CN1563145A - Preparing thermosetting phlyphenylether through Geliya reagent in polyphenylether halide and allyl group type - Google Patents
Preparing thermosetting phlyphenylether through Geliya reagent in polyphenylether halide and allyl group type Download PDFInfo
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- CN1563145A CN1563145A CN 200410017132 CN200410017132A CN1563145A CN 1563145 A CN1563145 A CN 1563145A CN 200410017132 CN200410017132 CN 200410017132 CN 200410017132 A CN200410017132 A CN 200410017132A CN 1563145 A CN1563145 A CN 1563145A
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Abstract
A thermosetting polyphenylether is prepared by reacting on polyphenylether halide and allyl Grignard reagent in solvent, collecting allylation polyphenylether from reacted product, analysing its structure and allylation substitution degree with nuclear magnetism.
Description
Technical Field
The invention relates to a thermosetting modification process of polyphenylene oxide, in particular to a preparation method of allylated polyphenylene oxide.
Background
With the rapid development of various electronic products such as computers and modern communication technologies, higher requirements are put on the performance of high-frequency substrate materials, and it is desirable that the high-frequency substrate materials can rapidly transmit signals and avoid interference and loss as much as possible. The high-frequency substrate material is correspondingly required to have excellent dielectric properties (such as low dielectric constant epsilon and low dielectric loss factor tan delta), small change along with temperature and frequency, and good comprehensive mechanical properties and molding processability. It is also desirable to have excellent heat resistance, dimensional stability, and resistance to organic solvent cleaning.
Polyphenylene ether (PPE for short) is a high-performance thermoplastic engineering plastic with the advantages of low dielectric constant, low dielectric loss factor, low hygroscopicity, high glass transition temperature, good flame retardance, good dimensional stability and the like. However, as a substrate of a high-frequency printed circuit board, high-temperature welding is required, and cleaning by an organic solvent is also required in the processing process, and thermosetting modification is urgently required due to the defects that thermoplastic polyphenylene oxide is easily soluble in organic solvents such as halogenated hydrocarbon and the like, and the dip soldering resistance is poor.
The Asahi company first invented a synthetic route to thermosetting modification of polyphenylene ethers by reaction with n-butyllithium and unsaturated halogenated hydrocarbons. The specific process is as follows in Polym.Mater.Sci.Eng.72: 448, 449 (1995);
the patents US4923932 and US5218030 further study the curing process and product properties of the allylated polyphenylene ether synthesized by the process. The polyphenylene ether is introduced with allyl functional groups, and the excellent characteristics of the original thermoplastic polyphenylene ether resin can be substantially maintained because the proportion of its chemical structural components in the whole polyphenylene ether structureis small; the solvent resistance of the modified thermosetting polyphenyl ether resin is obviously improved; the allyl is a non-polar group, which not only does not affect the excellent dielectric property of the original resin, but also has the advantages of proper curing temperature, no volatile matter during curing, large range of solvent selection and the like, and simultaneously improves the molding property of the resin. However, since n-butyllithium is involved in the reaction, and the preparation, storage and use of n-butyllithium have high requirements on equipment and environment, further improvement of the allylation reaction process of polyphenylene ether is desired by relevant departments to meet the needs of industrial production.
Disclosure of Invention
The technical problem to be solved by the invention is to disclose a method for preparing polyphenyl ether by adopting halogenated polyphenyl ether and allyl Grignard reagent, so as to overcome the defects in the prior art and meet the requirements of the related fields.
The technical idea of the invention is as follows:
the organic magnesium compound is also called Grignard reagent (Grignard), and the preparation process is simple and low in price, and is a common reagent in organic reaction. The carbon-metal bonds are polarized and the alkyl carbon atoms have significant carbanionic properties, which have important applications in the synthesis of C-C. The invention utilizes the property of Grignard reagent to lead halogenated polyphenyl ether to react with corresponding Grignard reagent, and introduces crosslinkable groups into polyphenyl ether molecules to realize thermosetting modification.
The method of the invention comprises the following steps:
the halogenated polyphenylene ether and allyl Grignard reagent are reacted in a solvent, and the allylic substitution degree of the final product can be controlled by controlling the halogenation degree of the halogenated polyphenylene ether and the concentration of the allyl Grignard reagent.
The halogenation degree of the halogenated polyphenyl ether is generally 10-50%; the molar concentration of the allyl Grignard reagent is generally 0.1-2 mol/l;
the solvent used in the reaction comprises one of benzene, toluene, ethylbenzene or tetrahydrofuran, etc.;
the reaction temperature is between the freezing point of the system and the boiling point of the solvent, and is generally 0-60 ℃; the reaction time is 0.5 to 35 hours.
After the reaction is finished, collecting target product allylated polyphenyl ether from the reaction product, and determining the structure and allylated substitution degree of the target product by nuclear magnetic analysis.
The halogenated polyphenyl ether is a compound with the following structural formula:
wherein X represents Cl, Br or I;
k, l and m are between 0 and n, and at least one is not 0;
n is the polymerization degree of the selected polyphenyl ether, and n is 30-300;
the allyl Grignard reagent is a compound with the following structural general formula:
CH2＝CHCH2MgX
wherein X represents Cl, Br or I;
the reaction formula of the corresponding halogenated polyphenylene ether is as follows:
wherein X represents Cl, Br, I;
k1+k2＝k；m1+m2＝m；
k, l and m are between 0 and n, and at least one is not 0;
n is the polymerization degree of the selected polyphenyl ether, and n is 30-300;
the halogenated polyphenylene ethers mentioned are prepared by:
the polyphenylene ether is halogenated with a halogenating agent in a solvent in the presence of a peroxide initiator, the halogenation reaction being carried out simultaneously in two reaction processes, two possible products arising: firstly, a halogenating reagent and a benzene ring of a polyphenyl ether main chain undergo electrophilic substitution reaction to generate a benzene ring halogenation product. Secondly, the halogenating agent and a side methyl on a benzene ring of the main chain of the polyphenyl ether carry out free radical reaction to generate a methyl halogenation product. The position of the halide directly affects the position of the allyl substitution. The control of the reaction conditions allows control of the position of the halogen. Methyl bromination is more prevalent at higher temperatures or in the presence of peroxides.
Said halogenating agent comprises Br2、Cl2、I2Or N-bromosuccinimide (NBS), etc.;
peroxidation initiators include Benzoyl Peroxide (BPO), dicumyl peroxide (DCP), 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexyne, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, 1, 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, t-butyl peroxybenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, and the like.
The solvent comprises chlorobenzene, bromobenzene, 1, 2-dichlorobenzene, chloroform or carbon tetrachloride;
the reaction temperature is 10-180 ℃, the benzene ring brominated product is mainly used when the reaction temperature is lower, the amount of the methyl brominated product is gradually increased along with the temperature rise, the methyl brominated product is mainly generated when the reaction temperature reaches more than 130 ℃, and the crosslinking reaction can occur when the temperature is too high; the reaction time is 0.5 to 35 hours.
After the reaction is finished, the halogenated polyphenylene ether is collected from the reaction product, dried and subjected to nuclear magnetic analysis to determine the microstructure and the degree of halogenation.
Polyphenylene oxide, a halogenating agent and an oxidation initiator in a molar ratio of 1: 0.1 to 5: 0.01 to 0.1;
the allyl Grignard reagent is prepared by:
reacting halogen compound containing allyl and magnesium metal in anhydrous solvent to obtain allyl Grignard reagent. The allylic halohydrocarbons are highly reactive and can undergo coupling reactions with the Grignard formed, affecting yield. The main approach to improvement is to activate magnesium metal, the most common method is to add a small amount of iodine or to add nitrogen for protection. In addition, the ratio of magnesium to allylic halohydrocarbon, the amount of solvent and the reaction time all have a certain influence on the reaction yield.
The allyl-containing halide comprises one of bromopropylene, chloropropene, 2-methyl-2-allyl bromide or 2-methyl-2-allyl chloride and the like;
the form of the magnesium can be a strip, a chip or a powder;
the molar ratio of magnesium to allyl halide is 0.1-20, excess magnesium can be recovered afterreaction, and the magnesium is washed by hydrochloric acid and water in sequence and dried for later use.
The solvent comprises diethyl ether, propyl ether, butyl ether, isopropyl ether, tetrahydrofuran and the like, and the solvent, the metal sodium and the benzophenone are refluxed together until the color is blue before use and are evaporated for standby;
the molar ratio of the solvent to the allyl halide is 0.1-35;
the reaction temperature is-20 ℃ to 35 ℃, and the reaction time is 0.5 to 50 hours;
the reaction formula is as follows:
wherein X represents Cl, Br, I
The allylic Grignard reagent obtained in the reaction can be calibrated by acid titration. The product should be used as soon as possible after preparation, and sealed and light-tight if it is to be stored.
According to the technical scheme disclosed by the invention, in the reaction, a reactant does not relate to n-butyllithium, and is replaced by a Grignard reagent, so that the raw materials are easy to obtain, the cost is low, the reaction condition in the preparation process is mild, the requirements on equipment and environment are low, and the industrial production is easier to carry out.
Drawings
FIG. 1 is a diagram of brominated polyphenylene ethers1HNMR spectrogram.
FIG. 2 is a diagram of allylated polyphenylene ethers1HNMR spectrogram.
Detailed description of the invention
In order to better understand the context of the present invention, the present invention will be further illustrated by the following examples, which are not intended to limit the scope of the present invention.
Example 1
Halogenation reaction of polyphenylene ether:
8g of polyphenyl ether is dissolved in 100ml of chlorobenzene, the chlorobenzene is placed in a four-neck flask provided with a stirring device and a thermometer, the stirring is carried out under the protection of nitrogen, the constant temperature is kept after the polyphenyl ether is heated to 110 ℃, 0.8g of benzoyl peroxide initiator and 24.8g of brominating reagent N-bromosuccinimide (NBS) are sequentially added for reaction after the polyphenyl ether is completely dissolved, and bromine brought out by nitrogen during the reaction is absorbed by sodium hydroxide solution through a recovery device. The reaction system is injected into a large amount of methanol to precipitate out solid, and the solid is filtered, washed by methanol and repeated for a plurality of times. The obtained powder is dried in an oven at 80 ℃ for 12 hours to obtain the product brominated polyphenylene oxide.
It is composed of1The HNMR spectrum is shown in figure 1. The analysis results are shown in Table 1.
TABLE 1 summary of the results of nuclear magnetic analysis of halogenated polyphenylene ethers
Table1 Analysis of1H-NMR spectrum
δ×106-H
2.0 -CH3
4.3 Ph-CH2Br*
～6.4Ar-H
From the above analysis, it was confirmed that almost no benzene ring bromination product was present in the structure.
Example 2
Preparation of allylic Grignard reagents
Before the experiment, the whole set of experimental device is subjected to dewatering treatment. Placing 5g of the treated magnesium chips into a four-mouth flask under the protection of nitrogen, adding 1-2 iodine particles, slightly heating to enable iodine steam to fill the flask. 15ml of pretreated tetrahydrofuran were added thereto and stirred. 15ml of chloropropene and 50ml of tetrahydrofuran are prepared into a mixed solution which is placed in a constant pressure funnel. Firstly, dripping a plurality of drops to initiate reaction, placing the four-mouth flask in an ice water bath after the bottom of the flask is slightly heated, and continuously dripping the mixed liquid of chloropropene and tetrahydrofuran. After the completion of the dropwise addition, the reaction was kept under stirring for 1 hour. After the reaction is finished, the obtained product is sealed and stored away from light and is used as soon as possible.
Example 3
Under the protection of nitrogen, 5g of brominated polyphenylene ether prepared in example 1 was dissolved in 100ml of tetrahydrofuran, the temperature was raised to 40 ℃ and kept constant, after complete dissolution, 50ml of a freshly prepared allylic Grignard reagent was added, the temperature was kept constant, and the reaction was stirred for 1 hour and stopped. The resulting reaction system was poured into a large amount of methanol to precipitate. Filtering, precipitating with methanol for several times, and drying the obtained solid in a vacuum oven at 80 deg.C for 12 hr to obtain the final product.
Product of1The HNMR spectrum is shown in figure 2. The analysis results are shown in Table 2:
TABLE 2 summary of nuclear magnetic analysis results
Table2 Analysis of1H-NMR spectrum
δ×106-H
2.0 -CH3
4.8 C-CH＝CH2 *
5.7 C-CH*＝CH2
6.4 Ar-H
The allyl structures grafted to the benzene ring and methyl group are as follows:
the chemical shift estimates for each hydrogen proton were calculated from empirical formulas for the olefinic hydrogen delta values, as listed in table 3.
TABLE 3 calculation of alkene hydrogen delta values
Table3 Calculating result of δ
NO. δ×106
1 6.30
2 4.93
3 4.96
4 5.70
5 4.97
6 5.00
1The HNMR spectrogram analysis result is shown in a table 3, and each chemical displacement value is basically consistent with the proton peak chemical displacement value of the methyl grafted allyl group calculated by an empirical formula.
Example 4
Using the same procedure as in example 1, the halogenating agent was changed to equimolar Br2The resulting halogenated polyphenylene ether was reacted with an allylic Grignard reagent prepared in the manner of example 2 to obtain a thermosetting modified polyphenylene ether as well.
Example 5
Using the same procedure as in example 1, but using equimolar DCP as the oxidation initiator, the resulting halogenated polyphenylene ether was further reacted with the allylic Grignard reagent prepared in example 2, and the resulting product was subjected to1HNMR analysis confirmed that a thermosetting modified polyphenylene ether having the same structure as in example 3 was also obtained.
Example 6
Using the same procedure as in example 1, but using an equal volume of carbon tetrachloride as the solvent, the resulting halogenated polyphenylene ether was reacted with the allylic Grignard reagent prepared in example 2, and the resulting product was subjected to1HNMR analysis confirmed that the thermosetting modified polyphenylene ether of the same structure as that obtained in example 3 was also obtained.
Example 7
The allylic Grignard reagent was prepared using the same process conditions of example 2, with only the amount of chloropropene being changed and reduced to 5 ml.
A thermosetting modified polyphenylene ether was prepared by the procedure of example 3, using 5g of the halogenated polyphenylene ether prepared by the procedure of example 1 and 5ml of the allylic Grignard reagent preparedby the procedure of comparative example 4. The obtained product has no allyl group by nuclear magnetic analysis, which shows that the reaction can not be carried out when the concentration of the format reagent is low and the dosage is small.
Example 8
Using the same procedure as in example 2, the allyl-containing halide was replaced with an equimolar amount of bromopropene, the obtained product was reacted with the halogenated polyphenylene ether prepared by the method of example 1, and the obtained product was subjected to1HNMR analysis confirmed that the thermosetting modified polyphenylene ether of the same structure as that obtained in example 3 was also obtained.
Example 9
Using the same procedure as in example 2, an equal volume of diethyl ether was used as a solvent, the resulting product was reacted with the halogenated polyphenylene ether prepared by the method of example 1, and the obtained product was subjected to1HNMR analysis confirmed that the same can be obtainedThe thermosetting modified polyphenylene ether of the same structure as that obtained in example 3 was obtained.
Example 10
The same procedure as in example 3 was followed using an equal volume of toluene as solvent and the product obtained was purified1HNMR analysis confirmed that the thermosetting modified polyphenylene ether of the same structure as that obtained in example 3 was also obtained.
Claims (10)
1. A process for preparing polyphenylene ether from a halogenated polyphenylene ether and an allylic Grignard reagent comprising the steps of:
reacting halogenated polyphenyl ether with an allyl Grignard reagent in a solvent, and collecting a target product, namely allylated polyphenyl ether from a reaction product after the reaction is finished;
the halogenated polyphenyl ether is a compound with the following structural formula:
wherein X represents Cl, Br or I;
k, l and m are between 0 and n, and at least one is not 0;
n is the polymerization degree of the selected polyphenyl ether, and n is 30-300;
the allyl Grignard reagent is a compound with the following structural general formula:
CH2＝CHCH2MgX
wherein X represents Cl, Br or I.
2. The method according to claim 1, wherein the degree of halogenation of the halogenated polyphenylene ether is 10 to 50%.
3. The method according to claim 1, wherein the molar concentration of the allylic Grignard reagent is 0.1 to 2 mol/l.
4. The process of claim 1, wherein the solvent used for the reaction comprises one of benzene, toluene, ethylbenzene or tetrahydrofuran.
5. The method according to claim 1, wherein the reaction temperature is 0 to 60 ℃; the reaction time is 0.5 to 35 hours.
6. The method according to claim 1, wherein the halogenated polyphenylene ether is prepared by:
halogenating polyphenylene ether with halogenating agent in solvent in the presence of peroxidation initiator, wherein said halogenating agent comprises Br2、Cl2Or one of N-bromosuccinimide;
the peroxide initiator comprises one of Benzoyl Peroxide (BPO), dicumyl peroxide (DCP), 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexyne, 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 1, 1-bis (tert-butylperoxy) -3, 3, 5-trimethylcyclohexane, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, di-tert-butyl peroxide or cumene hydroperoxide;
the solvent comprises chlorobenzene, bromobenzene, 1, 2-dichlorobenzene, chloroform or carbon tetrachloride.
7. The method according to claim 6, wherein the reaction temperature is 10 to 180 ℃ and the reaction time is 0.5 to 35 hours.
8. The method according to claim 6 or 7, wherein the molar ratio of polyphenylene ether to halogenating agent to oxidation initiator is 1: 0.1 to 5: 0.01 to 0.1.
9. The process according to claim 1, wherein the allylgrignard reagent is prepared by:
reacting an allyl-containing halide and magnesium metal in an anhydrous solvent, wherein the allyl-containing halide comprises one of bromopropene, chloropropene, 2-methyl-2-allyl bromide, 2-methyl-2-allyl chloride and the like; the molar ratio of magnesium to allyl halide is 0.1-20, the solvent comprises diethyl ether, propyl ether, butyl ether, isopropyl ether, tetrahydrofuran and the like, and the solvent, the metal sodium and the benzophenone are refluxed to blue for steaming out for later use before use; the molar ratio of the solvent to the allyl halide is 0.1 to 35.
10. The method according to claim 9, wherein the reaction temperature is in the range of-20 ℃ to 35 ℃ and the reaction time is 0.5 to 50 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409959A (en) * | 2018-04-09 | 2018-08-17 | 南阳师范学院 | A kind of bromomethylation polyphenylene oxide and preparation method thereof |
| CN108641337A (en) * | 2018-05-17 | 2018-10-12 | 苏州大学 | A kind of polyphenylene ether-poly siloxanes photo-crosslinking damping material and preparation method thereof |
| CN112210219A (en) * | 2020-10-12 | 2021-01-12 | 东莞市润银实业有限公司 | Silicon rubber with wide temperature range and long storage life and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5827719A (en) * | 1981-08-11 | 1983-02-18 | Mitsubishi Chem Ind Ltd | Polyphenylene ether having allyl group at side chain |
| JPH0747632B2 (en) * | 1989-03-06 | 1995-05-24 | 旭化成工業株式会社 | Functionalized polyphenylene ether resin composition |
| JPH0751625B2 (en) * | 1989-03-08 | 1995-06-05 | 旭化成工業株式会社 | End-functionalized polyphenylene ether resin and curable resin composition using the same |
| JPH02264257A (en) * | 1989-04-04 | 1990-10-29 | Asahi Chem Ind Co Ltd | Novel photosetting composition |
| CN1197895C (en) * | 2001-01-11 | 2005-04-20 | 财团法人工业技术研究院 | Crosslinkable polyphenyl ether resin, its compositions and its preparing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409959A (en) * | 2018-04-09 | 2018-08-17 | 南阳师范学院 | A kind of bromomethylation polyphenylene oxide and preparation method thereof |
| CN108641337A (en) * | 2018-05-17 | 2018-10-12 | 苏州大学 | A kind of polyphenylene ether-poly siloxanes photo-crosslinking damping material and preparation method thereof |
| CN112210219A (en) * | 2020-10-12 | 2021-01-12 | 东莞市润银实业有限公司 | Silicon rubber with wide temperature range and long storage life and preparation method thereof |
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