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WO1994028057A1 - Procede de preparation d'un agent moussant inorganique sous forme d'un melange maitre - Google Patents

Procede de preparation d'un agent moussant inorganique sous forme d'un melange maitre Download PDF

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Publication number
WO1994028057A1
WO1994028057A1 PCT/KR1994/000056 KR9400056W WO9428057A1 WO 1994028057 A1 WO1994028057 A1 WO 1994028057A1 KR 9400056 W KR9400056 W KR 9400056W WO 9428057 A1 WO9428057 A1 WO 9428057A1
Authority
WO
WIPO (PCT)
Prior art keywords
masterbatch
foaming agent
inorganic foaming
components
melt
Prior art date
Application number
PCT/KR1994/000056
Other languages
English (en)
Inventor
Byoung Kyu Song
Ho Kab Jeong
Min Woo Cho
Original Assignee
Daelim Industrial Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from KR1019930009102A external-priority patent/KR960005589B1/ko
Application filed by Daelim Industrial Co., Ltd. filed Critical Daelim Industrial Co., Ltd.
Priority to AU68568/94A priority Critical patent/AU6856894A/en
Publication of WO1994028057A1 publication Critical patent/WO1994028057A1/fr

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
    • C08J9/06—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 chemical blowing agent
    • C08J9/08—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 chemical blowing agent developing carbon dioxide
    • 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
    • C08J9/06—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 chemical blowing agent

Definitions

  • the present invention relates to a novel process for preparing an inorganic foaming agent in the form of a masterbatch, by using an intermediate masterbatch.
  • Foaming agents are widely used in such conventional processes as extrusion, calendering, injection molding, coating, expansion casting and rotation molding of plastics.
  • organic foaming agents such as azodicarbonamides have been mainly used due to the large amounts of gas generated and the low cost thereof.
  • the organic foaming agent has the critical deficiency of entailing harmful materials, which can cause an environmental problem, such as harmful materials during the production process of an organic foaming agent and ammonia gas during the foaming process thereof.
  • inorganic foaming agents known in the prior art contain polycarboxylic acids and inorganic carbonates.
  • the use of the acid/carbonate blowing agent may cause a premature reaction by acid/base reaction or with water and the premature reaction is accelerated by the presence of water.
  • most of commercially available inorganic foaming agents have been marketed with each of their components coated with a coating agent, e.g., stearic acid, monoglyceride, silane coupling agent and the like.
  • an inorganic foaming agent masterbatch which comprises melt- extruding one of the major components of the inorganic foaming agent with a carrier resin to prepare an intermediate masterbatch; and then blending the intermediate masterbatch with a composition containing the remaining component(s) or all of the components constituting the inorganic foaming agent.
  • the inorganic foaming agent generally contains a polycarboxylic acid or a salt thereof and an inorganic carbonate as major constituents thereof.
  • the polycarboxylic acid may be generally represented by the formula HOOC-R-COOH wherein R is a C.,_ 25 alkylene group which may contain one or more hydroxy substituents and, optionally, unsaturated group(s) .
  • Representative of the polycarboxylic acid and salts thereof which may be employed include citric acid, fumaric acid, tartaric acid, sodium hydrogen citrate, monosodium citrate and mixtures thereof, which may be employed alone or in combination.
  • the inorganic carbonate may be preferably a carbonate containing an alkali or alkaline earth metal such as Ca, K, Mg, Na and the like; and exemplary compounds thereof include sodium bicarbonate, potassium bicarbonate and mixtures thereof, which may be employed alone or in combination.
  • Any thermoplastic resin may be employed as a carrier resin for the inorganic foaming agent masterbatch of the present invention.
  • one of the components is encapsulated with a carrier resin at a temperature ranging from 40 to 235°C using a conventional extruder, e.g., a single or twin screw extruder having one or two inlets, to prepare an intermediate masterbatch in the form of a pellet.
  • the component constituting the intermediate masterbatch may be preferably employed in an amount of 5 to 60 parts by weight per 100 parts by weight of the carrier resin.
  • the intermediate masterbatch is blended with a composition containing the remaining component(s) constituting the inorganic foaming agent to produce an inorganic foaming agent masterbatch as a final product.
  • the composition containing the remaining components may be in the form of a coated powder, an uncoated raw powder or a melt-extruded intermediate masterbatch separately prepared by the inventive process.
  • the intermediate masterbatch may be blended with a composition containing all of the components constituting the inorganic foaming agent.
  • the composition is preferably prepared in such a form that the components cannot be reacted with each other, e.g., a mixture of a coated powder of each component, or a mixture of melt- extruded intermediate masterbatches of respective components separately prepared.
  • the inorganic foaming agent masterbatch of the present invention may optionally comprise wax, slip agent, lubricant and the like in an effective amount.
  • the inventive process has a number of advantages: expensive coating materials and procedures may be avoided; the step of preparing an inorganic foaming agent and the step of preparing a masterbatch are integrated into one step to shorten the preparation process; the inorganic foaming agent masterbatch thus obtained still has a good foamability comparable to a masterbatch of a conventional inorganic foaming agent produced by the prior art; and cell size and the amount of gas generated from the foaming agent can be easily controlled by adjusting the mix ratio of the constituents of the inorganic foaming agent.
  • a polyethylene is the one having a melt index of 45 g/lOmin as measured in accordance with ASTM D-1238 and a density of 0.915 g/cm 3 as measured in accordance with ASTM D-1505;
  • an ethylene vinyl acetate copolymer is the one having a melt index of 45 g/lOmin as measured in accordance with ASTM D-1238;
  • a polystyrene is the one having a melt index of 16 g/lOmin as measured in accordance with ASTM D-1238 and a density of 1.05 g/cm 3 as measured in accordance with ASTM D-1505;
  • a styrene-butadiene copolymer is the one having a butadiene monomer content of 25% and a melt index of 8 g/lOmin.
  • wax used in the Examples is the one having a softening point of 109
  • the blend was introduced into an inlet of a twin screw extruder and melt-extruded at a temperature ranging from 40 to 235°C and a speed ranging from 50 to 200 rpm.
  • a temperature ranging from 40 to 235°C and a speed ranging from 50 to 200 rpm During the melt-extrusion of the blend, 45 parts by weight of sodium bicarbonate was introduced into another inlet of the extruder to formulate and extrude it with the blend.
  • the extruder was designed to be temperature- controlled at nine portions. The extrudate was cooled in a water bath at room temperature and then cut to obtain a sodium bicarbonate masterbatch in the form of a pellet.
  • 100 parts by weight of polyethylene was introduced into an inlet of a twin screw extruder and melt-extruded at a temperature ranging from 40 to 235°C and a speed ranging from 50 to 200 rpm.
  • 12 parts by weight of sodium bicarbonate was introduced into another inlet of the extruder to formulate and extrude it with the polyethylene resin.
  • the extruder was designed to be temperature-controlled at nine portions. The extrudate was cooled in a water bath at room temperature and then cut to obtain a sodium bicarbonate masterbatch in the form of a pellet.
  • Example 1 The procedure described in Example 1 was repeated except that monosodium citrate was employed instead of anhydrous citric acid to obtain a desired inorganic foaming agent masterbatch.
  • a Henschel mixer 30 parts by weight of polyethylene, 63 parts by weight of polystyrene, 5 parts by weight of styrene-butadiene copolymer and 2 parts by weight of zinc stearate were blended for 5 minutes, and the blend was introduced into an inlet of a twin screw extruder and melt-extruded at a temperature ranging from 40 to 235°C and a speed ranging from 50 to 200 rpm. The extrudate was cooled in a water bath at room temperature and then cut to obtain a resin mixture in the form of a pellet.
  • the resulting resin pellet was introduced into an inlet of a twin screw extruder and melt-extruded at a temperature ranging from 40 to 235°C and a speed ranging from 50 to 200 rpm, and during the melt-extrusion of the resin mixture pellet, 10 parts by weight of sodium bicarbonate was introduced into another inlet of the extruder to formulate and extrude it with the resin mixture pellet.
  • the extruder was designed to be temperature-controlled at nine portions. The extrudate was cooled in a water bath at room temperature and then cut to obtain a sodium bicarbonate masterbatch in the form of a pellet.
  • the sodium bicarbonate masterbatch and the citric acid masterbatch prepared in the above were blended at a weight ratio of 70:30 in a tumbler mixer to obtain a desired inorganic foaming agent masterbatch.
  • Example 1 The procedure employed in Example 1 was repeated except that ethylene vinyl acetate copolymer was employed as a carrier resin, to obtain a desired inorganic foaming agent masterbatch.
  • a Henschel mixer 70 parts by weight of styrene- butadiene copolymer and 30 parts by weight of polyethylene were blended for 5 minutes, and the blend was introduced into an inlet of a twin screw extruder and melt-extruded at a temperature ranging from 40 to 235°C and a speed ranging from 50 to 200 rpm.
  • 10 parts by weight of sodium bicarbonate was introduced into another inlet of the extruder to formulate and extrude it with the blend.
  • the extruder was designed to be temperature-controlled at nine portions. The extrudate was cooled in a water bath at room temperature and then cut to obtain a sodium bicarbonate masterbatch in the form of a pellet.
  • the sodium bicarbonate masterbatch and the citric acid masterbatch prepared in the above were blended at a weight ratio of 70:30 in a tumbler, mixer to obtain a desired inorganic foaming agent masterbatch.
  • Example 1 were blened for 5 minutes in a tumbler mixer to obtain a desired inorganic foaming agent masterbatch.
  • Example 3 The procedure described in Example 3 was repeated except that tartaric acid was employed instead of anhydrous citric acid to obtain a desired inorganic foaming agent masterbatch.
  • Example 3 The procedure described in Example 3 was repeated except that fumaric acid was employed instead of anhydrous citric acid to obtain a desired inorganic foaming agent masterbatch.
  • Example 3 The procedure described in Example 3 was repeated except that potassium bicarbonate was employed instead of sodium bicarbonate to obtain a desired inorganic foaming agent masterbatch.
  • the sodium bicarbonate masterbatch prepared in Example 1 was blended with the citric acid masterbatch prepared in Example 1 in a tumbler mixer for 5 minutes at a mixing ratio of 2:1, 1:1 or 1:2 to obtain a mixed inorganic foaming agent masterbatch.
  • 2 parts by weight of the mixed masterbatch was blended with 98 parts by weight of polyethylene TR-144 (a product of Daelim Industry Co., Ltd.) having a density of 0.945 g/cm 3 in a tumbler mixer for 5 minutes, and the blend was extruded by using a twin screw extruder at a temperature ranging from 180 to 220°C to obtain a foamed polyethylene product.
  • Example 6 3 parts by weight of the inorganic foaming agent masterbatch produced in Example 6 was blended with 97 parts by weight of ethylene vinylacetate copolymer having a density of 0.935 g/cm 3 and a melt index of 3g/10min. in a tumbler mixer for 5 minutes, and the blend was extruded by using a single screw extruder at a temperature ranging from 180 to 220°C to obtain a foamed polyethylene product.
  • the foamed products were evaluated by measuring their densities using an automatic density tester (a product of DOYOSEIKI, Japan) and the results are shown in Table 2.
  • the plastic product foamed by the inorganic foaming agent masterbatch produced in accordance with the inventive process has a lower density (i.e., an excellent foamability) than those of the masterbatch produced by prior art methods.

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  • Chemical & Material Sciences (AREA)
  • General 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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un agent moussant inorganique est produit économiquement et rapidement sous la forme d'un mélange maître par l'extrusion à chaud d'un des principaux composants de l'agent moussant inorganique à l'aide d'une résine porteuse pour préparer un mélange maître intermédiaire et par le mélange de celui-ci avec une composition contenant les composants restants de tous les composants constituant l'agent moussant inorganique.
PCT/KR1994/000056 1993-05-25 1994-05-24 Procede de preparation d'un agent moussant inorganique sous forme d'un melange maitre WO1994028057A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU68568/94A AU6856894A (en) 1993-05-25 1994-05-24 Process for the preparation of inorganic foaming agent masterbatch

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1993/9102 1993-05-25
KR1019930009102A KR960005589B1 (ko) 1993-05-25 1993-05-25 마스터배치의 새로운 제조방법 및 그에 의해 제조된 마스터배치
KR1019940011182A KR100200237B1 (ko) 1993-05-25 1994-05-23 무기 발포제 마스터배치의 제조방법
KR1994/11182 1994-05-23

Publications (1)

Publication Number Publication Date
WO1994028057A1 true WO1994028057A1 (fr) 1994-12-08

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ID=26629673

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR1994/000056 WO1994028057A1 (fr) 1993-05-25 1994-05-24 Procede de preparation d'un agent moussant inorganique sous forme d'un melange maitre

Country Status (2)

Country Link
AU (1) AU6856894A (fr)
WO (1) WO1994028057A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3231858A1 (fr) * 2016-04-13 2017-10-18 Solvay SA Procédé d'extrusion (fusion) destiné à la préparation de formulations de carbonate , bicarbonate et sesquicarbonate de métal alcalin à l'aide d'un agent de fonctionnalisation fondu
CZ307244B6 (cs) * 2016-06-30 2018-04-25 Univerzita Tomáše Bati ve Zlíně Koncentrát na bázi organické biologicky aktivní látky určený pro antimikrobní stabilizaci plastových povrchů

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4632942A (en) * 1983-10-31 1986-12-30 Mitsubishi Petrochemical Co., Ltd. Resin composition for masterbatch of foaming agent
WO1993023463A2 (fr) * 1992-05-13 1993-11-25 Gaia Research L.P. Production de concentres porophores chimiques encapsules

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4632942A (en) * 1983-10-31 1986-12-30 Mitsubishi Petrochemical Co., Ltd. Resin composition for masterbatch of foaming agent
WO1993023463A2 (fr) * 1992-05-13 1993-11-25 Gaia Research L.P. Production de concentres porophores chimiques encapsules

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3231858A1 (fr) * 2016-04-13 2017-10-18 Solvay SA Procédé d'extrusion (fusion) destiné à la préparation de formulations de carbonate , bicarbonate et sesquicarbonate de métal alcalin à l'aide d'un agent de fonctionnalisation fondu
WO2017178623A1 (fr) * 2016-04-13 2017-10-19 Solvay Sa Procédé d'extrusion en fusion pour la préparation de formulations de carbonates, bicarbonates et sesquicarbonates de métal alcalin en utilisant un agent de fonctionnalisation fondu
CN109153945A (zh) * 2016-04-13 2019-01-04 索尔维公司 用于使用熔融的官能化试剂制备碱金属碳酸盐、碳酸氢盐和倍半碳酸盐配制品的（熔融）挤出方法
US11407648B2 (en) 2016-04-13 2022-08-09 Solvay Sa (Melt-) extrusion process for the preparation of alkali metal carbonate, bicarbonate and sesquicarbonate formulations using a melted functionalizing agent
CZ307244B6 (cs) * 2016-06-30 2018-04-25 Univerzita Tomáše Bati ve Zlíně Koncentrát na bázi organické biologicky aktivní látky určený pro antimikrobní stabilizaci plastových povrchů

Also Published As

Publication number Publication date
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