CN111100342A - 一种橡胶增韧塑料及其制备方法 - Google Patents
一种橡胶增韧塑料及其制备方法 Download PDFInfo
- Publication number
- CN111100342A CN111100342A CN201811247076.9A CN201811247076A CN111100342A CN 111100342 A CN111100342 A CN 111100342A CN 201811247076 A CN201811247076 A CN 201811247076A CN 111100342 A CN111100342 A CN 111100342A
- Authority
- CN
- China
- Prior art keywords
- component
- rubber
- unvulcanized
- total mass
- accounts
- 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.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 49
- 239000005060 rubber Substances 0.000 title claims abstract description 43
- 239000004033 plastic Substances 0.000 title claims abstract description 36
- 229920003023 plastic Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 229920002379 silicone rubber Polymers 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- 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 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims description 6
- 229920000768 polyamine Chemical class 0.000 claims description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 239000004945 silicone rubber Substances 0.000 claims description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- VMJLKERPLGRIQJ-UHFFFAOYSA-N propane-1,1,1-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(O)(O)O VMJLKERPLGRIQJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920006345 thermoplastic polyamide Polymers 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- XVKIXCFCFNUQQW-UHFFFAOYSA-N C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.OC(CC)(O)O Chemical compound C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.OC(CC)(O)O XVKIXCFCFNUQQW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000800 acrylic rubber Polymers 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 claims description 2
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 235000004692 Eucalyptus globulus Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000020289 caffè mocha Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了一种橡胶增韧塑料及其制备方法。该增韧塑料包括组分A,组分B,组分C和组分D,其中:组分A为未硫化的橡胶,组分B为热塑性树脂,组分C为热塑性弹性体,组分D为混合添加剂。该增韧塑料的制备方法为:将未硫化的橡胶A、热塑性树脂B、热塑性弹性体C和混合添加剂D在双螺杆挤出机中进行混合,使未硫化橡胶A在热与机械作用下硫化,组分A、B、C和D在双螺杆挤出机中充分混合,得到具有良好韧性和加工性的增韧塑料。
Description
技术领域
本发明属于塑料增韧领域,具体涉及一种韧性塑料,特别是采用未硫化橡胶和/或热塑性弹性体共同增韧的热塑性塑料及其制备方法。
背景技术
美国杜邦公司Souheng Wu博士提出的临界粒子间距判据的概念,对热塑性聚合物基体进行了科学分类并建立了脆韧转变的逾渗模型,将增韧理论由定性分析推向定量分析。该理论认为共混物韧性与基体的链结构间存在一定的联系,并给出了基体链结构参数——链缠结密度Ve和链的特征比C∞间的定量关系式,指出聚合物的基本断裂行为是银纹与屈服存在竞争。当Ve<0.15,C∞>7.5时,基体易于以银纹方式断裂,韧性较低;反之,基体则以屈服方式断裂,韧性较高。这是因为当橡胶粒子相距很远时,一个粒子周围的应力场对其它粒子影响很小,基体的应力场是这些孤立的粒子的应力场的简单加和,基体塑性变形的能力很小时,表现为脆性。当粒子间距很小时,基体总应力场是橡胶颗粒应力场相互作用的叠加,这样,使基体应力场的强度大为增强,产生塑性变形的幅度增加,表现为韧性对热塑性聚合物基体。也就是说,只有当体系中橡胶粒子间距小于临界值时才有增韧作用。相反,如果橡胶颗粒间距远大于临界值时,则材料表现为脆性。
目前增韧塑料的方法主要是通过添加橡胶粒子,若要达到较好的增韧效果,混合体系中橡胶胶粒间距必须足够小,因此可以通过降低胶粒粒径或增大橡胶添加剂的方法。专利CN00130385.6中,提供了一种平均粒径不大于0.5μm、具有交联结构的粉末橡胶增韧塑料的方法,但该法中的橡胶粒径达微米级,制备难度较大。而通过增加橡胶用量,会降低原塑料的热性能、刚性等。
发明内容
本发明提供了一种橡胶增韧塑料的方法及其制备方法,采用未硫化橡胶及添加剂、热塑性弹性体、塑料在双螺杆挤出机种熔融共混,使未硫化橡胶在螺杆种中发生硫化,并与热塑性弹性体、添加剂、塑料粒子熔融共混后造粒。该方法简单易行,可在不降低热性能的前提下,达到良好的增韧效果,且该方法适合于各类脆性塑料。
本发明提供了一种橡胶增韧塑料,该增韧塑料包括组分A,组分B,组分C和组分D,其中:所述的组分A选自未硫化的橡胶中的一种或几种;所述的组分B为热塑性树脂,其链缠结密度Ve≤0.15,极性特征比C∞≥7.5;所述的组分C选自苯乙烯类、烯烃类、酰胺类、酯类或有机硅类的热塑性弹性体中的一种或几种;所述的组分D为混合添加剂,选自硫磺粉末、有机过氧化物、金属氧化物、多胺类化合物或酯类中的一种或几种;以重量百分数计,组分A占组成物总质量的5%~65%;组分B占组成物总质量的5%~90%;组分C占组成物总质量的0~45%;组分D占组成物总质量的1%~45%。
优选地,所述的组分A占组成物总质量的5%~30%;组分B占组成物总质量的65%~90%;组分C占组成物总质量的0~25%;组分D占组成物总质量的1%~15%。
具体地,所述的组分A选自以下未硫化橡胶中的一种或几种:未硫化天然橡胶、未硫化丁苯橡胶、未硫化丁腈橡胶、未硫化异戊橡胶、未硫化氯丁橡胶、未硫化乙丙橡胶、未硫化丙烯酸橡胶、未硫化硅橡胶或未硫化丁基橡胶。所述的组分A常温下为固体。
所述的组分B选自以下热塑性树脂中的一种或几种:聚乙烯、聚丙烯、聚苯乙烯、聚丙烯腈-丁二烯-苯乙烯树脂、聚甲基丙烯酸甲酯或聚氯乙烯。
所述的组分C选自以下热塑性弹性体中的一种或几种:苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-苯乙烯嵌段共聚物、热塑性聚氨酯弹性体橡胶、聚烯烃热塑性弹性体、聚酰胺热塑性弹性体或有机硅类热塑性弹性体。
所述的组分D中:硫磺粉末占组分D总质量的0%-95%;有机过氧化物选自以下一种或几种物质:过氧化二苯甲酰、过氧化二异丙苯、过氧化二叔丁基、过或苯甲酸叔丁酯,有机过氧化物占组分D总质量的0%-95%;金属氧化物选自以下一种或几种物质:氧化锌、氧化镁、氧化铅或四氧化三铅,金属氧化物占组分D总质量的0%-95%;多胺类化合物选自以下一种或几种物质:三亚亚乙基四胺、四亚乙基五胺或1,6-己二胺,多胺类物质占组分D总质量的0%-95%;酯类选自以下一种或几种物质:三丙烯酸三羟基丙烷酯、三甲基丙烯酸三羟基丙烷酯、二丙烯酸乙二醇酯、二甲基丙烯酸乙二醇酯、N,N’-对苯基双马来酰亚胺、二丙烯酸锌、二甲基丙烯酸锌,氰尿酸三烯丙酯或异氰尿酸三烯丙酯,酯类占组分D总质量的0%-95%。
本发明还提供了一种上述橡胶增韧塑料的制备方法,包括如下步骤:
(1)将组分A置于粉碎机中,加工至碎片,速度:500~800rpm,温度:-7℃盘管水循环冷却物料;
(2)将组分A碎片、组分C在混料机中混合,速度:100~200rpm,温度:室温;
(3)将组分B、组分D在混料机中混合,速度:200~300rpm,温度:室温;
(4)将混合均匀的组分A碎片、组分C加入双螺杆/单螺杆挤出机的料斗1中;
(5)将混合均匀的组分B、组分D加入双螺杆/单螺杆挤出机的料斗2中;
(6)根据组分B的特性,为螺杆各区设定合适的温度;
(7)根据组分A、组分C的特性,选择合适的螺杆加入段;
(8)挤出机开机,带各区温度到达预设值后,开启主螺杆、料斗1中物料的加料螺杆、料斗2中物料的加料螺杆;
(9)根据实际情况,控制物料喂入量,调节螺杆温度和螺杆转速,挤出切断即获得橡胶增韧塑料。获得的产物橡胶增韧塑料在常温下为固体颗粒。
本发明的有益效果在于:其制备方法简单,无需将橡胶制成纳米级颗粒。由于用以改性的橡胶分以颗粒形式分散在基体中,因而几乎不会引起塑料玻璃化温度的下降,而韧性却可得到提升。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干调整和改进。这些都属于本发明的保护范围。
以下的实施例采用SANS/CMT4204型电子万能实验,按照国家标准GB/T 2567-2008对制备塑料的拉伸性能、冲击性能进行测试。采用差示扫描量热仪(DSC)测定玻璃化温度,升温速率5℃/min。
实施例中组分A选自未硫化氯丁橡胶、未硫化丁苯橡胶、未硫化硅橡胶中的任一种或几种。组分B选自聚丙烯、聚苯乙烯、聚丙烯腈-丁二烯-苯乙烯树脂中的任一种或几种。组分C选自热塑性聚氨酯弹性体、聚酰胺热塑性弹性体的任一种或几种。组分D选自硫磺、过氧化二苯甲酰、氧化锌、氧化镁、三丙烯酸三羟基丙烷酯、二丙烯酸乙二醇酯、异氰尿酸三烯丙酯的任一种或几种。
实例中,未硫化氯丁橡胶、未硫化丁苯橡胶购自上海圣义有限公司,未硫化硅橡胶TN-930E,购自东莞市天桉硅胶科技有限公司,聚丙烯M980M购自中国石化上海石化,聚苯乙烯GPPS525购自中国石化广州石化,聚丙烯腈-丁二烯-苯乙烯树脂3504购自中国石化高桥石化。热塑性聚氨酯弹性体G2701购自美国吉利士,GX-2014购自苏州莫卡,过氧化二苯甲酰L-W75购自阿克苏诺贝尔,氧化锌BA01-05购自广西锌品有限责任公司,氧化镁150购自神岛公司,异氰尿酸三烯丙酯购自大连天源基化学有限公司。
实施例1
将未硫化氯丁橡胶置于粉碎机中,打开冷却水,转速:500rpm,时间:15min。
取氧化锌、氧化镁各0.25kg,质量比1:1,取粉碎后的未硫化氯丁橡胶10kg,置于混合机中,转速150rpm,时间30min。
设置双螺杆各区温度,如下:
分区 | 模头 | TZ13 | TZ12 | TZ8 | TZ7 | TZ6 | TZ5 | TZ4 | TZ3 | TZ2 | 进料 |
温度 | 140 | 140 | 140 | 140 | 150 | 150 | 150 | 150 | 150 | 150 | 50 |
待各区温度达到设定值,并稳定一段时候后,将聚乙烯置于双螺杆料斗1中,将混合均匀的未硫化氯丁橡胶、氧化锌、氧化镁置于双螺杆料斗2中。
设定主螺杆转速为300rpm,侧喂料螺杆转速为240rpm,料斗1开始喂料,速度10kg/h。
调整链板、切刀参数,待造粒过程稳定后,料斗2开始喂料,速度1kg/h,进料区域TZ5。
实施例2
将未硫化硅橡胶置于粉碎机中,打开冷却水,转速:600rpm,时间:15min。
取过氧化二苯甲酰0.2kg、粉碎后的未硫化硅橡胶10kg,置于混合机中,转速150rpm,时间30min。
设置双螺杆各区温度,如下:
分区 | 模头 | TZ13 | TZ12 | TZ8 | TZ7 | TZ6 | TZ5 | TZ4 | TZ3 | TZ2 | 进料 |
温度 | 220 | 210 | 210 | 210 | 220 | 220 | 220 | 230 | 230 | 230 | 50 |
待各区温度达到设定值,并稳定一段时候后,将ABS置于双螺杆料斗1中,将混合均匀的未硫化硅橡胶、过氧化二苯甲酰置于双螺杆料斗2中。
设定主螺杆转速为300rpm,侧喂料螺杆转速为240rpm,料斗1开始喂料,速度10kg/h。
调整链板、切刀参数,待造粒过程稳定后,料斗2开始喂料,速度1kg/h,进料区域TZ4。
实施例3
将未硫化丁苯橡胶置于粉碎机中,打开冷却水,转速:600rpm,时间:15min。
取硫磺0.3kg、异氰尿酸三烯丙酯0.2kg、粉碎后的未硫化丁苯橡胶10kg,置于混合机中,转速150rpm,时间30min。
取热塑性聚氨酯弹性体5kg、聚苯乙烯树脂100kg,置于混合机中,转速200rpm,时间30min。
设置双螺杆各区温度,如下:
分区 | 模头 | TZ13 | TZ12 | TZ8 | TZ7 | TZ6 | TZ5 | TZ4 | TZ3 | TZ2 | 进料 |
温度 | 190 | 190 | 180 | 180 | 180 | 170 | 170 | 170 | 170 | 170 | 50 |
待各区温度达到设定值,并稳定一段时候后,将混合均匀的聚苯乙烯和热塑性聚氨酯弹性体混合物置于双螺杆料斗1中,将混合均匀的未硫化丁苯橡胶、硫磺、异氰尿酸三烯酯混合物置于双螺杆料斗2中。
设定主螺杆转速为300rpm,侧喂料螺杆转速为240rpm,料斗1开始喂料,速度10kg/h。
调整链板、切刀参数,待造粒过程稳定后,料斗2开始喂料,速度1kg/h,进料区域TZ4。
实施例4~9
实施例4~9所采用的原料组成见表1。
表1原料配比表
其中,实施例4~5制备方法如实施例1,实施例6~7制备方法如实施例2,实施例8~9制备方法如实施例3。
上述实施例1-3得到韧性塑料混合物的性能见表2。
表2性能测试结果
应用本发明中提及的方法,可在几乎不损失玻璃化转变温度的的前提下,提升脆性塑料的缺口冲击强度,达到塑料增韧的效果。
Claims (9)
1.一种橡胶增韧塑料,其特征在于,该增韧塑料包括组分A,组分B,组分C和组分D,其中:所述的组分A选自未硫化的橡胶中的一种或几种;所述的组分B为热塑性树脂,其链缠结密度Ve≤0.15,极性特征比C∞≥7.5;所述的组分C选自苯乙烯类、烯烃类、酰胺类、酯类或有机硅类的热塑性弹性体中的一种或几种;所述的组分D为混合添加剂,选自硫磺粉末、有机过氧化物、金属氧化物、多胺类化合物或酯类中的一种或几种;以重量百分数计,组分A占组成物总质量的5%~65%;组分B占组成物总质量的5%~90%;组分C占组成物总质量的0~45%;组分D占组成物总质量的1%~45%。
2.根据权利要求1所述的橡胶增韧塑料,其特征在于,所述的组分A占组成物总质量的5%~30%;组分B占组成物总质量的65%~90%;组分C占组成物总质量的0~25%;组分D占组成物总质量的1%~15%。
3.根据权利要求1所述的橡胶增韧塑料,其特征在于,所述的组分A选自以下未硫化橡胶中的一种或几种:未硫化天然橡胶、未硫化丁苯橡胶、未硫化丁腈橡胶、未硫化异戊橡胶、未硫化氯丁橡胶、未硫化乙丙橡胶、未硫化丙烯酸橡胶、未硫化硅橡胶或未硫化丁基橡胶。
4.根据权利要求1或2所述的橡胶增韧塑料,其特征在于,所述的组分A常温下为固体。
5.根据权利要求1所述的橡胶增韧塑料,其特征在于,所述的组分B选自以下热塑性树脂中的一种或几种:聚乙烯、聚丙烯、聚苯乙烯、聚丙烯腈-丁二烯-苯乙烯树脂、聚甲基丙烯酸甲酯或聚氯乙烯。
6.根据权利要求1所述的橡胶增韧塑料,其特征在于,所述的组分C选自以下热塑性弹性体中的一种或几种:苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-苯乙烯嵌段共聚物、热塑性聚氨酯弹性体橡胶、聚烯烃热塑性弹性体、聚酰胺热塑性弹性体或有机硅类热塑性弹性体。
7.根据权利要求1所述的橡胶增韧塑料,其特征在于,所述的组分D中:硫磺粉末占组分D总质量的0%-95%;有机过氧化物选自以下一种或几种物质:过氧化二苯甲酰、过氧化二异丙苯、过氧化二叔丁基、过或苯甲酸叔丁酯,有机过氧化物占组分D总质量的0%-95%;金属氧化物选自以下一种或几种物质:氧化锌、氧化镁、氧化铅或四氧化三铅,金属氧化物占组分D总质量的0%-95%;多胺类化合物选自以下一种或几种物质:三亚亚乙基四胺、四亚乙基五胺或1,6-己二胺,多胺类物质占组分D总质量的0%-95%;酯类选自以下一种或几种物质:三丙烯酸三羟基丙烷酯、三甲基丙烯酸三羟基丙烷酯、二丙烯酸乙二醇酯、二甲基丙烯酸乙二醇酯、N,N’-对苯基双马来酰亚胺、二丙烯酸锌、二甲基丙烯酸锌,氰尿酸三烯丙酯或异氰尿酸三烯丙酯,酯类占组分D总质量的0%-95%。
8.一种如权利要求1所述的橡胶增韧塑料的制备方法,其特征在于,包括如下步骤:
(1)将组分A置于粉碎机中,加工至碎片,速度:500~800rpm,温度:-7℃盘管水循环冷却物料;
(2)将组分A碎片、组分C在混料机中混合,速度:100~200rpm,温度:室温;
(3)将组分B、组分D在混料机中混合,速度:200~300rpm,温度:室温;
(4)将混合均匀的组分A碎片、组分C加入双螺杆/单螺杆挤出机的料斗1中;
(5)将混合均匀的组分B、组分D加入双螺杆/单螺杆挤出机的料斗2中;
(6)根据组分B的特性,为螺杆各区设定合适的温度;
(7)根据组分A、组分C的特性,选择合适的螺杆加入段;
(8)挤出机开机,带各区温度到达预设值后,开启主螺杆、料斗1中物料的加料螺杆、料斗2中物料的加料螺杆;
(9)根据实际情况,控制物料喂入量,调节螺杆温度和螺杆转速,挤出切断即获得橡胶增韧塑料。
9.根据权利要求8所述的橡胶增韧塑料的制备方法,其特征在于,步骤(9)中,获得的产物橡胶增韧塑料在常温下为固体颗粒。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811247076.9A CN111100342A (zh) | 2018-10-25 | 2018-10-25 | 一种橡胶增韧塑料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811247076.9A CN111100342A (zh) | 2018-10-25 | 2018-10-25 | 一种橡胶增韧塑料及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111100342A true CN111100342A (zh) | 2020-05-05 |
Family
ID=70417526
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811247076.9A Pending CN111100342A (zh) | 2018-10-25 | 2018-10-25 | 一种橡胶增韧塑料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111100342A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114773849A (zh) * | 2022-03-09 | 2022-07-22 | 金发科技股份有限公司 | 一种可反复加工的耐高温阻尼热塑性硅橡胶材料及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1353135A (zh) * | 2000-11-03 | 2002-06-12 | 中国石油化工股份有限公司 | 一种增韧塑料及其制备方法 |
CN1508170A (zh) * | 2002-12-18 | 2004-06-30 | 北京化工大学 | 热塑性硫化胶的制备方法 |
US20050148727A1 (en) * | 2004-01-06 | 2005-07-07 | Manoj Ajbani | Thermoplastic elastomer composition |
-
2018
- 2018-10-25 CN CN201811247076.9A patent/CN111100342A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1353135A (zh) * | 2000-11-03 | 2002-06-12 | 中国石油化工股份有限公司 | 一种增韧塑料及其制备方法 |
CN1508170A (zh) * | 2002-12-18 | 2004-06-30 | 北京化工大学 | 热塑性硫化胶的制备方法 |
US20050148727A1 (en) * | 2004-01-06 | 2005-07-07 | Manoj Ajbani | Thermoplastic elastomer composition |
Non-Patent Citations (1)
Title |
---|
高鹏等: "过氧化物动态硫化EPDM/PP热塑性弹性体的等温结晶行为", 《高分子材料科学与工程》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114773849A (zh) * | 2022-03-09 | 2022-07-22 | 金发科技股份有限公司 | 一种可反复加工的耐高温阻尼热塑性硅橡胶材料及其制备方法和应用 |
CN114773849B (zh) * | 2022-03-09 | 2023-08-29 | 金发科技股份有限公司 | 一种可反复加工的耐高温阻尼热塑性硅橡胶材料及其制备方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106633360B (zh) | 一种耐低温冲击的聚丙烯发泡珠粒成型体及其制备方法 | |
JP2004512426A (ja) | 靱性の強化されたプラスチックおよびその製造方法 | |
CN111662521B (zh) | 利用废弃nbr/pvc类橡塑保温材料增韧改性聚氯乙烯的方法 | |
CN113583396A (zh) | 一种耐循环注塑的pbt组合物及其制备方法和制品 | |
CN111100342A (zh) | 一种橡胶增韧塑料及其制备方法 | |
CN106751095B (zh) | 含有l-poss交联剂的同质异构改性回收ps及其制备方法 | |
CN107974024B (zh) | 热塑性弹性体组合物及其制备方法和应用 | |
CN108285629B (zh) | 一种pc/abs/pa6组合物及其制备方法 | |
CN113817270A (zh) | 一种聚丙烯复合材料及其制备方法 | |
CN104448679B (zh) | 一种辐射交联无卤阻燃abs/pc复合材料及其制备方法 | |
CN109294201A (zh) | 一种废旧聚碳酸酯的回收工艺 | |
CN113150464A (zh) | 一种可降解型pvc粒料 | |
CN102532706A (zh) | 一种高强度高韧性聚丙烯复合材料的制备方法 | |
CN112552633A (zh) | 一种tpe塑料及其制备方法 | |
CN103087438B (zh) | 一种抗冲聚氯乙烯组合物及其制备方法 | |
JP6740682B2 (ja) | ポリマ顆粒物の製造方法 | |
CN111704767A (zh) | 一种高刚高韧的聚丙烯复合材料及其制备方法 | |
CN113354910A (zh) | 一种高韧性pvc复合材料及其制备方法 | |
CN106589745A (zh) | 冰箱专用hips板材增韧色母料、其制备方法及其应用 | |
CN110791007A (zh) | 一种超柔软耐寒高阻燃热塑性低烟无卤电缆料及制备方法 | |
CN107868169B (zh) | 一种本体阻燃塑木复合材料及其制备方法 | |
CN106832739B (zh) | 一种含稠环结构交联剂的同质异构交联改性回收abs制备方法 | |
CN114149633B (zh) | 一种再生塑料管材及其制备方法 | |
WO2008048132A1 (fr) | Procédé pour fabriquer une matière hautement dispersée, prioritairement pour la fabrication de revêtements hydro-isolants, antibruits et de sports | |
CN110551358B (zh) | 一种高超声波焊接强度聚丙烯材料及其制备方法 |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200505 |