KR940006657B1 - Polyphenylene ether-alkenyl aromatic polymer blends having organobromine additives - Google Patents

Abstract

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Description

[Name of invention]

Polyphenylene Ether-alkenyl Aromatic Polymer Blends with Organobromine Additives

Detailed description of the invention

[Technical Field and Background Art]

The present invention relates to an expandable blend of polyphenylene ether and alkenyl aromatic polymerizers, and also to the addition of certain organobromines to the blend. The present invention encompasses this composition and its preparation.

Expandable blends of polyphenylene ether resins ("PPE") and alkenyl aromatic polymers ("PS") (hereinafter referred to as "PPE / PS" blends or compositions) are known. PPE may be added to alkenyl aromatic polymers such as polystyrene to improve impact strength, flammability, tensile strength and other mechanical properties, and PS may be added to polyphenylene ether resins to improve processability. Commercially useful PPE / PS blends can be used in the practice of the present invention. This PPE / PS blend is a thermoplastic that can be extruded and molded into a product. Such extrusion and molding techniques are well known to those skilled in the art. These PPE / PS blends are expandable through the use of swelling agents in materials having a density of less than 30 pounds / ft ³ .

PPE / PS blends are made from pellets, beads or other particulate forms. Pellets, beads, or other particles are expanded to produce expanded beads or other expanded particles. Inflators are typically used to promote expansion or for expansion. Such expansion techniques are well known to those skilled in the art. Beads or other expanded particles can be used for the production of shaped articles. Inject beads or other expanded particles into the mold and heat them to the selected or required temperature. The PPE / PS blend in the mold is then cooled. The mold cooling time required by a particular PPE / PS blend is an important characteristic of the blend.

One object of the present invention is to reduce the mold cooling time of PPE / PS blends. Another object of the present invention is to reduce the amount of residual expander associated with PPE / PS blends after expansion, in particular after molding.

These and other objects and immersions and other aspects of the invention are described in more detail below.

[Description of Invention]

We have found that some organobromine can reduce the mold cooling time of the PPE / PS composition. Moreover, this organobromine can reduce the amount of residual swelling agent associated with the PPE / PS composition after expansion, in particular after molding of the composition. The composition of the present invention comprises a PPE / PS blend and includes at least one of the following organobromines.

Tetrabromocyclooctane

Hexabromocyclododecane

Tetrabromovinyl cyclohexene

Bis (allyl ether) of tetrabromo bisphenol A

In addition, the inventors have found that documil peroxide is used in combination with organic bromine to further improve (reduce) the mold cooling time of the PPE / PS composition.

Detailed Description of the Invention

Examples of the Invention Useful polyphenylene ether resins ("PPE") (which may be combined with alkenyl aromatic polymers to make blends) are described in US Pat. Nos. 3,306,874 and 3,306,875 (Hey) and 3,257,357; 3,257,358 (Stamatov). These patents are described herein by reference.

Although the present invention is not limited thereto, it is preferable that the polyphenylene ether resin used in the PPE / PS blend is a homopolymer or a copolymer having a unit of the following structural formula.

Wherein Q, Q ', Q' 'and Q' '' are each selected from the group consisting of hydrogen, halogen, hydrocarbon, halogenated hydrocarbon, hydrocarbonoxy and halohydrocarbonoxy, n is the total number of monomer units It is an integer up to at least about 20, usually an integer up to about 50.

Polyphenylene ether resins can be prepared according to the known methods described in the above patents of Hay and Stamatoff from the reaction of phenols including but not limited to:

next :

2,6-dimethyl phenol, 2,6-diethyl phenol, 2,6-dibutyl phenol, 2,6-dipropyl phenol, 2,6-diphenyl phenol, 2-methyl-6-toryl phenol, 2 -Methyl-6-methoxy phenol, 2,3,6-trimethyl phenol, 2,3,5,6-tetramethyl phenol, 2,6-diethoxy phenol

Each of these may be reacted alone to make the corresponding homopolymer, or may be reacted in pairs or with another phenol to make the corresponding copolymer. Examples of homopolymers include the following.

Poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2,6-diolyl-1,4- Phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2-methyl-6-tolyl -1,4-phenylene ether), poly (2-methyl-6-methoxy-1,4, -phenylene ether), poly (2-methyl-6-butyl-1,4-phenylene ether), Poly (2,6-dimethoxy-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly (2,3,5,6-tetramethyl -1,4-phenylene ether). Poly (2,6-diethoxy-1,4-phenylene ether)

Examples of copolymers are poly [2.6-dimethyl-co-2,3,6-trimethyl-1,4-phenylene ether) and poly) 2,6-dimethyl-co-2-methyl-6-butyl Copolymers of 2,6-dimethylphenol with other phenols, such as -1,4-phenylene ether).

For the purposes of the present invention, particularly preferred polyphenylene ethers are two ortho-ether atoms in the ether atomic oxygen, which are alkyl at Q and Q 'of the above formula, very preferably alkyl having 1-4 carbon atoms. And those having alkyl substituents in position.

Examples of this class are:

Poly (2,6-dimethyl-1,4-phenylene) ether; Poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4 -Phenylene ether), poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether

Most preferred polyphenylene ether resins for the purposes of the present invention are poly (2,6-dimethyl-1,4-phenylene) ethers.

The polyphenylene ether in the composition of the present invention may be a single type of polyphenylene ether resin or may be a plurality of different types of polyphenylene ether resins. For example, polyphenylene ethers are polyphenylene ethers such as poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,6-dipropyl-1,4-phenylene) ether. It may be a mixture of resins.

Unless otherwise stated or otherwise required in the context, any reference in this specification or claims to polyphenylene ethers may be made from a single polyphenylene ether resin or other types of plural polyphenylene ethers. It may also mean or include a resin mixture.

Useful alkenyl aromatic polymers ("PS"), which can be blended with polyphenylene ethers to make a mixture, are described in patent publications including US Pat. No. 4,727,093 (Allen), which are examples of the present invention. Is described herein by reference. As used herein, the term “alkenyl aromatic polymer” is a terpolymer of an alkenyl aromatic compound of a homopolymer with a copolymer and one or more other materials, as is the case with modified high impact rubbers. It means through (polymer consisting of three types of monomers). Preferably, the alkenyl aromatic polymer should at least partially give off on the unit of the structure

Wherein R ¹ and R ² are selected from the group consisting of lower alkyl and lower alkenyl groups having 1-6 carbon atoms; R ³ and R ⁴ are selected from the group consisting of chloro, bromo, hydrogen and lower alkyl and lower alkenyl groups having 1-6 carbon atoms, and R ⁵ and R ⁶ are lower alkyl and lower eggs having 1-6 carbon atoms and hydrogen; Selected from the group consisting of kenyl groups, or R ⁵ and R ⁶ are linked in a chain together with a hydrocarbyl group, and may form a naphthyl group.

The above structural formulas include styrene, as are the single agents and analogs of styrene. Specific examples include, in addition to styrene, chlorostyrene, bromostyrene, alpha-methylstyrene, para-methyl styrene, vinylstyrene, divinylbenzene and vinylnaphthalene. Of these, styrene is particularly preferred.

For illustration purposes, the alkenyl aromatic polymer (PS) may be a single polystyrene or other alkenyl aromatic singles that have been improved by blending or interacting with synthetic rubbers such as natural rubber or polybutadiene, polyisoprene EPDM rubber or silicone rubber. May be a polymer, or may be a copolymer, or a block copolymer of styrene and butadiene (such as AB, ABA, ABAB or ABABA type), or acryl, including styrene and an elastomeric material, but a hydrogenated form of those described above Nitriles, terpolymers of styrene and butadiene (ABS), styrene-acrylonitrile copolymers (SAN) and copolymers of styrene and maleic anhydride (SMA), and styrene, butadiene and couples, including hydrogenated forms Terpolymers with other alkenyl aromatic compounds, such as radial teleblock copolymers of ring agents, or styrene-mar It may also be an improved alkenyl aromatic copolymer or ter-polymer as a rubber, such as a rubber improved with a lane acid anhydride copolymer. Most of these are described in a patent publication including the Cizek patent described below. .

The alkenyl aromatic polymer constituting the composition of the present invention may be a single kind of alkenyl aromatic polymer, or may be another kind of alkenyl aromatic polymer.

For example, the alkenyl aromatic polymer may be a mixture of polystyrene homopolymers and other kinds of alkenyl aromatic polymers such as block copolymers of styrene and butadiene. Unless otherwise stated or otherwise required in the context, any reference in the specification or claims to alkenyl aromatic polymers may refer to mixtures of a single alkenyl aromatic polymer or a plurality of different alkenyl aromatic polymers. May mean or include.

Blends of polyphenylene ethers with alkenyl aromatic polymers (“PPE / PS” blends) are described in patent publications, including US Pat. No. 3,383,435 (CeJ) and US Pat. No. 4,727,093 (Allen). These patents are described herein by reference.

Polyphenylene ether resins and alkenyl aromatic polymers may be blended in any proportion. However, PPE / PS blends or compositions used in the practice of the present invention should be considered to have at least 2% by weight PPE based on the total weight of PPE and PS. Blends or compositions comprising less than 2% by weight of PPE are believed to be primarily PS compositions and do not exhibit the beneficial property improvements associated with PPE / PS blends. In addition, PPE / PS used in the practice of the present invention. Admixtures or compositions should be considered to have at least 2% by weight of PS, based on the total weight of PPE and PS. Blends or compositions comprising less than 2% by weight of PS are considered to be primarily PPE compositions. Thus, the PPE content is in the range of weights ranging from 2-98 and the PS content is 98% in weights.

Typically, PPE / PS blends used in the practice of the present invention are characterized in that, based on the total weight of PPE and PS, the PPE amounts to about 10- about 90% by weight, preferably in this range. PS is about 20-80% by weight based on total weight. Therefore, the amount of PS is in the range from 90% to 10% by weight, preferably within about 80% to 20% by weight. For a given blend or composition, the sum of the weight percent PPE and the weight percent PS is almost because these weight percentages are based on the total amount of PPE and PS alone and do not include any amounts of any other ingredients in the blend or composition. It should always be 100.

Methods and processes for admixing polyphenylene ether (PPE) and alkenyl aromatic polymers (PS) to make PPE / PS blends are known to those skilled in the art. For example, PPE (typically powder or pellets) may be formulated by dry blending with PS (typically pellets) in a blender to produce a uniform mixture of PPE and PS. Can be. Thereafter, the mixture is mixed at a slit temperature and extruded from a conventional thermoplastic extruder that shears the thicker PPE / PS blend.

The extrudate, which is in the form of strands, is cooled as cooling water. Cooled strands (stranded extrudate) are made into pellets by conventional pelletizers. PPE / PS pellets are of convenient type, but other particles (other types of particles) can be used.

During the miscation step, additives as described may be added to the PPE / PS blend. Such additives include, but are not limited to, rubber impact modifiers, flame retardants, stabilizers for heat and color stability, antioxidants, processing aids and plasticizers, reinforcing and expanding fillers, pigments and the like. The choice and amount of additives depends on the properties and properties required for the finally obtained PPE / PS composition.

Expanding agents can be used in the compositions of the present invention to facilitate or expand the expansion of PPE / PS pellets (or other PPE / PS particles). Expanding agents and their purpose, function and use can be found in US Pat. No. 4,727,093 (Allen) and the Polymer Science and Technology Encyclopedia, 2nd Edition, Vol. 2, PP434-446, all of which are incorporated herein by reference.

The expanding agent may be a physical expanding agent or a chemical expanding agent. Suitable swelling agents include conventional hydrocarbon or fluorocarbon physical swelling agents. Preferred hydrocarbon expanders are aliphatic hydrocarbons having 4-7 carbon atoms. Known physical expanding agents include the following.

Pentane, n-pentane, 2-methyl butane, 2,2-dimethyl propane, 1-pentene, cyclopentane, hexane, n-hexane, 2-methyl pentane, 3-methyl pentane, 2,3-dimethyl butane, 2,2-dimethyl butane, 1-hexene, cyclohexane, heptane, n-heptane, 2-methylhexane, 2,2-dimethyl pentane, 2,3-dimethyl pentane, 2,4-dimethyl pentane, 3,3-Dimethyl pentane, 3-ethyl pentane, 2,2,3-trimethyl butane, 1-heptane, benzene, toluene, dichloromethane, trichloromethane, trichloroethylene, tetrachloromethane, 1,2- Dichloro ethane, 1,1,2-trichloro trifluoro ethane, methanol, ethanol, 2-propanol, ethyl ether, isopropyl ether, acetone, methyl ethyl ketone.

Fluorocarbon physical expanding agents include CCl ₃ F, CCl ₂ F ₂ , CHClF ₂ and CClF ₂ -CClF ₂ . These are compatible as Freon 11, Freon 12, Freon 22 and Freon 114. Still other halogenated hydrocarbon physical swelling agents may include methylene chloride, chloroform, CCl ₄ , and the like.

Compressants (eg carbon dioxide and nitrogen) can also be used as physical expansion agents.

Chemical expanding agents that can be used in conjunction with the PPE / PS compositions of the present invention include:

Sodium bicarbonate (sodium bicarbonate), dinitrosopentamethylene tetramine, P-toluene sulfonyl hydrazide, 4,4PPE / PS-oxybis (benzenesulfonyl hydrazide), azodicarbonamide (1,1PPE / PS-azobis formamide), P-toluene sulfonyl semicarbazide, 5-phenyl tetrazole, 5-phenyl tetrazol analogue diisopropyl hydrazodicarboxylate, 5-phenyl-3,5-dihydro -1,3,4-oxadiazin-2-one

Thermosetting polyester expanding agents can also be used in the practice of the present invention.

The amount of swelling agent used in the compositions of the present invention is an amount sufficient to effect swelling of the composition. Expansion occurs when the composition is subjected to expansion conditions (eg, steam heating as in the examples described below.) Typically, the expansion agent is about 2% by weight, based on the total amount of PPE, PS and the expansion agent. The amount may be in the range of about 15% by weight.

PPE / PS compositions of the present invention comprise organobromine selected from the following group.

(i) tetrabromocyclooctane,

(ii) tetrabromo vinyl cyclohexene,

(iii) hexa bromo cyclododecane,

(iv) bis (allyl ether) of tetrabromo bisphenol A, and

(v) certain mixtures (ie combinations) of these (two or more of (i), (ii), (iii) and (iv)).

Optionally one or more of these organobromines can be used in the PPE / PS composition. The amount of organobromine that can be used in the PPE / PS composition is the "effective amount". An effective amount means effective in reducing the cooling time of the mold and / or effective in reducing residual swelling agent when compared to the same composition without organobromine. It is contemplated that the present invention will be practiced within the following limitations.

(i) at least about 0.1% by weight of organic bromine, and

(ii) does not exceed about 6% by weight of organobromine.

More typically, the organobromine concentration is at least within the range of about 0.2% by weight and about 3% by weight, and preferred is within the range of about 0.5% by weight to about 2% by weight. The above weight percentages refer to the amount of organobromine in the PPE / PS composition based on the total amount of PPE and PS in the composition.

The composition of the present invention can be obtained by treating PPE / PS blend with organobromine. This treatment is made possible by saturating the PPE / PS blend with organobromine or by incorporating the organobromine into the PPE / PS blend, or by contacting or blending the PPE / PS blend with organobromine.

In addition to organobromine selected from the group, dicumyl peroxide may be included in the PPE / PS composition. The amount of dicumyl peroxide in the PPE / PS composition may be an amount effective to reduce the mold cooling time of the composition and / or an amount effective to reduce residual swelling agent as compared to the same composition without dicumyl peroxide. The amount of dicumyl peroxide is in the range of about 0.02% by weight to not more than 2% by weight. More typically the dicumyl peroxide concentration is in the range not exceeding at least 0.05% by weight to 1% by weight. Weight percent above means the amount of dicumyl peroxide in the PPE / PS composition based on the total amount of PPE and PS in the composition. If dicumyl peroxide is used in the PPE / PS composition, the preferred concentration of organobromine is in the range of about 0.5% to 1 wt%, and if dicumyl peroxide is not used in the PPE / PS composition, the preferred concentration of organobromine Is in the range of about 1% to about 2% by weight.

PPE / PS blends can be treated as dicumyl peroxide. This treatment saturates the PPE / PS blend as dicumyl peroxide, or incorporates the PPE / PS blend into dicumyl peroxide, or contacts the PPE / PS blend with dicumyl peroxide, or It becomes possible by mix | blending well.

EXAMPLE

The examples given below illustrate the treatment of the PPE / PS mixture with organobromine. Tables 1,2 and 3 below summarize the experimental data corresponding to the 13 PPE / PS compositions (eg mold cooling time and residual expander). The composition is referred to by the letters A, B, C, D, E, F, G, H, I, J, K, L and M. The composition is prepared from PPE / PS pellets made by General Electric Company (G.E.Co.). PPE / PS pellets are a blend of 20% by weight polypentylene ether resin and 80% by weight polystyrene, and polyphenylene ether is poly (2,6-dimethyl-1,4-phenylene) having a weight average molecular weight of 42,000. Ether polystyrene is a polystyrene homopolymer having a weight average molecular weight of 185,000. Experimental compositions consist of Control Compositions A and J (without organic bromine or excipients), Compositions F and G (with excipients but no organic bromine), Compositions B, C, D, E, H, I, K, L and M We include (we do not have organic spirit)

In Tables 1 and 2 the pF (prepuff) density is given by LB / ft ³ . In Tables 1 and 2 the residual pentane in the pF state (expansive agent) is given in weight percentages based on the total amount of PPE and PS alone in the pF state (including the expanding agent and additives). A prepuff (pF) is a PPE / PS composition after inflation just before molding.

In Table 3 the density of molded and conditioned blocks of the PPE / PS composition is given as LB / ft 3. The block is allowed to stand for 24 hours under laboratory ambient temperature conditions.

In Table 3, the residual pentane (expansive agent) in the molded and conditioned blocks of the PPE / PS composition is given in weight percent based on the total amount of such blocks.

The preparation and testing of composition C is described for the first time. In order to produce composition C, the batches were prepared by separately injecting the components identified below into a one-gallon, jacketed stainless steel Parr company reactor at room temperature (about 72 ^° F.). Initially PPE / PS pellets and demineralized water are introduced as follows; Mix 1.986 ml (g) of demineralized water with 1,109.5 g of PPE / PS pellets. The batch consists of 64% by weight of water and 36% of pellets. The batch is continuously stirred with a three blade shaker while adding other ingredients. 8.0 ml of 2% phosphoric acid is added to lower the pH from 5.7 to 3.0. It comprises 0.014% of the batch based on the weight of the phosphate pellets, or 0.008% based on the weight of the water.

Next, 7.76 g of tetrabromocyclooctane is added to the batch as the selected organic bromine. The amount of tetrabromocyclooctane is equivalent to about 0.7% by weight based on the amount of PPE / PS. Add 1.39 g of dicumyl peroxide as excipient. The amount of dicumyl peroxide is equivalent to about 0.125% by weight based on the amount of PPE / PS. 60.0 m1 of 5% polyvinyl alcohol ("PVA") (Kurary Poval 420) is dissolved in the composition as a suspending agent. PVA is equivalent to about 0.15% of the composition based on the amount of water. Finally, n-pentane. 97 656 g (8.8% based on the weight of the PPE / PS pellet) are added to the blend as expanding agent. Using a microricon computer (manufactured by Research Corporation), the time / temperature protopills of the batch process exceed the pre-selected time intervals upon injection of each component into the reactor as described above. Program the computer so that it runs in eight intervals or segments. At the start of the reaction, the reaction vessel is preheated to 71 ^o F within 2 minutes before introducing the batch components identified above. Shake the batch while fully injected and saturated. While maintaining the reaction vessel temperature at 72 ^° F. for about 30 minutes, the batch components are separately injected into the reaction vessel as described above. The reaction vessel is then sealed. The batch temperature is controlled using a loop / circulation system sealed with steam / mole. Heat the batch to 90.0 ^o F in 5 minutes. The batch is then heated to 28.0 ^o F for 82 minutes, then the reaction vessel is heated to 284.0 ⁰ F, the highest temperature in 6.0 minutes. The batch is held at 284.0 ^o F for 300 minutes. After cooling the batch to 84 ^o F, the composition is poured into a beaker and washed five times with tap water.

Under the conditions of the injection and saturation process, the pellets are thought to be almost spherical (ie beads). The saturated beads are split into two parts and then placed in an induction dryer using 35 ° C. inlet air for 35 minutes to dry one part. The other part is placed in an induction furnace using inlet air at room temperature for 35 minutes to dry the saturated beads. Tables 1 and 2 below describe the results and data for the parts dried using inlet air at 35 ° C. in an induction-phase dryer. 500 g of beads are smoothed as 0.05% Hi Sil 223, amorphous silica powder. Smoothly beaded beads are sifted through the sieve of the US NO.12 mesh and sifted through the NO.25 mesh. The beads are then stored in sealed glass jars for 6-10 days. The beads are then placed in a batch expander. Approximately 25-50 g of saturated beads are poured into an improved pressure cooker. The pressure cooker is already equipped with a shaker inside. 2Psig and 212 ° F steam are injected into the pressure cooker through the holes in the shaker. Shake the fresh beads and treat them with steam for 400 seconds to allow them to swell (the beads are inflated). Remove the expanded beads from the batch expander and leave for 12-24 hours. The expanded beads are then placed in a cylindrical mold 5 3/4 inches in diameter and 2 3/8 inches in length. The sealed mold is placed in an improved pressure cooker and heavy medium is injected into the pressure cooker for 20 seconds. Close the steam outlet and inject additional steam for 20 seconds. The steam is spooled to lock and the steam outlet is opened to cool the mold and the PPE / PS composition in the mold.

As the mold and PPE / PS composition cools, the mold pressure (ie, the strongfun pressure) is reduced. Thus, the temperature of the composition (steel piece) in the mold is a function of the mold pressure. The slab pressure as a function of time is recorded on a strip chart recorder using a transducer to measure distortion of the bottom surface of the mold. The decrease in pressure is timed. The mold pressure for composition C is reduced to 5.2 Psig in 14.0 minutes. Residual pentane (expansive agent) in the pF (prepuff) state immediately after swelling is 3.14 weight percent in weight percent based on the total amount of the pF (prepuff) state.

The above description of composition C can be used in other compositions, with the exception of the changes described below and the changes described in Tables 1,2 and 3. The weight percentages (% by weight) given below for organobromine (organobromine) and dicumyl peroxide are based on the total amount of PPE and PS alone.

Composition A does not include organobromine or excipients and excludes the corresponding organobromines and excipients in the process steps. The mold cooling time (at 5.2 Psig) for composition A is at least 60 minutes (see Table 1). Composition B comprises 0.2% by weight tetrabromo cyclooctane and 0.125% by weight dicumyl peroxide. The mold cooling time for composition B (5.2 Psig) is at least 60 minutes (see Table 1). Compositions A and B were also compared in Table 2, where the mold cooling time to 7.4 Psig was recorded. The cooling of composition B with organobromine to 7.4 Psig is 8.8 minutes, and the cooling of composition A without organobromination to 7.4 Psig takes 44.5 minutes.

Composition D comprises weighted organobromine (2 wt% tetrabromo cyclooctane). The mold cooling time (to 5.2 Psig) is only 4.3 minutes. Under this level of organobromine, apparent bead shrinkage and effects of the PPE / PS composition are observed, making this concentration undesirable for applications that may be affected by these properties.

Composition E comprises organobromine (0.7 wt% tetrabromo cyclooctane) but no excipient (dicumyl peroxide) (with 5.2 Psig) mold cooling time is 33.0 minutes, which gives a control (Composition A) While it is a significant improvement over that, it is practically not the only improvement made by Composition C comprising dicumyl peroxide.

Compositions F and G illustrate an example of using dicumyl peroxide as excipient without organobromine. The mold cooling time (in 5.2 Psig) for these compositions is at least 60 minutes.

Composition H comprises another organobromine (0.7% by weight of bis (allyl ether) of tetra bromo bisphenol A) which results in 24.3 minutes with improved mold cooling time (to 5.2 Psig) compared to control composition A.

Composition I contains two organobromines (0.7% by weight of tetrabromo cyclooctane and tetra bromo bisphenolol A) which achieve 26.0 minutes, which is an improved mold cooling time (to 5.2 Psig) compared to crude control composition A. 0.125% by weight of bis (allyl ether)).

Composition J is a control composition without organobromine and excipients. Mold cooling time (to 16.4 Psig) is greater than 90 minutes.

Composition K comprises other organobromine (0.7 wt% tetra bromo vinyl cyclohexene) and an excipient (0.125 wt% dicumyl peroxide). The mold cooling time (to 16.4 Psig) is significantly reduced to 10.7 minutes compared to Control Composition J.

Composition L comprises organobromine (0.7 wt% tetra bromo cyclooctane) and excipient (0.125 wt% dicumyl peroxide). Mold cooling time (to 16.4 Psig) is significantly reduced to 3.2 minutes when compared to Control Composition J.

Composition M comprises other organobromine (0.7% by weight hexa bromo cyclo dodecane) and an excipient (0.125% by weight dicumyl peroxide). Mold cooling time (to 16.4 Psig) is significantly reduced to 5.6 minutes compared to Control Composition J.

Xanthan pentane (less than 0.1% by weight) in the shaped and conditioned blocks of compositions K, L and M is substantially less than residual pentane (1.4% by weight) in the shaped and conditioned blocks of control composition J. Thus, it can be seen that organobromine is particularly influential and reduces the residual swelling agent content in the molded composition.

Tables 1,2 and 3 show that PPE / PS compositions prepared in accordance with the present invention reduce mold cooling time. Even small amounts of organobromine significantly reduce the mold cooling time of the composition. The use of dicumyl peroxide with organobromine further improves (ie reduces) mold cooling time. Tests show that the density of the composition does not substantially change with the addition of organobromine or excipients. The amount of residual pentane in the pF (prepuff) state is not substantially affected, but in some cases shows some improvement. Table 3 shows that residual pentane (ie molded PPE / PS composition) in molded and conditioned blocks is significantly reduced when organobromine is used.

The organobromine used in these examples is characterized according to the melting range and the average percentage of bromine as follows.

The organobromine of the present invention is not limited to the above properties.

Since the foregoing description of the invention has fully shown the general nature of the invention, it is possible to use other knowledge to readily modify this description or to make various modifications without departing from the broad concept. Therefore, such changes and modifications are intended to be included within the meaning and scope of the following claims, which define the subject matter regarded as the present invention.

TABLE 1

Molding Data for Expandable Polyphenylene Ether-Polystyrene Blends

TBCO tetrabromocyclooctane

DCP Dicumyl Peroxide

TBPA bis (allyl ether) tetrabromobisphenol A

TABLE 2

Molding Data for Expandable Polyphenylene Ether-Polystyrene Blends

TABLE 3

Molding Data for Expandable Polyphenylene Ether-Polystyrene Blends

TBCO tetrabromocyclooctane

TBVCH tetrabromovinylcyclohexene

HBCD hexabromocyclododecane

Claims (45)

(A) a blend comprising (i) a polyphenylene ether and (ii) an alkenyl aromatic polymer, and (b) (i) tetrabromocyclooctane (ii) hexa bromocyclo dodecane (iii) tetra Bromo vinyl cyclohexene (iv) tetrabromo bisphenol A bis (alkyl ether) and (v) organobromine selected from the group consisting of mixtures thereof and the like, wherein the amount of polyphenylene ether is about In the range of 2% to 98% by weight; Wherein the amount of the alkenyl aromatic polymerizer is in the range of about 98% by weight to 2% by weight, wherein the amount of the organic bromine is in the range of 0.1% by weight to 96-6%, wherein the weight percentage is poly Expandable PPE / PS composition, characterized in that based on the total amount of phenylene ether and alkenyl aromatic polymer. The polyphenylene ether of claim 1, wherein the polyphenylene ether has a unit having the structure , Wherein Q, Q ', Q "and Q' '' are each selected from the group consisting of hydrogen, halogen, hydrocarbon, halogenated hydrocarbon, hydrocarbonoxy and halohydrocarbonoxy, and n represents the total number of monomer units An expandable PPE / PS composition, having said unit being an integer of at least about 20. 3. The expandable PPE / PS composition according to claim 2, wherein Q and Q 'are alkyl and alkyl has 1-4 carbon atoms each. The expandable PPE / PS composition according to claim 1, wherein the poly phenylene ether is poly (2,6-dimethyl-1,4-phenylene) ether. The alkenyl aromatic polymer according to claim 1, wherein the alkenyl aromatic polymer is based in part on a unit of the following structural formula In this formula, R ¹ and R ² are selected from the group consisting of lower alkyl and alkenyl group having 1-6 carbon atoms and hydrogen; R ³ and R ⁴ are selected from the group consisting of chloro, bromo, hydrogen and lower alkyl and lower alkenyl groups having 1-6 carbon atoms; R ⁵ and R ⁶ are selected from the group consisting of hydrogen and lower alkyl and lower alkenyl groups having 1-6 carbon atoms; Or R ⁵ and R ⁶ based on a unit of the above structural formula wherein the R ⁵ and R ⁶ may be chained together with a hydrocarbyl group to form a naphthyl group. 6. The expandable PPE / PS composition according to claim 5, wherein said unit is styrene. The expandable PPE / PS composition according to claim 1, wherein the alkenyl aromatic polymerizer is a polystyrene homopolymer. 8. The expandable PPE / PS composition according to claim 7, wherein said poly phenylene ether is a poly (2,6-dimethyl-1,4-phenylene) ether. The expandable composition of claim 1 comprising dicumyl peroxide in a range of at least 0.02% by weight and not more than about 2% by weight based on the total amount of polyphenylene ether and alkenyl aromatic polymer. PPE / PS composition. 10. The expandable PPE / PS composition according to claim 9, wherein the amount of dicumyl peroxide is not greater than 0.05 wt% -1 wt%. 2. The expandable PPE / PS composition according to claim 1, wherein the amount of organobromine is not greater than 0 wt% to 3 wt%. 2. The expandable PPE / PS composition according to claim 1, wherein the amount of organobromine is not more than 0.5 wt% -2 wt%. The expandable PPE according to claim 1, wherein the amount of expanding agent is within the range of about 2% to 15% by weight, based on the total amount of polyphenylene ether, alkenyl aromatic polymer and expanding agent. PS composition. 15. The expandable PPE / PS composition as claimed in claim 13 wherein said expanding agent is a physical expanding agent. The expandable PPE / PS composition according to claim 1, wherein the organobromine is tetra bromo cyclooctane. The expandable PPE / PS composition according to claim 1, wherein the organobromine is hexa bromo cyclododecane. The expandable PPE / PS composition according to claim 1, wherein the organobromine is tetra bromo vinyl cyclohexene. The expandable PPE / PS composition according to claim 1, wherein the organobromine is bis (allylether) of tetrabromo bis phenol A. The expandable PPE / PS composition according to claim 1, wherein the amount of polyphenylene ether is in the range of 10% by weight to 90% by weight and the amount of the alkenyl aromatic polymer is in the range of 90% by weight to 10% by weight. (A) a mixture comprising (i) a polyphenylene ether and (ii) an alkenyl aromatic polymer, and (b) (i) tetrabromocyclooctane (ii) hexa bromocyclo dodecane (iii) tetrabro Movinyl cyclohexene (iv) bis (allylether) of tetra bromo bisphenol A, (v) a mixture thereof, and (c) an expanding agent, wherein the amount of polyphenylene ether is about 2% to 98% by weight Is in the range of%; Wherein the amount of alkenyl aromatic polymer is in the range of about 98% to 2% by weight, based on the total amount of the polyphenylene ether and the alkenyl aromatic polymer; Wherein the amount of organobromine is an amount sufficient to reduce the mold cooling time of the composition; Wherein the amount of expanding agent is an amount sufficient to expand the composition. The method of claim 20, wherein the polypentylene ether has a unit of the formula Wherein Q, Q ', Q' 'and Q' '' are each selected from the group consisting of hydrogen, halogen, hydrocarbons, halogenated hydrocarbons, hydrocarbonoxy and halohydrocarbonoxy; n represents the total number of monomer units and is an integer of at least 20; Wherein the alkenyl aromatic polymer is based at least in part on the unit of the following structural formula; Wherein R ¹ and R ² are selected from the group consisting of lower alkyl and lower alkenyl groups having up to 1 to 6 carbon atoms and hydrogen; R ³ and R ⁴ are selected from the group consisting of chloro, bromo, hydrogen and lower alkyl and lower alkenyl groups having 1-6 carbon atoms; R ⁵ and R ⁶ are selected from the group consisting of hydrogen, lower alkyl having 1-6 carbon atoms and lower alkenyl group; Or R ⁵ and R ⁶ based on a unit of the above structural formula, which may be linked in a chain together with a hydrocarbyl group to form a naphthyl group. The method of claim 21, wherein the weight percent of the polyphenylene eder is in the range of about 10% to 90% by weight, and the weight percent of the alkenyl aromatic polymer is in the range of about 90% to 10% by weight. Expandable PPE / PS composition. 23. The expandable PPE / PS composition as claimed in claim 22 wherein said expander is a physical expander. 24. The expandable PPE / PS composition according to claim 23, comprising an amount of dicumyl peroxide sufficient to reduce the mold cooling time of the composition. 24. The expandable PPE / PS composition according to claim 23, wherein said organobromine is tetrabromo cyclooctane. 24. The expandable PPE / PS composition according to claim 23, wherein the organobromine is hexa bromo cyclo dodecane. 24. The expandable PPE / PS composition as claimed in claim 23 wherein the organobromine is tetra bromo vinyl-cyclohexene. 24. The expandable PPE / PS composition according to claim 23, wherein the organobromine is bis (allylether) of tetra bromo bisphenol A. (A) a mixture comprising (i) a polyphenylene ether and (ii) an alkenyl aromatic polymer, and (b) (i) tetrabromocyclooctane (ii) hexa bromocyclo dodecane tetrabromovinyl cyclo Hexene (iv) bis (allyl ether) of tetrabromo bisphenol A and (v) a mixture thereof, and (c) an expanding agent, wherein the amount of polyphenylene ether is in the range of 2% to 98% by weight. ; Wherein the amount of alkenyl aromatic polymerizer is in the range of about 98% to 2% by weight, wherein the weight percentage is based on the total amount of polyphenylene ether and alkenyl aromatic polymer; Wherein the amount of organobromine is an amount sufficient to reduce the amount of residual swelling agent of the composition following the molding of the composition; Wherein the amount of swelling agent is an amount sufficient to effect swelling of the composition. 30. The expandable PPE / PS composition according to claim 29, wherein the alkenyl aromatic polymer is polystyrene. the amount of PPE / PS blend comprising (i) poly phenylene ether and (ii) alkenyl aromatic polymer, wherein the amount of poly phenylene ether is in the range of about 2% to 98% by weight; Wherein the weight percentage is based on the total amount of polyphenylene ether and alkenyl aromatic polymer; The organobromine is (i) tetra bromo cyclooctane, (ii) hexa bromo cyclo donenecan, (iii) tetra bromo vinyl cyclohexene, (iv) bis (allyl ether) of tetra bromo bisphenol A, and ( v) mixtures thereof; Selected from the group consisting of; Wherein the amount of organobromine is sufficient to reduce the mold cooling time of the PPE / PS composition, wherein the expandable PPE / PS composition is prepared by a process comprising treating the PPE / PS blend with the organic bromine. . 32. The expandable PPE / PS composition as claimed in claim 31 wherein the PPE / PS blend is treated with an amount of expanding agent sufficient to expand the composition. 33. The method of claim 32, wherein the PPE / PS composition is in pellet, bead, or other particulate form; Wherein the PPE / PS admixture is injected into the reaction vessel; Water is also injected into the reaction vessel; Organobromine is also injected into the reactor; The expander is also injected into the reactor and these components form a batch, wherein the batch is shaken and the batch is heated to a temperature sufficient to saturate or incorporate the organic bromine and the expander into the PPE / PS blend. PPE / PS composition. 34. The expandable PPE / PS composition according to claim 33, wherein dicumyl peroxide is also shaken at said temperature after injection into the reactor. PPE / PS blends comprising (i) polyphenylene ethers and (ii) alkenyl aromatic polymers; Wherein the amount of polyphenylene ether is in the range of about 2% to 98% by weight, wherein the weight percentage is based on the total amount of the polyphenylene ether and the alkenyl aromatic polymerizer, and the organic bromine is (i ) Tetrabromo cyclooctane, (ii) hexabromo cyclo dodecane, (iii) detrabromo vinyl cyclohexene (iv) bis (allyl ether) of tetra bromo bisphenol A and (v) mixtures thereof Select from the group consisting of; Wherein the amount of organobromine is an amount sufficient to reduce the mold cooling time of the PPE / PS composition. 5. A method of making an expandable PPE / PS composition comprising treating the PPE / PS blend with the organobromine. 36. The method of claim 35, wherein said PPE / PS composition is treated with an amount of expanding agent sufficient to expand said composition. 37. The method of claim 36, wherein the PPE / PS admixture is in pellet, bead, or other particulate form, wherein the PPE / PS admixture is injected into the reactor, water is injected therein, organobromine is injected therein, and An intumescent agent is injected therein, in which these components make up a batch, shaking the batch, wherein heating the batch to a temperature sufficient to saturate or mix the organobromine and the expanding agent with the PPE / PS blend. A process for producing an expandable PPE / PS composition. 38. The method of claim 37, wherein dicumyl peroxide is also injected into the reactor as described above, followed by shaking at the temperature. 38. The method of claim 37, wherein said alkenyl aromatic polymer is a polystyrene homopolymer. 38. The method of claim 37, wherein said poly phenylene ether is a poly (2,6-dimethyl-1,4-phenylene) ether. 36. The method of claim 35, comprising molding the treated PPE / PS blend. 37. The method of claim 36, comprising molding the treated PPE / PS blend. 38. The method of claim 37, comprising molding the treated PPE / PS blend. 40. The method of claim 39, comprising molding the treated PPE / PS blend. 41. The method of claim 40, wherein the treated PPE / PS blend is molded.