabromocyclohexane, bis (tribromophenyl) fumaramide, or N-methylhexabromodiphenyl amine;
preferably, the brominated flame retardant is at least one selected from brominated polystyrene or brominated polyphenylene ether; the preferred brominated flame retardant CTI is higher.
The flame retardant synergist is at least one selected from antimony white and zinc borate.
Wherein the content range of the brominated flame retardant is 8-35 parts, and the flame retardant synergist is 2-8 parts.
The optional metal salt may be lithium chloride, lithium carbonate, lithium sulfate, lithium acetate, sodium chloride, sodium carbonate, sodium nitrate, sodium sulfate, sodium acetate, potassium chloride, potassium carbonate, potassium sulfate, potassium acetate, calcium chloride, calcium carbonate, calcium sulfate, calcium acetate, zinc chloride, zinc carbonate, zinc sulfate, zinc acetate, copper chloride, copper carbonate, copper sulfate, copper acetate, and the like.
Preferably, the metal ion is selected from at least one of calcium ion, copper ion and zinc ion; more preferably, the metal ion is at least one selected from the group consisting of calcium ion and copper ion. Preferably, the metal ion in a divalent state, has a better technical effect on inhibiting cyclodextrin or a derivative thereof.
The polyamide resin is formed by stepwise polycondensation of diamine and diacid, or by ring-opening polymerization of lactam, or by stepwise polycondensation of amino acid, or by copolymerization of diamine, diacid, lactam and amino acid; the polyamide resin is selected from one or more of PA46、PA66、PA6、PA11、PA12、PA610、PA612、PA1010、PA1012、PA1212、PA4T、PA6T、PA9T、PA10T、PA6I、PAMXD6、PA6I、PA66/6、PA6/66、PA6T/6I、PA6T/66.
Additives such as an antioxidant, a lubricant and the like can be added in an amount of 0-2 parts according to the needs, so that the use requirements in certain environments can be met.
The preparation method of the polyamide composition comprises the following steps: weighing the components according to the proportion, premixing in a high-speed mixer to obtain a premix, putting the premix into a double-screw extruder for melt mixing, and extruding and granulating; the length-diameter ratio of the screw of the double-screw extruder is 40-48:1, the temperature of the screw cylinder is 240-300 ℃, and the rotating speed of the screw is 200-550 rpm; injection molding is carried out on the extruded and granulated particles, the injection molding temperature is 270-300 ℃, and the injection molding pressure is 55-100 MPa; and (3) carrying out irradiation crosslinking treatment on the injection molded part, wherein an electron beam is adopted as a radiation source in the treatment process, and the irradiation dose is 15-25 Mrad, so as to obtain the polyamide composition.
The polyamide composition is applied to preparing light and thin components, such as anti-creeping films, electronic and electric appliance shells and the like.
The invention has the following beneficial effects
In order to solve the defects of insufficient flowability of the polyamide composition after irradiation crosslinking and reduced anti-creeping performance after multiple processing. According to the invention, a certain amount of cyclodextrin or a derivative thereof is added, and the cyclodextrin or the derivative thereof is dispersed in the middle of the cross-linked structure to increase the free volume of molecules, so that the chain movement capability is improved, namely the melt fluidity is increased, and the defect of poor leakage resistance after multiple melt processing is overcome. Furthermore, cyclodextrin or its derivatives, although having a relatively high melting point, also decompose to produce small molecular oxides during high temperature melt processing, precipitate during prolonged use, and affect appearance and performance. Therefore, the present invention can suppress the decomposition and precipitation of cyclodextrin by adding a certain amount of metal salt.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The sources of the raw materials used in the examples and comparative examples are as follows:
PA66:85XFS, first Nuo in the United states;
PA10T: vicnyl 700, gold hair science and technology;
PA1010: g150, shandong Guangdong boundary;
TMAIC: FARIDA H-2, fang Rui to chemical Co.
Beta-cyclodextrin: sigma-Aldrich;
Gamma-cyclodextrin: sigma-Aldrich.
Lithium acetate: are commercially available;
sodium chloride: are commercially available;
Potassium carbonate: are commercially available;
Calcium chloride: are commercially available;
Calcium acetate: are commercially available;
Zinc chloride: are commercially available;
copper chloride: are commercially available;
Copper sulfate: are commercially available;
Ferric chloride: are commercially available.
Brominated polystyrene: PBS-64HW, a family poly;
decabromodiphenyl ethane: FR-1410, guangzhou green bird chemical industry;
tetrabromobisphenol S: FR-1524, guangzhou green bird chemical industry;
Antimony white: S-05N, chang Dechen, antimony Co., ltd;
zinc borate: HT-207, jinan Taixing fine chemical industry.
An antioxidant: hindered phenolic antioxidants, irganox 1098.
Preparation of polyamide compositions of examples and comparative examples: weighing polyamide resin, an irradiation crosslinking agent, cyclodextrin or a derivative thereof, metal salt and a flame retardant according to a proportion, premixing in a high-speed mixer to obtain a premix, putting the premix into a double-screw extruder for melt mixing, extruding and granulating to obtain a finished product; the length-diameter ratio of the screw of the double-screw extruder is 44:1, the temperature of the screw cylinder is 240-300 ℃, and the rotating speed of the screw is 360rpm; injection molding the extruded and granulated polyamide composite material (the precipitation test of the examples and the comparative examples is carried out to form a square plate according to the test requirement), wherein the injection molding temperature is 270-300 ℃, and the injection molding pressure is 55-100 MPa; and (3) carrying out irradiation crosslinking treatment on the workpiece, wherein an electron beam is adopted as a radiation source in the treatment process, and the irradiation dose is 20Mrad, so as to obtain the polyamide composition.
The performance testing method comprises the following steps:
(1) CTI test: the polyamide composition surface is capable of withstanding 50 drops of an electrolyte (0.1% aqueous ammonium chloride solution, about 0.1% pure by mass of not less than 99.8% of an analytically pure anhydrous ammonium chloride reagent dissolved in deionized water having a conductivity of not more than 1mS/m, and having a resistivity of 3.95. Omega..+ -. 0.052. Omega. M) at 23 ℃ C.+ -. 1 ℃ C. Without forming a maximum voltage value of no tracking, in V. CTI performance tests were performed according to the relevant regulations in standard IEC-60112, with sample thicknesses not less than 3mm.
(2) CTI stability test: repeatedly melting and injecting the polyamide composition at 240-320 ℃ (determining injection temperature according to the melting point of the polyamide composition), crushing a sample, testing CTI values after repeated melting and injection for 3 times, and indicating that the stability is better when the values are closer to the CTI of the raw material.
(3) Melt index: melt flow rate under the action of a 2.16kg weight, depending on the melting point T m +20℃of the polyamide composition.
(4) Test of the precipitability: the composition was injection molded into 100X 1mm square plates, placed in an environmental chamber at 85℃and 85% relative humidity for 100 hours, classified into 5 classes according to the degree of precipitation, class 1 representing no precipitation; grade 2 represents no visible separation but no visible mark on the surface by wiping; grade 3 represents slight bleeding visible to the naked eye; grade 4 represents a significant precipitate; grade 5 represents a severe precipitation.
Table 1: examples 1-5 Polyamide compositions each component was compounded in parts by weight and tested
Example 1 Example 2 Example 3 Example 4 Example 5
PA66 100 100
PA10T 100 100
PA1010 100
TMAIC 2 2 2 2 2
Beta-cyclodextrin 1 1 1 1
Gamma-cyclodextrin 1
Lithium acetate 0.2 0.2 0.2 0.2 0.2
Antioxidant 0.2
CTI，V 575 575 550 575 575
CTI stability test, V 550 550 525 525 550
Melt index, g/10min 15.7 12.1 23.6 12.3 15.6
Precipitation grade 2 1 1 2 2
Examples 1-4 in Table 1 also included 15 parts brominated polystyrene, 4 parts antimony white, 7 parts zinc borate; example 5 also includes 25 parts brominated polystyrene, 4 parts antimony white, 3 parts zinc borate.
As is evident from examples 1/4, gamma-cyclodextrin is more likely to precipitate, resulting in a somewhat poorer CTI stability and precipitate rating.
Table 2: examples 6-12 Polyamide compositions each component was compounded in parts by weight and tested
Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12
PA66 100 100 100 100 100 100 100
TMAIC 2 2 2 2 2 2 2
Beta-cyclodextrin 0.1 0.2 0.3 0.5 0.6 0.9 2
Lithium acetate 0.05 0.1 0.15 0.3 0.4 0.6 1
CTI，V 575 575 575 575 575 575 550
CTI stability test, V 525 550 575 575 575 550 525
Melt index, g/10min 7.5 10.4 11.7 12.5 14.0 18.6 25
Precipitation grade 2 1 1 1 1 1 2
Each example in table 2 also includes 15 parts brominated polystyrene, 4 parts antimony white, 7 parts zinc borate.
As is clear from examples 1/6 to 12, the composition having an increased amount of cyclodextrin and metal salt added had an increased fluidity, and CTI stability was improved and deposition was reduced even in the preferable amount.
Table 3: examples 13-19 Polyamide compositions each component was compounded in parts by weight and tested
Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19
PA66 100 100 100 100 100 100 100
TMAIC 2 2 2 2 2 2 2
Beta-cyclodextrin 1 1 1 1 1 1 1
Sodium chloride 0.2
Potassium carbonate 0.2
Calcium chloride 0.2
Calcium acetate 0.2
Zinc chloride 0.2
Copper chloride 0.2
Copper sulfate 0.2
CTI，V 575 575 575 575 575 575 575
CTI stability test, V 550 550 575 575 550 575 575
Melt index, g/10min 11 10.8 15.2 12.9 14.1 16.5 11.4
Precipitation grade 2 2 1 1 1 1 1
Each example in table 3 also includes 15 parts brominated polystyrene, 4 parts antimony white, 7 parts zinc borate.
As is clear from the comparison of examples 1 and 13 to 19, the metal ions are preferably calcium ions, copper ions and zinc ions, and more preferably calcium ions and copper ions, and CTI stability and precipitation resistance are better.
Table 4: examples 20-21 Polyamide compositions each component was compounded in parts by weight and tested
Example 20 Example 21
PA66 100 100
Brominated polystyrene
Decabromodiphenyl ethane 15
Tetrabromobisphenol S 15
Antimony white 4 4
Zinc borate 7 7
TMAIC 2 2
Beta-cyclodextrin 0.5 0.5
Lithium acetate 0.3 0.3
CTI，V 550 550
CTI stability test, V 550 550
Melt index, g/10min 20.5 23.7
Precipitation grade 1 1
As can be seen from examples 9/20-21, the preferred brominated flame retardant CTI is higher.
Table 5: comparative example Polyamide composition Each component was compounded in parts by weight and the results of the test
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
PA66 100 100 100 100 100 100
TMAIC 2 2 2 2 2 2
Beta-cyclodextrin 0.5 1 3 1
Lithium acetate 1 1
Ferric chloride 0.2
CTI，V 600 575 550 475 550 550
CTI stability test, V 475 475 425 400 425 425
Melt index, g/10min 2.8 9 12 28 3.5 10.4
Precipitation grade 1 3 3 4 1 3
Each comparative example in Table 5 also includes 15 parts of brominated polystyrene, 4 parts of antimony white, 7 parts of zinc borate.
As is clear from examples and comparative example 1, the addition of cyclodextrin and metal salt reduced CTI to some extent, but significantly improved CTI stability and increased practicality.
As can be seen from comparative example 2/3, cyclodextrin needs to be added together with metal salt in a compounding way, so that the decomposition and precipitation of cyclodextrin are avoided, and the CTI stability is further ensured.
As is clear from comparative example 4, the addition amount of cyclodextrin is not preferred to fall outside the scope of the present invention.

Claims (13)

1. A polyamide composition characterized by comprising the following components in parts by weight:
100 parts of polyamide resin;
10-40 parts of flame retardant;
0.01-10 parts of irradiation cross-linking agent;
0.1-2 parts of cyclodextrin or a derivative thereof;
0.05-1.5 parts of metal salt;
the polyamide molecules in the polyamide composition have a cross-linked structure;
The flame retardant is a brominated flame retardant/flame retardant synergist compound system;
The metal ion of the metal salt is at least one of lithium ion, sodium ion, potassium ion, calcium ion, zinc ion or copper ion, and the anion paired with the metal ion is at least one of halogen ion, carbonate ion, nitrate ion, sulfate ion or acetate ion;
the cyclodextrin or the derivative thereof is selected from at least one of beta-cyclodextrin, gamma-cyclodextrin, hydroxypropyl-beta-cyclodextrin, sulfobutyl ether-beta-cyclodextrin, disaccharide-beta-cyclodextrin, methyl-beta-cyclodextrin or hydroxyethyl-beta-cyclodextrin.
2. The polyamide composition according to claim 1, wherein the cyclodextrin or its derivative is contained in an amount of 0.2 to 0.9 part and the metal salt is contained in an amount of 0.1 to 0.6 part.
3. The polyamide composition according to claim 2, wherein the cyclodextrin or its derivative is contained in an amount of 0.3 to 0.6 part and the metal salt is contained in an amount of 0.15 to 0.4 part.
4. The polyamide composition of claim 1 wherein the radiation crosslinking agent is selected from at least one of triallyl cyanurate, triallyl isocyanurate, methyltriallyl isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, or propylene glycol diacrylate.
5. The polyamide composition according to claim 1, wherein the cyclodextrin or derivative thereof is selected from the group consisting of β -cyclodextrin.
6. The polyamide composition of claim 1, wherein the polyamide composition comprises, the brominated flame retardant is selected from brominated polystyrene, polybrominated styrene, brominated polyphenylene ether, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromobiphenyl, hexabromobiphenyl oxide, octabromobiphenyl oxide, decabromobiphenyl oxide, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2, 3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether) tetrabromobisphenol A derivative, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2, 3-dibromopropyl ether) tetrabromobisphenol S derivative, tetrabromophthalic anhydride at least one of tetrabromophthalimide, ethylene bis-tetrabromophthalimide, tetrabromophthalic anhydride derivative, hexabromocyclododecane, decabromodiphenyl ether, decabromodiphenyl ethane, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylene bis-tribromophenyl ether, ethylene bis-pentabromophenyl ether, tetradecyl bromopropylenol, brominated polycarbonate, brominated epoxy resin, poly-pentabromobenzyl methacrylate, brominated polyphenylene ether, poly-2, 6-dibromophenyl ether, octabromonaphthalene, pentabromocyclohexane, bis (tribromophenyl) fumaramide, or N-methylhexabromodiphenyl amine; the flame retardant synergist is at least one selected from antimony white and zinc borate; the content range of the brominated flame retardant is 8-35 parts, and the flame retardant synergist is 2-8 parts.
7. The polyamide composition of claim 6 wherein the brominated flame retardant is selected from at least one of brominated polystyrene or brominated polyphenylene ether.
8. The polyamide composition of claim 1 wherein the metal ion is selected from at least one of calcium ion, copper ion, or zinc ion.
9. The polyamide composition according to claim 8, wherein the metal ion is at least one selected from the group consisting of calcium ion and copper ion.
10. The polyamide composition according to claim 1, wherein the polyamide resin is obtained by stepwise polycondensation of diamine and diacid, or by ring-opening polymerization of lactam, or by stepwise polycondensation of amino acid, or by copolymerization of diamine, diacid, lactam, and amino acid; the polyamide resin is selected from one or more of PA46、PA66、PA6、PA11、PA12、PA610、PA612、PA1010、PA1012、PA1212、PA4T、PA6T、PA9T、PA10T、PA6I、PAMXD6、PA6I、PA66/6、PA6/66、PA6T/6I or PA 6T/66.
11. The polyamide composition according to claim 1, further comprising 0 to 2 parts of one or more of an antioxidant and a lubricant.
12. A process for the preparation of a polyamide composition according to any one of claims 1 to 11, characterized in that it comprises the following steps: weighing the components according to the proportion, premixing in a high-speed mixer to obtain a premix, putting the premix into a double-screw extruder for melt mixing, and extruding and granulating; the length-diameter ratio of the screw of the double-screw extruder is 40-48:1, the temperature of the screw cylinder is 240-300 ℃, and the rotating speed of the screw is 200-550 rpm; injection molding is carried out on the extruded and granulated particles, the injection molding temperature is 270-300 ℃, and the injection molding pressure is 55-100 MPa; and (3) carrying out irradiation crosslinking treatment on the injection molded part, wherein an electron beam is adopted as a radiation source in the treatment process, and the irradiation dose is 15-25 Mrad, so as to obtain the polyamide composition.
13. Use of a polyamide composition according to any one of claims 1 to 11 for the preparation of thin and light components.
CN202111255009.3A 2021-10-27 2021-10-27 Polyamide composition and preparation method and application thereof Active CN114031793B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111255009.3A CN114031793B (en) 2021-10-27 2021-10-27 Polyamide composition and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111255009.3A CN114031793B (en) 2021-10-27 2021-10-27 Polyamide composition and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114031793A CN114031793A (en) 2022-02-11
CN114031793B true CN114031793B (en) 2024-04-30

Family

ID=80135481

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111255009.3A Active CN114031793B (en) 2021-10-27 2021-10-27 Polyamide composition and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114031793B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015113740A1 (en) * 2014-01-29 2015-08-06 Clariant International Ltd Halogen-free solid flame retardant mixture and use thereof
WO2017131008A1 (en) * 2016-01-29 2017-08-03 東洋紡株式会社 Heat-resistant polyamide resin composition
CN108329678A (en) * 2018-01-12 2018-07-27 金发科技股份有限公司 A kind of Amilan polyamide resin composition and preparation method thereof
CN108727810A (en) * 2018-05-23 2018-11-02 江苏金发科技新材料有限公司 Long glass fiber reinforced daiamid composition and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015113740A1 (en) * 2014-01-29 2015-08-06 Clariant International Ltd Halogen-free solid flame retardant mixture and use thereof
WO2017131008A1 (en) * 2016-01-29 2017-08-03 東洋紡株式会社 Heat-resistant polyamide resin composition
CN108329678A (en) * 2018-01-12 2018-07-27 金发科技股份有限公司 A kind of Amilan polyamide resin composition and preparation method thereof
CN108727810A (en) * 2018-05-23 2018-11-02 江苏金发科技新材料有限公司 Long glass fiber reinforced daiamid composition and preparation method thereof

Also Published As

Publication number Publication date
CN114031793A (en) 2022-02-11

Similar Documents

Publication Publication Date Title
EP3699234B1 (en) Polyphenylene sulfide resin composition, method for preparing same, and injection molded product manufactured from same
JP6113941B1 (en) Method for producing polybutylene terephthalate resin composition and method for producing polybutylene terephthalate resin molding
CN110776736B (en) Crosslinked polyamide-based composite material, preparation method and application in intelligent water affair field
WO2013146281A1 (en) Polybutylene terephthalate resin composition and molded article
WO2022036986A1 (en) Halogen-free flame retardant polyamide composite material and preparation method and use therefor
JP7025604B1 (en) Method for manufacturing resin composition, molded product and plated molded product
CN113667218A (en) Spraying-free polypropylene material and preparation method thereof
CN114031793B (en) Polyamide composition and preparation method and application thereof
CN115304911A (en) Polyamide composite material and preparation method and application thereof
JPWO2014157132A1 (en) Phenoxy resin composition and cured product thereof
JPH07107132B2 (en) Polyarylene sulfide resin composition and combination molded product with metal
WO2002044277A1 (en) Molded resin for radiation shielding
CN113214554A (en) Preparation process of modified plastic particles
CN114854136B (en) High-haze high-light-transmittance polypropylene composition and preparation method and application thereof
CN108264688B (en) Antifogging master batch for packaging film and preparation method thereof
CN114854165B (en) Weather-resistant ABS composition, and preparation method and application thereof
CN107513262B (en) Polyketone compositions
JP3177606B2 (en) Polyacetal resin composition
JP3788493B2 (en) Norbornene resin composition
KR900004944B1 (en) Thermoplastic resin composition for shielding electronic wave
JPH06329891A (en) Weather-resistant resin composition
CN114031936B (en) MCA flame-retardant PA66 composition and preparation method and application thereof
GB2508601A (en) Flame Retardant Composition
CN110483878B (en) Radiation-resistant crosslinked ethylene-tetrafluoroethylene copolymer insulating material
CN112795151B (en) Antistatic TPEE composition and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant