CN115141452A - Preparation method and application of environment-friendly modified styrene TPE (thermoplastic elastomer) granules - Google Patents
Preparation method and application of environment-friendly modified styrene TPE (thermoplastic elastomer) granules Download PDFInfo
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- CN115141452A CN115141452A CN202111633180.3A CN202111633180A CN115141452A CN 115141452 A CN115141452 A CN 115141452A CN 202111633180 A CN202111633180 A CN 202111633180A CN 115141452 A CN115141452 A CN 115141452A
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 92
- 239000008187 granular material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title 1
- 238000002156 mixing Methods 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000003440 styrenes Chemical class 0.000 claims abstract description 42
- 239000000945 filler Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000011049 filling Methods 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 52
- 229920001971 elastomer Polymers 0.000 claims description 27
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 26
- 239000010456 wollastonite Substances 0.000 claims description 26
- 229910052882 wollastonite Inorganic materials 0.000 claims description 26
- 239000000806 elastomer Substances 0.000 claims description 19
- 238000005507 spraying Methods 0.000 claims description 13
- 239000004606 Fillers/Extenders Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 12
- 238000001125 extrusion Methods 0.000 abstract description 10
- 238000004073 vulcanization Methods 0.000 abstract description 6
- 230000009965 odorless effect Effects 0.000 abstract description 2
- 238000010094 polymer processing Methods 0.000 abstract description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 24
- 239000003921 oil Substances 0.000 description 22
- 239000005662 Paraffin oil Substances 0.000 description 13
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 235000019504 cigarettes Nutrition 0.000 description 5
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- MCOQHIWZJUDQIC-UHFFFAOYSA-N barban Chemical compound ClCC#CCOC(=O)NC1=CC=CC(Cl)=C1 MCOQHIWZJUDQIC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 benzene small molecules Chemical class 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- PJVWKTKQMONHTI-UHFFFAOYSA-N warfarin Chemical compound OC=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 PJVWKTKQMONHTI-UHFFFAOYSA-N 0.000 description 1
- 229960005080 warfarin Drugs 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polymer processing, in particular to a preparation method and application of environment-friendly modified styrene TPE granules. The preparation method of the environment-friendly modified styrene TPE granules comprises the following steps: s1, mixing styrene TPE and filling oil to obtain a mixed material A; s2, adding the thermoplastic elastomer, the filler and the interface compatilizer into the mixed material A, and uniformly mixing in a high-speed mixer to obtain a mixed material B; s3, adding an auxiliary agent into the mixed material B, and uniformly mixing in a high-speed mixer to obtain a mixed material C; and S4, conveying the mixed material C into a double-screw extruder to extrude and granulate to obtain the environment-friendly modified styrene TPE granules. The invention avoids the need of a vulcanization process in the traditional runway, uses a specific blending extrusion process, can obtain an odorless product by controlling specific process conditions, can realize that harmful substances are not detected, is far higher than the new standard requirements of the prior runway, and has good mechanical properties.
Description
Technical Field
The invention relates to the technical field of polymer processing, belongs to the IPC classification number of C08L23/08, and particularly relates to a preparation method and application of environment-friendly modified styrene TPE granules.
Technical Field
The plastic runway has good flatness and elasticity, and is beneficial to protecting joints of athletes, when the plastic runway is used, physical properties such as impact resistance, impact absorption, wear resistance and the like of the plastic runway need to be emphasized, and some chemical indexes of the plastic runway need to be emphasized, because if some chemical components of the runway exceed standards, the body health of a user can be affected, the traditional runway needs to use a vulcanization process, the vulcanization has odor, and various harmful substances exist in the current product.
Patent CN112590037A provides a method for processing an energy-saving rubber track, but it uses a waste tire rubber as raw material, and also performs processes such as press-mixing and banburying, and these raw materials and processes are combined together to prepare an internal mixer with relatively large energy consumption, and the prepared track also produces serious odor.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the present invention provides a method for preparing environment-friendly modified styrene TPE granules, comprising the following steps:
s1, mixing styrene TPE and filling oil to obtain a mixed material A;
s2, adding the thermoplastic elastomer, the filler and the interface compatilizer into the mixed material A, and uniformly mixing in a high-speed mixer to obtain a mixed material B;
s3, adding an auxiliary agent into the mixed material B, and uniformly mixing in a high-speed mixer to obtain a mixed material C;
and S4, feeding the mixed material C into a double-screw extruder to be extruded and granulated to obtain the environment-friendly modified styrene TPE particles.
The step of mixing in step S1 is: the styrene TPE was placed in a mixer and then the extender oil was added to the mixer.
In some embodiments the extender oil is added in multiple portions (multiple additions refer to the stepwise addition of extender oil to styrene TPE for blending). Preferably, the number of times of multiple addition is 2-5 (for example, 2 times, 3 times, 4 times, 5 times), and it is found that good effect can be achieved by adding the final product in 2 times.
In some preferred embodiments, the extender oil is added by direct mixing or spray addition (preferably for spray addition), wherein the spraying may be by means of a spray commonly used in the art, such as by means of a nozzle.
In some embodiments, the temperature during mixing in step S1 is from 25 to 80 deg.C (preferably from 30 to 60 deg.C).
Specifically, in some embodiments, the step in step S1 is: firstly adding the styrene TPE into a mixer, then spraying half part by weight of the softened filling rubber oil by using a nozzle, mixing for 1-20 min at 30-40 ℃, finally spraying the rest part by weight of the softened filling rubber oil by using the nozzle, and mixing for 1-20 min at 40-60 ℃ to obtain a mixed material A.
In some preferred embodiments, the step in step S1 is: firstly adding the styrene TPE into a mixer, then spraying half part by weight of the softened filling rubber oil by using a nozzle, mixing for 12-15 min at 30-40 ℃, finally spraying the rest part by weight of the softened filling rubber oil by using the nozzle, and mixing for 12-15 min at 40-60 ℃ to obtain a mixed material A.
Half the weight of the softened rubber filler oil refers to the weight of half of the total softened rubber filler oil that needs to be added.
More preferably, the rotation speed during mixing in step S1 is 1800 to 2500r/min (preferably 2000 to 2300 r/min).
In some embodiments, the extender oil is selected from one of white oil, naphthenic oil, paraffinic oil; preferably with petroleum waxes (e.g., medium petrochemical 22 paraffin).
The weight ratio of the styrene TPE to the filling oil is 1: (0.7-1.1); preferably, the weight ratio of the styrene TPE to the filling oil is 1:0.8.
in the invention, the filling oil is used to improve the processing performance of the styrene TPE, and meanwhile, in order to avoid the existence of a plurality of benzene harmful substances in processes such as vulcanization, the modified styrene TPE particles obtained by blending and extrusion are used in the invention, so that the defect of the vulcanization process is overcome, but in the research, the processing performance during extrusion is influenced when the styrene TPE and the filling oil are mixed, and if the mixing mode is not proper, the oil spitting phenomenon can occur in summer on a runway prepared by using the modified styrene TPE particles. In the invention, the special 2-time nozzle is used for spraying and mixing and is mixed at a higher rotating speed, so that the phenomenon of oil spitting of the runway is reduced. Probably because the nozzle of twice sprays and can make styrene TPE's absorption more even for the system homogeneity is better, and the mobility when processing man-hour is more, makes compounding A more stable at the condition of higher rotational speed and specific temperature simultaneously, compounding A can be better interact when extruding with materials such as thermoplastic elastomer, filler, interfacial compatilizer mixture, has more stable structural system, thereby further can increase the heat stability of goods.
The temperature during mixing in the step S2 is 30-60 ℃, and the mixing time is 1-20 min; preferably, the temperature during mixing in the step S2 is 40-50 ℃, and the mixing time is 10-18 min; more preferably, the temperature during mixing in step S2 is 45 ℃ and the mixing time is 15min.
In some embodiments, the weight ratio of thermoplastic elastomer to styrene TPE is (2 to 3.5): 1; preferably, the weight ratio of the thermoplastic elastomer to the styrene TPE is 2.8:1.
in some embodiments, the weight ratio of the styrene TPE, the filler, and the interfacial compatibilizer is 1: (1-2): (0.1 to 0.15); preferably, the weight ratio of the styrene TPE to the filler to the interfacial compatilizer is 1:1.68:0.12.
in some embodiments, the thermoplastic elastomer comprises a TPU elastomer and a SBS elastomer; the weight ratio of the TPU elastomer to the SBS elastomer is 1: (3 to 5), preferably 1:4.
the TPU elastomer is a fuming TPU1185.
In some embodiments, the SBS elastomer is a star structure; the SBS elastomer has an S/B ratio of (29-50): (50-71); preferably, the SBS elastomer has a S/B ratio of 40:60; the melt flow rate of the SBS elastomer is 1.5-6 g/min under the conditions of 200 ℃ and 5 kg; preferably, the SBS elastomer has a melt flow rate of 2g/min at 200 ℃ and 5kg, and an exemplary SBS may be Barlingite SBS815.
In some embodiments, the thermoplastic elastomer further comprises POE elastomer; the weight ratio of the POE elastomer to the TPU is 1: (2-3); POE elastomers which may be mentioned are
FORTIFY TM C1060D POE。
In some embodiments, the filler is selected from at least one of talc, attapulgite, ground calcium carbonate, silica, kaolin, acicular wollastonite; preferably heavy calcium carbonate, talcum powder and needle-shaped wollastonite; the weight ratio of the heavy calcium carbonate, the talcum powder and the needle-shaped wollastonite is (10-16): (1.5-2.5): 1, preferably 12:2:1.
the average grain diameter of the heavy calcium carbonate is 2000-3000 meshes; the average grain diameter of the talcum powder is 1000-2000 meshes; the average grain diameter of the needle-shaped wollastonite is 3000-5000 meshes. Wherein the heavy calcium carbonate, the talcum powder and the needle-shaped wollastonite can be obtained from markets, and the purchase manufacturers include but are not limited to Jiangxi Guangyuan chemical industry.
The research shows that the linear styrene TPE used in the system can better improve the processing performance during processing, but the linear structure is preferable to be better in flexibility, the formed structure is not compact, and the runway is easy to wear after being used for a long time. The inventor surprisingly found that the SBS elastomer has a star-shaped structure and the filler interacts with each other in the system, so that the phenomenon of oil spitting of the runway in the using process can be further improved, and the phenomenon that the filler densely filled in the system can better prevent the filling oil from migrating outwards can be possibly caused.
The interfacial compatilizer is a mixture of maleic anhydride grafted polypropylene and maleic anhydride grafted styrene TPE, and the weight ratio of the interfacial compatilizer to the maleic anhydride grafted styrene TPE is 1: (2.5-3); preferably 1:2.8. the maleic anhydride grafted polypropylene is commercially available and includes, but is not limited to, dow 105TY maleic anhydride grafted polypropylene. The maleic anhydride grafted styrene TPE is commercially available, including but not limited to kraton styrene TPE G1901 maleic anhydride graft.
The mixing conditions in step S3 are: mixing at room temperature for 1-20 min (preferably 10-15 min, more preferably 12 min).
In some embodiments, the weight of the adjuvant is 0.1 to 1% of the weight of the raw materials in the system; preferably, the weight of the auxiliary agent is 0.4-0.6% of the weight of the raw materials in the system.
The adjuvant may be selected as desired, and in some embodiments, the adjuvant is an antioxidant (e.g., antioxidant 168, etc.); in other embodiments, the auxiliaries are antioxidants and pigments, where pigments can be added as desired.
In some embodiments, the twin screw extruder is an asymmetric twin screw extruder, the twin screw extruder having a length to diameter ratio of 32.
In some embodiments, the single-head rotational speed of the asymmetric twin-screw extruder is greater than the double-head rotational speed of the asymmetric twin-screw extruder; preferably, the ratio of the single-head rotating speed of the asymmetric double-screw extruder to the double-head rotating speed of the asymmetric double-screw extruder is (2-5): 1, more preferably (2.5 to 3.5): 1; more preferably 3:1.
although the wear resistance of the runway can be increased to a certain extent by the filler and the novel SBS, due to certain characteristics of the filler and the novel SBS, the problem that the melt viscosity is too high during extrusion and extrusion is difficult is caused, the processability of modified styrene TPE granules prepared by an inventor just begins to be poor by using a traditional bidirectional parallel twin-screw extruder, a series of research inventors find that an asymmetric twin-screw extruder is selected, the processability can be well improved and the smoothness of the runway prepared by the modified styrene TPE granules can be increased by controlling the single-head rotating speed and the different rotating speeds of an asymmetric twin-screw extruder, probably because different rotating speeds are used in the extruder, the materials can be subjected to asymmetric stretching force in a charging barrel and can flow sufficiently, meanwhile, the inconsistency of the asymmetric stretching force in the melting process enables the system to possibly generate a ' sea-island ' melting model ', the filler can be sufficiently mixed with thermoplastic elastomers, mixed materials A and the like in the system and can be sufficiently dispersed and wrapped by high polymers, so that the modified styrene TPE granules prepared in the runway have good smoothness and are not easy to fall off.
In some embodiments, the double head rotation speed is 15 to 40r/min (preferably 20 to 25r/min; more preferably 22 r/min).
In some embodiments, the temperature in zones 1 to 7 of the twin screw extruder is 150 to 170 ℃, 160 to 195 ℃, 180 to 200 ℃, 190 to 220 ℃, 210 to 240 ℃, 230 to 260 ℃.
In some preferred embodiments, the temperature in zones 1 to 7 of the twin-screw extruder is 160 ℃, 180 ℃, 190 ℃, 200 ℃, 220 ℃, 250 ℃.
Compared with the prior art, the length-diameter ratio of the twin-screw extruder is 32, and the inventor finds that the odor of the modified styrene TPE particles and the content of some benzene small molecules can be better reduced by using a lower rotating speed in the invention, probably because the melt in the cylinder stays for a longer time under the condition of the rotating speed, and meanwhile, the exhaust area of the melt is larger due to the non-uniform characteristic, so that the small molecules can be effectively removed even if the generated small molecules are generated. Meanwhile, the fact that the SBS elastomer and the POE which are added in the invention in specific amounts and have specific melt indexes are mutually synergistic is found to be capable of better increasing the elasticity of the system track, probably because the SBS in star shape is dispersed in the system to form a certain amount of network structure, but when the amount is too low, the SBS in star shape cannot form continuous network structure in the system, so that the elasticity of the product is reduced. However, if the content of the SBS elastomer is too high, the inventors can further improve the rotation speed by increasing the temperature or the rotation speed of extrusion, but the final modified styrene TPE pellet has a high content of some small molecules and a high odor, probably because the rotation speed is too high, the melt can not stay in the barrel sufficiently, so that some benzene series small molecules or odor small molecules can not be effectively removed.
The invention provides an application of environment-friendly modified styrene TPE granules, and the environment-friendly modified styrene TPE granules are used for manufacturing runways or court.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects: the invention avoids the need of a vulcanization process in the traditional runway, uses a specific blending extrusion process, can obtain an odorless product by controlling specific process conditions, can realize that harmful substances are not detected, is far higher than the new standard requirements of the prior runway, and has good mechanical properties.
Drawings
Fig. 1 is a picture of a runway prepared using environmentally-friendly modified styrene TPE pellets prepared in the present invention.
Detailed Description
Example 1
A preparation method of environment-friendly modified styrene TPE granules comprises the following steps:
s1, adding the barban petrochemical SEBS503 into a mixer, spraying half part by weight of medium petrochemical No. 22 paraffin oil by using a nozzle, mixing for 15min at 30 ℃, and spraying the rest part by weight of medium petrochemical No. 22 paraffin oil by using a nozzle, mixing for 15min at 40 ℃ to obtain a mixed material A (wherein the weight ratio of the barban petrochemical SEBS503 to the medium petrochemical No. 22 paraffin oil is 1.7, and the rotating speed is 2000r/min during mixing);
s2, adding a thermoplastic elastomer, a filler and an interface compatilizer into the mixed material A, and mixing for 18min at 40 ℃ in a high-speed mixer to obtain a mixed material B (wherein the weight ratio of the thermoplastic elastomer to the ba ling petrochemical SEBS503 is 2
FORTIFY TM C1060D POE；
FORTIFY TM The weight ratio of C1060D POE to the cigarette platform Wanhua TPU1185 is 1:2; the filler is a composition of ground calcium carbonate, talcum powder and needle-shaped wollastonite; the weight ratio of the heavy calcium carbonate to the talcum powder to the needle-shaped wollastonite is 10:1.5:1; the average grain size of the heavy calcium carbonate is 2000 meshes; the average grain size of the talcum powder is 1250 meshes; the average grain diameter of the needle-shaped wollastonite is 3000 meshes; the heavy calcium carbonate, the talcum powder and the needle-shaped wollastonite are all purchased from Jiangxi Guangyuan chemical industry; the interfacial compatilizer is prepared by grafting 105TY maleic anhydride grafted polypropylene from Dow America and Coteng SEBS G1901 maleic anhydride in a weight ratio of 1:2.5 );
s3, adding an antioxidant 168 into the mixed material B, and mixing for 10min at normal temperature in a high-speed mixer to obtain a mixed material C (the weight of the antioxidant 168 is 0.4 percent of the weight of the raw materials in the system);
and S4, conveying the mixed material C into a double-screw extruder to extrude and granulate to obtain environment-friendly modified styrene TPE granules (wherein the double-screw extruder is an asymmetric double-screw extruder, the length-diameter ratio is 32, the ratio of the single-head rotating speed of the asymmetric double-screw extruder to the double-head rotating speed of the asymmetric double-screw extruder is 2.5.
Example 2
A preparation method of environment-friendly modified styrene TPE granules comprises the following steps:
s1, adding the ba ling petrochemical SEBS503 into a mixer, spraying half part by weight of medium petrochemical No. 22 paraffin oil by using a nozzle, mixing for 12min at 40 ℃, and finally spraying the rest part by weight of medium petrochemical No. 22 paraffin oil by using a nozzle, mixing for 12min at 60 ℃ to obtain a mixed material A (wherein the weight ratio of the ba ling petrochemical SEBS503 to the medium petrochemical No. 22 paraffin oil is 1.1, and the rotating speed is 2300r/min during mixing);
s2, adding a thermoplastic elastomer, a filler and an interface compatilizer into the mixed material A, mixing for 10min at 50 ℃ in a high-speed mixer to obtain a mixed material B (wherein the weight ratio of the thermoplastic elastomer to the baring petrochemical SEBS503 is 3.5
FORTIFY TM C1060D POE；
FORTIFY TM The weight ratio of C1060D POE to the cigarette platform Wanhua TPU1185 is 1:3; the filler is a composition of ground calcium carbonate, talcum powder and needle-shaped wollastonite; the weight ratio of the heavy calcium carbonate to the talcum powder to the needle-shaped wollastonite is 16:2.5:1; the average grain size of the heavy calcium carbonate is 3000 meshes; the average grain size of the talcum powder is 1250 meshes; the average grain diameter of the needle-shaped wollastonite is 5000 meshes; the heavy calcium carbonate, the talcum powder and the needle-shaped wollastonite are all purchased from Jiangxi Guangyuan chemical industry; the interfacial compatilizer is prepared by grafting 105TY maleic anhydride grafted polypropylene from Dow America and Coteng SEBS G1901 maleic anhydride in a weight ratio of 1: 3) (ii) a
S3, adding an antioxidant 168 into the mixed material B, and mixing for 15min at normal temperature in a high-speed mixer to obtain a mixed material C (the weight of the antioxidant 168 is 0.6 percent of the weight of the raw materials in the system);
and S4, feeding the mixed material C into a double-screw extruder for extrusion granulation to obtain environment-friendly modified styrene TPE granules (wherein the double-screw extruder is an asymmetric double-screw extruder, the length-diameter ratio is 32, the ratio of the single-head rotating speed of the asymmetric double-screw extruder to the double-head rotating speed of the asymmetric double-screw extruder is 3.5.
Example 3
A preparation method of environment-friendly modified styrene TPE granules comprises the following steps:
s1, adding the ba ling petrochemical SEBS503 into a mixer, spraying half part by weight of medium petrochemical No. 22 paraffin oil by using a nozzle, mixing for 14min at 35 ℃, and finally spraying the rest part by weight of medium petrochemical No. 22 paraffin oil by using a nozzle, mixing for 13min at 50 ℃ to obtain a mixed material A (wherein the weight ratio of the ba ling petrochemical SEBS503 to the medium petrochemical No. 22 paraffin oil is 1.8, and the rotating speed is 2200r/min during mixing);
s2, adding a thermoplastic elastomer, a filler and an interface compatilizer into the mixed material A, mixing for 15min at 45 ℃ in a high-speed mixer to obtain a mixed material B (wherein the weight ratio of the thermoplastic elastomer to the baring petrochemical SEBS503 is 2.8
FORTIFY TM C1060D POE；
FORTIFY TM The weight ratio of C1060D POE to the cigarette platform Wanhua TPU1185 is 1:2.5; the filler is a composition of ground calcium carbonate, talcum powder and needle-shaped wollastonite; the weight ratio of the heavy calcium carbonate to the talcum powder to the needle-shaped wollastonite is 12:2:1; the average grain size of the heavy calcium carbonate is 2500 meshes; the average grain size of the talcum powder is 1250 meshes; needleThe mean grain size of the tabular wollastonite is 4000 meshes; the heavy calcium carbonate, the talcum powder and the needle-shaped wollastonite are all purchased from Jiangxi Guangyuan chemical industry; the interfacial compatilizer is prepared by grafting 105TY maleic anhydride grafted polypropylene from Dow America and Coteng SEBS G1901 maleic anhydride in a weight ratio of 1:2.8 );
s3, adding an antioxidant 168 into the mixed material B, and mixing for 12min at normal temperature in a high-speed mixer to obtain a mixed material C (the weight of the antioxidant 168 is 0.5 percent of the weight of the raw materials in the system);
and S4, conveying the mixed material C into a double-screw extruder to extrude and granulate to obtain environment-friendly modified styrene TPE granules (wherein the double-screw extruder is an asymmetric double-screw extruder, the length-diameter ratio is 32, the ratio of the single-head rotating speed of the asymmetric double-screw extruder to the double-head rotating speed of the asymmetric double-screw extruder is 3, the double-head rotating speed is 22r/min, and the temperatures of 1-7 areas of the double-screw extruder are 160 ℃, 180 ℃, 190 ℃, 200 ℃, 220 ℃ and 250 ℃).
As shown in fig. 1, a picture of a runway prepared from environmentally friendly modified styrene TPE granules is shown.
Example 4
A preparation method of environment-friendly modified styrene TPE granules comprises the following steps:
s1, adding the ba ling petrochemical SEBS503 into a mixer, then directly adding the medium petrochemical No. 22 paraffin oil, and mixing at 50 ℃ for 27min to obtain a mixed material A (wherein the weight ratio of the ba ling petrochemical SEBS503 to the medium petrochemical No. 22 paraffin oil is 1;
s2, adding a thermoplastic elastomer, a filler and an interface compatilizer into the mixed material A, and mixing for 15min at 45 ℃ in a high-speed mixer to obtain a mixed material B (wherein the weight ratio of the thermoplastic elastomer to the baring petrochemical SEBS503 is 2.8
FORTIFY TM C1060D POE；
FORTIFY TM The weight ratio of C1060D POE to the cigarette platform Wanhua TPU1185 is 1:2.5; the filler is a composition of ground calcium carbonate, talcum powder and needle-shaped wollastonite; the weight ratio of the heavy calcium carbonate to the talcum powder to the needle-shaped wollastonite is 12:2:1; the average grain size of the heavy calcium carbonate is 2500 meshes; the average grain size of the talcum powder is 1250 meshes; the average grain size of the needle-shaped wollastonite is 4000 meshes; the heavy calcium carbonate, the talcum powder and the needle-shaped wollastonite are purchased from the Guangyuan chemical industry in Jiangxi; the interfacial compatilizer is prepared by grafting 105TY maleic anhydride grafted polypropylene of Dow America and Keteng SEBS G1901 maleic anhydride in a weight ratio of 1:2.8 );
s3, adding an antioxidant 168 into the mixed material B, and mixing for 12min at normal temperature in a high-speed mixer to obtain a mixed material C (the weight of the antioxidant 168 is 0.5 percent of the weight of the raw materials in the system);
and S4, feeding the mixed material C into a double-screw extruder for extrusion granulation to obtain environment-friendly modified styrene TPE granules (wherein the double-screw extruder is an asymmetric double-screw extruder, the length-diameter ratio is 32, the ratio of the single-head rotating speed of the asymmetric double-screw extruder to the double-head rotating speed of the asymmetric double-screw extruder is 3.
Example 5
A preparation method of environment-friendly modified styrene TPE granules comprises the following steps:
s1, adding the ba ling petrochemical SEBS503 into a mixer, then directly adding the medium petrochemical No. 22 paraffin oil, and mixing at 50 ℃ for 27min to obtain a mixed material A (wherein the weight ratio of the ba ling petrochemical SEBS503 to the medium petrochemical No. 22 paraffin oil is 1;
s2, adding the thermoplastic elastomer, the filler and the interface compatilizer into the mixed material A, and mixing for 15min at 45 ℃ in a high-speed mixer to obtain a mixed material B (wherein the weight ratio of the thermoplastic elastomer to the ba ling petrochemical SEBS503 is 2.8The weight ratio of SEBS503 to the filler to the interfacial compatilizer is 1:1.68:0.12; the thermoplastic elastomer comprises tabasheer TPU1185 and holy petrochemical SBS815; the weight ratio of the tabacco warfarin TPU1185 to the ba ling petrochemical SBS815 is 1:4; the thermoplastic elastomer further comprises
FORTIFY TM C1060D POE；
FORTIFY TM The weight ratio of C1060D POE to the cigarette platform Wanhua TPU1185 is 1:2.5; the filler is a composition of heavy calcium carbonate, talcum powder and needle-shaped wollastonite; the weight ratio of the heavy calcium carbonate to the talcum powder to the needle-shaped wollastonite is 12:2:1; the average grain size of the heavy calcium carbonate is 2500 meshes; the average grain size of the talcum powder is 1250 meshes; the average grain diameter of the needle-shaped wollastonite is 4000 meshes; the heavy calcium carbonate, the talcum powder and the needle-shaped wollastonite are all purchased from Jiangxi Guangyuan chemical industry; the interfacial compatilizer is prepared by grafting 105TY maleic anhydride grafted polypropylene of Dow America and Keteng SEBS G1901 maleic anhydride in a weight ratio of 1:2.8 );
s3, adding an antioxidant 168 into the mixed material B, and mixing for 12min at normal temperature in a high-speed mixer to obtain a mixed material C (the weight of the antioxidant 168 is 0.5 percent of the weight of the raw materials in the system);
and S4, feeding the mixed material C into a double-screw extruder for extrusion granulation to obtain environment-friendly modified styrene TPE granules (wherein the double-screw extruder is an asymmetric double-screw extruder, the length-diameter ratio is 32, the ratio of the single-head rotating speed of the asymmetric double-screw extruder to the double-head rotating speed of the asymmetric double-screw extruder is 1.5.
Performance test
The performance of the environmentally-friendly modified styrene TPE granules prepared by the preparation method of example 3 was tested according to the standard of GB 36246-2018, and the test results are shown in Table 1:
TABLE 1
The odor grade and the total polycyclic aromatic hydrocarbon content in 18 of the environment-friendly modified styrene TPE granules prepared by the preparation methods in examples 1 to 5 are checked according to the standard of GB 36246-2018, and the test results are shown in Table 2:
TABLE 2
Claims (10)
1. The preparation method of the environment-friendly modified styrene TPE granules is characterized by comprising the following steps:
s1, mixing styrene TPE and filling oil to obtain a mixed material A;
s2, adding the thermoplastic elastomer, the filler and the interface compatilizer into the mixed material A, and uniformly mixing in a high-speed mixer to obtain a mixed material B;
s3, adding an auxiliary agent into the mixed material B, and uniformly mixing in a high-speed mixer to obtain a mixed material C;
and S4, feeding the mixed material C into a double-screw extruder to be extruded and granulated to obtain the environment-friendly modified styrene TPE particles.
2. The method for preparing environment-friendly modified styrene TPE granules according to claim 1, wherein the mixing step in step S1 comprises the following steps: styrene TPE is first placed in a mixer and then extender oil is added to the mixer, the extender oil being added several times.
3. The method for preparing environment-friendly modified styrene TPE granules as claimed in claim 2, wherein the filling oil is added by direct mixing or spraying.
4. The method for preparing environment-friendly modified styrene TPE granules according to claim 1, wherein the weight ratio of the thermoplastic elastomer to the styrene TPE is (2-3.5): 1; the weight ratio of the styrene TPE to the filler to the interfacial compatilizer is 1: (1-2): (0.1-0.15).
5. The method for preparing environment-friendly modified styrene TPE granules according to claim 1 or 4, wherein the thermoplastic elastomer comprises TPU elastomer and SBS elastomer; the SBS elastomer is of a star-shaped structure.
6. The method for preparing environment-friendly modified styrene TPE granules as claimed in claim 1, wherein the temperature during mixing in step S2 is 30-60 ℃ and the mixing time is 1-20 min.
7. The method for preparing environment-friendly modified styrene TPE granules as claimed in claim 1 or 6, wherein the mixing conditions in step S3 are as follows: mixing for 1-20 min at normal temperature.
8. The method for preparing environment-friendly modified styrene TPE granules according to claim 1, wherein the filler is at least one selected from talc, attapulgite, ground calcium carbonate, silica, kaolin and acicular wollastonite.
9. The method for preparing environment-friendly modified styrene TPE granules as claimed in claim 8, wherein the temperature of the 1-7 zones of the twin-screw extruder is 150-170 ℃, 160-195 ℃, 180-200 ℃, 190-220 ℃, 210-240 ℃ and 230-260 ℃.
10. The use of the environmentally modified styrene TPE granules according to any one of claims 1 to 9, wherein the environmentally modified styrene TPE granules are used for the production of runways or court.
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| KR100780229B1 (en) * | 2007-09-05 | 2007-11-28 | 이태흥 | Thermoplastic elastic chip for artificial turf and method of manufacturing thereof |
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