CN105131587A - Compatibilizer-containing nylon 6 blend - Google Patents

Compatibilizer-containing nylon 6 blend Download PDF

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Publication number
CN105131587A
CN105131587A CN201510509255.5A CN201510509255A CN105131587A CN 105131587 A CN105131587 A CN 105131587A CN 201510509255 A CN201510509255 A CN 201510509255A CN 105131587 A CN105131587 A CN 105131587A
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district
nylon
pesam
expanding material
twin screw
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CN201510509255.5A
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CN105131587B (en
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宁春花
周弟
王涛
王树明
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Changshu intellectual property operation center Co.,Ltd.
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Changshu Institute of Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002Dendritic macromolecules
    • C08G83/003Dendrimers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/08Oxygen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

A disclosed compatibilizer-containing nylon 6 blend contains nylon 6, gypsum fiber and a compatibilizer, the compatibilizer is multi-amino-terminated dendritic macro-molecule PESAM, and the structural formula is shown as a formula (I). The invention also provides a preparation method for the compatibilizer-containing nylon 6 blend. The nylon 6 blend does not need adding of other additives, is good in toughening strength-increasing effects, and is substantially improved in tensile strength, elongation at break, impact strength and other mechanical performances.

Description

A kind of nylon 6 Blends containing expanding material
Technical field
The invention belongs to field of polymer composite material, be specifically related to a kind of nylon 6 Blends containing expanding material and preparation method thereof.
Background technology
Nylon 6, i.e. polymeric amide-6, be PA6 again, has excellent process based prediction model, has that mechanical strength is high, good toughness, wear-resisting, resistance to wet goods feature, thus receives increasing concern in fields such as electronic apparatus, mechanical means, life households.But the shortcomings such as its strong alkali-acid resistance is poor, low temperature impact strength is low, easy water suction and creep resistance are not enough, make it be very limited in the application.Generally, in resin, add appropriate fortifying fibre, as glass fibre, effectively can transmit stress, the mechanical property of plastics is significantly improved.But simple interpolation fortifying fibre, the surface fiber of the goods obtained exposes, and even occurs product deformation.
For above situation about occurring, people have also been made large quantifier elimination.Consider, when nylon 6 and other materials blended, add some expanding material and the consistency of co-mixing system can be made more stable, but some expanding material be harmful.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of nylon 6 Blends containing expanding material, and makes stable system, consumption few, improves the mechanical properties such as the elongation at break of blend, shock strength.
In order to solve above-mentioned technical problem, the invention provides a kind of nylon 6 Blends containing expanding material, it comprises nylon 6, gypsum fiber and expanding material, and described expanding material is end polyamino dendritic macromole PESAM, and its structural formula is such as formula shown in (I):
In of the present invention one concrete technical scheme, it is 0.1-5% ︰ 69-94% ︰ 5-30% that PESAM ︰ nylon 6 ︰ gypsum fiber accounts for nylon 6 Blends weight percent respectively; Preferably, in blend total amount, the weight percent of PESAM ︰ nylon 6 ︰ gypsum fiber is 0.1-3% ︰ 69-87% ︰ 10-30%; More preferably, in blend total amount, the weight percent of PESAM ︰ nylon 6 ︰ gypsum fiber is 0.1-2% ︰ 75-85% ︰ 15-23%; The weight percent being preferably PESAM ︰ nylon 6 ︰ gypsum fiber is again 1.5% ︰ 78.5% ︰ 20%.
The technical problem of a second aspect of the present invention, provide the preparation method also including gypsum fiber nylon 6 Blends, it comprises the steps:
First nylon 6 is placed in vacuum drying oven in 50 DEG C of dryings 2 hours, by formula, PESAM glue head dropper is added drop-wise in nylon 6, stirs; Then the material mixed is added twin screw extruder; gypsum fiber is added from first venting port of twin screw extruder simultaneously and melt extrude; various desired product is obtained through wire drawing, cooling, pelletizing; the machine barrel processing temperature of described twin screw extruder is set as 230 ~ 260 DEG C, and main-machine screw rotating speed is 600r.min -1.
In of the present invention one concrete technical scheme, described twin screw extruder Gong She seven district, the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.
Expanding material in the present invention is end polyamino dendritic macromole PESAM, and its structural formula is such as formula shown in (I), and end group is 16 amino:
The preparation method of end polyamino dendritic macromole PESAM, the method comprises the following steps:
By Viscoat 295 and quadrol, carry out Michael reaction 3-6 hour in room temperature, carry out separating-purifying with methyl alcohol as precipitation agent; Add three (2-amino-ethyl) amine again in room temperature reaction 6-10 hour, underpressure distillation, obtain end polyamino dendritic macromole, wherein, the mass ratio of trimethylolpropane tris Bing olefin(e) acid Zhi ︰ Yi bis-An ︰ tri-(2-amino-ethyl) amine is 20-30 ︰ 1 ︰ 40-50.
The nylon 6 Blends that the present invention will hold polyamino dendritic macromole PESAM and gypsum fiber to be added into preparation in nylon 6 on a small quantity, without the need to adding other additives, toughen and intensify is effective, and the mechanical properties such as tensile strength, elongation at break, shock strength all obtain significance and improve.
Embodiment
The following examples are to further elaboration of the present invention, but content of the present invention is not limited thereto.Embodiment in specification sheets of the present invention is only for the present invention will be described, and it does not play restriction effect to protection scope of the present invention.Protection scope of the present invention is only defined by the claims, and any omission that those skilled in the art make on the basis of embodiment disclosed by the invention, replacement or amendment all will fall into protection scope of the present invention.
Embodiment 1
The quadrol of the Viscoat 295 of 30 weight parts and 12 weight parts is carried out Michael reaction 4 hours in room temperature, carries out separating-purifying with methyl alcohol as precipitation agent; Three (2-amino-ethyl) amine adding 50 weight parts was again in room temperature reaction 8 hours, and underpressure distillation, obtains end polyamino dendritic macromole PESAM, shown in I.
Embodiment 2
According to weight part, 1 part of PESAM glue head dropper is added drop-wise in 99 parts of PA6, adds in twin screw extruder charging basket after stirring, open forcing machine.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Embodiment 3
According to weight part, 1 part of PESAM glue head dropper is added drop-wise in 89 parts of PA6, adds in twin screw extruder charging basket after stirring, open forcing machine.10 parts of gypsum fibers are added from first venting port simultaneously and melt extrude.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Embodiment 4
According to weight part, 1 part of PESAM glue head dropper is added drop-wise in 79 parts of PA6, adds in twin screw extruder charging basket after stirring, open forcing machine.20 parts of gypsum fibers are added from first venting port simultaneously and melt extrude.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Embodiment 5
According to weight part, 1 part of PESAM glue head dropper is added drop-wise in 69 parts of PA6, adds in twin screw extruder charging basket after stirring, open forcing machine.30 parts of gypsum fibers are added from first venting port simultaneously and melt extrude.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Embodiment 6
According to weight part, 1 part of PESAM glue head dropper is added drop-wise in 59 parts of PA6, adds in twin screw extruder charging basket after stirring, open forcing machine.40 parts of gypsum fibers are added from first venting port simultaneously and melt extrude.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Embodiment 7
According to weight part, 80 parts of nylon 6 add in twin screw extruder charging basket, open forcing machine.20 parts of gypsum fibers are added from first venting port simultaneously and melt extrude.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Embodiment 8
According to weight part, 0.1 part of PESAM glue head dropper is added drop-wise in 79.9 parts of PA6, adds in twin screw extruder charging basket after stirring, open forcing machine.20 parts of gypsum fibers are added from first venting port simultaneously and melt extrude.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Embodiment 9
According to weight part, 0.5 part of PESAM glue head dropper is added drop-wise in 79.5 parts of PA6, adds in twin screw extruder charging basket after stirring, open forcing machine.20 parts of gypsum fibers are added from first venting port simultaneously and melt extrude.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Embodiment 10
According to weight part, 1.5 parts of PESAM glue head droppers are added drop-wise in 78.5 parts of PA6, add in twin screw extruder charging basket after stirring, open forcing machine.20 parts of gypsum fibers are added from first venting port simultaneously and melt extrude.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Embodiment 11
According to weight part, 2 parts of PESAM glue head droppers are added drop-wise in 78 parts of PA6, add in twin screw extruder charging basket after stirring, open forcing machine.20 parts of gypsum fibers are added from first venting port simultaneously and melt extrude.Extruder barrel processing temperature is 230 ~ 260 DEG C, forcing machine Gong She seven district, and the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, and the 4th district is 255 DEG C, and the 5th district is 260 DEG C, 6th district is 255 DEG C, and SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.Main-machine screw rotating speed is 600r.min -1, then melt extrude, wire drawing, cooling, pelletizing obtain desired product.
Performance test
Melting index test is pressed ISO1133 and is performed, and testing apparatus is Mei Tesi industrial system company limited ZRZ1452 melt flow rate (MFR) trier; Tensile strength and elongation at break test are pressed ISO527 and are performed, and testing apparatus is permanent Rui Jin, Jinan trier company limited WDW-10G electronic universal tester; Shock strength test is pressed ISO179 and is performed, and testing apparatus is U.S. TiniusOisen company IT504 shock-testing machine.
The plasticizing enhancement nylon 6 composite material performance adopting the inventive method to produce is as shown in table 1 below:
Table 1 embodiment product performance
Above-mentioned example, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to spirit of the present invention or modification, all should be encompassed within protection scope of the present invention.

Claims (5)

1. the nylon 6 Blends containing expanding material, it is characterized in that, it comprises nylon 6, gypsum fiber and expanding material, and described expanding material is end polyamino dendritic macromole PESAM, and its structural formula is such as formula shown in (I):
2. the nylon 6 Blends containing expanding material according to claim 1, it is characterized in that, in blend total amount, PESAM ︰ nylon 6 ︰ gypsum fiber weight percent is 0.1-5% ︰ 69-94% ︰ 5-30%.
3. the nylon 6 Blends containing expanding material according to claim 1, it is characterized in that, in blend total amount, PESAM ︰ nylon 6 ︰ gypsum fiber weight percent is 0.1-3% ︰ 69-87% ︰ 10-30%.
4. the method for the nylon 6 Blends containing expanding material of preparation as described in any one of claim 1-3, it is characterized in that, it comprises the steps:
First nylon 6 is placed in vacuum drying oven in 50 DEG C of dryings 2 hours, then PESAM is added drop-wise in nylon 6, stir; Then the material mixed is added twin screw extruder; gypsum fiber is added from first venting port of twin screw extruder simultaneously and melt extrude; various desired product is obtained through wire drawing, cooling, pelletizing; the machine barrel processing temperature of twin screw extruder is set as 230 ~ 260 DEG C, and main-machine screw rotating speed is 600r.min -1.
5. preparation method according to claim 4, it is characterized in that, described twin screw extruder Gong She seven district, the firstth district is 230 DEG C, and the secondth district is 240 DEG C, 3rd district is 245 DEG C, 4th district is 255 DEG C, and the 5th district is 260 DEG C, and the 6th district is 255 DEG C, SECTOR-SEVEN is 250 DEG C, and head temperature is 245 DEG C.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892508A (en) * 2018-06-25 2020-11-06 上海龙灯环保科技有限公司 Preparation method of trimethylolpropane tri ((N, N-di (2-aminoethyl)) -3-aminopropionate)
CN111943860A (en) * 2018-06-25 2020-11-17 同济大学 Preparation method of trimethylolpropane tri ((N, N-di (6-aminohexylidene)) -3-aminopropionate)

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Publication number Priority date Publication date Assignee Title
US4518728A (en) * 1984-04-04 1985-05-21 Monsanto Company Carbon black filled nylons modified for improved toughness
CN104559152A (en) * 2014-12-19 2015-04-29 威海晨源分子新材料有限公司 Application of hyperbranched polyester in PA6 (polyamide 6)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4518728A (en) * 1984-04-04 1985-05-21 Monsanto Company Carbon black filled nylons modified for improved toughness
CN104559152A (en) * 2014-12-19 2015-04-29 威海晨源分子新材料有限公司 Application of hyperbranched polyester in PA6 (polyamide 6)

Non-Patent Citations (2)

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DONGMEI XU ET AL.: ""Fast growing dendritic poly(ester–amines) from alternate reaction of EDA and TMPTA"", 《TETRAHEDRON LETTERS》 *
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892508A (en) * 2018-06-25 2020-11-06 上海龙灯环保科技有限公司 Preparation method of trimethylolpropane tri ((N, N-di (2-aminoethyl)) -3-aminopropionate)
CN111943860A (en) * 2018-06-25 2020-11-17 同济大学 Preparation method of trimethylolpropane tri ((N, N-di (6-aminohexylidene)) -3-aminopropionate)
CN111943860B (en) * 2018-06-25 2021-07-06 同济大学 Preparation method of trimethylolpropane tri ((N, N-di (6-aminohexylidene)) -3-aminopropionate)
CN111892508B (en) * 2018-06-25 2021-12-03 上海龙灯环保科技有限公司 Preparation method of trimethylolpropane tri ((N, N-di (2-aminoethyl)) -3-aminopropionate)

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