CN101624444A - Method for preparing soft electronic material from polybenzoxazine - Google Patents
Method for preparing soft electronic material from polybenzoxazine Download PDFInfo
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- CN101624444A CN101624444A CN200810127860A CN200810127860A CN101624444A CN 101624444 A CN101624444 A CN 101624444A CN 200810127860 A CN200810127860 A CN 200810127860A CN 200810127860 A CN200810127860 A CN 200810127860A CN 101624444 A CN101624444 A CN 101624444A
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Abstract
The invention relates to a method for preparing a soft polybenzoxazine material, which comprises the following steps: dissolving formaldehyde into first dissolvent to form formaldehyde solution; dissolving a phenolic compound into second dissolvent to form phenolic solution; dissolving a primary amine compound into third dissolvent to form primary amine solution; mixing and evenly stirring the formaldehyde solution and the primary amine solution to form first solution; adding the phenolic solution into the first solution for mixing and reaction to generate soft polybenzoxazine monomers and oligomers; and heating the soft polybenzoxazine monomers and the oligomers to form the soft polybenzoxazine material, wherein the primary amine compound has groups of the aliphatic series with 2-20 carbon atoms. The method for preparing the soft polybenzoxazine material overcomes the defects of high hardness and poor flexibility of polybenzoxazine, and can be applied in the fields of soft copper foil substrates and other flexible materials.
Description
Technical field
The invention relates to a kind of polyphenyl and oxazines preparation methods, particularly about a kind of soft polyphenyl and oxazines preparation methods, it is applied to the field of flexible copper foil substrate and other flexible materials.
Background technology
Polyphenyl and oxazines (polybenzoxazine) are in recent years by the thermosetting resin of broad development and application, monomer whose is mainly synthesized by primary amine (primary amine), phenol (phenol) and formaldehyde (formaldehyde), and its structure is mainly the heterogeneous ring compound that oxazines ring (oxazine ring) is formed.
Benzoxazine (benzoxazine) monomer does not need to add any catalyzer or stiffening agent in the polymerization process of setting, can not produce when polyreaction human body and the deleterious gas of environment yet, also can not produce any by product.
Polyphenyl and oxazines (polybenzoxazine) have very high glass tansition temperature, high-module, low water absorbable, good dielectric properties, the expansion of adding that sclerosis the time can not be shunk even can be a little is also because the dimensional stability of its goods is good, so can be applied to make the part of precision, moreover because its viscosity is lower, so the degree of freedom of product design is higher.
Flexible copper foil substrate now and soft electronic material need possess softer and flexible preferable characteristic, but polyphenyl and oxazines are higher owing to hardness, thus do not have above-mentioned characteristic, so be not suitable for flexible copper foil substrate and electronics flexible material.
In order to improve the higher and flexible relatively poor shortcoming of polyphenyl and oxazines hardness and to have polyphenyl concurrently and the advantage of the low water absorbable of oxazines and good dielectricity, the invention provides a kind of soft polyphenyl and oxazines preparation methods, it improves polyphenyl and oxazines high rigidity and flexible relatively poor shortcoming, and have the advantage of the low water absorbable and the good dielectricity of polyphenyl and oxazines concurrently, make soft polyphenyl and oxazines material behind the upgrading can be applied to flexible copper foil substrate and other flexible materials.
Summary of the invention
One of purpose of the present invention is to provide a kind of soft polyphenyl and oxazines preparation methods, it can improve polyphenyl and oxazines high rigidity and flexible relatively poor shortcoming, the field that makes soft polyphenyl behind the upgrading and oxazines material can be applied to flexible copper foil substrate and other flexible materials.
Two of purpose of the present invention is to provide a kind of soft polyphenyl and oxazines preparation methods, the advantage that it can have the low water absorbable and the good dielectricity of polyphenyl and oxazines concurrently makes soft polyphenyl and oxazines material behind the upgrading can be applied to flexible copper foil substrate and other flexible materials.
For realizing that the object of the invention to solve the technical problems is achieved through the following technical solutions.
A kind of soft polyphenyl provided by the invention and oxazines preparation methods, its step comprises:
Formaldehyde is dissolved in first solvent forms formaldehyde solution;
Phenolic compound is dissolved in second solvent forms phenols solution;
The primary amine compounds is dissolved in the 3rd solvent forms one-level amine solution;
This formaldehyde solution is mixed with this one-level amine solution and stir, form first solution;
Add monomer and the oligomer of this phenols solution to this first solution mixing and reaction soft polyphenyl of formation and oxazines; And
Heating makes this soft polyphenyl and oxazines monomer and oligomer form soft polyphenyl and oxazines material;
Wherein this primary amine compounds has the aliphatic group of carbon atom number 2-20.
Among the present invention, wherein this primary amine compounds more comprises and contains oxygen functional group group.
Among the present invention, wherein this primary amine compounds more comprises the sulfur-bearing functional group.
Among the present invention, wherein this phenolic compound more comprises the aliphatic group of carbon atom number 2-20.
Among the present invention, wherein this phenolic compound more comprises the sulfur-bearing functional group.
Among the present invention, wherein this phenolic compound more comprises and contains oxygen functional group group.
Among the present invention, wherein this primary amine compounds is selected from primary amine, primary amine monofunctional compound, primary amine difunctionality based compound, primary amine trifunctional based compound and primary amine four functional group's compounds, and this phenolic compound is selected from group that phenol, single phenol functional group compound, bis-phenol functional group compound, triphenol functional group compound and four phenol functional group compounds are formed one of them.
Among the present invention, when phenolic compound is single phenol functional group compound and primary amine compounds when being primary amine, it is 1: 2: 1 that the not ear when phenol, formaldehyde and primary amine reaction is counted ratio.
Among the present invention, when phenolic compound is single phenol functional group compound and primary amine compounds when being primary amine difunctionality based compound, it is 2: 4: 1 that the not ear when single phenol functional group compound, formaldehyde and the reaction of primary amine difunctionality based compound is counted ratio.
Among the present invention, when phenolic compound is bis-phenol functional group compound and primary amine compounds when being primary amine, it is 1: 4: 2 that the not ear when bis-phenol functional group compound, formaldehyde and primary amine reaction is counted ratio.
Among the present invention, wherein this formaldehyde solution is mixed with this one-level amine solution and the step that stirs is carried out in ice bath below 5 ℃.
Among the present invention, wherein add this phenols solution to this first solution mixing and reaction and form in the step of this soft polyphenyl and oxazines monomer and oligomer, more comprise the step of a reflux.
Among the present invention, wherein after the step of this reflux, more comprise the step of an extraction.
Among the present invention, wherein heating forms in the step of this soft polyphenyl and oxazines material this soft polyphenyl and oxazines monomer and oligomer, more comprise one should soft polyphenyl and oxazines monomer and oligomer coat substrate, and with the step of 80oC-180oC temperature heated polymerizable.
The invention has the beneficial effects as follows that the present invention improves polyphenyl and oxazines high rigidity and flexible relatively poor shortcoming, and can be applied to the field of flexible copper foil substrate and other flexible materials.
Description of drawings
Fig. 1 is the flow chart of steps of soft polyphenyl of the present invention and oxazines preparation methods.
Embodiment
Further understand and understanding for the auditor is had constitutional features of the present invention and the effect reached, in order to preferred embodiment and cooperate detailed explanation, be described as follows:
Because polyphenyl and oxazines (polybenzoxazine) character are harder, can add some soft chain functional groups, make it have pliability, for example, primary amine (primary amine) or phenols that employing has soft group synthesize polyphenyl and oxazines, this softness group such as aliphatics (carbon atom number 2 to 20), contain oxygen functional group group (O-) or sulfur-bearing functional group (S-, S is last can to connect other functional group) etc.
The invention provides a kind of soft polyphenyl and oxazines preparation methods, its step comprises (as shown in Figure 1):
S11 is dissolved in first solvent with formaldehyde and forms formaldehyde solution;
S12 is dissolved in second solvent with phenolic compound and forms phenols solution;
S13 is dissolved in the 3rd solvent with the primary amine compounds and forms one-level amine solution;
S14 mixes this formaldehyde solution and stirs with this one-level amine solution, form first solution;
S15 adds this phenols solution to this first solution mixing and reaction and forms soft polyphenyl and oxazines monomer and oligomer; And
The S16 heating makes this soft polyphenyl and oxazines monomer and oligomer form soft polyphenyl and oxazines material.
Wherein this primary amine compounds has the aliphatic group of carbon atom number 2-20, and this primary amine compounds can comprise that more containing the oxygen functional group rolls into a ball and/or the sulfur-bearing functional group.
This phenolic compound more comprises the aliphatic group of carbon atom number 2-20, and this phenolic compound more comprises the sulfur-bearing functional group and/or contains oxygen functional group group.
Wherein this primary amine compounds is selected from primary amine, primary amine monofunctional compound, primary amine difunctionality based compound, primary amine trifunctional based compound and primary amine four functional group's compounds; And this phenolic compound is selected from group that phenol, single phenol functional group compound, bis-phenol functional group compound, triphenol functional group compound and four phenol functional group compounds are formed one of them.When phenolic compound is single phenol functional group compound and primary amine compounds when being primary amine, it is 1: 2: 1 that the not ear when phenol, formaldehyde and primary amine reaction is counted ratio.When phenolic compound is single phenol functional group compound and primary amine compounds when being primary amine difunctionality based compound, it is 2: 4: 1 that the not ear when single phenol functional group compound, formaldehyde and the reaction of primary amine difunctionality based compound is counted ratio.When phenolic compound is bis-phenol functional group compound and primary amine compounds when being the monofunctional primary amine, it is 1: 4: 2 that the not ear when bis-phenol functional group compound, formaldehyde and primary amine reaction is counted ratio.
Now enumerate the phenolic compound that some the present invention use, its chemical structure and title are as follows:
biphenyl-4，4′-diol
4，4′-(propane-2，2-diyl)diphenol
4，4′-thiodiphenol
4，4′-sulfonyldiphenol
Now enumerate the primary amine compounds that some the present invention use, its chemical structure and title are as follows:
ethanamine butan-1-amine ethane-1，2-diamine
butane-1，4-diamine O-methylhydroxylamine
oxydimethanamine 3，3-diethoxypropan-1-amine
Wherein this formaldehyde solution is mixed with this one-level amine solution and stir, the S14 step that forms first solution is carried out in ice bath below 5 ℃.
Wherein add this phenols solution to this first solution mixing and reaction and form in the S15 step of this soft polyphenyl and oxazines monomer and oligomer, more comprise the step of a reflux.Wherein after the step of this reflux, more comprise the step of an extraction.
Wherein heating forms in the S16 step of this soft polyphenyl and oxazines material this soft polyphenyl and oxazines monomer or oligomer, more comprise one should soft polyphenyl and oxazines monomer or oligomer coat substrate, and with the step of 80oC-180oC temperature heated polymerizable.
Embodiment
1. formaldehyde (formaldehyde) is added toluene, stir, form formaldehyde solution.
2. the primary amine (primary amine) with 2 carbonatomss adds toluene, stirs, and forms primary amine solution.
3. phenol (phenol) is added toluene, stir, form phenol solution.
4. formaldehyde solution is done with primary amine solution and mixed, under ice bath 5oC, stir, obtain first solution.
5. phenol solution is heated to 65oC and does backflow, and when 65oC, slowly add first solution, be warming up to 95oC backflow 6hr after stirring.
6. with last resulting liquid, extract respectively with ether, pure water, 2N sodium hydroxide (NaOH) again, and after removing excessive solution (solvent), can obtain the precursor of the stickiness of dark yellow brown (the product color can change to some extent with using the medicine difference) as polyphenyl and oxazines.
7. use the mode of scraper or rotary coating to be coated on the metal substrate precursor of polyphenyl and oxazines,, form soft polyphenyl and oxazines with 80oC-180oC and the polymerization that made in 1-3 hour.
Hence one can see that, the invention provides a kind of soft polyphenyl and oxazines preparation methods, can improve polyphenyl and oxazines high rigidity and flexible relatively poor shortcoming, and can have the advantage of the low water absorbable and the good dielectricity of polyphenyl and oxazines concurrently, make soft polyphenyl and oxazines material behind the upgrading can be applied to flexible copper foil substrate and other flexible materials.
In sum, it only is a preferred embodiment of the present invention, be not to be used for limiting scope of the invention process, all according to impartial for it variation of the described shape of claim scope of the present invention, structure, feature and spiritual institute and modification, all should be included in the claim scope of the present invention.
Claims (14)
1. soft polyphenyl and oxazines preparation methods is characterized in that its step comprises:
Formaldehyde is dissolved in first solvent forms formaldehyde solution;
Phenolic compound is dissolved in second solvent forms phenols solution;
The primary amine compounds is dissolved in the 3rd solvent forms one-level amine solution;
This formaldehyde solution is mixed with this one-level amine solution and stir, form first solution;
Add monomer and the oligomer of this phenols solution to this first solution mixing and reaction soft polyphenyl of formation and oxazines; And
Heating makes this soft polyphenyl and oxazines monomer and oligomer form soft polyphenyl and oxazines material;
Wherein this primary amine compounds has the aliphatic group of carbon atom number 2-20.
2. soft polyphenyl according to claim 1 and oxazines preparation methods is characterized in that, wherein this primary amine compounds more comprises and contains oxygen functional group group.
3. soft polyphenyl according to claim 1 and oxazines preparation methods is characterized in that, wherein this primary amine compounds more comprises the sulfur-bearing functional group.
4. soft polyphenyl according to claim 1 and oxazines preparation methods is characterized in that wherein this phenolic compound more comprises the aliphatic group of carbon atom number 2-20.
5. soft polyphenyl according to claim 1 and oxazines preparation methods is characterized in that wherein this phenolic compound more comprises the sulfur-bearing functional group.
6. soft polyphenyl according to claim 1 and oxazines preparation methods is characterized in that, wherein this phenolic compound more comprises and contains oxygen functional group group.
7. soft polyphenyl according to claim 1 and oxazines preparation methods, it is characterized in that, wherein this primary amine compounds is selected from primary amine, primary amine monofunctional compound, primary amine difunctionality based compound, primary amine trifunctional based compound and primary amine four functional group's compounds, and this phenolic compound is selected from group that phenol, single phenol functional group compound, bis-phenol functional group compound, triphenol functional group compound and four phenol functional group compounds are formed one of them.
8. soft polyphenyl according to claim 7 and oxazines preparation methods, it is characterized in that, when phenolic compound is single phenol functional group compound and primary amine compounds when being primary amine, it is 1: 2: 1 that the not ear when phenol, formaldehyde and primary amine reaction is counted ratio.
9. soft polyphenyl according to claim 7 and oxazines preparation methods, it is characterized in that, when phenolic compound is single phenol functional group compound and primary amine compounds when being primary amine difunctionality based compound, it is 2: 4: 1 that the not ear when single phenol functional group compound, formaldehyde and the reaction of primary amine difunctionality based compound is counted ratio.
10. soft polyphenyl according to claim 7 and oxazines preparation methods, it is characterized in that, when phenolic compound is bis-phenol functional group compound and primary amine compounds when being primary amine, it is 1: 4: 2 that the not ear when bis-phenol functional group compound, formaldehyde and primary amine reaction is counted ratio.
11. soft polyphenyl according to claim 1 and oxazines preparation methods is characterized in that, wherein this formaldehyde solution are mixed with this one-level amine solution and the step that stirs is carried out in ice bath below 5 ℃.
12. soft polyphenyl according to claim 1 and oxazines preparation methods, it is characterized in that, wherein add this phenols solution to this first solution mixing and reaction and form in the step of this soft polyphenyl and oxazines monomer and oligomer, more comprise the step of a reflux.
13. soft polyphenyl according to claim 12 and oxazines preparation methods is characterized in that, wherein after the step of this reflux, more comprise the step of an extraction.
14. soft polyphenyl according to claim 1 and oxazines preparation methods, it is characterized in that, wherein heating forms in the step of this soft polyphenyl and oxazines material this soft polyphenyl and oxazines monomer and oligomer, more comprise one should soft polyphenyl and oxazines monomer and oligomer coat substrate, and with the step of 80 ℃ of-180 ℃ of temperature heated polymerizables.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810127860A CN101624444A (en) | 2008-07-07 | 2008-07-07 | Method for preparing soft electronic material from polybenzoxazine |
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| CN200810127860A CN101624444A (en) | 2008-07-07 | 2008-07-07 | Method for preparing soft electronic material from polybenzoxazine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356084A (en) * | 2014-10-22 | 2015-02-18 | 苏州太湖电工新材料股份有限公司 | Preparation method of benzoxazine compound |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356084A (en) * | 2014-10-22 | 2015-02-18 | 苏州太湖电工新材料股份有限公司 | Preparation method of benzoxazine compound |
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Open date: 20100113 |