GB1562952A - Propylene polymer compositions containing calcium carbonat - Google Patents

Propylene polymer compositions containing calcium carbonat Download PDF

Info

Publication number
GB1562952A
GB1562952A GB12914/77A GB1291477A GB1562952A GB 1562952 A GB1562952 A GB 1562952A GB 12914/77 A GB12914/77 A GB 12914/77A GB 1291477 A GB1291477 A GB 1291477A GB 1562952 A GB1562952 A GB 1562952A
Authority
GB
United Kingdom
Prior art keywords
composition
weight
calcium carbonate
propylene polymer
sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB12914/77A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
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 Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Priority to GB12914/77A priority Critical patent/GB1562952A/en
Priority to US05/885,345 priority patent/UST980003I4/en
Priority to NZ186682A priority patent/NZ186682A/en
Priority to AU34225/78A priority patent/AU3422578A/en
Priority to DE19782812152 priority patent/DE2812152A1/en
Priority to IT21369/78A priority patent/IT1095481B/en
Priority to FR7808463A priority patent/FR2385769A1/en
Priority to BR7801843A priority patent/BR7801843A/en
Priority to NL7803240A priority patent/NL7803240A/en
Priority to JP3494578A priority patent/JPS53120756A/en
Publication of GB1562952A publication Critical patent/GB1562952A/en
Expired legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • 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
    • C08L23/14—Copolymers of propene
    • 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
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins

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)
  • Manufacturing Of Multi-Layer Textile Fabrics (AREA)

Description

(54) PROPYLENE POLYMER COMPOSITIONS CONTAINING CALCIUM CARBONATE (71) We. IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London, SW1P 3JF, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to crystalline propylene polymer compositions containing calcium carbonate as a filler: By "propylene polymers" is meant homopolymers and copolymers with up to 20% by weight of ethylene.
Fillers cheapen propylene polymer compositions but are less compatible than with ethylene copolymers or polyvinyl chloride and adversely affect the impact strength (or brittleness) of the propylene polymer composition especially when the polymer is a copolymer of propylene with 10 to 20% by weight of ethylene. W. J. Frissell ("Plastics Technology", November 1956, pages 723 to 746) described the effects of a wide variety of fillers (including calcium carbonate) on polyethylene compositions and he cautioned that "it is obvious that the effect of any filler will be to raise the brittle temperature drastically" (page 727).Technical Bulletin 3S3/70 dated May 1974 and published by Melbourn Chemicals Limited of Esher, Surrey, reports that loadings of 40% of calcium carbonate of small mean particle size (i.e. 0.7 or 2.0 ,u) reduce the impact strength of a wide range of polymers but adds that by choosing larger mean particle sizes (i.e. 4.5 Xu) the impact strength is only reduced to 70%.
It has now been discovered that at high concentrations of filler, for example, limestone or preferably coccolithic calcium carbonate, the selection of a specified small mean particle size has a more desirable effect on the impact strengths of propylene polymer compositions.
Accordingly this invention provides a propylene polymer composition containing from 30 to 85% (preferably 35 to 60%) by weight based on the weight of the composition of a particulate calcium carbonate in which the particles have a weight mean diameter of from 1.4 to 1.9 p (preferably 1.5 to 1.85 ).
The weight mean diameter is that diameter at which the weight of particles having a diameter greater than the weight mean diameter equals the weight of particles having a diameter less than rhe weight mean diameter.
Weight mean diameters can be conveniently determined using a Coulter counter. Preferably, none of the particles should have a diameter greater than 20,u and the number having diameters greater than 10 y should be kept low.
Coccolithic calcium carbonate can be found in Yorkshire, South-Eastern England, and the Champagne district of France. Preferably, it should contain small amounts (for example 2 to 15%) by weight of fibrous vegetable matter commonly called humus. The deposits in Sourh-Eastern England are softer and therefore preferred.
The polymer preferably has a melt flow index of 0.1 to 100 (especially 0.5 to 20) g/10 minutes when measured according to British Standard 2782: Part 1/105C/1970 using a 2.16 kg load and performed at 230"C.
The most beneficial results are obtained with copolymers of propylene with 10 to 20% by weight of ethylene or with homopolymers of propylene which have been blended with 0.5 to 15% by weight of a rubber. Preferably, the copolymer is made by injecting ethylene into the later stages of an otherwise propylene homopolymerisation process. Preferably, the rubbers are, for example, butyl rubber, a butadiene-styrene rubber or a diene modified rubbery copolymer of ethylene and propylene.
The impact strength of the polymer is further increased by adding preferably up to 5% by weight of the composition of organo titanate coupling agents of the kind described on pages 300 to 324 of the Proceedings of the 24rh International Wire and Cable Symposium, for example, isopropyl tri-isostearyl titanate.
The compositions of this invention are particularly suitable for conversion into press formable sheet (for example, sheet 0.5 to 2 mm thick) and are especially suitable for use in making thermoformed trims for motor vehicles. The sheets are preferably made by extrusion or calendering and in particular by a process in which an extruded web is fed to calender rolls which complete the formation of the sheet. Because of the presence of large amounts of filler, the freshly formed hot sheets are easily laminated to woven or non-woven natural or synthetic textile cloths by melt bonding, so avoiding the need to use adhesives. Articles (especially trims for motor vehicles) thermoformed from such laminated sheets have an integral melt-bonded textile finish.
This invention is furrher illustrated by the following Examples of which Examples A to I are comparative.
EXAMPLES A to I AND 1 to 4.
A copolymer of propylene and ethylene was made by injecring ethylene into the later stages of an otherwise propylene homopolymerisation process. Sufficient ethylene was injected to produce a copolymeric composition containing 12% by weight of ethylene. Conditions were selected so as to produce a copolymeric composition having a melt flow index (at 230"C) of 1 g/10 minutes and a crystallinity of over 40% as determined by the method of Natta et al (Rendiconti dell' Accademia dei Lincei, January 1957, pages 11 to 17).
Portions of the copolymeric composition were each blended with one of several samples of particulate Kentish coccolithic calcium carbonate. Blending was started in a Henschel mixer and completed using a two roll mill.
The various samples of calcium carbonate had weight mean particle diameters as set out in the Table. Sufficient calcium carbonate was used to produce filled polyolefin compositions containing 55% by weight (based on the total weight of the filled polyolefin compoosition) of calcium carbonate.
The filled compositions were injection moulded at 260"C into disc-defining moulds maintained at 50"C. The discs obtained were 1.56 mm thick and had diameters of 11.5 cm.
The discs were allowed to stand for 4 weeks and were then subjected to the drop impact test described in ASTM Test D 3029 of 1972 but using a shouldered dart comprising a hemisphere of diameter 1.2 cm whose flat face was mounted centrally on the leading end of a cylinder of diameter 2 cm so that the cylinder overhangs the hemisphere to form a shoulder. The results obtained are set out in the Table where they are also expressed as a percentage of the drop impact strength of the unfilled polyolefin composition.
The impact strengths of propylene homopolymers are increased by the presence of the specified calcium carbonates.
EXAMPLE 5.
Example 2 was repeated except that the composition contained 37.5% by weight of filler. The results are also set out in the Table.
TABLE
Impact strength as % of Weight mean particle Impact strength impact strength of Example diameter p kg. m unfilled composition A no filler 2.38 100 B 0.60 0.42 18 C 0.70 1.05 44 D 1.20 1.38 58 E 1.30 1.54 64 1 1.40 1.70 72 2 1.50 2.07 87 3 1.85 2.10 88 4 1.90 1.68 71 F 2.00 1.54 64 G 2.30 1.09 46 H 2.80 0.67 28 I 5.00 0.60 25 5 1.50 2.04 87 WHAT WE CLAIM IS: 1. A crystalline propylene polymer com position containing from 30 to 85% by weight based on the weight of the composition of a particulate calcium carbonate in which the particles have a weight mean diameter of from 1.4 to 1.9.
2. A composition as claimed in claim 1 in which the particles have a weight mean diameter of 1.50 to 1.85,a.
3. A composition as claimed in claim 1 or claim 2 comprising 2 to 15% (by weight of the calcium carbonate) of fibrous vegetable matter.
4. A composition according to any one of daims 1 to 3 in which the calcium carbonate is coccolithic.
5. A composition according to claim 4 in which the coccolithic calcium carbonate is of the type found in South-Eastern England.
6. A composition as claimed in any one of the preceding claims in which the polymer is a copolymer of propylene with 10 to 20% (by weight of the copolymer) of ethylene.
7. A crystalline propylene polymer composition comprising particulate calcium carbonate in wh'ich the particles have a.weight mean diameter of from 1.4 to 1.8cm substantially as hereinbefore described and as illustrated by any one or more of Examples 1 to 5.
8. A composition as claimed in claim 7 and as described in any one of Examples 1 to 4.
9. A process for making a composition as daimed in any one of the preceding claims in which the propylene polymer is mixed with a calcium carbonate as specified in any one of claims 1, 2, 4 or 5.
10. A sheet 0.5 to 2 mm thick formed from a composition as claimed in any one of claims 1 to 8.
11. A laminate comprising a textile cloth melt bonded to a sheet as claimed in claim 10.
12. An article thermoformed from a sheet as claimed in claim 10 or a laminate as claimed in claim 11.
13. An particle press formed from a sheet as claimed in claim 10 or a laminate as claimed in claim 11.
14. A trim for a motor vehicle thermoformed from a laminate as claimed in claim 11.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (14)

**WARNING** start of CLMS field may overlap end of DESC **. TABLE Impact strength as % of Weight mean particle Impact strength impact strength of Example diameter p kg. m unfilled composition A no filler 2.38 100 B 0.60 0.42 18 C 0.70 1.05 44 D 1.20 1.38 58 E 1.30 1.54 64 1 1.40 1.70 72 2 1.50 2.07 87 3 1.85 2.10 88 4 1.90 1.68 71 F 2.00 1.54 64 G 2.30 1.09 46 H 2.80 0.67 28 I 5.00 0.60 25 5 1.50 2.04 87 WHAT WE CLAIM IS: 1. A crystalline propylene polymer com position containing from 30 to 85% by weight based on the weight of the composition of a particulate calcium carbonate in which the particles have a weight mean diameter of from
1.4 to 1.9.
2. A composition as claimed in claim 1 in which the particles have a weight mean diameter of 1.50 to 1.85,a.
3. A composition as claimed in claim 1 or claim 2 comprising 2 to 15% (by weight of the calcium carbonate) of fibrous vegetable matter.
4. A composition according to any one of daims 1 to 3 in which the calcium carbonate is coccolithic.
5. A composition according to claim 4 in which the coccolithic calcium carbonate is of the type found in South-Eastern England.
6. A composition as claimed in any one of the preceding claims in which the polymer is a copolymer of propylene with 10 to 20% (by weight of the copolymer) of ethylene.
7. A crystalline propylene polymer composition comprising particulate calcium carbonate in wh'ich the particles have a.weight mean diameter of from 1.4 to 1.8cm substantially as hereinbefore described and as illustrated by any one or more of Examples 1 to 5.
8. A composition as claimed in claim 7 and as described in any one of Examples 1 to 4.
9. A process for making a composition as daimed in any one of the preceding claims in which the propylene polymer is mixed with a calcium carbonate as specified in any one of claims 1, 2, 4 or 5.
10. A sheet 0.5 to 2 mm thick formed from a composition as claimed in any one of claims 1 to 8.
11. A laminate comprising a textile cloth melt bonded to a sheet as claimed in claim 10.
12. An article thermoformed from a sheet as claimed in claim 10 or a laminate as claimed in claim 11.
13. An particle press formed from a sheet as claimed in claim 10 or a laminate as claimed in claim 11.
14. A trim for a motor vehicle thermoformed from a laminate as claimed in claim 11.
GB12914/77A 1977-03-28 1977-03-28 Propylene polymer compositions containing calcium carbonat Expired GB1562952A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
GB12914/77A GB1562952A (en) 1977-03-28 1977-03-28 Propylene polymer compositions containing calcium carbonat
US05/885,345 UST980003I4 (en) 1977-03-28 1978-03-10 Polyolefin compositions containing calcium carbonate
NZ186682A NZ186682A (en) 1977-03-28 1978-03-13 Crystalline propylene polymer containing calcium carbonate
AU34225/78A AU3422578A (en) 1977-03-28 1978-03-16 Polyolefin compositions containing calcium carbonate
DE19782812152 DE2812152A1 (en) 1977-03-28 1978-03-20 CALCIUM CARBONATE-CONTAINING PROPYLENE POLYMER COMPOSITION
IT21369/78A IT1095481B (en) 1977-03-28 1978-03-20 COMPOSITIONS OF PROPYLENE POLYMERS CONTAINING CALCIUM CARBONATE
FR7808463A FR2385769A1 (en) 1977-03-28 1978-03-23 COMPOSITIONS BASED ON PROPYLENE POLYMERS CONTAINING CALCIUM CARBONATE
BR7801843A BR7801843A (en) 1977-03-28 1978-03-27 PROPYLENE POLYMER COMPOSITION; AND SHEET, LAMINATE, TRANSFORMED ARTICLE AND VEHICLE ACCESSORIES, FORMED WITH IT
NL7803240A NL7803240A (en) 1977-03-28 1978-03-28 PROPENE POLYMER COMPOSITIONS.
JP3494578A JPS53120756A (en) 1977-03-28 1978-03-28 Propylene composition containing calcium carbonate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB12914/77A GB1562952A (en) 1977-03-28 1977-03-28 Propylene polymer compositions containing calcium carbonat

Publications (1)

Publication Number Publication Date
GB1562952A true GB1562952A (en) 1980-03-19

Family

ID=10013451

Family Applications (1)

Application Number Title Priority Date Filing Date
GB12914/77A Expired GB1562952A (en) 1977-03-28 1977-03-28 Propylene polymer compositions containing calcium carbonat

Country Status (10)

Country Link
US (1) UST980003I4 (en)
JP (1) JPS53120756A (en)
AU (1) AU3422578A (en)
BR (1) BR7801843A (en)
DE (1) DE2812152A1 (en)
FR (1) FR2385769A1 (en)
GB (1) GB1562952A (en)
IT (1) IT1095481B (en)
NL (1) NL7803240A (en)
NZ (1) NZ186682A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017627A (en) * 1980-10-09 1991-05-21 National Research Development Corporation Composite material for use in orthopaedics
US7459492B2 (en) 2004-09-30 2008-12-02 Universidad De Chile Polypropylene composites with reinforcement based on eggshells: procedure to obtain the said composite, reinforcement based on eggshells, and procedure for obtaining it

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56120742A (en) 1980-02-29 1981-09-22 Idemitsu Petrochem Co Ltd Polypropylene composition
GB8300523D0 (en) * 1983-01-10 1983-02-09 Bicc Plc Articles made from polymer compositions
JPH0692499B2 (en) * 1986-05-09 1994-11-16 三井東圧化学株式会社 Calcium carbonate for filler and method for producing the same
FR2712612B1 (en) * 1993-11-16 1995-12-15 Chomarat Textiles Plastiques Flexible sheet, gas tight, chemical resistant.
EP0725731B1 (en) * 1993-10-28 1998-04-08 TEXTILES ET PLASTIQUES CHOMARAT (Société anonyme) Method for making a flexible, fluid-tight sheet comprised of a textile support coated on both faces with a polypropylene-based coating layer
US5500131A (en) * 1994-04-05 1996-03-19 Metz; Jean-Paul Compositions and methods for water treatment

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU57712A1 (en) * 1968-01-02 1969-04-21
JPS4974224A (en) * 1972-11-17 1974-07-17
JPS5328181B2 (en) * 1973-11-29 1978-08-12

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017627A (en) * 1980-10-09 1991-05-21 National Research Development Corporation Composite material for use in orthopaedics
US7459492B2 (en) 2004-09-30 2008-12-02 Universidad De Chile Polypropylene composites with reinforcement based on eggshells: procedure to obtain the said composite, reinforcement based on eggshells, and procedure for obtaining it

Also Published As

Publication number Publication date
IT7821369A0 (en) 1978-03-20
NZ186682A (en) 1979-06-08
DE2812152A1 (en) 1978-10-05
IT1095481B (en) 1985-08-10
AU3422578A (en) 1979-09-20
BR7801843A (en) 1978-11-28
JPS53120756A (en) 1978-10-21
FR2385769A1 (en) 1978-10-27
NL7803240A (en) 1978-10-02
UST980003I4 (en) 1979-03-06

Similar Documents

Publication Publication Date Title
US4340513A (en) Polyolefin resin composition
DE69406798T2 (en) HOT SEALABLE FILMS AND ARTICLES
CA1188027A (en) Heat sealable high speed extrudable polyolefin blends
US4563504A (en) Propylene and ethylene/α-olefin copolymer combinations applicable to the manufacture of mono-oriented yarns
US4761451A (en) Acoustic vibration sheet and polypropylene composition for the same
US5214091A (en) Thermoplastic resin composition
DE69521044T2 (en) IMPROVED HOT SEAL RESIN MADE OF PROPYLENE COPOLYMER AND ITEMS THEREOF
US6319975B1 (en) Composition for air permeable film of high processability and permeability and production of air permeable film
US6015857A (en) Propylene resin compositions
US5145892A (en) Polypropylene resin composition
CA1199443A (en) Blends of butene-1-ethylene copolymers and polypropylene
GB1562952A (en) Propylene polymer compositions containing calcium carbonat
EP0337662A2 (en) Polymers
JP3398976B2 (en) Resin composition
EP0892006A2 (en) Hydrous pellets of ethylene-vinyl acetate copolymer hydrolyzate, production thereof and moldings from such hydrous pellets
CA2497690A1 (en) Toughened, glass filled polyamide compositions and blends having improved stiffness
US4172875A (en) Production of thinwalled articles
US5902848A (en) Polypropylene films suitable for packaging
WO1991018944A1 (en) Photodegradation and heat-seal agents for polymeric matrix materials
US5369181A (en) Olefinic polymer blends for improving polyolefins
US6211295B1 (en) Polyolefin compositions and blown films obtained therefrom
JPS58210950A (en) Propylene polymer resin composition
CA2211392A1 (en) Polyolefin compositions and blown films obtained therefrom
JPH068370B2 (en) Polyolefin resin composition and film
WO1990006966A1 (en) Photodegradation and heat-seal agents for polymeric matrix materials

Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee