CN108084432A - A kind of adamantyl polyamide - Google Patents
A kind of adamantyl polyamide Download PDFInfo
- Publication number
- CN108084432A CN108084432A CN201711388783.5A CN201711388783A CN108084432A CN 108084432 A CN108084432 A CN 108084432A CN 201711388783 A CN201711388783 A CN 201711388783A CN 108084432 A CN108084432 A CN 108084432A
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- Prior art keywords
- adamantane
- polyamide
- adamantyl
- another monomer
- solution
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
Abstract
The present invention relates to a kind of adamantyl method for making polyamide, belong to macromolecule material preparation area.The present invention, with another monomer by interfacial polymerization or polymerisation in solution or melt polycondensation reaction, prepares adamantyl polyamide using two degree of functionality adamantane derivatives as core monomer.By the way that adamantane group is introduced into polyamide molecule structure, the high temperature resistance of polyamide can be improved, improves its organic solvent-resistant corrosivity, new method is provided for the development and application of polyamide material.
Description
Technical field
The present invention relates to a kind of adamantyl polyamide, are related to the synthesis and application of a kind of high molecular material.
Background technology
Polyamide is the high polymer for containing amide group (- CONH-) in macromolecular main chain repetitive unit, and species is more, purposes
Extensively.With development in science and technology and social progress, various structures polyamide is developed in succession, in addition to nylon -66, nylon-6, nylon-
610th, nylon 1010 etc., nylon-3 4 and the condensation polymer of -56 grade straight chains saturation diamines of nylon and diacid are constantly gone into operation.It is in addition, fragrant
The condensation polymer of race's diamines and diacid such as Fanglun l414 and the polyamide product of aramid fiber 1313 and some semi-aromatics also exist already
The fields such as military affairs, fire-fighting play its excellent mechanical performance and temperature capacity.However, with natural one protein phase of polyamide materials
Than artificial synthesized polyamide either property or function all meet far away people and pursues a goal to high performance material.Thus,
Exploitation new construction, the polyamide of new capability are the striving direction of scientific and technical personnel always.For this purpose, this patent is with two functions
Adamantane derivative is spent as core monomer, and design has synthesized a series of polyamide, provided for the development and application of polyamide material
New material.
Adamantane is a kind of high degree of symmetry, rigid caged molecular structure.Intermolecular interaction is weaker, thus has good
Good lubricity, thermal stability is good, and fusing point is high, and adamantane and its derivative are widely used in fields such as high molecular materials.
Adamantane framework is introduced in polyamide material, the high temperature resistance, inoxidizability and directional stability of polyamide can be improved, changed
Kind organic solvent-resistant corrosivity.
The content of the invention
The purpose of the present invention is overcoming deficiency of the prior art, a kind of adamantyl polyamide is prepared.
Technical scheme is summarized as follows：
A kind of adamantyl polyamide, its preparation method are：Led to by two degree of functionality adamantane derivatives with another monomer
Cross interfacial polymerization or polymerisation in solution or melt polycondensation reaction synthesis.
Two degree of functionality adamantane acid derivatives include：
1,3- adamantane dimethyl chloride (I)；1,3- adamantane acid (II)；With 1,3- adamantane diamines (III).
Another monomer includes carrying out interfacial polymerization or solution polymerization with (I) 1,3- adamantane dimethyl chloride
Diaminomonomer (IV) and/or (V)；The diaminomonomer (IV) of melt polycondensation reaction is carried out with (II) 1,3- adamantane acids
And/or (V)；With the diacid chloride base monomer (VI) of (III) 1,3- adamantane diamine reactants and/or diacid (VII).
Reaction monomers described in patent are as shown in table 1：
Acry radical donor I and II can be carried out polymerizeing obtained adamantyl with any amino group donor in right row and gathered in left column in table 1
Amide, wherein being interfacial polymerization and/or polymerisation in solution with the reaction of I；Reaction with II is melt polycondensation.
III can carry out polymerizeing obtained adamantyl polyamide with any acry radical donor in left column in right row in table 1, wherein with
The reaction of I and/or VI is interfacial polymerization and/or polymerisation in solution；Reaction with II and/or VII is melt polycondensation.
Used in the interfacial polymerization with the immiscible organic solvent of water for n-hexane, hexamethylene, petroleum ether, benzene,
The mixing of one or more of toluene, ethyl acetate, dichloromethane, chloroform and carbon tetrachloride；The polymerisation in solution
The middle solvent used is n,N-Dimethylformamide, in n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone
One or more mixing.
1 reaction monomers of table
Wherein：R1=(CH2)nOr (CH2-CH2-O)n-CH2-CH2OrWherein n is 1~20 just
Integer；
R2=CH2CH2Or CH2CH2-O-CH2-CH；
R3=(CH2)nOrWherein n is 1~20 positive integer.
Prepare embodiment
Embodiment 1
2.62g (0.01mol) 1,3- adamantane dimethyl chlorides are dissolved in 100ml n-hexanes and are configured to solution；By 1.73g
(0.02mol) piperazine is dissolved in 100ml deionized waters.Under stirring, piperazine aqueous solution is added drop-wise to 1,3- adamantane dimethyl chlorides
In hexane solution, 0.5~3h is reacted, solid product is filtered, and be washed with deionized, obtain adamantyl polyamide.It is dry
It is dry, obtain the adamantane polyamide that fusing point is 273.44 DEG C.
Embodiment 2
Dry n,N-Dimethylformamide 100ml is added in into reactor, nitrogen protection is lower to add in 10g (0.01mol) both-end
Amino-PEG1000, stirring add in 1,3- adamantane dimethyl chloride 2.62g (0.01mol) to dissolving, react 2~3h, Ran Houjia
Enter calcium hydroxide powder 1.48g, stirring neutralizes 0.5~1h, solid product is filtered, and is cleaned with deionized water, dry, obtains golden
Firm alkyl polyamide.
Embodiment 3
4.49g (0.02mol) 1,3- adamantane acids and piperazine 1.73g (0.02mol) are weighed in reactor, is added in
0.002g catalyst hypophosphorous acid, under nitrogen protection stirring are warming up to 280 DEG C of isothermal reaction 3h, are then progressively warming up to 320 DEG C,
Isothermal reaction 3h.Product is rinsed through 80 DEG C of deionized waters, dry, obtains adamantyl polyamide.
Embodiment 4
2.62g (0.01mol) 1,3- adamantane dimethyl chlorides are dissolved in 100ml hexamethylenes and are configured to solution, by 4.0g
(0.005mol) double-end amino-PEG800 is dissolved in 100ml deionized waters, by the water-soluble drops of double-end amino-PEG800 under stirring
0.5~3h of reaction in 1,3- adamantane dimethyl chloride cyclohexane solutions is added to, solid product is filtered, and it is clear with deionized water
It washes, obtains the adamantane polyamide solid that fusing point is 295.91 DEG C.
Embodiment 5
Dry n,N-dimethylacetamide 100ml is added in into reactor, nitrogen protection is lower to add in 2.32g (0.02mol) 1,
6- hexamethylene diamines, stirring add in 1,3- adamantane dimethyl chloride 5.22g (0.02mol) to dissolving, react 2~3h.Then hydrogen is added in
Lime powder 2.96g, stirring neutralizes 0.5~1h, solid product is filtered, and is cleaned with deionized water, dry, obtains adamantane
Based polyamide.
Embodiment 6
2.62g (0.01mol) 1,3- adamantane dimethyl chlorides are dissolved in 100ml ethyl acetate and are configured to solution, it will
4.0g (0.005mol) double-end aminos-PEG800 is dissolved in 100ml deionized waters, obtained aqueous solution.Under stirring, by both-end ammonia
Base-PEG800 aqueous solutions are added drop-wise in acyl chlorides ethyl acetate solution, and solid product is filtered, is washed with deionized, dry, are obtained
Adamantyl polyamide.
Embodiment 7
Dry N-Methyl pyrrolidone 100ml is added in into reactor, nitrogen protection is lower to add in 3.32g (0.02mol) 1,3-
Adamantane diamines, stirring add in 1,3- adamantane dimethyl chloride 5.22g (0.02mol) to dissolving, react 2~3h, then add in
Calcium hydroxide powder 2.96g, stirring neutralizes 0.5~1h, solid product is filtered, and is cleaned with deionized water, dry, obtains Buddha's warrior attendant
Alkyl polyamide.
Claims (4)
1. a kind of adamantyl polyamide, it is characterised in that adamantyl polyamide by two degree of functionality adamantane derivatives with it is another
Monomer is synthesized by interfacial polymerization or polymerisation in solution or melt polycondensation reaction.
2. according to claim 1, the two degree of functionality adamantane derivatives include：
1,3- adamantane dimethyl chloride (I)；1,3- adamantane acid (II)；With 1,3- adamantane diamines (III), structural formula point
It is not as follows：
1,3- adamantane dimethyl chloride (I) be dissolved in it is one or more of with it is water-soluble with another monomer in the immiscible organic solvent of water
Adamantyl polyamide is made by interfacial polymerization in liquid；
1,3- adamantane dimethyl chloride (I) is dissolved in organic solvent of the same race with another monomer, and Buddha's warrior attendant is made by polymerisation in solution
Alkyl polyamide；
With another monomer, by melt polycondensation reaction, adamantyl polyamide is made in 1,3- adamantane acid (II)；
The dissolving water neutralization of 1,3- adamantane diamines (III) is dissolved in gather with another monomer of the immiscible organic solvent of water progress interface
It closes, adamantyl polyamide is made；
1,3- adamantane diamines (III) is dissolved in organic solvent of the same race with another monomer, and adamantane is made by polymerisation in solution
Based polyamide；
With another monomer, by melt polycondensation reaction, adamantyl polyamide is made in 1,3- adamantane diamines (III).
3. according to claim 1, another monomer includes two amidos that interfacial polymerization or solution polymerization are carried out with (I)
Monomer (IV) and/or (V)；The diaminomonomer (IV) and/or (V) of melt polycondensation reaction are carried out with (II)；With (III) 1,3- gold
The diacid chloride base monomer (VI) and/or diacid (VII) of firm alkane diamine reactant：
R1=(CH2)nOr (CH2-CH2-O)n-CH2-CH2OrWherein n is 1~20 positive integer；
R2=CH2CH2Or CH2CH2-O-CH2-CH；
R3=(CH2)nOrWherein n is 1~20 positive integer.
4. according to claim 1 and 2, it is n-hexane, ring with the immiscible organic solvent of water to be used in the interfacial polymerization
The mixing of one or more of hexane, petroleum ether, benzene, toluene, ethyl acetate, dichloromethane, chloroform and carbon tetrachloride；
The solvent used in the polymerisation in solution is n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N- first
The mixing of one or more of base pyrrolidones.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711388783.5A CN108084432A (en) | 2017-12-15 | 2017-12-15 | A kind of adamantyl polyamide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711388783.5A CN108084432A (en) | 2017-12-15 | 2017-12-15 | A kind of adamantyl polyamide |
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| CN108084432A true CN108084432A (en) | 2018-05-29 |
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| CN201711388783.5A Pending CN108084432A (en) | 2017-12-15 | 2017-12-15 | A kind of adamantyl polyamide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500561A (en) * | 2020-10-27 | 2021-03-16 | 烟台泰和新材料股份有限公司 | High-strength meta-aramid polymer and preparation method thereof |
| CN113307967A (en) * | 2020-02-27 | 2021-08-27 | 北京大学 | Polyaramide material containing adamantyl groups, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3356719A (en) * | 1965-04-22 | 1967-12-05 | Sun Oil Co | Preparation of dicarboxyadamantane coumpounds |
| US3464957A (en) * | 1967-10-30 | 1969-09-02 | Sun Oil Co | Novel polyamides of adamantane |
| GB1194481A (en) * | 1968-01-09 | 1970-06-10 | Yarsley Res Lab Ltd | Adamantane Polymers |
| US3832332A (en) * | 1971-10-22 | 1974-08-27 | Sun Research Development | Polyamide polymer of diamino methyl adamantane and dicarboxylic acid |
| JP2008069305A (en) * | 2006-09-15 | 2008-03-27 | Tokyo Ohka Kogyo Co Ltd | Thermosetting composition, thermoset article and method for forming pattern |
-
2017
- 2017-12-15 CN CN201711388783.5A patent/CN108084432A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3356719A (en) * | 1965-04-22 | 1967-12-05 | Sun Oil Co | Preparation of dicarboxyadamantane coumpounds |
| US3464957A (en) * | 1967-10-30 | 1969-09-02 | Sun Oil Co | Novel polyamides of adamantane |
| GB1194481A (en) * | 1968-01-09 | 1970-06-10 | Yarsley Res Lab Ltd | Adamantane Polymers |
| US3832332A (en) * | 1971-10-22 | 1974-08-27 | Sun Research Development | Polyamide polymer of diamino methyl adamantane and dicarboxylic acid |
| JP2008069305A (en) * | 2006-09-15 | 2008-03-27 | Tokyo Ohka Kogyo Co Ltd | Thermosetting composition, thermoset article and method for forming pattern |
Non-Patent Citations (2)
| Title |
|---|
| KAZUAKI ET AL: "Direct Polycondensation of Carboxylic Acids and Amines Catalyzed by 3,4,5-Trifluorophenylboronic Acid", 《MACROMOLECULES》 * |
| YAW-TERNG CHERN ET AL: "Preparation and properties of polyamides and polyimides derived from 1,3‐diaminoadamantane", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307967A (en) * | 2020-02-27 | 2021-08-27 | 北京大学 | Polyaramide material containing adamantyl groups, and preparation method and application thereof |
| CN112500561A (en) * | 2020-10-27 | 2021-03-16 | 烟台泰和新材料股份有限公司 | High-strength meta-aramid polymer and preparation method thereof |
| CN112500561B (en) * | 2020-10-27 | 2022-11-15 | 烟台泰和新材料股份有限公司 | High-strength meta-aramid polymer and preparation method thereof |
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