CN1233742C - Rare earth modified polyamide/montmorillonite composite material and its preparation method - Google Patents
Rare earth modified polyamide/montmorillonite composite material and its preparation method Download PDFInfo
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- CN1233742C CN1233742C CN 02134848 CN02134848A CN1233742C CN 1233742 C CN1233742 C CN 1233742C CN 02134848 CN02134848 CN 02134848 CN 02134848 A CN02134848 A CN 02134848A CN 1233742 C CN1233742 C CN 1233742C
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Abstract
The present invention relates to a polyamide / montmorillonite silicate composite material and a preparation method thereof. The composite material of the present invention contains rare earth modifying agents for the modification of montmorillonite, and the montmorillonite of which the total cation exchange capacity ranges from 50 to 200 meq/100g is montmorillonite raw soil or montmorillonite intercalation soil which is processed by the intercalation. The present invention can directly use montmorillonite raw soil which is processed by the rare earth modifying agents to prepare the polyamide / montmorillonite composite material and simplify the production technology.
Description
Technical field
The present invention relates to a kind of matrix material of forming by layered silicates such as polymeric amide and polynites and preparation method thereof, specifically, the present invention relates to a kind of polyamide/montmorillonite composite material that adopts the rare-earth modifier modification and preparation method thereof.
Background technology
Nylon is a kind of widely used engineering plastics, has excellent physical and mechanical properties.But since the effect of acid amides polar group, the water-intake rate height of nylon, and heat-drawn wire is low, has limited its application.Adopt the Inorganic Fillers Filled modification of nylon, for example, add lime carbonate or clay mineral mica etc., can improve dimensional stability and improve rigidity, and reduce cost, but also cause the particularly decline of impelling strength of the strength of materials.Adopting the filling-modified polymer materials of ultra-fine inorganic thing is one of approach that improves performance.When packing material size during less than 0.1 μ m, ultrafine particle adopts traditional blend method because of its great surface energy makes that interparticle self aggregation effect is very big, is difficult to prevent the autohemagglutination effect and makes filler obtain homodisperse on the nanometer level.For improving the bonding interface of filler and polymkeric substance, common employing silane coupling agent or titanate coupling agent or other have the interfacial compatibilizers such as organic polymer grafts to the similar group of matrix macromolecular chain, to improve the interfacial tension between filler and polymeric matrix, homodisperse of realizing ideal and bonding interface.But above-mentioned filling-modified matrix material only belongs to the microcosmic matrix material, has influenced the improvement of reinforcing effect and resistance toheat.Have only when between mineral filler and polymeric matrix strong interaction is arranged, and reach the dispersion of nanoscale, just rigidity, dimensional stability and the thermotolerance of inorganics and toughness, the workability of polymkeric substance ideally may be combined the Organic of obtained performance excellence.
Polynite is a kind of nonmetal stratiform silicate minerals.Its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two.The montmorillonite layer internal surface has negative charge, interlayer cation Na
+, Ca
2+, Mg
2+Deng being the interchangeability positively charged ion, after cationic exchange, can make macromole be inserted into interlayer.
Preparation polymeric amide/inorganics nano composite material adopts monomer intercalation polymeric method usually, makes monomer of polyamide such as hexanolactam carry out polymerization and form matrix material at the interlayer of layered silicate.But because silicate granules interlamellar spacing 1 nanometer scale only, monomer is difficult to infiltrate its interlayer, and the matrix material after the polymerization does not reach the ideal reinforced effects equally.United States Patent (USP) 4,739,007 discloses the method for preparing nanometer composite polyamide-clay material by intercalation polymeric.Above-mentioned patent can be called two step method, and its implementation process is: at first clay is carried out the processing of intercalation expansionization, its interlamellar spacing is enlarged.Polymerization single polymerization monomer and swelling clay mix and infiltrate its interlayer then.In the time of monomer polymerization, the clay laminate dissociates and disintegration becomes the nanometer fineness, is dispersed in the polymer, realizes the nano combined of polyamide-clay.But, this technology has two shortcomings, and the one, the expansion treating processes of clay need increase equipment, expends a large amount of time and energy and is used for drying and fragmentation, causes production cost to rise, and production efficiency descends; Another shortcoming is that the clay after handling mixes with monomer of polyamide, causes the difficulty of melt polycondensation operation.Chinese patent ZL 96105362.3 discloses the one-step polymerization process that a kind of preparation has the nanometer composite polyamide-clay material of excellent mechanical property, this in-situ polymerization intercalated technology is monomer to be inserted between accurate two-dimentional silicate clay material layer carry out in-situ polymerization, obtains high molecular polymer/clay composite material.Wherein the silicate component provides excellent mechanics and thermostability, and organic polymer has guaranteed good workability.
Above-mentioned patent preparation process is after the intercalation expansion process with clay, to carry out polymerization with polymerization single polymerization monomer again.Its shortcoming is that intercalation polymeric process need large quantity of moisture dispersion media will be done corresponding improvement to production unit with monomer and intercalation soil homodisperse before polymerization, mainly be applicable to the production in enormous quantities of fixing prescription, was unsuitable for the production of many kinds, short run.
Chinese patent 97112237.7 discloses a kind of nanometer composite polyamide-clay material and preparation method thereof, it will be extruded through clay and polymeric amide melt blending on twin screw extruder of intercalation processing, power chemical action by restricted clearance makes clay combine with polyamide substrate and with the nanoscale homodisperse, thereby is prepared into the high-performance nano matrix material.The technological process of this invention is simple, without solvent, does not need aftertreatment, has reduced cost, can reach the effect of intercalation polymeric.
In the prior art, the dispersion of montmorillonite particle in polyamide/montmorillonite composite material is still not ideal enough, be difficult to reach nano level dispersion, also be that existing matrix material is difficult to become nano material, and preparation method's complexity, in general, in order to reach better particles dispersed, polynite will be passed through intercalation processing.This has greatly increased production cost concerning industrial production.
Summary of the invention
The invention provides a kind of novel polyamide/montmorillonite layered silicate matrix material, contain the rare-earth modifier that the polynite of being adopted is carried out modification in this matrix material, the polynite of being adopted then is the original montmorillonoid soil of cationic exchange total volume (CEC) between 50-200meq/100g or the montmorillonite intercalation soil of crossing through intercalation processing, and preferred CEC is 70-160meq/100g.As CEC during greater than 200meq/100g, higher interlayer Coulomb's force makes polynite be difficult for being dispersed in the polymeric matrix; And when CEC was lower than 50meq/100g, polynite can not be compatible with polymeric matrix effectively, is difficult for being dispersed in the polymeric matrix.
In the present invention, adopt a kind of novel rare-earth modifier, used this rare-earth modifier can prepare polyamide/montmorillonite layered silicate matrix material simplely.This rare-earth modifier is a kind of rare earth organometallic compound or mixture, be mineral compound or its mixture by one or more lanthanon, saturated and/or undersaturated organic acid and/or the formed compound of organic acid derivatives, title complex and/or with one or more from aggressiveness.Wherein, said rare earth element can be a kind of in the lanthanon, two kinds and two or more mixtures, preferably light rare earthss such as lanthanum, cerium, praseodymium, neodymium, yttrium and composition thereof; Described organic acid and/or organic acid derivatives are C
4-C
36, monobasic and/or binary, saturated and/or undersaturated lipid acid, alicyclic acid, aromatic carboxylic acid or derivatives thereof, described derivative is organic acid ester, acid amides or has hydroxyl, ether, carbonyl or amino organic acid on carbon skeleton, as hard ester acid, ten dihydroxystearic acids, oleic acid, lauric acid, C
6-C
9Lipid acid, Succinic Acid, hexanodioic acid, pimelic acid, sebacic acid, 2 ethyl hexanoic acid, fumaric acid, maleic anhydride, octyl group toxilic acid, epoxyoleic acid, amino acid, Whitfield's ointment, phenylformic acid, stearin, pentaerythritol ester, amine hydroxybenzene, aromatic carboxylic acid and derivative etc., particularly hard ester acid, phenylformic acid, amino acid, tetramethylolmethane, hexanodioic acid, octyl group toxilic acid, aromatic carboxylic acid and derivative thereof also can be wherein several mixtures.Details is seen Chinese patent application 02134499.X.
The preferred rare-earth modifier of the present invention has asymmetric structure, at rare earth organic compounds, complex compound or in aggressiveness, is different with each organic group of rare earth element bonded promptly.For example, by rare earth oxide, muriate or its salt with two or more, organic acid and/or the formed rare-earth modifier of organic acid derivatives that the carbon skeleton structure is different.
In matrix material of the present invention, can also contain synergist.The main purpose that adds synergist is further to strengthen the modifying function of rare-earth modifier to polynite.Selected synergist can be C
4-C
36, monobasic and/or binary, saturated and/or undersaturated lipid acid, alicyclic acid, aromatic carboxylic acid or derivatives thereof, described derivative is organic acid ester, acid amides or has hydroxyl, ether, carbonyl or amino organic acid on carbon skeleton.In fact, synergist of the present invention can be that part of organic acid and/or the organic acid derivatives that does not react behind rare earth mineral compound and organic acid and/or the organic acid derivatives reaction formation rare-earth modifier, so, in the present invention, there is no need the reaction mixture of rare-earth separating mineral compound and organic acid and/or organic acid derivatives.Like this, just can simplify production technique greatly, reduce production cost.Certainly, also can add other organic acid and/or organic acid derivatives as synergist.In general, for the weight of rare-earth modifier, the add-on of synergist is 10-100 weight %.
If the present invention adopts the rare-earth modifier of unsymmetrical structure, the content of synergist can be very low, even be zero, and its modifying function is still good.
It is simple to utilize above-mentioned rare-earth modifier to prepare the method for polyamide/montmorillonite layered silicate matrix material.This rare-earth modifier can be used for directly handling original layered silicate, as the original soil of direct processing polynite.After the original polynite process rare-earth modifier for treatment of the present invention without any organic decoration, activation or expansion process, can melt extrude with polyamide blended.Test result shows, the dispersed obviously raising of polynite in polyamide substrate, and polyamide/montmorillonite composite material physical and mechanical properties correspondingly also promotes significantly, proves that the composite effect of polymeric amide and layered silicate significantly improves.
Certainly, the rare-earth modifier of the present invention polynite (intercalation soil) that also can be used for handling intercalation processing or organic decoration or activated.Will be through the polynite of intercalation processing again with after the rare-earth modifier for treatment, the method of extruding by blended melting can make the polyamide/montmorillonite nano composite material, and the similar nano composite material that the physical and mechanical properties of this nano composite material is reported than prior art has had significantly lifting.
In weight part, matrix material of the present invention can comprise following composition:
100 parts of polyamide resins
Polynite 0.05-60 part
Rare-earth modifier 0.0005-6 part
Synergist 0.0005-6 part
Fire retardant 0-25 part
Antimonous oxide 0-15 part
Oxidation inhibitor 0-1 part
Toughner 0-25 part
Wherein, the consumption of rare-earth modifier by the 0.01-10% of processing polynite weight; Polynite can be original montmorillonoid soil or intercalation polynite, and its content in matrix material is about 0.05-60 weight %; When polynite content was lower than 0.0005%, the polynite that is added was not enough to produce enough enhancements; When its content surpassed 60%, the matrix material of gained was Powdered, can not machine-shaping.In the present invention, the optimum content scope of polynite is 1-30%.
Polynite after rare-earth modifier for treatment both can add polyamide substrate by traditional filler adding method, and method is prepared into master batch or PP Pipe Compound also availablely to open refining, banburying, extrude etc.
Among the present invention, used polyamide resin can be PA6, PA66, PA1010, PA11, PA12; Used fire retardant can be decabromodiphenyl oxide, tetrabromo-bisphenol, poly-(2, the 6-dibromobenzene aether) etc.; Used oxidation inhibitor can be 1010,1098,168, B215, B225, B561, B900 etc.; Used toughner can be ethene-methyl-prop diluted acid multipolymer etc.
In the present invention, if the polynite of adopting when preparing above-mentioned matrix material is an original montmorillonoid soil, then in the gained matrix material size of montmorillonite particle between 10nm-40000nm; If the polynite of adopting when preparing above-mentioned matrix material is the montmorillonite intercalation soil through intercalation processing, the gained matrix material is a nano material so, and the particle of polynite wherein is less than 100nm.
On the other hand, the present invention also provides the method for preparing polyamide/montmorillonite layered silicate matrix material, and this method comprises and is prepared as follows step:
A) adopt above-mentioned rare-earth modifier under 60-140 ℃, original montmorillonoid soil to be handled;
B) original montmorillonoid soil that above-mentioned rare-earth modifier for treatment is crossed mixes with polymeric amide, carries out mixing then or extrudes.
Or:
A) with intercalator and tensio-active agent original montmorillonoid soil is carried out intercalation processing earlier, make montmorillonite intercalation soil; Then
B) adopt rare-earth modifier under 60-140 ℃, above-mentioned intercalation polynite to be handled;
C) the intercalation polynite that above-mentioned rare-earth modifier for treatment is crossed mixes with polymeric amide, carries out mixing then or extrudes.
The most outstanding characteristics of the present invention are that original montmorillonoid soil both can improve the dispersiveness of polynite in matrix after disposal methods of the present invention, can obtain part simultaneously again with nano-scale dispersive Nano composite material of montmorillonite; Intercalation soil for having crossed through intercalation processing after disposal methods of the present invention, can improve the dispersiveness of this intercalation soil in polymeric amide, further improves the performance of Nano composite material of montmorillonite.
By the following examples the present invention is further specified, composition wherein is parts by weight.
Embodiment 1
The used rare-earth modifier of present embodiment is gadolinium and oleic acid, stearin, stearic reactant.Add 2 parts of rare-earth modifiers, 1.5 parts of amine hydroxybenzenes in 100 part of 800 purpose original montmorillonoid soil (cationic exchange total volume 150meq/100g), 95 ℃ of following high-speed stirring are handled and were taken out in 10 minutes in super mixer.Processing is sent into polynite and undressed 800 order original montmorillonoid soils that rare earth was handled in the air dry oven before using simultaneously, dries 2 hours down for 120 ℃, and is stand-by.
Adopt twin screw extruder, 65 parts of polyamide resin PA66 add through the feeding funnel, and 20 parts of polynites and 15 parts of fire retardants etc. add through weight-loss type side direction feeder respectively, melt extrude, and the water-cooled pelletizing makes the PA66/ montmorillonite composite material.Test result is as follows:
Prescription A B
PA66 65 65
Original polynite 20
The polynite 20 of rare-earth modifier for treatment
Fire retardant, oxidation inhibitor etc. 15 15
Performance
Tensile strength/MPa 64 72
Flexural strength/MPa 106 113
Notched Izod impact strength KJ/m
24.3 4.1
Heat-drawn wire (1.82MPa)/℃ 148 174
Flame retardant resistance UL-94 V-0 V-0
CTI/V 350 350
Performance test shows, adopt the heat-drawn wire of the material B of the polynite that rare-earth modifier for treatment of the present invention crosses to exceed 26 ℃ of materials A, tensile strength and flexural strength also obviously improve, and prove that rare-earth modifier has improved the composite effect of polymeric amide and polynite effectively.
Embodiment 2
90 parts of polymeric amide PA6 are behind fusion plastification in the mill, and sheet, pelletizing are descended in 10 parts of the polynites that adding embodiment 1 middle-weight rare earths properties-correcting agent was handled after mixing 5 minutes.The heat-drawn wire (1.82MPa) that records the PA6/ montmorillonite composite material reaches 98 ℃, improves 32 ℃ than the pure Nylon 6 that does not add polynite.
Embodiment 3
The used rare-earth modifier of present embodiment is lanthanum and bi-tristearin, stearin, amine hydroxybenzene synthetic properties-correcting agent.
2.5 parts of rare-earth modifier agent and 1.0 parts of ethylenebisstearamides are added in 100 part of 400 order original montmorillonoid soil (cationic exchange total volume 150meq/100g), and 105 ℃ of following high-speed stirring are handled and were taken out in 10 minutes in super mixer.
90 parts of various polyamide resins add 10 parts of the polynites of above-mentioned processing respectively, mixing again 5 minutes following sheets, pelletizing respectively behind fusion plastification in the mill.The heat-drawn wire of test gained matrix material.Test data and the contrast of polymeric amide virgin resin heat-drawn wire are as follows.
PA66 PA6 PA1010
Polymeric amide virgin resin heat-drawn wire 72 66 54
(1.82MPa)/℃
Polyamide/montmorillonite composite material thermal distortion temperature 107 95 91
Degree (1.82MPa)/℃
Embodiment 4
With the cationic exchange total volume is the polynite 25g of 100meq/100g, adds water 600ml, and after waiting to be uniformly dispersed, high-speed stirring 20min gets suspending liquid A.6.5g trolamine is dissolved in the 150ml water, drips concentration and is 30% sulfuric acid 17ml and get solution B.Suspending liquid A is heated to 80 ℃, drips solution B, and temperature maintenance is incubated 1 hour at 80 ℃, naturally cools to 20-25 ℃, suction filtration, and wash with water repeatedly.This process has been finished the intercalation processing of cation exchange reaction and polynite.Last vacuum-drying is milled to powder to constant weight.It is that 4: 6 the samarium and the mishmetal of neodymium are raw material that present embodiment adopts with mol ratio, with stearic acid, glyceryl monostearate, amine hydroxybenzene synthetic rare-earth modifier.
Add 5.0 parts of rare-earth modifiers, 0.5 part of 75 ℃ of following high-speed stirring processing taking-up in 15 minutes in super mixer of 12-oxystearic acid in 100 parts of above-mentioned intercalation soil.
Add 30 parts of intercalation soil that rare-earth modifier for treatment is crossed in 70 parts of nylon 6, under 180 (240) ℃, causing master batch on the Banbury mixer.
Above-mentioned master batch adds in 100 parts of nylon 6 for 10 parts, mixes after twin screw melt extrudes pelletizing.The performance of gained nano composite material is as follows.
PA6 virgin resin PA6/ inserts PA6/ intercalation soil rare earth and changes
Layer soil nature agent nano composite material
Tensile strength/MPa 77 90 112
Tensile modulus/MPa 2,350 3,800 4950
Heat-drawn wire (1.82MPa)/℃ 66 108 138
Izod notched Izod impact strength/J/m 38 34 37
Embodiment 5
With the cationic exchange total volume is the polynite 100g of 150meq/100g, adds water 2500ml, and after waiting to be uniformly dispersed, high-speed stirring 30min gets suspending liquid A.30g octadecyl trimethylammonium ammonia chloride is dissolved in the 5000ml water, drips concentration and is 30% hydrochloric acid 50ml and get solution B.Suspending liquid A is heated to 80 ℃, drips solution B and stirs, and temperature maintenance is incubated 1 hour at 80 ℃, naturally cools to 20-25 ℃, suction filtration, and wash with water repeatedly, carry out the intercalation processing of cation exchange reaction and polynite.Last vacuum-drying is milled to powder to constant weight.Add 2 parts of rare-earth modifiers that formed by neodymium, gadolinium and amino acid, pentaerythritol adipate in 100 parts of above-mentioned intercalation soil, 2 parts of amino-nonanoic acids took out as synergist 120 ℃ of following high-speed stirring in super mixer in 15 minutes.
93 parts of nylon 6, the polynite that adds above-mentioned processing mixes extruding pelletization on forcing machine for 7 parts; The performance of gained nano composite material is as follows.
PA6 virgin resin PA6/ inserts PA6/ intercalation soil rare earth and changes
Layer soil nature agent nano composite material
Tensile strength/MPa 77 92 108
Tensile modulus/MPa 2,350 4,000 4820
Tension set/% 30 22 20
Flexural strength/MPa 112 134 178
Heat-drawn wire (1.82MPa)/℃ 66 110 142
Izod notched Izod impact strength/J/m 38 32 32
Embodiment 6
Handling the cationic exchange total volume by the method for embodiment 5 is the polynite of 80meq/100g.In 93 parts of nylon 6, add 7 parts of polynites, 8 parts of the toughner ethylene-methacrylic acid copolymers that above-mentioned processing obtains, after mixing, extruding pelletization on forcing machine, the notched Izod impact strength that records the gained nano composite material is 186J/m.
Claims (8)
1, a kind of polyamide/montmorillonite layered silicate matrix material, it is characterized in that, contain the rare-earth modifier that described polynite is carried out modification in the described matrix material, described polynite is the original montmorillonoid soil of cationic exchange total volume between 50-200meq/100g or the montmorillonite intercalation soil of crossing through intercalation processing, described rare-earth modifier is mineral compound or its mixture of one or more lanthanon, saturated and/or undersaturated organic acid and/or the formed compound of organic acid derivatives, title complex and/or from aggressiveness with one or more; And in weight part, described matrix material comprises following composition:
100 parts of polyamide resins
Polynite 0.05-60 part
Rare-earth modifier 0.0005-6 part
Synergist 0.0005-6 part
Fire retardant 0-25 part
Antimonous oxide 0-15 part
Oxidation inhibitor 0-1 part
Toughner 0-25 part.
2, matrix material according to claim 1 is characterized in that, described organic acid and/or organic acid derivatives are C
4-C
36, monobasic and/or binary, saturated and/or undersaturated lipid acid, alicyclic acid, aromatic carboxylic acid or derivatives thereof, described derivative is organic acid ester, acid amides or has hydroxyl, ether, carbonyl or amino organic acid on carbon skeleton.
3, matrix material according to claim 1 and 2 is characterized in that, in described rare-earth modifier, is different with each organic group of rare earth element bonded.
4, matrix material according to claim 1 is characterized in that, also contains synergist in the described matrix material, and described synergist is C
4-C
36, monobasic and/or binary, saturated and/or undersaturated lipid acid, alicyclic acid, aromatic carboxylic acid or derivatives thereof, described derivative is organic acid ester, acid amides or has hydroxyl, ether, carbonyl or amino organic acid on carbon skeleton.
5, matrix material according to claim 1 is characterized in that, used polynite is an original montmorillonoid soil, and the size of montmorillonite particle is between 10nm-40000nm in the gained matrix material.
6, matrix material according to claim 1 is characterized in that, used polynite is a montmorillonite intercalation soil, and the particle of polynite is less than 100nm in the gained matrix material.
7, a kind of method for preparing polyamide/montmorillonite layered silicate matrix material, it comprises and is prepared as follows step:
A) adopt rare-earth modifier under 60-140 ℃, original montmorillonoid soil to be handled;
B) original montmorillonoid soil that above-mentioned rare-earth modifier for treatment is crossed mixes with polymeric amide, carries out mixing then or extrudes.
8, a kind of method for preparing polyamide/montmorillonite layered silicate matrix material, it comprises and is prepared as follows step:
A) with intercalator and tensio-active agent original montmorillonoid soil is carried out intercalation processing, make montmorillonite intercalation soil;
B) adopt rare-earth modifier under 60-140 ℃, above-mentioned intercalation polynite to be handled;
C) the intercalation polynite that above-mentioned rare-earth modifier for treatment is crossed mixes with polymeric amide, carries out mixing then or extrudes.
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| US20060122309A1 (en) | 2004-12-02 | 2006-06-08 | Grah Michael D | Intercalated layered silicate |
| CN101265410B (en) * | 2007-03-12 | 2013-11-06 | 广东炜林纳功能材料有限公司 | Multifunctional flame-proof masterbatch |
| CN114702820B (en) * | 2022-04-02 | 2023-08-08 | 江苏扬农化工集团有限公司 | Natural mineral modified nylon composite material and preparation method thereof |
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