CN109735097A - A kind of low water suction High impact nylon composite material and preparation method - Google Patents
A kind of low water suction High impact nylon composite material and preparation method Download PDFInfo
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- CN109735097A CN109735097A CN201811403754.6A CN201811403754A CN109735097A CN 109735097 A CN109735097 A CN 109735097A CN 201811403754 A CN201811403754 A CN 201811403754A CN 109735097 A CN109735097 A CN 109735097A
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Abstract
The present invention relates to a kind of low water suction High impact nylon composite material and preparation methods, compatilizer maleic anhydride and polyphenylene oxide are mixed and squeezed out, obtain maleic anhydride grafted polyphenylene ether, graft and modified graphene oxide achieved above are obtained into graphene oxide grafted polyphenylene ether by solvent reaction again, by portion rate: 87-98.8 parts of nylon resin；0.1-5 parts of graphene oxide grafted polyphenylene ether；1-5 parts of antioxidant；0.1-3 parts of ultraviolet absorbing agent.Mixed melting obtains low water suction High impact nylon composite material.This patent is modified nylon using graphene oxide grafted polyphenylene ether, crystallization temperature, tensile strength, elongation at break, the notch impact strength for the low water suction High impact nylon composite material developed are improved, water absorption rate reduces, and product appearance is smooth, function admirable.The comprehensive performance for optimizing nylon matrix material has complied with the development trend of high-performance light.
Description
Technical field
The present invention relates to a kind of low water suction High impact nylon composite material and preparation methods.
Background technique
Nylon (PA) is first of five big general engineering plastics, and average annual demand speedup is up to 10%.Nineteen thirty-five Tomas Carothers is first
Secondary to synthesize polyamide nylon by hexanediamine and adipic acid, strand has a large amount of recurring amide radical group-[NHCO]-, makes this
Kind of material mechanical performance, durability, corrosion resistance, in terms of there are high-performance benefits, be widely used in electricity
The industries such as sub electrical, automobile, building, office equipment, machinery, aerospace.But it exists simultaneously water absorption rate height, shock resistance
The defect of difference limits nylon to mould for the development in steel trend.
American-European nylon manufacturer by its technology, fund, in terms of advantage occupy middle and high end nylon neck
The domain overwhelming majority market share.The nylon manufacturing enterprise quantity in China is many but scale is generally less than normal, production technology and production skill
Art tradition, product more low side.In recent years, people mostly use polymerization or blending technology high performance PA engineering plastics, wherein adding
Adding modifying agent blend modification technology is the most commonly used method of modification of nylon, easy to operate, at low cost, effect is obvious.Using poly-
The modified toughened nylon of phenylate has become a kind of common method, but when the additive amount of only polyphenylene oxide is greater than 20 parts, toughening effect
It could significantly show, biggish additive amount not only increases the cost of composite material and while toughening to reduce
The rigidity of nylon material is cost.
Summary of the invention
The purpose of the present invention is in view of the deficienciess of the prior art, providing that a kind of to be both able to maintain nylon material original low close
Degree, and nylon water absorption rate, the low water suction High impact nylon composite material of one kind for improving shock resistance and its preparation is greatly reduced
Method.
For achieving the above object, a kind of the technical solution adopted by the present invention are as follows: low water suction High impact nylon composite wood
Material, includes following components by portion rate: 87-98.8 parts of nylon resin；0.1-5 parts of graphene oxide grafted polyphenylene ether；Antioxidant
1-5 parts；0.1-3 parts of ultraviolet absorbing agent.
The nylon resin is graininess.
The nylon resin is polyamide 6, polyamide 6,6, polyamide 4,6, poly- (12 carbon diamines of paraphenylene terephthalamide)
(polyamide 12, T), poly- (paraphenylene terephthalamide's decamethylene diamine) (polyamide 10, T), poly- (paraphenylene terephthalamide's nonamethylene diamine) (polyamide 9, T)
One or more of the mixture that arbitrarily matches.
Graphene oxide in the graphene oxide graft polyether is that graphene oxide adds modifying agent to be prepared to change
Property graphene oxide, modifying agent is hexamethylene diamine, one of 2,3- epoxypropyltrimethylchloride chlorides.
The antioxidant is Hinered phenols antioxidant, phosphite antioxidant, organic sulfur antioxidant.
The preparation method of low water suction High impact nylon composite material, comprising the following steps:
1) preparation of maleic anhydride grafted polyphenylene ether
The compatilizer maleic anhydride (MAH) and 97-99.9 parts of polyphenylene oxide mixings that mass fraction is 0.1~3 part are taken, is added to
In double screw extruder, melting extrusion is cooling, dries up, and is granulated, obtains maleic anhydride grafted polyphenylene ether PPO-g-MAH；
2) preparation of modified graphene oxide solution
50-150ml modifying agent is added in the solution of 50-300ml graphene oxide, until there is no new brown is cotton-shaped
Object occurs, and centrifuge washing mixture, 50-60 DEG C of vacuum drying 18-24h obtains modified graphene oxide (GO)；
3) preparation of graphene oxide grafted polyphenylene ether
20~60mL dimethylbenzene and 1~5g PPO-g-MAH are added in three-necked flask, PPO-g-MAH dissolution is warming up to,
1~5h is reacted after 0.1~3mL deionized water is added, adds the modified GO of 0.3~5g and 0.1~1g tetrabutylammonium bromide 100
~150 DEG C of 1~5h of reaction, filtering, dimethylbenzene extracting obtain graphene oxide grafted polyphenylene ether (GO-g-PPO) after dry；
4) preparation of low water suction High impact nylon composite material
By 87-98.8 parts of nylon resin (PA)；0.1-5 parts of graphene oxide grafted polyphenylene ether (GO-g-PPO)；Antioxidant
1-5 parts；0.1-3 parts of ultraviolet absorbing agent mix in high-speed mixer, and double screw extruder melt blending is added in premix, is cut
Grain, obtains low water suction High impact nylon composite material (GO/PPO/PA).
Step 1) melting extrusion process is carried out by double screw extruder, revolving speed 200-500rpm, processing temperature 240-
320℃。
Step 4) melting extrusion process is carried out by double screw extruder, revolving speed 100-300rpm, processing temperature 230-
300℃。
This patent is modified nylon using graphene oxide graft polyether (GO-g-PPO), in the few feelings of additive amount
Under condition, the crystallization temperature of low water suction High impact nylon composite material (GO/PPO/PA) of the modification of development, tensile strength, fracture are stretched
Long rate, notch impact strength are improved, and crystallization temperature is high, and water absorption rate reduces, and product appearance is smooth, function admirable.Optimization
The comprehensive performance of nylon matrix material, has complied with the development trend of high-performance light.
The invention has the advantages that and the utility model has the advantages that
(1) for the present invention with graphene oxide graft polyether (GO-g-PPO) modified nylon materials, amount of modifier is minimum, changes
Property effect is obvious, and properties of product are excellent, cost efficiency.78
(2) low water suction High impact nylon composite material prepared by the present invention carries out performance according to standard ISO180, ISO527
Test: notch impact strength is by 6.8KJ/m2It improves to 9.5KJ/m2, for elongation at break by 38% raising to 45%, stretching is strong
Degree is improved by 68MPa to 74MPa.
(3) low water suction High impact nylon composite material prepared by the present invention has a wide range of application.
Specific embodiment
Production method of the invention is described in further detail below with reference to embodiment.
Embodiment 1
1) the compatilizer maleic anhydride MAH and 99 parts of polyphenylene oxide mixings that mass fraction is 1 part are taken, twin-screw extrusion is added to
In machine, melting extrusion is cooling, dries up, and is granulated, revolving speed 200rmp, and processing temperature is 240~300 DEG C, obtains maleic anhydride and connects
Branch polyphenylene oxide PPO-g-MAH；
2) 80ml hexamethylene diamine is added in the solution of 200ml graphene oxide GO, until there is no new brown floccules
Occur, centrifuge washing mixture, 50 DEG C of vacuum drying 18h obtain modified graphene oxide GO；
3) amount of 30mL dimethylbenzene and 1g maleic anhydride grafted polyphenylene ether PPO-g-MAH are added in three-necked flask, heating
It is dissolved to maleic anhydride grafted polyphenylene ether PPO-g-MAH, reacts 2h after 1mL deionized water is added, add the modified oxidized stone of 1g
Black alkene GO and 0.02g tetrabutylammonium bromide are filtered in 120 DEG C of reaction 2h, and dimethylbenzene extracting obtains graphene oxide after dry and connects
Branch polyphenylene oxide GO-g-PPO；
It 4) is 3 parts of graphene oxide grafted polyphenylene ether GO-g-PPO, 95 parts of graininess polyamide 6s (PA6) by mass fraction
With 1 part of Hinered phenols antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 1 part of BASF AG
Ultraviolet absorbing agent UV531 is mixed in high-speed mixer, and double screw extruder melt blending, pelletizing, revolving speed is added in premix
100rpm, processing temperature are 230-265 DEG C, obtain low water suction High impact nylon composite material GO/PPO/PA.
According to standard ISO180, ISO527, in balance weight impact testing machine INSTRON T7614, universal testing machine INSTRON
It is tested for the property respectively on 5966: notch impact strength 6.8KJ/m2, elongation at break 40%, tensile strength 74MPa.
Embodiment 2
1) the compatilizer maleic anhydride MAH and 98 parts of polyphenylene oxide mixings that mass fraction is 2 parts are taken, twin-screw extrusion is added to
In machine, melting extrusion is cooling, dries up, and is granulated, revolving speed 300rmp, and processing temperature is 260~320 DEG C, obtains maleic anhydride and connects
Branch polyphenylene oxide PPO-g-MAH；
2) the addition 220ml 2 in the solution of 180ml graphene oxide GO, 3- epoxypropyltrimethylchloride chloride, until
There is no the appearance of new brown floccule, centrifuge washing mixture, 60 DEG C of vacuum drying 18h obtain modified graphene oxide GO；
3) amount of 50mL dimethylbenzene and 2g maleic anhydride grafted polyphenylene ether PPO-g-MAH are added in three-necked flask, heating
It is dissolved to maleic anhydride grafted polyphenylene ether PPO-g-MAH, reacts 1h after 3mL deionized water is added, add the modified oxidized stone of 3g
Black alkene GO and 1g tetrabutylammonium bromide are filtered in 100 DEG C of reaction 5h, and dimethylbenzene extracting obtains graphene oxide grafting after dry
Polyphenylene oxide GO-g-PPO；
4) by mass fraction be 1 part of graphene oxide grafted polyphenylene ether GO-g-PPO, 95 parts of graininess polyamide 6s, 6
(PA66) with 2 parts of phosphite ester antioxidant three (2,4- di-t-butyl) phenyl-phosphites, 2 parts of BASF AG's ultraviolet absorbing agents
UV326 is mixed in high-speed mixer, and double screw extruder melt blending, pelletizing, revolving speed 100rpm, processing temperature is added in premix
Degree is 230-265 DEG C, obtains low water suction High impact nylon composite material GO/PPO/PA.
It is tested for the property according to standard ISO180, ISO527: notch impact strength 7.7KJ/m2, elongation at break
45%, tensile strength 68MPa.
Embodiment 3
1) the compatilizer maleic anhydride MAH and 97 parts of polyphenylene oxide mixings that mass fraction is 3 parts are taken, twin-screw extrusion is added to
In machine, melting extrusion is cooling, dries up, and is granulated, revolving speed 200rmp, and processing temperature is 260~320 DEG C, obtains maleic anhydride and connects
Branch polyphenylene oxide PPO-g-MAH；
2) the addition 120ml 2 in the solution of 240ml graphene oxide GO, 3- epoxypropyltrimethylchloride chloride, until
There is no the appearance of new brown floccule, centrifuge washing mixture, 50 DEG C of vacuum drying for 24 hours, obtain modified graphene oxide GO；
3) amount of 30mL dimethylbenzene and 2g maleic anhydride grafted polyphenylene ether PPO-g-MAH are added in three-necked flask, heating
It is dissolved to maleic anhydride grafted polyphenylene ether PPO-g-MAH, reacts 5h after 3mL deionized water is added, add the modified oxidized stone of 1g
Black alkene GO and 0.5g tetrabutylammonium bromide are filtered in 120 DEG C of reaction 5h, and dimethylbenzene extracting obtains graphene oxide after dry and connects
Branch polyphenylene oxide GO-g-PPO；
It 4) is 1 part of graphene oxide grafted polyphenylene ether GO-g-PPO by mass fraction, 96 parts of particulate nylon resins (PA6:
PA66 is 1:2) and 2 parts of Hinered phenols antioxidants four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 1
Part BASF AG ultraviolet absorbing agent Tinuvin 1130 is mixed in high-speed mixer, and double screw extruder is added in premix and is melted
Melt blending, pelletizing, revolving speed 100rpm, processing temperature is 230-265 DEG C, obtains low water suction High impact nylon composite material GO/
PPO/PA。
It is tested for the property according to standard ISO180, ISO527: notch impact strength 9.5KJ/m2, elongation at break
38%, tensile strength 70MPa.
Claims (8)
1. a kind of low water suction High impact nylon composite material, it is characterised in that by portion rate include following components: nylon resin 87-
98.8 parts；0.1-5 parts of graphene oxide grafted polyphenylene ether；1-5 parts of antioxidant；0.1-3 parts of ultraviolet absorbing agent.
2. low water suction High impact nylon composite material according to claim 1, it is characterised in that: the nylon resin is
It is granular.
3. low water suction High impact nylon composite material according to claim 1, it is characterised in that: the nylon resin is poly-
Amide 6, polyamide 6,6, polyamide 4,6, poly- (12 carbon diamines of paraphenylene terephthalamide) (polyamide 12, T), poly- (paraphenylene terephthalamide
Decamethylene diamine) (polyamide 10, T), one or more of poly- (paraphenylene terephthalamide's nonamethylene diamine) (polyamide 9, T) arbitrarily match it is mixed
Close object.
4. low water suction High impact nylon composite material according to claim 1, it is characterised in that: the graphene oxide connects
Graphene oxide in branch polyethers is that graphene oxide adds modifying agent to be prepared modified graphene oxide, modifying agent for oneself two
Amine, one of 2,3- epoxypropyltrimethylchloride chlorides.
5. low water suction High impact nylon composite material according to claim 1, it is characterised in that: the antioxidant is to be obstructed
Phenolic antioxidant, phosphite antioxidant, organic sulfur antioxidant.
6. the preparation method of low water suction High impact nylon composite material according to claim 1, it is characterised in that including following
Step:
1) preparation of maleic anhydride grafted polyphenylene ether
The compatilizer maleic anhydride (MAH) and 97-99.9 parts of polyphenylene oxide mixings that mass fraction is 0.1~3 part are taken, double spiral shells are added to
In bar extruder, melting extrusion is cooling, dries up, and is granulated, obtains maleic anhydride grafted polyphenylene ether PPO-g-MAH；
2) preparation of modified graphene oxide solution
50-150ml modifying agent is added in the solution of 50-300ml graphene oxide, until there is no new brown floccules to go out
Existing, centrifuge washing mixture, 50-60 DEG C of vacuum drying 18-24h obtains modified graphene oxide (GO)；
3) preparation of graphene oxide grafted polyphenylene ether
20~60mL dimethylbenzene and 1~5g PPO-g-MAH are added in three-necked flask, PPO-g-MAH dissolution is warming up to, is added
1~5h is reacted after 0.1~3mL deionized water, add the modified GO of 0.3~5g and 0.1~1g tetrabutylammonium bromide 100~
150 DEG C of 1~5h of reaction, filtering, dimethylbenzene extracting obtain graphene oxide grafted polyphenylene ether (GO-g-PPO) after dry；
4) preparation of low water suction High impact nylon composite material
By 87-98.8 parts of nylon resin (PA)；0.1-5 parts of graphene oxide grafted polyphenylene ether (GO-g-PPO)；Antioxidant 1-5
Part；0.1-3 parts of ultraviolet absorbing agent mix in high-speed mixer, and double screw extruder melt blending, pelletizing is added in premix,
Obtain low water suction High impact nylon composite material (GO/PPO/PA).
7. the preparation method of low water suction High impact nylon composite material according to claim 7, it is characterised in that: step 1) is molten
Melt extrusion process to carry out by double screw extruder, revolving speed 200-500rpm, processing temperature is 240-320 DEG C.
8. the preparation method of low water suction High impact nylon composite material according to claim 7, it is characterised in that: step 4) is molten
Melt extrusion process to carry out by double screw extruder, revolving speed 100-300rpm, processing temperature is 230-300 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114163809A (en) * | 2021-12-17 | 2022-03-11 | 徐州盛安化工科技有限公司 | Preparation method and application of kaolin grafted polyphenyl ether modified polyurethane resin |
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| CN108822532A (en) * | 2018-07-10 | 2018-11-16 | 芜湖市元奎新材料科技有限公司 | Graphene nylon composite materials and preparation method thereof |
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| JP2012171986A (en) * | 2011-02-17 | 2012-09-10 | Teijin Ltd | Thermally conductive composition |
| CN108822532A (en) * | 2018-07-10 | 2018-11-16 | 芜湖市元奎新材料科技有限公司 | Graphene nylon composite materials and preparation method thereof |
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| （日）栗原福次著，吴三硕译: "《塑料的老化》", 28 February 1977, 国防工业出版社 * |
| YAN JIA-LIN等: ""Functionalized grapheme oxide with ethylenediamine and 1,6-hexanediamine"", 《新型炭材料》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114163809A (en) * | 2021-12-17 | 2022-03-11 | 徐州盛安化工科技有限公司 | Preparation method and application of kaolin grafted polyphenyl ether modified polyurethane resin |
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