CN115124828B - Polyamide composition and preparation method thereof - Google Patents
Polyamide composition and preparation method thereof Download PDFInfo
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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 amine-functionalized polyolefin elastomer, 4-20 wt% of anhydride group-modified elastomer copolymer and 1-3 wt% of optional additive. The prepared polyamide composition 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 is used as engineering plastic, has excellent mechanical strength, fatigue strength and heat resistance, excellent chemical resistance, and meanwhile, has excellent processing performance and high forming speed, so that the nylon material is widely applied. However, the water absorption of the nylon material not only can cause dimensional change, but also can cause the mechanical property to be reduced, which limits the application of the nylon material in the related field, and along with the upgrading of the energy structure, the performance of the material in the automobile industry is required to be further upgraded, and the thermal management system has strict requirements on the water resistance of the nylon material. Although metal pipelines can meet the related requirements, metal is gradually banned by the problems of heavy weight, corrosion resistance and the like, and plastic pipelines meet the market demands more.
Nylon is susceptible to hydrolysis due to its own presence of amide linkages and terminal amino and carboxyl groups, resulting in its relative limitation in the relevant wading and alcohol-related 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, POE-g-MAH as a toughening agent, although improving the toughness of the material to some extent, the brittleness of nylon 66 itself and the extremely strong reactivity of the carbodiimide lead to difficulty in controlling the reaction degree in the processing process and increase in requirements on equipment due to excessive viscosity in subsequent processing, and at the same time, the pipeline becomes rough. Patent CN112480661a discloses a high temperature resistant hydrolysis resistant modified polyamide pipeline material, which uses nylon containing at least 10 carbons, and increases the toughening agent and hydrolysis resistant agent by adding related olefin toughening agent grafted by maleic anhydride and hydrolysis resistant agent, and is notable that the invention also uses benzenesulfonamide plasticizer, which belongs to small molecular plasticizer, used in automobile cooling system, is easy to precipitate into the cooling liquid, and can cause the cooling liquid to be doped with impurities, resulting in reduction of cooling efficiency. Patent CN102391431a discloses a toughening agent with two grafting monomers (maleic anhydride and GMA) to achieve toughening of PA66, although achieving a certain toughening effect, GMA will react with maleic anhydride in the system, self reaction of the toughening agent will occur, and meanwhile, the reactivity of the grafting functional group of GMA is very high, which is easy to cause excessive crosslinking of the system. Patent CN104610736a discloses that the low-temperature toughness of nylon material is improved by using a polar liquid rubber toughening agent, but the liquid rubber belongs to a low-molecular-weight toughening agent, the toughening effect of the liquid rubber is larger than that of the toughening agent with larger molecular weight, the ideal toughening effect is not achieved, and the prepared nylon material has poor hydrolysis resistance. Patent CN110591100a discloses a method of using an internal mixer, wherein POE is degraded by peroxide and then grafted with maleic anhydride, and amino silicone oil is added to prepare nylon toughening agent, so that the toughening agent prepared by the method has residual free maleic anhydride, and the content of maleic anhydride is reduced due to introducing amino silicone oil on POE, so that the content of polar groups capable of reacting with nylon in the toughening agent is reduced, the compatibility of the toughening agent and nylon is reduced, and the toughening effect is reduced. Patent CN112266609a discloses a fully renewable toughened nylon, and a preparation method and application thereof. The method is characterized in that the-CH 2-chain segment of nylon is grafted and connected with the double bond of the liquid toughening agent through the nylon, the liquid toughening agent, the antioxidant and the initiator, and the-CH 2-chain segment of nylon is subjected to the-CH 2-excited free radical of the nylon through the initiator, but the-CH 2-main chain of the nylon is distributed in a large amount and is initiated randomly, so that the reaction with the double bond of the toughening agent is easy to cause great uncertainty, further, the problem of the toughening agent in the dispersion of the system is caused, and the limitation of improving the toughness of nylon materials is caused. Patent CN104177825A, CN106496610a discloses a method for grafting polyolefin elastomer in situ with maleic anhydride, which utilizes the reaction of the maleic anhydride and nylon end groups to carry out chain extension toughening to a certain extent, plays a good role in compatibility, and has poor hydrolysis resistance although playing a role in toughening, because the maleic anhydride can only react with the terminal amino groups in the nylon, the strength of the chain extension is insufficient and the unreacted terminal carboxyl groups lead to insufficient improvement of the hydrolysis resistance of the nylon.
In view of this, in view of the problems of the prior art, such as difficulty in controlling extrusion processing due to reactivity of the existing materials, and reduction in cooling system efficiency due to precipitation of system components, there is a need to develop a material for cooling system, which solves the problems of high and low temperature resistance, hydrolysis resistance, extrusion processing 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. By selecting two different grafting type modified macromolecular plasticizers, one macromolecular plasticizer is added at the side feed, and the reaction of the macromolecular plasticizer 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 and low temperature resistance, high and low temperature toughness, hydrolysis resistance and low precipitation of the material are realized.
In order to achieve the above object, the present invention adopts the following technical scheme:
a polyamide composition comprising the following composition:
the invention realizes good toughening performance by using the synergistic effect of two macromolecular plasticizers with different grafting types, but the addition ratio of the amino functionalized polyolefin elastomer and the elastomer copolymer modified by containing anhydride groups has 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 group to the reactive functional group is high, and the corresponding amino group reaction ratio 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 the corresponding lactams of amino carboxylic acids. The polymerization reaction may be ring-opening polymerization, may be polycondensation, and the resin produced by the lactam contains at least 6 carbon atoms per nitrogen atom, and in the case of the 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 10 carbon atoms decanediamine and 12 carbon atoms dodecanedioic acid), PA12 (dodecalactam polycondensation), PA612, PA610, PA614, PA12, PA1212, PA614, PA616, PA618, and the like. Carboxyl end group concentration (eq-COOH) and amino end group concentration (eq-NH) 2 ) 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 amine-functionalized polyolefin elastomer according to the present invention is a macromolecular plasticizer A, and is a copolymer obtained by copolymerizing ethylene, alpha-olefin and an amine-functionalized monomer under the action of an organometallic-transition metal catalyst (Ziegler catalyst), preferably a metallocene catalyst, and can be prepared according to the method disclosed in U.S. Pat. No. 3,182 (A).
Preferably, the amine-functionalized polyolefin elastomer has a number average mw=5000 to 250000.
Preferably, the alpha-olefin is optionally a C3 to C10 alpha-olefin, 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 other isomeric groups such as methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, n-hexyl, isohexyl, t-hexyl, n-heptyl and the like; 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 dual 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 silicon-based butylamine, preferably dimethyl silicon-based tert-butylamine indenyl titanium dichloride and diethyl silicon-based tert-butylamine indenyl titanium dichloride, and the cocatalyst is a solution of aluminum metal compound, preferably methyl aluminoxane toluene solution and hexyl aluminoxane toluene solution.
Preferably, the copolymerization reaction pressure of the amine-functionalized polyolefin elastomer is 1.5-5.5MPa, preferably 2-4MPa, the reaction time is 5-90min, preferably 10-60min, and the reaction product needs to be precipitated and dried by using a solvent to obtain the amine-functionalized olefin polymers with different alpha-olefin insertion rates.
The elastomer copolymer modified by the acid anhydride group is macromolecular plasticizer B, and the acid anhydride group is maleic anhydride and itaconic anhydride preferably; the elastomeric copolymers are one or more of ethylene-alpha-olefin copolymers, terpolymers based on ethylene- (C3-C12) -alpha-olefins and non-conjugated dienes, ethylene/butene copolymers, ethylene/hexene copolymers, ethylene/octene copolymers and ethylene/alkyl (meth) acrylate copolymers, ethylene/styrene/butadiene copolymers, styrene/butadiene, suitable examples include, but are not limited to, CMG5805, N493, GR216, MD715, a560.
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, a conductive performance additive, other thermoplastic plastics and the like.
The light stabilizer comprises an ultraviolet absorber and a light stabilizer, wherein the ultraviolet absorber mainly comprises one or more of benzoic acids, benzophenone derivatives, benzotriazole and the like, and suitable examples include but are not limited to UV320, UV3346, UV1164 and UV328. The light stabilizer mainly comprises hindered amine stabilizers, and suitable examples include but are not limited to UV770, UV944, UV312 and the like, and the weight ratio of the two can be 0.5-2: 1 are compounded in proportion.
The lubricant is one or more of calcium stearate, polyethylene wax and ethylene distearate.
The antioxidant of the present invention comprises antioxidants used alone or in combination with each other, and as a specific embodiment, the antioxidants may include one or more of hindered amines, hindered phenol/semi-hindered phenol antioxidants, phosphites, inorganic copper salts, organic copper salts, etc., suitable examples are but not limited to 1098, 168, H10, H3336, H3386, H318, etc.
The invention selects two grafting type macromolecular plasticizers to play a synergistic effect, the hydrolysis resistance of the polymer is mainly related to the molecular weight of the polymer, the density of amide bonds and entanglement of molecular chains, if a single functional group can only react with one end, a maleic anhydride functional group mainly reacts with an amino end, an amino group reacts with a carboxyl, and if the two functional groups coexist, the reaction of the tail end of polyamide can be increased, so that a chain extension is formed to generate micro-crosslinking, thereby improving the toughness of the material and the hydrolysis resistance of the material. However, if the two are brought into contact in advance in the twin-screw granulation stage, they react with nylon, and they react with each other, which is disadvantageous in that toughness and hydrolysis resistance of the material are improved, and the reaction is suitably reversed. According to the invention, the macromolecular plasticizer is added in a twice adding mode, the amino functionalized olefin elastomer is added in advance, and then the elastomer copolymer modified by the acid anhydride group is added, so that the hydrolysis resistance of the material is greatly improved. Meanwhile, it has been unexpectedly found that the toughness of the material itself is improved by the process of adding the two materials in separate steps, which is better than that of either one of the two materials added independently.
A process for preparing the polyamide composition of the present invention comprising the steps of: the components of the invention are obtained through twin-screw granulation processing, and the length-diameter ratio of a twin-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 amine functionalized polyolefin elastomer or the elastomer copolymer modified by containing anhydride groups is fed at the side feed (5-zone screw) of the twin screw, other raw materials are fed from a main feed port, and attention needs to be paid to strict control of the melt temperature, if the melt temperature is too high, the reaction intensity in the system is more intense, the reaction intensity directly affects the performance appearance of the material, the addition of a general impact modifier can improve the toughness of the matrix material, the reaction intensity can cause excessive crosslinking reaction to a certain extent, and the toughness of a crosslinked excessive system can be reduced instead.
The polyamide composition effectively improves the toughness and hydrolysis resistance of nylon materials, almost no small molecules are separated out after being soaked in water-resistant and glycol-resistant solution, the problems are improved, and the polyamide composition is suitable for mass production and widens the application field of nylon materials.
Compared with the prior art, the invention has several advantages:
1) The two macromolecular plasticizers with different grafted functional groups can react with two end groups of nylon respectively, so that the compatibility of the system is improved, the amino and carboxyl of the active functional groups of the nylon are completely reacted, and the hydrolysis resistance of the material is improved.
2) The amination functional group and the carboxyl functional group selected by the invention belong to epoxy functional groups with relatively mild reactivity, and compared with epoxy functional groups with higher reactivity, the reaction activity is easier to control, and the system crosslinking caused by the reaction activity can be effectively avoided, so that the viscosity of the material is uncontrollable, and the subsequent processing of the material is further influenced.
3) According to the invention, the addition sequence of the modified macromolecular plasticizers with different grafting types is controlled, so that on one hand, the crosslinking caused by uncontrollable reaction due to too many reactive functional groups in unit volume due to 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 the better knowledge of the person skilled in the art of the composition, the process for the preparation and the properties of a polyamide according to the invention, the invention will be further described below with particular examples, but only in further detail
The description is not intended to limit the scope of the invention.
The sources of the raw materials are shown in Table 1:
TABLE 1 sources of raw materials
Amino-functionalized polyolefin elastomers
Preparation example 1
An amino-functional polyolefin elastomer synthesis step: firstly, preparing alpha-olefin monomer octene and amino functional monomer allyl amine into a solution with the concentration of 1g/10ml, wherein the ratio is 3:1, then adding the mixture into a reaction kettle, heating to 125 ℃, introducing ethylene gas, controlling the pressure in the kettle to be 3.0MPa, simultaneously adding 0.5mg of dimethyl silicon-based tertiary butylamino indenyl titanium dichloride serving as a main catalyst and 0.5ml of a cocatalyst of 5% methyl aluminoxane toluene solution in mass concentration, reacting for 20min, pouring the reaction solution into absolute ethyl alcohol at normal temperature to obtain solid precipitate, filtering and drying to obtain the amino-functionalized polyolefin elastomer A.
Preparation example 2
An amino-functional polyolefin elastomer synthesis step: firstly preparing alpha-olefin monomer butene and amino functional monomer allylamine into a solution with the concentration of 1g/10ml, 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-based tertiary butylamino indenyl titanium dichloride and 0.5ml of cocatalyst of 5% methyl aluminoxane toluene solution, reacting for 20min, pouring the reaction solution into absolute ethyl alcohol at normal temperature to obtain solid precipitate, filtering and drying to obtain the amino functional polyolefin elastomer B.
Example 1
79.5 percent (calculated by weight parts, the same applies below) of L3000, 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, the mixture is put into a main feeding metering scale of a double-screw extruder, 6 percent of MD715 is put into a side feeding metering scale, the extrusion temperature is set to 255 ℃, the rotating speed of the screw is 800rpm/min, and the mixture is drawn, cooled, cut and granulated by the double-screw extruder.
Example 2
79.5 percent (calculated by weight parts, the same applies below) of L3000, 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, put into a main feeding metering scale of a double-screw extruder, 8 percent of N493 is put into a side feeding metering scale, the extrusion temperature is set to 255 ℃, the rotating speed of the screw is set to 800rpm, and the materials are subjected to traction, cooling, cutting and granulation by the double-screw extruder.
Example 3
80.5 percent (calculated by weight parts, the same applies below) of L3000, 12 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, put into a main feeding metering scale of a double-screw extruder, 5 percent of MD715 is put into a side feeding metering scale, the extruding temperature is set to 255 ℃, the rotating speed of the screw is set to 800rpm, and the materials are subjected to traction, cooling, cutting and granulation by the double-screw extruder.
Example 4
82.5 percent (calculated by weight parts, the same applies 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, put into a main feeding metering scale of a double-screw extruder, 5 percent of MD715 is put into a side feeding metering scale, the extrusion temperature is set to 255 ℃, the rotating speed of the screw is set to 800rpm, and the materials are subjected to traction, cooling, cutting and granulation by the double-screw extruder.
Example 5
75.5% (calculated by weight parts, the same applies 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, placed in a main feeding metering scale of a double-screw extruder, 10% of N493 is placed in a side feeding metering scale, the extrusion temperature is set to 255 ℃, the rotating speed of the screw is set to 800rpm, and the materials are subjected to traction, cooling, cutting and granulation by the double-screw extruder.
Example 6
72.5 percent (calculated by weight parts, the same applies below) of L3000, 20 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, put into a main feeding metering scale of a double-screw extruder, 5 percent of N493 is put into a side feeding metering scale, the extruding temperature is set to 255 ℃, the rotating speed of the screw is set to 800rpm, and the materials are subjected to traction, cooling, cutting and granulation by the double-screw extruder.
Example 7
73.5% (calculated by weight parts, the same applies below) of L3000, 8% 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, placed into a main feeding metering scale of a double-screw extruder, 16% of MD715 is placed into a side feeding metering scale, the extrusion temperature is set to 255 ℃, the rotating speed of the screw is set to 800rpm, and the materials are subjected to traction, cooling, cutting and granulation by the double-screw extruder.
Comparative example 1
79.5 percent (calculated by weight parts, the same applies below) of L3000, 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, put into a main feeding metering scale of a double-screw extruder, set the extrusion temperature of 255 ℃, lead screw rotating speed of 800rpm/min, and are drawn, cooled, cut and granulated by the double-screw extruder.
Comparative example 2
79.5 percent (calculated by weight parts, the same is given 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, are put into a main feeding metering scale of a double-screw extruder, are set to the extruding temperature of 255 ℃, are subjected to screw rotating speed of 800rpm/min, and are drawn, cooled, cut and granulated by the double-screw extruder.
Comparative example 3
79.5 percent (calculated by weight parts, the same is given below) of L3000, 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, are put into a main feeding metering scale of a double-screw extruder, and are subjected to traction, cooling, cutting and granulation by the double-screw extruder at the extruding temperature of 255 ℃ and the screw rotating speed of 800 rpm/min.
Comparative example 4
79.5 percent (calculated by weight parts, the same applies below) of L3000, 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 masterbatch are mixed for 2 minutes by a high-speed mixer at the rotating speed of 700rpm, put into a main feeding metering scale of a double-screw extruder, 3 percent of N493 is put into a side feeding metering scale, the extruding temperature is set to 255 ℃, the rotating speed of the screw is set to 800rpm, and the materials are subjected to traction, cooling, cutting and granulation by the double-screw extruder.
Comparative example 5
90 percent (calculated by weight, the same as below) of EPDM (EPT 103A) and 5.5 percent of polyethylene wax (three-well 420P) are added into a high-speed mixer to be mixed for 1min, then the mixture is added into a double-screw extruder to be extruded, the temperature of a machine head is set to 160 ℃, the extrusion granulation and drying are carried out to obtain an EPDM and polyethylene wax extrudate, then 95.5 percent of EPDM and polyethylene wax extrudate, 0.5 percent of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) hexane, 1.0 percent of maleic anhydride, 1.0 percent of glycidyl methacrylate and 2.0 percent of styrene are added into the double-screw extruder from a first feeder to be mixed for 2min, the die temperature is set to 180 ℃, and the nylon toughening agent is obtained through extrusion granulation.
Adding 85% L3000 and 15% nylon toughening agent into a high-speed mixer, mixing for 1min, adding the mixture into a double-screw extruder, setting the temperature of a die head at 250 ℃, and the rotating speed of the screw at 700rpm/min, and carrying out traction, cooling, cutting and granulation by the double-screw extruder.
Comparative example 6
84 percent (calculated by weight parts, the same applies below) of L3000, 14.8 percent of polar liquid rubber (epoxidized hydroxyl terminated polybutadiene ETPB) are added into a high-speed mixer for blending for 15 minutes, then 0.3 percent of nucleating agent sodium phenyl hypophosphite, 0.5 percent of lubricant (montan wax: silicone powder MB-4=1:1) are added into the mixer, 0.4 percent of antioxidant (1098:168=1:1) is mixed for 30 minutes to obtain a formula, the formula is put into a main feeding metering scale of a double-screw extruder, the extrusion temperature is set to 245 ℃, the screw rotation speed is 700rpm/min, and the formula is subjected to traction, cooling, cutting and granulating by the double-screw extruder.
Comparative example 7
81.9 percent (calculated by weight portions, the following is the same) 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 melt blended at the temperature of 200 ℃, the revolution of the internal mixer is 100 revolutions per minute, 16 percent of amino silicone oil (LB-8040A) is added after 5 minutes to continue blending, and the nylon toughening agent is obtained after 8 minutes by sampling. Taking 13% of nylon toughening agent and 87% of L3000, uniformly mixing, putting into a main feeding metering scale of a double-screw extruder, setting the extrusion temperature to 250 ℃, and carrying out traction, cooling, cutting and granulation by the double-screw extruder at the screw rotating speed of 700 rpm/min.
Test standard and spline
Tensile properties: ISO 527 1A spline
Impact test: ISO 179 1eA notch
The results of the performance tests of the products of the examples and the comparative examples are shown in Table 2.
Table 2 performance of examples and comparative examples
| Elongation at break | The notch impact strength of the simply supported beam is 23 DEG C | Notched impact strength of simply supported beam at-30deg.C | |
| Testing | ISO527 | ISO179 | ISO179 |
| Unit (B) | ％ | 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 macromolecular plasticizers of two different grafting types are sequentially added in the invention, so that a certain strength is maintained, the high-low temperature toughness of the material is obviously improved, and the elongation at break is maintained 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 (mass ratio 1:1), respectively, at 120℃for 500h. The test was then performed and the results are shown in table 3.
TABLE 3 retention of Material Properties after hydrolysis resistance
| Elongation at break | The notch impact strength of the simply supported beam is 23 DEG C | Notched impact strength of simply supported beam at-30deg.C | |
| Testing | ISO527 | ISO179 | ISO179 |
| Unit (B) | ％ | 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 performance retention rate of table 3, the retention rate of the macromolecular plasticizers compounded with two different grafting types is better than that of the comparative example, so that the composition material with excellent high-low temperature toughness and hydrolysis resistance can be prepared by the method.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (8)
1. A polyamide composition comprising the following composition:
the amino-functionalized polyolefin elastomer is a copolymer prepared by copolymerization of ethylene, alpha-olefin and amino-functionalized monomer; the structure of the amino functional monomer is as follows:
wherein n is an integer of 1-10, R1 and R2 are H; the elastomer copolymer modified by the acid anhydride group is characterized in that the acid anhydride group is selected from maleic anhydride and itaconic anhydride; the elastomeric copolymer is selected from 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; the weight ratio of the amino functionalized polyolefin elastomer to the elastomer copolymer modified by containing anhydride groups is 0.5-4: 1, a step of; the preparation method of the polyamide composition comprises the following steps: the amine-functionalized polyolefin elastomer or the elastomer copolymer modified with anhydride groups is fed on the side of the twin-screw, the other raw materials are fed from the main feeding port and pelletized by means of the twin-screw.
2. The polyamide composition of claim 1, wherein the semi-crystalline polyamide comprises one or more of PA1012, PA12, PA612, PA610, PA1212, PA614, PA616, PA 618.
3. The polyamide composition of claim 1 wherein the semi-crystalline polyamide has a ratio of carboxyl end group concentration to amino end group concentration of eq-COOH/eq-NH 2 1 to 20.
4. The polyamide composition of claim 3 wherein the semi-crystalline polyamide has a ratio of carboxyl end group concentration to amino end group concentration eq-COOH/eq-NH 2 3 to 15.
5. The polyamide composition of any one of claims 1-4 wherein the amine-functionalized polyolefin elastomer Mw = 5000-250000.
6. The polyamide composition of any one of claims 1-4 wherein the alpha-olefin is a C3 to C10 alpha-olefin.
7. The polyamide composition of any one of claims 1-4 wherein the weight ratio of amine-functionalized polyolefin elastomer to anhydride group-containing modified elastomeric copolymer is from 1.5 to 2.5:1.
8. a process for preparing the polyamide composition of any one of claims 1-7 comprising the steps of: the amine functionalized polyolefin elastomer or the elastomer copolymer modified by containing anhydride groups is fed at the side of a twin screw, other raw materials are fed from a main feeding port, and the length-diameter ratio of a twin screw extruder is 35-44 through twin screw granulation: 1, the extrusion processing temperature is 240-280 ℃, and the melt temperature is 250-295 ℃.
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