CN107163245A - A kind of organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials and preparation method thereof - Google Patents
A kind of organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials, is prepared by the reaction of organic phosphoric acid zirconium, caprolactam monomer, catalyst, initiator and silane coupler.Organic phosphoric acid zirconium is modified through n-butylamine, Gemini surface active by α basic zirconium phosphates, prepared by coprecipitation, again silane coupler, catalyst are added after caprolactam monomer is scattered at a high speed, mixed after heating, high-speed stirred, insulation operation with adding the caprolactam monomer of initiator after melting, it is transferred in mould, it is placed in baking oven and adjusts temperature reaction, cooling and demolding obtains the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials.
Description
Technical field
The present invention relates to MC nylon composite materials technical fields, and in particular to a kind of organically-modified basic zirconium phosphate/MC Buddhist nun of nanometer
The preparation method of imperial composite.
Background technology
MC nylon products have the advantages that good physical stability, chemical corrosion resistance and high-wearing feature because of it, one
Determine the metal material such as alternative steel, copper, aluminium in scope, it is adaptable to the application field such as chemical industry, machinery, weaving, oil, electric.But
It is the defects such as pure MC nylon products have dimensional stability, heat endurance and low-temperature flexibility is poor, limits to a certain extent
Its application.At present, domestic modification to MC nylon, prepare composite and carried out many-sided research, and with inorganic
It is modified more to be concentrated with organically-modified.The Main Means of wherein inorganic modified method are that addition such as red phosphorus, glass is micro- into nylon
Ball, carbon fiber, titanium dioxide nano-particle etc. one or more inorganic filling materials, and achieve preferable dimensional stability and
Toughness.Such as new material limited company of Jieshijie Novel Materials Co., Ltd, Shanghai is risen in CN1982373 patents using caprolactam monomer into profit
In between inorganic cheating engaging layer afterwards, catalyst and activator are added, one kettle way directly reacts, cast molding obtains peeling off and covers de-
Soil/casting nylon nano-composite material.And Zhuzhou Times new materials Science Co., Ltd is in CN103073714A patents,
Organo montmorillonite is prepared by modified in liquid-phase system, then by two pots of method hybrid reactions, pours shaping to prepare
Organo montmorillonite/casting nylon nano-composite material.Sichuan University utilizes coupling and reduction in CN105254870A patents
The graphene oxide of processing is added into caprolactam monomer, reduced vacuum dehydration after polymerization prepare monomer moulding casting nylon/
Graphene nanocomposite material.According to information disclosed above, by adding a small amount of stratiform or flake nano material, by means of nanometer
The high-ratio surface effect and quantum size effect of material, can be effectively improved the property such as rigidity, intensity, toughness of polymeric matrix
Can, so as to strengthen the tensile strength of composite, impact strength and barrier property.
Research on this kind of material is concentrated merely on by adding unmodified montmorillonite, surface modified organic illiteracy
Take off soil or graphene oxide to improve the interaction between inorganic nano-filler and polymeric matrix, not yet find to prepare MC at present
Pass through the related scientific research report and patent of invention of doping vario-property zirconium phosphate nano particle in nylon preparation process.
The content of the invention
The primary and foremost purpose of the present invention is the defect for MC nylon prior arts, has good parallel construction by addition
There is provided a kind of receiving with more excellent physics, mechanical performance and barrier property than MC nylon for the laminar nano basic zirconium phosphate of arrangement
Organically-modified basic zirconium phosphate/MC the nylon composite materials of rice.
Another object of the present invention is to provide a kind of preparation side of the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials
Method and its application in automotive oil tank manufacture.
The present invention is achieved by the following technical programs：
A kind of organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials are by organic phosphoric acid zirconium, caprolactam monomer, catalysis
Agent, initiator and silane coupler reaction are prepared, and the organic phosphoric acid zirconium and caprolactam monomer total mass ratio are 1~5：
100；Silane coupler is 0.25~1 with organic phosphoric acid zirconium mass ratio:1；The mass ratio of the catalyst and organic phosphoric acid zirconium is 1
~5:1；The mass ratio of the initiator and organic phosphoric acid zirconium is 1~5:1.
The catalyst is NaOH, KOH, LiOH, NaH, one or more of compositions in LiH.
The initiator is polymeric isocyanate glue, dodecyl isocyanate, hexadecyl isocyanate, tert-butyl group isocyanide
Any one of acid esters, nonyl isocyanates, decyl isocyanates, octyl group isocyanates or a toluene diisocyanate.The silicon
Alkane coupling agent is that described silane coupler is 3- aminopropyl triethoxysilanes (KH550), γ-glycidyl ether oxygen propyl three
One or more compositions in methoxy silane (KH560), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570).
The organic phosphoric acid zirconium includes following preparation process：
S1. prepared by alpha zirconium phosphate, by 10g ZrOCl2.8H2O, 10gNaF are added in the reaction bulb of 100ml distilled water, stirring
Dissolving, adds 50mL 85wt% H3PO4, air in most bottle is taken out, N is passed through2, electromagnetic agitation reaction 196h at 25 DEG C, at a high speed from
Heart precipitation and separation, is neutral with distilled water cyclic washing to pH value, vacuum drying produces alpha zirconium phosphate powder at 60 DEG C；
S2. the alpha zirconium phosphate powder that 1.0g steps S1 is prepared is weighed, in the deionized water for adding 25mL, 0.1 is added dropwise
The n-butylamine of~0.4CEC equivalents is supportted in advance, after 40 DEG C of stirring in water bath 6h, is further continued for dropwise addition 0.6~0.9CEC equivalents
Gemini quaternary cationicses are modified, under 50 DEG C of water bath with thermostatic control stirring conditions continue react 24h, at a high speed from
Heart precipitation and separation, respectively with 50%v/v ethanol solution and deionized water centrifuge washing, vacuum drying produces organophosphor at 60 DEG C
Sour zirconium, the organic phosphoric acid zirconium layer spacing is 2.5~3.5nm.
Alpha zirconium phosphate is a kind of layered inorganic compound with regular shape, and each layer is conplane by being approximately at
Zr atoms and two layers of O up and down that Zr atoms are clipped in the middle3P-OH is constituted.It is accumulated by Van der Waals force between layers
Together, interlamellar spacing is 0.76nm, points to the O of inner layer space3P-OH groups share 3 oxygen atoms, its Hydrogen Proton with Zr atoms
(P-OH) it can be exchanged.Because the Hydrogen Proton of phosphate group in basic zirconium phosphate molecule can be in inner layer space free diffusing, in addition
The good thermal stability and chemical inertness of the inorganic compound, therefore prepare easy, good crystalline, purity height；And it is water insoluble and
Organic solvent, resistance to strong acid, heat endurance and chemical stability are high, high mechanical strength, and layer structure is stable, and hydrophobic with two
The Gemini quaternary cationicses of base and two hydrophilic radicals can effectively drop after alpha zirconium phosphate activation process
The surface tension of low nano material, prepares the nanometer organic phosphoric acid zirconium of single sheet.Can be real by layer complex technique
Existing nylon is compound on nanoscale with organic phosphoric acid zirconium, and gained nano composite material can be steady by the rigidity of inorganic matter, size
Qualitative and heat endurance combines with the toughness, machinability and dielectricity of polymer, can prepare high intensity, height heat-resisting
Property, the composite of high-barrier and anti-flammability, be widely used in terms of the machinery enhancing of polymer, gas permeability is improved
Prospect, can especially process be prepared into automotive oil tank auto industry manufacture in be applied.
The alpha zirconium phosphate grain size is 100~400nm, and interlamellar spacing is 0.76nm, and ion exchange capacity (CEC) is
190~200mmol/100g；
In the step S2, n-butylamine of the alpha zirconium phosphate first through 0.1~0.4CEC equivalents is supportted in advance, then adds 0.6
The Gemini quaternary cationicses of~0.9CEC equivalents carry out intercalation modifying, Gemini quaternary ammonium salt cationics surface
Activating agent is by ethylene group double (dodecyl dimethyl ammonium chlorides), ethylene group double (dodecyldimethylamine ammonium chloride), ethylene groups
Double (hexadecyldimethyl benzyl ammonium ammonium chlorides), ethylene group double (octadecyldimethyl ammonium chlorides), the double (dimethyls of trimethylene base
Ammonium chloride) in one or more compositions.
Alpha zirconium phosphate used in the present invention is a kind of with good choke, moisture barrier property, the inorganic nano of lamellar structure
Material.And alpha zirconium phosphate is by n-butylamine, the sun of the new type of Gemini quaternary ammonium salt with two hydrophobic groups and two hydrophilic radicals from
Sub- surfactant is supportted in advance successively, after chemical modification, and it is poly- to reduce wadding while with bigger interlamellar spacing, and dispersiveness is made
Good sheet organic phosphoric acid zirconium, its choke, moisture barrier property are further lifted.
The preparation method of the organically-modified basic zirconium phosphate of the nanometer/MC nylon composite materials comprises the following steps：
Y1. organic phosphoric acid zirconium is added in the reactor A equipped with 50%~90% caprolactam monomer gross mass, low speed
It is gradually heated up being warming up to 100~120 DEG C under stirring condition, after after caprolactam monomer completely melting, vacuumizes and heighten rotating speed,
The fine dispersion of organic phosphoric acid zirconium is realized under vacuum state, ultrahigh speed stirring condition, silane coupler is added, continues to stir
Catalyst is added after 15~60min and 130~140 DEG C are warming up to, material one is obtained, in 0.1MPa, insulation, ultrahigh speed stirring condition
It is lower to preserve；
Y2. in the reactor B that will be equipped with 10%~50% caprolactam monomer gross mass, warming while stirring to 70~80
DEG C vacuumize, after adding initiator after molten monomer, continue to be evacuated to 0.1MPa and be warming up to 130~140 DEG C, continue to take out true
Empty 10min, obtains material two；
Y3. step Y1 resulting materials one and step Y2 resulting materials two are mixed, in the mould for being transferred to 150~180 DEG C,
It is placed in 50~80 DEG C of baking ovens, 10~30min of insulation reaction, is stripped after natural cooling, obtains the organically-modified basic zirconium phosphate/MC Buddhist nun of nanometer
Imperial composite.Under caprolactam monomer molten condition, using high-speed stirred, by the shearing force of agitating solution, realization has
Machine zirconium phosphate nano particle is dispersed in caprolactam monomer, is realized by silane coupler in organic phosphoric acid zirconium and oneself
Effective combination of amide monomer.By the skin effect of nano-particle, bulk effect, quantum size effect and laminated structure, carry
High tensile strength, impact strength and the barrier property of organic phosphoric acid zirconium/MC nylon composite materials.
In the step Y1, stirring at low speed in reactor one is 400~800r/min, ultrahigh speed stirring for 8000~
10000r/min。
The mass ratio of the addition of catalyst and organic phosphoric acid zirconium is 1~5 in described reactor A:1.
The mass ratio of the addition of initiator and organic phosphoric acid zirconium is 1~5 in described reactor B:1.
The present invention has the following advantages and beneficial effect relative to prior art：
(1) the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials that the present invention is provided, creative by organically-modified phosphorus
Sour zirconium is poured in MC nylon systems, can be in layer using the Hydrogen Proton of basic zirconium phosphate molecule stratiform Stability Analysis of Structures, phosphate group
The good thermal stability and chemical inertness of the characteristics of space free diffusing, the in addition inorganic compound, prepare dimensionally stable, height
Intensity, high-fire resistance, the composite of high-barrier and anti-flammability.
(2) the organically-modified basic zirconium phosphate of nanometer provided by the present invention/MC nylon composite materials, during dispersed with stirring,
Summarized by many experiments, scientific design speed of agitator utilizes the shearing force of agitating solution, effectively enhancing organic phosphoric acid zirconium is equal
It is even scattered, the ratio of ingenious combination silane coupler and organic phosphoric acid zirconium, by the skin effect of nano-particle, bulk effect,
Quantum size effect and laminated structure, improve tensile strength, impact strength and the resistance of organic phosphoric acid zirconium/MC nylon composite materials
Separating performance.
(3) method of the organically-modified basic zirconium phosphate of present invention preparation nanometer/MC nylon composite materials is simple, equipment requirement is low,
Pollution-free, suitable industrialization can process and be prepared into automotive oil tank and be applied in automobile production industry.
Brief description of the drawings
The SEM figures of Fig. 1 alpha zirconium phosphates of the present invention.
The modified TEM figures for preparing organic phosphoric acid zirconium of Fig. 2.
Embodiment
The present invention is further described with specific embodiment below in conjunction with the accompanying drawings.Unless stated otherwise, the present invention is implemented
The various raw materials that example is used can be obtained by the way that routine is purchased in market, or be prepared according to the conventional method of this area, used to set
Standby is experiment common equipment.Unless otherwise defined or described herein, all specialties used herein and scientific words and this area
Meaning is identical known to person skilled in the art.
The present invention creatively adds organic phosphoric acid zirconium in MC nylon composite materials, and prepare one kind has than MC nylon
Nanometer basic zirconium phosphate/MC nylon composite materials of more excellent physics, mechanical performance and barrier property.
Embodiment 1
(1) preparation of organic phosphoric acid zirconium：
S1. 10g ZrOCl are added in reaction bulb2·8H2Added after O, 10g NaF and 100mL distilled water, stirring and dissolving
50mL 85wt% H3PO4, take out in most reaction bulb and be passed through N again after air2, electromagnetic agitation continues to react 196h at 25 DEG C, at a high speed
Precipitation is centrifuged, is neutral with distilled water cyclic washing to pH value, is ground after being dried in vacuo at 60 DEG C and alpha-phosphate zirconium powder is made
End, measures its CEC (cation exchange capacity (CEC)) for 195mmol/100g, interlamellar spacing is 0.76nm.
S2. the alpha zirconium phosphate powder that 4.0g steps S1 is prepared is weighed, is scattered in 100mL deionized water, then
The n-butylamine that 0.1CEC is added dropwise is supportted in advance, after 40 DEG C of water bath with thermostatic control stirring reaction 6h, is further continued for being added dropwise 0.9CEC ethylene group
Double (dodecyl dimethyl ammonium chlorides) carries out continuing to react 24h under chemical modification, 50 DEG C of water bath with thermostatic control stirring conditions.At a high speed from
Heart precipitation and separation, respectively with 50% (v/v) ethanol solution and deionized water centrifuge washing, grinds after being dried in vacuo at 60 DEG C
Organic phosphoric acid zirconium sample.Detected using XRD and bragg's formula calculates and obtains the interlamellar spacing of modified zirconium phosphate for 3.50nm.
(2) preparation of organic phosphoric acid zirconium/MC nylon composite materials：
Y1. the organic phosphoric acid zirconium for weighing 100g is added in the reactor A equipped with 10Kg caprolactam monomers, 400r/min
It is gradually heated up being warming up to 100~120 DEG C under stirring condition, after after caprolactam monomer completely melting, heightens rotating speed to 8000r/
Min is simultaneously vacuumized, and the dispersed of organic phosphoric acid zirconium is realized under the conditions of 0.1MPa vacuum, high-speed stirred.Add 100g's
3- aminopropyl triethoxysilanes (KH550), continue to stir 40% sodium hydroxide solution and liter that 1250mL is added after 15min
Temperature obtains material one and preserved under 0.1MPa, 130 DEG C, 8000r/min ultrahigh speed stirring conditions to 130 DEG C；
Y2. it will be equipped with 5Kg, the reactor B of 10% lactam monomers, warming while stirring begins to take out true to 70 DEG C
Sky, after the polymeric isocyanate glue that 100g is added after molten monomer, continues to be evacuated to 0.1MPa and is warming up to 130 DEG C, 10000r/
Continue to react 10min under the conditions of min, obtain material two；
Y3. step Y1 resulting materials one and step Y2 resulting materials two are mixed, in the mould for being transferred to 150 DEG C, are placed in
Adjust the temperature to 50 DEG C in baking oven, continue to be stripped after insulation reaction 10min, natural cooling organic phosphoric acid zirconium/MC nylon is combined
Material.
Embodiment 2
(1) preparation of organic phosphoric acid zirconium：
S1. it is same as Example 1；
S2. the alpha zirconium phosphate powder that 10g steps S1 is prepared is weighed, is scattered in 250mL deionized water, then drips
Plus 0.2CEC n-butylamine is supportted in advance, after 40 DEG C of water bath with thermostatic control stirring reaction 6h, the ethylene group for being further continued for being added dropwise 0.8CEC is double
(dodecyldimethylamine ammonium chloride) carries out continuing to react 24h under chemical modification, 50 DEG C of water bath with thermostatic control stirring conditions.High speed centrifugation
Precipitation and separation, respectively with 50% (v/v) ethanol solution and deionized water centrifuge washing, grinds and must have after being dried in vacuo at 60 DEG C
Machine basic zirconium phosphate sample.Detected using XRD and bragg's formula calculates and obtains the interlamellar spacing of modified zirconium phosphate for 3.30nm.
(2) preparation of organic phosphoric acid zirconium/MC nylon composite materials：
Y1. the organic phosphoric acid zirconium for weighing 200g is added in the reactor A equipped with 6Kg caprolactam monomers, 600r/min
It is gradually heated up being warming up to 110 DEG C under stirring condition, after after caprolactam monomer completely melting, heightens rotating speed to 9000r/min simultaneously
Vacuumize, the dispersed of organic phosphoric acid zirconium is realized under the conditions of 0.1MPa vacuum, high-speed stirred.Add 100g γ-contracting
Water glycerine ether oxygen propyl trimethoxy silicane (KH560), 80% sodium hydroxide for continuing to stir addition 500mL after 30min is molten
Liquid is simultaneously warming up to 135 DEG C, obtains material one, is preserved under 0.1MPa, 135 DEG C of 9000r/min ultrahigh speed stirring conditions；
Y2. it will be equipped with 4Kg, the reactor B of caprolactam monomer, warming while stirring begins to vacuumize to 75 DEG C,
After the polymeric isocyanate glue that 200g is added after molten monomer, continue to be evacuated to 0.1MPa and be warming up to 135 DEG C, 10000r/min
Under the conditions of continue react 20min, obtain material two；
Y3. step Y1 resulting materials one and step Y2 resulting materials two are mixed, in the mould for being transferred to 160 DEG C, are placed in
Adjust the temperature to 60 DEG C in baking oven, continue to be stripped after insulation reaction 15min, natural cooling organic phosphoric acid zirconium/MC nylon is combined
Material.
Embodiment 3
(1) preparation of organic phosphoric acid zirconium：
S1. it is same as Example 1；
S2. the alpha zirconium phosphate powder that 100g steps S1 is prepared is weighed, is scattered in 2500mL deionized water, then
The n-butylamine that 0.3CEC is added dropwise is supportted in advance, after 40 DEG C of water bath with thermostatic control stirring reaction 6h, is further continued for being added dropwise 0.7CEC ethylene group
Double (hexadecyldimethyl benzyl ammonium ammonium chlorides) carries out continuing to react 24h under chemical modification, 50 DEG C of water bath with thermostatic control stirring conditions.At a high speed from
Heart precipitation and separation, respectively with 50% (v/v) ethanol solution and deionized water centrifuge washing, grinds after being dried in vacuo at 60 DEG C
Organic phosphoric acid zirconium sample.Detected using XRD and bragg's formula calculates and obtains the interlamellar spacing of modified zirconium phosphate for 2.90nm.
(2) preparation of organic phosphoric acid zirconium/MC nylon composite materials：
Y1. the organic phosphoric acid zirconium for weighing 300g is added in the reactor A equipped with 7Kg caprolactam monomers, 800r/min
It is gradually heated up being warming up to 110 DEG C under stirring condition, after after caprolactam monomer completely melting, heightens rotating speed to 10000r/min simultaneously
Vacuumize, the dispersed of organic phosphoric acid zirconium is realized under the conditions of 0.1MPa vacuum, high-speed stirred.Add 100g γ-(first
Base acryloyl-oxy) propyl trimethoxy silicane (KH570), continues to stir 80% sodium hydroxide that 1000mL is added after 60min
Solution is simultaneously warming up to 140 DEG C, obtains material one and is preserved under 0.1MPa, 140 DEG C, 10000r/min ultrahigh speed stirring conditions；
Y2. in the reactor B that will be equipped with 3Kg caprolactam monomers, warming while stirring begins to vacuumize to 80 DEG C, treats
900g polymeric isocyanate glue is added after molten monomer, continues to be evacuated to 0.1MPa and is warming up to 140 DEG C, 10000r/min bars
Continue to react 10min under part, obtain material two；
Y3. step Y1 resulting materials one and step Y2 resulting materials two are mixed, in the mould for being transferred to 180 DEG C, are placed in
Adjust the temperature to 80 DEG C in baking oven, continue to be stripped after insulation reaction 30min, natural cooling organic phosphoric acid zirconium/MC nylon is combined
Material.
Embodiment 4
(1) preparation of organic phosphoric acid zirconium：
S1. it is same as Example 1；
S2. the alpha zirconium phosphate powder that 100g steps S1 is prepared is weighed, is scattered in 2500mL deionized water, then
The n-butylamine that 0.4CEC is added dropwise is supportted in advance, after 40 DEG C of water bath with thermostatic control stirring reaction 6h, is further continued for being added dropwise 0.6CEC ethylene group
Double (octadecyldimethyl ammonium chlorides) carries out continuing to react 24h under chemical modification, 50 DEG C of water bath with thermostatic control stirring conditions.At a high speed from
Heart precipitation and separation, respectively with 50% (v/v) ethanol solution and deionized water centrifuge washing, grinds after being dried in vacuo at 60 DEG C
Organic phosphoric acid zirconium sample.Detected using XRD and bragg's formula calculates and obtains the interlamellar spacing of modified zirconium phosphate for 2.70nm.
(2) preparation of organic phosphoric acid zirconium/MC nylon composite materials：
Y1. the organic phosphoric acid zirconium for weighing 400g is added in the reactor A equipped with 8Kg caprolactam monomers, 700r/min
It is gradually heated up being warming up to 110 DEG C under stirring condition, after after caprolactam monomer completely melting, heightens rotating speed to 9000r/min simultaneously
Vacuumize, the dispersed of organic phosphoric acid zirconium is realized under the conditions of 0.1MPa vacuum, high-speed stirred.Add 100g γ-(first
Base acryloyl-oxy) propyl trimethoxy silicane (KH570), continues to stir 40% sodium hydroxide that 1000mL is added after 40min
Solution is simultaneously warming up to 140 DEG C, obtains material one, is preserved under 0.1MPa, 140 DEG C, 9000r/min ultrahigh speed stirring conditions；
Y2. in the reactor B that will be equipped with 2Kg caprolactam monomers, warming while stirring begins to take out true to 70~80 DEG C
Sky, after the polymeric isocyanate glue that 2000g is added after molten monomer, continues to be evacuated to 0.1MPa and is warming up to 140 DEG C,
Continue to react 10min under the conditions of 10000r/min, obtain material two；
Y3. step Y1 resulting materials one and step Y2 resulting materials two are mixed, in the mould for being transferred to 170 DEG C, are placed in
Adjust the temperature to 80 DEG C in baking oven, continue to be stripped after insulation reaction 30min, natural cooling organic phosphoric acid zirconium/MC nylon is combined
Material 4.
Embodiment 5
(1) preparation of organic phosphoric acid zirconium：
S1. it is same as Example 1；
S2. the alpha zirconium phosphate powder that 100g steps S1 is prepared is weighed, is scattered in 250mL deionized water, then
The n-butylamine that 0.5CEC is added dropwise is supportted in advance, after 40 DEG C of water bath with thermostatic control stirring reaction 6h, is further continued for being added dropwise 0.5CEC ethylene group
Double (octadecyldimethyl ammonium chlorides) carries out continuing to react 24h under chemical modification, 50 DEG C of water bath with thermostatic control stirring conditions.At a high speed from
Heart precipitation and separation, respectively with 50% (v/v) ethanol solution and deionized water centrifuge washing, grinds after being dried in vacuo at 60 DEG C
Organic phosphoric acid zirconium sample.Detected using XRD and bragg's formula calculates and obtains the interlamellar spacing of modified zirconium phosphate for 2.50nm.
(2) preparation of organic phosphoric acid zirconium/MC nylon composite materials：
Y1. the organic phosphoric acid zirconium for weighing 500g is added in the reactor A equipped with 9Kg caprolactam monomers, 1000r/min
It is gradually heated up being warming up to 100 DEG C under stirring condition, after after caprolactam monomer completely melting, heightens rotating speed to 10000r/min simultaneously
Vacuumize, the dispersed of organic phosphoric acid zirconium is realized under the conditions of 0.1MPa vacuum, high-speed stirred.Add 500g γ-(first
Base acryloyl-oxy) propyl trimethoxy silicane (KH570), continues to stir 80% sodium hydroxide that 2500mL is added after 50min
Solution is simultaneously warming up to 140 DEG C, obtains material one, is preserved under 0.1MPa, 140 DEG C, 10000r/min ultrahigh speed stirring conditions；
Y2. in the reactor B that will be equipped with 1Kg caprolactam monomers, warming while stirring begins to vacuumize to 80 DEG C, treats
500g polymeric isocyanate glue is added after molten monomer, continues to be evacuated to 0.1MPa and is warming up to 140 DEG C, 10000r/min bars
Continue to react 10min under part, obtain material two；
Y3. step Y1 resulting materials one and step Y2 resulting materials two are mixed, in the mould for being transferred to 180 DEG C, are placed in
Adjust the temperature to 70 DEG C in baking oven, continue to be stripped after insulation reaction 20min, natural cooling organic phosphoric acid zirconium/MC nylon is combined
Material 5.
Comparative example 1：
Ratio as prior art is done using the MC nylon materials not mixed with organic phosphoric acid zirconium
Weigh quantitative caprolactam and be added to sealing in reactor, be warming up to 100~120 DEG C, treat caprolactam monomer
Vacuumized completely after melting, add NaOH after removing moisture and low boiling impurity, 30min at 0.1MPa vacuum, 120 DEG C, often
0.3mol NaOH is added in 100ml caprolactams, stirring vacuumizes and is warming up to 160 DEG C, then adds polymeric isocyanate glue, often
0.3mol PIC is added in 100ml caprolactams, continues stirring reaction 15min；Last fast transfer is to 170 DEG C
In mould, constant temperature polyase 13 0min obtains MC nylon materials after the demoulding after natural cooling.
Embodiment 1~5 and comparative example 1 are carried out to the measure of tensile strength, impact strength, bending modulus and barrier property.
Specific measurement result is as shown in table 1.
The organically-modified basic zirconium phosphate of 1 nanometer of table/MC nylon composite materials the performance test results
Result above shows to the addition of the nylon composite materials of organically-modified basic zirconium phosphate, and compared to comparative example, its tensile strength is carried
28% is risen, impact strength improves one times, and barrier, toughness are substantially due to comparative example.
The organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials of the present invention, alpha zirconium phosphate is by n-butylamine, with two
The new type of Gemini quaternary cationics of hydrophobic group and two hydrophilic radicals is supportted in advance successively, chemical modification
Afterwards, reduce wadding while the SEM figures of alpha zirconium phosphate as shown in Figure 1 have bigger interlamellar spacing to gather, favorable dispersibility is made
Sheet organic phosphoric acid zirconium, its barrier property, which has, to be obviously improved.Simultaneously by the skin effect of nano-particle, bulk effect,
Quantum size effect and laminated structure, improve tensile strength, the impact strength of organic phosphoric acid zirconium/MC nylon composite materials.Such as
The modified TEM figures for preparing organic phosphoric acid zirconium, basic zirconium phosphate molecule stratiform Stability Analysis of Structures, the hydrogen matter of phosphate group shown in Fig. 2
Son can be the characteristics of inner layer space free diffusing, and the good thermal stability and chemical inertness of the inorganic compound, can have in addition
Effect improves intensity, heat resistance, barrier and the anti-flammability of composite.
Inventor states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials, it is characterised in that the organically-modified phosphoric acid of nanometer
Zirconium/MC nylon composite materials are reacted by organic phosphoric acid zirconium, caprolactam monomer, catalyst, initiator and silane coupler to be prepared
Obtain, the organic phosphoric acid zirconium and caprolactam monomer total mass ratio are 1 ~ 5：100；Silane coupler and organic phosphoric acid zirconium quality
Than for 0.25 ~ 1:1；The mass ratio of the catalyst and organic phosphoric acid zirconium is 1 ~ 5:1；The matter of the initiator and organic phosphoric acid zirconium
Amount is than being 1 ~ 5:1.
2. the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials according to claim 1, it is characterised in that described to urge
Agent is NaOH, KOH, LiOH, NaH, one or more compositions in LiH.
3. the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials according to claim 1, it is characterised in that described to draw
Hair agent is polymeric isocyanate glue, dodecyl isocyanate, hexadecyl isocyanate, t-butylisocyanate, nonyl isocyanide
Any one of acid esters, decyl isocyanates, octyl group isocyanates or a toluene diisocyanate.
4. the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials according to claim 1, it is characterised in that the silicon
Alkane coupling agent is 3- aminopropyl triethoxysilanes, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryl
One or more compositions in oxygen propyl trimethoxy silicane.
5. the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials according to claim 1, it is characterised in that described to have
Machine basic zirconium phosphate includes following preparation process：
S1. prepared by alpha zirconium phosphate, by 10g ZrOCl2 . 8H2O, 10g NaF are added in the reaction bulb of 100 mL distilled water, stirring
The wt% of 50 mL 85 H is added after dissolving3PO4, air in most bottle is taken out, N is passed through2, 25oElectromagnetic agitation reacts 196 h under C, at a high speed
Precipitation is centrifuged, is neutrality, 60 with distilled water cyclic washing to pH valueoVacuum drying produces alpha zirconium phosphate powder under C；
S2. the alpha zirconium phosphate powder that 1.0 g steps S1 are prepared is weighed, in the deionized water for adding 25 mL, dropwise addition 0.1 ~
The n-butylamine of 0.4CEC equivalents is supportted in advance, and 40oAfter the h of C stirring in water bath 6, the Gemini of dropwise addition 0.6 ~ 0.9CEC equivalents is further continued for
Quaternary cationics is modified, and 50oContinue to react 24h under C water bath with thermostatic control stirring conditions, be centrifuged at a high speed
Precipitation, respectively with 50 %v/v ethanol solution and deionized water centrifuge washing, 60oVacuum drying produces organic phosphoric acid zirconium under C,
The interlamellar spacing of the organic phosphoric acid zirconium is 2.5 ~ 3.5nm.
6. the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials according to claim 5, it is characterised in that the α-
Basic zirconium phosphate grain size is 100 ~ 400nm, and interlamellar spacing is 0.76nm, and ion exchange capacity CEC is 190 ~ 200 mmol/100g.
7. the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials according to claim 5, it is characterised in that the step
Gemini quaternary cationicses are by dodecyl dimethyl ammonium chloride, dodecyldimethylamine base chlorination in rapid S2
Ammonium, hexadecyldimethyl benzyl ammonium ammonium chloride, octadecyldimethyl ammonium chloride, one kind in dodecyl dimethyl ammonium chloride or many
Plant composition.
8. a kind of preparation method of the organically-modified basic zirconium phosphate of nanometer described in claim 1 ~ 7 any one/MC nylon composite materials,
It is characterised in that it includes following steps：
Y1. organic phosphoric acid zirconium is added in the reactor A equipped with 50% ~ 90% caprolactam monomer gross mass, stirring at low speed bar
It is gradually heated up being warming up to 100 ~ 120 under partoC, after after caprolactam monomer completely melting, vacuumizes and heightens rotating speed, in vacuum
The fine dispersion of organic phosphoric acid zirconium is realized under state, ultrahigh speed stirring condition, silane coupler is added, continue to stir 15 ~
Catalyst is added after 60min and 130 ~ 140 are warming up tooC, obtains material one, and the material one is stirred in 0.1MPa, insulation, ultrahigh speed
Preserved under the conditions of mixing；
Y2. in the reactor B that will be equipped with 10% ~ 50% caprolactam monomer gross mass, warming while stirring to 70 ~ 80oC is vacuumized,
After after caprolactam monomer melting, initiator is added, continues to be evacuated to 0.1MPa and is warming up to 130 ~ 140 oC, continue to take out true
10 ~ 30min of sky, obtains material two；
Y3. step Y1 resulting materials one and step Y2 resulting materials two are mixed, pours into 150 ~ 180 oCMould in, be placed in 50 ~
80oIn C baking ovens, 10 ~ 30min of insulation reaction is stripped after cooling, obtains the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials.
9. the preparation method of the organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials according to claim 8, its feature exists
In in the step Y1, the stirring at low speed in reactor A is 400 ~ 800r/min, and ultrahigh speed stirring is 8000 ~ 10000r/
min。
10. the organically-modified basic zirconium phosphate of nanometer/MC nylon composite woods that a kind of preparation method according to claim 8 is prepared
Expect the application in automotive oil tank, automobile industry field is prepared.
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| CN107343506A (en) * | 2017-07-31 | 2017-11-14 | 绵竹耀隆化工有限公司 | A kind of organic phosphoric acid zirconium antiseptic |
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| CN107343506A (en) * | 2017-07-31 | 2017-11-14 | 绵竹耀隆化工有限公司 | A kind of organic phosphoric acid zirconium antiseptic |
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| CN108003608A (en) * | 2017-12-25 | 2018-05-08 | 桐城市祥泰塑业有限公司 | A kind of hard nylon material and preparation method thereof |
| CN108774397A (en) * | 2018-06-14 | 2018-11-09 | 惠州市华聚塑化科技有限公司 | A kind of fire retardation wear-resistance nylon composite material and preparation method |
| CN109679333A (en) * | 2018-12-28 | 2019-04-26 | 宁波高新区诠宝绶新材料科技有限公司 | A method of preparing knob composite material |
| CN110183730A (en) * | 2019-05-24 | 2019-08-30 | 武汉工程大学 | Organic modified nano basic zirconium phosphate cladded type ammonium polyphosphate and preparation method thereof |
| CN112726208A (en) * | 2019-10-28 | 2021-04-30 | 赵程 | Wear-resistant waterproof composite carbon fiber cloth and preparation method thereof |
| CN112726208B (en) * | 2019-10-28 | 2022-09-09 | 赵程 | Wear-resistant waterproof composite carbon fiber cloth and preparation method thereof |
| CN114479245A (en) * | 2022-02-14 | 2022-05-13 | 武汉材料保护研究所有限公司 | Wear-resistant composite material of zirconium phosphate tetraphenyltin synergistically modified UHMWPE (ultrahigh molecular weight polyethylene) and preparation method |
| CN114479245B (en) * | 2022-02-14 | 2023-06-09 | 中国机械总院集团武汉材料保护研究所有限公司 | Zirconium phosphate tetraphenyltin synergistically modified UHMWPE wear-resistant composite material and preparation method thereof |
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