CA2044176A1 - Aromatic triester plasticized copolymers of acrylonitrile and styrene - Google Patents
Aromatic triester plasticized copolymers of acrylonitrile and styreneInfo
- Publication number
- CA2044176A1 CA2044176A1 CA002044176A CA2044176A CA2044176A1 CA 2044176 A1 CA2044176 A1 CA 2044176A1 CA 002044176 A CA002044176 A CA 002044176A CA 2044176 A CA2044176 A CA 2044176A CA 2044176 A1 CA2044176 A1 CA 2044176A1
- Authority
- CA
- Canada
- Prior art keywords
- styrene
- acrylonitrile
- triester
- aromatic
- copolymers
- 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
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
Styrene/acrylonitrile copolymers containing a plasticizing quantity of an aromatic triester.
Styrene/acrylonitrile copolymers containing a plasticizing quantity of an aromatic triester.
Description
AROM~TIC TRIESTER PLASTICIZED COPOLYMERS OF
ACRYLONITRILE AND STYRENE
This invention relates to new, resinous compositions having a high degree of transparency, good color retention properties and unusual adaptability to injection molding techniques. More specifically the invention relates to copolymers of styrene and acrylonitrile suitably plasticized to result in compositions havlng good melt flow without sacrificing any of the desirable properties of the copolymer.
Copolymers of styrene and acrylonitrile, and methods for their preparation are well knowrl in the art.
The copolymers possess good resistance to organic solvents and are highly transparent. However, in some applications it is desirable to provide improved, i.e., increased melt flow properties in order to produce faster cycle tirnes and other molding improvements. This is accomplished by use of a plasticizer. For example, it is well known in the art to use epoxidized soybean oil as a suitable plasticizer for styreneJacrylonitrile copolymers. Disadvantageously, however, resins containing epoxidized soybean oil have a tendency to -2- 2 ~
discolor, especially when exposed to elevated temperatures for extended time periods.
In addition, molders of complex and intricately shaped objects of styrene/acrylonitrile resins often must employ very high molding temperatures in order to provide improved resin melt Plow. Previously known plasticizers such as alkyl phthalates have failed in such severe environments due to "sweating" or deposition of the plasticizer onto the mold surfaces.
The primary purpose of this invention is to provide methods of improving the melt flow rate and other properties of copolymers of acrylonitrile and styrene. ~ further purpose of this invention is to provide a means of plasticizing copolymers of acrylonitrile and styrene without sacrifice of the desirable transparency or color properties of the copolymer. A further purpose of the invention is to prepare a new and more useful composition of matter that may be utilized at extremes of temperature without encountering problems of "sweat out", i.e., loss of plasticizer and condensation thereof on cool surfaces of molding equipment or injection molded parts.
It has been found that triesters of aromatic tricarboxylic acids, especially trimellitlc acid, wherein the ester group contains an alkyl or aryl radical of up to 20 carbon atoms, are unusually compatible with copolymers of styrene and acrylonitrile, and effectively improve the melt flow properties of the molten polymer without loss of crystalline polymer properties. In particuiar such polymers demonstrate little discoloration or plasticizer sweat out.
_3~ J$
The invention is preferably used in copolymerY
of 65 to 80 weight percent styrene and 20 to 35 weight per-cent acryionitriie. An elastomeric impact modifier such as a butadiene based rubber, copolymers of ethylene and propylene and optionally a nonconjugated diene, and alkyl acrylate rubbers may be present in the copolymers as well. Suitable amounts of impact modifier are from 1-20~ preferably 5-15 percent by weight. The copolymer may be prepared by emulsion, mass, solution or suspension polymerization methods.
The preferred plasticizers for the practice of this invention are the acid triesters having the structural formulao Ar(C(O)OR)3 wherein Ar is an aromatic radical of up to 20 carbons, and R is an alkyl or aryl radical having up to 20 carbon atoms. Preferred triesters are linear C6_20 alkyl triesters of trimellitic acid. Particularly preferred esters are tridecyl trimellitate9 tridodecyl trimellitate, tri--n-octyl trimellitate, mixed C8~0 linear alkyl trimellitates, etc. The straight chain or linear alkyl triesters are particularly preferred due to the improved color stability. Additive di~coloration upon prolonged heating is believed to be due to the greater instability of tertiary hydrogen proton compared to a secondary hydrogen moiety.
3o The plasticized copolymers are prepared by mixing the desired plasticizer and copolymer in any of the conventional mixing ~achines, for example, roll mills, Banbury type mixers, extruders~ etc., which may be heated to soften the copolymers. The plzsticizer may 4 ~ 3 ~ ~1 also be coated onto the surface of polymer granules to be later melted and incorporated into the polymer or incorporated into the polymerization mixture and thus into the polymer prior to devolitalization and granulation. The quantity of plasticizer used will depend upon the ultimate use of the composition. A
plasticizing amount of the aromatic acid tri~ster, i.e., sufficient amount to improve the polymer's properties, is employed. Preferred amounts of plasticizer are from 0.1 to 5 percent, more preferable 0.5 to 2.5 percent by weight. The optimum proportion of triester may readil~
be determined by preparing test samples and measuring the melt flow rate enhancement, rheology, and other desired physical properties of the resulting resin.
The new compositions are unusually valuable for making injection molded articles which are of high clarity with improved molding properties. Compared to the use of epoxidized soybean oil (ESB0) plasticizers, the present invention results in improved melt flow rates and less discoloration of the resulting copolymer when exposed to high temperatures~ When compared to phthalate or terephthalate diester plasticizers, mold sweating is substantially improved and a modest improvement in flexural strength is noticed. These resu:Lts are not expected or predicted from known teachings.
Additional additives such as colorants, UV
ACRYLONITRILE AND STYRENE
This invention relates to new, resinous compositions having a high degree of transparency, good color retention properties and unusual adaptability to injection molding techniques. More specifically the invention relates to copolymers of styrene and acrylonitrile suitably plasticized to result in compositions havlng good melt flow without sacrificing any of the desirable properties of the copolymer.
Copolymers of styrene and acrylonitrile, and methods for their preparation are well knowrl in the art.
The copolymers possess good resistance to organic solvents and are highly transparent. However, in some applications it is desirable to provide improved, i.e., increased melt flow properties in order to produce faster cycle tirnes and other molding improvements. This is accomplished by use of a plasticizer. For example, it is well known in the art to use epoxidized soybean oil as a suitable plasticizer for styreneJacrylonitrile copolymers. Disadvantageously, however, resins containing epoxidized soybean oil have a tendency to -2- 2 ~
discolor, especially when exposed to elevated temperatures for extended time periods.
In addition, molders of complex and intricately shaped objects of styrene/acrylonitrile resins often must employ very high molding temperatures in order to provide improved resin melt Plow. Previously known plasticizers such as alkyl phthalates have failed in such severe environments due to "sweating" or deposition of the plasticizer onto the mold surfaces.
The primary purpose of this invention is to provide methods of improving the melt flow rate and other properties of copolymers of acrylonitrile and styrene. ~ further purpose of this invention is to provide a means of plasticizing copolymers of acrylonitrile and styrene without sacrifice of the desirable transparency or color properties of the copolymer. A further purpose of the invention is to prepare a new and more useful composition of matter that may be utilized at extremes of temperature without encountering problems of "sweat out", i.e., loss of plasticizer and condensation thereof on cool surfaces of molding equipment or injection molded parts.
It has been found that triesters of aromatic tricarboxylic acids, especially trimellitlc acid, wherein the ester group contains an alkyl or aryl radical of up to 20 carbon atoms, are unusually compatible with copolymers of styrene and acrylonitrile, and effectively improve the melt flow properties of the molten polymer without loss of crystalline polymer properties. In particuiar such polymers demonstrate little discoloration or plasticizer sweat out.
_3~ J$
The invention is preferably used in copolymerY
of 65 to 80 weight percent styrene and 20 to 35 weight per-cent acryionitriie. An elastomeric impact modifier such as a butadiene based rubber, copolymers of ethylene and propylene and optionally a nonconjugated diene, and alkyl acrylate rubbers may be present in the copolymers as well. Suitable amounts of impact modifier are from 1-20~ preferably 5-15 percent by weight. The copolymer may be prepared by emulsion, mass, solution or suspension polymerization methods.
The preferred plasticizers for the practice of this invention are the acid triesters having the structural formulao Ar(C(O)OR)3 wherein Ar is an aromatic radical of up to 20 carbons, and R is an alkyl or aryl radical having up to 20 carbon atoms. Preferred triesters are linear C6_20 alkyl triesters of trimellitic acid. Particularly preferred esters are tridecyl trimellitate9 tridodecyl trimellitate, tri--n-octyl trimellitate, mixed C8~0 linear alkyl trimellitates, etc. The straight chain or linear alkyl triesters are particularly preferred due to the improved color stability. Additive di~coloration upon prolonged heating is believed to be due to the greater instability of tertiary hydrogen proton compared to a secondary hydrogen moiety.
3o The plasticized copolymers are prepared by mixing the desired plasticizer and copolymer in any of the conventional mixing ~achines, for example, roll mills, Banbury type mixers, extruders~ etc., which may be heated to soften the copolymers. The plzsticizer may 4 ~ 3 ~ ~1 also be coated onto the surface of polymer granules to be later melted and incorporated into the polymer or incorporated into the polymerization mixture and thus into the polymer prior to devolitalization and granulation. The quantity of plasticizer used will depend upon the ultimate use of the composition. A
plasticizing amount of the aromatic acid tri~ster, i.e., sufficient amount to improve the polymer's properties, is employed. Preferred amounts of plasticizer are from 0.1 to 5 percent, more preferable 0.5 to 2.5 percent by weight. The optimum proportion of triester may readil~
be determined by preparing test samples and measuring the melt flow rate enhancement, rheology, and other desired physical properties of the resulting resin.
The new compositions are unusually valuable for making injection molded articles which are of high clarity with improved molding properties. Compared to the use of epoxidized soybean oil (ESB0) plasticizers, the present invention results in improved melt flow rates and less discoloration of the resulting copolymer when exposed to high temperatures~ When compared to phthalate or terephthalate diester plasticizers, mold sweating is substantially improved and a modest improvement in flexural strength is noticed. These resu:Lts are not expected or predicted from known teachings.
Additional additives such as colorants, UV
3 stabilizers, reinforcing aids, blowing agents, fibers, fillers, etc. may be included in the copolymeric compositions of the present invention. Further details of the preparation and evaluation of the new products _5_ 2 3~
are set forth with respect to the following specific examples:
Example 1 A recirculated coil reactor was employed to prepare catalytic styrene acrylonitrile containing approximately 25 percent by weight acrylonitrilc and molecular weight (Mw) of about 150,000. (Actual molecular weights o~ samples tested are provided in Table I.) A 0.8 inch (20 mm) Welding Engineers extruder was used to compound plasticizers into the styrene/acrylonitrile feedstock previously described.
Various plasticizers were added to provide a final plasticizer content o~ 1.0 percent by weight. Results of the physical property testing are contained in Table I.
2 ~ ci ~ 7 ~
Table I
Polymer Flex Strength3 Plasticizer (Percent) MW(1O3) MF~I Vicat2 psi (kPax_103) - 1409.8 229 18,400 5 ESBo4 1.0 13O11.2 Z25 17,800 DIDPs~ 1.0 14411.1 227 17,400 NODP6~ 1.0 13911.5 225 17,000 ToTM7 1.0 14511.4 225 17,600 10NONDTM8 1.0 14011.5 226 179600 I melt flow rate g/10 min/ASTM D1238 condition I
2 Vicat heat softening tem?erature, C
3 flexural strength ASTM D790 4 epoxidized soybean oil 5 di-isodecyl phthalate 156 n-octyl, n-decyl phthalate 7 tri-(2-ethyl hexyl) trimellitate 8 n-octyl, n-decyl trimellitate, triester formed by reaction of trimellitic acid with a mixture of linear . C8 tO alcohols Comparative As may be seen by examination of Table I the trimellitate esters gave slightly improved melt flow rate compared to the use of epoxidized soybean oil.
Additionally, the decreaqe in flexural strength ~or the trimellitate esters was not as great as with the phthalate diester ?lasticizers. When compared with the phthalate diesters for mold sweating problems, the trimellitate esters were shown to possess improved properties.
are set forth with respect to the following specific examples:
Example 1 A recirculated coil reactor was employed to prepare catalytic styrene acrylonitrile containing approximately 25 percent by weight acrylonitrilc and molecular weight (Mw) of about 150,000. (Actual molecular weights o~ samples tested are provided in Table I.) A 0.8 inch (20 mm) Welding Engineers extruder was used to compound plasticizers into the styrene/acrylonitrile feedstock previously described.
Various plasticizers were added to provide a final plasticizer content o~ 1.0 percent by weight. Results of the physical property testing are contained in Table I.
2 ~ ci ~ 7 ~
Table I
Polymer Flex Strength3 Plasticizer (Percent) MW(1O3) MF~I Vicat2 psi (kPax_103) - 1409.8 229 18,400 5 ESBo4 1.0 13O11.2 Z25 17,800 DIDPs~ 1.0 14411.1 227 17,400 NODP6~ 1.0 13911.5 225 17,000 ToTM7 1.0 14511.4 225 17,600 10NONDTM8 1.0 14011.5 226 179600 I melt flow rate g/10 min/ASTM D1238 condition I
2 Vicat heat softening tem?erature, C
3 flexural strength ASTM D790 4 epoxidized soybean oil 5 di-isodecyl phthalate 156 n-octyl, n-decyl phthalate 7 tri-(2-ethyl hexyl) trimellitate 8 n-octyl, n-decyl trimellitate, triester formed by reaction of trimellitic acid with a mixture of linear . C8 tO alcohols Comparative As may be seen by examination of Table I the trimellitate esters gave slightly improved melt flow rate compared to the use of epoxidized soybean oil.
Additionally, the decreaqe in flexural strength ~or the trimellitate esters was not as great as with the phthalate diester ?lasticizers. When compared with the phthalate diesters for mold sweating problems, the trimellitate esters were shown to possess improved properties.
Claims (5)
1. A composition of matter comprising a copolymer of from 65 to 80 weight percent styrene and from 35 to 20 weight percent acrylonitrile and a plasticizing quantity of a plasticizer characterized in that the plasticizer is an aromatic triester corresponding to the formula:
Ar(C(O)OR)3 wherein Ar is an aromatic radical of up to 20 carbons and R is an alkyl or aryl group of up to 20 carbons.
Ar(C(O)OR)3 wherein Ar is an aromatic radical of up to 20 carbons and R is an alkyl or aryl group of up to 20 carbons.
2. A composition according to Claim 1 wherein the aromatic triester is a trimellitic acid triester.
3. A composition according to Claim 1 comprising from 0.1 to 5 percent by weight aromatic triester.
4. A composition according to Claim 1 wherein R
is linear C6-20 alkyl.
is linear C6-20 alkyl.
5. A composition according to Claim 2 wherein the trimellitic acid ester is tri-n-octyl trimellitate, tridecyl trimellitate or a mixed C8-10 linear alkyl trimellitate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43685789A | 1989-11-14 | 1989-11-14 | |
| US436,857 | 1989-11-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2044176A1 true CA2044176A1 (en) | 1991-05-15 |
Family
ID=23734111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002044176A Abandoned CA2044176A1 (en) | 1989-11-14 | 1990-09-19 | Aromatic triester plasticized copolymers of acrylonitrile and styrene |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0453524A4 (en) |
| JP (1) | JPH04503083A (en) |
| KR (1) | KR920701346A (en) |
| AU (1) | AU6447390A (en) |
| CA (1) | CA2044176A1 (en) |
| WO (1) | WO1991007459A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19737793C1 (en) | 1997-08-29 | 1998-12-24 | Rwe Dea Ag | 2-Alkyl-alk-1-yl benzene-tri- and tetra-carboxylic esters with good lubricating property under load |
| US9307679B2 (en) | 2011-03-15 | 2016-04-05 | Kabushiki Kaisha Toshiba | Server room managing air conditioning system |
| PL3147317T3 (en) | 2015-09-28 | 2018-01-31 | Evonik Degussa Gmbh | Tripentylester of trimellitic acid |
| KR20230074746A (en) | 2020-09-25 | 2023-05-31 | 덴카 주식회사 | resin composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3280063A (en) * | 1961-03-29 | 1966-10-18 | Borden Co | Esters of a monohydric aliphatic alcohol having 10-20 carbon atoms with a mononuclear aromatic acid having 3-6 carboxy groups as flow promoters for sound record compositions |
| US4654390A (en) * | 1984-08-10 | 1987-03-31 | The Dow Chemical Company | Monomeric plasticizers for halogen-containing resins |
-
1990
- 1990-09-19 WO PCT/US1990/005333 patent/WO1991007459A1/en not_active Application Discontinuation
- 1990-09-19 CA CA002044176A patent/CA2044176A1/en not_active Abandoned
- 1990-09-19 AU AU64473/90A patent/AU6447390A/en not_active Abandoned
- 1990-09-19 JP JP2513792A patent/JPH04503083A/en active Pending
- 1990-09-19 EP EP19900914568 patent/EP0453524A4/en not_active Withdrawn
- 1990-09-19 KR KR1019910700734A patent/KR920701346A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991007459A1 (en) | 1991-05-30 |
| KR920701346A (en) | 1992-08-11 |
| EP0453524A1 (en) | 1991-10-30 |
| AU6447390A (en) | 1991-06-13 |
| EP0453524A4 (en) | 1992-05-13 |
| JPH04503083A (en) | 1992-06-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |