CN111100447B - Polyamide-polyester alloy composition and polyamide-6-polybutylene terephthalate alloy - Google Patents
Polyamide-polyester alloy composition and polyamide-6-polybutylene terephthalate alloy Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention relates to the field of polyamide 6-polybutylene terephthalate alloy, and discloses a polyamide-polyester alloy composition and a polyamide 6-polybutylene terephthalate alloy. The composition comprises: 100 parts by weight of polyamide 6, 5-50 parts by weight of polybutylene terephthalate and 0.05-10 parts by weight of mixed butylene-maleic anhydride copolymer microspheres; wherein the particle size of the mixed butylene-maleic anhydride copolymer microsphere is 0.05-2 μm. The polyamide-polyester alloy composition provided by the invention can be used for preparing polyamide 6-polybutylene terephthalate alloy with good compatibility, and has better mechanical property, and the tensile strength reaches more than 85 MPa; the bending strength reaches more than 100 MPa; the normal temperature impact strength is 6.8kJ/m2The above; the low-temperature impact strength is 6.5kJ/m2The above.
Description
Technical Field
The invention relates to the field of polyamide 6-polybutylene terephthalate alloy, in particular to a polyamide-polyester alloy composition and a polyamide 6-polybutylene terephthalate alloy prepared from the composition.
Background
The plastic alloy has the advantages of overcoming the defects of a single material and obtaining good comprehensive performance. The biggest problem with plastic alloys is compatibility, however, because of the difference in solubility parameters between the two materials, the alloy articles are generally more brittle and have poor mechanical properties. Therefore, improving the compatibility of plastic alloys is the key to obtaining alloy materials with excellent comprehensive properties. Polyamide 6(PA6) and polybutylene terephthalate (PBT) are widely used engineering plastics. The polyamide has the defects of strong water absorption, poor mechanical stability and dimensional stability of products, and the PBT has the defects of low notch impact strength, poor high-temperature rigidity and insufficient toughness.
The compatibilizers usually used for polyesters and polyamides are mainly epoxy resins, oxazolines and anhydrides. The problem with epoxy resin based compatibilizers is that they are brittle and their content needs to be carefully controlled, and a content of more than 2 parts leads to a decrease in the impact strength of the alloy. Oxazoline compatilizers are expensive, have a certain toxicity, and are not suitable for industrialization. The anhydride group, ester group and amino of the anhydride compatilizer have reactivity and good compatibilization effect, and the maleic anhydride graft and the block copolymer are mainly used at present, and the addition amount is generally 3-5 parts.
CN103214830A discloses a preparation method of a high-strength and high-toughness polyamide/polyester alloy, which comprises the following steps: 1) putting PET and sodium benzoate into a high-speed mixer according to the mass ratio of 100:1-3, mixing, and extruding by a double-screw extruder to obtain carboxyl-terminated PET; 2) adding polyamide and polyolefin grafted maleic anhydride into a high-speed mixer according to the mass ratio of 100:5-20, mixing, and extruding by a double-screw extruder to obtain carboxyl-terminated polyamide; 3) and (2) putting the carboxyl-terminated PET, the carboxyl-terminated polyamide, the bifunctional epoxy compound and the additive into a high-speed mixer according to the mass ratio of 25-40:60-75:0.5-1:5-10, mixing, and extruding by a double-screw extruder to obtain the high-strength and high-toughness polyamide/polyester alloy. Polyolefin grafted maleic anhydride and epoxy compound are used as compatilizers of polyester and nylon 6, but both the polyester and the nylon 6 need to be pretreated, so that the process is relatively complicated.
CN101508842A discloses a polyamide/polyester alloy, which comprises the following components in parts by mass: 65-87% of polyhexamethylene adipamide; 5-20% of polyethylene terephthalate; 6-10% of a toughening agent; 1-3% of a compatilizer; 0.2 to 0.6 percent of antioxidant; 0.1 to 2 percent of other auxiliary agents. PA6-PET block copolymer is used as a compatilizer, but the compatilizer has a complex production process and is difficult to produce on a large scale.
CN103304985A discloses a high-strength and high-toughness polyamide/polyester alloy, which is prepared from the following components in percentage by mass: polyamide: 1-97%, polyester: 1-97%, compatibilizer: 1-20% and auxiliary agent: 1 percent; the inherent viscosity of the polyamide is 1.8-3.0dL/g, and the inherent viscosity of the polyester is 0.6-0.9 dL/g; the compatilizer is more than one of polymer ionomer, polyamide-polyester segmented copolymer, phenyl sulfonate, epoxy resin, maleic anhydride graft copolymer or rubber phase-containing elastomer. The alloy adopts the traditional compatilizer, such as more than one of polymer ionomer, polyamide-polyester block copolymer, phenyl sulfonate, epoxy resin, maleic anhydride graft copolymer or rubber phase elastomer, but the compatilizer needs to be added in a compounding way, proper addition ratio needs to be determined among different compatilizers, and the alloy is more complex compared with a single compatilizer.
The prior art does not provide good compatibility between polyamide 6 and polybutylene terephthalate and there is a need to provide better solutions for obtaining alloys of polyamide 6 and polybutylene terephthalate with excellent mechanical properties.
Disclosure of Invention
The invention aims to overcome the problem that the prior art cannot provide good-performance alloy of polyamide 6 and polybutylene terephthalate, and provides a polyamide-polyester alloy composition and a polyamide 6-polybutylene terephthalate alloy, wherein the polyamide-polyester alloy composition uses mixed butylene-maleic anhydride copolymer microspheres, and the prepared polyamide 6 and polybutylene terephthalate alloy have better mechanical properties.
In order to achieve the above object, a first aspect of the present invention provides a polyamide-polyester alloy composition, wherein the composition comprises: 100 parts by weight of polyamide 6, 5-50 parts by weight of polybutylene terephthalate and 0.05-10 parts by weight of mixed butylene-maleic anhydride copolymer microspheres; wherein the particle size of the mixed butylene-maleic anhydride copolymer microsphere is 0.05-2 μm.
Preferably, the content of the maleic anhydride structural unit in the mixed butylene-maleic anhydride copolymerized microsphere is 30-70 mol%.
Preferably, the mixed butene-maleic anhydride copolymerized microspheres are maleic anhydride and carbon tetraene copolymerized microspheres prepared by copolymerizing mixed carbon four and maleic anhydride in the presence of nitrogen, an initiator and an organic solvent.
Preferably, the mixed butylene-maleic anhydride copolymer microspheres are copolymer microspheres of maleic anhydride and n-butylene and isobutylene.
Preferably, the weight ratio of the mixed C4 to the maleic anhydride is (0.2-3): 1; preferably (0.8-3): 1.
preferably, the initiator is used in an amount of 0.05 to 20 mol% based on the maleic anhydride.
Preferably, the concentration of maleic anhydride in the organic solvent is from 5% to 25% by weight; preferably 10 wt% to 20 wt%.
Preferably, the copolymerization reaction temperature is 50-100 ℃, preferably 70-90 ℃; the copolymerization pressure is 0.2-2MPa, preferably 0.5-1 MPa; the copolymerization reaction time is 5-10 h.
Preferably, the relative viscosity of the polyamide 6 is between 1.6 and 3.4; the intrinsic viscosity of the polybutylene terephthalate is 0.5-1.1 dl/g.
The second aspect of the invention provides a polyamide 6-polybutylene terephthalate alloy which is prepared by melt blending the polyamide-polyester alloy composition provided by the invention, wherein the modified polypropylene contains 0.1-6 wt% of maleic anhydride structural units.
Preferably, the tensile strength of the alloy reaches more than 85 MPa; the bending strength reaches more than 100 MPa; the normal temperature impact strength is 6.8kJ/m2The above; the low-temperature impact strength is 6.5kJ/m2The above; preferably, the tensile strength is 90MPa or more.
By adopting the technical scheme, the polyamide-polyester alloy composition provided by the invention contains the mixed butylene-maleic anhydride copolymer microspheres, can be used for preparing polyamide 6-polybutylene terephthalate alloy with good compatibility, and has better mechanical property and tensile strength of more than 85 MPa; the bending strength reaches more than 100 MPa; the normal temperature impact strength is 6.8kJ/m2The above; the low-temperature impact strength is 6.5kJ/m2The above.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The present invention provides in a first aspect a polyamide-polyester alloy composition, wherein the composition comprises: 100 parts by weight of polyamide 6, 5-50 parts by weight of polybutylene terephthalate and 0.05-10 parts by weight of mixed butylene-maleic anhydride copolymer microspheres; wherein the particle size of the mixed butylene-maleic anhydride copolymer microsphere is 0.05-2 μm.
In the invention, the composition contains the mixed butylene-maleic anhydride copolymer microspheres with the particle size, so that the compatibility of the polyamide-polyester alloy can be effectively improved, and the polyamide 6-polybutylene terephthalate alloy with improved mechanical properties is obtained. The particle size can be measured by a scanning electron microscope method. Preferably, the particle size of the mixed butylene-maleic anhydride copolymer microsphere is 0.2-2 μm.
In the present invention, preferably, the mixed butene-maleic anhydride copolymerized microspheres are maleic anhydride and tetraolefin copolymerized microspheres prepared by copolymerizing mixed C4 and maleic anhydride in the presence of nitrogen, an initiator and an organic solvent. The copolymerization may be a one-step reaction using a precipitation polymerization method.
In the present invention, preferably, the content of the maleic anhydride structural unit in the mixed butene-maleic anhydride copolymerized microsphere is 30 to 70 mol%. In the mixed butylene-maleic anhydride copolymer microsphere, the maleic anhydride structural unit can be in a main chain, a side chain or an end group. The content of the maleic anhydride structural unit can be determined by1H and13c nuclear magnetic measurement. The mixed butylene-maleic anhydride copolymer microspheres can also contain olefin structural units formed by at least one of 1-butylene, 1, 3-butadiene and isobutene. The content of the olefin structural unit in the mixed butylene-maleic anhydride copolymerized microsphere can be determined by1H and13c nuclear magnetic measurement. The olefin building block content may be from 30 to 70 mol%.
In the present invention, preferably, the mixed butylene-maleic anhydride copolymer microspheres are copolymer microspheres of maleic anhydride and n-butylene and isobutylene. The mixed butylene-maleic anhydride copolymer microspheres mainly contain structural units from n-butylene and isobutylene.
The mixed butylene-maleic anhydride copolymerized microspheres used in the invention can use mixed carbon four as a raw material, and the mixed carbonAnd the fourth can come from various petroleum processing and refining processes and can be C4A mixture of hydrocarbon compounds. Preferably, the mixed carbon c contains at least one of 1-butene, isobutene, 1, 3-butadiene, n-butane, isobutane, cis-2-butene and trans-2-butene, and may be, for example, liquefied fuel produced from petroleum refining, cracked gas produced from naphtha cracking, gas produced from methanol to olefins, and the like. The composition of the mixed C.sub.D can be analyzed by gas chromatography using Agilent's 7890A Gas Chromatograph (GC).
Preferably, the compositional content of the mixed C.sub.D can be 1-99 wt% of 1-butene, 1-99 wt% of isobutylene, 0-99 wt% of 1, 3-butadiene, 0-50 wt% of 1, 2-butadiene, 0-99 wt% of n-butane, 1-99 wt% of isobutane, 5-20 wt% of vinyl acetylene, 0-99 wt% of cis-2-butene, and 1-99 wt% of trans-2-butene.
According to a preferred embodiment of the present invention, the composition content of the mixed C.sub.D may be 5-10 wt% of 1-butene, 5-15 wt% of isobutene, 10-20 wt% of 1, 3-butadiene, 5-15 wt% of 1, 2-butadiene, 0.5-5 wt% of n-butane, 0.5-2 wt% of isobutane, 20-40 wt% of cis-2-butene, 2-10 wt% of trans-2-butene, 5-20 wt% of vinyl acetylene.
According to another preferred embodiment of the present invention, the composition content of the mixed C.sub.D may be 0.1-2 wt% of 1-butene, 10-30 wt% of isobutene, 0.01-0.1 wt% of 1, 3-butadiene, 0.5-5 wt% of n-butane, 30-40 wt% of isobutane, 20-40 wt% of cis-2-butene, 5-20 wt% of trans-2-butene.
According to another preferred embodiment of the present invention, the compositional content of mixed C.sub.D may be 5-15 wt% of 1-butene, 0.5-3 wt% of isobutene, 20-30 wt% of n-butane, 15-30 wt% of cis-2-butene, 35-45 wt% of trans-2-butene.
In the present invention, 1-butene, isobutylene and 1, 3-butadiene in the mixed C.sub.four can be copolymerized with maleic anhydride. Preferably, the weight ratio of the mixed C4 to the maleic anhydride is (0.2-3): 1; preferably (0.8-3): 1.
in the invention, the initiator is used in an amount which ensures that the copolymerization reaction is carried out. Preferably, the initiator is used in an amount of 0.05 to 20 mol% based on the maleic anhydride. The initiator may be dibenzoyl peroxide or azobisisobutyronitrile.
In the present invention, the organic solvent is an inert solvent that does not participate in the copolymerization reaction, and provides a dispersion medium for the copolymerization reaction. Preferably, the concentration of maleic anhydride in the organic solvent is from 5% to 25% by weight; preferably 10 wt% to 20 wt%. The organic solvent is preferably at least one of isoamyl acetate, butyl acetate, isopropyl acetate and ethyl acetate.
In the present invention, the copolymerization reaction conditions may be conditions that enable the copolymerization reaction of the carbon tetraene and the maleic anhydride in the mixed carbon four. Preferably, the copolymerization reaction temperature is 50-100 ℃, preferably 70-90 ℃; the copolymerization pressure is 0.2-2MPa, preferably 0.5-1 MPa; the copolymerization reaction time is 5-10 h.
In the invention, a certain amount of mixed C4 is introduced into a reaction kettle containing a certain amount of maleic anhydride, an initiator and an organic solvent to carry out copolymerization reaction under the conditions of nitrogen atmosphere and the copolymerization reaction, and then the reaction product is subjected to flash separation and centrifugal separation to obtain the mixed butene-maleic anhydride copolymerized microspheres. Wherein, the mixed C4, the maleic anhydride, the initiator and the organic solvent are used in the same amount as described above. The flash separation may be carried out in a flash separator at about 25 ℃ and 0 MPa. The centrifugation may be carried out at a rotation speed of about 4000rpm for about 20 min. The obtained microspheres can be further washed by hexane and filtered by a sand core to obtain a filter cake, and after the filter cake is dried in vacuum at about 90 ℃ for about 8 hours, the obtained product is the mixed butylene-maleic anhydride copolymer microspheres with the particle size of 0.05-2 mu m, preferably 0.2-2 mu m, and the composition structure and the content of the mixed butylene-maleic anhydride copolymer microspheres can be further analyzed and used for the polyamide-polyester alloy modified composition.
In the present invention, the polyamide 6(PA6) is selected to be sufficient for preparing the alloy, and preferably, the relative viscosity of the polyamide 6 is 1.6 to 3.4. The relative viscosity can be determined using the standard ISO 307. Commercially available as e.g. barSpiro nylon 6-1 (relative viscosity 3.4, density 1.13 g/cm)3) Nylon 6-2 (relative viscosity 2.8, density 1.13 g/cm)3) Nylon 6-3 (relative viscosity 1.6, density 1.13 g/cm)3)
In the invention, the polybutylene terephthalate can be selected to meet the requirement of preparing the alloy. Preferably, the polybutylene terephthalate has an intrinsic viscosity of 0.5 to 1.1 dl/g. Intrinsic viscosity can be determined using standard QSHYH 084411. Commercially available PBT-1, e.g., Chinese petrochemical (intrinsic viscosity 0.5dl/g, density 1.30 g/cm)3) PBT-2 (intrinsic viscosity 0.9dl/g, density 1.31 g/cm)3) PBT-3 (intrinsic viscosity 1.1dl/g, density 1.30 g/cm)3)。
In the invention, the composition can also contain other auxiliary agents, and the performance of the prepared alloy is not influenced. The auxiliary may be at least one selected from a slipping agent, an antistatic agent, a lubricant and a plasticizer. Preferably, the polyamide-polyester alloy composition further comprises glycerol monostearate added in an amount of 1-10% by weight of the mixed butene-maleic anhydride copolymer microspheres. Can help to improve the dispersibility of the mixed butylene-maleic anhydride copolymer microspheres in the polyamide 6-polybutylene terephthalate alloy.
The second aspect of the invention provides a polyamide 6-polybutylene terephthalate alloy which is prepared by melt blending the polyamide-polyester alloy composition provided by the invention, wherein the polyamide 6-polybutylene terephthalate alloy contains 0.1-6 wt% of maleic anhydride structural units. 100 parts by weight of polyamide 6, 5-50 parts by weight of polybutylene terephthalate and 0.05-10 parts by weight of mixed butylene-maleic anhydride copolymer microspheres, preferably 100 parts by weight of polyamide 6, 10-30 parts by weight of polybutylene terephthalate and 0.2-5 parts by weight of mixed butylene-maleic anhydride copolymer microspheres, can be mixed into a mixture in a high-speed mixer; then adding the mixture into a double-screw extruder, and carrying out melt extrusion blending at the extrusion temperature of 120-260 ℃ to obtain the polyamide 6-polybutylene terephthalate alloy.
In the present invention, preferably, the operating conditions of the twin-screw extruder are: the temperature of the first zone is 120-.
The polyamide 6-polybutylene terephthalate alloy prepared by the polyamide-polyester alloy composition provided by the invention has improved mechanical properties. The resulting polyamide 6-polybutylene terephthalate alloy can be prepared as a test specimen, which is subjected to a corresponding test. Preferably, the tensile strength of the alloy reaches more than 85 MPa; the bending strength reaches more than 100 MPa; the normal temperature impact strength is 6.8kJ/m2The above; the low-temperature impact strength is 6.5kJ/m2The above; preferably, the tensile strength is 90MPa or more.
In the present invention, the pressures involved are gauge pressures.
The present invention will be described in detail below by way of examples and comparative examples.
In the following examples, densities were tested according to ASTM D792-2007 standard;
the relative viscosity is determined according to the standard ISO 307;
intrinsic viscosity is measured according to standard QSHYH 084411;
the tensile properties are tested according to ISO-527 standard;
the bending property is tested according to the ISO-178 standard;
the impact performance is tested according to the standard of a simply supported beam notch ISO-179;
the content of the maleic anhydride structural unit in the mixed butene-maleic anhydride copolymer microsphere and the modified polypropylene is determined by1H and13c, nuclear magnetism measurement;
the particle size of the mixed butene-maleic anhydride copolymer microspheres was measured by scanning electron microscopy.
The mixed C-C A comprises (by weight percent) 1, 2-butadiene, 8.92%; 1, 3-butadiene, 14.14%; 1-butene, 8.38%; trans-2-butene, 5.84%; cis-2-butene, 31.7%; vinyl acetylene, 10.99%; isobutane, 1.3%; isobutene, 12.78%; n-butane 2.58%, others, 3.37%.
The mixed C-B comprises the following components in percentage by weight: 1, 3-butadiene, 0.06%; trans-2-butene, 12.67%; isobutane, 37.09%; 19.48 percent of isobutene; cis-2-butene, 27.79%; 1-butene, 1.02%; others, 1.89%.
The mixed C-C comprises the following components in percentage by weight: trans-2-butene, 40.83%; cis-2-butene, 18.18%; 24.29 percent of n-butane; 1-butene, 9.52%; isobutene, 2.78%; others, 4.4%.
Nylon 6-1 was purchased from Pasteur, had a relative viscosity of 3.4 and a density of 1.13g/cm3；
Nylon 6-2 was purchased from Pasteur, had a relative viscosity of 2.8 and a density of 1.13g/cm3；
Nylon 6-3 is obtained from Chinese petrochemicals, has relative viscosity of 1.6 and density of 1.13g/cm3；
PBT-1 is purchased from China petrochemical industry, has an intrinsic viscosity of 0.5dl/g and a density of 1.30g/cm3；
PBT-2 purchased from China petrochemical industry, with intrinsic viscosity of 0.9dl/g and density of 1.31g/cm3；
PBT-3 purchased from China petrochemical industry, with intrinsic viscosity of 1.1dl/g and density of 1.30g/cm3。
Examples 1 to 5, optimization examples 1 to 3
(1) Preparing mixed butylene-maleic anhydride copolymer microspheres:
under the protection of nitrogen, 15kg of mixed C-IV A is introduced into a 200L reaction kettle containing 20kg of organic reaction liquid of maleic anhydride, 4.8kg of dibenzoyl peroxide and 100L of isoamyl acetate for copolymerization reaction, the copolymerization reaction pressure is 0.9MPa, the copolymerization reaction temperature is 80 ℃, and the copolymerization reaction time is 8 h;
and introducing the copolymerization reaction product into a flash separator for gas-liquid separation at 26 ℃ and 0MPa, continuously performing liquid-solid separation on the obtained liquid-solid mixture in a centrifugal separator at 6000rpm for 25min to obtain a solid product, washing with hexane, and performing vacuum drying on a filter cake obtained by suction filtration of a sand core funnel for 8h at 90 ℃ to obtain copolymer powder. The copolymer powder was subjected to a test in which the content of maleic anhydride structural units was 53 mol%; the average particle size of the particles was 1 μm.
(2) According to the components and the using amount of the composition listed in the table 1, the copolymer powder (mixed butylene-maleic anhydride copolymerized microspheres) obtained in the step (1), nylon 6-1 and PET-1 are put into a high-speed mixer to be mixed; and adding the obtained mixture into a double-screw extruder for melt extrusion to obtain the polyamide 6-polybutylene terephthalate alloy.
The working conditions of the twin-screw extruder are as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 270 ℃, the temperature of the sixth zone is 260 ℃ and the temperature of the machine head is 260 ℃. Drying, injection molding by an injection molding machine to obtain a test sample strip, and performing mechanical test. The test results are shown in Table 2.
Comparative example 1
According to the proportion in the table 1, nylon 6-1 and PBT-1 are added into a high-speed mixer to be uniformly mixed, and then are added into a double-screw extruder, wherein the working conditions of the double-screw extruder are as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 270 ℃, the temperature of the sixth zone is 260 ℃ and the temperature of the machine head is 260 ℃. Drying, injection molding by an injection molding machine to obtain a test sample strip, and performing mechanical test. The test results are shown in Table 2.
Examples 6 to 10
(1) Preparing mixed butylene-maleic anhydride copolymer microspheres:
under the protection of nitrogen, 15.5kg of mixed C-IV B is introduced into a 200L reaction kettle containing 20kg of maleic anhydride, 2.5kg of azodiisobutyronitrile and 100L of isoamyl acetate to carry out copolymerization reaction, the pressure of the copolymerization reaction is 1.5MPa, the temperature of the copolymerization reaction is 80 ℃, and the time of the copolymerization reaction is 6 hours;
and introducing the copolymerization reaction product into a flash separator for gas-liquid separation at the temperature of 28 ℃ and under the pressure of 0MPa, continuously performing liquid-solid separation on the obtained liquid-solid mixture in a centrifugal separator at 8000rpm for 20min to obtain a solid product, washing with hexane, and performing vacuum drying on a filter cake obtained by suction filtration of a sand core funnel for 8h at the temperature of 90 ℃ to obtain copolymer powder. The copolymer powder was subjected to a test in which the content of maleic anhydride structural units was 52 mol%; the average particle size of the particles was 0.2. mu.m.
(2) Adding the copolymer powder (mixed butylene-maleic anhydride copolymer microspheres) obtained in the step (1), nylon 6-2 and PET-2 into a high-speed mixer to mix according to the components and the using amount of the composition listed in the table 1; and adding the obtained mixture into a double-screw extruder for melt extrusion to obtain the polyamide 6-polybutylene terephthalate alloy.
The working conditions of the twin-screw extruder are as follows: the temperature of the first zone is 120 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 230 ℃ and the temperature of the machine head is 230 ℃. Drying, injection molding by an injection molding machine to obtain a test sample strip, and performing mechanical test. The test results are shown in Table 2.
Comparative example 2
According to the mixture ratio in the table 1, the nylon 6-2 and the PBT-2 are added into a high-speed mixer to be uniformly mixed, and then are added into a double-screw extruder, wherein the working conditions of the double-screw extruder are as follows: the temperature of the first zone is 120 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 230 ℃ and the temperature of the machine head is 230 ℃. Drying, injection molding by an injection molding machine to obtain a test sample strip, and performing mechanical test. The test results are shown in Table 2.
Examples 11 to 15
(1) Preparing mixed butylene-maleic anhydride copolymer microspheres:
under the protection of nitrogen, 13.6kg of mixed C-C is introduced into a 200L reaction kettle containing 20kg of maleic anhydride, 4.2kg of dibenzoyl peroxide and 100L of isoamyl acetate to carry out copolymerization reaction, wherein the copolymerization reaction pressure is 0.9MPa, the copolymerization reaction temperature is 70 ℃, and the copolymerization reaction time is 6 h;
and introducing the copolymerization reaction product into a flash separator for gas-liquid separation at the temperature of 27 ℃ and under the pressure of 0MPa, continuously performing liquid-solid separation on the obtained liquid-solid mixture in a centrifugal separator at 8000rpm for 20min to obtain a solid product, washing with hexane, and performing vacuum drying on a filter cake obtained by suction filtration of a sand core funnel for 8h at the temperature of 90 ℃ to obtain copolymer powder. The copolymer powder was subjected to a test in which the content of maleic anhydride structural units was 55 mol%; the average particle size of the particles was 2 μm.
(2) According to the components and the using amount of the composition listed in the table 1, the copolymer powder (mixed butylene-maleic anhydride copolymerized microspheres) obtained in the step (1), nylon 6-3 and PET-3 are put into a high-speed mixer to be mixed; and adding the mixture into a double-screw extruder for melt granulation to obtain the polyamide 6-polybutylene terephthalate alloy.
The working conditions of the twin-screw extruder are as follows: the temperature of the first zone is 180 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 240 ℃ and the temperature of the machine head is 240 ℃. Drying, injection molding by an injection molding machine to obtain a test sample strip, and performing mechanical test. The test results are shown in Table 2.
Comparative example 3
According to the mixture ratio in the table 1, the nylon 6-3 and the PBT-3 are added into a high-speed mixer to be uniformly mixed, and then are added into a double-screw extruder, wherein the working conditions of the double-screw extruder are as follows: the temperature of the first zone is 180 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 240 ℃ and the temperature of the machine head is 240 ℃. Drying, injection molding by an injection molding machine to obtain a test sample strip, and performing mechanical test. The test results are shown in Table 2.
TABLE 1
Mixed butene-maleic anhydride copolymer microspheres
The data in table 1 are parts by weight.
TABLE 2
As can be seen from the results of examples, comparative examples and tables 1 to 2, the polyamide-6-polybutylene terephthalate alloy prepared using the polyamide-polyester alloy composition provided by the present invention can have excellent mechanical propertiesAnd (4) performance. Particularly, it has excellent tensile strength, bending strength and impact strength. Wherein the tensile strength is more than 85MPa, preferably more than 90 MPa; the bending strength reaches more than 100 MPa; normal temperature impact strength 6.8kJ/m2Above, low temperature impact strength of 6.5kJ/m2The above.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (32)
1. A polyamide-polyester alloy composition, characterized in that it comprises: 100 parts by weight of polyamide 6, 5-50 parts by weight of polybutylene terephthalate and 0.05-10 parts by weight of mixed butylene-maleic anhydride copolymer microspheres;
wherein the particle size of the mixed butylene-maleic anhydride copolymer microsphere is 0.05-2 μm.
2. The composition of claim 1, wherein the composition comprises: 100 parts by weight of polyamide 6, 10-30 parts by weight of polybutylene terephthalate and 0.2-5 parts by weight of mixed butylene-maleic anhydride copolymer microspheres;
wherein the particle size of the mixed butylene-maleic anhydride copolymer microsphere is 0.2-2 μm.
3. The composition of claim 1 or 2, wherein the mixed butene-maleic anhydride copolymerized microspheres have a maleic anhydride structural unit content of 30 to 70 mol%.
4. The composition of claim 1 or 2, wherein the mixed butene-maleic anhydride copolymerized microspheres are a copolymer of maleic anhydride and a carbon tetraene prepared by copolymerization of mixed carbon four and maleic anhydride in the presence of nitrogen, an initiator and an organic solvent.
5. The composition of claim 4, wherein the mixed butylene-maleic anhydride copolymer microspheres are copolymer microspheres of maleic anhydride and n-butylene and isobutylene.
6. The composition of claim 3, wherein the mixed butene-maleic anhydride copolymerized microspheres are a copolymer of maleic anhydride and a carbon tetraene prepared by copolymerization of mixed carbon four and maleic anhydride in the presence of nitrogen, an initiator and an organic solvent.
7. The composition of claim 6, wherein the mixed butylene-maleic anhydride copolymer microspheres are copolymer microspheres of maleic anhydride and n-butylene and isobutylene.
8. The composition of claim 4, wherein the weight ratio of mixed C4 to maleic anhydride is (0.2-3): 1;
and/or the initiator is used in an amount of 0.05 to 20 mol% based on the maleic anhydride.
9. The composition of claim 8, wherein the weight ratio of mixed carbon four to maleic anhydride is (0.8-3): 1.
10. the composition of any of claims 5-7, wherein the weight ratio of mixed C4 to maleic anhydride is (0.2-3): 1;
and/or the initiator is used in an amount of 0.05 to 20 mol% based on the maleic anhydride.
11. The composition of claim 10, wherein the weight ratio of mixed carbon four to maleic anhydride is (0.8-3): 1.
12. the composition of claim 4, wherein the concentration of maleic anhydride in the organic solvent is 5-25% by weight.
13. The composition of claim 12, wherein the concentration of maleic anhydride in the organic solvent is 10-20% by weight.
14. The composition of any of claims 5-7, wherein the concentration of maleic anhydride in the organic solvent is 5-25 wt%.
15. The composition of claim 14, wherein the concentration of maleic anhydride in the organic solvent is 10-20% by weight.
16. The composition of claim 4, wherein the copolymerization temperature is 50-100 ℃; the copolymerization pressure is 0.2-2 MPa; the copolymerization reaction time is 5-10 h.
17. The composition of claim 16, wherein the copolymerization temperature is 70-90 ℃; the copolymerization pressure is 0.5-1 MPa.
18. The composition of claim 10, wherein the copolymerization temperature is 50-100 ℃; the copolymerization pressure is 0.2-2 MPa; the copolymerization reaction time is 5-10 h.
19. The composition of claim 18, wherein the copolymerization temperature is 70-90 ℃; the copolymerization pressure is 0.5-1 MPa.
20. The composition of claim 14, wherein the copolymerization temperature is 50-100 ℃; the copolymerization pressure is 0.2-2 MPa; the copolymerization reaction time is 5-10 h.
21. The composition of claim 20, wherein the copolymerization temperature is 70-90 ℃; the copolymerization pressure is 0.5-1 MPa.
22. The composition of any of claims 5-9, 11-13, 15, wherein the copolymerization temperature is 50-100 ℃; the copolymerization pressure is 0.2-2 MPa; the copolymerization reaction time is 5-10 h.
23. The composition of claim 22, wherein the copolymerization temperature is 70-90 ℃; the copolymerization pressure is 0.5-1 MPa.
24. The composition of any of claims 1,2, 5-9, 11-13, 15-21, 23, wherein the polyamide 6 has a relative viscosity of 1.6-3.4; the intrinsic viscosity of the polybutylene terephthalate is 0.5-1.1 dL/g.
25. The composition of claim 3, wherein the polyamide 6 has a relative viscosity of 1.6 to 3.4; the intrinsic viscosity of the polybutylene terephthalate is 0.5-1.1 dL/g.
26. The composition of claim 4, wherein the polyamide 6 has a relative viscosity of 1.6 to 3.4; the intrinsic viscosity of the polybutylene terephthalate is 0.5-1.1 dL/g.
27. The composition of claim 10, wherein the polyamide 6 has a relative viscosity of 1.6 to 3.4; the intrinsic viscosity of the polybutylene terephthalate is 0.5-1.1 dL/g.
28. The composition of claim 14, wherein the polyamide 6 has a relative viscosity of 1.6 to 3.4; the intrinsic viscosity of the polybutylene terephthalate is 0.5-1.1 dL/g.
29. The composition of claim 22, wherein the polyamide 6 has a relative viscosity of 1.6 to 3.4; the intrinsic viscosity of the polybutylene terephthalate is 0.5-1.1 dL/g.
30. A polyamide 6-polybutylene terephthalate alloy made by melt blending the polyamide-polyester alloy composition of any one of claims 1-29, wherein the polyamide 6-polybutylene terephthalate alloy contains 0.1-6 wt% maleic anhydride structural units.
31. The alloy of claim 30, wherein the alloy has a tensile strength of 85MPa or greater; the bending strength reaches more than 100 MPa; the normal temperature impact strength is 6.8kJ/m2The above; the low-temperature impact strength is 6.5kJ/m2The above.
32. An alloy as set forth in claim 31 wherein the tensile strength is up to 90MPa or greater.
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