CA2033332C - High impact polystyrene containing low molecular weight brominated polystyrene - Google Patents
High impact polystyrene containing low molecular weight brominated polystyrene Download PDFInfo
- Publication number
- CA2033332C CA2033332C CA002033332A CA2033332A CA2033332C CA 2033332 C CA2033332 C CA 2033332C CA 002033332 A CA002033332 A CA 002033332A CA 2033332 A CA2033332 A CA 2033332A CA 2033332 C CA2033332 C CA 2033332C
- Authority
- CA
- Canada
- Prior art keywords
- percent
- weight
- polystyrene
- amount
- molecular weight
- 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.)
- Expired - Lifetime
Links
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 72
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 70
- 229920005669 high impact polystyrene Polymers 0.000 title claims abstract description 25
- 239000004797 high-impact polystyrene Substances 0.000 title claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 230000014759 maintenance of location Effects 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims description 32
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052794 bromium Inorganic materials 0.000 claims description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000000704 physical effect Effects 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 13
- 230000026030 halogenation Effects 0.000 abstract 1
- 238000005658 halogenation reaction Methods 0.000 abstract 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 230000031709 bromination Effects 0.000 description 5
- 238000005893 bromination reaction Methods 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 238000009757 thermoplastic moulding Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- -1 aromatic bromine compound Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000005526 organic bromine compounds Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 150000004045 organic chlorine compounds Chemical class 0.000 description 2
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012747 synergistic agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NDRKXFLZSRHAJE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4-tribromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=CC=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br NDRKXFLZSRHAJE-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JDCCCHBBXRQRGU-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile Chemical class N#CC=CC=CC1=CC=CC=C1 JDCCCHBBXRQRGU-UHFFFAOYSA-N 0.000 description 1
- 238000004972 CNDO calculation Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Effective amounts of low molecular weight brominated polystyrenes unexpected ly provide good property retention and yet achieve desired flame retardance, for example; UL-94 VO in high impact polystyrene. In contrast, high molecular weight brominated styrene polymers (degree of polymerization equals 2,000) do.not provide good property retention such as impact strength and toughness in high impact polystyrene. The degree of polymerization of th e brominated polystyrenes of the present invention is generally from'about 3 to about 20 and can have a considerable variation in the amount of halogenation. The high impact polystyrenes blended with the low molecular weight brominated polystyrenes a re readily processed by conventional equipment.
Description
WO 90/15095 _ ~ _ PCT/US90/03150 CONTAINING LOW MOLECULAR WEIGHT
BROMINATED POLYSTYRENE
FIELD OF THE TNVFNTT(1N
The present invention relates to the use of low molecular weight brominated polystyrenes in high impact polystyrene, whereby good retention of physical proper-ties including impact strength is obtained while achieving excellent flame retardancy.
A brominated polystyrene having a degree of polymerization of approximately 2,000 when used in high impact polystyrene provides excellent flame retardancy and stability but has a very negative effect on key physical properties such as impact strength. This effect is generally unacceptable.
U.S. Patent No. 3,075,944 relates to flame retardant compositions containing polyolefins which can be made by substituting a diaromatic or an aromatic-aliphatic ether containing at least three bromine atoms.
U.S. Patent No. 3,830,766 relates to flame-proofing acrylonitrile-butadiene-styrene (ABS)polymers by incorporating therein an aromatic bromine compound, antimony trioxide or antimony oxychloride and optionally an organo chlorine compound.
U.S. Patent No. 3,897,373 relates to thermoplastic molding compositions based on styrene polymers and flameproofed with an organic bromine com-pound. They contain a synergistic azo compound and may be converted to self-extinguishing shaped articles or G _2_ profiles.
U.S. Patent No. 3,943,195 relates to a thermo-plastic molding material based on styrene polymers and olefin polymers which have been flameproofed with an organic bromine compound. Brominated oligomers or poly-mers of dialkylbenzenes, trialkylbenzenes or tetraalkyl-benzenes serve as flameproofing agents. The molding material may be processed into self-extinguishing mold-ings.
U.S. Patent No. 3,962,164 relates to flame-proofing acrylonitrile-butadiene-styrene (ABS) polymers, incorporating therein certain mono- and diphenyl aromatic bromine compounds such as octabromodiphenyl, antimony trioxide, or antimony oxychloride and optionally an organo chlorine compound.
U.S. Patent No. 4,049,622 relates to thermo-plastic molding compositions based on styrene polymers, preferably formed styrene polymers, which have been flameproofed with an organic bromine compound.
U.S. Patent No. 4,074,032 relates to a process for the manufacture of heat-stable, brominated oligo-styrenes by brominating selectively hydrogenated oligo-styrenes in halogenated solvents in the presence of Lewis acids at from about minus 25°C to 20°C. The brominated oligomers are highly heat-stable and can be processed, by themselves or as components of mixtures with other thermoplastics, to give various shaped articles.
U.S. Patent No. 4,107,231 relates to flame proofed linear polyesters containing, as flameproofing agents, halogenated oligomeric styrenes and synergistic compounds.
U.S. Patent No. 4,137,212 relates to a flame-proofed nylon molding composition which can be processed by thermoplastic methods and which contains, as the flameproofing agent, from 5 to 30 percent by weight of .~ r ~
_3_ 2033332 brominated styrene oligomers and a synergistic metal oxide. The composition may be used for the manufacture of injection moldings for the electrical industry.
U.S. Patent No. 4,143,221 relates to styrene polymers or copolymers containing bromine which are manufactured by cationic polymerization of the monomer, or of the monomer plus a copolymerizable monomer of the isobutylene or nuclear-alkylated styrene type, in an organic solvent in the presence of a Lewis acid catalyst.
Bromine is then added to the solution without first working up the latter. The catalyst used for the bromi-nation is the same as that used for the polymerization.
If necessary, fresh catalyst may be added before the bromination. After completion of the bromination, the reaction solution is extracted with water until it is bromide-free, and the solvent, generally a halohydro-carbon, is then stripped off. Products containing up to about 80 percent by weight of bromine may be obtained.
They have a pale yellowish color and exhibit no signifi-cant decomposition up to 340oC. They may be used as flameproofing agents for thermoplastics.
U.S. patent No. 4,151,223 relates to fibers and filaments of linear thermoplastic polyesters, containing halogen-containing flameproofing agents and synergistic agents therefor, in which the flameproofing agents are chlorinated and/or brominated oligomeric styrenes. The fibers and filaments of the invention are used for the manufacture of textiles of low flammability.
U.S. Patent No. 4,200,702 relates to thermo plastic molding compositions based on rubber-modified styrene-acrylonitrile copolymers containing a halogenated styrene oligomer as the effective flameproofing agent which is sufficiently heat-stable, does not interfere with processing on conventional machinery, does not corrode or cause coatings on such machinery, and has virtually no adverse effect on the impact strength of the polymers. The flameproofing agent as a rule has a degree of polymerization of from 3 to 200 and can be incorporated into the polymer by conventional methods; the polymer may or may not contain additional synergistic agents and processing auxiliaries, which are incorporated in the conventional manner and in the conventional amounts.
U.S. Patent No. 4,360,455 relates to a mixture of brominated oligomeric polystyrenes having a degree of polymerization of from 3 to 400, and low molecular weight brominated aromatic compounds of the diphenyl ether type which are obtained by polymerizing the non-brominated starting materials, in a halohydrocarbon solvent, using a Lewis acid catalyst. The reaction mixture is then brominated and extracted with water to remove hydrogen bromine and catalyst, and the solvent and volatile constituents are separated from the product. The bromination is carried out at from minus 30°C to 130°C. The final mixtures have a low melt viscosity and are therefore particularly suitable for incorporation, as a flameproofing agent, into thermoplastics.
U.S. Patent No. 4,352,909, to Barda et al relates to a process for producing a trihalogenated polystyrene flame retardant for synthetic resins, whereby high molecular weight polystyrene is reacted with bromine chloride in a chlorinated hydrocarbon solvent, under substantially anhydrous conditions, in the presence of a catalytic amount of a Lewis acid.
East German Patent No. 151,075 published in 1981 relates to self-extinquishing polystyrene compositions containing brominated oligomers of alpha methyl-styrene as flame retardants with minimum loss of mechanical properties.
The oligomer contains from 40 to 70 weight percent ring-bound bromine and has a molecular weight of from about 1,000 to about 5,000.
SUMMARY OF THE INVENTION
It has been found that the molecular weight of a brominated low molecular weight polystyrene is an important factor in property retention in that unexpectedly good property retention has been obtained when said polystyrenes are blended with high impact polystyrene (HIPS) and that good or excellent flame retardancy, for example UL-94 VO at 1/8 inch thickness is also achieved. The low molecular weight brominated polystyrene of the present invention generally have a degree of polymerization of from about 3 to about 20 and a halogenated content, e.g., bromine, of from about 53 percent to about 76 percent by weight.
According to one aspect of the present invention there is provided a flame retarded high impact resistant polystyrene composition having a flame retardancy of UO at 1/8 inch in a UL-94 test, comprising: a high impact resistant polystyrene, an effective amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 to provide physical property retention, and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by - 5a -weight of said brominated polystyrene, wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
According to a further aspect of the present invention there is provided a high impact resistant polystyrene composition having a flame retardancy of VO at 1/8 inch in a UL-94 test, comprising: a blend of a high impact polystyrene, a sufficient amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 to provide effective property retention, and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by weight of said brominated polystyrene, wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
According to another aspect of the present invention there is provided a process for making a flame retarded, high impact polystyrene composition having a flame retardancy of UO
at 1/8 inch in a UL-94 test, comprising the steps of: melt blending a high impact polystyrene with an effective amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by weight of said low molecular weight brominated polystyrene to provide a f 2 03 3332 - 5b -composition having good physical retention of notched Izod wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
DETAILED DESCRIPTION OF THE INVENTION
High impact polystyrene is commercially available and is well known to the literature as well as to the art.
High impact polystyrene (HIPS) is produced from styrene monomers along with elastomers and is generally available in various impact-strength grades. HIPS is generally produced by introducing elastomers such as polybutadiene into the polystyrene matrix far impact modification and is generally produced by either a suspension process or more preferably by a mass continuous polymerization process.
The low molecular weight brominated polystyrenes of the present invention are oligomers and generally have a degree of polymerization, i.e., number of repeating units, of from about 3 to about 20, generally from about 5 to about 15, desirably from about 6 to about 12, and preferably from about 7 to about 9. The repeat-2~~3~32 ing units generally have the formula Xn The halogen X such as bromine is present in an amount of from about 1.5 to about 4.0 molecules per repeating unit.
The amount of the bromine is generally from about 53 percent to about 76 percent, desirably from about 61 percent to about 71 percent, and preferably from about 66 percent to about 70 percent by weight with regard to the total weight of each repeating unit. The molecular weight distribution of the oligomers is generally narrow such as at 4.0 or less, and preferably 2.5 or less.
Retention of impact properties when using low molecular weight brominated polystyrenes as flame retar dants is a function of molecular weight and the degree of bromination. As the molecular weight increases, impact retention will decline at a constant bromine level.
Conversely, as the bromine content incorporated with the polystyrene increases, impact retention will decline at a given or constant molecular weight. Therefore, optimiza-tion of property retention is generally a balancing of such factors.
The amount of the low molecular weight bromin ated polystyrene oligomer utilized is generally an effec tive amount to achieve good flame retardancy. In other words, effective amounts of the low molecular weight brominated polymers are utilized to produce good flame retardancy but as an unexpected result, effective or superior impact retention is obtained, especially in comparison with high molecular weight brominated poly-styrene having a degree of polymerization of approxi-mately 2,000. An effective level of flame retardance would be, for example, VO at 1/8 inch thickness UL-94.
Physical properties which are notably retained include -'- 203 3332 impact strength such as measured by notched Izod, reverse Izod, Gardner impact, elongation, and the like.
Effective amounts of the brominated polystyrene oligomer of the present invention are generally from about 3 percent to about 20 percent by weight, desirably from about 10 percent to about 18 percent by weight, and preferably from about 14 to about 16 percent by weight of the oligomer based upon the total weight of the oligomer and the high impact resistant polystyrene.
The compositions of the present invention can be readily mixed and processed on conventional equipment such as extruders, Banburys, two-roll mills, and the like, do not cause mold fouling, and are non-blooming.
Blending takes place at a temperature generally above the melting point of HIPS such as from about 250°F to about 500°F.
The blends of the present invention can contain various conventional additives in conventional amounts as known to the art as well as to the literature. For example, the HIPS can contain various conventional ultra-violet light inhibitors, various lubricant agents such as calcium stearate, and the like. Additives which are generally utilized due to their low cost and effective flame retarding properties are various antimony base synergists, equivalences thereof, derivatives thereof, and the like, with a typical example being antimony trioxide. The amount of antimony base synergists is generally based upon the amount of brominated polystyrene and generally ranges from about 1 part for every 2 to 5 parts by weight of the brominated polystyrene. The various additives and flame retardants such as antimony trioxide can either be added directly to the HIPS and blended therewith and subsequently this mixture blended with the low molecular weight brominated polystyrenes or, alternatively, added to and blended with the low molecu-v . 2033332 -8_ lar weight brominated polystyrenes and subsequently blended with the HIPS. The blends of the present invention generally have a flame retardance of VO at 1/8 inch UL-94. Generally, any conventional mixing device can be utilized such as an extruder, a Banbury, a two-roll mill, or the like. The blends of the present invent ion can be ut i 1 ized wherever f lame retardancy HIPS is desired such as for small appliances, television cabinets, computer housings, and the like.
The invention will be better understood by reference to the following examples.
Examples Test Procedures for Exam les ASTM TEST
METHOD
Tensile Strength (psi) D-638 Elongation at Break (°s) D-638 Flex Strength (psi) D-790 Tangent Modulus x 105 (psi) D-790 Notched Izod 1/8" (ft-lb/in) D-256-A
Reverse Izod 1/8" (ft-lb/in) D-256-E
Gardner Impact (in-lbs) D-3029 UL 94 1/8" Bars UL 94 Oxygen Index D-2863 Footnotes for Examples 1 throuah 8 PS Polystyrene DP Degree of polymerization which specifies the polymer chain length by the number of repeating _ 8a _ 2033332 units in the chain.
Pyro Chek* 68 PB
A brominated polystyrene having a DP = 2,000 and typically a bromine content of about 66.5 percent by weight.
* Trade-mark '' 75467-2 WO 90/15095 _ PCT/US90/03150 . . .
.-~1 V~ I ( I ~ 00 ~ 00 fr1 ~I c0 1~1 q N
01 C~ p N
D N~ .-1~' I 1 ~ I ~ 00 fr1O 1D 1D If1 P ar O I~
C) ~ ~ ~ I ~ I I 'r-i-ip M ri 0~ ~0 '~
00 O u1 O N
If1 O
0~ 10 n O
i>a ~ r-1~ ~ 1 1 I .fr1-1~ M O N f'~1i--1 p rv1 N
w ~c n o ,o a~ I I I I a'"~o0 o ~ w ~
..
~ ~' ~ ~ ..
~-~ ea . .~ I
o .~-I LQ, 8" o a~ a, o ~ x 1 ro y-1 N ~ s M -N r-~1 i~ i~
r-VI ~ ~ N ~~ ~ ~ ~ ~ ~ O~
9 0~
,,.I
c~ ~ r'~ w H ~ c~
-i o.~
~n a~ n ov O
1 1 1 ( 1 ~ 00 V1 00 r1 O vG
O N
N 1D 0D r-1 O
.
(fir I ~ e~ 1 I 1 1 1 th M O ~D M
~O M
r-1 ~ O 0~ N
W~~~f' I 1 1 I 1 00~00M O ltlM
1D N .-1 CO 1l1 ~1' 1 ( ~ 1 ( I M 00 M .~1 1~1 1f1 M
N 10 O~
o~1 O ~! '-1 0~ M
U I ~ r' I ~ 1 I 1 1 00 ~ oo eh ..i ~o ~o sr CD "~J
M O
a~ o~
N ~ 1!1 ~1 O
ar ~ 1 I 1 1 1 00 f~ 00 M O N M
O
O M \p 10 10 00 I 1 I I I I 1 oO ~ p M rl o~ N ..1 o w ..
.~, /~
M O O dP ~'. .-~I
0 A A A ~ v ~ ~ ~ t ' v v v v v v v M ~C
~~11 ~ ~ ~\ ~ G0 a -~v~ v ~x ~ ~~ ~ ~ ~ ~ ~ ~ w H ~
-1-1=- . .
2 ~3 3332 C M r-1 1C O
I 1 ( ~ ~ V~ ~ h1 .-~ CD If1 q '"'1 V~ 0~1 N O
G pip '~ 1 1 ~ ( ~ . o . . . .
~ 1t1 M C ~ .o~
q 1~1N 1~1O
C7) pip ~ 1 ~ 1 1 ~ eh N . .
M ~I CD n ~' O
M '1 W Il1If1 1C O
m ~ '" I I ~ 1C .-1fr1O N M
q p I I I I I ,op~~ f~ M '"'1,M.1M
~ ~
~ ~11~ ~
...
~ ~n w w M ~
.-~ ~ o ~. .r 1 s s _o _o ~ ~ o o .r b V ~ r\~11 ,~~~~1 ~ N
,~ ~ ~ '8 '8 N
1.1 .~ ~ ~ I~ r-I
M
wH~
-~ 3 '~ '~ 2 O
N P 1l1If1 1f1 ~ I I 1 1(1 er1r-1~
W ~ ~ 0 q N
I
a N ~ O~ d' CO
~ I 1 I O ~O fr1O O ~
O ~ I ~ ~ ~ N
O
O
t~ f~ t~ O ar ~ ~ ( I ( 0 111 fr1O N
UI p ~ f ~
p N t~ 9 ..~ er1 V~ O t~ 'd'tr1 l~
1 I I !~ 0 fr1r-11~
0 ~ N
O
~
V CO ~' O
' 0 1 1 1 1 1 M ~
I 0 N er vD r-I rl r-1 n V 0~
' v t~1 W W
M ~ ~ Q v r ~ ~ '.' ~ '~ ~
N ~ ~ N N 00 N ~ ~ a~
~I IT ~ ~!
I
M
iW -1 N fr1 W) ~ ~ 1 1 i ~ ~ 1MON M N rO-T
N
O
1'~M ~ O
DI ~ ~ 1 1 ~ 1 N 1NC~ fh N ~-i~~f'1 ~-1' M N
M
UI y r 1 ~ I 1 fO N ~ f"1"I N QN
M
M
alI O d' ~ I 1 1 ,Oa,CNDO r a t~ ~
M N r~-iN
M
f~ ~i M
Op 1 I 1 I I N 1~01~ M .~-1 M ~ w ..
S
..
y V V
W W
M ~ ~ ~ V V
o ~ D p ro '8 x ~ .-°'r ro c'~n '' ~' ''' '~r ~ c~ ~ ~ tr' ~ a ~' a~ ~ ~ a~ ~ H ~ ~ 5' 2p33332 . . . .
W) ~ I 1 o ~ ~ r~ O UI N
~ ~ ~
O~
O U1 0~
DI d' I 1 ~ ~ ~1'O r-IN t~
~ ~
n GO .-1 0v N
UI a c I I o M ~ ~ ..~ ui ~r ~ ~ f ~
a~ a~ N
all ~
~r 1 1 1 ~ ~ ~n ...1~c t~
~
o ~ ao 0 1 I 1 I o M N f~ C~
0 u ~ ~
,~
~ W
.-. ~
..
~.~ V
~ ~ O V V
_. ;~ o "
O
~o N H
v. ~' a~ ~ °N' a~
r U1 N If1O
III ~ r' I I ~ ..,~M , M ~ I ri D
M n c M
P 1D O r.
O) ~ V~ 1 ~ 1 ~ N ~ fr1O .-1N
M N
~D
UI ~ v~ ~ I 1 ~ ~ ~ M .-I ~o ui M N
n (~) 0~1 ~ O P
th I ( I O M O M N p~ M
M
N
~ ~i p I 1 I 1 N COD ~O M N O r..l,..1 ~1 ar M rl N
M
~ ~
~
A ~ ~ ~ a s w N c N ~ CO
La ~ ~-~1 b V~1 ~ .-i c~ w .
wo 9oiiso9s 2 0 3 3 3 3 2 PfT/US90/03150 The various Examples generally demonstrate that property retention is much better with a low molecular weight brominated polystyrene as opposed to a high molecular weight polystyrene such as Pyro Chek 68 PB.
Example 2 generally demonstrates that as the degree of polymerization of the brominated polystyrene is increas-ed, the physical property retentions such as notched Izod decreases. Examples 3 through 7 show good property retention using the low molecular weight brominated polystyrenes of the present invention as compared to a high molecular weight brominated polystyrene as well as that good property retention is obtained utilizing a variety of high impact polystyrenes made by different manufacturers.
While in accordance with the Patent Statutes, the best mode and preferred embodiment has been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.
n ,
BROMINATED POLYSTYRENE
FIELD OF THE TNVFNTT(1N
The present invention relates to the use of low molecular weight brominated polystyrenes in high impact polystyrene, whereby good retention of physical proper-ties including impact strength is obtained while achieving excellent flame retardancy.
A brominated polystyrene having a degree of polymerization of approximately 2,000 when used in high impact polystyrene provides excellent flame retardancy and stability but has a very negative effect on key physical properties such as impact strength. This effect is generally unacceptable.
U.S. Patent No. 3,075,944 relates to flame retardant compositions containing polyolefins which can be made by substituting a diaromatic or an aromatic-aliphatic ether containing at least three bromine atoms.
U.S. Patent No. 3,830,766 relates to flame-proofing acrylonitrile-butadiene-styrene (ABS)polymers by incorporating therein an aromatic bromine compound, antimony trioxide or antimony oxychloride and optionally an organo chlorine compound.
U.S. Patent No. 3,897,373 relates to thermoplastic molding compositions based on styrene polymers and flameproofed with an organic bromine com-pound. They contain a synergistic azo compound and may be converted to self-extinguishing shaped articles or G _2_ profiles.
U.S. Patent No. 3,943,195 relates to a thermo-plastic molding material based on styrene polymers and olefin polymers which have been flameproofed with an organic bromine compound. Brominated oligomers or poly-mers of dialkylbenzenes, trialkylbenzenes or tetraalkyl-benzenes serve as flameproofing agents. The molding material may be processed into self-extinguishing mold-ings.
U.S. Patent No. 3,962,164 relates to flame-proofing acrylonitrile-butadiene-styrene (ABS) polymers, incorporating therein certain mono- and diphenyl aromatic bromine compounds such as octabromodiphenyl, antimony trioxide, or antimony oxychloride and optionally an organo chlorine compound.
U.S. Patent No. 4,049,622 relates to thermo-plastic molding compositions based on styrene polymers, preferably formed styrene polymers, which have been flameproofed with an organic bromine compound.
U.S. Patent No. 4,074,032 relates to a process for the manufacture of heat-stable, brominated oligo-styrenes by brominating selectively hydrogenated oligo-styrenes in halogenated solvents in the presence of Lewis acids at from about minus 25°C to 20°C. The brominated oligomers are highly heat-stable and can be processed, by themselves or as components of mixtures with other thermoplastics, to give various shaped articles.
U.S. Patent No. 4,107,231 relates to flame proofed linear polyesters containing, as flameproofing agents, halogenated oligomeric styrenes and synergistic compounds.
U.S. Patent No. 4,137,212 relates to a flame-proofed nylon molding composition which can be processed by thermoplastic methods and which contains, as the flameproofing agent, from 5 to 30 percent by weight of .~ r ~
_3_ 2033332 brominated styrene oligomers and a synergistic metal oxide. The composition may be used for the manufacture of injection moldings for the electrical industry.
U.S. Patent No. 4,143,221 relates to styrene polymers or copolymers containing bromine which are manufactured by cationic polymerization of the monomer, or of the monomer plus a copolymerizable monomer of the isobutylene or nuclear-alkylated styrene type, in an organic solvent in the presence of a Lewis acid catalyst.
Bromine is then added to the solution without first working up the latter. The catalyst used for the bromi-nation is the same as that used for the polymerization.
If necessary, fresh catalyst may be added before the bromination. After completion of the bromination, the reaction solution is extracted with water until it is bromide-free, and the solvent, generally a halohydro-carbon, is then stripped off. Products containing up to about 80 percent by weight of bromine may be obtained.
They have a pale yellowish color and exhibit no signifi-cant decomposition up to 340oC. They may be used as flameproofing agents for thermoplastics.
U.S. patent No. 4,151,223 relates to fibers and filaments of linear thermoplastic polyesters, containing halogen-containing flameproofing agents and synergistic agents therefor, in which the flameproofing agents are chlorinated and/or brominated oligomeric styrenes. The fibers and filaments of the invention are used for the manufacture of textiles of low flammability.
U.S. Patent No. 4,200,702 relates to thermo plastic molding compositions based on rubber-modified styrene-acrylonitrile copolymers containing a halogenated styrene oligomer as the effective flameproofing agent which is sufficiently heat-stable, does not interfere with processing on conventional machinery, does not corrode or cause coatings on such machinery, and has virtually no adverse effect on the impact strength of the polymers. The flameproofing agent as a rule has a degree of polymerization of from 3 to 200 and can be incorporated into the polymer by conventional methods; the polymer may or may not contain additional synergistic agents and processing auxiliaries, which are incorporated in the conventional manner and in the conventional amounts.
U.S. Patent No. 4,360,455 relates to a mixture of brominated oligomeric polystyrenes having a degree of polymerization of from 3 to 400, and low molecular weight brominated aromatic compounds of the diphenyl ether type which are obtained by polymerizing the non-brominated starting materials, in a halohydrocarbon solvent, using a Lewis acid catalyst. The reaction mixture is then brominated and extracted with water to remove hydrogen bromine and catalyst, and the solvent and volatile constituents are separated from the product. The bromination is carried out at from minus 30°C to 130°C. The final mixtures have a low melt viscosity and are therefore particularly suitable for incorporation, as a flameproofing agent, into thermoplastics.
U.S. Patent No. 4,352,909, to Barda et al relates to a process for producing a trihalogenated polystyrene flame retardant for synthetic resins, whereby high molecular weight polystyrene is reacted with bromine chloride in a chlorinated hydrocarbon solvent, under substantially anhydrous conditions, in the presence of a catalytic amount of a Lewis acid.
East German Patent No. 151,075 published in 1981 relates to self-extinquishing polystyrene compositions containing brominated oligomers of alpha methyl-styrene as flame retardants with minimum loss of mechanical properties.
The oligomer contains from 40 to 70 weight percent ring-bound bromine and has a molecular weight of from about 1,000 to about 5,000.
SUMMARY OF THE INVENTION
It has been found that the molecular weight of a brominated low molecular weight polystyrene is an important factor in property retention in that unexpectedly good property retention has been obtained when said polystyrenes are blended with high impact polystyrene (HIPS) and that good or excellent flame retardancy, for example UL-94 VO at 1/8 inch thickness is also achieved. The low molecular weight brominated polystyrene of the present invention generally have a degree of polymerization of from about 3 to about 20 and a halogenated content, e.g., bromine, of from about 53 percent to about 76 percent by weight.
According to one aspect of the present invention there is provided a flame retarded high impact resistant polystyrene composition having a flame retardancy of UO at 1/8 inch in a UL-94 test, comprising: a high impact resistant polystyrene, an effective amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 to provide physical property retention, and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by - 5a -weight of said brominated polystyrene, wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
According to a further aspect of the present invention there is provided a high impact resistant polystyrene composition having a flame retardancy of VO at 1/8 inch in a UL-94 test, comprising: a blend of a high impact polystyrene, a sufficient amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 to provide effective property retention, and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by weight of said brominated polystyrene, wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
According to another aspect of the present invention there is provided a process for making a flame retarded, high impact polystyrene composition having a flame retardancy of UO
at 1/8 inch in a UL-94 test, comprising the steps of: melt blending a high impact polystyrene with an effective amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by weight of said low molecular weight brominated polystyrene to provide a f 2 03 3332 - 5b -composition having good physical retention of notched Izod wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
DETAILED DESCRIPTION OF THE INVENTION
High impact polystyrene is commercially available and is well known to the literature as well as to the art.
High impact polystyrene (HIPS) is produced from styrene monomers along with elastomers and is generally available in various impact-strength grades. HIPS is generally produced by introducing elastomers such as polybutadiene into the polystyrene matrix far impact modification and is generally produced by either a suspension process or more preferably by a mass continuous polymerization process.
The low molecular weight brominated polystyrenes of the present invention are oligomers and generally have a degree of polymerization, i.e., number of repeating units, of from about 3 to about 20, generally from about 5 to about 15, desirably from about 6 to about 12, and preferably from about 7 to about 9. The repeat-2~~3~32 ing units generally have the formula Xn The halogen X such as bromine is present in an amount of from about 1.5 to about 4.0 molecules per repeating unit.
The amount of the bromine is generally from about 53 percent to about 76 percent, desirably from about 61 percent to about 71 percent, and preferably from about 66 percent to about 70 percent by weight with regard to the total weight of each repeating unit. The molecular weight distribution of the oligomers is generally narrow such as at 4.0 or less, and preferably 2.5 or less.
Retention of impact properties when using low molecular weight brominated polystyrenes as flame retar dants is a function of molecular weight and the degree of bromination. As the molecular weight increases, impact retention will decline at a constant bromine level.
Conversely, as the bromine content incorporated with the polystyrene increases, impact retention will decline at a given or constant molecular weight. Therefore, optimiza-tion of property retention is generally a balancing of such factors.
The amount of the low molecular weight bromin ated polystyrene oligomer utilized is generally an effec tive amount to achieve good flame retardancy. In other words, effective amounts of the low molecular weight brominated polymers are utilized to produce good flame retardancy but as an unexpected result, effective or superior impact retention is obtained, especially in comparison with high molecular weight brominated poly-styrene having a degree of polymerization of approxi-mately 2,000. An effective level of flame retardance would be, for example, VO at 1/8 inch thickness UL-94.
Physical properties which are notably retained include -'- 203 3332 impact strength such as measured by notched Izod, reverse Izod, Gardner impact, elongation, and the like.
Effective amounts of the brominated polystyrene oligomer of the present invention are generally from about 3 percent to about 20 percent by weight, desirably from about 10 percent to about 18 percent by weight, and preferably from about 14 to about 16 percent by weight of the oligomer based upon the total weight of the oligomer and the high impact resistant polystyrene.
The compositions of the present invention can be readily mixed and processed on conventional equipment such as extruders, Banburys, two-roll mills, and the like, do not cause mold fouling, and are non-blooming.
Blending takes place at a temperature generally above the melting point of HIPS such as from about 250°F to about 500°F.
The blends of the present invention can contain various conventional additives in conventional amounts as known to the art as well as to the literature. For example, the HIPS can contain various conventional ultra-violet light inhibitors, various lubricant agents such as calcium stearate, and the like. Additives which are generally utilized due to their low cost and effective flame retarding properties are various antimony base synergists, equivalences thereof, derivatives thereof, and the like, with a typical example being antimony trioxide. The amount of antimony base synergists is generally based upon the amount of brominated polystyrene and generally ranges from about 1 part for every 2 to 5 parts by weight of the brominated polystyrene. The various additives and flame retardants such as antimony trioxide can either be added directly to the HIPS and blended therewith and subsequently this mixture blended with the low molecular weight brominated polystyrenes or, alternatively, added to and blended with the low molecu-v . 2033332 -8_ lar weight brominated polystyrenes and subsequently blended with the HIPS. The blends of the present invention generally have a flame retardance of VO at 1/8 inch UL-94. Generally, any conventional mixing device can be utilized such as an extruder, a Banbury, a two-roll mill, or the like. The blends of the present invent ion can be ut i 1 ized wherever f lame retardancy HIPS is desired such as for small appliances, television cabinets, computer housings, and the like.
The invention will be better understood by reference to the following examples.
Examples Test Procedures for Exam les ASTM TEST
METHOD
Tensile Strength (psi) D-638 Elongation at Break (°s) D-638 Flex Strength (psi) D-790 Tangent Modulus x 105 (psi) D-790 Notched Izod 1/8" (ft-lb/in) D-256-A
Reverse Izod 1/8" (ft-lb/in) D-256-E
Gardner Impact (in-lbs) D-3029 UL 94 1/8" Bars UL 94 Oxygen Index D-2863 Footnotes for Examples 1 throuah 8 PS Polystyrene DP Degree of polymerization which specifies the polymer chain length by the number of repeating _ 8a _ 2033332 units in the chain.
Pyro Chek* 68 PB
A brominated polystyrene having a DP = 2,000 and typically a bromine content of about 66.5 percent by weight.
* Trade-mark '' 75467-2 WO 90/15095 _ PCT/US90/03150 . . .
.-~1 V~ I ( I ~ 00 ~ 00 fr1 ~I c0 1~1 q N
01 C~ p N
D N~ .-1~' I 1 ~ I ~ 00 fr1O 1D 1D If1 P ar O I~
C) ~ ~ ~ I ~ I I 'r-i-ip M ri 0~ ~0 '~
00 O u1 O N
If1 O
0~ 10 n O
i>a ~ r-1~ ~ 1 1 I .fr1-1~ M O N f'~1i--1 p rv1 N
w ~c n o ,o a~ I I I I a'"~o0 o ~ w ~
..
~ ~' ~ ~ ..
~-~ ea . .~ I
o .~-I LQ, 8" o a~ a, o ~ x 1 ro y-1 N ~ s M -N r-~1 i~ i~
r-VI ~ ~ N ~~ ~ ~ ~ ~ ~ O~
9 0~
,,.I
c~ ~ r'~ w H ~ c~
-i o.~
~n a~ n ov O
1 1 1 ( 1 ~ 00 V1 00 r1 O vG
O N
N 1D 0D r-1 O
.
(fir I ~ e~ 1 I 1 1 1 th M O ~D M
~O M
r-1 ~ O 0~ N
W~~~f' I 1 1 I 1 00~00M O ltlM
1D N .-1 CO 1l1 ~1' 1 ( ~ 1 ( I M 00 M .~1 1~1 1f1 M
N 10 O~
o~1 O ~! '-1 0~ M
U I ~ r' I ~ 1 I 1 1 00 ~ oo eh ..i ~o ~o sr CD "~J
M O
a~ o~
N ~ 1!1 ~1 O
ar ~ 1 I 1 1 1 00 f~ 00 M O N M
O
O M \p 10 10 00 I 1 I I I I 1 oO ~ p M rl o~ N ..1 o w ..
.~, /~
M O O dP ~'. .-~I
0 A A A ~ v ~ ~ ~ t ' v v v v v v v M ~C
~~11 ~ ~ ~\ ~ G0 a -~v~ v ~x ~ ~~ ~ ~ ~ ~ ~ ~ w H ~
-1-1=- . .
2 ~3 3332 C M r-1 1C O
I 1 ( ~ ~ V~ ~ h1 .-~ CD If1 q '"'1 V~ 0~1 N O
G pip '~ 1 1 ~ ( ~ . o . . . .
~ 1t1 M C ~ .o~
q 1~1N 1~1O
C7) pip ~ 1 ~ 1 1 ~ eh N . .
M ~I CD n ~' O
M '1 W Il1If1 1C O
m ~ '" I I ~ 1C .-1fr1O N M
q p I I I I I ,op~~ f~ M '"'1,M.1M
~ ~
~ ~11~ ~
...
~ ~n w w M ~
.-~ ~ o ~. .r 1 s s _o _o ~ ~ o o .r b V ~ r\~11 ,~~~~1 ~ N
,~ ~ ~ '8 '8 N
1.1 .~ ~ ~ I~ r-I
M
wH~
-~ 3 '~ '~ 2 O
N P 1l1If1 1f1 ~ I I 1 1(1 er1r-1~
W ~ ~ 0 q N
I
a N ~ O~ d' CO
~ I 1 I O ~O fr1O O ~
O ~ I ~ ~ ~ N
O
O
t~ f~ t~ O ar ~ ~ ( I ( 0 111 fr1O N
UI p ~ f ~
p N t~ 9 ..~ er1 V~ O t~ 'd'tr1 l~
1 I I !~ 0 fr1r-11~
0 ~ N
O
~
V CO ~' O
' 0 1 1 1 1 1 M ~
I 0 N er vD r-I rl r-1 n V 0~
' v t~1 W W
M ~ ~ Q v r ~ ~ '.' ~ '~ ~
N ~ ~ N N 00 N ~ ~ a~
~I IT ~ ~!
I
M
iW -1 N fr1 W) ~ ~ 1 1 i ~ ~ 1MON M N rO-T
N
O
1'~M ~ O
DI ~ ~ 1 1 ~ 1 N 1NC~ fh N ~-i~~f'1 ~-1' M N
M
UI y r 1 ~ I 1 fO N ~ f"1"I N QN
M
M
alI O d' ~ I 1 1 ,Oa,CNDO r a t~ ~
M N r~-iN
M
f~ ~i M
Op 1 I 1 I I N 1~01~ M .~-1 M ~ w ..
S
..
y V V
W W
M ~ ~ ~ V V
o ~ D p ro '8 x ~ .-°'r ro c'~n '' ~' ''' '~r ~ c~ ~ ~ tr' ~ a ~' a~ ~ ~ a~ ~ H ~ ~ 5' 2p33332 . . . .
W) ~ I 1 o ~ ~ r~ O UI N
~ ~ ~
O~
O U1 0~
DI d' I 1 ~ ~ ~1'O r-IN t~
~ ~
n GO .-1 0v N
UI a c I I o M ~ ~ ..~ ui ~r ~ ~ f ~
a~ a~ N
all ~
~r 1 1 1 ~ ~ ~n ...1~c t~
~
o ~ ao 0 1 I 1 I o M N f~ C~
0 u ~ ~
,~
~ W
.-. ~
..
~.~ V
~ ~ O V V
_. ;~ o "
O
~o N H
v. ~' a~ ~ °N' a~
r U1 N If1O
III ~ r' I I ~ ..,~M , M ~ I ri D
M n c M
P 1D O r.
O) ~ V~ 1 ~ 1 ~ N ~ fr1O .-1N
M N
~D
UI ~ v~ ~ I 1 ~ ~ ~ M .-I ~o ui M N
n (~) 0~1 ~ O P
th I ( I O M O M N p~ M
M
N
~ ~i p I 1 I 1 N COD ~O M N O r..l,..1 ~1 ar M rl N
M
~ ~
~
A ~ ~ ~ a s w N c N ~ CO
La ~ ~-~1 b V~1 ~ .-i c~ w .
wo 9oiiso9s 2 0 3 3 3 3 2 PfT/US90/03150 The various Examples generally demonstrate that property retention is much better with a low molecular weight brominated polystyrene as opposed to a high molecular weight polystyrene such as Pyro Chek 68 PB.
Example 2 generally demonstrates that as the degree of polymerization of the brominated polystyrene is increas-ed, the physical property retentions such as notched Izod decreases. Examples 3 through 7 show good property retention using the low molecular weight brominated polystyrenes of the present invention as compared to a high molecular weight brominated polystyrene as well as that good property retention is obtained utilizing a variety of high impact polystyrenes made by different manufacturers.
While in accordance with the Patent Statutes, the best mode and preferred embodiment has been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.
n ,
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A flame retarded high impact resistant polystyrene composition having a flame retardancy of VO at 1/8 inch in a UL-94 test, comprising:
a high impact resistant polystyrene, an effective amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 to provide physical property retention, and an antimony based synergist in an amount of about 1 part by weight far every about 2 to about 5 parts by weight of said brominated polystyrene, wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
a high impact resistant polystyrene, an effective amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 to provide physical property retention, and an antimony based synergist in an amount of about 1 part by weight far every about 2 to about 5 parts by weight of said brominated polystyrene, wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
2. A composition according to Claim 1, wherein the amount of said low molecular weight brominated polystyrene is from about 3 percent to about 20 percent by weight based upon the total weight of said brominated polystyrene and said high impact resistant polystyrene.
3. A composition according to Claim 2, wherein the amount of said low molecular weight brominated polystyrene is from about 10 percent to about 18 percent by weight, wherein the amount of said bromine is from about 61 percent to about 71 percent by weight, and wherein said degree of polymerization is from about 5 to about 15.
4. A composition according to Claim 3, wherein said degree of polymerization is from about 6 to about 12.
5. A high impact resistant polystyrene composition having a flame retardancy of VO at 1/8 inch in a UL-94 test, comprising:
a blend of a high impact polystyrene, a sufficient amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 to provide effective property retention, and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by weight of said brominated polystyrene, wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
a blend of a high impact polystyrene, a sufficient amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 to provide effective property retention, and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by weight of said brominated polystyrene, wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
6. A composition according to Claim 5, wherein said sufficient amount of said low molecular weight brominated polystyrene is from about 3 percent to about 20 percent by weight based upon the total weight of said high impact polystyrene and said low molecular weight brominated polystyrene.
7. A composition according to Claim 6, wherein the amount of said low molecular weight brominated polystyrene is from about 10 percent to about 18 percent by weight.
8. A composition according to Claim 7, wherein said degree of polymerization is from about 5 to about 15, and wherein the amount of bromine in brominated polystyrene is from about 61 percent to about 71 percent by weight.
9. A composition according to Claim 8, wherein said degree of polymerization is from about 7 to about 9, and wherein the amount of said bromine is from about 66 percent to about 70 percent by weight.
10. A process for making a flame retarded, high impact polystyrene composition having a flame retardancy of VO at 1/8 inch in a UL-94 test, comprising the steps of:
melt blending a high impact polystyrene with an effective amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by weight of said low molecular weight brominated polystyrene to provide a composition having good physical retention of notched Izod wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
melt blending a high impact polystyrene with an effective amount of a low molecular weight brominated polystyrene having a degree of polymerization in the range of about 3 to about 20 and an antimony based synergist in an amount of about 1 part by weight for every about 2 to about 5 parts by weight of said low molecular weight brominated polystyrene to provide a composition having good physical retention of notched Izod wherein the amount of bromine in said brominated polystyrene based upon the total weight of said brominated polystyrene is from about 53 percent to about 76 percent by weight.
11. A process according to Claim 10, wherein the amount of said bromine is from about 61 percent to about 71 percent by weight.
12. A process according to Claim 10 or 11, wherein said degree of polymerization is from about 6 to about 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36212989A | 1989-06-06 | 1989-06-06 | |
| US362,129 | 1989-06-06 | ||
| PCT/US1990/003150 WO1990015095A1 (en) | 1989-06-06 | 1990-06-04 | High impact polystyrene containing low molecular weight brominated polystyrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2033332A1 CA2033332A1 (en) | 1990-12-07 |
| CA2033332C true CA2033332C (en) | 2001-03-20 |
Family
ID=23424801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002033332A Expired - Lifetime CA2033332C (en) | 1989-06-06 | 1990-06-04 | High impact polystyrene containing low molecular weight brominated polystyrene |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0431119A4 (en) |
| JP (1) | JPH04500382A (en) |
| KR (1) | KR0168325B1 (en) |
| AU (1) | AU5833890A (en) |
| CA (1) | CA2033332C (en) |
| WO (1) | WO1990015095A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100761653B1 (en) | 2005-12-29 | 2007-10-04 | 제일모직주식회사 | Flame retardant styrene resin composition excellent in impact resistance and heat resistance |
| TW200838919A (en) * | 2007-01-10 | 2008-10-01 | Albemarle Corp | Brominated styrenic polymer compositions and processes for producing same |
| KR101544226B1 (en) | 2007-06-07 | 2015-08-12 | 알베마를 코포레이션 | Adducts adducts and oligomers or adducts oligomers and low molecular weight polymers and their preparation |
| US8993684B2 (en) | 2008-06-06 | 2015-03-31 | Albemarle Corporation | Low molecular weight brominated polymers, processes for their manufacture and their use in thermoplastic formulations |
| SG171741A1 (en) * | 2008-12-02 | 2011-07-28 | Albemarle Corp | Toluene and styrene derived telomer distributions and brominated flame retardants produced therefrom |
| CN102232089B (en) | 2008-12-02 | 2013-11-13 | 雅宝公司 | Bromination of telomer mixtures derived from toluene and styrene |
| JO3423B1 (en) | 2008-12-02 | 2019-10-20 | Albemarle Corp | Brominated Flame Retardants And Precursors Therefor |
| CN102272176A (en) | 2008-12-02 | 2011-12-07 | 雅宝公司 | Branched and star-branched styrene polymers, telomers, and adducts, their synthesis, their bromination, and their uses |
| MX2011011302A (en) | 2009-05-01 | 2011-11-18 | Albemarle Corp | Pelletized low molecular weight brominated aromatic polymer compositions. |
| JO3059B1 (en) | 2009-05-01 | 2017-03-15 | Albemarle Corp | Bromination of low molecular weight aromatic polymer compositions |
| FR3107704B1 (en) * | 2020-02-27 | 2023-04-07 | Siamp Cedap Reunies | Material for food packaging based on polystyrene and method of preparation. |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2515473C3 (en) * | 1975-04-09 | 1987-01-22 | Basf Ag, 6700 Ludwigshafen | Flame retardant linear polyester |
| DE2703419B1 (en) * | 1977-01-28 | 1978-02-02 | Basf Ag | FLAME RESISTANT POLYAMIDE MOLDING COMPOUNDS |
| DE2727483A1 (en) * | 1977-06-18 | 1979-01-11 | Basf Ag | SELF-EXTINGUISHING THERMOPLASTIC MOLDING COMPOUNDS |
| NL7812461A (en) * | 1978-12-22 | 1980-06-24 | Stamicarbon | THERMOPLASTIC MOLDING MASS. |
| DE2905253C3 (en) * | 1979-02-12 | 1986-01-09 | Chemische Fabrik Kalk GmbH, 5000 Köln | Fire protection components for thermoplastics |
| DE3006448A1 (en) * | 1980-02-21 | 1981-08-27 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING MIXTURES FROM BROWNED POLYSTYRENE AND BROWNED AROMATIC COMPOUNDS |
| JPS61179249A (en) * | 1985-02-05 | 1986-08-11 | Mitsui Toatsu Chem Inc | Flame-retardant styrene resin composition |
| US4755573A (en) * | 1985-11-15 | 1988-07-05 | General Electric Company | Cationic polymerization of bromoalkenyl aromatic compounds with aromatic chain transfer agent, and products |
| CA1324227C (en) * | 1987-07-16 | 1993-11-09 | Masafumi Hongo | Impact resistant flame-retardant resin composition |
-
1990
- 1990-06-04 KR KR1019910700136A patent/KR0168325B1/en not_active Expired - Fee Related
- 1990-06-04 AU AU58338/90A patent/AU5833890A/en not_active Abandoned
- 1990-06-04 EP EP19900909421 patent/EP0431119A4/en not_active Withdrawn
- 1990-06-04 JP JP2508852A patent/JPH04500382A/en active Pending
- 1990-06-04 CA CA002033332A patent/CA2033332C/en not_active Expired - Lifetime
- 1990-06-04 WO PCT/US1990/003150 patent/WO1990015095A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| KR920700256A (en) | 1992-02-19 |
| KR0168325B1 (en) | 1999-03-20 |
| CA2033332A1 (en) | 1990-12-07 |
| AU5833890A (en) | 1991-01-07 |
| EP0431119A1 (en) | 1991-06-12 |
| WO1990015095A1 (en) | 1990-12-13 |
| JPH04500382A (en) | 1992-01-23 |
| EP0431119A4 (en) | 1992-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5112898A (en) | High impact polystyrene containing low molecular weight brominated polystyrene | |
| US5112897A (en) | High impact polystyrene containing low molecular weight brominated polystyrene | |
| EP0611798B1 (en) | Resin composition | |
| US5112896A (en) | High-impact polystyrene containing low molecular weight brominated polystyrene | |
| DE69327754T2 (en) | STYRENE RESIN COMPOSITION | |
| US5194482A (en) | Flame retardant resin composition containing styrenic polymers | |
| EP0171730B1 (en) | Fire-retardant moulding compositions based on polymers of styrene | |
| CA2033332C (en) | High impact polystyrene containing low molecular weight brominated polystyrene | |
| US6822026B2 (en) | Flame-retardant polypropylene resin composition | |
| KR101685771B1 (en) | Halogen based flame retardant glass fiber reinforced polyamide resin composition, and method for preparing the same | |
| DE69906616T2 (en) | Flame retardant resin composition | |
| JP2003529654A (en) | Transparent flame-retardant poly (arylene ether) blend | |
| GB2336158A (en) | Flameproof thermoplastic resin composition | |
| US4446272A (en) | Resin composition having nice color tone and high crack-resistance | |
| JPS63221146A (en) | Flame-retarding rubber-modified styrene resin composition | |
| GB2300860A (en) | Flame retardant styrene polymer | |
| JPH0344106B2 (en) | ||
| EP0523790B1 (en) | Flame-retardant thermoplastic composition | |
| KR20140092456A (en) | Polyamide Resin Composition | |
| US20020010238A1 (en) | Ignition resistant polymer compositions | |
| JPH09194739A (en) | Flame-retardant resin composition | |
| JPH111622A (en) | Flame retardant resin composition | |
| KR20020024638A (en) | Fire retardant styrene based resin composition having superior impact resistance | |
| KR20020046078A (en) | Flame Retardent Polypropylene Resin Composition | |
| JPH0428744A (en) | Resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed | ||
| MKEC | Expiry (correction) |
Effective date: 20121202 |