CA1038580A - Melt-extrusion of composition containing polyolefin styrene copolymer and lubricant - Google Patents
Melt-extrusion of composition containing polyolefin styrene copolymer and lubricantInfo
- Publication number
- CA1038580A CA1038580A CA183,284A CA183284A CA1038580A CA 1038580 A CA1038580 A CA 1038580A CA 183284 A CA183284 A CA 183284A CA 1038580 A CA1038580 A CA 1038580A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- olefin
- interpolymer
- copolymer
- melt
- 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
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
-
- 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
- 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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
The manufacture of dyeable polyolefin fibres, filaments, film and tape for use in the manufacture of textiles and carpets, which includes melt-extruding a polymer composition comprising a major proportion of a molecularly-orientable fibre-forming or film-forming olefin polymer component blended with a minor proportion of an additive component comprising a styrene copolymer or interpolymer, the melt-extrusion being carried out under con-ditions in which the extrudate in the form of a fibre or film is stretched whilst in the heat-softened condition.
The manufacture of dyeable polyolefin fibres, filaments, film and tape for use in the manufacture of textiles and carpets, which includes melt-extruding a polymer composition comprising a major proportion of a molecularly-orientable fibre-forming or film-forming olefin polymer component blended with a minor proportion of an additive component comprising a styrene copolymer or interpolymer, the melt-extrusion being carried out under con-ditions in which the extrudate in the form of a fibre or film is stretched whilst in the heat-softened condition.
Description
~385~
The present invention relates to the manufacture o dyeable poly-olefin fibres, filaments, film and tape which can be used in the manufacture of textiles and carpets. ~ `
The difficulties encountered in dyeing olefin polymers, for example, polypropylene are well known. These stem mainly fTOm the fact that, since such polymers consist solely of saturated aliphatic hydrocarbon chains, they ;~
do not contain chemical groups which, by reason of their reactivity or pol-arity, are able to act as receptive sites for dyes. ;
The present Applicants have found that the dyeability of olefin Jl 10 polymers can be improved by blending the polymers with a homopolymer, co-polymer or interpolymer of styrene. Reference is made to U.K. specification No. 1,317,577 in this respect. In particular, the dyeability of propylene polyl~ers can be improved by blending with a copolymer of styrene with butadiene I or acrylonitrile, or an acrylonitrile/butadiene/styrene tABS) interpolymer.
The commercially available ABS materials have been found to be particularly satisfactory for producing good dye receptivity.
., . ~
~ However, when such dyeable polymers are melt spun, i.e. are ~ ~
,;, ~ ~ ::, - - ,:
extruded to form fibres and filaments, or when they are melt-extruded into film or tape for certain applications, for instance conversion into fibres or filaments, globules of polymer can form round the die orifices. These glo-bules tend to break off at irregular intervals and adhere to the extrudate.
This phenomenon is known as "die-drool". Such adhering globules give rise to problems during the extrusion process. For example, when the extrudate is ;~
, stretched, fracturing is liable to occur at the points where the globules `~
.. . . .
~ adhere, and this can be particularly troublesome when melt-extrusion is car-. ~
` ried out under conditions in which the extrudate is stretched by being drawn ~`
; down from the die orifice whilst in the heat-softened condition.
An object of the present invention is to provide a process for ~! manufacturing fibres or filaments ~herein referred to as fibres) and film or . 30 tape(herein referred to as film) from which fibres can be made, from dyeable olefin polymers in which the above-mentioned extrusion problems can be avoided or reduced. ~
:~ 103~5~
Accordlng to the present invention a process for manufacturing ; -, from dyeable olefin polymers fibres or films capable o being processed into fibres, comprises melt-extruding a polymer composition comprising a major proportion of a molecularly-orientable fibre-forming or film forming polymer component derived from an olefin of 2-6 carbon atoms blended with 3-20% of , . , . ~
l an additive component comprising a styrene copolymer or interpolymer and ,~, ~ , .
1-15% lubricant which is compatible with said olefin polymer component and .. ~
s with said styrene copolymer or interpolymer, the melt-extrujion being carried -~ ~
., .
out under conditions in which the extrudate in the form of a -fibre or film is stretched whilst in the heat-softened condition.
The process of the present invention being applicable to the man-ufacture of fibres, in those cases in which the extrudate is in film or tape orm it can be converted into Eibres by methods known per se or, if it is a suitably narrow tape, it can be used as such as a fibre in the manufacture of textile articles or carpets. Preferably, the draw -down conditions are ~;
i- such as to achieve at least a 2:1 stretching as exemplified hereinafter in the `.:!
~, specific Examples.
The olefin polymer component is suitably a homopolymer or copo-;~ lymer derived from an olefin having from 2 to 6 carbon atoms, for example ~;j :
ethylene or propylene. A preferred oleEin polymer is polypropylene.
The styrene copolymer or interpolymer may be, for example, a styrene/butadiene copolymer or an acrylonitrile/butadiene/styrene interpoly-'!,',~ : .
~` mer, although other styrene copolymers or interpolymers are not excluded.
The amount of styrene copolymer or interpolymer which may be incorporated into ' the composition may vary within quite wide limits, but, in general, a s~*is-~ factory composition results when the amounts are from 3-20%~ preferably from ;-j 5 to 10%, by weight, based on the total weight of the composition.
; Any lubrica~t material may be used in forming the polymer compo-: ~...................................................................... . .
, sitions used in carrying out the process of the invention provided it is ~ `
'~'A,'`' 30 compatible with the other components of the composition. Thus, conventional organic lubricants such as carboxylic esters, e.g. butyl stearate, and low ,,,., `:~' r~
.i - 3 ~
.~ , : i, ~`: `~ , :103~580 molecular weight polyolefin waxes may be employed. ~lowever, a preferred lubri- ~ ;
cant is an olein/vinyl ester copolymer and in particular an ethylenetvinyl acetate (EVA) copolymer containing, for example 5 to 35~ preferably 10 to 15%
by weight vinyl acetate. Other lubricants which may be employed are fluoro-carbon polymers such as polytetrafluorethylene.
The amount of lubricant which may be incorporated into the compo-sition may also vary within quite wide limits, but, in general, a concentration of from 1 to 15%, preferably from 2 to 7%, by weight, based on the total weight of composition is satisfactory.
A particularly suitable composition for producing fibres or films are not materially affected by the phenomenon of die-drool, comprises 100 parts by weight of polypropylene, 10 parts by weight of ABS and 5 parts by weight of EVA.
In addition to exhibiting reduced die-drool the polymer composi-tLons used in carrying out the process of the invention can also produce fin-ished extrudates which show a reduced susceptibility to scuffing. Further advantages are obtained using the particularly preferred compositions, i.e.
those containing EVA. These are reduced water carry-over if the composition is quenched in water after extrusion, and an increased depth of shade when the composition is dyed.
The polymer compositions may be formed by any suitable mixing process. Thus, the dry components in the form of powders or granules may be blended, for example, in a tumble blender. Alternatively the components in the form of dry powder or granules may be pre-compounded before extrusion in, ,, for example, a Buss co-kneader. ~ -~
A wide variety of dye types may be used in dyeing or tinting fibres or films formed by the process of the invention; disperse dyes are, however, preferred. The latter give particularly satisfactory results in the dyeing of fibres or films derived from compositions comprising polypropylene, . .
~ 30 ABS and EVA.
,: .
; - 4 -: A
~ ~ ... . .
.; .. , . `- . . . . .. . .
As mentioned above the process of the present invention is of in-terest for the manufacture of dyeable fibres or films, for example, for use in making carpets and/or textiles; and the invention includes therefore car-pets and/or textile articles consisting of or comprising fibres or films manufactured by the process of the invention.
The present inven~ion is further illustrated in the following Examples, in which the olefin polymer is polypropylene of melt index 3-5 - (sold as "Carlona" PZ 61).
The word "Carlona" is a Registered Trade Mark.
Extrusion temperature 255 C
Screw speed 130 R.P.M.
Die lip separation 10 thou.
Pilm thickness 5 thou.
Stretc}l ratio 8 : 1 Stretch temperature 150C.
The results set out in Table 2 show the time at which die-drool was observed. ;
` The compositions~.were also dyed using either "Palanil"~Registered ,l~ Trade Mark) Brilliant Pink RF ~concentration 2.0%) or "Palanil" ~Registered Trade Mark) Blue R (concentration 2.5%). The dye bath temperature was 100C
` and the dyeing time was one hour.
Table 2 .:
;', , .
Composition ~parts by weight) : ;
. (1) ~2) ~3) .. . ...... . . . . - - - - - ~ -" _ _ ~
Polypropylene 100 100 100 .EVA - 2 5 : ;
~ .
; j~'i :
. :.
; - 5 -"~
. ~,. .
Die-drool 15 minutes 25 minutes 15 minutes ~ :
appreciable trace no trace Die-drool 1 hour 1 hour 1 hour build up trace no trace on die lips : .
Physical properties`of tape produced ~
Decitex gm/10,000 m 1632 1637 Tenacity gm/decitex 4.9 4.9 Dyeability increasing depth of dye ~
i! , ,,. .. . .. ~
, .
:' :
.~ :
::
'~, ~'"~'`"
i .~, ` :
... . .
- : : .
,:`f ~''`~,;
.. ', ` ' ~ . .
''1 ` ~ ~:
- 6 - ~
t ~';,. ' .
~', ~.' ';'`,' . .
The present invention relates to the manufacture o dyeable poly-olefin fibres, filaments, film and tape which can be used in the manufacture of textiles and carpets. ~ `
The difficulties encountered in dyeing olefin polymers, for example, polypropylene are well known. These stem mainly fTOm the fact that, since such polymers consist solely of saturated aliphatic hydrocarbon chains, they ;~
do not contain chemical groups which, by reason of their reactivity or pol-arity, are able to act as receptive sites for dyes. ;
The present Applicants have found that the dyeability of olefin Jl 10 polymers can be improved by blending the polymers with a homopolymer, co-polymer or interpolymer of styrene. Reference is made to U.K. specification No. 1,317,577 in this respect. In particular, the dyeability of propylene polyl~ers can be improved by blending with a copolymer of styrene with butadiene I or acrylonitrile, or an acrylonitrile/butadiene/styrene tABS) interpolymer.
The commercially available ABS materials have been found to be particularly satisfactory for producing good dye receptivity.
., . ~
~ However, when such dyeable polymers are melt spun, i.e. are ~ ~
,;, ~ ~ ::, - - ,:
extruded to form fibres and filaments, or when they are melt-extruded into film or tape for certain applications, for instance conversion into fibres or filaments, globules of polymer can form round the die orifices. These glo-bules tend to break off at irregular intervals and adhere to the extrudate.
This phenomenon is known as "die-drool". Such adhering globules give rise to problems during the extrusion process. For example, when the extrudate is ;~
, stretched, fracturing is liable to occur at the points where the globules `~
.. . . .
~ adhere, and this can be particularly troublesome when melt-extrusion is car-. ~
` ried out under conditions in which the extrudate is stretched by being drawn ~`
; down from the die orifice whilst in the heat-softened condition.
An object of the present invention is to provide a process for ~! manufacturing fibres or filaments ~herein referred to as fibres) and film or . 30 tape(herein referred to as film) from which fibres can be made, from dyeable olefin polymers in which the above-mentioned extrusion problems can be avoided or reduced. ~
:~ 103~5~
Accordlng to the present invention a process for manufacturing ; -, from dyeable olefin polymers fibres or films capable o being processed into fibres, comprises melt-extruding a polymer composition comprising a major proportion of a molecularly-orientable fibre-forming or film forming polymer component derived from an olefin of 2-6 carbon atoms blended with 3-20% of , . , . ~
l an additive component comprising a styrene copolymer or interpolymer and ,~, ~ , .
1-15% lubricant which is compatible with said olefin polymer component and .. ~
s with said styrene copolymer or interpolymer, the melt-extrujion being carried -~ ~
., .
out under conditions in which the extrudate in the form of a -fibre or film is stretched whilst in the heat-softened condition.
The process of the present invention being applicable to the man-ufacture of fibres, in those cases in which the extrudate is in film or tape orm it can be converted into Eibres by methods known per se or, if it is a suitably narrow tape, it can be used as such as a fibre in the manufacture of textile articles or carpets. Preferably, the draw -down conditions are ~;
i- such as to achieve at least a 2:1 stretching as exemplified hereinafter in the `.:!
~, specific Examples.
The olefin polymer component is suitably a homopolymer or copo-;~ lymer derived from an olefin having from 2 to 6 carbon atoms, for example ~;j :
ethylene or propylene. A preferred oleEin polymer is polypropylene.
The styrene copolymer or interpolymer may be, for example, a styrene/butadiene copolymer or an acrylonitrile/butadiene/styrene interpoly-'!,',~ : .
~` mer, although other styrene copolymers or interpolymers are not excluded.
The amount of styrene copolymer or interpolymer which may be incorporated into ' the composition may vary within quite wide limits, but, in general, a s~*is-~ factory composition results when the amounts are from 3-20%~ preferably from ;-j 5 to 10%, by weight, based on the total weight of the composition.
; Any lubrica~t material may be used in forming the polymer compo-: ~...................................................................... . .
, sitions used in carrying out the process of the invention provided it is ~ `
'~'A,'`' 30 compatible with the other components of the composition. Thus, conventional organic lubricants such as carboxylic esters, e.g. butyl stearate, and low ,,,., `:~' r~
.i - 3 ~
.~ , : i, ~`: `~ , :103~580 molecular weight polyolefin waxes may be employed. ~lowever, a preferred lubri- ~ ;
cant is an olein/vinyl ester copolymer and in particular an ethylenetvinyl acetate (EVA) copolymer containing, for example 5 to 35~ preferably 10 to 15%
by weight vinyl acetate. Other lubricants which may be employed are fluoro-carbon polymers such as polytetrafluorethylene.
The amount of lubricant which may be incorporated into the compo-sition may also vary within quite wide limits, but, in general, a concentration of from 1 to 15%, preferably from 2 to 7%, by weight, based on the total weight of composition is satisfactory.
A particularly suitable composition for producing fibres or films are not materially affected by the phenomenon of die-drool, comprises 100 parts by weight of polypropylene, 10 parts by weight of ABS and 5 parts by weight of EVA.
In addition to exhibiting reduced die-drool the polymer composi-tLons used in carrying out the process of the invention can also produce fin-ished extrudates which show a reduced susceptibility to scuffing. Further advantages are obtained using the particularly preferred compositions, i.e.
those containing EVA. These are reduced water carry-over if the composition is quenched in water after extrusion, and an increased depth of shade when the composition is dyed.
The polymer compositions may be formed by any suitable mixing process. Thus, the dry components in the form of powders or granules may be blended, for example, in a tumble blender. Alternatively the components in the form of dry powder or granules may be pre-compounded before extrusion in, ,, for example, a Buss co-kneader. ~ -~
A wide variety of dye types may be used in dyeing or tinting fibres or films formed by the process of the invention; disperse dyes are, however, preferred. The latter give particularly satisfactory results in the dyeing of fibres or films derived from compositions comprising polypropylene, . .
~ 30 ABS and EVA.
,: .
; - 4 -: A
~ ~ ... . .
.; .. , . `- . . . . .. . .
As mentioned above the process of the present invention is of in-terest for the manufacture of dyeable fibres or films, for example, for use in making carpets and/or textiles; and the invention includes therefore car-pets and/or textile articles consisting of or comprising fibres or films manufactured by the process of the invention.
The present inven~ion is further illustrated in the following Examples, in which the olefin polymer is polypropylene of melt index 3-5 - (sold as "Carlona" PZ 61).
The word "Carlona" is a Registered Trade Mark.
Extrusion temperature 255 C
Screw speed 130 R.P.M.
Die lip separation 10 thou.
Pilm thickness 5 thou.
Stretc}l ratio 8 : 1 Stretch temperature 150C.
The results set out in Table 2 show the time at which die-drool was observed. ;
` The compositions~.were also dyed using either "Palanil"~Registered ,l~ Trade Mark) Brilliant Pink RF ~concentration 2.0%) or "Palanil" ~Registered Trade Mark) Blue R (concentration 2.5%). The dye bath temperature was 100C
` and the dyeing time was one hour.
Table 2 .:
;', , .
Composition ~parts by weight) : ;
. (1) ~2) ~3) .. . ...... . . . . - - - - - ~ -" _ _ ~
Polypropylene 100 100 100 .EVA - 2 5 : ;
~ .
; j~'i :
. :.
; - 5 -"~
. ~,. .
Die-drool 15 minutes 25 minutes 15 minutes ~ :
appreciable trace no trace Die-drool 1 hour 1 hour 1 hour build up trace no trace on die lips : .
Physical properties`of tape produced ~
Decitex gm/10,000 m 1632 1637 Tenacity gm/decitex 4.9 4.9 Dyeability increasing depth of dye ~
i! , ,,. .. . .. ~
, .
:' :
.~ :
::
'~, ~'"~'`"
i .~, ` :
... . .
- : : .
,:`f ~''`~,;
.. ', ` ' ~ . .
''1 ` ~ ~:
- 6 - ~
t ~';,. ' .
~', ~.' ';'`,' . .
Claims
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for manufacturing fibres or films of dyeable olefin polymers, which comprises melt-extruding a polymer composition comprising a major proportion of a molecularly-orientable fibre-forming or film forming polymer component derived from an olefin of 2-6 carbon atoms blended with 3-20% of an additive component comprising a styrene copolymer or interpolymer and 1-15% lubricant which is compatible with said olefin polymer component and with said styrene copolymer or interpolymer, the melt-extrusion being car-ried out under conditions in which the extrudate in the form of a fibre or film is stretched whilst in the heat-softened condition.
2. A process as claimed in claim 1, in which the olefin polymer is polypropylene.
3. A process as claimed in claim 1, in which the styrene copolymer or interpolymer is a styrene/butadience copolymer or an acrylonitrile/buta-diene/styrene (ABS) interpolymer.
4. A process as claimed in claim 1, in which the amount of styrene copolymer or interpolymer is from 5 to 10%, by weight, based on the total weight of the polymer composition.
5. A process as claimed in claim 1, in which the lubricant is an olefin/vinyl ester copolymer.
6. A process as claimed in claim 5, in which the olefin/vinyl ester copolymer is an ethylene/vinyl acetate (EVA) copolymer containing 5 to 35%, by weight, of vinyl acetate.
7. A process as claimed in claim 1, in which the amount of lubricant is from 2 to 7%, by weight, based on the total weight of the polymer composi-tion.
8. A process as claimed in claim 1, in which the polymer composition comprises 100 parts, by weight, of polypropylene, 10 parts, by weight, of ABS and 5 parts, by weight, of EVA.
9. A dyeable fibre or film manufactured by the process claimed in
claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5082472A GB1451607A (en) | 1972-11-03 | 1972-11-03 | Dyeable polymer compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1038580A true CA1038580A (en) | 1978-09-19 |
Family
ID=10457522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA183,284A Expired CA1038580A (en) | 1972-11-03 | 1973-10-12 | Melt-extrusion of composition containing polyolefin styrene copolymer and lubricant |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS4997858A (en) |
| BE (1) | BE806707A (en) |
| BR (1) | BR7308574D0 (en) |
| CA (1) | CA1038580A (en) |
| DE (1) | DE2354922A1 (en) |
| FR (1) | FR2205539B1 (en) |
| GB (1) | GB1451607A (en) |
| IT (1) | IT999141B (en) |
| NL (1) | NL7314992A (en) |
| ZA (1) | ZA738428B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2555078A1 (en) * | 1975-12-06 | 1977-06-08 | Basf Ag | MOLDING COMPOUNDS WITH INCREASED RESISTANCE TO THE FORMATION OF STRESS Cracks AND GOOD LOW TEMPERATURE RESISTANCE |
| JPS572351A (en) * | 1980-06-04 | 1982-01-07 | Sumitomo Chem Co Ltd | Preparation of polypropylene resin molded article |
| US5733825A (en) * | 1996-11-27 | 1998-03-31 | Minnesota Mining And Manufacturing Company | Undrawn tough durably melt-bondable macrodenier thermoplastic multicomponent filaments |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1425566A (en) * | 1963-12-24 | 1966-01-24 | Union Carbide Corp | Film-forming polymer compositions and films obtained from these compositions |
| CA879910A (en) * | 1969-11-24 | 1971-08-31 | Walker John | Sealant tape softened for installation by heated electrically conducting core |
-
1972
- 1972-11-03 GB GB5082472A patent/GB1451607A/en not_active Expired
-
1973
- 1973-10-12 CA CA183,284A patent/CA1038580A/en not_active Expired
- 1973-10-30 BE BE1005466A patent/BE806707A/en unknown
- 1973-10-31 FR FR7338822A patent/FR2205539B1/fr not_active Expired
- 1973-10-31 IT IT30810/73A patent/IT999141B/en active
- 1973-11-01 BR BR8574/73A patent/BR7308574D0/en unknown
- 1973-11-01 NL NL7314992A patent/NL7314992A/xx not_active Application Discontinuation
- 1973-11-01 JP JP48122263A patent/JPS4997858A/ja active Pending
- 1973-11-01 ZA ZA738428A patent/ZA738428B/en unknown
- 1973-11-02 DE DE19732354922 patent/DE2354922A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| FR2205539B1 (en) | 1976-11-19 |
| BR7308574D0 (en) | 1974-09-05 |
| FR2205539A1 (en) | 1974-05-31 |
| IT999141B (en) | 1976-02-20 |
| ZA738428B (en) | 1974-10-30 |
| AU6210273A (en) | 1975-05-01 |
| JPS4997858A (en) | 1974-09-17 |
| DE2354922A1 (en) | 1974-05-16 |
| GB1451607A (en) | 1976-10-06 |
| NL7314992A (en) | 1974-05-07 |
| BE806707A (en) | 1974-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112210163B (en) | Polypropylene composite material, preparation method and application thereof | |
| US3359344A (en) | Mixed spun fibers containing polyamides or polyesters and a second component selected from the group of polyethylene, polypropylene or polystyrene | |
| US3226455A (en) | Polypropylene of improved dyeability containing ethylene-vinyl alcohol compolymers or derivatives thereof | |
| US3431322A (en) | Dyeable polyolefin compositions and products therefrom | |
| CA1038580A (en) | Melt-extrusion of composition containing polyolefin styrene copolymer and lubricant | |
| US3315014A (en) | Dyeable polypropylene fibers containing polymers of vinyl pyridines | |
| US3334153A (en) | Mixture of polyamide, polystyrene, and polyamide-styrene graft copolymer | |
| US3180845A (en) | Method of preparing void free fibers from acrylonitrile polymers | |
| US2571683A (en) | Mixtures comprising polyacrylonitrile and a polyvinyl acetal | |
| US3985933A (en) | Fibers | |
| KR0143900B1 (en) | Opacified molded product and process for producing it | |
| US3642945A (en) | Polyolefin-polyetherester alloy | |
| US3156745A (en) | Process for the manufacture of shaped structures of polyolefins having improved dyeing properties | |
| US3544662A (en) | High-melting polymer compositions comprising a 3-methyl-1-butene polymer and another polyolefin | |
| US3306955A (en) | Bacteriostatic acrylonitrile polymers | |
| US2589055A (en) | Mixtures comprising polyacrylonitrile and polyalkyl alpha-acylaminoacrylates and articles obtained therefrom | |
| US3607986A (en) | Vinyl chloride-propylene copolymer modified polypropylene | |
| US3668280A (en) | Dye-receptive polyolefin textile fibers comprising synthetic high polymers, and process for their preparation | |
| US3350489A (en) | Polyvinylidene cyanide composition and method of producing fibers and films | |
| US4016132A (en) | Coloration of polyolefine articles | |
| US3626025A (en) | Compatible polymers | |
| US2941972A (en) | Solutions of acrylonitrile polymer in chloral hydrate solvent and process for making same | |
| US3356642A (en) | Polyolefin stabilized with a salt of a piperazine-alkanoic acid | |
| US3439066A (en) | Dyeable polypropylene fibers containing copolymers of acrylamides | |
| JPH0321651A (en) | Ultra-high molecule polyolefin-based molecular-orientated molding |