[go: up one dir, main page]

CN1141330C - Preparation of Polyaryletherketone Liquid Crystal Polymer - Google Patents

Preparation of Polyaryletherketone Liquid Crystal Polymer Download PDF

Info

Publication number
CN1141330C
CN1141330C CNB011035226A CN01103522A CN1141330C CN 1141330 C CN1141330 C CN 1141330C CN B011035226 A CNB011035226 A CN B011035226A CN 01103522 A CN01103522 A CN 01103522A CN 1141330 C CN1141330 C CN 1141330C
Authority
CN
China
Prior art keywords
liquid crystal
polyaryletherketone
crystal polymer
preparation
hydroquinone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB011035226A
Other languages
Chinese (zh)
Other versions
CN1311263A (en
Inventor
王贵宾
姜振华
陈春海
张万金
吴忠文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CNB011035226A priority Critical patent/CN1141330C/en
Publication of CN1311263A publication Critical patent/CN1311263A/en
Application granted granted Critical
Publication of CN1141330C publication Critical patent/CN1141330C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Polyethers (AREA)

Abstract

The present invention belongs to a synthesis technique for a poly aromatic ether ketone liquid crystal polymer, which comprises the content that self-prepared 2-(3'-trifluoromethyl benzene) hydroquinone (FH), reagent-grade 2-chloro-hydroquinone (CH), 2-tert-butyl hydroquinone (BH), 2-methoxy hydroquinone (MH) and 2, 5-dihydroxybiphenyl (PH)4, 4'-difluorodiphenyl ketone (DF), 1, 4-(4-fluoro-prokeyl benzoy)-benzene (BF) and biphenyl diphenol (BP) are used for being prepared into a novel poly aromatic ether ketone liquid crystal polymer by a compatible substitution route. The material is similar to a heating liquid crystal polymer whose main chain contains medium crystal base units and flexible interval chain segments. The material not only has a nematic liquid crystal structure, but also represents a high ordered smectic structure.

Description

The preparation of poly aromatic ether ketone liquid crystal copolymer
The invention belongs to the synthetic technology of poly aromatic ether ketone liquid crystal copolymer.
In order to make excellent performance polyaryletherketone base polymer dealing with various requirements, people are by introducing various side groups or introducing liquid crystal unit and utilize thermic polyester liquid crystal and the polyaryletherketone base polymer carries out method such as compound and carried out many researchs in main chain in its structure.As everyone knows, it is that both must have consistency and the melt temperature that is complementary preferably that liquid crystalline polymers and matrix polymer obtain good original position compound primary condition, and the kind of commercial liquid crystalline polymers is limited and processing temperature is higher.Many research workers utilize the polyester liquid crystal to improve the polyaryletherketone base polymer, but owing to be subjected to the restriction of consistency and the melt temperature that is complementary, therefore also do not obtain good result always.
Introducing the destruction crystallization primitive contain the biphenyl mesomorphic unit and to contain side group in the polyaryletherketone main chain simultaneously can make polyaryletherketone have liquid crystal behavior.The destruction crystallization primitive that contains side group makes the crystallinity of polyaryletherketone molecular backbone chain descend; its solvability increases; the result contains the molecule segment that destroys the crystallization primitive and has the character of similar soft segment; when the monomer that contains side group reaches certain molar percentage; poly (aryl ether ketone) copolymer will form thermotropic liquid crystal; its synthetic method is to contain diphenol monomer [the 2-chlorohydroquinone (CH) that replaces side group R; 2-Tert. Butyl Hydroquinone (PH); 2-methoxyl group Resorcinol (MH); 2; 5-dihydroxybiphenyl (BH); (3 '-trifluoromethylbenzene) Resorcinol (FH)] and the mol ratio of '-biphenyl diphenol (BP) be 0.8～0.2: 0.2～0.8 with two fluorine monomers [4; 4 '-two fluoro benzophenones (DF); 1; 4-two (4 '-fluorobenzene acyl group) benzene (BF)] be 1: 1.05～1.50 copolymerization with mol ratio, generally be controlled at 1: 1.10～1.20 for well.With salt of wormwood is salt forming agent, is mixed to join in the reactor, adds organic solvent NMP (N, N-dimethyl pyrrolidone) or TMS (tetramethylene sulfone) and band aqua dimethylbenzene again, and heating zone water refluxes under nitrogen protection, removes H 2O is clear to phegma; Then temperature of reaction is controlled at 200-240 ℃ and continues reaction 2-12 hour, got final product in general 4-8 hour.Pour in the water polymers soln into precipitation and separate out, use the deionized water repetitive scrubbing through pulverizing, except that desolvating and ion, obtain poly (aryl ether ketone) copolymer, productive rate is 90～95%.This class materials similar contains mesomorphic unit and flexible spacer segmental TLCP in main chain, not only has the nematic liquid crystal structure, but also shows as high smectic structure in order.
Its reaction formula is:
Figure C0110352200031
R=Cl, Ph, CH 3O, t-C 4H 9,
Figure C0110352200032
X=
Embodiment one:
With 1 of the '-biphenyl diphenol (BP) of 2-(3 '-trifluoromethylbenzene) Resorcinol (FH) of 7.70g (0.03mol), 13.22 (0.07mol) and 37.59g (0.115mmol); 4-two (4-fluoro-benzoyl group)-benzene (BF) adds in the three-necked bottle, adds 15.36g (0.110mol) K 2CO 3, 240mlTMS and 60ml dimethylbenzene, heated and stirred under nitrogen protection, the band water that refluxes is removed H 2O to the phegma clear, reacted about 6 hours.After reaction is finished, pour in the water polymers soln into precipitation and separate out, use the deionized water repetitive scrubbing through pulverizing, except that desolvating and ion, obtain poly (aryl ether ketone) copolymer, product is white powder, and productive rate is about 93%.After tested, multipolymer has liquid crystal liquid crystal property.
Embodiment two:
Method only changes 240ml TMS into 290ml NMP with embodiment one, still can obtain poly aromatic ether ketone liquid crystal copolymer, and productive rate is 93%.
Embodiment three:
Method only will be extended for 12 hours the reaction times with embodiment one, still can obtain poly aromatic ether ketone liquid crystal copolymer, and productive rate is 93%.
Embodiment four:
Method is with embodiment one, only with X=
Figure C0110352200041
Monomer 1,4-two (4-fluoro-benzoyl group)-benzene (BF) changes X=into Monomer 4,4 '-two fluoro benzophenones (DF), still can obtain poly aromatic ether ketone liquid crystal copolymer, productive rate is 93%.
Embodiment five:
Method is with embodiment one, only 2-(3 '-trifluoromethylbenzene) Resorcinol (FH) is changed to the monomer CH of R=Cl, and experiment shows, when the amount of CH was in the 0.3-0.8mol scope, poly (aryl ether ketone) copolymer had liquid crystal behavior.
Embodiment six:
Method is with embodiment one, only 2-(3 '-trifluoromethylbenzene) Resorcinol (FH) is changed to the monomer PH of R=Ph, and experiment shows, when the amount of PH was in the 0.3-0.8mol scope, poly (aryl ether ketone) copolymer had liquid crystal behavior.
Embodiment seven:
Method only is changed to R=CH with 2-(3 '-trifluoromethylbenzene) Resorcinol (FH) with embodiment one 3The monomer M H of O, experiment shows, when the amount of MH was in the 0.3-0.8mol scope, poly (aryl ether ketone) copolymer had liquid crystal behavior.
Embodiment eight:
Method only is changed to R=t-C with 2-(3 '-trifluoromethylbenzene) Resorcinol (FH) with embodiment one 4H 9Monomers B H, experiment shows, when the amount of BH was in the 0.3-0.8mol scope, poly (aryl ether ketone) copolymer had liquid crystal behavior.

Claims (5)

1、一种聚芳醚酮液晶聚合物的制备方法，其特征在于含取代侧基R的双酚单体和联苯双酚的摩尔比为0.8～0.2∶0.2～0.8混合的双酚单体同含有X基团的双氟单体以摩尔比为1∶1.05～1.50共聚，以碳酸钾为成盐剂，混合加入到反应器中，再加入有机溶剂N，N-二甲基吡咯烷酮或环丁砜和带水剂二甲苯，在氮气保护下加热带水回流，除去H2O，至回流液呈澄清透明；然后将反应温度控制在200～240℃继续反应2～12小时，将聚合物溶液倒入水中沉淀析出，经粉碎用去离子水反复洗涤，除去溶剂和离子，得到聚芳醚酮共聚物。1. A preparation method of polyaryletherketone liquid crystal polymer, characterized in that the molar ratio of bisphenol monomer containing substituted side group R and biphenyl bisphenol is 0.8～0.2: 0.2～0.8 mixed bisphenol monomer Copolymerize with difluoro monomers containing X groups at a molar ratio of 1:1.05~1.50, use potassium carbonate as a salt-forming agent, mix and add to the reactor, and then add organic solvent N,N-dimethylpyrrolidone or sulfolane and water-carrying agent xylene, under the protection of nitrogen, heat and bring water back to reflux, remove H 2 O, until the reflux liquid is clear and transparent; then control the reaction temperature at 200-240°C to continue the reaction for 2-12 hours, pour the polymer solution Precipitate in water, grind and wash repeatedly with deionized water, remove solvent and ions, and obtain polyaryletherketone copolymer. 2、如权利要求1所述的聚芳醚酮液晶聚合物的制备方法，其特征在于控制双酚单体与双氟单体的摩尔比为1∶1.10～1.20。2. The method for preparing polyaryletherketone liquid crystal polymers according to claim 1, characterized in that the molar ratio of bisphenol monomers to bisfluoromonomers is controlled to be 1:1.10-1.20. 3、如权利要求1或2所述的聚芳醚酮液晶聚合物的制备方法，其特征在于除去H2O后，升温至200～240℃继续反应4～8小时。3. The preparation method of polyaryletherketone liquid crystal polymer according to claim 1 or 2, characterized in that after removing H 2 O, the temperature is raised to 200-240°C and the reaction is continued for 4-8 hours. 4、如权利要求1或2所述的聚芳醚酮液晶聚合物的制备方法，其特征含在于侧基R的双酚单体的R为Cl或Ph、CH3O、t-C4H9、 4. The preparation method of polyaryletherketone liquid crystal polymer as claimed in claim 1 or 2, characterized in that the R of the bisphenol monomer contained in the side group R is Cl or Ph, CH 3 O, tC 4 H 9 , 5、如权利要求1或2所述的聚芳醚酮液晶聚合物的制备方法，其特征在于双氟单体的X为 或
Figure C0110352200023
5. The preparation method of polyaryletherketone liquid crystal polymer as claimed in claim 1 or 2, characterized in that X of the bisfluoromonomer is or
Figure C0110352200023
CNB011035226A 2001-02-02 2001-02-02 Preparation of Polyaryletherketone Liquid Crystal Polymer Expired - Fee Related CN1141330C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB011035226A CN1141330C (en) 2001-02-02 2001-02-02 Preparation of Polyaryletherketone Liquid Crystal Polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB011035226A CN1141330C (en) 2001-02-02 2001-02-02 Preparation of Polyaryletherketone Liquid Crystal Polymer

Publications (2)

Publication Number Publication Date
CN1311263A CN1311263A (en) 2001-09-05
CN1141330C true CN1141330C (en) 2004-03-10

Family

ID=4653292

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB011035226A Expired - Fee Related CN1141330C (en) 2001-02-02 2001-02-02 Preparation of Polyaryletherketone Liquid Crystal Polymer

Country Status (1)

Country Link
CN (1) CN1141330C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100389138C (en) * 2006-03-28 2008-05-21 吴忠文 Synthesis of polyether-ether-ketone resin with sulfolane as solvent
CN100389139C (en) * 2006-05-30 2008-05-21 长春吉大特塑工程研究有限公司 Synthesis method of ternary copolymer containing PEDEK and PEEK using sulfolane as solvent

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101240063B (en) * 2008-01-18 2011-12-21 深圳大学 Sulfonated polyarylether with sulfonic group at side chain naphthalene ring and preparation method thereof
CN101245137B (en) * 2008-04-02 2010-08-25 吴忠文 Method for producing polyetherketone with sulfolane as solvent
CN102352033B (en) * 2011-09-14 2012-12-05 金发科技股份有限公司 Method for preparing powdered resin
WO2017087438A1 (en) 2015-11-20 2017-05-26 Ticona Llc High flow polyaryletherketone composition
CN108250413A (en) * 2018-01-15 2018-07-06 江西师范大学 A kind of methoxyl group ketone-grouped resin and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100389138C (en) * 2006-03-28 2008-05-21 吴忠文 Synthesis of polyether-ether-ketone resin with sulfolane as solvent
CN100389139C (en) * 2006-05-30 2008-05-21 长春吉大特塑工程研究有限公司 Synthesis method of ternary copolymer containing PEDEK and PEEK using sulfolane as solvent

Also Published As

Publication number Publication date
CN1311263A (en) 2001-09-05

Similar Documents

Publication Publication Date Title
Tian et al. Synthesis, nanostructures, and functionality of amphiphilic liquid crystalline block copolymers with azobenzene moieties
CN1141330C (en) Preparation of Polyaryletherketone Liquid Crystal Polymer
Wendorff et al. Nonlinear optical phenomena in liquid crystalline side chain polymers
GB2299333A (en) Monofunctional reactive terphenyls for polymerization and use in liquid crystalline materials
US5252251A (en) Mesomorphic polymer, monomeric mesomorphic compounds, liquid crystal composition and liquid crystal device
US5235008A (en) Polymer modified adducts of epoxy resins and active hydrogen containing compounds containing mesogenic moieties
JP3504275B2 (en) Chiral nematic polyester
Yao et al. Synthesis and self-assembly behaviours of side-chain smectic thiol–ene polymers based on the polysiloxane backbone
Han et al. An azoester-containing photoresponsive linear liquid crystal polymer with good mesophase stability
JP2002357815A (en) Infrared light control device
CN100387640C (en) Thermotropic pro-cholesteric liquid crystal polymer and preparation method thereof
KR101322592B1 (en) Compound having hydrocoumarin skeleton, liquid crystal composition and liquid crystal display element
Xue et al. Ionic naphthalene thermotropic copolyesters: effect of ionic content
Pracella et al. Polymer blends based on mesomorphic components, 1. Properties of poly (tetramethylene terephthalate)/poly (decamethylene 4, 4′‐terephthaloyldioxydibenzoate) blends
Percec et al. Cell membrane as a model for the design of ion-active nanostructured supramolecular systems
CN1091116C (en) Polyaryl ether-nitrile-sulfone containing phenolphthalein structure and its preparing process
CA2034896A1 (en) Use of polyaryl ether ketones as alignment layers
Chen et al. A novel type of optically active helical liquid crystalline polymers: Synthesis and characterization of poly (p‐phenylene) s containing terphenyl mesogen with different terminal groups
JP3909545B2 (en) Functional liquid crystalline polyamide polymer
Oh et al. Self-assembly of ABC coil-rod-coil triblock molecules with perforated lamellar mesophases
Philip et al. Synthesis and characterization of chiral main chain polyesters with polar segments tailored for second harmonic generation
JPH02229883A (en) Organic polymeric liquid crystal compound
CN1187304C (en) Synthesis of 1,5-bis (4-(4'-fluorophenyl carbonyl)phenoxy) naphthalene
Galli et al. The mesophase structure of chiral liquid crystalline polysiloxanes for electro-optical applications
Sahlén et al. Structural assessment of liquid-crystalline side-chain poly (vinyl ether) s: dependence on terminal group, orientation and temperature

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20040310

Termination date: 20140202