CN107936550A - A kind of polystyrene/nylon 6 composite material and preparation method thereof - Google Patents
A kind of polystyrene/nylon 6 composite material and preparation method thereof Download PDFInfo
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- CN107936550A CN107936550A CN201711229005.1A CN201711229005A CN107936550A CN 107936550 A CN107936550 A CN 107936550A CN 201711229005 A CN201711229005 A CN 201711229005A CN 107936550 A CN107936550 A CN 107936550A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
- C08G69/20—Anionic polymerisation characterised by the catalysts used
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- Polymers & Plastics (AREA)
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- Polyamides (AREA)
Abstract
The present invention relates to a kind of polystyrene/nylon 6 composite material and preparation method thereof.The percentage by weight of its component the following is：Caprolactam 88 91%, styrene 8 11%, compatilizer monomer 0.2 1%, radical polymerization initiator 0.05 0.1%, anionic polymerization initiator 0.15 0.2%, anionic polymerisation activator 0.4 0.7%；Using caprolactam, styrene as monomer, when adding compatilizer and small 60 75 DEG C of radical initiator reaction 24 after, rise temperature to 130 150 DEG C of vacuum distillations 1 it is small when remove remaining small molecule and water in mixed liquor.Addition anionic polymerization initiator, vacuum distillation reaction 20 minutes, is eventually adding anionic polymerisation activator, and mould is poured into rapid mixing, and nylon 6 composite material is obtained in 170 DEG C of one hours of reaction.The composite material has the advantages that low water absorbable, high impact toughness, and technique is simple, is adapted to large-scale production.
Description
Technical field
The present invention relates to a kind of polystyrene/nylon 6 composite material and preparation method thereof, more particularly to one kind to have low suction
PS/PA6 composite materials of water rate high impact toughness and preparation method thereof, belong to technical field of polymer materials.
Background technology
PA6 has excellent mechanical strength, wearability, self lubricity and corrosion resistance etc., but there are hygroscopicity is strong, ruler
The shortcomings of very little stability and poor heat endurance.Particularly water imbibition is higher and influence the dimensional stability and electrical property of product,
It cannot meet the insulating requirements and water resistance under high humility and condition of high voltage, greatly limit its application field.
The prominent characteristic of PS is electrical insulating property, hydrophobicity, cheap, additionally with good light resistance, preferable
Rigid and certain mechanical strength, major defect is more crisp, impact strength is low etc..PA6 and PS has preferable complementarity.But
It is that PA6 is polarity macromolecule, PS is nonpolar, if directly blending can not reach expected because compatibility is poor for both
Effect.Existing achievement in research shows that in the combination of polymers of numerous rigid chain/flexible chains, the compatibility of PS/PA6 is worst.
At present, for PS/PA6 alloys, the most common method for improving compatibility is that compatilizer is added during melt blending, example
Such as common compatilizer PS-g-PA6, PS-b-PEO, PS-co-GMA etc., but for the melt blending of PS/PA6, required adds
Work temperature is higher, high energy consumption, and viscosity is very big, poor fluidity, is unfavorable for processing.
The content of the invention
For it is existing the defects of, the present invention by adding compatilizer monomer, in caprolactam solution with styrene carry out
Free radicals copolymerization reaction, is further continued for carrying out afterwards the anionic polymerisation of PA6, improves the compatibility of PS/PA6.With it is traditional
Addition Macromolecular Compatibilizer is compared when PA6, PS are blended, and PS/PA6 composite materials compatibility, dispersiveness prepared by the present invention (reaches
Nano grade) it is more excellent, and the molecule of PS can be controlled in preparation process by adjusting the amount of radical polymerization initiator
Amount.Step of the present invention is simple, is method that is a kind of efficiently novel and can be mass-produced.
The purpose of the invention is to provide a kind of PS/PA6 composite materials with low water absorption high impact toughness.
A kind of polystyrene/nylon 6 composite material, it is characterised in that the component and weight percent of the composite material
Than as follows：
The compatilizer monomer is maleic anhydride, one or both of acrylamide,
The radical polymerization initiator is azodiisobutyronitrile, one or both of dibenzoyl peroxide, institute
The anionic polymerization initiator stated is sodium hydroxide,
The anionic polymerisation activator is Toluene-2,4-diisocyanate, 4- diisocyanate.
It is a further object of the present invention to provide a kind of preparation method of above-mentioned PS/PA6 composite materials.
A kind of polystyrene/nylon 6 composite material, it is characterised in that, the method includes the following steps：
(1) caprolactam monomer is melted at 130-150 DEG C, after being evaporated under reduced pressure 30 minutes, temperature is down to 60-75 DEG C and is led to
Nitrogen is protected；
(2) in the molten caprolactam obtained in step (1) in the ratio add styrene, compatilizer monomer and from
By base polymerization initiator, faint yellow sticky polystyrene/caprolactam mixed liquor is obtained when reaction 24 is small under nitrogen protection；
(3) mixed liquor that step (2) obtains is warming up to 130-150 DEG C, vacuum distillation 1 removes remaining small molecule when small
And water, anionic polymerization initiator is proportionally added into, and continue vacuum distillation 20 minutes；
(4) anionic polymerisation activator is proportionally added into the mixed liquor that step (3) obtains, rapid mixing, at 170 DEG C
React 1 it is small when obtain the PS/PA6 composite materials of low water absorption high impact toughness.
The present invention use continuous in-situ increase-volume and in-situ polymerization, and caprolactam monomer is solvent, styrene monomer with
Compatilizer monomer carries out free-radical polymerized, then caprolactam anionic ring-opening polymerization wherein.Compared with prior art, this hair
Bright obtained PS/PA6 composite materials have the advantages that low water absorbable, high impact toughness, excellent compatibility.
Brief description of the drawings
Fig. 1 is the contact angle figure in comparative example 1.
Fig. 2 is the contact angle figure in comparative example 2.
Fig. 3 is the cross-sectional scanning electron microscope figure in comparative example 2.
Fig. 4 is the contact angle figure in embodiment 1.
Fig. 5 is the cross-sectional scanning electron microscope figure in embodiment 1.
Fig. 6 is the contact angle figure in embodiment 2.
Fig. 7 is the cross-sectional scanning electron microscope figure in embodiment 2.
Embodiment
Example below further describes the present invention, and in the case where not violating spirit of the invention, the present invention should be not limited to following
The content that embodiment is specifically expressed.
Embodiment, comparative example are raw materials used as follows：
Caprolactam, German BASF joint-stock company；
Styrene, Shanghai Aladdin biochemical technology limited company；
Compatilizer monomer：Maleic anhydride, Shanghai Aladdin biochemical technology limited company；Acrylamide, Beijing Hua Wei
Rui Ke Chemical Co., Ltd.s；
Radical polymerization initiator：Azodiisobutyronitrile, the upper smooth Science and Technology Co., Ltd. of Haitai；Diphenyl peroxide first
Acyl, Shanghai Ling Feng chemical reagent Co., Ltd；
Anionic polymerization initiator：Sodium hydroxide, the upper smooth Science and Technology Co., Ltd. of Haitai
Anionic polymerisation activator：Toluene-2,4-diisocyanate, 4- diisocyanate, uncommon love (Shanghai) chemical conversion industry of ladder develop limited public affairs
Department；
Comparative example 1
Precise 90g caprolactams, are evaporated under reduced pressure 30 minutes in 130 DEG C of meltings, add 0.2g sodium hydroxides, and decompression is steamed
Evaporate 20 minutes and remove micro water, be eventually adding 0.7g Toluene-2,4-diisocyanates, 4- diisocyanate, pours into rapidly mould and exist after mixing
A hour is reacted in 170 DEG C of constant temperature oven.Obtained batten is boiled into 3 hours in boiling water, removes the small molecule of inside,
Then batten is statically placed in 25 DEG C, in the thermostatic constant wet chamber of 50% humidity 24 it is small when after test performance, the notch shock measured is strong
Spend for 4.5kJ/m2.Saturated water absorption is 3.8wt%, contact angle test result such as Fig. 1.
Comparative example 2
Precise 90g caprolactams, are evaporated under reduced pressure 30 minutes in 130 DEG C of meltings, after temperature is down to 75 DEG C, add
10g styrene, 0.1g azo-bis-isobutyl cyanides, faint yellow sticky mixed liquor is obtained when reaction 24 is small under nitrogen protection.It is warming up to
130 DEG C, remaining small molecule and water in mixed liquor are removed when vacuum distillation 1 is small.0.2g sodium hydroxides are added, are evaporated under reduced pressure 20 points
Clock removes micro water, is eventually adding 0.7g Toluene-2,4-diisocyanates, 4- diisocyanate, pours into rapidly mould at 170 DEG C after mixing
Constant temperature oven in react a hour.Obtained batten is boiled into 3 hours in boiling water, removes the small molecule of inside, then
Batten is statically placed in 25 DEG C, in the thermostatic constant wet chamber of 50% humidity 24 it is small when after test performance, the notch impact strength measured is
3.8kJ/m2.Saturated water absorption is 2.2wt%, and contact angle test result such as Fig. 2, cross-sectional scanning electron microscope figure such as Fig. 3 are (disconnected
Face through tetrahydrofuran etching 6 it is small when).It can be seen that compared to comparative example 1, the contact angle of comparative example 2 substantially becomes larger, and Fig. 3 occurs
Hole be to be left after polystyrene is etched, the polystyrene for illustrating to be dispersed in nylon-6 matrix body can improve material well
The water resistance of material.
Embodiment 1
Precise 90g caprolactams, are evaporated under reduced pressure 30 minutes in 130 DEG C of meltings, after temperature is down to 75 DEG C, add
10g styrene, 1g maleic anhydrides, 0.1g azo-bis-isobutyl cyanides, obtain faint yellow sticky mixed when reaction 24 is small under nitrogen protection
Close liquid.130 DEG C are warming up to, remaining small molecule and water in mixed liquor are removed when vacuum distillation 1 is small.0.2g sodium hydroxides are added,
Vacuum distillation removes micro water in 20 minutes, is eventually adding 0.7g Toluene-2,4-diisocyanates, 4- diisocyanate, is poured into rapidly after mixing
Mould reacts a hour in 170 DEG C of constant temperature oven.Obtained batten is boiled into 3 hours in boiling water, removes inside
Small molecule, is then statically placed in 25 DEG C by batten, in the thermostatic constant wet chamber of 50% humidity 24 it is small when after test performance, the notch measured
Impact strength is 6.5kJ/m2.Saturated water absorption is 2.1wt%, contact angle test result such as Fig. 4, cross-sectional scanning electron microscope
Figure as Fig. 5 (section through tetrahydrofuran etching 6 it is small when).It can be seen that compared to comparative example 2, the contact angle of embodiment 1 have again into
The increase of one step, the scanning figure after etching in addition show that aperture diminishes, and the compatilizer monomer for illustrating to add can be sent out with styrene
Raw copolyreaction, so as to improve the compatibility of polystyrene and nylon 6, and then improves the dispersiveness of polystyrene, water resistance
And mechanical property.
Embodiment 2
Precise 90g caprolactams, are evaporated under reduced pressure 30 minutes in 130 DEG C of meltings, after temperature is down to 75 DEG C, add
10g styrene, 1g acrylamides, 0.1g dibenzoyl peroxides, obtain faint yellow sticky when reaction 24 is small under nitrogen protection
Mixed liquor.130 DEG C are warming up to, remaining small molecule and water in mixed liquor are removed when vacuum distillation 1 is small.Add 0.2g hydroxides
Sodium, is evaporated under reduced pressure 20 minutes and removes micro water, is eventually adding 0.7g Toluene-2,4-diisocyanates, 4- diisocyanate, after mixing rapidly
Pour into mould and a hour is reacted in 170 DEG C of constant temperature oven.Obtained batten is boiled 3 hours in boiling water, in removing
The small molecule in portion, is then statically placed in 25 DEG C by batten, in the thermostatic constant wet chamber of 50% humidity 24 it is small when after test performance, measure
Notch impact strength is 6.8kJ/m2.Saturated water absorption is 2.0wt%, contact angle test result such as Fig. 6, and cross-sectional scanning electron is shown
Micro mirror figure such as Fig. 7 (section through tetrahydrofuran etching 6 it is small when).It can be seen that compared to embodiment 1, the contact angle of embodiment 2 is again
There is further increase, the scanning figure after etching in addition shows that aperture diminishes, and illustrates compared to maleic anhydride, acrylamide and benzene
The copolymer of ethylene synthesis is more advantageous to improving the compatibility of polystyrene and nylon 6, and then improves the scattered of polystyrene
Property, water resistance and mechanical property.
Claims (2)
1. a kind of polystyrene/nylon 6 composite material, it is characterised in that the component and percentage by weight of the composite material
It is as follows：
Its total amount meets 100%,
The compatilizer monomer is maleic anhydride, one or both of acrylamide,
The radical polymerization initiator is azodiisobutyronitrile, one or both of dibenzoyl peroxide,
The anionic polymerization initiator is sodium hydroxide,
The anionic polymerisation activator is Toluene-2,4-diisocyanate, 4- diisocyanate.
A kind of 2. preparation method of polystyrene/nylon 6 composite material as claimed in claim 1, it is characterised in that Yi Zhongju
Styrene/nylon 6 composite material, it is characterised in that, the method includes the following steps：
(1) caprolactam monomer is melted at 130-150 DEG C, after being evaporated under reduced pressure 30 minutes, temperature is down to 60-75 DEG C and logical nitrogen
Protection；
(2) in the molten caprolactam obtained in step (1) in the ratio add suitable styrene, compatilizer monomer and
Radical polymerization initiator, obtains faint yellow sticky polystyrene/caprolactam mixing when reaction 24 is small under nitrogen protection
Liquid；
(3) mixed liquor that step (2) obtains is warming up to 130-150 DEG C, vacuum distillation 1 removed when small remaining small molecule and
Water, is proportionally added into anionic polymerization initiator, and continues vacuum distillation 20 minutes；
(4) anionic polymerisation activator is proportionally added into the mixed liquor that step (3) obtains, is mixed, it is small in 170 DEG C of reactions 1
When obtain the polystyrene/nylon 6 composite material.
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| CN201711229005.1A CN107936550A (en) | 2017-11-29 | 2017-11-29 | A kind of polystyrene/nylon 6 composite material and preparation method thereof |
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| CN201711229005.1A CN107936550A (en) | 2017-11-29 | 2017-11-29 | A kind of polystyrene/nylon 6 composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940497A (en) * | 2021-03-22 | 2021-06-11 | 浙江工业大学 | Preparation method of electromagnetic shielding PA6/PS composite foam material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05179138A (en) * | 1991-12-26 | 1993-07-20 | Mitsubishi Kasei Corp | Preparation of polyamide resin composition |
| CN101077910A (en) * | 2006-05-23 | 2007-11-28 | 上海杰事杰新材料股份有限公司 | Method for preparing particle diameter controllable high molecular weight nylon micro-sphere |
| CN101469127A (en) * | 2007-12-24 | 2009-07-01 | 上海杰事杰新材料股份有限公司 | Preparation of polyolefin nylon in situ alloy |
| CN101469071A (en) * | 2007-12-24 | 2009-07-01 | 上海杰事杰新材料股份有限公司 | Preparation of compatilizer |
| CN102108126A (en) * | 2009-12-24 | 2011-06-29 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of nylon-6 conductive microsphere |
| CN102477156A (en) * | 2010-11-30 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of polystyrene-gamma-casting nylon 6 graft copolymer with nanoparticle structure |
| CN105566901A (en) * | 2016-02-01 | 2016-05-11 | 佳易容相容剂江苏有限公司 | Polyamide-polyolefin alloy material and in-situ grafting preparation method thereof |
-
2017
- 2017-11-29 CN CN201711229005.1A patent/CN107936550A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05179138A (en) * | 1991-12-26 | 1993-07-20 | Mitsubishi Kasei Corp | Preparation of polyamide resin composition |
| CN101077910A (en) * | 2006-05-23 | 2007-11-28 | 上海杰事杰新材料股份有限公司 | Method for preparing particle diameter controllable high molecular weight nylon micro-sphere |
| CN101469127A (en) * | 2007-12-24 | 2009-07-01 | 上海杰事杰新材料股份有限公司 | Preparation of polyolefin nylon in situ alloy |
| CN101469071A (en) * | 2007-12-24 | 2009-07-01 | 上海杰事杰新材料股份有限公司 | Preparation of compatilizer |
| CN102108126A (en) * | 2009-12-24 | 2011-06-29 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of nylon-6 conductive microsphere |
| CN102477156A (en) * | 2010-11-30 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of polystyrene-gamma-casting nylon 6 graft copolymer with nanoparticle structure |
| CN105566901A (en) * | 2016-02-01 | 2016-05-11 | 佳易容相容剂江苏有限公司 | Polyamide-polyolefin alloy material and in-situ grafting preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940497A (en) * | 2021-03-22 | 2021-06-11 | 浙江工业大学 | Preparation method of electromagnetic shielding PA6/PS composite foam material |
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