CN115260649A - Vacuum-assisted blow molding thermoplastic elastomer TPV for producing high melt strength and preparation method thereof - Google Patents

Vacuum-assisted blow molding thermoplastic elastomer TPV for producing high melt strength and preparation method thereof Download PDF

Info

Publication number
CN115260649A
CN115260649A CN202210886809.3A CN202210886809A CN115260649A CN 115260649 A CN115260649 A CN 115260649A CN 202210886809 A CN202210886809 A CN 202210886809A CN 115260649 A CN115260649 A CN 115260649A
Authority
CN
China
Prior art keywords
polypropylene
parts
melt strength
thermoplastic elastomer
high melt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210886809.3A
Other languages
Chinese (zh)
Other versions
CN115260649B (en
Inventor
胡朔
邬慧荣
王金华
徐敏娟
孟庆增
蔡健
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Ding Su Industry Co ltd
Original Assignee
Jiangsu Ding Su Industry Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Ding Su Industry Co ltd filed Critical Jiangsu Ding Su Industry Co ltd
Priority to CN202210886809.3A priority Critical patent/CN115260649B/en
Publication of CN115260649A publication Critical patent/CN115260649A/en
Application granted granted Critical
Publication of CN115260649B publication Critical patent/CN115260649B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The application relates to the technical field of TPV (thermoplastic vulcanizate) materials, in particular to a vacuum-assisted blow molding thermoplastic elastomer TPV with high melt strength 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; 0-40 parts of a filling material; 0.5-2 parts of light stabilizer; 5-10 parts of a compatilizer; 1-5 parts of phenolic resin; 0-1 part of stannous chloride; 2-4 parts of an 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; and S3, extruding and granulating for the second time. The vacuum-assisted blow molding thermoplastic elastomer TPV for producing high melt strength can be used for improving the melt strength of the TPV, and further improving the dimensional stability of a TPV product.

Description

Vacuum-assisted blow molding thermoplastic elastomer TPV for producing high melt strength and preparation method thereof
Technical Field
The application relates to the technical field of TPV (thermoplastic vulcanizate) materials, in particular to a vacuum-assisted blow molding thermoplastic elastomer TPV with high melt strength and a preparation method thereof.
Background
With the development of the automobile industry, the usage space of the vehicle-mounted equipment is further compressed, the structural design of the conveying pipeline becomes more complex, and the three-dimensional blow molding is also increasingly applied to the production and manufacturing of parts with complex shapes.
In the related art, the three-dimensional blow-molded hollow tube is made of a blow-molded thermoplastic elastomer TPV, and the preparation method of the TPV mainly comprises a chemical synthesis method and a physical blending method. In a daily use scene of the three-dimensional blow molding hollow pipe, the inner side of the pipeline is in a high-temperature oil and steam environment for a long time, and the outer side of the pipeline is influenced by high temperature of an engine compartment and high-concentration ozone generated by various electronic components of the engine compartment.
Disclosure of Invention
In order to improve the melt strength of the TPV, further improve the dimensional stability of a 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 solution:
a method for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV comprises 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;
0-40 parts of a filler;
0.5-2 parts of a light stabilizer;
5-10 parts of a compatilizer;
1-5 parts of phenolic resin;
0-1 part of stannous chloride;
2-4 parts of an auxiliary agent;
0-40 parts of white oil;
the high melt strength polypropylene is prepared by grafting and modifying polypropylene.
By adopting the technical scheme, firstly, under the action of the compatilizer, the high melt strength polypropylene molecules can be uniformly mixed with each component of the thermoplastic elastomer TPV; secondly, a branching structure exists in the high-melt-strength polypropylene molecules, so that the high-melt-strength polypropylene molecules are interwoven and tangled with other components to form a uniform and stable system, and the molecular motion among the components is dragged, so that the melt strength of the thermoplastic elastomer TPV can be increased, and the dimensional stability of a TPV product is 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 to increase the bonding strength among the components, so that 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 in a range convenient for blow molding, and the excessive hardening of the thermoplastic elastomer TPV due to the increase of the melt strength is reduced. Light stabilizers are used to increase the aging resistance of thermoplastic elastomer TPVs to increase their useful 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 melt strength can be prepared by controlling the mass ratio of the polypropylene, the polypropylene with high melt strength and the ethylene propylene diene monomer within the range.
Preferably, the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is 30.
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 rubber in 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 used as a matrix to be modified, the hexanediol diacrylate is used as a grafting monomer, the hydroxyethyl acrylate and the acrylic acid are used as an initiator and a crosslinking 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) The mixture is in an oxygen-free environment, and gamma rays are adopted to carry out irradiation treatment on the mixture to obtain the polypropylene with high melt strength.
By adopting the technical scheme, under the irradiation of gamma rays, the C-H bond of the polypropylene is excited to be broken to form a free radical, so that the hexanediol diacrylate is linked on the polypropylene and a grafting reaction is carried out to form the high-melt-strength polypropylene with a long-chain branched structure.
In a second aspect, the present application provides a preparation method for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV, which adopts the following technical scheme:
a preparation method for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV, comprising the preparation steps of:
s1, preparing materials: according to the formula, stannous chloride, 1/3-1/2 of polypropylene and half of auxiliary agent in parts by weight are mixed at room temperature, the rotating speed during mixing is 1200RPM-1500RPM, and the mixing time is 3-7 minutes, so that a mixture 1 is obtained;
mixing phenolic resin, 1/3-1/2 parts by weight of ethylene propylene diene monomer 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 to obtain a mixture 2;
s2, primary extrusion granulation: putting the mixture 1 in the S1 into a double-screw extruder, and extruding and granulating to obtain stannous chloride master batches, wherein the grain size of the stannous chloride master batches is 0.5-2 cm, 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 S1 into a double-pull type granulator, and extruding and granulating to obtain phenolic resin master batches, wherein the particle size of the phenolic resin master batches is 0.5-2 cm, the extrusion temperature of a double-screw extruder is 100-120 ℃, and the rotating speed of the double-screw extruder is 250-330 RPM;
s3, secondary extrusion granulation: adding the high-melt-strength polypropylene, the filling material, the white oil, the residual parts by weight of the ethylene propylene diene monomer, the residual parts by weight of the polypropylene, the stannous chloride master batch in the step S2 and the phenolic resin master batch into a double-screw extruder, and carrying out extrusion granulation to obtain the TPV for producing the high-melt-strength vacuum-assisted blow molding thermoplastic elastomer; the extrusion temperature of the double-screw extruder is 140-200 ℃, and the rotating speed of the double-screw extruder is 300-400 RPM.
By adopting the technical scheme, firstly, through the step S1, under the condition of high-speed stirring, part of polypropylene is taken as a carrier, stannous chloride and a half of auxiliary agent are loaded on the carrier, and a load body which can be well compatible with main raw materials of polypropylene, high-melt-strength polypropylene and ethylene propylene diene monomer is formed; a 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 load body which can be well compatible with the main raw material polypropylene, the high melt strength polypropylene and the ethylene propylene diene monomer.
Secondly, through the step S2, uniformly mixing all the components in the mixture 1, extruding and granulating to obtain uniform and stable stannous chloride master batches; and all the components in the mixture 2 are uniformly mixed and extruded for granulation to obtain uniform and stable phenolic resin master batches.
And finally, blending and extruding the stannous chloride master batch and the phenolic resin master batch with the rest components through the step S3, wherein the stannous chloride master batch and the phenolic resin master batch can be uniformly dispersed in the thermoplastic elastomer TPV, and the uniform and stable high-melt-strength vacuum-assisted blow molding thermoplastic elastomer TPV is obtained.
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 uniformity and stability of the stannous chloride master batch and the phenolic resin master batch can be respectively improved.
Preferably, the auxiliaries include 2, 5-dimethyl-2, 5-dioxane, 1, 4-butanediol diacrylate and copper N, N-dimethyldithiocarbamate.
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 the polypropylene, the high melt strength polypropylene, the ethylene propylene diene monomer rubber and the phenolic resin can be further cross-linked, grafted and intertwined during the secondary extrusion granulation in the step S3, thereby further improving the melt strength of the thermoplastic elastomer TPV. The N, N-dimethyl copper dithiocarbamate can regulate the degradation of polypropylene in the process of grafting the polypropylene and improve the grafting efficiency.
In summary, the present 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 inside the high melt strength polypropylene molecules, so that the high melt strength polypropylene molecules, and the high melt strength polypropylene molecules and other components are interwoven and intertwined to form a uniform and stable system, and the molecular motion among the components is dragged, so that the melt strength of the thermoplastic elastomer TPV can be increased, and the dimensional stability of a TPV product is 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 to increase the bonding strength among the components, so that 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 in a range convenient for blow molding, and the excessive hardening of the thermoplastic elastomer TPV due to the increase of the melt strength is reduced.
2. Under the irradiation of gamma rays, C-H bonds of the polypropylene are excited to be broken to form free radicals, so that the hexanediol diacrylate is linked on the polypropylene to generate a grafting reaction to form the high-melt-strength polypropylene with a long-chain branched 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 a half of auxiliary agent are loaded on the carrier, and a load body which is well compatible with main raw materials of polypropylene, high-melt-strength polypropylene and ethylene propylene diene monomer is formed; part of the ethylene propylene diene monomer is used as a carrier, and the phenolic resin and the other half of the auxiliary agent are loaded on the carrier to form a loading body which can be well compatible with the main raw material polypropylene, the high melt strength polypropylene and the ethylene propylene diene monomer. Secondly, through the step S2, uniformly mixing all the components in the mixture 1, extruding and granulating to obtain uniform and stable stannous chloride master batches; and all the components in the mixture 2 are uniformly mixed and extruded for granulation to obtain uniform and stable phenolic resin master batches. And finally, blending and extruding the stannous chloride master batch and the phenolic resin master batch with the rest components through the step S3, wherein the stannous chloride master batch and the phenolic resin master batch can be uniformly dispersed in the thermoplastic elastomer TPV, and the uniform and stable high-melt-strength vacuum-assisted blow molding thermoplastic elastomer TPV is obtained.
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) Mixing 10kg of polypropylene, 6kg of hexanediol diacrylate and 1kg of acrylic acid, and stirring to obtain a mixture;
(2) And (3) the mixture is in an oxygen-free environment, and the mixture is irradiated for 15min by gamma rays at room temperature to obtain the high-melt-strength polypropylene.
Preparation example 2
(1) Mixing 10kg of polypropylene, 6kg of hexanediol diacrylate, 0.5kg of hydroxyethyl acrylate and 1kg of acrylic acid, and stirring to obtain a mixture;
(2) And (3) the mixture is in an oxygen-free environment, and the mixture is irradiated for 15min by gamma rays at room temperature to obtain the high-melt-strength polypropylene.
Preparation examples of adjuvants
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 mixed and stirred to obtain the auxiliary agent.
Examples
Example 1
A process for producing a high melt strength vacuum assisted blow molded grade thermoplastic elastomer TPV made from the following raw materials: 3kg of polypropylene; 0.1kg of high melt strength polypropylene; 4kg of ethylene propylene diene monomer; 0kg of filling material; 0.05kg of light stabilizer; 0.5kg of compatilizer; 0.1kg of phenolic resin; 0kg of stannous chloride; 0.2kg of auxiliary agent; 0kg of white oil;
the high melt strength polypropylene is the high melt strength polypropylene of preparation example 1; the filler is prepared by mixing calcium carbonate, kaolin and silicon dioxide according to the mass ratio of 2; the light stabilizer adopts a light stabilizer 770; the compatilizer adopts ethylene-octene copolymer grafted maleic anhydride; the auxiliary agent used in preparation example 3 was used.
A preparation method for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV, comprising the preparation steps of:
s1, preparing materials: according to the formula, stannous chloride, polypropylene with the mass of 1/3-1/2 and half of the auxiliary agent are mixed at room temperature, the rotating speed during mixing is 1200RPMRPM, and the mixing time is 3 minutes, so that a mixture 1 is obtained;
mixing phenolic resin, 1/3 mass of ethylene propylene diene monomer and the other half mass of auxiliary agent at room temperature, wherein the rotating speed during mixing is 1200RPMRPM, and the mixing time is 3 minutes to obtain a mixture 2;
s2, primary extrusion granulation: putting the mixture 1 in the S1 into a double-screw extruder, and extruding and granulating to obtain stannous chloride master batches, wherein the grain 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 S1 into a double-pull type granulator, and 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 a double-screw extruder is 100 ℃, and the rotating speed of the double-screw extruder is 250RPM;
s3, secondary extrusion granulation: adding the high-melt-strength polypropylene, the filling material, the white oil, the residual parts by weight of the ethylene propylene diene monomer, the residual parts by weight of the polypropylene, the stannous chloride master batch in the step S2 and the phenolic resin master batch into a double-screw extruder, and carrying out extrusion granulation to obtain the TPV for producing the high-melt-strength vacuum-assisted blow molding thermoplastic elastomer; the extrusion temperature of the twin-screw extruder was 140 ℃ and the rotation speed of the twin-screw extruder was 300RPM.
Examples 2 to 3
The difference between the examples 2-3 and the example 1 is that the mixture ratio of the raw materials in the examples 2-3 is different, and the concrete is as follows:
example 2:
a vacuum assisted blow molding grade thermoplastic elastomer TPV for producing high melt strength, made from the following raw materials: 6kg of polypropylene; 3.5kg of high melt strength polypropylene; 6kg of ethylene propylene diene monomer; 2kg of filling material; 0.125kg of light stabilizer; 0.75kg of compatilizer; 0.3kg of phenolic resin; 0.05kg of stannous chloride; 0.3kg of auxiliary agent; 2kg of white oil.
Example 3
A vacuum assisted blow molding grade thermoplastic elastomer TPV for producing high melt strength, made from the following raw materials: 9kg of polypropylene; 7kg of high melt strength polypropylene; 8kg of ethylene propylene diene monomer; 4kg of filling material; 0.2kg of light stabilizer; 1kg of compatilizer; 0.5kg of phenolic resin; 0.1kg of stannous chloride; 0.4kg of auxiliary agent; 4kg of white oil.
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;
example 4: the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is 30;
example 5: the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is 50;
example 6: the mass ratio of polypropylene to ethylene propylene diene monomer is 50.
Examples 7 to 8
Examples 7-8 differ from example 4 in the process conditions in the preparation process, as shown in the following:
example 7:
a preparation method for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV, comprising the preparation steps of:
s1, preparing materials: according to the formula, mixing stannous chloride, 1/3-1/2 mass of polypropylene and half mass of auxiliary agent at room temperature, wherein the rotating speed during mixing is 1350RPM, and the mixing time is 5 minutes to obtain a mixture 1;
mixing phenolic resin, 2/5 mass of ethylene propylene diene monomer and the other half mass of auxiliary agent at room temperature, wherein the rotating speed during mixing is 1350RPM, and the mixing time is 5 minutes to obtain a mixture 2;
s2, primary extrusion granulation: putting the mixture 1 in the S1 into a double-screw extruder, and extruding and granulating to obtain stannous chloride master batches, wherein the grain 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 S1 into a double-pull type granulator, and 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 a double-screw extruder is 110 ℃, and the rotating speed of the double-screw extruder is 300RPM;
s3, secondary extrusion granulation: adding the high-melt-strength polypropylene, the filling material, the white oil, the residual parts by weight of the ethylene propylene diene monomer, the residual parts by weight of the polypropylene, the stannous chloride master batch in the step S2 and the phenolic resin master batch into a double-screw extruder, and carrying out extrusion granulation to obtain the TPV for producing the high-melt-strength vacuum-assisted blow molding thermoplastic elastomer; the extrusion temperature of the twin-screw extruder was 170 ℃ and the rotational speed of the twin-screw extruder was 350RPM.
Example 8:
a preparation method for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV, comprising the preparation 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 that a mixture 1 is obtained;
mixing phenolic resin, 1/2 mass of ethylene propylene diene monomer and the other half mass of auxiliary agent at room temperature, wherein the rotating speed during mixing is 1500RPM, and the mixing time is 7 minutes to obtain a mixture 2;
s2, primary extrusion granulation: putting the mixture 1 in the step S1 into a double-screw extruder, and extruding and granulating to obtain stannous chloride master batches, wherein the grain 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 S1 into a double-pull type granulator, and 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 a double-screw extruder is 120 ℃, and the rotating speed of the double-screw extruder is 330RPM;
s3, secondary extrusion granulation: adding the high-melt-strength polypropylene, the filling material, the white oil, the residual parts by weight of the ethylene propylene diene monomer, the residual parts by weight of the polypropylene, the stannous chloride master batch in the step S2 and the phenolic resin master batch into a double-screw extruder, and carrying out extrusion granulation to obtain the TPV for producing the high-melt-strength vacuum-assisted blow molding thermoplastic elastomer; 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 is selected, example 7 is the high melt strength polypropylene of preparative example 1 and example 9 is the high melt strength polypropylene of preparative example 2.
Example 10
Example 10 differs from example 9 in the different adjuvants selected, the high melt strength polypropylene of preparation 3 being selected for example 9 and the high melt strength polypropylene of preparation 4 being selected for example 10.
Comparative example
Comparative example 1
This comparative example differs from example 2 in that no high melt strength polypropylene was added.
Comparative example 2
This comparative example differs from example 2 in that no adjuvant was added.
Performance test
Detection method
Melt strength: melt strength is the ability of a polymer to support its own weight in the molten state. When a polymer melt is extruded from a melt flow rate meter die orifice under the action of gravity, the shear viscosity of an extruded strip at 200s is measured, and the higher the shear viscosity is, the higher the melt strength is.
TABLE 1 Performance test Table
Figure DEST_PATH_IMAGE002
Examples 1-3 are compared, with examples 1-3 differing in the proportions of the raw materials used to produce the high melt strength vacuum assisted blow molded grade thermoplastic elastomer TPV, and example 2 illustrates the best proportions of the raw materials for example 2 due to its best overall properties and highest shear viscosity.
Examples 4-6 were compared with example 2, and examples 4-6 were different from example 2 in that the mass ratio of the polypropylene, the high melt strength polypropylene and the ethylene propylene diene rubber in examples 4-6 was different from that in example 2. As the comprehensive performance and the shear viscosity of the embodiments 4-6 are better, the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is (30-80): 1-45): 50, and the thermoplastic elastomer TPV with excellent comprehensive performance and solution strength can be prepared. Since example 4 has the best overall properties and the highest shear viscosity, the mass ratio of polypropylene, high melt strength polypropylene and ethylene propylene diene monomer is 30.
Examples 7-8 were compared with example 4, and examples 7-8 differed from example 4 in the process conditions in the preparation process. The best process conditions in the preparation method of example 7 are illustrated due to the best overall performance and the highest shear viscosity of example 7.
Example 9 is compared to example 7, with example 9 differing from example 7 in the selection of the high melt strength polypropylene, example 7 selecting the high melt strength polypropylene of preparation 1 and example 9 selecting the high melt strength polypropylene of preparation 2. The scheme of the application is better due to the better comprehensive performance and higher shear viscosity of the embodiment 9.
Example 10 is compared to example 9, with example 10 differing from example 9 in the selection of the aid, 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 combination of properties and higher shear viscosity of example 10 indicates that the protocol of the present application is better.
Finally, comparative examples 1-2 are compared to example 2, with comparative example 1 being different from example 2 in that no high melt strength polypropylene is added to comparative example 1; comparative example 2 differs from example 2 in that no adjuvant was added in comparative example 2. The better combination property and the higher shear viscosity of the embodiment 2 show that the scheme of the application is better.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (8)

1. A vacuum-assisted blow molding thermoplastic elastomer TPV for producing high melt strength is characterized by 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;
0-40 parts of a filler;
0.5-2 parts of light stabilizer;
5-10 parts of a compatilizer;
1-5 parts of phenolic resin;
0-1 part of stannous chloride;
2-4 parts of an auxiliary agent;
0-40 parts of white oil;
the high melt strength polypropylene is prepared by grafting and modifying polypropylene.
2. A method for producing a high melt strength vacuum assisted blow molding grade thermoplastic elastomer TPV according to claim 1, wherein: the mass ratio of the polypropylene to the high melt strength polypropylene to the ethylene propylene diene monomer is (30-80): 1-45): 50.
3. A vacuum assisted blow molding grade thermoplastic elastomer TPV for producing high melt strength according to claim 2 characterized in that: the mass ratio of the polypropylene to the high-melt-strength polypropylene to the ethylene propylene diene monomer is 30.
4. A vacuum assisted blow molding grade thermoplastic elastomer TPV for producing high melt strength according to claim 1 characterized in that: the high melt strength polypropylene includes polypropylene, hexanediol diacrylate, hydroxyethyl acrylate, and acrylic acid.
5. A vacuum assisted blow moulding grade thermoplastic elastomer TPV for the production of high melt strength according to claim 4, characterized in that: 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) The mixture is in an oxygen-free environment, and gamma rays are adopted to carry out irradiation treatment on the mixture to obtain the polypropylene with high melt strength.
6. A process for the production of a high melt strength vacuum assisted blow molded grade thermoplastic elastomer TPV according to any one of claims 1 to 5, characterized in that: the preparation method comprises the following preparation steps:
s1, preparing materials: according to the formula, stannous chloride, 1/3-1/2 of polypropylene and half of auxiliary agent in parts by weight are mixed at room temperature, the rotating speed during mixing is 1200RPM-1500RPM, and the mixing time is 3-7 minutes, so that a mixture 1 is obtained;
mixing phenolic resin, 1/3-1/2 parts by weight of ethylene propylene diene monomer and the other half of auxiliary agent at room temperature, wherein the rotation speed during mixing is 1200RPM-1500RPM, and the mixing time is 3-7 minutes to obtain a mixture 2;
s2, primary extrusion granulation: putting the mixture 1 in the S1 into a double-screw extruder, and extruding and granulating to obtain stannous chloride master batches, wherein the grain size of the stannous chloride master batches is 0.5-2 cm, 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 S1 into a double-pull type granulator, and extruding and granulating to obtain phenolic resin master batches, wherein the particle size of the phenolic resin master batches is 0.5-2 cm, the extrusion temperature of a double-screw extruder is 100-120 ℃, and the rotating speed of the double-screw extruder is 250-330 RPM;
s3, secondary extrusion granulation: adding the high-melt-strength polypropylene, the filling material, the white oil, the residual parts by weight of the ethylene propylene diene monomer, the residual parts by weight of the polypropylene, the stannous chloride master batch in the step S2 and the phenolic resin master batch into a double-screw extruder, and carrying out extrusion granulation to obtain the TPV for producing the high-melt-strength vacuum-assisted blow molding thermoplastic elastomer; the extrusion temperature of the double-screw extruder is 140-200 ℃, and the rotating speed of the double-screw extruder is 300-400 RPM.
7. A process for the production of a high melt strength vacuum assisted blow molded grade thermoplastic elastomer TPV according to claim 6 characterized in that: in the step S1, the polypropylene is ground polypropylene pretreatment powder, and the ethylene propylene diene monomer is ground ethylene propylene diene monomer pretreatment powder.
8. Preparation process for the production of a high melt strength vacuum assisted blow molded grade thermoplastic elastomer TPV according to claim 6 characterized in that: the auxiliaries include 2, 5-dimethyl-2, 5-dioxane, 1, 4-butanediol diacrylate and copper N, N-dimethyldithiocarbamate.
CN202210886809.3A 2022-07-26 2022-07-26 Vacuum-assisted blow molding thermoplastic elastomer TPV (thermoplastic elastomer) for producing high melt strength and preparation method thereof Active CN115260649B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210886809.3A CN115260649B (en) 2022-07-26 2022-07-26 Vacuum-assisted blow molding thermoplastic elastomer TPV (thermoplastic elastomer) for producing high melt strength and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210886809.3A CN115260649B (en) 2022-07-26 2022-07-26 Vacuum-assisted blow molding thermoplastic elastomer TPV (thermoplastic elastomer) for producing high melt strength and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115260649A true CN115260649A (en) 2022-11-01
CN115260649B CN115260649B (en) 2023-11-21

Family

ID=83769194

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210886809.3A Active CN115260649B (en) 2022-07-26 2022-07-26 Vacuum-assisted blow molding thermoplastic elastomer TPV (thermoplastic elastomer) for producing high melt strength and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115260649B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101087851A (en) * 2004-12-24 2007-12-12 克雷顿聚合物研究公司 High melt strength thermoplastic elastomer composition
CN104927347A (en) * 2015-06-12 2015-09-23 河北省科学院能源研究所 High-damping mixing polyurethane damping material and preparation method thereof
CN105670134A (en) * 2016-03-08 2016-06-15 安徽韧达高分子材料有限公司 Blow-molding-grade TPV (thermoplastic vulcanizate) material for dust shields and preparation method thereof
CN110698771A (en) * 2019-09-27 2020-01-17 张家港市美特高分子材料有限公司 TPV micro-foaming material and production process thereof
CN112552292A (en) * 2020-12-23 2021-03-26 合肥工业大学 Method for synthesizing prucalopride impurity

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101087851A (en) * 2004-12-24 2007-12-12 克雷顿聚合物研究公司 High melt strength thermoplastic elastomer composition
CN104927347A (en) * 2015-06-12 2015-09-23 河北省科学院能源研究所 High-damping mixing polyurethane damping material and preparation method thereof
CN105670134A (en) * 2016-03-08 2016-06-15 安徽韧达高分子材料有限公司 Blow-molding-grade TPV (thermoplastic vulcanizate) material for dust shields and preparation method thereof
CN110698771A (en) * 2019-09-27 2020-01-17 张家港市美特高分子材料有限公司 TPV micro-foaming material and production process thereof
CN112552292A (en) * 2020-12-23 2021-03-26 合肥工业大学 Method for synthesizing prucalopride impurity

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王峰, 张丽叶: "敏化辐照法制备高熔体强度聚丙烯的研究", 塑料工业, no. 07, pages 21 - 23 *

Also Published As

Publication number Publication date
CN115260649B (en) 2023-11-21

Similar Documents

Publication Publication Date Title
JP2002138210A (en) Multiple polymer additive system
CN109265967B (en) Matte TPU material and preparation method thereof
CN106700287A (en) Foamed thermoplastic elastomer and preparation method thereof
CN104672630A (en) Modified ethylene propylene rubber and preparation method thereof
CN115785564B (en) High-strength modified PP material
CN111471245A (en) Polystyrene composite material and preparation method thereof
CN1064583C (en) Dispersive reactive entrusion of polymer gels
CN115260649B (en) Vacuum-assisted blow molding thermoplastic elastomer TPV (thermoplastic elastomer) for producing high melt strength and preparation method thereof
CN113980300A (en) Polypropylene with low gel content and high melt strength, preparation method and application thereof
EP1373406A1 (en) Chain branching agent and polyamide composition containing the same
CN109021583B (en) Three-component anti-tear silicone rubber and preparation method thereof
CN111040084A (en) Compatibilizer for low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof
CN103160130B (en) Organic silicon thermoplastic elastomer and preparation method for same
CN111484666A (en) Modified powdered rubber toughened polypropylene composite material and preparation method thereof
CN109423048A (en) A kind of polyphenyl thioether material and preparation method thereof of organosilicon toughening modifying
CN1156465A (en) Starch graft copolymer from wet starch
CN109422970B (en) High-gas-barrier thermoplastic vulcanized rubber and preparation method thereof
KR101951522B1 (en) Thermoplastic resin composition, method for preparing the same and article produced therefrom
CN113845770B (en) Composite plastic particle and preparation method thereof
CN113292847B (en) Flame-retardant nylon composite material and preparation method and application thereof
CN114230959B (en) Polypropylene composite material grafted by styrene-acrylic emulsion, and preparation method and application thereof
CN110862643B (en) TPE rubber coating and production method thereof
CN111019328B (en) Thermoplastic polyurethane filling master batch and preparation method thereof
CN116903982B (en) High-strength corrosion-resistant polypropylene composite material and preparation method thereof
CN115651204B (en) N-carbonyl-bisamide-polyolefin compound, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant