CN102030866A - Polybasic grafted ethylene propylene diene monomer rubber and preparation method thereof - Google Patents
Polybasic grafted ethylene propylene diene monomer rubber and preparation method thereof Download PDFInfo
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- CN102030866A CN102030866A CN2010106113503A CN201010611350A CN102030866A CN 102030866 A CN102030866 A CN 102030866A CN 2010106113503 A CN2010106113503 A CN 2010106113503A CN 201010611350 A CN201010611350 A CN 201010611350A CN 102030866 A CN102030866 A CN 102030866A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920002943 EPDM rubber Polymers 0.000 title abstract description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 25
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 150000002978 peroxides Chemical class 0.000 claims abstract description 17
- 238000005469 granulation Methods 0.000 claims abstract description 10
- 230000003179 granulation Effects 0.000 claims abstract description 10
- 229920001897 terpolymer Polymers 0.000 claims description 111
- 229920001971 elastomer Polymers 0.000 claims description 109
- 239000005060 rubber Substances 0.000 claims description 109
- 239000000203 mixture Substances 0.000 claims description 41
- 238000005303 weighing Methods 0.000 claims description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 239000004615 ingredient Substances 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 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 8
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- -1 pentaerythritol ester Chemical class 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- WSEFPKKOUNRCAJ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;octadecanoic acid Chemical compound OCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O WSEFPKKOUNRCAJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 23
- 238000001125 extrusion Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 6
- 230000035939 shock Effects 0.000 abstract description 6
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
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- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 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 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 238000003828 vacuum filtration Methods 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses polybasic grafted ethylene propylene diene monomer rubber and a preparation method thereof. The polybasic grafted ethylene propylene diene monomer rubber comprises the following formula components in part by weight: 86 to 97 parts of ethylene propylene diene monomer rubber, 0.05 to 0.5 part of peroxide initiator, 0.3 to 5 parts of methyl methacrylate, 0.3 to 5 parts of glycidyl methacrylate and 0.3 to 7 parts of assistant reactant. In the polybasic grafted ethylene propylene diene monomer rubber, the ethylene propylene diene monomer rubber is used as a matrix; the polybasic grafted ethylene propylene diene monomer rubber has high mechanical performance such as compatibility, shock resistance, tensile strength, breaking elongation and the like through interaction of all components in a proper content range in an extrusion process. In the preparation method of the polybasic grafted ethylene propylene diene monomer rubber, a process in which mixing reaction, extrusion and granulation are finished at on one time is adopted; and the preparation method is simple, convenient to operate and low in cost, has high benefit and is suitable for industrial production.
Description
Technical field
The invention belongs to chemical technology field, relate in particular to a kind of multi-grafted terpolymer EP rubber and preparation method thereof.
Background technology
Terpolymer EP rubber (EPDM) base polymer is the terpolymer of ethene, propylene and non-conjugated diene hydrocarbon, main polymer chain is fully saturated, this characteristic makes terpolymer EP rubber can resist heat, light, oxygen, especially ozone, polar solvent and chemicals had resistance, water-intake rate is low, has the good insulation performance characteristic, is widely used in non-polar plastic modifications such as polypropylene.But EPDM is a non-polar material, and is poor with polycarbonate (PC), nylon (PA), polyester (PET, PBT) isopolarity plastics and various mineral filler consistency.For the use field of further widening EPDM, satisfy in polarity plastics or filler user demand, therefore, need improve terpolymer EP rubber (EPDM) base polymer.
Summary of the invention
The purpose of the embodiment of the invention is to overcome the above-mentioned deficiency of prior art, and a kind of multi-grafted terpolymer EP rubber with good consistency, shock resistance is provided.
And, the preparation method of above-mentioned multi-grafted terpolymer EP rubber.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of multi-grafted terpolymer EP rubber comprises the recipe ingredient of following parts by weight:
86～97 parts of terpolymer EP rubbers
0.05～0.5 part of peroxide initiator
0.3～5 part of methyl methacrylate
0.3～5 part of glycidyl methacrylate
Help 0.3～7 part of reagent.
And a kind of multi-grafted terpolymer EP rubber preparation method comprises the steps:
Prescription according to above-mentioned multi-grafted terpolymer EP rubber takes by weighing each component;
Each component that takes by weighing is mixed, form mixture;
Described mixture is extruded, and granulation obtains described multi-grafted terpolymer EP rubber.
Above-mentioned multi-grafted terpolymer EP rubber is matrix with the terpolymer EP rubber, each component by the proper content scope interacts in extrusion, makes multi-grafted terpolymer EP rubber have mechanical propertys such as good consistency, shock resistance, tensile strength, elongation at break.Wherein, under the high speed shear effect in extrusion, peroxide initiator and help reagent to make between methyl methacrylate, glycidyl methacrylate reactant and the terpolymer EP rubber grafting to take place, form the graft copolymer of multi-grafted terpolymer EP rubber.This multi-grafted terpolymer EP rubber preparation method adopts the disposable technology of finishing of mixing reaction extruding pelletization, and its preparation method technology is simple, and is easy to operate, high efficiency, and cost is low, is suitable for suitability for industrialized production.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is the multi-grafted terpolymer EP rubber preparation method's of the present invention process flow diagram.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The embodiment of the invention provides a kind of multi-grafted terpolymer EP rubber with good consistency, shock resistance.This multi-grafted terpolymer EP rubber comprises the recipe ingredient of following parts by weight:
86～97 parts of terpolymer EP rubbers (EPDM)
0.05～0.5 part of peroxide initiator
0.3～5 part of methyl methacrylate (MMA)
0.3～5 part of glycidyl methacrylate (GMA)
Help 0.3～7 part of reagent.
Particularly, the parts by weight content of above-mentioned terpolymer EP rubber is preferably 90～97 parts.Terpolymer EP rubber, methyl methacrylate and glycidyl methacrylate can be commercial, can be EPDM3722P, the EPDM3745P that LG-DOW company produces as terpolymer EP rubber according to the method preparation of routine also; MMA can be the MMA of purity 〉=99.5% of MIT's production; GMA can be the GMA of purity 〉=99.5% of MIT's production.
The parts by weight content of above-mentioned peroxide initiator is preferably 0.05～0.2 part, and it is preferably in dicumyl peroxide (DCP), two (tert-butyl hydroperoxide sec.-propyl) benzene (BIBP) one or both.Wherein, DCP, BIBP can be selected from the product that Akzo Nobel N.V. produces.
The above-mentioned parts by weight content of reagent that helps is preferably 0.3～2 part, and it is preferably vinylbenzene, p-methylstyrene, at least a in the methoxy styrene.This help the purity of reagent be preferably 〉=99.5%.
This peroxide initiator with help under the high speed shear effect of reagent in extrusion, peroxide initiator and help reagent to make between methyl methacrylate, glycidyl methacrylate reactant and the terpolymer EP rubber grafting to take place, form the graft copolymer of constitutionally stable multi-grafted terpolymer EP rubber.The peroxide initiator of preferred content and kind and help reagent more can make methyl methacrylate and glycidyl methacrylate and terpolymer EP rubber generation graft reaction effectively, the structure of the multi-grafted terpolymer EP rubber of formation is more stable.
Further, above-mentioned multi-grafted terpolymer EP rubber also comprises the component of following parts by weight:
0～0.6 part in oxidation inhibitor
0～0.6 part of lubricant.
Wherein, oxidation inhibitor parts by weight content is more preferably 0～0.2 part; More preferably 0～0.3 part of the parts by weight content of lubricant.The existence of this antioxidant component in extrusion, with having an effect of components such as terpolymer EP rubber, methyl methacrylate and glycidyl methacrylate, thereby suppresses and has delayed the aging of multi-grafted terpolymer EP rubber.The existence of lubricant composition in extrusion, reduces the viscosity of each component effectively, has strengthened the dispersiveness of each component.
Particularly, above-mentioned oxidation inhibitor is preferably four, and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 3, at least a in 5-di-tert-butyl-4-hydroxy phenylpropionic acid octadecyl ester (Irganox 1010), three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, this oxidation inhibitor can be selected from the product of Switzerland Ciba company, as Irganox1010, Irganox 1076, Irganox 168 etc.Above-mentioned lubricant is preferably one or both in tetramethylolmethane stearate (PETS), the ethylene bis stearamide (EBS), and this lubricant can be selected from the product of three mouthfuls of companies of U.S. Long Sha company or Korea S.
By above-mentioned narration as can be known, in the preferred embodiment of the multi-grafted formula of ethylene propylene terpolymer with of the embodiment of the invention, this multi-grafted terpolymer EP rubber preferably includes the recipe ingredient of following parts by weight:
90～97 parts of terpolymer EP rubbers
0.05～0.2 part of peroxide initiator
0.3～5 part of methyl methacrylate
0.3～5 part of glycidyl methacrylate
Help 0.3～2 part of reagent.
In another preferred embodiment, this multi-grafted terpolymer EP rubber comprises the recipe ingredient of following parts by weight:
86～97 parts of terpolymer EP rubbers
0.05～0.5 part of peroxide initiator
0.3～5 part of methyl methacrylate
0.3～5 part of glycidyl methacrylate
Help 0.3～7 part of reagent
0～0.6 part in oxidation inhibitor
0～0.6 part of lubricant.
In the embodiment of the 3rd choosing, this multi-grafted terpolymer EP rubber comprises the recipe ingredient of following parts by weight:
90～97 parts of terpolymer EP rubbers
0.05～0.2 part of peroxide initiator
0.3～5 part of methyl methacrylate
0.3～5 part of glycidyl methacrylate
Help 0.3～2 part of reagent
0～0.6 part in oxidation inhibitor
0～0.6 part of lubricant.
In the 4th preferred embodiment, this multi-grafted terpolymer EP rubber comprises the recipe ingredient of following parts by weight:
90～97 parts of terpolymer EP rubbers
0.05～0.2 part of peroxide initiator
0.3～5 part of methyl methacrylate
0.3～5 part of glycidyl methacrylate
Help 0.3～2 part of reagent
0～0.2 part in oxidation inhibitor
0～0.3 part of lubricant.
Therefore, under the high speed shear effect in extrusion, above-mentioned peroxide initiator and help reagent to make between methyl methacrylate, glycidyl methacrylate reactant and the terpolymer EP rubber grafting to take place, form the graft copolymer of multi-grafted terpolymer EP rubber.The existence of antioxidant component in extrusion, with having an effect of components such as terpolymer EP rubber, methyl methacrylate and glycidyl methacrylate, thereby suppresses and has delayed the aging of multi-grafted terpolymer EP rubber.The existence of lubricant composition in extrusion, reduces the viscosity of each component effectively, has strengthened the dispersiveness of each component.Above-mentioned multi-grafted terpolymer EP rubber is matrix with the terpolymer EP rubber, each component by the proper content scope interacts in extrusion, make multi-grafted terpolymer EP rubber have mechanical property, antioxidant properties such as good shock resistance, tensile strength, elongation at break, and good consistency, as with the consistency of resins such as PC, PA, PPO.
The present invention also provides above-mentioned multi-grafted terpolymer EP rubber preparation method, and its technical process as shown in Figure 1.This method comprises the steps:
S1: the prescription according to above-mentioned multi-grafted terpolymer EP rubber takes by weighing each component;
S2: each component that will take by weighing is mixed, and forms mixture;
S3: described mixture is extruded, and granulation obtains described multi-grafted terpolymer EP rubber.
Particularly, in the above-mentioned multi-grafted terpolymer EP rubber preparation method S1 step, the prescription of aforesaid prescription of the prescription of this multi-grafted terpolymer EP rubber or preferred embodiment.In order to save length, do not repeat them here.
In the above-mentioned multi-grafted terpolymer EP rubber preparation method S2 step, each component should mix as much as possible.Preferably each component is put into high mixer and mix 10～20min.
In the above-mentioned multi-grafted terpolymer EP rubber preparation method S3 step, each component preferred employing twin screw extruder of extruding of formed mixture after mixing is extruded in the S2 step.This mixture temperature of each section in twin screw extruder is preferably respectively: 140～165 ℃ in a district, 150～180 ℃ in two districts, 150～180 ℃ in three districts, 150～180 ℃ in four districts, 150～180 ℃ in five districts; This mixture time of delivery in described twin screw extruder is preferably 2～8 minutes, and pressure is preferably 12～20MPa.
In above-mentioned S1～S3 step, each component makes that each component is intermolecular and has an effect between mutually heating up rapidly under the high speed shear effect, thereby form the multi-grafted terpolymer EP rubber of the embodiment of the invention, and give mechanical property and antioxidant properties such as the good consistency of this multi-grafted terpolymer EP rubber, shock resistance, tensile strength, elongation at break.This multi-grafted terpolymer EP rubber preparation method adopts the disposable technology of finishing of mixing reaction extruding pelletization, and its preparation method technology is simple, and is easy to operate, high efficiency, and cost is low, is suitable for suitability for industrialized production.
Now prescription and the preparation method with concrete multi-grafted terpolymer EP rubber is example, and the present invention is further elaborated.
Embodiment 1
The recipe ingredient of multi-grafted terpolymer EP rubber weight percent is as follows:
0.08 part of 96.72 parts of EPDM 3722P, DCP, 0.5 part of 0.7 part of MMA, GMA, 1.5 parts, 10100.1 parts, 1680.1 parts of vinylbenzene, 0.3 part of EBS.
Multi-grafted terpolymer EP rubber preparation method:
S11: the prescription according to above-mentioned multi-grafted terpolymer EP rubber takes by weighing each component;
S12: mixing tank mixing 15min is put in each component mixing that will take by weighing, and makes each component mix, and forms mixture;
S13: mixture is joined in the hopper of twin screw extruder, and extrude, granulation obtains multi-grafted terpolymer EP rubber; This mixture temperature of each section in twin screw extruder is respectively: district's temperature is 145 ℃, and two district's temperature are 150 ℃, and three district's temperature are 155 ℃, four district's temperature are 160 ℃, 165 ℃ in five districts, compound time of delivery in screw rod is 5 minutes, pressure is 14MPa.
Embodiment 2
The recipe ingredient of multi-grafted terpolymer EP rubber weight percent is as follows:
0.12 part of 94.58 parts of EPDM 3745P, DCP, 1.0 parts of 1.0 parts of MMA, GMA, 2.4 parts, 10100.2 parts, 1680.2 parts of vinylbenzene, 0.5 part of EBS.
Multi-grafted terpolymer EP rubber preparation method:
S11: the prescription according to above-mentioned multi-grafted terpolymer EP rubber takes by weighing each component;
S12: mixing tank mixing 15min is put in each component mixing that will take by weighing, and makes each component mix, and forms mixture;
S13: mixture is joined in the hopper of twin screw extruder, and extrude, granulation obtains multi-grafted terpolymer EP rubber; This mixture temperature of each section in twin screw extruder is respectively: district's temperature is 145 ℃, and two district's temperature are 155 ℃, and three district's temperature are 165 ℃, four district's temperature are 170 ℃, 175 ℃ in five districts, compound time of delivery in screw rod is 4 minutes, pressure is 15MPa.
Embodiment 3
The recipe ingredient of multi-grafted terpolymer EP rubber weight percent is as follows:
0.15 part of 93.15 parts of EPDM 3722P, DCP, 1.3 parts of 1.5 parts of MMA, GMA, 3.0 parts, 10100.2 parts, 1680.2 parts of vinylbenzene, 0.5 part of EBS.
Multi-grafted terpolymer EP rubber preparation method:
S11: the prescription according to above-mentioned multi-grafted terpolymer EP rubber takes by weighing each component;
S12: mixing tank mixing 20min is put in each component mixing that will take by weighing, and makes each component mix, and forms mixture;
S13: mixture is joined in the hopper of twin screw extruder, and extrude, granulation obtains multi-grafted terpolymer EP rubber; This mixture temperature of each section in twin screw extruder is respectively: district's temperature is 145 ℃, and two district's temperature are 155 ℃, and three district's temperature are 165 ℃, four district's temperature are 175 ℃, 180 ℃ in five districts, compound time of delivery in screw rod is 3 minutes, pressure is 12MPa.
Embodiment 4
The recipe ingredient of multi-grafted terpolymer EP rubber weight percent is as follows:
0.2 part of 93.25 parts of EPDM 3722P, BIBP, 1.7 parts of 2.0 parts of MMA, GMA, 3.5 parts, 10760.4 parts, 1680.2 parts of vinylbenzene, 0.6 part of EBS.
Multi-grafted terpolymer EP rubber preparation method:
S11: the prescription according to above-mentioned multi-grafted terpolymer EP rubber takes by weighing each component;
S12: mixing tank mixing 10min is put in each component mixing that will take by weighing, and makes each component mix, and forms mixture;
S13: mixture is joined in the hopper of twin screw extruder, and extrude, granulation obtains multi-grafted terpolymer EP rubber; This mixture temperature of each section in twin screw extruder is respectively: district's temperature is 145 ℃, and two district's temperature are 155 ℃, and three district's temperature are 165 ℃, four district's temperature are 175 ℃, 180 ℃ in five districts, compound time of delivery in screw rod is 3 minutes, pressure is 12MPa.
Embodiment 5
The recipe ingredient of multi-grafted terpolymer EP rubber weight percent is as follows:
0.35 part of 88.85 parts of EPDM 3722P, DCP, 0.3 part of 5.0 parts of MMA, GMA, to 5.5 parts of methoxy styrenes.
Multi-grafted terpolymer EP rubber preparation method:
S11: the prescription according to above-mentioned multi-grafted terpolymer EP rubber takes by weighing each component;
S12: mixing tank mixing 18min is put in each component mixing that will take by weighing, and makes each component mix, and forms mixture;
S13: mixture is joined in the hopper of twin screw extruder, and extrude, granulation obtains multi-grafted terpolymer EP rubber; This mixture temperature of each section in twin screw extruder is respectively: district's temperature is 145 ℃, and two district's temperature are 155 ℃, and three district's temperature are 165 ℃, four district's temperature are 175 ℃, 180 ℃ in five districts, compound time of delivery in screw rod is 6 minutes, pressure is 17MPa.
Embodiment 6
The recipe ingredient of multi-grafted terpolymer EP rubber weight percent is as follows:
0.4 part of 86.7 parts of EPDM 3745P, BIBP, 5.0 parts of 0.3 part of MMA, GMA, 7.0 parts, 10100.2 parts of p-methylstyrenes, 0.3 part of EBS.
Multi-grafted terpolymer EP rubber preparation method:
S11: the prescription according to above-mentioned multi-grafted terpolymer EP rubber takes by weighing each component;
S12: mixing tank mixing 20min is put in each component mixing that will take by weighing, and makes each component mix, and forms mixture;
S13: mixture is joined in the hopper of twin screw extruder, and extrude, granulation obtains multi-grafted terpolymer EP rubber; This mixture temperature of each section in twin screw extruder is respectively: district's temperature is 145 ℃, and two district's temperature are 155 ℃, and three district's temperature are 165 ℃, four district's temperature are 175 ℃, 180 ℃ in five districts, compound time of delivery in screw rod is 6 minutes, pressure is 17MPa.
The performance test experiment:
The multi-grafted terpolymer EP rubber that makes in the foregoing description 1 to embodiment 6 is carried out performance test:
1. the mensuration of percentage of grafting:
With the multi-grafted terpolymer EP rubber that obtains in the foregoing description 1～6 in 40～60 ℃ convection oven dry 4～6 hours respectively.Get the multi-grafted terpolymer EP rubber grafts in the 5g left and right sides, use the 150ml xylene soluble, the cooling back adds acetone and shakes up, be settled out grafts, vacuum filtration, use washing with acetone again 3 times, then spend oven dryings 4 hours, accurately take by weighing the 1g graft product then 70, put into the xylene solution of 100ml, reflux is treated grafts all after the dissolving, cooling 20min, KOH-ethanolic soln (self-control) 10ml that adds the about 0.05mol/L of concentration, reflux 10min uses hydrochloric acid-aqueous isopropanol (self-control) titration of concentration 0.05mol/L while hot, makes indicator with phenolphthalein.Be calculated as follows percentage of grafting:
Percentage of grafting=[(N
1V
1-N
2V
2) * 98 ÷ (100 * 2) * 100%
In the formula: N
1: the concentration of KOH-ethanolic soln, mol/L
V
1: the volume of KOH-ethanolic soln, ml
N
2: the concentration of HCl-aqueous isopropanol, mol/L
V
2: the volume of HCl-isopropyl acetone solution, ml
The prescription of the multi-grafted terpolymer EP rubber that makes among the embodiment 1 to embodiment 6, with and the percentage of grafting measurement result to state table 1 as follows described.
2. toughness reinforcing performance test
The adding parts by weight are 15 parts obtained multi-grafted terpolymer EP rubber in 85 parts of PA6627AE1 resins, add an amount of oxidation inhibitor, lubricant etc., thorough mixing stirs, mixture through twin screw extruder extrude, pelletizing, drying, extrusion temperature is 220～260 ℃, with the injection moulding sample preparation on the 80T injection moulding machine of exsiccant particle, keep the mould temperature in the sample making course between 40～80 ℃ again, carry out toughness reinforcing performance test by following standard at last:
Tensile strength: test batten size (mm) by ASTM D-638 standard: 165 (length) * 19 (end width) * 3.05 (thickness), draw speed is 50mm/min.
Flexural strength and modulus in flexure: test specimen size (mm) by standard A STM D-790: 127 * 12.67 * 3.67, span is 48, rate of bending is 20mm/min.
Simply supported beam notched Izod impact strength: test specimen size (mm): 63.5 * 12.45 * 3.1 by ASTM D-256 standard; The breach residual thickness is 1.9mm.
The prescription and the percentage of grafting thereof of the multi-grafted terpolymer EP rubber that table 1 embodiment 1 to embodiment 6 makes
The toughness reinforcing performance test-results of the multi-grafted terpolymer EP rubber that table 2 embodiment 1 to embodiment 6 makes
As shown in Table 1, along with peroxide initiator and the addition that helps reagent increase, the percentage of grafting of multi-grafted terpolymer EP rubber also increases accordingly.Associative list 1 and table 2 as can be seen, along with the raising of the percentage of grafting of multi-grafted terpolymer EP rubber, the multi-grafted terpolymer EP rubber of gained progressively improves the toughness of the composition of PA resin.This is because the introducing of methyl methacrylate and glycidyl methacrylate functional group, make multi-grafted terpolymer EP rubber and PA resin have better consistency, and then effectively improved the toughening effect of multi-grafted terpolymer EP rubber the PA resin.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. multi-grafted terpolymer EP rubber comprises the recipe ingredient of following parts by weight:
86～97 parts of terpolymer EP rubbers
0.05～0.5 part of peroxide initiator
0.3～5 part of methyl methacrylate
0.3～5 part of glycidyl methacrylate
Help 0.3～7 part of reagent.
2. multi-grafted terpolymer EP rubber according to claim 1 is characterized in that: described multi-grafted terpolymer EP rubber comprises the recipe ingredient of following parts by weight:
90～97 parts of terpolymer EP rubbers
0.05～0.2 part of peroxide initiator
0.3～5 part of methyl methacrylate
0.3～5 part of glycidyl methacrylate
Help 0.3～2 part of reagent.
3. multi-grafted terpolymer EP rubber according to claim 1 and 2 is characterized in that: described peroxide initiator is one or both in dicumyl peroxide, two (tert-butyl hydroperoxide sec.-propyl) benzene.
4. multi-grafted terpolymer EP rubber according to claim 1 and 2 is characterized in that: described to help reagent be vinylbenzene, p-methylstyrene, at least a in the methoxy styrene.
5. multi-grafted terpolymer EP rubber according to claim 1 and 2 is characterized in that: the component that also comprises following parts by weight:
0～0.6 part in oxidation inhibitor
0～0.6 part of lubricant.
6. multi-grafted terpolymer EP rubber according to claim 5 is characterized in that: the parts by weight content of described oxidation inhibitor is 0～0.2 part; The parts by weight content of described lubricant is 0～0.3 part.
7. multi-grafted terpolymer EP rubber according to claim 5, it is characterized in that: described oxidation inhibitor is that four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 3, at least a in 5-di-tert-butyl-4-hydroxy phenylpropionic acid octadecyl ester, three (2.4-di-tert-butyl-phenyl) phosphorous acid ester.
8. multi-grafted terpolymer EP rubber according to claim 5 is characterized in that: described lubricant is one or both in tetramethylolmethane stearate, the ethylene bis stearamide.
9. a multi-grafted terpolymer EP rubber preparation method comprises the steps:
Prescription according to the arbitrary described multi-grafted terpolymer EP rubber of claim 1～8 takes by weighing each component;
Each component that takes by weighing is mixed, form mixture;
Described mixture is extruded, and granulation obtains described multi-grafted terpolymer EP rubber.
10. multi-grafted terpolymer EP rubber preparation method according to claim 9, it is characterized in that: described extruding is to adopt twin screw extruder to extrude, the temperature of described mixture each section in described twin screw extruder is respectively: 140～165 ℃ in a district, 150～180 ℃ in two districts, 150～180 ℃ in three districts, 150～180 ℃ in four districts, 150～180 ℃ in five districts; Described mixture time of delivery in described twin screw extruder is 2～8 minutes, and pressure is 12～20MPa.
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| CN102504418A (en) * | 2011-10-26 | 2012-06-20 | 江苏恒峰线缆有限公司 | Reactive-extrusion addition ethylene-propylene diene monomer rubber sulfonate and preparation method thereof |
| CN103773305A (en) * | 2013-12-23 | 2014-05-07 | 南京工业大学 | Preparation method of modified EPDM (Ethylene-Propylene-Diene Monomer) adhesive |
| CN109111673A (en) * | 2018-08-28 | 2019-01-01 | 新亚电子有限公司 | A kind of low temperature resistant PVC composite cable material and preparation method thereof |
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| CN101068681A (en) * | 2003-10-21 | 2007-11-07 | Gdx北美公司 | Composite extrusion for trim seal strip and method for forming same |
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| CN1712441A (en) * | 2005-07-14 | 2005-12-28 | 上海交通大学 | Production of thermoplastic elastomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102391437A (en) * | 2011-10-09 | 2012-03-28 | 深圳市科聚新材料有限公司 | Multi-grafted acrylonitrile-butadiene-styrene (ABS) copolymer and preparation method thereof |
| CN102391437B (en) * | 2011-10-09 | 2013-04-24 | 深圳市科聚新材料有限公司 | Multi-grafted acrylonitrile-butadiene-styrene (ABS) copolymer and preparation method thereof |
| CN102504418A (en) * | 2011-10-26 | 2012-06-20 | 江苏恒峰线缆有限公司 | Reactive-extrusion addition ethylene-propylene diene monomer rubber sulfonate and preparation method thereof |
| CN102504418B (en) * | 2011-10-26 | 2013-12-25 | 江苏恒峰线缆有限公司 | Reactive-extrusion addition ethylene-propylene diene monomer rubber sulfonate and preparation method thereof |
| CN103773305A (en) * | 2013-12-23 | 2014-05-07 | 南京工业大学 | Preparation method of modified EPDM (Ethylene-Propylene-Diene Monomer) adhesive |
| CN103773305B (en) * | 2013-12-23 | 2015-12-30 | 南京工业大学 | A kind of preparation method of modified epdm binding agent |
| CN109111673A (en) * | 2018-08-28 | 2019-01-01 | 新亚电子有限公司 | A kind of low temperature resistant PVC composite cable material and preparation method thereof |
| CN111503133A (en) * | 2020-04-24 | 2020-08-07 | 江阴市明达胶辊有限公司 | Liquid silicon rubber roller and processing technology thereof |
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