CN1982373A - Production of peel montmorillonite/casting nylon nano-composite material - Google Patents
Production of peel montmorillonite/casting nylon nano-composite material Download PDFInfo
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- CN1982373A CN1982373A CN 200510111374 CN200510111374A CN1982373A CN 1982373 A CN1982373 A CN 1982373A CN 200510111374 CN200510111374 CN 200510111374 CN 200510111374 A CN200510111374 A CN 200510111374A CN 1982373 A CN1982373 A CN 1982373A
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Abstract
Production of peeled montmorillonite/cast nylon nanometer composite raw material is carried out by dispersing for montmorillonite in 10-200 time solution, agitating at 80degree for 2hrs, adding into caprolactam, dispersing for 0.5-6hrs, decompress distilling to remove water under 100degree, raising temperature to 140-180degree, supplying pump for 30mins, adding catalyst, activating agent and other auxiliaries into caprolactam proportionally, mixing, casting at 160-180degree, reacting for 10-20mins and cooling at 50degree in oven. It has better strength and modulus, higher molecular weight, crystallinity and heat-deformation temperature and lower shrinkage.
Description
Technical field
The present invention relates to a kind ofly be equipped with the novel method of peel montmorillonite/casting nylon nano-composite material, relate in particular to a kind of inorganic polynite and need not any organising and just can reach nano level dispersive novel method, new prescription by the anionic ring-opening polymerization legal system.
Background technology
Nano composite material is meant as the discrete state material size at least at the size of the one dimension direction matrix material less than 100nm.Because surface effects, volume effect, quantum size effect and the macroscopic quantum effect etc. of nanoparticle, the performances such as rigidity, intensity, toughness of polymeric matrix will be improved obviously.Because montmorillonite layer has very high intensity and hardness with respect to other material in polynite/nylon nano matrix material, make its nano composite material have high strength, high-modulus and high characteristics such as barrier property, therefore obtained extensive studies and application in recent decades.Japanese Unitika company just worked out a kind of nylon/layered silicate (inorganic clay) matrix material in 1976, and the patent No. is Japan, Patent No.JP-A-51-109998.Thereafter ε-Ji Neixianan polymeric product performance in the presence of unmodified polynite and organic montmorillonoid respectively, patent No. United States, Patent No.4739007 have further studied in Toyota company.Also have some to study organic modification montmonrillonite/nylon-6 matrix body melt processing in twin screw, United States for example, PatentNo.5747560.China's research has in this respect in recent years also obtained very big achievement, Chinese Academy of Sciences chemistry the QiZongNeng professor adopt monomer intercalation polycondensation technology to prepare the nylon/montmorillonoid nano composite material, the heat-drawn wire of its material is greatly improved.Chinese Academy of Sciences chemistry professor Wang Dexi also carried out the applied research of nylon 6/nanometer clay master batch.
Comprehensive present research contents mainly concentrates on organising and the dispersion extent of exfoliation in matrix etc. of polynite.Polynite mainly contains three kinds of forms in polymeric matrix: 1. incompatible phase, this situation is not worth, because this is not real nano composite material.2. intercalation configuration, this situation polymer molecular chain enters between montmorillonite layer, keeps tightr between cheating engaging layer, and just interlamellar spacing has certain increase.3. lift-off structure, this situation polynite is broken up into one lamella, is not piling up each other, reaches real nano level and disperses, and the performance of material will improve a lot like this.Therefore polynite/nylon nano the matrix material that obtains lift-off structure is the target that we pursue.
Nylon and MMT mechanical blending or in-situ polycondensation reaction are adopted in the preparation of above-mentioned nylon/MMT nano composite material usually.In order to reach lift-off structure, used polynite generally all is to handle through organising, and present result of study shows, this polynite meeting that organises obviously promotes the degraded of matrix.And with being that the polynite handled can obviously not promote the degraded of polynite but is difficult to reach lift-off structure.Therefore selecting for use suitable technology that polynite is reached in matrix and peel off is an of great value target.Because polynite/nylon nano matrix material has high strength and modulus, good barrier, advantages such as dimensional stability, higher heat-drawn wire, excellent flame, wear-resisting wiping, the oil resistant of anti-solvent the, uvioresistant preferably, has obtained valuable application in fields such as automobile (inside and outside car body and fuel tank), packing, electronics, aviations.Nylon monomer-cast nylon is compared common nylon simultaneously, and advantages such as its molecular weight is big, degree of crystallinity is high, the low rate of suction will further improve the performance of material.But for monomer moulding casting nylon is that the research of MC nylon/MMT nano composite material is less, its reason mainly is that MC nylon is taked anionic ring-opening polymerization, and used usually MMT is to organise through cationic exchange to handle in order to make hexanolactam can enter its lamella, these MMT that organise have tangible inhibition to negatively charged ion open loop system, have a strong impact on the molecular weight of MC nylon, thereby reduce the performance of nylon monomer-cast nylon.For then being difficult to evenly spread in the caprolactam monomer without the MMT that handles that organises, reason is that the specific surface area of polynite is very big, need overcome very big surface energy could be with the sheet layer open, therefore caprolactam monomer is difficult to infiltrate between the untreated MMT lamella, cause the MMT dispersiveness very poor, can not bring into play the advantage of itself.Therefore improving MMT is vital in dispersion, the extent of exfoliation of matrix.
Summary of the invention
Purpose of the present invention is exactly in order to overcome that there is defective in above-mentioned prior art and preparation method that a kind of peel montmorillonite/casting nylon nano-composite material is provided.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of peel montmorillonite/casting nylon nano-composite material, it is characterized in that, this method is to adopt the anionic ring-opening polymerization legal system to be equipped with peel montmorillonite/casting nylon nano-composite material, this method comprises following processing step: the dispersion of polynite, at first polynite is dispersed in 10～200 times the aqueous solution, 80 ℃ of stirred in water bath 2 hours, adding hexanolactam disperseed 0.5～6 hour, under 100 ℃, remove most of water then with underpressure distillation, heat up 140～180 ℃ again, vacuumized 30 minutes, with catalyzer, activator or other auxiliary agents add in the hexanolactam according to a certain ratio, mix, cast, 160～180 ℃ of mould temperature were reacted 10～20 minutes, cooled off in 50 ℃ of baking ovens.
Described polynite content is 0.05～10% of nylon nano matrix material weight.
The catalyst levels of described adding hexanolactam is 0.01～5% of a caprolactam monomer weight; The consumption of activator is 0.02～10% of a caprolactam monomer weight.
The vacuum tightness of described evacuation process is 99331～99997Pa.
Described catalyzer is selected from sodium caprolactam(ate), NaH, NaOH, KOH, LiH, Na
2CO
3In one or more.
Described activator is selected from 2,4 toluene diisocyanate (TDI), N-one or more in acyl caprolactam, N-benzoyl caprolactam, the trialkyl isonitrile uric acid fat.
Described other auxiliary agents are selected from one or more in commercially available oxidation inhibitor, fire retardant, the photostabilizer, and consumption is 0～2% of a caprolactam monomer weight.
The testing standard of the mechanical property of the nylon composite materials that the employing aforesaid method obtains is as follows:
| Performance index | Standard |
| Tensile strength, the MPa flexural strength, MPa socle girder notched Izod impact strength, the J/M heat-drawn wire/℃ | ASTM D638 ASTM D790 ASTM D256 ASTM D648 |
The peel montmorillonite/casting nylon nano-composite material that the inventive method obtains is compared with the polynite/nylon nano matrix material of standard machinery blend or the preparation of acid catalysis in-situ polymerization, not only have higher intensity, modulus and barrier, and have higher molecular weight, higher degree of crystallinity, higher heat-drawn wire and littler advantages such as shrinking percentage.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
In 500g distilled water, put into the 5g polynite,, left standstill 10 minutes, remove the impurity of bottom settlings 80 ℃ of stirred in water bath 2 hours.Add the 1000g hexanolactam then, ultrasonic 2 hours.Remove most of water in Rotary Evaporators, bath temperature is controlled at below 90 ℃.Pour into then in the there-necked flask, be heated to 140～180 ℃, vacuumize 10～60 minutes (vacuum tightness is 99331-99997Pa).Add sodium caprolactam(ate) 4%, 2,4 toluene diisocyanate (TDI) 0.8%, mix, cast, the mould temperature control is at 160～180 ℃.Reacted 10～20 minutes, and in 50 ℃ of baking ovens, cooled off.Polynite/nylon nano the composite property of preparation sees attached list one.
Embodiment 2
In 100g distilled water, put into the 10g polynite,, left standstill 10 minutes, remove the impurity of bottom settlings 80 ℃ of stirred in water bath 2 hours.Add the 1000g hexanolactam then, ultrasonic 2 hours.Remove most of water in Rotary Evaporators, bath temperature is controlled at below 90 ℃.Pour into then in the there-necked flask, be heated to 140～180 ℃, vacuumized 10～60 minutes, vacuum tightness is 99331Pa.Add 30gNaOH, 0.8g2,4-tolylene diisocyanate (TDI) mixes, and casts, and the mould temperature control is at 160～180 ℃.Reacted 10～20 minutes, and in 50 ℃ of baking ovens, cooled off.Polynite/nylon nano the composite property of preparation sees attached list one.
Embodiment 3
In 1500g distilled water, put into the 15g polynite,, left standstill 10 minutes, remove the impurity of bottom settlings 80 ℃ of stirred in water bath 2 hours.Add the 1000g hexanolactam then, ultrasonic 2 hours.Remove most of water in Rotary Evaporators, bath temperature is controlled at below 90 ℃.Pour into then in the there-necked flask, be heated to 140～180 ℃, vacuumized 10～60 minutes, vacuum tightness is 99680Pa.Add 45g KOH, 1.2g N-acyl caprolactam, mix, cast, the mould temperature control is at 160～180 ℃.Reacted 10～20 minutes, and in 50 ℃ of baking ovens, cooled off.Polynite/nylon nano the composite property of preparation sees attached list one.
Embodiment 4
In 2500g distilled water, put into the 20g polynite,, left standstill 10 minutes, remove the impurity of bottom settlings 80 ℃ of stirred in water bath 2 hours.Add the 1000g hexanolactam then, ultrasonic 2 hours.Remove most of water in Rotary Evaporators, bath temperature is controlled at below 90 ℃.Pour into then in the there-necked flask, be heated to 140～180 ℃, vacuumized 10～60 minutes, vacuum tightness is 99500Pa.Add 50g NaOH, 1.5g trialkyl isonitrile uric acid fat, mix, cast, the mould temperature control is at 160～180 ℃.Reacted 10～20 minutes, and in 50 ℃ of baking ovens, cooled off.Polynite/nylon nano the composite property of preparation sees attached list one.
Embodiment 5
In 4000g distilled water, put into the 100g polynite,, left standstill 10 minutes, remove the impurity of bottom settlings 80 ℃ of stirred in water bath 2 hours.Add the 1000g hexanolactam then, ultrasonic 2 hours.Remove most of water in Rotary Evaporators, bath temperature is controlled at below 90 ℃.Pour into then in the there-necked flask, be heated to 140～180 ℃, vacuumized 10～60 minutes, vacuum tightness is 99997Pa.Add 40g NaH, 2.5g N-benzoyl caprolactam, 2g oxidation inhibitor, mix, cast, the mould temperature control is at 160～180 ℃.Reacted 10～20 minutes, and in 50 ℃ of baking ovens, cooled off.Polynite/nylon nano the composite property of preparation sees attached list one.
Subordinate list one
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Polynite content (%) | 0 | 0.5 | 1 | 1.5 | 2 | 10 |
| The thermal deformation resistant temperature of bending modulus/MPa bending strength/Gpa hot strength/MPa elongation at break/% cantilever beam notched Izod impact strength/(J/m)/℃ | 103 2784 78.1 61 55 182 | 113 3256 88.9 52 39 196 | 110.9 3186 91.3 40 41 197 | 104 3049 84.3 35 30 205 | 98.1 2885 80.1 29 30 207 | 91.1 2883 78.4 15 26 203 |
Claims (7)
1. the preparation method of a peel montmorillonite/casting nylon nano-composite material, it is characterized in that, this method is to adopt the anionic ring-opening polymerization legal system to be equipped with peel montmorillonite/casting nylon nano-composite material, this method comprises following processing step: the dispersion of polynite, at first polynite is dispersed in 10～200 times the aqueous solution, 80 ℃ of stirred in water bath 2 hours, adding hexanolactam disperseed 0.5～6 hour, under 100 ℃, remove most of water then with underpressure distillation, heat up 140～180 ℃ again, vacuumized 30 minutes, with catalyzer, activator or other auxiliary agents add in the hexanolactam according to a certain ratio, mix, cast, 160～180 ℃ of mould temperature were reacted 10～20 minutes, cooled off in 50 ℃ of baking ovens.
2. the preparation method of a kind of peel montmorillonite/casting nylon nano-composite material according to claim 1 is characterized in that, described polynite content is 0.05～10% of nylon nano matrix material weight.
3. the preparation method of a kind of peel montmorillonite/casting nylon nano-composite material according to claim 1 is characterized in that, the catalyst levels of described adding hexanolactam is 0.01～5% of a caprolactam monomer weight; The consumption of activator is 0.02～10% of a caprolactam monomer weight.
4. the preparation method of a kind of peel montmorillonite/casting nylon nano-composite material according to claim 1 is characterized in that, the vacuum tightness of described evacuation process is 99331～99997Pa.
5. according to the preparation method of claim 1 or 3 described a kind of peel montmorillonite/casting nylon nano-composite materials, it is characterized in that described catalyzer is selected from sodium caprolactam(ate), NaH, NaOH, KOH, LiH, Na
2CO
3In one or more.
6. according to the preparation method of claim 1 or 3 described a kind of peel montmorillonite/casting nylon nano-composite materials; it is characterized in that; described activator is selected from 2,4 toluene diisocyanate (TDI), N-one or more in acyl caprolactam, N-benzoyl caprolactam, the trialkyl isonitrile uric acid fat.
7. the preparation method of a kind of peel montmorillonite/casting nylon nano-composite material according to claim 1, it is characterized in that, described other auxiliary agents are selected from one or more in commercially available oxidation inhibitor, fire retardant, the photostabilizer, and consumption is 0～2% of a caprolactam monomer weight.
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| CNB2005101113741A CN100547035C (en) | 2005-12-12 | 2005-12-12 | A kind of preparation method of peel montmorillonite/casting nylon nano-composite material |
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| CN100547035C CN100547035C (en) | 2009-10-07 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205361B (en) * | 2007-11-29 | 2010-06-09 | 东华大学 | Montmorillonite layered nylon6/montmorillonite nano composite material and preparation thereof |
| CN103012774A (en) * | 2012-11-22 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | High-temperature resistant and high-strength type casting nylon 6 composite material and preparation method thereof |
| CN103073714A (en) * | 2013-01-17 | 2013-05-01 | 株洲时代新材料科技股份有限公司 | Preparation method of cast nylon/ montmorillonite nanocomposite material |
| CN103172852A (en) * | 2013-01-17 | 2013-06-26 | 株洲时代新材料科技股份有限公司 | Preparation method of organic montmorillonoid/cast nylon nanometer composite material |
| CN103554484A (en) * | 2013-10-11 | 2014-02-05 | 合肥工业大学 | Hydrotalcite like-polyamide functional nanocomposite and preparation method thereof |
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| CN110330789A (en) * | 2019-08-02 | 2019-10-15 | 横店集团得邦工程塑料有限公司 | A kind of fire-retardant enhancing PA6 composite material and preparation method of long-acting light aging resisting |
| CN112029089A (en) * | 2020-08-05 | 2020-12-04 | 华东理工大学 | Intercalation type poly (butyrolactam)/montmorillonite nano composite material and preparation method thereof |
| CN116675978A (en) * | 2022-02-22 | 2023-09-01 | 合肥杰事杰新材料股份有限公司 | PA6/ABS/OMMT nanocomposite and preparation method thereof |
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2005
- 2005-12-12 CN CNB2005101113741A patent/CN100547035C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101205361B (en) * | 2007-11-29 | 2010-06-09 | 东华大学 | Montmorillonite layered nylon6/montmorillonite nano composite material and preparation thereof |
| CN103012774A (en) * | 2012-11-22 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | High-temperature resistant and high-strength type casting nylon 6 composite material and preparation method thereof |
| CN103073714B (en) * | 2013-01-17 | 2015-08-12 | 株洲时代新材料科技股份有限公司 | A kind of preparation method of nylon monomer-cast nylon/Nano composite material of montmorillonite |
| CN103073714A (en) * | 2013-01-17 | 2013-05-01 | 株洲时代新材料科技股份有限公司 | Preparation method of cast nylon/ montmorillonite nanocomposite material |
| CN103172852A (en) * | 2013-01-17 | 2013-06-26 | 株洲时代新材料科技股份有限公司 | Preparation method of organic montmorillonoid/cast nylon nanometer composite material |
| CN103172852B (en) * | 2013-01-17 | 2016-07-27 | 株洲时代新材料科技股份有限公司 | A kind of preparation method of organo montmorillonite/casting nylon nano-composite material |
| CN103554484A (en) * | 2013-10-11 | 2014-02-05 | 合肥工业大学 | Hydrotalcite like-polyamide functional nanocomposite and preparation method thereof |
| CN103554484B (en) * | 2013-10-11 | 2016-03-02 | 合肥工业大学 | A kind of Hydrotalcite like-polyamide functional nanocomposite and preparation method thereof |
| CN103585947B (en) * | 2013-11-21 | 2015-02-18 | 倪任林 | Densification and polycondensation reaction equipment and method for preparing nanometer polyamide composite material |
| CN103612342A (en) * | 2013-11-21 | 2014-03-05 | 倪任林 | Anhydrous nanometer polyamide mother pulp preparer and preparation method thereof |
| CN103612342B (en) * | 2013-11-21 | 2015-10-28 | 倪任林 | A kind of waterless nano polyamide mother slurry preparing device and preparation method thereof |
| CN103585947A (en) * | 2013-11-21 | 2014-02-19 | 倪任林 | Densification and polycondensation reaction equipment and method for preparing nanometer polyamide composite material |
| CN104212055A (en) * | 2014-10-09 | 2014-12-17 | 湖北科普达实业有限公司 | Inorganic modified high heat-resistant low-shrinkage low-smoke halogen-free flame retardant polyolefin cable material and preparation method thereof |
| CN110330789A (en) * | 2019-08-02 | 2019-10-15 | 横店集团得邦工程塑料有限公司 | A kind of fire-retardant enhancing PA6 composite material and preparation method of long-acting light aging resisting |
| CN112029089A (en) * | 2020-08-05 | 2020-12-04 | 华东理工大学 | Intercalation type poly (butyrolactam)/montmorillonite nano composite material and preparation method thereof |
| CN116675978A (en) * | 2022-02-22 | 2023-09-01 | 合肥杰事杰新材料股份有限公司 | PA6/ABS/OMMT nanocomposite and preparation method thereof |
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