CN102964823A - Super-tough green nylon 11 nano composite material and preparation method thereof - Google Patents
Super-tough green nylon 11 nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a super-tough green nylon 11 nano composite material and a preparation method thereof. The super-tough green nylon 11 nano composite material comprises the following raw materials in parts by weight: 55-95 parts of nylon 11, 5-45 parts of ethylene-propylene terpolymer, 0.01-1 part of initiator, 0.1-4 parts of maleic anhydride and 1-5 parts of organic montmorillonite, wherein the initiator is organic peroxide including hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester or peroxydicarbonate. According to the invention, the super-tough green nylon 11 nano composite material is excellent in comprehensive properties, and is especially high in notch impact strength, fine in low-temperature impact resistance and low in water absorption rate and oil absorption value; and the cost can be reduced by about 23%. Thus, the invention has high industrial application values.
Description
Technical field
The invention belongs to polymeric material field, particularly a kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material and preparation method thereof.
Background technology
Polymeric amide claims again nylon (PA), is that purposes is the widest in the five large general engineering plastic, kind is maximum, output is maximum, the base resin of high comprehensive performance.（Fen Mo/Ke Li） Nylon11 in powder/granular form is the long carbochain softness nylon synthetic take Viscotrol C as raw material, compares with nylon 66 with nylon 6, and it has low water-absorbent, good dimensional stability and lower temperature resistance, good advantages such as electrical insulation capability; And have elastic memory, when external force was removed, （Fen Mo/Ke Li） Nylon11 in powder/granular form can return to original shape; Stress cracking resistance is good, embeds metal parts and not easy to crack; Can satisfy the injection moulding of various melt viscosity scopes and extrude processing; The erosion of termite-proof moth, harmless, be a kind of bio-based materials.Thereby （Fen Mo/Ke Li） Nylon11 in powder/granular form is widely used in the fields such as automobile, machinery, electronics, military project, medical treatment, food and physical culture.But the （Fen Mo/Ke Li） Nylon11 in powder/granular form notched Izod impact strength is low have been limited it and has used widely.
Super-toughened nylon is as a large kind of modification of nylon, and is main by adding the toughner such as rubber elastomer, thermoplastic elastomer, metallocene-polyolefin, makes through the twin screw extruder blend.Toughner generally all is by the amino of grafting polar group and nylon tip or carboxyl reaction and the consistency between Reinforced Nylon resin and the toughner, the adding of toughner has improved notched Izod impact strength and the lower temperature resistance of PA11 significantly, has also reduced its water-absorbent.Therefore, modification PA11 has expanded the scope of its use, by the client is liked.Patent 03116291.6 discloses by polyolefin elastomer and peroxide cross-linking agent with nylon, maleic anhydride graft and has joined in the twin screw extruder, and the technology by dynamic vulcanization makes super-toughened nylon; Patent 200910039160.6 discloses by joining after nylon 6, ultra-fine barium sulfate, POE-g-MAH, oxidation inhibitor and mix lubricant is even and has prepared super-toughened nylon in the twin screw extruder; Patent 201010139598.4 discloses nylon, POE-g-ITA, oxidation inhibitor, lubricant joined and has prepared super-toughened nylon in the twin screw extruder.
Ethylene-propylene rubber(EPR) mainly comprises ethylene propylene rubber (EPM) and terpolymer EP rubber (EPDM), the multipolymer that formed by ethene, propylene and non-conjugated diene hydrocarbon of terpolymer EP rubber (EPDM) wherein, because ethene and propylene monomer on its molecular backbone chain are random arrangement, lost the regularity of polyethylene or polypropylene structure, thereby become elastomerics, and the diolefine of terpolymer EP rubber is positioned on the side chain, therefore the structure of terpolymer EP rubber is conducive to the carrying out of situ-formed graft reaction, and it has also kept the various characteristics of ethylene propylene rubber simultaneously.
Polynite (MMT) is a kind of clay that is made of the silicate lamella of nano thickness, and sheet interlayer spacing is 0.96～2.1nm.Polynite is filled in the polyamide 6 matrix by the compound method of intercalation, realizes compound on nanoscale of polynite and matrix resin.Because the bonding interface that the nanometer small-size effect is become reconciled, this matrix material have excellent mechanical property and thermotolerance, and its flame retardant resistance, barrier and weathering resistance all increase.
In situ reactive compatibilization refers to put into the vinyl monomer of two kinds of superpolymer, polar functionalities and initiator in the lump in the parallel double-screw extruder, produce the superpolymer of polar functionalities in extrusion, then this superpolymer and another superpolymer form the superpolymer with compatibilization.
The present invention adopts the method for In Situ Compatibilization, in parallel double-screw extruder, the EPDM molecule is the Malaysia anhydride group in grafting under the effect of initiator, make it have stronger polarity, utilize the anhydride group of EPDM-g-MAH and the amino reaction of end of （Fen Mo/Ke Li） Nylon11 in powder/granular form to improve the consistency of PA11/EPDM system, thereby obtain super-toughened nylon 11 nano composite materials of excellent performance.
Summary of the invention
The objective of the invention is to adopt the method for In Situ Compatibilization, with （Fen Mo/Ke Li） Nylon11 in powder/granular form, terpolymer EP rubber (EPDM), initiator, after MALEIC ANHYDRIDE and organo montmorillonite (OMMT) blend, in parallel double-screw extruder, original position generates the superpolymer EPDM-g-MAH of grafting, and condensation reaction formation can occur with the superpolymer EPDM-g-MAH-g-PA11 of compatibilization with the end of （Fen Mo/Ke Li） Nylon11 in powder/granular form is amino in the anhydride group of EPDM-g-MAH, thereby improve the consistency between （Fen Mo/Ke Li） Nylon11 in powder/granular form and the EPDM, prepare that to have notched Izod impact strength higher, low-temperature impact property is good, super-toughened nylon 11 nano composite materials of low water absorption and low oil-absorption(number).
In order to realize purpose of the present invention, technical scheme of the present invention is: a kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, one group of composition is provided, and said composition comprises the compound of following weight part:
55～95 parts of （Fen Mo/Ke Li） Nylon11 in powder/granular forms (PA11);
5～45 parts of terpolymer EP rubbers (EPDM);
（Fen Mo/Ke Li） Nylon11 in powder/granular form (PA11) is 100 parts with the weight part summation of terpolymer EP rubber (EPDM);
0.01～1 part of initiator;
0.1～4 part of MALEIC ANHYDRIDE (MAH);
1～5 part of organo montmorillonite (OMMT).
Initiator is the organic superoxide, comprise hydroperoxide type, dialkyl class, peroxidation two acyl classes, peroxyesters, peroxy dicarbonates, select arbitrarily a kind of initiator, their adding is played and is caused the effect that produces graft polymer EPDM-g-MAH.
Among embodiment, described organic superoxide is the dicumyl peroxide, 2 in the dialkyl class, 5-dimethyl-2,5-di-t-butyl hexane peroxide therein.
Another object of the present invention provides the preparation method of above-mentioned super-toughened nylon 11 nano composite materials, and concrete technical scheme is as follows:
(1), described weight part initiator and MALEIC ANHYDRIDE are dissolved in the thinner, obtain mixing solutions, place for subsequent use;
(2), place vacuum drying oven to carry out drying and processing described weight part （Fen Mo/Ke Li） Nylon11 in powder/granular form, the control oven temperature is at 80～100 ℃, dry 4～12 hours, described weight part terpolymer EP rubber places vacuum drying oven to carry out drying and processing, the control oven temperature dry 4～12 hours, then is cooled to room temperature with （Fen Mo/Ke Li） Nylon11 in powder/granular form and terpolymer EP rubber at 60～80 ℃, （Fen Mo/Ke Li） Nylon11 in powder/granular form and the terpolymer EP rubber that will carry out behind the drying and processing mix in proportion, and obtain blend;
(3), the mixing solutions in the step (1) is poured in the blend of （Fen Mo/Ke Li） Nylon11 in powder/granular form and terpolymer EP rubber, obtain premix, premix is positioned in the air, and thinner is volatilized away;
(4), the premix that mixes is placed parallel double-screw extruder, and after side direction the 4th district of parallel double-screw extruder adds organo montmorillonite, melt extrude, granulation, and get final product;
Complete processing is as follows: the parallel double-screw extruder screw speed is 25～200r/min, 150～190 ℃ of one district's temperature, 170～210 ℃ of two district's temperature, 180～230 ℃ of three district's temperature, 180～230 ℃ of four district's temperature, 180～230 ℃ of five district's temperature, 180～230 ℃ of six district's temperature, 180～230 ℃ of seven district's temperature, 180～230 ℃ of die head temperatures.
Therein among some embodiment, the initiator of choosing in the above-mentioned steps can be the dicumyl peroxide in the dialkyl class, 2,5-dimethyl-2,5-di-t-butyl hexane peroxide; Thinner can be acetone, butanone.
Among embodiment, its preferred version may further comprise the steps therein:
(1), described weight part initiator and MALEIC ANHYDRIDE are dissolved in the thinner acetone, obtain mixing solutions, place for subsequent use;
(2), place vacuum drying oven to carry out drying and processing described weight part （Fen Mo/Ke Li） Nylon11 in powder/granular form, the control oven temperature is at 80～100 ℃, dry 4～8 hours, described weight part terpolymer EP rubber places vacuum drying oven to carry out drying and processing, the control oven temperature dry 4～8 hours, then is cooled to room temperature with （Fen Mo/Ke Li） Nylon11 in powder/granular form and terpolymer EP rubber at 60～80 ℃, （Fen Mo/Ke Li） Nylon11 in powder/granular form and the terpolymer EP rubber that will carry out behind the drying and processing mix in proportion, and obtain blend;
(3), the mixing solutions in the step (1) is poured in the blend of （Fen Mo/Ke Li） Nylon11 in powder/granular form and terpolymer EP rubber, obtain premix, premix is positioned in the air, and thinner acetone is volatilized away;
(4), the premix that mixes is placed parallel double-screw extruder, and after side direction the 4th district of parallel double-screw extruder adds organo montmorillonite, melt extrude, granulation, and get final product;
Complete processing is as follows: the parallel double-screw extruder screw speed is 25～100r/min, 170～190 ℃ of one district's temperature, 190～200 ℃ of two district's temperature, 190～200 ℃ of three district's temperature, 190～200 ℃ of four district's temperature, 190～200 ℃ of five district's temperature, 190～200 ℃ of six district's temperature, 190～200 ℃ of seven district's temperature, 190～200 ℃ of die head temperatures.
Among embodiment, described screw rod is shaped as single thread therein; The ratio (L/D) of spiro rod length (L) and diameter (D) is 20～60, preferred 35～60; Screw rod must have more than one gear block district, preferred 2 gear block districts, and it is more even that the gear block district helps material to be mixed to get in forcing machine; Screw rod must have more than one left-hand thread district, preferred 2 left-hand thread districts, and it is more even that the left-hand thread district helps material to be mixed to get in forcing machine, and can prolong the time that material stops in forcing machine, so that the In Situ Compatibilization reaction is more abundant.
In the above-mentioned steps, the initiator of choosing is preferably: 2,5-dimethyl-2,5-di-t-butyl hexane peroxide; Thinner is preferably: acetone.
The method of a kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material provided by the present invention has the following advantages:
1. （Fen Mo/Ke Li） Nylon11 in powder/granular form used in the present invention is the long carbochain soft nylon synthetic take Viscotrol C as raw material, and it is a kind of bio-based materials, and therefore, the （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material has the characteristic of environmental protection.
2. adopt method of the present invention to prepare super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, excellent combination property, especially notched Izod impact strength is higher, low-temperature impact property is good, low water absorption and low oil-absorption(number), and its cost can reduce, and (price of PA11 is 120,000 yuan/tons about 23%, EPDM is 2.7 ten thousand yuan/tons, press the 7:3 blend, its cost reduces by 23.25% than pure PA11.), industrial application value is larger.
3. adopt method of the present invention to prepare super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, its technique is simple, is easy to control, and not high to equipment requirements, employed equipment is general polymer processing equipment, invests not high.
4. adopt method of the present invention to prepare super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, shortened technical process, save the energy, improved production efficiency, be easy to apply.
Description of drawings
Figure 1 shows that the embodiment schematic flow sheet;
Figure 2 shows that embodiment reaction mechanism synoptic diagram;
Figure 3 shows that embodiment 3 scanning electron microscope (SEM) photographs.
Embodiment
For further understanding feature of the present invention, technique means and the specific purposes that reach, function, resolve the advantages and spirit of the present invention, by the present invention is further elaborated by the following examples.
The reaction mechanism of a kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material of the present invention following (the reaction process synoptic diagram is asked for an interview Fig. 1, and the reaction mechanism synoptic diagram is asked for an interview Fig. 2): (molecular structure signal)
Wherein RO-OR is initiator.
Initiator at first all is cleaved into elementary free radical, sees formula (1); Then this elementary free radical is grabbed the hydrogen atom on terpolymer EP rubber (EPDM) main chain, forms macromolecular radical EPDM, sees formula (2); Hydrogen atom on the two keys of macromolecular radical EPDM and MALEIC ANHYDRIDE (MAH) forms EPDM-g-MAH, sees formula (3); The amino condensation reaction of the anhydride group of EPDM-g-MAH and the end of （Fen Mo/Ke Li） Nylon11 in powder/granular form forms EPDM-g-MAH-g-PA11, sees formula (4) and formula (5).
The employed raw material of the embodiment of the invention is as follows:
（Fen Mo/Ke Li） Nylon11 in powder/granular form (PA11) is available from French Arkema company;
Terpolymer EP rubber (EPDM) is available from Dupont Tao Shi product (DuPont-Dow), trade mark NordelIP3745P;
2,5-dimethyl-2,5-di-t-butyl hexane peroxide (L-101) is available from U.S. Sigma-Aldrich company;
Dicumyl peroxide (DCP) is available from Chemical Reagent Co., Ltd., Sinopharm Group;
MALEIC ANHYDRIDE (MAH) is available from Chemical Reagent Co., Ltd., Sinopharm Group;
Organo montmorillonite (OMMT) is available from Zhejiang Feng Hong novel material limited-liability company, trade mark DK5.
Comparative example 1:
Place vacuum drying oven to carry out drying and processing （Fen Mo/Ke Li） Nylon11 in powder/granular form, the control oven temperature dry 4 hours, then is cooled to room temperature with （Fen Mo/Ke Li） Nylon11 in powder/granular form at 90 ℃.（Fen Mo/Ke Li） Nylon11 in powder/granular form with drying and processing places parallel double-screw extruder to melt extrude at last, granulation.Complete processing is as follows: the parallel double-screw extruder screw speed is 75r/min, 170 ℃ of district's temperature, 190 ℃ of two district's temperature, 195 ℃ of three district's temperature, 200 ℃ of four district's temperature, 200 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 195 ℃ of die head temperatures.
Comparative example 2:
Place vacuum drying oven to carry out drying and processing （Fen Mo/Ke Li） Nylon11 in powder/granular form, the control oven temperature is at 90 ℃, and dry 4 hours, EPDM placed vacuum drying oven to carry out drying and processing, and the control oven temperature dry 4 hours, then is cooled to room temperature with （Fen Mo/Ke Li） Nylon11 in powder/granular form and EPDM at 70 ℃.After at last （Fen Mo/Ke Li） Nylon11 in powder/granular form and EPDM being mixed by 70 weight parts, 30 weight parts respectively, place parallel double-screw extruder, and after side direction the 4th district of parallel double-screw extruder (totally eight districts) adds the OMMT of 5 weight parts, melt extrude granulation.Complete processing is as follows: the parallel double-screw extruder screw speed is 75r/min, 170 ℃ of district's temperature, 190 ℃ of two district's temperature, 195 ℃ of three district's temperature, 200 ℃ of four district's temperature, 200 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 195 ℃ of die head temperatures.
Embodiment 1:
A kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material is formed by the raw material cooperation of following weight part: 90 parts of （Fen Mo/Ke Li） Nylon11 in powder/granular forms (PA11), 10 parts of terpolymer EP rubbers (EPDM), 0.1 part of dicumyl peroxide (DCP), 1 part of MALEIC ANHYDRIDE (MAH), 5 parts of organo montmorillonites (OMMT).
The preparation method of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material may further comprise the steps:
(1), initiator dicumyl peroxide (DCP) and MALEIC ANHYDRIDE (MAH) are dissolved in the butanone, obtain mixing solutions, place for subsequent use;
(2), （Fen Mo/Ke Li） Nylon11 in powder/granular form is placed vacuum drying oven carry out drying and processing, the control oven temperature is at 90 ℃, dry 4 hours, EPDM places vacuum drying oven to carry out drying and processing, the control oven temperature dry 4 hours, then is cooled to room temperature with （Fen Mo/Ke Li） Nylon11 in powder/granular form and EPDM at 70 ℃, （Fen Mo/Ke Li） Nylon11 in powder/granular form and the EPDM that will carry out behind the drying and processing mix according to the above ratio, obtain blend;
(3), the mixing solutions in the step (1) is poured in the blend of （Fen Mo/Ke Li） Nylon11 in powder/granular form and EPDM, obtain premix, premix is positioned in the air, and the thinner butanone is volatilized away;
(4), the premix that mixes is placed parallel double-screw extruder, and after side direction the 4th district of parallel double-screw extruder (totally eight districts) adds OMMT, melt extrude granulation.Complete processing is as follows: the parallel double-screw extruder screw speed is 200r/min, 170 ℃ of district's temperature, 190 ℃ of two district's temperature, 195 ℃ of three district's temperature, 200 ℃ of four district's temperature, 200 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 195 ℃ of die head temperatures.
Embodiment 2:
A kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material is formed by the raw material cooperation of following weight part: 80 parts of （Fen Mo/Ke Li） Nylon11 in powder/granular forms (PA11), 20 parts of terpolymer EP rubbers (EPDM), 2,5-dimethyl-2,0.1 part of 5-di-t-butyl hexane peroxide (L-101), 1 part of MALEIC ANHYDRIDE (MAH), 5 parts of organo montmorillonites (OMMT).
The preparation method of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material may further comprise the steps:
(1), with initiator 2,5-dimethyl-2,5-di-t-butyl hexane peroxide (L-101) and MALEIC ANHYDRIDE (MAH) are dissolved in the acetone, obtain mixing solutions, place for subsequent use;
(2), （Fen Mo/Ke Li） Nylon11 in powder/granular form is placed vacuum drying oven carry out drying and processing, the control oven temperature is at 90 ℃, dry 4 hours, EPDM places vacuum drying oven to carry out drying and processing, the control oven temperature dry 4 hours, then is cooled to room temperature with （Fen Mo/Ke Li） Nylon11 in powder/granular form and EPDM at 70 ℃, （Fen Mo/Ke Li） Nylon11 in powder/granular form and the EPDM that will carry out behind the drying and processing mix according to the above ratio, obtain blend;
(3), the mixing solutions in the step (1) is poured in the blend of （Fen Mo/Ke Li） Nylon11 in powder/granular form and EPDM, obtain premix, premix is positioned in the air, and thinner acetone is volatilized away;
(4), the premix that mixes is placed parallel double-screw extruder, and after side direction the 4th district of parallel double-screw extruder (totally eight districts) adds OMMT, melt extrude granulation.Complete processing is as follows: the parallel double-screw extruder screw speed is 100r/min, 170 ℃ of district's temperature, 190 ℃ of two district's temperature, 195 ℃ of three district's temperature, 200 ℃ of four district's temperature, 200 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 195 ℃ of die head temperatures.
Embodiment 3:
A kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material is formed by the raw material cooperation of following weight part: 70 parts of （Fen Mo/Ke Li） Nylon11 in powder/granular forms (PA11), 30 parts of terpolymer EP rubbers (EPDM), 2,5-dimethyl-2,0.1 part of 5-di-t-butyl hexane peroxide (L-101), 1 part of MALEIC ANHYDRIDE (MAH), 5 parts of organo montmorillonites (OMMT).
The preparation method of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material may further comprise the steps:
(1), with initiator 2,5-dimethyl-2,5-di-t-butyl hexane peroxide (L-101) and MALEIC ANHYDRIDE (MAH) are dissolved in the acetone, obtain mixing solutions, place for subsequent use;
(2), （Fen Mo/Ke Li） Nylon11 in powder/granular form is placed vacuum drying oven carry out drying and processing, the control oven temperature is at 90 ℃, dry 4 hours, EPDM places vacuum drying oven to carry out drying and processing, the control oven temperature dry 4 hours, then is cooled to room temperature with （Fen Mo/Ke Li） Nylon11 in powder/granular form and EPDM at 70 ℃, （Fen Mo/Ke Li） Nylon11 in powder/granular form and the EPDM that will carry out behind the drying and processing mix according to the above ratio, obtain blend;
(3), the mixing solutions in the step (1) is poured in the blend of （Fen Mo/Ke Li） Nylon11 in powder/granular form and EPDM, obtain premix, premix is positioned in the air, and thinner acetone is volatilized away;
(4), the premix that mixes is placed parallel double-screw extruder, and after side direction the 4th district of parallel double-screw extruder (totally eight districts) adds OMMT, melt extrude granulation.Complete processing is as follows: the parallel double-screw extruder screw speed is 75r/min, 170 ℃ of district's temperature, 190 ℃ of two district's temperature, 195 ℃ of three district's temperature, 200 ℃ of four district's temperature, 200 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 195 ℃ of die head temperatures.
The scanning electron microscope (SEM) photograph (10000 times) of super-toughened nylon 11 nano composite materials of present embodiment gained has shown EPDM and the OMMT dispersing morphology in PA11 as shown in Figure 3 among the figure.As can be seen from Figure 3, section has obvious crazing-shear zone to produce, and phase interface becomes very fuzzy, and EPDM particle and OMMT particle are scattered in the matrix of （Fen Mo/Ke Li） Nylon11 in powder/granular form well, show as ductile rupture.
Embodiment 4:
A kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material is formed by the raw material cooperation of following weight part: 70 parts of （Fen Mo/Ke Li） Nylon11 in powder/granular forms (PA11), 30 parts of terpolymer EP rubbers (EPDM), 2,5-dimethyl-2,1 part of 5-di-t-butyl hexane peroxide (L-101), 4 parts of MALEIC ANHYDRIDE (MAH), 5 parts of organo montmorillonites (OMMT).
The preparation method of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, its step is with embodiment 3.
Embodiment 5:
A kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material is formed by the raw material cooperation of following weight part: 70 parts of （Fen Mo/Ke Li） Nylon11 in powder/granular forms (PA11), 30 parts of terpolymer EP rubbers (EPDM), 2,5-dimethyl-2,0.01 part of 5-di-t-butyl hexane peroxide (L-101), 0.1 part of MALEIC ANHYDRIDE (MAH), 5 parts of organo montmorillonites (OMMT).
The preparation method of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, its step is with embodiment 3.
Embodiment 6:
A kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material is formed by the raw material cooperation of following weight part: 70 parts of （Fen Mo/Ke Li） Nylon11 in powder/granular forms (PA11), 30 parts of terpolymer EP rubbers (EPDM), 2,5-dimethyl-2,0.1 part of 5-di-t-butyl hexane peroxide (L-101), 1 part of MALEIC ANHYDRIDE (MAH), 1 part of organo montmorillonite (OMMT).
The preparation method of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, its step is with embodiment 3.
Embodiment 7:
A kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material is formed by the raw material cooperation of following weight part: 70 parts of （Fen Mo/Ke Li） Nylon11 in powder/granular forms (PA11), 30 parts of terpolymer EP rubbers (EPDM), 2,5-dimethyl-2,0.1 part of 5-di-t-butyl hexane peroxide (L-101), 1 part of MALEIC ANHYDRIDE (MAH), 3 parts of organo montmorillonites (OMMT).
The preparation method of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, its step is with embodiment 3.
Below be comparative example and embodiment table look-up:
Table 1 comparative example and embodiment parts by weight of raw materials table look-up
The made sample of the various embodiments described above is carried out following performance test:
Tensile property: press the GB/T1042-1992 standard testing, rate of extension 50mm/min;
Impact property: press the GB/T1843-1996 standard testing, batten thickness is 3.2mm;
The mensuration of water-intake rate: water-intake rate is tested by GB1034-1998.It is the square (sample is thick in 25mm) of 50 ± 1mm that sample is cut out, then put into the dry 24 ± 1h of 50 ± 2 ℃ of baking ovens, in moisture eliminator, be cooled to room temperature and be weighed as m1, again sample is dipped in 23 ± 0.5 ℃ of distilled water, take out behind soaking time 24 ± 1h and the water of wiping rapidly specimen surface with the filter paper of cleaning, drying again the weighing sample be m
2Water-intake rate W
mCalculation formula be:
The mensuration of oil-absorption(number): batten is cut into the thin plate of 32mm * 10mm * 4.5mm, 60 ℃ lower dry 15 hours, claim that its weight is W
1, then be immersed in 60 ℃ the dimethylbenzene and take out rapid weighing W after 15 hours
2, W again weighed after under 80 ℃ dry 20 hours
3The calculation formula of oil-absorption(number):
Table 2 comparative example and embodiment performance table look-up
Comparative Examples 1 is pure PA11, and Comparative Examples 2 prepares the （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material for the ex situ increase-volume that adds organo montmorillonite (OMMT); Embodiment 1～3 is a kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, fixedly the weight ratio of initiator and MAH is 1:10, and the weight ratio of adjustment PA11 and EPDM, can find out when the addition of EPDM is 30 parts, normal temperature and the low temperature notched shock strength of nano composite material are the highest, and water-intake rate and oil-absorption(number) are minimum; Embodiment 4～7 is a kind of super tough green （Fen Mo/Ke Li） Nylon11 in powder/granular form nano composite material, fixedly the weight ratio of PA11 and EPDM is 70:30, and the addition of adjustment initiator, MAH and OMMT, can find out that the over-all properties of embodiment 3 nano composite materials will be got well compared to the over-all properties of embodiment 4～7 nano composite materials.
The embodiments of the invention flow process is referring to Fig. 1; The embodiments of the invention reaction mechanism is referring to Fig. 2; Embodiments of the invention 3 scanning electron microscope (SEM) photographs (10000 times) are referring to Fig. 3.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (7)
1. super-toughened nylon 11 nano composite materials is characterized in that, its raw material forms and weight part is:
55～95 parts of （Fen Mo/Ke Li） Nylon11 in powder/granular forms,
5～45 parts of terpolymer EP rubbers,
The weight part summation of （Fen Mo/Ke Li） Nylon11 in powder/granular form and terpolymer EP rubber is 100 parts,
0.01～1 part of initiator,
0.1～4 part of MALEIC ANHYDRIDE,
1～5 part of organo montmorillonite;
Described initiator is the organic superoxide, comprises hydroperoxide type, dialkyl class, peroxidation two acyl classes, peroxyesters, peroxy dicarbonates.
2. super-toughened nylon 11 nano composite materials according to claim 1 is characterized in that, described organic superoxide is the dicumyl peroxide, 2 in the dialkyl class, 5-dimethyl-2,5-di-t-butyl hexane peroxide.
3. a method for preparing each described super-toughened nylon 11 nano composite materials of claim 1～2 is characterized in that, may further comprise the steps:
(1), described weight part initiator and MALEIC ANHYDRIDE are dissolved in the thinner, obtain mixing solutions, place for subsequent use;
(2), place vacuum drying oven to carry out drying and processing described weight part （Fen Mo/Ke Li） Nylon11 in powder/granular form, the control oven temperature is at 80～100 ℃, dry 4～12 hours, described weight part terpolymer EP rubber places vacuum drying oven to carry out drying and processing, the control oven temperature dry 4～12 hours, then is cooled to room temperature with （Fen Mo/Ke Li） Nylon11 in powder/granular form and terpolymer EP rubber at 60～80 ℃, （Fen Mo/Ke Li） Nylon11 in powder/granular form and the terpolymer EP rubber that will carry out behind the drying and processing mix in proportion, and obtain blend;
(3), the mixing solutions in the step (1) is poured in the blend of （Fen Mo/Ke Li） Nylon11 in powder/granular form and terpolymer EP rubber, obtain premix, premix is positioned in the air, and thinner is volatilized away;
(4), the premix that mixes is placed parallel double-screw extruder, and after side direction the 4th district of parallel double-screw extruder adds organo montmorillonite, melt extrude, granulation, and get final product;
Complete processing is as follows: the parallel double-screw extruder screw speed is 25～200r/min, 150～190 ℃ of one district's temperature, 170～210 ℃ of two district's temperature, 180～230 ℃ of three district's temperature, 180～230 ℃ of four district's temperature, 180～230 ℃ of five district's temperature, 180～230 ℃ of six district's temperature, 180～230 ℃ of seven district's temperature, 180～230 ℃ of die head temperatures.
4. preparation method according to claim 3 is characterized in that, may further comprise the steps:
(1), described weight part initiator and MALEIC ANHYDRIDE are dissolved in the thinner acetone, obtain mixing solutions, place for subsequent use;
(2), place vacuum drying oven to carry out drying and processing described weight part （Fen Mo/Ke Li） Nylon11 in powder/granular form, the control oven temperature is at 80～100 ℃, dry 4～8 hours, described weight part terpolymer EP rubber places vacuum drying oven to carry out drying and processing, the control oven temperature dry 4～8 hours, then is cooled to room temperature with （Fen Mo/Ke Li） Nylon11 in powder/granular form and terpolymer EP rubber at 60～80 ℃, （Fen Mo/Ke Li） Nylon11 in powder/granular form and the terpolymer EP rubber that will carry out behind the drying and processing mix in proportion, and obtain blend;
(3), the mixing solutions in the step (1) is poured in the blend of （Fen Mo/Ke Li） Nylon11 in powder/granular form and terpolymer EP rubber, obtain premix, premix is positioned in the air, and thinner acetone is volatilized away;
(4), the premix that mixes is placed parallel double-screw extruder, and after side direction the 4th district of parallel double-screw extruder adds organo montmorillonite, melt extrude, granulation, and get final product;
Complete processing is as follows: the parallel double-screw extruder screw speed is 25～100r/min, 170～190 ℃ of one district's temperature, 190～200 ℃ of two district's temperature, 190～200 ℃ of three district's temperature, 190～200 ℃ of four district's temperature, 190～200 ℃ of five district's temperature, 190～200 ℃ of six district's temperature, 190～200 ℃ of seven district's temperature, 190～200 ℃ of die head temperatures.
5. preparation method according to claim 3 is characterized in that, described thinner is acetone, butanone.
6. preparation method according to claim 3 is characterized in that, described screw rod is shaped as single thread; The ratio L/D of spiro rod length L and diameter D is 20～60.
7. preparation method according to claim 3 is characterized in that, described screw rod must have more than one gear block district, and described screw rod must have more than one left-hand thread district.
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| CN112126219A (en) * | 2020-09-27 | 2020-12-25 | 贵州森远增材制造科技有限公司 | Nylon raw material for medical nontoxic dust-free 3D printing isolation eye shield and manufacturing method thereof |
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| CN112126219A (en) * | 2020-09-27 | 2020-12-25 | 贵州森远增材制造科技有限公司 | Nylon raw material for medical nontoxic dust-free 3D printing isolation eye shield and manufacturing method thereof |
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