CN106220848A - Melt temperature and vitrification point difference fire resistant polyimide less than 30 degree and preparation method thereof - Google Patents
Melt temperature and vitrification point difference fire resistant polyimide less than 30 degree and preparation method thereof Download PDFInfo
- Publication number
- CN106220848A CN106220848A CN201610583530.2A CN201610583530A CN106220848A CN 106220848 A CN106220848 A CN 106220848A CN 201610583530 A CN201610583530 A CN 201610583530A CN 106220848 A CN106220848 A CN 106220848A
- Authority
- CN
- China
- Prior art keywords
- double
- amino
- benzene
- fire resistant
- degree
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention belongs to polymeric material field, specifically disclose melt temperature and vitrification point difference fire resistant polyimide being less than 30 degree and preparation method thereof, the monomer of preparing of described fire resistant polyimide includes: dianhydride monomer, diamine monomer；Described diamine monomer includes aromatic diamines, imidazoles diamidogen.The preparation method of described fire resistant polyimide, at least comprises the following steps: dianhydride monomer, diamine monomer carry out polycondensation reaction.In the present invention, its melt temperature of fire resistant polyimide and vitrification point difference are less than 30 degree, are highly suitable for 3D and print field.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of melt temperature and be less than 30 degree with vitrification point difference
Fire resistant polyimide and preparation method thereof.
Background technology
3D printing technique is as emerging materials processing forming technique, it has also become the important symbol of the 3rd industrial revolution it
One.3D prints, and originates from late 1970s to the beginning of the eighties, and the technical advantage of its key is to use digitized means quick
Manufacture the labyrinth goods of unlike material, can be applicable to some high-grade, precision and advanced advanced manufacture fields, technical process energy-saving material-saving.
Traditional subtracts material manufacturing technology, typically uses cutting, grinding, corrodes and melt etc. method, obtains the goods of given shape, then lead to
Crossing the Combination of Methods such as assembly, welding and become goods, fabrication cycle is longer, complex procedures, and product rejection rate is high, and cost is high.Carry on the back at this
Under scape, 3D prints rapid shaping technique and gradually grows up.
The operation principle of 3D printing technique is similar to inkjet printing, and i.e. the digital signal of RESPONSE CALCULATION machine, makes nozzle operation
Molten state material or the binding agent of intracavity form drop in moment, and squeeze out from nozzle with certain speed, are ejected into and prop up
In hold mode type, form the shape of profile, continue successively jet-stacking after thin layer solidification, obtain the molded component that precision is high.
Moulding material according to injection is different, and 3D printing technique can be divided into adhesive-powder 3D to print, light-cured resin 3D
Print and melted 3D prints three kinds of techniques.It is to spray liquid adhesive to layer of powder material, successively that adhesive-powder 3D prints
Bonding shaping；Light-cured resin 3D prints and uses liquid photosensitive resin to spray, and carries out solidified forming with ultraviolet light.Melted 3D
Macromolecular material is sent to high temperature heat source and melts by printing, then extrusion molten state macromolecule continuously, successively piles up profiled member, after
Process technique is simple, and 3DSystems company has been developed for spraying the 3D printer of thermoplastic.
The current kind of polymeric material that can be used for 3D printing is less, and that has reported mainly has acrylonitrile-butadiene-benzene second
Alkene terpolymer (ABS) and polylactic acid (PLA), wherein ABS resin have the graft copolymer with elastomer as main chain and with
Resin is the biphase heterogeneous system structure of the graft copolymer of main chain so that it is have the high chemical stability of acrylonitrile, oil resistant concurrently
Property and case hardness, the toughness of butadiene and tolerance to cold, the combination property such as cinnamic good dielectricity, gloss and processability.
But its intensity is the highest, and along with molecular weight increases, processing characteristics declines.And PLA poor mechanical property, easily there is brittle fracture,
Limit its processing characteristics.So, develop novel 3D printing functionalized polymer material to making up restriction 3D and print field
Fast-developing short slab significant.
Polyimides (polyimide, PI) be on main chain containing imide ring to have excellent heat resistance, chemically-resistant stable
Property, mechanical property and a family macromolecule material of electrical property, be possible not only in traditional Aeronautics and Astronautics and defense-related science, technology and industry
As structural resin based composites and special material, it is used as insulant in the electronics industry, in some current techiques
It is used as heat absorption and sound-absorbing material, structural adhesive and protective coating, and progressively starts in integrated circuit, liquid crystal display, luminescence
The high-tech areas such as device, fuel cell, optical-fibre communications, gas separation are widely used.Although standard type PI is in work
It is widely used in industry, but the application in some high-tech sectors at present, as 3D prints field, but special due to it
Molecular structure and be limited by very large, be mainly manifested in processing more difficulty.The vitrification point of polyimides is general
More than 260 degree, if its melt temperature is at 400 degree or lower, (current 3D printer is difficult to be printed by melt mode melt
Change the temperature consumptive material more than 400 degree), it is likely that printed by 3D and be prepared as the personalized workpiece that people need, as now
UAV, many parts on microrobot, such as miniature gears, miniature bent axle, miniature connecting rod etc..
Therefore, it is highly desirable to the adjustment by polyimide structures, is applicable to 3D printing technique synthesizing one
Fire resistant polyimide.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of melt temperature resistance to less than 30 degree poor with vitrification point
High temperature polyimide, the monomer of preparing of described fire resistant polyimide includes: dianhydride monomer, diamine monomer；Described diamine monomer
Including aromatic diamines, imidazoles diamidogen.
In a preferred embodiment, described aromatic diamines, the mol ratio of imidazoles diamidogen are: 1:(1～9).
In a preferred embodiment, described aromatic diamines, the mol ratio of imidazoles diamidogen are: 1:(2～5).
In a preferred embodiment, described aromatic diamines, the mol ratio of imidazoles diamidogen are: 1:3.
In a preferred embodiment, described dianhydride monomer is selected from: 3,3 '-(isophthalic two epoxide) double (O-phthalics
Anhydride), pyromellitic acid anhydride, the double phthalic anhydride of 4,4 '-oxygen, hexafluoro isopropyl phthalic anhydride, 3,3 ', 4,4 '-
Biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 5,5 '-[[1,1 '-xenyl]-4,4 '-dioxy] two-
Phthalic anhydride, 3,3 ', 4,4 '-sulfobenzide. tetrabasic carboxylic acid dicarboxylic anhydride, 1,4-bis-(3,4-di carboxyl phenyloxy) benzene dianhydride, 5,
5 '-oxo (4,1-phenoxy group)] double phthalic anhydrides, 4,4 '-(hexafluoro isopropyl)-two-(to phenoxy group) phthalic acid
Any one or a few mixing in acid anhydride, 1,4,5,8-naphthalene dianhydride, 3,4,9,10-tetracarboxylic acid dianhydride.
In a preferred embodiment, described aromatic diamines is selected from: p-phenylenediamine, benzidine, 4,4 '-diaminourea
Diphenyl ether, 1,4 ,-bis-(4-amino-benzene oxygen) benzene, 1,4 ,-bis-(3-amino-benzene oxygen) benzene, 1,3 ,-bis-(4-amino-benzene oxygens)
Double (the 4-amino-benzene oxygen)-3 of benzene, 2,5-'-trifluoromethyl-biphenyl, double (the 4-amino-benzene oxygen)-3 of 2,5-', 5 '-two (fluoroforms
Base) biphenyl, double (4-amino-2-4-trifluoromethylphenopendant) benzene of 1,4-, double (3-amino-5-4-trifluoromethylphenopendant) benzene of 1,4-,
Double (3-amino-benzene oxygen) benzonitrile of double (4-amino-benzene oxygen) benzonitrile of 2,6-, 2,6-, double (4-amino-benzene oxygen) benzonitrile of 2,4-, 2,
Double (3-amino-benzene oxygen) benzonitrile of 4-, double (2-cyano group-4-amino-benzene oxygen) benzene of 1,4-, the double (2-cyano group-4-aminobenzene oxygen of 2,5-
Base) cyanophenyl, 3,6-be double-(2-cyano group-4-amino-benzene oxygen) phthalic nitrile, double (4-amino-benzene oxygen) four fluorobenzenes of 1,4-, 1,
Double (3-the amino-4-hydroxylphenyl)-HFC-236fa of double (4-amino-2-4-trifluoromethylphenopendant) four fluorobenzenes of 4-, 2,2-, 3,
3 '-dihydroxy-2,2-bis-(4-aminophenyl), 3,3 '-dihydroxybiphenyl amine, benzidine-2,2 '-disulfonic acid, 4,4 '-diaminourea
Diphenyl ether-2,2 ' any one or a few mixing in-disulfonic acid.
In a preferred embodiment, described imidazoles diamidogen is selected from: 2-(4-aminophenyl)-5 aminophenyl benzo
Imidazoles, 2-amino-1H-imidazoles-5-ethamine, 5-(3-aminopropyl)-1H-imidazoles-2-amine, 2,2 '-bis-(4-aminophenyls)-5,
5 '-bibenzimidaz sigmale, 2,2 '-bis-(3-aminophenyls)-5,5 '-bisbenzimidazole, 2,2 '-bis-(4-aminophenyl) benzo miaows
In azoles, 2,2 '-bis-(3-aminophenyl) benzimidazoles, 4,5-imidazoles diamides, 1H-benzo [d] imidazoles-5,6-diamidogen any one
Kind or several mixing.
Another aspect provides the high temperature resistant polyamides that a kind of melt temperature is less than 30 degree with vitrification point difference
The preparation method of imines, at least comprises the following steps: dianhydride monomer, diamine monomer carry out polycondensation reaction.
In a preferred embodiment, the temperature that described polycondensation reaction is used is :-10 DEG C～0 DEG C.
The another aspect of the present invention provides fire resistant polyimide as above and prints the application in field at 3D.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Detailed description of the invention
Participate in the election of the detailed description being preferable to carry out method of the invention below and the embodiment that includes can be more easily understood this
Bright content.Unless otherwise defined, all technology used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, it is as the criterion with the definition in this specification.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " including ",
" have ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.Such as, the combination of listed elements is comprised
Thing, step, method, goods or device are not necessarily solely those key elements, but can include other not expressly listed key element or
The key element that this kind of compositions, step, method, goods or device are intrinsic.
Conjunction " Consists of " gets rid of any key element, step or component do not pointed out.If in claim, this
Phrase will make claim be closed so that it is does not comprise the material in addition to the material that those describe, but relative often
Except rule impurity.When being rather than immediately following during phrase " Consists of " occurs in the clause of claim main body after theme,
It is only limited to the key element described in this clause；Other key element is not excluded outside as overall described claim.
Equivalent, concentration or other value or parameter are excellent with scope, preferred scope or a series of upper limit preferred value and lower limit
During the Range Representation that choosing value limits, this is appreciated that and specifically discloses by any range limit or preferred value and any scope
All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether this scope separately discloses.Such as, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numerical range is described in this article, unless otherwise indicated, otherwise this scope is intended to include its end
Value and all integers within the range and mark.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or " arbitrarily
A kind of " refer to that the item described thereafter or event may or may not occur, and this description include situation that event occurs with
The situation that event does not occurs.
Approximation term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this concrete
Quantity, also includes close to this quantity acceptable without causing the part of the correction of the change of relevant basic function.Phase
Answer, modify a numerical value with " about ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximation
Term likely corresponds to measure the precision of the instrument of numerical value.In present specification and claims, scope limits permissible
Combination and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
Additionally, indefinite article " a kind of " before key element of the present invention or component and " one " are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one or at least one, and odd number
The key element of form or component also include plural form, unless the obvious purport of described quantity refers to singulative.
" copolymer " means the polymer prepared by polymerization at least two different monomers.Generic term " copolymer " includes
(it is general with term " terpolymer " for term " copolymer " (it is typically in order to refer to the polymer prepared by two kinds of different monomers)
In order to refer to the polymer prepared by three kinds of different monomers).It also comprises the polymerization manufactured by polymerization four or more kinds of monomers
Thing." blend " mean two or more polymer by physics or the method for chemistry jointly mix and the polymerization that formed
Thing.
The first aspect of the invention provides high temperature resistant less than 30 degree of a kind of melt temperature and vitrification point difference and gathers
Acid imide, the monomer of preparing of described fire resistant polyimide includes: dianhydride monomer, diamine monomer；Described diamine monomer includes virtue
Fragrant diamidogen, imidazoles diamidogen.
In a preferred embodiment, described aromatic diamines, the mol ratio of imidazoles diamidogen are: 1:(1～9).
In a preferred embodiment, described aromatic diamines, the mol ratio of imidazoles diamidogen are: 1:(2～5).
In a preferred embodiment, described aromatic diamines, the mol ratio of imidazoles diamidogen are: 1:3.
In a preferred embodiment, described dianhydride monomer is selected from: 3,3 '-(isophthalic two epoxide) double (O-phthalics
Anhydride), pyromellitic acid anhydride, the double phthalic anhydride of 4,4 '-oxygen, hexafluoro isopropyl phthalic anhydride, 3,3 ', 4,4 '-
Biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 5,5 '-[[1,1 '-xenyl]-4,4 '-dioxy] two-
Phthalic anhydride, 3,3 ', 4,4 '-sulfobenzide. tetrabasic carboxylic acid dicarboxylic anhydride, 1,4-bis-(3,4-di carboxyl phenyloxy) benzene dianhydride, 5,
5 '-oxo (4,1-phenoxy group)] double phthalic anhydrides, 4,4 '-(hexafluoro isopropyl)-two-(to phenoxy group) phthalic acid
Any one or a few mixing in acid anhydride, 1,4,5,8-naphthalene dianhydride, 3,4,9,10-tetracarboxylic acid dianhydride.
Dianhydride monomer in the present invention is preferably 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides).
The concrete synthetic route chart of 3,3 ' in the present invention-(isophthalic two epoxide) double (phthalic anhydrides) is:
The preparation method of described 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides) comprises the following steps:
(1) 3-monochloro phthalic anhydride is dissolved in acetic anhydride, to being completely dissolved, adds methylamine water solution, heating
After reaction 3.5-5h, it is cooled to room temperature, and is cooled to less than 10 DEG C with frozen water, filter, be dried, obtain product A；
(2) the product A in step (1) is dissolved in dimethyl sulfoxide with resorcinol, to being completely dissolved, adds catalyst
And heating reflux reaction, in course of reaction TLC follow the trail of resorcinol, to system without resorcinol after, continuation back flow reaction
0.5-2h, subsequently sucking filtration, cool down, wash, be centrifuged, be dried, obtain product B；
(3) the product B in step (2) is mixed with sodium hydroxide solution, be heated to boiling, anti-after solid dissolves
Answering 0.5-2h, being subsequently added concentrated hydrochloric acid regulation pH is 7-8, continues to boil 5-15min, is filtered to remove insoluble solids, filtrate is added
Heat is to boiling, and is 1-2 with concentrated hydrochloric acid regulation pH, and cooling obtains product C；
(4) the product C in step (3) is mixed with dehydrant, agitating heating, dewatering and filtering, wash, be dried, i.e.
Obtain 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides).
In a preferred embodiment, described aromatic diamines is selected from: p-phenylenediamine, benzidine, 4,4 '-diaminourea
Diphenyl ether, 1,4 ,-bis-(4-amino-benzene oxygen) benzene, 1,4 ,-bis-(3-amino-benzene oxygen) benzene, 1,3 ,-bis-(4-amino-benzene oxygens)
Double (the 4-amino-benzene oxygen)-3 of benzene, 2,5-'-trifluoromethyl-biphenyl, double (the 4-amino-benzene oxygen)-3 of 2,5-', 5 '-two (fluoroforms
Base) biphenyl, double (4-amino-2-4-trifluoromethylphenopendant) benzene of 1,4-, double (3-amino-5-4-trifluoromethylphenopendant) benzene of 1,4-,
Double (3-amino-benzene oxygen) benzonitrile of double (4-amino-benzene oxygen) benzonitrile of 2,6-, 2,6-, double (4-amino-benzene oxygen) benzonitrile of 2,4-, 2,
Double (3-amino-benzene oxygen) benzonitrile of 4-, double (2-cyano group-4-amino-benzene oxygen) benzene of 1,4-, the double (2-cyano group-4-aminobenzene oxygen of 2,5-
Base) cyanophenyl, 3,6-be double-(2-cyano group-4-amino-benzene oxygen) phthalic nitrile, double (4-amino-benzene oxygen) four fluorobenzenes of 1,4-, 1,
Double (3-the amino-4-hydroxylphenyl)-HFC-236fa of double (4-amino-2-4-trifluoromethylphenopendant) four fluorobenzenes of 4-, 2,2-, 3,
3 '-dihydroxy-2,2-bis-(4-aminophenyl), 3,3 '-dihydroxybiphenyl amine, benzidine-2,2 '-disulfonic acid, 4,4 '-diaminourea
Diphenyl ether-2,2 ' any one or a few mixing in-disulfonic acid.
Aromatic diamines in the present invention is preferably p-phenylenediamine.
In a preferred embodiment, described imidazoles diamidogen is selected from: 2-(4-aminophenyl)-5 aminophenyl benzo
Imidazoles, 2-amino-1H-imidazoles-5-ethamine, 5-(3-aminopropyl)-1H-imidazoles-2-amine, 2,2 '-bis-(4-aminophenyls)-5,
5 '-bibenzimidaz sigmale, 2,2 '-bis-(3-aminophenyls)-5,5 '-bisbenzimidazole, 2,2 '-bis-(4-aminophenyl) benzo miaows
In azoles, 2,2 '-bis-(3-aminophenyl) benzimidazoles, 4,5-imidazoles diamides, 1H-benzo [d] imidazoles-5,6-diamidogen any one
Kind or several mixing.
Imidazoles diamidogen in the present invention is preferably 2-(4-aminophenyl)-5 aminophenyl benzimidazole.
Another aspect provides the high temperature resistant polyamides that a kind of melt temperature is less than 30 degree with vitrification point difference
The preparation method of imines, at least comprises the following steps: dianhydride monomer, diamine monomer carry out polycondensation reaction.
In a preferred embodiment, the temperature that described polycondensation reaction is used is :-10 DEG C～0 DEG C.
Concretely comprise the following steps: in room temperature, the dianhydride powder weighed up under agitation is joined in the DMAc solution of diamidogen, stirring
About 6h obtains the polyamic acid solution that solid content is about 10%, adds end-capping reagent phthalic anhydride afterwards, continues stirring 20h and obtains benzene
The polyamic acid solution of acid anhydride end-blocking.It is subsequently added into a certain amount of anhydride and triethylamine carries out chemical imidization, after about reacting 20h
Precipitating in ethanol, the polyimide powder ethanol being settled out extracts 200 DEG C of heat treatments of final vacuum in apparatus,Soxhlet's
1h obtains polyimides sample, referred to as initial sample.
The another aspect of the present invention provides fire resistant polyimide as above and prints the application in field at 3D.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some nonessential improvement and adjustment that content according to the invention described above is made, still fall within protection scope of the present invention.
Illustrating without other, example below, comparative example are raw materials used is all commercially available.
Embodiment
Embodiment 1:
Embodiments of the present invention 1 provide the high temperature resistant polyamides that a kind of melt temperature is less than 30 degree with vitrification point difference
Imines, it is characterised in that the monomer of preparing of described fire resistant polyimide includes: dianhydride monomer, diamine monomer；Described diamidogen list
Body includes aromatic diamines, imidazoles diamidogen.
Embodiment 2:
Embodiments of the present invention 2 are identical with embodiment 1, and difference is, described aromatic diamines, the rubbing of imidazoles diamidogen
That ratio is: 1:(1～9).
Embodiment 3:
Embodiments of the present invention 3 are identical with embodiment 2, and difference is, described aromatic diamines, the rubbing of imidazoles diamidogen
That ratio is: 1:(2～5).
Embodiment 4:
Embodiments of the present invention 4 are identical with embodiment 3, and difference is, described aromatic diamines, the rubbing of imidazoles diamidogen
That ratio is: 1:3.
Embodiment 5:
Embodiments of the present invention 5 are identical with embodiment 1, and difference is, described dianhydride monomer is selected from: 3,3 '-(
Benzene two epoxide) double (phthalic anhydrides), pyromellitic acid anhydride, 4,4 '-oxygen double phthalic anhydride, hexafluoro isopropyl neighbour's benzene
Dicarboxylic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 5,5 '-[[1,1 '-connection
Phenyl]-4,4 '-dioxy] two-phthalic anhydride, 3,3 ', 4,4 '-sulfobenzide. tetrabasic carboxylic acid dicarboxylic anhydride, 1,4-bis-(3,4-bis-
Carboxyphenoxy) benzene dianhydride, 5,5 '-oxo (4,1-phenoxy group)] double phthalic anhydrides, 4,4 '-(hexafluoro isopropyl)-two-
In (to phenoxy group) phthalic anhydride, 1,4,5,8-naphthalene dianhydride, 3,4,9,10-tetracarboxylic acid dianhydride any one or a few
Mixing.
Embodiment 6:
Embodiments of the present invention 6 are identical with embodiment 1, and difference is, described aromatic diamines is selected from: to benzene two
Amine, benzidine, 4,4 '-diaminodiphenyl ether, 1,4 ,-bis-(4-amino-benzene oxygen) benzene, 1,4 ,-bis-(3-amino-benzene oxygens)
Benzene, 1,3, double (the 4-amino-benzene oxygen)-3 of-bis-(4-amino-benzene oxygen) benzene, 2,5-'-trifluoromethyl-biphenyl, double (the 4-amino of 2,5-
Phenoxy group)-3 ', double (4-amino-2-4-trifluoromethylphenopendant) benzene of 5 '-two (trifluoromethyl) biphenyl, 1,4-, double (the 3-ammonia of 1,4-
Base-5-4-trifluoromethylphenopendant) benzene, double (4-amino-benzene oxygen) benzonitrile of 2,6-, 2,6-double (3-amino-benzene oxygen) benzonitrile, 2,4-
Double (2-cyano group-4-amino-benzene oxygen) benzene of double (3-amino-benzene oxygen) benzonitrile of double (4-amino-benzene oxygen) benzonitrile, 2,4-, 1,4-,
Double (2-cyano group-4-amino-benzene oxygen) cyanophenyl of 2,5-, 3,6-be double-and (2-cyano group-4-amino-benzene oxygen) phthalic nitrile, 1,4-be double
Double (4-amino-2-4-trifluoromethylphenopendant) four fluorobenzenes of (4-amino-benzene oxygen) four fluorobenzenes, 1,4-, 2,2-double (3-amino-
4-hydroxy phenyl)-HFC-236fa, 3,3 '-dihydroxy-2,2-bis-(4-aminophenyl), 3,3 '-dihydroxybiphenyl amine, benzidine-
2,2 '-disulfonic acid, 4,4 '-diaminodiphenyl ether-2,2 ' any one or a few mixing in-disulfonic acid.
Embodiment 7:
Embodiments of the present invention 7 are identical with embodiment 1, and difference is, described imidazoles diamidogen is selected from: 2-(4-ammonia
Base phenyl)-5 aminophenyl benzimidazoles, 2-amino-1H-imidazoles-5-ethamine, 5-(3-aminopropyl)-1H-imidazoles-2-amine,
2,2 '-bis-(4-aminophenyls)-5,5 '-bibenzimidaz sigmale, 2,2 '-bis-(3-aminophenyls)-5,5 '-bisbenzimidazole, 2,2 '-
Double (4-aminophenyl) benzimidazole, 2,2 '-bis-(3-aminophenyl) benzimidazoles, 4,5-imidazoles diamides, 1H-benzo [d]
Any one or a few mixing in imidazoles-5,6-diamidogen.
Embodiment 8:
Embodiments of the present invention 8 provide the high temperature resistant polyamides that a kind of melt temperature is less than 30 degree with vitrification point difference
The preparation method of imines, at least comprises the following steps: dianhydride monomer, diamine monomer carry out polycondensation reaction.
Embodiment 9:
Embodiments of the present invention 9 are identical with embodiment 8, and difference is, the temperature that described polycondensation reaction is used
For :-10 DEG C～0 DEG C.
Embodiment 10:
Embodiments of the present invention 8 provide the high temperature resistant polyamides that a kind of melt temperature is less than 30 degree with vitrification point difference
Imines prints the application in field at 3D.
Specific embodiment
Embodiment 1:
The melt temperature that embodiments of the invention 1 provide and the vitrification point difference high temperature resistant polyamides less than 30 degree is sub-
Amine, the monomer of preparing of described fire resistant polyimide includes: dianhydride monomer, diamine monomer, described dianhydride monomer is 3,3 '-(
Benzene two epoxide) double (phthalic anhydrides)；Described diamine monomer is p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzene
And the mixture of imidazoles, and the mol ratio of p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzimidazole is: 1:1.
The synthetic method of 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides) comprises the following steps:
(1) 3-monochloro phthalic anhydride is placed in reaction vessel, 3-monochloro phthalic anhydride is pressed with acetic anhydride
According to the proportioning of 13g:45ml, add acetic anhydride, at 50 DEG C, stir 30min, be completely dissolved to 3-monochloro phthalic anhydride, will
3-monochloro phthalic anhydride and methylamine water solution are according to the proportioning of 13g:9ml, and the methylamine adding mass fraction 30% is water-soluble
Liquid, is heated to reflux, and after toluene band water reaction 3.5-5h, is cooled to room temperature, and is cooled to less than 10 DEG C with frozen water, filters, is dried,
Obtain product A；
(2) by the product A that weighs according to the quality proportioning of 1.5:1 in step (1) with resorcinol in reaction vessel, and
Adding the dimethyl sulfoxide of 100ml, stirring makes raw material be completely dissolved, adds the potassium carbonate of mass fraction is total raw material 2%
And be heated to reflux, in course of reaction TLC follow the trail of resorcinol, to system without resorcinol after, continuation back flow reaction 0.5-2h,
The most while hot, removing catalyst and the by-product of generation of excess, filtrate is cooled to room temperature, pours in water and is stirred continuously,
The precipitation machine by centrifugation that separates out is centrifugal obtains solid, obtains solid through hydrochloric acid acidifying, washing, dried, using dehydrated alcohol as
Solvent also removes the Resorcino filtered with cable type extractor according, then with chloroform, until TLC inspection does not measures resorcinol, i.e.
Obtain product B；
(3) the product B in step (2) is entered according to 4g:26ml proportioning with the sodium hydroxide solution that mass fraction is 22%
Row mixing, is heated to boiling, reacts 0.5-2h after solid dissolves, and is subsequently added the concentrated hydrochloric acid regulation pH that mass fraction is 38%
For 7-8, continue to boil 5-15min, be filtered to remove insoluble solids, filtrate is heated to boiling, and is 38% with mass fraction
Concentrated hydrochloric acid regulation pH is 1-2, and cooling obtains product C；
(4) the product C in step (3) is mixed with acetic anhydride, is heated with stirring to 120 DEG C, dewatering and filtering, washing,
Being dried, obtain 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides), productivity is 99%.
The synthetic method of described fire resistant polyimide comprises the following steps:
Dianhydride and diamidogen low-temperature polycondensation is taked to prepare polyamic acid solution: to weigh 3,3 '-(isophthalic two epoxide) of 0.05mol
Double (phthalic anhydrides) join the p-phenylenediamine of 0.025mol and 2-(4-aminophenyl)-5 aminophenyls of 0.025mol
The DMAc solution of benzimidazole adds in there-necked flask, add 230mLDMAc, put in low temperature bath (-5 DEG C), strong agitation,
After reaction 6h, adding phthalic anhydride end-capping reagent, period adds DMAc and progressively dilutes solution, and it is dense that continuation stirring about 20h obtains quality
Spend the PAA solution of 10% phthalic anhydride end-blocking.It is subsequently added into 0.3mol acetic anhydride, 0.015mol triethylamine and 0.035mol pyridine to carry out
Chemical imidization, in water precipitates after about reacting 20h at 60 DEG C, and the polyimide powder ethanol being precipitated out is in Soxhlet
Extractor extracts 200 DEG C of heat treatment 1h of final vacuum and obtains the high temperature resistant polyamides that melt temperature is less than 30 degree with vitrification point difference
Imines.
Embodiment 2:
The melt temperature that embodiments of the invention 2 provide and the vitrification point difference high temperature resistant polyamides less than 30 degree is sub-
Amine, the monomer of preparing of described fire resistant polyimide includes: dianhydride monomer, diamine monomer, described dianhydride monomer is 3,3 '-(
Benzene two epoxide) double (phthalic anhydrides)；Described diamine monomer is p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzene
And the mixture of imidazoles, and the mol ratio of p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzimidazole is: 1:2.
3, the synthetic method of 3 '-(isophthalic two epoxide) double (phthalic anhydrides) is with embodiment 1.
The synthetic method of fire resistant polyimide with embodiment 1,Difference be p-phenylenediamine and 2-(4-aminophenyl)-
The mol ratio of 5 aminophenyl benzimidazoles is: 1:2.
Embodiment 3:(most preferred embodiment)
The melt temperature that embodiments of the invention 3 provide and the vitrification point difference high temperature resistant polyamides less than 30 degree is sub-
Amine, the monomer of preparing of described fire resistant polyimide includes: dianhydride monomer, diamine monomer, described dianhydride monomer is 3,3 '-(
Benzene two epoxide) double (phthalic anhydrides)；Described diamine monomer is p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzene
And the mixture of imidazoles, and the mol ratio of p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzimidazole is: 1:3.
3, the synthetic method of 3 '-(isophthalic two epoxide) double (phthalic anhydrides) is with embodiment 1.
The synthetic method of fire resistant polyimide with embodiment 1,Difference be p-phenylenediamine and 2-(4-aminophenyl)-
The mol ratio of 5 aminophenyl benzimidazoles is: 1:3.
Embodiment 4:
The melt temperature that embodiments of the invention 4 provide and the vitrification point difference high temperature resistant polyamides less than 30 degree is sub-
Amine, the monomer of preparing of described fire resistant polyimide includes: dianhydride monomer, diamine monomer, described dianhydride monomer is 3,3 '-(
Benzene two epoxide) double (phthalic anhydrides)；Described diamine monomer is p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzene
And the mixture of imidazoles, and the mol ratio of p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzimidazole is: 1:5.
The synthetic method of 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides) is with embodiment 1.
The synthetic method of fire resistant polyimide with embodiment 1,Difference be p-phenylenediamine and 2-(4-aminophenyl)-
The mol ratio of 5 aminophenyl benzimidazoles is: 1:5.
Embodiment 5:
The melt temperature that embodiments of the invention 5 provide and the vitrification point difference high temperature resistant polyamides less than 30 degree is sub-
Amine, the monomer of preparing of described fire resistant polyimide includes: dianhydride monomer, diamine monomer, described dianhydride monomer is 3,3 '-(
Benzene two epoxide) double (phthalic anhydrides)；Described diamine monomer is p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzene
And the mixture of imidazoles, and the mol ratio of p-phenylenediamine and 2-(4-aminophenyl)-5 aminophenyl benzimidazole is: 1:9.
3, the synthetic method of 3 '-(isophthalic two epoxide) double (phthalic anhydrides) is with embodiment 1.
The synthetic method of fire resistant polyimide with embodiment 1,Difference be p-phenylenediamine and 2-(4-aminophenyl)-
The mol ratio of 5 aminophenyl benzimidazoles is: 1:9.
Comparative example 1:
The concrete steps of comparative example 1 are with embodiment 3, and difference is, described diamine monomer only includes p-phenylenediamine.
Comparative example 2:
The concrete steps of comparative example 2 are with embodiment 3, and difference is, described diamine monomer only includes 2-(4-aminobenzene
Base)-5 aminophenyl benzimidazoles.
Performance test:
By embodiment 1～5 and the fire resistant polyimide that obtains of comparative example 1～2 measure glass transition temperature respectively
With melt temperature, concrete data are as shown in table 1.
Table 1 performance evaluation
| No. | Tg(℃) | Tm(℃) | The difference (DEG C) of Tm Yu Tg |
| Embodiment 1 | 283 | 308 | 25 |
| Embodiment 2 | 289 | 305 | 16 |
| Embodiment 3 | 299 | 310 | 11 |
| Embodiment 4 | 287 | 305 | 18 |
| Embodiment 5 | 279 | 307 | 28 |
| Comparative example 1 | 260 | 326 | 66 |
| Comparative example 2 | 301 | 334 | 33 |
By the embodiment in table 1 and comparative example it can be seen that diamine monomer is aromatic diamines, the molar ratio of imidazoles diamidogen
For 1:(1～9) time, the melt temperature of the fire resistant polyimide obtained and vitrification point difference are respectively less than 30 DEG C, especially originally
Inventive embodiment 3, melt temperature and vitrification point difference are only 11 DEG C.The present inventor guesses that possible reason is, adds
After imidazoles diamidogen, the regularity of copolymer molecule segment declines, and strand ordered arrangement to be carried out is accomplished by higher energy, because of
This occurs that high-temperature region is shifted in the position of glass transition.Simultaneously because segment regularity declines, crystal degree of perfection is reduced,
Thus result in relatively low melt temperature.Embodiments of the invention and comparative example are all highly suitable to be applied for 3D and print field.
Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure, those skilled in the art
Present disclosure can be used for reference, be suitably modified technological parameter and realize.Special needs to be pointed out is, all similar replacements and change right
Being apparent from for those skilled in the art, they are considered as being included in the present invention.The method of the present invention and application are
Through being described by preferred embodiment, related personnel substantially can be to this in without departing from present invention, spirit and scope
Methods and applications described in literary composition are modified or suitably change and combine, and realize and apply the technology of the present invention.
Claims (10)
1. the fire resistant polyimide that a melt temperature is less than 30 degree with vitrification point difference, it is characterised in that described resistance to height
The monomer of preparing of temperature polyimides includes: dianhydride monomer, diamine monomer；Described diamine monomer includes aromatic diamines, imidazoles diamidogen.
2. melt temperature as claimed in claim 1 and the vitrification point difference fire resistant polyimide less than 30 degree, its feature
Being, described aromatic diamines, the mol ratio of imidazoles diamidogen be: 1:(1～9).
3. melt temperature as claimed in claim 2 and the vitrification point difference fire resistant polyimide less than 30 degree, its feature
Being, described aromatic diamines, the mol ratio of imidazoles diamidogen be: 1:(2～5).
4. melt temperature as claimed in claim 3 and the vitrification point difference fire resistant polyimide less than 30 degree, its feature
Being, described aromatic diamines, the mol ratio of imidazoles diamidogen be: 1:3.
5. melt temperature as claimed in claim 1 and the vitrification point difference fire resistant polyimide less than 30 degree, its feature
Being, described dianhydride monomer is selected from: 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides), pyromellitic acid anhydride, 4,4 '-
The double phthalic anhydride of oxygen, hexafluoro isopropyl phthalic anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-two
Benzophenone tetracarboxylic acid dianhydride, 5,5 '-[[1,1 '-xenyl]-4,4 '-dioxy] two-phthalic anhydrides, 3,3 ', 4,4 '-hexichol
Base sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4-bis-(3,4-di carboxyl phenyloxy) benzene dianhydride, 5,5 '-oxo (4,1-phenoxy group)] double adjacent benzene
Dicarboxylic acid anhydride, 4,4 '-(hexafluoro isopropyl)-two-(to phenoxy group) phthalic anhydride, 1,4,5,8-naphthalene dianhydride, 3,4,9,10-
Any one or a few mixing in tetracarboxylic acid dianhydride.
6. melt temperature as claimed in claim 1 and the vitrification point difference fire resistant polyimide less than 30 degree, its feature
Being, described aromatic diamines is selected from: p-phenylenediamine, benzidine, 4,4 '-diaminodiphenyl ether, Isosorbide-5-Nitrae ,-bis-(4-aminobenzene oxygen
Base) benzene, 1,4 ,-bis-(3-amino-benzene oxygen) benzene, 1,3 ,-bis-(4-amino-benzene oxygen) benzene, 2,5-double (4-amino-benzene oxygen)-
Double (the 4-amino-benzene oxygen)-3 of 3 '-trifluoromethyl-biphenyl, 2,5-', the double (4-amino-2-of 5 '-two (trifluoromethyl) biphenyl, 1,4-
4-trifluoromethylphenopendant) benzene, double (3-amino-5-4-trifluoromethylphenopendant) benzene of 1,4-, double (4-amino-benzene oxygen) benzonitrile of 2,6-,
Double (4-amino-benzene oxygen) benzonitrile of double (3-amino-benzene oxygen) benzonitrile of 2,6-, 2,4-, double (3-amino-benzene oxygen) benzonitrile of 2,4-, 1,
Double (2-cyano group-4-amino-benzene oxygen) cyanophenyl of double (2-cyano group-4-amino-benzene oxygen) benzene of 4-, 2,5-, 3,6-be double-(2-cyano group-4-
Amino-benzene oxygen) phthalic nitrile, double (4-amino-benzene oxygen) four fluorobenzenes of 1,4-, the double (4-amino-2-trifluoromethylbenzene oxygen of 1,4-
Base) four fluorobenzenes, 2, double (3-amino-4-hydroxylphenyl)-HFC-236fa of 2-, 3,3 '-dihydroxy-2,2-bis-(4-aminobenzene
Base), 3,3 '-dihydroxybiphenyl amine, in benzidine-2,2 '-disulfonic acid, 4,4 '-diaminodiphenyl ether-2,2 '-disulfonic acid arbitrarily
The mixing of one or more.
7. melt temperature as claimed in claim 1 and the vitrification point difference fire resistant polyimide less than 30 degree, its feature
Being, described imidazoles diamidogen is selected from: 2-(4-aminophenyl)-5 aminophenyl benzimidazole, 2-amino-1H-imidazoles-5-ethamine,
5-(3-aminopropyl)-1H-imidazoles-2-amine, 2,2 '-bis-(4-aminophenyls)-5,5 '-bibenzimidaz sigmale, 2,2 '-bis-(3-ammonia
Base phenyl)-5,5 '-bisbenzimidazole, 2,2 '-bis-(4-aminophenyl) benzimidazoles, 2,2 '-bis-(3-aminophenyl) benzo miaows
Any one or a few mixing in azoles, 4,5-imidazoles diamides, 1H-benzo [d] imidazoles-5,6-diamidogen.
8. the system of the melt temperature as described in claim 1～7 and the vitrification point difference fire resistant polyimide less than 30 degree
Preparation Method, it is characterised in that at least comprise the following steps: dianhydride monomer, diamine monomer carry out polycondensation reaction.
9. the preparation side of melt temperature as claimed in claim 8 and the vitrification point difference fire resistant polyimide less than 30 degree
Method, it is characterised in that the temperature that described polycondensation reaction is used is :-10 DEG C～0 DEG C.
10. the melt temperature as described in claim 1～7 and the vitrification point difference fire resistant polyimide less than 30 degree is at 3D
The application in printing field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610583530.2A CN106220848A (en) | 2016-07-22 | 2016-07-22 | Melt temperature and vitrification point difference fire resistant polyimide less than 30 degree and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610583530.2A CN106220848A (en) | 2016-07-22 | 2016-07-22 | Melt temperature and vitrification point difference fire resistant polyimide less than 30 degree and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106220848A true CN106220848A (en) | 2016-12-14 |
Family
ID=57532118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610583530.2A Pending CN106220848A (en) | 2016-07-22 | 2016-07-22 | Melt temperature and vitrification point difference fire resistant polyimide less than 30 degree and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106220848A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484412A (en) * | 2018-05-02 | 2018-09-04 | 同济大学 | A kind of aromatic diamines and preparation method thereof |
| CN111117241A (en) * | 2019-12-31 | 2020-05-08 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film and preparation method thereof |
| CN114456090A (en) * | 2022-02-24 | 2022-05-10 | 南京大学 | Cyanogen-containing polysubstituted aromatic diamine monomer and preparation method thereof |
| CN115109046A (en) * | 2021-03-18 | 2022-09-27 | 常州强力先端电子材料有限公司 | Imide sulfonate photo-acid generator with high acid yield, composition and application |
| CN115536845A (en) * | 2022-09-29 | 2022-12-30 | 科城铜业(英德)有限公司 | Preparation method of hydrophobic polyimide resin and application of hydrophobic polyimide resin in enameled wire |
| CN116355522A (en) * | 2023-02-20 | 2023-06-30 | 中国电子科技集团公司第四十九研究所 | Preparation method of humidity sensor with polyimide and halloysite nanotube composite humidity-sensitive sensing layer |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1976977A (en) * | 2003-06-03 | 2007-06-06 | 通用电气公司 | Benzimidazole diamine-based polyetherimide compositions and methods for making them |
| CN101200822A (en) * | 2007-11-30 | 2008-06-18 | 四川大学 | Polyimide fibre containing benzimidazole structure and preparation method thereof |
| CN101984157A (en) * | 2010-12-03 | 2011-03-09 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN102191581A (en) * | 2011-03-28 | 2011-09-21 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN102345177A (en) * | 2011-08-04 | 2012-02-08 | 北京化工大学 | High-strength high modulus polyimide fiber and preparation method thereof |
| CN102604091A (en) * | 2012-01-13 | 2012-07-25 | 东华大学 | Polyimide containing benzimidazole unit and preparation method thereof |
| CN103147253A (en) * | 2013-03-05 | 2013-06-12 | 中国科学院理化技术研究所 | High-strength polyimide nanofiber porous membrane and preparation method and application thereof |
| CN105131286A (en) * | 2015-09-28 | 2015-12-09 | 中国科学院化学研究所 | Polyimide film as well as preparation method, flexible substrate and application thereof |
| CN105330860A (en) * | 2015-12-01 | 2016-02-17 | 常州市尚科特种高分子材料有限公司 | Thermoplastic polyimide resin powder and preparation method thereof |
-
2016
- 2016-07-22 CN CN201610583530.2A patent/CN106220848A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1976977A (en) * | 2003-06-03 | 2007-06-06 | 通用电气公司 | Benzimidazole diamine-based polyetherimide compositions and methods for making them |
| CN101200822A (en) * | 2007-11-30 | 2008-06-18 | 四川大学 | Polyimide fibre containing benzimidazole structure and preparation method thereof |
| CN101984157A (en) * | 2010-12-03 | 2011-03-09 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN102191581A (en) * | 2011-03-28 | 2011-09-21 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN102345177A (en) * | 2011-08-04 | 2012-02-08 | 北京化工大学 | High-strength high modulus polyimide fiber and preparation method thereof |
| CN102604091A (en) * | 2012-01-13 | 2012-07-25 | 东华大学 | Polyimide containing benzimidazole unit and preparation method thereof |
| CN103147253A (en) * | 2013-03-05 | 2013-06-12 | 中国科学院理化技术研究所 | High-strength polyimide nanofiber porous membrane and preparation method and application thereof |
| CN105131286A (en) * | 2015-09-28 | 2015-12-09 | 中国科学院化学研究所 | Polyimide film as well as preparation method, flexible substrate and application thereof |
| CN105330860A (en) * | 2015-12-01 | 2016-02-17 | 常州市尚科特种高分子材料有限公司 | Thermoplastic polyimide resin powder and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484412A (en) * | 2018-05-02 | 2018-09-04 | 同济大学 | A kind of aromatic diamines and preparation method thereof |
| CN111117241A (en) * | 2019-12-31 | 2020-05-08 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film and preparation method thereof |
| CN115109046A (en) * | 2021-03-18 | 2022-09-27 | 常州强力先端电子材料有限公司 | Imide sulfonate photo-acid generator with high acid yield, composition and application |
| CN115109046B (en) * | 2021-03-18 | 2024-09-03 | 常州强力先端电子材料有限公司 | Imide sulfonate photoacid generator with high acid yield, composition and application |
| CN114456090A (en) * | 2022-02-24 | 2022-05-10 | 南京大学 | Cyanogen-containing polysubstituted aromatic diamine monomer and preparation method thereof |
| CN114456090B (en) * | 2022-02-24 | 2023-03-14 | 南京大学 | Cyanogen-containing poly-substituted aromatic diamine monomer and preparation method thereof |
| CN115536845A (en) * | 2022-09-29 | 2022-12-30 | 科城铜业(英德)有限公司 | Preparation method of hydrophobic polyimide resin and application of hydrophobic polyimide resin in enameled wire |
| CN116355522A (en) * | 2023-02-20 | 2023-06-30 | 中国电子科技集团公司第四十九研究所 | Preparation method of humidity sensor with polyimide and halloysite nanotube composite humidity-sensitive sensing layer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106220848A (en) | Melt temperature and vitrification point difference fire resistant polyimide less than 30 degree and preparation method thereof | |
| CN108219133A (en) | A kind of polyimide resin containing furan nucleus and preparation method thereof | |
| JPH03200838A (en) | Novel polyamide-polyimide and polybenzoazole- polyimide polymer | |
| CN105566630A (en) | Polyimide film and preparation method thereof | |
| JP6872023B2 (en) | Method for manufacturing polyamide-imide film | |
| KR101295653B1 (en) | Polyimide film and method for preparing same | |
| CN107722269A (en) | Polyamic acid resin, polyamidoimide film and preparation method thereof | |
| CN101392055B (en) | Iso-poly(sulfide-imide) and preparation method thereof | |
| CN105175722A (en) | Preparation method of aromatic polyamic acid with characteristics of high relative molecular mass and narrow molecular weight distribution | |
| JP2008081718A (en) | Method for producing polyimide resin particles | |
| CN105348512B (en) | A kind of polyarylether material containing acid imide side base and preparation method thereof | |
| CN105780177B (en) | Production method of polyimide color yarn | |
| CN109666143B (en) | Preparation method of polyamic acid solution | |
| KR100228722B1 (en) | Novel soluble polyimide resin having alkoxy substituent and its preparation process | |
| CN101225169B (en) | Sulfur fluoro self-crosslinkable polyimide material and preparation method thereof | |
| JP2006206825A (en) | Aromatic polyimide resin precursor and aromatic polyimide resin | |
| US4873295A (en) | Novel polyether sulfone imide copolymers | |
| CN106008976A (en) | High-performance polyimide 3D printing consumable material and preparation method thereof | |
| CN109666142A (en) | Polyamic acid solution and preparation method and application | |
| US4973651A (en) | Polyimide polymers having 12-F fluorine-containing linking groups | |
| JP2016196630A (en) | Novel polyimide copolymer | |
| CN102336892A (en) | Modified cyanate ester resin system for package substrate, and preparation method and application thereof | |
| CN114015044A (en) | Colorless transparent polyimide resin film and preparation method thereof | |
| JPH01123830A (en) | Production of polyimide of good heat stability | |
| US4384071A (en) | Fibers and filled molding compositions from copolyimides and polyimides derived from tetramethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride and diamines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161214 |