CN106009315A - Pre-dispersion masterbatch particle for high-performance microbead foaming agent and preparation method of pre-dispersion masterbatch particle - Google Patents
Pre-dispersion masterbatch particle for high-performance microbead foaming agent and preparation method of pre-dispersion masterbatch particle Download PDFInfo
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- 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
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- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- 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
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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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
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Abstract
The invention discloses a pre-dispersion masterbatch particle for a high-performance microbead foaming agent and a preparation method of the pre-dispersion masterbatch particle. The pre-dispersion masterbatch particle is prepared from the following components: 58 to 62 parts of a microbead foaming agent, 25 to 30 parts of a poly-hydrocarbon oligomer, 3 to 7 parts of stearic acid, 4 to 8 parts of a zinc fatty acid soap mixture and 2 to 6 parts of naphthenic rubber oil, wherein the microbead foaming agent consists of a plurality of dispersed microbeads; each microbead comprises a shell and a foaming agent body coated with the shell; each shell is made from thermoplastic resin; each foaming agent body consists of isobutene or isopentane. The poly-hydrocarbon oligomer is added to realize in-situ compatibility and modification of the microbead shell material of the microbead foaming agent, stearic acid, zinc fatty acid soap mixture and naphthenic rubber oil are added, and the microbead foaming agent is prepared into the form of the pre-dispersion masterbatch particle, so that such common technical problems as high probability of aggregation and difficult dispersion when the microbead foaming agent is directly put into rubber can be solved effectively, dust pollution is reduced, the environment is improved, and the requirement for 'green chemical industry' is satisfied.
Description
Technical field
The present invention relates to rubber chemicals and preparing technical field thereof, specifically a kind of high-performance pre-dispersed masterbatch particles of microsphere foaming agent and preparation method thereof.
Background technology
Microsphere foaming agent (DU) is thermal expansion type microspheres capsule, is a kind of unconventional physical blowing agent, is made up of multiple microspheres, and each microsphere is made up of the foaming agent of shell and Nei Bao, it is desirable to the softening point of shell is higher than the softening point of foaming agent.
Microsphere foaming agent is because of its stable foam characteristics, relatively low commercial cost, and is widely used in every field, such as printing-ink, coating, fluid sealant, the extrusion of thermoplastic and injection mo(u)lding, sole, the firming agent etc. of paper product.Microsphere foaming agent can obtain controlled abscess-size and hole-closing structure foamed shoe sole in polyurethane；In microfluid, microsphere foaming agent can be applicable to the pattern printing combining in the photoetching of self-assembling technique and micro-contact printing.
Though microsphere foaming agent brings great benefit for rubber foamed product and processing thereof, but microsphere foaming agent is a kind of powder auxiliary agent, in the preparation of rubber foamed product, microsphere foaming agent there is problems of the common technology problems such as dust is big, easily reunite, interpolation consumption is big.
Summary of the invention
The technical problem to be solved is: for the deficiencies in the prior art, it is provided that a kind of high-performance pre-dispersed masterbatch particles of microsphere foaming agent and preparation method thereof.
The present invention solves the technical scheme that above-mentioned technical problem used: the pre-dispersed masterbatch particles of high-performance microsphere foaming agent, count by weight, consisting of of this masterbatch particles: microsphere foaming agent 58～62 parts, poly-hydro carbons oligomer 25～30 parts, stearic acid 3～7 parts, the mixture 4 of fatty acid zinc soap～8 parts, naphthenic rubber oil 2～6 parts；Described microsphere foaming agent is made up of multiple scattered microspheres, and each microsphere includes shell and the foaming agent body being coated in described shell, and described shell is made up of thermoplastic resin, and described foaming agent body is made up of iso-butane or isopentane.
As preferably, described thermoplastic resin is vinylidene chloride based copolymer, acrylic copolymer or acrylic acid series copolymer.
As preferably, the particle diameter of the microsphere of the microsphere foaming agent described in composition is 5～100 μm.
As preferably, described poly-hydro carbons oligomer is any one in EP rubbers, natural rubber and Low Density Polyethylene.
As preferably, described EP rubbers is ethylene propylene diene rubber and/or ethylene propylene monomer.
As preferably, described EP rubbers be ethylene propylene diene rubber and ethylene propylene monomer with (5～10): the weight ratio of (3～7) mixes.
As preferably, count by weight, consisting of of this masterbatch particles: microsphere foaming agent 60 parts, ethylene propylene diene rubber 28 parts, stearic acid 4 parts, 5 parts of the mixture of fatty acid zinc soap, naphthenic rubber oil 3 parts.Or, as preferably, count by weight, consisting of of this masterbatch particles: microsphere foaming agent 59 parts, ethylene propylene diene rubber 18 parts, ethylene propylene monomer 13 parts, stearic acid 3 parts, 4 parts of the mixture of fatty acid zinc soap, naphthenic rubber oil 3 parts.
As preferably, the mixture of described fatty acid zinc soap is saturated and the mixture of unsaturated fatty acid zinc soap.
The preparation method of the above-mentioned high-performance pre-dispersed masterbatch particles of microsphere foaming agent, comprises the following steps:
(1) weigh according to proportion speed prepare masterbatch particles needed for each raw material；
(2) each raw material is put in banbury or mill, mixing at 35～45 DEG C, drop temperature 45 DEG C with bottom discharge, obtain sizing material；
(3) by mixing rear gained sizing material feeding to extruder, the temperature control region of this extruder is divided into seven sections from charging aperture to discharging opening, wherein the temperature of first paragraph is 25～35 DEG C, the temperature of second segment to the 7th section is 35～45 DEG C, extruding pelletization, sizing material is filtered by the drainage screen using 160 mesh during extruding pelletization, finally gives the high-performance pre-dispersed masterbatch particles of microsphere foaming agent.
Compared with prior art, it is an advantage of the current invention that:
(1) present invention carries out In Situ Compatibilization modification by adding poly-hydro carbons oligomer to the microsphere sheathing material of microsphere foaming agent, add stearic acid simultaneously, the mixture of fatty acid zinc soap and naphthenic rubber oil, microsphere foaming agent is made pre-dispersed masterbatch particles form, can effectively solve microsphere foaming agent to be directly thrown to present in rubber easily reunite, the common technology problem of difficulties in dispersion, this high-performance pre-dispersed masterbatch particles of microsphere foaming agent can significantly reduce the interpolation consumption of microsphere foaming agent in rubber, increase the cubical expansivity of microsphere foaming agent, and obtain the rubber with excellent allocation performance and dispersive property；
(2) foaming agent body is wrapped in masterbatch particles by the high-performance pre-dispersed masterbatch particles of microsphere foaming agent of the present invention, in follow-up use, it is convenient, accurately to weigh, and do not affect the performance of the good foam characteristics of microsphere foaming agent, it is effectively reduced dust pollution simultaneously, improve environment, meet the requirement of " green chemical industry "；
(3) preparation method of the present invention is easy, workable, first raw material is carried out low temperature mixing and control the drop temperature of sizing material in banbury or mill, again by sizing material extruding pelletization in an extruder, and while extruding pelletization, strictly control the temperature in each section of temperature control region of extruder, use the drainage screen of 160 mesh that sizing material is filtered during extruding pelletization simultaneously, when guaranteeing extruding pelletization, impurity and dust are filtered, make finally to prepare high-performance microsphere foaming agent pre-dispersed masterbatch particles component uniform, quality is high, subsequent applications can improve quality and the precision of rubber extruding goods, improve its yield rate.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent of embodiment one, counts, consisting of of this masterbatch particles: microsphere foaming agent 60 parts, ethylene propylene diene rubber 28 parts, stearic acid 4 parts, 5 parts of the mixture of fatty acid zinc soap by weight, naphthenic rubber oil 3 parts；Microsphere foaming agent is made up of the microsphere that multiple scattered particle diameters are 50～60 μm, and each microsphere includes shell and cladding foaming agent body in the enclosure, and shell is made up of vinylidene chloride based copolymer, and foaming agent body is made up of iso-butane.The preparation method of this masterbatch particles, comprises the following steps:
(1) weigh according to proportion speed prepare masterbatch particles needed for each raw material；
(2) each raw material is put in banbury or mill, mixing at 35～45 DEG C, drop temperature 45 DEG C with bottom discharge, obtain sizing material；
(3) by mixing rear gained sizing material feeding to extruder, the temperature control region of this extruder is divided into seven sections from charging aperture to discharging opening, wherein the temperature of first paragraph is 30 DEG C, the temperature of second segment to the 7th section is 40 DEG C, extruding pelletization, sizing material is filtered by the drainage screen using 160 mesh during extruding pelletization, finally gives the high-performance pre-dispersed masterbatch particles of microsphere foaming agent.After testing, density during this masterbatch particles 20 DEG C is 0.89 g/cm3, the Mooney viscosity ML(1+4 of 50 DEG C) and it is 70.21.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent of embodiment two, counts, consisting of of this masterbatch particles: microsphere foaming agent 61 parts, natural rubber 26 parts, stearic acid 5 parts by weight, saturated and 4 parts of the mixture of unsaturated fatty acid zinc soap, naphthenic rubber oil 4 parts；Microsphere foaming agent is made up of the microsphere that multiple scattered particle diameters are 55～65 μm, and each microsphere includes shell and cladding foaming agent body in the enclosure, and shell is made up of acrylic copolymer, and foaming agent body is made up of isopentane.The preparation method of this masterbatch particles, comprises the following steps:
(1) weigh according to proportion speed prepare masterbatch particles needed for each raw material；
(2) each raw material is put in banbury or mill, mixing at 35～45 DEG C, drop temperature 45 DEG C with bottom discharge, obtain sizing material；
(3) by mixing rear gained sizing material feeding to extruder, the temperature control region of this extruder is divided into seven sections from charging aperture to discharging opening, wherein the temperature of first paragraph is 28 DEG C, the temperature of second segment to the 7th section is 42 DEG C, extruding pelletization, sizing material is filtered by the drainage screen using 160 mesh during extruding pelletization, finally gives the high-performance pre-dispersed masterbatch particles of microsphere foaming agent.After testing, density during this masterbatch particles 20 DEG C is 0.90 g/cm3, the Mooney viscosity ML(1+4 of 50 DEG C) and it is 69.45.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent of embodiment three, counts, consisting of of this masterbatch particles: microsphere foaming agent 59 parts by weight, ethylene propylene diene rubber 18 parts, ethylene propylene monomer 13 parts, stearic acid 3 parts, 4 parts of the mixture of fatty acid zinc soap, naphthenic rubber oil 3 parts；Microsphere foaming agent is made up of the microsphere that multiple scattered particle diameters are 60～70 μm, and each microsphere includes shell and cladding foaming agent body in the enclosure, and shell is made up of acrylic acid series copolymer, and foaming agent body is made up of isopentane.The preparation method of this masterbatch particles, comprises the following steps:
(1) weigh according to proportion speed prepare masterbatch particles needed for each raw material；
(2) each raw material is put in banbury or mill, mixing at 35～45 DEG C, drop temperature 45 DEG C with bottom discharge, obtain sizing material；
(3) by mixing rear gained sizing material feeding to extruder, the temperature control region of this extruder is divided into seven sections from charging aperture to discharging opening, wherein the temperature of first paragraph is 29 DEG C, the temperature of second segment to the 7th section is 41 DEG C, extruding pelletization, sizing material is filtered by the drainage screen using 160 mesh during extruding pelletization, finally gives the high-performance pre-dispersed masterbatch particles of microsphere foaming agent.After testing, density during this masterbatch particles 20 DEG C is 0.87 g/cm3, the Mooney viscosity ML(1+4 of 50 DEG C) and it is 70.02.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent of embodiment four, counts, consisting of of this masterbatch particles: microsphere foaming agent 58 parts by weight, Low Density Polyethylene 27 parts, stearic acid 5 parts, saturated and 6 parts of the mixture of unsaturated fatty acid zinc soap, naphthenic rubber oil 4 parts；Microsphere foaming agent is made up of the microsphere that multiple scattered particle diameters are 70～80 μm, and each microsphere includes shell and cladding foaming agent body in the enclosure, and shell is made up of vinylidene chloride based copolymer, and foaming agent body is made up of iso-butane.The preparation method of this masterbatch particles, comprises the following steps:
(1) weigh according to proportion speed prepare masterbatch particles needed for each raw material；
(2) each raw material is put in banbury or mill, mixing at 35～45 DEG C, drop temperature 45 DEG C with bottom discharge, obtain sizing material；
(3) by mixing rear gained sizing material feeding to extruder, the temperature control region of this extruder is divided into seven sections from charging aperture to discharging opening, wherein the temperature of first paragraph is 31 DEG C, the temperature of second segment to the 7th section is 39 DEG C, extruding pelletization, sizing material is filtered by the drainage screen using 160 mesh during extruding pelletization, finally gives the high-performance pre-dispersed masterbatch particles of microsphere foaming agent.After testing, density during this masterbatch particles 20 DEG C is 0.91 g/cm3, the Mooney viscosity ML(1+4 of 50 DEG C) and it is 72.39.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent of embodiment five, counts, consisting of of this masterbatch particles: microsphere foaming agent 62 parts, ethylene propylene monomer 25 parts, stearic acid 3 parts, 4 parts of the mixture of fatty acid zinc soap by weight, naphthenic rubber oil 6 parts；Microsphere foaming agent is made up of the microsphere that multiple scattered particle diameters are 5～40 μm, and each microsphere includes shell and cladding foaming agent body in the enclosure, and shell is made up of acrylic acid series copolymer, and foaming agent body is made up of isopentane.The preparation method of this masterbatch particles, comprises the following steps:
(1) weigh according to proportion speed prepare masterbatch particles needed for each raw material；
(2) each raw material is put in banbury or mill, mixing at 35～45 DEG C, drop temperature 45 DEG C with bottom discharge, obtain sizing material；
(3) by mixing rear gained sizing material feeding to extruder, the temperature control region of this extruder is divided into seven sections from charging aperture to discharging opening, wherein the temperature of first paragraph is 27 DEG C, the temperature of second segment to the 7th section is 38 DEG C, extruding pelletization, sizing material is filtered by the drainage screen using 160 mesh during extruding pelletization, finally gives the high-performance pre-dispersed masterbatch particles of microsphere foaming agent.After testing, density during this masterbatch particles 20 DEG C is 0.89 g/cm3, the Mooney viscosity ML(1+4 of 50 DEG C) and it is 70.83.
Claims (10)
1. the pre-dispersed masterbatch particles of high-performance microsphere foaming agent, it is characterised in that count by weight, consisting of of this masterbatch particles: microsphere foaming agent 58～62 parts, poly-hydro carbons oligomer 25～30 parts, stearic acid 3～7 parts, the mixture 4 of fatty acid zinc soap～8 parts, naphthenic rubber oil 2～6 parts；Described microsphere foaming agent is made up of multiple scattered microspheres, and each microsphere includes shell and the foaming agent body being coated in described shell, and described shell is made up of thermoplastic resin, and described foaming agent body is made up of iso-butane or isopentane.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent the most according to claim 1, it is characterised in that described thermoplastic resin is vinylidene chloride based copolymer, acrylic copolymer or acrylic acid series copolymer.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent the most according to claim 1, it is characterised in that the particle diameter of the microsphere of the microsphere foaming agent described in composition is 5～100 μm.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent the most according to claim 1, it is characterised in that described poly-hydro carbons oligomer is any one in EP rubbers, natural rubber and Low Density Polyethylene.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent the most according to claim 4, it is characterised in that described EP rubbers is ethylene propylene diene rubber and/or ethylene propylene monomer.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent the most according to claim 5, it is characterised in that described EP rubbers be ethylene propylene diene rubber and ethylene propylene monomer with (5～10): the weight ratio of (3～7) mixes.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent the most according to claim 4, it is characterised in that count by weight, consisting of of this masterbatch particles: microsphere foaming agent 60 parts, ethylene propylene diene rubber 28 parts, stearic acid 4 parts, 5 parts of the mixture of fatty acid zinc soap, naphthenic rubber oil 3 parts.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent the most according to claim 4, it is characterized in that, count by weight, consisting of of this masterbatch particles: microsphere foaming agent 59 parts, ethylene propylene diene rubber 18 parts, ethylene propylene monomer 13 parts, stearic acid 3 parts, 4 parts of the mixture of fatty acid zinc soap, naphthenic rubber oil 3 parts.
The high-performance pre-dispersed masterbatch particles of microsphere foaming agent the most according to claim 1, it is characterised in that the mixture of described fatty acid zinc soap is saturated and the mixture of unsaturated fatty acid zinc soap.
10. the preparation method of the high-performance pre-dispersed masterbatch particles of microsphere foaming agent according to any one of claim 1-9, it is characterised in that comprise the following steps:
(1) weigh according to proportion speed prepare masterbatch particles needed for each raw material；
(2) each raw material is put in banbury or mill, mixing at 35～45 DEG C, drop temperature 45 DEG C with bottom discharge, obtain sizing material；
(3) by mixing rear gained sizing material feeding to extruder, the temperature control region of this extruder is divided into seven sections from charging aperture to discharging opening, wherein the temperature of first paragraph is 25～35 DEG C, the temperature of second segment to the 7th section is 35～45 DEG C, extruding pelletization, sizing material is filtered by the drainage screen using 160 mesh during extruding pelletization, finally gives the high-performance pre-dispersed masterbatch particles of microsphere foaming agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912510A (en) * | 2018-07-24 | 2018-11-30 | 四川宏亿复合材料工程技术有限公司 | A kind of Foamed rubber plate and its preparation process |
| CN109705464A (en) * | 2018-12-28 | 2019-05-03 | 金旸（厦门）新材料科技有限公司 | A kind of powdered rice hulls filling micro-foaming polypropylene composite material and preparation method thereof |
| CN115368727A (en) * | 2022-09-16 | 2022-11-22 | 上海嘉均瑞科技有限公司 | High-resilience polyurethane foam material and preparation method thereof |
| EP4174114A4 (en) * | 2020-06-30 | 2024-07-17 | Matsumoto Yushi Seiyaku Kk | Masterbatch for foam molding and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108912510A (en) * | 2018-07-24 | 2018-11-30 | 四川宏亿复合材料工程技术有限公司 | A kind of Foamed rubber plate and its preparation process |
| CN109705464A (en) * | 2018-12-28 | 2019-05-03 | 金旸（厦门）新材料科技有限公司 | A kind of powdered rice hulls filling micro-foaming polypropylene composite material and preparation method thereof |
| EP4174114A4 (en) * | 2020-06-30 | 2024-07-17 | Matsumoto Yushi Seiyaku Kk | Masterbatch for foam molding and use thereof |
| CN115368727A (en) * | 2022-09-16 | 2022-11-22 | 上海嘉均瑞科技有限公司 | High-resilience polyurethane foam material and preparation method thereof |
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