CN104817830B - A kind of aromatic polyester microcellular foam material and preparation method thereof - Google Patents

A kind of aromatic polyester microcellular foam material and preparation method thereof Download PDF

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CN104817830B
CN104817830B CN201510250083.4A CN201510250083A CN104817830B CN 104817830 B CN104817830 B CN 104817830B CN 201510250083 A CN201510250083 A CN 201510250083A CN 104817830 B CN104817830 B CN 104817830B
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aromatic polyester
weight portion
foam material
microcellular foam
benzal
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CN104817830A (en
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信春玲
何亚东
杨兆平
郭亚峰
闫宝瑞
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention discloses a kind of aromatic polyester microcellular foam material, prepared by the foamed technique of composition of aromatic polyester, this composition of aromatic polyester includes aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5 5 weight portion, antioxidant 0.1 0.3 weight portion, chain extender 02 weight portion, Nucleating Agent 02 weight portion；This aromatic polyester microcellular foam material apparent density is 0.05 1.10g/cm3, rate of closed hole is not less than 80%.The invention also discloses the multiple preparation method of this aromatic polyester microcellular foam material.The aromatic polyester microcellular foam material of the present invention has foaming wide temperature region, and technology controlling and process is easy, and abscess-size is little and uniform, and goods have thermostability and the feature of mechanical property of excellence.

Description

A kind of aromatic polyester microcellular foam material and preparation method thereof
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of aromatic polyester expanded material and Its preparation method.
Background technology
Foam plastics is with plastics as matrix, is wherein filled with the composite of a large amount of bubble, thus Have light weight, saving material, specific strength is high, thermal conductivity is low, heat insulation performance is excellent, energy Absorb the excellent properties such as shock loading, so being widely used as packaging, heat insulation, anti-freezing and heat-insulating, buffering Vibrationproof, quieter material, building, transport, daily living article, packaging and space flight, navigation, The fields such as national defence have obtained application widely.Traditional such as polyurethane foam (PU), polyethylene Foam (PE) and polystyrene foam (PS) etc., owing to all having one in material itself and processing method Fixed deficiency, such as polyurethane foam, to discharge isocyanates etc. in preparation process harmful Residue, and there is the problem that is difficult to reclaim in the polyurethane after foaming.Polystyrene foam is moulded Expect, owing to its temperature tolerance is relatively low, to use field by a definite limitation.Polyethylene foams mechanical property The shortcoming etc. that energy is poor and thermostability is the highest.Therefore, people are devoted to develop high performance bubble always Foam plastics, to widen the application of expanded material, increase in satisfied society and development in science and technology day by day Requirement to material property.
Aromatic polyester has thermostability and the mechanical property of excellence, compared to traditional foam plastics, Have good stability of the dimension under high temperature, excellent mechanical performance and fatigue resistance, low cigarette, fire-retardant, The advantage such as nontoxic, low water absorption, good barrier properties for gases and recyclable recycling, at electronics Industry, buffering package, construction material, transportation, field of wind power generation tool are widely used Prospect.
Chinese invention patent application CN201280042030.8 discloses a kind of foam-in-mould molding virtue Fragrant adoption ester resin foam particle and preparation method thereof, the expanded beads of this disclosure of the invention is by squeezing Go out after foaming agent mixed homogeneously with polyester fondant by method, obtain through mouth die extrusion foaming cooling and dicing Arriving, can use In-mold decoration method secondary frothing forming goods, the body density of this expandable particles is 0.05-0.7g/cm3, degree of crystallinity is less than 15%.In order to improve the rate of closed hole of expandable particles, use Intrinsic viscosity is the aromatic polyester of 0.8-1.1, and adds the cross-linking agent of 0.01-5 weight portion to carry The molecular weight of superpolyester resin so that it is Z-average molecular weight is higher than 2X105.The technical side of this disclosure of the invention Case, in order to enable preferably to carry out second time of foaming, controls the degree of crystallinity relatively low (less than 15%) of expandable particles, The thermostability of foaming product reduces, it is impossible to give full play to the performance of aromatic polyester.
United States Patent (USP) US5679295A discloses a kind of employing composite foamable agent extrusion preparation PET foaming The method of goods, the method uses the intrinsic viscosity PET resin more than 0.8dl/g, at least 50mol% Heptane, octane or Pentamethylene. and butane, tetrafluoroethane, CO2 etc. as composite foamable agent, regulation Under blowing temperature, the solution presasure in PET is less than 4.5MPa, in the vitrification of PET for foaming agent During transition temperature, solution presasure is less than 0.1MPa.The technical scheme of this disclosure of the invention uses multicomponent Foaming agent, complex process, and foaming time control pressing pressure ratio is relatively low, obtains the aperture of foaming product relatively Greatly, toughness and the heat conductivility of material reduces.
Chinese invention patent application CN102504498A discloses a kind of foaming PET sheet material and preparation side Method, this foam sheet is by PET resin 100 weight portion, and nucleator 0.1-10 weight portion, abscess is steady Determining agent 0.1-10 weight portion, composite foamable agent 1.5-1.8 weight portion forms, after the mixing of extruded machine, Foam shaping by extrusion.Disclosed in this patent, technical scheme employing CBA is as auxiliary blowing agent, CBA decomposes the little molecule produced and easily causes polyester thermal degradation, adds process complexity, Product properties is relatively low, and the apparent density obtaining foam sheet is big.
Chinese invention patent application CN101544812 discloses a kind of foaming CPET sheet material and preparation thereof Method, this sheet material, by PET100 weight portion, adds the blowing promotor of 0.1-40 weight portion, 0.1-5 The foaming agent mix homogeneously of weight portion, foam shaping by extrusion.Described blowing promotor is by 0.1-30 weight Part ethylene-acrylate-glycidyl methacrylate terpolymer composition or nucleocapsid structure Esters of acrylic acid material, 0.1-10 weight portion high activity polyfunctional group material, 0.3-10 weight portion are tied Brilliant nucleator and 10-100 weight portion vector resin are uniformly mixed with and obtain.
In the prior art, in order to overcome low being difficult to of aromatic polyester melt viscosity to maintain foam structure, Easily cause abscess to subside and the shortcoming such as merging, improve the viscosity of PET by adding cross-linking agent, But this technology easily causes formation cross-linked structure, and crosslinking dose of remnants are to the recycling of goods not Profit.On the other hand, aromatic polyester crystalline rate is relatively slow, and foaming product is difficult to shape, and is difficult to Obtain microporous PE T foaming product.
Summary of the invention
It is an object of the invention to overcome above-mentioned shortcoming of the prior art, it is provided that the adoption of a kind of fragrance Ester microcellular foam material and preparation method thereof, it has foaming wide temperature region, technology controlling and process easily, raw Producing low cost, goods have thermostability and the feature of mechanical property of excellence.
In order to realize the purpose of the present invention, the technical scheme is that
The present invention provides a kind of aromatic polyester microcellular foam material, by composition of aromatic polyester warp Prepared by foam process, this composition of aromatic polyester includes aromatic polyester 100 weight portion, Pyrusussuriensis Alcohol benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight Part, Nucleating Agent 0-2 weight portion.The apparent density of this aromatic polyester microcellular foam material is 0.05-0.50g/cm3, rate of closed hole is not less than 80%.
One enforcement of the preparation method of a kind of aromatic polyester microcellular foam material according to the present invention Mode, comprising: (1) is by aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5-5 Weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 Weight portion, adds in extruder after being mixed in proportion into composition of aromatic polyester；(2) to described Injecting physical blowing agent in extruder, the injection rate of described physical blowing agent is described aromatic polyester The 0.1-10% of composition total weight, mix homogeneously in described extruder；(3) will be containing described thing The described composition of aromatic polyester melt cooling to 220-250 DEG C of haircut infusion, mouth die pressure is more than 3MPa, obtains aromatic polyester microcellular foam material through mouth die foaming and setting.
Another of the preparation method of a kind of aromatic polyester microcellular foam material according to the present invention is real Execute mode, comprising: (1) is by aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5-5 Weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 Weight portion, CBA 0.1-5 weight portion, add in extruder after being mixed in proportion, adding Making it melt under heat and screw rod shearing plastication, described CBA decomposes to give off volatility gas Body, mix homogeneously in described extruder；(2) aromatic polyester containing described CBA Melt blend is by obtaining aromatic polyester microcellular foam material after die extrusion cooled sizing.
Another of the preparation method of a kind of aromatic polyester microcellular foam material according to the present invention is real Execute mode, including (1) by aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5-5 Weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 Weight portion, adds after being mixed in proportion in injection machine, makes under heating and screw rod shearing plastication It melts；(2) physical blowing agent is sent into the aromatic polyester polymer melt in described injection machine In, the addition of described physical blowing agent is the 0.1-1% of composition of aromatic polyester gross weight, Mix homogeneously in injection machine；(3) by the aromatic polyester melt mixed containing described physical blowing agent Thing is injected in mould by injection nozzle and obtains aromatic polyester microcellular foam material after cooled sizing.
Another of the preparation method of a kind of aromatic polyester microcellular foam material according to the present invention is real Execute mode, including: (1) is by aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5-5 Weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 Weight portion, CBA 0.1-1 weight portion adds in injection machine after being mixed in proportion, in heating And under screw rod shearing plastication, make it melt；(2) by the aromatic series containing described CBA Polyester fondant mixture is injected in mould by injection nozzle and obtains aromatic polyester after cooled sizing Microcellular foam material.
Accompanying drawing explanation
Fig. 1 is to represent at 260 DEG C, add different content DMDBS PET melt storage modulus with Frequency relation figure.
Fig. 2 is to represent at 260 DEG C, adds complex viscosity and the frequency of the PET of different content DMDBS Graph of a relation.
Fig. 3 is the PET microporous foam stereoscan photograph that embodiment 1 obtains.
Fig. 4 is the PET microporous foam stereoscan photograph that comparative example 1 obtains.
Detailed description of the invention
The aromatic polyester microcellular foam material that the present invention provides, by composition of aromatic polyester through sending out Prepared by bubble technique, this composition of aromatic polyester includes aromatic polyester 100 weight portion, sorbitol Benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 weight portion.
Aromatic polyester refers to the polymerization obtained by aromatic dicarboxylic acid and dihydroxylic alcohols by polyreaction Thing, containing benzene ring structure in its macromolecular main chain structure, such as polyethylene terephthalate, gathers Propylene glycol ester terephthalate, polybutylene terephthalate (PBT) etc., preferably poly terephthalic acid Glycol ester.Additionally, aromatic polyester resins is in addition to aromatic dicarboxylic acid and dihydroxylic alcohols, also may be used Containing the 3rd copolymerization component, such as resorcinol etc..Aromatic polyester can be one or more fragrance The blend of adoption ester.Relatively it is suitably for homopolymer or the copolymer of polyethylene terephthalate. Can also be general fiber polyester or polyester for bottle, or the polyester for bottle reclaimed is modified through chain extension Arrive.
The intrinsic viscosity of aromatic polyester is not less than 0.8dl/g, and the characteristic of appropriate aromatic polyester is glued Degree tests (solvent employing not less than 1.0dl/g, intrinsic viscosity according to GB/T14190-2008 method Phenol/sym-tetrachloroethane (mass ratio 50/50)).The intrinsic viscosity of aromatic polyester is the lowest can not wrap up The bubble of growth, easily causes bubble and merges or rupture.
Sorbitol benzal derivant refers to that sorbitol carries out, with aldehyde compound, the benzyl that condensation reaction obtains The glucitol derivative of fork base, its molecular formula is as follows:
R1, R2 represent the alkyl or alkoxyl, hydroxyl or halogen that hydrogen atom, carbon number are 1～4 The alkyl of element.Conventional include 2,4-O-(3,4-dimethyl benzylidene)-D-glucitol (DMDBS), Dibenzylidene-sorbitol (DBS), to methyl benzylidene sorbitol (DMBS).The present invention is suitableeer Closing and select the glucitol compounds with high thermal stability, its heat decomposition temperature is not less than 300 DEG C, Relatively being suitable for being not less than 320 DEG C, heat decomposition temperature uses the test of thermal weight loss method, and atmosphere is air.
Inventor experimental studies have found that through substantial amounts of, and sorbitol benzal derivant is at aromatic polyester Melt can become Nanofiber Network by H-bonding self-assembly.This Nanofiber Network can be with virtue Form physical entanglement point between fragrant adoption ester large molecule chain, improve aromatic polyester melt viscosity and Melt elasticity, as illustrated in fig. 1 and 2.Fig. 1 and 2 is different 2,4-O-(3,4-dimethylbenzylidene Base) PET melt of-D-glucitol (DMDBS) the content rotation rheology test result at 260 DEG C, Fig. 1 is storage modulus-frequency scanning curve, and Fig. 2 is complex viscosity-frequency scanning curve.From Fig. 1 Can see, when DMDBS content is 0, PET melt shows more significantly frequency in low frequency range Dependency and liquid phase rheological behavior, when DMDBS content be 0.5wt% and above time, low frequency range store up Energy modulus is significantly raised, and a platform area occurs, shows solid material behavior, and this is due to DMDBS The nanometer fiber net being self-assembly of causes the result that PET melt elasticity increases.Another permissible from Fig. 2 Finding out, the PET melt of the interpolation DMDBS complex viscosity in low frequency range significantly increases, and with frequency Change viscosity reduces more, shows that shear shinning becomes apparent from, and this is due to DMDBS self assembly network Mutually tangle with PET macromolecular chain, the entanglement density of system increase so that shear shinning phenomenon more Substantially.PET resin melt viscosity and melt elasticity increase and are conducive to cell wall holding in foaming process, The merging between abscess is avoided to subside.
The 0.5-5% that addition is aromatic polyester weight of sorbitol benzal derivant in the present invention, Appropriate for 1-3%.Very little, the network structure of formation is not enough to sorbitol benzal derivant addition With polyester generation physical entanglement, the melt viscoelasticity of polyester is affected less；Sorbitol benzal derives Thing addition is more than 5%, and the nanometer microfiber network structure of formation can suppress cell growth, and can cause The viscoelasticity of polyester fondant deteriorates, and foam process is wayward.
In order to improve the molecular weight of aromatic polyester, composition of aromatic polyester of the present invention also can add Entering chain extender, chain extender refers to containing the double officials that can react with the carboxyl of polyester end or hydroxyl Can roll into a ball or polyfunctional compound, to increase the molecular weight of polyester or to produce branched structure.Including many Unit's anhydrides such as pyromellitic acid anhydride (PMDA), polyfunctional epoxy resin such as four-functional group epoxy Resin, bis-oxazoline etc..The content of chain extender is the 0-2% of aromatic polyester gross weight, appropriate For 0.3-1.0%.
Heretofore described Nucleating Agent can be inorganic nucleator or organic nucleating agent, inorganic Nucleator includes Pulvis Talci, calcium carbonate, nano silicon, nano imvite etc., organic nucleation Agent is azodicarbonamide (AC) etc., is relatively suitably for the one in Pulvis Talci, azodicarbonamide. The addition of Nucleating Agent is the 0-2% of aromatic polyester gross weight,.
In order to avoid the thermal degradation of polyester in high temperature process, composition of aromatic polyester of the present invention adds Adding the antioxidant of 0.1-0.3 weight portion, described antioxidant is antioxygen conventional in Polymer Processing Agent, such as four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, commodity Entitled antioxidant 1010.Antioxidant can also be by the compound of primary antioxidant Yu aid anti-oxidants.
The apparent density of aromatic polyester microcellular foam material of the present invention is 0.05-1.10g/cm3, Relatively it is suitably for 0.10-0.80g/cm3.Apparent density is tested according to standard GB1033-86.
The rate of closed hole of aromatic polyester microcellular foam material of the present invention is not more than 80%, uses ULTRAFOAM 1000 (Quantachrome Instruments company of the U.S.) measures foamed sample Rate of closed hole.
In order to improve the fire resistance of material, in aromatic polyester microcellular foam material of the present invention Also can add fire retardant, including inorganic combustion inhibitor and organic fire-retardant.
One embodiment of the preparation method of the aromatic polyester microcellular foam material according to the present invention, It uses physics extrusion foaming process, including: (1) is by aromatic polyester 100 weight portion, sorbitol Benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 weight portion, adds after being mixed in proportion in extruder, at heating and threaded rod shear Cut and under plastication, make it melt；(2) by physical blowing agent by being arranged on extruder barrel Gas injection port dosing pump is sent in the polymer melt in extruder, and the addition of physical blowing agent is virtue The 0.1-10% of fragrant adoption ester composition total weight, mix homogeneously in extruder；(3) foaming is reduced Agent inlet to head export between temperature, control melt temperature at head and be 220-250 DEG C, molten Body pressure is not less than 3MPa；Aromatic polyester melt blend containing foaming agent passes through die extrusion And obtain aromatic polyester microcellular foam material after cooled sizing.
Here, extruder is that physical blowing commonly uses extrusion system, can use single screw extrusion machine, Double screw extruder or single screw extrusion machine Series Sheet screw extruder, double screw extruder Series Sheet Screw extruder, the machine barrel of extruder offers blowing agent injection port.
Aromatic polyester needs before extruder to be fully dried to remove moisture in order to avoid at extruder adding Middle degradation.Appropriate vacuum drying 12 hours at 100 DEG C, are then dried at 140 DEG C 12 hours.Other adding ingredients are also required to be pre-dried.Aromatic polyester after dried and interpolation Agent need to seal preservation, or adds immediately in extruder.Appropriate extruder drawing-in device has drying Device, or have inert gas seal protection device.
Physical blowing agent is the low molecular weight alkanes class foaming agent such as pentane, butane, heptane, or dioxy Change the inert gas blown agent such as carbon, nitrogen.Relatively it is suitably for carbon dioxide, pentane.
During foaming, sheet die or sheet material mouth die can be used, obtain aromatic polyester foam sheet Or foaming plate.Obtain needing cross sectional shape after mouth die outlet after cooling and shaping device cooling and shaping Goods.
The another kind of embodiment party of the preparation method of the aromatic polyester microcellular foam material according to the present invention Formula, it is chemistry extrusion foaming process, including: (1) is by aromatic polyester 100 weight portion, Pyrusussuriensis Alcohol benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight Part, Nucleating Agent 0-2 weight portion, CBA 0.1-5 weight portion, after being mixed in proportion Adding in extruder, make it melt under heating and screw rod shearing plastication, CBA divides Solve and release escaping gas, mix homogeneously in extruder；(2) the fragrant adoption containing foaming agent Ester melt blend is by obtaining aromatic polyester microporous foam material after die extrusion cooled sizing Material.
CBA is heat absorption class foaming agent, can be azodicarbonamide, (4,4)-dioxygen benzene Sulfohydrazide, para toluene sulfonamide semicarbazides, and 5-phenyltetrazole.Relatively it is suitable for azodicarbonamide.
The yet another embodiment of the preparation method according to aromatic polyester microcellular foam material of the present invention, It uses physical blowing injection molding process, including: (1) by aromatic polyester 100 weight portion, Sorbitol benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 Weight portion, Nucleating Agent 0-2 weight portion, add after being mixed in proportion in injection machine, in heating And under screw rod shearing plastication, make it melt；(2) by physical blowing agent by being arranged on extruder Gas injection port dosing pump on machine barrel is sent in the polymer melt in injection machine, adding of physical blowing agent Enter the 0.1-1% that amount is composition of aromatic polyester gross weight, mix homogeneously in injection machine；(3) Aromatic polyester melt blend containing physical blowing agent is injected warp in mould by injection nozzle Aromatic polyester microcellular foam material is obtained after cooling and shaping.This physical blowing agent, such as titanium dioxide Carbon or nitrogen, appropriate for nitrogen.Injection rate is the 0.1-1% of aromatic polyester total weight of the mixture, Appropriate for 0.3-0.6%.
The yet another embodiment of the preparation method according to aromatic polyester microcellular foam material of the present invention, It uses chemical blowing injection molding process, including: (1) by aromatic polyester 100 weight portion, Sorbitol benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 Weight portion, Nucleating Agent 0-2 weight portion, CBA 0.1-1 weight portion is mixed in proportion In rear addition injection machine, it is made to melt under heating and screw rod shearing plastication；(2) will contain The aromatic polyester melt blend of described CBA is injected in mould through cold by injection nozzle But aromatic polyester microcellular foam material is obtained after sizing.Appropriate CBA is azo two Methanamide, addition is the 0.1-1% of aromatic polyester gross weight, is relatively suitably for 0.2-0.5%.
Embodiment:
Technical solution of the present invention is described in detail by the following example and comparative example.
Embodiment 1:
Raw material: polyethylene terephthalate (PET), intrinsic viscosity 0.80dl/g is (according to GB/T 14190-2008) test, solvent is phenol/1,1,2,2 ,-sym-tetrachloroethane (mass ratio 50/50), Middle petrochemical industry Yizheng Fiber Optical plant company limited；1,3:2,4-bis--(3,4-bis-subunit benzal base)-sorbitol English Literary fame claims 1,3:2-4-bis (3,4-dimethylbenzylidene) sorbitol, is called for short DMDBS, Heat decomposition temperature 320 DEG C, model ZC-3, Yantai Chu Hecheng Chemical Co., Ltd..Thermal decomposition temperature Degree uses thermal gravimetric analyzer test, 10 DEG C/min of heating rate, and on thermogravimetric curve, weightlessness is fast Rate maximum is heat decomposition temperature.
Anti-oxidant Irganox 1010, BASF Corp. of Germany.
Pulvis Talci, 1000 mesh, Beijing benefits the nation great achievement powder body material company limited.
Carbon dioxide, purity 99.5%, Beijing oxygen installation.
Foam process: will be to polyethylene terephthalate (PET), DMDBS, antioxidant, cunning Stone powders etc. are pre-dried, and drying process is: PET, 100 DEG C, are vacuum dried 12 hours, then 140 DEG C, It is vacuum dried 12 hours；DMDBS, antioxidant, Pulvis Talci drying process, 100 DEG C, forced air drying 2 Hour.After dried raw material is weighed according to certain ratio (as shown in table 1), at a high speed Stirrer for mixing is uniform.The material mixed is added the homodromal twin-screw extrusion rotated In machine (a diameter of 45mm of twin screw, draw ratio is 40), by metering pumping system by a definite proportion The carbon dioxide of example is pumped into the polymer melt in extruder.Under screw rod rotates, the dioxy of injection Change carbon and PET resin melt composition homogeneous phase solution, carry to head exit, double screw extruder Outlet series connection one Melt Pump, Melt Pump outlet has sheet die, sheet die a size of 200X0.6mm. Controlling the temperature at single screw extrusion machine and head, making melt temperature at head is 250 DEG C, head pressure Power is 5MPa, and extruder each segment process parameter is shown in Table 2.Obtain PET foam sheet.
Performance characterization: use analytical balance, tests the apparent of foaming product by standard GB1033-86 Density.ULTRAFOAM 1000 (Quantachrome Instruments company of the U.S.) is used to survey Determine the rate of closed hole of foamed sample.Foam structure is primarily referred to as abscess-size and cell density, specifically surveys Method for testing is: sample is immersed liquid nitrogen, then takes out brittle failure, makes print, then to its fracture table Face metal spraying, observes fracture apperance with SEM.Utilize image analysis software Image-pro that Electronic Speculum is swept Retouching photo to process, added up abscess number is more than 100.Abscess-size is foamed sample bubble The average diameter in hole, is directly calculated by software；Cell density is in every cubic centimetre of unexpanded sample The number of abscess.
PET foam sheet tensile property according to GB/T9641-1988 test, compressive strength according to GB/T8813-2008 tests, and impact strength is tested according to GB/T 1043.1-2008
Test result is shown in Table 1.
Embodiment 2-3
Using foam process same as in Example 1, difference is containing of each component in raw material Amount difference, in foam process, melt temperature is different.Wherein in embodiment 3-4, add chain extender equal PMDA (PMDA), analytical pure, chemical reagents corporation of traditional Chinese medicines group produces.
Embodiment 4
Polyethylene terephthalate, intrinsic viscosity 1.0dl/g (according to GB/T 14190-2008) Test, solvent is phenol/1,1,2,2 ,-sym-tetrachloroethane (mass ratio 50/50), middle petrochemical industry Yizheng Fine company limited；
Dibenzyl sorbitol, Millad NX8001, heat decomposition temperature 300 DEG C, U.S. Millken is public Department
Anti-oxidant Irganox 1010, BASF Corp. of Germany.
Pulvis Talci, 1000 mesh, Beijing benefits the nation great achievement powder body material company limited.
Azodicarbonamide, chemical pure, commercially available
Will to polyethylene terephthalate (PET), dibenzyl sorbitol Millad NX8001, Antioxidant, Pulvis Talci, CBA etc. are pre-dried, and drying process is: PET, 100 DEG C, It is vacuum dried 12 hours, then 140 DEG C, is vacuum dried 12 hours；Millad NX8001, antioxygen Agent, Pulvis Talci drying process, 100 DEG C, forced air drying 2 hours.By dried raw material according to one After fixed ratio (as shown in table 1) is weighed, mix homogeneously in homogenizer.To mix Material add in the single screw extrusion machine rotated (single screw diameter be 65mm, draw ratio is 40), Polymer melt under screw rod turning effort, CBA decomposition discharges volatile gas, And uniform with Mixing of Polymer Melt, it is being gradually lowered each district temperature near head exit, is making mouth Mould exit melt temperature carries to head exit between 245 DEG C, and mouth die outlet is sheet die, Sheet die a size of 200X0.6mm.Extruder each segment process parameter is shown in Table 2, and obtains PET Foam sheet.
The performance of the method for testing test gained PET foam sheet identical with embodiment, result such as table 1 Shown in.
Embodiment 5
Material same as in Example 1, difference is that each constituent content is different, is specifically shown in Table 1 Shown in；Foam process is different, for injection foaming, specific as follows:
Will to polyethylene terephthalate (PET), DMDBS, antioxidant, Pulvis Talci etc. in advance Being dried, drying process is: PET, 100 DEG C, is vacuum dried 12 hours, then 140 DEG C, vacuum It is dried 12 hours；DMDBS, antioxidant, Pulvis Talci drying process, 100 DEG C, forced air drying 2 is little Time.After dried raw material is weighed according to certain ratio (as shown in table 1), in high-speed stirring Mix mix homogeneously in machine.The material mixed is added (screw in injection molding machine diameter in the injection machine rotated For 25mm, draw ratio is 30), by metering pumping system, a certain proportion of nitrogen is pumped into crowded Go out the polymer melt in machine.Under screw rod rotates, the nitrogen of injection and PET resin melt composition Homogeneous phase solution, controlling injection machine back pressure is 18MPa, melt temperature 260 DEG C, injection machine in injection machine Each segment process parameter is shown in Table 3, and the PET melt containing foaming agent mixing plastified is injected In flat plate mold, obtain PET microcellular foam material.The PET microcellular foam material obtained is entered Row the performance test results is as shown in table 4.
Embodiment 6
Identical with the material of embodiment 5 and technique, difference is that each constituent content is different, tool Body is shown in Table 3, and the microcellular foam material obtained is carried out performance test, test result such as table 4 Shown in.
Embodiment 7
Identical with the material of embodiment 4, difference is that the content of each component is different, is specifically shown in Shown in table 3.Foam process is CBA injection foaming, specific as follows:
Will to polyethylene terephthalate (PET), dibenzyl sorbitol, Millad NX8001, Antioxidant, Pulvis Talci, CBA etc. are pre-dried, and drying process is: PET, 100 DEG C, It is vacuum dried 12 hours, then 140 DEG C, is vacuum dried 12 hours；DMDBS, antioxidant, Talcum Dried bean noodles drying process, 100 DEG C, forced air drying 2 hours.By dried raw material according to certain ratio After (as shown in table 1) weighs, mix homogeneously in homogenizer.The material mixed is added Enter in the injection machine rotated (a diameter of 25mm of screw in injection molding machine, draw ratio is 30), turn at screw rod Under Dong, CBA decomposition discharges volatile gas, and equal with PET resin melt composition Phase solution, controlling injection machine back pressure is 18MPa, and melt temperature 275 DEG C in injection machine, injection machine is each Segment process parameter is shown in Table 3, and the PET melt containing foaming agent that mixing has plastified is injected into In flat plate mold, obtain PET microporous foam goods, the PET microcellular foam material obtained is carried out The performance test results is as shown in table 4.
Embodiment 8
Material same as in Example 7 and technique, difference is that each constituent content is different, sends out Bubble technological parameter is different, is specifically shown in Table 3, obtains the performance test of PET microcellular foam material Result is as shown in table 4.
Comparative example 1
Foam process same as in Example 1, difference is composition of aromatic polyester composition Difference, without glucitol compounds in this comparative example, concrete each constituent content and process conditions are shown in Shown in table 1, the performance obtaining PET expanded material is as shown in table 2.
Comparative example 2
Foam process the same as in Example 4, difference is the one-tenth of composition of aromatic polyester Divide difference, without glucitol compounds in this comparative example, concrete each constituent content and process conditions Being shown in Table 1, the performance obtaining PET expanded material is as shown in table 2.
Comparative example 3
Foam process same as in Example 5, difference is the one-tenth of composition of aromatic polyester Divide difference, without glucitol compounds in this comparative example, concrete each constituent content and process conditions Being shown in Table 3, the performance obtaining PET expanded material is as shown in table 4.
Comparative example 4
Foam process same as in Example 7, difference is the one-tenth of composition of aromatic polyester Dividing difference, this comparative example is without glucitol compounds, and concrete each constituent content and process conditions are shown in Shown in table 3, the performance obtaining PET expanded material is as shown in table 4.
Table 1
Table 2
Table 3
Table 4
Although description above and accompanying drawing represent the exemplary embodiment of present invention, it will be appreciated that In the case of the spirit, scope and sphere of the equivalent feature without departing from appended claims, can To make various supplement, to revise and replace.Specifically, it will be apparent to those skilled in the art that In the case of without departing from its spirit or basic feature, the present invention can with other form, structure, Layout, ratio, size, and implement with other element, material and parts.Additionally, can be Many changes of method described herein/technique are carried out in the range of present invention.The skill of this area Art personnel it will be further understood that, this embodiment can be used for structure, layout, ratio, size, Material and many amendments of parts, or, in the practice of present invention, it is particularly suitable for spy Determine environment and operation requirement, without departing from principles described in this document.Therefore, the reality of invention at present It should be considered as the most all illustrative and not restrictive for executing example.Claims Should be construed broadly, to include to pass through those skilled in the art without departing from equivalent feature The various modification of the present invention that may be made that in the case of scope and sphere and embodiment.

Claims (11)

1. an aromatic polyester microcellular foam material, prepared by the foamed technique of composition of aromatic polyester, it is characterized in that: described composition of aromatic polyester includes aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 weight portion；Described aromatic polyester microcellular foam material apparent density is 0.05-1.10g/cm3, rate of closed hole is not less than 80%, and the molecular formula of described sorbitol benzal derivant is as follows:
Wherein, R1、R2Represent alkyl or the alkyl of alkoxyl, hydroxyl or halogen that hydrogen atom, carbon number are 1～4.
Aromatic polyester microcellular foam material the most according to claim 1, it is characterised in that: described aromatic polyester is polyethylene terephthalate.
Aromatic polyester microcellular foam material the most according to claim 1 and 2, it is characterised in that: the heat decomposition temperature of described sorbitol benzal derivant is not less than 300 DEG C.
Aromatic polyester microcellular foam material the most according to claim 3, it is characterised in that: the heat decomposition temperature of described sorbitol benzal derivant is not less than 320 DEG C.
Aromatic polyester microcellular foam material the most according to claim 1, it is characterised in that described sorbitol benzal derivant is 2,4-O-(3,4-dimethyl benzylidene)-D-glucitol (DMDBS).
Aromatic polyester microcellular foam material the most according to claim 1, it is characterised in that the 1-3% that addition is described aromatic polyester gross weight of described sorbitol benzal derivant.
7. a preparation method for aromatic polyester microcellular foam material, including:
(1) by aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 weight portion, add in extruder after being mixed in proportion into composition of aromatic polyester；The molecular formula of described sorbitol benzal derivant is as follows:
Wherein, R1、R2Represent alkyl or the alkyl of alkoxyl, hydroxyl or halogen that hydrogen atom, carbon number are 1～4；
(2) injecting physical blowing agent in described extruder, the injection rate of described physical blowing agent is the 0.1-10% of described composition of aromatic polyester gross weight, mix homogeneously in described extruder；
(3) by the described composition of aromatic polyester melt cooling to 220-250 DEG C containing described physical blowing agent, mouth die pressure is more than 3MPa, obtains aromatic polyester microcellular foam material through mouth die foaming and setting.
8. a preparation method for aromatic polyester microcellular foam material, including
(1) by aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 weight portion, CBA 0.1-5 weight portion, add after being mixed in proportion in extruder, making it melt under heating and screw rod shearing plastication, described CBA decomposes to give off escaping gas, mix homogeneously in described extruder；The molecular formula of described sorbitol benzal derivant is as follows:
Wherein, R1、R2Represent alkyl or the alkyl of alkoxyl, hydroxyl or halogen that hydrogen atom, carbon number are 1～4；
(2) the aromatic polyester melt blend containing described CBA is by obtaining aromatic polyester microcellular foam material after die extrusion cooled sizing.
9. a preparation method for aromatic polyester microcellular foam material, including:
(1) by aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 weight portion, adds after being mixed in proportion in injection machine, makes it melt under heating and screw rod shearing plastication；The molecular formula of described sorbitol benzal derivant is as follows:
Wherein, R1、R2Represent alkyl or the alkyl of alkoxyl, hydroxyl or halogen that hydrogen atom, carbon number are 1～4；
(2) being sent into by physical blowing agent in the aromatic polyester polymer melt in described injection machine, the addition of described physical blowing agent is the 0.1-1% of composition of aromatic polyester gross weight, mix homogeneously in injection machine；
(3) by the aromatic polyester melt blend containing described physical blowing agent by injection nozzle injection mould obtains aromatic polyester microcellular foam material after cooled sizing.
10. a preparation method for aromatic polyester microcellular foam material, including:
(1) by aromatic polyester 100 weight portion, sorbitol benzal derivant 0.5-5 weight portion, antioxidant 0.1-0.3 weight portion, chain extender 0-2 weight portion, Nucleating Agent 0-2 weight portion, CBA 0.1-1 weight portion adds in injection machine after being mixed in proportion, and makes it melt under heating and screw rod shearing plastication；The molecular formula of described sorbitol benzal derivant is as follows:
Wherein, R1、R2Represent alkyl or the alkyl of alkoxyl, hydroxyl or halogen that hydrogen atom, carbon number are 1～4；
(2) by the aromatic polyester melt blend containing described CBA by injection nozzle injection mould obtains aromatic polyester microcellular foam material after cooled sizing.
11. according to the preparation method of the aromatic polyester microcellular foam material according to any one of claim 7 to 10, it is characterised in that: the 1-3% that addition is described aromatic polyester gross weight of described sorbitol benzal derivant.
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