CN116948106A - Toughening agent, preparation method and application thereof in PVC material - Google Patents
Toughening agent, preparation method and application thereof in PVC material Download PDFInfo
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- CN116948106A CN116948106A CN202310940472.4A CN202310940472A CN116948106A CN 116948106 A CN116948106 A CN 116948106A CN 202310940472 A CN202310940472 A CN 202310940472A CN 116948106 A CN116948106 A CN 116948106A
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- toughening agent
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- 239000012745 toughening agent Substances 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920001971 elastomer Polymers 0.000 claims abstract description 35
- 238000004132 cross linking Methods 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000000806 elastomer Substances 0.000 claims abstract description 29
- 230000008961 swelling Effects 0.000 claims abstract description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 8
- 229920003052 natural elastomer Polymers 0.000 claims description 8
- 229920001194 natural rubber Polymers 0.000 claims description 8
- 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
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000005060 rubber Substances 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 claims description 4
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 claims description 2
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- KUQWZSZYIQGTHT-UHFFFAOYSA-N hexa-1,5-diene-3,4-diol Chemical compound C=CC(O)C(O)C=C KUQWZSZYIQGTHT-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 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
- AJKLVSRUKOZBMY-UHFFFAOYSA-N 2-ethylhexoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COOC(=O)OCC(CC)CCCC AJKLVSRUKOZBMY-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- RECMXUUCYFGBEZ-UHFFFAOYSA-N cyclohexyl cyclohexyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC1CCCCC1 RECMXUUCYFGBEZ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 63
- 229920000915 polyvinyl chloride Polymers 0.000 description 62
- 239000004709 Chlorinated polyethylene Substances 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012760 heat stabilizer Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- -1 2-ethylhexyl Chemical group 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F253/00—Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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
The invention discloses a toughening agent, a preparation method and application thereof in PVC materials, and belongs to the technical field of high polymer materials. The preparation method of the toughening agent comprises the following steps: swelling the elastomer, the initiator and the crosslinking agent in a crosslinking monomer; carrying out copolymerization on the product after swelling in the step S1 to obtain the toughening agent; the crosslinking monomer is one or more of methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate or styrene; the weight ratio of the elastomer to the crosslinking monomer is (0.3-3): 1, a step of; the swelling time is 1-24h, and the swelling temperature is 25-80 ℃; the copolymerization reaction temperature is 60-120 ℃, the copolymerization time is 20-100min, and the shear rate is 10-100rpm. The toughening agent prepared by the invention has remarkable toughening effect on PVC hard pipes, and hardly has remarkable negative influence on the tensile strength of PVC.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a toughening agent, a preparation method and application thereof in PVC materials.
Background
Polyvinyl chloride (PVC) resin has good physical and mechanical properties and is widely used in the fields of construction, packaging and the like. But PVC has lower toughness. Chlorinated Polyethylene (CPE) is commonly used as a toughening agent for general PVC tubular products, but the Tg of the CPE is still higher, the toughness of the modified product is poorer at low temperature, and the CPE contains chlorine atoms, so that PVC decomposition can be effectively prevented by adding a heat stabilizer during processing, but the decomposition prevention of the CPE is limited, and the weather resistance of the CPE modified PVC is poorer.
The prior art discloses a toughening agent which comprises 70-80% of low-density polyethylene and 20-30% of nitrile rubber, and is suitable for PVC pipe materials and capable of improving the low-temperature shock resistance of PVC pipes. However, phase separation is easily occurred during blending due to poor compatibility of low density polyethylene and PVC. Moreover, since the strength of low density polyethylene is much lower than that of PVC, although this toughening agent can improve the toughness of PVC, it can result in a significant decrease in the strength of PVC.
Disclosure of Invention
The invention aims to overcome the defects that the strength of the PVC material is reduced and the compatibility of the toughening agent and PVC is poor due to the toughening agent for the existing PVC material, and provides a preparation method of the toughening agent.
It is another object of the present invention to provide a toughening agent.
It is a further object of the present invention to provide a rigid PVC material.
It is a further object of the present invention to provide the use of a rigid PVC material for the manufacture of electrical bushings.
The above object of the present invention is achieved by the following technical scheme:
a method of preparing a toughening agent comprising the steps of:
s1, swelling an elastomer, an initiator and a crosslinking agent in a crosslinking monomer;
s2, mixing and copolymerizing the product after swelling in the step S1 to obtain the toughening agent;
in the step S1, the crosslinking monomer is one or more of methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate or styrene;
the weight ratio of the elastomer to the crosslinking monomer is (0.3-3): 1, a step of;
in the step S1, the swelling time is 1-24h, and the swelling temperature is 25-80 ℃;
in the step S2, the copolymerization reaction temperature is 60-120 ℃, the copolymerization time is 20-100min, and the shear rate is 10-100rpm.
The toughening agent prepared by the invention has better compatibility with PVC materials, has good toughening effect on PVC hard pipes, and hardly has obvious negative influence on the tensile strength of PVC.
The invention swells the elastomer in the crosslinking monomer containing the initiator, adds the swelled product into a continuous internal mixer, carries out reactive copolymerization and blending by controlling the temperature, the blending time and the shearing rate, and can prepare the toughening agent by extruding and granulating the product through the continuous internal mixer after the reaction is completed.
In the reaction process, due to the action of the initiator and the cross-linking agent, part of cross-linking monomers are connected to the macromolecular chains of the elastomer to generate elastomer grafted cross-linking monomers, the cross-linking monomers are self-polymerized to form a polymer, and part of macromolecular chains of the elastomer can also generate cross-linking reaction. Due to the barrier effect and chain transfer reaction of the macromolecule of the elastomer, the crosslinking monomer can not generate the explosion polymerization phenomenon in the process, and a small amount of crosslinking agent is helpful to improve the molecular weight of the polymer and the micro-crosslinking reaction of the elastomer.
The process belongs to a bulk polymerization mode, does not require a diluent, almost generates no pollution, has good shearing uniformity of an internal mixer, is easy to control reaction, and has no danger. Proper cross-linking agent is added to crosslink the elastomer macromolecules to a certain extent, so that the viscosity of the product is ensured to be high enough to match the processing viscosity of PVC.
The initiator is used in an amount of 0.1% to 2.5%, preferably 0.5% to 1.5%, based on the total weight of elastomer and monomer, and the cross-linking agent is used in an amount of 0.05% to 1%, preferably 0.1% to 0.5%, based on the total weight of elastomer and monomer.
In practical application, in the step S2, the copolymerization reaction can occur in a continuous internal mixer, and the toughening agent can be prepared by directly extruding and granulating through the continuous internal mixer.
Preferably, in step S1, the weight ratio of elastomer to crosslinking monomer is (0.6-2): 1.
preferably, in step S1, the swelling time is 4-7 hours and the temperature is 25-50 ℃.
In step S2, the product after swelling of S1 may be first mixed and then copolymerized.
Wherein the initial mixing temperature can be 30-70deg.C, the time can be 2-10min, and the rotation speed can be 50rpm.
Wherein the initial mixing temperature can be 50-60deg.C, preferably 3-5min.
Preferably, in step S2, the copolymerization reaction temperature is 85-95 ℃, the copolymerization time is 30-60min, and the shear rate is 20-50rpm.
Preferably, the crosslinking monomer is one or more of methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate or styrene.
More preferably, the crosslinking monomer is methyl methacrylate.
Methyl methacrylate has better compatibility with PVC, so the methyl methacrylate can be used as a main crosslinking monomer of the toughening agent.
Preferably, the elastomer is one or more of natural rubber, styrene-butadiene rubber, nitrile rubber, ethylene propylene diene rubber, epoxidized natural rubber, ethyl acrylate rubber, butyl acrylate rubber, SBS thermoplastic elastomer or SEBS thermoplastic elastomer.
Preferably, the cross-linking agent is one or more of divinylbenzene, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol divinyl ether, divinyl glycol or triethylene glycol divinyl ether.
Preferably, the initiator is one or more of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3, 5-trimethylhexanoate, dicyclohexyl percarbonate or di (2-ethylhexyl) percarbonate.
More preferably, the cross-linking agent is one or more of diethylene glycol diacrylate or diethylene glycol divinyl ether.
More preferably, the elastomer is one or more of natural rubber or styrene-butadiene rubber.
This is because the double bond content on the molecular chain of the natural rubber or styrene-butadiene rubber is high, and the glass transition temperature is low, which is favorable for the subsequent copolymerization reaction and the viscosity improvement.
More preferably, the initiator is dibenzoyl peroxide, dilauroyl peroxide.
This is because the half-life of the initiator at this reaction temperature is relatively matched to the reaction time.
The invention also provides a toughening agent prepared by the preparation method of any one of the toughening agents.
Preferably, the toughening agent has a viscosity greater than 5.0X10 5 Pa.s。
More preferably, the toughening agent has a viscosity of 6.0X10 5 ～17.0×10 5 Pa.s
Preferably, the toughening agent has a solubility parameter difference Ra <5.
Preferably, the toughening agent has a dispersion component δD of 16.9-17.9MPa 1/2 。
Preferably, the toughening agentIs 6.5-10.5MPa 1/2 。
Preferably, the toughening agent has a hydrogen bond component δH of 4.6 to 5.7MPa 1/2 。
The invention also provides a hard PVC material, which comprises the toughening agent.
In practical application, the dosage of the toughening agent can be 5.5-20% of the total weight of the PVC material.
The invention also protects the application of the PVC material in the preparation of the electrical bushing.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a toughening agent, which comprises the following steps: s1, swelling an elastomer, an initiator and a crosslinking agent in a crosslinking monomer; s2, carrying out copolymerization on the product obtained after swelling in the step S1 to obtain the toughening agent.
The toughening agent has good toughening effect on PVC materials, and hardly has obvious negative influence on the tensile strength of PVC. The notch impact strength of the cantilever beam of the PVC material can reach 13.8-28.0 kJ/m 2 The tensile strength can reach 32.2-40 MPa.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Toughening agent: CPE, brand name 135A, manufacturer is Shandong Weifang subsatellite Chemie Co., ltd.
Styrene-butadiene rubber: SBR-1502, rubber chemical Co., ltd.
Natural rubber: 3L standard rubber, dongguan Xin synthetic rubber Co., ltd.
PVC material: and (5) combining plastic raw materials.
The remaining materials are commercially available and the same is used in the parallel examples and comparative examples.
Example 1
A method of preparing a toughening agent comprising the steps of:
s1, swelling elastomer styrene-butadiene rubber, initiator dibenzoyl peroxide and cross-linking agent diethylene glycol diacrylate in cross-linking monomer methyl methacrylate;
s2, transferring the swelling body into a continuous internal mixer for primary mixing, wherein the temperature is 50 ℃, the time is 5min, and the rotating speed is 50rpm;
copolymerizing the primarily mixed product to obtain the toughening agent;
in the step S1, the crosslinking monomer is methyl methacrylate;
the weight ratio of the elastomer to the crosslinking monomer is 1:1, a step of; the benzoyl peroxide is used in an amount of 1% of the total weight of the methyl methacrylate monomer, and the cross-linking agent is used in an amount of 0.1% of the total weight of the methyl methacrylate monomer;
in the step S1, the swelling time is 7 hours, and the swelling temperature is 25 ℃;
in step S2, the copolymerization reaction temperature was 95℃and the copolymerization time was 30min, and the shear rate was 50rpm.
Example 2
A process for preparing a toughening agent, different from example 1, is:
the weight ratio of elastomer to crosslinking monomer is 2:1.
the remainder is the same as in example 1 and will not be described again here.
Example 3
A process for preparing a toughening agent, different from example 1, is:
the weight ratio of elastomer to crosslinking monomer was 0.67:1.
the remainder is the same as in example 1 and will not be described again here.
Example 4
A method of preparing a toughening agent comprising the steps of:
s1, swelling elastomer natural rubber, an initiator dilauroyl peroxide and a cross-linking agent diethylene glycol divinyl ether in a cross-linking monomer methyl methacrylate and styrene;
s2, transferring the swelling body into a continuous internal mixer for primary mixing, wherein the temperature is 60 ℃, the time is 3min, and the rotating speed is 30rpm;
copolymerizing the primarily mixed product to obtain the toughening agent;
in the step S1, the crosslinking monomers are methyl methacrylate and styrene, and the weight ratio of the methyl methacrylate to the styrene is 3:1;
the weight ratio of the elastomer to the crosslinking monomer is 1:1, a step of; the benzoyl peroxide is 0.5 percent of the total weight of the methyl methacrylate and the styrene monomer, and the cross-linking agent is 0.5 percent of the total weight of the methyl methacrylate and the styrene monomer;
in the step S1, the swelling time is 4 hours, and the swelling temperature is 25 ℃;
in step S2, the copolymerization reaction temperature was 85℃and the copolymerization time was 60 minutes, and the shear rate was 30rpm.
Example 5
A process for preparing a toughening agent, different from example 4, is:
the weight ratio of elastomer to crosslinking monomer was 1.5:1.
the remainder is the same as in example 1 and will not be described again here.
Example 6
A process for preparing a toughening agent, different from example 4, is:
the weight ratio of elastomer to crosslinking monomer was 0.8:1, a step of; the weight ratio of methyl methacrylate to styrene was 4:1.
The remainder is the same as in example 1 and will not be described again here.
Examples 7 to 12
A PVC pipe comprises the following components: 100 parts of PVC, 3.5 parts of Ca/Zn heat stabilizer, 1.2 parts of stearic acid, 1 part of PE wax, 25 parts of calcium carbonate and 15 parts of toughening agent, wherein the toughening agent is the toughening agent of examples 1-6 respectively.
The preparation method of the PVC pipe comprises the following steps: after mixing the components in a high speed mixer for 10min and fully drying, melt blending is performed in a torque rheometer at a speed of 50rpm and at a temperature of 180 ℃ for 10min.
Examples 13 to 18
A PVC pipe comprises the following components: 100 parts of PVC, 3.5 parts of Ca/Zn heat stabilizer, 1.2 parts of stearic acid, 1 part of PE wax, 25 parts of calcium carbonate and 8 parts of toughening agent, wherein the toughening agent is the toughening agent of examples 1-6 respectively.
The preparation method of the PVC pipe is the same as that of examples 7 to 12, and is not repeated here.
Examples 19 to 24
A PVC pipe comprises the following components: 100 parts of PVC, 3.5 parts of Ca/Zn heat stabilizer, 1.2 parts of stearic acid, 1 part of PE wax, 25 parts of calcium carbonate and 32 parts of toughening agent, wherein the toughening agent is the toughening agent of examples 1-6 respectively.
The preparation method of the PVC pipe is the same as that of examples 7 to 12, and is not repeated here.
Comparative example 1
A PVC pipe comprises the following components: 100 parts of PVC, 3.5 parts of Ca/Zn heat stabilizer, 1.2 parts of stearic acid, 1 part of PE wax, 25 parts of calcium carbonate and 15 parts of toughening agent, wherein the toughening agent is toughening agent CPE.
The preparation method of the PVC pipe is the same as that of examples 7 to 12, and is not repeated here.
Comparative example 2
A PVC pipe comprises the following components: 100 parts of PVC, 3.5 parts of Ca/Zn heat stabilizer, 1.2 parts of stearic acid, 1 part of PE wax, 25 parts of calcium carbonate and 0 part of toughening agent.
The preparation method of the PVC pipe is the same as that of examples 7 to 12, and is not repeated here.
Result detection
The tougheners of examples 1-6 and CPE toughener, labeled as subsatellite 135A, were each tested by the following performance test methods:
viscosity of the toughening agent: at 180 ℃, a sample to be measured is manufactured into a circular sheet with the radius of 12.5mm and the thickness of 1mm by using a flat vulcanizing machine, a dynamic frequency scanning test is carried out on the circular sheet by using a rotary rheometer, the scanning temperature is set to 180 ℃, and the frequency=0.1 s -1 The strain was 2.5%.
Hansen solubility parameter of tougheners HSP: soaking toughening agent in dichloromethane, acetone, tetrahydrofuran, and methyl acetate respectivelyBenzene, xylene, cyclohexane, cyclohexanone, ethyl acetate, dimethylformamide, methanol, dimethyl sulfoxide, carbon tetrachloride, styrene, methyl acrylate, N-heptane, N-hexane, N-methylpyrrolidone, ethanol, acetonitrile, dimethylacetamide, the number of swellable marks is 1, and the number of non-swellable marks is 0. Then, the three components of HSP of the toughening agent, respectively dispersion components (delta D ) Polar component (delta) P ) And hydrogen bond component (delta) H )。
Calculating the solubility parameter difference Ra between the toughening agent and the PVC,(subscripts 1 and 2 refer to PVC and toughener, respectively).
The test results are shown in Table 1 below
Delta of PVC D ，δ P ，δ H 18.6,6.6,8 respectively.
TABLE 1
As can be seen from Table 1, the dispersion component (delta D ) Polar component (delta) P ) And hydrogen bond component (delta) H ) Are all identical to the dispersion component (delta) of PVC D ) Polar component (delta) P ) And hydrogen bond component (delta) H ) Close, it is demonstrated that the toughening agent of the present invention can have good compatibility with PVC.
The PVC materials of examples 7 to 24 and comparative example 1 above were all tested by the following performance test methods:
the blend was pressed into flat plates of 120mm, 120mm and 4mm length, width and height by a flat vulcanizing machine at 180 c, and cut into rectangular test strips and dumbbell-shaped test strips by a universal cutter. And 5 sample bars are measured on each group of samples, the measured data are calculated, and the average value is taken to obtain the mechanical strength, and the test temperature is room temperature.
Tensile strength: the dumbbell type test strip has the test standard of GB/T1040.3-2006 and the stretching speed of 50mm/min.
Notched Izod impact Strength: rectangular test strip, test standard is GB/T1843-2008, and notch type is V-type.
The specific results of the PVC materials of each example are shown in Table 2 below:
TABLE 2
| Sample preparation | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| Tensile Strength/MPa | 38.5 | 34.4 | 37.9 | 36.3 | 35.5 | 35.2 |
| Impact strength/kJ/m 2 | 20.7 | 21.1 | 18.9 | 19.2 | 19.7 | 16.4 |
Continuous table 2
| Sample preparation | Example 13 | Example 14 | Example 15 | Example 16 | Example 17 | Example 18 |
| Tensile Strength/MPa | 40 | 39.2 | 41.3 | 39.5 | 38.1 | 39.8 |
| Impact strength/kJ/m 2 | 14.2 | 15.5 | 13.8 | 15.7 | 15 | 13.7 |
Continuous table 2
| Sample preparation | Example 19 | Example 20 | Example 21 | Example 22 | Example 23 | Example 24 |
| Tensile Strength/MPa | 35.4 | 33.7 | 36.1 | 33.1 | 32.2 | 32.9 |
| Impact strength/kJ/m 2 | 26.2 | 28 | 21.9 | 23.4 | 25.7 | 20.6 |
The specific results of the PVC materials of each comparative example are shown in Table 3 below:
TABLE 3 Table 3
| Sample preparation | Comparative example 1 | Comparative example 2 |
| Tensile Strength/MPa | 36.8 | 42.5 |
| Impact strength/kJ/m 2 | 13.2 | 8.9 |
From the above data, it can be seen that the toughening agent of the present invention can significantly improve the notched impact strength of PVC materials with little significant negative impact on tensile strength. The notch impact strength of the cantilever beam of the PVC material can reach 13.8-28.0 kJ/m 2 The tensile strength can reach 32.2-40 MPa.
When the proportion of the toughening agent in the PVC material is 10%, the notch impact strength of the prepared PVC material can reach 18.9kJ/m 2 The maximum value of the catalyst can reach 21.1kJ/m 2 The above. While the CPE toughening agent used in comparative example 1, the notch impact strength of the prepared PVC material is only 13.2kJ/m 2 . This is probably due to the too low viscosity of the CPE toughening agent used in comparative example 1 and thus does not significantly improve the toughness of the PVC material.
When the proportion of the toughening agent in the PVC material is 6%, the notch impact strength of the prepared PVC material can reach 13.8kJ/m 2 The maximum value of the catalyst can reach 15.7kJ/m 2 The above.
When the proportion of the toughening agent in the PVC material is 20%, the notch impact strength of the prepared PVC material can reach 20.6kJ/m 2 The maximum value of the catalyst can reach 28.0kJ/m 2 The above.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The preparation method of the toughening agent is characterized by comprising the following steps:
s1, swelling an elastomer, an initiator and a crosslinking agent in a crosslinking monomer;
s2, mixing and copolymerizing the product after swelling in the step S1 to obtain the toughening agent;
in the step S1, the crosslinking monomer is one or more of methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate or styrene;
the weight ratio of the elastomer to the crosslinking monomer is (0.3-3): 1, a step of;
in the step S1, the swelling time is 1-24h, and the swelling temperature is 25-80 ℃;
in the step S2, the copolymerization reaction temperature is 60-120 ℃, the copolymerization time is 20-100min, and the shear rate is 10-100rpm.
2. The method of preparing a toughening agent according to claim 1, wherein in step S1, the weight ratio of the elastomer to the crosslinking monomer is (0.6 to 2): 1.
3. the method of preparing a toughening agent according to claim 1, wherein in step S1, the swelling time is 4 to 7 hours and the temperature is 25 ℃ to 50 ℃.
4. The method of preparing a toughening agent according to claim 1, wherein in the step S2, the copolymerization reaction temperature is 85-95 ℃, the copolymerization time is 30-60min, and the shear rate is 20-50rpm.
5. The method of preparing a toughening agent according to claim 1, wherein the cross-linking monomer is one or more of methyl methacrylate or styrene.
6. The method for preparing the toughening agent according to claim 1, wherein the elastomer is one or more of natural rubber, styrene-butadiene rubber, nitrile rubber, ethylene propylene diene monomer rubber, epoxidized natural rubber, ethyl acrylate rubber, butyl acrylate rubber, SBS thermoplastic elastomer or SEBS thermoplastic elastomer; the cross-linking agent is one or more of divinylbenzene, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol divinyl ether, divinyl glycol or triethylene glycol divinyl ether; the initiator is one or more of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3, 5-trimethylhexanoate, dicyclohexyl peroxycarbonate or di (2-ethylhexyl) peroxycarbonate.
7. A toughening agent prepared by the method of any one of claims 1 to 6.
8. Toughening according to claim 7An agent characterized in that the viscosity of the toughening agent is greater than 5.0X10 5 Pa.s。
9. A rigid PVC material comprising the toughening agent of claim 7.
10. Use of the rigid PVC material according to claim 9 for the preparation of electrical bushings.
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