CN113773508A - Polyester/nylon composite material, preparation method and application thereof - Google Patents

Polyester/nylon composite material, preparation method and application thereof Download PDF

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CN113773508A
CN113773508A CN202110963653.XA CN202110963653A CN113773508A CN 113773508 A CN113773508 A CN 113773508A CN 202110963653 A CN202110963653 A CN 202110963653A CN 113773508 A CN113773508 A CN 113773508A
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polyester
nylon
composite material
nylon composite
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CN113773508B (en
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姚臻
叶骐瑜
马小珺
陈宁洁
胡激江
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Zhejiang University ZJU
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    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a polyester/nylon composite material, a preparation method and application thereof, wherein the polyester/nylon composite material comprises amide group- [ NHCO ]]- [ COO ] ester group]-and an inner compatibilising segment; the mass content of polyester in the polyester/nylon composite material is 20-80%; the internal compatiblizing segment comprises-SO2-NH-groups and having a polyester/nylon internal compatibilising interface, said internal compatibilising segment having a characteristic shoulder peak in the nuclear magnetic carbon spectrum with a chemical shift in the interval 118ppm to 119 ppm. According to the invention, the modified polyester grafted on the polyester macromolecular chain by the sulfonate compound and the nylon are subjected to ester exchange reaction, and the formed internal compatibilization chain segment can enhance the compatibility of the polyester and the nylon, so that the prepared polyester/nylon composite material has good mechanical properties, and can also be applied to the fields of textile fibers, engineering plastics and the like.

Description

Polyester/nylon composite material, preparation method and application thereof
Technical Field
The invention relates to the field of polymer composite materials, in particular to a polyester/nylon composite material, a preparation method and application thereof.
Background
Nylon is a general name of thermoplastic resin containing repeated amide groups- [ NHCO ] -on the main chain of the molecule, and is a polymer material with wide application, and the annual output is in the ten million ton class. The aliphatic nylon as engineering plastic has the advantages of low specific gravity, high tensile strength, excellent impact resistance, good wear resistance and self-lubrication, and difficult thermal cracking during molding; the fiber has the advantages of good wear resistance, rebound resilience, color fastness, static resistance and pilling resistance, and the fabric has soft hand feeling; the defects are easy water absorption, large shrinkage ratio, poor dimensional stability, insufficient light resistance, no acid and alkali resistance and poor fabric shape retention. For example: nylon 6(PA6) and nylon 66(PA 66). The (semi) aromatic nylon has excellent heat resistance and mechanical properties, but has high melting point and is difficult to process. For example: poly (m-xylylene adipamide) (MXD6), poly (hexamethylene (p) terephthalamide) (PA6 ICoT).
The polyester is a general name of thermoplastic resin which is obtained by polycondensing polyhydric alcohol and polybasic acid and contains repeated ester bonds- (COO) -on the main chain, and is a polymer material with wide application, and the annual output is in the level of ten million tons. The polyester mainly comprises (semi) aromatic polymers, and has the advantages of high strength, high rigidity, good creep resistance, low hygroscopicity, outstanding electrical insulation, small thermal expansion coefficient, good high-temperature dimensional stability and excellent UV resistance when being used as engineering plastics; the heat resistance of the chemical fiber is good, and the prepared fabric is stiff and smooth and is not easy to deform. The disadvantages are that: high specific gravity, easy degradation during processing, low long-term use temperature in water, acid and alcohol resistance, insufficient fiber resilience, poor hygroscopicity, poor fabric air permeability, easy generation of static accumulation and easy fluffing. Such as polyethylene terephthalate (PET), which is the most used synthetic fiber, and polybutylene terephthalate (PBT), which is mainly used as engineering plastic. In addition, aliphatic polyester is a main biodegradable polymer material, but has poor thermal and mechanical properties and limited application range. For example: polylactic acid (PLA), polybutylene succinate (PBS), and the like.
With the increasing demand for high performance materials, it is increasingly important to modify nylon and polyester with a single component. In a two-phase system, some degree of permeation between the different components occurs, thereby forming a new interface where interfacial tension can drive the two-phase aggregation to occur. The smaller the interfacial tension, the better the compatibility of the two phases, which is expressed in that the interface becomes irregular and the volume of the dispersed phase becomes small, and the boundary between the dispersed phase and the matrix phase becomes fuzzy.
Polyesters and nylons are affected by structure and end groups, have very high enthalpy of mixing, are thermodynamically incompatible, exhibit an incompatible state upon blending, cause macroscopic phase separation, and greatly affect the thermal and mechanical properties of the composite (e.g., HUANG Y Q, LIU Y X, ZHAO C H. morphology and properties of PET/PA-6/E-44blends [ J ].1998,69(8): 1505-. As in comparative example 1, the content of nylon is high, and when the composite material obtained by directly reacting polyester and nylon is used as a matrix phase, SEM images of the composite material after etching are shown in fig. 9 (b)/fig. 3 (a)/fig. 10(a), and the polyester particles are in the form of agglomerated and stacked spherical particles, which shows that the interfacial tension between the two phases is very large, and the compatibility is poor. As comparative example 2, when the polyester content is high and the polyester is used as a matrix phase, SEM images of the composite obtained by directly reacting the polyester and the nylon after etching are shown in fig. 9 (a)/3 (c), the shape of the etched hole interface is a regular circle, which indicates that the interface tension between the two phases is very large, and the compatibility is poor. Therefore, the compatibility of the two polymers is improved to change the microscopic chain structure and the aggregation state structure of the copolymer, so that a macroscopically compatible and microscopically separated composite material is obtained, the excellent performances of the two materials are expressed, and the method has very important significance.
At present, only a third component, mainly a compatibilizer or a compatilizer (external compatibilizer and external compatilizer for short) or an external catalyst (external catalyst for short), can be added in the method for improving the compatibility of the polyester/nylon composite material. And adding an external compatibilizer or an external catalyst of the third component to promote the ester-amide exchange reaction of the polyester and the nylon (the reaction general formula is shown as follows):
Figure BDA0003223065380000021
an external Compatibilizer (compatilizer), namely a third component is added to participate in the blending process, generally, the principle of compatibilization of the external Compatibilizer is that the external Compatibilizer can react with two raw materials respectively, so that the bonding force of an interface is enhanced, the compatibility of a system is further improved, and the external Compatibilizer is also called a Chain extender (Chain extender) in some occasions. Epoxy compounds, bisoxazoline compounds, diisocyanate compounds and the like, which are commonly used as external compatibilizers for polyester/nylon systems, and also triphenyl phosphite, pyromellitic dianhydride and the like have been studied. Among epoxy compounds, low molecular weight bisphenol A epoxy resin E-44 is particularly widely used. Huang et al (Huang Y Q, LIU Y X, ZHAO C H. morphology and properties of PET/PA-6/E-44blends [ J ].1998,69(8): 1505-. Other test results show that the mechanical property of the blend added with the external compatibilizer is greatly improved, and the impact strength and the bending strength can be improved by 500 percent and 400 percent. Phenoxy resins are the reaction product of diglycidyl ether of bisphenol a with other bisphenol a and are essentially thermoplastics. Dharaiya et al (DHARAIYA D, JANA S C, SHAFI A.A study on the use of phenoxy resins as compatibilizers of polyamide 6(PA6) and polybutylene terephthalate (PBT) [ J ] PolymEng Sci,2003,43(3):580-595.) add two phenoxy resins to the PA6/PBT blend system to improve the compatibility of the blend, the principle of compatibilization is that PBT and phenoxy resins can form a copolymer in situ, and form a super-strong interaction with PA6 through hydrogen bonds, improving the binding force between the raw materials. The grafted maleic anhydride reacts readily with the amino end groups of the polyamide and with the hydroxyl end groups of the polyester, linking the two materials to form a block copolymer. A study by Kim et al (KIM S J, KIM D K, CHO W J, et al. morphology and properties of PBT/nylon6/EVA-g-MAH tertiary blends passive by reactive exclusion [ J ]. PolymEng Sci,2003,43(6):1298 and 1311.) produced a PBT/PA6/EVA-g-MAH ternary blend which was melt blended in a twin screw extrusion. The experimental result shows that the compatibility of the ternary blend is better than that of the PBT/PA 6blend, and the structure characterization result shows that the PBT-g-EVA-g-MAH copolymer is generated. However, the grafting rate of PA6 grafted to MAH is extremely high, which also results in weakening the compatibility with PBT and reducing the performance, so that the control of the addition sequence of EVA-g-MAH is the key for greatly improving the compatibility and optimizing the performance. Jubinville et al (Jubinville D, Chang B P, PIN J M, et al. synthetic thermo-oxidative catalysis of PA11 as compatibility development for PA6 and PBT blend [ J ] Polymer,2019,179:391) explored the effect of PA11C bio-based compatibilizers on PBT/PA 6blend systems. The combination of maleation and the thermal oxidation of the main chain of PA11 can improve the hydrophilic/hydrophobic balance and provide functional groups participating in the reaction during reactive extrusion, the dispersed phase has large size and reduced amplitude, and the Tan delta curve in the DMA result changes from two wider peaks to one narrower peak, which can indicate that the compatibility of the system is improved. After the addition of the external compatibilizer, the mechanical properties of the blend are improved, and become remarkable along with the increase of the content of PA 11C.
The polyester and the nylon can also generally have ester exchange reaction, and the compatibility of a blending system can be improved by adding an external compatibilizer, and the compatibility can also be improved by promoting the ester exchange reaction. For polyester/nylon blend systems, transesterification reactions can generally be promoted by the addition of an external catalyst. The most commonly used catalyst is p-toluenesulfonic acid (TsOH). Sun et al (YAO Z, SUN J M, WANG Q, et al. study on Ester-Amide Exchange Reaction between PBS and PA6ICOT [ J ],2012,51(2):751-757.) add TsOH in the system of poly (butylene succinate) (PBS) and poly (p-phenylene terephthalamide hexamethylene diamine) (PA6ICOT), and perform transesterification Reaction in a horizontal Reaction kettle for 0.5 h-2 h to improve the thermal and mechanical properties of the synthesized biodegradable polymer. Chloroform is used as a solvent for solubility experiments, and the structure of the product is subjected to detailed characterization analysis. The results show that the interfacial tension between the two phases is significantly reduced after adding TsOH, the size of the dispersed phase becomes smaller, the uniformity is improved, and the compatibility is greatly improved, as shown in fig. 2 (Figure 4 in the literature). After quantitative analysis, TsOH was found to be an effective catalyst for the transesterification reaction. The degree of randomness and degree of reaction of the copolymer reaches a maximum when the ratio of the two polymers approaches 1: 1. Samperi et al (SAMPERI F, MONTAUDO M, PUGLISIS C, et al. essential role of chains in the Ny6/PBT exchange. A combined NMR and MALDI approach [ J ]. Macromolecules,2003,36(19):7143-7154.) have emphatically used this method to quantitatively analyze the transesterification reaction of PA6/PBT blend systems, and have shown that the carboxyl end groups play a decisive role in the exchange reaction, only the carboxyl end groups of PBT and PA6 are able to react in the PA6/PBT blend and the composition of the copolymer depends on the extent of the exchange reaction. TsOH can catalyze the transesterification of polyester with a single nylon or with multiple nylons. Evstatiev et al (EVSTATIEV M, SCHULTZ J M, FAKIROV S, et al. in situ particulate Reinforced PET/PA-6/PA-66blend [ J ]. PolymEng Sci,2001,41(2): 192-. 204.) prepared a ternary blend of PET/PA6/PA66, and added TsOH as a catalyst, improved the compatibility of the system and improved the mechanical properties of the blend.
The direct addition of external compatibilizers complicates the process steps and increases the cost, there are differences in the reactivity of the groups during the reaction, the reaction is difficult to control, undesirable side reactions such as crosslinking can occur, and the addition of a third component of external compatibilizers can also cause the weakening of certain properties (e.g., KIM S J, KIM D K, CHO W J, et al. morphology and properties of PBT/nylon6/EVA-g-MAH tertiary blends predicted by reactive extrusion [ J ]. polymEng Sci,2003,43(6):1298 + 1311.). In comparative example 3, after etching a composite material obtained by reacting polyester and nylon for 3min in the presence of a catalyst, an SEM image is shown in FIG. 10(c), and polyester particles are in a form of agglomeration and accumulation of spherical particles, which indicates that the interfacial tension between two phases is very large and the compatibility is poor; and the requirement on the reaction kettle is high, and nitrogen is required to be continuously blown, so that the cost of the production process is increased, the period of the preparation process of the composite material is prolonged, and meanwhile, the polymer can be degraded due to long-time high temperature, and the structure of a molecular chain is damaged.
At present, the composite material with compatible polyester and nylon interfaces cannot be obtained under the condition of not adding a third component (external compatibilizer or external catalyst) compatibilizer. If the external compatibilizer is added, the process steps become complicated, the cost is increased, undesirable side reactions such as crosslinking and the like can occur in the reaction process, and certain properties can be weakened; if the external catalyst is added, longer reaction time is needed, which is not beneficial to the application of the polyester/nylon composite material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polyester/nylon composite material, a preparation method and application thereof, wherein the polyester/nylon composite material is characterized in that a sulfonic acid group in a sulfonate compound is directly grafted to a macromolecular chain of polyester to form modified polyester, and the sulfonic acid group and an amide group of nylon are subjected to chemical reaction to obtain an inner compatibilization chain segment, so that the compatibility problem of the polyester/nylon composite material is solved.
Different from the existing method for improving the compatibility of the polyester/nylon composite material by adding a third component (an external compatibilizer or an external catalyst), the method has the advantages that the third component is not added, the modified polyester containing sulfonate groups is reacted with nylon, the polyester/nylon composite material can be obtained within a few minutes by a simple melting reaction process, the sulfonate groups of the modified polyester and the amide groups of the nylon are subjected to chemical reaction to obtain the internal compatibilization chain segments, and the mass content of the polyester in the polyester/nylon composite material is 20-80%; the internal compatiblizing segment comprises-SO2The polyester/nylon composite material has an NH-group and a polyester/nylon internal compatibilization interface, the internal compatibilization chain segment has a characteristic shoulder peak with a chemical shift in a range of 118ppm to 119ppm in a nuclear magnetic carbon spectrum, the internal compatibilization chain segment plays a role of a compatilizer, and the problem of compatibility between polyester and nylon is solved under the condition that a third component (an external compatibilizer or an external catalyst) is not added, so that the polyester/nylon composite material with better mechanical property is obtained.
The invention adopts the following technical scheme:
the invention provides a polyester/nylon composite material, which comprises amide group- [ NHCO ]]Ester group- (R) -methyl ester[COO]-and an inner compatibilising segment; the mass content of polyester in the polyester/nylon composite material is 20-80%; the internal compatiblizing segment comprises-SO2-an NH-group and having a polyester/nylon internal compatibilising interface, said internal compatibilising segment having a characteristic shoulder peak in the nuclear magnetic carbon spectrum with a chemical shift in the interval 118ppm to 119 ppm; preferably, the mass content of the polyester in the polyester/nylon composite material is 40-60%; preferably, the method for detecting the mass content of the polyester in the polyester/nylon composite material comprises the following steps: the polyester/nylon composite material is etched by formic acid for more than 2 hours, the rest part is dried in vacuum for 24 hours, and the mass content of the polyester in the polyester/nylon composite material obtained by the detection method is that
Figure BDA0003223065380000041
Wherein w represents the mass of the polyester/nylon composite material before etching with formic acid, and w1Represents the mass of the remaining part after vacuum drying; preferably, the mass content of the polyester in the polyester/nylon composite material obtained by the detection method is allowed to have an error of 20% with the mass content of the polyester in the actual polyester/nylon composite material, and the mass content of the polyester in the actual polyester/nylon composite material is within a range
Figure BDA0003223065380000042
Wherein w represents the mass of the polyester/nylon composite material before etching with formic acid, and w1Representing the mass of the remaining portion after vacuum drying.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.
Preferably, the detection method of the polyester/nylon internal compatibilization interface comprises the following steps: the polyester/nylon composite material is etched by formic acid for more than 2 hours, the appearance of the rest part is observed by SEM images with the magnification of 1000-20000 times, and the internal compatibilization interface is in an irregular structure or an amorphous structure; preferably, the etching time is 2-6 h; preferably, the inner volume-increasing interface does not have an agglomerated and stacked structure of spherical particles or a regular pore structure, the particle size of the spherical particles is 0.1-3 μm, and the pore size of the regular pores is 0.5-3 μm.
Preferably, the regular hole structure is a regular circular structure. Preferably, the irregular structure is selected from an irregular gully-like structure and an irregular honeycomb-like structure.
Preferably, the length-diameter ratio of the irregular gully-shaped structure is more than or equal to 3.
Preferably, the surface of the irregular gully-shaped structure is provided with spherical particles; the particle diameter of the spherical particles is 10 nm-500 nm.
Preferably, the surface of the irregular honeycomb structure is provided with micropores; the aperture of the micropore is 50 nm-800 nm.
Preferably, the amorphous structure is a smooth amorphous structure.
Preferably, the smooth amorphous structure surface is provided with spherical particles; the particle diameter of the spherical particles is 100 nm-500 nm.
Preferably, the amorphous structure is formed by mutually binding and stacking irregular particles, and the particle size of the irregular particles is 1 nm-50 nm.
Preferably, the surface of the amorphous structure formed by mutually bonding and stacking the irregular particles is provided with micropores, and the pore diameter of the micropores is 10 nm-100 nm.
The invention also provides a preparation method of the polyester/nylon composite material, which comprises the following steps: mixing modified polyester and nylon, reacting in a molten state, and rapidly cooling to a temperature below a specific temperature to obtain the polyester/nylon composite material;
the modified polyester comprises a sulfonate group; preferably, the modified polyester is obtained by modifying polyester with a sulfonate compound; more preferably, the sulfonate compound is selected from one or more of sodium 2-hydroxy-3-allyloxypropanesulfonate, sodium 2-hydroxy-3-methacryloxypropanesulfonate, isoprene sulfonate, sodium sulfonate and potassium sulfonate;
the mass ratio of the modified polyester to the nylon is 8: 2-2: 8; preferably, the mass ratio of the modified polyester to the nylon is 6: 4-4: 6;
the specific temperature is lower than the temperature of the lower of the glass transition temperatures of both the modified polyester and the nylon; preferably, the specific temperature is 20 ℃ or more lower than that lower than the glass transition temperature;
the time for rapid cooling is less than or equal to 2 min. I.e., cooled to below the glass transition temperature of both the modified polyester and the nylon (a temperature lower than the lower glass transition temperature of both the modified polyester and the nylon) within 2 min.
Preferably, the polyester is selected from one or more of single-component polyester or modified polyester, the single-component polyester is selected from one or more of polyethylene terephthalate, polybutylene terephthalate, polylactic acid and polybutylene succinate, and the modified polyester is selected from one or more of cationic dyeable modified polyester, antistatic modified polyester and flame retardant modified polyester of the single-component polyester;
preferably, the nylon is selected from one-component polyamide or copolyamide, and the one-component polyamide is selected from one or more of nylon6, nylon 66, nylon 610, nylon 612, nylon 6I, polyhexamethylene terephthalamide, polyhexamethylene isophthalamide, polyhexamethylene adipamide and modified nylon; the modified nylon is selected from one or more of single-component polyamide reinforced nylon, flame-retardant nylon, transparent nylon, wear-resistant nylon and toughened nylon.
Preferably, the sulfonate compound is grafted onto the backbone of the polyester.
Preferably, the sulfonate compound accounts for 1-8 wt% of the modified polyester.
Preferably, the modified polyester accounts for 20 wt% -80 wt% of the polyester/nylon composite material.
Preferably, the nylon accounts for 20 wt% -80 wt% of the polyester/nylon composite material.
Preferably, the sufficient drying is performed by using high-temperature vacuum; the temperature range of the high temperature is as follows: 80-120 ℃; the pressure range of the vacuum is 100 Pa-50000 Pa; the time for fully drying is 8-24 h.
Preferably, the time for rapid cooling is less than or equal to 1 min; more preferably, the time for the rapid cooling is less than or equal to 0.5 min.
Preferably, the reaction is carried out in a twin screw extruder; the reaction temperature is 150-350 ℃; the reaction time is 1-10 min.
Preferably, the temperature of the reaction is 250-280 ℃; the reaction time is 1-5 min.
Preferably, the method comprises the following steps: after the reaction is finished, carrying out solid-phase reaction for 1-20 h in an inert gas atmosphere at the temperature of 120-280 ℃ to obtain the polyester/nylon composite material; preferably, the inert gas is nitrogen.
The invention also provides a composite comprising the polyester/nylon composite material; preferably, the compound comprises an additive, wherein the additive refers to an auxiliary material for improving the performance of the compound or reducing the cost; preferably, the additive is selected from one or more of fillers, pigments, plasticizers, antioxidants, and the filler is selected from one or more of inorganic fillers, flame retardants, impact modifiers, electrically conductive fillers, thermally conductive fillers, and reinforcing fibers.
The invention also provides a polyester/nylon composite material and application of the composite containing the polyester/nylon composite material in the field of fibers.
The polyester/nylon composite material in the prior art overcomes the defect that an external compatibilizer or an external catalyst must be added for the compatibility of polyester and nylon, the preparation method of the polyester/nylon composite material overcomes the technical bias of the prior art, modified polyester is obtained by grafting a sulfonic acid group on the polyester, the modified polyester reacts with the nylon to form an internal compatibilization chain segment, the internal compatibilization chain segment plays the role of the compatibilizer, the problem of the compatibility between the polyester and the nylon is solved, the polyester/nylon composite material with better mechanical property is obtained, and at least one of the following technical effects is achieved:
1. the sulfonate compound is connected to a polyester macromolecular chain to form new modified polyester, the modified polyester reacts with nylon to generate polyester/nylon composite in one step, the sulfonate group of the modified polyester and the amide group of the nylon react chemically to obtain an internal compatibilization chain segment, and the mass content of the polyester in the polyester/nylon composite material is 20-80%; the internal compatiblizing segment comprises-SO2-NH-group and having an internal compatibilization interface of polyester/nylon, said internal compatibilizing segment having a characteristic shoulder peak in the nuclear magnetic carbon spectrum with a chemical shift in the interval 118ppm to 119ppm, said internal compatibilizing segment substantially increasing the compatibility of polyester and nylon.
2. Compared with the prior art, the invention has short reaction time, can generate the block copolymer in a few minutes, realizes the micro-mixing of the polyester and the nylon, and has the effect superior to the reaction result of the prior art for three hours.
3. Due to the improvement of compatibility, the composite product prepared by the invention has outstanding performance and mechanical property superior to that of a nylon raw material; meanwhile, the polyester contained in the product has better cost than nylon, low price and high quality, and has wide application occasions.
4. The method has the advantages of short reaction time, simple process, less side reaction and good industrialization capability.
Drawings
FIG. 1 is a SEM cross-section of a PET/PA-6/E-44blend (HUANG Y Q, LIU Y X, ZHAO C H. morphology and properties of PET/PA-6/E-44blends [ J ].1998,69(8): 1505-;
FIG. 2 is a diagram of the morphology of the dispersed phase with PBS as the matrix phase in a PBS/PA6ICOT mixture [ PBS/PA/catalyst (wt%), mixing time ] (YAO Z, SUN J M, WANG Q, et al. study on Ester-Amide Exchange Reaction between PBS and PA6ICOT [ J ],2012,51(2): 751-757.);
FIG. 3 is a SEM image of compatibility testing standard for polyester/nylon systems (magnification 5.00 kSE);
FIG. 4 shows the soluble phases in the solubility test of the starting C-PET and of the composite PET/PA6, C-PET/PA613C NMR spectrum ((a) C-PET, (b) PA6, (C) PET/PA6 complexA composite soluble phase; (d)&(e) C-PET/PA6 composite soluble phase);
FIG. 5 is a schematic structural view of modified polyester C-PET and PA 6;
FIG. 6 is a nuclear magnetic signal peak diagram of carbon in the benzene ring ((a) & (C) C-PET/PA6 composite soluble phase, (b) & (d) C-PET);
FIG. 7 shows 13C NMR spectra of insoluble phases in solubility tests of raw C-PET and composite materials PET/PA6 and C-PET/PA6 ((a) C-PET, (b) insoluble phase of PET/PA6 composite material, (C) insoluble phase of C-PET/PA6 composite material);
FIG. 8 is a diagram showing nuclear magnetic signal peaks of carbons in a benzene ring ((a) & (d) C-PET/PA6 composite insoluble phase, (b) & (e) C-PET, (C) & (f) PET);
FIG. 9 is an SEM image (5.00 kSE magnification) of a composite PET/PA6 material at different scales;
FIG. 10 is an SEM image (5.00 kSE magnification) of a PET/PA6 composite material of different mixing methods of sulfonate compounds;
FIG. 11 is an SEM image (5.00 magnification 5.00kSE) of PET/PA6 composite modified with a sulfonate compound at different ratios.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.
The invention provides a polyester/nylon composite material, which comprises amide group- [ NHCO ]]- [ COO ] ester group]-and an inner compatibilising segment; the mass content of polyester in the polyester/nylon composite material is 20-80%; the internal compatiblizing segment comprises-SO2-an NH-group and having a polyester/nylon internal compatibilising interface, said internal compatibilising segment having a characteristic shoulder peak in the nuclear magnetic carbon spectrum with a chemical shift in the range 118-119 ppm; preferably, the internal compatibilization interface exhibits an irregular or amorphous structure; preferably, the mass content of the polyester in the polyester/nylon composite material is 40-60%; preferably, the method for detecting the mass content of the polyester in the polyester/nylon composite material comprises the following steps: the polyester/nylon composite material is etched by formic acid for more than 2 hours, the rest part is dried in vacuum for 24 hours, and the mass content of the polyester in the polyester/nylon composite material obtained by the detection method is that
Figure BDA0003223065380000081
Wherein w represents the mass of the polyester/nylon composite material before etching with formic acid, and w1Represents the mass of the remaining part after vacuum drying; preferably, the mass content of the polyester in the polyester/nylon composite material obtained by the detection method is allowed to have an error of 20% with the mass content of the polyester in the actual polyester/nylon composite material, and the mass content of the polyester in the actual polyester/nylon composite material is within a range
Figure BDA0003223065380000082
Wherein w represents the mass of the polyester/nylon composite material before etching with formic acid, and w1Representing the mass of the remaining portion after vacuum drying.
Wherein the polyester is obtained by polycondensation of polyhydric alcohol and polybasic acid, and the main chainContains a repeating ester bond of [ COO ]]The thermoplastic resins mentioned above are collectively referred to as "thermoplastic resins". The nylon contains repeated amide groups on the molecular main chain [ NHCO ]]The thermoplastic resins mentioned above are collectively referred to as "thermoplastic resins". The internal compatiblizing segment comprises-SO2An NH-group, detected by nuclear magnetism (carbon spectrum one-dimensional spectrogram), the electronic environment corresponding to the chemical shift of the internal compatibilization chain segment in the range of 118ppm to 119ppm is changed, and a new characteristic shoulder peak appears; meanwhile, the inner compatibilization chain segment has a polyester/nylon inner compatibilization interface.
In the method for detecting the mass content of the polyester in the polyester/nylon composite material, the polyester/nylon composite material is weighed with the mass w before being etched by formic acid; etching the polyester/nylon composite material by formic acid for more than 2h, centrifuging and decanting the rest part of the material to obtain solid, and vacuum drying the solid for 24h to obtain the material with the mass w1(ii) a An error of 20 percent is allowed to exist between the mass content of the polyester in the polyester/nylon composite material obtained by the detection method and the mass content of the polyester in the actual polyester/nylon composite material, namely the mass content of the polyester in the polyester/nylon composite material obtained by the detection method is
Figure BDA0003223065380000083
The actual polyester/nylon composite has a polyester content by mass in the range of
Figure BDA0003223065380000084
Further, the detection method of the polyester/nylon internal compatibilization interface comprises the following steps: the polyester/nylon composite material is etched by formic acid for more than 2 hours, the appearance of the rest part is observed by SEM images with the magnification of 1000-20000 times, and the internal compatibilization interface is in an irregular structure or an amorphous structure; preferably, the etching time is 2-6 h; preferably, the inner volume-increasing interface does not have a spherical particle agglomeration stacking structure or a regular hole structure; the particle size of the spherical particles is 0.1-3 mu m, and the aperture of the regular holes is 0.5-3 mu m; preferably, the regular hole structure is a regular circular structure.
In a two-phase system, some degree of penetration between the different components occurs, thereby forming a new interface (internal compatibilization interface) where interfacial tension can drive the two phases to aggregate. The smaller the interfacial tension, the better the compatibility of the two phases, which is expressed in that the interface becomes irregular and the volume of the dispersed phase becomes small, and the boundary between the dispersed phase and the aggregated phase becomes fuzzy.
The method for detecting the compatibility of the polyester/nylon system comprises the following steps: the phase morphology was characterized by SEM images to evaluate compatibility. SEM is scanning electron microscopy imaging, which uses a focused very narrow high energy electron beam to scan a sample, excites various physical information through the interaction between the beam and the material, and collects, magnifies, and reimages the information to achieve the purpose of characterizing the microscopic appearance of the material. For the polyester/nylon system, nylon is soluble in formic acid, while polyester is insoluble in formic acid, so that the nylon portion is dissolved away after etching with formic acid, and the morphology of the remaining polyester portion can be observed by SEM images.
The matrix phase refers to the phase of the material that constitutes its basic structure, and generally has a continuous spatial distribution. Dispersed phase: the dispersed substance is referred to as the dispersed phase. For example, in the preparation of polyester/nylon composites, when the modified polyester content is greater than the nylon content, the modified polyester is referred to as the matrix phase and the nylon is referred to as the dispersed phase. When the polyester content is low and the sample is spherical as a dispersed phase, as shown in FIG. 3 (a)/FIG. 9 (b)/FIG. 10(a), it is indicated that the interfacial tension between the two phases is very large and is incompatible; if the shape becomes irregular and does not form a form of agglomerated and piled spherical particles, the interfacial tension between the two phases is small and the compatibility is good, and a certain form is shown in FIG. 3 (b)/FIG. 10 (b)/FIG. 11 (g). When the polyester content is higher and is used as a matrix phase, if the shape of the etched hole interface is circular, as shown in fig. 3 (c)/fig. 9(a), it indicates that the interfacial tension between the two phases is very large and is in an incompatible state; if it is an irregular pattern, the interface shape of the etched hole is not a regular circle, which indicates that the interface tension between two phases is small, the compatibility is good, and a certain pattern even has a gully pattern, as shown in fig. 3 (d)/fig. 11 (c). Whether compatibility is enhanced or not can be determined through the polyester/nylon internal compatibilization interface, the compatibility of the modified polyester and the nylon is enhanced, namely, the internal compatibilization interface is generated in the polyester/nylon composite material, and the expression form is as follows: the interface of the modified polyester etched by formic acid is irregular and the volume of the dispersed phase is reduced, the interface of the dispersed phase and the aggregation phase is in an irregular structure or an amorphous structure, specifically, the interface can be in an irregular gully shape, an irregular honeycomb shape and the like, if the compatibility of the modified polyester and the nylon is poor, an internal compatibilization interface is not generated in the polyester/nylon composite material, and the micro-morphology of the composite material is represented by that the particles of the polyester are in a form of the conglomeration and accumulation of spherical particles or the shape of the etched hole interface is in a regular circular structure.
Furthermore, the length-diameter ratio of the irregular gully-shaped structure is more than or equal to 3. Wherein, the direction of the longest gully in the gully-shaped structure is the radial direction, and the direction which forms an angle of 90 degrees with the radial direction is the longitudinal direction; the aspect ratio is the radial length/longitudinal length.
Further, the surface of the irregular gully-shaped structure is provided with spherical particles; the particle diameter of the spherical particles is 10 nm-500 nm.
Further, the surface of the irregular honeycomb structure is provided with micropores; the aperture of the micropore is 50 nm-800 nm.
Further, the amorphous structure is a smooth amorphous structure. Wherein the amorphous structure is in the form of a mosaic or stack of structures without fixed shapes; by smooth amorphous structures, it is meant that the amorphous structures are connected by a substantially continuous flat interface, as opposed to a gully pattern.
Further, the smooth amorphous structure surface is provided with spherical particles; the particle diameter of the spherical particles is 100 nm-500 nm.
Furthermore, the amorphous structure is formed by mutually bonding and stacking irregular particles, and the particle size of the irregular particles is 1 nm-50 nm.
Furthermore, the surface of the amorphous structure is provided with micropores, and the pore diameter of the micropores is 10 nm-100 nm.
When the content of polyester is low and the polyester is used as a dispersed phase, the polyester part of the sample is in an amorphous structure formed by mutually bonding and stacking irregular particles of 50-500 nm, and the compatibility of the polyester and nylon can be determined to be good; the partial appearance of the polyester is that micropores with the size of 100 nm-1000 nm are formed on an amorphous structure formed by mutually bonding and stacking irregular particles with the size of 50 nm-500 nm, and the polyester and nylon have good compatibility; preferably, the polyester part appearance is a smooth amorphous structure, and the compatibility between the polyester and nylon is considered to be good; preferably, the polyester part shape is a smooth spherical particle with an amorphous structure of 100 nm-500 nm, and the compatibility between the polyester and nylon is considered to be good.
When the polyester content is higher and is used as a matrix phase, the polyester part of the sample is in an irregular honeycomb structure, and the compatibility of the polyester and nylon can be determined to be good; the partial appearance of the polyester is that micropores with the diameter of 50 nm-800 nm are arranged on an irregular honeycomb structure, and the polyester and nylon have good compatibility; preferably, the polyester part has irregular gully shape, and the polyester and nylon have good compatibility; preferably, the partial appearance of the polyester is an irregular gully-shaped structure with the length-diameter ratio of more than or equal to 3, and the polyester and nylon are considered to have good compatibility; preferably, the polyester part is spherical particles with irregular ravines of 10 nm-500 nm, and the polyester and nylon have good compatibility.
The invention also provides a preparation method of the polyester/nylon composite material, which comprises the following steps:
mixing modified polyester and nylon, reacting in a molten state, and rapidly cooling to a temperature below a specific temperature to obtain the polyester/nylon composite material;
the modified polyester comprises a sulfonate group; preferably, the modified polyester is obtained by modifying polyester with a sulfonate compound; more preferably, the sulfonate compound is selected from one or more of sodium 2-hydroxy-3-allyloxypropanesulfonate, sodium 2-hydroxy-3-methacryloxypropanesulfonate, isoprene sulfonate, sodium sulfonate and potassium sulfonate;
the mass ratio of the modified polyester to the nylon is 8: 2-2: 8; preferably, the mass ratio of the modified polyester to the nylon is 6: 4-4: 6;
the specific temperature is lower than the temperature of the lower of the glass transition temperatures of both the modified polyester and the nylon; preferably, the specific temperature is 20 ℃ or more lower than that lower than the glass transition temperature.
The time for rapid cooling is less than or equal to 2 min.
The modified polyester can be formed by grafting a sulfonate compound on a macromolecular chain of the polyester, the modified polyester and the nylon are subjected to ester exchange reaction to form an inner compatibilization chain segment, and the inner compatibilization chain segment plays a role of a compatilizer to enhance the compatibility of the modified polyester and the nylon. The melting state is the melting point which is higher than the melting points of the modified polyester and the nylon.
The mass ratio of the modified polyester to the nylon and the cooperative control of the quick cooling condition enable the polyester/nylon composite material prepared by the reaction to generate an internal compatibilization chain segment with a specific function, overcome the prejudice of the prior art and realize the unexpected technical effect of the invention.
In one embodiment, 20 to 80 parts by mass of modified polyester modified by a sulfonate compound and 20 to 80 parts by mass of nylon which are fully dried are weighed, mixed, reacted in a molten state (the temperature is higher than the melting point of the polyester and the nylon which have higher melting points), and rapidly cooled to be lower than the glass transition temperature of the polyester and the nylon (the temperature is lower than the temperature of the polyester and the nylon which have lower glass transition temperatures), so as to obtain the polyester/nylon composite material.
The reason for greatly improving the compatibility of the polyester/nylon composite material is illustrated by one of the examples, a sulfonate compound is connected to a PET macromolecular chain to form a new modified polyester (represented by C-PET), the C-PET reacts with PA6 to obtain a new composite material C-PET/PA6, and nuclear magnetic analysis is carried out on the PET/PA6 and the C-PET/PA 6. The nuclear magnetic spectrum of the soluble part and the amplified spectrum of each characteristic peak are shown in FIG. 4 after etching the raw material C-PET, the composite materials PET/PA6 and C-PET/PA6 with formic acid respectively (the temperature is 45 ℃ and the time is 4 h). FIG. 5 is a structural formula of the starting materials C-PET and PA 6.
FIG. 4 (I) is a nuclear magnetic signal in the range of 140ppm to 180ppm, corresponding to the carbon atom in the carbon-oxygen double bond in PA6 and PET. By comparing several spectra, it can be found that the soluble fraction of the experimental group based on PET is only PA6, but the soluble fraction of the experimental group based on C-PET presents a characteristic peak of 157ppm polyester.
FIG. 4 (II) shows nuclear magnetic signals in the range of 124ppm to 116ppm, which includes carbon atoms in the benzene ring of the polyester. By comparing several spectra, it was found that the soluble fraction of the test group using PET as a raw material showed no signal peak of the polyester in this range, and the soluble fraction of the test group using C-PET as a raw material showed a characteristic peak of the polyester (near 122 ppm).
FIG. 4 (III) is a nuclear magnetic signal in the range of 60ppm to 0ppm, which includes the single bond of the polyester to a carbon-hydrogen in the structure of PA 6. Similarly, the characteristic peak (57ppm) of polyester was observed in the soluble portion of the test group using C-PET as a raw material, but the characteristic peak was not observed in the soluble portion of the test group using PET as a raw material. In summary, the soluble fraction after formic acid etching should be the only fraction of PA6 in the blend. By comparing the nuclear magnetic spectra of the various parts, the nuclear magnetic spectrum of the experimental group of PET/PA6 is basically consistent with that of pure PA6, but the nuclear magnetic spectrum of the soluble substance of C-PET/PA6 shows a characteristic peak of the polyester. Thus, a portion of the polyester segments in the C-PET/PA6 experimental group were combined with PA6 to form the inner compatible segment.
As shown in FIG. 6, the signal peak corresponding to the carbon atom on the benzene ring of the polyester was further amplified, and it was found that the signal peak in the soluble portion of the composite material C-PET/PA6 is different from that in the raw material C-PET. The characteristic peak corresponding to the carbon atoms d 'and f' connected with the carbonyl group on the benzene ring of the soluble matter of the composite material C-PET/PA6 becomes wider, and the characteristic peak corresponding to other carbon atoms (e ', g', h ', i') on the benzene ring has new shoulders. This indicates that the electronic environment of the benzene ring in C-PET has changed.
For the insoluble part, as shown in fig. 7 and fig. 8, by enlarging the characteristic peak of the carbon on the benzene ring of the insoluble part of the composite material C-PET/PA6 and comparing with the raw material polyester C-PET, the characteristic peak of the carbon atom on the benzene ring of the insoluble part of the experimental group C-PET/PA6 is also widened, further indicating that new substances are generated after the C-PET is reacted and blended with PA 6.
The structural analysis shows that the reason for greatly improving the compatibility of the C-PET and the PA6 is that a new substance is generated. The specific reaction mechanism analysis is as follows, C-PET is different from PET structure, PET end group is hydroxyl and carboxyl, C-PET structure in addition to end group, in the chain middle also can exist sulfonic acid group. The benzenesulfonic acid group attacks the amide bond in PA6 and binds to the amino group thereof. At the moment, PET is linked with PA6 through a benzenesulfonic acid group to form an internal compatibilization chain segment; meanwhile, the electron environment of the benzene ring on the benzenesulfonic acid is changed, so that the nuclear magnetic spectrum is changed. The inner compatibilization chain segment plays a role of a compatilizer and solves the problem that polyester and nylon are incompatible.
Further, the polyester is selected from one or more of mono-component polyester or modified polyester, the mono-component polyester is selected from one or more of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid (PLA) and polybutylene succinate (PBS), and the modified polyester is selected from one or more of cationic dyeable modified polyester, antistatic modified polyester and flame retardant modified polyester of the mono-component polyester; the nylon is selected from one or more of single-component polyamide or copolyamide, wherein the single-component polyamide is selected from nylon 6(PA6), nylon 66(PA66), nylon 610(PA610), nylon 612(PA612), nylon 6I (PA6I), polyhexamethylene terephthalamide (PA6T), polyhexamethylene isophthalamide (PA6ICoT), polyhexamethylene adipamide (MXD6) and modified nylon; the modified nylon is selected from one or more of single-component polyamide reinforced nylon, flame-retardant nylon, transparent nylon, wear-resistant nylon and toughened nylon.
Wherein, the nylon can be selected from single-component nylon, such as nylon6, nylon 66 and the like; copolyamides such as nylon6 and nylon 66 copolyamides are also possible. More preferably, the nylon is selected from copolyamides, since copolyamides have better shrinkage characteristics.
Further, the sulfonate compound is grafted on the backbone of the polyester. I.e. the sulfonate compound is grafted onto the macromolecular chain of the polymer.
Further, the sulfonate compound accounts for 1-8 wt% of the modified polyester.
Further, the modified polyester accounts for 20-80 wt% of the polyester/nylon composite material.
Further, the nylon accounts for 20 wt% -80 wt% of the polyester/nylon composite material.
Wherein, the prepared polyester/nylon composite material has good mechanical property by changing the content of the modified polyester, the content of the nylon or the content of the sulfonate compound in the modified polyester.
Further, the full drying is carried out by utilizing high-temperature vacuum; the temperature range of the high temperature is as follows: 80-120 ℃; the pressure range of the vacuum is 100 Pa-50000 Pa; the time for fully drying is 8-24 h.
Further, the time for rapid cooling is less than or equal to 1 min. I.e., cooled to below the glass transition temperature of both the modified polyester and the nylon within 1min (20 ℃ and above below the temperature of the lower of the glass transition temperatures of both the modified polyester and the nylon).
Furthermore, the time for rapid cooling is less than or equal to 0.5 min. I.e., cooled to below the glass transition temperature of both the modified polyester and the nylon within 0.5min (20 ℃ and above below the temperature of the lower of the glass transition temperatures of both the modified polyester and the nylon).
Further, the reaction is carried out in a twin-screw extruder; the reaction temperature is 150-350 ℃; the reaction time is 1-10 min.
Wherein the temperature of the reaction in the twin-screw extruder is selected to match the shear viscosity of the two polymers of the modified polyester and the nylon, and the sample is not degraded as much as possible. Specifically, when the same temperature is selected, the shear viscosity of the modified polyester is similar to that of the nylon at the same shear rate.
Further, the reaction temperature is 250-280 ℃; the reaction time is 1-5 min. For example, PET modified with a sulfonate compound and PA6/PA66 are mixed and reacted in a twin-screw extruder at a temperature in the range of 250 ℃ to 280 ℃, a residence time within 5min, and an extrusion shear rate of 100r/min to 500 r/min. And simultaneously, cooling to below 50 ℃ within 1min to obtain the polyester/nylon composite material.
Further, the method comprises the following steps: after the reaction is finished, carrying out solid-phase reaction for 1-20 h in an inert gas atmosphere at the temperature of 120-280 ℃ to obtain the polyester/nylon composite material. Preferably, the inert gas is nitrogen. The term "after the reaction" means after the reaction in a molten state is completed.
The invention also provides a composite comprising the polyester/nylon composite material; preferably, the compound comprises an additive selected from one or more of fillers, pigments, plasticizers, antioxidants, and one or more of inorganic fillers, flame retardants, impact modifying materials, electrically conductive fillers, thermally conductive fillers, reinforcing fibers.
The polyester/nylon composite material can be added with inorganic filler, flame retardant, impact-resistant modified material, conductive filler, heat-conducting filler, reinforcing fiber and the like. The inorganic filler may be glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, aluminosilicate, alumina, silica, magnesia, zirconia, titania, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass bead, ceramic bead, boron nitride, silicon carbide, silica, or the like. These materials may be hollow, and two or more of the above inorganic filler materials may be used. As the swellable layered silicate such as bentonite, montmorillonite, hectorite, synthetic mica, or the like, organic montmorillonite in which interlayer ions (interlayer ions) are cation-exchanged with an organic ammonium salt can be used. Among the above fillers, glass fibers and carbon fibers are particularly preferable for enhancing the performance of the polyester/nylon composite material. In order to obtain a composite having excellent surface appearance, the average particle size of the inorganic filler is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm, and still more preferably 0.05 to 3 μm. The average particle diameter of these inorganic fillers is measured by a sedimentation method. In order to reinforce the composite and to have a good surface appearance, talc, kaolin, wollastonite, swellable layered silicate are preferably used as the inorganic filler.
In order to obtain more excellent mechanical strength, the inorganic filler is preferably used after being pretreated with a coupling agent such as an isocyanate compound, an organosilane compound, an organotitanate compound, an organoborane compound, or an epoxy compound. Particularly preferred are organic silane-based compounds, and specific examples thereof include
Figure BDA0003223065380000131
Epoxy-containing alkoxysilane compounds such as glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane and gamma- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, mercapto-containing alkoxysilane compounds such as gamma-mercaptopropyldimethoxysilane and gamma-mercaptopropyldiethoxysilane, ureido-containing alkoxysilane compounds such as gamma-ureidopropyldiethoxysilane, gamma-ureidopropyldimethoxysilane and gamma- (2-ureidoethyl) aminopropyldimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatopropylmethyldimethoxysilane, gamma-isocyanatopropylmethyldiethoxysilane, gamma-epoxypropyltrimethoxysilane, gamma-epoxyethyltrimethoxysilane, gamma-epoxypropyltrimethoxysilane, gamma-epoxypropyl-methoxysilane, gamma-epoxysilane, gamma-epoxypropyl-epoxysilane, gamma-epoxypropyl-epoxysilane, gamma-epoxypropyl-epoxysilane, gamma-epoxypropyl-epoxysilane, gamma-epoxypropyl-epoxysilane, gamma-beta-epoxypropyl-gamma-epoxypropyl-epoxysilane, gamma-epoxypropyl-epoxysilane, gamma-beta-epoxysilane, gamma-epoxypropyl-epoxysilane, gamma-epoxysilane, gamma-epoxypropyl-epoxysilane, gamma-epoxy, Gamma-isocyanatopropylethyl bisAn alkoxysilane compound containing an isocyanate group such as methoxysilane, gamma-isocyanatopropylethyldiethoxysilane and gamma-isocyanatopropyltrichlorosilane, an alkoxysilane compound containing an amino group such as gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyldimethoxysilane and gamma-aminopropyldimethoxysilane, an alkoxysilane compound containing a hydroxyl group such as gamma-hydroxypropyldimethoxysilane and gamma-hydroxypropyldiethoxysilane, an alkoxysilane compound containing a carbon-carbon unsaturated group such as gamma-methacryloxypropyldimethoxysilane, vinyldimethoxysilane and N-N' - (N-vinylbenzylaminoethyl) -aminopropyldimethoxysilane hydrochloride, an alkoxysilane compound containing a carbon-carbon unsaturated group such as gamma-methacryloxypropyldimethoxysilane, gamma-isocyanatopropyldiethoxysilane and gamma-isocyanatopropyldimethoxysilane, a method for producing the same, and a process for producing the same, An alkoxysilane compound having an acid anhydride group such as 3-dimethoxysilylpropylsuccinic anhydride. Particularly preferred are gamma-methacryloxypropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. The flame retardant can be magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate (APP), octabromoether, triphenyl phosphate, hexabromocyclododecane, melamine triisocyanate melamine salt (MCA), ammonium polyphosphate melamine salt (MPP), zinc borate, decabromodiphenylethane, coated red phosphorus, p-tert-butylcatechol (TBC), decabromodiphenyl ether, phosphorus-nitrogen flame retardant, tetrabromobisphenol A, brominated polystyrene, hexabromocyclododecane and chlorinated paraffin, chlordiazepoxide, and Chlorinated Polyethylene (CPE).
The impact modifier may be Chlorinated Polyethylene (CPE), vinyl acetate copolymer (EVA), acrylate rubber (ACR), ABS, SBS, Ethylene Propylene Rubber (EPR), ethylene propylene diene monomer rubber (EPDM), natural rubber (NBR), styrene butadiene rubber, etc.
The conductive filler can be carbon black, carbon fiber, graphite, carbon nano tube, aluminum powder, copper powder, nickel powder, iron powder, silver powder, gold powder, brass fiber, stainless steel fiber, iron fiber, silver-plated glass fiber, glass microsphere silver-plated powder and the like.
The heat conductive filler may be alumina, magnesia, zinc oxide, aluminum nitride, boron nitride, silicon carbide, fibrous carbon powder, flaky carbon powder, silica, or the like.
The reinforcing fiber may be glass fiber, carbon fiber, boron fiber, whisker, asbestos fiber, metal fiber, aramid fiber, orlon fiber, polyester fiber, nylon fiber, vinylon fiber, polypropylene fiber, polyimide fiber, or the like.
The plasticizer may be Benzenesulfonamide (BSA), N-methyl-p-toluenesulfonamide (MTSA), N-ethyl-p-toluenesulfonamide (NEPTSA), N-butylbenzenesulfonamide (BBSA), N- (2-hydroxypropyl) benzenesulfonamide (HPBSA), N-cyclohexyl-p-toluenesulfonamide (CTSA), N-bis (2-hydroxyethyl) p-toluenesulfonamide, toluenesulfonamide formaldehyde resin (MH/MS), or the like.
The antioxidant is selected from common commercial antioxidants, such as antioxidant grades 1010, 1076, 168, BHT, T501, 246, TPP, etc.
The invention also provides a polyester/nylon composite material and application of the composite containing the polyester/nylon composite material in the field of materials. For example: textile fiber field and engineering plastic field.
In summary, the following steps: (1) the polyester/nylon composite material with good compatibility and mechanical property is obtained by a simple method, the polyester/nylon composite material comprises polyester and nylon modified by a sulfonate compound, the polyester and the nylon react, and the mass content of the polyester in the polyester/nylon composite material is 20-80%; (ii) a The internal compatiblizing segment comprises-SO2An NH-group and a polyester/nylon internal compatibilization interface, wherein the internal compatibilization chain segment has a characteristic shoulder peak with a chemical shift in a range of 118ppm to 119ppm in a nuclear magnetic carbon spectrum, and the generated internal compatibilization chain segment plays a role of a compatibilizer and enhances the compatibility of the two.
(2) Compared with the prior art, the invention can generate the internal compatibilization chain segment within a few minutes by controlling the reaction conditions of the modified polyester and the nylon, realizes the micro mixing of the polyester and the nylon, and has the effect superior to the result of three-hour reaction in the prior art.
(3) Due to the improvement of compatibility, the composite product prepared by the invention has outstanding performance and mechanical property superior to that of a nylon raw material; meanwhile, the polyester contained in the product has better cost than nylon, low price and high quality, and has wide application occasions.
(4) The method has the advantages of short reaction time, simple process, less side reaction and good industrialization capability.
(5) The polyester/nylon composite material has the advantages of low cost, strong stability and high performance repeatability, and can be applied to the fields of textile fibers, engineering plastics and the like.
The present invention will be further described with reference to the following specific examples and comparative examples.
The performance test criteria involved in the present invention are as follows:
tensile modulus: GB/T1040.1-2018 determination of tensile properties of plastics;
tensile strength: GB/T1040.1-2018 determination of tensile properties of plastics;
elongation at break: GB/T1040.1-2018 determination of tensile properties of plastics;
impact strength: GB/T1843 measurement of impact strength of 2008 Plastic cantilever beam.
Example 1
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 100 ℃ for 12 hours; wherein the molar ratio of the sulfonate compound to the PET is 4: 96; the sulfonate compound is selected from one or more of sodium 2-hydroxy-3-allyloxypropanesulfonate, sodium 2-hydroxy-3-methacryloxypropanesulfonate, isoprene sulfonate, sodium sulfonate and potassium sulfonate (the sulfonate compounds in the following examples and comparative examples are selected the same as the sulfonate compound in this example).
The preparation process comprises the following steps: mixing 20 parts by mass of the modified PET granules and 80 parts by mass of the PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 3min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material C20/A80.
And (3) performance testing: the composite pellets C20/A80 are dried in vacuum at 110 ℃ for 10h, made into sample strips by an injection molding machine, set the injection molding temperature to be 240-270 ℃, and are tested after being placed in an environment with 23-27 ℃ and 50% humidity for 48h, and the performance test results are shown in Table 1.
And (4) SEM test: 1.5g of the composite material C20/A80 was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. Observing the morphology of the undissolved polyester part through SEM images, and as shown in FIG. 10 (b)/FIG. 11 (g)/FIG. 3(b), the polyester part is used as a matrix phase, the etched nylon is used as a dispersed phase, and the morphology of the polyester part is an amorphous structure formed by mutually bonding and stacking irregular particles with the particle size of 1nm to 50 nm; meanwhile, the surface of the amorphous structure is provided with irregular micropores with the aperture of 10 nm-100 nm.
Determination of the polyester content in the composite material C20/A80: weighing 1.50g of the composite material C20/A80, placing the composite material C20/A80 in 150mL of formic acid, etching the formic acid for more than 2h, centrifuging the rest part to decant the formic acid to obtain a solid, drying the solid in vacuum for 24h to obtain 0.0935g of the solid, and detecting that the polyester content in the composite material C20/A80 is 6.23% by mass and the polyester content in the actual composite material C20/A80 is 0-26.23% by mass.
Comparative example 1
Pretreatment: the PET pellets and PA6 pellets were dried in vacuo at 100 ℃ for 12 h;
the preparation process comprises the following steps: mixing 20 parts by mass of PET granules and 80 parts by mass of PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 3min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material P20/A80.
And (3) performance testing: and (3) performance testing: the sample is too brittle, i.e., the impact strength is too low, and thus, a sample bar cannot be produced.
And (4) SEM test: 1.5g of the composite material P20/A80 was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. As a result of observing the morphology of the remaining polyester portion by SEM image, as shown in FIG. 3 (a)/FIG. 9 (b)/FIG. 10(a), the polyester portion was used as a dispersed phase, the etched nylon was used as a matrix phase, and the polyester was agglomerated together in the form of small spherical particles having a particle size of 0.1 μm to 3 μm, and the particle size was relatively uniform.
Example 2
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 110 ℃ for 10 h; wherein the molar ratio of the sulfonate compound to the PET is 4: 96;
the preparation process comprises the following steps: mixing 80 parts by mass of the modified PET granules and 20 parts by mass of the PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 3min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material C80/A20.
And (3) performance testing: the sample is too brittle, i.e., the impact strength is too low, and thus, a sample bar cannot be produced.
And (4) SEM test: 1.5g of the composite material C80/A20 was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. As a result of observing the morphology of the undissolved polyester portion through SEM images, as shown in fig. 11(a), the polyester portion serves as a matrix phase, the etched nylon serves as a dispersed phase, the polyester portion has irregular ravines in morphology, and spherical particles having a particle size of 1nm to 50nm are carried on the surface of the irregular ravines.
Determination of the polyester content in the composite material C80/A20: weighing 1.50g of the composite material C80/A20, placing the composite material C80/A20 in 150mL of formic acid, etching the formic acid for more than 2h, centrifuging the rest part to decant the formic acid to obtain a solid, drying the solid in vacuum for 24h to obtain the solid with the mass of 1.145g, and detecting that the mass content of polyester in the composite material C80/A20 is 76.35%, so that the mass content of polyester in the actual composite material C80/A20 is 56.35% -96.35%.
Comparative example 2
Pretreatment: the PET pellets and PA6 pellets were dried in vacuo at 100 ℃ for 12 h;
the preparation process comprises the following steps: mixing 80 parts by mass of PET granules and 20 parts by mass of PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 3min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material P80/A20.
And (3) performance testing: and (3) performance testing: the sample is too brittle, i.e., the impact strength is too low, and thus, a sample bar cannot be produced.
And (4) SEM test: 1.5g of the composite material P80/A20 was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. The morphology of the remaining polyester portion was observed by SEM images, and as shown in FIG. 9 (a)/FIG. 3(c), the polyester portion was used as a matrix phase, the etched nylon was used as a dispersed phase, and a regular pore structure having a pore diameter of 0.5 μm to 3 μm was dispersed in a smooth and continuous matrix phase.
In both cases, the P80/A20 material shown in FIG. 9 (a)/FIG. 3(c) and the P20/A80 material shown in FIG. 9 (b)/FIG. 3 (a)/FIG. 10(a) clearly show that the dispersed phase is an agglomerated and piled structure of spherical particles, indicating that the interfacial tension between the two phases is very large and the two phases are incompatible.
Example 3
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 80 ℃ for 24 h; wherein the molar ratio of the sulfonate compound to the PET is 4: 96;
the preparation process comprises the following steps: mixing 70 parts by mass of the modified PET granules and 30 parts by mass of the PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 10min, and the temperature is reduced to 30 ℃ within 0.5min by water cooling to obtain the composite material C70/A30.
And (3) performance testing: the sample is too brittle, i.e., the impact strength is too low, and thus, a sample bar cannot be produced.
And (4) SEM test: 1.5g of the composite material C70/A30 was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. The morphology of the undissolved polyester portion was observed by SEM image, and as a result, as shown in fig. 11(b), the polyester portion was used as a matrix phase, the etched nylon was used as a dispersed phase, and the morphology of the polyester portion was an irregular honeycomb structure; meanwhile, the surface of the irregular honeycomb structure is provided with micropores with the aperture of 50 nm-800 nm.
Example 4
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 120 ℃ for 8 h; wherein the molar ratio of the sulfonate compound to the PET is 4: 96;
the preparation process comprises the following steps: mixing 60 parts by mass of the modified PET granules and 40 parts by mass of the PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 1min, and the temperature is reduced to 30 ℃ within 2min by water cooling to obtain the composite material C60/A40.
And (3) performance testing: the sample is too brittle, i.e., the impact strength is too low, and thus, a sample bar cannot be produced.
And (4) SEM test: 1.5g of the composite material C60/A40 was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. The morphology of the undissolved polyester portion was observed by SEM image, and as a result, as shown in fig. 3 (d)/fig. 11(c), the morphology of the polyester portion was an irregular honeycomb structure; meanwhile, the surface of the irregular honeycomb structure is provided with micropores with the aperture of 100 nm-800 nm.
Example 5
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 110 ℃ for 10 h; wherein the molar ratio of the sulfonate compound to the PET is 4: 96;
the preparation process comprises the following steps: mixing 50 parts by mass of the modified PET granules and 50 parts by mass of the PA6 granules (for example, 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 5min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material C50/A50.
And (3) performance testing: the composite pellets C50/A50 are dried in vacuum at 110 ℃ for 10h, made into sample strips by an injection molding machine, set the injection molding temperature to be 240-270 ℃, and are tested after being placed in an environment with 23-27 ℃ and 50% humidity for 48h, and the performance test results are shown in Table 1.
And (4) SEM test: 1.5g of the composite material C50/A50 was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. Observing the morphology of the undissolved polyester part through SEM images, and as a result, as shown in FIG. 11(d), the polyester part has continuous morphology and irregular gullies with the length-diameter ratio of more than or equal to 3; meanwhile, the surfaces of the irregular ravines are provided with particles with the particle size of 10 nm-50 nm.
Determination of the polyester content in the composite material C50/A50: weighing 1.50g of the composite material C50/A50, placing the composite material C50/A50 in 150mL of formic acid, etching the formic acid for more than 2h, centrifuging the rest part to decant the formic acid to obtain a solid, drying the solid in vacuum for 24h, weighing the mass of the solid to be 0.6344g, and detecting that the mass content of polyester in the composite material C50/A50 is 42.29%, so that the mass content of polyester in the actual composite material C80/A20 is 22.29% -62.29%.
The measurement results of the polyester content in the composite materials prepared in example 1, example 2 and example 5 are shown in the table below, and the insoluble matter ratio in the table is the detected polyester mass content in the composite material.
Examples Sample name Insoluble matter proportion (%) Soluble matter proportion (%)
Example 1 C20/A80 6.23 93.77
Example 2 C80/A20 76.35 23.65
Example 5 C50/A50 42.29 57.71
Example 6
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 110 ℃ for 10 h; wherein the molar ratio of the sulfonate compound to the PET is 4: 96;
the preparation process comprises the following steps: mixing 40 parts by mass of the modified PET granules and 60 parts by mass of the PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 3min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material C40/A60.
And (3) performance testing: the composite pellets C40/A60 were dried in vacuum at 110 ℃ for 10 hours, molded into sample bars by an injection molding machine, set the injection molding temperature at 240 ℃ to 270 ℃ respectively, and were placed in an environment of 23 ℃ to 27 ℃ and 50% humidity for 48 hours for testing, with the performance test results shown in Table 1.
And (4) SEM test: 1.5g of the composite material C40/A60 was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. The morphology of the undissolved polyester portions was observed by SEM images, and as a result, as shown in fig. 11(e), the polyester portions were continuous irregular ravines; meanwhile, the surfaces of the irregular ravines are provided with particles with the particle size of 10 nm-500 nm.
Example 7
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 110 ℃ for 10 h; wherein the molar ratio of the sulfonate compound to the PET is 4: 96;
the preparation process comprises the following steps: mixing 30 parts by mass of the modified PET granules and 70 parts by mass of the PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 3min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material C30/A70.
And (3) performance testing: the composite pellets C30/A70 were dried in vacuum at 110 ℃ for 10 hours, molded into sample bars by an injection molding machine, set the injection molding temperature at 240 ℃ to 270 ℃ respectively, and were placed in an environment of 23 ℃ to 27 ℃ and 50% humidity for 48 hours for testing, with the performance test results shown in Table 1.
And (4) SEM test: 1.5g of the composite material C30/A70 was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. The morphology of the undissolved polyester portion was observed by SEM images, and as a result, as shown in fig. 11(f), the polyester portion was used as a dispersed phase, the etched nylon was used as a matrix phase, and the morphology of the polyester portion was a smooth amorphous structure; meanwhile, the smooth surface of the amorphous structure is provided with spherical particles with the particle size of 1 nm-50 nm.
From the morphology of the polyester part in fig. 11, it can be found that the grafting of the sulfonate compound onto the PET macromolecular chain causes the polyester part to have irregular shape and greatly reduced volume, even having a ravine-shaped morphology. The result shows that the interfacial tension of the PET containing sulfonic acid groups and the PA6 is very small after melt extrusion, the degree of mutual permeation of the two phases is improved, and the compatibility is greatly improved. Meanwhile, for the examples with different raw material contents, when the adding amount ratio of the PET modified by the sulfonate compound to the PA6 is the same, the compatibility of the composite material is the best.
Example 8
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 100 ℃ for 10 hours; wherein the molar ratio of the sulfonate compound to the PET is 2: 98;
the preparation process comprises the following steps: mixing 50 parts by mass of the modified PET granules and 50 parts by mass of the PA6 granules (for example, 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: 230 ℃ in the I region, 240 ℃ in the II region, 250 ℃ in the III region, 250 ℃ in the IV region, 250 ℃ in the V region, 250 ℃ in the VI region, 250 ℃ in the VII region, 250 ℃ in the VIII region and 250 ℃ in the nose; the reaction time is 3min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material EC 50/A50.
And (3) performance testing: the composite granules EC50/A50 are dried in vacuum for 10h at 100 ℃, made into sample strips by an injection molding machine, set the injection molding temperature to be 240-255 ℃, and are tested after being placed in an environment with 23-27 ℃ and 50% humidity for 48h, and the performance test results are shown in Table 1.
Example 9
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 100 ℃ for 12 hours; wherein the molar ratio of the sulfonate compound to the PET is 2: 98;
the preparation process comprises the following steps: mixing 30 parts by mass of the modified PET granules and 70 parts by mass of the PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: 230 ℃ in the I region, 240 ℃ in the II region, 250 ℃ in the III region, 250 ℃ in the IV region, 250 ℃ in the V region, 250 ℃ in the VI region, 250 ℃ in the VII region, 250 ℃ in the VIII region and 250 ℃ in the nose; the reaction time is 3min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material EC 30/A70.
And (3) performance testing: the composite granules EC30/A70 are dried in vacuum for 10h at 100 ℃, sample bars are made by an injection molding machine, the injection molding temperature is set to be 240-255 ℃, the test is carried out after the composite granules EC30/A70 are placed in an environment with 23-27 ℃ and 50% humidity for 48h, and the performance test results are shown in Table 1.
Example 10
Pretreatment: the PET pellets modified with the sulfonate compound and the PA6 pellets were dried under vacuum at 100 ℃ for 12 hours; wherein the molar ratio of the sulfonate compound to the PET is 2: 98;
the preparation process comprises the following steps: mixing 30 parts by mass of the modified PET granules and 70 parts by mass of the PA6 granules (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: 230 ℃ in the I region, 240 ℃ in the II region, 250 ℃ in the III region, 250 ℃ in the IV region, 250 ℃ in the V region, 250 ℃ in the VI region, 250 ℃ in the VII region, 250 ℃ in the VIII region and 250 ℃ in the nose; the reaction time is 3min, the temperature is reduced to 30 ℃ within 1min by water cooling to obtain a composite material EC30/A70, and the solid phase polycondensation reaction is carried out on the composite material EC30/A70 for 8h under the conditions of 200 ℃ and the nitrogen flow rate of 10L/min to obtain the composite material EC 30/A70-8.
And (3) performance testing: the composite granules EC30/A70-8 are dried in vacuum for 12h at 100 ℃, sample bars are made by an injection molding machine, the injection molding temperature is set to be 240-255 ℃, the test is carried out after the composite granules EC30/A70-8 are placed in an environment with 23-27 ℃ and 50% humidity for 48h, and the performance test results are shown in Table 1.
Examples 11 to 15
Both pretreatment and preparation methods were carried out as in example 9, with only the starting materials (polyester and nylon) being changed, as shown in the following table.
Figure BDA0003223065380000211
Wherein: C-PBT represents a modified polyester obtained by modifying PBT with a sulfonate compound;
C-PLA represents a modified polyester obtained by modifying PLA with a sulfonate compound;
C-PBS means a modified polyester obtained by modifying PBS with a sulfonate compound.
The polyester/nylon composite materials with good performance can be obtained in the embodiments 11 to 15.
Comparative example 3
Pretreatment: the PET pellets and PA6 pellets were dried in vacuo at 100 ℃ for 12 h;
the preparation process comprises the following steps: directly mixing 19 parts by mass of modified PET granules, 80 parts by mass of PA6 granules and 1 part by mass of sodium p-toluenesulfonate (for example: 5min), and adding the mixed materials into a double-screw extruder, wherein the reaction temperature of the double-screw extruder is set as follows: zone I250 deg.C, zone II 260 deg.C, zone III 265 deg.C, zone IV 265 deg.C, zone V265 deg.C, zone VI 265 deg.C, zone VII 265 deg.C, zone VIII 265 deg.C, and zone head 265 deg.C; the reaction time is 3min, and the temperature is reduced to 30 ℃ within 1min by water cooling to obtain the composite material P20/A80-S.
And (3) performance testing: the sample is too brittle, i.e., the impact strength is too low, and thus, a sample bar cannot be produced.
And (4) SEM test: 1.5g of the composite material P20/A80-S was weighed into 150mL of formic acid and magnetically stirred at 45 ℃ for 4 h. Standing for 24h, centrifuging to separate solid phase, and vacuum oven drying for 12 h. As a result of observing the morphology of the undissolved polyester portion by SEM image, FIG. 10(c) shows that the polyester portion is a dispersed phase, the nylon etched away is a matrix phase, and the polyester portion is agglomerated and stacked together in spherical particles having a particle diameter of 0.1 to 3 μm, and the difference in particle size is large.
As can be seen from FIG. 10 (b)/FIG. 11 (g)/FIG. 3(b), when the sulfonate compound is grafted onto the PET macromolecular chain, the shape of the polyester part becomes irregular and the volume is greatly reduced, which indicates that the interfacial tension of the PET containing sulfonic acid group and PA6 after melt extrusion is very small and the compatibility is greatly improved. Comparing fig. 10 (a)/fig. 3 (a)/fig. 9(b) and fig. 10(c), it can be seen that in P20/a80-S, PET still exists in the form of small spheres as a dispersed phase, and the two have large interfacial tension and poor compatibility, which is comparable to P20/a 80. In the presence of a ester exchange reaction catalyst, namely a sulfonate compound, namely sodium p-toluenesulfonate, PET and PA6 have extremely low reaction degree in a short time, and the sulfonate compound is grafted to a PET macromolecular chain, so that a block copolymer can be generated in a short few minutes, and the microcosmic compatible mixing of polyester and nylon is realized.
Comparative example 4
The PA6 granules are dried in vacuum for 10h at 100 ℃, made into sample strips by an injection molding machine, set the injection molding temperature to be 200-240 ℃, and are tested after being placed in an environment with 23-27 ℃ and 50% humidity for 48h, and the performance test results are shown in Table 1.
TABLE 1 results of Performance test of each example and comparative example
Figure BDA0003223065380000221
As can be seen from the comparison of the test results of example 1, comparative example 1 and comparative example 3, the compatibility of the obtained composite material is too poor to be made into a sample strip by injection molding by directly carrying out a melt reaction on polyester and nylon or directly carrying out a melt reaction on a sulfonate compound, polyester and nylon; the composite material obtained by the melt reaction of polyester modified by a sulfonate compound and nylon is etched by formic acid, and an image observed by SEM shows that the composite material has good shape compatibility, the tensile modulus can reach 1.33GPa, the tensile strength can reach 70.4MPa, the elongation at break can reach 401.9 percent, and the impact strength can reach 1.9kJ/m2。
Carrying out melt extrusion on modified polyester obtained by modifying a sulfonate compound and nylon, wherein the composite material with high modified polyester mass content cannot be prepared into a sample strip by injection molding; the modified polyester has low mass content, the composite material with higher content of the sulfonate compound has better tensile property, and partial performance indexes are even better than those of the raw material; the modified polyester has low mass content, the composite material with low content of the sulfonic acid group compound has good tensile property, almost the same as the raw material nylon, and the impact strength is greatly improved compared with the raw material nylon.
The modified polyester obtained by modifying the sulfonate compound and the nylon are subjected to melt extrusion and then subjected to solid phase polycondensation reaction, so that the tensile modulus of the obtained composite material is almost the same as that of the raw material nylon, and the tensile strength, the elongation at break and the impact strength of the composite material are greatly improved and are superior to that of the raw material nylon.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features. When technical features in different embodiments are represented in the same drawing, it can be seen that the drawing also discloses a combination of the embodiments concerned.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (10)

1. A polyester/nylon composite, characterized in that the polyester/nylon composite comprises an amide group- [ NHCO ]]- [ COO ] ester group]-and an inner compatibilising segment; the mass content of polyester in the polyester/nylon composite material is 20-80%; the internal compatiblizing segment comprises-SO2-an NH-group and having a polyester/nylon internal compatibilising interface, said internal compatibilising segment having a characteristic shoulder peak in the nuclear magnetic carbon spectrum with a chemical shift in the interval 118ppm to 119 ppm; preferably, the internal compatibilization interface exhibits an irregular or amorphous structure; preferably, the mass content of the polyester in the polyester/nylon composite material is 40-60%; preferably, the method for detecting the mass content of the polyester in the polyester/nylon composite material comprises the following steps: the polyester/nylon composite material is etched by formic acid for more than 2 hours, the rest part is dried in vacuum for 24 hours, and the mass content of the polyester in the polyester/nylon composite material obtained by the detection method is that
Figure FDA0003223065370000011
Wherein w represents the mass of the polyester/nylon composite material before etching with formic acid, and w1Represents the mass of the remaining part after vacuum drying; preferably, the mass content of the polyester in the polyester/nylon composite material obtained by the detection method is allowed to have an error of 20% with the mass content of the polyester in the actual polyester/nylon composite material, and the mass content of the polyester in the actual polyester/nylon composite material is within a range
Figure FDA0003223065370000012
Wherein w represents the mass of the polyester/nylon composite material before etching with formic acid, and w1Representing the mass of the remaining portion after vacuum drying.
2. The polyester/nylon composite material according to claim 1, wherein the detection method of the polyester/nylon internal compatibilization interface is as follows: the polyester/nylon composite material is etched by formic acid for more than 2 hours, the appearance of the rest part is observed by SEM images with the magnification of 1000-20000 times, and the internal compatibilization interface is in an irregular structure or an amorphous structure; preferably, the etching time is 2-6 h; preferably, the inner volume-increasing interface does not have an agglomerated and stacked structure of spherical particles or a regular pore structure, the particle size of the spherical particles is 0.1-3 μm, and the pore size of the regular pores is 0.5-3 μm; preferably, the regular hole structure is a regular circular structure.
3. The polyester/nylon composite of claim 1, wherein the irregular structure is selected from an irregular gully-like structure, an irregular honeycomb-like structure; preferably, the length-diameter ratio of the irregular gully-shaped structure is more than or equal to 3; preferably, the surface of the irregular ravine-shaped structure is provided with spherical particles, and the particle size of the spherical particles is 10 nm-500 nm; preferably, the surface of the irregular honeycomb structure is provided with micropores, and the pore diameter of the micropores is 50 nm-800 nm.
4. The polyester/nylon composite of claim 2, wherein the amorphous structure is a smooth amorphous structure; preferably, the smooth amorphous structure surface is provided with spherical particles, and the particle size of the spherical particles is 100 nm-500 nm; preferably, the amorphous structure is formed by mutually stacking irregular particles, and the particle size of the irregular particles is 1 nm-50 nm; preferably, the surface of the amorphous structure formed by stacking the irregular particles has micropores, and the pore diameter of the micropores is 10nm to 100 nm.
5. A method for preparing the polyester/nylon composite material as claimed in any one of claims 1 to 4, which comprises the following steps:
mixing modified polyester and nylon, reacting in a molten state, and rapidly cooling to a temperature below a specific temperature to obtain the polyester/nylon composite material;
the modified polyester comprises a sulfonate group; preferably, the modified polyester is obtained by modifying polyester with a sulfonate compound; more preferably, the sulfonate compound is selected from one or more of sodium 2-hydroxy-3-allyloxypropanesulfonate, sodium 2-hydroxy-3-methacryloxypropanesulfonate, isoprene sulfonate, sodium sulfonate and potassium sulfonate;
the mass ratio of the modified polyester to the nylon is 8: 2-2: 8; preferably, the mass ratio of the modified polyester to the nylon is 6: 4-4: 6;
the specific temperature is lower than the temperature of the lower of the glass transition temperatures of both the modified polyester and the nylon; preferably, the specific temperature is 20 ℃ and above lower than the lower of the glass transition temperatures;
the time for rapid cooling is less than or equal to 2 min;
preferably, the sulfonate compound accounts for 1-8 wt% of the modified polyester; the modified polyester accounts for 20-80 wt% of the polyester/nylon composite material; the nylon accounts for 20-80 wt% of the polyester/nylon composite material.
6. The preparation method of the polyester/nylon composite material according to claim 5, wherein the polyester is selected from one or more of single-component polyester or modified polyester, the single-component polyester is selected from one or more of polyethylene terephthalate, polybutylene terephthalate, polylactic acid and polybutylene succinate, and the modified polyester is selected from one or more of cationic dyeable modified polyester, antistatic modified polyester and flame retardant modified polyester of the single-component polyester; the nylon is selected from one-component polyamide or copolyamide, and the one-component polyamide is selected from one or more of nylon6, nylon 66, nylon 610, nylon 612, nylon 6I, polyhexamethylene terephthalamide, polyhexamethylene isophthalamide, polyhexamethylene adipamide and modified nylon; the modified nylon is selected from one or more of single-component polyamide reinforced nylon, flame-retardant nylon, transparent nylon, wear-resistant nylon and toughened nylon.
7. The method for preparing polyester/nylon composite material according to claim 5, wherein the modified polyester and the nylon are sufficiently dried, and the sufficient drying is performed by using a high-temperature vacuum, and the high-temperature range is as follows: the vacuum pressure range is 100 Pa-50000 Pa at the temperature of 80-120 ℃, and the time for fully drying is 8-24 h; the reaction is carried out in a double-screw extruder, the reaction temperature is 150-350 ℃, and the reaction time is 1-10 min; preferably, the temperature of the reaction is 250-280 ℃; the reaction time is 1-5 min; preferably, the time for rapid cooling is less than or equal to 1 min; more preferably, the time for the rapid cooling is less than or equal to 0.5 min.
8. The method for preparing a polyester/nylon composite material according to any one of claims 5 to 7, comprising the steps of: after the reaction is finished, carrying out solid-phase reaction for 1-20 h in an inert gas atmosphere at the temperature of 120-280 ℃ to obtain the polyester/nylon composite material; preferably, the inert gas is nitrogen.
9. A composite comprising the polyester/nylon composite material according to any one of claims 1 to 4 or the polyester/nylon composite material obtained by the production method according to any one of claims 5 to 8; preferably, the compound comprises an additive, preferably, the additive is selected from one or more of a filler, a pigment, a plasticizer and an antioxidant; more preferably, the filler is selected from one or more of inorganic fillers, flame retardants, impact modifying materials, electrically conductive fillers, thermally conductive fillers, reinforcing fibers.
10. Use of the polyester/nylon composite material according to any one of claims 1 to 4, the polyester/nylon composite material obtained by the preparation method according to any one of claims 5 to 8, and the composite material according to claim 9 in the field of materials.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115489188A (en) * 2022-10-09 2022-12-20 安徽国风新材料股份有限公司 Polyester film for home protection and preparation method thereof
CN115489188B (en) * 2022-10-09 2023-08-29 安徽国风新材料股份有限公司 Polyester film for household protection and preparation method thereof

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