AU2001277168A1 - High molecular weight monovinylidene aromatic polymers with good processability - Google Patents
High molecular weight monovinylidene aromatic polymers with good processabilityInfo
- Publication number
- AU2001277168A1 AU2001277168A1 AU2001277168A AU7716801A AU2001277168A1 AU 2001277168 A1 AU2001277168 A1 AU 2001277168A1 AU 2001277168 A AU2001277168 A AU 2001277168A AU 7716801 A AU7716801 A AU 7716801A AU 2001277168 A1 AU2001277168 A1 AU 2001277168A1
- Authority
- AU
- Australia
- Prior art keywords
- furfuryl
- polymer
- molecular weight
- alkyl
- acrylate
- 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.)
- Abandoned
Links
- 229920000642 polymer Polymers 0.000 title claims description 31
- 125000003118 aryl group Chemical group 0.000 title claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- DWXAVNJYFLGAEF-UHFFFAOYSA-N furan-2-ylmethyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC1=CC=CO1 DWXAVNJYFLGAEF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical class CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 5
- 229920005669 high impact polystyrene Polymers 0.000 description 5
- 239000004797 high-impact polystyrene Substances 0.000 description 5
- 239000004793 Polystyrene Chemical class 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 229920002223 polystyrene Chemical class 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000012667 polymer degradation Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical class C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical class C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical class CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- -1 n-dodecyl Chemical group 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical class CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical class C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/06—Vinyl aromatic monomers and methacrylates as the only monomers
-
- 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
- C08L51/04—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 rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
HIGH MOLECULAR WEIGHT MONOVINYLIDENE AROMATIC POLYMERS WITH GOOD PROCESSABILITY
The process of the present invention relates to monovinylidene aromatic polymers.
Many desirable properties of monovinylidene aromatic polymers are dependent upon the weight average molecular weight (Mw) of the polymer, wherein higher molecular weights provide better properties . The problem which arises with high molecular weight polymers is that of ■ processability. Typically, high molecular weight polymers have high viscosities, making them difficult to process. Processing at higher temperatures will lower the viscosity, but in most circumstances the high temperatures needed for desirable viscosities cause polymer degradation as well. U.S. Patent No. 3,678,016 discloses a process wherein crosslinking addition reactions are reversible at elevated temperatures so that polymer-curing agent compositions can be maintained as fluid compositions at such elevated temperatures, long enough to be fabricated into shaped articles, and the fabricated articles are then set by cooling. However, this process requires two separate components maintained at very high temperatures (200 to 300°C) and long reaction times, which still lead to polymer degradation.
Therefore, there remains a need for a polymer composition having a high molecular weight, enhanced processability and good balance of mechanical and thermal properties.
The present invention relates to a high molecular weight monovinylidene aromatic polymer produced by polymerizing a vinyl aromatic monomer in the presence of a small amount of furfuryl (alkyl) acrylate. Surprisingly, the incorporation of a small amount of furfuryl (alkyl) acrylate allows the monovinylidene aromatic polymer to be rheologically modified such that it has high flow at elevated temperatures, yet maintains a high molecular weight and excellent . mechanical and thermal properties, without polymer degradation.
Suitable vinyl aromatic monomers used to produce the monovinylidene aromatic polymer include, but are not limited to, those described in U.S. Patents 4,666,987, 4,572,819 and 4,585,825. Preferably, the monomer is of the formula:
R I
Ar-C=CH2
wherein R' is hydrogen or methyl, Ar is an aromatic ring structure having from 1 to 3 aromatic rings with or without alkyl, halo, or haloalkyl substitution, wherein any alkyl group contains 1 to 6 carbon atoms and haloalkyl refers to a halo substituted alkyl group. Preferably, Ar is phenyl or alkylphenyl, wherein alkylphenyl refers to an alkyl substituted phehyl group, with phenyl being most preferred. Typical vinyl aromatic monomers which can be used include: styrene, alpha-methylstyrene, all isomers of vinyl toluene, especially paravinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. The vinyl aromatic monomers may also be combined with other copolymerizable monomers. Examples of such monomers include, but are not limited to acrylic monomers such as acrylonitrile, methacrylonitrile, methacrylic acid, methyl methacrylate, acrylic acid, and methyl acrylate; maleimide, phenylmaleimide, and maleic anhydride. In addition, the polymerization of the vinyl aromatic monomer may be conducted in the presence of predissolved elastomer, such as butadiene or isoprene homopolymer or copolymer, to prepare impact modified, or grafted rubber containing products, examples of which are described in U.S. Patent Nos. 3,123,655, 3,346,520, 3,639,522, and 4,409,369.
Polymerization processes and process conditions for the polymerization of vinyl aromatic monomers are well known in the art. Although any polymerization process can be used, typical processes are continuous bulk or solution polymerizations as described in U.S. Patent No. 2,727,884 and U.S. Patent No. 3,639,372.
The polymerization can be conducted at any temperature at which a high molecular weight polymer will be produced. Suitable polymerization temperatures are from 80°C to 170°C, preferably from 110°C to 160°C, with 115°C to 150°'C being the most preferred. An initiator may optionally be used, such as azo compounds and peroxides. Exemplary peroxides include tert-butylperoxybenzoate, tert- butylperoxyacetate, di-tert-butylperoxide, dibenzoylperoxide, dilauroylperoxide, 1, 1-bis-tert-butylperoxycyclohexane, 1,1, -bis -tert- butylperoxy-3, 3, 5-trimethylcyclohexane and dicumylperoxide. Additionally, molecular weight regulators can also be used in the production of the polymers of the present invention, including ethylbenzene, n-dodecyl mercaptan, polystyrene dimers and trimers, acrylate and (alkyl) acrylate dimers and trimers. Other additives which may be present include plasticizers such as mineral oil, and polybutene, and antioxidants such as hindered phenols.
The furfuryl (alkyl) acrylates useful in producing the high molecular weight monovinylidene aromatic polymers include furfuryl acrylates, furfuryl methacrylates, and furfuryl ethacrylates. Alkyl substituted furfuryl (alkyl) acrylates can also be used, wherein the furfuryl group is
additionally substituted with, a Cι-C10 alkyl group such as methyl, ethyl, butyl, isobutyl, propyl, isopropyl, and pentyl, for example 2- (5- methylfurfuryl)methacrylate. Preferably, furfuryl methacrylate is used.
The amount of furfuryl (alkyl) acrylate used in the polymerization is an amount such that the resulting monovinylidene aromatic polymer is rheologically modified to give high flow at elevated temperatures, such as 180 to 280°C, yet maintain a high Mw and good mechanical and thermal properties. Preferably from 0.1, more preferably from 0.3, most preferably from 0.5 to less than 3, preferably less than 2.9, more . preferably less than 2.8 and most preferably less than 2.7 weight percent furfuryl (alkyl) acrylate is present, based on the total weight of the vinyl aromatic monomer and furfuryl (alkyl) acrylate. It has been surprisingly discovered. that such monovinylidene aromatic polymers have enhanced flow and rheological properties, yet maintain high molecular weights and excellent physical properties.
Copolymers of furfuryl methacrylate and styrene have been disclosed in various references including European Polymer Journal, vol. 30', No. 4, pp. 489-494. However, the amounts of furfuryl methacrylate used, causes increased amounts of crosslinking and decreased processability. Unexpectedly, the applicants have found that small amounts as claimed herein, offer increased molecular weight with good flow and processability and excellent physical properties.
The molecular weight of the resulting polymer is dependent upon a number of factors including the temperature, the (optional) initiator concentration, and the time of reaction. The term molecular weight (Mw) refers to the weight average molecular weight as determined by gel permeation chromatography calibrated with narrow polystyrene standards and using a refractive index detector.
The molecular weight of the high molecular weight polymer formed is typically from 100,000 to 500,000, most preferably from 120,000 to
450,000, as measured by gel permeation chromatography. Polymers having molecular weights greater than 450,000 are undesirable because they are difficult to process. Polymers having molecular weights less than 100,000 will not have the desirable properties obtained by the present invention. The high Mw monovinylidene aromatic polymer produced by the process of the present invention can be employed in applications where high molecular weight vinyl aromatic polymers are suitably used, such as foam sheet, films and injection molding processes. They can also be combined with polymers of differing Mw to make polymer compositions having a multimodal molecular weight distribution, preferably a bimodal molecular weight distribution, hereinafter referred to as bimodal compositions.
In one embodiment, the high molecular weight monovinylidene aromatic polymer is produced by polymerizing a composition consisting essentially of a vinyl aromatic monomer ath a small amount of furfuryl
(alkyl) acrylate. The phrase 'consisting essentially of refers to the components which are essential in order to obtain the advantages of the present invention and any other components present would not significantly change the properties related to the inventive advantage. The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and they should not be so interpreted. Amounts are in weight parts or weight percentages unless otherwise indicated. Examples 1-4. Polystyrene
Styrene is polymerized in the presence of 2-propenoic acid, 2- methyl, 2 - furanylmethyl ester (also known as Furfuryl methacrylate (FMA) ) at ratios shown in TABLE 1. The polymerizations are conducted in test tubes using an initiator (1, 1-di (tert-butylperoxy) cyclohexane (BPC)) and two molecular weight moderators (ethylbenzene (EB) and n-dodecyl mercaptane (nDM) ) .
The temperature profile is: 35 minutes at 115°C and 45 minutes at each of the following temperatures: 125, 130, 140, 150, 160, 170, 180 and 185°C.
Prior to the polymerization, the samples are degassed, then polymerized to a conversion of 88 percent and dried in a vacuum oven at 30°C for 48 hours. Note that the Example codes refer to the amount of polymerized FMA and styrene (S) in the dried polymers as determined by NMR. The molecular weights are measured by gel permeation chromatography and are given in TABLE 2. General Purpose polystyrene (GPPS) resin is also included as a control in order to show the optimized rheology.
The samples obtained are analyzed by molten state dynamic mechanical spectroscopy (DMS) at 200°C in the frequency range from 0.1 rad/s to 100 rad/s, using 25 mm diameter parallel plates. The dynamic strain frequency sweep mode is used at a strain of 10 %.
TABLE 1
■■furfuryl methacrylate (FMA)
21 , 1 -di (tert -butylperoxy) cyclohexane (BPC)
3ethylbenzene (EB)
4n-dodecyl mercaptan (nDM)
*Comparative Examples
Mw stands for weight average molecular weig t, Mn for the number average and Mz for the z average Comparative Examples
TABLE 3 Complex viscosity (Pa.s) as a function of shear rate associated with the resins given in Table 2.
Comparative Examples
TABLE 3 shows results for the complex viscosity as a function of shear rates. It is apparent from this Table that:
All samples containing FMA have higher Mw' s than the straight GPPS resin produced under the same conditions.
Example 2 has a higher viscosity than the commercial GPPS material at low shear rates and a lower viscosity at higher shear rates. The higher zero shear rate viscosity is expected from the molecular weight features associated with this resin, specifically with Mw; however, the lower viscosity values observed at higher shear rates gives an indication of the improved rheological behaviour associated with these polymers: increased mechanical strength (from zero shear rate viscosity values) in combination with higher flow at higher shear rates.
Example 5. High Impact Polystyrene
Compositions as shown in TABLE 4 are polymerized using a batch reactor. Two temperature ramps are used: from 95 to 120°C in 45 minutes and from 120 to 140°C in 120 minutes. The agitator speed is 100 rpm in both cases. The conversion obtained for both samples of HIPS (the control and Example 5) is 38 %. The samples are dried under vacuum at 30°C for 90 minutes and at 200°C for 10 minutes. The final composition of the HIPS
samples is given in TABLE 5 The properties associated with each HIPS sample are given in TABLE 6 .
TABLE 4
Comparative Example
Diene 55 is available from Firestone.
TABLE 5
Comparative Example
TABLE 6
Comparative Example
Note the decreased MFR and increased izod and tensile properties of the present invention over the Control HIPS.
Claims (10)
1. A high molecular weight polymer produced by polymerizing a composition comprising a vinyl aromatic monomer and from 0.1 to less than 3 weight percent furfuryl (alkyl) acrylate, based on the total weight of the vinyl aromatic monomer and furfuryl (alkyl) acrylate.
2. The polymer of Claim 1, wherein the vinyl aromatic monomer is styrene.
3. The polymer of Claim 1, wherein the composition additionally comprises a predissolved elastomer.
4. The polymer of Claim 4, wherein the predissolved elastomer is a butadiene homopolymer or copolymer.
5. The polymer of Claim 1, wherein the furfuryl (alkyl) acrylate is furfuryl methacrylate.
6. The polymer of Claim 1, having a Mw of from 100,000 to 500,000.
7. A process of producing a high molecular weight monovinylidene aromatic polymer comprising polymerizing a vinyl aromatic monomer in the presence of from 0.1 to less than 3 weight percent furfuryl
(alkyl) acrylate, based on the total weight of the vinyl aromatic monomer and the furfuryl (alkyl) acrylate.
8. The process of Claim 7, wherein the vinyl aromatic monomer is styrene.
9. The process of Claim 7, wherein the furfuryl (alkyl) acrylate is furfuryl methacrylate.
10. An article produced by the polymer of Claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22217700P | 2000-08-01 | 2000-08-01 | |
| US60222177 | 2000-08-01 | ||
| PCT/US2001/023385 WO2002010238A1 (en) | 2000-08-01 | 2001-07-25 | High molecular weight monovinylidene aromatic polymers with good processability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2001277168A1 true AU2001277168A1 (en) | 2002-02-13 |
Family
ID=22831192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2001277168A Abandoned AU2001277168A1 (en) | 2000-08-01 | 2001-07-25 | High molecular weight monovinylidene aromatic polymers with good processability |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6573349B2 (en) |
| EP (1) | EP1311569A1 (en) |
| JP (1) | JP2004505133A (en) |
| KR (1) | KR20030036662A (en) |
| CN (1) | CN1443206A (en) |
| AU (1) | AU2001277168A1 (en) |
| BR (1) | BR0112992A (en) |
| TW (1) | TW554003B (en) |
| WO (1) | WO2002010238A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7597962B2 (en) * | 2005-06-07 | 2009-10-06 | Centre Luxembourgeois De Recherches Pour Le Verre Et La Ceramique S.A. (C.R.V.C.) | Coated article with IR reflecting layer and method of making same |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2548186A (en) | 1950-02-25 | 1951-04-10 | Goodrich Co B F | Interpolymers of an alkyl acrylate, an aromatic monoolefin, and a vinyl ester of an aromatic monocarboxylic acid |
| US2843561A (en) | 1955-03-29 | 1958-07-15 | Dow Chemical Co | Compositions of interpolymerized vinyl aromatic hydrocarbons, acrylic acid esters and rubbery butadiene-styrene copolymers and method of making same |
| US3029223A (en) * | 1959-02-11 | 1962-04-10 | Dow Chemical Co | Process for preparing transparent compositions from styrene, methyl methacrylate and rubbery copolymers of styrene and butadiene and resinous products thereof |
| ES314354A1 (en) * | 1964-07-16 | 1966-01-01 | Du Pont | A procedure to prepare a copolymer of graft. (Machine-translation by Google Translate, not legally binding) |
| US3678016A (en) | 1967-02-27 | 1972-07-18 | Dow Chemical Co | Fabrication of shaped articles cross-linked by chemical addition reactions |
| US3993624A (en) | 1972-11-08 | 1976-11-23 | Fuji Photo Film Co., Ltd. | Light-sensitive high molecular weight compound capable of being cross-linked by irradiation with light or an electron beam |
| DE2310307C2 (en) | 1973-03-01 | 1983-12-29 | Hoechst Ag, 6230 Frankfurt | Photosensitive recording material |
| US4100228A (en) * | 1977-04-04 | 1978-07-11 | The Dow Chemical Company | Transparent impact styrene polymer structure |
| US4451615A (en) | 1980-05-09 | 1984-05-29 | Loctite (Ireland) Limited | Polyisoprene toughened adhesive composition |
| IE50787B1 (en) * | 1980-05-09 | 1986-07-23 | Loctite Corp | Polyisoprene toughened adhesive composition |
| US4497929A (en) | 1982-07-19 | 1985-02-05 | Eastman Kodak Company | Latex compositions comprising loadable polymeric particles |
| US4530973A (en) * | 1983-03-11 | 1985-07-23 | The Dow Chemical Company | Transparent impact resistant polymeric compositions and process for the preparation thereof |
| EP0357110A1 (en) | 1988-08-05 | 1990-03-07 | Akzo N.V. | Two component coating curable at ambient temperature via a Diels-Alder reaction |
| US5250391A (en) | 1990-05-10 | 1993-10-05 | Hughes Aircraft Company | Photopolymer composition and its use |
| DE4104319A1 (en) * | 1991-02-13 | 1992-08-20 | Roehm Gmbh | Reversibly crosslinkable polymethacrylate moulding compsn. - comprising methyl-methacrylate, furfuryl (meth)acrylate, vinyl] monomer(s) and bis:maleimide cpd. |
| DE4121946A1 (en) | 1991-07-03 | 1993-01-07 | Basf Ag | AT ROOM TEMPERATURE CROSS-LINKING, AQUEOUS RESIN PREPARATION AND THEIR USE AS COATING GLUE |
| JPH0538883A (en) | 1991-08-03 | 1993-02-19 | Sony Corp | Video printing paper |
| US5756625A (en) | 1996-10-11 | 1998-05-26 | Minnesota Mining And Manufacturing Company | Stabilized adhesive microspheres |
-
2001
- 2001-07-25 AU AU2001277168A patent/AU2001277168A1/en not_active Abandoned
- 2001-07-25 BR BR0112992-9A patent/BR0112992A/en not_active Application Discontinuation
- 2001-07-25 EP EP01954956A patent/EP1311569A1/en not_active Withdrawn
- 2001-07-25 CN CN01813228A patent/CN1443206A/en active Pending
- 2001-07-25 JP JP2002515966A patent/JP2004505133A/en active Pending
- 2001-07-25 KR KR10-2003-7001449A patent/KR20030036662A/en not_active Withdrawn
- 2001-07-25 US US09/915,065 patent/US6573349B2/en not_active Expired - Fee Related
- 2001-07-25 WO PCT/US2001/023385 patent/WO2002010238A1/en not_active Ceased
- 2001-07-31 TW TW090118672A patent/TW554003B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1443206A (en) | 2003-09-17 |
| WO2002010238A1 (en) | 2002-02-07 |
| US20020099236A1 (en) | 2002-07-25 |
| TW554003B (en) | 2003-09-21 |
| BR0112992A (en) | 2003-07-01 |
| JP2004505133A (en) | 2004-02-19 |
| EP1311569A1 (en) | 2003-05-21 |
| US6573349B2 (en) | 2003-06-03 |
| KR20030036662A (en) | 2003-05-09 |
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