CA2037232C - High strength papers from floc and fibrids - Google Patents
High strength papers from floc and fibrids Download PDFInfo
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- CA2037232C CA2037232C CA002037232A CA2037232A CA2037232C CA 2037232 C CA2037232 C CA 2037232C CA 002037232 A CA002037232 A CA 002037232A CA 2037232 A CA2037232 A CA 2037232A CA 2037232 C CA2037232 C CA 2037232C
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- floc
- fibrids
- phenylene
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/38—Inorganic fibres or flakes siliceous
- D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/902—High modulus filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/903—Microfiber, less than 100 micron diameter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
- Y10T428/2969—Polyamide, polyimide or polyester
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Abstract
Fibrid-floc papers yield unexpected improvements in strength when made from a combination of carbon, aramid, or glass fibers and fibrids consisting essentially of
Description
Title HicTh Strength Papers From Floc aHd Fi.br~g Backctround of the Invention Wet-laid nonwoven sheets of synthetic polymeric fibrids and short length staple fibers are known from U.S.
Patent No. 2,999,788. Increased bonding of these sheets can be obtained by appli<:ation of heat and/or pressure. As taught in said pateni~, the fibrids are prepared by shear precipitation of solutions of the polymer, preferably in an aqueous medium. Generally, the fibrids are directly converted into nonwoven sheet structures or paper by paper-forming techniques similar to those employed with wood pulp.
Preferably, the aqueous mix used to prepare the nonwoven sheets by paper-making methods will include short fiber or floc in addition to the fibrids: Other materials may be added as desired.
The nature of the floc and fibrids as well as the interaction between them will, of course, determine the sheet properties and the end use applications to which they may be applied. It is an object of the present invention to obtain sheet structures exhibiting high strength and a high glass transition temperature, (Tg). Some of the novel sheet products exhibit outstanding electrical properties as well.
Summary of the Invention The invention provides high strength nonwoven sheet structures conscisting essentially of from 10 to 90 wt.
% of floc of carbon, aramid or glass fiber held in place with from 90 to l0 wt. % of fused fibrids consisting essentially of the following units 3 5 C-- ~ ( -C N-,-A c-N a nd il'i'-2755-A 1.
~~3 ~i~~
Patent No. 2,999,788. Increased bonding of these sheets can be obtained by appli<:ation of heat and/or pressure. As taught in said pateni~, the fibrids are prepared by shear precipitation of solutions of the polymer, preferably in an aqueous medium. Generally, the fibrids are directly converted into nonwoven sheet structures or paper by paper-forming techniques similar to those employed with wood pulp.
Preferably, the aqueous mix used to prepare the nonwoven sheets by paper-making methods will include short fiber or floc in addition to the fibrids: Other materials may be added as desired.
The nature of the floc and fibrids as well as the interaction between them will, of course, determine the sheet properties and the end use applications to which they may be applied. It is an object of the present invention to obtain sheet structures exhibiting high strength and a high glass transition temperature, (Tg). Some of the novel sheet products exhibit outstanding electrical properties as well.
Summary of the Invention The invention provides high strength nonwoven sheet structures conscisting essentially of from 10 to 90 wt.
% of floc of carbon, aramid or glass fiber held in place with from 90 to l0 wt. % of fused fibrids consisting essentially of the following units 3 5 C-- ~ ( -C N-,-A c-N a nd il'i'-2755-A 1.
~~3 ~i~~
Q
H
c--~. ( i;a~a )~ ---N ~ ~ c-4--ci~ ~ c cog ), ._N -x where n is 4 or 5. X is from 0.01 to 0.50, preferably from 0.03 to 0.30, and Ar is a ra~iiaal selected from 3,4'-oxydiphenylene, 4,4'-oxydipiaenylene, 4,4'-sulfonyldiphenylene, 1,3-phenylene, 1-methyl-2,4-phenylene, and mixtures of such radicals with each other or mixtures of such radicals with up to 50 mol percent of 1,4--phenylene radicals based on the mixture of such radicals. The novel fibrils are also part of i~his invention.
petailed Description of the Invention Sheet products of the present invention are wet-laid, hot-pressed sheets of floc of carbon, aramid or glass and certain novel fibrils.
The term "floc" is used to describe short length fibers as customarily used in the preparation of wet-laid sheets. Floc suitable for use in this invention will normally have lengths less than 2.5 cm. In the examples, the floc fibexs had a linear density of 2.2 dtex and a cut length of about 0.68 am. Such floc provides maximum strength and resistance to siarinkage of resultant sheet.
Fibrils are very small, nongranular, flexible, fibrous or film-lake particles. At least one of their three dimensions is of minor magnitude relative to the 2argest dimension. They are prepared by precipitation of a solution of polymeric material using a non-solvent under very high shear. Su3.table fibrils and methods for their preparation are described in U.S. Pafient Ido. 2,999,788 issued September 12,,1961, to P. W. Morgan. Fibrils are always prepared as dispersions in liquid. They can be converted to aqueous slurries by suitable washing techniques. Fibrils characteristically have a high absorptive capacity for water and when deposited on a screen have sufficient strength even ., when wet to permit processing on a paper machine.
Suitable sheets can be made by wniformly depositing an aqueous slurry of the paper-making fibrous material onto a foram:inous surface (e. g., a fine-mesh screen or fabric) through which much of the water quickly drains to form an initial sheet,. Sheets prepared one at a time on laboratory-scale paper-forming equipment are designated "handsheets".
The fibrids employed in the present invention are prepared from a polymer having the following repeat units in the indicated proportions:
O 0 f! H
C- ~ -C N-Ar-N and \ 1-X, 1-X
0 H O C~l~ H
C-(CHI )p-N or C-Cti-(CHI )~-N
X X
2o where n is 4 or 5; X is from 0.01 to 0.50; and Ar is a radical selected from 3,4'-oxydiphenylene,. 1,3-phenylene, 1-methyl-2,4-phenylene, and mixtures of such radicals with each other or with up to equimolar amounts of 1,4-phenylene radicals.
2!i The following examples except for the controls are illustrative of this iinrrention and are not intended as limiting.
Example 1 This example shows preparation of fibrids of this 3CI invention.
A polymer haring the following repeat units wa$
prepared in accordance with the procedures of U.S. Patent No. 5,136,016.
O O N
H
-D- I -N and 0.7 0.7 PI I
- C-(CHI )x--..,N _ 0.3 About 36 g of the polymer (inherent viscosity 0.5) was combined with 264 g of dimethylacetamide (DMAc) containing 9% LiCl to yield a 12% polymer solution. This solutiola was heated to 85°C to dissolve the polymer until a clear, light brown/gold solution is obtained.
A Waning 703.1 blender (model 31BL02j was filled with 50 mL of DMAc (4% LiClj and 200 mL distilled water.
With the blender run on high speed, 75 mL of polymer solution was poured slowly into top of the blender (stream ~0.3 cm wide at toy of blender). The resultilag fibrils were ' vacuum filtered onto Whatman International Ltd. #41 filter paper and washed 5 times with with 500 mL of water to remove excess DMAc. The fibril cake obtained was not allowed to dry out.
Example 2 This example shows the preparation of a nonwoven sheet structure of the present invention using the fibrils of Example 1 and an aramid floc. This floc was prepared from paraphenylene terephthalamide fiber (PPD-Tj tCevlar 29 fiber from E. T. du Pont de Nemours and Company, Inc.
A handsheet containing 70 wt, % of the fibrils and wt. % of the floc described above was prepared from 683 mL of a 0.3% solids fibril slurry arid 1.1052 g of 0.32 cm (0.125 inch] floc. The handsheet was produced by putting the f~.brids and floc, and 2400 mls of water into British Pulp 30 Evaluation Apparatus (Mavis Engineering, Ltd. No. 8233) and dispersing them for 5 minutes. This stock was added to a Noble and Woods handsheet mold and additional water added.
The stock solution case agitated l0 times w~.th an agitator plate, then vacuum drained through a screen having screen openings of 0.15 mm diameter (100 mesh screen). The sample was couched between 2 plies (each side) of blotter paper to ~~~rr~~~
remove excess moisture. The handsheet was then transferred to blotter paper by slapping the sample and screen onto a table top. The sample was dried on handsheet hot plate drier (Noble & Waod Model No. FlOj. Sample strength was 5 fudged to be sufficient to produce on a fourdrinier paper machine.
The handsheet was pressed an a hot press (Farrel Watson-Stillman, Model No. 9175-MR) at 690 kPa (100 psi), 279°C (535°F) for 1 minute. Sample was measured per ASTM D-828 and determined to have break strength of 0.52 N/m width (29.44 lbs/inah width) and modulus of 4227 MPa {613 kpsi).
Example 3 This example employs the fibrids of Example 1 in making sheet structures with several different types of floc. In some instances, proportions wire varied. Item G is a control using fibrils of metaphenylene isophthalamide (MPD-I). Items A and H use floc similar to that of Example 2 while Items E and F employ an aramid floc from MPD-I
fiber.
The same methodfar producingthe formed papers of Example for of Items B-F, 2 was making used the handsheets with the followingcompositions:
Floc Item ~ Fibri~ds Floc Type Length, cm(in.l A 70 30 PPD-T 0.32(0.125) B 60 40 PPD-T 0.32{0.125) C 60 40 CARBON 0.32(0.125) D 70 30 CARBON 0.32(0.125) E 60 40 MPD-I 0.64(0.25) F 70 30 MPD-I 0.64{0.25) G 60 40 MPD-I 0.64{0.25) All papers judged to suf ficient strength were have to be produced on paper machine..
a A11 of th e handsheets from above were pressed on a hot ress (Farrel tillman, ModelNo. 9175-MR) at p Watson-S
H
c--~. ( i;a~a )~ ---N ~ ~ c-4--ci~ ~ c cog ), ._N -x where n is 4 or 5. X is from 0.01 to 0.50, preferably from 0.03 to 0.30, and Ar is a ra~iiaal selected from 3,4'-oxydiphenylene, 4,4'-oxydipiaenylene, 4,4'-sulfonyldiphenylene, 1,3-phenylene, 1-methyl-2,4-phenylene, and mixtures of such radicals with each other or mixtures of such radicals with up to 50 mol percent of 1,4--phenylene radicals based on the mixture of such radicals. The novel fibrils are also part of i~his invention.
petailed Description of the Invention Sheet products of the present invention are wet-laid, hot-pressed sheets of floc of carbon, aramid or glass and certain novel fibrils.
The term "floc" is used to describe short length fibers as customarily used in the preparation of wet-laid sheets. Floc suitable for use in this invention will normally have lengths less than 2.5 cm. In the examples, the floc fibexs had a linear density of 2.2 dtex and a cut length of about 0.68 am. Such floc provides maximum strength and resistance to siarinkage of resultant sheet.
Fibrils are very small, nongranular, flexible, fibrous or film-lake particles. At least one of their three dimensions is of minor magnitude relative to the 2argest dimension. They are prepared by precipitation of a solution of polymeric material using a non-solvent under very high shear. Su3.table fibrils and methods for their preparation are described in U.S. Pafient Ido. 2,999,788 issued September 12,,1961, to P. W. Morgan. Fibrils are always prepared as dispersions in liquid. They can be converted to aqueous slurries by suitable washing techniques. Fibrils characteristically have a high absorptive capacity for water and when deposited on a screen have sufficient strength even ., when wet to permit processing on a paper machine.
Suitable sheets can be made by wniformly depositing an aqueous slurry of the paper-making fibrous material onto a foram:inous surface (e. g., a fine-mesh screen or fabric) through which much of the water quickly drains to form an initial sheet,. Sheets prepared one at a time on laboratory-scale paper-forming equipment are designated "handsheets".
The fibrids employed in the present invention are prepared from a polymer having the following repeat units in the indicated proportions:
O 0 f! H
C- ~ -C N-Ar-N and \ 1-X, 1-X
0 H O C~l~ H
C-(CHI )p-N or C-Cti-(CHI )~-N
X X
2o where n is 4 or 5; X is from 0.01 to 0.50; and Ar is a radical selected from 3,4'-oxydiphenylene,. 1,3-phenylene, 1-methyl-2,4-phenylene, and mixtures of such radicals with each other or with up to equimolar amounts of 1,4-phenylene radicals.
2!i The following examples except for the controls are illustrative of this iinrrention and are not intended as limiting.
Example 1 This example shows preparation of fibrids of this 3CI invention.
A polymer haring the following repeat units wa$
prepared in accordance with the procedures of U.S. Patent No. 5,136,016.
O O N
H
-D- I -N and 0.7 0.7 PI I
- C-(CHI )x--..,N _ 0.3 About 36 g of the polymer (inherent viscosity 0.5) was combined with 264 g of dimethylacetamide (DMAc) containing 9% LiCl to yield a 12% polymer solution. This solutiola was heated to 85°C to dissolve the polymer until a clear, light brown/gold solution is obtained.
A Waning 703.1 blender (model 31BL02j was filled with 50 mL of DMAc (4% LiClj and 200 mL distilled water.
With the blender run on high speed, 75 mL of polymer solution was poured slowly into top of the blender (stream ~0.3 cm wide at toy of blender). The resultilag fibrils were ' vacuum filtered onto Whatman International Ltd. #41 filter paper and washed 5 times with with 500 mL of water to remove excess DMAc. The fibril cake obtained was not allowed to dry out.
Example 2 This example shows the preparation of a nonwoven sheet structure of the present invention using the fibrils of Example 1 and an aramid floc. This floc was prepared from paraphenylene terephthalamide fiber (PPD-Tj tCevlar 29 fiber from E. T. du Pont de Nemours and Company, Inc.
A handsheet containing 70 wt, % of the fibrils and wt. % of the floc described above was prepared from 683 mL of a 0.3% solids fibril slurry arid 1.1052 g of 0.32 cm (0.125 inch] floc. The handsheet was produced by putting the f~.brids and floc, and 2400 mls of water into British Pulp 30 Evaluation Apparatus (Mavis Engineering, Ltd. No. 8233) and dispersing them for 5 minutes. This stock was added to a Noble and Woods handsheet mold and additional water added.
The stock solution case agitated l0 times w~.th an agitator plate, then vacuum drained through a screen having screen openings of 0.15 mm diameter (100 mesh screen). The sample was couched between 2 plies (each side) of blotter paper to ~~~rr~~~
remove excess moisture. The handsheet was then transferred to blotter paper by slapping the sample and screen onto a table top. The sample was dried on handsheet hot plate drier (Noble & Waod Model No. FlOj. Sample strength was 5 fudged to be sufficient to produce on a fourdrinier paper machine.
The handsheet was pressed an a hot press (Farrel Watson-Stillman, Model No. 9175-MR) at 690 kPa (100 psi), 279°C (535°F) for 1 minute. Sample was measured per ASTM D-828 and determined to have break strength of 0.52 N/m width (29.44 lbs/inah width) and modulus of 4227 MPa {613 kpsi).
Example 3 This example employs the fibrids of Example 1 in making sheet structures with several different types of floc. In some instances, proportions wire varied. Item G is a control using fibrils of metaphenylene isophthalamide (MPD-I). Items A and H use floc similar to that of Example 2 while Items E and F employ an aramid floc from MPD-I
fiber.
The same methodfar producingthe formed papers of Example for of Items B-F, 2 was making used the handsheets with the followingcompositions:
Floc Item ~ Fibri~ds Floc Type Length, cm(in.l A 70 30 PPD-T 0.32(0.125) B 60 40 PPD-T 0.32{0.125) C 60 40 CARBON 0.32(0.125) D 70 30 CARBON 0.32(0.125) E 60 40 MPD-I 0.64(0.25) F 70 30 MPD-I 0.64{0.25) G 60 40 MPD-I 0.64{0.25) All papers judged to suf ficient strength were have to be produced on paper machine..
a A11 of th e handsheets from above were pressed on a hot ress (Farrel tillman, ModelNo. 9175-MR) at p Watson-S
6.895 DiPa (1000 psi), 279°C (535°f) for 1 minute.
Properties are given below.
Hreak Strength Normalized Modules Normalized N/m Brk Str MPa Modules Item ~~lbs,~i~~-wiath) m f~Cpsi1 ~a A 0.52(29.44) 0.39 4227(61 3.53) 3230 B ~ 0.38(21..97) 0.26 2819(40 8.80) 1977 C 0.11( 6.28) 0.19 562( 81.47j 972 D 0.20(11.37) 0.34 81.8(118.70) 1385 E 0.39(x9.25) 0.18 2164(32 3.83) 1143 F 0.29(16.85) 0.14 2282(33 0.92) 1118 G 0.28(16.15) 0.14 1584(22 9.79) 798 The break strength and modules are "normalized" to the same density and basis weight as the Item G control. .
The carbon papers will not densify as much as less stiff fibers under the same pressing conditions. As one can see, Items A-f are superior to Item G.
Example 4 About 22.7 kg (50 lbs) of the polymer described in Example 1 (0.5-0.6 Lnherent) was dissolved in enough DMAc (4% F.iCl) to produce a 30% solids solution. The 30% solids solution above was passed to a fibridator of the type disclosed in TJ.S. 3,018,091 . The resulting f.ibrids are washed with water to reduce DMAc and chloride content to about 1.0% and 0.3%, based on polymer, respectively.
3.1.4 kg (25.2 lbs) of the fibrils were put into a hydrapulper with 11.4 kg (25.2 lbs) of 0.6A cm (0.25 in), PPD-T floc and 3762 1 (999: gallons) of water and dispersed for 15 minutes.
This stock was diluted to 0.35% solids and then pumped, through a double-disc refiner (Sprout-Waldron 12"
Twin-Flo, Model no. 12-MA, Serial No. 671432, to a standard fourdrinier paper machine at a rate of 9.26 1/min/cm width (2.86 gallons per min./inch width) to form a sheet of 27.2 ,kg/914 m ream (60 lbs/3000 ft. ream) at 15.2 m (50 ft.) per ~~~~2r3r~
Properties are given below.
Hreak Strength Normalized Modules Normalized N/m Brk Str MPa Modules Item ~~lbs,~i~~-wiath) m f~Cpsi1 ~a A 0.52(29.44) 0.39 4227(61 3.53) 3230 B ~ 0.38(21..97) 0.26 2819(40 8.80) 1977 C 0.11( 6.28) 0.19 562( 81.47j 972 D 0.20(11.37) 0.34 81.8(118.70) 1385 E 0.39(x9.25) 0.18 2164(32 3.83) 1143 F 0.29(16.85) 0.14 2282(33 0.92) 1118 G 0.28(16.15) 0.14 1584(22 9.79) 798 The break strength and modules are "normalized" to the same density and basis weight as the Item G control. .
The carbon papers will not densify as much as less stiff fibers under the same pressing conditions. As one can see, Items A-f are superior to Item G.
Example 4 About 22.7 kg (50 lbs) of the polymer described in Example 1 (0.5-0.6 Lnherent) was dissolved in enough DMAc (4% F.iCl) to produce a 30% solids solution. The 30% solids solution above was passed to a fibridator of the type disclosed in TJ.S. 3,018,091 . The resulting f.ibrids are washed with water to reduce DMAc and chloride content to about 1.0% and 0.3%, based on polymer, respectively.
3.1.4 kg (25.2 lbs) of the fibrils were put into a hydrapulper with 11.4 kg (25.2 lbs) of 0.6A cm (0.25 in), PPD-T floc and 3762 1 (999: gallons) of water and dispersed for 15 minutes.
This stock was diluted to 0.35% solids and then pumped, through a double-disc refiner (Sprout-Waldron 12"
Twin-Flo, Model no. 12-MA, Serial No. 671432, to a standard fourdrinier paper machine at a rate of 9.26 1/min/cm width (2.86 gallons per min./inch width) to form a sheet of 27.2 ,kg/914 m ream (60 lbs/3000 ft. ream) at 15.2 m (50 ft.) per ~~~~2r3r~
min. wire speed. This sheet was dried to a moisture level of 1.15$.
Break Strength and Modules values of this paper and a comparably made paper using MPD-I fibrids is given below for the machine direction MD and the cross direction CD.
Break Strength Modules N/m MPa (lbs/in width) (kpsij ~ ~~ CD ~Q CD
a above palymer 0.04(2.34)0.03(1.55) 95(13.77) 46(6.68) b MPD-~T 0.10(5.58)0.06(3:38) 265(38.41) 126(18.30) The sheet samples were pressed on a hot press (Farrel Watson-Stillman, Model No. 9175-MR) at 6.895 MPa (1000 psij, 279°G (535°F) for 1 minute.
Break strength was measured and is shown below.
Included is date fox the same comparably made paper using MPD--T fibrids and PPD-T floc as a control.
MD Break CD Break MD CD
Strength Strength Modules Moclulus ta/m N/m MPa M~a Item lbs i iw dth) ~~i~ iw,athyCP.i.~Lsi) a 0.47(26.98) 0.36(20.65) 3286(476.56)2380(345.24) b 0.28(16.09) 0.20(11.31) 1174(170.25) 438( 63.51) Tt can be seen that while fibrids are employed for both Items a and b, the Item a fibrids result in substanta.ally improvod sheets. The use of glas~e floc ~:n place of the aramid floc of Items a and b would be expected to give a similar improvements.
Exampl a 5 In this example the fibrids were prepared from a polymer consisting essbntially of the following repeat units in the indicated mol ar proportions.
C-- -C N-Ar-N . and .?3, .73 g ~~~'~~3 . ~-- ( cfa, ) s -:--~
.27 V
wherein Ar is a 70/30 mixture of 1,3-phenylene and 1,4-phenylene radicals, and a FPD-T floc was employed The copolymer was prepared in a 2 liter resin kettle fitted with a stirrer, heating mantle, and continuous nitrogen flow. A mixture of rBC (862.5 g, 2.4 mol), MPD
(183.2 g, 1.7 mol), and PPD {78.5 g, 0.73 mol) was maintained at a temperature between 250° and 260°C for 4 hours. The clear amber plasticized copolymer produced, in solution with residual caprolactam was allowed to cool to room temperature. The inherent viscosity of the copolymer was determined to be 0.8 and its Tg was 217°C. Its proton -NMR spectrum showed X to be 0.27.
Sixty gms of above polymer was combined with 440 gms of DMAc (4% LiGI) to yield 12% polymer solution. This solution was heated to 85°C to dissolve the polymer until a clear, light brownjgold solution is obtained.
A blaring 7011 blender was filled with 50 mL of DMAc (4% L.iCI) and 200 mL distilled water. With the blender run on high speed, 75 mL of polymer solution were poured slowly into top of blender (stream -0.3 cm wide at top of bleaider). The fibrils (Fibril A) were vacuum filtered and washed 5 times with -500 mL of water to remove excess DMAc.
The fibril caDce obtained was not allowed to dry out.
The 21~ gms of 'this fibril cake was mixed with 2181 mL o~ water to produce a 1.2% solids slurry. This slurry was dispersed for 5 minutes as described in Example 2. 750 mL of this fibril slurry was added to 2250 mL of water to produce a 0.3% solids slurry. The 0.3% fibril 3o slurry was refined in a blaring Commercial Blender (CB-6, Model 33BL12) for 30 seconds on high speed.
An additional sample using MPD-T Fibrils (Fibril B) was treated to the same slurry preparation and refining .
steps.
A handsheet comprising 70% of Fibril A/30% PPD-T
floc was\made using 683 mL of the 0.3% solids fibril slurry and 1..1052 gms 0.125 in. PPD-T floc. The handsheet was produced by putting the fibrids and floc and an additional 2000 mls of water into British Pulp Evaluation Apparatus (Mavis Engineering, Ltd. duo. 8233) and dispersing them for 5 minutes. This stock was added to a handsheet mold and additional water added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained through a screen having openings of 0.15 mm diameter (100 mesh screen). The sample was couched between 2 plies (each side) of blotter paper to remove excess moisture. The handsheet was then transferred to blotter paper by slapping the sample and screen onto a table top. The sample dried on a handsheet hot plate drier. A similar sample was produced using the MPD--I fibril slurry mentioned above as a control.
Hreak Strength and Modules values of this paper and a comparataly made paper using Fibril B is given below.
Hreak Strength Modules M/m MPa ibr s (lbs~0~-r~idthl tKpsil A U.03 (1.75) 72 (10.51) H o.a5 (8.50) 219 (31.80) The handsheet was then pressed on a hot press at 6.895 MPa (1000 psi), 279°C (535°F) for 1 minute, Break Strength and Modules values of this paper and a comparably made paper using MPD-T fibrils is given below.
Hrea Htrenath Mo ul s N,~t Fibrils _(lbs~ir~--width, IC si A 0.58 (33.64) 4358 (b31.98) 0:38 (22.17) 2508 (363.78) Example 6 This example is a control showing the use of thermoplastic polymer fibrils.
Thirty g of polyetherimide (PET, L1LTEM 1000 produced by G.E.) polymer were combined with 270 g of DMAc to yield 10~ polymer solution. This solution was heated to ~~'~2~
l0 85°C to dissolve the polymer until a clear, light brown/gold solution is obtained.
A blaring blender, was filled with 50 mL of DMAc (4% LiG1) and 200 mL distilled water. With the blender run on high speed, 75 mL of polymer solution were poured slowly into the top of the blender (stream -0.3 cm wide at top of blender). The fibrils were vacuum filtered onto Whatman International Ltd. #41 filter paper and washed 5 times w~ah 500 mL of water to remove excess DMAc. The fibril cake obtained was not allowed to dry out.
A handsheet 60% PEI fibrids/30% PPD-T floc was prepared using 308 mL of a 0.3% solids fibril slurry and 0.616 dry gms 0.64 cm (0.25 in) floc. The handsheet was produced by putting the fibrils and floc and 2400 mL of water into the Oritish Pulp Evaluation Apparatus and dispersing them for 5 minutes. This stock was added to a handsheet mold arid additional water added. The stock solution was agitated 10 times with an agitator plane, then vacuum drained through a screen having sateen openings of 0.15 mm diameter {100 mesh screen). The sample was couched between 2 plies (each side) of blotter paper to remove excess moisture. The handsheet was then transferred to blotter paper to remove excess moisture. The handsheet was then transferred to blotter paper by slapping the sample and screen onto a table top. The sample dried on a handsheet hot plate drier. Sample strength was judged to be sufficient to produce on a fourdrinier paper machine.
The handsheet was then pressed on a hot press at 6.895 MPa (1000 psi), 279°C {535°F) For 1 minute. Sample 3o was determined to have break strength of 0.02 {0.86 lbs/inch width) arid modulus of 168 MPa (24.43 kpsi).
Similarly formed handsheets were made from Example 1 fibrils (B) and PPD-T 0.64 cm (0.25 in) floc or MPD-I fibrils (C) and PPD-T 0.64 cm (0.25 in) floc.
Properties are below:
on _B~e_a_.51 t~ormal.~.zec_i ~Iormali.zed Strength _B~ Str Io ulus To ~talus,~
basis wt Basis tat Fibrids ~lbs,(iN,-w~.d~ ~t j~~ ~
PET Fibrids 0.02 ( 0.86) 0.02 168 (24.43) 255 B 0.35 (20.02) 0.44 2862 (415.09) 3623 C 0.24 (13.65) 01.20 3483 (504.90) 2950 The break strength and modules of all. samples are "normalized" to a basis weight of 33.9 g/sq. in (1.00 ounces per square yard). As one can sea the B fibrid paper are superior to both the A and flue C fibrid papers.
Example 7 A series of copolymers was prepared from IBC and an aromatic diamine, Ar(Cii2)2, or a mixture of aromatic diamines. Each copolymer was prepared in a test tube fitted with a cap lined with polytetrafluoroethylene. In each of the copolymer preparations, IBC (10.0 g, 28 mmol) and the appropriate diamine or diamines (28 mmol total, see table below) were held at 250°C in the test tube under nitrogen for four hours. The molten mixture was swirled during the initial part of the reaction.
The aromatic diamines used to make the copolymers were the following diamines:
Metaphenylenediamine (MPD}, in which Ar = 1,3-phenylene.
Paraphenyl.enediamine (PPD}, in which Ar = 1,4-phenylene.
2,4=Diaminotoluene (DATj, in which Ar = 1-methyl-2,4-phenylene.
4,4°-Diaminodiphenylsulfone (DDS}, i.n which Ar =
4,4°-sulfonyldiphenylene.
3,4'-Uxyd.iphenylamine (3,4°-ODA), in which Ar =
3,4'-oxydiphenylene. . .
4,4'-Oxydiphenylamine (4,4'-ODA}, in which Ar =
9,4'-oxydiphenylene. ' The bis(lactam) monomer used to make the copolymers were N,N'-isophthaloyl bis(caprolactam) (IBC).
~~'~~3 The copolymers evaluated were as follows:
Polymer mmol i s A DAT/MPD-IBC 8.4/19.6 D 4,4' ODA/DAT-IBC 19.6/8.4 F 3,4° ODA/MPD-IBC 8.4/19.6 O 4,4' ODA/DDS-IBC 19.0/8.4 H 4,4° ODA-IBC 28 I 4,4° ODA/PPD-IHC l9.Ea/8.4 A 12% polymer solution was produced by dissolving each of the above copolymers in the appropriate amount of solvent, which was 100% DMAc for items A, B, E, F, T, or DMAc containing 4% LiCI for items C, D, G, H. A light brown/gold solution was obtained, and it was filtered through glass wool. This solution was heated to 85°C.
A blaring 703.1 blender was filled with 50 mL of DMAc (4% LiCI) and 200 mL distilled water. With the blender 2o run on high speed, 75 mL of polymer solution was poured slowly into the top of the b ender, the stream being about 0.32~cm (1/8 in.) wide at the top of the blender. Each sample of fibrils (Fibrils A-I) was vacuum filtered and washed 5 times with about 500 mL of water to remove excess DMAc. The fibril cake obtained was not permitted to dry out.
Each fibril cake was mixed with the proper amount of.water to produce a 1.2% solidsslurry. This slurry was dispersed for,5 minutes as described in Example 2. 750mL of this fibril slurry was added to 2250 mL of water to produce a 0.3% solids slurry. The o.3% fibril slurry was °'refined°' in a blaring Commercial Blender (CB-6, Model 33BL12) for 30 seconds on high speed.
An additional sample using MPD-I fibrils (Item J) was treated to the same slurry preparation and refining steps.
A handsheet comprising 70% of fibrils A-I/30%PPp-T
floc was made using 683 mL of the 0.3% solids fibril slurry and 1.1052 g of 0.32 cm (0.125 in.) PPD-T floc. The handsheet was produced by putting the fibrils and floc and an additional 2000 mL of water into British Pulp Evaluation Apparatus (Mavis Engineering, Ltd. No. 8233) and dispersing them for 5 minutes. This stock was added to a handsheet mold and additional water added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained thxaugh a fine screen with 0.15-mm openings. The sample was couched between 2 plies (each side) of blotter paper to remove excess moisture. The handsheet was then ' transferred to blotter paper by slapping the sample and 200 mesh screen onto a table top. The sample was produced using the MPD-I fibril slurry mentioned above as a control (Item J). All handsheets were judged to have sufficient strength to be produced on a fourdrinier paper machine.
Each handsheet was then pressed on a hot press at 6895 kPa (1000 psi), 280°C (535°F) for 1 minute.
Breaking Strength and Modules values of these papers and the comparably made papers using MPD-I fibrils are given below.
Breaking Normalized Modules Normalized Strength N/m Brk Str MPa Modules MPa Item ~Llbs,Lindwidth Lbs in-width) ~kpsi~ (kgsi~
A 0.35 (19.93) 0.82 (47.18) 1331 (193.06) 3151 (457.05) B 0.20 (11:62) 0.33 (18.73) 1815 (263.27) 2926 (424.36) C 0.44 (25.44} 0.67 (38.54) 1672 (242.50} 2532 (367.37) D 0.56 (32.37) 0.80 (45.64) 2288 (331.86) 3226 (46?.87) E 0.24 (14.02) 0.34 (19.65) 975 (141.417) 1367 (198.30) F 0.50 (28.86} 0.59 (34.11) 1858 (269.51) 2197 (318.57) 0.44 (25.77) 0.48 (27.32) 2068 (299.98} 2236 (324.30}
H 0.42 (24.21) 0.37 (21.04) 2265 (328.50) 1969 (285.53) I 0.70 (40.07} 0.55 (31.40) 2469 (358.02) 1935 (280.58) J 0.2a (14.48) 0.21 (12.30} 1528 (221.61) 1298 (188.28) 1. 3 The breaking strength and modulus are "normalized"
to the same density and basis weight as the Item J control.
As will be seen from these data, Items A-I are superior to Item J.
Example 8 N,N'-isophthaloyl bis(valerolactam) and 3,4'-Oxydiphenylamine were reacted together in accordance with the procedures of U.S. Patent No. 5,136,016 to form a copolymer having the following repeat units:
[O=C-m-phenylene-C=O]O,gl [HN-3,4'-oxyd.iphenylene-NH]O.gl and [O=C-(CH2)4-NH]0.09 -Abaut 50 lbs, of this polymer (having an inherent viscosity of 0.5-0.6) was dissolved in enough DMAc (4% LiCl) to produce a 30% solids solution. The 30% solids solution was passed to a fibrilator of the type disclosed in U.S.
3,018,091. The resulting fibrids are washed with water to reduce DMAc and chloride content to about 1.0% and 0.3%, based on polymer, respecaively. The fibrid cake obtained was not allowed to dry out.
The fibrid cake was mixed with the proper amount of water to produce a 1..2% solids slurry. This slurry was dispersed, for 5 minutes as described in Example 2 above.
750 mL of this fibrid slurry was added. The 0.3% fibrid slurry was refined in a blaring Commercial Blender (CB-6, Model 33HL12) for 30 seconds at high speed.
An additional sample using MPD-I fibrids (see Ex.
7, Item J) was treated t:a the same slurry preparation and refining steps.
A handsheet comprising 70% of Fibrids A-I/30% PPD-T floc was made using 6s~3 mL of the 0.3% solids fibrid slurry and 1.1052 gms 0.125 in. PPD-T floc. The handsheet was produced by putting the fibrids and floc and an additional 2000 mls of water into British Pulp Evaluation Apparatus (Mauis Engineering, Ltd. No. 8223) and dispersing them for 5 minutes. This stock was added to a handsheet mold, and additional water was added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained through a 100 mesh careen. The sample was couched between 2 plies (each side) of blotter paper to remove excess moisture. The handsheet was then transferred to blotter paper by slapping the sample and 3.00 mesh screen onto a table top. The sample dried on a handsheet hot plate drier. A similar sample was produced using the MPD-I fibrid slurry mentioned above as a control (Example 7, Item J).
All handsheets were judged to have sufficient, strength to be produced on a fourdrinier paper machine.
Each handsheet was then pressed on a hot press at 6895 kPa (1000 psi), 280°C (535°F} for 1 minute.
Breaking Strength and Modules values of these papers and the comparably made papers using MPD-I fibrids are given below, Breaking Normalized Normalized Strength N/m Brk Str N/m Modules MPa Modules MPa Item (lbs~~-Width" llbs/in-width j_ _ Lk~~si.l fkpsil A 0.41 (23.62} 0.8? (49.73) 1201 (174.27) 2530 (366.88) B 0.25 (14.48) 0.21 (12.30) 1528 (221.61) 1298 (188.2.8}
The breaking strength and modules are °'normalized"
to the same density and basis weight as the Item J control.
As will be seen from these data, Item A is superior to Item J.
Break Strength and Modules values of this paper and a comparably made paper using MPD-I fibrids is given below for the machine direction MD and the cross direction CD.
Break Strength Modules N/m MPa (lbs/in width) (kpsij ~ ~~ CD ~Q CD
a above palymer 0.04(2.34)0.03(1.55) 95(13.77) 46(6.68) b MPD-~T 0.10(5.58)0.06(3:38) 265(38.41) 126(18.30) The sheet samples were pressed on a hot press (Farrel Watson-Stillman, Model No. 9175-MR) at 6.895 MPa (1000 psij, 279°G (535°F) for 1 minute.
Break strength was measured and is shown below.
Included is date fox the same comparably made paper using MPD--T fibrids and PPD-T floc as a control.
MD Break CD Break MD CD
Strength Strength Modules Moclulus ta/m N/m MPa M~a Item lbs i iw dth) ~~i~ iw,athyCP.i.~Lsi) a 0.47(26.98) 0.36(20.65) 3286(476.56)2380(345.24) b 0.28(16.09) 0.20(11.31) 1174(170.25) 438( 63.51) Tt can be seen that while fibrids are employed for both Items a and b, the Item a fibrids result in substanta.ally improvod sheets. The use of glas~e floc ~:n place of the aramid floc of Items a and b would be expected to give a similar improvements.
Exampl a 5 In this example the fibrids were prepared from a polymer consisting essbntially of the following repeat units in the indicated mol ar proportions.
C-- -C N-Ar-N . and .?3, .73 g ~~~'~~3 . ~-- ( cfa, ) s -:--~
.27 V
wherein Ar is a 70/30 mixture of 1,3-phenylene and 1,4-phenylene radicals, and a FPD-T floc was employed The copolymer was prepared in a 2 liter resin kettle fitted with a stirrer, heating mantle, and continuous nitrogen flow. A mixture of rBC (862.5 g, 2.4 mol), MPD
(183.2 g, 1.7 mol), and PPD {78.5 g, 0.73 mol) was maintained at a temperature between 250° and 260°C for 4 hours. The clear amber plasticized copolymer produced, in solution with residual caprolactam was allowed to cool to room temperature. The inherent viscosity of the copolymer was determined to be 0.8 and its Tg was 217°C. Its proton -NMR spectrum showed X to be 0.27.
Sixty gms of above polymer was combined with 440 gms of DMAc (4% LiGI) to yield 12% polymer solution. This solution was heated to 85°C to dissolve the polymer until a clear, light brownjgold solution is obtained.
A blaring 7011 blender was filled with 50 mL of DMAc (4% L.iCI) and 200 mL distilled water. With the blender run on high speed, 75 mL of polymer solution were poured slowly into top of blender (stream -0.3 cm wide at top of bleaider). The fibrils (Fibril A) were vacuum filtered and washed 5 times with -500 mL of water to remove excess DMAc.
The fibril caDce obtained was not allowed to dry out.
The 21~ gms of 'this fibril cake was mixed with 2181 mL o~ water to produce a 1.2% solids slurry. This slurry was dispersed for 5 minutes as described in Example 2. 750 mL of this fibril slurry was added to 2250 mL of water to produce a 0.3% solids slurry. The 0.3% fibril 3o slurry was refined in a blaring Commercial Blender (CB-6, Model 33BL12) for 30 seconds on high speed.
An additional sample using MPD-T Fibrils (Fibril B) was treated to the same slurry preparation and refining .
steps.
A handsheet comprising 70% of Fibril A/30% PPD-T
floc was\made using 683 mL of the 0.3% solids fibril slurry and 1..1052 gms 0.125 in. PPD-T floc. The handsheet was produced by putting the fibrids and floc and an additional 2000 mls of water into British Pulp Evaluation Apparatus (Mavis Engineering, Ltd. duo. 8233) and dispersing them for 5 minutes. This stock was added to a handsheet mold and additional water added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained through a screen having openings of 0.15 mm diameter (100 mesh screen). The sample was couched between 2 plies (each side) of blotter paper to remove excess moisture. The handsheet was then transferred to blotter paper by slapping the sample and screen onto a table top. The sample dried on a handsheet hot plate drier. A similar sample was produced using the MPD--I fibril slurry mentioned above as a control.
Hreak Strength and Modules values of this paper and a comparataly made paper using Fibril B is given below.
Hreak Strength Modules M/m MPa ibr s (lbs~0~-r~idthl tKpsil A U.03 (1.75) 72 (10.51) H o.a5 (8.50) 219 (31.80) The handsheet was then pressed on a hot press at 6.895 MPa (1000 psi), 279°C (535°F) for 1 minute, Break Strength and Modules values of this paper and a comparably made paper using MPD-T fibrils is given below.
Hrea Htrenath Mo ul s N,~t Fibrils _(lbs~ir~--width, IC si A 0.58 (33.64) 4358 (b31.98) 0:38 (22.17) 2508 (363.78) Example 6 This example is a control showing the use of thermoplastic polymer fibrils.
Thirty g of polyetherimide (PET, L1LTEM 1000 produced by G.E.) polymer were combined with 270 g of DMAc to yield 10~ polymer solution. This solution was heated to ~~'~2~
l0 85°C to dissolve the polymer until a clear, light brown/gold solution is obtained.
A blaring blender, was filled with 50 mL of DMAc (4% LiG1) and 200 mL distilled water. With the blender run on high speed, 75 mL of polymer solution were poured slowly into the top of the blender (stream -0.3 cm wide at top of blender). The fibrils were vacuum filtered onto Whatman International Ltd. #41 filter paper and washed 5 times w~ah 500 mL of water to remove excess DMAc. The fibril cake obtained was not allowed to dry out.
A handsheet 60% PEI fibrids/30% PPD-T floc was prepared using 308 mL of a 0.3% solids fibril slurry and 0.616 dry gms 0.64 cm (0.25 in) floc. The handsheet was produced by putting the fibrils and floc and 2400 mL of water into the Oritish Pulp Evaluation Apparatus and dispersing them for 5 minutes. This stock was added to a handsheet mold arid additional water added. The stock solution was agitated 10 times with an agitator plane, then vacuum drained through a screen having sateen openings of 0.15 mm diameter {100 mesh screen). The sample was couched between 2 plies (each side) of blotter paper to remove excess moisture. The handsheet was then transferred to blotter paper to remove excess moisture. The handsheet was then transferred to blotter paper by slapping the sample and screen onto a table top. The sample dried on a handsheet hot plate drier. Sample strength was judged to be sufficient to produce on a fourdrinier paper machine.
The handsheet was then pressed on a hot press at 6.895 MPa (1000 psi), 279°C {535°F) For 1 minute. Sample 3o was determined to have break strength of 0.02 {0.86 lbs/inch width) arid modulus of 168 MPa (24.43 kpsi).
Similarly formed handsheets were made from Example 1 fibrils (B) and PPD-T 0.64 cm (0.25 in) floc or MPD-I fibrils (C) and PPD-T 0.64 cm (0.25 in) floc.
Properties are below:
on _B~e_a_.51 t~ormal.~.zec_i ~Iormali.zed Strength _B~ Str Io ulus To ~talus,~
basis wt Basis tat Fibrids ~lbs,(iN,-w~.d~ ~t j~~ ~
PET Fibrids 0.02 ( 0.86) 0.02 168 (24.43) 255 B 0.35 (20.02) 0.44 2862 (415.09) 3623 C 0.24 (13.65) 01.20 3483 (504.90) 2950 The break strength and modules of all. samples are "normalized" to a basis weight of 33.9 g/sq. in (1.00 ounces per square yard). As one can sea the B fibrid paper are superior to both the A and flue C fibrid papers.
Example 7 A series of copolymers was prepared from IBC and an aromatic diamine, Ar(Cii2)2, or a mixture of aromatic diamines. Each copolymer was prepared in a test tube fitted with a cap lined with polytetrafluoroethylene. In each of the copolymer preparations, IBC (10.0 g, 28 mmol) and the appropriate diamine or diamines (28 mmol total, see table below) were held at 250°C in the test tube under nitrogen for four hours. The molten mixture was swirled during the initial part of the reaction.
The aromatic diamines used to make the copolymers were the following diamines:
Metaphenylenediamine (MPD}, in which Ar = 1,3-phenylene.
Paraphenyl.enediamine (PPD}, in which Ar = 1,4-phenylene.
2,4=Diaminotoluene (DATj, in which Ar = 1-methyl-2,4-phenylene.
4,4°-Diaminodiphenylsulfone (DDS}, i.n which Ar =
4,4°-sulfonyldiphenylene.
3,4'-Uxyd.iphenylamine (3,4°-ODA), in which Ar =
3,4'-oxydiphenylene. . .
4,4'-Oxydiphenylamine (4,4'-ODA}, in which Ar =
9,4'-oxydiphenylene. ' The bis(lactam) monomer used to make the copolymers were N,N'-isophthaloyl bis(caprolactam) (IBC).
~~'~~3 The copolymers evaluated were as follows:
Polymer mmol i s A DAT/MPD-IBC 8.4/19.6 D 4,4' ODA/DAT-IBC 19.6/8.4 F 3,4° ODA/MPD-IBC 8.4/19.6 O 4,4' ODA/DDS-IBC 19.0/8.4 H 4,4° ODA-IBC 28 I 4,4° ODA/PPD-IHC l9.Ea/8.4 A 12% polymer solution was produced by dissolving each of the above copolymers in the appropriate amount of solvent, which was 100% DMAc for items A, B, E, F, T, or DMAc containing 4% LiCI for items C, D, G, H. A light brown/gold solution was obtained, and it was filtered through glass wool. This solution was heated to 85°C.
A blaring 703.1 blender was filled with 50 mL of DMAc (4% LiCI) and 200 mL distilled water. With the blender 2o run on high speed, 75 mL of polymer solution was poured slowly into the top of the b ender, the stream being about 0.32~cm (1/8 in.) wide at the top of the blender. Each sample of fibrils (Fibrils A-I) was vacuum filtered and washed 5 times with about 500 mL of water to remove excess DMAc. The fibril cake obtained was not permitted to dry out.
Each fibril cake was mixed with the proper amount of.water to produce a 1.2% solidsslurry. This slurry was dispersed for,5 minutes as described in Example 2. 750mL of this fibril slurry was added to 2250 mL of water to produce a 0.3% solids slurry. The o.3% fibril slurry was °'refined°' in a blaring Commercial Blender (CB-6, Model 33BL12) for 30 seconds on high speed.
An additional sample using MPD-I fibrils (Item J) was treated to the same slurry preparation and refining steps.
A handsheet comprising 70% of fibrils A-I/30%PPp-T
floc was made using 683 mL of the 0.3% solids fibril slurry and 1.1052 g of 0.32 cm (0.125 in.) PPD-T floc. The handsheet was produced by putting the fibrils and floc and an additional 2000 mL of water into British Pulp Evaluation Apparatus (Mavis Engineering, Ltd. No. 8233) and dispersing them for 5 minutes. This stock was added to a handsheet mold and additional water added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained thxaugh a fine screen with 0.15-mm openings. The sample was couched between 2 plies (each side) of blotter paper to remove excess moisture. The handsheet was then ' transferred to blotter paper by slapping the sample and 200 mesh screen onto a table top. The sample was produced using the MPD-I fibril slurry mentioned above as a control (Item J). All handsheets were judged to have sufficient strength to be produced on a fourdrinier paper machine.
Each handsheet was then pressed on a hot press at 6895 kPa (1000 psi), 280°C (535°F) for 1 minute.
Breaking Strength and Modules values of these papers and the comparably made papers using MPD-I fibrils are given below.
Breaking Normalized Modules Normalized Strength N/m Brk Str MPa Modules MPa Item ~Llbs,Lindwidth Lbs in-width) ~kpsi~ (kgsi~
A 0.35 (19.93) 0.82 (47.18) 1331 (193.06) 3151 (457.05) B 0.20 (11:62) 0.33 (18.73) 1815 (263.27) 2926 (424.36) C 0.44 (25.44} 0.67 (38.54) 1672 (242.50} 2532 (367.37) D 0.56 (32.37) 0.80 (45.64) 2288 (331.86) 3226 (46?.87) E 0.24 (14.02) 0.34 (19.65) 975 (141.417) 1367 (198.30) F 0.50 (28.86} 0.59 (34.11) 1858 (269.51) 2197 (318.57) 0.44 (25.77) 0.48 (27.32) 2068 (299.98} 2236 (324.30}
H 0.42 (24.21) 0.37 (21.04) 2265 (328.50) 1969 (285.53) I 0.70 (40.07} 0.55 (31.40) 2469 (358.02) 1935 (280.58) J 0.2a (14.48) 0.21 (12.30} 1528 (221.61) 1298 (188.28) 1. 3 The breaking strength and modulus are "normalized"
to the same density and basis weight as the Item J control.
As will be seen from these data, Items A-I are superior to Item J.
Example 8 N,N'-isophthaloyl bis(valerolactam) and 3,4'-Oxydiphenylamine were reacted together in accordance with the procedures of U.S. Patent No. 5,136,016 to form a copolymer having the following repeat units:
[O=C-m-phenylene-C=O]O,gl [HN-3,4'-oxyd.iphenylene-NH]O.gl and [O=C-(CH2)4-NH]0.09 -Abaut 50 lbs, of this polymer (having an inherent viscosity of 0.5-0.6) was dissolved in enough DMAc (4% LiCl) to produce a 30% solids solution. The 30% solids solution was passed to a fibrilator of the type disclosed in U.S.
3,018,091. The resulting fibrids are washed with water to reduce DMAc and chloride content to about 1.0% and 0.3%, based on polymer, respecaively. The fibrid cake obtained was not allowed to dry out.
The fibrid cake was mixed with the proper amount of water to produce a 1..2% solids slurry. This slurry was dispersed, for 5 minutes as described in Example 2 above.
750 mL of this fibrid slurry was added. The 0.3% fibrid slurry was refined in a blaring Commercial Blender (CB-6, Model 33HL12) for 30 seconds at high speed.
An additional sample using MPD-I fibrids (see Ex.
7, Item J) was treated t:a the same slurry preparation and refining steps.
A handsheet comprising 70% of Fibrids A-I/30% PPD-T floc was made using 6s~3 mL of the 0.3% solids fibrid slurry and 1.1052 gms 0.125 in. PPD-T floc. The handsheet was produced by putting the fibrids and floc and an additional 2000 mls of water into British Pulp Evaluation Apparatus (Mauis Engineering, Ltd. No. 8223) and dispersing them for 5 minutes. This stock was added to a handsheet mold, and additional water was added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained through a 100 mesh careen. The sample was couched between 2 plies (each side) of blotter paper to remove excess moisture. The handsheet was then transferred to blotter paper by slapping the sample and 3.00 mesh screen onto a table top. The sample dried on a handsheet hot plate drier. A similar sample was produced using the MPD-I fibrid slurry mentioned above as a control (Example 7, Item J).
All handsheets were judged to have sufficient, strength to be produced on a fourdrinier paper machine.
Each handsheet was then pressed on a hot press at 6895 kPa (1000 psi), 280°C (535°F} for 1 minute.
Breaking Strength and Modules values of these papers and the comparably made papers using MPD-I fibrids are given below, Breaking Normalized Normalized Strength N/m Brk Str N/m Modules MPa Modules MPa Item (lbs~~-Width" llbs/in-width j_ _ Lk~~si.l fkpsil A 0.41 (23.62} 0.8? (49.73) 1201 (174.27) 2530 (366.88) B 0.25 (14.48) 0.21 (12.30) 1528 (221.61) 1298 (188.2.8}
The breaking strength and modules are °'normalized"
to the same density and basis weight as the Item J control.
As will be seen from these data, Item A is superior to Item J.
Claims (9)
1. A high strength sheet structure consisting essentially of from 10 to 90 wt. % of floc of carbon, aramid or glass fiber held in place with from 90 to 10 wt. % of fused fibrids consisting essentially of the following units:
where n is 4 or 5; X is from 0.01 to 0.50 and Ar is a radical selected from 3,4'-oxydiphenylene, 4,4'-oxydiphenylene, 4,4'-sulfanyldiphenylene, 1,3-phenylene, 1-methyl-2,4 phenylene, and mixtures of such radicals with each other or mixtures of such radicals with up to 50 mol percent of 1,4-phenylene radicals based on the mixture of radicals.
where n is 4 or 5; X is from 0.01 to 0.50 and Ar is a radical selected from 3,4'-oxydiphenylene, 4,4'-oxydiphenylene, 4,4'-sulfanyldiphenylene, 1,3-phenylene, 1-methyl-2,4 phenylene, and mixtures of such radicals with each other or mixtures of such radicals with up to 50 mol percent of 1,4-phenylene radicals based on the mixture of radicals.
2. A sheet structure according to claim 1 wherein carbon floc is employed.
3. A sheet structure according to claim 1 wherein aramid floc is employed.
4. A sheet structure according to claim 1 wherein glass floc is employed.
5. A sheet structure according to claim 1 wherein x is from 0.03 to 0.30.
6. A sheet structure according to claim 1 wherein the fibrids consist essentially of the following units:
wherein x is from 0.01 to 0.50.
wherein x is from 0.01 to 0.50.
7. A sheet structure according to claim 1 wherein the fibrids consist essentially of the following units:
wherein X is from 0.01 to 0.50.
wherein X is from 0.01 to 0.50.
8. A sheet structure according to claim 1 where the fibrids consist essentially of the following units:
wherein Ar is a 70/30 mixture of 1,3-phenylene and 1,4-phenylene radicals and X is from 0. 01 to 0.50.
wherein Ar is a 70/30 mixture of 1,3-phenylene and 1,4-phenylene radicals and X is from 0. 01 to 0.50.
9. Fibrids consisting essentially of the following units:
where n is 4 or 5; X is from 0.01 to 0.50 and Ar is a radical selected from 3,4'-oxydiphenylene, 4,4'-oxydiphenylene, 4,4'-sulfonyldiphenylene, 1,3-phenylene and mixtures of such radicals with each other or mixtures of such radicals with up to 50 mol percent of 1,4-phenylene radicals based on the mixture of radials.
l0. Fibrids according to claim 9 wherein x is from 0.03 to 0.30.
where n is 4 or 5; X is from 0.01 to 0.50 and Ar is a radical selected from 3,4'-oxydiphenylene, 4,4'-oxydiphenylene, 4,4'-sulfonyldiphenylene, 1,3-phenylene and mixtures of such radicals with each other or mixtures of such radicals with up to 50 mol percent of 1,4-phenylene radicals based on the mixture of radials.
l0. Fibrids according to claim 9 wherein x is from 0.03 to 0.30.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49158190A | 1990-03-12 | 1990-03-12 | |
| US07/491,581 | 1990-03-12 | ||
| US07/640,592 | 1991-01-18 | ||
| US07/640,592 US5126012A (en) | 1990-03-12 | 1991-01-18 | High strength papers from floc and fibrids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2037232A1 CA2037232A1 (en) | 1991-09-13 |
| CA2037232C true CA2037232C (en) | 2002-01-29 |
Family
ID=27050489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002037232A Expired - Fee Related CA2037232C (en) | 1990-03-12 | 1991-02-27 | High strength papers from floc and fibrids |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0446870B1 (en) |
| JP (1) | JP2841905B2 (en) |
| AU (1) | AU645529B2 (en) |
| CA (1) | CA2037232C (en) |
| DE (1) | DE69101997T2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232737A (en) * | 1990-04-12 | 1993-08-03 | E. I. Du Pont De Nemours And Company | Method of coating a metal wire with a temperature and stress resistant polymeric coating |
| IL102338A (en) * | 1991-07-01 | 1996-11-14 | Du Pont | Polymeric febrids containing activated carbon |
| US5482773A (en) * | 1991-07-01 | 1996-01-09 | E. I. Du Pont De Nemours And Company | Activated carbon-containing fibrids |
| US5320892A (en) * | 1993-02-22 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Tough layered papers with improved surface adhesion |
| CN1098392C (en) * | 1997-06-10 | 2003-01-08 | 帝人株式会社 | Heat resistant fiber paper |
| US7803247B2 (en) * | 2007-12-21 | 2010-09-28 | E.I. Du Pont De Nemours And Company | Papers containing floc derived from diamino diphenyl sulfone |
| US8118975B2 (en) * | 2007-12-21 | 2012-02-21 | E. I. Du Pont De Nemours And Company | Papers containing fibrids derived from diamino diphenyl sulfone |
| US8114251B2 (en) * | 2007-12-21 | 2012-02-14 | E.I. Du Pont De Nemours And Company | Papers containing fibrids derived from diamino diphenyl sulfone |
| JP7466565B2 (en) * | 2019-04-05 | 2024-04-12 | アールストローム オーワイジェイ | Combustion Gas Filtration Media |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL246230A (en) * | 1958-12-09 | |||
| US4183782A (en) * | 1978-07-11 | 1980-01-15 | Gaf Corporation | Method of producing glass mats using novel glass fiber dispersion composition |
| US4515656A (en) * | 1981-08-28 | 1985-05-07 | E. I. Du Pont De Nemours And Company | Low density nonwoven sheets |
| US4840838A (en) * | 1988-09-08 | 1989-06-20 | E. I. Du Pont De Nemours And Company | High temperature filter felt |
| EP0366316B1 (en) * | 1988-10-14 | 1994-12-07 | E.I. Du Pont De Nemours And Company | Melt-processible aromatic polyamides |
-
1991
- 1991-02-27 CA CA002037232A patent/CA2037232C/en not_active Expired - Fee Related
- 1991-03-07 AU AU72747/91A patent/AU645529B2/en not_active Ceased
- 1991-03-08 JP JP3067571A patent/JP2841905B2/en not_active Expired - Fee Related
- 1991-03-12 EP EP91103757A patent/EP0446870B1/en not_active Expired - Lifetime
- 1991-03-12 DE DE69101997T patent/DE69101997T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0446870A1 (en) | 1991-09-18 |
| JP2841905B2 (en) | 1998-12-24 |
| EP0446870B1 (en) | 1994-05-18 |
| CA2037232A1 (en) | 1991-09-13 |
| DE69101997D1 (en) | 1994-06-23 |
| JPH0533289A (en) | 1993-02-09 |
| AU7274791A (en) | 1991-09-12 |
| AU645529B2 (en) | 1994-01-20 |
| DE69101997T2 (en) | 1994-12-01 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |