CN1796458A - Method for toughening and reinforcing nylon by using new type organic montmorillonite - Google Patents
Method for toughening and reinforcing nylon by using new type organic montmorillonite Download PDFInfo
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- CN1796458A CN1796458A CN 200410099163 CN200410099163A CN1796458A CN 1796458 A CN1796458 A CN 1796458A CN 200410099163 CN200410099163 CN 200410099163 CN 200410099163 A CN200410099163 A CN 200410099163A CN 1796458 A CN1796458 A CN 1796458A
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Abstract
This invention provides a process for producing a new type of organic montmorillonite reinforced nylon, comprising the steps of: swelling the montmorillonite with a polar solvent, then adding an organic solution of the interlayer insertion agent, omega-laurolactam, to obtain organic montmorillonite; adding the organic montmorillonite into hexanolactam and stirring the mixture at 100-120 DEG C for 4-8h under nitrogen atmosphere; vacuum pumping at a vacuum degree of 99331-99997Pa for 15-60min, then adding sodium hexanolactam, 2,4-toluene diisocyanate and other assistants to the mixture for casting or reactive extrusion to obtain the product. The process of this invention produces an interlayer insertion agent that can improve the adhesion between the montmorillonite and the nylon matrix, and the montmorillonite/nylon nanocomposite produced from the interlayer insertion agent treated montmorillonite has high strength, modulus, resistance, impact strength and rupture extension rate.
Description
Technical field
The present invention relates to the intercalation polymeric casting or the reaction extrusion manufacture method of a kind of toughness reinforcing enhancement type polynite/nylon nano matrix material, relate in particular to a kind of novel polynite the treatment process that organises,, prescription, technology.
Background technology
So-called nano composite material is meant, as the discrete state material size at least at the size of 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.
The main component of polynite is a silicates, and its lamellar spacing only is 0.96-2.1nm, and when reaching the nano level dispersion in material, very big change will take place the performance of its material as mentioned above.Polynite/nylon nano matrix material has obtained extensive studies and application owing to have high strength, high-modulus and high barrier property.Japan Unitika company just worked out a kind of nylon/layered silicate (inorganic clay) matrix material in 1976, 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, Patent No.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.
The quality of polynite/nylon nano performance of composites, key factor are dispersion in polymeric matrix of the selection of montmorillonite intercalation agent and processing mode and it, peel off situation.About a lot of patent report that organises of polynite, the patent that U.S. Nanocor Ltd.. has applied for a lot of this respects.Such as: US Patent No.6,399,690,6,391,449,6,387,996,6,380,295,6,376,591,6,287,634,6,262,162,6,251,980,6,242,500,6,235,533,6,232,388,6,228,903,6,225,394,6,126,734,6,124,365,6,107,387,6,090,734,6,057,396,6,050,509,5,998,528,5,952,059,5,880,197,5,877,248,5,849,830,5,844,032,5,830,528,5,804,613,5,760,121,5,721,306,5,698,624,5,578,672,5,552,496.
Usually prepare polynite/used organo montmorillonite of nylon nano matrix material, generally polynite is organised and handle with the amino acids intercalation of different carbon chain lengths, the polynite and the nylon that organise are then extruded in twin screw, perhaps carry out polycondensation with hexanolactam.Zhi Bei the polynite like this/common modulus of nylon nano matrix material, intensity, thermal deformation resistant temperature and barriering effect improve, but notch shock and tension fracture elongation rate all have tangible reduction, significantly reduced the use range of polynite/nylon nano matrix material, the principal element that causes polynite/nylon nano composite material toughness to reduce is not have strong bonding force between polynite and nylon matrix, thereby causes toughness of material to descend.
If exist certain treatment agent to connect polynite and nylon matrix, then can significantly improve the toughness of this polynite/nylon nano matrix material and do not reduce the intensity of material with chemical bonding force.
Summary of the invention
The technical issues that need to address of the present invention are the methods that disclose a kind of toughening and reinforcing nylon by using new type organic montmorillonite, to overcome the defective of polynite/nylon nano matrix material that above-mentioned technology exists.
Method of the present invention comprises the steps:
Polynite is dissolved in the polar solvent, swelling 4～8 hours, add organic solution then as the omega-lauric lactam of intercalator, the add-on of omega-lauric lactam counts 10～50% with the polynite gross weight, stirred 20～28 hours, and filtered, washing, 60～90 ℃ of vacuum-drying 20～26 hours, be ground to 180～220 orders, obtain the polynite that organises;
Described polar solvent is selected from organic solvents such as ethanol, acetone or dimethylbenzene;
Described omega-lauric lactam organic solution is selected from a kind of mixing solutions in omega-lauric lactam and ethanol, acetone, dimethylbenzene, hydrochloric acid, phosphoric acid or the sulfuric acid etc., and the weight concentration of solution is 0-30%;
The polynite that organises is added in the hexanolactam; under nitrogen protection; 100-120 ℃ was stirred 4～8 hours; in vacuum tightness is to vacuumize under the 99331-99997Pa 15～60 minutes; add sodium caprolactam(ate), 2,4 toluene diisocyanate and other auxiliary agents then, cast or react and extrude; promptly obtain product, the parts by weight of reaction process are:
The polynite 0.4-2 part that organises
100 parts of hexanolactams
Sodium caprolactam(ate) 0.2-4 part
2,4 toluene diisocyanate 0.2-1 part
0～1 part of other auxiliary agent
Said other auxiliary agents can be oxidation inhibitor, fire retardant, remover etc.
Method of the present invention, prepared a kind of can be effectively in conjunction with the intercalator that is connected power between polynite and nylon matrix, polynite/nylon nano the matrix material of the polynite preparation that this intercalator is handled had both had the characteristics of high strength, high-modulus, high-barrier, had high notched Izod impact strength and elongation at break again.
The testing standard of the mechanical property of described Reinforced Nylon matrix material 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 |
Embodiment
Embodiment 1
The preparation of organo montmorillonite: the omega-lauric lactams of 7 grams are dissolved in the middle of the 100ml ethanol, and the concentrated hydrochloric acid (36w%) that adds 3ml stirs.The na montmorillonites (cation exchange capacity CEC=100mmol/100g) of getting 20 grams were dissolved in the 500ml acetone swelling 6 hours, omega-lauric lactam solution poured in the montmorillonite suspension liquid heat, keep temperature to stir 24 hours for 60 ℃, filtration washing is to there not being chlorion, 70 ℃ of vacuum-drying 22 hours is ground to 200 orders.
The organic montmorillonoid for preparing as stated above of 1% amount is added in the hexanolactam, feed the high pure nitrogen protection and stirred 6 hours, temperature is controlled at 110 ℃.Vacuumized 30 minutes, vacuum tightness is 99997Pa, adds sodium caprolactam(ate) 4%, 2,4 toluene diisocyanate (TDI) 0.6%, mixes, and casts under 180 ℃ of conditions.Polynite/nylon nano the composite property of preparation sees attached list 1.
Embodiment 2
With embodiment 2, only changing organic montmorillonoid content is 2%, and the polynite of preparation/nylon nano composite property sees attached list 1.
Embodiment 3
With embodiment 2, only changing organic montmorillonoid content is 3%, and the polynite of preparation/nylon nano composite property sees attached list 1.
Embodiment 4
With embodiment 2, only changing organic montmorillonoid content is 5%, the polynite of preparation/nylon nano matrix material, and the polynite of preparation/nylon nano composite property sees attached list 1.
Comparative Examples 1
Replenish the comparative example, adopt the identical method of embodiment 2, still, polynite does not organise, and the polynite of preparation/nylon nano composite property sees attached list 1.
Performance sees attached list 1.
| Comparative Examples 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Organic montmorillonoid content | 0％ | 1％ | 2％ | 3％ | 5％ |
| The thermal deformation resistant temperature of modulus in flexure/MPa flexural strength/Gpa tensile strength/MPa elongation at break/% socle girder notched Izod impact strength/(J/m)/℃ | 111 2.17 83.5 52 39 65 | 117 2.23 62.8 72 91 130 | 125 2.36 68.2 112 113 155 | 133 2.61 84.3 69 112 160 | 136 2.65 88.4 47 86 160 |
Claims (6)
1. the preparation method of an organic montmorillonoid plasticizing enhancement nylon is characterized in that, comprises the steps:
Polynite is dissolved in the polar solvent, and swelling adds the organic solution as the omega-lauric lactam of intercalator then, the add-on of omega-lauric lactam counts 10～50% with the polynite gross weight, stirs, and filters, washs, vacuum-drying is ground, and obtains the polynite that organises;
The polynite that organises is added in the hexanolactam; under nitrogen protection; mix; in vacuum tightness is to vacuumize under the 99331-99997Pa; add sodium caprolactam(ate), 2,4 toluene diisocyanate and other auxiliary agents then, cast or react and extrude; promptly obtain product, the parts by weight of reaction process are:
The polynite 0.4-2 part that organises
100 parts of hexanolactams
Sodium caprolactam(ate) 0.2-4 part
2,4 toluene diisocyanate 0.2-1 part
0～1 part of other auxiliary agent.
2. method according to claim 1 is characterized in that, stirs after the adding of omega-lauric lactam 20～28 hours, and 70-80 ℃ of vacuum-drying 20～26 hours is ground to 180～220 orders.
3. method according to claim 1 is characterized in that described polar solvent is selected from ethanol, acetone or dimethylbenzene.
4. method according to claim 1 is characterized in that, described omega-lauric lactam organic solution is selected from a kind of mixing solutions in omega-lauric lactam and ethanol, acetone, dimethylbenzene, hydrochloric acid, phosphoric acid or the sulfuric acid etc.
5. method according to claim 4 is characterized in that, the weight concentration of solution is 0-30%.
6. method according to claim 1 is characterized in that, the polynite that organises is added in the hexanolactam, and under nitrogen protection, 100-120 ℃ mixed 4～8 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410099163 CN1796458A (en) | 2004-12-28 | 2004-12-28 | Method for toughening and reinforcing nylon by using new type organic montmorillonite |
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| CN 200410099163 CN1796458A (en) | 2004-12-28 | 2004-12-28 | Method for toughening and reinforcing nylon by using new type organic montmorillonite |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580815A (en) * | 2007-12-17 | 2009-11-18 | 赢创德固赛有限责任公司 | Omega-amino carboxylic acids, omega-amino carboxylic acid esters, or recombinant cells which produce lactams thereof |
| CN101148540B (en) * | 2007-10-26 | 2010-08-04 | 华中科技大学 | Method for enhancing nylon selectivity laser sintering forming element by clay |
| 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 |
| CN103613922A (en) * | 2013-11-29 | 2014-03-05 | 江门市奇德工程塑料科技有限公司 | High-barrier nano PA6 composite material and preparation method thereof |
| CN103804900A (en) * | 2012-11-07 | 2014-05-21 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature-resistant semi-aromatic nylon nanocomposite and its preparation method |
| CN108003609A (en) * | 2017-12-25 | 2018-05-08 | 桐城市祥泰塑业有限公司 | A kind of bromination intercalated montmorillonite modified nylon materials and preparation method thereof |
-
2004
- 2004-12-28 CN CN 200410099163 patent/CN1796458A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148540B (en) * | 2007-10-26 | 2010-08-04 | 华中科技大学 | Method for enhancing nylon selectivity laser sintering forming element by clay |
| CN101580815A (en) * | 2007-12-17 | 2009-11-18 | 赢创德固赛有限责任公司 | Omega-amino carboxylic acids, omega-amino carboxylic acid esters, or recombinant cells which produce lactams thereof |
| CN101580815B (en) * | 2007-12-17 | 2013-12-25 | 赢创德固赛有限责任公司 | Omega-amino carboxylic acids, omega-amino carboxylic acid esters, or recombinant cells which produce lactams thereof |
| CN103804900A (en) * | 2012-11-07 | 2014-05-21 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature-resistant semi-aromatic nylon nanocomposite and its preparation method |
| 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 |
| 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 |
| 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 |
| CN103613922A (en) * | 2013-11-29 | 2014-03-05 | 江门市奇德工程塑料科技有限公司 | High-barrier nano PA6 composite material and preparation method thereof |
| CN108003609A (en) * | 2017-12-25 | 2018-05-08 | 桐城市祥泰塑业有限公司 | A kind of bromination intercalated montmorillonite modified nylon materials and preparation method thereof |
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