WO1996009331A1 - Flexible nonhalogen-containing thermoplastic polyolefin compositions - Google Patents

Flexible nonhalogen-containing thermoplastic polyolefin compositions Download PDF

Info

Publication number
WO1996009331A1
WO1996009331A1 PCT/US1995/011052 US9511052W WO9609331A1 WO 1996009331 A1 WO1996009331 A1 WO 1996009331A1 US 9511052 W US9511052 W US 9511052W WO 9609331 A1 WO9609331 A1 WO 9609331A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
blend
vinyl acetate
component
ethylene
Prior art date
Application number
PCT/US1995/011052
Other languages
French (fr)
Inventor
Juan-Antonio Garcia Duran
Loïc Pierre ROLLAND
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to JP51090096A priority Critical patent/JP3693674B2/en
Priority to EP95932353A priority patent/EP0782590B1/en
Priority to DE69510555T priority patent/DE69510555T2/en
Publication of WO1996009331A1 publication Critical patent/WO1996009331A1/en
Priority to NO19971308A priority patent/NO312637B1/en

Links

Classifications

    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • 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
    • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • This invention relates to polyolefin compositions and more particularly to such compositions which are flexible and to shaped articles made from them.
  • PVC sheets have been on the market for many years and have become the standard roof liner material in the housing industry. PVC sheets are characterized as being flexible over a variable temperature range, heat-sealable, and oil- resistant. However, with the trend toward a chlorine-free environment, there is a need for a PVC sheeting alternative. Ethylene-propylene-diamine-methylene (EPDM) rubbers are alternatives, but these are difficult to seal. Thus, there is a need for roof and other types of liner sheets which are thermoplastic and heat-sealable, halogen-free and flexible.
  • EPDM Ethylene-propylene-diamine-methylene
  • WO 93/19118 and WO 89/06256 disclose PVC-free compositions that are suitable for use as coatings for electrical cables. These compositions contain several components that are similar to those described, but lack, i.a., the terpolymer described herein.
  • a flexible, nonhalogen-containing polymer composition which comprises a blend of: ( 1 ) ethylene vinyl acetate containing 30-90% by weight ethylene and 10-70% by weight vinyl acetate,
  • composition according to the invention may further contain:
  • a compatibilizer blend comprising (i) a polar olefinic polymer containing 15 to 60% by weight ethylene vinyl acetate; and (ii) a non-polar olefinic polymer,
  • one of components (4)(i) and (4)(ii) contains 0.01 to 10% by weight of glycidyl acrylate or methacrylate or a derivative thereof, and the other of components (4)(i) and (4)(ii) contains 0.01 to 10% by weight of a carboxylic acid or a derivative thereof.
  • composition of the present invention includes aluminium trihydrate (for flame retardancy), antioxidants, titanium dioxide (for UV resistance and to give a white color to the product) and UV stabilizers.
  • the present invention relates to flexible, non-halogen containing thermoplastic polymer blends which are useful in sheet form, and particularly as roofing liners.
  • These blends generally are formed by combining an ethylene vinyl acetate (EVA) copolymer and a very low density polyethylene (VLDPE) having a specific gravity below 0.920, both of which are chlorine free.
  • the blend may further contain an ethylene vinyl acetate carbon monoxyde (EVACO) terpolymer.
  • EVACO ethylene vinyl acetate carbon monoxyde
  • Compatibilizing agents can be added in order to improve the properties of the blend.
  • Polymer blends according to the present invention can be formed into sheets which have many properties comparable to polyvinyl chloride (PVC) containing blends, but with better elongation and being free from chlorine.
  • PVC polyvinyl chloride
  • the EVA copolymer (component (1 )) useful in this invention preferably contains 30-90% by weight of ethylene and 10-70% by weight of vinyl acetate, more preferably 55-75 % by weight of ethylene and 25-45 % by weight of vinyl acetate.
  • these EVA's have a melt flow index (MFI) in the range of 0.05-100 g/10 min., preferably less than 50 g/lOmin. as determined by ASTM D- 1238 (measured at 2.16 kg and 190 °C) and are well-known in the art.
  • Component (1 ) preferably comprises 5-65% by weight of the composition of the present invention, more preferably 20-50% by weight, still more preferably 20-30% by weight.
  • the VLDPE (component (2)) is used herein to mean polyethylene having a density below about 0.920 g/cc and includes linear polyethylene as well as copolymers of ethylene which are thermoplastic resins, but non-polar.
  • the term VLDPE includes copolymers of ethylene and other alpha-olefins such as 1 -butene, 1-hexene, and 1-octene.
  • the processes for producing VLDPE are well known in the art and commercial grades of this polyolefin are available.
  • Component (2) preferably comprises 5-65% by weight of the composition of the present invention, more preferably 10-40% by weight, still more preferably 10-30% by weight.
  • the EVACO terpolymer (component (3)) useful in this invention preferably contains 30-90% by weight of ethylene, 10-70% by weight of vinyl acetate and 1 -20% by weight of carbon monoxide, more preferably 55-65% by weight of ethylene and 20-30% by weight of vinyl acetate and 5-15% by weight carbon monoxide.
  • these EVACO's have a melt flow index (MFI) in the range of 1 -50 g/10 min., preferably in the range of 10-40 g/lOmin. as determined by ASTM D-1238 (measured at 2.16 kg and 190 °C) and are well-known in the art.
  • MFI melt flow index
  • Component (3) preferably comprises 5-65% by weight of the composition of the present invention, more preferably 20-50% by weight, still more preferably 20-30% by weight.
  • component (4) is a relatively polar olefin polymer containing 15- 60% by weight vinyl acetate, more preferably 25-40% by weight vinyl acetate, and optionally containing 1 -20% by weight of carbon monoxide; compatibilizing polymer (4)(ii)) is a substantially non- polar olefin polymer containing less than 15% by weight of a copolymerized polar monomer, more preferably containing less than 5% by weight of a copolymerized polar monomer.
  • One of components (4)(i) and (4)(ii) will contain 0.01-10% by weight, preferably 0.5-5% by weight, of reactive groups selected from glycidyl acrylate or methacrylate or a derivative thereof, and the other of components (4)(i) and (4)(ii) will contain 0.01 -10% by weight, preferably 0.5-5% by weight, of reactive groups selected from a carboxylic acid or a derivative thereof (such as an anhydride) .
  • This olefin backbone polymer of components (4)(i) and (4)(ii) can be functionalized by grafting the desired reactive group to the polymer by known processes.
  • the grafting of the polyolefin can be carried out in the melt state, in solution or in suspension as described in the state-of-the-art literature. While the melt viscosity of the modified polyolefin is not restricted, the most effective compatibilization with modified polyolefin is found if the melt index, measured at 2.16 kg and 190°C is between 1 to 50 g/10 min. Glycidyl methacrylate and maleic anhydride are the preferred functionalizing agents.
  • Such modified polyolefins can be prepared as described, for example, in published European Patent Application Nos. 370,735 and 370,736.
  • the compatibilizer blend will contain 20-80% by weight component (4)(i) and 80-20% by weight component (4)(ii), more preferably 25-35% by weight component (4)(i) and 65-75% by weight component (4)(ii).
  • component (4) preferably comprises 0.5-10% by weight of the composition of the present invention, more preferably 3-5% by weight.
  • the composition of the present invention can be blended with common additives such as reinforcing and non-reinforcing fillers, flame retardant fillers such as aluminium trihydrate, antioxidants, UV stabilizers, lubricants (e.g., oleamide), antiblocking agents, antistatic agents, waxes, coupling agents for fillers, pigments, titanium dioxide, talc and other processing aids known in the polymer compounding art.
  • the pigments and other additives may comprise up to about 50 weight percent of the total composition based on polymer components plus additives (the polymer components being present in amounts with respect to each other in the proportions previously specified); preferably pigments and fillers comprise above about 0 to about 30 weight percent of the total composition.
  • the blends of the invention can be prepared by mixing the polymeric ingredients and optional additives by use of conventional masticating equipment, for example, a rubber mill, Brabender Mixer, Banbury Mixer, Buss-ko kneader, Farrel continuous mixer or twin screw continuous mixer. Mixing times should be sufficient to obtain homogeneous blends. Satisfactory mixing times depend upon the types of polymers and upon the type and amount of compatibilizer. Typically, mixing times of about 5 minutes are satisfactory. If the polymer blend is obviously non-homogeneous, additional mixing is required.
  • the invention can be further understood by the following examples in which parts and percentages are by weight or in parts per hundred rubber (phr) and temperatures are in degrees Celsius.
  • VLDPE very low density polyethylene
  • EGMA ethylene glycidyl methacrylate
  • EVACO ethylene vinyl acetate carbon monoxide
  • a blend is prepared by melt-compounding the following components in the proportions set forth in Table 1 below.
  • VLDPE 1 having a density of 0.911 g/cc and a MFI (19072.16 kg) of 2.2 - VLDPE2 having a density of 0.887 g/cc and a MFI (19072.16 kg) of 1.5
  • EVACO 62.5% ethylene, 28.5% vinyl acetate and 9% carbon monoxide having a MFI (19072.16 kg) of 35 EGMA (1.8 % glycidyl methacrylate having a MFI (28072.16 kg) of 5 titanium dioxide aluminium trihydrate - UV stabilizers (blend of 50% by weight TINUVIN 622 LD (an antioxidant - phenolic type available under the name IRGANOX 1010 from Ciba
  • VLDPE2 13.6 16.5 10.0
  • Titanium dioxide 5.0 1.0 5.0

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)
  • Laminated Bodies (AREA)

Abstract

Nonhalogen-Containing Thermoplastic Polyolefin blends are provided which are flexible and are particularly useful in replacing polyvinyl chloride sheeting used as roofing liners. The blends comprise, in general, (1) ethylene vinyl acetate, (2) very low density polyethylene, (3) ethylene vinyl acetate carbon monoxide terpolymer and optionally contains (4) a compatibilizer blend comprising (i) a polar olefinic polymer and (ii) a non-polar olefinic polymer; all of which are chlorine free.

Description

lii
Flexible Nonhalogen-Containing Thermoplastic Polyolefin Compositions
Background of the Invention
Field of Invention:
This invention relates to polyolefin compositions and more particularly to such compositions which are flexible and to shaped articles made from them.
Background Discussion:
Polyvinyl chloride (PVC) sheets have been on the market for many years and have become the standard roof liner material in the housing industry. PVC sheets are characterized as being flexible over a variable temperature range, heat-sealable, and oil- resistant. However, with the trend toward a chlorine-free environment, there is a need for a PVC sheeting alternative. Ethylene-propylene-diamine-methylene (EPDM) rubbers are alternatives, but these are difficult to seal. Thus, there is a need for roof and other types of liner sheets which are thermoplastic and heat-sealable, halogen-free and flexible.
WO 93/19118 and WO 89/06256 disclose PVC-free compositions that are suitable for use as coatings for electrical cables. These compositions contain several components that are similar to those described, but lack, i.a., the terpolymer described herein.
Summary of the Invention
According to the present invention there is provided a flexible, nonhalogen-containing polymer composition which comprises a blend of: ( 1 ) ethylene vinyl acetate containing 30-90% by weight ethylene and 10-70% by weight vinyl acetate,
(2) very low density polyethylene having a specific gravity less than 0.920, and
(3 ) ethylene vinyl acetate carbon monoxide terpolymer containing 30-90% by weight ethylene, 10-70% by weight vinyl acetate and 1 -20% by weight carbon monoxide.
The composition according to the invention may further contain:
(4) a compatibilizer blend comprising (i) a polar olefinic polymer containing 15 to 60% by weight ethylene vinyl acetate; and (ii) a non-polar olefinic polymer,
wherein one of components (4)(i) and (4)(ii) contains 0.01 to 10% by weight of glycidyl acrylate or methacrylate or a derivative thereof, and the other of components (4)(i) and (4)(ii) contains 0.01 to 10% by weight of a carboxylic acid or a derivative thereof.
Common additives which may be included in the composition of the present invention include aluminium trihydrate (for flame retardancy), antioxidants, titanium dioxide (for UV resistance and to give a white color to the product) and UV stabilizers.
Detailed Description of the Invention
The present invention relates to flexible, non-halogen containing thermoplastic polymer blends which are useful in sheet form, and particularly as roofing liners. These blends generally are formed by combining an ethylene vinyl acetate (EVA) copolymer and a very low density polyethylene (VLDPE) having a specific gravity below 0.920, both of which are chlorine free. The blend may further contain an ethylene vinyl acetate carbon monoxyde (EVACO) terpolymer. Compatibilizing agents can be added in order to improve the properties of the blend.
Polymer blends according to the present invention can be formed into sheets which have many properties comparable to polyvinyl chloride (PVC) containing blends, but with better elongation and being free from chlorine.
Unless otherwise stated, percentage weight ranges for each of the components in the composition of the present invention are calculated exclusive of any additives which may be present.
The EVA copolymer (component (1 )) useful in this invention preferably contains 30-90% by weight of ethylene and 10-70% by weight of vinyl acetate, more preferably 55-75 % by weight of ethylene and 25-45 % by weight of vinyl acetate. In general, these EVA's have a melt flow index (MFI) in the range of 0.05-100 g/10 min., preferably less than 50 g/lOmin. as determined by ASTM D- 1238 (measured at 2.16 kg and 190 °C) and are well-known in the art.
Component (1 ) preferably comprises 5-65% by weight of the composition of the present invention, more preferably 20-50% by weight, still more preferably 20-30% by weight.
The VLDPE (component (2)) is used herein to mean polyethylene having a density below about 0.920 g/cc and includes linear polyethylene as well as copolymers of ethylene which are thermoplastic resins, but non-polar. The term VLDPE includes copolymers of ethylene and other alpha-olefins such as 1 -butene, 1-hexene, and 1-octene. The processes for producing VLDPE are well known in the art and commercial grades of this polyolefin are available.
Component (2) preferably comprises 5-65% by weight of the composition of the present invention, more preferably 10-40% by weight, still more preferably 10-30% by weight. The EVACO terpolymer (component (3)) useful in this invention preferably contains 30-90% by weight of ethylene, 10-70% by weight of vinyl acetate and 1 -20% by weight of carbon monoxide, more preferably 55-65% by weight of ethylene and 20-30% by weight of vinyl acetate and 5-15% by weight carbon monoxide. In general, these EVACO's have a melt flow index (MFI) in the range of 1 -50 g/10 min., preferably in the range of 10-40 g/lOmin. as determined by ASTM D-1238 (measured at 2.16 kg and 190 °C) and are well-known in the art.
Component (3) preferably comprises 5-65% by weight of the composition of the present invention, more preferably 20-50% by weight, still more preferably 20-30% by weight.
The compatibilizing polymer (4)(i) in the compatibilizer blend
(component (4)) is a relatively polar olefin polymer containing 15- 60% by weight vinyl acetate, more preferably 25-40% by weight vinyl acetate, and optionally containing 1 -20% by weight of carbon monoxide; compatibilizing polymer (4)(ii)) is a substantially non- polar olefin polymer containing less than 15% by weight of a copolymerized polar monomer, more preferably containing less than 5% by weight of a copolymerized polar monomer.
One of components (4)(i) and (4)(ii) will contain 0.01-10% by weight, preferably 0.5-5% by weight, of reactive groups selected from glycidyl acrylate or methacrylate or a derivative thereof, and the other of components (4)(i) and (4)(ii) will contain 0.01 -10% by weight, preferably 0.5-5% by weight, of reactive groups selected from a carboxylic acid or a derivative thereof (such as an anhydride) .
This olefin backbone polymer of components (4)(i) and (4)(ii) can be functionalized by grafting the desired reactive group to the polymer by known processes. The grafting of the polyolefin can be carried out in the melt state, in solution or in suspension as described in the state-of-the-art literature. While the melt viscosity of the modified polyolefin is not restricted, the most effective compatibilization with modified polyolefin is found if the melt index, measured at 2.16 kg and 190°C is between 1 to 50 g/10 min. Glycidyl methacrylate and maleic anhydride are the preferred functionalizing agents. Such modified polyolefins can be prepared as described, for example, in published European Patent Application Nos. 370,735 and 370,736.
The compatibilizer blend will contain 20-80% by weight component (4)(i) and 80-20% by weight component (4)(ii), more preferably 25-35% by weight component (4)(i) and 65-75% by weight component (4)(ii).
When present, component (4) preferably comprises 0.5-10% by weight of the composition of the present invention, more preferably 3-5% by weight.
In addition to its polymer components, the composition of the present invention can be blended with common additives such as reinforcing and non-reinforcing fillers, flame retardant fillers such as aluminium trihydrate, antioxidants, UV stabilizers, lubricants (e.g., oleamide), antiblocking agents, antistatic agents, waxes, coupling agents for fillers, pigments, titanium dioxide, talc and other processing aids known in the polymer compounding art. The pigments and other additives may comprise up to about 50 weight percent of the total composition based on polymer components plus additives (the polymer components being present in amounts with respect to each other in the proportions previously specified); preferably pigments and fillers comprise above about 0 to about 30 weight percent of the total composition.
The blends of the invention can be prepared by mixing the polymeric ingredients and optional additives by use of conventional masticating equipment, for example, a rubber mill, Brabender Mixer, Banbury Mixer, Buss-ko kneader, Farrel continuous mixer or twin screw continuous mixer. Mixing times should be sufficient to obtain homogeneous blends. Satisfactory mixing times depend upon the types of polymers and upon the type and amount of compatibilizer. Typically, mixing times of about 5 minutes are satisfactory. If the polymer blend is obviously non-homogeneous, additional mixing is required. The invention can be further understood by the following examples in which parts and percentages are by weight or in parts per hundred rubber (phr) and temperatures are in degrees Celsius.
Examples 1 -4
Legend
MFI = melt flow index
EVA - ethylene vinyl acetate
VLDPE = very low density polyethylene
MAH = maleic anhydride
EGMA = ethylene glycidyl methacrylate EVACO = ethylene vinyl acetate carbon monoxide
Procedure
A blend is prepared by melt-compounding the following components in the proportions set forth in Table 1 below.
EVA ] (60% ethylene and 40% vinyl acetate) having a MFI (190 2.16 kg) of 0.8
EVA2 (72% ethylene and 28% vinyl acetate) having a MFI (19072.16 kg) of 3.0
EVA3 (66% ethylene and 33% vinyl acetate) having a MFI
(19072.16 kg) of 18, grafted with 1% MAH
VLDPE 1 having a density of 0.911 g/cc and a MFI (19072.16 kg) of 2.2 - VLDPE2 having a density of 0.887 g/cc and a MFI (19072.16 kg) of 1.5
EVACO (62.5% ethylene, 28.5% vinyl acetate and 9% carbon monoxide) having a MFI (19072.16 kg) of 35 EGMA (1.8 % glycidyl methacrylate having a MFI (28072.16 kg) of 5 titanium dioxide aluminium trihydrate - UV stabilizers (blend of 50% by weight TINUVIN 622 LD (an antioxidant - phenolic type available under the name IRGANOX 1010 from Ciba
Melt compounding is carried out on a two roll mill with batches from 100 grams at 130-150°C for ca. 5 minutes. The milled product is formed into a testing plaque in a hydraulic press at 130-150°C for 5 minutes. Afterwards stress-strain testing (ASTM D-638) and Shore A hardness (DIN 53505) are carried out. Results are shown in Table 1.
T a b 1 e 1.
Exam Dle numbers 1 2 3
EVAl 5.0
EVA2 22.6 25.2 14.2
EVACO 25.0 25.0 23.0
VLDPE i 5.0 1 1 .2 -
VLDPE2 13.6 16.5 10.0
EGMA 1.0 - 4.0
EVA3 + 1% MAH 1.9 - 4.0
Titanium dioxide 5.0 1.0 5.0
Aluminium trihydrate 20.0 20.0 30.0
UV stabilizer 0.4 0.6 0.4
Antioxidant 0.5 0.5 0.4
Zinc stearate 5.0 - 4.0
Tensile strength (MPa) 12.0 13.5 13.5
Tensile elongation (%) 740 750 700
Shore A hardness 78 80 80 Specific gravity (g/cc) 1 .150 1 .094 1 .180
One can see that the formulations containing compatibilizers show a particularly lower hardness and specific gravity. For roofing membranes, this brings a significant benefit.
Moreover, it can be shown that flame retardancy and chemical resistance are improved in formulations containing compatibilizers in comparison to those which do not contain compatibilizers.

Claims

Claims
1 . A flexible, nonhalogen-containing polymer composition comprising a blend of
( 1 ) ethylene vinyl acetate containing 30-90% by weight ethylene and 10-70% by weight vinyl acetate;
(2) very low density polyethylene having a specific gravity less than 0.920; and
(3 ) ethylene vinyl acetate carbon monoxide terpolymer containing 30-90% by weight ethylene, 10-70% by weight vinyl acetate and 1 -20% by weight carbon monoxide.
2. A blend according to claim 1 wherein component (1 ) comprises 5-65 % by weight of the blend, component (2) comprises
5-65 % by weight of the blend, and component (3) comprises 5-65 % by weight of the blend.
3. A blend according to claim 1 wherein component (1 ) comprises 20-50% by weight of the blend, component (2) comprises 10-40% by weight of the blend and component (3) comprises 20-50% by weight of the blend.
4. A blend according to claim 1 further comprising
(4) a compatibilizer blend comprising (i) a polar olefinic polymer containing 15 to 60% by weight ethylene vinyl acetate; and
(ii) a non-polar olefinic polymer
wherein one of components (4)(i) and (4)(ii) contains 0.01 to
10% by weight of glycidyl acrylate or methacrylate or a derivative thereof, and the other of components (4)(i) and (4)(ii) contains 0.01 to 10% by weight of a carboxylic acid or a derivative thereof. 5. A blend according to claim 4 wherein component (4) comprises 0.
5-10% by weight of the blend.
6. A shaped article formed from a blend according to claim 1.
PCT/US1995/011052 1994-09-22 1995-09-13 Flexible nonhalogen-containing thermoplastic polyolefin compositions WO1996009331A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP51090096A JP3693674B2 (en) 1994-09-22 1995-09-13 Flexible thermoplastic polyolefin composition containing no halogen
EP95932353A EP0782590B1 (en) 1994-09-22 1995-09-13 Flexible nonhalogen-containing thermoplastic polyolefin compositions
DE69510555T DE69510555T2 (en) 1994-09-22 1995-09-13 FLEXIBLE NON-HALOGENIC THERMOPLASTIC POLYOLEFIN COMPOSITION
NO19971308A NO312637B1 (en) 1994-09-22 1997-03-20 Flexible, halogen-free, thermoplastic polyolefin material and its use

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP94202736A EP0703271A1 (en) 1994-09-22 1994-09-22 Flexible nonhalogen containing thermoplastic polyolefin compositions
EP94202736.8 1994-09-22

Publications (1)

Publication Number Publication Date
WO1996009331A1 true WO1996009331A1 (en) 1996-03-28

Family

ID=8217218

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/011052 WO1996009331A1 (en) 1994-09-22 1995-09-13 Flexible nonhalogen-containing thermoplastic polyolefin compositions

Country Status (7)

Country Link
EP (2) EP0703271A1 (en)
JP (1) JP3693674B2 (en)
CA (1) CA2200183A1 (en)
DE (1) DE69510555T2 (en)
ES (1) ES2135087T3 (en)
NO (1) NO312637B1 (en)
WO (1) WO1996009331A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001510872A (en) * 1997-07-25 2001-08-07 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Flame retardant polyolefin composition
US6833333B2 (en) 2000-05-26 2004-12-21 E. I. Du Pont De Nemours And Company Water resistant fabric and method for making
CN114402022A (en) * 2019-08-28 2022-04-26 陶氏环球技术有限责任公司 Polyethylene copolymer blends

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0874022A1 (en) * 1997-04-23 1998-10-28 Du Pont De Nemours International S.A. Flexible thermoplastic polyolefin compositions
US6329464B1 (en) 1997-04-23 2001-12-11 E.I. Du Pont De Nemours And Company Flexible thermoplastic polyolefin compositions
US6133367A (en) * 1997-06-17 2000-10-17 E. I. Du Pont De Nemours And Company Ethylene vinyl acetate blends
US6211291B1 (en) 1997-07-01 2001-04-03 E. I. Du Pont De Nemours And Company Polyolefin compositions
US6034176A (en) * 1998-03-31 2000-03-07 Teknor Apex Company Polymer compositions
US6558809B1 (en) 1999-05-18 2003-05-06 The Dow Chemical Company Flexible, halogen-free, radio-frequency sealable films
DE10153408A1 (en) * 2001-09-20 2003-04-17 Benecke Kaliko Ag High-frequency weldable and cold-flexible polymer mixture and its use

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5089556A (en) * 1986-09-05 1992-02-18 The Dow Chemical Company Adhesive, RF heatable grafted polymers and blends
US5395881A (en) * 1994-03-04 1995-03-07 E. I. Du Pont De Nemours And Company Flexible polar thermoplastic polyolefin compositions
US5434217A (en) * 1994-03-04 1995-07-18 E. I. Du Pont De Nemours And Company Flexible polar thermoplastic polyolefin compositions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4775567A (en) * 1986-10-24 1988-10-04 Hyload Corporation Waterproofing laminate
FR2625508B1 (en) * 1987-12-30 1992-05-22 Charbonnages Ste Chimique FLAME RETARDANT POLYMER COMPOSITIONS AND THEIR APPLICATION TO THE COATING OF ELECTRIC CABLES
US5378539A (en) * 1992-03-17 1995-01-03 E. I. Du Pont De Nemours And Company Cross-linked melt processible fire-retardant ethylene polymer compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5089556A (en) * 1986-09-05 1992-02-18 The Dow Chemical Company Adhesive, RF heatable grafted polymers and blends
US5395881A (en) * 1994-03-04 1995-03-07 E. I. Du Pont De Nemours And Company Flexible polar thermoplastic polyolefin compositions
US5434217A (en) * 1994-03-04 1995-07-18 E. I. Du Pont De Nemours And Company Flexible polar thermoplastic polyolefin compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0782590A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001510872A (en) * 1997-07-25 2001-08-07 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Flame retardant polyolefin composition
JP4663112B2 (en) * 1997-07-25 2011-03-30 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Flame retardant polyolefin composition
US6833333B2 (en) 2000-05-26 2004-12-21 E. I. Du Pont De Nemours And Company Water resistant fabric and method for making
CN114402022A (en) * 2019-08-28 2022-04-26 陶氏环球技术有限责任公司 Polyethylene copolymer blends

Also Published As

Publication number Publication date
NO971308L (en) 1997-03-20
EP0703271A1 (en) 1996-03-27
JPH10506139A (en) 1998-06-16
NO971308D0 (en) 1997-03-20
EP0782590A1 (en) 1997-07-09
ES2135087T3 (en) 1999-10-16
CA2200183A1 (en) 1996-03-28
DE69510555D1 (en) 1999-08-05
EP0782590A4 (en) 1998-01-21
DE69510555T2 (en) 2000-01-20
JP3693674B2 (en) 2005-09-07
EP0782590B1 (en) 1999-06-30
NO312637B1 (en) 2002-06-10

Similar Documents

Publication Publication Date Title
US5434217A (en) Flexible polar thermoplastic polyolefin compositions
EP1687371B1 (en) Flame retardant, halogen-free compositions
US7935765B2 (en) Miscible blends of ethylene copolymers with improved temperature resistance
US5395881A (en) Flexible polar thermoplastic polyolefin compositions
AU740250B2 (en) Flame retardant polyolefin compositions
KR100570260B1 (en) Polyolefin Compositions
US6211291B1 (en) Polyolefin compositions
EP0782590B1 (en) Flexible nonhalogen-containing thermoplastic polyolefin compositions
EP0977807B1 (en) Flexible thermoplastic polyolefin compositions
EP0655079B1 (en) Flexible polar thermoplastic polyolefin compositions
US6329464B1 (en) Flexible thermoplastic polyolefin compositions

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP NO US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1995932353

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2200183

Country of ref document: CA

Ref country code: CA

Ref document number: 2200183

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1995932353

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1995932353

Country of ref document: EP