CN110964288A - Styrene-ethylene-butylene-styrene segmented copolymer foamed bead and preparation method thereof - Google Patents
Styrene-ethylene-butylene-styrene segmented copolymer foamed bead and preparation method thereof Download PDFInfo
- Publication number
- CN110964288A CN110964288A CN201911093392.XA CN201911093392A CN110964288A CN 110964288 A CN110964288 A CN 110964288A CN 201911093392 A CN201911093392 A CN 201911093392A CN 110964288 A CN110964288 A CN 110964288A
- Authority
- CN
- China
- Prior art keywords
- styrene
- butylene
- ethylene
- block copolymer
- styrene block
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- 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
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to styrene-ethylene-butylene-styrene block copolymer expanded beads, which comprise a styrene-ethylene-butylene-styrene block copolymer with Shore hardness of 30-80A. The foamed bead obtained by using the styrene-ethylene-butylene-styrene block copolymer with hardness as a raw material has the characteristics of high cell closing rate, compact cells and small cell size, so that the produced foamed material has the characteristics of good mechanical properties (including tensile strength, fracture productivity and rebound resilience) and low density.
Description
Technical Field
The invention relates to the field of lightweight material preparation, and particularly relates to styrene-ethylene-butylene-styrene segmented copolymer expanded beads and a preparation method thereof.
Background
According to Baidu encyclopedia, styrene-ethylene-butylene-styrene block copolymer (SEBS for short) SEBS is a linear triblock copolymer with polystyrene as a terminal block and an ethylene-butylene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block. SEBS does not contain unsaturated double bonds, so the SEBS has good stability and aging resistance. The SEBS has excellent ageing resistance, plasticity and high elasticity, can be processed and used without vulcanization, can reuse leftover materials, and is widely used for producing high-grade elastomers, plastic modification, adhesives, lubricating oil tackifiers, fillers and sheath materials of wires and cables and the like. The SEBS has good weather resistance, heat resistance, compression deformation resistance and excellent mechanical property.
Based on the excellent performance of SEBS substrate, research and development and production of SEBS foam material have also been carried out to present numerous enterprises, and SEBS foam material wide application in fields such as shoes material, yoga mat, children's ground mat has the light, and the resilience is good, and anti-skidding performance is excellent. Patent No. CN107471509A discloses a foaming method and a foaming material of a thermoplastic elastomer, which are characterized in that the crosslinking of an SEBS substrate is realized through a radiation process, then the SEBS substrate is put into a supercritical reaction kettle, gas is introduced, and the SEBS foaming material is prepared by adopting a supercritical intermittent heating method. Because the SEBS needs to be pretreated by radiation crosslinking, the crosslinked SEBS has the problem of difficult degradation, and tends to cause certain pollution to the environment, and meanwhile, the radiation crosslinking process also influences the body health of production line operators. Patent No. CN102888067A discloses a preparation method of a SEBS, PP and EVA blended foaming material, and patent No. CN103087383A discloses a preparation method of a LDPE/EVA/SEBS composite material, wherein a bridge erecting machine is adopted to chemically crosslink a mixture, a chemical foaming agent is used for foaming, a product decomposed by a chemical foaming machine is harmless to a human body to a certain extent, and meanwhile, the SEBS subjected to chemical crosslinking is difficult to degrade, so that the problem of environmental pollution exists.
Disclosure of Invention
The invention aims to solve the technical problem of providing styrene-ethylene-butylene-styrene segmented copolymer expanded beads and a preparation method thereof.
The technical scheme for solving the technical problems is as follows: a styrene-ethylene-butylene-styrene block copolymer expanded bead comprising a styrene-ethylene-butylene-styrene block copolymer having a Shore hardness of 30 to 80A.
The invention has the beneficial effects that: the foamed bead obtained by using the styrene-ethylene-butylene-styrene block copolymer with hardness as a raw material has the characteristics of high cell closing rate, compact cells and small cell size, so that the produced foamed material has the characteristics of good mechanical properties (including tensile strength, fracture productivity and rebound resilience) and low density.
Preferably, the shore hardness of the styrene-ethylene-butylene-styrene block copolymer is 35 to 75A.
At this preferred shore hardness, expanded beads with better performance can be obtained.
Particularly preferably, the shore hardness of the styrene-ethylene-butylene-styrene block copolymer is 40 to 70A.
The expanded beads having the best performance can be obtained at the particularly preferred shore hardness.
On the basis of the technical scheme, the invention can be further improved as follows:
further, the styrene-ethylene-butylene-styrene block copolymer has a styrene content of 15% to 45% based on the styrene-ethylene-butylene-styrene block copolymer content.
The beneficial effect of adopting the above further scheme is that the inventor unexpectedly finds that the content of the styrene defined in the invention enables the obtained expanded bead to have excellent performance, and the inventor analyzes that when the content of the styrene in the styrene-ethylene-butylene-styrene block copolymer is lower than 15%, the strength of the substrate molecular skeleton is lower, cell breakage is easily caused during the foaming process, and when the content of the styrene in the styrene-ethylene-butylene-styrene block copolymer is higher than 45%, the molecular skeleton rigidity is too high, and the brittleness of the finally prepared expanded material is increased.
Further, the flat beads of the styrene-ethylene-butylene-styrene block copolymer expanded beadsThe average cell size is 1-200um, and the average cell number of the styrene-ethylene-butylene-styrene block copolymer expanded beads is 103-107/cm3The styrene-ethylene-butylene-styrene block copolymer expanded beads have a closed cell ratio of 95% or more, and the density of the styrene-ethylene-butylene-styrene block copolymer expanded beads is 0.01 to 0.3g/cm3。
The further scheme has the beneficial effect that under the parameters, the obtained foaming material has better mechanical property.
Further, the melting point of the styrene-ethylene-butylene-styrene block copolymer was 150-250 ℃.
The melting point of the copolymer was measured by DSC at a heating rate of 20K/min. The specific test mode is as follows: using DSC Q100 from TA Instruments, 8-10mg of the test sample was heated at a heating rate of 20 ℃/min in a first run at 20 ℃ to 280 ℃, followed by cooling to 20 ℃ at 10 ℃/min, and then further heating cycles at a heating rate of 10 ℃/min (second run). The temperature of the peak maximum in the second run was recorded as the melting point.
The further scheme has the advantages that in the melting point range, the closed pore rate of the foam pores is high, the foam pores are compact and the size of the foam pores is small, and the obtained product has excellent mechanical property and rebound resilience. Since the heat resistance of the foamed material product is affected when the melting point of the styrene-ethylene-butylene-styrene block copolymer is lower than 150 ℃, the physical properties and resilience of the product are seriously degraded when the product is used under a high temperature environment for a long time. In addition, when the melting point of the styrene-ethylene-butylene-styrene block copolymer is higher than 250 ℃, the prepared expanded beads need higher steam pressure in the subsequent processing and forming process (such as steam molding), so that the problems of rough surface and many holes of the product are caused, and the production cost is increased due to the need of higher-pressure steam.
Further, the styrene-ethylene-butylene-styrene block copolymer has a melt flow rate of 1 to 50g/10 min.
The melt flow rate of the copolymer was measured according to ASTM D1238 at 200 ℃ with a weight of 5 kg.
The method has the advantages that in the melt flow rate range, the bubble closing rate is high, the bubbles are compact and the size of the bubbles is small, and the obtained product has excellent mechanical property and rebound resilience. When the melt flow rate of the copolymer is less than 1g/10min, the melt viscosity of the copolymer matrix becomes too high and foaming becomes difficult. In addition, when the melt flow rate of the copolymer is higher than 50g/10min, the problems of cell breakage, shrinkage of expanded beads and collapse are easily caused during the expansion process.
The invention also relates to a preparation method of the styrene-ethylene-butylene-styrene block copolymer expanded bead, which comprises the following steps: step 1: adding 100 parts by weight of styrene-ethylene-butylene-styrene block copolymer, 1-60 parts by weight of physical foaming agent and 500 parts by weight of water into a high-pressure reaction kettle, and stirring to form suspension; step 2: heating the suspension to 80-160 ℃, keeping the pressure at 10-250bar, and keeping the constant temperature and the constant pressure for 0-180 min; and step 3: and (3) discharging the heated suspension in the step (2) to the atmospheric environment to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
Preferably, the temperature of the suspension is preferably raised to 100-140 ℃. For this purpose, the suspension is generally heated to the desired temperature at a heating rate of preferably 2 ℃/min or more.
The time is 0, which means that the operation of step 3 can be performed after the set temperature and pressure are reached.
The method has the advantages that the method does not need radiation crosslinking or blending modification, is environment-friendly, retains the performance of the base material to the maximum extent, simplifies the production process, reduces the production cost, can ensure that the density (or multiplying power) of the obtained foaming bead is easy to control, has wide adjustment range, has the characteristics of high closed pore rate of the foam pores, compact foam pores and small size of the foam pores, and has excellent mechanical performance and rebound resilience.
The invention also relates to a preparation method of the styrene-ethylene-butylene-styrene block copolymer expanded bead, which comprises the following steps: step 1: putting 100 parts by weight of the styrene-ethylene-butylene-styrene block copolymer into an extruder for melting; step 2, injecting 0.1 to 100 parts by weight of physical foaming agent into the extruder to obtain a first mixture, and keeping the pressure in the extruder to be 20 to 300bar in the process; and step 3: and extruding the mixture through the extruder die head, and then carrying out underwater granulation to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
The method has the advantages that the method does not need radiation crosslinking or blending modification, is environment-friendly, retains the performance of the base material to the maximum extent, simplifies the production process, reduces the production cost, can ensure that the density (or multiplying power) of the obtained foaming bead is easy to control, has wide adjustment range, has the characteristics of high closed pore rate of the foam pores, compact foam pores and small size of the foam pores, and has excellent mechanical performance and rebound resilience.
The invention also relates to a preparation method of the styrene-ethylene-butylene-styrene block copolymer expanded bead, which comprises the following steps: step 1: putting 100 parts by weight of the styrene-ethylene-butylene-styrene block copolymer into a high-pressure reaction kettle; step 2: injecting 1-100 parts by weight of physical foaming agent into the high-pressure reaction kettle to obtain a second mixture, so that the pressure value in the high-pressure reaction kettle reaches 10-350bar, and maintaining the pressure for 1-48 h; and step 3: and heating the second mixture to 140 ℃ at the temperature of 100 ℃ for 1-10 minutes to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
The method has the advantages that the method does not need radiation crosslinking or blending modification, is environment-friendly, retains the performance of the base material to the maximum extent, simplifies the production process, reduces the production cost, can ensure that the density (or multiplying power) of the obtained foaming bead is easy to control, has wide adjustment range, has the characteristics of high closed pore rate of the foam pores, compact foam pores and small size of the foam pores, and has excellent mechanical performance and rebound resilience.
Further, the preparation method of the styrene-ethylene-butylene-styrene block copolymer expanded beads is characterized in that the physical foaming agent comprises one or more of nitrogen, carbon dioxide, air, methane, propane, butane and pentane.
Preferably, carbon dioxide in a supercritical state or nitrogen in a supercritical state is used.
The invention also relates to a foamed molding comprising said styrene-ethylene-butylene-styrene block copolymer expanded beads.
The further scheme has the advantages of providing the styrene-ethylene-butylene-styrene block copolymer expanded bead material with good mechanical properties (including tensile strength, fracture productivity and rebound resilience), low density and environmental friendliness.
The invention also relates to the use of the foamed moulded part as a sole, leather, a tire, a bicycle seat, a sofa cushion, a car seat, upholstery, a cushioning pad, a sound insulation pad, a children's toy and/or a floor covering.
The invention has the beneficial effects that:
(1) the invention utilizes the styrene-ethylene-butylene-styrene block copolymer particles commonly used in the market, does not need radiation crosslinking or blending modification, furthest retains the performance of the base material, simplifies the production process and reduces the production cost.
(2) The density (or multiplying power) of the expanded beads obtained by the invention is easy to control, the adjustment range is wide, and the expanded beads with the density of 0.01-0.3g/cm3 can be obtained.
(3) The product obtained by the invention has the characteristics of high pore closing rate of the pores, compact pores and small pore size, and the obtained product has the characteristics of excellent mechanical property, rebound resilience and environment optimization.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
A styrene-ethylene-butylene-styrene block copolymer expanded bead comprising a styrene-ethylene-butylene-styrene block copolymer having a Shore hardness of 30 to 80A.
Preferably, the shore hardness of the styrene-ethylene-butylene-styrene block copolymer is 35 to 75A.
Particularly preferably, the shore hardness of the styrene-ethylene-butylene-styrene block copolymer is 40 to 70A.
As a further alternative to this example, the styrene content of the styrene-ethylene-butylene-styrene block copolymer was 15% to 45% based on the styrene-ethylene-butylene-styrene block copolymer content.
As a further alternative of this example, the styrene-ethylene-butylene-styrene block copolymer expanded beads had an average cell size of 1 to 200um and an average number of cells of 103-107/cm3The styrene-ethylene-butylene-styrene block copolymer expanded beads have a closed cell ratio of 95% or more, and the density of the styrene-ethylene-butylene-styrene block copolymer expanded beads is 0.01 to 0.3g/cm3。
As a further variation of this example, the styrene-ethylene-butylene-styrene block copolymer has a melting point of 150 ℃ to 250 ℃.
As a further alternative to this example, the styrene-ethylene-butylene-styrene block copolymer has a melt flow rate of 1 to 50g/10 min.
Example 1
The preparation of the styrene-ethylene-butylene-styrene block copolymer expanded beads comprises the following steps: step 1: 100kg of the styrene-ethylene-butylene-styrene block copolymer (with Shore hardness of 30A, styrene content in the copolymer of 15%, melting point of 150 ℃, melt flow rate of 1g/10min), 1kg of butane and 100kg of water are added into a high-pressure reaction kettle and stirred to form suspension; step 2: heating the suspension to 80 ℃, and keeping the pressure at 10 bar; and step 3: and (3) discharging the heated suspension in the step (2) to the atmospheric environment, and drying to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
Example 2
The preparation of the styrene-ethylene-butylene-styrene block copolymer expanded beads comprises the following steps: step 1: 100kg of the styrene-ethylene-butylene-styrene segmented copolymer (with Shore hardness of 70A, styrene content in the copolymer of 30%, melting point of 230 ℃ and melt flow rate of 5g/10min), 30kg of carbon dioxide and 250kg of water are added into a high-pressure reaction kettle and stirred to form suspension; step 2: heating the suspension to 120 ℃, keeping the pressure at 150bar, and keeping constant temperature and pressure for 90 min; and step 3: and (3) discharging the heated suspension in the step (2) to the atmospheric environment, and drying to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
Example 3
The preparation of the styrene-ethylene-butylene-styrene block copolymer expanded beads comprises the following steps: step 1: 100kg of the styrene-ethylene-butylene-styrene segmented copolymer (with Shore hardness of 80A, styrene content in the copolymer of 45%, melting point of 250 ℃ and melt flow rate of 50g/10min), 60kg of nitrogen and 500kg of water are added into a high-pressure reaction kettle and stirred to form suspension; step 2: heating the suspension to 160 ℃, keeping the pressure at 250bar, keeping constant temperature and pressure for 180min to obtain heated suspension; and step 3: discharging the heated suspension in the step 2 into the atmospheric environment, and drying to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
Example 4
The preparation of the styrene-ethylene-butylene-styrene block copolymer expanded beads comprises the following steps: step 1: 100kg of the styrene-ethylene-butylene-styrene segmented copolymer (with Shore hardness of 75A, styrene content in the copolymer of 33%, melting point of 245 ℃ and melt flow rate of 10g/10min) is put into a double-screw extruder to be melted, the temperature of a screw is controlled to be 100 ℃, the temperature of a die head of the extruder is controlled to be 100 ℃, and the pressure of the die head is controlled to be 100 bar; step 2, injecting 0.1kg of pentane into the extruder to obtain a first mixture, and keeping the pressure in the extruder at 20bar in the process; and step 3: and extruding the mixture through the extruder die head, and then carrying out underwater granulation to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
Example 5
The preparation of the styrene-ethylene-butylene-styrene block copolymer expanded beads comprises the following steps: step 1: 100kg of the styrene-ethylene-butylene-styrene segmented copolymer (with Shore hardness of 80A, styrene content in the copolymer of 30%, melting point of 230 ℃ and melt flow rate of 15g/10min) is put into a double-screw extruder to be melted, the temperature of a screw is controlled to be 120 ℃, the temperature of a die head of the extruder is controlled to be 100 ℃, and the pressure of the die head is controlled to be 100 bar; step 2, injecting 50kg of methane into the extruder to obtain a first mixture, and keeping the pressure in the extruder at 150bar in the process; and step 3: and extruding the mixture through the extruder die head, and then carrying out underwater granulation to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
Example 6
The preparation of the styrene-ethylene-butylene-styrene block copolymer expanded beads comprises the following steps: step 1: 100kg of the styrene-ethylene-butylene-styrene segmented copolymer (with Shore hardness of 75A, styrene content in the copolymer of 35%, melting point of 250 ℃ and melt flow rate of 8g/10min) is put into a double-screw extruder to be melted, the temperature of a screw is controlled to be 180 ℃, the temperature of a die head of the extruder is controlled to be 100 ℃, and the pressure of the die head is controlled to be 100 bar; step 2, injecting 100kg of propane into the extruder to obtain a first mixture, wherein the pressure in the extruder is kept at 300bar in the process; and step 3: and extruding the mixture through the extruder die head, and then carrying out underwater granulation to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
Example 7
The preparation of the styrene-ethylene-butylene-styrene block copolymer expanded beads comprises the following steps: step 1: 100kg of the styrene-ethylene-butylene-styrene segmented copolymer (with Shore hardness of 72A, styrene content in the copolymer of 40%, melting point of 245 ℃, and melt flow rate of 15g/10min) is put into a 200ml high-pressure reaction kettle; step 2: 1kg of butane is injected into the high-pressure reaction kettle to obtain a second mixture, the pressure value in the high-pressure reaction kettle reaches 10bar, and the pressure is maintained for 1 hour; and step 3: and after the physical foaming agent reaches the dissolution balance in the styrene-ethylene-butylene-styrene block copolymer particles, heating the second mixture in water vapor at 100 ℃ for foaming, wherein the heating time is 1 minute, and thus obtaining the styrene-ethylene-butylene-styrene block copolymer expanded beads.
Example 8
The preparation of the styrene-ethylene-butylene-styrene block copolymer expanded beads comprises the following steps: step 1: 100kg of the styrene-ethylene-butylene-styrene block copolymer (with Shore hardness of 65A, styrene content in the copolymer of 30%, melting point of 225 ℃ and melt flow rate of 20g/10min) is put into a 200ml high-pressure reaction kettle; step 2: 50kg of pentane is injected into the high-pressure reaction kettle to obtain a second mixture, so that the pressure value in the high-pressure reaction kettle reaches 250bar, and the pressure is maintained for 24 hours; and step 3: and after the physical foaming agent reaches the dissolution balance in the styrene-ethylene-butylene-styrene block copolymer particles, heating the second mixture in water vapor at 120 ℃ for foaming, wherein the heating time is 5 minutes, and thus obtaining the styrene-ethylene-butylene-styrene block copolymer expanded beads.
Example 9
The preparation of the styrene-ethylene-butylene-styrene block copolymer expanded beads comprises the following steps: step 1: 100kg of the styrene-ethylene-butylene-styrene segmented copolymer (with Shore hardness of 55A, styrene content in the copolymer of 25%, melting point of 240 ℃ and melt flow rate of 5g/10min) is put into a 200ml high-pressure reaction kettle; step 2: injecting 100kg of nitrogen into the high-pressure reaction kettle to obtain a second mixture, enabling the pressure value in the high-pressure reaction kettle to reach 350bar, and maintaining the pressure for 48 hours; and step 3: and after the physical foaming agent reaches the dissolution balance in the styrene-ethylene-butylene-styrene block copolymer particles, heating the second mixture in steam at 140 ℃ for foaming, wherein the heating time is 10 minutes, and obtaining the styrene-ethylene-butylene-styrene block copolymer foamed beads.
Comparative example 1
The conditions were the same as in example 2 except that the styrene-ethylene-butylene-styrene block copolymer used had a Shore hardness of 20.
Comparative example 2
The conditions were the same as in example 2 except that the styrene-ethylene-butylene-styrene block copolymer used had a Shore hardness of 90.
Comparative example 3
The conditions were the same as in example 2 except that the styrene-ethylene-butylene-styrene block copolymer used had a styrene content of 13%.
Comparative example 4
The conditions were the same as in example 2 except that a styrene-ethylene-butylene-styrene block copolymer having a styrene content of 55% was used.
Comparative example 5
The conditions were the same as in example 2 except that the melting point of the styrene-ethylene-butylene-styrene block copolymer used was 280.
Example 6
The conditions were the same as in example 2 except that a styrene-ethylene-butylene-styrene block copolymer having a melt flow rate of 65g/10min was used.
The hot expanded beads obtained above were filled into molds 300mm in length by 250mm in width by 50mm in thickness. And (3) compressing 10% of water vapor along the thickness direction of the mould to bond and shape the expanded beads, and finally obtaining a molded foam product. The resulting foam article was allowed to stand at 50 ℃ x 50% RH for 2 hours, then dried in a thermostatic chamber at 80 ℃ for 2 hours, and finally allowed to stand at 25 ℃ x 50% RH for 2 hours, and then evaluated for properties.
TABLE 1 Properties of the beads of the examples of the invention and of the molded foam articles produced therefrom
TABLE 2 Properties of the comparative example beads of the present invention and the Properties of the molded foam articles produced therefrom
From the experimental results in tables 1 and 2, it can be seen that the foamed beads obtained by foaming the styrene-ethylene-butylene-styrene block copolymer according to the present invention have the characteristics of high cell closing rate, dense cells and small cell size under the conditions of shore hardness, styrene content, melting point and melt flow rate defined in the present invention, and the obtained products have excellent mechanical properties and rebound resilience. The production of the foaming beads by using the method disclosed by the invention can realize the foaming of a single SEBS base material, the method is simple and easy to operate, especially the pollution to the environment can be reduced to the maximum extent, and the method has the characteristic of environmental friendliness compared with the prior art.
It should be noted that:
the underwater pelletizing process is the prior art, and the operation process is selected from the prior art to operate according to needs.
Optional additives in the granulation process include optional conventional additives such as antioxidants, stabilizers, flame retardants, waxes, fillers, pigments and dyes. Nucleating agents, including talc, carbon black, graphite, fumed silica, diatomaceous earth, are preferably used to regulate the cell structure. These are generally used in amounts of 0.01 to 1 part by weight, based on the weight of the styrene-ethylene-butylene-styrene block copolymer particles.
The average mass of the styrene-ethylene-butylene-styrene block copolymer particles is 1 to 50mg, preferably 5 to 25 mg. Generally, the styrene-ethylene-butylene-styrene block copolymer material of the present invention is preferably used in the form of particles. The average mass of the individual particles is the arithmetic mean of the tests by weighing 10 particles in each case in triplicate. The prepared particles are cylindrical, elliptical or spherical in shape. These preferred cylindrical or round pellets can be prepared by all compounding methods known to the person skilled in the art and subsequently as cold or hot cut. For example by compounding, optionally together with other additives, in a twin-screw extruder, extruding from the extruder, optionally cooling and pelletizing.
The test method comprises the following steps:
the average cell size is obtained by collecting an image of a cut surface of the expanded bead in the diameter direction by using a scanning electron microscope, and calculating the distance (L) of 2 intersection points on the surface of the expanded bead and the number (n) of cells on the straight line in the diameter direction. The size of the cells is L/n;
the average cell number is obtained by acquiring an image of a cutting surface of the thermoplastic block polyether amide foamed bead along the diameter direction by using a scanning electron microscope, and calculating the cell density by using the following formula:
wherein in the above-mentioned formula,
nf-cell density in units/cm 3;
n-the number of cells in the selected statistical area in the scanning electron microscope image, the unit is one;
m is the magnification of the scanning electron microscope image;
a-statistical area selected in SEM images in cm 2.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A styrene-ethylene-butylene-styrene block copolymer expanded bead, characterized by comprising a styrene-ethylene-butylene-styrene block copolymer having a Shore hardness of 30 to 80A.
2. The expanded beads of styrene-ethylene-butylene-styrene copolymer according to claim 1, wherein the styrene content of the styrene-ethylene-butylene-styrene block copolymer is 15 to 45% based on the content of the styrene-ethylene-butylene-styrene block copolymer.
3. The expanded beads of styrene-ethylene-butylene-styrene copolymer as claimed in claim 1, wherein the melting point of the styrene-ethylene-butylene-styrene block copolymer is 150 ℃ or more and 250 ℃ or less.
4. The expanded beads of styrene-ethylene-butylene-styrene copolymer according to claim 1, wherein the melt flow rate of the styrene-ethylene-butylene-styrene block copolymer is 1 to 50g/10 min.
5. A method for preparing the styrene-ethylene-butylene-styrene block copolymer expanded beads according to any one of claims 1 to 4, comprising the steps of:
step 1: adding 100 parts by weight of styrene-ethylene-butylene-styrene block copolymer, 1-60 parts by weight of physical foaming agent and 500 parts by weight of water into a high-pressure reaction kettle, and stirring to form suspension;
step 2: heating the suspension to 80-160 ℃, keeping the pressure at 10-250bar, and keeping the constant temperature and the constant pressure for 0-180 min;
and step 3: and (3) discharging the heated suspension in the step (2) to the atmospheric environment to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
6. A method for preparing the styrene-ethylene-butylene-styrene block copolymer expanded beads according to any one of claims 1 to 4, comprising the steps of:
step 1: putting 100 parts by weight of the styrene-ethylene-butylene-styrene block copolymer into an extruder for melting;
step 2, injecting 0.1 to 100 parts by weight of physical foaming agent into the extruder to obtain a first mixture, and keeping the pressure in the extruder to be 20 to 300bar in the process;
and step 3: and extruding the first mixture through the extruder die head, and then carrying out underwater granulation to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
7. A method for preparing the styrene-ethylene-butylene-styrene block copolymer expanded beads according to any one of claims 1 to 4, comprising the steps of:
step 1: putting 100 parts by weight of the styrene-ethylene-butylene-styrene block copolymer into a high-pressure reaction kettle;
step 2: injecting 1-100 parts by weight of physical foaming agent into the high-pressure reaction kettle to obtain a second mixture, so that the pressure value in the high-pressure reaction kettle reaches 10-350bar, and maintaining the pressure for 1-48 h;
and step 3: and heating the second mixture to 140 ℃ at the temperature of 100 ℃ for 1-10 minutes to obtain the styrene-ethylene-butylene-styrene block copolymer expanded beads.
8. The method for preparing styrene-ethylene-butylene-styrene block copolymer expanded beads according to any one of claims 5 to 7, wherein the physical blowing agent comprises one or more of nitrogen, carbon dioxide, air, methane, propane, butane and pentane.
9. A foamed article comprising expanded beads of the styrene-ethylene-butylene-styrene block copolymer according to any one of claims 1 to 4 or expanded beads produced by the method for producing expanded beads of the styrene-ethylene-butylene-styrene block copolymer according to any one of claims 5 to 8.
10. Use of the foam molding according to claim 9 in shoe soles, leather, tires, bicycle seats, sofa cushions, car seats, upholstery, cushioning, sound insulation mats, children's toys or floor coverings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911093392.XA CN110964288A (en) | 2019-11-11 | 2019-11-11 | Styrene-ethylene-butylene-styrene segmented copolymer foamed bead and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911093392.XA CN110964288A (en) | 2019-11-11 | 2019-11-11 | Styrene-ethylene-butylene-styrene segmented copolymer foamed bead and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110964288A true CN110964288A (en) | 2020-04-07 |
Family
ID=70030379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911093392.XA Pending CN110964288A (en) | 2019-11-11 | 2019-11-11 | Styrene-ethylene-butylene-styrene segmented copolymer foamed bead and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110964288A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804764A (en) * | 2012-11-05 | 2014-05-21 | 上海凯波特种电缆料厂有限公司 | Foaming elastomer outer sheath material applied to charging cable and preparation method and application thereof |
| CN104817754A (en) * | 2015-03-27 | 2015-08-05 | 常州大学 | High hardness, high elasticity and wear resistance composite foam material and preparation method thereof |
| CN105885326A (en) * | 2015-01-10 | 2016-08-24 | 杨云 | High-elasticity antistatic foaming composite material |
| CN108676310A (en) * | 2018-06-07 | 2018-10-19 | 正定县恒润塑胶有限公司 | Slippers SEBS composite material and preparation methods, application |
| CN109503880A (en) * | 2017-09-14 | 2019-03-22 | 上海译科实业有限公司 | A kind of foaming master batch and preparation method thereof |
-
2019
- 2019-11-11 CN CN201911093392.XA patent/CN110964288A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804764A (en) * | 2012-11-05 | 2014-05-21 | 上海凯波特种电缆料厂有限公司 | Foaming elastomer outer sheath material applied to charging cable and preparation method and application thereof |
| CN105885326A (en) * | 2015-01-10 | 2016-08-24 | 杨云 | High-elasticity antistatic foaming composite material |
| CN104817754A (en) * | 2015-03-27 | 2015-08-05 | 常州大学 | High hardness, high elasticity and wear resistance composite foam material and preparation method thereof |
| CN109503880A (en) * | 2017-09-14 | 2019-03-22 | 上海译科实业有限公司 | A kind of foaming master batch and preparation method thereof |
| CN108676310A (en) * | 2018-06-07 | 2018-10-19 | 正定县恒润塑胶有限公司 | Slippers SEBS composite material and preparation methods, application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104877335B (en) | A kind of thermoplastic polyurethane elastomer expanded bead and preparation method thereof | |
| KR20190022727A (en) | Method for producing foam particles composed of a thermoplastic elastomer having polyamide segments | |
| JPWO2016194737A1 (en) | Thermoplastic polyurethane expanded particles and molded articles of thermoplastic polyurethane expanded particles | |
| CN105218850B (en) | A kind of preparation method of high-elastic thermoplastic polyurethane foam particle and its formed body | |
| CN107082943A (en) | A kind of acrylonitrile butadiene rubber modified EVA expanded materials and its manufacture method | |
| CN110343286B (en) | Poly (butylene succinate) ionomer foam and preparation method and application thereof | |
| CN109504068A (en) | A kind of thermoplastic polyurethane blending foaming material and preparation method thereof | |
| KR102562308B1 (en) | Olefin-based thermoplastic elastomer expanded particles | |
| CN113072767B (en) | EVA/TPAE composite material foam and preparation method thereof | |
| CN109689752B (en) | Thermoplastic polyurethane foamed particles | |
| TWI740010B (en) | Foamed particle molded article | |
| CN110964288A (en) | Styrene-ethylene-butylene-styrene segmented copolymer foamed bead and preparation method thereof | |
| CN114605623B (en) | Flexible PET-based copolyester and bead foam prepared from same | |
| KR101928925B1 (en) | Polyolefin foam particle with excellent impact resistance | |
| CN104479165A (en) | Method for preparing polypropylene low-temperature solid-phase formed beads | |
| CN113423781B (en) | Gel and cushioning material based on thermoplastic elastomer and preparation method thereof | |
| KR20180133607A (en) | Ethylene vinyl acetate foam particle with excellent impact resistance and method for producing the same | |
| CN114395161A (en) | Foamable thermoplastic polyurethane elastomer and preparation method and application thereof | |
| CN107141627A (en) | A kind of expanded material for tables and chairs of being played for children and preparation method thereof | |
| KR20110085443A (en) | High fuse-bondable polypropylene composition for expanded polypropylene | |
| KR101928926B1 (en) | Polyolefin elastomer foam particle with excellent impact resistance | |
| KR101215057B1 (en) | Soft polypropylene resin composition having superior fine foam property | |
| JP2505543B2 (en) | Method for producing foam containing crystalline propylene resin | |
| CN115678083B (en) | Preparation method of PBAT high-resilience sheet with adjustable multiplying power and product thereof | |
| CN110845781B (en) | PE foam material yoga mat and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200407 |
|
| RJ01 | Rejection of invention patent application after publication |