WO2002031044A1 - Polyalphaolefin plastisizers for elastomers - Google Patents

Polyalphaolefin plastisizers for elastomers Download PDF

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Publication number
WO2002031044A1
WO2002031044A1 PCT/FI2001/000888 FI0100888W WO0231044A1 WO 2002031044 A1 WO2002031044 A1 WO 2002031044A1 FI 0100888 W FI0100888 W FI 0100888W WO 0231044 A1 WO0231044 A1 WO 0231044A1
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Prior art keywords
styrene
rubber
polyalphaolefin
elastomers
elastomer
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PCT/FI2001/000888
Other languages
French (fr)
Inventor
Matti Kaarnakari
Kari Alha
Original Assignee
Duraban Oy
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Publication date
Priority claimed from FI20002245A external-priority patent/FI110157B/en
Application filed by Duraban Oy filed Critical Duraban Oy
Priority to AU2002210589A priority Critical patent/AU2002210589A1/en
Publication of WO2002031044A1 publication Critical patent/WO2002031044A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to polyalphaolefin plastisizers for elastomers, and elastomer compositions containing polyalphaolefins.
  • Polyalphaolefins may be used as plastisizing agents in elastomers and blends containing elastomers to plastisize the hardness of the product and to provide more flexible products with a lower residual compression suitable for lower working temperatures.
  • Plastisizers are commonly used in elastomers to lower the raw material costs of the products and to improve the processibility thereof. Addition of a plastisizer is used to improve the collapse resistance of an article made of rubber or thermoplastic elastomer exposed to oil in the environment. Plastisizers present in the product reduce the ability thereof to absorb additional hydrocarbons. Most common plastisizers are compounds based on mineral oil.
  • Patent application Fl 971338 discloses coatings of structures and profiled articles containing a mixture of thermoplastic elastomer with a non-elastomeric polyolefm, in general with homopolymers or random copolymers of propylen.
  • An oligomer of poly- ⁇ -olefine type is used as polyolefm plastisizer in a matrix plastic (EPR, EBR, EPBR, PBR, SBR, EPM, EPDM).
  • the monomers used comprise at least 3 carbon atoms, preferably 6 to 12 carbon atoms.
  • Patent publication EP 300 689 discusses mixtures containing oligomeric polyalphaolefin, and an olefin elastomer.
  • the object of the present invention is to provide polyalphaolefin plastisizers for elastomers, and elastomer compositions containing polyalphaolefins.
  • the characteristic features of the polyalphaolefin plastisizers for elastomers, and elastomer compositions containing polyalphaolefins of the invention are disclosed in the appended claims.
  • polyalphaolefins may be used as plastisizing agents in elastomers.
  • Suitable polyalphaolefins include polyalphaolefin oils, h this connection, polyalphaolefin oil means an oil, preferably a food grade hydrogenated oil consisting of the polymerization product of a polyalphaolefin or a mixture of polyalphaolefins, having a molecular weight between 400 and 1000 g/mol.
  • Suitable alphaolefins include butene, pentene, hexene, heptene, octene, nonene, decene, undodecene and dodecene, preferably decene.
  • a particularly preferable polyalphaolefin is food grade polydecene.
  • the content of polyalphaolefin oil or oils in the composition of the invention varies between 5 and 60 %.
  • Suitable elastomers include the following rubber mixtures (a), thermoplastic elastomers (b) and vulcanizates thereof (c), and silicones (d):
  • EPR ethylene-propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • ACM/EAM polyacrylate rubber
  • SBR styrene-butadiene rubber
  • 1,2-sPB 1,2-syndio tactic polybutadiene rubber.
  • SBC styrene-butadiene blockcopolymers, unl ydrogenated version hydrogenated version
  • Vulcanization is accomplished while mixing either with a sulfur compound, organic peroxide or with a phenolic resin depending on the type of the elastomer.
  • Unplastisized plastics typically include polycar- bonates, polyolefins (PE and PP), polyamides and polyuretanes. Compounding these plastics with elastomers provides in certain cases mixtures that may be plastisized.
  • the elastomers may be imvulcanized or partly or totally vulcanized.
  • Particularly preferable elastomers are the following polymers and mixtures thereof:
  • composition of the invention contains from 20 to 95 % by weight of elastomer or mixture of elastomers.
  • the ratio of polyalphaolefin oil to the elastomer is 0.05 to 1.5.
  • compositions may comprise thermoplastics, inorganic fillers, other plastisizers based on mineral oil, antioxidants, pigments, agents protecting against ultraviolet light, agents deactivating metals, flame retardants, conductive fillers, and vulcanizing chemicals.
  • polyalphaolefins have several advantages in plastisizing applications. For instance:
  • polyalphaolefin is a pure product, thus facilitating the approval by the authorities.
  • a low working temperature is an important characteristic of polyalphaolefins. They crystallize at very low temperatures, thus making possible to lower the brittle temperature of rubber or a thermoplastic elastomer. This is advantageous particularly for styrene elastomers. In applications of the automobile industry, the required lowest working temperature is commonly below -40 °C.
  • polyalphaolefins have the following advantages in comparison with a mineral oil based plastisizer:
  • a typical feature of polyalphaolefins is the chemical purity thereof, that is the lack of aromatic, naphtalenic, paraffmic (with the exception of isoparaffinic) components commonly present in mineral oils.
  • mineral oil typically contains sulfur and other heteroatoms absent from synthetic polyalphaolefins.
  • Elastomers plastisized with polyalphaolefin oil are more heat stable since heteroatoms causing autocatalytic decomposition are absent.
  • the use of relatively expensive antioxidants may be reduced to provide the required thermal ageing properties, h
  • the original colour of elastomers plastisized with polyalphaolefins is purer than that of products plastisized with mineral oils, thus allowing for the production of lighter products by means of pigments without using paints to provide a pure white colour.
  • pigments are a preferable alternative.
  • colour fastness in pigmented elastomers is clearly better when a polyalphaolefin plastisizer is used instead of mineral oil.
  • an advantage is the better preservation of transparency for instance of the tubing of healt care apparatuses being sterilized.
  • Polyalphaolefins are particularly advantageous as plastisizers for elastomeric insulating materials of cables and conductors. Polar impurities present in mineral oil lower the loss factor causing increasing power losses in power transmission for medium and high voltage insulating materials. With respect to electrical properties, polyalphaolefin is comparable to commonly used insulating materials, polyethylene and EP(D)M rubber.
  • Aromatic components present in mineral oil dissolve styrene blocks present in polystyrene containing elastomers, thus lowering the tensile strenght.
  • Polyalphaolefin has no influence on polystyrene blocks since it is free of aromatic components.
  • polyalphaolefins The molecular weight distribution of polyalphaolefins is very narrow compared to that of mineral oils that are originally distillates. This narrow molecular weight distribution brings about several advantages. Of these, the most important for elastomers is the low weight loss at increased temperatures. A polyalphaolefin oil and mineral oil having identical viscosities differ considerably from each other with respect to weight loss in favour of polyalphaolefin. Volatile oils cause following problems in practical applications of elastomers:
  • polyalphaolefin oils include the lack of odour and the lower flash point at a constant viscosity, thus contributing to process safety.
  • isoparaffins and paraffins have lower dissolving powers in elastomers, which directly influences the compatibility of the oils with elastomers.
  • the absence of relatively heavy molecules from polyalphaolefin oils makes a polyalphaolefin oil more preferable than mineral oils, the final result with respect to compatibility being equally good.
  • polyalphaolefins have a very low solidification point, about -60 °C, whereas the solidification point of paraffin oils is about -15 °C, that of naphtalene oil being about -30 °C.
  • polyalphaolefin plastisizers are best preserved at extremely low temperatures. This is important for instance for buffering rubber strips of automobiles and protective rubbers of joints.
  • Polyalphaolefins have a very high viscosity index compared to mineral oils. This is important in processing of elastomers. Particularly when elastomers are mixed at high temperatures, the viscosity of the mixture will not decrease as much as that of mixtures containing mineral oils, and thus higher shear forces are provided for mixing, thus improving the dispersion of components. This has a direct effect on almost all performance values of elastomers. Depending on the composition, the following factors are improved:
  • compositions of the invention containing polyalphaolefins may be used as interior elastomers of automobiles such as seals in passages to the engine room, rubbers in the engine room such as tubes and seals, buffering rubber strips, protective rubbers of joints, in medical apparatuses and devices such as the tubings and seals of medical instruments, seals of food packages, isolating materials of cables, cable jackets, and further, in elastomeric articles that are generally white, and in applications being demanding with respect to transparency.
  • Elastomers and plastics used in medical applications and having a very high compatibility with polyalphaolefins include:
  • the combination PP/SEBS is generally used in those applications of styrene elastomers that are demanding with respect to working temperature and environmental pollution.
  • Typical medical uses of elastomers are syringes and needles, intravenous urinary catheters, dosage tubings and devices, clinical cardiac valves and vessel implants, disposable packages and trays.
  • the composition of the invention has several advantages.
  • the glass transition temperature of the elastomer and plastic is lowered, thus making the products very suitable to applications requiring good low temperature resistance properties (cables, exterior parts of automobiles).
  • the evaporated amounts of organic compounds are lowered, being advantageous for medical applications and for interior elastomers of automobiles.
  • the products are colourless and transparent. The products resist sterilization and exposure to high temperatures for extended periods of time without losing their properties.
  • Polyalphaolefin may be mixed with elastomers and plastics during the production thereof. In this manner, elastomer and plastic products particularly suitable for medical and medicinal apparatus applications are obtained. Medical applications have high special requirements on materials, such as resistance to sterilization. These require- ments are restricted in no way by the composition of the invention.
  • Elastomer for medical, automobile industry, and cable applications PP/EPDM or PP/EPR blend
  • composition of the example good processing characteristics and a Shore A hardness of 85 are attained. Thermal ageing properties of the mixture are also especially good.
  • the example is directed to a basic SEBS blend.
  • the combination PP/SEBS is gener- ally used in those applications of styrene elastomers that are demanding with respect to working temperature and environmental pollution.
  • the ability to plastisize SEBS elastomers greatly depends on the styrene content thereof.
  • An elastomer with a low styrene content accepts a plastisizer in an amount that is more than 1.5 times its own weight.
  • polyalphaolefin plastisizers The effect of polyalphaolefin plastisizers on low temperature resistance was studied by means of the glass transition temperature T g .
  • a common plastisizer i.e. paraffin oil was used.
  • the samples to be studied were the formulations of Examples 1 and 2.
  • Example 5 The use of a polyalphaolefin oil as the plastisizer is particularly preferable for the production of clear white elastomer products.
  • the translucency of translucent elastomers suitable for instance for health care applications is better preseved by using a polyalphaolefin oil instead of mineral oil.
  • Thermoplastic elastomers were sterilized in an autoclave for 15 minutes at 121 °C. Elastomers may be hardened by autoclaving as the plastisizing oils are evaporated. This was not the case for polyalphaolefin oils due to the low volatile matter thereof.

Abstract

The present invention relates to polyalphaolefin plastisizers for elastomers, and elastomer compositions containing polyalphaolefins. Polyalphaolefins may be used as plastisizing agents in elastomers and blends containing elastomers to plastisize the hardness of the product and to provide more flexible products with a lower residual compression suitable for lower working temperatures. Elastomer composition of the invention containing a plastisizing agent comprises between 20 and 95 % by weight of an elastomer or a mixture of elastomers, and between 5 and 60 % by weight of polyalphaolefin or a mixture of polyalphaolefins.

Description

Polyalphaolefin plastisizers for elastomers
The present invention relates to polyalphaolefin plastisizers for elastomers, and elastomer compositions containing polyalphaolefins. Polyalphaolefins may be used as plastisizing agents in elastomers and blends containing elastomers to plastisize the hardness of the product and to provide more flexible products with a lower residual compression suitable for lower working temperatures.
Plastisizers are commonly used in elastomers to lower the raw material costs of the products and to improve the processibility thereof. Addition of a plastisizer is used to improve the collapse resistance of an article made of rubber or thermoplastic elastomer exposed to oil in the environment. Plastisizers present in the product reduce the ability thereof to absorb additional hydrocarbons. Most common plastisizers are compounds based on mineral oil.
Patent application Fl 971338 discloses coatings of structures and profiled articles containing a mixture of thermoplastic elastomer with a non-elastomeric polyolefm, in general with homopolymers or random copolymers of propylen. An oligomer of poly- α-olefine type is used as polyolefm plastisizer in a matrix plastic (EPR, EBR, EPBR, PBR, SBR, EPM, EPDM). The monomers used comprise at least 3 carbon atoms, preferably 6 to 12 carbon atoms.
Patent publication EP 300 689 discusses mixtures containing oligomeric polyalphaolefin, and an olefin elastomer.
The object of the present invention is to provide polyalphaolefin plastisizers for elastomers, and elastomer compositions containing polyalphaolefins. The characteristic features of the polyalphaolefin plastisizers for elastomers, and elastomer compositions containing polyalphaolefins of the invention are disclosed in the appended claims.
It has been found that colourless, odourless, tasteless and clear polyalphaolefins may be used as plastisizing agents in elastomers. Suitable polyalphaolefins include polyalphaolefin oils, h this connection, polyalphaolefin oil means an oil, preferably a food grade hydrogenated oil consisting of the polymerization product of a polyalphaolefin or a mixture of polyalphaolefins, having a molecular weight between 400 and 1000 g/mol. Suitable alphaolefins include butene, pentene, hexene, heptene, octene, nonene, decene, undodecene and dodecene, preferably decene. A particularly preferable polyalphaolefin is food grade polydecene.
The content of polyalphaolefin oil or oils in the composition of the invention varies between 5 and 60 %.
Suitable elastomers include the following rubber mixtures (a), thermoplastic elastomers (b) and vulcanizates thereof (c), and silicones (d):
(a) Normally plastisized rubbers (elastomers) used in health care applications and in automobile industry, and for cables:
EPR = ethylene-propylene rubber
EPDM = ethylene-propylene-diene rubber
NR = natural rubber IIR = butyl rubber
ACM/EAM = polyacrylate rubber
SBR = styrene-butadiene rubber
1,2-sPB = 1,2-syndio tactic polybutadiene rubber. (b) Plastisized thermoplastic elastomers; polypropylene commonly as a crystalline thermoplastic in a mixture.
SBC = styrene-butadiene blockcopolymers, unl ydrogenated version hydrogenated version
SBS SEBS
SB SEB
SI SEP
EPR, EPDM, NR, IIR, 1,2-sPE = as above.
(c) Thermoplastic vulcanizates:
Vulcanization is accomplished while mixing either with a sulfur compound, organic peroxide or with a phenolic resin depending on the type of the elastomer.
(d) Silicones.
No plastisizers may be used in crystalline plastics since the crystalline structure will not tolerate the presence of an oil. Unplastisized plastics typically include polycar- bonates, polyolefins (PE and PP), polyamides and polyuretanes. Compounding these plastics with elastomers provides in certain cases mixtures that may be plastisized.
In the compositions of the invention, the elastomers may be imvulcanized or partly or totally vulcanized. Particularly preferable elastomers are the following polymers and mixtures thereof:
- ethylene-propylene-diene rubber
- ethylene-propylene rubber
- styrene-butadiene rubber
- 1,2-syndio tactic polybutadiene rubber - natural rubber
- polybutyl rubber
- styrene-isoprene-styrene blockcopolymer
- styrene-butadiene-(styrene) blockcopolymer - styrene-ethylene-butene-styrene blockcopolymer.
The composition of the invention contains from 20 to 95 % by weight of elastomer or mixture of elastomers. The ratio of polyalphaolefin oil to the elastomer is 0.05 to 1.5.
In addition to the elastomers, the compositions may comprise thermoplastics, inorganic fillers, other plastisizers based on mineral oil, antioxidants, pigments, agents protecting against ultraviolet light, agents deactivating metals, flame retardants, conductive fillers, and vulcanizing chemicals.
With respect to performance, polyalphaolefins have several advantages in plastisizing applications. For instance:
- Superior heat resistance is an important feature in medical apparatus and device applications requiring repeated sterilization or heating of the article in a micro- wave oven, for instance as a component of a food tray. There are also other applications profiting from the high heat resistance, such as cable applications and engine room applications in automobile industry.
- Strictly limited composition, that is, a narrow molecular weight distribution al- lows for the selection of the desired molecular weight, thus minimizing the evaporation effects of the plastisizing agent or oil. In addition, the flash point of polyalphaolefin is generally higher at the desired viscosity than that of conventional mineral oils, this being favourable for processing. With respect to its qual- ity, polyalphaolefin is a pure product, thus facilitating the approval by the authorities.
- A low working temperature is an important characteristic of polyalphaolefins. They crystallize at very low temperatures, thus making possible to lower the brittle temperature of rubber or a thermoplastic elastomer. This is advantageous particularly for styrene elastomers. In applications of the automobile industry, the required lowest working temperature is commonly below -40 °C.
In addition, polyalphaolefins have the following advantages in comparison with a mineral oil based plastisizer:
a) Chemical properties
A typical feature of polyalphaolefins is the chemical purity thereof, that is the lack of aromatic, naphtalenic, paraffmic (with the exception of isoparaffinic) components commonly present in mineral oils. Moreover, mineral oil typically contains sulfur and other heteroatoms absent from synthetic polyalphaolefins.
Elastomers plastisized with polyalphaolefin oil are more heat stable since heteroatoms causing autocatalytic decomposition are absent. The use of relatively expensive antioxidants may be reduced to provide the required thermal ageing properties, h addition, the original colour of elastomers plastisized with polyalphaolefins is purer than that of products plastisized with mineral oils, thus allowing for the production of lighter products by means of pigments without using paints to provide a pure white colour. Compared to painting, pigments are a preferable alternative. Moreover, colour fastness in pigmented elastomers is clearly better when a polyalphaolefin plastisizer is used instead of mineral oil. For transparent elastomer products, an advantage is the better preservation of transparency for instance of the tubing of healt care apparatuses being sterilized.
Polyalphaolefins are particularly advantageous as plastisizers for elastomeric insulating materials of cables and conductors. Polar impurities present in mineral oil lower the loss factor causing increasing power losses in power transmission for medium and high voltage insulating materials. With respect to electrical properties, polyalphaolefin is comparable to commonly used insulating materials, polyethylene and EP(D)M rubber.
Aromatic components present in mineral oil dissolve styrene blocks present in polystyrene containing elastomers, thus lowering the tensile strenght. Polyalphaolefin has no influence on polystyrene blocks since it is free of aromatic components.
b) Physical properties
The molecular weight distribution of polyalphaolefins is very narrow compared to that of mineral oils that are originally distillates. This narrow molecular weight distribution brings about several advantages. Of these, the most important for elastomers is the low weight loss at increased temperatures. A polyalphaolefin oil and mineral oil having identical viscosities differ considerably from each other with respect to weight loss in favour of polyalphaolefin. Volatile oils cause following problems in practical applications of elastomers:
- volatile oils cause fogging of the glass surfaces and bad odour in the interior of an automobile,
- elastomers in the engine room of an automobile become hard and brittle,
- elastomers become hard when sterilized in an autoclave. These problems may be considerably reduced by using polyalphaolefin oils as plastisizers.
Further, the advantages of polyalphaolefin oils include the lack of odour and the lower flash point at a constant viscosity, thus contributing to process safety.
Compared to naphtenes and aromates, isoparaffins and paraffins have lower dissolving powers in elastomers, which directly influences the compatibility of the oils with elastomers. The absence of relatively heavy molecules from polyalphaolefin oils makes a polyalphaolefin oil more preferable than mineral oils, the final result with respect to compatibility being equally good.
As is known, polyalphaolefins have a very low solidification point, about -60 °C, whereas the solidification point of paraffin oils is about -15 °C, that of naphtalene oil being about -30 °C.
The properties of polyalphaolefin plastisizers are best preserved at extremely low temperatures. This is important for instance for buffering rubber strips of automobiles and protective rubbers of joints.
Polyalphaolefins have a very high viscosity index compared to mineral oils. This is important in processing of elastomers. Particularly when elastomers are mixed at high temperatures, the viscosity of the mixture will not decrease as much as that of mixtures containing mineral oils, and thus higher shear forces are provided for mixing, thus improving the dispersion of components. This has a direct effect on almost all performance values of elastomers. Depending on the composition, the following factors are improved:
- tensile strength
- elongation effectivity of flame retardants amount of the filler may be increased.
In practice, the compositions of the invention containing polyalphaolefins may be used as interior elastomers of automobiles such as seals in passages to the engine room, rubbers in the engine room such as tubes and seals, buffering rubber strips, protective rubbers of joints, in medical apparatuses and devices such as the tubings and seals of medical instruments, seals of food packages, isolating materials of cables, cable jackets, and further, in elastomeric articles that are generally white, and in applications being demanding with respect to transparency.
Elastomers and plastics used in medical applications and having a very high compatibility with polyalphaolefins include:
Type of plastic Most common plastisizers Compatibility with polyalphaolefins
PP/EPDM Paraffin oil, naphtalene oil Very high
PP/SBC Paraffin oil, naphtalene oil Nery high
Next, the use of polyalphaolefins as plastisizing agents in plastics is discussed in more detail.
1. Use of polyalphaolefins in elastomers: PP/EPDM or PP/EPR blend Raw material %, by weight
EPDM or EPR 5 to 80
Polypropylene 15 to 90
Plastisizer 1 5 to 30 polyalphaolefin
Plastisizer 2 0 to 35 mineral oil
Antioxidant 0 to 0.3
Peroxide 0 to 0.1 di-tert-butyl peroxide
Internal lubricant 0 to 0.2 magnesium stearate
2. Use of polyalphaolefins in styrene based thermoplastic elastomer: SEBS blend.
The combination PP/SEBS is generally used in those applications of styrene elastomers that are demanding with respect to working temperature and environmental pollution.
Raw material % by weight
SEBS 30 to 50
CaCO3 0 to 20
Polypropylene 0 to 30
Plastisizer 1 5 to 30 polyalphaolefin
Plastisizer 2 0 to 35 mineral oil
Antioxidant 0 to 0.3
Typical medical uses of elastomers are syringes and needles, intravenous urinary catheters, dosage tubings and devices, clinical cardiac valves and vessel implants, disposable packages and trays. The composition of the invention has several advantages. The glass transition temperature of the elastomer and plastic is lowered, thus making the products very suitable to applications requiring good low temperature resistance properties (cables, exterior parts of automobiles). Further, the evaporated amounts of organic compounds are lowered, being advantageous for medical applications and for interior elastomers of automobiles. The products are colourless and transparent. The products resist sterilization and exposure to high temperatures for extended periods of time without losing their properties.
Polyalphaolefin may be mixed with elastomers and plastics during the production thereof. In this manner, elastomer and plastic products particularly suitable for medical and medicinal apparatus applications are obtained. Medical applications have high special requirements on materials, such as resistance to sterilization. These require- ments are restricted in no way by the composition of the invention.
The invention will now be illustrated in more detail with the following examples without wishing to limit it to these exemplary solutions.
Example 1
Elastomer for medical, automobile industry, and cable applications: PP/EPDM or PP/EPR blend
Raw material % by weight Products
EPDM or EPR59.8 / 59.5 Nistalon 805 / Νordel IP 3745P
Polypropylene 29 Escorene PP 4152
Plastisizer 1 10 polydecene
Plastisizer 2 0 mineral oil
Antioxidant 0.3 rganox B-225
Peroxide 0.1 di-tert-butyl peroxide
Internal lubricant 0.2 magnesium stearate
With the composition of the example, good processing characteristics and a Shore A hardness of 85 are attained. Thermal ageing properties of the mixture are also especially good.
Example 2
Styrene based thermoplastic elastomer: SEBS blend
The example is directed to a basic SEBS blend. The combination PP/SEBS is gener- ally used in those applications of styrene elastomers that are demanding with respect to working temperature and environmental pollution. Raw material % by weight Products:
SEBS 30 Shell Kraton G- 1651
CaCO3 15 Omycarb 2A, OMYA
Polypropylene 13.4 Escorene PP 4152
Plastisizer 1 35 polydecene
Plastisizer 2 0 mineral oil
Antioxidant 0.3 Irganox B-225
The ability to plastisize SEBS elastomers greatly depends on the styrene content thereof. An elastomer with a low styrene content accepts a plastisizer in an amount that is more than 1.5 times its own weight.
Example 3
Glass transition temperature
The effect of polyalphaolefin plastisizers on low temperature resistance was studied by means of the glass transition temperature Tg. As a reference sample, a common plastisizer, i.e. paraffin oil was used. The samples to be studied were the formulations of Examples 1 and 2.
Table I Glass transition temperature of elastomers
Figure imgf000013_0001
The results show that glass transition temperatures are lowered more by polyalphaolefin oil than by paraffin oil. For SEBS formulation, the glass transition temperature was lowered considerably more, that is, by -6 °C, whereas for EPDM formulation, it was -3 °C lower. Due to these superior low temperature resistance properties, thermoplastic elastomers plastisized with polyalphaolefin oil are very suitable for the production of cables and automobile components.
Example 4
Colour and colour stability
Original colours of the mixtures were considerably better with polyalphaolefin oil than with paraffin oil. Especially the colour of EPDM mixtures was clearly improved by using polyalphaolefin oil. For both tested elastomers (EPFM and SEBS), the colour change was by dE 2.5 better compared to paraffin oil before ageing. Paraffin oil made the colour of the samples yellowish. During ageing, the colour change was identical in all samples independent of the plastisizer used.
Table II Colour change dE (125 °C)
The use of a polyalphaolefin oil as the plastisizer is particularly preferable for the production of clear white elastomer products. The translucency of translucent elastomers suitable for instance for health care applications is better preseved by using a polyalphaolefin oil instead of mineral oil. Example 5
Loss on evaporation
By comparing several plastisizers, it was found that by using a polyalphaolefin oil the volatile matter (100 h, 125 °C) was 40 to 50 % lower that that obtained with paraffin oil. The difference increases with time. Due to this lower volatile matter, products containing a polyalphaolefin as plastisizer are very suitable for the production of materials for e.g. the interior of an automobile.
Table III Volatile matter [% by weight] at 125 °C
Figure imgf000015_0001
Example 6
Sterilizability
Thermoplastic elastomers were sterilized in an autoclave for 15 minutes at 121 °C. Elastomers may be hardened by autoclaving as the plastisizing oils are evaporated. This was not the case for polyalphaolefin oils due to the low volatile matter thereof.

Claims

Claims
1. Elastomer composition containing a plastisizing agent, characterized in that the composition comprises between 20 and 95 % by weight of an elastomer or a mixture of elastomers, and between 5 and 60 % by weight of polyalphaolefin or a mixture of polyalphaolefins.
2. Composition of Claim 1, characterized in that the polyalphaolefin is a food grade hydrogenated polyalphaolefin oil, preferably polybutene, polypentene, polyhexene, polyheptene, polyoctene, polynonene, polydecene, polyundodecene, or polydodecene, preferably polydecene.
3. Composition of Claim 1 or 2, characterized in that the elastomer is a rubber or a thermoplastic elastomer or thermoplastic vulcanizate or a silicone, preferably a ethyl- ene-propylene-diene rubber, ethylene-propylene rubber, styrene-butadiene rubber,
1,2-syndiotactic polybutadiene rubber, natural rubber, polybutyl rubber, styrene- isoprene-styrene blockcopolymer, styrene-butadiene-(styrene) blockcopolymer, sty- rene-ethylene-butene-styrene blockcopolymer, or a styrene-ethylene-propylene- (styrene) blockcopolymer.
4. Use of polyalphaolefin as a plastisizer for an elastomer, characterized in that a polyalphaolefin or a mixture of polyalphaolefins is added to the elastomer or mixture of elastomers or a mixture containing the elastomer.
5. Use of Claim 4, characterized in that the elastomer or the mixture of elastomers is used in an amount ranging between 20 and 95 % by weight, and the polyalphaolefin or the mixture of polyalphaolefins is used in an amount ranging between 5 and 60 % by weight.
6. Use of Claim 4 or 5, characterized in that the polyalphaolefin is a food grade hy- drogenated polyalphaolefin oil, preferably polybutene, polypentene, polyhexene, polyheptene, polyoctene, polynonene, polydecene, polyundodecene, or polydodecene, preferably polydecene.
7. Use according to any of Claims 4 - 6, characterized in that the elastomer is a rubber or a thermoplastic elastomer or thermoplastic vulcanizate or a silicone, preferably a ethylene-propylene-diene rubber, ethylene-propylene rubber, styrene-butadiene rubber, 1,2-syndiotactic polybutadiene rubber, natural rubber, polybutyl rubber, sty- rene-isoprene-styrene blockcopolymer, styrene-butadiene-(styrene) blockcopolymer, styrene-ethylene-butene-styrene blockcopolymer, or a styrene-ethylene-propylene- (styrene) blockcopolymer.
8. Use of the composition according to any of Claims 1 - 3 in medical and medicinal apparatus applications, interior elastomers of automobiles, rubbers of the engine room, seals in passages to the engine room, buffering rubber strips, protective rubbers of joints, isolating materials of cables, cable jackets, seals of food packages, white elastomeric articles and in applications demanding with respect to transparency.
PCT/FI2001/000888 2000-10-12 2001-10-12 Polyalphaolefin plastisizers for elastomers WO2002031044A1 (en)

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004014997A2 (en) 2002-08-12 2004-02-19 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
WO2005080495A1 (en) * 2004-02-12 2005-09-01 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
WO2005080504A1 (en) * 2004-02-20 2005-09-01 Idemitsu Kosan Co., Ltd. Polyurethane composition and molded article thereof
WO2007011541A1 (en) * 2005-07-15 2007-01-25 Exxonmobil Chemical Patents Inc. Elastomeric compositions
US7208442B2 (en) 2002-02-28 2007-04-24 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalyst thereof, their making and use in conversion processes
WO2008094741A1 (en) 2007-02-02 2008-08-07 Exxonmobil Chemical Patents Inc. Improved properties of peroxide-cured elastomer compositions
US7413784B2 (en) 2006-06-19 2008-08-19 Advanced Elastomer Systems, L.P. Thermoplastic vulcanizates for potable water applications
US7470740B2 (en) * 2005-03-11 2008-12-30 Henkel Ag & Co. Kgaa Peelable hot melt adhesive
WO2009020706A1 (en) 2007-08-07 2009-02-12 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7622523B2 (en) * 2002-08-12 2009-11-24 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7629416B2 (en) 2002-08-12 2009-12-08 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7652092B2 (en) * 2002-08-12 2010-01-26 Exxonmobil Chemical Patents Inc. Articles from plasticized thermoplastic polyolefin compositions
US7662885B2 (en) 2002-08-12 2010-02-16 Exxonmobil Chemical Patents Inc. Method to make an article comprising polymer concentrate
US7671132B1 (en) 2008-12-17 2010-03-02 The Goodyear Tire & Rubber Company Pneumatic tire with tread
US7795366B2 (en) 2002-08-12 2010-09-14 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
WO2013077866A1 (en) 2011-11-22 2013-05-30 3M Innovative Properties Company Integrated films for use in solar modules
US20130157173A1 (en) * 2011-04-18 2013-06-20 Tokai Rubber Industries, Ltd. Adhesive seal member for fuel cell
US9276151B2 (en) 2011-11-04 2016-03-01 3M Innovative Properties Company Polyolefin adhesive material for use in solar modules
US9379263B2 (en) 2011-11-04 2016-06-28 3M Innovative Properties Company Durable polyolefin adhesive material for solar modules
US10221267B2 (en) 2016-12-13 2019-03-05 Afton Chemical Corporation Microstructure-controlled copolymers of ethylene and C3-C10 alpha-olefins
US10584297B2 (en) 2016-12-13 2020-03-10 Afton Chemical Corporation Polyolefin-derived dispersants
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DE102019131078A1 (en) * 2019-11-18 2021-05-20 Silgan White Cap Manufacturing Gmbh Vessel closure with sealing element

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4166057A (en) * 1977-07-05 1979-08-28 Dainichi-Nippon Cables, Ltd. Poly-4-methylpentene-1 composition
EP0300689A2 (en) * 1987-07-20 1989-01-25 Advanced Elastomer Systems, L.P. High flow drapable polymer compositions
US5290886A (en) * 1993-04-20 1994-03-01 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved low temperature properties
JPH07292167A (en) * 1994-04-21 1995-11-07 Idemitsu Kosan Co Ltd Softening agent as admixture for rubber and rubber composition containing the same
WO1998044041A1 (en) * 1997-04-02 1998-10-08 Upofloor Oy Plastic-based material
JPH10279750A (en) * 1997-04-04 1998-10-20 Sumitomo Rubber Ind Ltd Rubber composition consisting essentially of epdm polymer and rubber roller for paper feed using the same
EP0940433A1 (en) * 1998-03-06 1999-09-08 Rohm And Haas Company Plasticizers and processing aids for elastomers
JP3144895B2 (en) * 1992-06-30 2001-03-12 積水化学工業株式会社 Medical adhesive tape or sheet

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4166057A (en) * 1977-07-05 1979-08-28 Dainichi-Nippon Cables, Ltd. Poly-4-methylpentene-1 composition
EP0300689A2 (en) * 1987-07-20 1989-01-25 Advanced Elastomer Systems, L.P. High flow drapable polymer compositions
JP3144895B2 (en) * 1992-06-30 2001-03-12 積水化学工業株式会社 Medical adhesive tape or sheet
US5290886A (en) * 1993-04-20 1994-03-01 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved low temperature properties
JPH07292167A (en) * 1994-04-21 1995-11-07 Idemitsu Kosan Co Ltd Softening agent as admixture for rubber and rubber composition containing the same
WO1998044041A1 (en) * 1997-04-02 1998-10-08 Upofloor Oy Plastic-based material
JPH10279750A (en) * 1997-04-04 1998-10-20 Sumitomo Rubber Ind Ltd Rubber composition consisting essentially of epdm polymer and rubber roller for paper feed using the same
EP0940433A1 (en) * 1998-03-06 1999-09-08 Rohm And Haas Company Plasticizers and processing aids for elastomers

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200116, Derwent World Patents Index; AN 1994-061981, "Medical adhesive tape or sheet which does not cause physical irritation - has adhesive lazer comprising styrene)heat elastic elastomer, rubber adhesive lazer contg. paraffin and/or naphthene type hydrocarbon and adhesive, etc on lining" *
PATENT ABSTRACTS OF JAPAN *

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US7662885B2 (en) 2002-08-12 2010-02-16 Exxonmobil Chemical Patents Inc. Method to make an article comprising polymer concentrate
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