CN114276690B - PA6/PP alloy and preparation method and application thereof - Google Patents
PA6/PP alloy and preparation method and application thereof Download PDFInfo
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- CN114276690B CN114276690B CN202111643317.3A CN202111643317A CN114276690B CN 114276690 B CN114276690 B CN 114276690B CN 202111643317 A CN202111643317 A CN 202111643317A CN 114276690 B CN114276690 B CN 114276690B
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Abstract
The invention discloses a PA6/PP alloy which comprises the following components in parts by weight: PA610-40 parts; 5-40 parts of bisphenol A epoxy resin grafted PA 6; 6-15 parts of polyether amine substituted polar monomer grafted polypropylene; 10-30 parts of homopolymerized polypropylene; wherein, the proportion of the bisphenol A epoxy resin chain segment is 5-16.5wt% based on the total weight of the bisphenol A epoxy resin grafted PA 6; the proportion of the polyether amine chain segment is 13-41.5wt% based on the total weight of the polyether amine substituted polar monomer grafted polypropylene. The PA6/PP alloy has excellent aging resistance, particularly the notch impact and unnotched impact performance related to the impact before and after aging are obviously improved, and the requirements of electric tools and the electronic and electrical industry on the PA6/PP alloy can be completely met.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PA6/PP alloy and a preparation method and application thereof.
Background
Nylon 6 is an engineering plastic with wide application, is prepared by polymerizing caprolactam, has a melting point of 215-225 ℃ and a use temperature range of-40-150 ℃, and is greatly limited in application because the performance of common nylon 6 is greatly changed under the influence of temperature and environment. Therefore, the comprehensive performance of the composite material can be obviously improved by filling, reinforcing and modifying the composite material.
The modified nylon 6 material can be widely used in industries such as electric tools, electronic and electric connectors and the like. However, nylon 6 material is very easy to absorb water due to the existence of amide groups in the molecular chain, which results in poor dimensional stability, in order to inhibit the absorption of water by nylon 6 material, a common modification method is to add non-polar polypropylene, and in order to solve the problem of compatibility between nylon 6 and polypropylene, polypropylene grafted polar monomers, such as polypropylene grafted maleic anhydride, polypropylene grafted acrylic acid, polypropylene grafted glycidyl methacrylate, etc., are usually added to improve the compatibility between nylon 6 and polypropylene, but these polar monomer grafted polypropylene and amide groups in nylon 6 can undergo chemical crosslinking reaction, which results in serious decrease in impact performance of the alloy material after long-term use or thermal aging test.
Disclosure of Invention
The invention aims to overcome the technical defects and provide the PA6/PP alloy with good aging resistance and particularly high impact strength retention rate after aging.
The invention also aims to provide a preparation method and application of the PA6/PP alloy.
The invention is realized by the following technical scheme:
wherein, the proportion of bisphenol A epoxy resin chain segments is 5-16.5wt% based on the total weight of the bisphenol A epoxy resin grafted PA 6;
the proportion of the polyether amine chain segment is 13-41.5wt% based on the total weight of the polyether amine substituted polar monomer grafted polypropylene.
In the polyether amine substituted polar monomer grafted polypropylene, the polar monomer grafted polypropylene chain segment is at least one of maleic anhydride grafted polypropylene, acrylic acid grafted polypropylene and glycidyl methacrylate grafted polypropylene; glycidyl methacrylate grafted polypropylene is preferred.
In the polyether amine substituted polar monomer grafted polypropylene, the polyether amine is diamine with polypropylene glycol as a main chain, and the number average molecular weight of the diamine is 5000-10000, preferably 7000-8000.
The structural formula of the polyether amine is as follows:
the polyether amine is prepared by ammoniating polypropylene alcohol. The preparation process of the polyether amine comprises the following steps: polypropylene glycol is used as a raw material, a metal mixture of copper, nickel, chromium, aluminum and the like is used as a catalyst, catalytic ammoniation hydrogenation reaction is carried out at the reaction temperature of 250-300 ℃ and the pressure of 12-20MPa, and polyether amine with different molecular weights is produced by controlling the reaction time.
The polyether amine substituted polar monomer grafted polypropylene adopted by the invention can be a self-made raw material, and the process comprises the following steps: according to the proportion, the polyether amine and the polar monomer grafted polypropylene are mixed in a mixing roll at the temperature of 180-220 ℃ and the rotating speed of 40-100rpm, or can be prepared by a double-screw extruder at the screw temperature of 180-220 ℃ and the rotating speed of 300-600rpm.
The structural formula of the bisphenol A type epoxy resin is as follows:
wherein n =2 to 4.
The relative viscosity of PA6 is not particularly limited in the invention, and the relative viscosity of the concentrated sulfuric acid solution with the concentration of 0.01g/mL of PA6 tested at 25 ℃ is 2.0-4.0 through experiments, so that the aim of the invention can be achieved. PA6 viscosity detection method: weighing 0.5g of PA6 resin, transferring the PA6 resin into a 50mL volumetric flask, adding about 40ml of concentrated sulfuric acid with the mass fraction of 96%, performing ultrasonic oscillation until the PA6 is completely dissolved, cooling the solution to 25 ℃, diluting the solution to a scale by using the concentrated sulfuric acid, uniformly mixing, testing the flow-through time of 0.01g/mL of the PA6 solution passing through a Ubbelohde viscometer at 25 ℃, and marking as t1, testing the flow-through time of a solvent concentrated sulfuric acid by using the same viscometer, and marking as t2, wherein the t1/t2 is the relative viscosity.
The bisphenol A epoxy resin grafted PA6 can be a self-made raw material, and the process comprises the following steps: the PA6 resin and the bisphenol A epoxy resin are firstly mixed in a mixer at the temperature of 210-260 ℃ and the rotating speed of 40-100rpm, or can be prepared by a double-screw extruder at the screw temperature of 210-260 ℃ and the rotating speed of 300-600rpm.
The melt index of the homopolymerized polypropylene is 3-60g/10min under the conditions of 230 ℃ and 2.16kg (ISO 1133).
Preferably, the proportion of the bisphenol A epoxy resin chain segment is 8-13wt% based on the total weight of the bisphenol A epoxy resin grafted PA 6; the proportion of the polyether amine chain segment is 20-30wt% based on the total weight of the polyether amine substituted polar monomer grafted polypropylene.
In order to improve the mechanical property of the PA6/PP alloy, 0-60 parts by weight of glass fiber can be further included.
0-0.5 part of heat stabilizer; the heat stabilizer is at least one selected from hindered phenol heat stabilizers, phosphite ester heat stabilizers and thioester heat stabilizers.
The preparation method of the PA6/PP alloy comprises the following steps: according to the proportion, all the components except the glass fiber are uniformly mixed and then fed into a double-screw extruder through a main feeding port for extrusion granulation, if the glass fiber exists, the feeding is carried out in a side feeding mode, the temperature range of a screw cylinder is 210-260 ℃, the rotating speed of a screw is 300-600rpm, and the PA6/PP alloy is obtained.
The PA6/PP alloy is applied to the field of electric tools or electronic and electric appliances.
The invention has the following beneficial effects
According to the invention, bisphenol A epoxy resin grafted PA6 and polyether amine substituted polar monomer grafted polypropylene are introduced into PA6 and PP alloys, so that under the cooperation of the two components, the comprehensive mechanical property of the alloy can be improved, and especially the impact property after aging is obviously improved.
Firstly, the polypropylene is grafted by adopting the polyether amine to replace the polar monomer, so that the reaction of the polar monomer and the terminal amino group of PA6 can be improved, and the introduction of the polyether amine can further improve the toughness.
Secondly, bisphenol A epoxy resin is adopted to modify part of PA6 resin, so that the content of terminal amino groups of the PA6 resin is reduced, the reaction of polar monomer grafted polypropylene and PA6 can be reduced while the toughness is further improved, and the aging resistance is improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
The raw materials used in the invention are as follows:
PA6-A: relative viscosity 2.0, designation PA 6M 2000, xinhui Meida;
PA6-B: relative viscosity 4.0, designation PA6 BL40H, barlingite;
homo-polypropylene A: the melt index is 3g/10min, the mark is PP K1003, and the Yanshan petrochemical is adopted;
homo-polypropylene B: melt index 60g/10min, designation PP M60T, zhenhai refining;
copolymerized polypropylene: the melt index is 20g/10min, the mark is PP K9020, and the Yanshan petrochemical is adopted;
bisphenol a type epoxy resin a: under the trademark KD-211G, national institute of chemistry.
Bisphenol a type epoxy resin B: CYD-012, balling petrochemical.
Bisphenol a-type epoxy resin C: designation DER 671, dow chemical.
Glycidyl ester type epoxy resin: TDE-85, chengdong Chengcheng chemical industry.
Polyether amine A: the number average molecular weight is 5000, and the molecular weight is self-made according to the method of the invention;
polyether amine B: the number average molecular weight is 7000, which is self-made according to the method of the invention content part;
polyether amine C: the number average molecular weight is 8000, which is self-made according to the method of the invention content;
polyether amine D: number average molecular weight 10000, self-made according to the method of the invention content part;
maleic anhydride-grafted polypropylene a: trade name Polybond 3200, cheopian;
maleic anhydride-grafted polypropylene B: trade mark LEP-1A, shenyang Ketong;
maleic anhydride-grafted polypropylene C: number CA100, arkema;
acrylic acid grafted polypropylene a: brand KT-A1, shenyang Ketong;
acrylic acid grafted polypropylene B: brand BA306, dupont;
glycidyl methacrylate grafted polypropylene a: KT-G1, shenyang Ketong.
Glycidyl methacrylate grafted polypropylene B: brand Bondyram 1006, pulang.
Glass fiber: diameter 11 micron, ECS11-4.5-560A, giant rock group;
examples and comparative examples preparation of bisphenol a type epoxy resin grafted PA 6: the PA6 resin and the bisphenol A epoxy resin were kneaded at a temperature of 210 to 260 ℃ and a rotation speed of 80rpm (the amounts of PA6 and bisphenol A epoxy resin used are shown in the table).
Examples and comparative examples preparation of polyetheramine substituted polar monomer grafted polypropylene: mixing the polyether amine and the polar monomer grafted polypropylene in a mixing roll at 180-220 ℃ and 80rpm (the dosage of the polyether amine and the polar monomer grafted polypropylene is shown in a table).
Examples and comparative examples preparation of PA6/PP alloys: PA6, homo-polypropylene, polyether amine substituted polar monomer grafted polypropylene and bisphenol A epoxy resin grafted PA6 are uniformly mixed and then fed into a double-screw extruder through a main feeding port to be extruded and granulated, if glass fiber exists, the glass fiber is fed in a side feeding mode, and the temperatures of a screw cylinder are 210 ℃ in a first area, 230 ℃ in a second area, 220 ℃ in a third area, 220 ℃ in a fourth area, 210 ℃ in a fifth area, 210 ℃ in a sixth area, 210 ℃ in a seventh area, 220 ℃ in an eighth area, 220 ℃ in a ninth area and 260 ℃ in a die head. The screw rotating speed is 350rpm, and the PA6/PP alloy is obtained.
The test methods are as follows:
(1) Aging resistance: adopting an injection molding machine to injection mold the sample material into a standard ISO tensile sample strip and an impact sample strip, then testing the tensile strength according to ISO 527-2 2012, and testing the notch impact strength according to ISO 180/1A 2019; the sample bars were divided into two batches, the first batch was tested for tensile strength and notched impact strength, the second batch was aged at 150 ℃ for 1000 hours, the tensile strength and notched impact strength were tested again, and the tensile strength retention rate and notched impact strength retention rate were calculated.
Table 1: examples 1-7PA6/PP alloy compositions in parts by weight and test results
From examples 1/3/4/5, it is understood that the number average molecular weight of the polyetheramine is preferably 7000 to 8000, and not only the tensile strength and the notched impact strength are higher, but also the retention rate is better.
Table 2: examples 8-13PA6/PP alloy compositions in parts by weight and test results
As can be seen from examples 1/8/9/10/11, glycidyl methacrylate grafted polypropylene segments are preferred in the polyetheramine substituted polar monomer grafted polypropylene.
Table 3: examples 14-20PA6/PP alloys content of each component (parts by weight) and test results
As can be seen from examples 17 to 20, the ratio of the bisphenol A epoxy resin segment in the bisphenol A epoxy resin-grafted PA6 is preferably 8 to 13wt%, and the retention is higher when the ratio of the polyether amine segment in the polyether amine-substituted polar monomer-grafted polypropylene is 20 to 30wt%.
Table 4: comparative example PA6/PP alloy the contents of the components (in parts by weight) and the results
As can be seen from comparative examples 1 to 4, when the amounts of the polyetheramine-substituted polar monomer-grafted polypropylene, the epoxy resin-grafted PA6, and the homopolypropylene added were too low, a high mechanical property retention rate could not be achieved.
As can be seen from comparative example 5, the content of the bisphenol A epoxy resin A segment in the epoxy resin grafted PA6 was too low to achieve a high mechanical property retention rate.
As can be seen from comparative example 6, the content of the polyether amine segment in the polyether amine substituted polar monomer grafted polypropylene is too low, and high mechanical property retention rate cannot be realized.
As can be seen from comparative example 7, the glycidyl ester type epoxy resin could not be substituted for the bisphenol A type epoxy resin.
As can be seen from comparative example 8, the substitution of the copolymerized polypropylene for the homopolypropylene did not achieve the object of the present invention.
Claims (9)
1. The PA6/PP alloy is characterized by comprising the following components in parts by weight:
10-40 parts of PA 6;
5-40 parts of bisphenol A epoxy resin grafted PA (polyamide);
6-15 parts of polyether amine substituted polar monomer grafted polypropylene;
10-30 parts of homopolymerized polypropylene;
wherein, the proportion of bisphenol A epoxy resin chain segments is 5-16.5wt% based on the total weight of the bisphenol A epoxy resin grafted PA 6;
based on the total weight of the polyether amine substituted polar monomer grafted polypropylene, the proportion of the polyether amine chain segment is 13-41.5wt%;
in the polyether amine substituted polar monomer grafted polypropylene, the number average molecular weight of a polyether amine chain segment is 5000-10000, and in the polyether amine substituted polar monomer grafted polypropylene, the polar monomer grafted polypropylene chain segment is at least one of maleic anhydride grafted polypropylene, acrylic acid grafted polypropylene and glycidyl methacrylate grafted polypropylene.
2. The PA6/PP alloy of claim 1, wherein in the polyetheramine-substituted polar monomer grafted polypropylene, the polar monomer grafted polypropylene segment is glycidyl methacrylate grafted polypropylene.
3. The PA6/PP alloy of claim 1, wherein in the grafted polypropylene, the number average molecular weight of the polyether amine segment is 7000-8000.
4. The PA6/PP alloy according to claim 1, characterized in that the PA6 has a relative viscosity of 2.0 to 4.0; the melt index of the homopolymerized polypropylene is 3-60g/10min.
5. The PA6/PP alloy according to claim 1, wherein the proportion of the bisphenol A epoxy resin segment is 8 to 13wt% based on the total weight of the bisphenol A epoxy resin grafted PA 6; the proportion of the polyether amine chain segment is 20-30wt% based on the total weight of the polyether amine substituted polar monomer grafted polypropylene.
6. The PA6/PP alloy of claim 1, further comprising 0 to 60 parts by weight of glass fiber.
7. The PA6/PP alloy according to claim 1, further comprising 0 to 0.5 parts by weight of a heat stabilizer; the heat stabilizer is at least one selected from hindered phenol heat stabilizers, phosphite ester heat stabilizers and thioester heat stabilizers.
8. A process for the preparation of the PA6/PP alloy according to any of claims 1 to 7, characterized in that it comprises the following steps: according to the proportion, all the components except the glass fiber are uniformly mixed and then fed into a double-screw extruder through a main feeding port for extrusion and granulation, if the glass fiber exists, the glass fiber is fed in a side feeding mode, the temperature range of a screw cylinder is 210-260 ℃, the rotating speed of a screw is 300-600rpm, and the PA6/PP alloy is obtained.
9. Use of the PA6/PP alloy according to any of claims 1 to 7 in the field of electric tools or electronics.
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| US5091469A (en) * | 1990-06-28 | 1992-02-25 | Eastman Kodak Company | Compatibilized epoxy/polyamide compositions containing polyolefins |
| US5783630A (en) * | 1993-07-13 | 1998-07-21 | Huntsman Petrochemical Corporation | Polyether amine modification of polypropylene |
| DE10060819A1 (en) * | 2000-12-07 | 2002-06-13 | Cognis Deutschland Gmbh | Production of polyethylene moldings, fibers and films, comprises shaping a mixture of polyethylene and a polyetheramine derivative as adhesion promoter |
| CN101195707B (en) * | 2007-12-25 | 2010-08-11 | 上海金发科技发展有限公司 | Glass fiber-reinforced nylon 6-polypropylene alloy material |
| CN102408705A (en) * | 2011-09-22 | 2012-04-11 | 贵州凯科特材料有限公司 | Nylon 6 with high performance and low melting-point and preparation method thereof |
| CN103194023B (en) * | 2013-03-19 | 2015-12-23 | 深圳市亚塑科技有限公司 | A kind of fiberglass reinforced PP/PA6 matrix material and preparation method thereof and application |
| CN104098885B (en) * | 2013-04-15 | 2017-12-05 | 上海杰事杰新材料(集团)股份有限公司 | A kind of glass fiber reinforced polyester phenylate/polyamide alloy material and preparation method thereof |
| CN103709512A (en) * | 2013-12-25 | 2014-04-09 | 上海金发科技发展有限公司 | Long glass fiber-reinforced polypropylene/nylon composite material and preparation method thereof |
| CN104559153A (en) * | 2014-12-19 | 2015-04-29 | 上海金发科技发展有限公司 | High-thermal-aging-resistant PA/PP alloy material and preparation method thereof |
| CN105199374B (en) * | 2015-09-25 | 2017-12-08 | 成都金发科技新材料有限公司 | A kind of polyamide polynropylene alloy of heat-proof aging hydrolysis |
| CN108570182B (en) * | 2017-03-09 | 2021-01-19 | 江苏金发科技新材料有限公司 | Glass fiber reinforced polypropylene alloy and preparation method thereof |
| CN112538260B (en) * | 2020-10-28 | 2023-01-03 | 广东轻工职业技术学院 | Glass fiber reinforced polypropylene/polyamide composite material and preparation method thereof |
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