CN109605708A - A kind of thermoplastic polyester foam shaping by extrusion method - Google Patents
A kind of thermoplastic polyester foam shaping by extrusion method Download PDFInfo
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- CN109605708A CN109605708A CN201811534002.3A CN201811534002A CN109605708A CN 109605708 A CN109605708 A CN 109605708A CN 201811534002 A CN201811534002 A CN 201811534002A CN 109605708 A CN109605708 A CN 109605708A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/03—Extrusion of the foamable blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention provides a kind of thermoplastic polyester foam shaping by extrusion methods, comprising: thermoplastic polyester, lubricant and blowing promotor are added in double screw extruder and melted, the outlet pressure of double screw extruder is 3MPa~10MPa；It is passed through physical blowing agent in thermoplastic polyester melt, is pumped in single screw extrusion machine after mixing through melt, the inlet pressure of single screw extrusion machine is 15MPa~25MPa；The temperature of the thermoplastic polyester melt containing physical blowing agent is reduced by single screw extrusion machine, through mouth mold extrusion foaming, cooling and shaping obtains thermoplastic polyester foaming product.Party's normal plane realizes the efficient, stable of thermoplastic polyester foaming, high-quality production by addition fire-resistant lubricants and using Melt Pump regulation.
Description
Technical field
The present invention relates to polymer extruding forming method, in particular to a kind of side of thermoplastic polyester foam shaping by extrusion
Method.
Background technique
Foamed plastics is that wherein being filled with the composite material of a large amount of bubbles, thus have light weight, section using plastics as matrix
Save that material, specific strength are high, thermal conductivity is low, heat-insulating sound-insulating, can absorb the excellent properties such as shock loading, so be widely used as packaging,
Heat-insulated, anti-freezing and heat-insulating, buffering vibrationproof, quieter material, in building, transport, daily necessities, packaging and space flight, navigation, state
Anti- equal fields have been widely used.Conventional polymeric foams such as polyurethane foam (PU), polyethylene (PE) with
And polystyrene foam (PS) etc., there is certain deficiency in material performance itself and processing method.For example, polyurethane foam
The residue that isocyanates etc. is harmful to the human body can be released during the preparation process, and the polyurethane presence after foaming is difficult to back
The problem of receipts, polystyrene foam plastics are subject to certain restrictions, polyethylene since its high temperature resistance is poor using field
Plastics the disadvantages of there are poor mechanical property and not high heat resistances.Therefore, people have been devoted to develop high performance foam plastic
Expect to meet the increasingly increased requirement to material property in society and development in science and technology to widen the application field of foamed material.
Thermoplastic polyester has excellent heat resistance and mechanical property, compared to traditional foamed plastics, thermoplastic polyester
Foam has good dimensional stability, excellent mechanical performance and fatigue resistance under high temperature, low cigarette, fire-retardant, nontoxic, low water suction
Rate, good barrier properties for gases and recyclable the advantages that recycling, in electronics industry, buffering package, construction material, traffic fortune
Defeated, field of wind power generation has wide application prospect.
In order to overcome thermoplastic polyester melt strength is low to be difficult to maintain foam structure, abscess is be easy to cause to collapse and merge
The disadvantages of, the prior art mainly passes through addition chain extender or crosslinking agent improves the viscosity of polyester.For example, United States Patent (USP) US
US4981631 discloses polyethylene terephthalate (PET) foaming pallet, using branching agent pyromellitic acid anhydride
(PMDA) PET melt viscoplasticity is improved, and adds the polyolefin (PP, PE) of 1-6% as nucleating agent, 2 times of maximum expansion ratio.
US3553157 is disclosed the PMDA of 0.5-1wt% is mixed with PET after be added extruder improve PET melt viscosity method, but
Without reference to foam production.Japan Patent 59-210955 (1984) discloses PET foaming method, by PET and 0.01-
The multi-group epoxy compound of 2mol%PMDA and 0.03-2.5mol% mixes the melt strength for improving PET.US5000991
The technique for preparing PET foaming is disclosed with US5134028, the characteristics of process is the change containing two or more anhydride groups
Object is closed, as PMDA is added in PET.Wherein, US5000991 patent discloses the dosage of PMDA in 0.05-5.0wt%, it is indicated that when
PMDA content is more than 5%, will there is gel generation.PMDA include: with the mixed method of PET extruder is added after directly mixing, or
It causes masterbatch (using PET or other polymers as matrix) to add in advance, or PET is first added, PMDA is added after melting, but simultaneously
The advantage and disadvantage of more not these types of technique and the influence foamed to PET.In addition, US5000991 patent also discloses addition 0.05-
5% sodium carbonate, and illustrate that sodium carbonate, which is added, can make foamed material have higher stretch percentage elongation and more tiny abscess.
US5958164 discloses a kind of thermoplastic polyester extrusion foaming method, using recycling and primary PET as raw material, exempts from dry straight
Extrusion foaming is connect, using PMDA and sodium carbonate as chain extender, butane prepares PET foam sheet as foaming agent, and sheet material is close
Spend 0.23-0.26g/cm3.EP2163577A1 discloses the preparation process of expanded polyester chain extender master batch, chain extender master batch packet
Anhydride compound, antioxidant and oxazoline compound etc. are included, the pressure and torque ripple in energy balanced reaction extrusion process make
The more stable progress of reactive extrursion foaming process.
The above patent disclosure is to improve the viscosity of PET resin using polyfunctional group chain extender to improve its foaminess
Energy.The functional group number of usual chain extender is greater than 2, preferably greater than 4 or more.This is resulted in during squeezing out chain extending reaction, body
It is that viscosity can increase suddenly, so that pressure rise in extrusion system, torque increases, and melt transports difficulty, and mistake to head downstream
High melt viscosity and melt elasticity, so that melt is broken by being easy to appear serious melt when the small mouth mold gap of foaming die
Phenomenon is split, causes product surface coarse and gas escape, such as sharkskin phenomenon, it is difficult to obtain qualified foaming product.
Summary of the invention
To realize the efficient, stable of thermoplastic polyester foaming, high-quality production, the present invention provides a kind of thermoplasticity
The method of polyester foam shaping by extrusion.
The method of thermoplastic polyester foam shaping by extrusion provided by the invention, comprising: by thermoplastic polyester, lubricant and hair
Bubble auxiliary agent, which is added in double screw extruder, to be melted, and the outlet pressure of double screw extruder is 3MPa~10MPa；It is squeezed in twin-screw
It is passed through physical blowing agent in the thermoplastic polyester melt in machine out, is pumped in single screw extrusion machine after mixing through melt, single spiral shell
The inlet pressure of bar extruder is 15MPa~25MPa；By single screw extrusion machine by the thermoplastic polyester containing physical blowing agent
The temperature of melt reduces, and through mouth mold extrusion foaming, cooling and shaping obtains thermoplastic polyester foaming product.
In the above-mentioned methods, it is preferable that the additive amount of lubricant is the 0.5%~5% of thermoplastic polyester total weight.
In the above-mentioned methods, it is preferable that the thermal decomposition temperature of lubricant is higher than 350 DEG C and lubricant is selected from alicyclic organic
Fat acid esters, amides compound, low molecular weight polyethylene wax, low molecular weight oxidized polyethylene wax, in dimethyl silicone polymer
One or more combinations.
In the above-mentioned methods, it is preferable that lubricant is added in a manner of master batch, by weight, master batch include 10%~
50% lubricant.
In the above-mentioned methods, it is preferable that be connected between double screw extruder and single screw extrusion machine by Melt Pump, melted
The inlet pressure of body pump is 3MPa~10MPa, and outlet pressure is 15MPa~20MPa.
In the above-mentioned methods, it is preferable that blowing promotor includes chain extender, nucleating agent, antioxidant and heat stabilizer.
In the above-mentioned methods, it is preferable that chain extender is anhydride compound, and additive amount is thermoplastic polyester total weight
0.2%~1%.
In the above-mentioned methods, it is preferable that chain extender is multifunction group epoxy class compound, and additive amount is that thermoplastic polyester is total
The 0.5%~3% of weight.
In the above-mentioned methods, it is preferable that chain extender is added in a manner of master batch, by weight, in master batch include 8%~
30% chain extender.
In the above-mentioned methods, it is preferable that physical blowing agent be carbon dioxide, nitrogen, iso-butane, isopentane, pentamethylene, oneself
Alkane, heptane, one of fluorochemical or multiple combinations, total addition level are the 1%~10% of thermoplastic polyester total weight.
The method of thermoplastic polyester foam shaping by extrusion provided by the invention, on the one hand by addition fire-resistant lubricants come
Melt temperature and improvement products surface quality effectively in control process；On the other hand, regulated and controled using Melt Pump, pass through control
Double screw extruder outlet pressure processed and single screw extrusion machine inlet pressure, to avoid thermoplastic polyester in double screw extruder
Thermal decomposition and guarantee head pressure reach foaming require.To realize thermoplastic polyester foaming it is efficient, stable,
High-quality production.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described.
Fig. 1 is the flow chart of the method for the thermoplastic polyester foam shaping by extrusion of embodiment according to the present invention.
Fig. 2 is the schematic diagram of the device for thermoplastic polyester foam shaping by extrusion of embodiment according to the present invention.
Fig. 3 is the thermogravimetric curve according to the lubricant pentaerythritol stearate of the embodiment of the present invention.
Specific embodiment
As shown in Figure 1, the invention discloses a kind of methods of thermoplastic polyester foam shaping by extrusion, comprising the following steps:
Thermoplastic polyester, lubricant and blowing promotor are added in double screw extruder and melt by S1, double screw extruder
Outlet pressure be 3MPa~10Mpa.Wherein, blowing promotor includes chain extender, nucleating agent, antioxidant and heat stabilizer
S2 is passed through physical blowing agent in the thermoplastic polyester melt in double screw extruder, is pumped to after mixing through melt
In single screw extrusion machine, the inlet pressure of single screw extrusion machine is 15MPa~25MPa.In this step, in double screw extruder
Thermoplastic polyester melt in be passed through physical blowing agent after, form homogeneous phase solution after the screw mixes of double screw extruder.
The temperature of thermoplastic polyester melt containing physical blowing agent is reduced to T, T by single screw extrusion machine by S3m-10
℃≤T≤Tm+ 30 DEG C, wherein TmFor the fusing point of thermoplastic polyester.Through mouth mold extrusion foaming, cooling and shaping obtains thermoplastic polyester
Foaming product.In this step, when thermoplastic polyester is PET, the temperature of melt is reduced to 240 by single screw extrusion machine
DEG C~260 DEG C.Through mouth mold extrusion foaming, foaming product is cooled and shaped on cooling and shaping device and obtains thermoplastic poly ester foaming system
The density of product, final gained thermoplastic polyester foaming product is 60kg/m3~300kg/m3。
Wherein, thermoplastic polyester is primarily referred to as aromatic polyester, specifically passes through contracting by aromatic dicarboxylic acid and dihydric alcohol
It is poly- to react obtained polymer, such as polyethylene terephthalate, polypropylene terephthalate, poly terephthalic acid fourth
Diol ester and their copolymer, preferably polyethylene terephthalate (PET).In addition, thermoplastic polyester removes
Outside aromatic dicarboxylic acid and dihydric alcohol, it can also contain third component copolymer, such as resorcinol.The characteristic of aromatic polyester
Viscosity is between 0.6~0.85dl/g, and according to the test of GB/T14190-2008 method, (solvent uses phenol/tetrachloro to inherent viscosity
Ethane (mass ratio 50/50))).It can also be using the thermoplastic polyester of recycling as raw material, such as PET of recycling, inherent viscosity
More than or equal to 0.6dl/g.
Wherein, chain extender refers to and can react with the terminal hydroxy group of thermoplastic polyester or carboxyl end group containing two or more
One of compound, including anhydride compound, epoxy compounds and/or oxazoline class compound or multiple combinations.Acid anhydrides
Class compound such as pyromellitic acid anhydride (PMDA), naphthalene tetracarboxylic acid acid anhydride, benzene tetrone tetracarboxylic anhydride and pentamethylene tetracarboxylic anhydride, preferably
For pyromellitic acid anhydride (PMDA).Epoxy compounds include multi-group epoxy compound or epoxy oligomer, such as Bath
Husband companyADR-4368, four glycidyl group diaminodiphenyl-methane (TGDDM) etc..Oxazoline class chemical combination
Object refers to the compound containing nitrogen oxygen five-ring heterocycles in molecular structure, can be monosubstituted oxazolyl quinoline or double oxazolines, preferably double evils
The double oxazolines of oxazoline, such as 1,3- phenyl or the double oxazolines of Isosorbide-5-Nitrae-phenyl.The additive amount of anhydride chain extender is usually thermoplastic poly
The 0.2%~1% of ester total weight, preferably 0.3%~0.5%；The additive amount of ADR class epoxy compounds chain extender is thermoplastic
The 0.5%~3%, preferably 0.6%~1.5% of property polyester total weight, more preferably 0.8%~1.2%；The addition of oxazoline
Amount is the 0.5%~2% of thermoplastic polyester total weight, preferably 0.8%~1.2%.In the present invention, anhydride chain extender can
To be used together with epoxies chain extender or be used together with oxazoline class chain extender.Chain extender is added in a manner of master batch,
It can be specifically processed into the master batch using thermoplastic polyester as matrix, by weight, in master batch include 8%~30% chain extension
Agent, preferably 10%~20%.
Physical blowing agent is carbon dioxide, nitrogen, low molecular weight alkanes, such as iso-butane, isopentane, pentamethylene, hexane, heptan
Alkane, fluorochemical, such as HCFC-142a, HCFC-22, HFC-134a, HFC-152a, HFO-1234ze, HFO-1233zd, 1,
One of HCFO-1233zd etc. or multiple combinations, total addition level are the 1%~10% of thermoplastic polyester total weight.
Nucleating agent, i.e. Nucleating Agent can be inorganic nucleator or organic nucleating agent, and inorganic nucleator includes talcum
Powder, calcium carbonate, nano silica, nano montmorillonite etc., organic nucleating agent are azodicarbonamide (AC) etc., and nucleating agent adds
Enter amount for the 0%~5% of thermoplastic polyester total weight, preferably 1%~3%.
Wherein, antioxidant is hindered phenol antioxygen, such as (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta
Four alcohol esters) (antioxidant 1010), (3- (1,1- dimethyl ethyl)-β-[3- (1,1- dimethyl ethyl) -4- hydroxyphenyl] -4- hydroxyl
Base-Beta-methyl benzoic acid -1,2- ethylidene ester) (antioxidant O3), 18 carbon of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid
Bis- [3,5- di-tert-butyl-hydroxy phenyl] acrylate (antioxidant 259) of acid esters (antioxidant 1076), hexylene glycol, (1,3,5
Three (3,5- di-tert-butyl-4-hydroxyl benzyl) -1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones) (antioxidant 3114), antioxygen
Agent additive amount is the 0.1%~0.2% of thermoplastic polyester total weight.
Wherein, heat stabilizer is phosphate compounds, such as triphenyl phosphate, phosphonoacetate, (bis- (2,4-
Di-tert-butyl-phenyl) pentaerythritol phosphite), four (2,4- di-tert-butyl-phenyl -4,4 ' xenyl) bis-phosphites, three
The additive amount of (2,4- di-tert-butyl-phenyl) phosphite ester and heat stabilizer be thermoplastic polyester total weight 0.2%~
0.5%.Antioxidant individually or is used in compounding with heat stabilizer.Antioxidant and/or heat stabilizer can be processed into thermoplastic poly
Ester is the master batch of matrix, is added in thermoplastic polyester in the form of master batch.
In order to improve the foam performance of thermoplastic polyester, it is added to chain extender or branching agent in double screw extruder, squeezes
Chain extending reaction occurs during out, so that the viscoplasticity of thermoplastic polyester melt significantly improves.But thermoplastic polyester melt
Viscoplasticity significantly improves and can make in extrusion process that Shear heating is serious, easily causes polyester thermal degradation, influences product quality, separately
On the one hand in the high shear zone of foaming die melt fracture phenomena easily occurs, so that product surface is coarse or even foaming product table
Phenomena such as face is cracked.
In order to overcome these disadvantages in polyester extrusion and foaming process, the present invention adds lubricant in extrusion process, and one
Aspect reduces the interaction between polyester macromolecule chain, reduces shear heat, on the other hand, reduces melt and machine barrel, head gold
Belong to the friction between inner wall, significantly improves products surface quality.The thermal decomposition temperature of lubricant is higher than 350 DEG C, is selected from alicyclic organic
In fat acid esters, amides compound, low molecular weight polyethylene wax, low molecular weight oxidized polyethylene wax and dimethyl silicone polymer
One or more combinations.For example, pentaerythritol stearate, modified ethylene bis stearic amide EBS etc..The additive amount of lubricant is
The 0.5%~5% of thermoplastic polyester total weight, preferably 1%~5%, more preferable 1%~3%.Lubricant can pass through the side of master batch
Formula is added in thermoplastic polyester extrusion and foaming process, preferably using thermoplastic polyester as master batch carrier, such as poly terephthalic acid second two
Alcohol ester, polybutylene terephthalate (PBT), wherein by weight, master batch includes 10%~50% lubricant.
Device for thermoplastic polyester foaming of the invention uses Dual inoculation train, and the first rank is same
To rotating twin-screw extruder, second-order is single screw extrusion machine, uses melt series connection of pumps between two extruders, Fig. 2 be for
One preferred embodiment of the device of thermoplastic polyester foaming, Fig. 2 label declaration are as follows: the bis- spiral shells of 1- twin-screw feeder 2-
Bar extruder 3- counterbalance valve 4- gas dosing pumps 5- shut-off valve 6- gas source 7- test point 8- Melt Pump 9- test point 10- single screw rod and squeezes
Machine 11- foaming die out.
As shown in Fig. 2, device includes: co-rotating twin screw extruder 2 (screw diameter 65mm, L/D=32；Nanjing
Chuan Bo mechanical equipment Co., Ltd), Melt Pump 8 (ZB-C300, Zhengzhou Bart's Melt Pump Co., Ltd), a set of vacuum system, list
Screw extruder 10 (diameter 150mm, draw ratio 23), static mixer, foaming die 11 (fish tail based plate head) and peace
Cooling and shaping device loaded on 11 outlet downstream of foaming die.Wherein, vacuum system is connected with 2 exhaust outlet of double screw extruder
It connects.Melt Pump 8 is installed in series in double screw extruder outlet and single screw extrusion machine inlet connection, that is, double screw extruder
Outlet is connected with melt pump intake, and melt pump discharge is connected with single screw extrusion machine entrance.Single screw extrusion machine outlet with
Foaming die 11 is connected.Cooling and shaping device is mounted on 11 downstream of foaming die.In foamed forming process, peace can be passed through
Double screw extruder outlet pressure P1 and single screw extrusion machine are monitored respectively mounted in the pressure sensor of test point 7 and test point 9
Inlet pressure P2.Device further includes gas injection system, and gas injection system includes gas source 6, shut-off valve 5, counterbalance valve 3, gas dosing pump 4,
In foamed forming process, physical blowing agent is injected into the melt of double screw extruder 2 by gas injection system.
In the foaming process of thermoplastic polyester, on the one hand, double screw extruder head pressure is excessively high to be easy to cause material
The resistance being subject in twin-screw increases, and foaming agent injection is difficult, and the Shear heating that in addition material is subjected in twin-screw increases,
Thermal degradation easily occurs；Hypotony will cause foaming agent and dissolve difficulty in polyester fondant, on the other hand, in order to improve foaming system
Product nucleation density usually requires that with sufficiently high head pressure, and second-order single screw rod is primarily to reduce melt temperature,
So the conveying capacity of melt is weaker, especially to low temperature high-viscosity melt conveying capacity.To solve the above-mentioned problems, of the invention
In by control Melt Pump and single screw rod revolving speed so that twin-screw exit melt pressure P1 is lower than 10MPa, even lower than 5MPa,
Single screw extrusion machine inlet pressure P2 is higher than 12MPa, preferably higher than 15MPa.For example, preferred embodiment in accordance with the present invention, it will
Pressure P1 is maintained at any setting value between 3MPa~10MPa, preferably between 3MPa~8MPa, more preferable 5MPa~8MPa it
Between.By controlling Melt Pump, so that single screw rod inlet pressure P2 is more than or equal to 15MPa, it is appropriate to be more than or equal to 18MPa.
Control melt pump inlet pressure is 3MPa~10MPa, preferably 3MPa~8MPa, more preferable 5MPa~8MPa；Control
Melt pump discharge pressure is more than or equal to 15MPa, and preferably greater than or equal to 18MPa is more selected as 15MPa~20MPa.
Twin-screw outlet pressure and single screw rod outlet pressure can be by manually adjusting melt revolution speed and single screw rod revolving speed
It realizes, can also be realized by automatic feedback control system.Such as pressure is separately installed in Melt Pump entrance melt junction
Sensor monitors double screw extruder outlet pressure P1 and single screw extrusion machine inlet pressure P2, using double-closed-loop control system
System is control target with twin-screw inlet pressure P1 and single screw rod outlet pressure P2, adjusts control Melt Pump by PLC program and turns
Speed and single screw rod revolving speed realize two close cycles automatic feedback control, so that P1 maintains any setting value between 3MPa~10MPa, it is excellent
Select any setting value between 3MPa~8MPa, any setting value between more preferable 5MPa~8MPa；P2 maintain 15MPa~
Any setting value of 20MPa.Specific embodiment is as follows:
Embodiment 1:
Raw material: polyethylene terephthalate (PET), BG80, Sinopec Yizheng Fiber Optical plant Co., Ltd, inherent viscosity
0.8dl/g；
Chain extender, pyromellitic dianhydride (PMDA), Sinopharm Chemical Reagent Co., Ltd.；
Nucleating agent: talcum powder, 1000 mesh；
Antioxidant: four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters (antioxidant 1010), Nanjing
Bright Chemical Co., Ltd., Holley；
Lubricant: pentaerythritol stearate PETs, photochemistry auxiliary agent Co., Ltd, Jiangsu Xingtai state, thermal decomposition temperature
400℃.Decomposition temperature is tested using thermal gravimetric analyzer, 10 DEG C/min of heating rate, and atmosphere is nitrogen, heat on TG temperature curve
Temperature when weight loss rate maximum is defined as thermal decomposition temperature.Fig. 3 is the thermogravimetric curve of pentaerythritol stearate.
Foam process: entire extrusion system, dry PET are preheated；After system to be extruded reaches set temperature, single screw rod is opened
Then extruder successively opens Melt Pump, double screw extruder, feed system, by the PET 100kg of drying process, chain extender
PMDA 0.3kg, antioxidant 1010,0.1kg, talcum powder 1kg, lubricant pentaerythritol stearate PETs 0.5kg mixing are equal
It is added after even from the feed opening of twin-screw feeder 1 (as shown in Figure 2), it is then molten by PET of the gas injection system into twin-screw
Physical blowing agent pentamethylene is injected in body, agent additive amount is the 2wt% of PET total addition level, after waiting heads to have gassiness material extrusion,
Each section of single screw extrusion machine of temperature is reduced, melt revolution speed and single screw rod revolving speed are controlled, so that double screw extruder exit
Pressure P1 and single screw extrusion machine inlet pressure P2 control in setting value, specific process parameter is as shown in table 1.Head pressure
Power 10MPa obtains PET foaming plate.The density of PET foaming plate is tested according to GB/T6343-2009, the results are shown in Table 1.
Embodiment 2
Raw material and technique are with embodiment 1, the difference is that lubricant pentaerythritol stearate is added in the form of master batch
Enter, master batch concentration 50wt%, master batch matrix is PET, and additive amount is the 6% of PET total weight, adds up to pentaerythritol stearate
Additive amount is the 3wt% of PET total weight.
Embodiment 3
Raw material and technique are with embodiment 1, the difference is that chain extender uses epoxy group chain extender, the ADR of BASF AG
4368, additive amount 1wt%；Lubricant is 300 DEG C of thermal decomposition temperature, female with 50% using modified ethylene bis stearic acid amide EBS
Grain Concentration Forms are added, and master batch additional amount is the 10wt%, foaming agent CO of PET total weight2And pentamethylene, it is pumped respectively from two sets
Send system and two gas injection port injections, CO2Injection rate be PET total weight 1wt%, the injection rate of pentamethylene is PET gross weight
The 2wt% of amount.
Embodiment 4
Raw material and technique are added in the form of master batch with embodiment 1 the difference is that lubricant is oxidized polyethylene wax,
Master batch concentration 20wt%, matrix PET, master batch additional amount is the 10wt% of PET total weight, adds up to polydimethyl siloxane content
For the 2wt% of PET total weight, heat stabilizer four (2, di-tert-butyl-phenyl -4 4-, 4 ' xenyls) bis-phosphite, addition are added
Amount is the 0.2wt% of PET total weight.
Embodiment 5
Raw material and technique are with embodiment 1, the difference is that addition uses carbon dioxide for foaming agent, foaming agent injection rate
For the 1wt% of PET total weight.
Comparative example 1
Raw material is a difference in that with embodiment 3 and does not add lubricant, and extrusion system is double screw extruder Series Sheet spiral shell
Bar extruder, screw diameter and draw ratio do not have Melt Pump with embodiment 1 between twin-screw and single screw rod, PET extrusion foaming
When, pressure transient between double screw extruder and single screw extrusion machine is in cyclic fluctuation, ranges up to 20MPa, pass through tune
Single screw rod revolving speed is saved, pressure can be reduced to 3MPa, and it as a result causes head pressure and discharging fluctuation larger, can not normally produce, and
Obtain PET foaming product rough surface.
Comparative example 2
Raw material is with embodiment 2, the difference is that lubricant is not added, in extrusion and foaming process, each tune of extruder
Temperature setting is same as Example 2, as a result, exit PET melt temperature is high, extrudate rough surface, has apparent melt broken
Phenomenon is split, gas escape obtains PET foaming plate apparent density 350kg/m3。
Thermoplastic polyester foam shaping by extrusion method provided by the invention is added to high temperature resistant lubrication in foaming process
Agent, reduces after chain extension between polyester macromolecule and the friction between polyester fondant and extruder inner wall, mould inner wall, on the one hand
The Shear heating of extrusion process can be reduced, effectively control melt temperature；On the other hand facing for melt fracture generation can be improved
Boundary's shear rate avoids that melt fracture occurs, improves products surface quality.Also using the outlet of Melt Pump regulation double screw extruder
On the one hand pressure and single screw extrusion machine inlet pressure keep double screw extruder to export relatively low melt pressure, are lower than
5MPa, is conducive to the smooth injection of foaming agent, while reducing the Shear heating of double screw extruder, avoids thermoplastic polyester double
Thermal decomposition in screw extruder, lays the foundation for steady extruding；On the other hand, the high inlet pressure of single screw extrusion machine is to expand
The conveying of high viscosity polyester fondant provides power after chain, can guarantee that head pressure reaches foaming and requires.It provides through the invention
It is raw to realize the efficient, stable of thermoplastic polyester foam shaping by extrusion, high-quality for thermoplastic polyester foam shaping by extrusion method
It produces.
Above embodiments, only a specific embodiment of the invention, to illustrate technical solution of the present invention, rather than to it
Limitation, scope of protection of the present invention is not limited thereto, although the present invention is described in detail referring to the foregoing embodiments,
Those skilled in the art should understand that: anyone skilled in the art the invention discloses technology model
In enclosing, still it can modify to technical solution documented by previous embodiment or variation can be readily occurred in, or to it
Middle some technical characteristics are equivalently replaced；And these modifications, variation or replacement, do not make the essence of corresponding technical solution de-
Spirit and scope from technical solution of the embodiment of the present invention, should be covered by the protection scope of the present invention.Therefore, of the invention
Protection scope shall be subject to the protection scope of the claim.
Claims (10)
1. a kind of thermoplastic polyester foam shaping by extrusion method characterized by comprising
Thermoplastic polyester, lubricant and blowing promotor are added in double screw extruder and melted, the double screw extruder
Outlet pressure is 3MPa~10MPa；
It is passed through physical blowing agent in the thermoplastic polyester melt in the double screw extruder, is pumped to list through melt after mixing
In screw extruder, the inlet pressure of the single screw extrusion machine is 15MPa~25MPa；
The temperature of the thermoplastic polyester melt containing the physical blowing agent is reduced by the single screw extrusion machine, through mouth mold
Extrusion foaming, cooling and shaping obtain thermoplastic polyester foaming product.
2. the method according to claim 1, wherein the additive amount of the lubricant is that the thermoplastic polyester is total
The 0.5%~5% of weight.
3. the method according to claim 1, wherein the thermal decomposition temperature of the lubricant be higher than 350 DEG C, and
The lubricant is selected from organic fatty acid esters, amides compound, low molecular weight polyethylene wax, low molecular weight oxidic polyethylene
One of wax, dimethyl silicone polymer or multiple combinations.
4. method described in any one of claim 1 to 3, which is characterized in that the lubricant is added in a manner of master batch
Enter, by weight, the master batch includes 10%~50% lubricant.
5. the method according to claim 1, wherein the double screw extruder and the single screw extrusion machine it
Between be connected by the Melt Pump, the inlet pressure of the Melt Pump is 3MPa~10MPa, outlet pressure be 15MPa~
20MPa。
6. the method according to claim 1, wherein the blowing promotor includes chain extender, nucleating agent, antioxidant
And heat stabilizer.
7. according to the method described in claim 6, additive amount is institute it is characterized in that, the chain extender is anhydride compound
State the 0.2%~1% of thermoplastic polyester total weight.
8. additive amount is the heat according to the method described in claim 6, the chain extender is multifunction group epoxy class compound
The 0.5%~3% of plasticity polyester total weight.
9. the method according to any one of claim 6~8, which is characterized in that the chain extender is added in a manner of master batch
Enter, by weight, in the master batch includes 8%~30% chain extender.
10. according to the method described in claim 6, it is characterized in that, the physical blowing agent is carbon dioxide, nitrogen, isobutyl
Alkane, isopentane, pentamethylene, hexane, heptane, one of fluorochemical or multiple combinations, total addition level are the thermoplasticity
The 1%~10% of polyester total weight.
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| CN201811534002.3A CN109605708B (en) | 2018-12-14 | 2018-12-14 | Thermoplastic polyester extrusion foaming forming method |
| PCT/CN2019/082356 WO2020118986A1 (en) | 2018-12-14 | 2019-04-12 | Thermoplastic polyester extrusion foam molding method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204771A (en) * | 2019-06-11 | 2019-09-06 | 宁波邦泰汽车配件有限公司 | A kind of compound TPE foam shaping by extrusion technique |
| CN110561676A (en) * | 2019-09-18 | 2019-12-13 | 北京李尔岱摩斯汽车系统有限公司 | automatic detection system of foaming equipment |
| CN110624225A (en) * | 2019-09-24 | 2019-12-31 | 江苏正和体育用品有限公司 | Racket |
| CN113121949A (en) * | 2021-03-18 | 2021-07-16 | 浙江恒澜科技有限公司 | Master batch for polyester extrusion foaming and application thereof |
| CN114196173A (en) * | 2021-12-29 | 2022-03-18 | 丹江口东筌新材料有限公司 | PET (polyethylene terephthalate) foam material and preparation method thereof |
| CN115124834A (en) * | 2022-07-13 | 2022-09-30 | 北京化工大学 | Thermoplastic polyamide elastomer blending foaming material and preparation method thereof |
| CN115181319A (en) * | 2022-08-09 | 2022-10-14 | 北京化工大学 | Preparation method of polyphenyl ether foamable particles |
| CN115286903A (en) * | 2022-07-29 | 2022-11-04 | 维赛(江苏)复合材料科技有限公司 | Fiber-reinforced high-performance high-rate PET foam material and preparation method thereof |
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| CN114921066A (en) * | 2022-03-29 | 2022-08-19 | 浙江天振科技股份有限公司 | Foamed PET composite board and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392041A (en) * | 1994-12-27 | 2003-01-22 | 积水化成品工业株式会社 | Continuous producing method for thermoplastic polyester serial resin foamer |
| CN104349890A (en) * | 2012-06-06 | 2015-02-11 | 美国圣戈班性能塑料公司 | Thermoplastic elastomer tubing and method to make and use same |
| CN107722602A (en) * | 2017-09-26 | 2018-02-23 | 上海德亿化工有限公司 | Foamed profile of Memorability multiple spot positive feedback resilient material and preparation method thereof |
| CN108864662A (en) * | 2018-07-25 | 2018-11-23 | 南通德亿新材料有限公司 | A kind of thermoplastic polyether ester elastomer foamed material and preparation method thereof |
| CN110549582A (en) * | 2018-03-26 | 2019-12-10 | 南京法宁格节能科技股份有限公司 | Production method of thermoplastic polyurethane elastomer foamed sheet |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19800166A1 (en) * | 1998-01-05 | 1999-07-08 | Buehler Ag | Closed cell polyester foam production by reactive extrusion without granulation |
| DE10000712A1 (en) * | 2000-01-11 | 2001-07-12 | Buehler Ag | Modified thermoplastic polyester resin suitable for use in foam production are obtained by mixing and kneading a polyester with a preferably reactive chain-breaker and an elasticity-increasing additive |
| JP3686002B2 (en) * | 2001-03-16 | 2005-08-24 | 株式会社日本製鋼所 | Kneading and mixing extrusion equipment using supercritical fluid |
| CN106928663A (en) * | 2017-02-09 | 2017-07-07 | 上海越科新材料股份有限公司 | High foamability PET products and continuously extrude preparation method |
-
2018
- 2018-12-14 CN CN201811534002.3A patent/CN109605708B/en active Active
-
2019
- 2019-04-12 WO PCT/CN2019/082356 patent/WO2020118986A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392041A (en) * | 1994-12-27 | 2003-01-22 | 积水化成品工业株式会社 | Continuous producing method for thermoplastic polyester serial resin foamer |
| CN104349890A (en) * | 2012-06-06 | 2015-02-11 | 美国圣戈班性能塑料公司 | Thermoplastic elastomer tubing and method to make and use same |
| CN107722602A (en) * | 2017-09-26 | 2018-02-23 | 上海德亿化工有限公司 | Foamed profile of Memorability multiple spot positive feedback resilient material and preparation method thereof |
| CN110549582A (en) * | 2018-03-26 | 2019-12-10 | 南京法宁格节能科技股份有限公司 | Production method of thermoplastic polyurethane elastomer foamed sheet |
| CN108864662A (en) * | 2018-07-25 | 2018-11-23 | 南通德亿新材料有限公司 | A kind of thermoplastic polyether ester elastomer foamed material and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204771A (en) * | 2019-06-11 | 2019-09-06 | 宁波邦泰汽车配件有限公司 | A kind of compound TPE foam shaping by extrusion technique |
| CN110561676A (en) * | 2019-09-18 | 2019-12-13 | 北京李尔岱摩斯汽车系统有限公司 | automatic detection system of foaming equipment |
| CN110561676B (en) * | 2019-09-18 | 2020-08-14 | 北京李尔现代坦迪斯汽车系统有限公司 | Automatic foaming detection equipment |
| CN110624225A (en) * | 2019-09-24 | 2019-12-31 | 江苏正和体育用品有限公司 | Racket |
| CN110624225B (en) * | 2019-09-24 | 2022-03-01 | 江苏正和体育用品有限公司 | Racket |
| CN113121949A (en) * | 2021-03-18 | 2021-07-16 | 浙江恒澜科技有限公司 | Master batch for polyester extrusion foaming and application thereof |
| CN114196173A (en) * | 2021-12-29 | 2022-03-18 | 丹江口东筌新材料有限公司 | PET (polyethylene terephthalate) foam material and preparation method thereof |
| CN115124834A (en) * | 2022-07-13 | 2022-09-30 | 北京化工大学 | Thermoplastic polyamide elastomer blending foaming material and preparation method thereof |
| CN115286903A (en) * | 2022-07-29 | 2022-11-04 | 维赛(江苏)复合材料科技有限公司 | Fiber-reinforced high-performance high-rate PET foam material and preparation method thereof |
| CN115181319A (en) * | 2022-08-09 | 2022-10-14 | 北京化工大学 | Preparation method of polyphenyl ether foamable particles |
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| Publication number | Publication date |
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| WO2020118986A1 (en) | 2020-06-18 |
| CN109605708B (en) | 2020-07-17 |
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