CA2405376C - Anti-lumping compounds for use with expandable polystyrene beads - Google Patents

Abstract

An anti-lumping agent for use with expandable polystyrene beads is disclosed.
The expandable polystyrene beads comprise a styrene or styrene derivative polymer in combination with a blowing agent, Typical blowing agents are C3-C6 hydrocarbons, with pentane being especially preferred. The anti-lumping agents include block copolymers formed from blocks of ethylene oxide and propylene oxide. Preferably, the copolymers have a number average molecular weight of from about 4,000 to 15,000, and a hydrophilic-lipophilic balance number of from about 16 to 29. The anti-lumping agents significantly reduce the lumping potential of the expandable polystyrene beads, especially when they are expanded to low densities of from about 1.5 to 0.75 lbs. per cubic foot, and more preferably to densities of from about 1.2 to 0.85.

Description

ANTI-LUMPING COMPOUNDS FOR USE WITH
EXPANDABLE POLYSTYRENE BEADS
FIELD OF THE INVENTION
This invention relates generally to expandable polystyrene beads and, more particularly, to an anti-lumping agent useful for the formation of expandable polystyrene beads and low density foams formed therefrom.
BACKGROUND OF THE INVENTION
Methods for the production of expandable polystyrene beads are well known. Such expandable beads generally comprise a mixture of an expandable styrene or styrene derivative polymer and a blowing agent. The expandable polystyrene beads are generally initially formed into beads of relatively small size having a diameter of from about 0.2 to 4 millimeters.
The beads are generally formed in a suspension polymerization reaction. The blowing agent is introduced into the beads either during or after the polymerization reaction. The blowing agent is generally homogeneously dispersed within the polymer and the blowing agent may be, in general, a hydrocarbon which is gaseous or liquid under normal conditions and which does not dissolve the polymer. In addition, the boiling point of the blowing agent must be below that of the softening point of the polymer.
Typically, the expandable polystyrene beads go through at least a two-step process prior to molding. In the first step, the expandable polystyrene beads are expanded to form what are ymown as "grills" or as a "pre-puff', This step comprises heating the beads to a tc;mperaturc above their softening temperature and thereby above the boiling point of the blowinc agent resulting in vaporization of the blowinC ajent and expansion of the beads to form individual particles of foam grills. These grills are quite fragile and prior_to molding in the second step it is generally necessary to allow the grills to age for a period of time. To age the grills they are maintained under a normal atmosphere. Auring the wing process blowing agent within the grills diffuses out and air from outside diffuses into the grills. Once the grills have aged they can be placed in a mold and heated main such that the grills expand to fill the molding space and form a molded objet-t. During this period the grills expand and fuse ox to adhere to each other to form the molded object. The molded objects can either be large blocks 'which are subsequently cut u'ith a. hot wire cutter into sheets or the grills can be molded directly into a particular shape.
Increasingly manufacturers of molded expanded polystyrene are attempting to shorten the expansion time frame and to mold increasingly lower density foams, thereby leading to an i5 increase in profitability. One ncaative result of expanding foams to lower densities is that as the density of the foam decreases there is a significant increase in "lumping"
of the pulls.
This problem is especially setrere for expandable polystyrene beads that include low levels of bJawin~ agents. Lumpintr is defined as the expandable polystyrene beads fusing together during the initial expansion step, which results in forn~ation of large lumps of grills. These 20 )arge lumps create at least tyro problems. First, the expansion process becomes difficult to control becau~c of the formation of these Iarge lumps. The second problem is that if the Lumps are sufficiently latae enough the material becomes onus able for the subsequent molding steps. In an attempt to control this lumping phenomenon, a number of external coatings have been utilized. Some examples of commonly used external coatings include zinc ste~irate, glycerol mono stearate, ethylene-bis stearamide (acrawaxj, and silica. Unfortunately, these cotrm~only used lubricants are not successful in preventing lumping when the expandable polystyrene beads an expanded to very low densities.
Thus, it would b~ very advantageous to provide an anti-lumping compound that could be utilized with expandable polysytrene beads containing low levels of a blowing agent that would permit these beads to be expanded to very low densities previously not routinely obtainable.
io SUM1MARY Ol~ TF~E INVLNTION
In general terms, t)ris in~~ention provides expandable polystyrene beads having a reduced lumping tendency. Tn particular, this invention provides a class of anti-lumping agents for use with expandable polystyrene beads which significantly reduces lumpino- when expandin; the polystyrene beads into low-d4nsity foams of from about 1.5 to 0.75 pounds per cubic foot (pcf), and more preferably from about 1.2 to 0.85 pcf. This invention also finds special utilization when preparin' expandable polyst5~rene beads having low ievels of blo«~ing agents.
In a fit~st embodiment, the present invention is an expandable polystyrene bead comprising an expandable styrene or styrene derivative polymer and from about 2. to about ?0 5% by weight, based on the total weiCht of the bead, of a C; to C~
hydrocarbon blowing agent, wherein the bead is coated with an anti-lumping agent comprising a block copolyn~.cr of propylene oxide and ethylene oxide blocks, said block copolymer. comprising from about 800 to 65% ethylene oxide and from about 20% to 35% propylene oxide, and having a hydrophilic-lipophilic balance {HLB) value of from about 16 to 29.
In a second embodiment, the present invention is a method for the formation of an expandable polystyrene bead comprising the steps of: forming an expandable polystyrene bead containing from about 2% to about 5% by weight, based on the total weight of the bead, of a C3 to Cg hydrocarbon blowing agent; and coating the expandable polystyrene bead with an anti-lumping agent comprising a block copolymer comprising blocks of ethylene oxide and propylene oxide, wherein the block copolymer comprises from 80% to 65% ethylene oxide and from 20% to 35% propylene oxide, and has an HLB
value of from about 19 to 29, said anti-lumping agent present in an amount of from 250 to 2500 ppm based on the weight of the bead.
These and other features and advantages of this invention will become more apparent to those skilled in the art from the detailed description of a preferred embodiment.
DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
In general terms, this invention provides expandable polystyrene beads having a reduced lumping tendency. In particular, this invention provides a class of anti-lumping agents for use with expandable polystyrene beads that significantly reduces lumping when expanding the polystyrene beads into low density foams of from about 1.5 to 0.75 pcf. This invention also finds special utilization when preparing expandable polymer beads having low levels of blowing agents.
The expandable polystyrene beads are generally formed via the well known aqueous suspension method wherein the monomers are polymerized and combined with a blowing agent and other additives to form the beads. The beads are then separated from the aqueous portion of the suspension, washed and dried. In at least a first expansion step the beads are heated, usually via steam, to a temperature above the boiling point of the blowing agent. This heating causes vaporization of the biowinc anent and expansion of the beads into a form known as a grill or prepuff, The prepuff is then allowed to age for a.
sufficient period of time, usually suspended in mesh bags. During the aging process external air equilibrates across the prepuff and some residual blowing agent leaves the prepuffs. The prepuff is then placed into a closed mold and heated again to form a shaped object, be it a block or a more complex shape. Zn some procedures the prepuffs are expanded 2 to 4 times prior to their use in the closed mold.
1o In the aqueous suspension polymerization reaction. the monomers used to forth the polymer comprise styrene or styrene derivati~e.s_ The styrene derivatives include: alpha-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ar-ethylstyrene, ar-vinylxylene, ar-chlorostyrene; and ar-bron~ostyrene. The derivatives may include minor amounts of divinylbenaene, methylmethacrylate, or acrylonitrile. The preferred monomer is styrene. The monomer or mixture of monomers is suspended in an aqueous solution and polymerised. The blowing agent is ceneraliy added during the suspension polymerization, bur can be added durinG Inter processing steps. The suspension polymerization also generally inelud,es: chain transfer agents, suspension stabilizers, and polymerization catalysts. Typical chain transfer agents include: dimeric oc-methylstyrene. After polymerization, the polymer is 2o generally present in an amount of from about 93 to 98 weight percent based on the weight of the bead.
Blowing agents suitable for the present in~~ention generally comprise C;-C6 hydrocarbons and nurtures thereof, with pentane isomers being preferred. The blowing agent IIRH 65,205.063 must have a boiling point below that of the melting point of the polymer so that upon healing of the expandable polystyrene beads the blowing agent will vaporize anal leave the beads thereby expanding the bead. Generally a boiling point below 70° C is preferred. Suitable blowing agents include, for example_ propane; butane; isobutane; n-pentane;
isopentane;
neopentane; cycJopentane; methylcyclopentane; 2-methyl pentane; 3-methyl pentane; 2,2-dimethylbutane; 2,3-dimethylbutane; pentane petroleum distillate fractions;
hexane;
cyclohexane; methylcyclohexane; and hexane isomers. Blowing agents are generally used at levels of from about 2 to about 5 weight percent, more preferably from about 2.5 to about 4 weight percent based on the total weight of the bead.
1o As discussed above, the suspension polymerization usually is carried out in the presence of suspension stabilizers and polymerization catalysts. Common suspension stabilizers include: molecular colloids, such as, polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (1'VP); the pickering salts such as Ca;(,PO,~)~ in combination with an extender such as dodeeylbenzol sulfate. Typical polymerization catalysts include radical catalysts such ~5 as dibenzoylperoxide, tent-butyl perbenzoate, and dicumyl peroxide. Other suitable catalysts are well lcno~m to one of ordinary skill in the art.
The expandable polystyrene beads can also include other additives like flame retardants based on orcanie bromo ox c.hloro compounds, such as, rris(dibromopropyl) phosphate, hexabromocyclododecane, chloroparaffin. Other additives include antistatic 2o a~cnts, stabilizers, dyes, lubricants, and fillers. To aid in demolding the object formed from the expandable polystyrene beads one may also include compounds like glycerine ester, hydroxycarboxylic acrid ester.

As discussed above, typical anti-lumping agents include zinc stearate, melamine fotrnaldehyde condensates of silica eel, glycerol mono stearate, ethylene-bis steararnide (acrawa~;j, and silica. The typical agents are not ef..fective when expanding beads to Iower densities or when using the indicated love levels of blowing agents. The present invention discloses a new class of anti-lumping agents that are. block copolymers.
By the term block copolymers it is meant a polymer having blocks formed of a plurality of a repeating unit, such as ethylene oxide (E0), that are attached to additional blocks of a plurality of another repeating unit, such as, propylene oxide (~'O). A given anti-lumping copolymer may comprise a series of these blocks in an arrangement such as: EOX-to POy; EO;~-POy-EO,.; POx-EO~ PO,; etc. The particular arrangement of the blocks along with the overall HLB value for the polym~:r are important characteristics. rt is preferable to match the arrangement of the bloclrs to the overall hydrophobicity of the expandable bead. In other words, when the bead is more hydrophilic, then an anangernent of EOr-POYEOZ is beneficial.
When the bead is more lipophilic, then an arranUement of POr EOYPOz is more beneficial.
t5 in general, it is preferable that the amount of EO, which is generally hydrophilic, in the block copolymer range between about 65 and ~0% by weight based on the total weight of the copolymer. The amount of P0, which is generally lipophilic. is preferably from about 2.0 to 35~o based on the total weight of the copolymer. Tt is preferable that the number average molecular weight of the copolymer be from appro~cimately 4,000 to 15,000, preferably from 2o about 6,000 to 11,000, most preferably from about 7,000 to 10,000_ In Qeneral, the viscosity of these copolymers is from about x.50 to 2.500 cps at 77°C, provided they are in a solid form at ?0°C. The melt point of the copolymers ranbes from approximately 45 to 60°C.

1n gencra.l, it is preferable that the HLB value of the copolymer range from about 1G to 29, depending on thz surface characteristics of the bead as discussed above, when it is utilized to coat an expandable polystyrene bead prepared by an aqueous suspension reaction. The HI..,B value is a semi-empirical number determined from the weight percentage of hydrophilic stoups to lipophilic groups within a molecule or mixture. The value is a general indication of the polarity of the molecules and ranges from 1 to 40. The HLB value increases with increasing hydrophilicity. Preferred HI.B values of the block copolymers are from about 19-29, and most preferably fzom about ~~ to 29.
Methods for formation of the block copolymers described above an: well known in the to art and will only briefly be described. Typically, one utilizes an initiator molecule such as a lower molecular polyhydroxyl or polyamine initiator molecule. Ey way of example, the initiator can be a diol, triol, diamine or triamine. Examples include propylene glycol, ethylene Glycol, glycerol, and ethylenediamine. The initiator is utilized in an alkali-catalyzed polymerization reaction v~ith a.Ikylene oxide compounds such as ethylene:
oxide or propylene oxide to generate a polyctherol. When one caxries out the alkali-catalyzed polymerization sequentially using only a Single alkylene oxide at a time, one can form block copolymer polyetherols that are useful as the anti-lumping agents of the presont invention. One can also utilize amines such as ethylenediamine as the initiator in these reactions.
Suitable block copolymers include the Pluronic'" or Pluronic R~' copolymer series produced by BASK
2o Corporation. Preferred block copolymers include the PL.URONiC F68 and F108 products.
After formation of the polystyrene beads they are separated from the aqueous phase, washed and dried. One method of drying the beads is to pass them into a screw conveyor that feeds a heated airveyor for flash drying. One method for application of the ne~~~ anti-lumping S

aCcnts is to add i.t to the beads in the screw conveyor. Some mixing occurs in the screw conveyor and the rest occurs in the flash dryer. The block copolymer anti-lumpinG agent can be added alone or with other anti-lumping agents. The ant-lumping agent is Generally incorporated into the polymer bead in an amount of from about 2~0 to 2500 ppm, based on the we.i~ht of the polymer. Preferably, the anti-lumping agent is present in an amount of from about 300 to 1250 ppm.
Once dried the beads are sized into fraction<. The formed beads generally have a diameter of from about 0.2 to 4.0 mm. Another method for adding the new block copolymer anti-lumping agents to the. beads comprises adding the agent to a powder blending system to after sizing of the beads. These blending systems typically include a plow blade mixer such as the Littleford FKIvI mixer'. The anti-lumping agent and other additives a:re combined with the beads and mixed usinC a plow blade mixer.
The initial expansion of the beads is generally carried out in a closed vessel batch expander with a. steam injection. process. Typical eaam.ples of such expanders include:
Weiser VIrT400, Kurtz 1~V 10U0, and Dingledein VA2000. The beads are passed throuQ.h the expander and are heated such that the blowing agent vapoi~zus thereby expanding the beads.
The flow rate of the beads through the expander deterniines the amount of expansion and it is generally reported as pounds per hour per cubic foot of expander volume, or for a given expander as pounds per hour. During the initial expansion stage lumping of the expanding 2o polystyn;ne beads can. occur. To achieve low density polystyrene beads the expansion time must be increased, but in the past increasinC the expansion time has also increased the arn.ount of lumping. With tho anti-lumping went of the present in~~ention it is possible to achieve low density polystyrene beads ~~ithout an inczease in the amount of lumping. As explained above, when the beads lump, they can be difficult to use in a subsequent molding process.
.E~~,Z~PLE 1 To demonstrate the effectiveness of the block copolymer anti-lumping agents of the present invention, a series of expandable polystyrene beads containing from about 2~o to about 5%a by weight, based on the total weight of the bead, of a C~ to C6 hydrocarbon blowing agent are prepared in the presence or absence of PLURONIC F68 (F68). PLURONIC
F68 is formed by initially adding propylene oxide (PO) to the hydroxyl groups of propylene glycol 1U initiator molecule to form a PO block, then ethylene oxide (E0) is added to the reactive ends of the PO block and polymerisation continues to form a structure of EO~-POYEOZ. This block copolymer has 80~u by weight EO and 20% by weight PO, a number average molecular weight of 8400, an HLB of L9, a melt point of 5?° C and a viscosity of 1000 at 77° C. The F68 was present in an amount of 1000 ppmbased on the total weight oFthe unexpanded beads. The aqueous suspension z~action for formation of the expandable beads is carried out using a typical aqueous suspension polymerization. The pLUIZONrC F68 is added to the beads by adding it to a powder blending system after suing of the beads. The blending system included a ploy: blade Littlcford FkM mixer.
The expandable beads foamed utilizing the above-referenced aqueous suspensions are then tasted for lumping, the minimal density that could be formed during the initial expansion step (prepuffs) and the ma:ximaI rate at v~~hich the beads could be expanded during the initial step. Tn addition, each sample is tested for a number of parameters durinc a molding step ;o including the averace cycle time for a block mold and the average cycle tine for a shaped mold. The results of these experiments are presented in Tabl-c z below:
Table 1 Measured X'ro _X 2 ~3 ert ' ~

Minimal density 0.90 0.88 1.05 in pci;

w/out F68. ' Maxin.xl flow 300 3~0 244 rate in lbsmr v~lout FGS

Minimal density 0.86 0.90 1.00 in pcf with F6S

Maximal flow 315 3d'? 315 rate in 1bslhr with FG3 ___ Avera?e cycle 7-10 rains. 7-10 rains. Not determined time. blook mold wlaut F68 Average cycle 100 sees. SO-100 sets. 55 5ecs.
time sha ed mold w/out Cycle time shapedsees. 92 sees. 65-110 sets.
mald with FGR ~

Lumping w/out 5.0-10.0 10.0-15.0 10.0-20.0 ~fo by wt;ight of the ex anded buds Lumping with 0.0 0.0 0.0 Vii, by weight of the ex anded beads The data in the Table I demonstrate that PL~fJRONIC FGfi utilized in an amount of 1000 ppm enables one to f()IZlI a prepuff havity a similar or lower density than that obtainable without FG8 and to foam the prepuff at a much hither rate. Thus, inclusion of the PLURONIC F68 anti-lumping agent increases the rate of formation of prepuff. In addition, inclusion of the F68 permitted a faster cycle time during the molding step when molding a shape. In addition, the data clearly show the complete prevention of lumpinC
by inclusion of the PL:UROI~TIC F68. The amount of lumping in the absence of the anti-lumping agent of the present invention was significant.

Thus, use of these anti-lumping agents will enable one to create prepuffs with no lumping, at a faster rate and to substantially reduce the average cycle time for the molding step, thereby leading to faster production of molded parts.

Claims (13)

1. ~A method for the formation of an expandable bead comprising the steps of:
a) ~forming an expandable polystyrene bead containing from

2% to 5% by weight, based on the total weight of the bead, of a C3 to C6 hydrocarbon blowing agent; and b) ~coating the expandable polystyrene bead with an anti-lumping agent comprising a block copolymer comprising blocks of ethylene oxide and propylene oxide, wherein the block copolymer comprises from 80% to 65% by weight ethylene oxide and from 20% to 35% by weight propylene oxide, based on the total weight of the copolymer, and has a hydrophilic-lipophilic balance (HLB) value of from 19 to 29 said anti-lumping agent present in an amount of from 250 to 2500 ppm based on the weight of the bead.

2. ~A method as defined in claim 1, wherein step a) is further defined by forming the expandable polystyrene bead by polymerizing at least one monomer selected from the group consisting of styrene, alpha-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ar-ethylstyrene, ar-vinylxylene, ar-chlorostyrene, ar-bromostyrene, mono- and polyhalogenated vinyltoluenes.

3. ~A method as defined in any one of claims 1 to 2, wherein the expandable polystyrene bead comprises polystyrene.

4. ~A method as defined in any one of claims 1 to 3, wherein step b) is further defined by providing the anti-lumping agent in an amount of from 300 to 1250 ppm.

5. ~A method as defined in any one of claims 1 to 4, wherein the block copolymer has a number average molecular weight of from 4,000 to 15,000.

6. ~A method as defined in any one of claims 1 to 4, wherein the block copolymer has a number average molecular weight of from 7,000 to 10,000.

7. ~A method as defined in any one of claims 1 to 6, for the formation of an expandable polystyrene bead having a density of from 1.5 to 0.75 pounds per cubic foot.

8. ~A method as defined in any one of claims 1 to 6, for the~
formation of an expandable polystyrene bead having a density of from 1.2 to 0.85 pounds per cubic foot.

9. ~A method as defined in any one of claims 1 to 8, wherein the blowing agent comprises at least one of propane; butane; isobutane; n-pentane;
isopentane; neopentane; cyclopentane; methylcyclopentane; 2-methyl pentane;
3-methyl pentane; 2,2-dimethylbutane; 2,3-dimethylbutane; pentane petroleum distillate fractions; hexane; cyclohexane; methylcyclohexane; and hexane isomers.

10. ~A method as defined in any one of claims 1 to 9, wherein the blowing agent is present in an amount of from 2.5% to 4% by weight, based on the total weight of the bead.

11. ~A method as defined in any one of claims 1 to 10, wherein said block copolymer has an HLB value of from 24 to 29.

12. ~A method as defined in any one of claims 1 to 11, wherein step b) is further defined by combining the expandable bead formed in step a) with the anti-lumping agent in a screw conveyor, thereby coating the bead with the anti-lumping agent.

13. ~A method as defined in any one of claims 1 to 11, wherein step b) is further defined by combining the expandable bead formed in step a) with the anti-lumping agent in a plow blade mixer, thereby coating the bead with the anti-lumping agent.