CN108530764B - 一种无卤阻燃型的热塑性弹性体及其制备方法 - Google Patents
一种无卤阻燃型的热塑性弹性体及其制备方法 Download PDFInfo
- Publication number
- CN108530764B CN108530764B CN201810195646.8A CN201810195646A CN108530764B CN 108530764 B CN108530764 B CN 108530764B CN 201810195646 A CN201810195646 A CN 201810195646A CN 108530764 B CN108530764 B CN 108530764B
- Authority
- CN
- China
- Prior art keywords
- parts
- flame retardant
- thermoplastic elastomer
- halogen
- carbon black
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
- 238000004073 vulcanization Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 11
- 239000004760 aramid Substances 0.000 claims abstract description 11
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 silane modified flame retardant Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 4
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 230000003712 anti-aging effect Effects 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002216 antistatic agent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 5
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 4
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 4
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- RNPXCFINMKSQPQ-UHFFFAOYSA-N dicetyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCC RNPXCFINMKSQPQ-UHFFFAOYSA-N 0.000 claims 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims 1
- 239000003245 coal Substances 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 229910000077 silane Inorganic materials 0.000 abstract description 4
- 229910052787 antimony Inorganic materials 0.000 abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- PCDQPRRSZKQHHS-CCXZUQQUSA-N Cytarabine Triphosphate Chemical compound O=C1N=C(N)C=CN1[C@H]1[C@@H](O)[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)O1 PCDQPRRSZKQHHS-CCXZUQQUSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
-
- 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
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开一种无卤阻燃型的热塑性弹性体及其制备方法,选择EPDM/PP/SEPS高分子复合体系、导电炭黑/白炭黑/芳纶浆粕补强导电体系和不含卤锑的复配阻燃体系为热塑性弹性体的主要成分,通过制备EPDM母炼胶、硅烷改性处理阻燃剂、高速混合预塑化、密炼机和挤出机联合动态硫化等工艺过程,在密炼机转速40转/分钟,温度160℃‑165℃的条件下动态硫化2‑3分钟,再经过挤出机动态硫化,在螺杆转速30‑50转/分钟,温度165℃‑180℃的条件下动态硫化5‑7分钟制得。本发明的产品具有优良的物理机械性能,安全性能和环保性能,满足煤矿橡胶制品、汽车橡胶制品和轨道交通橡胶制品对热塑性弹性体的性能要求。
Description
技术领域
本发明涉及热塑性弹性体技术领域,具体地说,是一种无卤阻燃型的热塑性弹性体及其制备方法。
背景技术
阻燃热塑性弹性体是煤矿橡胶制品、汽车橡胶制品、家电橡胶制品、轨道交通橡胶制品和电缆等产品重要的材料,市场需求很大。目前我国使用及生产的阻燃热塑性弹性体多是含卤含锑的,要么使用含卤的主题材料,要么添加含卤、锑的阻燃剂,一旦引燃会产生大量的有毒有害的气体,影响人们的身体健康和生命安全,污染环境和腐蚀机械设备,造成严重的次生灾害。现有的一些无卤阻燃的热塑性弹性体,因大量添加无机阻燃剂,使力学性能大幅度下降,不能用于制造阻燃输送带、电缆、汽车配件、轨道交通减震件等重要产品。
发明内容
本发明的目的是克服现有技术的不足,提供一种无卤阻燃型的热塑性弹性体,具有优良的物理机械性能,安全性能和环保性能,满足煤矿橡胶制品、汽车橡胶制品和轨道交通橡胶制品对热塑性弹性体的性能要求。
本发明的第二个目的是提供该热塑性弹性体的制备方法,工艺简单,易于制造,生产成本低。
本发明的目的通过下述方案予以实现。
本发明提供一种无卤阻燃型的热塑性弹性体及其制备方法。所述的热塑性弹性体,按重量份数计,由下述原料制成:
三元乙丙橡胶(EPDM) 40-60份,氢化苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SEPS)10-20份,聚丙烯(PP) 30-40份,氧化锌 3-5份,硬脂酸 1-2份,硫磺 1-1.5份,过氧化二异丙苯(DCP) 2-4份,异氰脲酸三烯丙酯(TAIC) 0.5-1份,促进剂 1-2份,防老剂1-2份,防焦剂CTP 1份,抗氧剂1010 1-2份,白炭黑 6-8份,导电炭黑 10-15份,芳纶浆粕 6-8份,抗静电剂P 2-4份,硅烷偶联剂(Si69) 0.5-1.0份,磷酸酯类阻燃剂 8-12份,无卤阻燃剂 15-25份。
所述的促进剂可选用促进剂M、促进剂DM、促进剂CZ、促进剂TMTD中的一种或组合;防老剂可选用防老剂BLE、防老剂RD、防老剂2246-S、防老剂4010NA中的一种或组合;磷酸酯类阻燃剂可选用磷酸二苯异辛酯(DPOP)、磷酸三甲苯酯(TCP)、磷酸三辛酯(TOP)中的任意一种;无卤阻燃剂可选用氢氧化铝[Al(OH)3]、氢氧化镁[Mg(OH)2]、硼酸锌、聚磷酸铵(APP)、三聚氰胺磷酸盐(MPP)、三聚氰胺氰脲酸盐(MCA)的一种或其组合。
所述制备方法包括以下步骤:
(1)制备EPDM母炼胶
将EPDM、导电炭黑、氧化锌、硬脂酸、促进剂、防老剂、防焦剂加入密炼机中混炼,密炼机转速40转/分钟,混炼时间5分钟,排胶温度140℃,出片、冷却,制成EPDM母炼胶。
(2) 阻燃剂改性处理
将白炭黑、芳纶桨粕、无卤阻燃剂 、磷酸酯类阻燃剂、抗氧剂加入捏合机中加热搅拌,搅拌速度为375-400转/分钟,加热至40-60℃,开始喷洒硅烷偶联剂,继续加热搅拌,在115℃-125℃的温度下搅拌10-15分钟,制成表面改性阻燃剂。
(3)高速混合预塑化
将PP、SEPS、抗静电剂、表面改性阻燃剂依次加入高速混合机中,混合速度为1200-1400转/分钟,在140℃-150℃的温度下混合10-15分钟,排料、冷却,制得预塑化料。
(4)动态硫化
将预塑化料、EPDM母炼胶、硫磺、DCP 、TAIC一起加入到密炼机中混炼,密炼机转速40转/分钟,在温度160℃-165℃的条件下动态硫化2-3分钟,制得预硫化的热塑性弹性体。预硫化的热塑性弹性体再经过双螺杆挤出机,螺杆转速30-50转/分钟,在温度165℃-180℃的条件下动态硫化6-8分钟,制得本发明的热塑性弹性体。
与现有技术相比,本发明具有以下有益效果:
1、SEPS是热塑性苯乙烯-异戊二烯-苯乙烯(SIS)分子中橡胶段聚异戊二烯不饱和双键经过选择性加氢改性而制得的新型热塑性弹性体材料,具有优良的机械性能和耐候性能、超强的柔韧性和高弹性,且与EPDM 及PP有极好的相容性,本发明选择SEPS与EPDM/PP共混制备热塑性弹性体(TPV),可降低TPV的动态硫化温度和时间,提高TPV的力学性能。
2、本发明选择导电炭黑与经过表面硅烷处理的白炭黑和芳纶浆粕组成TPV补强体系,可显著提高TPV的导电性能和力学性能。
3、本发明选择由经过表面硅烷处理的无卤阻燃剂、白炭黑和磷酸酯类阻燃剂复配组成的阻燃体系,对TPV有协同阻燃作用,阻燃效果好,用量较少,与EPDM/PP/SEPS共混制备TPV, TPV的阻燃性能和力学性能较佳。
4、本发明采用密炼机和挤出机联合动态硫化,首先经过密炼机低温预硫化,然后再经过螺杆挤出机高温硫化制备TPV,降低了硫化的温度和时间,TPV分散均匀,硫化充分,阻燃性能和力学性能较佳。
5、本发明选择EPDM/PP/SEPS高分子复合体系、导电炭黑/白炭黑/芳纶浆粕补强导电体系和不含卤锑的复配阻燃体系为TPV的主要成分,通过制备EPDM母炼胶、硅烷改性处理阻燃剂、高速混合预塑化、密炼机和挤出机联合动态硫化等工艺过程,制备的TPV 具有优良的物理机械性能,安全性能和环保性能,满足煤矿橡胶制品、汽车橡胶制品和轨道交通橡胶制品对TPV的性能要求。
具体实施方式
通过下述实施例有助于对本发明的理解,但不能限制本发明的内容。
实施例1
本实施例提供一种无卤阻燃型的热塑性弹性体,按重量份数计,由下述原料制成:
EPDM 40份,SEPS 20份,PP 40份,氧化锌3份,硬脂酸1份,硫磺1份,DCP 4份,TAIC1份,促进剂M 0.5份,促进剂TMTD 0.5份,防老剂RD 0.5份,防老剂BLE 0.5份,防焦剂CTP 1份,抗氧剂1010 2份,白炭黑8份,导电炭黑10份,芳纶浆粕8份,抗静电剂P 4份,硅烷偶联剂Si69 0.5份,TOP 8份,Al(OH)3 10份,APP 15份。
本实施例提供的无卤阻燃型热塑性弹性体的制备方法包括以下步骤:
(1)制备EPDM母炼胶
将EPDM、导电炭黑、氧化锌、硬脂酸、促进剂、防老剂、防焦剂加入密炼机中混炼,密炼机转速40转/分钟,混炼时间5分钟,排胶温度140℃,出片、冷却,制成EPDM母炼胶。
(2)阻燃剂改性处理
将白炭黑、芳纶桨粕、无卤阻燃剂 、磷酸酯类阻燃剂、抗氧剂加入捏合机中加热搅拌,搅拌速度为375-400转/分钟,加热至40-60℃,开始喷洒硅烷偶联剂,继续加热搅拌,在115℃-125℃的温度下搅拌10-15分钟,制成表面改性阻燃剂。
(3) 高速混合预塑化
将PP、SEPS、抗静电剂、表面改性阻燃剂依次加入高速混合机中,混合速度为1200-1400转/分钟,在140℃-150℃的温度下混合10-15分钟,排料、冷却,制得预塑化料。
(4)动态硫化
将预塑化料、EPDM母炼胶、硫磺、DCP 、TAIC一起加入到密炼机中混炼,密炼机转速40转/分钟,在温度160℃-165℃的条件下动态硫化2-3分钟,制得预硫化的热塑性弹性体。预硫化的热塑性弹性体再经过双螺杆挤出机,螺杆转速30-50转/分钟,在温度165℃-180℃的条件下动态硫化6-8分钟,制得本发明的热塑性弹性体。
实施例2
本实施例提供一种无卤阻燃型的热塑性弹性体,按重量份数计,由下述原料制成:
EPDM 50份,SEPS 15份,PP 35份,氧化锌4份,硬脂酸1.5份,硫磺1.2份,DCP 3份,TAIC 0.8份,促进剂CZ 1份,促进剂TMTD 0.5份,防老剂2246-S 1份,防老剂4010NA 0.5份,防焦剂CTP 1份,抗氧剂1010 1.5份,白炭黑7份,导电炭黑12份,芳纶浆粕7份,抗静电剂P 3份,硅烷偶联剂si69 0.8份,TCP 12份,硼酸锌 5份,MCA 10份。
本实施例的制备方法同实施例1。
实施例3
本实施例提供一种无卤阻燃型的热塑性弹性体,按重量份数计,由下述原料制成:
EPDM 60份,SEPS 10份,PP 30份,氧化锌5份,硬脂酸2份,硫磺1.5份,DCP 2份,TAIC 0.5份,促进剂DM 1份,促进剂TMTD 1份,防老剂RD 1份,防老剂4010NA 1份,防焦剂CTP 1份,抗氧剂1010 1份,白炭黑6份,导电炭黑15份,芳纶浆粕6份,抗静电剂P 2份,硅烷偶联剂Si69 1份,DPOP 10份,Mg(OH)210份,MPP 10份。
本实施例的制备方法同实施例1。
上述实施例的检测数据见下表:
Claims (2)
1.一种无卤阻燃型的热塑性弹性体,其特征在于,按重量份数计,由下述原料制成:
三元乙丙橡胶40-60份,氢化苯乙烯-异戊二烯-苯乙烯嵌段共聚物10-20份,聚丙烯30-40份,氧化锌3-5份,硬脂酸1-2份,硫磺1-1.5份,过氧化二异丙苯2-4份,异氰脲酸三烯丙酯0.5-1份,促进剂1-2份,防老剂1-2份,防焦剂CTP 1份,抗氧剂1010 1-2份,白炭黑6-8份,导电炭黑10-15份,芳纶浆粕6-8份,抗静电剂P 2-4份,硅烷偶联剂Si69 0.5-1.0,磷酸酯类阻燃剂8-12份,无卤阻燃剂15-25份;
所述的促进剂选用促进剂M、促进剂DM、促进剂CZ、促进剂TMTD中的一种或组合;
所述的防老剂选用防老剂BLE、防老剂RD、防老剂2246-S、防老剂4010NA中的一种或组合;
所述的磷酸酯类阻燃剂选用磷酸二苯异辛酯、磷酸三甲苯酯、磷酸三辛酯中的任意一种;
所述的无卤阻燃剂选用氢氧化铝、氢氧化镁、硼酸锌、聚磷酸铵、三聚氰胺磷酸盐、三聚氰胺氰脲酸盐的一种或组合。
2.根据权利要求1所述的一种无卤阻燃型的热塑性弹性体的制备方法,其特征在于,包括以下步骤:
(1)制备EPDM母炼胶
将EPDM、导电炭黑、氧化锌、硬脂酸、促进剂、防老剂、防焦剂CTP加入密炼机中混炼,密炼机转速40转/分钟,混炼时间5分钟,排胶温度140℃,出片、冷却,制成EPDM母炼胶;
(2)阻燃剂改性处理
将白炭黑、芳纶浆粕、无卤阻燃剂 、磷酸酯类阻燃剂、抗氧剂1010加入捏合机中加热搅拌,搅拌速度为375-400转/分钟,加热至40-60℃,开始喷洒硅烷偶联剂Si69,继续加热搅拌,在115℃-125℃的温度下搅拌10-15分钟,制成表面改性阻燃剂;
(3)高速混合预塑化
将PP、SEPS、抗静电剂P、表面改性阻燃剂依次加入高速混合机中,混合速度为1200-1400转/分钟,在140℃-150℃的温度下混合10-15分钟,排料、冷却,制得预塑化料;
(4)动态硫化
将预塑化料、EPDM母炼胶、硫磺、DCP 、TAIC一起加入到密炼机中混炼,密炼机转速40转/分钟,在温度160℃-165℃的条件下动态硫化2-3分钟,制得预硫化的热塑性弹性体;预硫化的热塑性弹性体再经过双螺杆挤出机,螺杆转速30-50转/分钟,在温度165℃-180℃的条件下动态硫化6-8分钟,制得热塑性弹性体。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810195646.8A CN108530764B (zh) | 2018-03-09 | 2018-03-09 | 一种无卤阻燃型的热塑性弹性体及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810195646.8A CN108530764B (zh) | 2018-03-09 | 2018-03-09 | 一种无卤阻燃型的热塑性弹性体及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108530764A CN108530764A (zh) | 2018-09-14 |
CN108530764B true CN108530764B (zh) | 2020-12-15 |
Family
ID=63483426
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810195646.8A Active CN108530764B (zh) | 2018-03-09 | 2018-03-09 | 一种无卤阻燃型的热塑性弹性体及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108530764B (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109943054A (zh) * | 2019-03-29 | 2019-06-28 | 华中科技大学 | 一种适用于fdm成形的高阻燃pc复合材料及制备方法 |
CN110283392A (zh) * | 2019-07-19 | 2019-09-27 | 江苏金陵奥普特高分子材料有限公司 | 兼顾高导电性和力学性的热塑性弹性体及其制备方法 |
CN111944241B (zh) * | 2020-07-06 | 2023-05-23 | 台州学院 | 一种环保阻燃型热塑性弹性体及其制备方法 |
CN113025234A (zh) * | 2021-04-18 | 2021-06-25 | 安徽中意胶带有限责任公司 | 耐高温阻燃输送带帆布粘合橡胶复合材料及其制备方法 |
CN113234286A (zh) * | 2021-04-18 | 2021-08-10 | 安徽中意胶带有限责任公司 | 耐高温钢丝绳芯阻燃输送带粘合橡胶复合材料及其制备方法 |
CN113233089B (zh) * | 2021-04-18 | 2022-12-27 | 安徽中意胶带有限责任公司 | 一种耐高温的帆布芯阻燃输送带及其制造方法 |
CN113061306A (zh) * | 2021-04-18 | 2021-07-02 | 安徽中意胶带有限责任公司 | 一种抗灼烧的钢丝绳芯阻燃输送带及其制造方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0230115A1 (en) * | 1985-11-29 | 1987-07-29 | American National Can Company | Polymeric compositions and films, plural layer sheet structures and packaging made from such films and structures |
WO2001012717A1 (en) * | 1999-08-12 | 2001-02-22 | Baxter International Inc. | Thermoplastic composition |
CN103740032A (zh) * | 2013-12-27 | 2014-04-23 | 安徽科聚新材料有限公司 | 一种热塑性弹性体材料及其制备方法 |
CN103849133A (zh) * | 2014-02-25 | 2014-06-11 | 深圳市欧龙优新材料科技有限公司 | 一种耐高温免辐照交联无卤阻燃电线电缆材料 |
CN105255092A (zh) * | 2015-10-26 | 2016-01-20 | 深圳达普林科技有限公司 | 一种sbc热塑性弹性材料及其制备工艺 |
CN105670117A (zh) * | 2016-03-02 | 2016-06-15 | 安徽蓝通科技股份有限公司 | 一种氧化石墨烯改性聚丙烯复合材料 |
CN106221034A (zh) * | 2016-08-29 | 2016-12-14 | 四川金开特种电线电缆有限公司 | 一种无卤热塑性阻燃线缆料 |
-
2018
- 2018-03-09 CN CN201810195646.8A patent/CN108530764B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0230115A1 (en) * | 1985-11-29 | 1987-07-29 | American National Can Company | Polymeric compositions and films, plural layer sheet structures and packaging made from such films and structures |
WO2001012717A1 (en) * | 1999-08-12 | 2001-02-22 | Baxter International Inc. | Thermoplastic composition |
CN103740032A (zh) * | 2013-12-27 | 2014-04-23 | 安徽科聚新材料有限公司 | 一种热塑性弹性体材料及其制备方法 |
CN103849133A (zh) * | 2014-02-25 | 2014-06-11 | 深圳市欧龙优新材料科技有限公司 | 一种耐高温免辐照交联无卤阻燃电线电缆材料 |
CN105255092A (zh) * | 2015-10-26 | 2016-01-20 | 深圳达普林科技有限公司 | 一种sbc热塑性弹性材料及其制备工艺 |
CN105670117A (zh) * | 2016-03-02 | 2016-06-15 | 安徽蓝通科技股份有限公司 | 一种氧化石墨烯改性聚丙烯复合材料 |
CN106221034A (zh) * | 2016-08-29 | 2016-12-14 | 四川金开特种电线电缆有限公司 | 一种无卤热塑性阻燃线缆料 |
Non-Patent Citations (1)
Title |
---|
EPDM/PP共混型热塑性弹性体的研究现状;于莉等;《橡胶工业》;20031010(第10期);第625-629页 * |
Also Published As
Publication number | Publication date |
---|---|
CN108530764A (zh) | 2018-09-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108530764B (zh) | 一种无卤阻燃型的热塑性弹性体及其制备方法 | |
US7414094B2 (en) | Rubber composition for inner liner | |
CN105330995B (zh) | 一种环保阻燃发泡橡胶及其制备方法 | |
CN104558714B (zh) | 一种耐寒型的阻燃热塑性弹性体及其制备方法 | |
CN104558965B (zh) | 一种阻燃抗静电的热塑性弹性体及其制备方法 | |
CN100429274C (zh) | 一种硫化体系及氯化丁基橡胶/聚烯烃热塑性弹性体 | |
CN106543505A (zh) | 一种高性能丁腈橡胶密封材料及其制备方法 | |
EP2345693A1 (en) | Rubber composition for inner liner and pneumatic tire | |
US3419639A (en) | Ozone-resistant composition | |
CN112321952B (zh) | 一种三元乙丙复合橡胶材料及其制备方法 | |
CN104592631A (zh) | 一种环保型的阻燃热塑性弹性体及其制备方法 | |
CN115710402B (zh) | 一种高耐候性的环保阻燃橡胶复合材料及其制备方法 | |
JPWO2019077883A1 (ja) | ガラス組成物、綿状ガラス繊維、複合形成材料、成形品、および、綿状ガラス繊維の製造方法 | |
CN104530550B (zh) | 一种热塑性弹性体及其制备方法和用于输送带的成型工艺 | |
CN108485240B (zh) | 聚氨酯弹性体材料及其制备方法和应用 | |
CN105199167B (zh) | 环保型耐高低温耐油阻燃纳米复合热塑性弹性体及其制备工艺 | |
CN108485011B (zh) | 一种绿色节能耐磨耐寒阻燃型热塑性橡胶及其制备方法 | |
CN112375306A (zh) | 一种密封胶条用橡胶材料 | |
CN103059401B (zh) | 一种耐油热塑性弹性体及其制备方法 | |
CN115975270A (zh) | 一种耐寒阻燃橡胶大底混炼胶 | |
KR101509772B1 (ko) | 아연분말 충전 웨더스트립 및 글래스런 조성물 | |
EP3940026B1 (en) | FLAME-RETARDANT VIBRATION 
ISOLATION RUBBER COMPOSITION AND FLAME-RETARDANT VIBRATION ISOLATION RUBBER MEMBER | |
KR101776413B1 (ko) | 나노 산화 아연 충전 웨더스트립 고무 조성물 및 이를 이용한 자동차용 웨더스트립 | |
JP7234493B2 (ja) | 空気入りタイヤ | |
JP2017141326A (ja) | タイヤ用ゴム組成物およびタイヤ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |