CN114933784B - TPEE extrusion grade material and preparation method thereof - Google Patents
TPEE extrusion grade material and preparation method thereof Download PDFInfo
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- CN114933784B CN114933784B CN202210774872.8A CN202210774872A CN114933784B CN 114933784 B CN114933784 B CN 114933784B CN 202210774872 A CN202210774872 A CN 202210774872A CN 114933784 B CN114933784 B CN 114933784B
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- 229920006346 thermoplastic polyester elastomer Polymers 0.000 title claims abstract description 148
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000001125 extrusion Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000001746 injection moulding Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000004970 Chain extender Substances 0.000 claims description 56
- 239000003963 antioxidant agent Substances 0.000 claims description 39
- 230000003078 antioxidant effect Effects 0.000 claims description 37
- 239000000314 lubricant Substances 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 238000012545 processing Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical group S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 13
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012748 slip agent Substances 0.000 claims description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 17
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001035 drying Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000010720 hydraulic oil Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention belongs to the technical field of modification of high polymer materials, and relates to a TPEE extrusion grade material and a preparation method thereof. The technical problem that raw materials for preparing TPEE rod among the prior art are most injection molding grade, can't extrude because of the restriction of viscosity, the application provides a TPEE extrusion grade material for when the TPEE rod preparation of major Diameter (Diameter is greater than or equal to 25 mm), the rod surface is round smooth, and ovality is not higher than 0.2mm. The application also provides a preparation method of the TPEE extrusion grade material, which is easy to weld, simple and feasible in process and saves production time.
Description
Technical Field
The invention belongs to the field of high polymer material modification, and particularly relates to a TPEE extrusion grade material and a preparation method thereof.
Background
The hydraulic oil pipe used in the engineering machinery field needs to take a thermoplastic polyester elastomer (TPEE) bar as a mandrel in the manufacturing process, and carries out multi-layer coating on rubber and steel wires on the surface of the mandrel to finally form the hydraulic oil pipe capable of resisting high pressure. The TPEE extrusion grade raw materials used by TPEE bars currently used domestically are basically monopolized by foreign companies such as dupont and siranis, etc., which are mainly limited by domestic technical bottlenecks. The TPEE materials supplied in the domestic market at present are injection molding grade products, and extrusion of TPEE bars cannot be performed at all due to the limitation of viscosity. Chinese patent application publication No. CN111154235A, entitled "Environment-friendly TPEE tackifying reinforced composite and preparation method thereof", the disclosed material is composed of chain extender, primary antioxidant, auxiliary antioxidant, light stabilizer, transesterification inhibitor, nucleating agent and TPEE waste. The preparation method comprises the following steps: pretreating a base material, namely pretreating the recovered TPEE waste material serving as the base material; mixing and stirring, namely adding the pretreated TPEE waste into the compounded tackifying and reinforcing composition, and uniformly stirring by adopting a high-speed stirrer; extruding and granulating, namely sending the materials into a double-screw extruder for extruding and granulating to prepare the tackifying and reinforcing TPEE material. The scheme effectively improves the molecular weight of the TPEE recovered waste, increases the viscosity of the material, radically reduces the content of carboxyl end groups, simultaneously inhibits and slows down the thermal degradation and transesterification reaction in the reprocessing process, and improves the mechanical property and the thermal stability of the material. However, the melt index of the material obtained by the scheme reaches 12-19 g/10min, for a TPEE bar oil pipe with a large Diameter (Diameter is more than or equal to 25 mm) for a hydraulic oil pipe, the surface of the bar is required to be round and smooth, the ellipticity is required to be controlled below 0.2mm, otherwise, the section of the bar is similar to a round and non-round, and the pressure resistance of the hydraulic oil pipe processed later is not uniform. In addition, the TPEE bars are easy to weld, so that the TPEE bars with different lengths are connected into a whole, and the continuous production of subsequent oil pipes is facilitated.
For the above reasons, the injection molding grade TPEE materials on the existing market must be further modified in order to meet the extrusion of large diameter TPEE bars for hydraulic oil pipes. The Chinese patent application publication No. CN112011158A, entitled "preparation method of blending material and blending material", discloses a method, which comprises firstly melt blending thermoplastic polyether ester elastomer TPEE with epoxy chain extender to make TPEE and epoxy chain extender undergo chain extension reaction, introducing epoxy chain extender and its multiple epoxy groups into TPEE macromolecular chain to obtain epoxidized TPEE, and then melt blending the epoxidized TPEE with polylactic acid PLA. The PLA/TPEE blend which is compatibilized by the epoxy chain extender reaction is obtained by a two-step blending method. In the two-step method, the epoxidized TPEE contains high-concentration epoxy groups, so that more PLA-epoxy chain extender-TPEE multiblock compatibilizer macromolecules can be generated by in-situ reaction after the reaction with PLA, the compatibilization effect of the blending material is improved, and meanwhile, the interfacial tension of the TPEE disperse phase is reduced, so that the particle size of the TPEE disperse phase is greatly reduced. The scheme improves the tensile toughness of the material to a certain extent, but needs two chain extension processes, has complex process and is still not suitable for preparing the large-diameter TPEE bar for the hydraulic oil pipe.
Disclosure of Invention
1. Problems to be solved
The technical problem that raw materials for preparing TPEE rod among the prior art are most injection molding grade, can't extrude because of the restriction of viscosity, the application provides a TPEE extrusion grade material for when the TPEE rod preparation of major Diameter (Diameter is greater than or equal to 25 mm), the rod surface is round smooth, and ovality is not higher than 0.2mm. The application also provides a preparation method of the TPEE extrusion grade material, which is easy to weld, simple and feasible in process and saves production time.
2. Technical proposal
In order to achieve the above purpose, the technical scheme provided is as follows:
the TPEE extrusion grade material consists of the following components in parts by weight:
TPEE resin: 90.4 to 92.45 percent,
slip agent: 6 to 8 percent,
chain extender: 0.35 to 0.4 percent,
antioxidant: 0.4 percent,
and (3) a lubricant: 0.8%;
the chain extender is obtained by copolymerizing styrene and glycidyl acrylate and contains a plurality of epoxy groups.
The epoxy group is a functional group having a-CH (O) CH-structure.
Further, the chain extender is ADR-4468.
ADR-4468 molecular chain contains a plurality of epoxy groups, has more reactive sites, and has higher probability of coupling or branching reaction with carboxyl end groups and hydroxyl groups on TPEE molecular chain, and better tackifying effect.
Further, the TPEE resin is an injection molded pole with an MFR of 25g/10min and Shore D of 50.
Further, the slipping agent is molybdenum disulfide.
The molybdenum disulfide can lead the TPEE bar to be easy to deviate from when being used as a mandrel of the hydraulic oil pipe, and can be repeatedly used for 6-8 times.
Further, the antioxidant is a mixture of 1010 and 168.
Further, the mass ratio of the antioxidants 1010 and 168 is 1:1.
Further, the lubricant is PETS.
A method for preparing a TPEE extrusion grade material comprising the steps of:
and uniformly mixing the components according to the parts by weight, granulating by a double-screw extruder, wherein the temperature is 230-255 ℃, the screw rotating speed is 380-420rpm, and the feeding rotating speed is 20rpm, so that the TPEE extrusion grade material is obtained.
Further, the twin screw extruder includes one to nine zone processing temperatures of 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃, respectively.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The TPEE extrusion grade material comprises the following raw materials: 90.4 to 92.45 percent of slipping agent: 6-8% of chain extender: 0.35 to 0.4 percent of antioxidant: 0.4%, lubricant: 0.8%; the chain extender is obtained by copolymerizing styrene and glycidyl acrylate and contains a plurality of epoxy groups. The end capping and coupling reaction of the carboxyl and hydroxyl terminal groups on the molecular chain of TPEE and the epoxy group of the chain extender are carried out. The injection molding TPEE is prepared from the existing injection molding TPEE in the current market as a basic raw material, and the viscosity of the injection molding TPEE is increased by adding a plurality of epoxy group chain extenders, so that the injection molding TPEE meets the requirements of extrusion TPEE. When the material is used for preparing extrusion-grade bars with large Diameter (Diameter is more than or equal to 25 mm), the melt viscosity is proper, and the phenomena of silver wires and broken skins are easy to occur on the surface of the extruded bars due to low melt viscosity, so that the ovality is larger; and the phenomenon that gel is generated due to excessive branching reaction of the material in the chain extension reaction process and the phenomenon that uneven pits are easily formed on the surface of the bar in the subsequent bar extrusion process can not be normally extruded can be avoided due to high melt viscosity.
(2) The TPEE extrusion grade material is prepared by uniformly mixing the components in parts by weight, granulating by a double-screw extruder at the temperature of 230-255 ℃, and the screw rotating speed of 380-420rpm and the feeding rotating speed of 20rpm. The residence time of the double-screw extruder is controlled by adjusting the rotation speed of the main machine and the feeding rotation speed in the extrusion process, so that the reaction degree of the TPEE material and the chain extender is controlled, and the extrusion grade material for the large-diameter TPEE bar is prepared. In particular, for extrusion-grade TPEE materials, the polymerization reaction may be terminated by the addition of a capping agent near the end of the polymerization reaction, thereby achieving control over the viscosity of the material. However, for injection molding grade TPEE materials, it is necessary to add a chain extender to achieve the tackifying effect due to the inherent imperfections in melt viscosity. However, the addition of the chain extender can cause a branching reaction to form a gel phenomenon in addition to the end capping and coupling reactions with the terminal carboxyl groups and hydroxyl groups on the molecular chain. The residence time of the reaction must be controlled to the extent that the chain extension reaction is controlled. The technological parameters of the invention, namely, the reaction time of TPEE and chain extender is short when the TPEE is melt extruded because of short residence time, the tackifying effect is poor, the surface of the TPEE bar is easy to weld, but the surface of the TPEE bar has the phenomenon of skin breaking, and the ovality is large; the reaction time of the TPEE and the chain extender is long during melt extrusion because of long residence time, the tackifying effect is good, but the gelation phenomenon is easy to occur, the uneven pits are easy to occur on the surface of the TPEE bar, and the TPEE bar is not easy to weld.
Detailed Description
For a further understanding of the present invention, the present invention will be described in detail with reference to examples.
Example 1
The TPEE extrusion grade material of the embodiment comprises the following raw materials in percentage by mass: 92.45% TPEE resin, 6% slip agent, 0.35% chain extender, 0.4% antioxidant and 0.8% lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; the chain extender is ADR-4468 of the German BASF company, contains a plurality of epoxy reaction groups and has a plurality of active reaction centers; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 380rpm, and the feeding rotating speed is 20rpm.
Example 2
The TPEE extrusion grade material of this example is substantially the same as example 1, except that the raw materials consist of, in mass percent: 91.425% of TPEE resin, 7% of slipping agent, 0.375% of chain extender, 0.4% of antioxidant and 0.8% of lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; the chain extender is ADR-4468 of the German BASF company; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 400rpm, and the feeding rotating speed is 20rpm.
Example 3
The TPEE extrusion grade material of this example is substantially the same as example 1, except that the raw materials consist of, in mass percent: 90.4% of TPEE resin, 8% of slipping agent, 0.4% of chain extender, 0.4% of antioxidant and 0.8% of lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; ADR-4468 of the chain extender German BASF company; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 420rpm, and the feeding rotating speed is 20rpm.
Comparative example 1
The TPEE extrusion grade material of the comparative example comprises the following raw materials in percentage by mass: 92.55% TPEE resin, 6% slip agent, 0.25% chain extender, 0.4% antioxidant and 0.8% lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; the chain extender is ADR-4468 of the German BASF company; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 400rpm, and the feeding rotating speed is 20rpm.
Comparative example 2
The TPEE extrusion grade material of the comparative example comprises the following raw materials in percentage by mass: 91.3% of TPEE resin, 7% of slipping agent, 0.5% of chain extender, 0.4% of antioxidant and 0.8% of lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; the chain extender is ADR-4468 of the German BASF company; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 400rpm, and the feeding rotating speed is 20rpm.
Comparative example 3
The TPEE extrusion grade material of the comparative example comprises the following raw materials in percentage by mass: 94.45% of TPEE resin, 4% of slipping agent, 0.35% of chain extender, 0.4% of antioxidant and 0.8% of lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; the chain extender is ADR-4468 of the German BASF company; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 400rpm, and the feeding rotating speed is 20rpm.
Comparative example 4
The TPEE extrusion grade material of this example is substantially the same as example 2, except that the raw materials consist of, in mass percent: 91.425% of TPEE resin, 7% of slipping agent, 0.375% of chain extender, 0.4% of antioxidant and 0.8% of lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; the chain extender is BASF ADR-4400; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 400rpm, and the feeding rotating speed is 20rpm.
Comparative example 5
The TPEE extrusion grade material of this example is substantially the same as example 2, except that the raw materials consist of, in mass percent: 91.425% of TPEE resin, 7% of slipping agent, 0.375% of chain extender, 0.4% of antioxidant and 0.8% of lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; the chain extender is bisoxazoline; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 400rpm, and the feeding rotating speed is 20rpm.
Comparative example 6
The TPEE extrusion grade material of the comparative example comprises the following raw materials in percentage by mass: 91.425% of TPEE resin, 7% of slipping agent, 0.375% of chain extender, 0.4% of antioxidant and 0.8% of lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; the chain extender is ADR-4468 of the German BASF company; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 500rpm, and the feeding rotating speed is 20rpm.
Comparative example 7
The TPEE extrusion grade material of the comparative example comprises the following raw materials in percentage by mass: 91.425% of TPEE resin, 7% of slipping agent, 0.375% of chain extender, 0.4% of antioxidant and 0.8% of lubricant. The TPEE is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50; the slipping agent is molybdenum disulfide; the chain extender is ADR-4468 of the German BASF company; the antioxidant is a mixture of 1010 and 168, and the proportion is 1:1; the lubricant is PETS.
Uniformly mixing the dried TPEE, the slipping agent, the chain extender, the antioxidant and the lubricant in a mixer according to the mass percentage for later use; then pouring the prepared premix into a feed hopper, and performing melt extrusion by a double-screw extruder, granulating and drying to prepare an extrusion grade material for the large-diameter TPEE bar; the processing temperature control of each region of the twin-screw extruder comprises processing temperature control of one region to nine regions, wherein the processing temperature control of one region to eight regions is 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃ respectively; the temperature of the head of the double-screw extruder is 240 ℃, the screw rotating speed is 300rpm, and the feeding rotating speed is 20rpm.
Table 1 comparative large diameter TPEE bars prepared in examples and comparative examples
As is clear from examples 1-3 and comparative examples 1-7, when the twin-screw main machine is controlled at 380-420rpm and the ADR-4468 content of the chain extender is 0.35-0.4%, the MFR is in the range of 1.3-1.9, the surface of the TPEE bar is round and smooth, the ovality is controlled below 0.2mm, the welding is easy, the repeated use times reach 6-8, but when the slipping agent is reduced to 4, the TPEE bar can only be reused 3 times. When the ADR-4468 content of the chain extender is 0.25%, the MFR is 7.2, the melt viscosity of the TPEE material is low, silver wires and skin breakage occur on the surface of the extruded TPEE bar, and the ovality is more than 0.32mm, so that the TPEE bar cannot be normally used. When the ADR-4468 content of the chain extender is 0.5%, the MFR is 0.2, the melt viscosity of the TPEE material is very high, the inside of the material has serious gel phenomenon, and fine uneven pits appear on the surface of the bar during extrusion, so that the TPEE bar cannot be normally used even if the ovality is only 0.1 mm. In addition, on the basis of the embodiment 2, on the premise of unchanged percentage content, ADR-4468 is only replaced by ADR-4400 or bisoxazoline, at the moment, the MFR is greatly increased from 1.7 to 7.8 and 8.9 respectively, silver wires and skin breakage phenomena occur on the surface of the TPEE bar, the ovality reaches 0.35mm and 0.37mm respectively, and the TPEE bar cannot be normally used, so that the chain extension effect of the bisoxazoline and the ADR-4400 on the TPEE material is far lower than that of the ADR-4468.
The melt viscosity of the TPEE material is controlled by using the chain extender under certain process conditions. The same material composition, under different process conditions, may vary widely. Comparative examples 6 and 7 are TPEE materials obtained by adjusting only the process conditions on the basis of the unchanged material composition of example 2, respectively. From the results, when the rotating speed of the screw is 500rpm, the residence time is short, namely the chain extension reaction time is short, the reaction is insufficient, the melt viscosity is low, silver wires and skin breakage phenomena appear on the surface of the TPEE bar during extrusion, and the ovality reaches 0.32mm; when the screw rotating speed is 300rpm, the residence time is long, namely the chain extension reaction time is long, the reaction is sufficient, at the moment, the inside of the TPEE material has serious gel phenomenon, and fine uneven pits appear on the surface of the bar during extrusion.
In summary, the extrusion-grade TPEE material suitable for large-diameter TPEE bars is prepared by adopting proper component proportion and combining process conditions. Under the blank condition of the domestic TPEE extrusion grade raw material, an extrusion grade material for large-diameter TPEE bars can be prepared by adding a proper amount of chain extender ADR-4468 on the basis of the injection grade TPEE raw material and controlling the reaction degree of the TPEE and the chain extender through the technological parameters of an extruder. The material can be used for preparing bars with the D of more than or equal to 25mm, the surfaces of the bars are round and smooth, the ellipticity is controlled to be about 0.15mm, the bars are easy to weld, and the repeated use times can reach 6-8 times.
Claims (8)
1. A TPEE extrusion grade material characterized by: the composite material consists of the following components in parts by weight:
TPEE resin: 90.4 to 92.45 percent,
slip agent: 6-8%,
chain extender: 0.35 to 0.4 percent,
antioxidant: 0.4 percent,
and (3) a lubricant: 0.8%;
the TPEE resin is an injection molding pole, the MFR is 25g/10min, and the Shore D is 50;
the chain extender is obtained by copolymerizing styrene and glycidyl acrylate and contains a plurality of epoxy groups.
2. A TPEE extrusion grade material as in claim 1, wherein: the chain extender is ADR-4468.
3. A TPEE extrusion grade material as in claim 1, wherein: the slipping agent is molybdenum disulfide.
4. A TPEE extrusion grade material as in claim 1, wherein: the antioxidant is a mixture of 1010 and 168.
5. A TPEE extrusion grade material as in claim 4, wherein: the mass ratio of the antioxidants 1010 and 168 is 1:1.
6. A TPEE extrusion grade material as in claim 1, wherein: the lubricant is PETS.
7. A process for preparing a TPEE extrusion grade material as claimed in any one of claims 1-6, wherein: the method comprises the following steps:
and uniformly mixing the components according to the parts by weight, granulating by a double-screw extruder at the temperature of 230-255 ℃ and the screw rotation speed of 380-420rpm, and feeding at the rotation speed of 20rpm to obtain the TPEE extrusion grade material.
8. A process for preparing TPEE extruded grade material as claimed in claim 7, wherein: the twin screw extruder comprises one to nine zones of processing temperatures, 230 ℃, 245 ℃, 255 ℃, 250 ℃, 245 ℃,240 ℃ and 240 ℃, respectively.
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