CN118325069A

CN118325069A - Preparation method of double-end vinyl low-molecular-weight polyphenyl ether

Info

Publication number: CN118325069A
Application number: CN202410423412.XA
Authority: CN
Inventors: 周步杰; 宋顺刚; 杨用峰; 张慧波
Original assignee: Hangzhou Jufeng New Material Co ltd
Current assignee: Hangzhou Jufeng New Material Co ltd
Priority date: 2024-04-09
Filing date: 2024-04-09
Publication date: 2024-07-12

Abstract

The application relates to the technical field of chemical raw materials, and particularly discloses a preparation method of double-end vinyl low-molecular-weight polyphenyl ether. According to the application, a certain proportion of polyphenyl ether oligomer is introduced in the redistribution process, and the polyphenyl ether oligomer can play a role in stabilizing free radicals and improving the reaction rate, so that the yield of degradation reaction is improved, the high-efficiency preparation of double-end vinyl low-molecular-weight polyphenyl ether is realized under the condition of less consumption of distribution auxiliary agents, and the production cost of the double-end vinyl low-molecular-weight polyphenyl ether is reduced.

Description

Preparation method of double-end vinyl low-molecular-weight polyphenyl ether

Technical Field

The application relates to the technical field of chemical raw materials, in particular to a preparation method of double-end vinyl low-molecular-weight polyphenyl ether.

Background

The double-end vinyl low-molecular-weight polyphenyl ether is mainly used for an insulating layer of a high-speed copper-clad plate, and vinyl groups at two ends of molecules can undergo a crosslinking curing reaction, so that the double-end vinyl low-molecular-weight polyphenyl ether is an ideal substitute for epoxy resin. When in downstream use, the product is usually dissolved in solvents such as toluene, and then is dip-coated on glass fiber cloth, and the solvent is dried to prepare the prepreg. And then, copper foil is covered on two sides of the prepreg, and then high-temperature lamination is performed, so that the production of the copper-clad plate can be realized. In order to provide a polyphenylene ether product with good solubility, it is generally necessary to control the molecular weight of the polyphenylene ether to 5000 or less.

The double-ended vinyl low molecular weight polyphenylene ether is generally prepared by subjecting a double-ended hydroxyl low molecular weight polyphenylene ether to a capping treatment, such as a methacrylic anhydride esterification capping process of Sabic and a chloromethylstyrene capping process of mitsubishi gas. There are two approaches to the preparation of double-end hydroxyl low molecular weight polyphenylene ether, namely, copolymerization of monomer 2, 6-dimethylphenol and double-end phenol monomer (polymerization method) and degradation of high molecular weight polyphenylene ether by double-end phenol monomer (degradation method). Essentially, both routes are by the oxidative coupling redistribution reaction of polyphenylene ether.

In view of the above-mentioned related art, the inventors believe that in order to obtain a polyphenylene ether product which has good solubility and can be used in the copper-clad plate production process, BPO is generally used as an initiator, and a peroxide initiator such as BPO is easily connected to a terminal group of the polyphenylene ether or a side methyl group in a large amount after reaction to form a byproduct. The use of tetramethyl-diphenoquinone as an initiator can avoid the problem of by-product formation to some extent, but the consumption of the initiator is large, and it often takes a long time to reach the target yield, resulting in difficulty in sufficiently improving the production efficiency of the double-ended vinyl low molecular weight polyphenylene ether.

Disclosure of Invention

In the related art, peroxide initiators such as BPO and the like have the defect of more byproducts, and when tetramethyl-diphenoquinone is used as the initiator, the defects of high consumption of the initiator and long reaction time exist although the byproducts are less generated, so that the production efficiency of double-end vinyl low-molecular-weight polyphenyl ether is difficult to sufficiently improve. To ameliorate this disadvantage, the present application provides a process for preparing double-ended vinyl low molecular weight polyphenylene ethers.

The application provides a preparation method of double-end vinyl low-molecular-weight polyphenyl ether, which adopts the following technical scheme:

a preparation method of double-end vinyl low-molecular-weight polyphenyl ether comprises the following steps:

(1) In 300 parts by weight of toluene, 100 parts by weight of polyphenyl ether and 8.33-8.73 parts by weight of distribution auxiliary agent are mixed, 1.3 parts by weight of tetramethyl-diphenoquinone is added after heating and dissolving, and the heat preservation reaction is continued for 1.5 hours, so as to obtain redistribution liquid; the dispensing aid comprises bisphenol a; the polyphenyl ether comprises 95-96.2 parts by weight of macromolecular polyphenyl ether and 3.8-5.0 parts by weight of polyphenyl ether oligomer, wherein the number average molecular weight of the polyphenyl ether oligomer is 421-623, and the number average molecular weight of the macromolecular polyphenyl ether is 22000;

(2) Carrying out end-capping treatment on the redistribution liquid, stirring and mixing a product and methanol, then carrying out solid-liquid separation, and drying the separated solid to obtain a polyphenyl ether crude product; in the end-capping treatment operation, the auxiliary agent used comprises methacrylic anhydride; mixing methanol and toluene to obtain a dissolving agent with the mass fraction of 20% of methanol for later use;

(3) Adding the polyphenyl ether crude product into a dissolving agent, stirring and suction filtering to remove filter residues, adding the residual filtrate into methanol, collecting precipitated solid and drying to obtain double-end vinyl low-molecular-weight polyphenyl ether.

According to the technical scheme, toluene is used as a solvent, the polyphenyl ether is subjected to redistribution reaction under the combined action of bisphenol A in a distribution auxiliary agent and an initiator tetramethyl-diphenoquinone to obtain double-end hydroxyl polyphenyl ether, the double-end hydroxyl polyphenyl ether is converted into double-end vinyl polyphenyl ether through end capping treatment, and then methanol is used for preliminary purification to obtain a polyphenyl ether crude product. After the treatment of the dissolving agent and the filtration, the double-end vinyl polyphenyl ether with relatively low molecular weight is dissolved, the residual double-end vinyl polyphenyl ether with relatively high molecular weight and impurities are removed by filtration, and then the double-end vinyl low molecular weight polyphenyl ether can be recovered from the filtrate. According to the application, a certain proportion of polyphenyl ether oligomer is introduced in the redistribution process, and free radicals formed by the polyphenyl ether oligomer can participate in the degradation reaction of macromolecular polyphenyl ether, so that relatively high free radical concentration is kept in a reaction initial system, the free radicals formed by an initiator are stabilized, the invalid consumption of the initiator is reduced, the degradation reaction efficiency is improved, the time required for degrading macromolecular polyphenyl ether to be below the target molecular weight is shortened, and the defect of low degradation speed of macromolecular polyphenyl ether is overcome. Under the condition of the same reaction time, the preparation method is more conducive to improving the yield of degradation reaction, can realize the efficient preparation of the double-end vinyl low-molecular-weight polyphenyl ether under the condition of less consumption of distribution auxiliary agents, and is conducive to reducing the production cost of the double-end vinyl low-molecular-weight polyphenyl ether.

Preferably, the capping process comprises the following operations: 19.4 parts by weight of triethylamine and 1 part by weight of dimethylaminopyridine are mixed and added into a distribution liquid, 30 parts by weight of methacrylic anhydride is added into the distribution liquid, and the mixture is subjected to thermal insulation reaction for 7 hours to obtain a product.

By adopting the technical scheme, the application uses methacrylic anhydride as the main component of the auxiliary agent for end-capping treatment, and makes the methacrylic anhydride and the end hydroxyl groups of the double-end hydroxyl polyphenyl ether generate esterification reaction under the action of triethylamine and dimethylaminopyridine, so that vinyl is introduced into the two ends of polyphenyl ether molecules, and double-end vinyl polyphenyl ether is obtained.

Preferably, the capping process comprises the following operations: toluene and isopropanol are added into the distribution liquid, a sodium hydroxide solution is added into the obtained mixed solution, a catalyst and chloromethyl styrene are added, the mixture is stirred at 80 ℃ for 5 hours, a water layer is removed by centrifugation, an organic phase is washed, then methanol is added for precipitation, the precipitate is washed and purified by chloroform, then filtration is carried out, and filter residues are dried in vacuum, thus obtaining the product.

By adopting the technical scheme, the application enables phenolic hydroxyl groups of the double-end hydroxyl polyphenyl ether and chlorine atoms of chloromethyl styrene to have hydrocarbylation reaction under the action of sodium hydroxide and a catalyst, thereby forming an aromatic ether structure and obtaining the styrene-terminated double-end vinyl polyphenyl ether.

Preferably, the catalyst comprises a phase transfer catalyst and potassium iodide.

By adopting the technical scheme, under the condition that a phase transfer catalyst exists, the activity of nucleophilic substitution reaction can be improved by adding potassium iodide, and the end-capping treatment of the polyphenyl ether can be fully carried out.

Preferably, tetrabutylammonium bromide is used as the phase transfer catalyst.

By adopting the technical scheme, tetrabutylammonium bromide has the function of transferring nucleophilic reagent and can be used as a phase transfer catalyst.

Preferably, the distribution aid further comprises 3- (pentadec-8, 11, 14-triene) phenol, and the 3- (pentadec-8, 11, 14-triene) phenol is used in an amount of 7.2-8% by weight of the polyphenyl ether.

By adopting the technical scheme, the application optimizes the components of the distribution auxiliary agent, and by selecting 3- (pentadec-8, 11, 14-triene) phenol as one of the components of the distribution auxiliary agent, extra unsaturated bonds can be introduced into the polyphenyl ether molecules, thereby being beneficial to improving the vinyl equivalent of the double-end vinyl low-molecular-weight polyphenyl ether.

Preferably, the 3- (pentadec-8, 11, 14-triene) phenol is used in an amount of 7.6 to 8% by weight of the polyphenylene ether.

By adopting the technical scheme, the application prefers the dosage of 3- (pentadeca-8, 11, 14-triene) phenol, which is helpful for sufficiently improving the vinyl equivalent of double-end vinyl low molecular weight polyphenyl ether.

In summary, the application has the following beneficial effects:

1. According to the application, a certain proportion of polyphenyl ether oligomer is introduced in the redistribution process, and the polyphenyl ether oligomer can play a role in stabilizing free radicals and improving the reaction rate, so that the yield of degradation reaction is improved, the high-efficiency preparation of double-end vinyl low-molecular-weight polyphenyl ether is realized under the condition of less consumption of distribution auxiliary agents, and the production cost of the double-end vinyl low-molecular-weight polyphenyl ether is reduced.

2. The application prefers the components of the distribution aid, and by selecting 3- (pentadec-8, 11, 14-triene) phenol as one of the components of the distribution aid, additional unsaturated bonds can be introduced into the polyphenyl ether molecule, which is helpful for improving the vinyl equivalent of the double-end vinyl low-molecular weight polyphenyl ether.

Detailed Description

The present application will be described in further detail with reference to examples, preparations and comparative examples, and the raw materials according to the present application are all commercially available.

Preparation example of polyphenylene ether oligomer

The following is an example of preparation 1.

Preparation example 1

In this preparation example, the polyphenylene ether oligomer was prepared as follows:

In a three-neck flask with a condensing reflux device, 30g of 2, 6-Dimethylphenol (DMP) is dissolved in 120g of methanol solution, then 0.01g of Cu (Ac) 2 catalyst and 0.1g of glacial acetic acid are added, 3g of 30% hydrogen peroxide solution is dropwise added in 0.5h at the reaction temperature of 64 ℃, the reaction is carried out for 30 minutes after the dropwise addition, the temperature is reduced to 30 ℃ after the reaction is finished, ammonia water is added to adjust the pH value to be neutral, 0.007g of phase transfer agent bisdodecyl dimethyl ammonium chloride is added, 13g of 30% hydrogen peroxide solution is dropwise added in 5 hours, and the reaction is carried out for 1 hour after the dropwise addition. After the reaction is finished, precipitating a product by using distilled water, filtering, washing for three times, and vacuum drying for 8 hours at 110 ℃ to obtain a polyphenyl ether oligomer; 30g of toluene was used to dissolve the crude polyphenylene ether oligomer and the insoluble matter was filtered to give a toluene solution containing 20g of oligomer for use.

As shown in Table 1, preparation examples 1 to 5 were different in the amount of hydrogen peroxide added for the second time (abbreviated as hydrogen peroxide addition amount in Table 1), the incubation reaction time after dropping hydrogen peroxide (abbreviated as incubation time in Table 1), and the number average molecular weight (abbreviated as number average molecular weight in Table 1) of the obtained polyphenylene ether oligomer.

TABLE 1 Hydrogen peroxide addition, incubation time and number average molecular weight

Sample of	Hydrogen peroxide addition/g	Holding time/h	Number average molecular weight
				Preparation example 1	13	1	421
Preparation example 2	13.5	1	468
				Preparation example 3	14	1.5	548
Preparation example 4	14.5	1.5	615
				Preparation example 5	14.5	2	623

Examples

Examples 1 to 5

The following description will take example 1 as an example.

Example 1

The embodiment provides a preparation method of double-end vinyl low-molecular-weight polyphenyl ether, which comprises the following steps:

(1) Mixing 100kg of polyphenyl ether and 8.73kg of distribution auxiliary agent in 300kg of toluene, heating and dissolving at 95 ℃ (heating temperature is abbreviated as heating temperature in table 2), adding 1.3kg of tetramethyl-diphenoquinone, and continuing to perform heat preservation reaction for 1.5h (first heat preservation time is abbreviated as first heat preservation time in table 2) to obtain redistribution liquid; bisphenol A is selected as the distribution aid, the polyphenyl ether comprises 96.2kg of macromolecular polyphenyl ether and a toluene solution containing 3.8kg of polyphenyl ether oligomer, the polyphenyl ether oligomer is prepared according to the method of preparation example 1, and the number average molecular weight (abbreviated as high polymer molecular weight in table 2) of the macromolecular polyphenyl ether is 22000;

(2) The redistribution liquid is subjected to end capping treatment, and the specific operation is that 19.4kg of triethylamine and 1kg of dimethylaminopyridine are mixed and added into the redistribution liquid, 30kg of methacrylic anhydride is added into the redistribution liquid at the speed of 1.5kg/min, and the product is obtained after the thermal insulation reaction is carried out for 7 hours (the second thermal insulation time is abbreviated as in table 2); after the end capping treatment is finished, stirring and mixing the product and 2500kg of methanol, then carrying out solid-liquid separation, and drying the separated solid to obtain a polyphenyl ether crude product; mixing methanol and toluene to obtain a dissolving agent with a methanol mass fraction of 20% (the dissolving agent is abbreviated as the methanol content in table 2) for standby;

As shown in Table 2, examples 1-5 differ mainly in the raw material ratios and the part of the production process parameters.

TABLE 2 raw material ratios and part of the production processing parameters

Example 6

This example differs from example 5 in that in the method step (2) of producing a double-ended vinyl low molecular weight polyphenylene ether, the specific operation of the capping treatment is:

Adding a certain amount of toluene and isopropanol into the distribution liquid to obtain a mixed solution, wherein the weight ratio of toluene to isopropanol in the mixed solution is 7:3, the weight ratio of the polyphenyl ether added in the step (1) to the mixed solution obtained in the step (2) is 1:5, adding a sodium hydroxide solution with the mass concentration of 50%, adding a catalyst and chloromethyl styrene into the mixed solution, stirring for 5 hours at 80 ℃, centrifuging to remove a water layer, washing an organic phase, adding methanol for precipitation, washing and purifying a precipitate with chloroform, filtering, and vacuum drying filter residues to obtain a product; the molar ratio of sodium hydroxide in the sodium hydroxide solution to the polyphenyl ether in the mixed solution is 3:1, the weight ratio of the catalyst to the sodium hydroxide is 1:10, the catalyst comprises a phase transfer catalyst (tetrabutylammonium bromide) and potassium iodide, the weight ratio of the phase transfer catalyst to the potassium iodide is 1:10, and the molar ratio between chloromethyl styrene and hydroxyl-terminated groups of the polyphenyl ether in the mixed solution is 1.2:1.

Example 7

This example differs from example 5 in that the dispensing aid is formed by mixing bisphenol A and 3- (pentadec-8, 11, 14-triene) phenol, the amount of 3- (pentadec-8, 11, 14-triene) phenol being 7.2% by weight of the polyphenylene ether.

As shown in Table 3, examples 7 to 11 were different in that 3- (pentadeca-8, 11, 14-trien) phenol was used in a different amount as a percentage by weight of the polyphenylene ether (referred to as the second component ratio of the distribution aid in Table 4).

TABLE 3 distribution aid second component ratio

Sample of	Distribution aid second component ratio/%
		Example 7	7.2
Example 8	7.4
		Example 9	7.6
Example 10	7.8
		Example 11	8

Comparative example

Comparative example 1

This comparative example differs from example 1 in that the polyphenylene ether consisted of only the macromolecular polyphenylene ether of example 1, and the distribution aid was changed to 10kg, the macromolecular polyphenylene ether having a number average molecular weight of 22000.

Comparative example 2

This comparative example is different from example 1 in that the polyphenylene ether consists of only the macromolecular polyphenylene ether of example 1, and the distribution aid is changed to 10kg, the first heat-retaining time is changed to 3 hours, and the number average molecular weight of the macromolecular polyphenylene ether is 22000.

Performance detection test method

1. Molecular weight detection

Molecular weight detection means: the molecular weight and distribution of the polyphenylene ether were measured by a gel permeation chromatograph (GPC, waters 1525/2414) equipped with a capillary column HT4/HT3/HR1 and a differential refractive index detector, and the measurement temperature was 35 ℃. Tetrahydrofuran was used as a eluent at a flow rate of 1.0mL/min, calibrated with monodisperse Polystyrene Standards (PS).

The molecular weight of the polyphenylene ether was measured for changes in the step (1) of the preparation method of each example and comparative example by combining the above molecular weight means, and the results are shown in Table 4.

2. Vinyl equivalent

The 1HNMR spectra of the double-ended vinyl low molecular weight polyphenylene ether were determined on a GSX-270 (400MHz,JEOL Japan Electronics Co, tokyo, japan) nuclear magnetic resonance apparatus with TMS as an internal standard by dissolving the double-ended vinyl low molecular weight polyphenylene ether in CDCl ₃ solvent. The terminal vinyl equivalent was determined from the integral ratio in the spectrum, and the results are shown in Table 5.

3. Yield comparison

The yields of the double-ended vinyl low molecular weight polyphenylene ethers of the examples and comparative examples were calculated based on the sum of the mass of the macromolecular polyphenylene ether and the mass of the polyphenylene ether oligomer, and the results are shown in Table 6.

TABLE 4 molecular weight

Sample of	Molecular weight	Sample of	Molecular weight
				Example 1	2830	Example 8	2760
Example 2	2780	Example 9	2786
				Example 3	2764	Example 10	3000
Example 4	2746	Example 11	3200
				Example 5	2732	Comparative example 1	3020
Example 6	2740	Comparative example 2	2960
				Example 7	2743	/	/

TABLE 5 vinyl equivalent weight

Sample of	Vinyl equivalent	Sample of	Vinyl equivalent
				Example 1	1.89	Example 7	1.95
Example 2	1.90	Example 8	1.96
				Example 3	1.90	Example 9	1.96
Example 4	1.91	Example 10	1.97
				Example 5	1.90	Example 11	1.98
Example 6	1.92	Comparative example 1	1.89

TABLE 6 yield

Sample of	Yield/%	Sample of	Yield/%
				Example 1	80	Example 8	82
Example 2	82	Example 9	80
				Example 3	84	Example 10	79
Example 4	85	Example 11	78
				Example 5	86	Comparative example 1	72
Example 6	85	Comparative example 2	78
				Example 7	86	/	/

As can be seen from the combination of examples 1 to 11 and comparative example 1 and from Table 4 to 6, even when comparative example 1 was selected for a larger amount of the distribution aid in the case of the same first heat-retaining time, the molecular weight of the polyphenylene ether finally obtained in the present application was still lower than that in comparative example 1, and the vinyl equivalent could be maintained in the vicinity of 2, and a higher product yield was obtained, indicating that the process of the present application improved the production efficiency of the double-ended vinyl low molecular weight polyphenylene ether, and that the obtained polyphenylene ether product had more desirable properties.

It can be seen from the combination of example 1 and comparative example 2 and the combination of Table 4 that even if comparative example 2 further extends the first heat-retaining time, it is still difficult to achieve the effect of example 1, and it is difficult to sufficiently lower the molecular weight of the polyphenylene ether and to sufficiently increase the yield of the polyphenylene ether on the basis of comparative example 1.

It can be seen from the combination of example 1 and comparative examples 1 to 2 and the combination of table 4 that under the condition of the same reaction time, the preparation method of the present application is more conducive to improving the yield of the degradation reaction, and can realize the efficient preparation of the double-end vinyl low molecular weight polyphenyl ether under the condition of less dosage of the distribution auxiliary agent, and is conducive to reducing the production cost of the double-end vinyl low molecular weight polyphenyl ether, and as can be seen from the combination of example 5 and example 6 and the combination of table 5, the double-end vinyl low molecular weight polyphenyl ether with the vinyl equivalent of about 2 can be obtained by both end-capping modes provided by the present application.

It can be seen from the combination of examples 5, examples 7-11 and tables 4 and 5 that the addition of 3- (pentadec-8, 11, 14-triene) phenol helps to further increase the degradation efficiency of polyphenylene ether, and also increases the vinyl equivalent of double-ended vinyl low molecular weight polyphenylene ether, making the vinyl equivalent closer to the ideal value of 2.

The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims

1. The preparation method of the double-end vinyl low-molecular-weight polyphenyl ether is characterized by comprising the following steps of:

2. The method for producing a double-ended vinyl low molecular weight polyphenylene ether according to claim 1, wherein the end-capping treatment comprises the following operations: 19.4 parts by weight of triethylamine and 1 part by weight of dimethylaminopyridine are mixed and added into a distribution liquid, 30 parts by weight of methacrylic anhydride is added into the distribution liquid, and the mixture is subjected to thermal insulation reaction for 7 hours to obtain a product.

3. The method for producing a double-ended vinyl low molecular weight polyphenylene ether according to claim 1, wherein the end-capping treatment comprises the following operations: toluene and isopropanol are added into the distribution liquid, a sodium hydroxide solution is added into the obtained mixed solution, a catalyst and chloromethyl styrene are added, the mixture is stirred at 80 ℃ for 5 hours, a water layer is removed by centrifugation, an organic phase is washed, then methanol is added for precipitation, the precipitate is washed and purified by chloroform, then filtration is carried out, and filter residues are dried in vacuum, thus obtaining the product.

4. The method for producing double-ended vinyl low molecular weight polyphenylene ether according to claim 3, wherein the catalyst comprises a phase transfer catalyst and potassium iodide.

5. The method for producing double-ended vinyl low molecular weight polyphenylene ether according to claim 4, wherein tetrabutylammonium bromide is used as the phase transfer catalyst.

6. The method for preparing double-ended vinyl low molecular weight polyphenylene ether according to claim 1, wherein the distribution aid further comprises 3- (pentadec-8, 11, 14-triene) phenol, and the amount of 3- (pentadec-8, 11, 14-triene) phenol is 7.2-8% by weight of the polyphenylene ether.

7. The method for producing double-ended vinyl low molecular weight polyphenylene ether according to claim 6, wherein the amount of 3- (pentadec-8, 11, 14-triene) phenol is 7.6 to 8% by weight of the polyphenylene ether.