CN103992609A - Olefin block copolymer foam material and preparation method thereof - Google Patents
Olefin block copolymer foam material and preparation method thereof Download PDFInfo
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- CN103992609A CN103992609A CN201410213327.7A CN201410213327A CN103992609A CN 103992609 A CN103992609 A CN 103992609A CN 201410213327 A CN201410213327 A CN 201410213327A CN 103992609 A CN103992609 A CN 103992609A
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Abstract
The invention provides an olefin block copolymer foam material and a preparation method thereof. The material is prepared from the following components in parts by weight: 80-100 parts of olefin block copolymer, 10-30 parts of filler, 4-7 parts of foamer, 0.5-1.0 part of crosslinking agent, 05-1.2 parts of crosslinking assistant and 1.0-1.8 parts of lubricant. The preparation method comprises the following steps: putting olefin block copolymer resin and the filler in an internal mixer to be uniformly mixed; then, putting the assistants such as the foamer, the crosslinking agent and the crosslinking assistant into the internal mixer to be fully mixed; pouring out the mixed materials and immediately carrying out secondary blending on an opened plastifying machine; and discharging slices after uniform blending, and putting in a flat die of a vulcanizing machine to press moulds, vulcanize and foam, thus preparing the thermoplastic polyolefin block copolymer foam material. The preparation method provided by the invention is simple and easy to operate, and the foam material has the advantages of high flexibility, excellent heat resistance, good wear resistance and the like and is excellent in elastic recovery and compression deformation performance.
Description
[technical field]
The invention belongs to polymeric material field, be specifically related to a kind of olefin block copolymers foam materials and preparation method thereof.
[background technology]
Olefin block copolymers (OBCs) be Dow Chemical with catalysis block copolymerization technological development, its segmented copolymer has the molecular chain that replaces block hard and that soft chain segment forms.Compare with other existing polyolefin elastomers (POE), olefin block copolymers (OBCs) has the advantage of following uniqueness: the balance between flexibility and resistance to elevated temperatures is better; Under room temperature and high temperature, all there is better elastic recovery and compressive set performance; Tc is higher, shortens the process-cycle; Wear resisting property is higher.These advantages make olefin block copolymers (OBCs) can be used as the extraordinary surrogate of a lot of soft polymers, as styrene block copolymer (SEBS), ethylene vinyl acetate (EVA), Thermoplastic Vulcanizate, flexible polyolefins ethylene-octene copolymer (POE) etc.Present stage mainly concentrates on resins for universal use as the toughening modifying of the materials such as polypropylene, olefin block copolymers (OBCs) base material is carried out to the aspects such as graft modification by grafted monomer to the applied research of olefin block copolymers (OBCs).
OBCs had both had plastomer and elastomeric flexible, the thermotolerance also with high density polyethylene(HDPE), material property for this novelty, it is made to the probe into application in foaming technique field, can solve prior elastic body foam materials, as the elastic resins such as ethylene-octene copolymer (POE), terpolymer EP rubber (EPDM), thermoplastic elastomer (TPE) foam after foam materials thermo-labile, the defect such as Compression Set is poor.
[summary of the invention]
One of the technical problem to be solved in the present invention, is to provide a kind of olefin block copolymers foam materials, and this foam materials has the advantages such as high-flexibility, thermotolerance is good, wear resistance is good, and elastic recovery and compressive set excellent performance.
The present invention realizes one of above-mentioned technical problem like this:
An olefin block copolymers foam materials, this foam materials is made by the raw material that comprises following weight part proportioning:
Further, described olefin block copolymers be shore hardness between 60-80A, DSC fusing point in 118-125 ℃, melt flow rate (MFR) 0.5～5.0g/10min.
Further, described weighting agent is one or both in talcum powder and calcium carbonate; Described lubricant is one or both in stearic acid and unsaturated fatty acids zinc.
Further, described whipping agent is Cellmic C 121,4, at least one in 4-OBSH, p-toluene sulfonylsemicarbazide.
Further, described linking agent is one or both in dual-tert-butyl peroxidation isopropyl benzene and dicumyl peroxide; Described crosslinking coagent is at least one in cyanacrylate, triallyl cyanurate, trimethylolpropane trimethacrylate, 1,6 hexanediol diacrylate.
Two of the technical problem to be solved in the present invention, be to provide a kind of preparation method of olefin block copolymers foam materials, the method is simple to operation, and the foam materials of preparation has the advantages such as high-flexibility, thermotolerance is good, wear resistance is good, and elastic recovery and compressive set excellent performance.
The present invention realizes two of above-mentioned technical problem like this:
A preparation method for olefin block copolymers foam materials, the preparation method of this foam materials is as follows:
1) olefin block copolymers resin and weighting agent are together dropped in Banbury mixer mixing evenly after, then whipping agent, linking agent, crosslinking coagent, lubricant are dropped in Banbury mixer and together to carry out first mixing with material;
2) material after mixing is for the first time poured out, proceeded to open refining broken-(down)rubber machine and carry out mixing for the second time;
3) for the second time mixing evenly after slice, weigh and pack in vulcanizer and carry out molded vulcanization foaming in flat plate mold, obtain olefin block copolymers foam materials;
The weight part proportioning of above-mentioned each raw material is as follows:
Further, described mixing mixing time is for the first time 10～15min, and melting temperature is 118～135 ℃; Described mixing mixing time is for the second time 8～10min, and melting temperature is 110～120 ℃; The described sulfur foam time is 30～35min, and mold pressing air pressure is 0.7～0.8MPa.Flat plate mold thickness is 2.0～3.0cm.
Further, described olefin block copolymers be shore hardness between 60-80A, DSC fusing point in 118-125 ℃, melt flow rate (MFR) 0.5～5.0g/10min.
Further, described weighting agent is one or both in talcum powder and calcium carbonate; Described lubricant is one or both in stearic acid and unsaturated fatty acids zinc; Described whipping agent is Cellmic C 121,4, at least one in 4-OBSH, p-toluene sulfonylsemicarbazide.
Further, described linking agent is one or both in dual-tert-butyl peroxidation isopropyl benzene and dicumyl peroxide; Described crosslinking coagent is at least one in cyanacrylate, triallyl cyanurate, trimethylolpropane trimethacrylate, 1,6 hexanediol diacrylate.
Tool of the present invention has the following advantages:
The present invention has realized the application of olefin block copolymers (OBCs) in foaming technique field by the combination of formula and operational path, the mechanical property that the olefin block copolymers foam materials of preparation shows under certain foam expansion, as elongation at break, elastic recovery, thermotolerance, compression set performance, it is similar soft polymer (ethylene-octene copolymer POE) incomparable characteristic under equal foam expansion, this characteristic will directly be improved existing traditional flexible foams defect, as caused greatly foam articles low work-ing life because of tension set, picture traditional E VA molded shoe pad, and because material thermal resistance is poor, cause in processing or applied at elevated temperature environment the problems such as poor dimensional stability, the easy incipient scorch of material, as secondary press abnormity toy, sound-insulating and heat-insulating foam etc.Outside it, the olefin block copolymers of preparation (OBCs) foam materials has obvious antiskid property and rubber sense allows this material become to substitute the rubbery foam of traditional price costliness to become possibility.
[embodiment]
The present invention relates to a kind of olefin block copolymers foam materials, this foam materials is made by the raw material that comprises following weight part proportioning:
Described olefin block copolymers be shore hardness between 60-80A, DSC fusing point in 118-125 ℃, melt flow rate (MFR) 0.5～5.0g/10min (according to ASTM D-1238,190 ℃/2.16Kg records); Described weighting agent is one or both in talcum powder and calcium carbonate; Described lubricant is one or both in stearic acid and unsaturated fatty acids zinc; Described whipping agent is Cellmic C 121,4, at least one in 4-OBSH, p-toluene sulfonylsemicarbazide.
Described linking agent is one or both in dual-tert-butyl peroxidation isopropyl benzene and dicumyl peroxide; Described crosslinking coagent is at least one in cyanacrylate, triallyl cyanurate, trimethylolpropane trimethacrylate, 1,6 hexanediol diacrylate.
The invention still further relates to the preparation method of above-mentioned a kind of olefin block copolymers foam materials, the preparation method of this foam materials is as follows:
1) olefin block copolymers resin and weighting agent are together dropped in Banbury mixer mixing evenly after, then whipping agent, linking agent, crosslinking coagent, lubricant are dropped in Banbury mixer and together to carry out first mixing with material;
2) material after mixing is for the first time poured out, proceeded to open refining broken-(down)rubber machine and carry out mixing for the second time;
3) for the second time mixing evenly after slice, weigh and pack in vulcanizer and carry out molded vulcanization foaming in flat plate mold, obtain olefin block copolymers foam materials;
The weight part proportioning of above-mentioned each raw material is as follows:
Described mixing mixing time is for the first time 10～15min, and melting temperature is 118～135 ℃; Described mixing mixing time is for the second time 8～10min, and melting temperature is 110～120 ℃; The described sulfur foam time is 30～35min, and mold pressing air pressure is 0.7～0.8MPa.Flat plate mold thickness is 2.0～3.0cm.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment mono-
Olefin block copolymers (OBCs) foam materials, this foam materials is made by following raw material:
Above-mentioned olefin block copolymers (OBCs), model INFUSE9500, purchased from Dow Chemical company; Talcum powder DH1250, purchased from the ultra-fine calcium powder of Youxi County Rong Xin factory; Cellmic C 121, purchased from Longhua, Longyan Chemical Co., Ltd.; Dicumyl peroxide (DCP), purchased from Akzo Nobel's chemical company limited; Cyanacrylate (TAIC), purchased from Shanghai, Fang Rui reaches Chemical Co., Ltd.; Stearic acid, commercially available.
The method that above-mentioned raw materials is prepared foam materials is as follows:
1) olefin block copolymers (OBCs) resin and talcum powder are together dropped in Banbury mixer mixing even, again Cellmic C 121, dicumyl peroxide, cyanacrylate (TAIC), stearic acid are together dropped into carry out together with material in Banbury mixer mixing, mixing time 15min, 130 ℃ of melting temperatures;
2) material after mixing is for the first time poured out, move into rapidly open refining broken-(down)rubber machine carry out mixing for the second time, mixing time 10min, 120 ℃ of melting temperatures;
3) for the second time mixing evenly after slice, slice thickness is 0.8-1.0mm, weigh and pack in vulcanizer and carry out molded vulcanization foaming in flat plate mold, flat plate mold thickness 2.0cm, sulfur foam time 30min, sulfuration air pressure 0.70-0.75MPa, obtains olefin block copolymers (OBCs) foam materials.Normal temperature is parked after cooling 24 hours, carries out physical properties test.Its physicals of the prepared foam material of the present embodiment is as following table 1:
Table 1
| Project | Testing standard | Unit | Performance |
| Shore hardness | GB/T10807-2006 | SHOREA | 30-35 |
| Density | GBT6343-2009 | g/cm 3 | 0.125 |
| Impact rebound degree | GB/T1681-2009 | ％ | 55 |
| Compression Set | GB/T6669-2008 | ％ | 30 |
| Elongation at break | GB/T6344-2008 | ％ | 280 |
Embodiment bis-
Olefin block copolymers (OBCs) foam materials, this foam material is made by following raw material:
Above-mentioned olefin block copolymers (OBCs), model INFUSE9100, purchased from Dow Chemical company; Calcium carbonate, purchased from Fujian agriculture-countryside-farmer Chemical Co., Ltd.; 4,4-OBSH, import; Dual-tert-butyl peroxidation isopropyl benzene (BIPB), purchased from Akzo Nobel's chemical company limited; 1,6 hexanediol diacrylate (HDDA), commercially available; Stearic acid, commercially available.
The method that above-mentioned raw materials is prepared foam materials is as follows:
1) olefin block copolymers (OBCs) resin and talcum powder are together dropped in Banbury mixer mixing even, by Cellmic C 121, dicumyl peroxide, cyanacrylate (TAIC), stearic acid together drop into carry out together with material in Banbury mixer mixing, mixing time 8min, 125 ℃ of melting temperatures;
2) material after mixing is for the first time poured out, move into rapidly open refining broken-(down)rubber machine carry out mixing for the second time, mixing time 8min, 115 ℃ of melting temperatures;
3) for the second time mixing evenly after slice, slice thickness is 0.6-0.8mm, weigh and pack in vulcanizer and carry out molded vulcanization foaming in flat plate mold, flat plate mold thickness 2.5cm, sulfur foam time 35min, sulfuration air pressure 0.75MPa, obtains olefin block copolymers (OBCs) foam materials.Normal temperature is parked after cooling 24 hours, carries out physical properties test.Its physicals of the prepared foam material of the present embodiment is as following table 2:
Table 2
| Project | Testing standard | Unit | Performance |
| Shore hardness | GB/T10807-2006 | SHOREA | 25-30 |
| Density | GBT6343-2009 | g/cm 3 | 0.108 |
| Impact rebound degree | GB/T1681-2009 | ％ | 62 |
| Compression Set | GB/T6669-2008 | ％ | 35 |
| Elongation at break | GB/T6344-2008 | ％ | 310 |
In summary, the present invention has realized the application of olefin block copolymers (OBCs) in foaming technique field by the combination of formula and operational path, the mechanical property that the olefin block copolymers foam materials of preparation shows under certain foam expansion, as elongation at break, elastic recovery, thermotolerance, compression set performance, it is similar soft polymer (ethylene-octene copolymer POE) incomparable characteristic under equal foam expansion, this characteristic will directly be improved existing traditional flexible foams defect, as caused greatly foam articles low work-ing life because of tension set, picture traditional E VA molded shoe pad, and because material thermal resistance is poor, cause in processing or applied at elevated temperature environment the problems such as poor dimensional stability, the easy incipient scorch of material, as secondary press abnormity toy, sound-insulating and heat-insulating foam etc.Outside it, the olefin block copolymers of preparation (OBCs) foam materials has obvious antiskid property and rubber sense allows this material become to substitute the rubbery foam of traditional price costliness to become possibility.
Although more than described the specific embodiment of the present invention; but being familiar with those skilled in the art is to be understood that; our described specific embodiment is illustrative; rather than for the restriction to scope of the present invention; those of ordinary skill in the art are in equivalent modification and the variation done according to spirit of the present invention, all should be encompassed in the scope that claim of the present invention protects.
Claims (10)
1. an olefin block copolymers foam materials, is characterized in that: this foam materials is made by the raw material that comprises following weight part proportioning:
2. a kind of olefin block copolymers foam materials according to claim 1, is characterized in that: described olefin block copolymers be shore hardness between 60-80A, DSC fusing point in 118-125 ℃, melt flow rate (MFR) 0.5～5.0g/10min.
3. a kind of olefin block copolymers foam materials according to claim 1 and 2, is characterized in that: described weighting agent is one or both in talcum powder and calcium carbonate; Described lubricant is one or both in stearic acid and unsaturated fatty acids zinc.
4. a kind of olefin block copolymers foam materials according to claim 1 and 2, is characterized in that: described whipping agent is Cellmic C 121,4, at least one in 4-OBSH, p-toluene sulfonylsemicarbazide.
5. a kind of olefin block copolymers foam materials according to claim 1 and 2, is characterized in that: described linking agent is one or both in dual-tert-butyl peroxidation isopropyl benzene and dicumyl peroxide; Described crosslinking coagent is at least one in cyanacrylate, triallyl cyanurate, trimethylolpropane trimethacrylate, 1,6 hexanediol diacrylate.
6. a preparation method for olefin block copolymers foam materials, is characterized in that: the preparation method of this foam materials is as follows:
1) olefin block copolymers resin and weighting agent are together dropped in Banbury mixer mixing evenly after, then whipping agent, linking agent, crosslinking coagent, lubricant are dropped in Banbury mixer and together to carry out first mixing with material;
2) material after mixing is for the first time poured out, proceeded to open refining broken-(down)rubber machine and carry out mixing for the second time;
3) for the second time mixing evenly after slice, weigh and pack in vulcanizer and carry out molded vulcanization foaming in flat plate mold, obtain olefin block copolymers foam materials;
The weight part proportioning of above-mentioned each raw material is as follows:
7. the preparation method of a kind of olefin block copolymers foam materials according to claim 6, is characterized in that: described mixing mixing time is for the first time 10～15min, and melting temperature is 118～135 ℃; Described mixing mixing time is for the second time 8～10min, and melting temperature is 110～120 ℃; The described sulfur foam time is 30～35min, and mold pressing air pressure is 0.7～0.8MPa.Flat plate mold thickness is 2.0～3.0cm.
8. the preparation method of a kind of olefin block copolymers foam materials according to claim 7, it is characterized in that: described olefin block copolymers is that shore hardness is between 60-80A, DSC fusing point in 118-125 ℃, melt flow rate (MFR) 0.5～5.0g/10min.
9. according to the preparation method of a kind of olefin block copolymers foam materials described in claim 6～8 any one, it is characterized in that: described weighting agent is one or both in talcum powder and calcium carbonate; Described lubricant is one or both in stearic acid and unsaturated fatty acids zinc; Described whipping agent is Cellmic C 121,4, at least one in 4-OBSH, p-toluene sulfonylsemicarbazide.
10. according to the preparation method of a kind of olefin block copolymers foam materials described in claim 6～8 any one, it is characterized in that: described linking agent is one or both in dual-tert-butyl peroxidation isopropyl benzene and dicumyl peroxide; Described crosslinking coagent is at least one in cyanacrylate, triallyl cyanurate, trimethylolpropane trimethacrylate, 1,6 hexanediol diacrylate.
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Cited By (7)
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| CN105199298A (en) * | 2015-10-28 | 2015-12-30 | 辽宁石油化工大学 | Olefin blocked copolymer foam material |
| CN105801755A (en) * | 2014-12-04 | 2016-07-27 | 财团法人工业技术研究院 | Modified polyolefins, methods of forming the same, and blends thereof |
| CN106349633A (en) * | 2016-08-28 | 2017-01-25 | 福建晋江市山水鞋材有限公司 | High-fitting TPE (thermoplastic elastomer) foam material as well as preparation method and application thereof |
| CN111592721A (en) * | 2020-05-25 | 2020-08-28 | 南京金陵塑胶化工有限公司 | Propylene-based elastomer composition and preparation method thereof |
| CN112521711A (en) * | 2019-09-19 | 2021-03-19 | 台橡股份有限公司 | Thermoplastic elastomer composition, foamed material thereof and manufacturing method thereof |
| CN112920539A (en) * | 2021-03-30 | 2021-06-08 | 京泰控股集团有限公司 | Soft material for sofa seat |
| CN115028955A (en) * | 2022-05-24 | 2022-09-09 | 江苏集萃先进高分子材料研究所有限公司 | Olefin block copolymer foam material, preparation method and performance prediction method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105801755A (en) * | 2014-12-04 | 2016-07-27 | 财团法人工业技术研究院 | Modified polyolefins, methods of forming the same, and blends thereof |
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| CN105199298A (en) * | 2015-10-28 | 2015-12-30 | 辽宁石油化工大学 | Olefin blocked copolymer foam material |
| CN106349633A (en) * | 2016-08-28 | 2017-01-25 | 福建晋江市山水鞋材有限公司 | High-fitting TPE (thermoplastic elastomer) foam material as well as preparation method and application thereof |
| CN112521711A (en) * | 2019-09-19 | 2021-03-19 | 台橡股份有限公司 | Thermoplastic elastomer composition, foamed material thereof and manufacturing method thereof |
| CN111592721A (en) * | 2020-05-25 | 2020-08-28 | 南京金陵塑胶化工有限公司 | Propylene-based elastomer composition and preparation method thereof |
| CN112920539A (en) * | 2021-03-30 | 2021-06-08 | 京泰控股集团有限公司 | Soft material for sofa seat |
| CN115028955A (en) * | 2022-05-24 | 2022-09-09 | 江苏集萃先进高分子材料研究所有限公司 | Olefin block copolymer foam material, preparation method and performance prediction method |
| CN115028955B (en) * | 2022-05-24 | 2023-08-18 | 江苏集萃先进高分子材料研究所有限公司 | Olefin block copolymer foaming material, preparation method and performance prediction method |
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Application publication date: 20140820 |