CN111690253A - Ethylene propylene diene monomer modified polyurethane elastomer foam material and preparation method thereof - Google Patents
Ethylene propylene diene monomer modified polyurethane elastomer foam material and preparation method thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- 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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- 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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- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
Abstract
The invention discloses an ethylene propylene diene monomer modified polyurethane elastomer foam material and a preparation method thereof, wherein the foam material comprises the following components in parts by weight: 100-150 parts of a polyurethane elastomer; 10-40 parts of ethylene propylene diene monomer; 2-6 parts of a compatibilizer; 3-30 parts of a foaming agent; 2-6 parts of an antioxidant; 1-5 parts of a foam stabilizer; wherein the TPU is a polyester TPU. The preparation method comprises the steps of mixing the polyurethane elastomer and the ethylene propylene diene monomer, adding the compatibilizer for granulation, and then adding the foaming agent, the foam stabilizer and the antioxidant for melt foaming. The ethylene propylene diene monomer modified thermoplastic polyurethane elastomer foaming material prepared by the invention has excellent performance, compared with pure TPU, the elongation at break is increased by 10%, the impact resilience is improved by about 40%, the ethylene propylene diene monomer modified thermoplastic polyurethane elastomer foaming material has higher strength, wear resistance elasticity and low temperature resistance, the rheological property and the molding processability are greatly improved, and the foaming material is lower in preparation cost and has extremely high application value.
Description
Technical Field
The invention relates to an ethylene propylene diene monomer modified polyurethane elastomer foam material and a preparation method thereof.
Background
Thermoplastic polyurethane elastomers (TPU) are high polymer materials prepared by taking oligomer polyols, polyisocyanates and chain extenders as main raw materials, and since the invention was invented in the last 40 th century, the TPU is widely applied in the fields of industry, agriculture and the like and is listed as one of five materials in the world. The molecular chain of polyurethane generally consists of two parts, namely a 'soft segment' and a 'hard segment', and because the hard segment and the soft segment are partially incompatible, a microphase separation structure which is separated from each other and is connected with each other is formed, and the unique performance causes that compared with other thermoplastic elastomers, the TPU has poor melt processability and has obvious defects in processing, and is considered to be an elastomer which is difficult to process, and the specific performance is as follows: (1) the TPU has poor flowability and is greatly influenced by temperature and pressure; (2) the TPU resin has high shearing heat and large shearing force during plasticizing; (3) the strength and the extensibility of the TPU melt are low; (4) the molten TPU resin has a strong adhesion to the metal surfaces of the machine tool making it difficult to machine.
In order to obtain the TPU material which is high temperature resistant, easy to process and form, excellent in toughness, higher in hardness, low in price and good in performance, besides continuously developing and synthesizing novel polymers, blending and modifying the known polymers becomes a highly effective way for developing high-performance polymer materials. Compared with the development of novel high molecular polymers, the modification of the known polymer has the characteristics of short period, low cost and easy industrial production. The main purposes and effects of polymer blending modification are as follows: (1) comprehensively balancing the performance of each polymer component, making up for the deficiencies of each polymer component, and eliminating the weakness of each single polymer component in performance; (2) a small amount of one polymer can be used as a modifier of another polymer, so that the modification effect is remarkable; (3) polymer processability can be improved by blending; (4) the polymer processability can meet some special requirements; (5) for some engineering plastics with excellent performance and expensive unit price, the raw material cost can be reduced by blending without influencing the use requirement.
Ethylene Propylene Diene Monomer (EPDM) is a rubber with excellent elastic property, is copolymerized by ethylene, propylene and a third elastomer, can still keep high flexibility even at a low temperature, and is an ideal elastomer similar to natural rubber (polyisoprene). By blending EPDM and TPU, the rheological property and the forming and processing performance of TPU can be improved to a certain extent. However, EPDM is a non-polar copolymer, and when it is blended with thermoplastic polyurethane elastomer (TPU), polyethylene terephthalate (PET), Polyamide (PA), etc., it is difficult to obtain a modified material having excellent properties because of differences in molecular structure, solubility parameters, polarity, etc. The compatilizer is required to be added to improve the compatibility of the ethylene propylene diene monomer modified polyurethane elastomer and the compatilizer, so that the tensile strength, the elongation at break and the processing performance of the prepared ethylene propylene diene monomer modified polyurethane elastomer are greatly improved, and the ethylene propylene diene monomer modified polyurethane elastomer has extremely important scientific significance and application value.
Disclosure of Invention
Aiming at the problems and achieving the purpose, the invention provides an ethylene propylene diene monomer modified polyurethane elastomer foaming material and a preparation method thereof. The specific technical scheme is as follows:
an ethylene propylene diene monomer modified polyurethane elastomer foaming material comprises the following components in parts by weight:
100-150 parts of a polyurethane elastomer;
10-40 parts of ethylene propylene diene monomer;
2-6 parts of a compatibilizer;
3-30 parts of a foaming agent;
2-6 parts of an antioxidant;
1-5 parts of a foam stabilizer;
wherein the TPU is a polyester TPU.
Preferably, the compatibilizer is a composite compatibilizer and is formed by compounding and blending one or more of block copolymer compatibilizer polyolefin elastomer, olefin block copolymer and styrene-butadiene block copolymer with one or more of reactive compatibilizer maleic anhydride type compatibilizer, acrylic compatibilizer, isocyanate type compatibilizer, organosilicon compatibilizer and titanate compatibilizer, wherein the ratio of the two compatibilizers is 1: 1-3.
Preferably, the foaming agent is one or more of azodicarbonamide, baking soda, calcium carbonate and expandable microspheres.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164 and antioxidant DNP.
Preferably, the foam stabilizer is polysilane-olefin oxide block copolymer silicone oil.
The preparation method of the ethylene propylene diene monomer modified polyurethane elastomer foaming material comprises the following steps:
1) preparing an EPDM/TPU mixture: weighing TPU and EPDM according to the weight parts, adding the weighed TPU and EPDM into a high-speed mixer, stirring and mixing to obtain an EPDM/TPU mixture;
2) preparation of EPDM/TPU pellets: adding a compatibilizer into the EPDM/TPU mixture obtained in the step 1), putting the mixture into a co-rotating double-screw extruder for melting, and then extruding and granulating to obtain EPDM/TPU granules;
3) preparation of EPDM/TPU foam: and 2) placing the EPDM/TPU granules obtained in the step 2) and the foaming agent, the antioxidant and the foam stabilizer in parts by weight into a heating charging barrel of an injection molding machine for melting, and then injecting into a mold to obtain a foamed product, namely the EPDM modified thermoplastic polyurethane elastomer foamed material.
According to the preferable technical scheme, in the step 1), the stirring speed of the prepared EPDM/TPU mixture is controlled to be 75-120 rpm, the temperature is controlled to be 35-60 ℃, and the stirring time is 6-12 mim.
Preferably, in the step 2), the diameter D of the screw is 35mm, the length-diameter ratio is 28:1, the melt grafting reaction is carried out from the feeding port to the machine head, and the temperature ranges from the I area to the VIII area of the machine barrel are respectively controlled to be 170 ℃, 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 190 ℃; the rotating speed of the reaction type double-screw extruder is controlled to be 110-130 rpm.
In a preferable technical scheme, in the step 3), the temperature of a machine barrel for preparing the EPDM modified polyurethane elastomer foaming material is controlled to be 190-200 ℃, and the pressure maintaining time is 10-30 s.
The invention has the beneficial effects that:
the preparation method has simple steps and easy control of the process; the ethylene propylene diene monomer and the polyurethane elastomer are blended and modified, one or more of block copolymer compatibilizer polyolefin elastomer, olefin block copolymer and styrene-butadiene block copolymer is selected to be compounded and blended with one or more of reactive compatibilizer, maleic anhydride compatibilizer, acrylic compatibilizer, isocyanate compatibilizer, organosilicon compatibilizer and titanate compatibilizer, strong polar reactive groups are introduced to improve the compatibility of a non-polar system and a polar system, so that the material has high activity and reactivity, the tensile strength, the impact strength and the elongation at break of the product are improved, and the processing rheological property is improved.
When the foaming material is prepared, the modified EPDM/TPU mixed material is prepared firstly, the compatibility of the EPDM and the TPU is improved, and then the high-performance TPU foaming material is obtained through injection foaming and one-time injection molding. The ethylene propylene diene monomer modified thermoplastic polyurethane elastomer foaming material prepared by the invention has excellent performance, compared with pure TPU, the modified TPU prepared by the invention has the advantages that the elongation at break is increased by 10 percent, the impact resilience is improved by about 40 percent, the high strength, the high wear-resisting elasticity and the high low-temperature resistance are realized, the rheological property and the molding processability are greatly improved, the preparation cost of the foaming material is low, and the application value is high.
Drawings
FIG. 1 is a schematic diagram of a preparation process of the EPDM modified polyurethane elastomer foam material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. Examples 1 to 3 are examples of preparing TPU graft-OBC modified thermoplastic polyurethane elastomer foam materials, and example 4 is an effect example.
Example 1
The embodiment is to prepare an ethylene propylene diene monomer modified polyurethane elastomer foam material, the preparation process is as shown in figure 1, and the following components are weighed according to parts by weight: 100 parts of polyurethane elastomer (TPU), 10 parts of Ethylene Propylene Diene Monomer (EPDM), 2 parts of composite compatibilizer obtained by mixing polyolefin elastomer (POE) compatibilizer and maleic anhydride compatibilizer according to the ratio of 1:1, 5 parts of baking soda foaming agent, 10102 parts of antioxidant and 1 part of polysilane-alkylene oxide block copolymer silicone oil foam stabilizer. Firstly, adding TPU and EPDM into a high-speed mixer, stirring and mixing to obtain an EPDM/TPU mixture, wherein the stirring speed is controlled to be 75rpm, the temperature is controlled to be 35 ℃, and the stirring time is 6 mim; then adding a compatibilizer, melting the mixture in a co-rotating double-screw extruder, and then extruding and granulating, wherein the diameter D of a screw is 35mm, the length-diameter ratio is 28:1, the temperatures from a barrel temperature I area to a barrel temperature VIII area (from a charging port to a machine head) of the melt grafting reaction are respectively controlled to be 170 ℃, 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 190 ℃, and the rotating speed of the reactive double-screw extruder is controlled to be 110rpm, so that EPDM/TPU granules are obtained; and finally, placing the granules, the foaming agent, the antioxidant and the foam homogenizing agent into a heating charging barrel of an injection molding machine for melting, and then injecting into a mold to obtain a foamed product, wherein the temperature of a machine barrel is controlled to be 190 ℃, and the pressure maintaining time is 10s, so that the EPDM modified thermoplastic polyurethane elastomer foamed material is obtained.
Example 2
The embodiment also prepares the ethylene propylene diene monomer modified polyurethane elastomer foam material, and the following components are weighed according to parts by weight: 120 parts of polyurethane elastomer (TPU), 15 parts of Ethylene Propylene Diene Monomer (EPDM), 3 parts of Olefin Block Copolymer (OBC) compatibilizer and 2 parts of maleic anhydride compatibilizer which are mixed according to the ratio of 1:1, 4 parts of expanded microsphere foaming agent, 10763 parts of antioxidant and 2 parts of polysilane-olefin oxide block copolymer silicone oil foam stabilizer. Firstly, adding TPU and EPDM into a high-speed mixer, stirring and mixing at the rotating speed of 800rpm for 8mim at the temperature of 45 ℃ to obtain an EPDM/TPU mixture; then adding a compatibilizer, putting the mixture into a co-rotating double-screw extruder for melting, extruding and granulating, wherein the diameter D of a screw is 35mm, the length-diameter ratio is 28:1, and the temperatures of a barrel temperature I area to a barrel temperature VIII area (from a charging port to a machine head) of the melt grafting reaction are respectively controlled at 170 ℃, 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 190 ℃; controlling the rotating speed of the reaction type double-screw extruder to be 120rpm to obtain EPDM/TPU granules; and finally, placing the granules, the foaming agent, the antioxidant and the foam homogenizing agent into a heating charging barrel of an injection molding machine for melting, and then injecting into a mold to obtain a foamed product, wherein the temperature of a machine barrel is controlled to be 195 ℃, and the pressure maintaining time is 15s, so that the EPDM modified thermoplastic polyurethane elastomer foamed material is obtained.
Example 3
The embodiment also prepares the ethylene propylene diene monomer modified polyurethane elastomer foaming material, which comprises the following components in parts by weight: 130 parts of polyurethane elastomer (TPU), 18 parts of Ethylene Propylene Diene Monomer (EPDM), 3 parts of composite compatibilizer obtained by polyolefin elastomer (POE) compatibilizer and acrylic compatibilizer according to the proportion of 1:2, 6 parts of baking soda foaming agent, 10102 parts of antioxidant and 2 parts of polysilane-alkylene oxide block copolymer silicone oil foam stabilizer. Firstly, adding TPU and EPDM into a high-speed mixer, stirring and mixing to prepare an EPDM/TPU mixture; the stirring speed was controlled at 100rpm, the temperature was controlled at 35 ℃ and the stirring time was 7 mm. Then adding a compatibilizer, melting the mixture in a co-rotating double-screw extruder, extruding and granulating, wherein the diameter D of a screw is 35mm, the length-diameter ratio is 28:1, and the temperatures of a barrel temperature I area to a barrel temperature VIII area (from a charging port to a machine head) of the melt grafting reaction are respectively controlled to be 170 ℃, 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 190 ℃; the rotational speed of the reactive twin-screw extruder was controlled to 130rpm, and EPDM/TPU pellets were obtained. And finally, placing the EPDM/TPU granules, a foaming agent, an antioxidant and a foam stabilizer into a heating charging barrel of an injection molding machine for melting, and then injecting into a mold to obtain a foamed product, wherein the temperature of the machine barrel is controlled to be 190 ℃, and the pressure maintaining time is 15s, so that the EPDM modified thermoplastic polyurethane elastomer foamed material is obtained.
Example 4 Effect example
In this example, the epdm modified polyurethane elastomer foam materials prepared in examples 1 to 3 were molded into test bars S1, S2, and S3 in an injection molding machine, and then the test bars were punched out for mechanical testing. A test specimen D was also prepared under the same preparation conditions with the same commercially available polyurethane elastomers of the same type as the test specimen. The test results are shown in table 1.
TABLE 1 mechanical test results of various test sample strips
| Item | Sample strip D | Spline S1 | Spline S2 | Spline S3 |
| Tensile stress 100% (MPa) | 8.9 | 17.2 | 15.7 | 16.9 |
| Tensile stress 300% (MPa) | 17.6 | 30.7 | 28.6 | 31.2 |
| Yield strength (MPa) | 44 | 58 | 60 | 61 |
| Elongation at Break (%) | 450 | 540 | 550 | 520 |
| Tearing (graves) (kN/m) | 102 | 111 | 115 | 114 |
| Impact resilience (%) | 45 | 72 | 69 | 72 |
| Density (g/mm3) | 1.14 | 1.04 | 1.03 | 1.02 |
As can be seen from the above table, the compatibility of the ethylene propylene diene monomer modified polyurethane elastomer prepared by the method of the invention with the polyurethane elastomer is improved by adding the compatibilizer, and compared with the common polyurethane elastomer on the market, the density is reduced, but the tensile stress is greatly improved, the tear strength is improved by about 8%, and the impact resilience is improved by about 40%. The product has excellent performance, higher impact resistance and strength.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Furthermore, it should be understood that although the present specification describes embodiments, this does not include only one embodiment, and such description is for clarity only, and those skilled in the art should be able to make the specification as a whole, and the embodiments may be appropriately combined to form other embodiments understood by those skilled in the art.
Claims (10)
1. The ethylene propylene diene monomer modified polyurethane elastomer foam material is characterized by comprising the following components in parts by weight:
100-150 parts of a polyurethane elastomer;
10-40 parts of ethylene propylene diene monomer;
2-6 parts of a compatibilizer;
3-30 parts of a foaming agent;
2-6 parts of an antioxidant;
1-5 parts of a foam stabilizer;
wherein the TPU is a polyester TPU.
2. The ethylene propylene diene monomer modified polyurethane elastomer foam material as claimed in claim 1, wherein: the compatibilizer is a composite compatibilizer and is formed by compounding and blending one or more of block copolymer compatibilizer polyolefin elastomer, olefin block copolymer and styrene-butadiene block copolymer with one or more of reactive compatibilizer, maleic anhydride compatibilizer, acrylic compatibilizer, isocyanate compatibilizer, organosilicon compatibilizer and titanate compatibilizer.
3. The ethylene propylene diene monomer modified polyurethane elastomer foam material as claimed in claim 1, wherein: the compounding and blending ratio of the composite compatibilizer is 1: 1-3.
4. The ethylene propylene diene monomer modified polyurethane elastomer foam material as claimed in claim 1, wherein: the foaming agent is one or more of azodicarbonamide, baking soda, calcium carbonate and expandable microspheres.
5. The ethylene propylene diene monomer modified polyurethane elastomer foam material as claimed in claim 1, wherein: the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164 and antioxidant DNP.
6. The ethylene propylene diene monomer modified polyurethane elastomer foam material as claimed in claim 1, wherein: the foam stabilizer is polysilane-olefin oxide segmented copolymer silicone oil.
7. A preparation method of an ethylene propylene diene monomer modified polyurethane elastomer foaming material is characterized by comprising the following steps:
1) preparing an EPDM/TPU mixture: weighing TPU and EPDM according to the weight parts, adding the weighed TPU and EPDM into a high-speed mixer, stirring and mixing to obtain an EPDM/TPU mixture;
2) preparation of EPDM/TPU pellets: adding a composite compatibilizer into the EPDM/TPU mixture obtained in the step 1), putting the mixture into a co-rotating double-screw extruder for melting, and then extruding and granulating to obtain EPDM/TPU granules;
3) preparation of EPDM/TPU foam: and 2) placing the EPDM/TPU granules obtained in the step 2) and the foaming agent, the antioxidant and the foam stabilizer in parts by weight into a heating charging barrel of an injection molding machine for melting, and then injecting into a mold to obtain a foamed product, namely the EPDM modified thermoplastic polyurethane elastomer foamed material.
8. The preparation method of the ethylene propylene diene monomer modified polyurethane elastomer foam material according to claim 4, wherein the preparation method comprises the following steps: in the step 1), the stirring speed of the prepared EPDM/TPU mixture is controlled to be 75-120 rpm, the temperature is controlled to be 35-60 ℃, and the stirring time is 6-12 mim.
9. The preparation method of the ethylene propylene diene monomer modified polyurethane elastomer foam material according to claim 4, wherein the preparation method comprises the following steps: in the step 2), the diameter D =35mm of the screw rod is used, the length-diameter ratio =28:1, the melt grafting reaction is carried out from a feed inlet to a machine head, and the temperatures from a machine barrel temperature I area to a machine barrel VIII area are respectively controlled at 170 ℃, 180 ℃, 190 ℃, 210 ℃, 200 ℃ and 190 ℃; the rotating speed of the reaction type double-screw extruder is controlled to be 110-130 rpm.
10. The preparation method of the ethylene propylene diene monomer modified polyurethane elastomer foam material according to claim 4, wherein the preparation method comprises the following steps: in the step 3), the temperature of a machine barrel for preparing the EPDM modified polyurethane elastomer foaming material is controlled to be 190-200 ℃, and the pressure maintaining time is 10-30 s.
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| CN113089480A (en) * | 2021-04-23 | 2021-07-09 | 诚邦生态环境股份有限公司 | Steel bridge deck combined paving structure and paving method thereof |
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Application publication date: 20200922 |