CN108587079A - A kind of modified poly ester composite material and preparation method - Google Patents
A kind of modified poly ester composite material and preparation method Download PDFInfo
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- CN108587079A CN108587079A CN201810281236.5A CN201810281236A CN108587079A CN 108587079 A CN108587079 A CN 108587079A CN 201810281236 A CN201810281236 A CN 201810281236A CN 108587079 A CN108587079 A CN 108587079A
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- C08K3/28—Nitrogen-containing compounds
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- 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
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention belongs to polymer composites technical fields, specifically provide a kind of modified poly ester composite material.Modified poly ester composite material provided by the invention, is prepared by the raw material including following mass parts：100 parts of polyester raw materials and 0.5~6 part of metal organic salt intercalated houghite.It include metal organic salt intercalated houghite in modified poly ester composite material provided by the invention, wherein, metal organic salt is combined generation by organic anion with the metal cation of hydrotalcite layers, make organic anion intercalation and hydrotalcite layers, the compatibility for promoting hydrotalcite and polyester, makes hydrotalcite can be uniformly distributed in polyester, and as out-phase nucleus, crystallizing polyester is induced, the crystallization time of polyester is shortened.Embodiment the result shows that, modified poly ester composite material provided by the invention is under 220 DEG C of isothermy, and crystalline rate is up to 10~30min.
Description
Technical field
The invention belongs to polymer composites technical field, more particularly to a kind of modified poly ester composite material and its preparation
Method.
Background technology
Polyester is that a kind of polymer, this kind of polymer made of polyalcohol and polyacid polycondensation are thermoplastic materials, can
To be processed into fiber, film and plastic products.Currently used polyester material contains benzene ring structure more, and phenyl ring is formed with ester group
Rigid conjugated system make polyester have good mechanical performance, hot property and chemical resistance, can be used as product packaging film,
Agricultural film, battery diaphragm or seperation film use, and have fabulous market application value.On the other hand, phenyl ring is formed rigid with ester group
Property conjugated system can also hinder the movement of molecule segment, reduce the activity of molecule segment, crystallization rate is slower, and then leads to polyester
For material when preparing each based article, molding cycle is longer, affects application of the polyester as engineering material.
Invention content
In order to overcome the deficiencies of the prior art, the present invention provides a kind of modified poly ester composite material and preparation method, this hair
When in use, energy rapid crystallization shortens the molding cycle of modified poly ester composite material to the modified poly ester composite material of bright offer.
In order to achieve the above object, the present invention provides the following technical solutions：
The present invention provides a kind of modified poly ester composite materials, are prepared by the raw material including following mass parts：100 parts
Polyester raw material and 0.5~6 part of metal organic salt intercalated houghite.
Preferably, the polyester raw material includes polyethylene terephthalate, polyarylate, polypropylene or poly- terephthaldehyde
Sour fourth diester.
Preferably, the metal organic salt intercalated houghite include hydrotalcite and by electrostatic interaction intercalation in the neatly
Metal organic salt between rock layers；The metal organic salt includes metal cation and organic anion.
Preferably, the preparation method of the metal organic salt intercalated houghite includes the following steps：
(a) Organic Sodium Salt, alkali and water are mixed, obtains Organic Sodium Salt aqueous solution；The quality of the Organic Sodium Salt, alkali and water
Than being 1:(0.4~0.8):(18~30)；
(b) the Organic Sodium Salt aqueous solution that the step (a) obtains is mixed with polyvalent metal saline solution, is carried out compound anti-
It answers, obtains metal organic salt intercalated houghite；
Metal cation in the multivalent metal salt includes divalent metal and trivalent metal cation, and described two
The molar ratio of valence metal cation and trivalent metal cation is 1~3:1.
Preferably, the Organic Sodium Salt includes in odium stearate, neopelex and dodecyl sodium sulfate
It is one or more.
Preferably, the divalent metal includes magnesium ion, zinc ion or calcium ion；The trivalent metal cation
Including aluminium ion, iron ion or chromium ion.
Preferably, the corresponding metal salt of the divalent metal includes magnesium salts, zinc salt or calcium salt；
The magnesium salts includes magnesium chloride, magnesium nitrate or magnesium sulfate；The zinc salt includes zinc chloride, zinc nitrate or zinc sulfate；
The calcium salt includes calcium chloride or calcium nitrate；
The corresponding metal salt of the trivalent metal cation includes aluminium salt, molysite or chromic salts；
The aluminium salt includes aluminium chloride, aluminum nitrate or aluminum sulfate；The molysite includes ferric nitrate, ferric sulfate or iron chloride；
The chromic salts includes chromium trichloride or chromic nitrate.
The present invention provides the preparation methods of modified poly ester composite material described in above-mentioned technical proposal, include the following steps：
(1) polyester raw material is dissolved in organic solvent, obtains polyester liquid；Temperature >=135 DEG C of the dissolving；
(2) polyester liquid that the step (1) obtains is mixed with metal organic salt intercalated houghite, heating is modified
Reaction obtains modified poly ester composite material after cooling；The mass ratio of the metal organic salt intercalated houghite and polyester raw material is
0.5~6:100.
Preferably, the quality of step (1) polyester raw material and the volume ratio of organic solvent are 1g:15~30mL.
Preferably, the temperature of modified-reaction is 135~145 DEG C in the step (2), and the time of the modified-reaction is 50
~80min.
The present invention provides a kind of modified poly ester composite material, is prepared by the raw material including following mass parts：100 parts poly-
Ester raw material and 0.5~6 part of metal organic salt intercalated houghite.Modified poly ester composite material provided by the invention is prepared in raw material
Including metal organic salt intercalated houghite, wherein hydrotalcite can be promoted and gather by being connected to the metal organic salt of hydrotalcite layers
The compatibility of ester, makes hydrotalcite can be uniformly distributed in polyester, and as out-phase nucleus, induces crystallizing polyester, shortens polyester
Crystallization time.Embodiment the result shows that, modified poly ester composite material provided by the invention under 220 DEG C of isothermy, knot
Brilliant rate is up to 10~30min；And the gas barrier properties and tensile property of modified poly ester composite material have and obviously carry relative to polyester
It rises.
Description of the drawings
Fig. 1 is the XRD diagram of 1 metal organic salt intercalated houghite of embodiment；
Fig. 2 is that the SEM of 1 metal organic salt intercalated houghite of embodiment schemes；
Fig. 3 is that the SEM of 1 modified poly ester composite material of embodiment schemes；
Fig. 4 is the XRD diagram of Examples 1 to 3 modified poly ester composite material；
Fig. 5 is the non-isothermal differential thermal analysis cooling of Examples 1 to 3 modified poly ester composite material, 1 polyester material of comparative example
Figure；
Fig. 6 is the non-isothermal differential thermal analysis heating of Examples 1 to 3 modified poly ester composite material, 1 polyester material of comparative example
Figure；
Fig. 7 is the equal temperature difference heat analysis cooling figure of Examples 1 to 3 modified poly ester composite material, 1 polyester material of comparative example；
Fig. 8 is the equal temperature difference heat analysis heating figure of Examples 1 to 3 modified poly ester composite material, 1 polyester material of comparative example；
Fig. 9 is the POM figures of Examples 1 to 3 modified poly ester composite material, 1 polyester material of comparative example；
Figure 10 is that 1 modified poly ester composite material of embodiment and the TG of 1 polyester material of comparative example scheme；
Figure 11 is the tensile property comparison diagram of embodiment 1 modified poly ester composite material and 1 polyester material of comparative example；
Figure 12 is the hardness performance comparison diagram of embodiment 1 modified poly ester composite material and 1 polyester material of comparative example.
Specific implementation mode
The present invention provides a kind of modified poly ester composite materials, are prepared by the raw material including following mass parts：100 parts
Polyester raw material and 0.5~6 part of metal organic salt intercalated houghite.
In the present invention, the raw material for preparing of the modified poly ester composite material includes polyester raw material, and the polyester raw material is excellent
Choosing includes polyethylene terephthalate (PET), polyarylate (PAR), polypropylene (PP) or polybutylene terephthalate
(PBT), further preferably polyethylene terephthalate or polybutylene terephthalate.
In the present invention, on the basis of 100 mass parts of the polyester raw material, the preparation of the modified poly ester composite material
Raw material includes 0.5~6 part of metal organic salt intercalated houghite, further preferably 0.8~5.5 part, more preferably 1~5 part.
In the present invention, the chemical composition of the hydrotalcite is preferably [M2+ 1-xM3+ x(OH)2]x+·[(An-)x/n]·mH2O,
M in chemical composition2+Indicate divalent metal, M3+Indicate that trivalent metal cation, x indicate trivalent metal cation in water
Mol ratio, A in talcumn-Indicate that the anion with n negative electrical charge, m indicate the mol ratio of hydrone in hydrotalcite.
In the present invention, the x is preferably 0.25~0.5；The M2+Preferably include Mg2+、Zn2+Or Ca2+；The M3+Preferably include Al3+、
Fe3+Or Cr3+；The An-Preferably include Cl-、NO3 -、SO4 2-Or CO3 2-, further preferably CO3 2-.In the present invention, described
Cl-、NO3 -Or SO4 2-Multivalent metal salt by preparing hydrotalcite provides, the CO3 2-By in air carbon dioxide and prepare water
Raw material alkali in talcum is obtained by the reaction.In the present invention, the hydrotalcite has layer structure.
Metal organic salt intercalated houghite of the present invention refers to the metal cation of organic anion and hydrotalcite layers
It is combined by electrostatic interaction and generates metal organic salt, make the organic-inorganic composite body of hydrotalcite layers connection organic anion.This
Invention can improve the compatibility of nucleating agent and polyester using above-mentioned metal organic salt intercalated houghite as nucleating agent, moreover it is possible to
Accelerate the crystalline rate of polyester.
In the present invention, the metal organic salt intercalated houghite preferably include hydrotalcite and by electrostatic interaction intercalation in
The metal organic salt of the hydrotalcite layers.In the present invention, the metal organic salt preferably includes metal cation and organic
Anion；The metal cation is the metal cation in hydrotalcite；The organic anion preferably includes to carry carboxyl
Or sulfonic organic chain.In the present invention, the carbon chain lengths of the organic anion are preferably C8~C18, further preferably
For C10~C14.
In the present invention, the preparation method of the metal organic salt intercalated houghite preferably includes following steps：
(a) Organic Sodium Salt, alkali and water are mixed, obtains Organic Sodium Salt aqueous solution；The quality of the Organic Sodium Salt, alkali and water
Than being 1:(0.4~0.8):(18~30)；
(b) the Organic Sodium Salt aqueous solution that the step (a) obtains is mixed with polyvalent metal saline solution, is carried out compound anti-
It answers, obtains metal organic salt intercalated houghite；
The polyvalent metal saline solution includes divalent metal and trivalent metal cation, the divalent metal sun
The molar ratio of ion and trivalent metal cation is 1~3:1.
The present invention preferably mixes Organic Sodium Salt, alkali and water, obtains Organic Sodium Salt aqueous solution.In the present invention, described to have
Machine sodium salt preferably include it is one or more in odium stearate, neopelex and dodecyl sodium sulfate, further
Preferably odium stearate or dodecyl sodium sulfate.In the present invention, the alkali preferably includes soluble hydroxide, further
Preferably include sodium hydroxide or potassium hydroxide, more preferably sodium hydroxide.In the present invention, the Organic Sodium Salt, alkali and water
Mass ratio is preferably 1:(0.4~0.8):(18~30), further preferably 1:(0.5~0.7):(20~25).
The present invention does not have particular/special requirement to the hybrid mode of the Organic Sodium Salt, alkali and water, using those skilled in the art
Well known hybrid mode, the Organic Sodium Salt aqueous solution that each component fully dissolves can be obtained.
After obtaining Organic Sodium Salt aqueous solution, the present invention is preferably by the Organic Sodium Salt aqueous solution and polyvalent metal saline solution
Mixing carries out recombination reaction, obtains metal organic salt intercalated houghite.In the present invention, metal sun in the multivalent metal salt
Ion preferably includes divalent metal and trivalent metal cation, the divalent metal and trivalent metal cation
Molar ratio be preferably 1~3:1, further preferably 1.2~2.8:1.Divalent metal sun in multivalent metal salt of the present invention
Ion and trivalent metal cation and the M in hydrotalcite chemical composition described in above-mentioned technical proposal2+And M3+Unanimously, herein no longer
It repeats.In the present invention, the hydroxide ion in the Organic Sodium Salt aqueous solution and the gold in the polyvalent metal saline solution
Belong to the ratio between cationic total mole number preferably 1:1.2~1.25, further preferably 1:1.25.In the present invention, described organic
The mixing of sodium-salt aqueous solution and polyvalent metal saline solution preferably carries out under agitation, and the speed of the stirring is preferably
2000~4000r/min, further preferably 2500~3500r/min；The time of the stirring is preferably 3~7min, into one
Step is preferably 4~6min.Stirring of the present invention carries out preferably in colloidal mill.
The present invention carries out recombination reaction after mixing the Organic Sodium Salt aqueous solution and polyvalent metal saline solution, generates gold
Belong to organic salt intercalated houghite.In the present invention, alkali, the OH that the alkali ionizes out are contained in Organic Sodium Salt aqueous solution-It can be with
Divalent metal M in polyvalent metal saline solution2+With trivalent metal cation M3+Reaction, generates the hydrotalcite of stratiform
(LDHs)；Meanwhile Organic Sodium Salt ionizes out organic anion in the solution, organic anion can pass through electrostatic interaction and neatly
Cation connection between rock layers, forms metal organic salt intercalated houghite (LDH-A).
Recombination reaction of the present invention preferably carries out under alkaline condition, and the pH value of the alkaline condition is preferably 9~11,
Further preferably 9.5~10.5.In the present invention, above-mentioned pH value range is preferably realized by adjusting the additive amount of alkali.This hair
It is bright that the recombination reaction system is limited to above-mentioned alkaline environment, multivalent metal cation can be made to be reacted with hydroxyl, generate institute
Need the hydrotalcite of shape.
In the present invention, the temperature of the recombination reaction is preferably 100~130 DEG C, further preferably 105~125 DEG C；
The time of the recombination reaction is preferably 20~30h, further preferably 24~28h.Tool of the present invention to the recombination reaction
Body embodiment does not have particular/special requirement, using well known to those skilled in the art.Recombination reaction of the present invention preferably exists
It is carried out in reaction kettle.
After recombination reaction, the present invention preferably cools down the material after recombination reaction, obtains metal organic salt intercalation water
Talcum.The present invention does not have particular/special requirement to the mode of the cooling, using conventional natural cooling.
After cooling, the present invention is preferably separated by solid-liquid separation material after cooling, obtains metal organic salt intercalated houghite
Crude product.The present invention does not have particular/special requirement to the mode of the separation of solid and liquid, preferably filters or centrifuges, further preferably centrifuges.
The present invention does not have particular/special requirement to the specific implementation mode of the centrifugation, can realize separation of solid and liquid.
After separation of solid and liquid, the present invention is preferably washed and is dried successively to metal organic salt intercalated houghite crude product, institute
It is preferably deionized water that washing, which is stated, with detergent, and the once used amount of the deionized water is preferably well known to those skilled in the art
Dosage；The number of the washing is preferably 1~5 time, further preferably 2~3 times.Specific implementation of the present invention to the washing
Mode does not have particular/special requirement, using mode well known to those skilled in the art.
After washing, the present invention is preferably dried the material after washing, obtains metal organic salt intercalated houghite.This hair
The bright specific implementation mode to the drying does not have particular/special requirement, can remove the moisture after washing in material.
In the present invention, the modified poly ester composite material is white solid.In the present invention, the modified poly ester is compound
The crystallization rate of material measures under 220 DEG C of isothermys, and the crystallization rate of the modified poly ester composite material is preferably 10~
30min, further preferably 12~25min.In the present invention, the modified poly ester composite material is in 220 DEG C of hypocrystalline
Between preferably≤12min, further preferably 4~11min；The modified poly ester composite material is for pure polyester, institute
It states modified poly ester compound material ball crystal size and reduces amplitude >=30%；In the present invention, the resistance of the modified poly ester composite material
Gas performance preferably≤58cm3/m2Day atm, further preferably 45~0.5cm3/m2day atm；The modified poly ester is compound
The thermostabilization of material and hardness performance are consistent with polyester material.
The present invention also provides the preparation methods of modified poly ester composite material described in above-mentioned technical proposal, including walk as follows
Suddenly：
(1) polyester raw material is mixed with organic solvent, obtains polyester liquid；Temperature >=135 of the organic solvent
℃；
(2) polyester liquid that the step (1) obtains is mixed with metal organic salt intercalated houghite, is modified anti-
It answers, modified poly ester composite material is obtained after cooling；
The mass ratio of the metal organic salt intercalated houghite and polyester raw material in the blend melt is 0.5~6:100.
The present invention mixes the polyester raw material with organic solvent, obtains polyester liquid.Before mixing, the present invention is preferably to institute
It states polyester raw material and carries out drying and processing, to remove the water in raw material, avoid the moisture that polyester hydrophilic radical absorbs from influencing modified anti-
It answers.The present invention does not have particular/special requirement to the specific implementation mode of the drying, preferably does polyester raw material in air dry oven
Dry 24~48h, further preferably 30~45h.
In the present invention, the organic solvent temperature preferably >=135 DEG C, further preferably 140~160 DEG C.This hair
It is bright preferably by the limit temperature of organic solvent in above range, the dissolving of polyester raw material can be promoted.In the present invention, described organic
Solvent preferably includes one or more of cresols, chlorophenol and nitrobenzene, further preferably cresols.In the present invention, institute
It states cresols and preferably includes metacresol, paracresol or o-cresol, further preferably metacresol.In the present invention, described organic molten
When agent is the mixture of several components, the present invention does not have particular/special requirement to the mass ratio of each component in the mixture.
In the present invention, the quality of the polyester raw material and the volume ratio of organic solvent are preferably 1g:15~30mL, into one
Step is preferably 1g:16~28mL.The present invention does not have particular/special requirement to the hybrid mode of the polyester raw material and organic solvent, preferably
Organic solvent is added in polyester, is then heated, organic solvent is made to be warming up to above-mentioned solution temperature, when preventing addition polyester
Organic solvent is caused to splash.
After obtaining polyester liquid, the present invention preferably mixes the polyester liquid with metal organic salt intercalated houghite, into
Row modified-reaction obtains modified poly ester composite material after cooling.In the present invention, the polyester in the polyester raw material solution and gold
Modified poly ester composite material prepares required polyester raw material described in the mass ratio and above-mentioned technical proposal of category organic salt intercalated houghite
It is consistent with the mass ratio of metal organic salt intercalated houghite, it is not repeated herein.The present invention has the polyester liquid with metal
The hybrid mode of machine salt intercalated houghite does not have particular/special requirement, using hybrid mode well known to those skilled in the art.
In the present invention, the modified-reaction refers to that the polyester of metal organic salt intercalated houghite and molten state uniformly mixes
Process.In the present invention, the temperature of the modified-reaction is preferably 135~145 DEG C, further preferably 137~142 DEG C；
The time of the modified-reaction is preferably 50~80min, further preferably 55~75min.In the present invention, the modification is anti-
The temperature answered preferably is realized by oil bath heating.The present invention does not have particular/special requirement to the specific implementation mode of the modified-reaction,
Can realize the control of above-mentioned reaction condition.
After modified-reaction, the present invention cools down material after modified-reaction, obtains modified poly ester composite material.The present invention
There is no particular/special requirement, preferably natural cooling to the specific implementation mode of the cooling.
After cooling, the present invention is preferably separated by solid-liquid separation, washs and dries to material after cooling successively, to remove cooling
Solvent in material afterwards obtains the higher modified poly ester composite material of purity.In the present invention, the separation of solid and liquid is preferably taken out
Filter.The present invention does not have particular/special requirement to the specific implementation mode of the suction filtration, can realize that solid-liquid is sufficiently separated.In this hair
In bright, the washing is preferably ethyl alcohol with detergent.The present invention does not have particular/special requirement to the specific implementation mode of the washing, with
The impurity on solid material surface can be removed.The present invention does not have particular/special requirement to the specific implementation mode of the drying, with energy
Remove the ethyl alcohol of solid material remained on surface.
In order to further illustrate the present invention, multiple to a kind of modified poly ester provided by the invention with reference to the accompanying drawings and examples
Condensation material and preparation method thereof is described in detail, but cannot they be interpreted as limiting the scope of the present invention.
Embodiment 1
12.82g magnesium nitrates, 9.38g aluminum nitrates and 300ml deionized waters are mixed, ultrasound 30min under the conditions of 60KHz is obtained
To containing magnesium ion and aluminum ions aqueous solution；
6gNaOH, 10.89g odium stearate and 200g water are mixed, ultrasound 30min under the conditions of 60KHz obtains odium stearate
Mixed liquor；
Magnesium ion will be contained and aluminum ions aqueous solution is mixed with odium stearate mixed liquor, poured into colloid mill machine,
Under the rotating speed of 3000r/min, stir 5min, then the mixed material after stirring is poured into reaction kettle, under the conditions of 110 DEG C into
Row recombination reaction, takes out afterwards for 24 hours, and metal organic salt intercalated houghite is obtained after centrifuging, wash and drying.
2.5gPET is placed in 100ml three-necked flasks, the good agitating device of frame, condensed water of having friendly relations, 50ml metacresols is claimed to pour into
In three-necked flask, start to stir, rotating speed 140r/min, waits for oil bath heating to 140 DEG C, for PET in after molten state, addition accounts for PET matter
The metal organic salt intercalated houghite of amount 1% continues to stir 60min, take out, stands, to be cooled to arrive room temperature, filters, ethyl alcohol is washed
It washs, until substance is white in Buchner funnel；Then it dries under vacuum for 24 hours, obtains modified poly ester composite material.
The structure of metal organic salt intercalated houghite obtained above is characterized using X-ray diffraction, as a result such as Fig. 1
It is shown.In Fig. 1, occurs 1 diffraction maximum respectively at 3 °, 23 ° and 35.9 °, belongs to LDH [003], [006], [012] characteristic peak,
Prove the layer structure LDH that the LDH-ST prepared by the present invention has ideal long chain anion intercalated.Due to having
Chain anion intercalation hydrotalcite, thickness becomes larger between leading to neatly stone veneer, and (normal hydrotalcite should be at 11 ° for the Forward of [003] peak value
Appearance), illustrate the success of stearate radical intercalation.Occurs the feature diffraction of (110) crystal face and (113) crystal face of LDH at 60 ° or so
Peak.
Metal organic salt intercalated houghite pattern is characterized using scanning electron microscope, as shown in Figure 2.By Fig. 2
It is found that the metal organic salt intercalated houghite that the present invention is prepared is in six square piece layer structures.
The pattern in obtained modified poly ester composite material is characterized using scanning electron microscope, as shown in figure 3,
Metal organic salt intercalated houghite and poly- para Toluic Acid's glycol ester compatibility are preferable, and still maintain original sheet pattern
Feature.
Embodiment 2
Modified poly ester composite material is prepared according to the method for embodiment 1, the difference is that the metal organic salt intercalation
The loading of hydrotalcite is 3%.
Embodiment 3
Modified poly ester composite material is prepared according to the method for embodiment 1, the difference is that the metal organic salt intercalation
The loading of hydrotalcite is 5%.
Embodiment 4
Modified poly ester composite material is prepared according to the method for embodiment 1, the difference is that the polyester components are PP, gold
The loading for belonging to organic salt intercalated houghite is 1%.
Comparative example 1
Using pure PET as test sample.
Comparative example 2
Using PET as raw material, using magnalium hydrotalcite as nucleating agent, form with PET/MgAl LDH-CO3 2-It indicates, wherein magnalium
The quality percentage amounts of the filling of hydrotalcite are 1%.
Comparative example 3
Using pure PP materials as test sample.
Using X-ray diffraction to the structure of modified poly ester composite material and 1 test sample of comparative example obtained by Examples 1 to 2
It is characterized, as shown in Figure 4.In Fig. 4, the test sample of embodiment 2 is 1. indicated, 2. indicate the test sample of embodiment 1,3. table
Show the test sample of comparative example 1, as seen from the figure, the XRD of modified poly ester composite material 16.2 °, 17.5 °, 22 °, 23.2 °,
26.9 ° of appearance, 5 diffraction maximums, correspond to [011], [010], [111], [110] and [100] of poly- para Toluic Acid's glycol ester respectively
5 characteristic peaks, it is corresponding with the characteristic peak of pure PET, but peak intensity increases, and illustrates that the PET of crystalline state accounts for the percentage of PET total amounts
Increase, i.e. the crystalline state of PET increases.
The material of each embodiment or comparative example is conventionally pressed into the film of 100 μ m thicks as sample, test
The crystal property and gas barrier properties of sample：
Utilize 1~3 gained modified poly ester composite material of non-isothermal Differential scanning calorimetry analysis (DSC) method testing example and comparative example
The crystal property of 1 test sample observes the change of the crystallization temperature of modified poly ester composite material under the cooling rate of 10 DEG C/min
Change situation, as shown in Figure 5.By crystallization curve in figure it is found that the crystallization temperature of modified poly ester composite material obtained by Examples 1 to 3
For pure polyester material, crystallization temperature increases, while crystallizing peak width and to be narrower than pure polyester material, this illustrates metal
The addition of organic salt intercalated houghite can induce polyester faster to crystallize.
Under the heating rate of 10 DEG C/min, modified poly ester composite material and comparative example 1 obtained by observation Examples 1 to 3 are surveyed
The melting situation of test agent, as shown in Figure 6.By melting curve in figure it is found that modified poly ester composite material obtained by Examples 1 to 3
Melting peak become sharp, this illustrates the addition of metal organic salt intercalated houghite, and polyester material can be made in narrower temperature
Range melts.
Utilize 1~3 gained modified poly ester composite material of equal temperature difference heat analytic approach testing example and 1 test sample of comparative example
Crystal property observe the crystalline rate of modification polyester materials under the conditions of 220 DEG C, as shown in fig. 7, by crystallization curve in figure
It is found that pure polyester material under the conditions of 220 DEG C, needs 40min that could crystallize completion, and the crystallization of modified poly ester composite material is fast
Rate is very fast, and metal organic salt intercalated houghite loading is more, and crystallization rate is faster.
Under 220 DEG C of isothermys, the crystallinity of 1~3 modified poly ester composite material of testing example and comparative example 1 and when
Between variation relation, as shown in Figure 8.In figure, 1 test sample of comparative example is 1. indicated, 2.~Examples 1 to 3 is 4. indicated respectively
Modified poly ester composite material.By crystallinity in figure with time curve it is found that the crystallization process of modified poly ester composite material is equal
" S " is presented and needs the homogeneous nucleation by itself this is because when crystallizing polyester, this process is slower；And modified poly ester
Composite material can provide external boundary directly using metal organic salt intercalated houghite as nucleating point for the crystallization of polyester fondant
Face, needs not move through slow homogeneous nucleation, just starts to crystallize, and then shortens crystallization time.In short, under equal conditions, implementing
The modified poly ester composite material that example 1~3 is prepared reaches time needed for identical crystallinity relatively for polyester
It is short, and the loading of metal organic salt intercalated houghite is more, it is shorter the time required to reaching same crystallinity.
It is observed in Examples 1 to 3 modified poly ester composite material and 1 test sample of comparative example using petrographic microscope (POM)
Nucleation density, as shown in Figure 9.In Fig. 9,1 test sample of comparative example is 1. indicated, 2.~changing for Examples 1 to 3 is 4. indicated respectively
Property polyester composite, as seen from the figure, the corresponding nucleation density of modified poly ester composite material, for polyester (Fig. 9 is 1.),
The nucleation density of crystallization obviously increases, and spherulite size reduces.
Using the thermal stability of 1 gained modified poly ester composite material of thermogravimetric analyzer testing example, test result is as schemed
Shown in 10.In Figure 10,1 test sample of comparative example is 1. indicated, 2. indicate 1 test sample of embodiment, by 1. and 2. curve it is found that changing
The thermal stability of polyester composite is not significantly affected after property.
It is tested according to 1 gained modified poly ester composite material of GB/T 1040.2-2006 standard testings embodiment and comparative example 1
The tensile strength of sample, as a result as shown in figure 11.As seen from the figure, the tensile strength of 1 test sample of comparative example reaches 53.3MPa,
The tensile strength of 1 modified poly ester composite material of embodiment reaches 57.2, and tensile strength is promoted.
According to GB/T 2411-2008 standards, 1 gained modified poly ester composite material of hardometer testing example and right is utilized
Identation hardness (shore hardness) hardness of 1 test sample of ratio, as a result as shown in figure 12.As seen from the figure, 1 test sample of comparative example
Hardness reach 73, the hardness of 1 modified poly ester composite material of embodiment reaches 73, illustrates adding for metal organic salt intercalated houghite
Add, does not influence the hardness performance of polyester.
1~3 crystallization peak temperature of testing example 1~4 and comparative example under non-isothermal condition；Under the conditions of 220 DEG C, various kinds is tested
Product flexible chain；Utilize scanning electron microscope test each sample spherocrystal grain size；Utilize use for laboratory gaseousness film permeation
Instrument measures the film gas barrier properties of each sample, by taking oxygen as an example, gas barrier properties, test result such as table 1 is indicated with infiltration rate
It is shown.
1~2 counter sample crystal property test result of 1 Examples 1 to 5 of table and comparative example
From the data in table 1, it can be seen that for pure polyester material and the polyester material being modified with inorganic nucleator, the present invention
The crystallization peak temperature of the modified poly ester composite material of offer is higher, can shorten crystallization time；Moreover, loading is more, peak crystallization
Temperature is higher, and crystallization rate is quick.
The spherocrystal grain size of modified poly ester composite material is substantially reduced, advantageous for the promotion of strength of materials performance.
For modified poly ester composite material choke performance for pure polyester material, promotion is more apparent, increases this kind
Application of the modified poly ester composite material as food packaging.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiment according to the present embodiment under the premise of without creativeness, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of modified poly ester composite material, is prepared by the raw material including following mass parts：100 parts of polyester raw materials and 0.5
~6 parts of metal organic salt intercalated houghites.
2. modified poly ester composite material as described in claim 1, which is characterized in that the polyester raw material includes poly terephthalic acid
Glycol ester, polyarylate, polypropylene or polybutylene terephthalate.
3. modified poly ester composite material as described in claim 1, which is characterized in that the metal organic salt intercalated houghite packet
Include hydrotalcite and by electrostatic interaction intercalation in the metal organic salt of the hydrotalcite layers；The metal organic salt includes metal
Cation and organic anion.
4. the modified poly ester composite material as described in claim 1 or 3, which is characterized in that the metal organic salt intercalation neatly
The preparation method of stone includes the following steps：
(a) Organic Sodium Salt, alkali and water are mixed, obtains Organic Sodium Salt aqueous solution；The mass ratio of the Organic Sodium Salt, alkali and water is
1:(0.4~0.8):(18~30)；
(b) the Organic Sodium Salt aqueous solution that the step (a) obtains is mixed with polyvalent metal saline solution, carries out recombination reaction,
Obtain metal organic salt intercalated houghite；
Metal cation in the multivalent metal salt includes divalent metal and trivalent metal cation, the divalent gold
The molar ratio for belonging to cation and trivalent metal cation is 1~3:1.
5. modified poly ester composite material as claimed in claim 4, which is characterized in that the Organic Sodium Salt include odium stearate,
It is one or more in neopelex and dodecyl sodium sulfate.
6. modified poly ester composite material as claimed in claim 4, which is characterized in that the divalent metal include magnesium from
Son, zinc ion or calcium ion；The trivalent metal cation includes aluminium ion, iron ion or chromium ion.
7. modified poly ester composite material as claimed in claim 6, which is characterized in that the corresponding gold of the divalent metal
It includes magnesium salts, zinc salt or calcium salt to belong to salt；
The magnesium salts includes magnesium chloride, magnesium nitrate or magnesium sulfate；The zinc salt includes zinc chloride, zinc nitrate or zinc sulfate；It is described
Calcium salt includes calcium chloride or calcium nitrate；
The corresponding metal salt of the trivalent metal cation includes aluminium salt, molysite or chromic salts；
The aluminium salt includes aluminium chloride, aluminum nitrate or aluminum sulfate；The molysite includes ferric nitrate, ferric sulfate or iron chloride；It is described
Chromic salts includes chromium trichloride or chromic nitrate.
8. the preparation method of any one of the claim 1~7 modified poly ester composite material, includes the following steps：
(1) polyester raw material is dissolved in organic solvent, obtains polyester liquid；Temperature >=135 DEG C of the dissolving；
(2) polyester liquid that the step (1) obtains is mixed with metal organic salt intercalated houghite, heating is modified anti-
It answers, modified poly ester composite material is obtained after cooling；The mass ratio of the metal organic salt intercalated houghite and polyester raw material is 0.5
~6:100.
9. preparation method as claimed in claim 8, which is characterized in that the quality of step (1) polyester raw material with it is organic molten
The volume ratio of agent is 1g:15~30mL.
10. preparation method as claimed in claim 8, which is characterized in that the temperature of modified-reaction is 135 in the step (2)
~145 DEG C, the time of the modified-reaction is 50~80min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114525016A (en) * | 2022-02-22 | 2022-05-24 | 广东卓尔新材料有限公司 | Low-shrinkage polyester film |
| CN117165052A (en) * | 2023-10-09 | 2023-12-05 | 山东长泽新材料科技有限公司 | Ultraviolet-resistant PET composite film material for back plate and preparation method thereof |
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| CN104558775A (en) * | 2015-01-12 | 2015-04-29 | 北京化工大学 | Hydrotalcite acid acceptor for polyolefin |
| CN106188929A (en) * | 2015-05-07 | 2016-12-07 | 河北精信化工集团有限公司 | A kind of modified hydrotalcite and preparation method thereof and its application in polrvinyl chloride is processed |
| CN107129597A (en) * | 2017-03-21 | 2017-09-05 | 北京化工大学 | A kind of uvioresistant composite of hydrotalcite confinement synthesis Schiff base molecule, preparation method and application |
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| US5484583A (en) * | 1992-08-13 | 1996-01-16 | Aluminum Company Of America | Filler material containing an anion substituted hydrotalcite |
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| CN117165052B (en) * | 2023-10-09 | 2024-04-16 | 山东长泽新材料科技有限公司 | Ultraviolet-resistant PET composite film material for back plate and preparation method thereof |
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