WO1994028057A1 - Process for the preparation of inorganic foaming agent masterbatch - Google Patents
Process for the preparation of inorganic foaming agent masterbatch Download PDFInfo
- 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
Links
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 79
- 239000004088 foaming agent Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 50
- 239000002253 acid Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052806 inorganic carbonate Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002524 monosodium citrate Substances 0.000 claims description 3
- 235000018342 monosodium citrate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 32
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 description 16
- 229960004106 citric acid Drugs 0.000 description 11
- -1 e.g. Substances 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229960004543 anhydrous citric acid Drugs 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000010944 pre-mature reactiony Methods 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241000795633 Olea <sea slug> Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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.
Landscapes
- 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
An inorganic foaming agent is economically and readily produced in the form of a masterbatch by melt-extruding one of the major components of the inorganic foaming agent with a carrier resin to prepare an intermediate masterbatch and blending the intermediate masterbatch with a composition containing the remaining component(s) or all of the components constituting the inorganic foaming agent.
Description
PROCESS FOR THE PREPARATION OF INORGANIC FOAMING AGENT MASTERBATCH
Field of the Invention
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.
Background of the Invention
Foaming agents are widely used in such conventional processes as extrusion, calendering, injection molding, coating, expansion casting and rotation molding of plastics. Hithereto, organic foaming agents such as azodicarbonamides have been mainly used due to the large amounts of gas generated and the low cost thereof. However, 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.
Generally, inorganic foaming agents known in the prior art contain polycarboxylic acids and inorganic carbonates. However, 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. Accordingly, 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.
Various coating methods and materials for each component of the inorganic foaming agent are disclosed, for example, in U.S. Patent Nos. 5,009,809; 5,009,810;
5,037,580; 5,045,570; 5,106,534 and 5,137,655. However, such coating methods generally suffer from a high processing cost due to the requirements of using the additional coating procedure and expensive coating agent.
Summary of the Invention
It is, therefore, a primary object of the invention to provide a process for the production of an inorganic foaming agent in the form of a masterbatch at a low cost.
In accordance with one aspect of the present invention, there is provided a process for economical production of 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.
Detailed Description of the Invention
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. Further, 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.
The term "masterbatch", as used herein, represents an encapsulated ingredient concentrate with a carrier resin. Such masterbatch is typically prepared by melt-extruding the ingredients thereof with the carrier resin. However, in the case of an inorganic foaming agent, such conventional masterbatch preparation method cannot be employed due to the premature reaction by acid/base reaction or premature reaction with water.
In accordance with the inventive process, therefore, in order to prevent such premature reaction of the major components of the inorganic foaming agent, first, 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.
Subsequently, 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. Alternatively, 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.
The following Examples are given for the purpose of illustration only and are not intended to limit the scope of the invention. In the Examples, as a carrier resin, 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/cm3 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/cm3 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.
Further, wax used in the Examples is the one having a softening point of 109°C and a number average molecular weight of 3,000, which is prepared by thermally decomposing of a polyethylene resin.
Example 1
In a Henschel mixer (a dry mixer), 94.5 parts by weight of polyethylene as a carrier resin, 5 parts by weight of wax and 0.5 part by weight of calcium 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. 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.
Separately, in accordance with the procedure as above,
66 parts by weight of polyethylene, 31 parts by weight of anhydrous citric acid and 3 parts by weight of wax were employed to obtain a citric acid masterbatch. Finally, the respective masterbatches prepared above were blended at a weight ratio of 50:50 in a tumbler mixer to obtain a desired inorganic foaming agent masterbatch.
Example 2
97 parts by weight of the citric acid masterbatch prepared in Example 1, 2 parts by weight of sodium bicarbonate as a powder form and 1 part by weight of dioctyl phthalate, which was added to uniformly disperse the sodium bicarbonate powder into the citric acid masterbatch, were
blended for 5 minutes in a tumbler mixer to obtain a desired inorganic foaming agent masterbatch.
Example 3
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. During the melt-extrusion, 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.
Separately, in accordance with the procedure as above, 12 parts by weight of anhydrous citric acid was employed to obtain a citric acid masterbatch. Finally, the sodium bicarbonate masterbatch and the citric acid masterbatch prepared above were blended at a weight ratio of 30:70 in a tumbler mixer to obtain a desired inorganic foaming agent masterbatch.
Example 4
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.
Example 5
In 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.
Separately, 80 parts by weight of polystyrene and 20 parts by weight of anhydrous citric acid were blended for 5 minutes in a Henschel mixer and melt-extruded by using a twin screw extruder 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 citric acid masterbatch in the form of a pellet.
Finally, 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 6
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.
Example 7
In 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. During the melt-extrusion of the blend, 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.
Separately, 80 parts by weight of styrene-butadiene copolymer and 20 parts by weight of anhydrous citric acid were employed to obtain a citric acid masterbatch.
Finally, 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.
Comparative Example 1
In a Henschel mixer, 91.5 parts by weight of polyethylene as a carrier resin, 7 parts by weight of wax, 0.5 part by weight of olea ide and 1 part by weight of calcium 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. During the melt- extrusion of the blend, 45 parts by weight of inorganic
foaming agent C#850 (a product of Dongjin Whasung Co., Ltd.) was introduced into another inlet of the extruder to formulate and extrude it with the blend. The extrudate was cooled in a water bath at room temperature and then cut to obtain an inorganic foaming agent masterbatch in the form of a pellet.
Comparative Example 2
The procedure described in Comparative Example 1 was repeated except that ethylene vinyl acetate copolymer was employed as a carrier resin.
Example 8
20 parts by weight of the inorganic foaming agent masterbatch prepared in Comparative Example 1 and 80 parts by weight of the sodium bicarbonate masterbatch prepared in
Example 1 were blened for 5 minutes in a tumbler mixer to obtain a desired inorganic foaming agent masterbatch.
Example 9
20 parts by weight of the inorganic foaming agent masterbatch prepared in Comparative Example 1 and 80 parts by weight of the inorganic foaming agent masterbatch finally prepared in Example 1 were blened for 5 minutes in a tumbler mixer to obtain a desired inorganic foaming agent masterbatch.
Example 10
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 11
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 12
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.
Foamability Test 1
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/cm3 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.
As a control, 2 parts by weight of the inorganic foaming agent masterbatch produced in Comparative Example 1 was also employed to obtain a foamed 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 1.
Table 1
Masterbatch Mixed Masterbatch Comparative Employed Example 1
2:1 1:1 1:2
Density(g/cm3) 0.72 0.76 0..79 0.81
Foamability Test 2
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/cm3 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.
As a control, 3 parts by weight of the inorganic foaming agent masterbatch produced in Comparative Example 2 was also employed to obtain a foamed 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.
Table 2
Masterbatch Example 6 Comparative Employed Example 2
Density(g/cm3) 0.67 0.78
As can be shown in Tables 1 and 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.
While the invention has been described in connection with the above specific embodiments, it should be recognized that various modifications and changes may be made by those skilled in the art to the invention which also fall within the scope of the invention as defined by the appended claims.
Claims
1. A process for preparing an inorganic foaming agent having a number of components in the form of a masterbatch, which comprises melt-extruding one of the components with a carrier resin to prepare an intermediate masterbatch and further blending the intermediate masterbatch with a composition containing the remaining component(s) .
2. The process of claim 1, wherein the composition is in the form of a coated powder, uncoated raw powder or melt- extruded masterbatch of the remaining component(s) .
3. A process for preparing an inorganic foaming agent having a number of components in the form of a masterbatch, which comprises melt-extruding one of the components with a carrier resin to prepare an intermediate masterbatch and further blending the intermediate masterbatch with a composition containing all of the components constituting the inorganic foaming agent.
4. The process of claim 3, wherein the composition is in the form of a mixture of a coated powder of each of the components, or a mixture of melt-extruded masterbatches of the respective components.
5. The process of any one of claims 1 to 4, wherein the inorganic foaming agent contains a polycarboxylic acid having the formula of HOOC-R-COOH wherein R is a C.,_25 alkylene group including one or more hydroxy substituents and, optionally, an unsaturated group(s), or a salt thereof, and an inorganic carbonate as its components.
6. The process of claim 5, wherein the polycarboxylic acid or a salt thereof is selected from the group consisting of citric acid, fumaric acid, tartaric acid, sodium hydrogen citrate, monosodium citrate and a mixture thereof; and the inorganic carbonate is selected from the group consisting of sodium bicarbonate, potassium bicarbonate and a mixture thereof.
7. An inorganic foaming agent produced in accordance with the process recited in any one of claims 1 to 6.
8. An intermediate masterbatch for producing an inorganic foaming agent having a number of components in the form of a masterbatch, prepared by melt-extruding one of the components with a carrier resin.
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 (en) | 1993-05-25 | 1993-05-25 | Method for manufacturing new master batch |
| KR1019940011182A KR100200237B1 (en) | 1993-05-25 | 1994-05-23 | Forming method of inorganic foaming agent master batch |
| KR1994/11182 | 1994-05-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994028057A1 true WO1994028057A1 (en) | 1994-12-08 |
Family
ID=26629673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR1994/000056 WO1994028057A1 (en) | 1993-05-25 | 1994-05-24 | Process for the preparation of inorganic foaming agent masterbatch |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU6856894A (en) |
| WO (1) | WO1994028057A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3231858A1 (en) * | 2016-04-13 | 2017-10-18 | Solvay SA | (melt-)extrusion process for the preparation of alkali metal carbonate, bicarbonate and sesquicarbonate formulations using a melted functionalizing agent |
| CZ307244B6 (en) * | 2016-06-30 | 2018-04-25 | Univerzita Tomáše Bati ve Zlíně | A concentrate based on an organic biologically active substance designed for antimicrobial stabilization of plastic surfaces |
Citations (2)
| 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 (en) * | 1992-05-13 | 1993-11-25 | Gaia Research L.P. | Production of encapsulated chemical foaming concentrates |
-
1994
- 1994-05-24 WO PCT/KR1994/000056 patent/WO1994028057A1/en active Application Filing
- 1994-05-24 AU AU68568/94A patent/AU6856894A/en not_active Abandoned
Patent Citations (2)
| 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 (en) * | 1992-05-13 | 1993-11-25 | Gaia Research L.P. | Production of encapsulated chemical foaming concentrates |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3231858A1 (en) * | 2016-04-13 | 2017-10-18 | Solvay SA | (melt-)extrusion process for the preparation of alkali metal carbonate, bicarbonate and sesquicarbonate formulations using a melted functionalizing agent |
| WO2017178623A1 (en) * | 2016-04-13 | 2017-10-19 | Solvay Sa | (melt-) extrusion process for the preparation of alkali metal carbonate, bicarbonate and sesquicarbonate formulations using a melted functionalizing agent |
| CN109153945A (en) * | 2016-04-13 | 2019-01-04 | 索尔维公司 | Functionalized reagent for using melting prepares (melting) extrusion method of alkali carbonate, bicarbonate and sesquicarbonate preparation |
| 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 (en) * | 2016-06-30 | 2018-04-25 | Univerzita Tomáše Bati ve Zlíně | A concentrate based on an organic biologically active substance designed for antimicrobial stabilization of plastic surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6856894A (en) | 1994-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5009809A (en) | High temperature endothermic blowing agents compositions and applications | |
| USRE35239E (en) | Endothermic blowing agents compositions and applications | |
| US5366675A (en) | Foamable polyethylene-based composition for rotational molding | |
| US4632942A (en) | Resin composition for masterbatch of foaming agent | |
| US4596832A (en) | Process for producing thermoplastic resin foam | |
| US5302455A (en) | Endothermic blowing agents compositions and applications | |
| JPH0328237A (en) | Manufacture of ethylene- trifluorinated chloride copolymer foam | |
| EP0482007B1 (en) | Endothermic blowing agents compositions and applications | |
| US4247651A (en) | Process for preparing foamed synthetic resin products | |
| US5106534A (en) | Endothermic blowing agents compositions and applications | |
| CN110982171A (en) | A kind of low-density toughened polypropylene open-cell micro-foaming material | |
| PT77393B (en) | Process for the preparation of low density closed-cell foamed articles from ethylene copolymer/vinyl or vinylidene halide blends | |
| KR100722518B1 (en) | Resin Composition for Hard PCC Foam Sheet | |
| US5252618A (en) | Endothermic blowing agents for strengthening weld lines in molded thermoplastic resins and products | |
| WO1994028057A1 (en) | Process for the preparation of inorganic foaming agent masterbatch | |
| EP0027688B1 (en) | New blowing agent compositions and their preparation and use | |
| US4940735A (en) | Blowing agent masterbatch for the preparation of polystyrene foams | |
| US5137655A (en) | High temperature endothermic blowing agents compositions and applications | |
| JP3729977B2 (en) | Polyester resin with improved rheological properties | |
| US5250224A (en) | Foamed products containing endothermic blowing agents and processes | |
| KR100200237B1 (en) | Forming method of inorganic foaming agent master batch | |
| CA1206700A (en) | Low density cellular polyvinyl chloride | |
| CN116218074A (en) | Polypropylene functional master batch and preparation method and application thereof | |
| JPS5910741B2 (en) | Mixtures for the production of foamed plastic bodies | |
| US5306736A (en) | Endothermic blowing agents for surface migration of components in foamed products, compositions and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENP | Entry into the national phase |
Ref country code: US Ref document number: 1994 256598 Date of ref document: 19940623 Kind code of ref document: A Format of ref document f/p: F |
|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AT AU BB BG BR BY CA CH CN CZ DE DK ES FI GB HU JP KZ LK LU LV MG MN MW NL NO NZ PL PT RO RU SD SE SK UA US UZ VN |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
| 122 | Ep: pct application non-entry in european phase | ||
| NENP | Non-entry into the national phase |
Ref country code: CA |