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CN1150440A - Coating composition for expandable beads - Google Patents

Coating composition for expandable beads Download PDF

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Publication number
CN1150440A
CN1150440A CN 95193483 CN95193483A CN1150440A CN 1150440 A CN1150440 A CN 1150440A CN 95193483 CN95193483 CN 95193483 CN 95193483 A CN95193483 A CN 95193483A CN 1150440 A CN1150440 A CN 1150440A
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CN
China
Prior art keywords
coating composition
coating
molecular weight
expandable beads
polymer
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
Application number
CN 95193483
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Chinese (zh)
Inventor
R·J·帕尔加
D·P·维利尔斯
M·J·维莱姆斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of CN1150440A publication Critical patent/CN1150440A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22After-treatment of expandable particles; Forming foamed products
    • C08J9/228Forming foamed products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22After-treatment of expandable particles; Forming foamed products
    • C08J9/224Surface treatment

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  • 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)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention relates to the use of low molecular weight polymers of vinylaromatic compounds having a weight average molecular weight of 200-15000 for the coating of expandable beads, in particular of vinylaromatic compounds polymers containing blowing agents. Furthermore, the invention relates to coating compositions for such beads, to coated expandable beads and to pre-expanded beads pre-expanded from coated expandable beads, and to articles produced by melting and expanding these beads by heat treatment above the boiling point of the blowing agent and above the softening point of the polymer.

Description

Coating composition for expandable beads
The low-molecular weight polymer that the present invention relates to vinyl aromatic compounds is used to be coated with expandable beads, particularly contains the application of expandable beads of the vinyl aromatic compounds polymkeric substance of whipping agent.And, the invention still further relates to a kind of coating composition that is used for such bead material: the expandable beads of coating and send out the prefoaming beading material of preparation in advance by the expandable beads of coating, and relate to the goods that these bead materials make by fusing of the heat-treated more than the softening temperature of the boiling point of whipping agent and polymkeric substance and foaming.Particularly, the present invention has found application aspect expandable polystyrene beads.
Expandable beads (polymkeric substance that " EPS " bead material hereinafter is often referred to vinyl aromatic compounds is the expandable beads of polystyrene particularly), the existing many different purposes of various expandable polystyrenes of selling with trade mark STYROCELL as Shell company.The application that everybody is familiar with is to cut off with piece material, high-intensity special-shaped moulded product, wall thickness greater than 10 millimeters pack, fish box, floor panels etc. at low density or middle density piece material or through-plate moulded product, Large Box and middle density insulcrete, laminate.Except regular grade, also can provide flame retardant grade and extraordinary level product.
Preferably, the EPS bead material in the quite short production cycle with seldom measuring the whipping agent several times volume (relevant) that foams with end-use.Certainly, the goods that made by the EPS bead material should be dimensional stabilizings, promptly warpage and/or contraction should not occur.
The production of molded block of material of micropore or be that everybody is familiar with by the goods that expandable beads makes, it mainly comprises two steps: (a) the pre-of expandable beads sends out according to maturation stage, and (b) heating prefoaming beading material in mould, generate the single foam article that microvoid structure is arranged.For the ease of handling and making satisfied moulded product, wish that bead material can unrestricted flow, and avoid as far as possible before pre-sending out, send out that neutralization is pre-sends out the tendency that the back bead material lumps in advance.
Usually with the present bead material of producing of coating composition coating that contains glycerine list (two or three) stearate and/or metal stearate ester (normally Zinic stearas) and other additives, to address these problems.Other components that can find usually in coating composition comprise antithrombotics, static inhibitor, stablizer, tinting material etc.The composition that is fit to is for example open in GB-A-1409285.
But foaming product must satisfy another condition, promptly enough flexural strengths.So use EPS bead material can obtain high maximum flexural strength or the goods of typical flexural strength are arranged, and can make under low foam/water vapor pressure.
The inventor finds that amazedly these purposes can reach with the low-molecular weight polymer of weight-average molecular weight (Mw) for the vinyl aromatic compounds of 200-15000 in the coating of expandable beads.Particularly, these purposes can be coated with typical expandable beads with new coating composition and reach.Therefore, the present invention also provides a kind of expandable beads with containing common coating and weight-average molecular weight (Mw) coating composition for the low-molecular weight polymer of the vinyl aromatic compounds of 200-15000.Preferably, the Mw of polymkeric substance is 300-1000, more preferably 400-1500.
Though the accurate quantity of low-molecular weight polymer can change in very wide scope, by total composition, new coating composition preferably contains 5-50% (weight) polymkeric substance, more preferably 10-25% (weight) polymkeric substance.
The low-molecular weight polymer that is fit to is the polymkeric substance of alpha-methyl styrene and/or vinylbenzene (also available other comonomers), and what be more suitable for is styrene homopolymers.
Available any normally used traditional method is coated onto coating composition on the expandable beads, thus the expandable beads that obtains being coated with, and they also are new bead materials.Therefore, it can be used as dry-coated material (rolling mixed) in ribbon blender, as slurries (in water) or solution (in the on-aqueous liquid of vaporization easily).The solvent-free effect of this liquid reply expandable beads.Such liquid is preferably low-carbon alcohol such as methyl alcohol, ethanol, Virahol, or aliphatic hydrocrbon such as hexane, heptane or sherwood oil.The dry-coated material that is easy to get most and obtains best result is preferred.Under the situation of dry-coated material, low-molecular-weight polymkeric substance is if solid, and its granularity is preferably less than 65 microns.If the use granularity is greater than 65 microns polymkeric substance, if carefully do not handle, coating composition may be because of causing damage in conjunction with loss.
By expandable beads, expandable beads should be used the coating of 0.1-2.0% (weight) (preferred 0.2-0.5% (weight)) coating composition.
Expandable beads is preferably made by vinylbenzene, perhaps independent vinylbenzene (styrene homopolymers) or with the copolymerization combination of monomers.Expandable beads is made by the polymkeric substance that Mw is at least 100000 (being at least 160000 usually).The most normally used and should make by polystyrene by the expandable beads of the present invention coating.Before the vinyl aromatic compounds polymerization, in the polymerization or the whipping agent that adds after polymerization low boiling point hydrocarbon normally, as (ring) pentane etc.But for polymkeric substance, whipping agent and other additives, the technology of relevant expandable beads is very widely; For those skilled in the art, this technology is known.So (uncoated) expandable beads does not constitute a part of the present invention.
Expandable beads through coating is easy to send out in advance with the modelling step and does not stop up, and does not therefore disturb the prefoaming beading material is transferred to treatment facility in the mould.The flowability of former bead material (before promptly pre-the sending out) also is fabulous, can not produce flow difficulties.
The foam article that high flexural strength is arranged that the invention still further relates to new coating bead material and make by these coating bead materials.
With reference now to following examples, further describe the present invention.But, limit the scope of the invention without it.
In an embodiment, use PICCOLASTIC A5 (trade mark of Her cules company, the various liquid phase mixtures of styrene oligomer (trimer and tetramer) (molecular weight about 430)) and a kind of Mw are about 10000 powdery lower molecular weight PS (by 63 tm screen).In addition, GMS (Zerol), GTS (tristearin) and Zust (Zinic stearas) are traditional coating, and its function is to prevent expandable beads caking and static.
Embodiment 1-2, comparative example A-B
(Mw is about 180000 with the uncoated expandable beads of 1 kilogram of mixture that contains have an appointment 6% (weight) Skellysolve A and iso-pentane, particle diameter is the 0.7-1.0 millimeter) at ribbon blender (the Hermann Linden machine of 1 kilogram of batch of material, turned round 10 minutes) with the listed coating composition of table 1 roll mixed, until increment reaches 4 grams (0.4% (weight)).
Bead material through coating is sent out in advance in the device (productions of H  ndle company) at intermittent type and is sent out in advance, and water vapor pressure is 0.20 to cling to gauge pressure, and the steam-treated time is 26 seconds.Density all is about 23 grams per liters, shows that new coating composition is to the pre-only limited effect of process of sending out.With bead material cured overnight in pre-issuance of materials storehouse of sending out in advance, the machine modelling becomes 300 millimeters * 300 millimeters * 50 millimeters brick in the steam-heated closed die of operating under 0.5-1.2 crust gauge pressure then.For each brick record maximum foam pressure and pressure fall time.Then under 70 ℃ with dry 2 days of brick, modulate and test flexural loads again.For each brick, record maximum flexural strength (when fracture).
Can draw from table 1, replace general coating composition not influence the characteristic of moulded product basically with new coating composition.Compare with the coating that uses pure GMS, when using lower molecular weight PS (embodiment 1 and 2), the result of the anti-foam pressure of flexural strength is much higher.For embodiment 1 and 2, the high about 45-50 newton of maximum accessible intensity contrast example A.When comparing with Comparative Examples B, embodiment 1 and 2 maximum accessible intensity improve about 75-80 newton, though this is to be issued in the more following cycle.
Table 1 formulation for coating material (1 kilogram is not coated with bead material)
Composition GMS (gram) GTS (gram) low-molecular-weight PS (gram) adds up to the flexural strength of (gram) character prefoam foam density (grams per liter) prefoam foam gas content (% (weight)) under 0.6 bar gauge pressure steam pressure1(ox) maximum flexural strength 1(ox) maximum cycle (second) Embodiment A embodiment 1 Embodiment B embodiment 2 0.40 0.20 0.20 0.10--0.20 0.10-0.20-0.20 0.40 0.40 0.40 0.40 22.7 23.2 23.8 23.8 3.84 3.73 3.78 3.86 1,098 1,259 1,090 1,277 1,468 1,510 1,434 1,516 356 397 260 377
1Being corrected to density is 23 grams per liters
Embodiment 3-5 and Comparative Examples C
In method similar to the above, produce the bead material of high Mw polystyrene (about 260000) coating that contains 6% (weight) whipping agent.Use 25 seconds steam treatment time, make density reach about 20 grams per liters.Coating composition and the results are shown in table 2.
Can draw from table 2, replace general coating composition not influence the characteristic of moulded product basically with new coating composition.Compare with using pure GMS coating (Comparative Examples C), when using PICCOLASTIC AS, the result of the anti-foam pressure of flexural strength is much higher.C compares with Comparative Examples, the high approximately 50-60 newton of the maximum accessible intensity of embodiment 3-4.Total cycle and the Comparative Examples C of embodiment 3-4 are similar.Embodiment 5 explanations, the coating composition that contains 50% (weight) or more low-molecular weight polymers produces and improves, but the increase that improves with quantity descends.
Table 2 formulation for coating material (1 kilogram of uncoated bead material)
Composition GMS (gram) Znst (gram) PICCOLASTIC A5 (gram) adds up to the flexural strength of (gram) character prefoam foam density (grams per liter) prefoam foam gas content (% (weight)) under 0.6 bar gauge pressure steam pressure1(ox) maximum flexural strength 1(ox) maximum cycle (second) Embodiment C embodiment 3 embodiment 4 embodiment 5 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10-0.05 0.10 0.20 0.20 0.25 0.30 0.40 20.0 20.2 20.0 20.0 3.80 3.82 3.82 3.80 1,150 1,200 1,210 1,180 1,210 1,245 1,245 1,230 320 310 310 305
1Being corrected to density is 20 grams per liters
Embodiment 6-7 and Comparative Examples D-E
In method similar to the above, produce the bead material of the coating of the polystyrene (Mw about 180000) that contains 6% (weight) whipping agent.Use 20 seconds steam treatment time to reach density and be about 20 grams per liters.Coating composition and result list table 3 in.Embodiment 7 and Comparative Examples E explanation are compared with the coating composition that contains GMS, use the coating composition that contains GTS to produce lower flexural strength, but the cycle much shorter.
Can draw from table 3, replace general coating composition not influence the characteristic of moulded product basically with new coating composition.Compare (Comparative Examples D-E) with using GMS/Znst, GMS/GTS/Znst coating, when using PICCOLASTIC A5, flexural strength is high slightly under the fixed foam pressure.Under the quite short cycle, can obtain this improved intensity.
Table 3 formulation for coating material (1 kilogram of uncoated bead material)
Composition GMS (gram) Embodiment D embodiment 6 embodiment E embodiment 7 0.40 0.40 0.20 0.20
GTS (gram) Znst (gram) PICCOLASTIC A5 (gram) adds up to the flexural strength of (gram) character prefoam foam density (grams per liter) prefoam foam gas content (% (weight)) under 0.6 bar gauge pressure steam pressure1(ox) maximum flexural strength 1(ox) maximum cycle (second) - - 0.20 0.20 0.08 0.08 0.08 0.08 - 0.10 - 0.10 0.48 0.58 0.48 0.58 20.0 20.0 20.0 20.0 3.70 3.69 3.10 3.10 1143 1148 883 902 1146 1148 1013 975 295 216 113 99
1Being corrected to density is 20 grams per liters
On the basis of listed in the above experimental data, the coating composition that can make new advances has favorable influence to maximum deflection load and/or cycle.

Claims (14)

1. the purposes of weight-average molecular weight (Mw) expandable beads that is used to be coated with for the low-molecular weight polymer of the vinyl aromatic compounds of 200-15000.
2. coating composition for expandable beads, it contains one or more common coating and a kind of Mw is the low-molecular weight polymer of the vinyl aromatic compounds of 200-15000.
3. according to the coating composition of claim 2, wherein the Mw of low-molecular weight polymer is 300-10000, preferred 400-1500.
4. according to the coating composition of claim 2 or 3, wherein press total restatement of coating composition, contain 5-50% (weight), preferred 10-25% (weight) low-molecular weight polymer.
5. according to each coating composition among the claim 2-4, wherein low-molecular weight polymer is the polymkeric substance of vinylbenzene and/or alpha-methyl styrene.
6. according to the coating composition of claim 5, wherein low-molecular weight polymer is a styrene polymer.
7. according to each coating composition among the claim 2-6, wherein common coating is one or more glycerine lists (two or three) stearates, also can be the metal stearate ester, and wherein coating composition also contains paint additive.
8. one kind by the method with the vinylaromatic polymer expandable beads of the method preparation coating of each coating composition coating expandable beads among the claim 2-5.
9. method according to Claim 8, wherein coating composition uses as dry-coated material.
10. according to the method for claim 9, wherein low-molecular weight polymer is as being solid, and its granularity is less than 65 microns.
11. send out and the pre-bead material of sending out with the vinylaromatic polymer of each coating composition coating among the claim 2-7.
12. send out and the pre-bead material of sending out according to claim 11 wherein is coated with each coating composition among the claim 2-7, by expandable beads, the consumption of coating composition is 0.1-2.0% (weight), preferred 0.2-0.5% (weight).
13. according to send out and the pre-bead material of sending out of claim 11 or 12, wherein bead is the polystyrene bead pellet.
14. can be by making the goods of the vinyl aromatic compounds polymer foaming bead material that each bead material foaming makes among the claim 11-13.
CN 95193483 1994-06-07 1995-06-02 Coating composition for expandable beads Pending CN1150440A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP94201628 1994-06-07
EP94201628.8 1994-06-07

Publications (1)

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CN1150440A true CN1150440A (en) 1997-05-21

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JP (1) JPH10501563A (en)
CN (1) CN1150440A (en)
AU (1) AU2674895A (en)
WO (1) WO1995033790A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100371374C (en) * 2001-10-18 2008-02-27 波利玛利欧洲股份公司 Expandable vinyl aromatic polymer and its preparation method

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Publication number Priority date Publication date Assignee Title
JP4789307B2 (en) * 2000-06-23 2011-10-12 旭化成ケミカルズ株式会社 Functional polyolefin resin expanded particles and in-mold molded articles thereof
JP2002212300A (en) * 2001-01-19 2002-07-31 Dainichiseika Color & Chem Mfg Co Ltd Hollow fine particles treated with amphipathic acid, method for producing the same, composition containing the hollow fine particles, and treated articles using the same
TW200934843A (en) * 2007-12-21 2009-08-16 Basf Se Insecticide-modified bead material composed of expandable polystyrene and insecticide-modified moldings obtainable therefrom
EP3717559A4 (en) 2017-11-28 2021-11-17 GreenMantra Recycling Technologies Ltd ENCAPSULATION OF MODIFIER IN DEPOLYMERIZED PRODUCTS
BR112020024507A2 (en) 2018-05-31 2021-03-02 Greenmantra Recycling Technologies Ltd. latex, paint, adhesive, coating, immunoassay test and solution
JP2022513219A (en) * 2018-12-14 2022-02-07 グリーンマントラ リサイクリング テクノロジーズ リミテッド Styrene copolymers derived from depolymerized polystyrene for use in the manufacture of foam materials and as melt flow modifiers

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BE603822A (en) * 1960-05-17 1900-01-01
DE1298274B (en) * 1963-07-13 1969-06-26 Basf Ag Production of foamable, finely divided styrene polymers
CS204926B1 (en) * 1979-11-27 1981-04-30 Otakar Seycek Foaming able polystyrene with improved workability and method of producing the same
CS209137B1 (en) * 1980-04-15 1981-10-30 Otakar Seycek Agent for improvement of forming properties of foamable polystarene and method of its production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100371374C (en) * 2001-10-18 2008-02-27 波利玛利欧洲股份公司 Expandable vinyl aromatic polymer and its preparation method

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JPH10501563A (en) 1998-02-10
EP0764186A1 (en) 1997-03-26
AU2674895A (en) 1996-01-04
WO1995033790A1 (en) 1995-12-14

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