CN115260649B - Vacuum-assisted blow molding thermoplastic elastomer TPV (thermoplastic elastomer) for producing high melt strength and preparation method thereof - Google Patents
Vacuum-assisted blow molding thermoplastic elastomer TPV (thermoplastic elastomer) for producing high melt strength and preparation method thereof Download PDFInfo
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000071 blow moulding Methods 0.000 title claims abstract description 25
- -1 polypropylene Polymers 0.000 claims abstract description 127
- 239000004743 Polypropylene Substances 0.000 claims abstract description 124
- 229920001155 polypropylene Polymers 0.000 claims abstract description 124
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 40
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 38
- 239000005011 phenolic resin Substances 0.000 claims abstract description 38
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 37
- 239000001119 stannous chloride Substances 0.000 claims abstract description 37
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 37
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 32
- 238000001125 extrusion Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000005469 granulation Methods 0.000 claims abstract description 12
- 230000003179 granulation Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000004611 light stabiliser Substances 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 34
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 239000000155 melt Substances 0.000 abstract description 7
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The application relates to the technical field of TPV materials, in particular to a thermoplastic elastomer TPV for producing high melt strength vacuum assisted blow molding and a preparation method thereof. The method is used for producing the high melt strength vacuum assisted blow molding thermoplastic elastomer TPV and comprises the following raw materials in parts by weight: 30-90 parts of polypropylene; 0-70 parts of high melt strength polypropylene; 40-80 parts of ethylene propylene diene monomer rubber; 0-40 parts of filling material; 0.5-2 parts of light stabilizer; 5-10 parts of compatilizer; 1-5 parts of phenolic resin; 0-1 part of stannous chloride; 2-4 parts of auxiliary agent; 0-40 parts of white oil; the preparation method comprises the following steps: s1, preparing materials; s2, extruding and granulating for the first time; s3, secondary extrusion granulation. The thermoplastic elastomer TPV for producing the high melt strength vacuum assisted blow molding grade can be used for improving the melt strength of the TPV, thereby improving the dimensional stability of the TPV product.
Description
Technical Field
The application relates to the technical field of TPV materials, in particular to a thermoplastic elastomer TPV for producing high melt strength vacuum assisted blow molding and a preparation method thereof.
Background
With the development of the automobile industry, the use space of the vehicle-mounted equipment is further compressed, the structural design of the conveying pipeline is more complicated, and the three-dimensional blow molding is increasingly applied to the production and manufacture of products with complex shapes.
In the related art, a three-dimensional blow-molded hollow tube is made of a blow-molded thermoplastic elastomer TPV, and the preparation method of the TPV mainly includes a chemical synthesis method and a physical blending method. In the daily use scene of the three-dimensional blow molding hollow tube, the inner side of the pipeline is in a high-temperature oil-gas environment for a long time, and the outer side of the pipeline is influenced by high-temperature of an engine cabin and high-concentration ozone generated by various electronic components of the engine cabin, but the solution strength of the TPV is poor in the related technology, so that the dimensional stability of the three-dimensional blow molding hollow tube is reduced, and the problem of inconvenient use is caused.
Disclosure of Invention
In order to improve the solution strength of the TPV, further improve the dimensional stability of the TPV product and facilitate the use of the TPV product, the application provides a vacuum assisted blow molding thermoplastic elastomer TPV for producing high melt strength and a preparation method thereof.
In a first aspect, the present application provides a method for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV, using the following technical scheme:
a process for producing a high melt strength vacuum assisted blow molded thermoplastic elastomer TPV comprising the following raw materials in parts by weight:
30-90 parts of polypropylene;
1-70 parts of high melt strength polypropylene;
40-80 parts of ethylene propylene diene monomer rubber;
0-40 parts of filling material;
0.5-2 parts of light stabilizer;
5-10 parts of compatilizer;
1-5 parts of phenolic resin;
0-1 part of stannous chloride;
2-4 parts of auxiliary agent;
0-40 parts of white oil;
the high melt strength polypropylene is prepared by grafting modification of polypropylene.
By adopting the technical scheme, firstly, under the action of a compatilizer, high melt strength polypropylene molecules can be uniformly mixed with each component of the thermoplastic elastomer TPV; secondly, a branched structure exists in the high melt strength polypropylene molecules, so that the high melt strength polypropylene molecules and the high melt strength polypropylene molecules are interwoven and entangled with other components to form a uniform and stable system, and therefore, the molecular movement among the components is stumbled, the melt strength of the thermoplastic elastomer TPV can be increased, and the dimensional stability of the TPV product is further improved.
In addition, under the catalysis of stannous chloride and the action of an auxiliary agent, polypropylene, high melt strength polypropylene, ethylene propylene diene monomer and phenolic resin can react, so that the bonding strength of the components is increased, and the melt strength of the thermoplastic elastomer TPV is synergistically increased.
The addition of the white oil can control the hardness of the thermoplastic elastomer TPV, so that the hardness of the thermoplastic elastomer TPV is controlled within a range convenient for blow molding, and the occurrence of the situation that the thermoplastic elastomer TPV is excessively hardened due to the increase of the solution strength is reduced. Light stabilizers are used to increase the aging resistance of thermoplastic elastomer TPVs to increase their service life.
Preferably, the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is (30-80): (1-45): 50.
By adopting the technical scheme, the thermoplastic elastomer TPV with excellent comprehensive performance and solution strength can be prepared by controlling the mass ratio of polypropylene, high melt strength polypropylene and ethylene propylene diene monomer in the above range.
Preferably, the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is 30:45:50.
By adopting the technical scheme, the thermoplastic elastomer TPV with excellent comprehensive performance and solution strength can be further prepared by the polypropylene, the high melt strength polypropylene and the ethylene propylene diene monomer with the mass ratio.
Preferably, the high melt strength polypropylene comprises polypropylene, hexanediol diacrylate, hydroxyethyl acrylate, and acrylic acid.
By adopting the technical scheme, the polypropylene is taken as a matrix to be modified, the hexanediol diacrylate is taken as a grafting monomer, the hydroxyethyl acrylate and the acrylic acid are taken as an initiator and a cross-linking agent, and the hexanediol diacrylate can be grafted on the polypropylene to obtain the high melt strength polypropylene. The hydroxyethyl acrylate and the acrylic acid have good compatibility with polypropylene and hexanediol diacrylate.
Preferably, the preparation method of the high melt strength polypropylene comprises the following steps:
(1) Mixing polypropylene, hexanediol diacrylate, hydroxyethyl acrylate and acrylic acid to obtain a mixture;
(2) And (3) putting the mixture in an anaerobic environment, and adopting gamma rays to irradiate the mixture to obtain the high melt strength polypropylene.
By adopting the technical scheme, under the irradiation of gamma rays, C-H bond of polypropylene is stimulated to break to form free radicals, so that hexanediol diacrylate is linked on the polypropylene to undergo a grafting reaction to form the high melt strength polypropylene with a long chain branching structure.
In a second aspect, the application provides a method for producing a high melt strength vacuum assisted blow molding thermoplastic elastomer TPV, comprising the following steps:
a process for producing a high melt strength vacuum assisted blow molded thermoplastic elastomer TPV comprising the steps of:
s1, preparing materials: according to the formula, stannous chloride, 1/3-1/2 parts by weight of polypropylene and half parts by weight of auxiliary agent are mixed at room temperature, wherein the rotating speed during mixing is 1200RPM-1500RPM, and the mixing time is 3-7 minutes, so as to obtain a mixture 1;
mixing phenolic resin, 1/3-1/2 parts by weight of ethylene propylene diene monomer rubber and the other half part by weight of auxiliary agent at room temperature, wherein the rotating speed during mixing is 1200RPM-1500RPM, and the mixing time is 3-7 minutes, so as to obtain a mixture 2;
s2, primary extrusion granulation: putting the mixture 1 in the step S1 into a double-screw extruder, extruding and granulating to obtain stannous chloride master batches, wherein the particle size of the stannous chloride master batches is 0.5cm-2cm, the extrusion temperature of the double-screw extruder is 180-220 ℃, and the rotating speed of the double-screw extruder is 250-330 RPM;
putting the mixture 2 in the step S1 into a double-pull granulator, extruding and granulating to obtain phenolic resin master batches, wherein the particle size of the phenolic resin master batches is 0.5cm-2cm, the extrusion temperature of the double-screw extruder is 100-120 ℃, and the rotating speed of the double-screw extruder is 250-330 RPM;
s3, secondary extrusion granulation: adding high melt strength polypropylene, filler, white oil, the rest weight parts of ethylene propylene diene monomer, the rest weight parts of polypropylene, stannous chloride master batch and phenolic resin master batch in the step S2 into a double-screw extruder, extruding and granulating to obtain the thermoplastic elastomer TPV for producing high melt strength vacuum auxiliary blow molding grade; the extrusion temperature of the twin-screw extruder is 140-200 ℃, and the rotating speed of the twin-screw extruder is 300-400 RPM.
Through adopting the technical scheme, firstly, through the step S1, under the condition of high-speed stirring, part of polypropylene is used as a carrier, stannous chloride and half of auxiliary agents are loaded on the carrier, and a carrier which can be well compatible with main raw materials of polypropylene, high-melt-strength polypropylene and ethylene propylene diene monomer is formed; and part of ethylene propylene diene monomer is used as a carrier, and phenolic resin and the other half of auxiliary agent are loaded on the carrier to form a carrier which can be well compatible with the main raw materials of polypropylene, high melt strength polypropylene and ethylene propylene diene monomer.
Secondly, uniformly mixing the components in the mixture 1 and extruding and granulating to obtain uniform and stable stannous chloride master batches through the step S2; and uniformly mixing the components in the mixture 2, extruding and granulating to obtain uniform and stable phenolic resin master batch.
And finally, blending and extruding stannous chloride master batches, phenolic resin master batches and the rest components through a step S3, wherein the stannous chloride master batches and the phenolic resin master batches can be uniformly dispersed in the thermoplastic elastomer TPV to obtain uniform and stable high-melt-strength vacuum-assisted blow molding thermoplastic elastomer TPV.
Preferably, the polypropylene in the step S1 is ground polypropylene pretreatment powder, and the ethylene propylene diene monomer is ground ethylene propylene diene monomer pretreatment powder.
By adopting the technical scheme, the polypropylene pretreatment powder and the ethylene propylene diene monomer pretreatment powder have smaller particle sizes, and the uniform stability of stannous chloride master batches and phenolic resin master batches can be respectively improved.
Preferably, the auxiliary comprises 2, 5-dimethyl-2, 5-dioxane, 1, 4-butanediol diacrylate and copper N, N-dimethyl-dithiocarbamate.
By adopting the technical scheme, 2, 5-dimethyl-2, 5-dioxane is used as an initiator, and 1, 4-butanediol diacrylate is used as a cross-linking agent, so that polypropylene, high melt strength polypropylene, ethylene propylene diene monomer and phenolic resin can be further cross-linked, grafted and entangled during secondary extrusion granulation in the step S3, and the melt strength of the thermoplastic elastomer TPV is further improved. The N, N-dimethyl dithiocarbamic acid ester copper can regulate and control the degradation of polypropylene in the process of polypropylene grafting, and the grafting efficiency is improved.
In summary, the application has the following beneficial effects:
1. firstly, under the action of a compatilizer, high melt strength polypropylene molecules can be uniformly mixed with each component of the thermoplastic elastomer TPV; secondly, a branched structure exists in the high melt strength polypropylene molecules, so that the high melt strength polypropylene molecules and the high melt strength polypropylene molecules are interwoven and entangled with other components to form a uniform and stable system, and therefore, the molecular movement among the components is stumbled, the melt strength of the thermoplastic elastomer TPV can be increased, and the dimensional stability of the TPV product is further improved. In addition, under the catalysis of stannous chloride and the action of an auxiliary agent, polypropylene, high melt strength polypropylene, ethylene propylene diene monomer and phenolic resin can react, so that the bonding strength of the components is increased, and the melt strength of the thermoplastic elastomer TPV is synergistically increased. The addition of the white oil can control the hardness of the thermoplastic elastomer TPV, so that the hardness of the thermoplastic elastomer TPV is controlled within a range convenient for blow molding, and the occurrence of the situation that the thermoplastic elastomer TPV is excessively hardened due to the increase of the solution strength is reduced.
2. Under the irradiation of gamma rays, C-H bond of polypropylene is excited to break to form free radical, so that hexanediol diacrylate is linked to polypropylene to undergo grafting reaction to form high melt strength polypropylene with long chain branching structure.
3. According to the method, firstly, through the step S1, under the condition of high-speed stirring, part of polypropylene is used as a carrier, stannous chloride and half of auxiliary agents are loaded on the carrier, and a carrier which can be well compatible with main raw materials of polypropylene, high-melt-strength polypropylene and ethylene propylene diene monomer is formed; and part of ethylene propylene diene monomer is used as a carrier, and phenolic resin and the other half of auxiliary agent are loaded on the carrier to form a carrier which can be well compatible with the main raw materials of polypropylene, high melt strength polypropylene and ethylene propylene diene monomer. Secondly, uniformly mixing the components in the mixture 1 and extruding and granulating to obtain uniform and stable stannous chloride master batches through the step S2; and uniformly mixing the components in the mixture 2, extruding and granulating to obtain uniform and stable phenolic resin master batch. And finally, blending and extruding stannous chloride master batches, phenolic resin master batches and the rest components through a step S3, wherein the stannous chloride master batches and the phenolic resin master batches can be uniformly dispersed in the thermoplastic elastomer TPV to obtain uniform and stable high-melt-strength vacuum-assisted blow molding thermoplastic elastomer TPV.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation of high melt Strength Polypropylene
Preparation example 1
(1) 10kg of polypropylene, 6kg of hexanediol diacrylate and 1kg of acrylic acid are taken, mixed and stirred to obtain a mixture;
(2) And (3) putting the mixture in an anaerobic environment, and irradiating the mixture with gamma rays for 15min at room temperature to obtain the high melt strength polypropylene.
Preparation example 2
(1) 10kg of polypropylene, 6kg of hexanediol diacrylate, 0.5kg of hydroxyethyl acrylate and 1kg of acrylic acid are taken, mixed and stirred to obtain a mixture;
(2) And (3) putting the mixture in an anaerobic environment, and irradiating the mixture with gamma rays for 15min at room temperature to obtain the high melt strength polypropylene.
Preparation example of auxiliary agent
Preparation example 3
1kg of 2, 5-dimethyl-2, 5-dioxane and 1kg of 1, 4-butanediol diacrylate are mixed and stirred to obtain the auxiliary agent.
Preparation example 4
1kg of 2, 5-dimethyl-2, 5-dioxane, 1kg of 1, 4-butanediol diacrylate and 0.2kg of copper N, N-dimethyl dithiocarbamate are taken, mixed and stirred to obtain the auxiliary agent.
Examples
Example 1
A process for producing a high melt strength vacuum assisted blow molded thermoplastic elastomer TPV made from the following raw materials: 3kg of polypropylene; 0.1kg of high melt strength polypropylene; ethylene propylene diene monomer 4kg; 0kg of filling material; 0.05kg of light stabilizer; 0.5kg of compatilizer; 0.1kg of phenolic resin; stannous chloride 0kg; 0.2kg of auxiliary agent; 0kg of white oil;
the high melt strength polypropylene of preparation example 1 was used as the high melt strength polypropylene; the filler is prepared by mixing calcium carbonate, kaolin and silicon dioxide according to a mass ratio of 2:2:1; the light stabilizer 770 is used as the light stabilizer; the compatilizer adopts ethylene-octene copolymer grafted maleic anhydride; the above auxiliary agent was the auxiliary agent of preparation example 3.
A process for producing a high melt strength vacuum assisted blow molded thermoplastic elastomer TPV comprising the steps of:
s1, preparing materials: according to the formula, stannous chloride, 1/3-1/2 mass of polypropylene and half mass of auxiliary agent are mixed at room temperature, the rotating speed during mixing is 1200RPMRPM, and the mixing time is 3 minutes, so as to obtain a mixture 1;
mixing phenolic resin, ethylene propylene diene monomer with the mass of 1/3 and the other half of auxiliary agent at room temperature, wherein the rotating speed during mixing is 1200RPMRPM, and the mixing time is 3 minutes, so as to obtain a mixture 2;
s2, primary extrusion granulation: putting the mixture 1 in the step S1 into a double-screw extruder, extruding and granulating to obtain stannous chloride master batches, wherein the particle size of the stannous chloride master batches is 0.5cm, the extrusion temperature of the double-screw extruder is 180 ℃, and the rotating speed of the double-screw extruder is 250RPM;
putting the mixture 2 in the step S1 into a double-pull granulator, extruding and granulating to obtain phenolic resin master batches, wherein the particle size of the phenolic resin master batches is 0.5cm, the extrusion temperature of the double-screw extruder is 100 ℃, and the rotating speed of the double-screw extruder is 250RPM;
s3, secondary extrusion granulation: adding high melt strength polypropylene, filler, white oil, the rest weight parts of ethylene propylene diene monomer, the rest weight parts of polypropylene, stannous chloride master batch and phenolic resin master batch in the step S2 into a double-screw extruder, extruding and granulating to obtain the thermoplastic elastomer TPV for producing high melt strength vacuum auxiliary blow molding grade; the extrusion temperature of the twin-screw extruder was 140℃and the rotational speed of the twin-screw extruder was 300RPM.
Examples 2 to 3
Examples 2-3 differ from example 1 in the proportions of the raw materials in examples 2-3, as shown in detail below:
example 2:
a process for producing a high melt strength vacuum assisted blow molded thermoplastic elastomer TPV made from the following raw materials: 6kg of polypropylene; 3.5kg of high melt strength polypropylene; ethylene propylene diene monomer rubber 6kg; 2kg of filling material; 0.125kg of light stabilizer; 0.75kg of compatilizer; 0.3kg of phenolic resin; stannous chloride 0.05kg; 0.3kg of auxiliary agent; white oil 2kg.
Example 3
A process for producing a high melt strength vacuum assisted blow molded thermoplastic elastomer TPV made from the following raw materials: 9kg of polypropylene; 7kg of high melt strength polypropylene; ethylene propylene diene monomer rubber 8kg; 4kg of filling material; 0.2kg of light stabilizer; 1kg of a compatilizer; 0.5kg of phenolic resin; stannous chloride 0.1kg; 0.4kg of auxiliary agent; white oil 4kg.
Examples 4 to 6
Examples 4-6 differ from example 2 in that the mass ratio of polypropylene, high melt strength polypropylene and ethylene propylene diene monomer in examples 4-6 differs from example 2, as follows:
example 2: the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is 60:45:60;
example 4: the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is 30:45:50;
example 5: the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is 50:25:50;
example 6: the mass ratio of polypropylene to ethylene propylene diene monomer is 50:1:50, while the mass of high melt strength polypropylene is 0kg.
Examples 7 to 8
Examples 7-8 differ from example 4 in the process conditions in the preparation process, as shown in detail below:
example 7:
a process for producing a high melt strength vacuum assisted blow molded thermoplastic elastomer TPV comprising the steps of:
s1, preparing materials: according to the formula, stannous chloride, 1/3-1/2 mass of polypropylene and half mass of auxiliary agent are mixed at room temperature, the rotating speed during mixing is 1350RPM, and the mixing time is 5 minutes, so as to obtain a mixture 1;
mixing phenolic resin, ethylene propylene diene monomer with the mass of 2/5 and the other half of auxiliary agent at room temperature, wherein the rotating speed during mixing is 1350RPM, and the mixing time is 5 minutes, so as to obtain a mixture 2;
s2, primary extrusion granulation: putting the mixture 1 in the step S1 into a double-screw extruder, extruding and granulating to obtain stannous chloride master batches, wherein the particle size of the stannous chloride master batches is 1cm, the extrusion temperature of the double-screw extruder is 200 ℃, and the rotating speed of the double-screw extruder is 300RPM;
putting the mixture 2 in the step S1 into a double-pull granulator, extruding and granulating to obtain phenolic resin master batches, wherein the particle size of the phenolic resin master batches is 12cm, the extrusion temperature of the double-screw extruder is 110 ℃, and the rotating speed of the double-screw extruder is 300RPM;
s3, secondary extrusion granulation: adding high melt strength polypropylene, filler, white oil, the rest weight parts of ethylene propylene diene monomer, the rest weight parts of polypropylene, stannous chloride master batch and phenolic resin master batch in the step S2 into a double-screw extruder, extruding and granulating to obtain the thermoplastic elastomer TPV for producing high melt strength vacuum auxiliary blow molding grade; the extrusion temperature of the twin-screw extruder was 170℃and the rotational speed of the twin-screw extruder was 350RPM.
Example 8:
a process for producing a high melt strength vacuum assisted blow molded thermoplastic elastomer TPV comprising the steps of:
s1, preparing materials: according to the formula, stannous chloride, 1/2 mass of polypropylene and half mass of auxiliary agent are mixed at room temperature, the rotating speed during mixing is 1500RPM, and the mixing time is 7 minutes, so as to obtain a mixture 1;
mixing phenolic resin, ethylene propylene diene monomer with the mass of 1/2 and the other half of auxiliary agent at room temperature, wherein the rotating speed during mixing is 1500RPM, and the mixing time is 7 minutes, so as to obtain a mixture 2;
s2, primary extrusion granulation: putting the mixture 1 in the step S1 into a double-screw extruder, extruding and granulating to obtain stannous chloride master batches, wherein the particle size of the stannous chloride master batches is 2cm, the extrusion temperature of the double-screw extruder is 220 ℃, and the rotating speed of the double-screw extruder is 330RPM;
putting the mixture 2 in the step S1 into a double-pull granulator, extruding and granulating to obtain phenolic resin master batches, wherein the particle size of the phenolic resin master batches is 2cm, the extrusion temperature of the double-screw extruder is 120 ℃, and the rotating speed of the double-screw extruder is 330RPM;
s3, secondary extrusion granulation: adding high melt strength polypropylene, filler, white oil, the rest weight parts of ethylene propylene diene monomer, the rest weight parts of polypropylene, stannous chloride master batch and phenolic resin master batch in the step S2 into a double-screw extruder, extruding and granulating to obtain the thermoplastic elastomer TPV for producing high melt strength vacuum auxiliary blow molding grade; the extrusion temperature of the twin-screw extruder was 200℃and the rotational speed of the twin-screw extruder was 400RPM.
Example 9
Example 9 differs from example 7 in that the high melt strength polypropylene selected is the high melt strength polypropylene of preparation 1 for example 7 and the high melt strength polypropylene of preparation 2 for example 9.
Example 10
Example 10 differs from example 9 in that the auxiliary agent selected is different, example 9 selects the high melt strength polypropylene of preparation 3, and example 10 selects the high melt strength polypropylene of preparation 4.
Comparative example
Comparative example 1
This comparative example differs from example 2 in that no high melt strength polypropylene was added to this comparative example.
Comparative example 2
This comparative example differs from example 2 in that no auxiliary agent was added in this comparative example.
Performance test
Detection method
Solution strength: melt strength is the ability of a polymer to support its own weight in the molten state. When the polymer melt was extruded from the melt flow rate meter die under gravity, the shear viscosity of the extruded strand at 200s was measured, with greater shear viscosity resulting in greater melt strength.
Table 1 performance test table
Examples 1-3 were compared and examples 1-3 differ in the proportions of the materials used to produce the high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV, and the best proportions of the materials in example 2 are indicated by the best overall performance of example 2, the greatest shear viscosity.
Examples 4-6 and example 2 were compared, examples 4-6 and example 2 differing in the mass ratio of polypropylene, high melt strength polypropylene and ethylene propylene diene monomer in examples 4-6 from example 2. Because of the good comprehensive performance and the high shear viscosity of examples 4-6, it is indicated that the mass ratio of polypropylene, high melt strength polypropylene and ethylene propylene diene monomer is (30-80): (1-45): 50, and a thermoplastic elastomer TPV with excellent comprehensive performance and melt strength can be prepared. The best combination of properties of example 4, the highest shear viscosity, indicates that the mass ratio of polypropylene, high melt strength polypropylene and ethylene propylene diene monomer is 30:45:50.
Examples 7-8 were compared to example 4, examples 7-8 differing from example 4 in the process conditions in the preparation process. Since the combination of properties of example 7 is best, the shear viscosity is greatest, indicating that the process conditions in the preparation method of example 7 are best.
Example 9 is compared to example 7, example 9 differing from example 7 in that the high melt strength polypropylene selected is the high melt strength polypropylene of preparation 1, example 7, and example 9 is the high melt strength polypropylene of preparation 2. The better overall performance of example 9, greater shear viscosity, demonstrates a better solution of the present application.
Example 10 was compared to example 9, example 10 differing from example 9 in the selection of adjuvants, example 9 selecting the high melt strength polypropylene of preparation 3 and example 10 selecting the high melt strength polypropylene of preparation 4. The better overall performance of example 10, greater shear viscosity, demonstrates a better solution of the present application.
Finally, comparative examples 1-2 were compared with example 2, with the difference that comparative example 1 was not added with high melt strength polypropylene in comparative example 1; comparative example 2 is different from example 2 in that no auxiliary agent is added in comparative example 2. The better overall performance of example 2, greater shear viscosity, demonstrates a better solution of the present application.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (4)
1. A process for producing a high melt strength vacuum assisted blow molded thermoplastic elastomer TPV comprising the following raw materials in parts by weight:
30-90 parts of polypropylene; 1-70 parts of high melt strength polypropylene; 40-80 parts of ethylene propylene diene monomer rubber; 0-40 parts of filling material; 0.5-2 parts of light stabilizer; 5-10 parts of compatilizer; 1-5 parts of phenolic resin; 0-1 part of stannous chloride; 2-4 parts of auxiliary agent; 0-40 parts of white oil;
the auxiliary agent comprises 2, 5-dimethyl-2, 5-dioxane, 1, 4-butanediol diacrylate and N, N-dimethyl-dithio-carbamate copper; the high melt strength polypropylene is prepared by grafting modification of polypropylene;
the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is 30:45:50; the high melt strength polypropylene comprises polypropylene, hexanediol diacrylate, hydroxyethyl acrylate and acrylic acid;
the preparation method of the high melt strength polypropylene comprises the following steps: (1) Mixing polypropylene, hexanediol diacrylate, hydroxyethyl acrylate and acrylic acid to obtain a mixture;
(2) And (3) putting the mixture in an anaerobic environment, and adopting gamma rays to irradiate the mixture to obtain the high melt strength polypropylene.
2. A process for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV according to claim 1, characterized in that: the preparation method comprises the following preparation steps: s1, preparing materials: according to the formula, stannous chloride, 1/3-1/2 parts by weight of polypropylene and half parts by weight of auxiliary agent are mixed at room temperature, wherein the rotating speed during mixing is 1200RPM-1500RPM, and the mixing time is 3-7 minutes, so as to obtain a mixture 1; mixing phenolic resin, 1/3-1/2 parts by weight of ethylene propylene diene monomer rubber and the other half part by weight of auxiliary agent at room temperature, wherein the rotating speed during mixing is 1200RPM-1500RPM, and the mixing time is 3-7 minutes, so as to obtain a mixture 2; s2, primary extrusion granulation: putting the mixture 1 in the step S1 into a double-screw extruder, extruding and granulating to obtain stannous chloride master batches, wherein the particle size of the stannous chloride master batches is 0.5cm-2cm, the extrusion temperature of the double-screw extruder is 180-220 ℃, and the rotating speed of the double-screw extruder is 250-330 RPM; putting the mixture 2 in the step S1 into a double-pull granulator, extruding and granulating to obtain phenolic resin master batches, wherein the particle size of the phenolic resin master batches is 0.5cm-2cm, the extrusion temperature of the double-screw extruder is 100-120 ℃, and the rotating speed of the double-screw extruder is 250-330 RPM; s3, secondary extrusion granulation: adding high melt strength polypropylene, filler, white oil, the rest weight parts of ethylene propylene diene monomer, the rest weight parts of polypropylene, stannous chloride master batch and phenolic resin master batch in the step S2 into a double-screw extruder, extruding and granulating to obtain the thermoplastic elastomer TPV for producing high melt strength vacuum auxiliary blow molding grade; the extrusion temperature of the twin-screw extruder is 140-200 ℃, and the rotating speed of the twin-screw extruder is 300-400 RPM.
3. A process for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV according to claim 2, characterized in that: the polypropylene in the step S1 is ground polypropylene pretreatment powder, and the ethylene propylene diene monomer is ground ethylene propylene diene monomer pretreatment powder.
4. A process for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV according to claim 3, characterized in that: the auxiliary agent comprises 2, 5-dimethyl-2, 5-dioxane, 1, 4-butanediol diacrylate and N, N-dimethyl-dithio-carbamate copper.
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