CN100500764C - Preparation method of polyamide/nano montmorillonite masterbatch - Google Patents
Preparation method of polyamide/nano montmorillonite masterbatch Download PDFInfo
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- CN100500764C CN100500764C CNB2007100697896A CN200710069789A CN100500764C CN 100500764 C CN100500764 C CN 100500764C CN B2007100697896 A CNB2007100697896 A CN B2007100697896A CN 200710069789 A CN200710069789 A CN 200710069789A CN 100500764 C CN100500764 C CN 100500764C
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Abstract
The present invention is preparation process of polyamide/nanometer montmorillonite base material. The polyamide/nanometer montmorillonite base material comprising montmorillonite 1-30 wt% and polyamide 70-99 wt% is prepared with deionized water in 9-15 times the weight of montmorillonite as the intercalating agent, and through mixing purified montmorillonite with deionized water to form slurry, adding molten polyamide, blending at 210-300 for 10-60 min, and pelletizing. The polyamide/nanometer montmorillonite base material has simple preparation process, low production cost and high stripping performance.
Description
(1) technical field
The invention belongs to technical field of composite materials, be specifically related to a kind of preparation method of polyamide/nano montmorillonite masterbatch.
(2) background technology
Polynite fully peeling off in polymer is the gordian technique that realizes high performance composite.The preparation method of polymer-montmorillonoid matrix material is generally following two kinds at present: a kind of is in-situ inserted polymerization process, so-called in-situ inserted method be meant the polymer precursor small molecules at first intercalation between the cheating engaging layer of the intercalation processing that organises, in the polymerization of cheating engaging layer chien shih small molecules, a large amount of heats of emitting when utilizing polymerization, make polynite expand and peel off, thereby obtain matrix material.
Another kind is the fusion intercalation method, so-called melt intercalated method is meant molten polymer mixing with the polynite of passing through the intercalation processing that organises under the high temperature high shear, macromolecular chain inserts between cheating engaging layer, but this method generally can only obtain the intercal type matrix material, the montmorillonite composite material that difficult acquisition is peeled off fully.
In-situ inserted polymerization technique can obtain the exfoliated montmorillonite composite material of high-performance, but organic intercalation agent and polynite are had higher technical requirements, and the industrialization investment of in-situ inserted polymerization is big, and the cycle is long, is difficult for applying.Melt intercalated method can carry out in general plastic milling apparatus, easy to process, yet need early stage earlier to the polynite intercalation processing that organises, and thermally-stabilised poor, the allochroic defective of the intercalator that organises has also obviously influenced matrix material, the montmorillonite composite material that is not easy to be peeled off has fully restricted the application of this method.
(3) summary of the invention
The object of the invention provide a kind of process simple, production cost is low, the preparation method of the polyamide/nano montmorillonite masterbatch of applied range.For finishing the object of the invention, the present invention adopts the auxilliary legal system of water to be equipped with polyamide/nano montmorillonite masterbatch.
Described polyamide/nano montmorillonite masterbatch composed as follows:
Polynite: 1%～30%
Polymeric amide: 70%～99%
Preparation method of the present invention is to be intercalator with deionized water, the mass ratio of described deionized water and polynite is 9～15:1, and preparation according to the following steps: will polynite and deionized water mix earlier, fully decentralized system gets polynite mud, progressively mud is joined in the complete fused polymeric amide of prescription amount, under 210～300 ℃ of temperature mixing 10～60 minutes, select long mixing time when polynite content is high for use, promptly obtain described polyamide/nano montmorillonite masterbatch through extruding pelletization again.
Polymeric amide of the present invention preferably temperature be in 210～300 ℃ the Banbury mixer banburying to fusion fully.
Polynite in the montmorillonite masterbatch of the present invention, polymeric amide quality group become: polynite 1～30%, polymeric amide 70%～99%, preferred polynite 20～30%, polymeric amide 70%～80%.
Polynite of the present invention is that natural montmorillonite makes through purification process, described treatment process is: natural montmorillonite is mixed with deionized water with 1:20～40 ratios stirred 1-2 hour, after leaving standstill 24 hours, choose the clear liquid on upper strata, will obtain the polynite of purifying after the clear liquid drying.Polymeric amide of the present invention is polyamide 6 or polyamide 66.
The preparation method of polyamide/nano montmorillonite masterbatch of the present invention, its mixing temperature is preferably 220～280 ℃; The mixing time is 40～60 minutes.
The auxilliary method of water of the present invention is to utilize deionized water to replace organic intercalation agent, polynite is a kind of water-based thickener, absorb water in a large number by its interlayer, effective enlargement layer spacing, water is again the natural softening agent of polymeric amide simultaneously, under the effect of high temperature, high shear force, heat and pressure that vaporization by the polynite middle water produces, the montmorillonite layer structure is peeled off, by shearing action it is distributed in the polyamide substrate simultaneously, the polyamide/nano montmorillonite masterbatch of being peeled off fully.
Polyamide/montmorillonite masterbatch of the present invention, polynite content can be up to more than 30%, by XRD figure spectrum test: polynite content is 10% when following, can prepare the complete exfoliated polyamide/nano montmorillonite masterbatch of high-performance, polynite content can obtain the exfoliated polyamide/nano montmorillonite masterbatch of part at 20%～30% o'clock.
The polyamide/nano montmorillonite masterbatch of the present invention's preparation can be applied to extrude high-isolation film and injection premium quality product etc. direct the mixing with polyamide resin, polyester in general plastic working enterprise, add the matrix material of masterbatch of the present invention through the XRD test, 001 diffraction peak does not appear in 2 θ angles in 1-15 °, illustrate that polynite peels off in macromolecular material fully, the thermotolerance of material, tensile strength and flexural strength are significantly improved.
In sum, beneficial effect of the present invention is embodied in technology in the past and compares, the method of polyamide/nano montmorillonite masterbatch provided by the invention is simple, production cost is low promotes easily, and can obtain the exfoliated montmorillonite composite material of high-performance with the inventive method.
(4) description of drawings:
Fig. 1 is the XRD figure of polyamide/nano montmorillonite masterbatch
A: the montmorillonoid-containing amount is 20% masterbatch;
B: the montmorillonoid-containing amount is 30% masterbatch;
C: the montmorillonoid-containing amount is 10% masterbatch;
Fig. 2 content nano imvite is the TEM photo of polyamide 6/nano montmorillonite masterbatch of 10%
Fig. 3 is the XRD figure of polyamide/nano montmorillonite masterbatch material after diluting
A: contain the nano imvite amount and be 20% masterbatch XRD figure through 1:10 dilution back material
B: contain the nano imvite amount and be 30% masterbatch XRD figure through 1:10 dilution back material
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
10 parts of purifying polynites, 90 parts of deionized waters, dispersed with stirring obtains polynite mud, 90 parts of polyamide 6s are joined in 220 ℃ the Banbury mixer, after treating the complete fusion of polyamide 6, progressively add polynite mud, added the back and continue 220 ℃ of mixer mixings 10 minutes in 20 minutes, obtaining the polyamide/montmorillonite master batch through extruding pelletization again is polyamide/nano montmorillonite masterbatch.The XRD figure of masterbatch is seen Fig. 1, and the TEM photo is seen Fig. 2.
20 parts of purifying polynites, 300 parts of deionized waters, dispersed with stirring obtains polynite mud, 80 parts of polyamide 6s are joined in 220 ℃ the Banbury mixer, after treating the complete fusion of polyamide 6, progressively add polynite mud, in 40 minutes, add the back and continue mixing 15 minutes at 220 ℃.Obtain the polyamide/montmorillonite master batch of polynite content 20% through extruding pelletization.The XRD of master batch sees Fig. 1.10 parts of master batches are joined in 90 parts of pure polyamide 6 resins, at 230 ℃ of extruding pelletizations, correspondingly obtain the polyamide/montmorillonite nano composite material, (001) diffraction peak of polynite all disappears in its XRD spectra, sees Fig. 3.
Embodiment 3:
15 parts of purifying polynites, 150 parts of deionized waters, dispersed with stirring obtains polynite mud, 85 parts of polyamide 66s are joined in 260 ℃ the Banbury mixer, after treating the complete fusion of polyamide 66, progressively add polynite mud, in 30 minutes, add the back continue 220 ℃ mixing 10 minutes, obtain the polyamide/montmorillonite master batch of polynite content 15% through extruding pelletization.The XRD figure of masterbatch is seen Fig. 1.
Embodiment 4:
30 parts of purifying polynites, 270 parts of deionized waters, dispersed with stirring obtains polynite mud, 70 parts of polyamide 6s are joined in 220 ℃ the Banbury mixer, after treating the complete fusion of polyamide 6, progressively add polynite mud, in 50 minutes, add the back continue 220 ℃ mixing 10 minutes, obtain the polyamide/montmorillonite master batch of polynite content 30% through extruding pelletization.The XRD figure of masterbatch is seen Fig. 1.10 parts of master batches are joined in 90 parts of pure polyamide 6 resins, at 230 ℃ of extruding pelletizations, correspondingly obtain the polyamide/montmorillonite nano composite material, (001) diffraction peak of polynite all disappears in its XRD spectra, sees Fig. 3.
Embodiment 5:
1 part of purifying polynite, 11 parts of deionized waters, dispersed with stirring obtains polynite mud, 99 parts of polyamide 66s are joined in 300 ℃ the Banbury mixer, after treating the complete fusion of polyamide 66, progressively add polynite mud, in 2 minutes, add the back continue 300 ℃ mixing 8 minutes, obtain the polyamide/montmorillonite composite material of polynite content 1% through extruding pelletization.
Embodiment 6:
5 parts of purifying polynites, 60 parts of deionized waters, dispersed with stirring obtains polynite mud, 95 parts of polyamide 6s are joined in 210 ℃ the Banbury mixer, after treating the complete fusion of polyamide 6, progressively add polynite mud, in 10 minutes, add the back continue 300 ℃ mixing 10 minutes, obtain the polyamide/montmorillonite composite material of polynite content 5% through extruding pelletization.
Embodiment 7:
10 parts of purifying polynites, 130 parts of deionized waters, dispersed with stirring obtains polynite mud, 90 parts of polyamide 6s are joined in 220 ℃ the Banbury mixer, after treating the complete fusion of polyamide 6, progressively add polynite mud, in 15 minutes, add the back continue 220 ℃ mixing 15 minutes, obtain the polyamide/montmorillonite composite material of polynite content 10% through extruding pelletization.
Embodiment 8:
25 parts of purifying polynites, 325 parts of deionized waters, dispersed with stirring obtains polynite mud, 75 parts of polyamide 6s are joined in 220 ℃ the Banbury mixer, after treating the complete fusion of polyamide 6, progressively add polynite mud, in 35 minutes, add the back continue 220 ℃ mixing 15 minutes, obtain the polyamide/montmorillonite master batch of polynite content 25% through extruding pelletization.
Claims (7)
1. the preparation method of a polyamide/nano montmorillonite masterbatch is characterized in that the composed as follows of described polyamide/nano montmorillonite masterbatch:
Polynite: 1%～30%,
Polymeric amide: 70%～99%,
Described preparation method is to be intercalator with deionized water, the mass ratio of described deionized water and polynite is 9～15:1, and preparation according to the following steps: will polynite and deionized water mix earlier, fully decentralized system gets polynite mud, mud is progressively joined in the complete fused polymeric amide of prescription amount, under 210～300 ℃ of temperature mixing 10～60 minutes, promptly obtain described polyamide/nano montmorillonite masterbatch through extruding pelletization again.
2. the preparation method of polyamide/nano montmorillonite masterbatch according to claim 1, it is characterized in that described polymeric amide temperature be in 210～300 ℃ the Banbury mixer banburying to fusion fully.
3. the preparation method of polyamide/nano montmorillonite masterbatch according to claim 1 is characterized in that polynite in the described polyamide/nano montmorillonite masterbatch, polymeric amide quality group become: polynite 20～30%, polymeric amide 70%～80%.
4. according to the preparation method of the described polyamide/nano montmorillonite masterbatch of one of claim 1～3, it is characterized in that described polynite is that natural montmorillonite makes through purification process, described treatment process is: natural montmorillonite and deionized water were stirred 1～2 hour with 1:20～40 mixed, after leaving standstill 24 hours, choose the clear liquid on upper strata, will obtain the purifying polynite after the clear liquid drying.
5. the preparation method of polyamide/nano montmorillonite masterbatch according to claim 1 is characterized in that described polymeric amide is polyamide 6 or polyamide 66.
6. the preparation method of polyamide/nano montmorillonite masterbatch according to claim 1 is characterized in that mixing temperature is 220～280 ℃.
7. the preparation method of polyamide/nano montmorillonite masterbatch according to claim 1 is characterized in that the described mixing time is 40～60 minutes.
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| CN110229501B (en) * | 2018-03-06 | 2021-02-05 | 中国科学院化学研究所 | Nylon elastomer nano composite material and preparation method thereof |
| CN110229423B (en) * | 2018-03-06 | 2021-03-23 | 中国科学院化学研究所 | Thermoplastic vulcanized rubber nano composite material and preparation method thereof |
| CN110229474B (en) * | 2018-03-06 | 2021-01-26 | 中国科学院化学研究所 | PBT (polybutylene terephthalate) nano composite material and preparation method thereof |
| CN110229490B (en) * | 2018-03-06 | 2021-02-02 | 中国科学院化学研究所 | PC (polycarbonate) nano composite material and preparation method thereof |
| CN111070568A (en) * | 2019-12-27 | 2020-04-28 | 苏州耐思特塑胶有限公司 | Water-assisted injection molding processing technology of plastic part |
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Assignee: Cangnan County Huifeng Plastic Co., Ltd. Assignor: Zhejiang University of Technology Contract record no.: 2010330001489 Denomination of invention: Preparation method of polyamide/nano montmorillonite masterbatch Granted publication date: 20090617 License type: Exclusive License Open date: 20071205 Record date: 20100728 |
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