CN102476440A - Extrusion equipment and extrusion processing method of thermoplastic polyester elastomer - Google Patents
Extrusion equipment and extrusion processing method of thermoplastic polyester elastomer Download PDFInfo
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- CN102476440A CN102476440A CN2010105554320A CN201010555432A CN102476440A CN 102476440 A CN102476440 A CN 102476440A CN 2010105554320 A CN2010105554320 A CN 2010105554320A CN 201010555432 A CN201010555432 A CN 201010555432A CN 102476440 A CN102476440 A CN 102476440A
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- thermoplastic polyester
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/397—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using a single screw
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention belongs to the technical field of polymer material processing, and particularly relates to extrusion equipment and an extrusion processing method of a thermoplastic polyester elastomer. The extrusion equipment provided by the invention is an extruder; and an extrusion system of the extruder comprises a screw, a machine barrel, a material port and a nitrogen storage device, wherein the nitrogen storage device is connected with the feeding port of the extruder through a hose and a fractional pressure regulating valve is installed on the hose. The invention also provides a method for extrusion processing of the thermoplastic polyester elastomer by using the extrusion equipment. By adopting the extrusion equipment and extrusion processing method provided by the invention, the thermoplastic polyester elastomer can be well protected from being oxidized in the modification processing process and the gel generation is reduced.
Description
Technical field
The invention belongs to the processing of high molecular material technical field, be specifically related to a kind of extrusion equipment and extruding process thereof thereof of thermoplastic polyester elastomer.
Background technology
Thermoplastic polyester elastomer is the block copolymer that contains hard section of polyester and polyester soft segment.Wherein polyester soft segment and uncrystallized polyester form amorphous phase, and the hard section of polyester partially crystallizable forms the crystallization microcell, plays physical crosslinking point.This thermoplastic polyester elastomer is called for short TPEE (Thermoplastic Elastomer Ether-ester).TPEE has the elasticity of rubber and the intensity of engineering plastics, gives its elasticity for soft section, makes it as rubber; Hard section is given its processing characteristics, makes it as plastics.With the rubber phase ratio, it has better processability ability and longer service life; Compare with engineering plastics, it has advantages of high strength equally, and pliability and dynamic mechanical are better.TPEE has high strength, high resiliency, oil resistant, acid and alkali-resistance, high temperature resistant, radiation hardness, the special excellent characteristic of dynamic mechanical, and the serviceability temperature scope is very wide, is-55 ℃～+ 150 ℃, hardness range 30-75D.Difference according to molecular weight can be divided into injection grade, extrusion grade, blowing level and modification level etc.
The purpose of initial research and development TPEE is to prepare highly elastic fiber for textile industry.But now TPEE has become irreplaceable high-performance novel elastomer material, progressively is applied to safe automobile air bag and launches at the bottom of door, industrial wheel, fire engine hose hose lining, vehicle dust protector, the ski boots and field such as electronic cables.Be meeting the market requirement, widen application, need carry out modification, develop products such as heat-resisting, fire-retardant and glass enhancing this thermoplastic polyester's elastomer.But TPEE being extruded in the process of modification, gelatin phenomenon takes place easily, this structure with TPEE is relevant.Contain more strong polar group in the TPEE molecule; Like ester group and ether etc.; Intermolecular strong active force and the hydrogen bond formation physical crosslinking of existing of these groups; Be reversible " tie point " under the acting in conjunction of these physical crosslinkings chance heat, empty G&W equal solvent, these tie points are not chemical crosslinkings, but play a part chemical crosslinking.These points are called as gel.If gel in extrusion process, occurs, in the follow-up use of material, will go wrong.Such as in the process of injection moulding, if these gel shifts to product surface, will produce the kick of similar pit.Particularly in some thin-gage goods, these gels not only can produce kick, also can cause phenomenons such as surperficial broken hole.
The extruder main frame generally is made up of extrusion system, transmission system and heating and cooling system three parts.Extrusion system comprises screw rod, machine barrel, hopper, head and mould, and plastics plastify into uniform melt through extrusion system, and in this course under institute's build-up pressure, by the continuous extruder head of screw rod; The effect of transmission system is a drive screw, supplies with screw rod needed moment and rotating speed in extrusion, is made up of motor, decelerator and bearing etc. usually; And heating and cooling system is the necessary condition that the plastics extrusion can carry out.Can be divided into transportation section, compression section and metering section during extruder work.Begin to cry the transportation section from material mouthful last one screw thread, material requirement herein can not plastify, but wants preheating, pressurized compacted.The flight channel volume of compression section is by diminishing greatly gradually, and temperature will reach the material plasticizing degree, material compressed plasticizing according to certain compression ratio here, delivers to the 3rd section then.The 3rd section is metering section, and material keeps plasticization temperature here, is accurate as measuring pump, quantitative melt conveying material, and to supply with head, this moment, temperature can not be lower than plasticization temperature, generally slightly high point.Because generally the hopper of extruder opens wide, also directly contact between material mouth and the transportation section with air, material is carrying some air and moisture after material mouthful adding; These air and moisture and the material coexistence in the transportation section, because screw rod shearing power becomes big, temperature raises during to the compression section; Can some gases be discharged from exhaust outlet; But every kind of material all has a proper compression ratio, and gas can not be discharged fully, still can stay in the material through metering section arrival discharging opening by some gas.Can produce gel when under this air, water and hot coefficient situation, producing thermoplastic elastomer.
General similar with common plastics or engineering plastics of the processing method of existing thermoplastic polyester elastomer described in patent CN101608056A, limits the temperature of extruder and screw speed etc.Recommended processing method also only is that screw-type, draw ratio, compression ratio and temperature setting etc. are set on the products propaganda data of the thermoplastic polyester elastomer of some producers at present.When thermoplastic polyester elastomer was extruded under such method, air can get into screw rod inside with raw material, and then formed the acting in conjunction of air, water and heat and produce gel.
Summary of the invention
One object of the present invention has just provided a kind of screw extruder that is used for the modification processing usefulness of thermoplastic polyester elastomer.
Another object of the present invention provides the above-mentioned extrusion equipment of a kind of usefulness thermoplastic polyester elastomer is extruded method for processing, to prevent or to reduce the generation of gel in the process.
Technical scheme of the present invention is following:
The invention provides a kind of screw extruder that is used for thermoplastic polyester elastomer modification processing usefulness; What this extrusion equipment adopted is extruder; The extrusion system of extruder comprises screw rod, machine barrel, material mouth, head; Also comprise a nitrogen save set, the nitrogen save set is connected with a flexible pipe with the charge door of extruder, and the dividing potential drop control valve is installed on the flexible pipe.
Described extruder can be selected from single screw rod or double screw extruder, and wherein, the draw ratio of extruder is 40: 1～10: 1, and compression ratio is 2: 1～6: 1, and processing temperature is more than the thermoplastic polyester elastomer fusing point 5～40 ℃; Comparatively preferred extruder draw ratio is 30: 1～20: 1, and comparatively preferred compression ratio is 2.5: 1～4.5: 1, and comparatively preferred processing temperature is more than the thermoplastic polyester elastomer fusing point 10～20 ℃.
Described nitrogen save set is selected from nitrogen bag, nitrogen cylinder or nitrogen pot.
Described nitrogen is high pure nitrogen, and purity is more than 99%.
Described flexible pipe is selected from teflon hose, and tolerable temperature is-70～250 ℃, and proof pressure is 0～30MPa.
The present invention also provides the above-mentioned extrusion equipment of a kind of usefulness that thermoplastic polyester elastomer is extruded method for processing, and this method may further comprise the steps: respectively that TPEE, heat stabilizer and mix lubricant is even, add loading hopper; Before extruder starts, the flexible pipe that connects the nitrogen save set is put into the charge door place, and open dividing potential drop control valve switch, nitrogen partial pressure pressure is adjusted to 0.01～2MPa, open extruder after 2～10 minutes; In extrusion, continue to feed nitrogen, and guarantee that nitrogen partial pressure pressure is between 0.01～2MPa.
Described TPEE is made up of the block copolymer of hard section of polyester and polyester soft segment; Wherein the hard section of polyester be high rigidity crystallinity Poly (butylene terephthalate) (PBT), Poly (ethylene terephthalat (PET) or Polytrimethyleneterephthalate (PTT) etc., polyester soft segment is selected from polyethers or polyester; Wherein polyethers is optional from polyglycol ether Polyethyleneglycol (PEG), polypropylene glycol ether Polypropylene glycol (PPG) or polytetramethylene glycol ether Poly butylene ether (PTMG), wherein polyester optional from polylactide Polylactide (PLLA), gather glycolide Polyglycolide (PGA) or polycaprolactone Polycaprolactone (PCL).
Described heat stabilizer can be selected from one or several of antioxidant 1010, antioxidant 168 and anti ultraviolet agent 5411 etc.
Described lubricant is selected from one or several among A-C540A, zinc stearate, calcium stearate and the EBS etc.
Described feeding nitrogen gas pressure is 0.05～0.8MPa comparatively preferably.
In a preferred embodiment of the present invention, can further add glass fibre or fire retardant.
Described fire retardant is selected from one or several of melamine pyrophosphate, MCA and MPP etc.
The present invention compared with prior art has following advantage and beneficial effect:
The flexible pipe that first extrusion equipment of the present invention only needs to be pressed into a logical nitrogen at extruder charge door place gets final product, and is simple, and effect is obvious, can not bring too high cost to production.
Second extruding process thereof of the present invention passes through to feed nitrogen from charge door in extrusion; Reduce even got rid of the existence of extrusion air; So just can not produce the common condition that exists of heat, oxygen and airborne water; Gel just can or seldom not produce, and smooth surface when the thermoplastic polyester elastomer of extruding is used to make thin-gage goods does not almost have the property of touching gel.
Description of drawings
Fig. 1 representes the structural representation that is used for the extrusion equipment of thermoplastic polyester elastomer of the present invention.
1: the nitrogen save set; 2: flexible pipe; 3: charge door; 4: the dividing potential drop control valve; 5: extruder.
The specific embodiment
Below in conjunction with the accompanying drawing illustrated embodiment the present invention is further described.
In following examples,
TPEE1 representes: the block copolymer that crystallinity PBT and polyglycol ether PEG form, and fusing point is 210 ℃, hardness is 70D.
TPEE2 representes: the block copolymer that crystallinity PET and polycaprolactone (PCL) are formed, and fusing point is 204 ℃, hardness is 55D.
TPEE3 representes: the block copolymer that crystallinity PTT and polylactide PLLA form, fusing point are 200 degree, and hardness is 30D.
GF representes: glass fibre, ECS303H, Chongqing glass.
FR representes: fire retardant, and melamine pyrophosphate, commercially available.
Heat stabilizer: comprise antioxidant 1010, antioxidant 168 and anti ultraviolet agent 5411 etc., commercially available.
Lubricant: A-C540A, Ciba.
Used nitrogen save set 1 is one 10 liters a nitrogen cylinder in the present embodiment; Storage is 99.5% high pure nitrogen in the device 1; Used extruder 5 is that compression ratio is 4: 1, and draw ratio is 25: 1 a double screw extruder, and used flexible pipe 2 is teflon hoses.Is to be connected with flexible pipe 2 nitrogen save set 1 with the charge door 3 of extruder 5, and dividing potential drop control valve 4 is installed on the flexible pipe 2.
The used thermoplastic polyester elastomer of present embodiment is TPEE1; The TPEE1 that specifically comprises 70 weight portions, the glass fibre ECS303H of 30 weight portions, the heat stabilizer of 0.5 weight portion; Heat stabilizer comprises the antioxidant 1010 that mixed according to 1: 1: 1, antioxidant 168 and anti ultraviolet agent 5411; And the lubricant of 0.5 weight portion.Extruder is a double screw extruder, and draw ratio is 20: 1, and compression ratio is 4.5: 1, and each section temperature is made as 220～240 ℃ respectively.
Glass fibre ECS303H, 0.5 weight portion heat stabilizer and 0.5 weight portion mix lubricant with 70 weight portion TPEE1,30 weight portions is even respectively; Add loading hopper; Before extruder starts, the teflon hose that connects the nitrogen save set is put into the charge door place, and open dividing potential drop control valve switch; Nitrogen partial pressure pressure is adjusted to 0.8MPa, opens extruder after 2 minutes.The purity that in extrusion, continues feeding 0.8MPa is 99.0% nitrogen, and adds the ECS303H of 30 weight portions from the short glass fiber charge door.It is smooth that the glass fibre that this method obtains strengthens the thermoplastic polyester elastomer material surface, and the extruded stock bar is touched less than obvious gel point.
The used thermoplastic polyester elastomer of present embodiment is TPEE2; The TPEE2 that specifically comprises 65 weight portions; The heat stabilizer of the fire retardant FR of 35 weight portions and 1 weight portion, heat stabilizer are meant according to the antioxidant 1010 of mixing in 1: 1 and the lubricant of antioxidant 168,1 weight portions.Extruder is a single screw extrusion machine, and draw ratio is 30: 1, and compression ratio is 2.5: 1, and each section temperature is made as 215～230 ℃ respectively.
Respectively that above-mentioned TPEE2, fire retardant FR, heat stabilizer and mix lubricant is even; Add loading hopper; Before extruder starts, the teflon hose that connects the nitrogen save set is put into the charge door place, and open dividing potential drop control valve switch; Nitrogen partial pressure pressure is adjusted to 0.05MPa, opens extruder after 10 minutes.The purity that in extrusion, continues feeding 0.05MPa is 99.9% nitrogen.It is smooth that the glass fibre that this method obtains strengthens the thermoplastic polyester elastomer material surface, and the extruded stock bar is touched less than obvious gel point.
The used thermoplastic polyester elastomer of present embodiment is TPEE3; The TPEE3 that specifically comprises 97 weight portions, the heat stabilizer of 3 weight portions, heat stabilizer are meant the antioxidant 1010 that mixed according to 1: 1: 1; The lubricant of antioxidant 168 and anti ultraviolet agent 5411,1.5 weight portions.Extruder is a double screw extruder, and draw ratio is 40: 1, and compression ratio is 6: 1, and each section temperature is made as 205～240 ℃ respectively.
Respectively that above-mentioned TPEE3, heat stabilizer and mix lubricant is even; Add loading hopper; Before extruder starts, the teflon hose that connects the nitrogen save set is put into the charge door place, and open dividing potential drop control valve switch; Nitrogen partial pressure pressure is adjusted to 0.2MPa, opens extruder after 5 minutes.The purity that in extrusion, continues feeding 0.2MPa is 99.5% nitrogen.It is smooth that the glass fibre that this method obtains strengthens the thermoplastic polyester elastomer material surface, and the extruded stock bar is touched less than obvious gel point.
The above-mentioned description to embodiment is can understand and use the present invention for ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. the extrusion equipment of a thermoplastic polyester elastomer; What this extrusion equipment adopted is extruder; The extrusion system of extruder comprises screw rod, machine barrel, material mouth, head; It is characterized in that: also comprise a nitrogen save set (1), nitrogen save set (1) is connected with a flexible pipe (2) with the charge door (3) of extruder (5), and dividing potential drop control valve (4) is installed on the flexible pipe (2).
2. extrusion equipment according to claim 1; It is characterized in that: described extruder can be selected from single screw rod or double screw extruder; The draw ratio of extruder is 40: 1～10: 1, and compression ratio is 2: 1～6: 1, and processing temperature is more than the thermoplastic polyester elastomer fusing point 5～40 ℃.
3. extrusion equipment according to claim 1 is characterized in that: described nitrogen save set is selected from nitrogen bag, nitrogen cylinder or nitrogen pot; And nitrogen is high pure nitrogen, and purity is more than 99%.
4. extrusion equipment according to claim 1 is characterized in that: described flexible pipe is optional from the polytetrafluoroethylene (PTFE) flexible pipe, and tolerable temperature is-70～250 ℃, and proof pressure is 0～30MPa.
5. according to the described extrusion equipment of the arbitrary claim of claim 1 to 4 thermoplastic polyester elastomer is extruded method for processing for one kind; It is characterized in that: this method may further comprise the steps; Respectively that TPEE, heat stabilizer and mix lubricant is even, add loading hopper; Before extruder starts, the flexible pipe that connects the nitrogen save set is put into the charge door place, and open dividing potential drop control valve switch, nitrogen partial pressure pressure is adjusted to 0.01～2MPa, open extruder after 2～10 minutes; In extrusion, continue to feed nitrogen, and guarantee that nitrogen partial pressure pressure is between 0.01～2MPa.
6. method according to claim 5 is characterized in that: described TPEE is made up of the block copolymer of hard section of polyester and polyester soft segment; Wherein the hard section of polyester is high rigidity crystallinity PBT, PET or PTT, and polyester soft segment is selected from polyethers or polyester; Wherein polyethers is optional from polyglycol ether, polypropylene glycol ether or polytetramethylene glycol ether, wherein polyester optional from polylactide, gather glycolide or polycaprolactone.
7. method according to claim 5 is characterized in that: described heat stabilizer is selected from one or several of antioxidant 1010, antioxidant 168 and anti ultraviolet agent 5411.
8. method according to claim 5 is characterized in that: described lubricant is selected from one or several among A-C540A, zinc stearate, calcium stearate and the EBS.
9. extruding process thereof according to claim 5 is characterized in that: this method can further add glass fibre or fire retardant.
10. extruding process thereof according to claim 9 is characterized in that: described fire retardant is selected from one or several of melamine pyrophosphate, MCA and MPP.
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| CN2010105554320A CN102476440A (en) | 2010-11-23 | 2010-11-23 | Extrusion equipment and extrusion processing method of thermoplastic polyester elastomer |
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| CN2010105554320A CN102476440A (en) | 2010-11-23 | 2010-11-23 | Extrusion equipment and extrusion processing method of thermoplastic polyester elastomer |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194283A (en) * | 2014-09-02 | 2014-12-10 | 安特普工程塑料（苏州）有限公司 | High-performance thermoplastic elastomer and processing method thereof |
| CN104822770A (en) * | 2013-03-11 | 2015-08-05 | 东洋纺株式会社 | Solvent-soluble elastic resin composition |
| CN106519590A (en) * | 2016-11-17 | 2017-03-22 | 无锡明盛纺织机械有限公司 | Engineering plastic material and preparation method thereof |
| CN106519591A (en) * | 2016-11-17 | 2017-03-22 | 过冬 | Engineering plastic material and preparation method thereof |
| CN107868645A (en) * | 2017-11-02 | 2018-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Thermal-induced deformation plastic sheeting and preparation of sections method and products thereof and application |
| CN108795016A (en) * | 2018-05-17 | 2018-11-13 | 株洲时代新材料科技股份有限公司 | A kind of modified thermoplastic material and preparation method |
| CN109021506A (en) * | 2018-02-09 | 2018-12-18 | 扬州金森光电材料有限公司 | Modified TPEE optical cable loose tube material of the glass of a kind of resistance to ultralow temperature and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2910535Y (en) * | 2006-03-29 | 2007-06-13 | 广州合成材料研究院 | Polymer processing extruder |
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2010
- 2010-11-23 CN CN2010105554320A patent/CN102476440A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2910535Y (en) * | 2006-03-29 | 2007-06-13 | 广州合成材料研究院 | Polymer processing extruder |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104822770A (en) * | 2013-03-11 | 2015-08-05 | 东洋纺株式会社 | Solvent-soluble elastic resin composition |
| CN104194283A (en) * | 2014-09-02 | 2014-12-10 | 安特普工程塑料（苏州）有限公司 | High-performance thermoplastic elastomer and processing method thereof |
| CN106519590A (en) * | 2016-11-17 | 2017-03-22 | 无锡明盛纺织机械有限公司 | Engineering plastic material and preparation method thereof |
| CN106519591A (en) * | 2016-11-17 | 2017-03-22 | 过冬 | Engineering plastic material and preparation method thereof |
| CN107868645A (en) * | 2017-11-02 | 2018-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Thermal-induced deformation plastic sheeting and preparation of sections method and products thereof and application |
| CN109021506A (en) * | 2018-02-09 | 2018-12-18 | 扬州金森光电材料有限公司 | Modified TPEE optical cable loose tube material of the glass of a kind of resistance to ultralow temperature and preparation method thereof |
| CN108795016A (en) * | 2018-05-17 | 2018-11-13 | 株洲时代新材料科技股份有限公司 | A kind of modified thermoplastic material and preparation method |
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Application publication date: 20120530 |