CN109575284A - Polyimide resin and preparation method thereof of the one kind containing asymmetric methyl and meta position benzene ring structure - Google Patents
Polyimide resin and preparation method thereof of the one kind containing asymmetric methyl and meta position benzene ring structure Download PDFInfo
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- CN109575284A CN109575284A CN201811507972.4A CN201811507972A CN109575284A CN 109575284 A CN109575284 A CN 109575284A CN 201811507972 A CN201811507972 A CN 201811507972A CN 109575284 A CN109575284 A CN 109575284A
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- Prior art keywords
- polyimide resin
- containing asymmetric
- benzene ring
- ring structure
- meta position
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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
- 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
- C08G73/1003—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
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention belongs to polyimides high-performance polymer and its preparation field, in particular to a kind of polyimide resin and preparation method thereof containing asymmetric methyl and meta position benzene ring structure.Preparation process are as follows: under nitrogen protection; by containing asymmetric methyl structural aromatic diamine monomers, 4; 4 '-diaminodiphenyl ethers and diphenyl ether tetracid dianhydride monomer are to measure than being dissolved in organic solvent; it is stirred to react 12 at room temperature~for 24 hours, it further heats up to 170~190 DEG C, passes through nitrogen stream band water; after being stirred to react 6~12h; reaction was completed, through sedimentation, filtering, drying, obtains the copolymerization polyimide type resin of threadiness；Such polyimide resin has excellent processing performance, can directly carry out thermoplasticity processing or solution casting film forming, have important potential using value in special engineering plastics and high performance membrane Material Field.
Description
Technical field
The invention belongs to polyimides high-performance polymer and its preparation field, in particular to it is a kind of containing asymmetric methyl and
The polyimide resin and preparation method thereof of meta position benzene ring structure.
Background technique
Polyimides is a kind of important aromatic heterocyclic polymer, can be used as high-performance fiber, film, special engineering plastics etc.
Applied in modern high-tech field.However, usually making polyamides sub- due to the high degree of rigidity and regularity of polymer molecular chain
Amine polymer indissoluble infusibility is difficult to direct processed and applied.Polyimides needs to form in its presoma polyamic acid stage, into one
Step is converted into corresponding polyimides product by high temperature hot-imide.High-temperature heat treatment process can generate the performance of product
Large effect, and the polyimides product after imidizate can not secondary operation use.Therefore, further improve polyimides
Processing performance, design and develop can the new type polyimide resin of directly hot-working or solution moulding by casting there is important research
Meaning.
Summary of the invention
In order to solve the technical problems existing in the prior art, the invention patent is modified using copolycondensation, poly- by optimizing
Adduct molecule chain structure, while asymmetric methyl and meta position benzene ring structure are introduced in polyimide molecule structure, it is prepared
A kind of copolymerization polyimide type resin.The introducing of methyl can increase the distance of polymer molecule interchain in molecular structure, not right
Claim and the introducing of meta position benzene ring structure can effectively destroy the regularity of polymer molecular chain, to be effectively improved polyimide resin
Dissolubility, being synthetically prepared and directly provided convenience using its solution moulding by casting for polyimides；In addition, copolymerized diamine
Introducing with ehter bond in dianhydride structure can be effectively improved the hot-working character of polyimide resin.
The purpose of the invention is to improve conventional polyimide indissoluble infusibility, it is difficult to the defects of direct processed and applied, adopt
It is modified with copolycondensation, by optimizing polymer molecule chain structure, while asymmetric methyl is introduced in polyimide molecule structure
With meta position benzene ring structure, it has been prepared a kind of containing asymmetric methyl and meta position benzene ring structure polyimide resin.Molecular structure
The introducing of middle methyl can increase the distance of polymer molecule interchain, and asymmetric and meta position benzene ring structure introducing can effectively destroy poly-
The regularity of adduct molecule chain, to be effectively improved the dissolubility of polyimide resin, for being synthetically prepared and directly for polyimides
It connects and is provided convenience using its solution moulding by casting；In addition, the introducing of ehter bond can be effectively improved in copolymerized diamine and dianhydride structure
The hot-working character of polyimide resin.
One kind provided by the invention patent contains asymmetric methyl and meta position benzene ring structure polyimide resin, structural formula
It is as follows,
Wherein 0.3 < x < 1, n=50~100,
Containing asymmetric methyl and meta position benzene ring structure in copolymerized diamine structural unit；Such copolymerization polyimide type resin exists
There are important potential using values for special engineering plastics and high performance membrane Material Field.
The present invention also provides a kind of above-mentioned a kind of systems containing asymmetric methyl and meta position benzene ring structure polyimide resin
Preparation Method, the specific steps are as follows:
Under nitrogen protection, by x parts of aromatic diamine monomers (0.3 < x < 1) containing asymmetric methyl structural, the 4 of 1-x parts,
4 '-diaminodiphenyl ether monomers and 1 part of diphenyl ether tetracid dianhydride monomer are dissolved in organic solvent, it is stirred to react 12 at room temperature~
For 24 hours, it further heats up to 170~190 DEG C, by nitrogen stream band water, after being stirred to react 6~12h, reaction was completed, to reactant
System is cooled to room temperature, and pours into dispersing and settling in alcohols solvent, filtering, drying, obtains the polyimide resin of threadiness.
Wherein, the aromatic diamine monomers containing asymmetric methyl structural are 2,4- diaminotoluene, structural formula
For
The polymerization is one of N-Methyl pyrrolidone or n,N-dimethylacetamide, dosage with organic solvent
It is 5~10 times of aromatic diamine monomers and dianhydride monomer gross mass.
It is of the invention containing asymmetric methyl and meta position benzene ring structure polyimide resin to be specifically synthetically prepared route as follows:
The beneficial effects of the present invention are:
(1) the present invention provides one kind containing asymmetric methyl and meta position benzene ring structure polyimide resin and its preparation side
Method, cost of material is low, and it is simple to be synthetically prepared route, can directly utilize the lower N-Methyl pyrrolidone of toxicity or N, N- diformazan
Yl acetamide makees solvent, and polyimide resin is prepared in polymerization.
(2) such, which contains asymmetric methyl and meta position benzene ring structure polyimide resin, has good processing performance, can be straight
It connected thermoforming or utilized its solution casting film forming.
(3) such contains asymmetric methyl and meta position benzene ring structure polyimide resin, can have by the content of copolymerized diamine
Effect regulates and controls its thermodynamic property, has important potential using value in special engineering plastics and high performance membrane Material Field.
Detailed description of the invention
Fig. 1 is containing asymmetric methyl and meta position benzene ring structure polyimide resin1H NMR spectra (wherein 2,4- diamino
50%) content of base toluene structural unit and 4,4 '-diaminodiphenyl ether structural units is.
Specific embodiment
Embodiment 1
In the dry flask with three necks,round bottom of 100ml for being connected with nitrogen, it is separately added into 2, the 4- diamino of 0.3665g (3mmol)
Three kinds of lists of diphenyl ether tetracid dianhydride of base toluene, the 4,4 '-diaminodiphenyl ethers of 0.6006g (3mmol) and 1.861g (6mmol)
Body adds 15mL N-Methyl pyrrolidone, is stirred to react 12h at room temperature, further heats up to 190 DEG C, passes through nitrogen stream band
After water is stirred to react 6h, reaction solution is poured into 500ml ethyl alcohol, is filtered, is dry to get the polyimides tree for arriving threadiness
Rouge, yield 99%.1H NMR (400M, DMSO): 8.06 (H6,H6’),7.62(H4,H4’,H5,H5’),7.54(H1),7.48(H2,
H3,H7),7.22(H8),2.19(-CH3).
Embodiment 2
In the dry flask with three necks,round bottom of 100ml for being connected with nitrogen, it is separately added into 2, the 4- diamino of 0.3665g (3mmol)
Three kinds of lists of diphenyl ether tetracid dianhydride of base toluene, the 4,4 '-diaminodiphenyl ethers of 0.6006g (3mmol) and 1.861g (6mmol)
Body, adds 27mL n,N-dimethylacetamide, is stirred to react at room temperature for 24 hours, further heats up to 170 DEG C, passes through nitrogen stream
After band water is stirred to react 12h, reaction solution is poured into 500ml ethyl alcohol, is filtered, is dry to get the polyimides for arriving threadiness
Resin, yield 99%.
Embodiment 3
In the dry flask with three necks,round bottom of 100ml for being connected with nitrogen, being separately added into 0.4887g (4mmol), (dosage can change
Become) 2,4 di amino toluene, the 4,4 '-diaminodiphenyl ethers of 0.4004g (2mmol) and the diphenyl ether of 1.861g (6mmol)
Three kinds of monomers of tetracid dianhydride, add 15mL N-Methyl pyrrolidone, are stirred to react 12h at room temperature, further heat up to 190
DEG C, after being stirred to react 6h by nitrogen stream band water, reaction solution is poured into 500ml ethyl alcohol, is filtered, is dried to get fiber is arrived
The polyimide resin of shape, yield 99%.
Embodiment 4
In the dry flask with three necks,round bottom of 100ml for being connected with nitrogen, being separately added into 0.6109g (5mmol), (dosage can change
Become) 2,4 di amino toluene, the 4,4 '-diaminodiphenyl ethers of 0.2002g (1mmol) and the diphenyl ether of 1.861g (6mmol)
Three kinds of monomers of tetracid dianhydride, add 15mL n,N-dimethylacetamide, are stirred to react at room temperature for 24 hours, further heat up to
170 DEG C, after being stirred to react 12h by nitrogen stream band water, reaction solution is poured into 500ml ethyl alcohol, is filtered, is dry to get arriving
The polyimide resin of threadiness, yield 99%.
Claims (4)
1. a kind of polyimide resin containing asymmetric methyl and meta position benzene ring structure, it is characterised in that: the chemistry of the resin
Structural formula is as follows,
Wherein, 0.3 < x < 1, n=50~100, containing asymmetric methyl and meta position benzene ring structure in copolymerized diamine structural unit.
2. a kind of preparation method as described in being required right 1 containing asymmetric methyl and meta position benzene ring structure polyimide resin,
Be characterized in that: steps are as follows for the preparation method:
Under nitrogen protection, by x parts of aromatic diamine monomers (0.3 < x < 1) containing asymmetric methyl structural, the 4 of 1-x parts, 4 '-
Diaminodiphenyl ether monomer and 1 part of diphenyl ether tetracid dianhydride monomer are dissolved in organic solvent, it is stirred to react 12 at room temperature~
For 24 hours, it further heats up to 170~190 DEG C, by nitrogen stream band water, after being stirred to react 6~12h, reaction was completed, to reactant
System is cooled to room temperature, and pours into dispersing and settling in alcohols solvent, filtering, drying, obtains the polyimide resin of threadiness.
3. the preparation method containing asymmetric methyl and meta position benzene ring structure polyimide resin as claimed in claim 2, feature
Be: the aromatic diamine monomers containing asymmetric methyl structural are 2,4 di amino toluene.
4. the preparation method containing asymmetric methyl and meta position benzene ring structure polyimide resin as claimed in claim 2, feature
Be: the polymerization is one of N-Methyl pyrrolidone or n,N-dimethylacetamide with organic solvent, and dosage is
5~10 times of aromatic diamine monomers and dianhydride monomer gross mass.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811507972.4A CN109575284A (en) | 2018-12-11 | 2018-12-11 | Polyimide resin and preparation method thereof of the one kind containing asymmetric methyl and meta position benzene ring structure |
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| CN201811507972.4A CN109575284A (en) | 2018-12-11 | 2018-12-11 | Polyimide resin and preparation method thereof of the one kind containing asymmetric methyl and meta position benzene ring structure |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113436689A (en) * | 2021-06-25 | 2021-09-24 | 平安科技（深圳）有限公司 | Drug molecular structure prediction method, device, equipment and storage medium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5442031A (en) * | 1994-04-21 | 1995-08-15 | E. I. Du Pont De Nemours And Company | Polyimides from oxydiphthalic anhydride and 2,4-diaminotoluene |
-
2018
- 2018-12-11 CN CN201811507972.4A patent/CN109575284A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5442031A (en) * | 1994-04-21 | 1995-08-15 | E. I. Du Pont De Nemours And Company | Polyimides from oxydiphthalic anhydride and 2,4-diaminotoluene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113436689A (en) * | 2021-06-25 | 2021-09-24 | 平安科技（深圳）有限公司 | Drug molecular structure prediction method, device, equipment and storage medium |
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