TW201908368A - Modified polyphenylene oxide polymer compound, polymeric layer, and method for making the same - Google Patents

Abstract

A polyphenylene oxide polymer compound has a chemical structural formula selected from. A method for making the polyphenylene oxide polymer compound, a polymeric layer using the polyphenylene oxide polymer compound, and a method for making the polymeric layer are also provided.

Description

Modified polyphenylene ether polymer, polymer film and corresponding preparation method

The present invention relates to a modified polyphenylene ether polymer, a method for preparing the modified polyphenylene ether polymer, a polymer film using the modified polyphenylene ether polymer, and the polymer A method of preparing a film.

In the era of big data, the information processing of electronic products continues to develop in the direction of high-frequency signal transmission and high-speed digitalization. To ensure that the electronic product has good signal transmission quality under the condition of high-frequency signal transmission, it is required that the transmission line in the conductive copper foil of the flexible circuit board and the electronic components connected thereto are in an impedance matching state to avoid signal reflection. Scattering, attenuation, and delay. The dielectric constant and dielectric loss factor of the material of the adhesive layer in contact with the conductive line in the flexible circuit board are an important factor affecting the impedance matching of the high frequency transmission. The polyimide film layer used in the flexible printed circuit board in the prior art is generally prepared by using a diamine compound and a dianhydride compound, and the dielectric constant of the film layer is often caused by containing a polar functional group therein. Above 3.0, the flexible circuit board cannot achieve high-frequency signal transmission impedance matching, which affects the high-frequency signal transmission and high-speed digitalization.

In view of the above, it is necessary to provide a modified polyphenylene ether polymer having a low dielectric constant and good heat resistance.

Further, it is also necessary to provide a process for preparing the above modified polyphenylene ether high molecular polymer.

Further, it is also necessary to provide a polymer film obtained by applying the modified polyphenylene ether polymer.

A modified polyphenylene ether polymer, the chemical structure of the modified polyphenylene ether polymer , or .

A method for preparing a modified polyphenylene ether polymer comprises the following steps:

A polyphenylene ether polymer, an active reactant and a solvent are uniformly mixed to obtain a resin composition, wherein the polyphenylene ether polymer has a chemical structural formula of The active reactant is 2-methacrylic anhydride, 4-chloromethylstyrene or trans-cinnamonium chloride;

The above resin composition is heated to react to obtain a modified polyphenylene ether polymer, wherein the chemical structure of the modified polyphenylene ether polymer is , or .

Further, in the resin composition, the weight ratio of the polyphenylene ether polymer to the active reactant is 1:10 to 50:1.

Further, the step of “heating the above resin composition to react to obtain a modified polyphenylene ether polymer” specifically includes:

Sodium acetate and N,N-dimethylacetamide were sequentially added to the resin composition, stirred and uniformly mixed, and then heated under a nitrogen atmosphere to obtain the modified polyphenylene ether polymer.

Further, the polyphenylene ether polymer is prepared by the following steps:

4,4'-difluorobenzophenone and chemical formula The polyphenylene ether copolymer is heated under a nitrogen atmosphere and a potassium carbonate catalyzed reaction to obtain a first product, and the chemical structure of the first product is ;and

The first product, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and phenol are mixed and heated to obtain the polyphenylene ether polymer.

Further, the solvent is N,N-dimethylacetamide.

A polymer film obtained by baking and curing a resin containing a modified polyphenylene ether polymer, wherein the polymer film comprises the modified polyphenylene ether polymer a chemical cross-linking structure formed by a cross-linking reaction, wherein the chemical structure of the modified polyphenylene ether polymer is , or .

A method for preparing a polymer film, comprising the steps of: pre-baking a resin comprising a modified polyphenylene ether polymer, and curing at a temperature, wherein the modified polyphenylene ether is high A cross-linking reaction occurs between the molecular polymers to form a chemical cross-linking structure, and the chemical structure of the modified polyphenylene ether polymer is , or .

Further, the baking curing temperature is 140 degrees Celsius, and the baking curing time is 30 minutes.

Due to the long-chain structure of the modified polyphenylene ether polymer, the polymer film formed by the modified polyphenylene ether polymer is increased in flexibility, and the modified polyphenylene ether is high. The polyphenylene ether structure in the molecular polymer allows the polymer film formed of the modified polyphenylene ether polymer to have a low dielectric constant. In addition, since the modified polyimine polymer compound indirectly has a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group, the resulting polyfluorene is obtained. The amine film has excellent flame retardancy.

The modified polyphenylene ether polymer of the preferred embodiment of the present invention can be used in a substrate, a glue layer or a cover film of a circuit board such as a rigid-flex board. The chemical structure formula of the modified polyphenylene ether polymer is , or . A preferred embodiment of the present invention also provides a method for preparing the above modified polyphenylene ether polymer, which comprises the following steps:

In step S1, a polyphenylene ether polymer, an active reactant and a solvent are uniformly mixed to obtain a resin composition. In the resin composition, the weight ratio of the polyphenylene ether polymer to the active reactant is 1:10 to 50:1. The solvent may dissolve the polyphenylene ether polymer and the active reactant. In the present embodiment, the viscosity of the resin composition is from 40,000 cps to 60000 cps.

The chemical structural formula of the polyphenylene ether polymer is .

The active reactant may be selected from, but not limited to, one of 2-methacrylic anhydride, 4-chloromethylstyrene, and trans-cinnamonium chloride.

In the present embodiment, the solvent is N,N-dimethylacetamide (DMAc). In other embodiments, the solvent may be other organic solvents commonly used in the art for dissolving ether polymer compounds and epoxy resins.

Step S2, sequentially adding sodium acetate and N,N-dimethylacetamide to the resin composition, stirring and mixing uniformly, and then heating the reaction for a period of time under a nitrogen atmosphere to obtain the modified polyphenylene ether. Molecular polymer.

The sodium acetate is a catalyst for the reaction, and the N,N-dimethylacetamide is used to dissolve and mix the resin composition and the sodium acetate uniformly.

In the present embodiment, the heating temperature is 60 degrees Celsius to 100 degrees Celsius, and the reaction time is 10 hours to 13 hours.

Wherein, the reaction mechanism of the resin composition to form the modified polyphenylene ether polymer is as follows: , or .

In the present embodiment, the polyphenylene ether polymer is prepared by the following steps:

Step S11, .

The heating temperature in the above step S21 is 100 degrees Celsius to 140 degrees Celsius, and the reaction time is 10 hours to 13 hours, and the potassium carbonate is a catalyst.

Step S12, .

The heating temperature in the above step S22 is 120 degrees Celsius to 150 degrees Celsius, and the reaction time is 10 hours to 13 hours.

A polymer film obtained by baking and curing a resin containing the modified polyphenylene ether polymer. Wherein, the polymer film comprises a chemical crosslinked network structure formed by a crosslinking reaction between the modified polyphenylene ether high molecular polymers.

In this embodiment, the baking curing temperature is 140 degrees Celsius, and the baking curing time is 30 minutes.

Due to the long-chain structure of the modified polyphenylene ether polymer, the polymer film formed by the modified polyphenylene ether polymer is increased in flexibility, and the modified polyphenylene ether is high. The polyphenylene ether structure in the molecular polymer allows the polymer film formed of the modified polyphenylene ether polymer to have a low dielectric constant. In addition, since the modified polyimine polymer compound indirectly has a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group, the resulting polyfluorene is obtained. The amine film has excellent flame retardancy.

The invention will now be specifically described by way of examples and comparative examples.

Example 1

60 g of 4,4'-difluorobenzophenone was added to the first reaction flask in sequence, and the chemical structure of 71 g was A polyphenylene ether copolymer, 77 g of potassium carbonate, 30 mL of xylene, and 393.6 g of N,N-dimethylacetamide were stirred and dissolved, and then heated at 130 ° C for 12 hours in a nitrogen atmosphere to prepare a chemical structure. Formula The first product.

50 g of the first product and 23.6 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were sequentially added to the second reaction flask. ), 102.7 g of phenol and 0.9 g of 97% sulfuric acid were stirred and dissolved, and then heated at 140 ° C for 12 hours in a nitrogen atmosphere to prepare a chemical structural formula. Polyphenylene ether polymer.

10 g of the above polyphenylene ether polymer, 3.5 g of 2-methacrylic anhydride, 0.1 g of sodium acetate and 100 mL of N,N-dimethylacetamide were sequentially added to the third reaction flask and stirred and dissolved. And then heated in a nitrogen atmosphere at 80 ° C for 12 hours to prepare a chemical structural formula Modified polyphenylene ether polymer. The modified polyphenylene ether polymer has a viscosity of 49000 cps.

Example 2

10 g of the polyphenylene ether polymer of Example 1, 3.5 g of 4-chloromethylstyrene, 0.1 g of sodium acetate, and 100 mL of N,N-dimethylacetamide were sequentially added to the reaction flask. And stirred and dissolved, and then heated at 80 ° C for 12 hours in a nitrogen atmosphere to prepare a chemical structural formula. Modified polyphenylene ether polymer. The modified polyphenylene ether polymer has a viscosity of 51 s000 cps.

Comparative example 1

4.8 g of DOPO, 3.0 g of 4-aminoacetophenone, 4.8 g of 2-aminophenol, 0.19 g of p-toluenesulfonamide and 10 g of dimethyl hydrazine were sequentially added to the fourth reaction flask and stirred and dissolved. And then heating at 100 degrees Celsius for 24 hours in a nitrogen atmosphere to prepare a chemical structural formula The second product.

In the fifth reaction flask, 1.0 g of the second product, 0.7 g of 4,4'-oxydiphthalic anhydride, 6.8 g of N-methylpyrrolidone and 3.4 g of xylene were sequentially added and stirred to dissolve, followed by nitrogen gas. Heating in the atmosphere at 140 ° C for 20 hours to remove water to prepare chemical structure The third product.

10 g of the third product, 3.5 g of 2-methacrylic anhydride, 0.1 g of sodium acetate and 100 mL of N,N-dimethylacetamide were sequentially added to the sixth reaction flask and stirred to dissolve, and then in a nitrogen atmosphere. The chemical structure was prepared by heating at a temperature of 80 ° C for 12 hours. Modified polyimine polymer. The modified polyimine polymer has a viscosity of 51,000 cps.

Comparative example 2

The 3.5 g of 2-methacrylic anhydride in Comparative Example 1 was replaced with 3.5 g of 4-chloromethylstyrene and the other chemical conditions were unchanged. Modified polyimine polymer. The modified polyimine polymer has a viscosity of 48,000 cps.

The modified polyphenylene ether polymer prepared in Examples 1 and 2 and the modified polyimine polymer prepared in Comparative Examples 1 and 2 were respectively coated on one surface of four copper foils to form one surface. Experimental samples 1 to 4, and the test samples 1 to 2 were baked at 140 ° C for 30 minutes to cause cross-linking reaction of the modified polyphenylene ether polymer on the surface of the copper foil and curing to obtain two polymers. For the film, the test samples 3 to 4 were baked at 140 ° C for 10 minutes to cause a cross-linking reaction of the modified polyimine polymer on the surface of the copper foil and curing to obtain two kinds of polyimide films.

The dielectric constant D _k and the dielectric loss D _f of the two kinds of polymer films formed in the above Examples 1 and 2 and the two kinds of polyimine films formed in Comparative Examples 1 and 2 were respectively tested. Four kinds of experimental samples were tested for copper peel strength and solder heat resistance. Refer to the performance test data in Table 1 for the test results. Among them, if the soldering heat resistance test condition is greater than or equal to 320 ° C, 10 sec, the rubber layer does not cause foaming, peeling, etc., the soldering heat resistance test result is "pass", indicating that the circuit board meets the heat resistance requirements.

Table 1 Measurements on the relevant information of the adhesive layer in each of the above boards

As can be seen from Table 1, the modified poly-polymers of Examples 1 to 2 of the present invention were formed by two kinds of polyimine films formed separately from the modified polyimine polymer of Comparative Examples 1 and 2. The two polymer films formed by the phenyl ether polymer have a low dielectric constant D _k . Further, the two kinds of polymer films formed by the modified polyphenylene ether polymer of Examples 1 to 2 of the present invention have good heat resistance, and the copper peeling strength and the modified polycondensation of Comparative Examples 1 and 2 The copper peeling strength of the two kinds of polyimide films formed by the quinone imine polymer was equivalent.

Due to the long-chain structure of the modified polyphenylene ether polymer, the polymer film formed by the modified polyphenylene ether polymer is increased in flexibility, and the modified polyphenylene ether is high. The polyphenylene ether structure in the molecular polymer allows the polymer film formed of the modified polyphenylene ether polymer to have a low dielectric constant. In addition, since the modified polyimine polymer compound indirectly has a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group, the resulting polyfluorene is obtained. The amine film has excellent flame retardancy.

In addition, various other changes and modifications may be made in accordance with the technical concept of the present invention, and all such changes and modifications are intended to fall within the scope of the invention.

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Claims (9)

A modified polyphenylene ether polymer, the chemical structure of the modified polyphenylene ether polymer , or . A method for preparing a modified polyphenylene ether polymer comprises the steps of: uniformly mixing a polyphenylene ether polymer, an active reactant and a solvent to obtain a resin composition, wherein The chemical structural formula of the polyphenylene ether polymer is The active reactant is 2-methacrylic anhydride, 4-chloromethylstyrene or trans-cinnamonium chloride; and the above resin composition is heated to react to obtain a modified polyphenylene ether polymer. Wherein, the chemical structural formula of the modified polyphenylene ether polymer is , or . The method for producing a modified polyphenylene ether polymer according to claim 2, wherein in the resin composition, the polyphenylene ether polymer and the The weight ratio of the active reactants is from 1:10 to 50:1. The method for producing a modified polyphenylene ether polymer according to claim 2, wherein the step of "heating the resin composition to react to obtain a modified polyphenylene ether polymer" is specifically The method comprises the steps of: sequentially adding sodium acetate and N,N-dimethylacetamide to the resin composition, stirring and mixing uniformly, and then heating the reaction under a nitrogen atmosphere to obtain the modified polyphenylene ether polymer. . The method for producing a modified polyphenylene ether polymer according to claim 2, wherein the polyphenylene ether polymer is prepared by the following steps: 4,4'-difluoro Benzophenone and chemical structure are The polyphenylene ether copolymer is heated under a nitrogen atmosphere and a potassium carbonate catalyzed reaction to obtain a first product, and the chemical structure of the first product is And the first product, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and phenol are mixed and heated to obtain the polyphenylene ether polymer. The method for producing a modified polyphenylene ether polymer according to claim 2, wherein the solvent is N,N-dimethylacetamide. A polymer film obtained by baking and curing a resin containing a modified polyphenylene ether polymer, wherein the polymer film comprises the modified polyphenylene ether polymer a chemical cross-linking structure formed by a cross-linking reaction, wherein the chemical structure of the modified polyphenylene ether polymer is , or . A method for preparing a polymer film, comprising the steps of: curing a resin comprising a modified polyphenylene ether polymer; wherein crosslinking of the modified polyphenylene ether polymer occurs The reaction forms a chemical cross-linking structure, and the chemical structure of the modified polyphenylene ether polymer is , or . The method for producing a polymer film according to claim 8, wherein the baking curing temperature is 140 degrees Celsius, and the baking curing time is 30 minutes.