WO2001051543A2 - Tricarboxylate plasticizer for halogenated polymers - Google Patents

Tricarboxylate plasticizer for halogenated polymers Download PDF

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Publication number
WO2001051543A2
WO2001051543A2 PCT/US2001/000791 US0100791W WO0151543A2 WO 2001051543 A2 WO2001051543 A2 WO 2001051543A2 US 0100791 W US0100791 W US 0100791W WO 0151543 A2 WO0151543 A2 WO 0151543A2
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composition
plasticizer
parts
tricarboxylate
hexane
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PCT/US2001/000791
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French (fr)
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WO2001051543A3 (en
Inventor
John A. Buono
Maryellen Cobb
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Teknor Apex Company
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Priority to AU2001227804A priority Critical patent/AU2001227804A1/en
Publication of WO2001051543A2 publication Critical patent/WO2001051543A2/en
Publication of WO2001051543A3 publication Critical patent/WO2001051543A3/en

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    • 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
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids

Definitions

  • This invention relates generally to plasticizers.
  • Polyvinyl chloride (PVC) compositions are used in numerous applications. For example. PVC compositions are used as wire and cable insulation and jacketing, in automotive applications, and as components in medical devices such as facial masks, drip chambers, tube connectors and valves. PVC compositions used in these applications often include plasticizers to improve the flexibility and brittle point of the compositions. The brittle point is the temperature generally below which the composition becomes brittle, rather than ductile and flexible. PVC compositions also are used as flame retardants. These compositions typically contain, in addition to PVC. one or more flame retardant compounds, plasticizers. lubricants, and/or fillers. It is desirable for these compositions to exhibit low smoke generation and low flame travel.
  • the invention features a plasticizer that can be used, for example, in PVC compositions.
  • the plasticizer has the following structure:
  • each R independently, is an alkyl, alkenyl. alkynyl, or aromatic group containing 2 and
  • each R contains between 4 and 10 carbon atoms.
  • a preferred plasticizer is tri-n-hexyl-l,3,6-hexane-tricarboxylate.
  • the plasticizer when used, for example, in PVC compositions, can provide the composition with good flexibility and good performance at low temperature.
  • PVC compositions including the plasticizer have a brittle point of less than -30 °C. and even more preferably, less than -60 °C. when tested according procedures described below. Such compositions are useful in applications exposed to low temperatures such as in cryogenics.
  • the plasticizer can provide good performance even at low concentrations, thereby providing the compositions with low smoke values and high oxygen indexes (as described below) since lower amounts of plasticizers are used. Such compositions, therefore, exhibit good fire retardancy.
  • PVC compositions including the plasticizer have smoke values less than 2.0% decharred, less than 5.0% not decharred, and an oxygen index of greater than 50%o O 2 .
  • a preferred polymeric composition for use in a medical device includes polyvinyl chloride, a plasticizer having the structure described above, and one or more additives, such as a stabilizer.
  • Polyvinyl chloride or "PVC,” as used herein, includes homopolymers of vinyl chloride. as well as polymerization products of vinyl chloride and one or more co-monomers.
  • PVCs include copolymers of vinyl chloride and ethylene and copolymers of vinyl chloride and propylene.
  • An example of such a resin is a copolymer of a vinyl chloride monomer and a methyl methacrylate monomer. These resins may be used alone or in combination.
  • PVC resins include BCP 70 available from Borden Chemical, and Shintech SE 1200 available from Shintech.
  • the plasticizer is added to the polymeric composition to alter the physical properties of the PVC. Adding the plasticizer can improve, for example, the flexibility, brittle point, and processability of the PVC.
  • plasticizers having the structure described above include tri-n-pentyl- 1.3,6-hexane-tricarboxylate, tri-butoxyethyl- 1 ,3,6-hexane-tricarboxylate. tri-2-(2- methoxyethoxy) ethyl- 1 , 3,6-hexane-tricarboxylate, tri-n-octyl- 1 , 3,6-hexane-tricarboxylate.
  • the compositions preferably include from about 20 to about 100 parts of the plasticizer. and more preferably, from about 25 to about 80 parts of the plasticizer. and most preferably from about 40 to about 60 parts of the plasticizer.
  • a preferred plasticizer is tri-n-hexyl-1, 3,6-hexane-tricarboxylate, which can be synthesized by esterification according to the following method.
  • the temperature is set to 220 °C, and the stream rate of N 2 is set at 0.7 L/min.
  • the acid number is below lmg KOH/g, the flask is cooled.
  • the charge is neutralized with NaOH, as
  • aqueous NaOH solution 3% w/v aqueous NaOH solution.
  • the temperature of the charge is 60 °C when the NaOH solution is added.
  • the charge is washed to neutral with water, dried in vacuo at a pressure of 25 torr at 160 °C, and stripped free of alcohol with steam.
  • the product of the reaction is treated with carbon and filtered.
  • Alcohols such as pentanol, butoxyethanol, 2-(2-methoxyethoxy) ethanol. or n-octanol can be substituted for n-hexanol, and using the same general procedure, other esters of 1,3,6-hexane tricarboxylic acid can be prepared.
  • the polymeric compositions may also contain additional ingredients such as one or more stabilizers.
  • suitable stabilizers include calcium/zinc stabilizers, available from CKWitco under the trade name Mark QT-S, and epoxidized soybean oil, also available from
  • the stabilizers can be used alone or in combination.
  • the compositions preferably include from about 0.1 to about 20 parts of the stabilizer, and more preferably, from about 0.2 to about 15 parts of the stabilizer.
  • compositions are prepared according to conventional dry blend or wet blend methods known to those skilled in the art of PVC compounding.
  • the mixtures obtained from the blending process can further be compounded with a mixer such as a BANBURY® batch mixer, extruder, or multiple screw extruder.
  • Exemplary PVC compositions including tri-n-hexyl-1, 3,6-hexane-tricarboxylate are compared below with compositions having di-2-ethyl-hexyl phthalate (DOP) as a plasticizer. Samples were prepared and tested according to ASTM protocols.
  • DOP di-2-ethyl-hexyl phthalate
  • a preferred polymer composition for use as a fire retardant compound includes polyvinyl chloride, a plasticizer having the structure discussed above, a clay filler, hydrated alumina and/or magnesium hydroxide, and one or more stabilizers or other additives such as lubricants and smoke suppressant.
  • the preferred PVC and the plasticizer were discussed above.
  • the fire retardant PVC compositions preferably include from about 2 to about 35 parts of plasticizer. More preferably from about 5 to about 30 parts of plasticizer, and most preferably about 10 to about 25 parts of plasticizer.
  • the clay filler can be a calcined aluminum silicate clay, a calcined kaolin clay or a combination thereof.
  • Clay filler are available from, for example, JM Huber Corporation. Burgess Pigment Company, and Englehard Corporation.
  • the compositions preferably include from about 2 to about 20 parts of clay filler, more preferably from about 4 to about 10 parts of clay filler, and most preferably about 5 parts of clay filler.
  • a hydrated alumina is aluminum trihydrate. Hydrated aluminas are available from, for example, Alcoa Aluminum and Chemicals. Lonza and Pluess-Staufer Industries.
  • the compositions preferably include from about 10 to about 100 parts hydrated alumina and/or magnesium hydroxide, more preferably from about 20 to about 70 parts hydrated alumina and/or magnesium hydroxide, and most preferably about 40 parts hydrated alumina and/or magnesium hydroxide.
  • the compositions also can include a lead stabilizer.
  • the compositions preferably include about 3 to about 12 parts of lead stabilizer, more preferably from about 5 to about 9 parts of lead stabilizer, and most preferably about 7 parts of lead stabilizer.
  • lead stabilizers include dibasic lead phthalate, tetrabasic lead fumarate, tribasic lead sulphate and combinations thereof. Lead stabilizers are available from, for example, Hammond Corporation.
  • the compositions can include a fatty acid lubricant.
  • the compositions preferably include from about 0.1 parts to about 0.5 parts carboxylic lubricant, more preferably from about 0.2 parts to about 0.4 carboxylic acid lubricant, and most preferably about 0.25 parts carboxylic acid lubricant.
  • carboxylic acid lubricant is stearic acid which is available from, for example, Humko, a division of CKWitco.
  • the compositions can include a smoke suppressant containing antimony (i.e., an antimony smoke suppressant).
  • the compositions preferably include from about 2 part to about 15 parts antimony smoke suppressant, more preferably from about 3 to about 10 parts antimony smoke suppressant, and most preferably about 5 parts antimony smoke suppressant.
  • An example of an antimony smoke suppressant is antimony oxide KR. available from Amstec Chemical Corp.
  • the compositions are prepared according to conventional dry blend or wet blend methods known to those skilled in the art of PVC compounding.
  • the mixtures obtained from the blending process can further be compounded with a mixer such as a BANBURY® batch mixer, extruder, or multiple screw extruder.
  • a flame-retardant formulation having trihexyl-l,3,6-hexane tricarboxylate is compared below with a composition having trimellitate as a plasticizer. Samples were prepared and tested according to ASTM protocols.

Abstract

A plasticizer having the structure (I) wherein each R, independently, is an alkyl, alkenyl, alkynyl, or aromatic group containing 2 and 15 carbon atoms. Preferably, each R contains between 4 and 10 carbon atoms. A preferred plasticizer is a tri-n-hexyl-1,3,6-hexane-tricarboxylate.

Description

Plasticizer
BACKGROUND
This invention relates generally to plasticizers.
Polyvinyl chloride (PVC) compositions are used in numerous applications. For example. PVC compositions are used as wire and cable insulation and jacketing, in automotive applications, and as components in medical devices such as facial masks, drip chambers, tube connectors and valves. PVC compositions used in these applications often include plasticizers to improve the flexibility and brittle point of the compositions. The brittle point is the temperature generally below which the composition becomes brittle, rather than ductile and flexible. PVC compositions also are used as flame retardants. These compositions typically contain, in addition to PVC. one or more flame retardant compounds, plasticizers. lubricants, and/or fillers. It is desirable for these compositions to exhibit low smoke generation and low flame travel.
SUMMARY OF THE INVENTION The invention features a plasticizer that can be used, for example, in PVC compositions.
The plasticizer has the following structure:
COOR COOR
COOR
wherein each R. independently, is an alkyl, alkenyl. alkynyl, or aromatic group containing 2 and
15 carbon atoms. Preferably, each R contains between 4 and 10 carbon atoms. A preferred plasticizer is tri-n-hexyl-l,3,6-hexane-tricarboxylate.
The plasticizer, when used, for example, in PVC compositions, can provide the composition with good flexibility and good performance at low temperature. Preferably. PVC compositions including the plasticizer have a brittle point of less than -30 °C. and even more preferably, less than -60 °C. when tested according procedures described below. Such compositions are useful in applications exposed to low temperatures such as in cryogenics. Furthermore, the plasticizer can provide good performance even at low concentrations, thereby providing the compositions with low smoke values and high oxygen indexes (as described below) since lower amounts of plasticizers are used. Such compositions, therefore, exhibit good fire retardancy. Preferably, PVC compositions including the plasticizer have smoke values less than 2.0% decharred, less than 5.0% not decharred, and an oxygen index of greater than 50%o O2.
Other features and advantages of the invention will be apparent from the description of the preferred embodiment thereof, and from the claims.
DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred polymeric composition for use in a medical device includes polyvinyl chloride, a plasticizer having the structure described above, and one or more additives, such as a stabilizer.
"Polyvinyl chloride" or "PVC," as used herein, includes homopolymers of vinyl chloride. as well as polymerization products of vinyl chloride and one or more co-monomers. Examples of PVCs include copolymers of vinyl chloride and ethylene and copolymers of vinyl chloride and propylene. The PVC resins can also be the polymerization product of vinyl chloride and an ester monomer having the formula H2C=C(R')C(=O)OR2. where R1 and R2 are. independently. C M 2 alkyl. An example of such a resin is a copolymer of a vinyl chloride monomer and a methyl methacrylate monomer. These resins may be used alone or in combination. Examples of PVC resins include BCP 70 available from Borden Chemical, and Shintech SE 1200 available from Shintech.
The plasticizer is added to the polymeric composition to alter the physical properties of the PVC. Adding the plasticizer can improve, for example, the flexibility, brittle point, and processability of the PVC. Examples of plasticizers having the structure described above include tri-n-pentyl- 1.3,6-hexane-tricarboxylate, tri-butoxyethyl- 1 ,3,6-hexane-tricarboxylate. tri-2-(2- methoxyethoxy) ethyl- 1 , 3,6-hexane-tricarboxylate, tri-n-octyl- 1 , 3,6-hexane-tricarboxylate. and tri-n-hexyl-1.3,6-hexane-tricarboxylate. Other types of plasticizers such as phthalates, trimelletates, and polyesters, can be included in the composition. For 100 parts of PVC resin, the compositions preferably include from about 20 to about 100 parts of the plasticizer. and more preferably, from about 25 to about 80 parts of the plasticizer. and most preferably from about 40 to about 60 parts of the plasticizer.
A preferred plasticizer is tri-n-hexyl-1, 3,6-hexane-tricarboxylate, which can be synthesized by esterification according to the following method. A 3-L round bottom four-neck flask, equipped with a stirrer, N2 inlet, temperature controller. Dean-Stark receiver, and condenser, is charged with: 3.18 mol (695.4 g) of 1.3.6- hexane tricarboxylic acid; 12.43 mol (1270 g; 30% excess) of n-hexanol; and 0.3750 g
(0.025wt%> of the ester) titanium alkoxide catalyst.
The temperature is set to 220 °C, and the stream rate of N2 is set at 0.7 L/min. When the acid number is below lmg KOH/g, the flask is cooled. The charge is neutralized with NaOH, as
3% w/v aqueous NaOH solution. The temperature of the charge is 60 °C when the NaOH solution is added. The charge is washed to neutral with water, dried in vacuo at a pressure of 25 torr at 160 °C, and stripped free of alcohol with steam. The product of the reaction is treated with carbon and filtered. Alcohols such as pentanol, butoxyethanol, 2-(2-methoxyethoxy) ethanol. or n-octanol can be substituted for n-hexanol, and using the same general procedure, other esters of 1,3,6-hexane tricarboxylic acid can be prepared.
The polymeric compositions may also contain additional ingredients such as one or more stabilizers. Examples of suitable stabilizers include calcium/zinc stabilizers, available from CKWitco under the trade name Mark QT-S, and epoxidized soybean oil, also available from
CKWitco, under the trade name Drapex 6.8. The stabilizers can be used alone or in combination.
For 100 parts of PVC resin, the compositions preferably include from about 0.1 to about 20 parts of the stabilizer, and more preferably, from about 0.2 to about 15 parts of the stabilizer.
The compositions are prepared according to conventional dry blend or wet blend methods known to those skilled in the art of PVC compounding. The mixtures obtained from the blending process can further be compounded with a mixer such as a BANBURY® batch mixer, extruder, or multiple screw extruder.
Exemplary PVC compositions including tri-n-hexyl-1, 3,6-hexane-tricarboxylate are compared below with compositions having di-2-ethyl-hexyl phthalate (DOP) as a plasticizer. Samples were prepared and tested according to ASTM protocols.
Figure imgf000005_0001
Figure imgf000005_0002
Figure imgf000005_0003
Figure imgf000005_0004
The data indicate that tri-n-hexyl-1, 3,6-hexane-tricarboxylate improves the low temperature properties of PVC when used in place of DOP.
A preferred polymer composition for use as a fire retardant compound, e.g., for wire and cable compounds, includes polyvinyl chloride, a plasticizer having the structure discussed above, a clay filler, hydrated alumina and/or magnesium hydroxide, and one or more stabilizers or other additives such as lubricants and smoke suppressant. The preferred PVC and the plasticizer were discussed above. For 100 parts of PVC resin, the fire retardant PVC compositions preferably include from about 2 to about 35 parts of plasticizer. more preferably from about 5 to about 30 parts of plasticizer, and most preferably about 10 to about 25 parts of plasticizer.
The clay filler can be a calcined aluminum silicate clay, a calcined kaolin clay or a combination thereof. Clay filler are available from, for example, JM Huber Corporation. Burgess Pigment Company, and Englehard Corporation. For 100 parts of the PVC resin, the compositions preferably include from about 2 to about 20 parts of clay filler, more preferably from about 4 to about 10 parts of clay filler, and most preferably about 5 parts of clay filler.
An example of a hydrated alumina is aluminum trihydrate. Hydrated aluminas are available from, for example, Alcoa Aluminum and Chemicals. Lonza and Pluess-Staufer Industries. For 100 parts of PVC resin, the compositions preferably include from about 10 to about 100 parts hydrated alumina and/or magnesium hydroxide, more preferably from about 20 to about 70 parts hydrated alumina and/or magnesium hydroxide, and most preferably about 40 parts hydrated alumina and/or magnesium hydroxide.
The compositions also can include a lead stabilizer. For 100 parts of PVC resin, the compositions preferably include about 3 to about 12 parts of lead stabilizer, more preferably from about 5 to about 9 parts of lead stabilizer, and most preferably about 7 parts of lead stabilizer. Examples of lead stabilizers include dibasic lead phthalate, tetrabasic lead fumarate, tribasic lead sulphate and combinations thereof. Lead stabilizers are available from, for example, Hammond Corporation. The compositions can include a fatty acid lubricant. For 100 parts PVC resin, the compositions preferably include from about 0.1 parts to about 0.5 parts carboxylic lubricant, more preferably from about 0.2 parts to about 0.4 carboxylic acid lubricant, and most preferably about 0.25 parts carboxylic acid lubricant. An example of a carboxylic acid lubricant is stearic acid which is available from, for example, Humko, a division of CKWitco. The compositions can include a smoke suppressant containing antimony (i.e., an antimony smoke suppressant). For 100 parts of PVC resin, the compositions preferably include from about 2 part to about 15 parts antimony smoke suppressant, more preferably from about 3 to about 10 parts antimony smoke suppressant, and most preferably about 5 parts antimony smoke suppressant. An example of an antimony smoke suppressant is antimony oxide KR. available from Amstec Chemical Corp. The compositions are prepared according to conventional dry blend or wet blend methods known to those skilled in the art of PVC compounding. The mixtures obtained from the blending process can further be compounded with a mixer such as a BANBURY® batch mixer, extruder, or multiple screw extruder.
A flame-retardant formulation having trihexyl-l,3,6-hexane tricarboxylate is compared below with a composition having trimellitate as a plasticizer. Samples were prepared and tested according to ASTM protocols.
Figure imgf000007_0001
Figure imgf000007_0002
The data indicate that, even at a low concentration, tri-n-hexyl-1, 3,6-hexane- tricarboxylate maintains about the same brittleness temperature and hardness of PVC compositions when used in place of trimellitate. Other embodiments are within the claims.

Claims

WHAT IS CLAIMED IS:
1. A composition comprising a polymer and a plasticizer having a structure:
COOR COOR
COOR
wherein each R, independently, is an alkyl, alkenyl, alkynyl, or aromatic group containing 2 and 15 carbon atoms.
2. The composition of claim 1, wherein each R contains between 4 and 10 carbon atoms.
3. The composition of claim 1 , wherein the plasticizer is tri-n-pentyl- 1 ,3,6-hexane- tricarboxylate.
4. The composition of claim 1 , wherein the plasticizer is tri-butoxyethyl- 1.3.6-hexane- tricarboxylate.
5. The composition of claim 1, wherein the plasticizer is tri-2-(2-methoxyethoxy) ethyl- 1 ,3,6-hexane-tricarboxylate.
6. The composition of claim 1, wherein the plasticizer is tri-n-octyl- 1 , 3,6-hexane- tricarboxylate.
7. The composition of claim 1 , wherein the plasticizer is tri-n-hexyl- 1 ,3,6-hexane- tricarboxylate.
8. The composition of claim 1 , wherein the polymer is polyvinyl chloride.
9. The composition of claim 1, wherein the polymer is polyvinyl chloride and the plasticizer is tri-n-hexyl-1.3,6-hexane-tricarboxylate.
10. The composition of claim 1. wherein the composition comprises from about
30 to about 90 parts of plasticizer per 100 parts of polymer.
11. The composition of claim 1 , wherein the composition comprises from about 50 to about 90 parts of plasticizer per 100 parts of polymer.
12. The composition of claim 1, wherein the composition comprises from about 80 to about 90 of plasticizer per 100 parts of polymer.
13. The composition of claim 7, wherein the composition comprises from about 30 to about 90 of tri-n-hexyl-1, 3,6-hexane-tricarboxylate per 100 parts of polyvinyl chloride.
14. The composition of claim 7, wherein the composition comprises from about
80 to about 90 of tri-n-hexyl-1, 3,6-hexane-tricarboxylate per 100 parts of polyvinyl chloride.
15. The composition of claim 1 , further comprising an oil.
16. The composition of claim 1 , further comprising a stabilizer.
17. The composition of claim 1, wherein the composition has a brittle point of less than -30 °C.
18. The composition of claim 1 , wherein the composition has a brittle point of less than -60 °C.
19. A medical device comprising polyvinyl chloride and a plasticizer having tri-n-hexyl- 1 ,3,6-hexane-tricarboxylate.
PCT/US2001/000791 2000-01-14 2001-01-10 Tricarboxylate plasticizer for halogenated polymers WO2001051543A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001227804A AU2001227804A1 (en) 2000-01-14 2001-01-10 Plasticizer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US48343000A 2000-01-14 2000-01-14
US09/483,430 2000-01-14

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WO2001051543A3 WO2001051543A3 (en) 2002-03-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140116750A1 (en) * 2012-10-31 2014-05-01 Yazaki Corporation Flat cable
WO2017176504A1 (en) * 2016-04-07 2017-10-12 Ascend Performance Materials Operations Llc Tri-carboxylic compounds as low-voc coalescing agents and plasticizing agents

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04342748A (en) * 1991-05-21 1992-11-30 Dainippon Ink & Chem Inc Plasticizer and halogen-containing resin composition comprising the same plasticizer

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140116750A1 (en) * 2012-10-31 2014-05-01 Yazaki Corporation Flat cable
EP2728587A1 (en) * 2012-10-31 2014-05-07 Yazaki Corporation Flat cable
US9230715B2 (en) 2012-10-31 2016-01-05 Yazaki Corporation Flat cable
WO2017176504A1 (en) * 2016-04-07 2017-10-12 Ascend Performance Materials Operations Llc Tri-carboxylic compounds as low-voc coalescing agents and plasticizing agents
CN109195939A (en) * 2016-04-07 2019-01-11 奥升德高性能材料公司 As the coalescent of low-VOC and the tricarboxylic acid compound of plasticizer
CN109195939B (en) * 2016-04-07 2022-06-28 奥升德高性能材料公司 Tricarboxylic acid compounds as low-VOC coalescents and plasticizers
US11390762B2 (en) 2016-04-07 2022-07-19 Ascend Performance Materials Operation LLC Tri-carboxylic compounds as low-VOC coalescing agents and plasticizing agents

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