CN110437604A - A kind of polyolefin alloy process for preparation of thermoplastic elastomer - Google Patents
A kind of polyolefin alloy process for preparation of thermoplastic elastomer Download PDFInfo
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- 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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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Abstract
The invention belongs to the technical field of battery material more particularly to a kind of polyolefin alloy process for preparation of thermoplastic elastomer.This application provides a kind of polyolefin alloy process for preparation of thermoplastic elastomer, comprising the following steps: step 1, will plasticate after thermoplastic polyether urethane elastomer rubber, compatilizer and ethylene propylene diene rubber be kneaded, obtain blend composition;Step 2 mixes the blend composition, activating agent, antioxidant, promotor and vulcanizing agent, and polyolefin alloy thermoplastic elastomer (TPE) is then obtained after dynamic vulcanization.This application provides a kind of polyolefin alloy process for preparation of thermoplastic elastomer, efficiently solve TPU in the prior art and EPDM by screw rod melting extrusion and form the technical problem that raw material dosage existing for TPV is big, process conditions are uncontrollable.
Description
Technical field
The invention belongs to the technical field of battery material more particularly to a kind of preparations of polyolefin alloy thermoplastic elastomer (TPE)
Method.
Background technique
Polyolefin alloy thermoplastic elastomer (TPE) (Thermoplastic Vulcanizate, TPV) belongs to special one kind heat
Thermoplastic elastic is made of two parts, first is that plastics are as continuous phase, second is that rubber is as dispersed phase, rubber in co-mixing system
It produces crosslinking and with the even particulate dispersion of 0.2~2 μm or so particle size in thermoplastic resin matrix, is formed with rubber
It is mutually dispersed phase, plastics are mutually the island structure of continuous phase.Since resin mutually imparts the good processability of TPV, and be crosslinked
Rubber phase makes TPV have the characteristics such as higher elasticity, impact resistance, endurance and thermostabilization, therefore, compared to thermoplastic poly
Olefin material, the performance of TPV, which has, to be obviously improved.Further, since there was only the crosslinking of rubber phase in TPV system, waste material can lead to
Heating plasticizing forming again is crossed, reusable, the feature of environmental protection is good, so that TPV has more wide application prospect.Many plastics
TPV can be formed between rubber, but only individual blends have a practical value after dynamic vulcanization, existing TPV can be with
Pass through the thermoplastic polyurethane elastomer rubber (Thermoplastic polyurethanes, TPU) that will be dried and dry three
First EP rubbers (Ethylene-Propylene-Diene Monomer, EPDM) melting extrusion is formed, due to TPU's and EPDM
Two-phase difficulties in dispersion is needed using screw rod melting extrusion, but the method for using screw rod melting extrusion makes TPV material, point
It is poor to dissipate property, because being blended when squeezing out, two kinds of material distributing homogeneities of EPDM and TPU are difficult to control for screw rod melting extrusion
System, the distribution of auxiliary agent such as activating agent, antioxidant, promotor and vulcanizing agent is also uneven, may cause the auxiliary agent of a bit of material
Distribution is excessive, and in addition the auxiliary agent distribution of a bit of material is very few;Since the small-sized effective raw material of extrusion device at least needs
800g or more, the raw material dosage resulted in the need for are very big, it is difficult to small-scale production.
Summary of the invention
This application provides a kind of polyolefin alloy process for preparation of thermoplastic elastomer, efficiently solve in the prior art
Technical problem TPU and EPDM big by bad dispersibility existing for screw rod melting extrusion formation TPV and raw material dosage.
In view of this, this application provides a kind of polyolefin alloy process for preparation of thermoplastic elastomer, including following step
It is rapid:
Step 1, will plasticate after thermoplastic polyurethane elastomer rubber, compatilizer and ethylene propylene diene rubber be kneaded, obtain
Blend composition;
Step 2 mixes the blend composition, activating agent, antioxidant, promotor and vulcanizing agent, then after dynamic vulcanization
To polyolefin alloy thermoplastic elastomer (TPE).
Wherein, thermoplastic polyurethane elastomer rubber can be polyester polyurethane or/and polyether polyurethane, preferably
, thermoplastic polyurethane elastomer rubber is polyether polyurethane, and the system viscosity of polyether polyurethane is low, easily mutual with auxiliary agent
Molten, processing performance is excellent.
Preferably, the compatilizer is selected from ethylene propylene diene rubber grafted maleic zinc ionomer, maleic acid in step 1
Acid anhydride grafted ethene-octene copolymer, maleic anhydride grafted ABS, maleic anhydride grafting PE, maleic anhydride graft PP and maleic anhydride
It is grafted one of PS or a variety of.
Preferably, in parts by weight, the step 1 includes: in step 1
40~70 parts of thermoplastic polyurethane elastomer rubber;
1~2 part of compatilizer;
30~60 parts of ethylene propylene diene rubber.
More preferably, in step 1, in parts by weight, the step 1 includes:
60~70 parts of thermoplastic polyurethane elastomer rubber;
1~2 part of compatilizer;
30~40 parts of ethylene propylene diene rubber.
More preferably, the mass ratio of thermoplastic polyurethane elastomer rubber and ethylene propylene diene rubber is 1:1.
Preferably, in step 1, it is described plasticate after the preparation method of thermoplastic polyurethane elastomer rubber include:
Elastic polyurethane body rubber at 170~180 DEG C plasticate obtained, the time of plasticating is 2~3min.
Wherein, step 1 is plasticated as existing conventional operation of plasticating, and the elastic polyurethane body rubber after plasticating can be more preferable
It is kneaded with ethylene propylene diene rubber.
Preferably, the preparation method of the elastic polyurethane body rubber includes by elastic polyurethane body rubber micelle 80
Elastic polyurethane body rubber is made in~120 DEG C of dry 1~2h.
Preferably, in parts by weight, the step 2 includes:
Preferably, the activating agent is selected from ZnO, stearic acid SA, zinc stearate, polyethylene glycol and activating agent in step 2
One of NH-2 or a variety of;The antioxidant is selected from antioxidant 1010;The promotor is selected from the thio thiuram of tetramethyl two
One in TMTD, 2,2'- dithio-bis-benzothiazole DM, N- cyclohexyl -2-[4-morpholinodithio sulfenamide and N, N '-diphenylguanidine
Kind is a variety of;The vulcanizing agent is selected from sulphur or/and vulcanizing agent DCP.
Wherein, activating agent NH-2 is ZnO and ZnCl2The complex compound of formation;Promotor is existing conventional promotor, is promoted
Agent CZ (N- cyclohexyl -2-[4-morpholinodithio sulfenamide), diphenylguanidine (N, N '-diphenylguanidine), vulcanizing agent DCP are peroxidating two
Isopropylbenzene.
Preferably, including: in the step 1
Thermoplastic polyether urethane elastomer rubber and compatilizer after plasticating are kneaded, and obtain mixture 1;
The mixture 1 is kneaded with ethylene propylene diene rubber, obtains blend composition.
More preferably, including: in the step 1
Thermoplastic polyether urethane elastomer rubber and compatilizer after plasticating are kneaded 1~2min, obtain mixture 1;
The mixture 1 is kneaded 4~6min with ethylene propylene diene rubber, obtains blend composition.
Preferably, including: in the step 2
The blend composition, activating agent and antioxidant are kneaded, and obtain mixture 2;
The mixture 2, promotor are kneaded, and obtain mixture 3;
The mixture 3 and vulcanizing agent dynamic vulcanization, obtain polyolefin alloy thermoplastic elastomer (TPE).
More preferably, including: in the step 2
The blend composition, activating agent and antioxidant are kneaded 2~3min, obtain mixture 2;
The mixture 2, promotor are kneaded 0.5~1min, obtain mixture 3;
The mixture 3 and 5~8min of vulcanizing agent dynamic vulcanization, obtains polyolefin alloy thermoplastic elastomer (TPE).
Preferably, the temperature range of the dynamic vulcanization is 170-190 DEG C, the time range of the dynamic vulcanization is 5
~12min.
Wherein, step 1 and step 2 can be completed in torque rheometer.
Belong to thermoset articles after traditional vulcanization of rubber, form cross-bond, is unable to post forming, therefore, traditional rubber
Processing cannot be repeated after glue vulcanization to use, and lead to not recycle.
As can be seen from the above technical solutions, the application has the following advantages:
This application discloses the preparation methods of TPV a kind of, after TPU plasticates, are conducive to preferably mix with EPDM phase, separately
Outside, TPU is polar material, and EPDM is non-polar material, and the interface compatibility that compatilizer is conducive to improve two-phase is added, makes him
Mix more uniform, the sea-island structure of TPV is preferably formed, from the cross-section morphology of quenching of the electron microscope of experiment it is found that phase is added
Hold agent and certain improvement is distributed with to two-phase.The application adds compatilizer progress surface and is modified after first TPU melting is plasticated, then
It adds EPDM to be blended and activating agent, antioxidant, promotor and vulcanizing agent mixing, the TPV material of the application is straight compared to traditional
Material made from mixing method is connect, TPU mixes more uniform with EPDM.There are TPU resin phase, TPU resin in the TPV system of the application
Mutually guarantee that TPV can repeat to process, material mechanical performance mutually can be improved in resin, and the bullet of material mutually can be improved in EPDM rubber
Property, in addition the blend method of the application keeps two-phase dispersion more uniform, improves the mechanical property of the TPV of the application.Meanwhile this Shen
The problem of TPV material please can repeat processing and use, and cannot repeat to process after solving traditional vulcanization of rubber, recycling.
In addition, the processing instrument that the application uses can be convenient under the processing conditions of laboratory, more just for torque rheometer
Just TPV material is made in small lot, and the preparation method process flow of the application is simple, easy to operate, and TPV material is widely applied
In fields such as automobile, sealing, cable, building, medical treatment, have potential application and Development volue.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the vulcanization characteristics curve of the product 5 of the application comparative example 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of product 1 made from the embodiment of the present application 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of product 2 made from the embodiment of the present application 2;
Fig. 4 is the scanning electron microscope (SEM) photograph of product 3 made from the embodiment of the present application 3;
Fig. 5 is the scanning electron microscope (SEM) photograph of product 4 made from the embodiment of the present application 4;
Fig. 6 is the scanning electron microscope (SEM) photograph of product 5 made from the application comparative example 1;
Fig. 7 is the scanning electron microscope (SEM) photograph of product 6 made from the application comparative example 2;
Fig. 8 is the scanning electron microscope (SEM) photograph of product 7 made from the application comparative example 3.
Specific embodiment
The present invention provides a kind of polyolefin alloy process for preparation of thermoplastic elastomer, can effectively solve in the prior art
TPU and EPDM forms the technical problem that raw material dosage existing for TPV is big, process conditions are uncontrollable by screw rod melting extrusion.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Wherein, it is commercially available or self-control that following embodiment is raw materials used.
Embodiment 1
The embodiment of the present application provides the first polyolefin alloy process for preparation of thermoplastic elastomer, and specific steps are such as
Under:
Thermoplastic polyether urethane elastomer rubber micelle (TPU) is dried to 1h under 100 DEG C of baking ovens first, is gathered
Ether-based polyurethane elastomer rubber.
Then torque rheometer is utilized, first polyether polyurethane elastomer rubber is plasticated 2min at a high temperature of 170 DEG C,
Polyether polyurethane elastomer rubber after being plasticated.
Then torque rheometer is utilized, the polyether polyurethane elastomer rubber after plasticating is added ethylene-propylene-diene monomer and is glued
Branch MALEIC ACID, ZINC SALT ionomer (EPDM-g-MA) is kneaded 1min, is eventually adding ethylene propylene diene rubber (EPDM) and is kneaded 4min, is total to
Mixing.
Then ZnO, SA and antioxidant 1010 are added in blend composition and are kneaded 2min, Vulcanization accelerator TMTD and rush are added later
It is kneaded 1min into agent DM, Sulfur is eventually adding, polyolefin alloy thermoplastic elastomer (TPE) (TPV material is obtained after dynamic vulcanization 5min
Material).
Obtained TPV material is pressed on compression molding instrument in 170 DEG C of lower sheetings with 0.3T pressure preheating 60s with 10T
Power is vented 5 times, with 20T pressure hot pressing 300s, is cold-pressed 180s with 20T pressure, product 1 is made.
The mass parts of substance used in above step are as follows: 40 parts of TPU, 60 parts of EPDM, 1 part of EPDM-g-MA, 4 parts of ZnO,
2 parts of SA, 0.5 part of antioxidant 1010,1 part of Vulcanization accelerator TMTD, 0.5 part of altax, 1 part of sulphur.
Embodiment 2
The embodiment of the present application provides second of polyolefin alloy process for preparation of thermoplastic elastomer, and specific steps are such as
Under:
Thermoplastic polyether urethane elastomer rubber micelle (TPU) is dried to 1h under 100 DEG C of baking ovens first, is gathered
Ether-based polyurethane elastomer rubber.
Then torque rheometer is utilized, first polyether polyurethane elastomer rubber is plasticated 2min at a high temperature of 170 DEG C,
Polyether polyurethane elastomer rubber after being plasticated.
Then torque rheometer is utilized, the polyether polyurethane elastomer rubber after plasticating is added ethylene-propylene-diene monomer and is glued
Branch MALEIC ACID, ZINC SALT ionomer (EPDM-g-MA) is kneaded 1min, is eventually adding ethylene propylene diene rubber (EPDM) and is kneaded 4min, is total to
Mixing.
Then ZnO, SA and antioxidant 1010 are added in blend composition and are kneaded 2min, Vulcanization accelerator TMTD and rush are added later
It is kneaded 1min into agent DM, Sulfur is eventually adding, polyolefin alloy thermoplastic elastomer (TPE) (TPV material is obtained after dynamic vulcanization 5min
Material).
Obtained TPV material is pressed on compression molding instrument in 170 DEG C of lower sheetings with 0.3T pressure preheating 60s with 10T
Power is vented 5 times, with 20T pressure hot pressing 300s, is cold-pressed 180s with 20T pressure, product 2 is made.
The mass parts of substance used in above step are as follows: 50 parts of TPU, EPDM50 parts, 1 part of EPDM-g-MA, 4 parts of ZnO, SA
2 parts, 0.5 part of antioxidant 1010,1 part of Vulcanization accelerator TMTD, 0.5 part of altax, 1 part of sulphur.
Embodiment 3
The embodiment of the present application provides the third polyolefin alloy process for preparation of thermoplastic elastomer, and specific steps are such as
Under:
Thermoplastic polyether urethane elastomer rubber micelle (TPU) is dried to 1h under 100 DEG C of baking ovens first, is gathered
Ether-based polyurethane elastomer rubber.
Then torque rheometer is utilized, first polyether polyurethane elastomer rubber is plasticated 2min at a high temperature of 170 DEG C,
Polyether polyurethane elastomer rubber after being plasticated.
Then torque rheometer is utilized, the polyether polyurethane elastomer rubber after plasticating is added ethylene-propylene-diene monomer and is glued
Branch MALEIC ACID, ZINC SALT ionomer (EPDM-g-MA) is kneaded 1min, is eventually adding ethylene propylene diene rubber (EPDM) and is kneaded 4min, is total to
Mixing.
Then ZnO, SA and antioxidant 1010 are added in blend composition and are kneaded 2min, Vulcanization accelerator TMTD and rush are added later
It is kneaded 1min into agent DM, Sulfur is eventually adding, polyolefin alloy thermoplastic elastomer (TPE) (TPV material is obtained after dynamic vulcanization 5min
Material).
Obtained TPV material is pressed on compression molding instrument in 170 DEG C of lower sheetings with 0.3T pressure preheating 60s with 10T
Power is vented 5 times, with 20T pressure hot pressing 300s, is cold-pressed 180s with 20T pressure, product 3 is made.
The mass parts of substance used in above step are as follows: 60 parts of TPU, 40 parts of EPDM, 1 part of EPDM-g-MA, 4 parts of ZnO,
2 parts of SA, 0.5 part of antioxidant 1010,1 part of Vulcanization accelerator TMTD, 0.5 part of altax, 1 part of sulphur.
Embodiment 4
The embodiment of the present application provides the 4th kind of polyolefin alloy process for preparation of thermoplastic elastomer, and specific steps are such as
Under:
Thermoplastic polyether urethane elastomer rubber micelle (TPU) is dried to 1h under 100 DEG C of baking ovens first, is gathered
Ether-based polyurethane elastomer rubber.
Then torque rheometer is utilized, first polyether polyurethane elastomer rubber is plasticated 2min at a high temperature of 170 DEG C,
Polyether polyurethane elastomer rubber after being plasticated.
Then torque rheometer is utilized, the polyether polyurethane elastomer rubber after plasticating is added ethylene-propylene-diene monomer and is glued
Branch MALEIC ACID, ZINC SALT ionomer (EPDM-g-MA) is kneaded 1min, is eventually adding ethylene propylene diene rubber (EPDM) and is kneaded 4min, is total to
Mixing.
Then ZnO, SA and antioxidant 1010 are added in blend composition and are kneaded 2min, Vulcanization accelerator TMTD and rush are added later
It is kneaded 1min into agent DM, Sulfur is eventually adding, polyolefin alloy thermoplastic elastomer (TPE) (TPV material is obtained after dynamic vulcanization 5min
Material).
Obtained TPV material is pressed on compression molding instrument in 170 DEG C of lower sheetings with 0.3T pressure preheating 60s with 10T
Power is vented 5 times, with 20T pressure hot pressing 300s, is cold-pressed 180s with 20T pressure, product 4 is made.
The mass parts of substance used in above step are as follows: 70 parts of TPU, 30 parts of EPDM, 1 part of EPDM-g-MA, 4 parts of ZnO,
SA2 parts, 0.5 part of antioxidant 1010,1 part of Vulcanization accelerator TMTD, 0.5 part of altax, 1 part of sulphur.
Embodiment 5
The embodiment of the present application provides the preparation method of the post forming of TPV material, the specific steps are as follows:
The product 2 that embodiment 2 had formed is cut into small pieces with scissors first, obtains recycling TPV material.
Then recycling TPV material is put into vulcanizing press and carries out post forming, in 170 DEG C of lower sheetings, pressed with 0.3T
Power preheats 60s, with 10T pressure exhaust 5 times, with 20T pressure hot pressing 300s, is cold-pressed 180s with 20T pressure, product 9 is made.
Comparative example 1
The application comparative example provides the preparation method of product 5 (EPDM vulcanized rubber), the specific steps are as follows:
First by ethylene propylene diene rubber raw rubber (EPDM raw rubber), plasticate 3min on a mill, after packet roller 2min, by EPDM,
ZnO, SA, antioxidant 1010, Vulcanization accelerator TMTD 1, altax and sulphur are added, after eating powder, each 4 times of left and right rubber tapping,
It is eventually adding Sulfur, after eating powder, each 4 times of left and right rubber tapping is beaten triangle bag 4 times, Bao Tong 4 times, slice is vulcanized with no rotor
Instrument carries out the test of vulcanization characteristics, condition are as follows: 170 DEG C × 10min, after obtaining T90, in 170 DEG C of lower sheetings, product 5 is made.
The mass parts of substance used in above step are as follows: 100 parts of EPDM, 4 parts of ZnO, SA2 parts, 0.5 part of antioxidant 1010,
1 part of Vulcanization accelerator TMTD, 0.5 part of altax, 1 part of sulphur.
Comparative example 2
The application comparative example provides the method that product 6 made from compatilizer is not added, the specific steps are as follows:
This comparative example is that TPV made from compatilizer is not added, and specific implementation method and embodiment 2 are identical, and distinctive points are
EPDM-g-MA is not added, as step product 6 is made, i.e., by following mass parts material composition: TPU in the raw material of other additions
50 parts, 50 parts of EPDM, 4 parts of ZnO, SA2 parts, 0.5 part of antioxidant 1010,1 part of Vulcanization accelerator TMTD, 0.5 part of altax,
1 part of sulphur.
Comparative example 3
The application comparative example provides the method that product 7 made from compatilizer is not added, the specific steps are as follows:
Thermoplastic polyether urethane elastomer rubber micelle (TPU) is dried to 1h under 100 DEG C of baking ovens first, is gathered
Ether-based polyurethane elastomer rubber.
Then torque rheometer is utilized, directly by polyether polyurethane elastomer rubber and ethylene propylene diene rubber (EPDM) In
It is kneaded 6min at a high temperature of 170 DEG C, obtains blend composition.
Then ZnO, SA, antioxidant 1010 are added in blend composition and are kneaded 2min, Vulcanization accelerator TMTD and rush are added later
It is kneaded 1min into agent DM, Sulfur is eventually adding, obtains TPV after dynamic vulcanization 5min.
By obtained TPV with, in 170 DEG C of lower sheetings, 60s is preheated on compression molding instrument with 0.3T pressure, with 10T pressure row
Gas 5 times, with 20T pressure hot pressing 300s, 180s is cold-pressed with 20T pressure, product 7 is made.
The mass parts of substance used in above step are as follows: 50 parts of TPU, 50 parts of EPDM, 4 parts of ZnO, SA2 parts, antioxidant
1010 0.5 parts, 1 part of Vulcanization accelerator TMTD, 0.5 part of altax, 1 part of sulphur.
Comparative example 4
The preparation method of the application comparative example offer TPU rubber, the specific steps are as follows:
Thermoplastic polyether urethane elastomer rubber micelle (TPU) is dried to 1h under 100 DEG C of baking ovens first, is gathered
Ether-based polyurethane elastomer rubber.
Then it is added in antioxidant 1010 and is kneaded 2min, then discharge.
By the TPU of discharging with, in 190 DEG C of lower sheetings, 150s is preheated on compression molding instrument with 0.3T pressure, with 10T pressure row
Gas 5 times, with 20T pressure hot pressing 300s, 300s is cold-pressed with 20T pressure, product 8 is made.
The mass parts of substance used in above step are as follows: 100 parts of TPU, 0.5 part of antioxidant 1010.
Detect the tensile strength of product 1-9 made from embodiment 1-5 and comparative example 1-4, elongation at break, tearing strength,
Hardness, tensile set and elastic performance, as a result as described in Table 1.Electronic Speculum is scanned to product 1-7, as a result as schemed
2-8。
As known from Table 1, product 1-4 compares product 5, and product 5 is EPDM vulcanized rubber, the tensile strength of product 1-4 and tears
Resistance to spalling is improved, and tensile strength and tearing strength increase with the mass parts of TPU and increased;Product 1-4 compares product 8, produces
Product 8 are pure TPU, and the tensile set of product 1-4 is greatly improved.Product 2, can from SEM figure compared with to product 6
Out, the TPU and EPDM two of product 2 is combined more preferably.Product 2 is compared with product 7, from SEM figure as can be seen that directly will be dry
TPU and EPDM is blended, and is added without compatilizer, is unfavorable for the combination of two-phase, mechanical property is lost, from the result of SEM figure
Show: the dispersibility of the comixing compatibility of EPDM and TPU and various auxiliary agents on the surface of the material sorts from good to difference: product 2 >
6 > product of product 7.The product 9 of the post forming of TPV material has certain loss compared to product 2, tensile strength and tearing strength
But no more than 10%, product is influenced less using upper, it was demonstrated that the TPV of the application can be reused.
Table 2 and Fig. 1 illustrate the vulcanization characteristics of the pure EPDM of product 5, and the T90 time of pure EPDM is that 5.34 minutes explanations are dynamic
State vulcanization time is at least that can vulcanize within 5.34 minutes completely, and the dynamic vulcanization time for the TPV material of the application provides reference.This
The T10 time of the vulcanization characteristics of the TPV material of application is longer, and the T90 time is shorter, illustrates the TPV material of the TPV material of the application
It is not susceptible to incipient scorch in material forming process and vulcanizes in advance, and the time produced is shorter.
The mechanical property of 1 product 1-8 of table
The vulcanization characteristics of 2 product 5 of table
The description of the present application and term " first " in above-mentioned attached drawing, " second ", " third ", " the 4th " etc. are (if deposited
) it is to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that use in this way
Data are interchangeable under appropriate circumstances, so that embodiments herein described herein for example can be in addition to illustrating herein
Or the sequence other than those of description is implemented.In addition, term " includes " and " having " and their any deformation, it is intended that
Cover it is non-exclusive include, for example, containing the process, method, system, product or equipment of a series of steps or units need not limit
In step or unit those of is clearly listed, but may include be not clearly listed or for these process, methods, produce
The other step or units of product or equipment inherently.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of polyolefin alloy process for preparation of thermoplastic elastomer, which comprises the following steps:
Step 1, will plasticate after thermoplastic polyurethane elastomer rubber, compatilizer and ethylene propylene diene rubber be kneaded, be blended
Material;
Step 2 mixes the blend composition, activating agent, antioxidant, promotor and vulcanizing agent, is then gathered after dynamic vulcanization
Alkene alloy thermoplastic elastomer (TPE).
2. preparation method according to claim 1, which is characterized in that in step 1, the compatilizer is selected from ethylene-propylene-diene monomer
It is glued branch MALEIC ACID, ZINC SALT ionomer, maleic anhydride grafted ethene-octene copolymer, maleic anhydride grafted ABS, maleic anhydride grafting
One of PE, maleic anhydride graft PP and maleic anhydride grafting PS or a variety of.
3. preparation method according to claim 1, which is characterized in that in step 1, in parts by weight, the step 1
Include:
40~70 parts of thermoplastic polyurethane elastomer rubber;
1~2 part of compatilizer;
30~60 parts of ethylene propylene diene rubber.
4. preparation method according to claim 1, which is characterized in that in step 1, it is described plasticate after thermoplastic polyurethane
The preparation method of elastomer rubber includes:
Elastic polyurethane body rubber at 170~180 DEG C plasticate obtained, the time of plasticating is 2~3min.
5. the preparation method according to claim 4, which is characterized in that the preparation method packet of the elastic polyurethane body rubber
It includes elastic polyurethane body rubber micelle in 80~120 DEG C of dry 1~2h, elastic polyurethane body rubber is made.
6. preparation method according to claim 1, which is characterized in that in parts by weight, the step 2 includes:
7. preparation method according to claim 1, which is characterized in that in step 2, the activating agent is selected from ZnO, stearic acid
One of SA, zinc stearate, polyethylene glycol and activating agent NH-2 or a variety of;The antioxidant is selected from antioxidant 1010;It is described
Promotor is selected from the thio thiuram TMTD of tetramethyl two, 2,2'- dithio-bis-benzothiazole DM, N- cyclohexyl -2-[4-morpholinodithio
Sulfenamide and N, one of N '-diphenylguanidine or a variety of;The vulcanizing agent is selected from sulphur or/and vulcanizing agent DCP.
8. preparation method according to claim 1, which is characterized in that include: in the step 1
Thermoplastic polyether urethane elastomer rubber and compatilizer after plasticating are kneaded, and obtain mixture 1;
The mixture 1 is kneaded with ethylene propylene diene rubber, obtains blend composition.
9. preparation method according to claim 1, which is characterized in that include: in the step 2
The blend composition, activating agent and antioxidant are kneaded, and obtain mixture 2;
The mixture 2, promotor are kneaded, and obtain mixture 3;
The mixture 3 and vulcanizing agent dynamic vulcanization, obtain polyolefin alloy thermoplastic elastomer (TPE).
10. preparation method according to claim 1, which is characterized in that the temperature range of the dynamic vulcanization is 170-190
DEG C, the time range of the dynamic vulcanization is 5~12min.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1739127A1 (en) * | 2005-07-01 | 2007-01-03 | Advanced Elastomer Systems, L.P. | Thermoplastic Vulcanizates and Sealing Devices Made Therewith |
WO2009017868A1 (en) * | 2007-07-27 | 2009-02-05 | Dow Global Technologies Inc. | Compositions of thermoplastic polyurethane (tpu), polybutadiene and polydiene-based tpu |
CN103012971A (en) * | 2012-12-04 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | EPDM/EVOH-MAA (ethylene-propylene-diene monomer/ethylene vinyl alcohol-methacrylic acid) dynamically vulcanizled thermoplastic elastomer for separating gas and resisting water vapor and preparation method thereof |
CN103709720A (en) * | 2013-11-28 | 2014-04-09 | 青岛科技大学 | Polyurethane/polylactic acid thermoplastic vulcanized rubber and preparation method thereof |
CN106939100A (en) * | 2017-04-20 | 2017-07-11 | 贵州省材料产业技术研究院 | A kind of fire-retardant TPV composites of dynamic vulcanization and preparation method thereof |
CN106939099A (en) * | 2017-04-20 | 2017-07-11 | 贵州省材料产业技术研究院 | A kind of antistatic TPV composites of dynamic vulcanization and preparation method thereof |
CN106977813A (en) * | 2017-04-20 | 2017-07-25 | 贵州省材料产业技术研究院 | A kind of dynamic vulcanization has fire-retardant TPV composites of halogen and preparation method thereof |
CN107245187A (en) * | 2017-04-20 | 2017-10-13 | 贵州省材料产业技术研究院 | A kind of dynamic vulcanization antibacterial TPV composites and preparation method thereof |
-
2019
- 2019-08-20 CN CN201910770129.3A patent/CN110437604A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1739127A1 (en) * | 2005-07-01 | 2007-01-03 | Advanced Elastomer Systems, L.P. | Thermoplastic Vulcanizates and Sealing Devices Made Therewith |
WO2009017868A1 (en) * | 2007-07-27 | 2009-02-05 | Dow Global Technologies Inc. | Compositions of thermoplastic polyurethane (tpu), polybutadiene and polydiene-based tpu |
CN103012971A (en) * | 2012-12-04 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | EPDM/EVOH-MAA (ethylene-propylene-diene monomer/ethylene vinyl alcohol-methacrylic acid) dynamically vulcanizled thermoplastic elastomer for separating gas and resisting water vapor and preparation method thereof |
CN103709720A (en) * | 2013-11-28 | 2014-04-09 | 青岛科技大学 | Polyurethane/polylactic acid thermoplastic vulcanized rubber and preparation method thereof |
CN106939100A (en) * | 2017-04-20 | 2017-07-11 | 贵州省材料产业技术研究院 | A kind of fire-retardant TPV composites of dynamic vulcanization and preparation method thereof |
CN106939099A (en) * | 2017-04-20 | 2017-07-11 | 贵州省材料产业技术研究院 | A kind of antistatic TPV composites of dynamic vulcanization and preparation method thereof |
CN106977813A (en) * | 2017-04-20 | 2017-07-25 | 贵州省材料产业技术研究院 | A kind of dynamic vulcanization has fire-retardant TPV composites of halogen and preparation method thereof |
CN107245187A (en) * | 2017-04-20 | 2017-10-13 | 贵州省材料产业技术研究院 | A kind of dynamic vulcanization antibacterial TPV composites and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
张乃仁主编: "《设计辞典》", 31 January 2002, 北京理工大学出版社 * |
罗欣等: ""TPU/EPDM共混体系相态与力学性能的研究"", 《中国塑料》 * |
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