CN109280372B - Polyphenyl ether/nylon alloy material product and preparation method thereof - Google Patents
Polyphenyl ether/nylon alloy material product and preparation method thereof Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention provides a polyphenyl ether/nylon alloy material product and a preparation method thereof, wherein the preparation raw materials of the alloy material product comprise the following components in percentage by mass: 18-70% of polymerized nylon; 25-60% of polyphenyl ether; 2-10% of a first auxiliary agent; 0.2-12% of second assistant, wherein the polymerized nylon is obtained by polymerizing alicyclic diamine, aromatic diacid, lactam and epoxy compound, and the first assistant is a compatilizer. The epoxy group of the epoxy compound in the polymeric nylon adopted by the invention can react with amino or carboxyl in the polymeric nylon and also react with hydroxyl in the polyphenyl ether, so that the epoxy group can be used as a bridge to combine the polymeric nylon and the polyphenyl ether to generate a copolymer containing a polymeric nylon-epoxy compound-polyphenyl ether structure, namely, the non-crystalline non-polar copolymer polyphenyl ether and the crystalline polar copolymer nylon are well compatible, so that the prepared polyphenyl ether/nylon alloy material can simultaneously have the performances of the polyphenyl ether and the polymeric nylon.
Description
Technical Field
The invention relates to a nylon product, in particular to a polyphenyl ether/nylon alloy material product and a preparation method thereof.
Background
Polyphenylene oxide, abbreviated as PPO, is one of five general engineering plastics in the world, and has the advantages of high rigidity, high heat resistance, flame retardancy, high strength, excellent electrical property and the like. In addition, the polyphenyl ether also has the advantages of wear resistance, no toxicity, pollution resistance and the like. Polyphenylene oxide is one of the varieties with the minimum dielectric constant and dielectric loss in engineering plastics, is hardly influenced by temperature and humidity, and can be used in the fields of low, medium and high-frequency electric fields. Polyamide is commonly known as Nylon (Nylon), and is called Polyamide (PA for short) in English, which is a general name of thermoplastic resin containing repeated amide groups- [ NHCO ] -on a molecular main chain, and comprises aliphatic Nylon, aliphatic-aromatic Nylon and aromatic Nylon. The aliphatic nylon has many varieties, large output and wide application, and the nylon has good comprehensive properties including mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubricity, low friction coefficient, certain flame retardance and easy processing, is suitable for being filled, reinforced and modified by glass fiber and other fillers, and can improve the performance and expand the application range. The product has wide application, uses plastics to replace good materials of steel, iron, copper and other metals, is important engineering plastics, and has application in the aspects of automobiles, electronic appliances, sports and machinery.
Among the polyphenyl ether/nylon alloys, nylon provides good solvent resistance and processability, and polyphenyl ether has high heat resistance, low water absorption and dimensional stability, and the higher the content of the polyphenyl ether is, the better the heat resistance is. Polyphenylene oxide is a non-crystalline non-polar copolymer, nylon is a crystalline polar copolymer, the compatibility of the polyphenylene oxide and the nylon has certain difficulty, most of the polyphenylene oxide/nylon alloys on the market at present are polyphenylene oxide/styrene/nylon alloys, so that the heat distortion temperature of the polyphenylene oxide/nylon alloys is not very high, and the application is limited to a certain extent.
Therefore, it is desired to expand the range of applications of polyphenylene ether/nylon alloys by improving the compatibility between polyphenylene ether and nylon.
Disclosure of Invention
The invention aims to provide a polyphenyl ether/nylon alloy material product and a preparation method thereof, which can solve the problem of compatibility between polyphenyl ether and nylon and can improve various properties of polyphenyl ether/nylon alloy so as to expand the application range of the polyphenyl ether/nylon alloy.
In order to achieve the above purpose, the invention provides a polyphenylene oxide/nylon alloy material product in a first aspect, which is prepared from the following components in percentage by mass:
the polymerized nylon is obtained by polymerizing alicyclic diamine, aromatic diacid, lactam and epoxy compound,
the first auxiliary agent is a compatilizer.
The polymerized nylon adopted by the invention is obtained by polymerizing alicyclic diamine, aromatic dibasic acid, lactam and epoxy compound, is a semi-aromatic nylon material, and has the characteristics of high temperature resistance, low water absorption and high strength; epoxy groups of epoxy compounds in the polymeric nylon can react with amino groups or carboxyl groups in the polymeric nylon and also react with hydroxyl groups in the polyphenyl ether, so that the epoxy groups can be used as bridges to combine the polymeric nylon with the polyphenyl ether to generate a copolymer containing a polymeric nylon-epoxy compound-polyphenyl ether structure, namely, the non-crystalline nonpolar copolymer polyphenyl ether and the crystalline polar copolymer nylon are well compatible, so that the prepared polyphenyl ether/nylon alloy material can simultaneously have the performances of the polyphenyl ether and the polymeric nylon; meanwhile, the compatilizer can further promote the compatibility between the polyphenyl ether and the polymeric nylon, particularly the problem that the obtained product has poor local compatibility and uneven dispersion is solved, and the prepared polyphenyl ether/nylon alloy material has the excellent performances of the polyphenyl ether and the polymeric nylon, namely higher heat resistance, lower water absorption and dimensional stability.
The melting point of the polymerized nylon prepared by the method is up to 235-305 ℃, and the saturated water absorption is 4.5-6.5%, which means that the polymerized nylon has high temperature resistance and low water absorption.
Further, the mass percentage of the polymeric nylon may be 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, the mass percentage of the polyphenylene ether may be 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, the mass percentage of the compatibilizer may be 2%, 4%, 5%, 8%, 10%, and the mass percentage of the second auxiliary agent may be 0.2%, 0.4%, 0.5%, 0.8%, 1%, 2%, 4%, 6%, 8%, 10%, 12%. The second auxiliary agent is selected from one or more of a toughening agent, an antioxidant, a lubricant and a light stabilizer, preferably, the second auxiliary agent at least comprises the toughening agent, and the toughening agent accounts for 50-100% of the mass of the second auxiliary agent, more preferably, the second auxiliary agent comprises the toughening agent, the antioxidant, the lubricant and the light stabilizer, and in terms of mass percentage of the preparation raw materials of the polyphenyl ether/nylon alloy material product, the toughening agent accounts for 2-10%, the antioxidant accounts for 0.2-0.5%, the lubricant accounts for 0.2-0.6%, and the light stabilizer accounts for 0.2-0.6%. The toughening agent can improve the toughness of the polyphenyl ether/nylon alloy material, and can be one or more of styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer and maleic anhydride grafted ethylene-octene copolymer, and preferably is styrene-ethylene-butylene-styrene block copolymer. The antioxidant can reduce volatilization of various substances at high temperature, and can be selected from N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and/or tris [2, 4-di-tert-butylphenyl ] phosphite. The lubricant can be one or more of calcium stearate, modified ethylene bis fatty acid amide and ethylene bis stearamide, and can enhance the surface of the alloy material to ensure that the surface of the obtained product is bright. The light stabilizer can prevent the polyphenylene oxide/nylon alloy material product from yellowing due to photooxidation, and is preferably an ultraviolet absorbent, such as benzophenones, benzotriazoles and the like.
Furthermore, the alicyclic diamine and the aromatic diacid are in an equimolar ratio, the lactam accounts for 1-30% of the mass sum of the alicyclic diamine and the aromatic diacid, the epoxy compound accounts for 0.2-4% of the mass sum of the alicyclic diamine and the aromatic diacid, and the ratio of the lactam to the epoxy compound is small, so that the mechanical performance of the main structure of the polymerized nylon is not affected.
Further, the alicyclic diamine is selected from one or two of 4,4' -diaminodicyclohexylmethane and isophorone diamine, the aromatic diacid is selected from one or two of isophthalic acid and terephthalic acid, and the lactam is selected from one or two of caprolactam and lauryllactam.
Furthermore, the epoxy compound is N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, and the epoxy group is more, so that the compatibility between the polyphenyl ether and the polymeric nylon can be better under the same content.
Furthermore, the compatilizer is maleic anhydride grafted polyphenyl ether or citric acid, preferably citric acid, and the citric acid can degrade the polymerized nylon, so that the performance of a final product is reduced, so that the citric acid and the polyphenyl ether need to be grafted to form a polyphenyl ether-citric acid graft copolymer, and the grafted citric acid can also react with carboxyl in the polymerized nylon to form an amide or imide graft copolymer, namely, the citric acid between the polyphenyl ether and the polymerized nylon also plays a role of a bridge, so that the compatibility between the polyphenyl ether and the polymerized nylon is improved.
The second aspect of the invention provides a preparation method of a copolymerized nylon product, which comprises the following steps in sequence:
1) preparation of polymeric nylons
Adding the alicyclic diamine, the aromatic diacid, the lactam and the epoxy compound with the formula ratio into a polymerization kettle in a nitrogen atmosphere, heating and stirring, then exhausting and draining, cooling and pelletizing after belt casting forming to obtain the polymerized nylon;
2) preparation of compatilizer grafted polyphenyl ether
Blending the compatilizer and polyphenyl ether according to the formula ratio, extruding and drying to obtain the composite material;
3) preparation of polyphenyl ether/nylon alloy material product
Uniformly mixing the polymerized nylon, the compatilizer grafted polyphenyl ether and the second additive according to the formula ratio, shearing and extruding, and granulating and drying to obtain the composite material.
According to the preparation method, the compatilizer is blended with the polyphenyl ether to prepare the compatilizer grafted polyphenyl ether, and then the compatilizer grafted polyphenyl ether is blended with the polymeric nylon, so that the compatilizer can be prevented from degrading the polymeric nylon to influence the performance of the prepared alloy material product. Meanwhile, the polymeric nylon and the polyphenyl ether have good compatibility, and high-temperature melt extrusion is not needed, so that the performance influence on the alloy material during high-temperature melting can be avoided.
Further, in the step 3) of preparing the polyphenyl ether/nylon alloy material product, the rotation speed adopted by shearing is more than or equal to 250r/min, so that the dispersion of the polyphenyl ether is facilitated.
Furthermore, the preparation method of the polyphenyl ether/nylon alloy material product specifically comprises the following steps:
1) preparation of polymeric nylons
Under the protection of nitrogen, dissolving alicyclic diamine, aromatic dibasic acid, lactam and epoxy compound in a formula amount in water, heating to 80-180 ℃, reacting for 2-4 hours until the reaction liquid becomes clear or uniform suspension solution, transferring the solution into a polymerization kettle, continuously stirring and heating, starting to exhaust when the temperature reaches 240 ℃ and the air pressure is increased to 10-20 bar, raising the temperature to 300-340 ℃ in the exhaust process, removing water under the action of nitrogen, carrying out die head casting belt molding, cooling and pelletizing to obtain the polymerized nylon;
2) preparation of compatilizer grafted polyphenyl ether
Blending the compatilizer with the formula amount and the polyphenyl ether with the formula amount, extruding the mixture by a double-screw extruder and drying the mixture to obtain the composite material;
3) preparation of polyphenyl ether/nylon alloy material product
Uniformly mixing the polymerized nylon with the compatilizer grafted polyphenyl ether according to the formula amount and the second auxiliary agent according to the formula amount, adding the mixture into a main feeding hopper of an extruder, shearing and extruding at the rotating speed of 250-300 r/min, and extruding, granulating and drying the mixture by using a double-screw extruder to obtain the composite material.
The invention also provides another preparation method for the compatilizer without grafting reaction in advance, which comprises the following steps in sequence:
1) preparation of polymeric nylons
Adding alicyclic diamine, aromatic dibasic acid, lactam and epoxy compound into a polymerization kettle in nitrogen atmosphere, heating and stirring, then exhausting and draining, cooling and dicing after belt casting forming to obtain the polymerized nylon;
2') preparation of polyphenyl ether/nylon alloy material product
The preparation method comprises the following steps of uniformly mixing the polymeric nylon, the polyphenyl ether, the compatilizer and the second aid according to the formula ratio, shearing, extruding, granulating and drying.
Furthermore, the preparation method of the polyphenyl ether/nylon alloy material product specifically comprises the following steps:
1) preparation of polymeric nylons
Under the protection of nitrogen, dissolving alicyclic diamine, aromatic dibasic acid, lactam and epoxy compound in a formula amount in water, heating to 80-180 ℃, reacting for 2-4 hours until the reaction liquid becomes clear or uniform suspension solution, transferring the solution into a polymerization kettle, continuously stirring and heating, starting to exhaust when the temperature reaches 240 ℃ and the air pressure is increased to 10-20 bar, raising the temperature to 300-340 ℃ in the exhaust process, removing water under the action of nitrogen, carrying out die head casting belt molding, cooling and pelletizing to obtain the polymerized nylon;
2') preparation of polyphenyl ether/nylon alloy material product
Uniformly mixing the polymerized nylon, the polyphenyl ether, the compatilizer and the second assistant according to the formula ratio, adding the mixture into a main feeding hopper of an extruder, shearing and extruding at a rotating speed of 250-300 r/min, and extruding, granulating and drying the mixture by using a double-screw extruder to obtain the composite material.
Detailed Description
The technical solutions of the present invention are further illustrated below by specific examples, and the raw materials according to the examples of the present invention are all commercially available.
For convenience, some of the substances referred to herein are described in the specification by abbreviation, and specifically include: polyphenylene oxide/nylon (PPO/PA), polyphenylene oxide (PPO), nylon (PA), polymerized nylon (HPA), isophorone diamine (IPDA), 4 '-diaminodicyclohexylmethane (DDCM), isophthalic acid (IPA), terephthalic acid (TPA), Citric Acid (CA), N, N, N', N '-tetraglycidyl-4, 4' -diaminodiphenylmethane (TGDDM), laurolactam (LL), Caprolactam (CPL), maleic anhydride grafted polyphenylene oxide (PPO-g-MAH), citric acid grafted polyphenylene oxide (PPO-co-CA), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), maleic anhydride grafted ethylene-octene copolymer (POE-g-MAH), N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant TH-168), modified ethylene bis fatty acid amide (TAF), Ethylene Bis Stearamide (EBS), nylon 66(PA 66).
Example 1
A polyphenyl ether/nylon alloy material product is prepared from the following raw materials in percentage by mass:
the polymerized nylon HPA is obtained by polymerizing IPDA, TPA, LL and TGDDM, the compatilizer is CA, the flexibilizer is SEBS, the antioxidant is antioxidant 1098, the lubricant is TAF, and the light stabilizer is benzophenone ultraviolet absorbent.
The preparation method of the polyphenyl ether/nylon alloy material comprises the following steps:
1) preparation of HPA
Under the protection of nitrogen, dissolving IPDA and TPA in equal molar, LL accounting for 18 percent of the mass sum of IPDA and TPA and TGDDM accounting for 2 percent of the mass sum of IPDA and TPA in water, heating to 120 ℃, reacting for 3 hours until the reaction solution becomes clear or uniform suspension solution, transferring the solution into a polymerization kettle, continuously stirring and heating, starting to exhaust when the temperature reaches 240 ℃ and the air pressure is increased to 15bar, raising the temperature to 320 ℃ in the exhaust process, removing water under the action of nitrogen, then casting a belt through a die head for molding, cooling and pelletizing to obtain the polymerized nylon;
2) preparation of PPO-co-CA
Blending CA with the formula amount and PPO with the formula amount, extruding by a double-screw extruder, and drying to obtain the final product;
3) preparation of PPO/PA alloy material product
Uniformly mixing HPA, PPO-co-CA, SEBS, antioxidant 1098, TAF and benzophenone ultraviolet absorbent according to the formula amounts, adding the mixture into a main feeding hopper of an extruder, shearing and extruding at a rotating speed of 300r/min, extruding by a double-screw extruder, granulating and drying to obtain the high-performance ultraviolet absorbent.
Example 2
A polyphenyl ether/nylon alloy material product is prepared from the following raw materials in percentage by mass:
the polymerized nylon HPA is obtained by polymerizing IPDA, TPA, LL and TGDDM, the compatilizer is CA, the flexibilizer is SEBS, the antioxidant is antioxidant 1098, the lubricant is TAF, and the light stabilizer is benzophenone ultraviolet absorbent.
The preparation method of the polyphenyl ether/nylon alloy material comprises the following steps:
1) preparation of HPA
Under the protection of nitrogen, dissolving IPDA and TPA in equal molar, LL accounting for 18 percent of the mass sum of IPDA and TPA and TGDDM accounting for 2 percent of the mass sum of IPDA and TPA in water, heating to 120 ℃, reacting for 3 hours until the reaction solution becomes clear or uniform suspension solution, transferring the solution into a polymerization kettle, continuously stirring and heating, starting to exhaust when the temperature reaches 240 ℃ and the air pressure is increased to 15bar, raising the temperature to 320 ℃ in the exhaust process, removing water under the action of nitrogen, then casting a belt through a die head for molding, cooling and pelletizing to obtain the polymerized nylon;
2) preparation of PPO-co-CA
Blending CA with the formula amount and PPO with the formula amount, extruding by a double-screw extruder, and drying to obtain the final product;
3) preparation of PPO/PA alloy material product
Uniformly mixing HPA, PPO-co-CA, SEBS, antioxidant 1098, TAF and benzophenone ultraviolet absorbent according to the formula amounts, adding the mixture into a main feeding hopper of an extruder, shearing and extruding at a rotating speed of 300r/min, extruding by a double-screw extruder, granulating and drying to obtain the high-performance ultraviolet absorbent.
Example 3
A polyphenyl ether/nylon alloy material product is prepared from the following raw materials in percentage by mass:
the polymerized nylon HPA is obtained by polymerizing IPDA, TPA, LL and TGDDM, the compatilizer is CA, the flexibilizer is SEBS, the antioxidant is antioxidant 1098, the lubricant is TAF, and the light stabilizer is benzophenone ultraviolet absorbent.
The preparation method of the polyphenyl ether/nylon alloy material comprises the following steps:
1) preparation of HPA
Under the protection of nitrogen, dissolving IPDA and TPA in equal molar, LL accounting for 18 percent of the mass sum of IPDA and TPA and TGDDM accounting for 2 percent of the mass sum of IPDA and TPA in water, heating to 120 ℃, reacting for 3 hours until the reaction solution becomes clear or uniform suspension solution, transferring the solution into a polymerization kettle, continuously stirring and heating, starting to exhaust when the temperature reaches 240 ℃ and the air pressure is increased to 15bar, raising the temperature to 320 ℃ in the exhaust process, removing water under the action of nitrogen, then casting a belt through a die head for molding, cooling and pelletizing to obtain the polymerized nylon;
2) preparation of PPO-co-CA
Blending CA with the formula amount and PPO with the formula amount, extruding by a double-screw extruder, and drying to obtain the final product;
3) preparation of PPO/PA alloy material product
Uniformly mixing HPA, PPO-co-CA, SEBS, antioxidant 1098, TAF and benzophenone ultraviolet absorbent according to the formula amounts, adding the mixture into a main feeding hopper of an extruder, shearing and extruding at a rotating speed of 300r/min, extruding by a double-screw extruder, granulating and drying to obtain the high-performance ultraviolet absorbent.
Example 4
A polyphenyl ether/nylon alloy material product is prepared from the following raw materials in percentage by mass:
the polymerized nylon HPA is obtained by polymerizing DDCM, IPA, CPL and TGDDM, the compatilizer is CA, the flexibilizer is SBS, the antioxidant is antioxidant TH-168, the lubricant is EBS, and the light stabilizer is benzotriazole ultraviolet absorbent.
The preparation method of the polyphenyl ether/nylon alloy material comprises the following steps:
1) preparation of HPA
Under the protection of nitrogen, dissolving equimolar DDCM and IPA, CPL accounting for 18 percent of the mass sum of the DDCM and the IPA and TGDDM accounting for 2 percent of the mass sum of the DDCM and the IPA in water, heating to 120 ℃, reacting for 3 hours until the reaction liquid becomes clear or uniform suspension solution, transferring the solution into a polymerization kettle, continuously stirring and heating until the temperature reaches 240 ℃, starting to exhaust when the air pressure is increased to 15bar, increasing the temperature to 320 ℃ in the exhaust process, removing water under the action of nitrogen, then casting a belt through a die head, cooling and pelletizing to obtain the polymerized nylon;
2) preparation of PPO-co-CA
Blending CA with the formula amount and PPO with the formula amount, extruding by a double-screw extruder, and drying to obtain the final product;
3) preparation of PPO/PA alloy material product
Uniformly mixing HPA, PPO-co-CA, SBS, antioxidant TH-168, EBS and benzotriazole ultraviolet absorbent in formula amounts, adding into a main feeding hopper of an extruder, shearing and extruding at a rotating speed of 300r/min, extruding by a double-screw extruder, granulating and drying to obtain the high-performance high-temperature-resistant high-pressure-resistant high-temperature.
Example 5
A polyphenyl ether/nylon alloy material product is prepared from the following raw materials in percentage by mass:
the polymerized nylon HPA is obtained by polymerizing IPDA, TPA, LL and TGDDM, the compatilizer is PPO-g-MAH, the flexibilizer is SEBS, the antioxidant is antioxidant 1098, the lubricant is TAF, and the light stabilizer is benzophenone ultraviolet absorbent.
The preparation method of the polyphenyl ether/nylon alloy material comprises the following steps:
1) preparation of HPA
Under the protection of nitrogen, dissolving IPDA and TPA in equal molar, LL accounting for 18 percent of the mass sum of IPDA and TPA and TGDDM accounting for 2 percent of the mass sum of IPDA and TPA in water, heating to 120 ℃, reacting for 3 hours until the reaction solution becomes clear or uniform suspension solution, transferring the solution into a polymerization kettle, continuously stirring and heating, starting to exhaust when the temperature reaches 240 ℃ and the air pressure is increased to 15bar, raising the temperature to 320 ℃ in the exhaust process, removing water under the action of nitrogen, then casting a belt through a die head for molding, cooling and pelletizing to obtain the polymerized nylon;
2') preparation of PPO/PA alloy material product
Uniformly mixing HPA, PPO-g-MAH, SEBS, antioxidant 1098, TAF and benzophenone ultraviolet absorbent according to the formula amounts, adding the mixture into a main feeding hopper of an extruder, shearing and extruding at a rotating speed of 300r/min, extruding by a double-screw extruder, granulating and drying to obtain the high-performance high-temperature-resistant high-.
Example 6
A polyphenyl ether/nylon alloy material product is prepared from the following raw materials in percentage by mass:
the polymerized nylon HPA is obtained by polymerizing IPDA, TPA, LL and TGDDM, the compatilizer is CA, the flexibilizer is SEBS, and the antioxidant is antioxidant 1098.
The preparation method of the polyphenyl ether/nylon alloy material comprises the following steps:
1) preparation of HPA
Under the protection of nitrogen, dissolving IPDA and TPA in equal molar, LL accounting for 18 percent of the mass sum of IPDA and TPA and TGDDM accounting for 2 percent of the mass sum of IPDA and TPA in water, heating to 120 ℃, reacting for 3 hours until the reaction solution becomes clear or uniform suspension solution, transferring the solution into a polymerization kettle, continuously stirring and heating, starting to exhaust when the temperature reaches 240 ℃ and the air pressure is increased to 15bar, raising the temperature to 320 ℃ in the exhaust process, removing water under the action of nitrogen, then casting a belt through a die head for molding, cooling and pelletizing to obtain the polymerized nylon;
2) preparation of PPO-co-CA
Blending CA with the formula amount and PPO with the formula amount, extruding by a double-screw extruder, and drying to obtain the final product;
3) preparation of PPO/PA alloy material product
HPA, PPO-co-CA, SEBS and antioxidant 1098 are mixed uniformly, added into a main feeding hopper of an extruder, sheared and extruded at a rotating speed of 300r/min, and extruded, granulated and dried by a double-screw extruder to obtain the high-performance high-strength high-toughness high-strength high-toughness high-strength high-toughness.
Example 7
A polyphenyl ether/nylon alloy material product is prepared from the following raw materials in percentage by mass:
the polymerized nylon HPA is obtained by polymerizing IPDA, TPA, LL and TGDDM, the compatilizer is CA, and the flexibilizer is SEBS.
The preparation method of the polyphenyl ether/nylon alloy material comprises the following steps:
1) preparation of HPA
Under the protection of nitrogen, dissolving IPDA and TPA in equal molar, LL accounting for 18 percent of the mass sum of IPDA and TPA and TGDDM accounting for 2 percent of the mass sum of IPDA and IPA in water, heating to 120 ℃, reacting for 3 hours until the reaction liquid becomes clear or uniform suspension solution, transferring the solution into a polymerization kettle, continuously stirring and heating until the temperature reaches 240 ℃, starting to exhaust when the air pressure is increased to 15bar, increasing the temperature to 320 ℃ in the exhaust process, removing water under the action of nitrogen, then casting a belt through a die head for molding, cooling and pelletizing to obtain the polymerized nylon;
2) preparation of PPO-co-CA
Blending CA with the formula amount and PPO with the formula amount, extruding by a double-screw extruder, and drying to obtain the final product;
3) preparation of PPO/PA alloy material product
HPA, PPO-co-CA and SEBS are uniformly mixed according to the formula amount, added into a main feeding hopper of an extruder, sheared and extruded at the rotating speed of 300r/min, extruded by a double-screw extruder, granulated and dried to obtain the high-performance high-strength high-toughness high-strength high-toughness high-strength high-toughness high.
Comparative example 1
A polyphenyl ether/nylon alloy material product is prepared from the following raw materials in percentage by mass:
the toughening agent is SEBS, the antioxidant is antioxidant 1098, the lubricant is TAF, and the light stabilizer is benzophenone ultraviolet absorbent.
The preparation method of the polyphenyl ether/nylon alloy material comprises the following steps:
(1) mixing the components uniformly with PA66, PPO, SEBS, antioxidant 1098, TAF and benzophenone ultraviolet absorbent in formula amount;
(2) and (2) putting the blended material obtained in the step (1) into a double-screw extruder, uniformly mixing, performing melt extrusion at 290 ℃ and 300r/min, cooling, granulating and screening to obtain the material.
Comparative example 2
A polyphenyl ether/nylon alloy material product is prepared from the following raw materials in percentage by mass:
the compatilizer is PPO-g-MAH, the flexibilizer is SEBS, the antioxidant is antioxidant 1098, the lubricant is TAF, and the light stabilizer is benzophenone ultraviolet absorbent.
The preparation method of the polyphenyl ether/nylon alloy material comprises the following steps:
(1) mixing with PA66, PPO-g-MAH, SEBS, antioxidant 1098, TAF, and benzophenone ultraviolet absorbent;
(2) and (2) putting the blended material obtained in the step (1) into a double-screw extruder, uniformly mixing, performing melt extrusion at 290 ℃ and 300r/min, cooling, granulating and screening to obtain the material.
The polyphenylene ether/nylon alloy material products of examples 1 to 7 and comparative examples 1 to 2 were tested for various mechanical properties, high temperature resistance and shrinkage, and the test results are shown in table 1.
And (3) detecting mechanical properties: the tensile strength is tested by adopting GB/T1040-;
high temperature resistance: the high temperature resistance is characterized by adopting the heat distortion temperature, and the heat distortion temperature is tested by adopting the ASTM D648 standard;
shrinkage rate: shrinkage was measured using astm d955 standard.
TABLE 1 test results of examples 1 to 7 and comparative examples 1 to 2
Based on the examples 1 to 7 and the comparative examples 1 to 2 in table 1, it can be seen that the polyphenylene ether/nylon alloy material product prepared by using the polymeric nylon of the present invention instead of a common nylon material has excellent high temperature resistance, mechanical strength and dimensional stability, is a polyphenylene ether/nylon alloy material product with low warpage and high thermal deformation, and shows that the compatibility of polyphenylene ether and nylon in the polyphenylene ether/nylon alloy material product of the present invention is good.
Based on examples 3 and 5, it can be seen that citric acid is used as a compatibilizer, and the performances are better.
It should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will be able to modify the invention in various equivalent ways after reading this disclosure.
Claims (7)
1. A polyphenyl ether/nylon alloy material product is characterized in that the preparation raw materials comprise the following components in percentage by mass:
18-70% of polymerized nylon;
25-60% of polyphenyl ether;
2-10% of a first auxiliary agent;
0.2 to 12 percent of second auxiliary agent,
the polymerized nylon is obtained by polymerizing alicyclic diamine, aromatic diacid, lactam and epoxy compound,
the first auxiliary agent is a compatilizer,
the compatilizer is citric acid, the compatilizer and the polyphenyl ether are blended to prepare compatilizer grafted polyphenyl ether,
the epoxy compound is N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane;
the preparation method of the polyphenyl ether/nylon alloy material product comprises the following steps in sequence:
1) preparation of the polymeric nylon
Adding the alicyclic diamine, the aromatic dibasic acid, the lactam and the epoxy compound in formula ratio into a polymerization kettle in nitrogen atmosphere, heating and stirring, then exhausting and draining, cooling and pelletizing after belt casting forming to obtain the polymerized nylon;
2) preparation of the compatilizer grafted polyphenyl ether
Blending the compatilizer and the polyphenyl ether according to the formula ratio, extruding and drying to obtain the composite material;
3) preparation of the polyphenyl ether/nylon alloy material product
Uniformly mixing the polymerized nylon, the compatilizer grafted polyphenyl ether and the second auxiliary agent according to the formula ratio, shearing and extruding, and granulating and drying to obtain the modified polypropylene composite material.
2. The polyphenylene ether/nylon alloy material product according to claim 1, wherein the alicyclic diamine and the aromatic diacid are in an equimolar ratio, the lactam accounts for 1 to 30% of the sum of the alicyclic diamine and the aromatic diacid by mass, and the epoxy compound accounts for 0.2 to 4% of the sum of the alicyclic diamine and the aromatic diacid by mass.
3. The polyphenylene ether/nylon alloy material article of claim 1, wherein the cycloaliphatic diamine is selected from one or both of 4,4' -diaminodicyclohexylmethane and isophoronediamine.
4. The polyphenylene ether/nylon alloy material article of claim 1, wherein the aromatic dibasic acid is selected from one or both of isophthalic acid and terephthalic acid.
5. The polyphenylene ether/nylon alloy material article of claim 1, wherein the lactam is selected from one or both of caprolactam and lauryllactam.
6. The polyphenylene ether/nylon alloy material article of claim 1, wherein the second aid is selected from one or more of a toughening agent, an antioxidant, a lubricant, and a light stabilizer.
7. A preparation method of a polyphenyl ether/nylon alloy material product is characterized in that the polyphenyl ether/nylon alloy material product is as claimed in any one of claims 1 to 6.
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| CN103333490A (en) * | 2013-06-13 | 2013-10-02 | 江苏安格特科技发展有限公司 | Low gloss, high impact and high temperature resistance nylon alloy material and preparation method thereof |
| CN103923314A (en) * | 2014-04-10 | 2014-07-16 | 东莞市意普万尼龙科技股份有限公司 | High temperature resistant copolymer nylon with low hygroscopicity and preparation method thereof |
| CN104212161A (en) * | 2013-05-29 | 2014-12-17 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenyl ether/polyamide alloy material and preparation method |
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| CN103333490A (en) * | 2013-06-13 | 2013-10-02 | 江苏安格特科技发展有限公司 | Low gloss, high impact and high temperature resistance nylon alloy material and preparation method thereof |
| CN103923314A (en) * | 2014-04-10 | 2014-07-16 | 东莞市意普万尼龙科技股份有限公司 | High temperature resistant copolymer nylon with low hygroscopicity and preparation method thereof |
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