CN102477156B - Preparation method of polystyrene-gamma-casting nylon 6 graft copolymer with nanoparticle structure - Google Patents
Preparation method of polystyrene-gamma-casting nylon 6 graft copolymer with nanoparticle structure Download PDFInfo
- Publication number
- CN102477156B CN102477156B CN201010565545.9A CN201010565545A CN102477156B CN 102477156 B CN102477156 B CN 102477156B CN 201010565545 A CN201010565545 A CN 201010565545A CN 102477156 B CN102477156 B CN 102477156B
- Authority
- CN
- China
- Prior art keywords
- preparation
- graft copolymer
- initiator
- sodium
- nanoparticle structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Polyamides (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention belongs to the high-molecular material preparation technical field, and relates to a preparation method of a polystyrene-gamma-casting nylon 6 graft copolymer with a nanoparticle structure. The method comprises the following steps: using an in-situ polymerization, carrying out radical copolymerization of styrene and a certain amount of isocyanate to obtain a free radical copolymer as a macro-molecule activator, adding in a certain amount of fused caprolactam, initiating an anion ring opening polymerization of caprolactam to obtain the polystyrene-gamma-casting nylon 6 graft copolymer with the nanoparticle structure. The invention has the advantages of simple operation, unique morphology of the graft copolymer structure and large application potential.
Description
Technical field
The invention belongs to field of polymer material preparing technology, relate to a kind of preparation method of polystyrene-g-nylon monomer-cast nylon 6 graft copolymers of nanoparticle structure.
Background technology
Graftomer is owing to forming respectively skeleton main chain and graft side chain by two kinds of different polymer molecular chains, and therefore they have noticeable property.Up to the present, crosslinking technology has developed into one of basic skills of polymer materials being carried out modification.Graftomer is widely used as expanding material, polymeric surfactant, surface-modifying agent of polymer alloy etc.
Polystyrene and polyamide 6 are two kinds of incompatible polymers, and the graft copolymer that utilizes crosslinking technology to prepare them can increase the consistency of alloy greatly.Preparation method (Grafting of polyamide 6 by the anionic polymerization of ε-caprolactam from an isocyanate bearing polystyrene backbone of polystyrene-g-polyamide 6 graft copolymer of bibliographical information, Journal of Polymer Science:Part A:Polymer Chemistry, Vol.46, 4766-4776 (2008)), to utilize vinylbenzene and 3-sec.-propyl-dimethylbenzyl based isocyanate (TMI) in-situ polymerization to obtain copolymerization product PS-co-TMI, then with hexanolactam, catalyzer is mechanical blending together, gained graft copolymer is for being total to continuous structure.Separately there is bibliographical information (Preparation of PS-g-PA6 copolymers by anionic polymerization of ε-caprolactam using PS precursors with N-carbamated caprolactam pendants as macroactivators, Journal of Applied Polymer Science, Vol.108, 3177-3184 (2008)), vinylbenzene carries out radical copolymerization with the allyl group N-amino caproate that contains hexanolactam functional group, copolymerization product is as macromole evocating agent, cause hexanolactam anionoid polymerization, the graft copolymer pattern that this method obtains does not have different from general graftomer.
Summary of the invention
The object of this invention is to provide a kind of preparation method of polystyrene-g-nylon monomer-cast nylon 6 graft copolymers of nanoparticle structure, the method adopts home position polymerization reaction, first utilize a certain amount of vinylbenzene and isocyanic ester copolymerization to obtain free-radical polymerized thing as macromole activator, then original position causes hexanolactam anionic ring-opening polymerization, obtains the graft copolymer of nanoparticle structure.Polystyrene-g-nylon monomer-cast nylon 6 graft copolymers that the inventive method is synthetic, have unique nanoparticle structure.
Technical scheme of the present invention is as follows:
The preparation method who the invention provides a kind of polystyrene-g-nylon monomer-cast nylon 6 graft copolymers of nanoparticle structure, the method comprises the following steps:
(1) by volume ratio, be 1: (20～30): the isocyanic ester/styrene monomer/toluene solution of (10～75), join and in three-necked bottle, mix 5min, then add the radical initiator that accounts for vinylbenzene and isocyanic ester total mass 0.1～5%, 80 ℃ of nitrogen protections, reaction 12～48h, reaction solution is poured in anhydrous methanol and precipitated, obtain white sticky solid, with tetrahydrofuran (THF), dissolve, use again methanol extraction, three times repeatedly, products therefrom is at vacuum drying oven 80-100 ℃ of dry 24h;
(2) product of the above-mentioned steps that is 10～40% by massfraction (1), joins in the hexanolactam that massfraction is 30～45% meltings, at 120～160 ℃ of underpressure distillation 15～20min;
(3) simultaneously, get the hexanolactam that massfraction is 30～45% meltings, add the catalyzer of whole polymkeric substance and monomer total mass 0.1～5%, 120～160 ℃ of underpressure distillation 15～20min;
(4) above-mentioned steps (2) and step (3) gained mixture are mixed, shake up, pour at once in the mould of 150～180 ℃ of preheatings polymerization 20～120min into; Obtain having the graft copolymer of nanoparticle structure.
Described isocyanic ester is the bifunctional isocyanic ester that contains unsaturated double-bond, is preferably 3-pseudoallyl-dimethylbenzyl based isocyanate (TMI).
Described radical initiator is selected from the one in azo-initiator, organic peroxy class initiator or oil soluble oxidation-reduction trigger system; Described azo-initiator is selected from Diisopropyl azodicarboxylate (AIBN) or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described organic peroxy class initiator is selected from the one in dibenzoyl peroxide, cyclohexanone peroxide or tertbutyl peroxide; Described oil soluble oxidation-reduction trigger system is selected from dibenzoyl peroxide or BPO-N, accelerine.
Described catalyzer is selected from one or more in lactan metallic compound, basic metal, alkalimetal hydride, alkali metal hydroxide, alkali metal alcoholates or alkaline carbonate; The preferably one in sodium caprolactam(ate), butyrolactam sodium, spicy inner formyl amine sodium, laurolactam sodium, sodium hydroxide or potassium hydroxide.
Compared with the existing technology, tool has the following advantages and beneficial effect in the present invention:
Polystyrene-g-polyamide 6 graft copolymer that the inventive method is synthetic, has unique nanoparticle structure.Not only can be used as expanding material, surface-modifying agent, and, because having high strength, high-wearing feature, high resistance chemical and good deformation resistance, resistance to deterioration and surface, polyamide 6 contains abundant-NH
2active group, utilizes its special nanoparticle structure, and its preparation is become to nano-powder, very big at aspect application potentials such as bioseparation, solid phase diagnosis and biocatalysis.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph (20000 times) of Fig. 1 PS-g-PA6 graft copolymer.
The scanning electron microscope (SEM) photograph (50000 times) of Fig. 2 PS-g-PA6 graft copolymer.
embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
(1) by 2mLTMI, 60mL styrene monomer, 120mL toluene solution joins in three-necked bottle and mixes 5min, adds 0.5g initiator A IBN, 80 ℃ of nitrogen protections, reaction 24h, pours above-mentioned reaction solution in anhydrous methanol into and precipitates, and obtains white sticky solid.With tetrahydrofuran (THF), dissolve, then use methanol extraction, three times repeatedly.Gained final product P (St-co-TMI) is at vacuum drying oven 80-100 ℃ of dry 24h.
(2) by above-mentioned 20g product (1), join in the hexanolactam of 40g melting.At 120～160 ℃ of underpressure distillation 15～20min.
(3) separately get the hexanolactam of 40g melting, add 0.5g sodium hydroxide, 120～160 ℃ of underpressure distillation 15～20min.
(4) above-mentioned steps (2) and (3) two kinds of hexanolactam liquid through underpressure distillation of step are mixed, shake up, pour at once in the mould of 160 ℃ of preheatings polymerization 1h into.So, obtain having the PS-g-PA6 graft copolymer of nanoparticle structure.
The pattern of prepared graft copolymer is shown in accompanying drawing 1 and Fig. 2.
Embodiment 2
(1) by 2mLTMI, 65mL styrene monomer, 150mL toluene solution joins and in three-necked bottle, mixes 5min; add 1g initiator dibenzoyl peroxide, 80 ℃ of nitrogen protections, reaction 28h; above-mentioned reaction solution is poured in anhydrous methanol and precipitated, obtain white sticky solid.With tetrahydrofuran (THF), dissolve, then use methanol extraction, three times repeatedly.Gained final product is at vacuum drying oven 80-100 ℃ of dry 24h.
(2) by above-mentioned 10g product (1), join in the hexanolactam of 45g melting.At 120～160 ℃ of underpressure distillation 15～20min.
(3) separately get the hexanolactam of 45g melting, add 0.5g sodium caprolactam(ate), 120～160 ℃ of underpressure distillation 15～20min.
(4) above-mentioned steps (2) and (3) two kinds of hexanolactam liquid through underpressure distillation of step are mixed, shake up, pour at once in the mould of 160 ℃ of preheatings polyase 13 0min into.So, obtain having the PS-g-PA6 graft copolymer of nanoparticle structure.
Embodiment 3
(1) by 2mL TMI, 40mL styrene monomer, 140mL toluene solution joins and in three-necked bottle, mixes 5min; add 0.5g initiator B PO-N, accelerine, 80 ℃ of nitrogen protections; reaction 24h, pours above-mentioned reaction solution in anhydrous methanol into and precipitates, and obtains white sticky solid.With tetrahydrofuran (THF), dissolve, then use methanol extraction, three times repeatedly.Gained final product is at vacuum drying oven 80-100 ℃ of dry 24h.
(2) by above-mentioned 30g product (1), join in the hexanolactam of 35g melting.At 120～160 ℃ of underpressure distillation 15～20min.
(3) separately get the hexanolactam of 35g melting, add 1g sodium caprolactam(ate), 120～160 ℃ of underpressure distillation 15～20min.
(4) above-mentioned steps (2) and (3) two kinds of hexanolactam liquid through underpressure distillation of step are mixed, shake up, pour at once in the mould of 170 ℃ of preheatings polymerization 1h into.So, obtain having the PS-g-PA6 graft copolymer of nanoparticle structure.
Embodiment 4
(1) by 2mLTMI, 70mL styrene monomer, 150mL toluene solution joins and in three-necked bottle, mixes 5min; add 2.5g initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), 80 ℃ of nitrogen protections, reaction 24h; above-mentioned reaction solution is poured in anhydrous methanol and precipitated, obtain white sticky solid.With tetrahydrofuran (THF), dissolve, then use methanol extraction, three times repeatedly.Gained final product is at vacuum drying oven 80-100 ℃ of dry 24h.
(2) by above-mentioned 40g product (1), join in the hexanolactam of 30g melting.At 120～160 ℃ of underpressure distillation 15～20min.
(3) separately get the hexanolactam of 30g melting, add 1.5g spicy inner formyl amine sodium, 120～160 ℃ of underpressure distillation 15～20min.
(4) above-mentioned steps (2) and (3) two kinds of hexanolactam liquid through underpressure distillation of step are mixed, shake up, pour at once in the mould of 160 ℃ of preheatings polymerization 1h into.So, obtain having the PS-g-PA6 graft copolymer of nanoparticle structure.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (7)
1. a preparation method for polystyrene-g-nylon monomer-cast nylon 6 graft copolymers of nanoparticle structure, is characterized in that: the method comprises the following steps,
(1) by volume ratio, be 1:(20～30): the isocyanic ester/styrene monomer/toluene solution of (10～75), join and in three-necked bottle, mix 5min, then add the radical initiator that accounts for vinylbenzene and isocyanic ester total mass 0.1～5%, 80 ℃ of nitrogen protections, reaction 12～48h, reaction solution is poured in anhydrous methanol and precipitated, obtain white sticky solid, with tetrahydrofuran (THF), dissolve, then use methanol extraction, three times repeatedly, products therefrom is at vacuum drying oven 80-100 ℃ of dry 24h;
(2) product of the above-mentioned steps that is 10～40% by massfraction (1), joins in the hexanolactam that massfraction is 30～45% meltings, at 120～160 ℃ of underpressure distillation 15～20min;
(3) simultaneously, get the hexanolactam that massfraction is 30～45% meltings, add the catalyzer of whole polymkeric substance and monomer total mass 0.1～5%, 120～160 ℃ of underpressure distillation 15～20min;
(4) above-mentioned steps (2) and step (3) gained mixture are mixed, shake up, pour at once in the mould of 150～180 ℃ of preheatings polymerization 20～120min into; Obtain having the graft copolymer of nanoparticle structure;
Described isocyanic ester is the bifunctional isocyanic ester that contains unsaturated double-bond.
2. preparation method according to claim 1, is characterized in that: described isocyanic ester is 3-pseudoallyl-dimethylbenzyl based isocyanate.
3. preparation method according to claim 1, is characterized in that: described radical initiator is selected from azo-initiator, organic peroxy class initiator or BPO-N, the one in N xylidine.
4. preparation method according to claim 3, is characterized in that: described azo-initiator is selected from Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
5. preparation method according to claim 3, is characterized in that: described organic peroxy class initiator is selected from the one in dibenzoyl peroxide, cyclohexanone peroxide or tertbutyl peroxide.
6. preparation method according to claim 1, is characterized in that: described catalyzer is selected from one or more in lactan metallic compound, basic metal, alkalimetal hydride, alkali metal hydroxide, alkali metal alcoholates or alkaline carbonate.
7. preparation method according to claim 6, is characterized in that: described catalyzer is selected from the one in sodium caprolactam(ate), butyrolactam sodium, spicy inner formyl amine sodium, laurolactam sodium, sodium hydroxide or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010565545.9A CN102477156B (en) | 2010-11-30 | 2010-11-30 | Preparation method of polystyrene-gamma-casting nylon 6 graft copolymer with nanoparticle structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010565545.9A CN102477156B (en) | 2010-11-30 | 2010-11-30 | Preparation method of polystyrene-gamma-casting nylon 6 graft copolymer with nanoparticle structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102477156A CN102477156A (en) | 2012-05-30 |
| CN102477156B true CN102477156B (en) | 2014-04-16 |
Family
ID=46089944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010565545.9A Active CN102477156B (en) | 2010-11-30 | 2010-11-30 | Preparation method of polystyrene-gamma-casting nylon 6 graft copolymer with nanoparticle structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102477156B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629580B (en) * | 2016-11-08 | 2018-07-20 | 华南理工大学 | A kind of preparation method of graphite oxide/silicon/carbon dioxide nanotube various dimensions composite nano materials |
| CN108034232B (en) * | 2017-11-29 | 2020-12-04 | 华东理工大学 | PS/PA6 composite material and preparation method thereof |
| CN107936550A (en) * | 2017-11-29 | 2018-04-20 | 华东理工大学 | A kind of polystyrene/nylon 6 composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556139A (en) * | 2004-01-08 | 2004-12-22 | 东华大学 | Method of preparing polystyrenel polyamide-6 nano blend |
-
2010
- 2010-11-30 CN CN201010565545.9A patent/CN102477156B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556139A (en) * | 2004-01-08 | 2004-12-22 | 东华大学 | Method of preparing polystyrenel polyamide-6 nano blend |
Non-Patent Citations (4)
| Title |
|---|
| Preparation of PS-g-PA6 Copolymers by Anionic Polymerization of e-Caprolactam Using PS Precursors with N-Carbamated Caprolactam Pendants as Macroactivators;Yao-Chi Liu .etl;《Journal of Applied Polymer Science》;20080629;第108卷;第3177-3184页 * |
| PS-co-TMI与己内酰胺反应研究;李广赞;《高校化学工程学报》;20081215;第22卷(第6期);第966-971页 * |
| Yao-Chi Liu .etl.Preparation of PS-g-PA6 Copolymers by Anionic Polymerization of e-Caprolactam Using PS Precursors with N-Carbamated Caprolactam Pendants as Macroactivators.《Journal of Applied Polymer Science》.2008,第108卷 |
| 李广赞.PS-co-TMI与己内酰胺反应研究.《高校化学工程学报》.2008,第22卷(第6期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102477156A (en) | 2012-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8048967B2 (en) | Method for preparing nylon microspheres and nylon microspheres prepared thereby | |
| CN107428913B (en) | Improve the hardening resin composition containing polymer particles of impact resistance removing cementability | |
| CN102477156B (en) | Preparation method of polystyrene-gamma-casting nylon 6 graft copolymer with nanoparticle structure | |
| CN103865275B (en) | A kind of poly(lactic acid) and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance | |
| CN101945943A (en) | Thermoplastic polymer composition and molded article composed of the same | |
| CN105622932B (en) | Nano nylon microsphere and preparation method thereof | |
| CN102477220B (en) | Magnetic nylon microspheres with controllable particle size and preparation method thereof | |
| Goikoetxea et al. | Polymerization kinetics and microstructure of waterborne acrylic/alkyd nanocomposites synthesized by miniemulsion | |
| CN104692321B (en) | A kind of method that mode utilizing orthogonal impressing induction prepares ordered porous membrane | |
| Eagan | The Divergent Reactivity of Lactones Derived from Butadiene and Carbon Dioxide in Macromolecular Synthesis | |
| CN102587132B (en) | Modification method of aramid fiber in supercritical CO2 by surface grafting polymerization | |
| CN103665839B (en) | Polyamide microspheres and preparation method thereof | |
| CN109485795A (en) | A kind of copolymer compatilizer and its preparation method and application | |
| CN101768282B (en) | Method for preparing nylon random copolymer micro-sphere with controllable melting point and grain diameter | |
| CN105153354A (en) | Preparation method of highly-branched polymer | |
| Li et al. | Synthesis of High‐Molecular‐Weight Brush Polymers via RAFT Polymerization within the Micellar Nanoreactor of a PEG‐Based Macromonomer | |
| CN108250735B (en) | Nylon microsphere with porous surface and preparation method thereof | |
| CN102964548A (en) | Preparation method of polyethylene di-segmented copolymer and product thereof | |
| CN101003590A (en) | Hydrophilic macromonomer, and preparation method | |
| Kong et al. | Preparation of dendrimer-like copolymers based on polystyrene and poly (l-lactide) and formation of hollow microspheres | |
| RU2012126318A (en) | Dendritic polyurea for solubilization of hard-soluble active substances | |
| CN102167782A (en) | Method for grafting polymer in double bond position of natural rubber by adopting atom transfer radical polymerization (ATRP) | |
| Chang et al. | Solvated-electron initiated rapid polymerization at ambient-temperature: a case of monomer solubility | |
| CN102532527B (en) | Preparation method of polyamide grafted copolymer self-assembling micelle | |
| CN101824121B (en) | Formula of POE graft copolymer and method for preparing water-phase suspension of POE graft copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |