CN101802302A - Paper comprising polybenzazole or precursor thereof - Google Patents
Paper comprising polybenzazole or precursor thereof Download PDFInfo
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- CN101802302A CN101802302A CN200880106946A CN200880106946A CN101802302A CN 101802302 A CN101802302 A CN 101802302A CN 200880106946 A CN200880106946 A CN 200880106946A CN 200880106946 A CN200880106946 A CN 200880106946A CN 101802302 A CN101802302 A CN 101802302A
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- flocculate
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- 239000002243 precursor Substances 0.000 title claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- -1 phosphorus compound Chemical class 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 5
- 229920001131 Pulp (paper) Polymers 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 150000002475 indoles Chemical class 0.000 claims description 18
- 230000003252 repetitive effect Effects 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000001041 indolyl group Chemical group 0.000 claims description 9
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000012777 electrically insulating material Substances 0.000 claims description 3
- 239000004035 construction material Substances 0.000 claims description 2
- 239000012772 electrical insulation material Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 25
- 238000009987 spinning Methods 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 21
- 239000002002 slurry Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000004760 aramid Substances 0.000 description 6
- 229920003235 aromatic polyamide Polymers 0.000 description 6
- 238000007306 functionalization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229920002577 polybenzoxazole Polymers 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Artificial Filaments (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention relates to a paper comprising at least one of a fiber, pulp, fibril, floc, and fibrid having a polybenzazole structure with a repeating unit of formula (I) and/or (II) or its precursor structure with a repeating unit of formula (III): wherein Ar1and Ar2 are independently a para or meta aromatic group having 4 to 12 carbon atoms, X and Y are the same or different and selected from O, S, and NH; and n is O or 1, and wherein the paper is free or essentially free of non-extractable phosphorus compound. The paper is particularly suitable for making an electrical insulation material, a honeycomb structure, or a constructive material.
Description
The present invention relates to a kind of at least a paper that contains in fiber, paper pulp, fibril, flocculate and the fibrid with poly-indoles (polybenzazole) structure or poly-indoles front body structure.The invention still further relates to a kind of method for preparing such paper and uses thereof.
EP 07008742 has described fiber, paper pulp, fibril or fibrid with the excellent properties that comprises mechanical performance and can obtain by following technology: wherein utilize humid air gap spinning technique, jet spinning technology or any other conventional method to be applied in to comprise in the acid flux material the optical anisotropy slurries of high molecular aromatic polyamides that high concentration has substituting group such as hydroxyl, sulfydryl or amido to obtain fiber, paper pulp, fibril or fibrid, then it is heat-treated.
The present invention relates to a kind of at least a paper that contains in fiber, paper pulp, fibril, flocculate and the fibrid, described fiber, paper pulp, fibril, flocculate and fibrid contain have formula (I) and/or (II) the poly-indole structure of repetitive:
Or it has the front body structure of formula (III) repetitive:
Ar wherein
1And Ar
2Independent for have 4-12 carbon atom to or an aryl, X and Y are identical or different and be selected from O, S and NH; With n be 0 or 1, wherein said paper does not contain or does not contain substantially inextractable phosphorus compound.Wherein said paper bag contains the inextractable phosphorus compound less than 0.15 weight %.
The paper of being made by the fiber with poly-indole structure is known by for example JP 10096175, JP2001 248091 and WO 2007/076332 in this area.JP 10 096175 relates to nonwoven sheet but not paper.In addition, these sheet materials and paper are by the fiber production from poly-phosphorus spinning slurry spinning.Therefore, these paper bags contain significant inextractable phosphorus compound, even if because the method for the most complicated removal polyphosphoric acid still stays at least 0.25 weight %.Normal industrial procedure stays about 0.4 weight % in fiber polyphosphoric acid (is seen for example Hu X.B. and Lesser A.J.; Abstracts of Papers of the American ChemicalSociety 2004,227:U562-U562).
Term " to " and " " relate to the position of two amino on the aromatic ring or two carbonyls.If Ar
1And/or Ar
2Comprise the fused aromatic rings that does not in form have a contraposition and a position, but the relevant position be called between pseudo-contraposition and puppet the position, with its be included in definition " to " and " " in.
Paper does not contain or does not contain substantially inextractable phosphorus compound, and this is meant that paper contains the inextractable phosphorus compound less than 0.15 weight %, does not preferably contain inextractable phosphorus compound.
Fiber of the present invention, paper pulp, fibril, flocculate or fibrid are solidified into coagulating liq by comprising the slurries spinning or extruding with it, then as the method for the step of operation gained fiber as described in the EP 07008742 and prepare.
The present invention also relates to precursor paper, itself have excellent performance, but therefore former state is used.This precursor paper contains the poly-indoles precursor of the repetitive shown in (III) that has formula:
Ar wherein
1And Ar
2Independent of having the aryl of 4-12 carbon atom, Ar
1And Ar
2Have to or a configuration, X and Y are identical or different and to be selected from O, S and NH and n be 0 or 1.
Ar
1Example be phenylene, naphthalene two bases and divalence heteroaryl.Ar
1Can be replaced by hydroxyl and/or halogen group.
Ar
1Be preferably selected from:
Ar
2For having three of 4-12 carbon atom-or tetravalence aryl.Ar
2Example be benzene three-or four bases, naphthalene three-or four bases, biphenyl three-or four bases, and three-or the tetravalence heterocyclic group can classify Ar as
2These Ar
2Structure division can be replaced by hydroxyl and/or halogen group.
Ar
2Be preferably selected from:
Phenyl is most preferred Ar
2Group.
In preferred embodiments, Ar
1Be right-or metaphenylene:
And Ar
2For:
Wherein X and Y are O, and straight line is represented key.
Except that above-mentioned poly-indoles, described fiber also can be the copolymer that contains repetitive shown in the formula (IV):
In formula (III), Ar
1Group independently has the implication that above provides.Preferred Ar
1Group is right-or metaphenylene.
Poly-indoles preferably contain 40-100 mole % formula (I) and/or (II) shown in repetitive and the repetitive shown in the 60-0 mole % formula (IV), total amount is 100 moles of %.
Poly-indoles more preferably contain 60-100 mole % formula (I) and/or (II) shown in repetitive and the repetitive shown in the 40-0 mole % formula (IV), total amount is 100 moles of %.
Since X be oxygen atom (O-), sulphur atom (S-) or imino group therefore (NH-), can comprise imidazoles, thiazole He/Huo oxazole ring by the poly-indoles that polymer precursor obtains.
Especially preferably the poly-indoles precursor that contains one or more following repetitives:
European Patent Application No. EP 07008742 discloses the method for preparing these polymer and its fiber of preparation, paper pulp, fibril, flocculate or fibrid, by reference with its combination.
Though PBO paper is known in the art, promptly as described in the patent US 6890636, this type of paper contains inherently as the spinning slurry of preparation fiber and a large amount of phosphoric acid that can not remove fully.PBO paper of the present invention contains less than the inextractable phosphorus compound of 0.15 weight % (promptly being mainly phosphoric acid), and is preferred considerably less as less than 30ppm, most preferably do not contain or phosphorus-containing compound (when spinning slurry does not contain any phosphoric acid) not substantially.Because known trace phosphoric acid may decomposed P the BO fibrous material, and then cause paper intensity significantly to be lost, so, then may the most important thing is to prepare and do not contain or the PBO paper of phosphoric acid not at least substantially if this type of paper should keep its intensity for a long time.The peculiar methods that the present invention prepares PBO paper is that the PBO structure of closed loop wherein is by still having OH, SH or NH
2The method that the open loop front body structure of group obtains.These hydrophilic radicals allow described precursor to be dissolved in hydrophilic solvent such as water, the alcohol and water alcohol mixture etc.Yet in fact PBO may only be dissolved in the spinning slurry of phosphoric acid, and precursor of the present invention can form spinning slurry in described hydrophilic solvent, and does not use any phosphoric acid.This type of spinning slurry causes fully or the virtually completely not fiber of phosphorus-containing compound, paper pulp, fibril, flocculate or fibrid.The PBO paper that has less than the phosphorus compound of 0.15 weight % is unknown.Known PBO paper is prepared by the spinning slurry that contains the PBO-polyphosphoric acid, and then causes paper to have (far away) greater than the inextractable phosphorus of 0.15 weight %.Though this generally is not preferred, small amounts of phosphoric acid or other phosphorus compound can be added in the spinning slurry, and then cause paper to have on a small quantity (promptly less than 0.15 weight %) phosphorus.The amount that is present in the phosphorus in the paper can utilize standard method such as spectroscopic methodology or titration to measure easily.
Paper of the present invention can contain the combination of fiber, paper pulp, fibril, flocculate or fibrid, for example fibrid and flocculate.Paper of the present invention can be by traditional paper technology preparation, and described technology allows conventional additives and auxiliary material are added the material that is used for papermaking, for example adds pigment, adhesive, silicate, filler and other additive.The paper of gained can further be processed as passing through to use the density of known calendering method with further raising paper thus.
Term " fiber, paper pulp, fibril, flocculate and fibrid " is known in the art, for example visible Textile Terms and Definitions (fabric term and definition), the 2nd edition, 1955.Term " fibrid " refer to the film sample particle of on-granulated.The average length of fibrid is 0.2-1mm, and the length and width aspect ratio is 5: 1-10: 1.Gauge is several microns the order of magnitude.When fresh, with wet this type of fibrid of use, and fibrid is as the binder deposition around the flocculate component that physically is wrapped in paper.Fresh fibrid and the dry in advance fibrid of crossing can be used in the paper of the present invention.Term " flocculate " refers to that normal length is that 2-12mm and linear density are the staple fibre of 1-10 dtex.Flocculate can be fresh or it can be dry in advance the mistake.If fresh, then be not used in any product before it.
Paper pulp can be generally contains flocculate and fibrid with the amount of about 50-60 weight % fibrid and 40-50 weight % flocculate.Even after pulverizing and grinding, the flocculate in the aromatic polyamides paper pulp is still by fibrid combination to a certain extent.The fibrid that is in drying regime combines, or break and not as fresh, never the dry fibrid of crossing can be used as adhesive material like that; But, help to improve the porous of final paper structure because it is random, rigidity, irregular shape.Be the object of the invention, fibrid and the flocculate component that those can be taken from dry paper are called dry in advance fibrid of crossing and the dry in advance flocculate of crossing.
The dry paper that contains poly-indoles precursor also can be handled as the turbulent airflow grater that is called turbo-mill or Ultra-Rotor by high-speed grinder, wet then correct grinding.The turbulent airflow grater is preferred for pulverizing the paper of press polish; But grater causes the fibre length that shortens slightly.The present invention uses the paper of the paper pulp with the fibre length that shortens to show the wet strength that reduces slightly and makes the trend of paper machine continuity variation.
But the paper former state by poly-indoles precursor material preparation is used.It has as the experiment part excellent properties shown in further.Yet, by making the performance that can change or improve this paper to the free XH of small part and YH group such as OH group functionalization easily.These free groups can and have the monomer of active group and polymer such as ester, isocyanates, epoxides and other functionalized reagent and react the covalent bond of acquisition between X and/or Y and functionalized reagent.If make part free XH and YH group functionalization, but then these paper also heat treatment polymer precursor being converted into the PBO polymer of closed loop by cyclization process, thereby obtain functionalized PBO paper.
The functionalized of all or part XH and YH group can carry out in each stage of paper technology.Therefore can make (part) XH and YH group functionalization in the following monomer:
Then with monomer ClOOC-Ar
1-COOCl polymerization.Then can handle functionalized polymeric to obtain paper of the present invention by any aforesaid way.Functionalized also can to as polymerization by the monomer precursor polymer or the poly-indoles that obtain carry out.These polymer can contain can be by functionalized XH and/or the YH group with functionalized reagent's reaction.Can any stage in papermaking process make described functionalization of polymers.Therefore can just in time the polymerization of monomer after, make described functionalization of polymers, but its also can fiber, the form of paper pulp, fibril, flocculate or fibrid or functionalized after preparing paper.In the kind method of back, under most of situation, have only the outer surface of fiber, paper pulp, fibril, flocculate or fibrid can be functionalized easily, may be favourable if only need functionalized this of part.In this mode, can prepare its performance by the paper of functionalized change, described performance for example for painted, smoothing, make waterproof, raising or reduce conductibility and the preparation incombustible paper.
Because polymer precursor is synthetic and spinning from the solution of phosphorus-containing compound not, so also phosphorus-containing compound not of gained PBO.Further be no longer need be by insoluble,practically PBO polymer manufacture paper for advantage, and paper technology can utilize easily molten polymer precursor to carry out, and carry out the conversion to PBO after formation paper.
Generally speaking, show the porous lower, thereby make it be very suitable for electrical application such as electrically insulating material than PPTA paper from paper of the present invention.Described paper also is applicable in honeycomb and the construction material.
Shown in EAB (extension at break) and TI (toughness index) data, paper of the present invention (paper and the PBO paper that contain the PBO precursor) has the intensity much larger than known paper.Paper for example of the present invention is better than PPTA paper, even is better than being considered at present known the strongest paper
The extra high intensity of paper of the present invention makes it can prepare extremely thin paper.With PPTA paper and
Compare, paper of the present invention also has excellent heat endurance.Because the unusual intensity of paper of the present invention, therefore can prepare grammes per square metre is 1-16g/m
2Paper.Term " grammes per square metre " is the metric system based on the paper weight of identical square metre of paper, and the grade of paper no matter.
More specifically explain the present invention by following embodiment.Yet the present invention is not limited to these embodiments.
General provisions:
These utilizations as a result have the polymer precursor of following repetitive:
The corresponding closed loop polymer that has following repetitive with utilization obtains:
Ar wherein
1=to phenylene, Ar
2=biphenylene
Abbreviation:
The NMP=N-methyl pyrrolidone
DHB=dihydroxybiphenyl amine (4,4 '-diaminourea-3,3 '-dihydroxybiphenyl)
The TDC=tere-phthaloyl dichloride
The PPD=p-phenylenediamine (PPD)
The PPTA=poly P phenylene diamine terephthalamide
Embodiment 1
Be polymerized to the polybenzoxazole precursor
With 2.25L NMP/CaCl
2(140 ℃, vacuum 24h) adds in the 10L Drais reactor together, stirs 30 minutes so that DHB dissolves with the dry DHB that crosses in advance with 1.75L NMP.Be cooled to after 5 ℃, add TDC, simultaneously continuous stirring (250rpm).Sampling after 50 minutes adds 1.8L NMP.Stirred the mixture 30 minutes, and got another sample, add 1.8L NMP once more.Stirred the mixture 30 minutes, by bottom valve turned letter reactor.By using this program, the polymer concentration of first sample is that the concentration of 7.4%, the second sample (with NMP dilution back) is 5%, and the polymer concentration of end product is 4%.The relative viscosity of product is 3.43.The polymerization procedure that is used for second batch materials is similar, just sampling after 60 minutes, and add 4.0L NMP.Stirred the mixture 30 minutes, then turned letter.By using this program, the polymer concentration of first sample is 7.4%, and the polymer concentration of end product is 4%.The relative viscosity of product is 3.06.Before the spinning polymer material is mixed.
Comparative Examples 1
The polymerization of PPTA poly P phenylene diamine terephthalamide utilizes 160L Drais reactor to carry out.After the intensive drying reactor, with 64L CaCl
2Concentration is the NMP/CaCl of 2.5 weight %
2Add in the reactor.Then, at room temperature add 1522g PPD and make its dissolving.Then PPD solution is cooled to 5 ℃, and adds 2824g TDC.After adding TDC, polymerisation is proceeded 45 minutes.Use calcium oxide/NMP slurry (780g CaO is in NMP) that polymer solution is neutralized then.After adding the CaO slurry, again polymer solution was stirred 30 minutes.Carry out this neutralization to remove the hydrochloric acid (HCl) that in polymerization process, forms.Obtain gel sample polymer solution, PPTA content is 4.5 weight %, and relative viscosity is the 3.0 (H 0.25%
2SO
4In).The η of this product
RelBe 2.4, polymer concentration is 3.6%, and is used for spinning fibrid and paper pulp.Water is used as coagulating agent.
Embodiment 2
Preparation fibrid and paper pulp
By jet spinning nozzle (spinneret orifice is 500 μ m) with the solvent spinning of 20L/h with embodiment 1 and Comparative Examples 1.Add entry by the circular passage of flowing perpendicular to polymer fluid.In the process with the polymer spinning, it is constant that flow velocity keeps, but change coagulating agent pressure to change the SR (° SR) of product at different samples.
Spinning paper pulp
By 1 hole jet spinning nozzle (spinneret orifice is 350 μ m) solvent spinning of embodiment 1 and Comparative Examples 1 is become paper pulp.With solvent spinning in the area of low pressure.By the circular passage of leading to same area air-spray separately, vertically is applied to polymerization feed streams, the expansion of air wherein takes place.Then, in same area, paper pulp is condensed by means of using coagulating agent jet water at the polymer material flow path direction at a certain angle by the circular passage.For spinning has the paper pulp of different SR values (° SR), air pressure is kept constant, but change the polymer flow velocity.After the spinning, wash all samples with water.
The fibrid that obtains in embodiment 2 and the technology and the performance data of paper pulp see Table 1:
Embodiment 3
By fibrid papermaking
100% fibrid by sample A1 and B1-B4 and Comparative Examples D1-D4 and E1 on quick Kothen machine prepares the handsheet with different grammes per square metres.Between two blotting paper under vacuum with the handsheet drying (95 ℃, 1000 millibars, 20 minutes) of dehydration.The paper data see Table 2.What note is to compare with contrast paper, and the thickness of paper of the present invention (paper thickness) is littler, and density is bigger.When comparing under identical grammes per square metre, the TL of paper of the present invention (tensile figure) is than the high 3-5 of contrast paper times based on paper pulp.The EAB of paper of the present invention is also higher.
Table 2: from the performance of the pattern product of fibrid
Embodiment 4
By paper pulp papermaking
Utilizing the program identical with embodiment 3 is about 100g/m by the 100% pulp preparation grammes per square metre of sample A and E on quick Kothen machine
2Handsheet.The paper data see Table 3.
Table 3: from the performance of the pattern product of paper pulp
Embodiment 5
The heat treatment of paper
For above-mentioned poly-indoles precursor paper being converted into poly-indoles paper, under inert atmosphere, heat-treat.Program is as follows: in stream of nitrogen gas sample is enclosed in the stove, and heats with 5 ℃/minute the rate of heat addition.When the temperature that reaches 440 ℃, immediately sample is taken out from stove.The performance data of sample sees Table 4 before and after the heat treatment.At the IR spectrogram that record sample on the Varian FTS-575c infrared spectrometer of Thunderdome ATR annex is housed.Spectrogram has confirmed to be converted into poly-indoles paper, and transforming factor is higher than 95%.Utilize Setaram TGA/DSC 111 in nitrogen, to carry out the TGA experiment.At first the pattern product are cut into pieces, place platinum (opening) chamber then.Specimen in use weight is 10-20mg.With 10 ℃/minute the rates of heat addition sample is heated to 20-700 ℃.Under the temperature of finding 1 weight % weightlessness, measure the Td that begins to degrade.Under the situation of sample B5 and A1, transform the back fully 250-400 ℃ of generation and measure Td.The results are shown in Table 4.
Table 4
Embodiment 6
Prepare functionalized paper
According to following program with active colouring agent (the dark blue S-GL of Cibacron; From Ciba, Switzerland) polybenzoxazole paper and PPTA paper (the pattern product D1) dyeing that obtains with precursor paper (pattern product B5), by heat treatment precursor paper (pattern product B6): 80 ℃ down preparation 6 restrain the solution of NaCl in the 200mL demineralized water.After adding the dark blue S-GL of 0.4g Cibacron,, and be cooled to 60 ℃ with solution stirring 20 minutes.Add 4.3 gram Na
2CO
310H
2O obtained dyeing liquid in 30 minutes with solution stirring under 60 ℃.
60 ℃ down separately length be that 5cm and width are that sample B5, the B6 of 1cm and D1 immersed in the dyeing liquid 45 minutes, then rinsing 10 minutes in about 50 ℃ flowing water.In 1% acetic acid is bathed with the sample neutralization, and with mobile cold water washing 15 minutes.
Table 5: the color behind primitive color and the dye paper sample
The invention provides with the aromatic polyamides that can be used for promoting that aromatic polyamides is functionalized with the reactive functional groups that combines the object combination.As shown in table 5, compare with sample B6 with not functionalized aromatic polyamides D1, functionalized aromatic polyamides (sample B5) shows excellent stainability, and sample B6 is because by B5 heat treatment is not contained reactive functional groups for B6 transforms fully, it has the polybenzoxazole structure of complete closed loop.
Claims (13)
1. at least a paper that contains in fiber, paper pulp, fibril, flocculate and the fibrid, described fiber, paper pulp, fibril, flocculate and fibrid contain have formula (I) and/or (II) the poly-indole structure of repetitive:
Or it has the front body structure of formula (III) repetitive:
Ar wherein
1And Ar
2Independent for have 4-12 carbon atom to or an aryl, X and Y are identical or different and be selected from O, S and NH; With n be 0 or 1, wherein said paper does not contain or does not contain substantially inextractable phosphorus compound.
2. the paper of claim 1, described paper can by do not contain or do not make about equimolar amounts substantially in the liquid of phosphoric acid have a formula ClOOC-Ar
1The monomer of-COOCl and
Ar wherein
1And Ar
2Independent for have 4-12 carbon atom to or an aryl, X and Y are identical or different and be selected from O, S and NH; With n be 0 or 1,
Be polymerized to the front body structure that contains formula (III) repetitive:
Ar wherein
1, Ar
2, X, Y and n have the implication that above provides,
Optional then by with described front body structure cyclisation for have formula (I) and/or (II) the poly-indole structure of repetitive obtain:
Ar wherein
1, Ar
2, X and Y have the implication that above provides.
3. claim 1 or 2 paper, wherein to small part XH and/or YH be functionalized.
4. each paper among the claim 1-3, described paper has 1-16g/m
2Grammes per square metre.
5. each paper among the claim 1-4, described paper contains the mixture of at least a and PPTA fibrid in fiber, paper pulp, fibril, flocculate and the fibrid, and described fiber, paper pulp, fibril, flocculate and fibrid have the poly-indoles front body structure of formula (I) and/or poly-indole structure (II) or formula (III).
6. method for preparing each paper among the claim 1-5, described method be included in do not contain or do not make about equimolar amounts substantially in the liquid of phosphoric acid have a formula ClOOC-Ar
1The monomer of-COOCl and
Ar wherein
1And Ar
2Independent for have 4-12 carbon atom to or an aryl, X and Y are identical or different and be selected from O, S and NH; With n be 0 or 1,
Be polymerized to the front body structure that contains repetitive shown in the formula (III):
Ar wherein
1, Ar
2, X, Y and n have the implication that above provides,
Optional then under heating and in the inert atmosphere with described front body structure cyclisation for having the formula (I) and/or (II) the poly-indole structure of repetitive:
Ar wherein
1, Ar
2, X and Y have the implication that above provides,
Then prepare fiber, paper pulp, fibril, flocculate or fibrid by described precursor or poly-indole structure, then prepare its paper by traditional paper technology, optional is one or more following steps afterwards: press polish step, heating steps, drying steps and functionalisation step.
7. according to the method for claim 6, Ar wherein
2Functionalized to small part XH and/or YH group by handle monomer and/or front body structure and/or poly-indole structure with the functionalized reagent.
8. method for preparing each paper among the claim 1-5, described method be included in do not contain or do not make about equimolar amounts substantially in the liquid of phosphoric acid have a formula ClOOC-Ar
1The monomer of-COOCl and
Ar wherein
1And Ar
2Independent for have 4-12 carbon atom to or an aryl, X and Y are identical or different and be selected from O, S and NH; With n be 0 or 1,
Be polymerized to the precursor of (III) repetitive that has formula:
Ar wherein
1, Ar
2, X, Y and n have the implication that above provides,
Then by described precursor preparation fiber, paper pulp, fibril, flocculate or fibrid, then prepare its paper with traditional paper technology, optional is one or more following steps afterwards: press polish step, heating steps, drying steps and functionalisation step.
9. according to the method for claim 7, wherein with the paper that obtains in inert atmosphere in making the have formula poly-indoles precursor cyclisation of (III) for containing formula (I) and/or (II) heating under the temperature of the poly-indoles of structure.
10. according to Claim 8 or 9 method, wherein Ar
2Functionalized to small part XH and/or YH group by handle monomer and/or front body structure and/or poly-indole structure with the functionalized reagent.
11. a method for preparing each paper among the claim 6-10 comprises and uses traditional paper technology, described method is also used at least a in fiber, paper pulp, fibril, flocculate and the fibrid with structure I V:
Ar wherein
1Structure division independently has the implication that above provides.
12. an electrically insulating material, described material contain among the claim 1-5 each paper.
13. the purposes of each paper in preparation electrically insulating material, honeycomb or construction material among the claim 1-5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07017825.6 | 2007-09-12 | ||
| EP07017825A EP2037039A1 (en) | 2007-09-12 | 2007-09-12 | Paper comprising polybenzazole or precursor thereof |
| PCT/EP2008/061554 WO2009033983A1 (en) | 2007-09-12 | 2008-09-02 | Paper comprising polybenzazole or precursor thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101802302A true CN101802302A (en) | 2010-08-11 |
Family
ID=39201583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880106946A Pending CN101802302A (en) | 2007-09-12 | 2008-09-02 | Paper comprising polybenzazole or precursor thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20110083820A1 (en) |
| EP (2) | EP2037039A1 (en) |
| JP (1) | JP2010539341A (en) |
| CN (1) | CN101802302A (en) |
| WO (1) | WO2009033983A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114790664A (en) * | 2021-01-26 | 2022-07-26 | 中国科学院化学研究所 | High-strength polyphenylene benzobisoxazole paper base material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150354144A1 (en) * | 2013-03-01 | 2015-12-10 | Jiansheng Chen | An electrically insulating composite material and an electrical device comprising the same |
| JP6424518B2 (en) * | 2014-09-01 | 2018-11-21 | 東洋紡株式会社 | Polybenzazole pulp |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4533693A (en) * | 1982-09-17 | 1985-08-06 | Sri International | Liquid crystalline polymer compositions, process, and products |
| GB2191496A (en) * | 1986-05-30 | 1987-12-16 | Central Glass Co Ltd | Method of preparing aromatic polyamides and polybenzoxazoles |
| US4917714A (en) * | 1988-12-08 | 1990-04-17 | James River Corporation | Filter element comprising glass fibers |
| US5294390A (en) * | 1992-12-03 | 1994-03-15 | The Dow Chemical Company | Method for rapid spinning of a polybenzazole fiber |
| US5756040A (en) * | 1994-08-03 | 1998-05-26 | Toyobo Co., Ltd. | Process of making polybenzazole nonwoven fabric |
| JPH1096175A (en) * | 1996-09-17 | 1998-04-14 | Toyobo Co Ltd | Highly heat resistant label |
| JPH11181093A (en) * | 1997-12-24 | 1999-07-06 | Toyobo Co Ltd | Production of polybenzazole |
| JP2001248091A (en) * | 2000-03-01 | 2001-09-14 | Toyobo Co Ltd | Highly heat resistant and highly flame retardant organic fiber paper and composite material using the same fiber paper |
| US6890636B2 (en) * | 2000-04-11 | 2005-05-10 | Sordal Incorporated | Thermally stable, non-woven, fibrous paper, derivatives thereof, and methods for manufacturing the same |
| US20060046049A1 (en) * | 2002-06-26 | 2006-03-02 | Yukihiro Abe | Highly durable polybenzazole composition, fiber and film |
| JP2007063399A (en) * | 2005-08-31 | 2007-03-15 | Teijin Techno Products Ltd | Wet friction material and method for producing the same |
| US7740741B2 (en) * | 2005-12-21 | 2010-06-22 | E.I. Du Pont De Nemours And Company | Para-aramid pulp including meta-aramid fibrids and processes of making same |
| US7727356B2 (en) * | 2005-12-21 | 2010-06-01 | E.I. Du Pont De Nemours And Company | Polyareneazole/wood pulp and methods of making same |
| WO2007076332A2 (en) * | 2005-12-21 | 2007-07-05 | E. I. Du Pont De Nemours And Company | Polypyridobisimidazole pulp and a process for making same |
| US7727358B2 (en) * | 2005-12-21 | 2010-06-01 | E.I. Du Pont De Nemours And Company | Pulp comprising polypyridobisimidazole and other polymers and methods of making same |
| JP2007177113A (en) * | 2005-12-28 | 2007-07-12 | Teijin Techno Products Ltd | Organic macromolecular polymer fine particle and method for producing the same |
| CN101687988A (en) * | 2007-04-30 | 2010-03-31 | 帝人芳纶有限公司 | polybenzazoles and polybenzazole precursors |
| US8268434B2 (en) * | 2007-11-30 | 2012-09-18 | E I Du Pont De Nemours And Company | Honeycomb having a high compression strength and articles made from same |
-
2007
- 2007-09-12 EP EP07017825A patent/EP2037039A1/en not_active Withdrawn
-
2008
- 2008-09-02 CN CN200880106946A patent/CN101802302A/en active Pending
- 2008-09-02 US US12/674,819 patent/US20110083820A1/en not_active Abandoned
- 2008-09-02 WO PCT/EP2008/061554 patent/WO2009033983A1/en active Application Filing
- 2008-09-02 JP JP2010524454A patent/JP2010539341A/en not_active Withdrawn
- 2008-09-02 EP EP08803525A patent/EP2191067B1/en not_active Not-in-force
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114790664A (en) * | 2021-01-26 | 2022-07-26 | 中国科学院化学研究所 | High-strength polyphenylene benzobisoxazole paper base material |
| CN114790664B (en) * | 2021-01-26 | 2023-02-24 | 中国科学院化学研究所 | High-strength polyphenylene benzobisoxazole paper base material |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2191067B1 (en) | 2012-06-20 |
| EP2037039A1 (en) | 2009-03-18 |
| WO2009033983A1 (en) | 2009-03-19 |
| JP2010539341A (en) | 2010-12-16 |
| US20110083820A1 (en) | 2011-04-14 |
| EP2191067A1 (en) | 2010-06-02 |
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