CN101475745B - Nano composite material synthetic compound and its production method - Google Patents
Nano composite material synthetic compound and its production method Download PDFInfo
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- CN101475745B CN101475745B CN2008101894985A CN200810189498A CN101475745B CN 101475745 B CN101475745 B CN 101475745B CN 2008101894985 A CN2008101894985 A CN 2008101894985A CN 200810189498 A CN200810189498 A CN 200810189498A CN 101475745 B CN101475745 B CN 101475745B
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- 239000000463 material Substances 0.000 title claims abstract description 55
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- 239000000203 mixture Substances 0.000 claims abstract description 34
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 claims abstract description 21
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 11
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention relates to a nano composite material compound and a manufacturing method thereof, more specifically to a nano composite material compound used for manufacturing a multi-layer container having excellent durability, transparency, gas barrier property and strip resistance, and a manufacturing method thereof. The invention is characterized in (a) adding relative 10 parts by weight of mixture and 0.5-10 parts by weight of phyllosilicate organically treated into a mixture of 60wt%-99wt% of polyamide resin MXD6 containing metaxylol or MXDI containing metaxylol and m-phthalic acid, and 40wt%-1wt% of more than one of nylon 6, nylon66, nylon 6/12, 6I/6T and copolymers thereof.
Description
Technical field
The present invention relates to nano composite material and preparation method thereof, more specifically relate to nano composite material that is used to make laminated vessel and preparation method thereof with excellent durability, the transparency, gas barrier property, antistripping property.
Background technology
The existing container of being processed by the PET resin is owing to have good formability, the transparency, chemical resistance, thermotolerance, physical strength etc., so be widely used as film or the container etc. of wrap food, beverage, medicine.But because the gas barrier property of said PET resin is limited, its as the application in field that gas barrier property is had relatively high expectations such as the beverage (coffee, tea) of tomato composition goods (tomato-sauce, tomato juice), juice (fruit juice and dish juice), alcohol soda pop (beer, malt drink, champagne) and use heating container in be restricted.
One of scheme that solves said problem is the manufacturing laminated vessel.Promptly be manufactured on and form the laminated vessel of one deck barrier material in the thermoplastic polyester layer, with the maximization gas barrier property as the middle layer.
Day disclosure special permission bulletin discloses for clear 56-64839 number outer and internal layer is a pet layer, and the multilayered structure prefab that the middle layer is made up of the polyamide resin that contains the m-xylene base reaches the method through two-way stretch blow molding manufacturing laminated vessel.MXD6 nylon is owing to the fusing point of its fusing point near PET, through showing good formability with polyester combination.Again because the free temperature of two resins is close, so when draw blow molding, set the forming temperature that is fit to easily.
Although (MXD6 Aegis) waits the laminated vessel of processing more excellent than single-layer PET container gas barrier property, because when it is used for said high-grade drink to gas sensitization (being beverages such as beer, coffee, tea) to use the conventional choke resin that uses; Need to increase the content of the choke resin that uses; To strengthen the gas barrier property of laminated vessel, cause cost to increase, also can expedite the emergence of the problem of cycling and reutilization; And increase along with the barrier resins amount; Cause amalgamation to reduce, (MDX6, Aegis) the antistripping property with pet layer weakens thereby cause barrier resins.
Therefore; When using said patent disclosed method to make prefab; The tackiness of polyester layer and aramid layer is relatively poor, and the formation of prefab is not in good state, and causes the final laminated vessel weather resistance variation that is shaped; Thereby take place separating of polyester layer and aramid layer, and the formability variation of laminated vessel.Moreover, because a little less than its barrier, thereby need to use a large amount of barrier materials to keep the gas barrier property of the beverage that gas barrier property is had relatively high expectations, so cost is higher.
Summary of the invention
The problem that the invention quasi-solution is determined
The present invention is intended to address the above problem, and it is low both to aim to provide in laminated vessel usage quantity, also can keep good gas barrier property, also is difficult for from what other layer peeled off being used to nano composite material for preparing barrier material and preparation method thereof.
The method of dealing with problems
The nano composite material with good antistripping property that is used to make laminated vessel of the present invention is characterised in that, MXDI and 40wt%-1wt% that 60wt%-99wt% is contained the polyamide resin MXD6 of m-xylene base or contains m-xylene base and m-phthalic acid are selected from and add the layered silicate through organising and handling that relative 100 weight part mixtures close the 0.5-10 weight part in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof in more than one blended mixtures.
Another preferred feature of the present invention is; The said layered silicate of handling through organising is that organism is embedded layered silicate, and wherein said organism is selected from the organism that contains the functional group that is selected from quaternary ammonium salt, monovalence phosphorus, PHENRAMINE MALEATE, SUMATRIPTAN SUCCINATE, acrylate, benzylic hydrogens and oxazolinyl more than one.
Another preferred feature of the present invention is, layered silicate is selected from XMP 4, hectorite, beidellite, saponite, nontronite, mica, the fluoronated mica more than one.
The method for preparing nano composite material of the present invention comprises: the MXDI and the 40wt%-1wt% that i) 60wt%-99wt% are contained the polyamide resin MXD6 of m-xylene base or contain m-xylene base and m-phthalic acid are selected from more than one blended mixtures dry 4-5 hour drying stage to water cut 50-400pprn under 80-90 ℃ of condition in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof; Ii), make said mixture and layered silicate blended mix stages through organising and handling to the said layered silicate that in dry mixture, adds the 0.5-10 weight part through organising and handling; And iii) use tube machine to process the preparatory phase of the nano composite material that contains layered silicate with said mixture with through the layered silicate of the processing that organises.
Another preferred feature of the present invention is that said water cut is 50-200ppm.
Below specify the present invention.
Nano composite material of the present invention is characterised in that, MXDI and 40wt%-1wt% that 60wt%-99wt% is contained the polyamide resin MXD6 of m-xylene base or contains m-xylene base and m-phthalic acid are selected from and add the layered silicate through organising and handling that relative 100 weight part mixtures close the 0.5-10 weight part in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof in more than one blended mixtures.
MXD6 is the polyamide resin that contains the m-xylene base, processes by metaxylylene diamine and lipid acid, since good to the gas barrier property of gases such as oxygen, carbonic acid gas, water vapour, be widely used in film for packaging and laminated vessel.Again because the MXD-6 resin shows the consistency good with vibrin, and its second-order transition temperature, fusing point, crystallization velocity be near polyester, therefore the resin for being suitable for using with the vibrin combination.
MXDI is the polymer resin that contains m-xylene base and m-phthalic acid, processes MXD6 by MXDI and lipid acid that metaxylylene diamine and m-phthalic acid reaction generate.
Said MXD6 or MXDI are resins well known in the art, can prepare or be purchased acquisition by means commonly known in the art, and its weight percent is 60wt%-99wt%.If the content of MXD6 or MXDI surpasses 99wt% in the nano composite material; Then uncontrollablely raise by the percent crystallinity due to the organising of layered silicate; Cause making that the percent crystallinity in the IR heat-processed sharply raises in bottle industry, thereby reduce the weather resistance and the stability of the final container that is shaped.In contrast, if when the content of MXD6 or MXDI is lower than 60wt%, then since in the composition ratio of aromatics nylon reduce, cause gas barrier property sharply to reduce.
Through the layered silicate of handling that organises is thick 1nm, the clay of long 500-1000nm left and right sides nanometer scale.Layered silicate is because interlayer gravitation is strong; Cause being difficult to it is peeled off, is scattered in macromolecule resin; For addressing this problem, it can be through organising between the laminate structure that the low-molecular-weight agent that organises is embedded silicate, thereby obtain the layered silicate handled through organising.Layered silicate has XMP 4, hectorite, beidellite, saponite, nontronite, mica, fluoronated mica etc., preferred choosing wherein more than one; Organism is preferably the organism that contains the functional group that is selected from quaternary ammonium salt, monovalence phosphorus, PHENRAMINE MALEATE, SUMATRIPTAN SUCCINATE, acrylate, benzylic hydrogens and oxazolinyl.
Said layered silicate through the processing that organises can prepare or be purchased acquisition by means commonly known in the art, and its weight percent is that the said mixture of relative 100 weight parts closes the 0.5-10 weight part.If the laminar silicic acid salts contg of handling through organising surpasses 10 weight parts of nano composite material; Embedding formula thin layer between then the layered silicate of nanometer scale can not peel off and in macromolecule resin, form; Thereby cause transparency to descend by the percent crystallinity rising, instead can not guarantee the gas barrier property of aspiration level.And if be lower than 1 weight part, then be difficult to obtain effect of the present invention.
Polymeric amide is meant the synthetic macromolecule that the monomer that constitutes its main chain is formed by connecting carboxamido-group, will be called nylon by the polymeric amide that the unit is mainly aliphatic monomers that constitutes that carboxamido-group connects.
Nylon is divided into nylon mn and nylon m again, and the former is the situation that dicarboxylicacid and diamine reactant generate carboxamido-group, and wherein that diamines is contained carbonatoms is expressed as m, and the carbonatoms that dicarboxylicacid is contained is expressed as n.In addition, carboxamido-group also can be formed by the monomer that has amino and carboxyl concurrently, and be expressed as m with monomer institute carbon atom quantity this moment, and this kind polymeric amide is called nylon m.
Through nylon 6 is processed in the caprolactam ring-opening polymerization.Prepare nylon 66 through polycondensation by cyclohexyl diamine and lipid acid.Through nylon 12 is processed in the laurolactam ring-opening polymerization.Polycondensation through by cyclohexyl diamine, m-phthalic acid and terephthalic acid prepares 6I/6T.Inferior nylon raw material by more than 2 kinds prepares multipolymer, and said multipolymer is owing to crystallinity reduces, thereby fusing point reduces, and the transparency raises.
The laminated vessel that comprises the interlayer that is made up of said nano composite material of the present invention is characterised in that and comprises: (a) comprise MXDI and 40wt%-1wt% that 60wt%-99wt% is contained the polyamide resin MXD6 of m-xylene base or contains m-xylene base and m-phthalic acid and be selected from nylon 6; Nylon 66; Nylon 6/12; Add in more than one blended mixtures in 6I/6T and the multipolymer thereof that relative 100 weight part mixtures close the layered silicate of handling through organising of 0.5-10 weight part and the interlayer of the nano composite material processed; And (b) polyester resin layer more than one deck that the one or both sides of said interlayer form.
The laminated vessel that comprises the interlayer that contains said nano composite material of the present invention is characterised in that, is included in the above polyester resin layer of one deck of the one or both sides formation of said interlayer.
Vibrin is as the dicarboxylicacid composition with terephthalic acid; With terepthaloyl moietie as the dihydroxyl composition; The resin of processing through esterification (or transesterify), liquid polycondensation and solid-phase polymerization well known in the art; Be selected from polyethyleneterephthalate, polytrimethylene terephthalate, polybutylene terephthalate, Polyclear N 100 or its multipolymer more than one, be more preferably polyethyleneterephthalate.
Said laminated vessel is to be the center with said interlayer, engages the form of polyester resin layer more than 1 layer at its one or both sides, preferably is the center respectively engages one deck vibrin on the two sides 3-tier architecture with the interlayer.
The method for preparing nano composite material of the present invention comprises:
I) MXDI and the 40wt%-1wt% that 60wt%-99wt% are contained the polyamide resin MXD6 of m-xylene base or contain m-xylene base and m-phthalic acid are selected from more than one blended mixtures dry 4-5 hour drying stage to water cut 50-400ppm under 80-90 ℃ of condition in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof;
Ii), make said mixture and layered silicate blended mix stages through organising and handling to the said layered silicate that in dry mixture, adds the 0.5-10 weight part through organising and handling; And
Iii) use tube machine to process the preparatory phase of the nano composite material that contains layered silicate with said mixture with through the layered silicate of the processing that organises.
In drying stage, if the water cut of nylon composite is lower than 50ppm, then thermolysis takes place in nylon in extruding the course of processing; And if water cut is higher than 400ppm, then extrudes and take place in the course of processing to cause preparing generation problem in the laminated nm-silicate composite material by the hydrolysis due to the water.
If dry nylon resin was less than 4 hours under 80-90 ℃ of condition; Then can't reach the suitable water cut about 50ppm; Cause in extruding the course of processing, layered silicate appropriateness in macromolecule resin is peeled off with interlayer embed, also quicken thermolysis.In contrast, if dry above 5 hours under 80-90 ℃ of condition, the aging of nylon resin itself being taken place then, therefore will observe said drying conditions.
In mix stages; If the content of nano composite material surpasses 10 weight parts; Embedding formula thin layer between then the layered silicate of nanometer scale can not peel off and in macromolecule resin, form, thus cause transparency to reduce by the percent crystallinity rising, instead can not guarantee the gas barrier property of aspiration level.And if be lower than 1 weight part, then be difficult to obtain effect of the present invention.
Tube machine is a twin screw extruder machine, and L/D is greater than 35 (L: spiro rod length, D: screw diameter); For peeling off the layered silicate of nanometer scale, increase its dispersity between MXD6 and MXDI, need comprise kneading piece and the inverse block more than 2 more than 4.Also to extruder rate be set at more than the 300RPM, so that nano layered silicate that peels off and MXD6 or MXDI are fully mixing.
Set the temperature of tube machine like table 1.With after nano layered silicate mixes in tube machine, make extrudate pass through profiled sheeting MXD6 or MXDI, in tank, cool off again, and finally process nano composite material.
Table 1
The laminated vessel that comprises the interlayer that contains said nano composite material of the present invention is characterised in that, is included in the above polyester resin layer of one deck of the one or both sides formation of said interlayer.
Vibrin is as the dicarboxylicacid composition with terephthalic acid; With terepthaloyl moietie as the dihydroxyl composition; The resin of processing through esterification (or transesterify), liquid polycondensation and solid-phase polymerization well known in the art; Be selected from polyethyleneterephthalate, polytrimethylene terephthalate, polybutylene terephthalate, Polyclear N 100 or its multipolymer more than one, be more preferably polyethyleneterephthalate.
Said laminated vessel is to be the center with said interlayer, engages the form of the above polyester resin layer of one deck at its one or both sides, preferably is the center respectively engages one deck vibrin on the two sides 3-tier architecture with the interlayer.
The method of manufacture that comprises the laminated vessel of the interlayer that is made up of nano composite material of the present invention is the method that comprises fusion, the injection of multilayer prefab, multilayer prefab reheat and the manufacturing laminated vessel in blow molding stage, comprising:
I) said nano composite material is maintained 50-400ppm in 80～90 ℃ of drying machine inner dryings 4-5 hour to water cut before injection, more preferably maintain the pretreatment stage of the drying nano matrix material of 50-200ppm; And
Ii) in the course of processing of multilayer prefab; With the injection temperature of 290-295 ℃ (polyester bucket) and 270-285 ℃ (nano composite material) the said resin of fusion separately, and respectively with the spraying pressure of 1300-1900psi (polyester) and 1000-1200psi (nano composite material) stage of reaction-injection moulding multilayer prefab simultaneously.
Dewatered nano composite material and vibrin are transported to from drying machine in the funnel of injector, quantitatively supply in the reciprocating screw reaction-injection moulding device, after fusion plasticising, make its reaction-injection moulding in mould.Need certain hour owing to accomplish injection, with the resin of residual a great deal of, absorb moisture again in the injector funnel, preferably it is incubated in more than 100 ℃, more preferably it is incubated in more than 160 ℃ for preventing it.And the interior temperature of injector funnel that will deliver nano composite material is controlled at more than 70 ℃, thereby prevents to be raise by the percent crystallinity due to the moisture.
If the water cut of nano composite material is lower than 50ppm; Then in the melting process of the basal component MXD6 of nano composite material, take place by the loss due to the friction; And if water cut is increased to 400ppm when above; Moisture in the nano composite material plays the effect of crystallization nucleating agent, makes the prefab excessive crystallization of reaction-injection moulding, peels off when causing blow molding.
If the temperature of bucket is too high when reaction-injection moulding; Then take place spraying the back prefab, to cool off incomplete possibility higher, increases the crystallinity of prefab, thereby expedite the emergence of the problem of peeling off after the blow molding; If the temperature of bucket is low excessively; Then appropriately fusion of macromolecule resin is sheared viscous thereby over-drastic takes place, and causes carrying out continuous injection and is shaped.
Besides spraying pressure if the spraying pressure of PET is lower than 1300psi, then can not form the prefab of target weight and model, and " short penetrating " phenomenon promptly takes place; And if spraying pressure is higher than 1900psi, then, causes spraying and compare the more PET of volume of jet particle size, thereby cause " bar " quality problems such as (bar) because spraying pressure is excessive.The position of prefab internal portioning layer and thickness are by the speed decision of the interlayer of relative pet layer.Thus, when the spraying pressure of interlayer is excessive or too small, be difficult to appropriately regulate obstruct speed, thereby be difficult to the position of interlayer from being adjusted to below the support of prefab below the joint line of bottom.
The present invention has used Kostec48 die cavity multiple nozzle spraying former (Fig. 2).The multiple nozzle spraying device be utilize 2 screw rods with 2 kinds of polyester and as the nano composite material of barrier resins simultaneously with the open intravital shaping system in said chamber that is ejected into, it uses following reaction-injection moulding condition to make the preformed articles prefab.As shown in Figure 2, prefab is the structure that comprises between polyester outer layer as the internal layer of the nano composite material of barrier material.Table 2 has been listed the reaction-injection moulding condition of multiple nozzle spraying former.
Table 2
Use prefab heating unit shown in Figure 3 to reach 104 ℃ with the temperature of heater heats to multilayer prefab according to the prefab of above-mentioned condition reaction-injection moulding, through the 1st pressure 9bar, the condition of the 2nd pressure 40bar is carried out draw blow molding.The stretch ratio of keeping transverse axis is more than 2 times, and the stretch ratio of the longitudinal axis is more than 4 times.
The invention effect
The laminated vessel that contains nano composite material of the present invention is compared the laminated vessel that uses existing known barrier resins to make, and gas barrier property and antistripping property improve, thereby have good weather resistance and morphological stability.In addition,, therefore do not expedite the emergence of the problem of cycling and reutilization yet, and have the competitive power on the price, and have the advantage that to use existing injection/blowing processing units etc. owing to can reduce the usage quantity of barrier resins.Therefore applicable to the beer container of dissolving carbonic acid, require the coffee of hotness, the heating container of tea, the container of oxygen beverage etc.
The accompanying drawing summary
Fig. 1 is shown the cyclogenic ultrathin section(ing) photo of dispersiveness of the nano silicate of the shaping print that affirmation obtains through embodiments of the invention and Comparative Examples;
Fig. 2 shows the mode chart of Kortec 48 die cavity multilayer spray devices;
Fig. 3 shows the mode chart of prefab heating unit.
The embodiment of invention
Embodiment that following basis is concrete and Comparative Examples more specify formation of the present invention and effect, but these embodiment only more definitely understand the present invention auxiliary, are not to be intended to limit scope of the present invention.
Embodiment
The degree of scatter of the nano composite material that following evaluation is produced according to the present invention and the layered silicate of laminated vessel and weather resistance (spalling improvement), gas barrier property.
1) to the evaluation of the dispersiveness of the nano material of nano composite material
Use the cyclogenic ultrathin sectioning will process the print of 30 μ m size, and use FE-TEM to measure the nano silicate dispersion of particles degree in the MXD6 resinous substrates through the nano composite material resin that extrudes processing.
2) to the crystalline evaluation of prefab interlayer
The prefab of reaction-injection moulding bottom is cut off, utilize X ray according to crystallite size and intermolecular distance evaluation percent crystallinity after obtaining the print of interlayer.
3) DSC of mensuration prefab interlayer
Estimate crystallization according to the fusing point Tm that uses DSC detected maximum value definition by the absorption peak due to the crystallization dissolving in process with from the difference of molten state crystallized temperature Tc2 of detected maximum value definition by the emission peak due to the crystallization with 10 ℃/minute cooling rate refrigerative process with 20 heat-up rate heating.
4) to the evaluation of prefab interlayer mist degree
To cut off through the prefab of reaction-injection moulding bottom, obtain the mist degree of measuring print behind the print of interlayer.
5) weigh down the bottle experiment
After will highly falling from 50cm through the laminated vessel of blow molding, detect laminated vessel and whether peel off.
6) detect the oxygen permeability
After will placing the device (Mocon company, OX-TRAN 2/20) of measuring the oxygen permeability to go up through the laminated vessel of blow molding, at 23 ℃, stablize 24 hours with nitrogen under the temperature of 50RH% after, measure the oxygen permeability when the oxygen transit dose reaches equilibrium state.
7) permeability of detection carbonic acid gas
To place device (the Mocon company that measures the carbonic acid gas permeability through the laminated vessel of blow molding; PermatranC 4/41) go up after; Use plastic lousing at outside 100% carbon dioxide atmosphere that forms of laminated vessel; And, stablize laminated vessel after inner 24 hours with nitrogen under the temperature of 50RH% at 23 ℃, measure the carbonic acid gas permeability when the carbonic acid gas of multilayer external container sees through internal tank and reaches equilibrium state.
Embodiment and Comparative Examples
Polyamide resin 90 ℃ of dryings after 4 hours, is joined the polymeric amide and the layered silicate of the amount of kind as shown in table 3 in the whisking appliance, stir, carry out pre-treatment to encapsulate nano layered silicate at polyamide surface with the speed of 50rpm.It is 35 delivery screw rod that the resin of preparation is used L/D, under 245 ℃ of temperature condition, with the processing of the extruder rate shown in the table 3, makes extrudate pass through profiled sheeting, in tank, cools off again, finally processes nano composite material.
Selected intrinsicviscosity is that the polyethyleneterephthalate of 0.8dl/g is following dry 4 hours in 160 ℃; The nano composite material resin of the ratio of components shown in the dry following table uses the said dry resin of crossing so that the content of nano composite material reaches 7% reaction-injection moulding multilayer prefab.
Make the surface temperature of multilayer prefab reach 104 ℃ with heater heats, with the 1st pressure 9bar, the condition draw blow molding of the 2nd pressure 40bar.
Table 3
Shown that layered silicate flakes off into the nano composite material phase, thereby be scattered in the state (embodiment) in the MXD6 resinous substrates; Layered silicate is not dispersed in the Comparative Examples 3 in the polymer, because when using nano composite material shaping multilayer bottle, gas barrier property synergy is very little, and layered silicate plays the effect of crystallization nucleating agent, thereby becomes the reason that the multilayer bottle peels off.
Table 4. crystal analysis/DSC/ mist degree
Annotate:
The crystallite size of C.S
nanometer composite layer; Percent crystallinity is high more, and this value is big more.
Distance between the molecular chain of D002
nanometer composite layer; Orientation degree (percent crystallinity) is high more, and this value is big more.
Tm-Tc2: because in the general reaction-injection moulding process, temperature head is more little, crystallization velocity is fast more, thereby owing to form crystallization easily, percent crystallinity is high.
As above shown in the table, along with the difference of Tm-Tc2 reduces the tensility variation during blow molding, thereby the spalling variation of container after the blow molding.
The present invention confirms, when the exploitation nano composite material, time of drying that can be through regulating barrier material is with temperature condition and regulate injection conditions and improve the problem (weakness of laminated vessel) of peeling off, thus the weather resistance of improvement container.
Table 5 Gas permeability/antistripping property
| Oxygen-barrier property (cc/pack.day) | Carbonic acid gas barrier (cc/pack.day) | The experiment (peel off/all sample) of falling | |
| Embodiment 1 | 0.0045 | 0.432 | 0/5 |
| Embodiment 2 | 0.0051 | 0.466 | 1/5 |
| Embodiment 3 | 0.0046 | 0.421 | 0/5 |
| Embodiment 4 | 0.0049 | 0.443 | 0/5 |
| Embodiment 5 | 0.0044 | 0.423 | 1/5 |
| Embodiment 6 | 0.0043 | 0.453 | 0/5 |
| Comparative Examples 1 | 0.0061 | 0.782 | 0/5 |
| Comparative Examples 2 | 0.0070 | 0.912 | 4/5 |
| Comparative Examples 3 | 0.0066 | 0.872 | 3/5 |
| Comparative Examples 4 | 0.0075 | 0.977 | 1/5 |
Although Comparative Examples 1 has good antistripping property, gas barrier property is not good.The container that can have good antistripping property and gas barrier property according to the formation manufacturing of said exploitation.
Claims (7)
1. be used to make the nano composite material of the good transparency of having of laminated vessel and antistripping property; It is characterized in that MXDI and 40wt%-1wt% that 60wt%-99wt% is contained the polyamide resin MXD6 of m-xylene base or contains m-xylene base and m-phthalic acid are selected from and add the layered silicate through organising and handling that relative 100 weight part mixtures close the 0.5-10 weight part in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof in more than one blended mixtures.
2. the nano composite material that is used to make the good transparency of having of laminated vessel and antistripping property of claim 1; It is characterized in that; The said layered silicate of handling through organising is that organism is embedded layered silicate, and wherein said organism is selected from the organism that contains the functional group that is selected from quaternary ammonium salt, monovalence phosphorus, PHENRAMINE MALEATE, SUMATRIPTAN SUCCINATE, acrylate, benzylic hydrogens and oxazolinyl more than one.
3. the nano composite material that is used to make the good transparency of having of laminated vessel and antistripping property of claim 2; It is characterized in that layered silicate is selected from XMP 4, hectorite, beidellite, saponite, nontronite, mica, the fluoronated mica more than one.
4. the method for preparing nano composite material is characterized in that comprising:
(i) MXDI and the 40wt%-1wt% that 60wt%-99wt% are contained the polyamide resin MXD6 of m-xylene base or contain m-xylene base and m-phthalic acid are selected from more than one blended mixtures dry 4-5 hour drying stage to water cut 50-400ppm under 80-90 ℃ of condition in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof;
(ii),, make said mixture and layered silicate blended mix stages through organising and handling to the said layered silicate that in dry mixture, adds the 0.5-10 weight part through organising and handling with respect to the said mixture of 100 weight parts; And
(iii) use tube machine to process the preparatory phase of the nano composite material that contains layered silicate with said mixture with through the layered silicate of the processing that organises.
5. the method for preparing nano composite material of claim 4; It is characterized in that; The said layered silicate of handling through organising is that organism is embedded layered silicate, and wherein said organism is selected from the organism that contains the functional group that is selected from quaternary ammonium salt, monovalence phosphorus, PHENRAMINE MALEATE, SUMATRIPTAN SUCCINATE, acrylate, benzylic hydrogens and oxazolinyl more than one.
6. the method for preparing nano composite material of claim 5 is characterized in that, layered silicate is selected from XMP 4, hectorite, beidellite, saponite, nontronite, mica, the fluoronated mica more than one.
7. the method for preparing nano composite material of claim 4 is characterized in that, said water cut is 50-200ppm.
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