CN101225228A - Fiber glass, elastomer and inorganic nano-particle synergistic modified nylon and preparation thereof - Google Patents
Fiber glass, elastomer and inorganic nano-particle synergistic modified nylon and preparation thereof Download PDFInfo
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- CN101225228A CN101225228A CNA2008100329066A CN200810032906A CN101225228A CN 101225228 A CN101225228 A CN 101225228A CN A2008100329066 A CNA2008100329066 A CN A2008100329066A CN 200810032906 A CN200810032906 A CN 200810032906A CN 101225228 A CN101225228 A CN 101225228A
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- nylon
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- glass fibre
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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Abstract
The invention relates to a nylon modified by fiberglass, elastomer and inorganic nanometer fine particles cooperatively and a preparation of the nylon. The nylon is prepared by nylon 6, fiberglass, elastomer, inorganic nanometer fine particles modified by a silane coupling agent and prepared by melt blending. The preparation process comprises: (1) the surface of the inorganic nanometer fine particles are modified by the silane coupling agent; (2) the nylon and the fiberglass are melt and blended to extrusion pelletizing; (3) the grains produced by blending the nylon and the fiberglass, the elastomer and the inorganic nanometer fine particles modified by silane coupling agent are blended to prepare the modified nylon. The nylon modified by fiberglass, elastomer and inorganic nanometer fine particles cooperatively has the advantages that: the uniformity of the mixture with the fiberglass, the elastomer and the nylon is improved effectively, the dispersion and the stability of the multicomponent complex system are enhanced, thus, the aims of increasing the strength and the toughness are realized at the same time; furthermore, the melt blending craft which is suitable for the practical application in industry is simple and practical.
Description
Technical field
The invention belongs to the high molecule nano composite material field, particularly relate to a kind of glass fibre, elastomerics and inorganic nano-particle synergistic modified nylon and preparation method thereof.
Background technology
Nylon has advantages such as mechanical strength height, fusing point height, wear-resisting, oil resistant, is widely used in fields such as automobile, electromechanics, electronics, weaving, household electrical appliances.Along with the continuous expansion of Application Areas, its toughness is had higher requirement.Common method for toughening is to add toughner such as PP (polypropylene), PE (polyethylene) non-polar polymer of etc.ing, and this class non-polar polymer can effectively reduce the water-absorbent of nylon, thereby reaches toughness reinforcing purpose, but this often makes the intensity reduction amplitude of nylon bigger.Therefore to strengthen toughness reinforcing nylon simultaneously very important in exploitation.The intensity of glass fibre and Young's modulus are bigger 10～20 times than nylon 6, and glass fibre and nylon 6 combined strength bination height might replace metal to use.Chinese patent " a kind of preparation method of glass fibre reinforcement " (application number: 200310112780.0) disclose glass fiber reinforced nylon 6 and had the excellent mechanical strength and the achievement in research of forming process preferably, also found to adopt the nylon 6 of toughner POE modification can satisfy the toughness reguirements of motorcycle helmet simultaneously.
In recent years, the polymer-based carbon Organic has caused people's extensive concern.Compare with traditional polymkeric substance enhancing toughening modifying method, nano material can be improved the over-all properties of polymkeric substance more all sidedly, must make inorganic nano-particle good dispersion in polymkeric substance but will reach good modified effect.
The research of Reinforced Nylon or tenacity increased nylon has at present obtained certain achievement, but the research report that reaches the modification of nylon that strengthens toughening effect preferably simultaneously is less.
Summary of the invention
The purpose of this invention is to provide a kind of glass fibre, elastomerics and inorganic nano-particle synergistic modified nylon and preparation thereof, adopt glass fibre, elastomerics, come polynary synergistic modified nylon with silane coupler modified inorganic nano-particle, can realize simultaneously strengthening toughness reinforcing purpose, satisfy the needs that different field is used.
A kind of glass fibre of the present invention, elastomerics and inorganic nano-particle synergistic modified nylon, be to be that raw material prepares through melt blending by nylon 6, glass fibre, elastomerics with silane coupler modified inorganic nano-particle, the composition of its each raw material (mass fraction) is 45～60 parts of nylon 6,15～20 parts in glass fibre, 10～30 parts on elastomerics, with 2～20 parts of silane coupler modified inorganic nano-particles.
Described elastomerics is selected from one or more mixtures in the maleic anhydride graft product of ethylene-propylene rubber(EPR), terpolymer EP rubber, ethylene-alpha-olefin polymkeric substance, their (ethylene-propylene rubber(EPR), terpolymer EP rubber, ethylene-alpha-olefin polymkeric substance);
Described inorganic nano-particle is selected from nanometer CaCO
3, nanometer SiO
2, nanometer Al
2O
3In one or more mixtures;
Described silane coupling agent is selected from one or more mixtures in tetramethoxy-silicane, vinyltrimethoxy silane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-(methacryloxypropyl) propyl trimethoxy silicane.
The preparation method of glass fibre of the present invention, elastomerics and inorganic nano-particle synergistic modified nylon is the technology for preparing modification of nylon with two step melt-blending processes, and concrete steps are as follows:
(1) with silane coupling agent inorganic nano-particle is carried out surface modification, inorganic nano-particle and the silane coupling agent mol ratio according to 1: 1～3: 1 is added in the three-necked bottle, behind ultra-sonic dispersion 10min～30min, add the second alcohol and water, stirred in water bath 1～2h at 60～80 ℃, regulate pH value to 8.5～9.5 with ammoniacal liquor again, cooling, filter, after the washing, 100～120 ℃ of dryings, obtain with silane coupler modified inorganic nano-particle;
(2) the first step melt blending
With nylon and glass fibre melt blending extruding pelletization, 220～260 ℃ of blending temperatures, blend pressure are 0.1～1.0Mpa;
(3) second step melt blendings
With the first step gained particle, elastomerics with silane coupler modified inorganic nano-particle blend, 210～240 ℃ of blending temperatures, blend pressure are 0.1～1.0Mpa, and the blend time is 5～15min, makes modification of nylon.
Beneficial effect of the present invention:
(1) owing to adopts silane coupling agent that inorganic nano-particle is carried out surface modification, solved the problem that inorganic nano-particle is easily reunited preferably, improved the dispersing property of inorganic nano-particle in polymeric matrix, the hydrophilic radical of silane coupling agent links to each other with inorganic nano-particle simultaneously, lipophilic group and polymeric matrix are compatible, have improved the consistency of inorganic nano-particle and polymeric matrix effectively;
(2) adopt two step melt blending technologies, improved glass fibre, elastomerics and nylon blended homogeneity effectively, improved the dispersed and stable of polynary compound system, thereby can realize strengthening toughness reinforcing purpose simultaneously, melt blending technology is simple and easy to do, helps industrial practical application.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
1), with nanometer CaCO
3And N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan is according in 1: 1 the mol ratio adding three-necked bottle, behind ultra-sonic dispersion 10min, add the second alcohol and water, stirred in water bath 2h at 80 ℃, regulating the pH value with ammoniacal liquor again is 9.0, cooling, filter, after the washing, 120 ℃ of dryings, obtain with silane coupler modified nanometer CaCO
3
2), the composition of each raw material (mass fraction) is: 60 parts of nylon 6,20 parts in glass fibre, 15 parts of ethylene-propylene-diene monomer glue elastomers (EPDM), with the nanometer CaCO of N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan modification
35 parts;
3), the first step blend, with nylon and glass fibre melt blending extruding pelletization, 220～260 ℃ of blending temperatures, pressure are 0.1～1.0Mpa;
4), the second step blend, with the sample that makes in the step 3), elastomerics with the nanometer CaCO of N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan modification
3Melt blending, 210～240 ℃ of blending temperatures, pressure are 0.1～1.0Mpa, blend time 9min takes out sample at 240～250 ℃, 1.0～2.5Mpa lower sheeting, static pressurize 5～10min makes modification of nylon.
Embodiment 2
In the present embodiment, the composition of each raw material (mass fraction) is: 60 parts of nylon 6,20 parts in glass fibre, EPDM10 part, with silane coupler modified nanometer CaCO
310 parts, other is as embodiment 1.
Embodiment 3
In the present embodiment, the composition of each raw material (mass fraction) is: 60 parts of nylon 6,20 parts in glass fibre, 15 parts on grafting maleic anhydride with ethylene propylene terpolymer elastomerics (EPDM-g-MAH), with silane coupler modified nanometer CaCO
35 parts, other is as embodiment 1.
Embodiment 4
In the present embodiment, the composition of each raw material (mass fraction) is: 60 parts of nylon 6,20 parts in glass fibre, EPDM-g-MAH10 part, with silane coupler modified nanometer CaCO
310 parts, other is as embodiment 1.
Embodiment 5
In the present embodiment, the composition of each raw material (mass fraction) is: 60 parts of nylon 6,20 parts in glass fibre, EPDM10 part, EPDM-g-MAH5 part, with silane coupler modified nanometer CaCO
35 parts, other is as embodiment 1.
Embodiment 6
In the present embodiment, the composition of each raw material (mass fraction) is: 45 parts of nylon 6,15 parts in glass fibre, EPDM15 part, EPDM-g-MAH15 part, with silane coupler modified nanometer CaCO
310 parts, other is as embodiment 1.
Embodiment 7
In the present embodiment, the composition of each raw material (mass fraction) is: 45 parts of nylon 6,15 parts in glass fibre, EPDM15 part, EPDM-g-MAH10 part, with silane coupler modified nanometer CaCO
315 parts, other is as embodiment 1.
Claims (7)
1. a glass fibre, elastomerics and inorganic nano-particle synergistic modified nylon is characterized in that: this modification of nylon is to be that raw material prepares gained through melt blending by nylon 6, glass fibre, elastomerics with silane coupler modified inorganic nano-particle.
2. glass fibre according to claim 1, elastomerics and inorganic nano-particle synergistic modified nylon is characterized in that: each raw materials quality umber of described modification of nylon consists of 45～60 parts of nylon 6,15～20 parts in glass fibre, 10～30 parts on elastomerics, with 2～20 parts of silane coupler modified inorganic nano-particles.
3. glass fibre according to claim 1 and 2, elastomerics and inorganic nano-particle synergistic modified nylon is characterized in that: described elastomerics is selected from one or more mixtures in ethylene-propylene rubber(EPR), terpolymer EP rubber, ethylene-alpha-olefin polymkeric substance, their the maleic anhydride graft product.
4. glass fibre according to claim 1 and 2, elastomerics and inorganic nano-particle synergistic modified nylon is characterized in that: described inorganic nano-particle is selected from nanometer CaCO
3, nanometer SiO
2, nanometer Al
2O
3In one or more mixtures.
5. glass fibre according to claim 1 and 2, elastomerics and inorganic nano-particle synergistic modified nylon is characterized in that: described silane coupling agent is selected from one or more mixtures in tetramethoxy-silicane, vinyltrimethoxy silane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-(methacryloxypropyl) propyl trimethoxy silicane.
6. the preparation method of a glass fibre, elastomerics and inorganic nano-particle synergistic modified nylon comprises step:
(1) with silane coupling agent inorganic nano-particle is carried out surface modification, inorganic nano-particle and the silane coupling agent mol ratio according to 1: 1～3: 1 is added in the reaction flask, ultra-sonic dispersion, add the second alcohol and water, stirring in water bath, regulate the pH value with ammoniacal liquor again, after cooling, filtration, washing, the drying, obtain with silane coupler modified inorganic nano-particle;
(2) the first step melt blending
With nylon and glass fibre melt blending extruding pelletization, 220～260 ℃ of blending temperatures, blend pressure are 0.1～1.0Mpa;
(3) second step melt blendings
With the first step melt blending gained particle, elastomerics with silane coupler modified inorganic nano-particle blend, 210～240 ℃ of blending temperatures, blend pressure are 0.1～1.0Mpa, and the blend time is 5～15min, makes modification of nylon.
7. the preparation method of glass fibre according to claim 6, elastomerics and inorganic nano-particle synergistic modified nylon, it is characterized in that: the ultra-sonic dispersion 10min～30min in the described step (1), stirred in water bath 1～2h of 60～80 ℃, ammoniacal liquor is regulated pH value to 8.5～9.5,100～120 ℃ of dryings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100329066A CN101225228A (en) | 2008-01-22 | 2008-01-22 | Fiber glass, elastomer and inorganic nano-particle synergistic modified nylon and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100329066A CN101225228A (en) | 2008-01-22 | 2008-01-22 | Fiber glass, elastomer and inorganic nano-particle synergistic modified nylon and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101225228A true CN101225228A (en) | 2008-07-23 |
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|---|---|---|---|
| CNA2008100329066A Pending CN101225228A (en) | 2008-01-22 | 2008-01-22 | Fiber glass, elastomer and inorganic nano-particle synergistic modified nylon and preparation thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675869A (en) * | 2012-05-22 | 2012-09-19 | 苏州新区华士达工程塑胶有限公司 | Formula of high-elasticity PA6-GF10HB |
| CN102850784A (en) * | 2012-09-06 | 2013-01-02 | 江苏兆鋆新材料科技有限公司 | Nylon 6 modified material and preparation method thereof |
| CN102924994A (en) * | 2012-11-13 | 2013-02-13 | 汕头市东和机械有限公司 | Abrasion-resistant agents and preparation method thereof |
| CN103242649A (en) * | 2012-02-06 | 2013-08-14 | 金发科技股份有限公司 | Glass fiber reinforced nylon material used for extrusion molding, preparation method and application |
| CN101775208B (en) * | 2009-12-23 | 2013-12-18 | 中国电力科学研究院 | Composite material for preparing stringing pulley and preparation method thereof |
| CN104530693A (en) * | 2014-12-19 | 2015-04-22 | 广东奇德新材料股份有限公司 | Preparation method of high-performance nano PA6 nanocomposite |
| CN104530692A (en) * | 2014-12-19 | 2015-04-22 | 广东奇德新材料股份有限公司 | Preparation method of high-strength toughened nylon |
| CN108517113A (en) * | 2018-05-07 | 2018-09-11 | 安徽悦尔伟塑料机械有限公司 | High rigidity plastics machinery hand and preparation method thereof |
| CN108925213A (en) * | 2018-08-31 | 2018-12-04 | 杭州富阳佳畅机械有限公司 | A kind of hand-held weeder rotating head |
-
2008
- 2008-01-22 CN CNA2008100329066A patent/CN101225228A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775208B (en) * | 2009-12-23 | 2013-12-18 | 中国电力科学研究院 | Composite material for preparing stringing pulley and preparation method thereof |
| CN103242649A (en) * | 2012-02-06 | 2013-08-14 | 金发科技股份有限公司 | Glass fiber reinforced nylon material used for extrusion molding, preparation method and application |
| CN103242649B (en) * | 2012-02-06 | 2015-09-30 | 金发科技股份有限公司 | A kind of glass fiber reinforced nylon material for extrusion moulding and preparation method and application |
| CN102675869A (en) * | 2012-05-22 | 2012-09-19 | 苏州新区华士达工程塑胶有限公司 | Formula of high-elasticity PA6-GF10HB |
| CN102850784A (en) * | 2012-09-06 | 2013-01-02 | 江苏兆鋆新材料科技有限公司 | Nylon 6 modified material and preparation method thereof |
| CN102924994A (en) * | 2012-11-13 | 2013-02-13 | 汕头市东和机械有限公司 | Abrasion-resistant agents and preparation method thereof |
| CN104530693A (en) * | 2014-12-19 | 2015-04-22 | 广东奇德新材料股份有限公司 | Preparation method of high-performance nano PA6 nanocomposite |
| CN104530692A (en) * | 2014-12-19 | 2015-04-22 | 广东奇德新材料股份有限公司 | Preparation method of high-strength toughened nylon |
| CN108517113A (en) * | 2018-05-07 | 2018-09-11 | 安徽悦尔伟塑料机械有限公司 | High rigidity plastics machinery hand and preparation method thereof |
| CN108925213A (en) * | 2018-08-31 | 2018-12-04 | 杭州富阳佳畅机械有限公司 | A kind of hand-held weeder rotating head |
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Open date: 20080723 |