CN106397767A - Benzoxazine intermediate, and preparation method and application thereof - Google Patents
Benzoxazine intermediate, and preparation method and application thereof Download PDFInfo
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- CN106397767A CN106397767A CN201610793481.5A CN201610793481A CN106397767A CN 106397767 A CN106397767 A CN 106397767A CN 201610793481 A CN201610793481 A CN 201610793481A CN 106397767 A CN106397767 A CN 106397767A
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- benzimidazole dihydrochloride
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to the field of resin preparation, and especially relates to a benzoxazine intermediate, and a preparation method and an application thereof. The invention provides a benzoxazine intermediate, a preparation method of the benzoxazine intermediate, and an application of the benzoxazine intermediate or a product prepared by the abovementioned preparation method in the preparation of high Tg and/or highly heatproof resin. The provided benzoxazine intermediate has a more stable chemical structure and can be stored for a longer time. The experiment results show that compared with the conventional products, the provided benzoxazine intermediate has a higher crosslinking density after being cured, and thus has higher Tg and longer storage time. The technical shortages of short storage time and insufficient Tg in the prior art are overcome, the industrial production can be realized, and the application range is enlarged.
Description
Technical field
The invention belongs to resin preparation field, more particularly, to a kind of benzimidazole dihydrochloride intermediate and preparation method and application.
Background technology
Traditional printed circuit copper-clad laminate, mainly to realize the fire-retardant work(of sheet material using brominated epoxy resin
Energy.But in recent years, the combustion product of the waste electrical and electronic equipment of the halogens such as brominated, chlorine verifies two English, hexichol
And the carcinogen such as furan, and halogen product is possible to discharge extremely toxic substance hydrogen halides in combustion.In July, 2006
1 day, two parts of environmental protection instructions of European Union《With regard to scrapping electric/electronic device instruction》With《Make with regard to limiting in electric/electronic device
Use some Hazardous Substances Directive》Formal enforcement.The enforcement of this two parts instructions makes halogen-free flameproof cover copper and moors being developed into of laminate
The focus of industry, the producer of each copper-clad laminate all releases the halogen-free flameproof copper-clad laminate of oneself one after another.
Polybenzoxazine traditional prepare phenolic resin method on the basis of, carry out annulation and obtain by primary amine, phenol, aldehyde
The benzimidazole dihydrochloride intermediate arriving, under conditions of heating or catalyst, benzimidazole dihydrochloride open loop generates has a cancellated class
Novel hot setting resin, solidfied material has preferable thermostability, anti-flammability and electric property.Preparing in the middle of benzimidazole dihydrochloride at present
In body, mainly based on dihydric phenol type benzimidazole dihydrochloride and diamine benzimidazole dihydrochloride, in the benzimidazole dihydrochloride that such synthetic method is obtained
, there is phenolic hydroxyl group and the amido of non-closed loop in mesosome, have that storage time is short, Tg (glass transition in use in structure
Temperature) not enough technological deficiency, affect it and further apply.Can draw from above-mentioned technical background, benzene of the prior art
And piperazine intermediate, there is the technological deficiency that storage time is short, Tg is not enough, cause it to be difficult to industrialized production, application
Limited.
Therefore, a kind of benzimidazole dihydrochloride intermediate and preparation method and application, for solving in prior art, benzene are developed
And piperazine intermediate exists storage time is short, Tg is not enough technological deficiency, realize its industrialized production, expand range of application,
Become those skilled in the art's problem demanding prompt solution.
Content of the invention
In view of this, the invention provides a kind of benzimidazole dihydrochloride intermediate and preparation method and application, existing for solving
Have in technology, benzimidazole dihydrochloride intermediate has the technological deficiency that storage time is short, Tg is not enough, achievable industrialized production, expands
Big range of application.
The invention provides a kind of benzimidazole dihydrochloride intermediate, the structural formula of described benzimidazole dihydrochloride intermediate is：
Wherein, n is more than 0；R1It is selected from：O, C=O, S, SO2, in alicyclic ring hydrocarbons and their derivates and fatty hydrocarbons and their derivates
Any one；R2It is selected from：O, C=O, S, SO2, any one in alicyclic ring hydrocarbons and their derivates and fatty hydrocarbons and their derivates；R3
It is selected from：O, C=O, S, SO2, any one in alicyclic ring hydrocarbons and their derivates and fatty hydrocarbons and their derivates.
Preferably, in described alicyclic ring hydrocarbons and their derivates, backbone c atoms number is less than 20, described fat hydrocarbons and their derivates
Middle backbone c atoms number is less than 20.
Present invention also offers a kind of preparation method including the described benzimidazole dihydrochloride intermediate of any of the above one, described system
Preparation Method is：
Phenols chemicals, aminated compoundss are dissolved in solvent after being mixed with aldehyde compound, heating, obtain product.
Preferably, catalyst need to be added during described melting synthesis；
The addition of described catalyst accounts for the 0.01%～5% of reaction system gross mass.
Preferably, described catalyst is selected from：In KOH aqueous solution, NaOH aqueous solution, ammonia, triethanolamine and triethylamine
One or more.
Preferably, in described phenols chemicals, aminated compoundss and aldehyde compound, functional group's phenolic hydroxyl group, amido and aldehyde
The mol ratio of base is 1:(0.8～1.2):(1.5～2.5)；The temperature of described heating is 60～120 DEG C.
Preferably, described solvent is selected from：Toluene, dimethylbenzene, ethanol, acetone, butanone, methylisobutylketone, ethylene glycol list first
One of ether, ethylene glycol, glycol monoethyl ether, glycol methyl ether acetate, methylformamide and oxolane or many
Kind.
Preferably, the general structure of described phenolic compound is：
Preferably, described aminated compoundss include：Unary primary amine and/or binary primary amine；The structure of described unary primary amine is led to
Formula is：R3-NH2, the general structure of described binary primary amine is：H2N-R2-NH2；
Described aldehyde compound is：Formalin and/or paraformaldehyde.
Present invention also offers a kind of benzimidazole dihydrochloride intermediate including described in any of the above one or more any one
Application in preparing high Tg and/or high heat stable resin for the product that described preparation method obtains.
In sum, the invention provides a kind of benzimidazole dihydrochloride intermediate, the invention provides a kind of above-mentioned benzimidazole dihydrochloride
The preparation method of intermediate, present invention also offers the product that a kind of above-mentioned benzimidazole dihydrochloride intermediate or above-mentioned preparation method obtain
Application in preparing high Tg and/or high heat stable resin.In the technical scheme that the present invention provides, benzimidazole dihydrochloride intermediate structure has
There is more stable chemical constitution.Can obtain through measuring, the benzimidazole dihydrochloride intermediate in the present invention, compared with prior art, tool
There is higher Tg, product gelation time significantly shortens, meanwhile, storage time extends.Solve in prior art, benzimidazole dihydrochloride
Intermediate has the technological deficiency that storage time is short, Tg is not enough, achievable industrialized production, expands range of application.
Specific embodiment
The invention provides a kind of benzimidazole dihydrochloride intermediate and preparation method and application, for solving in prior art,
Benzimidazole dihydrochloride intermediate has the technological deficiency that storage time is short, Tg is not enough, achievable industrialized production, expands application model
Enclose.
The enforcement it is clear that described will be clearly and completely described to the technical scheme in the embodiment of the present invention below
Example is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of not making creative work, broadly falls into the model of present invention protection
Enclose.
In order to the present invention is described in more detail, a kind of benzimidazole dihydrochloride intermediate of the present invention being provided with reference to embodiment and
Its preparation method and application, are specifically described.
Embodiment 1
The present embodiment is the specific embodiment preparing product 1, and the structural formula of product 1 sees below.
Under room temperature condition, weigh and/or measure Bisphenol F (1mol), 4,4'- diaminodiphenyl ether (0.2mol) aniline
(1.6mol) and mass concentration be 36% formalin 333.3g, add catalyst n aOH0.025mol, be dissolved in toluene
(1000ml) mixed solution with ethanol (20ml).
In the present embodiment, catalyst is 10% NaOH aqueous solution, and catalyst accounts for the 0.5% of reaction system gross mass；Phenol
In class chemicals, aminated compoundss and aldehyde compound, the mol ratio of functional group's phenolic hydroxyl group, amido and aldehyde radical is 1:1:2.
After reaction system stirring, under the conditions of 60-120 DEG C, it is heated at reflux 4h.After being heated at reflux end, sequentially pass through decompression and steam
Evaporate, cool down, washing, purification and after being dried, obtain product 1, add butanone dilution, obtain 70% resin solution.
The yield of product 1 is 96.7%, and in product 1, the meansigma methodss of n are 0.4.
Embodiment 2
The present embodiment is the specific embodiment that preparation produces 2, and the structural formula of product 2 sees below.
Under room temperature condition, weigh and/or measure bisphenol-A 2mol, 4,4'- MDA 0.2mol, aniline 4mol
With paraformaldehyde 9.6mol, after adding catalyst 0.2mol, it is dissolved in toluene 1000ml and the mixed solution of ethanol 10ml.
In the present embodiment, catalyst is 25% ammonia spirit, and catalyst accounts for the 1% of reaction system gross mass；Phenol generalization
Learn in thing, aminated compoundss and aldehyde compound, the mol ratio of functional group's phenolic hydroxyl group, amido and aldehyde radical is 1:1.05:2.4.
After reaction system stirring, under the conditions of 60-120 DEG C, it is heated at reflux 4h.After being heated at reflux end, sequentially pass through decompression and steam
Evaporate, cool down, washing, purification and be dried after, obtain product 2.Add butanone dilution, obtain 70% resin solution.
The yield of product 2 is 95.8%, and in product 2, the meansigma methodss of n are 0.2.
Embodiment 3
Embodiment is to prepare the specific embodiment of product 3, and the structural formula of product 3 sees below.
Under room temperature condition, weigh and/or measure bisphenol-A 0.1mol, methylamine 0.09mol, 4,4'- MDA
0.05mol and paraformaldehyde 0.4mol, after adding catalyst 0.02mol, is dissolved in toluene 100ml and the mixed solution of ethanol 5ml
In.
In the present embodiment, catalyst is 25% ammonia spirit, and catalyst accounts for the 1% of reaction system gross mass；；Phenol generalization
Learn in thing, aminated compoundss and aldehyde compound, the mol ratio of functional group's phenolic hydroxyl group, amido and aldehyde radical is 1.1:1:2.
After reaction system stirring, under the conditions of 60-120 DEG C, it is heated at reflux 4h.After being heated at reflux end, sequentially pass through decompression and steam
Evaporate, cool down, washing, purification and be dried after, obtain product 3.Add butanone dilution, obtain 70% resin solution.
The yield of product 3 is 96.1%, and in product 3, the meansigma methodss of n are 1.0.
Embodiment 4
Embodiment is to prepare the specific embodiment of product 4, and the structural formula of product 4 sees below.
Under room temperature condition, weigh and/or measure 4,4' dihydroxy two methyl phenyl ethers anisole 1mol, 4,4'- MDA
0.1mol, cyclohexylamine 0.9mol and paraformaldehyde 4.4mol, after adding catalyst 0.1mol, are dissolved in toluene 500ml and ethanol
In the mixed solution of 10ml.
In the present embodiment, catalyst is 25% ammonia spirit, and catalyst accounts for the 1% of reaction system gross mass；Phenol generalization
Learn in thing, aminated compoundss and aldehyde compound, the mol ratio of functional group's phenolic hydroxyl group, amido and aldehyde radical is 1:1:1.1.
After reaction system stirring, under the conditions of 60-120 DEG C, it is heated at reflux 4h.After being heated at reflux end, sequentially pass through decompression and steam
Evaporate, cool down, washing, purification and after being dried, obtain product 4, add butanone dilution, obtain 70% resin solution.
The yield of product 4 is 95.8%, and in product 4, the meansigma methodss of n are 0.2.
Comparative example 1
This comparative example is to prepare the specific embodiment of reference substance, and the structural formula of reference substance sees below.
Under room temperature condition, weigh and/or measure bisphenol-A 1mol, aniline 2mol, paraformaldehyde 4mol, add catalyst
After 0.1mol, it is dissolved in toluene 500ml and the mixed solution of ethanol 10ml.
In the present embodiment, catalyst is 25% ammonia spirit, and catalyst accounts for the 1% of reaction system gross mass；Phenol generalization
Learn in thing, aminated compoundss and aldehyde compound, the mol ratio of functional group's phenolic hydroxyl group, amido and aldehyde radical is 1:1:2.
After reaction system stirring, under the conditions of 60-120 DEG C, it is heated at reflux 4h.After being heated at reflux end, sequentially pass through decompression and steam
Evaporate, cool down, washing, purification and after being dried, obtain product 5, add butanone dilution, obtain 70% resin solution.
The yield of reference substance is 97.8%, and in reference substance, the meansigma methodss of n are 0.
Embodiment 5
The present embodiment is Tg determination experiment, Heat-tolerance Determination experiment and the storage measuring product 1～product 4 and reference substance
Deposit the specific embodiment of timing experiment.Experimental results refer to table 1.
In the present embodiment, the concrete grammar of related assays experiment belongs to conventional determining well-known to those skilled in the art
Method, will not be described here.
Table 1
As can be drawn from Table 1, in the technical scheme that the present invention provides, a kind of involved benzimidazole dihydrochloride intermediate, has more
High Tg, meanwhile, storage time extends.
In sum, the invention provides a kind of benzimidazole dihydrochloride intermediate, the invention provides a kind of above-mentioned benzimidazole dihydrochloride
The preparation method of intermediate, present invention also offers the product that a kind of above-mentioned benzimidazole dihydrochloride intermediate or above-mentioned preparation method obtain
Application in preparing high Tg and/or high heat stable resin.In the technical scheme that the present invention provides, in benzimidazole dihydrochloride intermediate structure
There is more stable chemical constitution.Can obtain through measuring, the benzimidazole dihydrochloride intermediate in the present invention, compared with prior art,
After its solidification, there is higher crosslink density, thus there is higher Tg, meanwhile, storage time extends.Solve prior art
In, benzimidazole dihydrochloride intermediate has the technological deficiency that storage time is short, Tg is not enough, achievable industrialized production, expands application
Scope.
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of benzimidazole dihydrochloride intermediate is it is characterised in that the structural formula of described benzimidazole dihydrochloride intermediate is：
Wherein, n is more than 0；R1It is selected from：O, C=O, S, SO2, any in alicyclic ring hydrocarbons and their derivates and fatty hydrocarbons and their derivates
A kind of；R2It is selected from：O, C=O, S, SO2, any one in alicyclic ring hydrocarbons and their derivates and fatty hydrocarbons and their derivates；R3Choosing
From：O, C=O, S, SO2, any one in alicyclic ring hydrocarbons and their derivates and fatty hydrocarbons and their derivates.
2. benzimidazole dihydrochloride intermediate according to claim 1 is it is characterised in that main chain in described alicyclic ring hydrocarbons and their derivates
Carbon number is less than 20, and in described fat hydrocarbons and their derivates, backbone c atoms number is less than 20.
3. a kind of preparation method including claim 1 or benzimidazole dihydrochloride intermediate described in 2 any one is it is characterised in that institute
Stating preparation method is：
Phenols chemicals, aminated compoundss are dissolved in solvent after being mixed with aldehyde compound, heating, obtain product.
4. preparation method according to claim 3 is it is characterised in that need to add catalyst during described synthesis；
The addition of described catalyst accounts for the 0.01%～5% of reaction system gross mass.
5. preparation method according to claim 4 is it is characterised in that described catalyst is selected from：KOH aqueous solution, NaOH water
One or more of solution, ammonia, triethanolamine and triethylamine.
6. preparation method according to claim 3 is it is characterised in that described phenols chemicals, aminated compoundss and aldehydes
In compound, the mol ratio of functional group's phenolic hydroxyl group, amido and aldehyde radical is 1:(0.8～1.2):(1.5～2.5)；Described heating
Temperature is 60～120 DEG C.
7. preparation method according to claim 3 is it is characterised in that described solvent is selected from：Toluene, dimethylbenzene, ethanol, third
Ketone, butanone, methylisobutylketone, glycol monoethyl ether, ethylene glycol, glycol monoethyl ether, glycol methyl ether acetate, methyl
One or more of Methanamide and oxolane.
8. preparation method according to claim 3 is it is characterised in that the general structure of described phenolic compound is：
9. preparation method according to claim 3 is it is characterised in that described aminated compoundss include：Unary primary amine and two
First primary amine；The general structure of described unary primary amine is：R3-NH2, the general structure of described binary primary amine is：H2N-R2-NH2；
Described aldehyde compound is：Formalin and/or paraformaldehyde.
10. the benzimidazole dihydrochloride intermediate described in a kind of claim 1 or 2 or the preparation side described in claim 3 to 9 any one
Application in preparing high Tg and/or high heat stable resin for the product that method obtains.
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| CN201610793481.5A CN106397767B (en) | 2016-08-31 | 2016-08-31 | A kind of benzoxazine intermediate and the preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818868A (en) * | 2019-11-29 | 2020-02-21 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof |
| CN112059104A (en) * | 2020-09-01 | 2020-12-11 | 和县华顺铸造有限公司 | Preparation method of hot core box resin for casting |
| US20210371657A1 (en) * | 2020-05-27 | 2021-12-02 | Elite Electronic Material (Kunshan) Co., Ltd. | Resin composition and article made therefrom |
| CN114957155A (en) * | 2021-12-31 | 2022-08-30 | 山东圣泉新材料股份有限公司 | High-heat-resistance low-dielectric benzoxazine prepolymer containing double cross-linked network, copolymer resin and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103097422A (en) * | 2010-03-19 | 2013-05-08 | 迈图专业化学股份有限公司 | Main-chain benzoxazine oligomer compositions, and method for the preparation thereof |
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2016
- 2016-08-31 CN CN201610793481.5A patent/CN106397767B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103097422A (en) * | 2010-03-19 | 2013-05-08 | 迈图专业化学股份有限公司 | Main-chain benzoxazine oligomer compositions, and method for the preparation thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818868A (en) * | 2019-11-29 | 2020-02-21 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof |
| CN110818868B (en) * | 2019-11-29 | 2023-12-12 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer, monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer resin and preparation method of monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer |
| US20210371657A1 (en) * | 2020-05-27 | 2021-12-02 | Elite Electronic Material (Kunshan) Co., Ltd. | Resin composition and article made therefrom |
| CN113736255A (en) * | 2020-05-27 | 2021-12-03 | 台光电子材料(昆山)有限公司 | Resin composition and product thereof |
| US11549014B2 (en) * | 2020-05-27 | 2023-01-10 | Elite Electronic Material (Kunshan) Co., Ltd. | Resin composition and article made therefrom |
| CN113736255B (en) * | 2020-05-27 | 2023-07-14 | 台光电子材料(昆山)有限公司 | Resin composition and product thereof |
| CN112059104A (en) * | 2020-09-01 | 2020-12-11 | 和县华顺铸造有限公司 | Preparation method of hot core box resin for casting |
| CN114957155A (en) * | 2021-12-31 | 2022-08-30 | 山东圣泉新材料股份有限公司 | High-heat-resistance low-dielectric benzoxazine prepolymer containing double cross-linked network, copolymer resin and preparation method thereof |
| CN114957155B (en) * | 2021-12-31 | 2024-02-27 | 山东圣泉新材料股份有限公司 | High heat-resistant low-dielectric benzoxazine prepolymer and copolymer resin containing double cross-linked network and preparation method thereof |
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| CN106397767B (en) | 2019-09-17 |
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