CN114181522A - Alcoholysis-resistant thermal-stable PPA composite material and preparation method thereof - Google Patents
Alcoholysis-resistant thermal-stable PPA composite material and preparation method thereof Download PDFInfo
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- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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Abstract
The invention belongs to the technical field of high polymer materials, and discloses an alcoholysis-resistant thermally stable PPA composite material and a preparation method thereof. The alcoholysis-resistant thermal-stable PPA composite material comprises, by weight, 60-75 parts of PPA resin, 0.5-2 parts of epoxy group pre-hydrolysis coupling agent, 1-4 parts of heat stabilizer, 25-40 parts of chopped glass fiber, 0.1-0.4 part of nucleating agent, 0.4-0.8 part of antioxidant and 0.4-0.8 part of lubricant. The material provided by the invention has excellent mechanical properties and processing properties, and can solve the problems of high water absorption, poor hydrolysis resistance, poor creep resistance, poor thermal stability, poor dimensional stability and the like of long carbon chain nylon reinforced materials used in the industries of automobiles, electric tools and electronic and electric appliances.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to an alcoholysis-resistant thermally stable PPA composite material and a preparation method thereof.
Background
The long carbon chain nylon such as PA66 and PA6 has the characteristics of oil resistance, organic solvent resistance, excellent mechanical property and the like, and is widely applied to the fields of electronic appliances, automobiles, household appliances, office equipment and the like. However, long carbon chain nylons tend to absorb water, have poor hydrolysis resistance, poor thermal stability, and poor dimensional stability, which limits their use in high temperature and high humidity or water environments. On the other hand, metal materials have the characteristics of high strength, corrosion resistance, stable size, creep resistance and the like, and are widely applied to the field of machine manufacturing. However, as the industrial modernization process is continuously advanced, the disadvantages of heavy metal materials and low cost performance are gradually highlighted.
Polyphthalamide (PPA) is semi-aromatic polyamide synthesized by taking terephthalic acid or phthalic acid and adipic acid hexamethylene diamine salt as raw materials. The semi-aromatic nylon is a semi-crystalline polymer, and the melting point is between 290 ℃ and 320 ℃. Compared with common long carbon chain nylon, the nylon has the following characteristics: 1. the high-strength high-creep-resistance high-strength water-absorbing alloy has low water absorption, good rigidity and strong creep resistance, particularly keeps better strength under the high-temperature and high-humidity environment, and is widely applied to parts working underwater; 2. the modified PPA material can work in the environment of 150 ℃ for a long time and can be widely applied to structural parts working in a high-temperature environment; 3. the PPA material has good dimensional stability and low thermal expansion coefficient and water absorption, and can be widely applied to the field with high dimensional accuracy.
In recent years, with the progress of the technology level, products in various industries are continuously upgraded and updated. The intelligent products in industries such as automobiles, household electrical appliances, furniture, office appliances and the like are continuously released. The artificial intelligence products are continuously reduced in size and more components are integrated inside, which means that the distance between internal components is smaller and smaller, and the heat generation amount inside is larger and larger, so that the updating of materials for manufacturing the internal components is urgent. On the other hand, ecological civilization construction has called for energy conservation and emission reduction, and large equipment manufacturers, especially automobile factories, are required to set consumption reduction targets, which greatly accelerates the process of replacing steel by plastics in automobiles and even the whole mechanical industry. The glass fiber reinforced high-temperature nylon has the highest specific strength in engineering plastics, has excellent temperature resistance and hydrolysis resistance, is very suitable for replacing metal materials to be applied to high-temperature and high-humidity environments, but the performance of the existing nylon material needs to be improved, particularly the performances in the aspects of hydrolysis resistance, size stability, thermal ageing and the like.
Disclosure of Invention
The invention aims to overcome the defects of the background art and provide an alcoholysis-resistant thermal-stable PPA composite material and a preparation method thereof.
In order to achieve the purpose of the invention, the alcoholysis-resistant thermal-stable PPA composite material comprises the following components in parts by weight:
further, in some embodiments of the invention, the PPA resin is one or more of poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer (poly (hexamethylene terephthalamide), block copolymer of hexamethylene adipamide), poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, and poly (hexamethylene terephthalamide-co-poly (hexamethylene terephthalamide)).
Preferably, in some embodiments of the invention, the PPA resin is a polyhexamethylene terephthalamide-co-hexamethylene adipamide copolymer, preferably wherein the molar ratio of copolymerization of the monomers is 5:4: 1; more preferably, the viscosity of the PPA resin is from 0.7 to 1.0 dL/g.
Further, in some embodiments of the invention, the epoxy-based pre-hydrolytic coupling agent is a hydrolysate of one or more of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldiethoxysilane, and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
Preferably, in some embodiments of the present invention, the epoxy pre-hydrolysis coupling agent is β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane hydrolysate.
Further, in some embodiments of the present invention, the epoxy pre-hydrolytic coupling agent is a product of hydrolysis using a methanol, acetic acid mixture as a hydrolysis solution.
Preferably, in some embodiments of the present invention, the mass ratio of the epoxy-based coupling agent in the epoxy-based pre-hydrolytic coupling agent is 85-95%.
Preferably, in some embodiments of the present invention, the weight ratio of methanol to acetic acid in the mixture of methanol and acetic acid is 20-30: 1.
further, in some embodiments of the present invention, the epoxy pre-hydrolytic coupling agent is prepared by the following steps: a. dripping an epoxy group coupling agent into the hydrolysis solution, and stirring; b. standing for 2-4 hours, then putting into an oven with the temperature of 60-80 ℃ for reduced pressure distillation for 1-2 hours, and taking out.
Preferably, in some embodiments of the present invention, the dropping time is 30-40 minutes, and the stirring rate is 100-150 rpm.
Further, in some embodiments of the present invention, the chopped glass fiber is a surface-treated hydrolysis-resistant alkali-free chopped glass fiber, and the chopped glass fiber has a length of 1-4mm and a diameter of 9-12 μm.
Further, in some embodiments of the present invention, the heat stabilizer is one or more of polyether polyol, sorbitol, dipentaerythritol, preferably dipentaerythritol.
Further, in some embodiments of the present invention, the nucleating agent is a complex formed by reacting zinc phenylphosphonate and calcium montanate in a solution.
Preferably, in some embodiments of the present invention, the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1: 3-5.
Further, in some embodiments of the present invention, the antioxidant is a rare earth compound.
Preferably, in some embodiments of the present invention, the antioxidant is one or more of neodymium stearate, praseodymium stearate, lanthanum stearate, samarium oxide, yttrium oxide, and bait oxide, more preferably neodymium stearate.
Preferably, in some embodiments of the present invention, the lubricant is one or more of silicone powder, ethylene bis stearamide, pentaerythritol stearate, calcium stearate, ethylene acrylic acid ionomer, more preferably ethylene acrylic acid ionomer.
In still another aspect, the present invention further provides a preparation method of the alcoholysis-resistant thermal-stable PPA composite, wherein the preparation method comprises the following steps:
(1) the PPA resin is placed in an oven to be dried, the drying temperature is 110-130 ℃, the drying time is 2-4 hours, and the water content after drying is controlled below 0.1%;
(2) weighing raw materials except the chopped glass fiber and the epoxy pre-hydrolytic coupling agent according to the required weight parts;
(3) uniformly mixing the raw materials weighed in the step (2) for later use;
(4) and (3) granulation: and (3) putting the uniformly mixed raw materials into a double-screw extruder for melt extrusion, adding the chopped glass fibers through side feeding, dripping the epoxy group pre-hydrolysis coupling agent from a second air outlet of the extruder, and keeping the temperature of each temperature zone of the extruder at 290-335 ℃ to finally obtain the product.
Furthermore, the adding amount of the epoxy group pre-hydrolysis coupling agent can be accurately controlled by a micro-injection pump at the feed opening, and the coupling agent is contained in a heat-insulating barrel, wherein the temperature of the heat-insulating barrel is 60-80 ℃; the coupling agent is added in the mixing section, so that the coupling agent is prevented from being subjected to excessive shear heat in the machine barrel, the chemical structure of the coupling agent is protected, the volatilization amount of the coupling agent is reduced, and the matrix resin and the glass fiber surface impregnating compound are subjected to chemical reaction with the coupling agent under the condition of melting, so that the binding power among the components of the material is improved.
Compared with the prior art, the invention has the following advantages:
(1) the invention greatly improves the dispersibility of the nucleating agent in the PPA resin by adding the complexing nucleating agent, thereby greatly improving the performances of the material in the aspects of hydrolysis resistance, stable size, thermal aging and the like;
(2) the invention uses rare earth compound as antioxidant and polyol compound as heat stabilizer, and the combination of the rare earth compound and the polyol compound shows good synergistic effect. Wherein, the rare earth element can be complexed with amide group of nylon under high temperature condition to prevent chain scission degradation of the material; the polyhydric alcohol can generate self dehydration reaction under the high temperature condition to form ether, a compact protective layer is formed on the surface of the material to prevent oxygen from entering, and the retention rate of the mechanical property of the prepared PPA material is more than 60% after the PPA material is subjected to thermal aging at 210 ℃ for 1000 hours.
(3) The composite material comprises the epoxy group pre-hydrolysis coupling agent, and the coupling agent after hydrolysis has stronger cohesiveness and reactivity, and plays a good role of an interface binder. In addition, the epoxy pre-hydrolyzed coupling agent is added in the extrusion process through a micro pump, so that the coupling agent is prevented from being degraded by heat or volatilized by heat, and the epoxy pre-hydrolyzed coupling agent and the coupling agent are subjected to chemical reaction under the condition that the matrix resin and the glass fiber surface impregnating agent are molten. Therefore, the hydrolysis resistance of the material is greatly improved in both formula design and process improvement, and the mechanical property retention rate of the prepared PPA material is over 80 percent after the alcoholysis test at 130 ℃ for 1000 hours.
(4) The production process is safe and environment-friendly, the production process and equipment are simple, the industrial production is very easy to realize, the cost is low, and the method is suitable for large-scale popularization and has good economic benefit.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Furthermore, the description below of the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily for the same embodiment or example. Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
An alcoholysis-resistant thermally stable PPA composite material comprises the following components in parts by weight:
the materials except the chopped glass fiber and the epoxy group pre-hydrolysis coupling agent are put into a high-speed mixer to be mixed and mixed uniformly (the mixture is mixed for 3 minutes, the rotating speed of the high-speed mixer is 500RPM), then the mixed materials are put into a main blanking barrel of an extruder to be granulated through the extruder, 30 parts of chopped fiber are added in the extrusion process in a side feeding mode, 0.5 part of epoxy group pre-hydrolysis coupling agent is added through a micro pump, the vacuum opening is kept, and the temperature of each temperature zone of the extruder is as follows: one zone at 150 deg.C, two zones at 320 deg.C, three zones at 320 deg.C, four zones at 320 deg.C, five zones at 310 deg.C, six zones at 300 deg.C, seven zones at 290 deg.C, eight zones at 290 deg.C, nine zones at 290 deg.C, ten zones at 290 deg.C, eleven zones at 300 deg.C, head at 310 deg.C, and extruder speed at 400 RPM.
The PPA resin is poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, wherein the copolymerization molar ratio of monomers is 5:4: 1; the epoxy group pre-hydrolysis coupling agent is beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex generated by reacting zinc phenylphosphonate and calcium montanate in a solution mode, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1: 4; the antioxidant is neodymium stearate; the lubricant is an ethylene-acrylic acid ionomer.
Example 2
The present embodiment is different from embodiment 1 in that: firstly, weighing the following materials in parts by weight:
the materials except the chopped glass fiber and the epoxy group pre-hydrolysis coupling agent are put into a high-speed mixer to be mixed and mixed uniformly (the mixture is mixed for 3 minutes, the rotating speed of the high-speed mixer is 500RPM), then the mixed materials are put into a main blanking barrel of an extruder to be granulated through the extruder, 30 parts of chopped fiber are added in the extrusion process in a side feeding mode, 1 part of epoxy group pre-hydrolysis coupling agent is added through a micro pump, the vacuum opening is kept, and the temperature of each temperature zone of the extruder is as follows: one zone at 150 deg.C, two zones at 320 deg.C, three zones at 320 deg.C, four zones at 320 deg.C, five zones at 310 deg.C, six zones at 300 deg.C, seven zones at 290 deg.C, eight zones at 290 deg.C, nine zones at 290 deg.C, ten zones at 290 deg.C, eleven zones at 300 deg.C, head at 310 deg.C, and extruder speed at 400 RPM.
The PPA resin is poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, wherein the copolymerization molar ratio of monomers is 5:4: 1; the epoxy group pre-hydrolysis coupling agent is beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex generated by reacting zinc phenylphosphonate and calcium montanate in a solution mode, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1: 4; the antioxidant is neodymium stearate; the lubricant is an ethylene-acrylic acid ionomer.
Example 3
The present embodiment is different from embodiment 1 in that: firstly, weighing the following materials in parts by weight:
the materials except the chopped glass fiber and the epoxy group pre-hydrolysis coupling agent are put into a high-speed mixer to be mixed and mixed uniformly (the mixture is mixed for 3 minutes, the rotating speed of the high-speed mixer is 500RPM), then the mixed materials are put into a main blanking barrel of an extruder to be granulated through the extruder, 40 parts of chopped fiber are added in the extrusion process in a side feeding mode, 1 part of epoxy group pre-hydrolysis coupling agent is added through a micro pump, the vacuum opening is kept, and the temperature of each temperature zone of the extruder is as follows: one zone at 150 deg.C, two zones at 320 deg.C, three zones at 320 deg.C, four zones at 320 deg.C, five zones at 310 deg.C, six zones at 300 deg.C, seven zones at 290 deg.C, eight zones at 290 deg.C, nine zones at 290 deg.C, ten zones at 290 deg.C, eleven zones at 300 deg.C, head at 310 deg.C, and extruder speed at 400 RPM.
The PPA resin is poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, wherein the copolymerization molar ratio of monomers is 5:4: 1; the epoxy group pre-hydrolysis coupling agent is beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex generated by reacting zinc phenylphosphonate and calcium montanate in a solution mode, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1: 4; the antioxidant is neodymium stearate; the lubricant is an ethylene-acrylic acid ionomer.
Comparative example 1
Comparative example 1 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
the materials except the chopped glass fiber and the alkyl coupling agent are put into a high-speed mixer to be mixed and mixed uniformly (the mixing time is 3 minutes, the rotating speed of the high-speed mixer is 500RPM), then the mixed materials are put into a main blanking barrel of an extruder to be granulated through the extruder, 30 parts of chopped fiber are added in the extrusion process in a side feeding mode, 0.5 part of alkyl coupling agent is added through injection of a micro pump, the vacuum opening is kept, and the temperature of each temperature zone of the extruder is as follows: one zone at 150 deg.C, two zones at 320 deg.C, three zones at 320 deg.C, four zones at 320 deg.C, five zones at 310 deg.C, six zones at 300 deg.C, seven zones at 290 deg.C, eight zones at 290 deg.C, nine zones at 290 deg.C, ten zones at 290 deg.C, eleven zones at 300 deg.C, head at 310 deg.C, and extruder speed at 400 RPM.
The PPA resin is poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, wherein the copolymerization molar ratio of monomers is 5:4: 1; the alkyl coupling agent is octaalkyltrimethoxysilane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex generated by reacting zinc phenylphosphonate and calcium montanate in a solution mode, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1: 4; the antioxidant is neodymium stearate; the lubricant is an ethylene-acrylic acid ionomer.
Comparative example 2
Comparative example 2 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
the materials except the chopped glass fiber and the epoxy group pre-hydrolysis coupling agent are put into a high-speed mixer to be mixed and mixed uniformly (the mixture is mixed for 3 minutes, the rotating speed of the high-speed mixer is 500RPM), then the mixed materials are put into a main blanking barrel of an extruder to be granulated through the extruder, 30 parts of chopped fiber are added in the extrusion process in a side feeding mode, 0.5 part of epoxy group pre-hydrolysis coupling agent is added in through injection of a micro pump, the vacuum opening is kept, and the temperature of each temperature zone of the extruder is as follows: one zone at 150 deg.C, two zones at 320 deg.C, three zones at 320 deg.C, four zones at 320 deg.C, five zones at 310 deg.C, six zones at 300 deg.C, seven zones at 290 deg.C, eight zones at 290 deg.C, nine zones at 290 deg.C, ten zones at 290 deg.C, eleven zones at 300 deg.C, and a head at 310 deg.C. The extruder speed was 400 RPM.
The PPA resin is poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, wherein the copolymerization molar ratio of monomers is 5:4: 1; the epoxy group pre-hydrolysis coupling agent is beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the nucleating agent is a complex generated by reacting zinc phenylphosphonate and calcium montanate in a solution mode, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1: 4; the antioxidant is neodymium stearate; the lubricant is an ethylene-acrylic acid ionomer.
Comparative example 3
Comparative example 3 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
the materials except the chopped glass fiber and the epoxy group pre-hydrolysis coupling agent are put into a high-speed mixer to be mixed and mixed uniformly (the mixture is mixed for 3 minutes, the rotating speed of the high-speed mixer is 500RPM), then the mixed materials are put into a main blanking barrel of an extruder to be granulated through the extruder, 30 parts of chopped fiber are added in the extrusion process in a side feeding mode, 0.5 part of epoxy group pre-hydrolysis coupling agent is added in through injection of a micro pump, the vacuum opening is kept, and the temperature of each temperature zone of the extruder is as follows: one zone at 150 deg.C, two zones at 320 deg.C, three zones at 320 deg.C, four zones at 320 deg.C, five zones at 310 deg.C, six zones at 300 deg.C, seven zones at 290 deg.C, eight zones at 290 deg.C, nine zones at 290 deg.C, ten zones at 290 deg.C, eleven zones at 300 deg.C, and a head at 310 deg.C. The extruder speed was 400 RPM.
The PPA resin is poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, wherein the copolymerization molar ratio of monomers is 5:4: 1; the epoxy group pre-hydrolysis coupling agent is beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex generated by reacting zinc phenylphosphonate and calcium montanate in a solution mode, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1: 4; the lubricant is an ethylene-acrylic acid ionomer.
Comparative example 4
Comparative example 4 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
the materials except the chopped glass fiber and the epoxy group pre-hydrolysis coupling agent are put into a high-speed mixer to be mixed and mixed uniformly (the mixture is mixed for 3 minutes, the rotating speed of the high-speed mixer is 500RPM), then the mixed materials are put into a main blanking barrel of an extruder to be granulated through the extruder, 30 parts of chopped fiber are added in the extrusion process in a side feeding mode, 0.5 part of epoxy group pre-hydrolysis coupling agent is added in through injection of a micro pump, the vacuum opening is kept, and the temperature of each temperature zone of the extruder is as follows: one zone at 150 deg.C, two zones at 320 deg.C, three zones at 320 deg.C, four zones at 320 deg.C, five zones at 310 deg.C, six zones at 300 deg.C, seven zones at 290 deg.C, eight zones at 290 deg.C, nine zones at 290 deg.C, ten zones at 290 deg.C, eleven zones at 300 deg.C, and a head at 310 deg.C. The extruder speed was 400 RPM.
The PPA resin is poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, wherein the copolymerization molar ratio of monomers is 5:4: 1; the epoxy group pre-hydrolysis coupling agent is beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the antioxidant is neodymium stearate; the lubricant is an ethylene-acrylic acid ionomer.
Comparative example 5
Comparative example 5 differs from example 1 in that: firstly, weighing the following materials in parts by weight:
the materials except the chopped glass fibers are put into a high-speed mixer to be mixed and mixed uniformly (the mixture is mixed for 3 minutes, the rotating speed of the high-speed mixer is 500RPM), then the mixed materials are put into a main blanking barrel of an extruder to be granulated through the extruder, 30 parts of chopped fibers are added in the extrusion process in a side feeding mode, the vacuum opening is kept, and the temperature of each temperature zone of the extruder is as follows: one zone at 150 deg.C, two zones at 320 deg.C, three zones at 320 deg.C, four zones at 320 deg.C, five zones at 310 deg.C, six zones at 300 deg.C, seven zones at 290 deg.C, eight zones at 290 deg.C, nine zones at 290 deg.C, ten zones at 290 deg.C, eleven zones at 300 deg.C, and a head at 310 deg.C. The extruder speed was 400 RPM.
The PPA resin is poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, wherein the copolymerization molar ratio of monomers is 5:4: 1; the epoxy group pre-hydrolysis coupling agent is beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane; the chopped glass fiber is hydrolysis-resistant alkali-free chopped glass fiber subjected to surface treatment, the length of the chopped glass fiber is 1-4mm, and the diameter of the chopped glass fiber is 9-12 mu m; the heat stabilizer is dipentaerythritol; the nucleating agent is a complex generated by reacting zinc phenylphosphonate and calcium montanate in a solution mode, and the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1: 4; the antioxidant is neodymium stearate; the lubricant is an ethylene-acrylic acid ionomer.
TABLE 1 test data for examples 1-3 and comparative examples 1-5
Note: the alcoholysis solution is ethylene glycol and water, and the alcoholysis solution and the water are subjected to alcoholysis for 1000 hours at 130 ℃ according to the mass ratio of 1: 1; the heat aging conditions were 210 ℃ for 1000 hours.
It can be seen from the table that the alcoholysis resistance and the thermal aging resistance of the material are improved along with the addition of the epoxy pre-hydrolysis coupling agent, the thermal stabilizer, the antioxidant and the nucleating agent and by changing the addition mode of the coupling agent. Under the condition that the dosage of the coupling agent is not changed, along with the increase of the content of the glass fiber, the alcoholysis resistance and the thermal aging resistance of the material are improved.
It will be understood by those skilled in the art that the foregoing is only exemplary of the present invention, and is not intended to limit the invention, which is intended to cover any variations, equivalents, or improvements therein, which fall within the spirit and scope of the invention.
Claims (10)
1. An alcoholysis-resistant thermally stable PPA composite material, comprising in parts by weight:
2. the alcoholysis and heat stable PPA composite of claim 1, wherein the PPA resin is one or more of poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer, and poly (hexamethylene terephthalamide) -co-poly (hexamethylene terephthalamide); preferably, the PPA resin is poly (hexamethylene terephthalamide) -co-hexamethylene adipamide copolymer; preferably, the copolymerization molar ratio of the monomers in the poly (hexamethylene terephthalamide) -co-hexamethylene adipamide) copolymer is 5:4: 1; more preferably, the PPA resin has an intrinsic viscosity of 0.7 to 1.0 dL/g.
3. The alcoholysis resistant, thermally stable PPA composite of claim 1, wherein the epoxy-based pre-hydrolytic coupling agent is a hydrolysate of one or more of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldiethoxysilane, and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; preferably, the epoxy group pre-hydrolysis coupling agent is β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane hydrolysate.
4. The alcoholysis resistant, thermally stable PPA composite of claim 1, wherein the epoxy-based pre-hydrolytic coupling agent is a product of hydrolysis using a mixture of methanol and acetic acid as a hydrolysis solution; preferably, the mass ratio of the epoxy group coupling agent in the epoxy group pre-hydrolysis coupling agent is 85-95%; preferably, the weight ratio of methanol to acetic acid in the mixture of methanol and acetic acid is 20-30: 1.
5. the alcoholysis resistant, thermally stable PPA composite according to claim 4 wherein the epoxy-based pre-hydrolytic coupling agent is prepared by a process comprising: a. dripping an epoxy group coupling agent into the hydrolysis solution, and stirring; b. standing for 2-4 hours, then putting into a 60-80 ℃ oven for reduced pressure distillation for 1-2 hours, and taking out; preferably, the dropping time is 30-40 minutes, and the stirring speed is 100-150 rpm.
6. The alcoholysis-resistant and thermal-stable PPA composite material according to claim 1, wherein the chopped glass fiber is a surface-treated hydrolysis-resistant alkali-free chopped glass fiber, the chopped glass fiber has a length of 1-4mm and a diameter of 9-12 μm; preferably, the heat stabilizer is one or more of polyether polyol, sorbitol and dipentaerythritol, and dipentaerythritol is preferred.
7. The alcoholysis resistant, thermally stable PPA composite according to claim 1, wherein the nucleating agent is a complex formed by the solution reaction of zinc phenylphosphonate and calcium montanate; preferably, the mass ratio of the zinc phenylphosphonate to the calcium montanate is 1: 3-5.
8. The alcoholysis resistant, thermally stable PPA composite of claim 1, wherein the antioxidant is a rare earth compound; preferably, the antioxidant is one or more of neodymium stearate, praseodymium stearate, lanthanum stearate, samarium oxide, yttrium oxide and oxidized bait, and more preferably neodymium stearate; preferably, the lubricant is one or more of silicone powder, ethylene bis stearamide, pentaerythritol stearate, calcium stearate, ethylene acrylic acid ionomer, more preferably ethylene acrylic acid ionomer.
9. The method of making the alcoholysis resistant, thermally stable PPA composite of any of claims 1 to 8, comprising the steps of:
(1) the PPA resin is placed in an oven to be dried, the drying temperature is 110-130 ℃, the drying time is 2-4 hours, and the water content after drying is controlled below 0.1%;
(2) weighing raw materials except the chopped glass fiber and the epoxy pre-hydrolytic coupling agent according to the required weight parts;
(3) uniformly mixing the raw materials weighed in the step (2) for later use;
(4) and (3) granulation: and putting the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the chopped glass fiber is added through side feeding, the epoxy group pre-hydrolysis coupling agent is dripped from a second air outlet of the extruder, and the temperature of each temperature zone of the extruder is kept at 290-335 ℃, so that the product is finally obtained.
10. The method of claim 9, wherein the amount of epoxy-based pre-hydrolytic coupling agent added is precisely controlled by a micro-syringe pump at the feed opening, and the coupling agent is contained in a thermal insulating barrel at a temperature of 60-80 ℃.
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