CN104177822A - Injection-molding-grade nylon 6 composite material and application thereof - Google Patents
Injection-molding-grade nylon 6 composite material and application thereof Download PDFInfo
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- CN104177822A CN104177822A CN201410351078.8A CN201410351078A CN104177822A CN 104177822 A CN104177822 A CN 104177822A CN 201410351078 A CN201410351078 A CN 201410351078A CN 104177822 A CN104177822 A CN 104177822A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
- B29C69/02—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore of moulding techniques only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention provides an injection-molding-grade nylon 6 composite material which comprises the following components in parts by weight: 65-90 parts of nylon 6 resin, 1-20 parts of first maleic anhydride graft copolymer, 0.1-10 parts of second maleic anhydride graft copolymer and 0.01-5 parts of nucleating agent. The injection-molding-grade nylon 6 composite material fills the blank in the injection-molding-grade nylon for special-function pieces, has favorable bonding property with zinc-base alloy materials, and can implement quick stripping in the injection molding process; and the prepared part has stable size, keeps stable in the alternating temperature experiment of 90 DEG C (2 hours) to 30 DEG C (2 hours), and widens the application range of the nylon 6.
Description
Technical field
The present invention relates to a kind of nylon (polymeric amide) material, relate in particular to a kind of injection-level nylon 6 matrix material and application thereof.
Background technology
In nylon series, nylon 6 and nylon 66 are most important kinds, are mostly former raw slicers (being basic material) after polymerization granulation, are also crystalline material, can be used for blown film, extrude, coating and injection moulding etc.But above material is if do not improved, and during injection moulding, the crystallization velocity of product is slow, by cooling and demolding (and easy sticking to mould), not only production efficiency is low, and product contraction is large, and buckling deformation is serious, cannot reach and be satisfied with quality, and production cost is high.Injection grade material after improvement can fast demoulding, production efficiency is high, the follow-up not warpage of preparation, dimensional stabilizing, product is without defective products, and abroad, all there are the production of injection grade material in BASF (BASF), DSM (DSM) and space portion (UBE), although domestic, there are a lot of nylon 6, nylon 66 polymerizations and modification factory, but can reach external same quality seldom, only respectively have one, and functional part conversion injection-level nylon is blank especially.
CN102924914A discloses a kind of injection-level nylon 6 material, by properties-correcting agent, nylon 6 is carried out to modification, thereby obtains the injection-level nylon of-40 ℃ of tolerances.
CN102924911A discloses a kind of injection-level nylon 6, comprises nylon 6, nucleator, thermo-stabilizer and toughner, can realize higher mechanical property.
CN102382455A discloses a kind of injection-level nylon 6, adds the components such as crosslinked anti-wear agent, fiber reinforced material, thermo-stabilizer, oxidation inhibitor in nylon 6, can reduce the wearing and tearing of nylon 6.
CN102618024A discloses a kind of Nylon Nanocomposite, comprises nylon resin, polymer carrier, inorganic nano-filler, toughner, can be prepared into injection grade and blowing level product; This material has higher barrier property to fuel oil, ethanol, oxygen, carbonic acid gas isopolarity and nonpolar volatile small molecule material, high low temperature over-all properties is superior, and prepared product can be applicable to the application scenario that fuel tank, lubricated oil can, oil fuel pipe, wrapping material etc. have higher requirements to barrier property.
In the part joint of braking automobile sensor, what adopt now is the outside Zn-base alloy tubular of making and the injection moulding plastic that is positioned at an inwall, plastic by mould in the compression molding of Zn-base alloy inwall, the two need to firmly bond, common nylon 6 is after injection moulding depanning, shrinkage of injection molded parts, departs from zinc base alloy.Because this nylon injection-molding part is translucent, therefore range estimation can be found the vestige that wire departs from.In addition, although part nylon 6 products wish to increase cohesive force, solve the problem of coming off, although can realize and zinc base alloy bonding, between nylon 6 material and mould, also bond, causing cannot the demoulding.
Therefore, at present injection-level nylon 6 plastic or the product of a lot of field, especially function special purpose parts depend on from external import product, the special-purpose injection-level nylon 6 material of Development of Domestic injection grade, especially function, expand nylon 6 Application Areass, the competitive power that strengthens domestic injection-level nylon 6 has been the task of top priority.
Summary of the invention
For the existing the problems referred to above of current injection-level nylon 6, the invention provides a kind of injection-level nylon 6 matrix material, there is the performance with Zn-base alloy bonds well, and in injection moulding, can realize fast demoulding, product dimensional stabilizing.
First aspect of the present invention is to provide a kind of injection-level nylon 6 matrix material, and component comprises:
Wherein, described nylon 6 is preferably that to have viscosity be 2-3.0dL/g, more preferably 2-2.8dL/g, more preferably 2.2-2.8dL/g, more preferably 2.4-2.6dL/g.
Wherein, described the first maleic anhydride graft copolymer is preferably any one or a few of maleic anhydride grafted polyethylene alcohol copolymer, maleic anhydride inoculated polypropylene acid copolymer, maleic anhydride graft polymethyl acid copolymer.
Wherein, described the second maleic anhydride graft copolymer is preferably maleic anhydride stem grafting polyolefin multipolymer.Described polyolefine can olefin copolymer or homopolymer.
Wherein, described polyvinyl alcohol can be polyvinyl alcohol homopolymer, vinyl alcohol and ethylene monomer copolymer, described polyacrylic acid can be acrylate homopolymer, vinylformic acid and ethylene monomer copolymer, and described polymethyl acrylic acid can be methacrylic acid homo thing, methacrylic acid and ethylene monomer copolymer.
Wherein, described vinyl monomer is preferably alkene.
In foregoing of the present invention, described alkene is preferably alhpa olefin, and the alkene of C2-C10 more preferably, as ethene, propylene, vinylbenzene, octene etc.
Preferably, described polyvinyl alcohol is preferably ethylene/vinyl alcohol copolymer (EVA).
Preferably, described polyacrylic acid is preferably ethylene/acrylic acid copolymer (EAA).
Preferably, described polyolefine is preferably ethylene/octene (POE).
In a preferred embodiment of the present invention, component comprises:
Nylon 6 65-90 weight parts, more preferably 70-85 weight part, more preferably 75-85 weight part;
(EAA/EVA)-g-MAH graft copolymer 1-20 weight part, more preferably 5-10 weight part;
POE-g-MAH graft copolymer 0.1-2 weight part, more preferably 0.2-1.5 weight part;
Nucleator 0.01-5 weight part.
Described (EAA/EVA)-g-MAH graft copolymer is prepared by the following method: ethylene/vinyl alcohol copolymer mixes with ethylene/acrylic acid copolymer afterwards and maleic anhydride carries out graft reaction.
Wherein, during ethylene/vinyl alcohol copolymer mixes with ethylene/acrylic acid copolymer, EAA and EVA part by weight are preferably (3-7): (3-7), and more preferably (4-6): (4-6).
Wherein, described nucleator is preferably heterogeneous nucleation agent, and is preferably metal organic sulfonate.
Wherein, described metal organic sulfonate can be alkylsulfonate, arylsulphonate or alkylaryl sulphonate, alkylaryl sulfonate, and more preferably arylsulphonate, as serial in nucleator SANWELL HK, as SANWELL HK145.
Described metal-salt can be any one or a few in IA, IIA, 1B-VIIB, group VIII metal in the periodic table of elements, more preferably any one or a few in sodium salt, calcium salt, sylvite, magnesium salts, molysite, mantoquita.
Described alkyl is preferably C1-C12 alkyl, more preferably C1-C10 alkyl, more preferably C1-C8 alkyl, more preferably C1-C6 alkyl, more preferably methyl, ethyl, propyl group.
Described aryl is preferably C6-C20 aryl, and C6-C12 aryl more preferably, as phenyl, naphthyl.
In a kind of preferred embodiment in the present invention aspect first, component can also comprise:
Inorganic spherical powder 0.01-5 weight part.
Wherein, described inorganic spherical powder diameter is preferably 0.1-5 μ m, more preferably 0.5-4 μ m, more preferably 1-3.5 μ m, more preferably 1.5-3 μ m, more preferably 2-25 μ m.
Described inorganic spherical powder can be any one or a few in SILICA FUME, talcum powder, calcium carbonate, kaolin, mica, more preferably SILICA FUME.
More preferably, described SILICA FUME is carried out surface treatment through silane coupling agent.
In a kind of preferred embodiment in the present invention aspect first, component can also comprise any one or a few in following component:
Lubrication dispersing agent 0.01-5 weight part;
Softening agent 1-15 weight part;
Ultra-fine filling material 0.01-5 weight part.
Described ultra-fine filling material particle diameter is preferably 10000-50000 order, 20000-50000 order more preferably, as 30000 orders or above, 40000 orders or more than.
Described ultra-fine filling material is preferably mineral filler, as barium sulfate, calcium carbonate, talcum powder, polynite, silicon-dioxide, diatomite, wollastonite, calcium sulfate etc.
Wherein, described lubrication dispersing agent is preferably any one or a few in stearic acid, stearate, stearylamide, stearate.Described salt is preferably any one or a few in sodium salt, calcium salt, magnesium salts, zinc salt, and described ester can be C1-C6 alkyl ester, as any one or a few in methyl esters, ethyl ester.
Described lubrication dispersing agent most preferably is any one or a few in calcium stearate, stearylamide.
Wherein, in the above-mentioned component of the present invention, can also comprise extra auxiliary agent, described extra auxiliary agent, can be any one or a few in fire retardant, oxidation inhibitor, compatilizer, flow agent, photostabilizer, pigment, static inhibitor.Preferably, the part by weight of described extra auxiliary agent in described flame-retardant reinforced nylon material is no more than 5wt%.
Second aspect of the present invention is to provide a kind of method of preparing nylon layer on zinc base alloy surface, comprising: above-mentioned injection-level nylon 6 matrix material is extruded and is injected into zinc base alloy surface, compression molding.
In a preferred embodiment aspect second of the present invention, the dwell time is preferably at least 1s, more preferably 1-10s, more preferably 1-5s, more preferably 2-3s.
Wherein, described in extrude can be by single screw extrusion machine, twin screw extruder or more multiple screw extruder carry out, and be preferably twin screw extruder.
Wherein, described screw slenderness ratio (L/D) is preferably (30-60): 1, more preferably (35-55): 1, (40-50): 1.
In foregoing of the present invention, described POE-g-MAH graft copolymer is preferably elder generation and part nylon 6 is made masterbatch, then with partly or entirely mixing in other component.
Wherein, in described masterbatch, (EAA/EVA)-g-MAH graft copolymer part by weight is preferably 20-35%, more preferably 25-35%, more preferably 30-33%.
Injection-level nylon 6 matrix material provided by the present invention, can realize out-phase crystallization fast, thereby can fast demoulding, simultaneously, there is good cohesive force with zinc base alloy surface, and there is excellent cold-resistant thermotolerance and dimensional stability (in 90 ℃ to 30 ℃ alternating temperature experiments, keeping stable), in use can there is not the break-off with zinc base alloy surface, also can there is identical effect with other metals, alloy material, expand the Application Areas of nylon 6, filled up domestic blank.
Embodiment
Embodiment 1
Wherein, POE-g-MAH graft copolymer is first made the masterbatch of 30wt% with part nylon 6, then mix.
Said components is extruded by twin screw extruder after mixing, and is injected into ring-type zinc base alloy inwall, compression molding, wherein, dwell time 2-3s., there is not the phenomenon of locking mould in the demoulding.Complete moulding and only need 16.5s.
After cooling, resin layer and zinc base alloy do not depart from, and are heated to 90 ℃ (keeping 2h), are then cooled to 30 ℃ (keeping 2h), carry out 10 circulations, and the linear vestige departing from does not occur for resin layer and zinc base alloy.
Embodiment 2
Wherein, POE-g-MAH graft copolymer is first made the masterbatch of 30wt% with part nylon 6, then mix.
Said components is extruded by twin screw extruder after mixing, and is injected into ring-type zinc base alloy inwall, compression molding, wherein, dwell time 2-3s., there is not the phenomenon of locking mould in the demoulding.
After cooling, resin layer and zinc base alloy do not depart from, and are heated to 90 ℃ (keeping 2h), are then cooled to 30 ℃ (keeping 2h), carry out 10 circulations, and the linear vestige departing from does not occur for resin layer and zinc base alloy.
Embodiment 3
Wherein, POE-g-MAH graft copolymer is first made the masterbatch of 30wt% with part nylon 6, then mix.
After cooling, resin layer and zinc base alloy do not depart from, and are heated to 90 ℃ (keeping 2h), are then cooled to 30 ℃ (keeping 2h), carry out 10 circulations, and the linear vestige departing from does not occur for resin layer and zinc base alloy.
Embodiment 4
Wherein, POE-g-MAH graft copolymer is first made the masterbatch of 30wt% with part nylon 6, then mix.
After cooling, resin layer and zinc base alloy do not depart from, and are heated to 90 ℃ (keeping 2h), are then cooled to 30 ℃ (keeping 2h), carry out 10 circulations, and the linear vestige departing from does not occur for resin layer and zinc base alloy.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (10)
1. an injection-level nylon 6 matrix material, is characterized in that, component comprises:
Wherein, described the first maleic anhydride graft copolymer is any one or a few in maleic anhydride grafted polyethylene alcohol copolymer, maleic anhydride inoculated polypropylene acid copolymer, maleic anhydride graft polymethyl acid copolymer; Described the second maleic anhydride graft copolymer is maleic anhydride stem grafting polyolefin multipolymer.
2. injection-level nylon 6 matrix material according to claim 1, is characterized in that, described nylon 6 viscosity are 2-3.0dL/g.
3. injection-level nylon 6 matrix material according to claim 1, is characterized in that, component comprises:
4. injection-level nylon 6 matrix material according to claim 1, it is characterized in that, described (EAA/EVA)-g-MAH graft copolymer is prepared by the following method: ethylene/vinyl alcohol copolymer mixes with ethylene/acrylic acid copolymer afterwards and maleic anhydride carries out graft reaction.
5. injection-level nylon 6 matrix material according to claim 1, is characterized in that, described nucleator is metal organic sulfonate.
6. injection-level nylon 6 matrix material according to claim 5, is characterized in that, described nucleator is selected from SANWELL HK series.
7. injection-level nylon 6 matrix material according to claim 1, is characterized in that, component also comprises:
Inorganic spherical powder 0.01-5 weight part;
Described inorganic spherical powder diameter is 0.1-5 μ m.
8. injection-level nylon 6 matrix material according to claim 7, is characterized in that, described inorganic spherical powder is SILICA FUME.
9. injection-level nylon 6 matrix material according to claim 1, is characterized in that, component also comprises any one or a few in following component:
Lubrication dispersing agent 0.01-5 weight part;
Softening agent 1-15 weight part;
Ultra-fine filling material 0.01-5 weight part;
Wherein, described ultra-fine filling material particle diameter is preferably 10000-50000 order.
10. at zinc alloy surface, prepare a method for nylon layer, it is characterized in that, comprising: injection-level nylon 6 matrix material described in claim 1 is extruded and is injected into zinc alloy surface, compression molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410351078.8A CN104177822A (en) | 2014-07-22 | 2014-07-22 | Injection-molding-grade nylon 6 composite material and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410351078.8A CN104177822A (en) | 2014-07-22 | 2014-07-22 | Injection-molding-grade nylon 6 composite material and application thereof |
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| CN104177822A true CN104177822A (en) | 2014-12-03 |
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| CN201410351078.8A Pending CN104177822A (en) | 2014-07-22 | 2014-07-22 | Injection-molding-grade nylon 6 composite material and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974307A (en) * | 2015-06-01 | 2015-10-14 | 浙江工业大学 | inorganic silicon-maleic anhydride grafted polyvinyl alcohol material and preparation method and application thereof |
| CN106633841A (en) * | 2017-01-05 | 2017-05-10 | 江苏弘盛新材料股份有限公司 | Special material for injection molding of nylon 6 and preparation method thereof |
| CN106718252A (en) * | 2017-02-28 | 2017-05-31 | 遵义医学院 | A kind of preparation method of combined type dried flower flowerpot and its basin body structure |
| CN109535698A (en) * | 2018-12-05 | 2019-03-29 | 上海继尔新材料科技有限公司 | A kind of white silicon powder modified polyamide material and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389515A (en) * | 2002-07-18 | 2003-01-08 | 上海交通大学 | Prepn. of composite nylon material capable of being blow moulded |
| CN103772966A (en) * | 2013-12-24 | 2014-05-07 | 贵州蓝图新材料有限公司 | Micro-silica fume reinforced nylon material and preparation method thereof |
-
2014
- 2014-07-22 CN CN201410351078.8A patent/CN104177822A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389515A (en) * | 2002-07-18 | 2003-01-08 | 上海交通大学 | Prepn. of composite nylon material capable of being blow moulded |
| CN103772966A (en) * | 2013-12-24 | 2014-05-07 | 贵州蓝图新材料有限公司 | Micro-silica fume reinforced nylon material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974307A (en) * | 2015-06-01 | 2015-10-14 | 浙江工业大学 | inorganic silicon-maleic anhydride grafted polyvinyl alcohol material and preparation method and application thereof |
| CN104974307B (en) * | 2015-06-01 | 2017-12-05 | 浙江工业大学 | inorganic silicon-maleic anhydride grafted polyvinyl alcohol material and preparation method and application thereof |
| CN106633841A (en) * | 2017-01-05 | 2017-05-10 | 江苏弘盛新材料股份有限公司 | Special material for injection molding of nylon 6 and preparation method thereof |
| CN106718252A (en) * | 2017-02-28 | 2017-05-31 | 遵义医学院 | A kind of preparation method of combined type dried flower flowerpot and its basin body structure |
| CN106718252B (en) * | 2017-02-28 | 2022-10-21 | 遵义医学院 | Combined dry flower pot and preparation method of pot body structure thereof |
| CN109535698A (en) * | 2018-12-05 | 2019-03-29 | 上海继尔新材料科技有限公司 | A kind of white silicon powder modified polyamide material and its preparation method and application |
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Application publication date: 20141203 |