CN110172243A - A kind of modified Pa 6 of low water absorption/PA12 alloy material and preparation method - Google Patents
A kind of modified Pa 6 of low water absorption/PA12 alloy material and preparation method Download PDFInfo
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- CN110172243A CN110172243A CN201910536939.2A CN201910536939A CN110172243A CN 110172243 A CN110172243 A CN 110172243A CN 201910536939 A CN201910536939 A CN 201910536939A CN 110172243 A CN110172243 A CN 110172243A
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The present invention relates to field of high polymer material processing, disclose the modified Pa 6/PA12 alloy material and preparation method of a kind of low water absorption.The alloy material includes 50-65 parts of PA6 resin by weight；5-10 parts of PA12 resin；3-10 parts of toughener；0.1-1 parts of lanthana；25-35 parts of glass fibre；0.1-0.5 parts of antioxidant；0.1-0.5 parts of lubricant；Invention also discloses a kind of modified Pa 6/PA12 alloy material preparation method of low water absorption.Compounding toughened system and lanthana carry out the modification of composite material while the present invention compounds alloy with PA12 by PA6, while so that composite material reaches existing PA6 properties of product, substantially reduce the water absorption rate of material.Low water absorption PA6 material has lower shrinking percentage, improves the dimensional contraction problem that nylon product is generated by water suction.
Description
Technical field
The present invention relates to field of high polymer material processing, are specifically related to a kind of modified Pa 6/PA12 alloy of low water absorption
Material and preparation method.
Background technique
The synthesis of polyamide is an important milestone of polymer chemistry development, petro chemical industry and other industry
Development is the development of nylon engineering plastic, provides abundant, inexpensive raw material and wide market.Nylon is mainly used for automobile work
Industry, electric and electronic industry, transportation, machine building industry, wire and cable communications industry, film and articles for daily use.In PA6 plus
Enter 30% glass fibre, mechanical property, dimensional stability, heat resistance, the ageing-resistant performance of PA6 is significantly improved, endurance
Intensity is 2.5 times before not reinforcing, and greatly expands the application field of PA6 material.
With the gradually development of PA6 product, application of the PA6 product in life is also more and more wide, is increasingly becoming life
In indispensable important engineering plastics.But the advantage and disadvantage of PA6 product are also more and more clear, wherein the water absorption rate of PA6 product and
Shrinking percentage is the major issue having to take into account that.It is sharp that Chinese invention patent (CN107266905A) discloses a kind of selectivity
Light is sintered 3D printing PA12/PA6 alloy material powder and preparation method thereof；By to PA12 raw material and PA6 raw material into
Row physical blending squeezes out modification, the cost of material is effectively reduced, while can effectively improve the mechanical property of material again, increases
Add the tensile strength and flexural strength of printing product, reduces the warpage generated when printing.Chinese invention patent
(CN102732004A) it discloses and a kind of high CTI, low precipitation property flame-proof PA 6/PA12 alloy composite and preparation method thereof, it should
The composition of invention has the advantages such as high CTI value, low fire retardant precipitation property, halogen-free environmental, comprehensive performance equilibrium, can answer extensively
Product for field of electronics such as contactor, earth leakage protective device, case for circuit breaker.But do not have in existing patent of invention
PA6/PA12 material water absorption rate and dimensional stability are related to and studied.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of modified Pa 6 of low water absorption/PA12 alloy materials
Material, compounding toughened system and lanthana carry out changing for composite material while which compounds alloy with PA12 by PA6
Property, while so that composite material reaches existing PA6 properties of product, substantially reduce the water absorption rate of material.Low water absorption PA6 material
With lower shrinking percentage, the present invention reduces the water absorption rate of PA6 product by the method for nano-filled modification, so as to improve
Dimensional contraction problem that nylon product is generated by water suction (such as pump shell, tool outer casing, after long-play, because water suction is led
Change in size is caused, it is abnormal leak, wiping iron etc. occur), it has a vast market foreground and good economic results in society, it is contemplated that
The water pump industry related raw material of mainstream will be become in the coming years, and realize and apply in other field.
To achieve the object of the present invention, by weight, the modified Pa 6 of low water absorption of the present invention/PA12 alloy material packet
50-65 parts of resin containing PA6,5-10 parts of PA12 resin, 3-10 parts of toughener, 0.1-1 parts of lanthana, 5-35 parts of glass fibre, resist
0.1-0.5 parts of oxygen agent, 0.1-0.5 parts of lubricant.
In the present invention, the PA6 resin is a kind of translucent or opaque milky PA6 resin particle, and viscosity is in 2.7-
Between 2.8.
In the present invention, the PA12 resin is a kind of amorphous polyamides resin, and crystallinity is excellent between 50%-65%
Select 55-65%.
In the present invention, the toughener is a kind of maleic anhydride grafted ethene-octene copolymer.
In the present invention, the lanthana is a kind of nano lanthanum oxide, it is preferable that the average grain diameter of the nano lanthanum oxide is
40nm。
In the present invention, the glass fibre is a kind of glass fibre of hydrolysis, 9-11 microns a diameter of.
In the present invention, the antioxidant is hindered phenol and phosphite ester compound system.
In the present invention, the lubricant is pentaerythritol stearate.
The present invention also provides a kind of modified Pa 6 of above-mentioned low water absorption/PA12 alloy material preparation methods, including with
Lower step:
(1) 50-65 parts of PA6 resin are weighed by weight, 5-10 parts of PA12 resin, 3-10 parts of toughener, lanthana
0.1-1 parts, 25-35 parts of glass fibre, 0.1-0.5 parts of antioxidant, 0.1-0.5 parts of lubricant；
(2) PA6 resin and PA12 resin are added in high-speed mixer, toughener, lanthana, antioxygen is then added
Then agent, lubricant are stirred in high mixer equal under room temperature；Glass fibre is squeezing out the side feed material form addition in segment process；
(3) material mixed through step (2) is placed in parallel dual-screw extruding machine, through fusion plastification, extrusion, cold
But, pelletizing obtains PP composite material；The draw ratio of double screw extruder used, screw diameter 40-65mm, screw rod is
40:1, mixed melting temperature are set as 220 DEG C -240 DEG C of first segment, and 220 DEG C -240 DEG C of second segment, 220 DEG C -240 DEG C of third section,
4th section 210 DEG C -230 DEG C, the 5th section 220 DEG C -225 DEG C, the 6th section 220 DEG C -225 DEG C, the 7th section 220 DEG C -225 DEG C, the 8th
220 DEG C -225 DEG C of section, the 9th section 220 DEG C -225 DEG C, the tenth section 220 DEG C -230 DEG C, 230 DEG C -250 DEG C of melt temperature, head temperature
240 DEG C -250 DEG C of degree.
The present invention compared with the existing technology the advantages of and effect are as follows: use PA6/PA12 alloy system, PA12 has well
Erosion-resisting characteristics, lower water absorption rate, then good hydrolysis short glass fiber is selected to enhance has the physical property of material entirety greatly
Amplitude is promoted；The addition of maleic anhydride grafted ethene-octene copolymer plays the role of completely cutting off moisture on phase interface, makes
The water absorption rate of material reduces；Nano lanthanum oxide is added can play the role of heterogeneous nucleation in PA6 matrix, shorten the knot of PA6
The brilliant time increases the crystallization temperature of PA6, the distribution narrow of the size of crystal size, it is easier to crystallize, reduce the same of water absorption rate
When, improve the rigidity of material.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under
Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below
It is bright, it is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want
Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one"
Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular
Element or component also include plural form, unless the quantity obviously only refers to singular.
Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can
To be combined with each other.
Embodiment
A kind of modified Pa 6 of low water absorption/PA12 alloy material includes following components by weight:
Press the material of noodle producing method preparation embodiment 1-4 and comparative example 1-5:
(1) PA6 and PA12 resin is added in high-speed mixer, toughener, lanthana, antioxidant, profit is then added
Lubrication prescription, then stirs evenly that (material being specifically added is subject to table 1, and the PA12 resin is a kind of in high mixer under room temperature
Amorphous polyamides resin, crystallinity is between 55-65%)；
(2) material mixed is placed in parallel dual-screw extruding machine, glass fibre is squeezing out the side feed in segment process
Material form is added, and through fusion plastification, extrusion, cooling, pelletizing, obtains PP composite material；Double screw extruder used, spiral shell
The draw ratio of shank diameter 40-65mm, screw rod are 40:1, and mixed melting temperature is set as 220 DEG C -240 DEG C of first segment, second segment
220 DEG C -240 DEG C, 220 DEG C -240 DEG C of third section, the 4th section 210 DEG C -230 DEG C, the 5th section 220 DEG C -225 DEG C, the 6th section 220
DEG C -225 DEG C, the 7th section 220 DEG C -225 DEG C, the 8th section 220 DEG C -225 DEG C, the 9th section 220 DEG C -225 DEG C, the tenth section 220 DEG C -
230 DEG C, 230 DEG C -250 DEG C of melt temperature, 240 DEG C -250 DEG C of head temperature.
The material specific formula of table 1 embodiment 1-4 and comparative example 1-5 (unit is kilogram)
By the 120 DEG C of bakings in an oven of the modified Pa 6 of low water absorption obtained in embodiment and comparative example/PA12 alloy material
It is molded after drying in case, injection molding batten is batten, and injection temperature is as follows:
Blanking section: 240 DEG C；Second segment: 245 DEG C；Third section: 245 DEG C；Nozzle: 250 DEG C；
Finally injection molding batten is put in drier and carries out status adjustment: adjusting 23 DEG C of temperature, regulating time: for 24 hours；Each reality
Applying example, test result is as follows shown in table 2
Each embodiment and comparative example material properties test result of table 2
The test result of embodiment 1-4 and comparative example 1-2, which can be seen that, to be added PA12 and is answered in 6 system of fiberglass reinforced PA
With toughener and nano lanthanum oxide, the impact strength of composite material is significantly improved, under equilibrium water absorption and shrinking percentage have
Drop.
Embodiment 1-4 can be seen that PA6 compounds PA11 and PA1012 system overall performance with the test result of comparative example 3-4
The effect compounded without PA6 and PA12 with equilibrium water absorption is good.
The test result of embodiment 1-4 and comparative example 5 can be seen that the addition of lanthana to PA6/PA12 alloy material of the present invention
The equilibrium water absorption of material has greatly improved.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of modified Pa 6 of low water absorption/PA12 alloy material, which is characterized in that the modified Pa 6 of the low water absorption/
PA12 alloy material include 50-65 parts of PA6 resin, 5-10 parts of PA12 resin, 3-10 parts of toughener, 0.1-1 parts of lanthana, glass
5-35 parts of fiber, 0.1-0.5 parts of antioxidant, 0.1-0.5 parts of lubricant.
2. the modified Pa 6 of low water absorption according to claim 1/PA12 alloy material, which is characterized in that the PA6 tree
Rouge is a kind of translucent or opaque milky PA6 resin particle, and viscosity is between 2.7-2.8.
3. the modified Pa 6 of low water absorption according to claim 1/PA12 alloy material, which is characterized in that the PA12 tree
Rouge is a kind of amorphous polyamides resin, and crystallinity is between 50%-65%.
4. the modified Pa 6 of low water absorption according to claim 3/PA12 alloy material, which is characterized in that the PA12 tree
Rouge is a kind of amorphous polyamides resin, and crystallinity is between 55-65%.
5. the modified Pa 6 of low water absorption according to claim 1/PA12 alloy material, which is characterized in that the toughener
It is a kind of maleic anhydride grafted ethene-octene copolymer.
6. the modified Pa 6 of low water absorption according to claim 1/PA12 alloy material, which is characterized in that the lanthana
It is a kind of nano lanthanum oxide, it is preferable that the average grain diameter of the nano lanthanum oxide is 40nm.
7. the modified Pa 6 of low water absorption according to claim 1/PA12 alloy material, which is characterized in that the glass fibers
Dimension is a kind of glass fibre of hydrolysis, 9-11 microns a diameter of.
8. the modified Pa 6 of low water absorption according to claim 1/PA12 alloy material, which is characterized in that the antioxidant
It is hindered phenol and phosphite ester compound system.
9. the modified Pa 6 of low water absorption according to claim 1/PA12 alloy material, which is characterized in that the lubricant
It is pentaerythritol stearate.
10. the modified Pa 6 of -9 described in any item low water absorptions/PA12 alloy material according to claim 1, which is characterized in that
The preparation method of the alloy material the following steps are included:
(1) 50-65 parts of PA6 resin are weighed by weight, 5-10 parts of PA12 resin, 3-10 parts of toughener, lanthana 0.1-1
Part, 25-35 parts of glass fibre, 0.1-0.5 parts of antioxidant, 0.1-0.5 parts of lubricant；
(2) PA6 resin and PA12 resin are added in high-speed mixer, add toughener, lanthana, antioxidant, lubrication
Then agent is stirred in high mixer equal under room temperature；Glass fibre is squeezing out the side feed material form addition in segment process；
(3) material mixed through step (2) is placed in parallel dual-screw extruding machine, through fusion plastification, extrusion, cooling, is cut
Grain, obtains PP composite material；Double screw extruder used, screw diameter 40-65mm, the draw ratio of screw rod are 40:1,
Mixed melting temperature is set as 220 DEG C -240 DEG C of first segment, and 220 DEG C -240 DEG C of second segment, 220 DEG C -240 DEG C of third section, the 4th
210 DEG C -230 DEG C, the 5th section 220 DEG C -225 DEG C, the 6th section 220 DEG C -225 DEG C, the 7th section 220 DEG C -225 DEG C, the 8th section 220 of section
DEG C -225 DEG C, the 9th section 220 DEG C -225 DEG C, the tenth section 220 DEG C -230 DEG C, 230 DEG C -250 DEG C of melt temperature, head temperature 240
℃-250℃。
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| CN111138855A (en) * | 2020-01-08 | 2020-05-12 | 柳州塑友科技有限公司 | Modified nylon material for automobile bumper |
| CN111483991A (en) * | 2020-03-24 | 2020-08-04 | 江苏温塑实业有限公司 | Preparation method of lanthanum phosphite |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804304A (en) * | 2019-12-02 | 2020-02-18 | 南京勇聚新材料科技有限公司 | Low-water-absorption nylon master batch and preparation method thereof |
| CN111040433A (en) * | 2019-12-27 | 2020-04-21 | 聚威工程塑料(上海)有限公司 | Low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material and preparation method thereof |
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| CN111483991A (en) * | 2020-03-24 | 2020-08-04 | 江苏温塑实业有限公司 | Preparation method of lanthanum phosphite |
| CN111909510A (en) * | 2020-08-11 | 2020-11-10 | 广东聚邦兴材科技有限公司 | Nylon composite material and preparation method thereof |
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Application publication date: 20190827 |