CN115124828A - Polyamide composition and preparation method thereof - Google Patents
Polyamide composition and preparation method thereof Download PDFInfo
- Publication number
- CN115124828A CN115124828A CN202210897411.XA CN202210897411A CN115124828A CN 115124828 A CN115124828 A CN 115124828A CN 202210897411 A CN202210897411 A CN 202210897411A CN 115124828 A CN115124828 A CN 115124828A
- Authority
- CN
- China
- Prior art keywords
- polyamide composition
- ethylene
- percent
- amino
- olefin
- 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.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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 and a preparation method thereof. A polyamide composition comprising the following composition: 70-90 wt% of semi-crystalline polyamide, 4-20 wt% of amino functionalized polyolefin elastomer, 4-20 wt% of modified elastomer copolymer containing anhydride group, and 1-3 wt% of optional additive. The polyamide composition prepared by the twin-screw extrusion granulation process has excellent high-low temperature toughness and hydrolysis resistance, and is suitable for hydrolysis-resistant pipelines, cables, structural parts and the like.
Description
Technical Field
The invention belongs to the field of synthesis and processing of high polymer materials, and particularly relates to a polyamide composition and a preparation method thereof.
Background
The nylon material as an engineering plastic has excellent mechanical strength, fatigue strength and heat resistance, excellent chemical resistance, excellent processing performance and high forming speed, so that the nylon material has wide application. However, the water absorption of nylon materials not only causes dimensional change, but also causes the reduction of mechanical properties, which limits the application of nylon materials in related fields, with the upgrade of energy structures, the properties of materials required in the automobile industry need to be further upgraded, and the thermal management system puts a strict requirement on the water resistance of nylon materials. Although metal pipes can meet the related requirements, metal is gradually banned from problems of heavy weight, non-corrosion resistance and the like, and plastic pipes are more suitable for the market.
Nylon is easily hydrolyzed due to the amide bond existing in the nylon and the terminal amino and carboxyl groups, so that the nylon can be relatively limited in the relevant wading and alcohol wading fields. Patent CN112480664A discloses a polyamide material using a mixture of nylon 66 and long carbon chain nylon as a resin matrix, carbodiimide as a hydrolysis resistant agent, and POE-g-MAH as a toughening agent, which improves the toughness of the material to a certain extent, but the brittleness of nylon 66 itself and the extremely strong reactivity of carbodiimide lead to difficulty in controlling the reaction degree in the processing process and the requirement for equipment will be increased due to too large viscosity in the subsequent processing, and at the same time, the pipeline becomes rough. Patent CN112480661A discloses a high-temperature-resistant hydrolysis-resistant modified polyamide pipeline material, wherein nylon containing at least 10 carbons is used, and the toughening agent and the hydrolysis-resistant agent are improved by adding a relative olefin toughening agent and a hydrolysis-resistant agent grafted by maleic anhydride. Patent CN102391431A discloses a toughening agent with two grafting monomers (maleic anhydride and GMA), which realizes toughening of PA66, and achieves a certain toughening effect, but GMA will react with maleic anhydride in the system, and the reaction of the toughening agent will occur, and the reactivity of GMA-like grafting functional groups is very high, which easily causes excessive crosslinking of the system. Patent CN104610736A discloses that polar liquid rubber toughener is used to improve the low temperature toughness of nylon material, but the liquid rubber itself is low molecular weight toughener, but the toughener with larger toughening effect and molecular weight still has a larger difference, which cannot achieve the ideal toughening effect, and the prepared nylon material has poor hydrolysis resistance. Patent CN110591100A discloses a method for using an internal mixer, POE is degraded by peroxide and then grafted with maleic anhydride, and amino silicone oil is added to prepare a nylon toughening agent. Patent CN112266609A discloses a fully renewable toughened nylon, its preparation method and application. The method is characterized in that a-CH 2-chain segment of nylon is grafted and connected with double bonds of a liquid toughening agent through nylon, the liquid toughening agent, an antioxidant and an initiator, and although the initiator excites free radicals with-CH 2-of the nylon, the-CH 2-main chain of the nylon is distributed in a large amount and is randomly initiated, so that the reaction with the double bonds of the toughening agent is easily uncertain, the problem of dispersion of the toughening agent in a system is caused, and the improvement of the toughness of the nylon material has certain limitation. Patents CN104177825A and CN106496610A disclose methods of grafting polyolefin elastomer with maleic anhydride in situ, which utilize the reaction between maleic anhydride and nylon terminal group to perform a certain degree of chain extension toughening, so as to achieve a good compatibility effect, and although the toughening effect is achieved, the hydrolysis resistance is poor, because maleic anhydride can only react with terminal amino groups in nylon, the strength of chain extension is not sufficient, and unreacted terminal carboxyl groups improve the hydrolysis resistance of nylon insufficiently.
In view of the above, in the prior art, it is necessary to improve the problem that the extrusion process is difficult to control due to the reactivity of the existing material, and on the other hand, the problem that the efficiency of the cooling system is reduced due to the precipitation of the system components, so it is necessary to develop a material for the cooling system to solve the problems of high and low temperature resistance, hydrolysis resistance, extrusion process and cooling efficiency maintenance of the product.
Disclosure of Invention
The invention provides a polyamide composition and a preparation method thereof, which are suitable for hydrolysis-resistant pipelines, cables, structural parts and the like. The method selects two different grafting type modified macromolecule plasticizers, wherein one macromolecule plasticizer is added in a side feeding way, and the reaction with a nylon material is realized through a specific process, so that the effect of chain extension micro-crosslinking is achieved, and the performances of high-low temperature resistance, toughness, hydrolysis resistance and low precipitation of the material are realized.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a polyamide composition comprising the following composition:
according to the invention, two different grafting types of macromolecular plasticizers are used to realize good toughening performance in a synergistic manner, but the addition ratio of the amino-functionalized polyolefin elastomer to the anhydride group-containing modified elastomer copolymer is within a certain range, and the optional ratio is 0.5-4: 1, preferably 1.5 to 2.5: 1, the ratio of the carboxyl end groups is in a certain relation with the ratio of the reactive functional groups, the ratio of the carboxyl end groups is high, and the reaction ratio of the corresponding amine groups is high, so that a better toughening effect is realized.
The polyamide resin according to the invention comprises at least one semi-crystalline polyamide, which can be prepared from diamines and dicarboxylic acids or from lactams corresponding to aminocarboxylic acids. The polymerization reaction may be a ring-opening polymerization, may be a polycondensation, and the resin prepared by the lactam contains at least 6 carbon atoms per nitrogen atom, and in the case of a combination of the diamine and the dicarboxylic acid, the arithmetic average of the carbon atoms in the mixed components of the diamine and the dicarboxylic acid must be at least 6.
Examples of suitable semi-crystalline polyamides include, but are not limited to: PA1012 (prepared from decamethylenediamine having 10 carbon atoms and dodecanedioic acid having 12 carbon atoms), PA12 (condensation of laurolactam), PA612, PA610, PA614, PA12, PA1212, PA614, PA616. PA618, etc. Carboxyl end group concentration (eq-COOH) and amino end group concentration (eq-NH) 2 ) The ratio eq-COOH/eq-NH 2 1 to 20, preferably 3 to 15. Suitable examples include, but are not limited to, Wanamid L3000, Wanamid L2000.
The amino-functionalized polyolefin elastomer of the present invention is a macromolecular plasticizer a, and is a copolymer obtained by copolymerization of ethylene, α -olefin, and amino-functionalized monomer in the presence of an organometallic-transition metal catalyst (ziegler-type catalyst), preferably a metallocene catalyst, and can be prepared according to the method disclosed in US3755279 (a).
Preferably, the amine-functionalized polyolefin elastomer has a number average Mw of 5000-.
Preferably, the alpha-olefin may be selected from C3-C10 alpha-olefins, suitable examples include, but are not limited to, propylene, butene, octene, more preferably butene and/or octene.
Preferably, the amine functional monomer has the following structure:
wherein n is an integer from 1 to 10, R1, R2 are each independently H, alkyl or aralkyl, preferably C1-C10 alkyl, C6-C19 aryl or aralkyl; C1-C10 alkyl is selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, n-hexyl, isohexyl, t-hexyl, n-heptyl and other isomeric groups; the C6-C19 aryl or aralkyl group is selected from other isomeric groups such as phenyl, benzyl, benzhydryl, trityl, phenethyl, diphenylethyl, phenylpropyl, phenylbutyl and the like.
Preferably, the metallocene catalyst may be one or more of a non-bridged bis-metallocene, a bridged half-metallocene, a non-bridged half-metallocene catalyst. The catalyst needs to comprise a main catalyst and a cocatalyst, wherein the main catalyst is selected from titanium dichloride containing silyl butylamino, preferably dimethyl silyl tert-butyl amino indenyl titanium dichloride and diethyl silyl tert-butyl amino indenyl titanium dichloride, and the cocatalyst is a solution of an aluminum metal compound, preferably a methyl aluminoxane toluene solution and a hexyl aluminoxane toluene solution.
Preferably, the copolymerization pressure of the amino-functionalized polyolefin elastomer is 1.5-5.5MPa, preferably 2-4MPa, the reaction time is 5-90min, preferably 10-60min, and the product after the reaction needs to be precipitated and dried by using a solvent to obtain the amino-functionalized olefin polymers with different alpha-olefin insertion rates.
The modified elastomer copolymer containing the anhydride group is a macromolecular plasticizer B, and the anhydride group is preferably maleic anhydride or itaconic anhydride; the elastomeric copolymer is one or more of ethylene-alpha-olefin copolymer, terpolymer based on ethylene- (C3-C12) -alpha-olefin and non-conjugated diene, ethylene/butene copolymer, ethylene/hexene copolymer, ethylene/octene copolymer, and ethylene/alkyl (meth) acrylate copolymer, ethylene/styrene/butadiene copolymer, styrene/butadiene, suitable examples include, but are not limited to, CMG5805, N493, GR216, MD715, a 560.
The additive component comprises one or more of an antioxidant, a light stabilizer, a lubricant, a flame retardant, a pigment, a leveling agent, a chain extender, a heat conducting agent, an electric conduction additive, other thermoplastic plastics and the like.
The light stabilizer provided by the invention comprises an ultraviolet absorber and a light stabilizer, wherein the ultraviolet absorber mainly comprises one or more of benzoic acid, benzophenone derivatives, benzotriazole and the like, and suitable examples include but are not limited to UV320, UV3346, UV1164 and UV 328. The light stabilizer mainly comprises hindered amine stabilizers, suitable examples include but are not limited to UV770, UV944, UV312 and the like, and the hindered amine stabilizers and the UV944 and the UV312 can be mixed according to the weight ratio of 0.5-2: 1 is used in combination.
The lubricant is one or more of calcium stearate, polyethylene wax and ethylene distearate.
The antioxidant of the present invention includes antioxidants used alone or in combination with each other, and as a specific embodiment, the antioxidant may include one or more of hindered amine type, hindered phenol/semi-hindered phenol type antioxidants, phosphite esters, inorganic copper salts, organic copper salts, and the like, and suitable examples are not limited to 1098, 168, H10, H3336, H3386, H318, and the like.
The two grafting types of macromolecular plasticizers are selected to play a synergistic role, the hydrolysis resistance of the polymer is mainly related to the molecular weight of the polymer, the density of amido bonds and the entanglement of molecular chains, if a single functional group can only react with one end, the maleic anhydride functional group mainly reacts with an amino end, the amino group and the carboxyl group can react, and if the single functional group and the amino end exist at the same time, the reaction at the tail end of the polyamide is increased, so that the chain extension is formed to generate micro-crosslinking, the toughness of the material is improved, and the hydrolysis resistance of the material is improved. However, if the two materials are in contact with each other in advance in the twin-screw granulation stage, the two materials can react with nylon and react with each other, which is unfavorable for improving the toughness and hydrolysis resistance of the material and can be suitably reflected. The macromolecular plasticizer is added in a mode of adding twice, the amino functionalized olefin elastomer is added firstly, and then the anhydride group-containing modified elastomer copolymer is added, so that the hydrolysis resistance of the material is greatly improved. At the same time, it has been unexpectedly found that the process of adding both in portions provides better toughness improvement for the material itself than either addition alone.
A process for preparing the polyamide composition of the invention, comprising the steps of: the components are obtained by double-screw granulation processing, and the length-diameter ratio of a double-screw extruder is 35-42: 1, the extrusion processing temperature is 240-280 ℃, the melt temperature is 250-295 ℃, the screw rotation speed is 600-800 rpm/min, and the extrusion speed is 100-240 kg/h. The amino-functionalized polyolefin elastomer or the anhydride group-containing modified elastomer copolymer is fed in a side feed (5-zone screw) of a double screw, other raw materials are fed in from a main feed port, attention needs to be paid to strictly controlling the melt temperature, if the melt temperature is too high, the reaction degree in the system is more violent, the violent degree of the reaction directly influences the performance appearance of the material, the toughness of the matrix material is improved due to the addition of a general impact modifier, excessive crosslinking reaction can be caused to a certain degree due to the violent reaction, and the toughness of the excessive crosslinking system is reduced on the contrary.
The polyamide composition provided by the invention effectively improves the toughness and hydrolysis resistance of the nylon material, hardly separates out small molecules after being soaked in water-resistant and glycol-resistant solutions, improves the problems, is suitable for mass production, and widens the application field of the nylon material.
Compared with the prior art, the invention has the following advantages:
1) the macromolecular plasticizers with two different grafting functional groups can react with two end groups of nylon respectively, so that the compatibility of the system is improved, the active functional groups of the nylon can completely react with amino and carboxyl, and the hydrolysis resistance of the material is improved.
2) The selected aminated functional group and carboxyl functional group belong to relatively mild reaction activities, and compared with epoxy functional groups with higher activity, the reaction activity is easier to control, and the problem that the viscosity of the material is uncontrollable and the subsequent processing of the material is influenced due to the fact that the system is crosslinked due to the reaction activity can be effectively avoided.
3) According to the invention, by controlling the adding sequence of the macromolecular plasticizers modified by different grafting types, on one hand, the phenomenon that the reaction is uncontrollable to cause crosslinking due to too many reaction functional groups in unit volume because of simultaneous addition is avoided, and on the other hand, the reaction between two macromolecular plasticizers can be effectively avoided.
Detailed Description
In order to facilitate better understanding of the composition, preparation and properties of a polyamide prepared according to the invention by the skilled person, the invention will be further described below with specific examples, but only in order to describe it in further detail
The scope of the invention is not limited to the above description.
The source of the raw materials is shown in table 1:
TABLE 1 sources of raw materials
Amino-functional polyolefin elastomer
Preparation example 1
Amino-functionalized polyolefin elastomer synthesis step: firstly, preparing a solution with the concentration of 1g/10ml by using an alpha-olefin monomer octene and an amino functional monomer butylamine according to the proportion of 3: 1, then adding the mixture into a reaction kettle, heating the mixture to 125 ℃, introducing ethylene gas, controlling the pressure in the kettle to be 3.0MPa, simultaneously adding 0.5mg of main catalyst dimethylsilyl tert-butylamine indenyl titanium dichloride and 0.5ml of cocatalyst of 5% methylaluminoxane toluene solution, reacting for 20min, pouring the reaction liquid into absolute ethyl alcohol at normal temperature to obtain solid precipitate, filtering and drying to prepare the amino-functionalized polyolefin elastomer A.
Preparation example 2
Amino-functionalized polyolefin elastomer synthesis step: firstly preparing a solution with the concentration of 1g/10ml by using an alpha-olefin monomer butene and an amino functional monomer allylamine, adding the solution into a reaction kettle according to the weight ratio of 1:2.5, heating to 125 ℃, introducing ethylene gas, controlling the pressure in the kettle to be 3.0MPa, simultaneously adding 0.5mg of main catalyst dimethyl silicon tert-butylamine indenyl titanium dichloride and 0.5ml of cocatalyst of 5% methylaluminoxane toluene solution by mass, reacting for 20min, pouring the reaction liquid into normal-temperature absolute ethyl alcohol to obtain a solid precipitate, filtering and drying to prepare the amino functional polyolefin elastomer B.
Example 1
79.5 percent (calculated by weight parts, the same below) of L3000 and 12 percent of amino-functionalized polyolefin elastomer A, 0.4 percent of antioxidant 1098, 0.3 percent of antioxidant 168, 0.6 percent of antioxidant H3336, 0.2 percent of zinc stearate and 1 percent of black master are mixed for 2 minutes at the rotating speed of 700rpm by a high-speed mixer, put into a main feed weighing scale of a double-screw extruder, put 6 percent MD715 into a side feed weighing scale, set the extrusion temperature of 255 ℃ and the rotating speed of a screw of 800rpm/min, and are dragged, cooled, cut and granulated by the double-screw extruder.
Example 2
79.5 percent (calculated by weight, the same below) of L3000 and 10 percent of amino-functionalized polyolefin elastomer A, 0.4 percent of antioxidant 1098, 0.3 percent of antioxidant 168, 0.6 percent of antioxidant H3336, 0.2 percent of zinc stearate and 1 percent of black master are mixed for 2 minutes at the rotating speed of 700rpm by a high-speed mixer, put into a main feed weighing scale of a double-screw extruder, 8 percent of N493 is put into a side feed weighing scale, the extrusion temperature is set to be 255 ℃, the rotating speed of the screw is set to be 800rpm/min, and the mixture is dragged, cooled, cut and granulated by the double-screw extruder.
Example 3
Mixing 80.5% (by weight, the same applies below) of L3000 and 12% of amino-functionalized polyolefin elastomer B, 0.4% of antioxidant 1098, 0.3% of antioxidant 168, 0.6% of antioxidant H3336, 0.2% of zinc stearate and 1% of black master batch at the rotating speed of 700rpm by a high-speed mixer for 2 minutes, putting the mixture into a main feeding weighing scale of a double-screw extruder, putting 5% of MD715 into a side feeding weighing scale, setting the extrusion temperature to be 255 ℃, setting the rotating speed of the screw to be 800rpm/min, and carrying out traction, cooling, cutting and granulation by the double-screw extruder.
Example 4
82.5 percent (calculated by weight parts, the same is shown below) of PA1012, 10 percent of amino-functionalized polyolefin elastomer B, 0.4 percent of antioxidant 1098, 0.3 percent of antioxidant 168, 0.6 percent of antioxidant H3336, 0.2 percent of zinc stearate and 1 percent of black master batch are mixed for 2 minutes at the rotating speed of 700rpm by a high-speed mixer, put into a main feed weighing scale of a double-screw extruder, 5 percent of MD715 is put into a side feed weighing scale, the extrusion temperature is set to be 255 ℃, the rotating speed of a screw is set to be 800rpm/min, and the mixture is subjected to traction, cooling, cutting and granulation by the double-screw extruder.
Example 5
Mixing 75.5% (by weight, the same below) of PA1012, 12% of amino-functionalized polyolefin elastomer B, 0.4% of antioxidant 1098, 0.3% of antioxidant 168, 0.6% of antioxidant H3336, 0.2% of zinc stearate and 1% of black master batch at the rotating speed of 700rpm by a high-speed mixer for 2 minutes, putting the mixture into a main feeding weighing scale of a double-screw extruder, putting 10% of N493 into a side feeding weighing scale, setting the extrusion temperature to be 255 ℃, setting the rotating speed of a screw to be 800rpm/min, and carrying out traction, cooling, cutting and granulation by the double-screw extruder.
Example 6
Mixing 72.5% (by weight, the same below) L3000, 20% of amino-functionalized polyolefin elastomer A, 0.4% of antioxidant 1098, 0.3% of antioxidant 168, 0.6% of antioxidant H3336, 0.2% of zinc stearate and 1% of black master batch at the rotating speed of 700rpm by a high-speed mixer for 2 minutes, putting the mixture into a main feeding weighing scale of a double-screw extruder, putting 5% of N493 into a side feeding weighing scale, setting the extrusion temperature to be 255 ℃, setting the rotating speed of a screw to be 800rpm/min, and carrying out traction, cooling, cutting and granulation by the double-screw extruder.
Example 7
73.5 percent (calculated by weight parts, the same below) of L3000 and 8 percent of amino-functionalized polyolefin elastomer A, 0.4 percent of antioxidant 1098, 0.3 percent of antioxidant 168, 0.6 percent of antioxidant H3336, 0.2 percent of zinc stearate and 1 percent of black master are mixed for 2 minutes at the rotating speed of 700rpm by a high-speed mixer, put into a main feed weighing scale of a double-screw extruder, 16 percent of MD715 is put into a side feed weighing scale, the extrusion temperature is set to be 255 ℃, the rotating speed of the screw is set to be 800rpm/min, and the mixture is dragged, cooled, cut and granulated by the double-screw extruder.
Comparative example 1
79.5 percent (calculated by weight parts, the same below) of L3000 and 18 percent of amino-functionalized polyolefin elastomer A, 0.4 percent of antioxidant 1098, 0.3 percent of antioxidant 168, 0.6 percent of antioxidant H3336, 0.2 percent of zinc stearate and 1 percent of black master are mixed for 2 minutes at the rotating speed of 700rpm by a high-speed mixer, put into a main feed weighing scale of a double-screw extruder, set the extrusion temperature to be 255 ℃ and the rotating speed of a screw to be 800rpm/min, and are dragged, cooled, cut and granulated by the double-screw extruder.
Comparative example 2
Mixing 79.5 percent (calculated by weight parts, the same is shown below) of L3000, 18 percent of N493, 0.4 percent of antioxidant 1098, 0.3 percent of antioxidant 168, 0.6 percent of antioxidant H3336, 0.2 percent of zinc stearate and 1 percent of black master batch at the rotating speed of 700rpm for 2 minutes by a high-speed mixer, putting the mixture into a main feed weighing scale of a double-screw extruder, setting the extrusion temperature to be 255 ℃, setting the rotating speed of a screw to be 800rpm/min, and carrying out traction, cooling, cutting and granulation by the double-screw extruder.
Comparative example 3
79.5 percent (calculated by weight parts, the same below) of L3000 and 10 percent of amino-functionalized polyolefin elastomer A, 8 percent of N493, 0.4 percent of antioxidant 1098, 0.3 percent of antioxidant 168, 0.6 percent of antioxidant H3336, 0.2 percent of zinc stearate and 1 percent of black master are mixed for 2 minutes at the rotating speed of 700rpm by a high-speed mixer, put into a main feeding metering scale of a double-screw extruder, set the extrusion temperature of 255 ℃ and the rotating speed of a screw of 800rpm/min, and are dragged, cooled, cut and granulated by the double-screw extruder.
Comparative example 4
79.5 percent (calculated by weight parts, the same below) of L3000 and 15 percent of amino-functionalized polyolefin elastomer A, 0.4 percent of antioxidant 1098, 0.3 percent of antioxidant 168, 0.6 percent of antioxidant H3336, 0.2 percent of zinc stearate and 1 percent of black master are mixed for 2 minutes at the rotating speed of 700rpm by a high-speed mixer, put into a main feed weighing scale of a double-screw extruder, 3 percent of N493 is put into a side feed weighing scale, the extrusion temperature is set to be 255 ℃, the rotating speed of the screw is set to be 800rpm/min, and the mixture is dragged, cooled, cut and granulated by the double-screw extruder.
Comparative example 5
Adding 90% (by weight, the same below) EPDM (EPT103A) and 5.5% polyethylene wax (Mitsui 420P) into a high-speed stirrer, mixing for 1min, adding into a double-screw extruder, extruding, setting the head temperature to 160 ℃, extruding, granulating and drying to obtain an EPDM and polyethylene wax extrudate, adding 95.5% of the EPDM and polyethylene wax extrudate, 0.5% of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) hexane, 1.0% of maleic anhydride, 1.0% of glycidyl methacrylate and 2.0% of styrene into the high-speed mixer, mixing for 2min, adding into a double screw from a first feeder, setting the die head temperature to 180 ℃, and extruding and granulating to obtain the nylon toughening agent.
Adding 85% L3000 and 15% nylon toughening agent into a high-speed mixer, mixing for 1min, adding into a double screw, setting the die head temperature at 250 ℃ and the screw rotation speed at 700rpm/min, and carrying out traction, cooling, cutting and granulation by a double screw extruder.
Comparative example 6
Adding 84% (by weight, the same below) of L3000 and 14.8% of polar liquid rubber (epoxidized hydroxyl-terminated polybutadiene ETPB) into a high-speed mixer, blending for 15min, adding 0.3% of nucleating agent sodium phenylphosphinate, 0.5% of lubricant (montan wax: silicone powder MB-4 ═ 1:1) and 0.4% of antioxidant (1098:168 ═ 1:1) into the mixer, mixing for 30min to obtain a formula material, putting the formula material into a main feed weighing scale of a double-screw extruder, setting the extrusion temperature at 245 ℃, and the screw rotation speed at 700rpm/min, and carrying out traction, cooling, cutting and granulation by the double-screw extruder.
Comparative example 7
81.9 percent (calculated by weight parts, the same below) of POE, 0.08 percent of dicumyl peroxide and 1.6 percent of polar monomer maleic anhydride are added into an internal mixer to be melted and blended at the temperature of 200 ℃, the revolution of the internal mixer is 100 r/min, after 5 minutes, 16 percent amino silicone oil (LB-8040A) is added to continue blending, and after 8 minutes, a sample is taken to obtain the nylon toughening agent. And (3) uniformly blending 13% of nylon toughening agent and 87% of L3000, putting the mixture into a main feed metering scale of a double-screw extruder, setting the extrusion temperature to be 250 ℃ and the screw rotation speed to be 700rpm/min, and carrying out traction, cooling, cutting and granulation by the double-screw extruder.
Test standards and sample strips
Tensile property: ISO 5271A spline
And (3) impact test: ISO 1791 eA notch
The results of the product performance tests of the examples and comparative examples are shown in Table 2.
TABLE 2 examples and comparative examples Properties
| Elongation at break | The impact strength of the notch of the simply supported beam is 23 DEG C | Impact strength of a simple beam notch is-30 DEG C | |
| Testing | ISO527 | ISO179 | ISO179 |
| Unit of | ％ | KJ/m 2 | KJ/m 2 |
| Example 1 | 220 | 84 | 71 |
| Example 2 | 210 | 82 | 69 |
| Example 3 | 200 | 79 | 62 |
| Example 4 | 200 | 75 | 60 |
| Example 5 | 230 | 97 | 75 |
| Example 6 | 230 | 99 | 78 |
| Example 7 | 230 | 93 | 74 |
| Comparative example 1 | 170 | 65 | 53 |
| Comparative example 2 | 180 | 71 | 58 |
| Comparative example 3 | 140 | 58 | 22 |
| Comparative example 4 | 180 | 70 | 57 |
| Comparative example 5 | 145 | 48 | 18 |
| Comparative example 6 | 175 | 61 | 30 |
| Comparative example 7 | 165 | 37 | 13 |
As can be seen from the results in Table 2, the two different grafting types of macromolecular plasticizers sequentially added in the invention maintain a certain strength, so that the high-low temperature toughness of the material is obviously improved, and the elongation at break is kept at a higher level.
The tensile and impact bars of the above examples and comparative examples were placed in a solution of ethylene glycol and water (1: 1 by mass), respectively, at a temperature of 120 ℃ for a period of 500 hours. The test was then carried out and the results are shown in Table 3.
TABLE 3 retention of Material Properties after hydrolysis resistance
| Elongation at break | Impact strength of a simple supported beam notch is 23 DEG C | Impact strength of a simple beam notch is-30 DEG C | |
| Testing | ISO527 | ISO179 | ISO179 |
| Unit of | ％ | KJ/m 2 | KJ/m 2 |
| Example 1 | 79％ | 77％ | 75％ |
| Example 2 | 80％ | 75％ | 82％ |
| Example 3 | 78％ | 72％ | 70％ |
| Example 4 | 69％ | 69％ | 65％ |
| Example 5 | 84％ | 79％ | 78％ |
| Example 6 | 88％ | 84％ | 81％ |
| Example 7 | 85％ | 84％ | 79％ |
| Comparative example 1 | 59％ | 61％ | 53％ |
| Comparative example 2 | 62％ | 52％ | 62％ |
| Comparative example 3 | 47％ | 41％ | 58％ |
| Comparative example 4 | 61％ | 57％ | 60％ |
| Comparative example 5 | 41％ | 38％ | 32％ |
| Comparative example 6 | 51％ | 58％ | 47％ |
| Comparative example 7 | 45％ | 34％ | 50％ |
From the property retention rate shown in Table 3, the property retention rate of the compounded macromolecular plasticizer of two different grafting types is superior to that of the comparative example, so that the composition material with excellent high and low temperature toughness and hydrolysis resistance can be prepared by the method.
The embodiments described above are intended to facilitate a person skilled in the art to understand and use the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A polyamide composition comprising the following composition:
2. the polyamide composition of claim 1, wherein the semi-crystalline polyamide comprises one or more of PA1012, PA12, PA612, PA610, PA614, PA12, PA1212, PA614, PA616, PA 618.
3. Polyamide composition according to claim 1 or 2, characterized in that the semi-crystalline polyamide has a ratio eq-COOH/eq-NH of the concentration of carboxyl end groups to the concentration of amino end groups 2 1 to 20, preferably 3 to 15.
4. Polyamide composition according to any one of claims 1 to 3, characterized in that the amine-functionalized polyolefin elastomer is a copolymer obtained by copolymerization of ethylene, an α -olefin, an amine-functionalized monomer; the number average Mw of the amino-functionalized polyolefin elastomer is 5000-.
5. Polyamide composition according to claim 4, characterized in that the alpha-olefin is a C3-C10 alpha-olefin, preferably one or more of propylene, butene, octene; the structure of the amine functional monomer is as follows:
wherein n is an integer from 1 to 10, R1, R2 are each independently H, alkyl or aralkyl, preferably C1-C10 alkyl, C6-C19 aryl or aralkyl.
6. The polyamide composition of claim 5, wherein the C1-C10 alkyl group is selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, n-hexyl, isohexyl, t-hexyl, n-heptyl; the C6-C19 aryl or aralkyl group is selected from phenyl, benzyl, benzhydryl, trityl, phenethyl, diphenylethyl, phenylpropyl, phenylbutyl.
7. Polyamide composition according to any one of claims 1 to 6, wherein the elastomeric copolymer modified with anhydride groups, preferably derived from maleic anhydride, itaconic anhydride; the elastomeric copolymer is preferably one or more of ethylene-alpha-olefin copolymers, terpolymers based on ethylene, a C3-C12-alpha-olefin and a non-conjugated diene, ethylene/butene copolymers, ethylene/hexene copolymers, ethylene/octene copolymers and ethylene/alkyl (meth) acrylate copolymers, ethylene/styrene/butadiene copolymers, styrene/butadiene copolymers.
8. Polyamide composition according to any one of claims 1 to 7, wherein the weight ratio of the amine-functionalized polyolefin elastomer to the modified elastomeric copolymer containing anhydride groups is from 0.5 to 4: 1, preferably 1.5 to 2.5: 1.
9. a process for preparing a polyamide composition according to any one of claims 1 to 8, comprising the steps of: the amino-functionalized polyolefin elastomer or the modified elastomer copolymer containing the anhydride group is fed in through side feeding of a double screw, other raw materials are fed in through a main feeding port, and granulation is carried out through the double screw, wherein the length-diameter ratio of a double screw extruder is 35-44: 1, the extrusion processing temperature is 240-280 ℃, and the melt temperature is 250-295 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210897411.XA CN115124828B (en) | 2022-07-28 | 2022-07-28 | Polyamide composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210897411.XA CN115124828B (en) | 2022-07-28 | 2022-07-28 | Polyamide composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115124828A true CN115124828A (en) | 2022-09-30 |
| CN115124828B CN115124828B (en) | 2023-10-13 |
Family
ID=83386275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210897411.XA Active CN115124828B (en) | 2022-07-28 | 2022-07-28 | Polyamide composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115124828B (en) |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755279A (en) * | 1965-06-25 | 1973-08-28 | Exxon Research Engineering Co | Copolymerization of alpha olefins with sterically hindered alkenyl amines using ziegler catalysts |
| JPS62129351A (en) * | 1985-11-30 | 1987-06-11 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| JPS6436647A (en) * | 1987-07-31 | 1989-02-07 | Shinetsu Polymer Co | Polyamide resin composition |
| JPH0324157A (en) * | 1989-06-22 | 1991-02-01 | Showa Denko Kk | Polyamide resin composition |
| WO1994012575A1 (en) * | 1992-11-20 | 1994-06-09 | Exxon Chemical Patents Inc. | Toughened thermoplastic nylon compositions |
| US5342886A (en) * | 1988-03-24 | 1994-08-30 | Atochem | α-monoolefinic graft copolymers |
| CN1390234A (en) * | 1999-10-19 | 2003-01-08 | 埃克森化学专利公司 | Amine-containing graft polymers, a method for making same, and their use |
| CN1858113A (en) * | 2006-03-30 | 2006-11-08 | 上海大学 | Tenacity reinforced nylon and its preparing method |
| WO2011066495A1 (en) * | 2009-11-30 | 2011-06-03 | E. I. Du Pont De Nemours And Company | Polyamide alloy and its usage |
| CN103450666A (en) * | 2013-09-03 | 2013-12-18 | 金发科技股份有限公司 | Polyamide composite material and preparation method and applications thereof |
| CN103502282A (en) * | 2011-03-25 | 2014-01-08 | 埃克森美孚化学专利公司 | Amine functionalized polyolefin and methods for preparation thereof |
| CN109722020A (en) * | 2018-12-27 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of nylon composite materials and preparation method thereof of amino functionalization polyolefin elastomer toughening |
| CN109722014A (en) * | 2018-12-17 | 2019-05-07 | 会通新材料股份有限公司 | A kind of ultra-toughness low-temperature impact-resistant polyamide material and preparation method thereof |
| CN109749433A (en) * | 2018-12-27 | 2019-05-14 | 会通新材料股份有限公司 | A kind of daiamid composition and preparation method thereof |
| CN110194894A (en) * | 2019-06-25 | 2019-09-03 | 平顶山市科隆新材料有限公司 | A kind of high-ductility nylon material and preparation method thereof |
| CN111205636A (en) * | 2020-02-28 | 2020-05-29 | 金旸（厦门）新材料科技有限公司 | Polyamide material and preparation method and application thereof |
| CN113956650A (en) * | 2021-09-23 | 2022-01-21 | 万华化学集团股份有限公司 | Nylon 12 toughening modifier and preparation method and application thereof |
| CN114410105A (en) * | 2022-02-25 | 2022-04-29 | 金发科技股份有限公司 | High-impact-resistance wear-resistant polyamide composition and preparation method and application thereof |
-
2022
- 2022-07-28 CN CN202210897411.XA patent/CN115124828B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755279A (en) * | 1965-06-25 | 1973-08-28 | Exxon Research Engineering Co | Copolymerization of alpha olefins with sterically hindered alkenyl amines using ziegler catalysts |
| JPS62129351A (en) * | 1985-11-30 | 1987-06-11 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| JPS6436647A (en) * | 1987-07-31 | 1989-02-07 | Shinetsu Polymer Co | Polyamide resin composition |
| US5342886A (en) * | 1988-03-24 | 1994-08-30 | Atochem | α-monoolefinic graft copolymers |
| JPH0324157A (en) * | 1989-06-22 | 1991-02-01 | Showa Denko Kk | Polyamide resin composition |
| WO1994012575A1 (en) * | 1992-11-20 | 1994-06-09 | Exxon Chemical Patents Inc. | Toughened thermoplastic nylon compositions |
| CN1390234A (en) * | 1999-10-19 | 2003-01-08 | 埃克森化学专利公司 | Amine-containing graft polymers, a method for making same, and their use |
| CN1858113A (en) * | 2006-03-30 | 2006-11-08 | 上海大学 | Tenacity reinforced nylon and its preparing method |
| WO2011066495A1 (en) * | 2009-11-30 | 2011-06-03 | E. I. Du Pont De Nemours And Company | Polyamide alloy and its usage |
| CN103502282A (en) * | 2011-03-25 | 2014-01-08 | 埃克森美孚化学专利公司 | Amine functionalized polyolefin and methods for preparation thereof |
| CN103450666A (en) * | 2013-09-03 | 2013-12-18 | 金发科技股份有限公司 | Polyamide composite material and preparation method and applications thereof |
| CN109722014A (en) * | 2018-12-17 | 2019-05-07 | 会通新材料股份有限公司 | A kind of ultra-toughness low-temperature impact-resistant polyamide material and preparation method thereof |
| CN109722020A (en) * | 2018-12-27 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of nylon composite materials and preparation method thereof of amino functionalization polyolefin elastomer toughening |
| CN109749433A (en) * | 2018-12-27 | 2019-05-14 | 会通新材料股份有限公司 | A kind of daiamid composition and preparation method thereof |
| CN110194894A (en) * | 2019-06-25 | 2019-09-03 | 平顶山市科隆新材料有限公司 | A kind of high-ductility nylon material and preparation method thereof |
| CN111205636A (en) * | 2020-02-28 | 2020-05-29 | 金旸（厦门）新材料科技有限公司 | Polyamide material and preparation method and application thereof |
| CN113956650A (en) * | 2021-09-23 | 2022-01-21 | 万华化学集团股份有限公司 | Nylon 12 toughening modifier and preparation method and application thereof |
| CN114410105A (en) * | 2022-02-25 | 2022-04-29 | 金发科技股份有限公司 | High-impact-resistance wear-resistant polyamide composition and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YUDONG WANG ET AL.: "Morphology of nylon 1212 toughened with a maleated EPDM rubber", 《POLYMER INTERNATIONAL》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115124828B (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1974663B (en) | Crosslinkable compositions, thermoplastic elastomers obtained therefrom and their use | |
| CN1109075C (en) | Polyamide resin composition and process for producing the same | |
| JP6360068B2 (en) | Heat aging resistant ethylene vinyl acetate copolymer composition and process for producing the same | |
| JP6603347B2 (en) | Heat resistant hydrocarbon elastomer composition | |
| CN111548622A (en) | PA/PE (polyamide/polyethylene) blend alloy with low water absorption and high dimensional stability and preparation method thereof | |
| US9051460B2 (en) | Heat resistant hydrocarbon elastomer compositions | |
| CN109679243B (en) | Heat-resistant corrosion-resistant polyvinyl chloride water supply and drainage pipe and preparation method thereof | |
| JP4991528B2 (en) | Modifiers for thermoplastic alloys and alloys produced using the modifiers | |
| CN116867812A (en) | Graft modified vinyl polymer, polyamide composition containing graft modified vinyl polymer and use thereof | |
| CN115124828B (en) | Polyamide composition and preparation method thereof | |
| CA2146362C (en) | Polyamide resin composition | |
| CN109722020B (en) | Nylon composite material toughened by amino-functionalized polyolefin elastomer and preparation method thereof | |
| JP4068162B2 (en) | Process for producing polyacrylate / polyolefin blends | |
| CN112029276A (en) | Special material for low-temperature toughened polyamide cable tie with high water absorption rate, cable tie and preparation method | |
| CN110776691B (en) | High-modulus high-impact polypropylene composite material and preparation method thereof | |
| JP6076210B2 (en) | Polyamide resin composition and molded article comprising the same | |
| US9803073B2 (en) | Heat resistant ethylene vinyl acetate copolymer composition and process for its production | |
| CN115521566B (en) | Nylon toughening agent and preparation method and application thereof | |
| CN115044103B (en) | Polyethylene composite auxiliary agent special for high altitude area | |
| JP3476551B2 (en) | Polyamide resin composition | |
| JPH0782477A (en) | Polyamide resin composition | |
| JPS5991148A (en) | Polyamide composition | |
| CN118772536A (en) | Flame-retardant laminated material and preparation method and application thereof | |
| EP3077456A1 (en) | Heat resistant ethylene vinyl acetate copolymer composition and process for its production |
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 |