CN116041869A - Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof - Google Patents

Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof Download PDF

Info

Publication number
CN116041869A
CN116041869A CN202211649307.5A CN202211649307A CN116041869A CN 116041869 A CN116041869 A CN 116041869A CN 202211649307 A CN202211649307 A CN 202211649307A CN 116041869 A CN116041869 A CN 116041869A
Authority
CN
China
Prior art keywords
polyphenyl ether
dielectric
low
modified polystyrene
polystyrene material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202211649307.5A
Other languages
Chinese (zh)
Other versions
CN116041869B (en
Inventor
王植源
张赛
乔文强
粟俊华
席奎东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanya New Material Technology Co ltd
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN202211649307.5A priority Critical patent/CN116041869B/en
Priority claimed from CN202211649307.5A external-priority patent/CN116041869B/en
Publication of CN116041869A publication Critical patent/CN116041869A/en
Application granted granted Critical
Publication of CN116041869B publication Critical patent/CN116041869B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides

Abstract

The invention provides a low dielectric polyphenyl ether modified polystyrene material and a preparation method thereof, wherein the low dielectric polyphenyl ether modified polystyrene material is prepared by reacting styrene and N-acetoxy methacrylamide to prepare a polystyrene copolymer, then solidifying the polystyrene copolymer with polyphenyl ether polyol capped by alcoholic hydroxyl groups, wherein the polystyrene copolymer can undergo Lossen rearrangement under a heating condition to be converted into a polystyrene polymer with high-activity NCO groups in side chains, the polystyrene copolymer and the polyphenyl ether polyol capped by alcoholic hydroxyl groups are dissolved in an organic solvent, and the polystyrene material modified by the dielectric polyphenyl ether can be prepared by a tape casting film forming method and undergoing Lossen rearrangement and chemical crosslinking reaction under the heating condition. According to the invention, the alcoholic hydroxyl group-terminated polyphenyl ether polyol is introduced into a polystyrene system, so that the dielectric property of the crosslinked polymer can be improved, the heat resistance of the polymer can be improved, and meanwhile, the preparation method is short in period and low in energy consumption, and meets the development requirement of a low-dielectric material under the current new technology.

Description

Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer material modification, in particular to a low-dielectric polyphenyl ether modified polystyrene material and a preparation method thereof.
Background
With the development of electronic information technology, electronic products are being developed toward weight reduction, high performance and multi-functionalization, and there is an increasing need to develop low dielectric materials with good performance. The low dielectric material can reduce dielectric loss in communication equipment, integrated circuits and other systems, reduce loss of electric signals, leakage current of the integrated circuits, capacitance effect between wires and the like, and is widely applied to the industries of microwave communication, semiconductors and the like.
The dielectric constant and dielectric loss of the crosslinked polystyrene material are stable and extremely low in a wide frequency range, and the crosslinked polystyrene material is a low dielectric material with excellent performance. However, as the communication technology further advances, higher demands are being placed on the dielectric and thermal properties of crosslinked polystyrene materials at high frequencies.
Therefore, research and development of crosslinked polystyrene materials excellent in combination properties has become one of the hot spots of attention.
At present, the crosslinked polystyrene material is mainly prepared by a free radical bulk polymerization method, however, the method has obvious disadvantages: a large amount of reaction heat is generated in the reaction process, so that the conduction of the reaction heat is difficult to control; and the phenomenon of automatic acceleration reaction is also caused along with the increase of the viscosity of the reaction system, so that the phenomenon of 'sudden aggregation' is very easy to occur.
Disclosure of Invention
Based on the technical background, the inventor has made a sharp advance, styrene, N-Acetoxy Methacrylamide (AMAA) and alcoholic hydroxyl group-terminated polyphenyl ether polyol are taken as raw materials, styrene and N-acetoxy methacrylamide are reacted to prepare a polystyrene copolymer, then the polystyrene copolymer is solidified with the alcoholic hydroxyl group-terminated polyphenyl ether polyol to obtain a low-dielectric polyphenyl ether modified polystyrene material, the prepared polystyrene copolymer can undergo Lossen rearrangement to be converted into a polystyrene polymer with high-activity NCO groups in side chains under a heating condition, then the polystyrene polymer is solidified with hydroxyl groups at two ends of the alcoholic hydroxyl group-terminated polyphenyl ether polyol, and the low-dielectric polyphenyl ether modified polystyrene material is obtained through a tape casting film forming method.
In a first aspect, the present invention provides a low dielectric polyphenylene ether modified polystyrene material prepared from styrene, N-acetoxymethacrylamide (i.e., AMAA) and an alcoholic hydroxyl terminated polyphenylene ether polyol.
In a second aspect, the present invention provides a method for preparing the low dielectric polyphenylene ether modified polystyrene material of the first aspect of the present invention, comprising the steps of:
step 1, in the presence of an initiator, styrene and N-acetoxy methacrylamide react in a solvent by heating to obtain a polystyrene copolymer;
step 2, mixing a polystyrene copolymer and an alcoholic hydroxyl group-terminated polyphenyl ether polyol (PPOD) in a solvent to obtain a mixed solution;
and step 3, placing the mixed solution on a die, and heating and curing to obtain the low-dielectric polyphenyl ether modified polystyrene material.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
The first aspect of the present invention is to provide a low dielectric polyphenylene ether modified polystyrene material prepared from styrene, N-acetoxymethacrylamide (AMAA) and an alcoholic hydroxyl terminated polyphenylene ether polyol.
The structural formula of the N-acetoxy methacrylamide is shown as a formula (1):
Figure BDA0004011247130000031
the hydroxyethyl-terminated polyphenylene ether polyol (PPOD) is represented by the following formula (2):
Figure BDA0004011247130000032
in the formula (2), the value of x+y is 10-100, the value of m+n is 1-100, and R is selected from one of hydrogen, alkyl and cycloalkyl.
Preferably, the value of x+y is (10-50), the value of m+n is 1-50, and R is selected from one of hydrogen and alkyl.
More preferably, x+y has a value of (10-20), m+n has a value of 1 to 10, and R is selected from hydrogen or methyl.
PPOD is etherified polyol of polyphenyl ether, and has the properties of high temperature resistance, low expansion coefficient, low dielectric loss and the like of common polyphenyl ether.
According to a preferred embodiment of the present invention, the alcoholic hydroxyl group-terminated polyphenylene ether polyol is prepared by reacting a double-ended hydroxyl group polyphenylene ether (i.e., PPO) as a raw material with an alkylene carbonate or epoxide in the presence of a basic catalyst.
The double-end hydroxyl polyphenyl ether is shown as the following formula:
Figure BDA0004011247130000041
wherein x+y has a value of 10 to 100, preferably x+y has a value of (10 to 50), and more preferably x+y has a value of (10 to 20).
The alkylene carbonate is selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC) and Butylene Carbonate (BC), preferably one or two of ethylene carbonate and propylene carbonate.
The epoxide is selected from one or more of Ethylene Oxide (EO), propylene Oxide (PO) and butylene oxide (EB), preferably one or two of ethylene oxide and propylene oxide.
According to a preferred embodiment of the present invention, the low dielectric polyphenylene ether-modified polystyrene material is prepared by reacting styrene with N-acetoxy methacrylamide to prepare a polystyrene copolymer, and then curing the polystyrene copolymer with an alcoholic hydroxyl group-terminated polyphenylene ether polyol.
The mol ratio of the styrene to the N-acetoxy methacrylamide is (1-30): 1, preferably (2 to 25): 1, more preferably (4 to 20): 1.
the mass ratio of the alcoholic hydroxyl group-terminated polyphenylene ether polyol to the polystyrene copolymer is (0.01 to 1): 1, preferably (0.02 to 0.8): 1, more preferably (0.03 to 0.6): 1.
the temperature rise curing system is 30-50 ℃/0.5-3h+50-70 ℃/0.5-3h+70-90 ℃/0.5-3h+90-110 ℃/0.5-3h+110-140 ℃/0.5-4h+140-170 ℃/0.5-4 h.
Preferably 35-45 ℃/0.5-2h+55-65 ℃/0.5-2h+75-85 ℃/0.5-2h+95-105 ℃/0.5-2h+115-130 ℃/1-3h+145-160 ℃/1-3 h.
The low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.1-0.2 mm and good heat resistance and dielectric property. The dielectric constant of the glass fiber reinforced plastic material can reach 2.34 or below at the minimum of 10GHz, 2.22 or below at the minimum of 20GHz, and the glass transition temperature is 129-160 ℃.
In a second aspect, the present invention provides a method for preparing the low dielectric polyphenylene ether modified polystyrene material of the first aspect of the present invention, comprising the steps of:
step 1, in the presence of an initiator, styrene and N-acetoxy methacrylamide react in a solvent by heating to obtain a polystyrene copolymer;
step 2, mixing a polystyrene copolymer and an alcoholic hydroxyl group-terminated polyphenyl ether polyol (PPOD) in a solvent to obtain a mixed solution;
and step 3, placing the mixed solution on a die, and heating and curing to obtain the low-dielectric polyphenyl ether modified polystyrene material.
This step is specifically described and illustrated below.
And step 1, in the presence of an initiator, styrene and N-acetoxy methacrylamide react in a solvent by heating to obtain the polystyrene copolymer.
The structural formula of the AMAA is shown as a formula (1):
Figure BDA0004011247130000051
the mol ratio of the styrene to the AMAA is (1-30): 1, preferably (2 to 25): 1, more preferably (4 to 20): 1.
the addition of AMAA to styrene gives the polystyrene copolymer obtained (designated PSAA polymer) a potential NCO group (isocyanate group) which is stable at normal temperature, and which is converted into a polymer containing NCO groups by rearrangement at high temperature, and which can be reacted with a compound containing hydroxyl or amino groups. Meanwhile, the addition of AMAA can reduce the dielectric constant of the prepared modified polystyrene and improve the dielectric property.
The initiator is selected from one or more of Azodiisobutyronitrile (AIBN), benzoyl Peroxide (BPO), azodiisoheptonitrile (ABVN) and benzoyl peroxide tert-butyl ester (BPB), preferably one or two of azodiisobutyronitrile and benzoyl peroxide.
The addition amount of the initiator is 0.1-0.3% of the total mass of the styrene and the AMAA, and preferably 0.15-0.2%.
The solvent is selected from one or more of tetrahydrofuran, benzene, toluene, xylene and N, N dimethylformamide, preferably one or two of tetrahydrofuran and toluene.
The reaction is carried out in a Schlenk tube, and the reaction system is preferably vacuumized for 5-20 min before the temperature rising reaction, and the tube sealing treatment is carried out after the vacuumization.
The reaction is carried out under closed conditions with continuous stirring during the reaction, the reaction temperature being 40-80 ℃, preferably 50-70 ℃, more preferably 60 ℃.
The reaction time is 24 to 60 hours, preferably 30 to 50 hours, more preferably 48 hours.
Cooling to room temperature after the reaction is completed, adding a precipitating agent, filtering, and finally carrying out vacuum drying.
The precipitant is one or more selected from methanol, ethanol and n-hexane, preferably methanol.
The drying temperature is 35-50 ℃ and the drying time is 10-20 h.
Step 2, mixing the polystyrene copolymer and the alcoholic hydroxyl group-terminated polyphenyl ether polyol (PPOD) in a solvent to obtain a mixed solution.
The mass ratio of the alcoholic hydroxyl group-terminated polyphenylene ether polyol to the polystyrene copolymer is (0.01 to 1): 1, preferably (0.02 to 0.8): 1, more preferably (0.03 to 0.6): 1.
experiments show that the dielectric constant of the polyphenyl ether polyol with the end capped by the alcoholic hydroxyl group can be reduced, the heat resistance of the polyphenyl ether polyol with the end capped by the alcoholic hydroxyl group can be improved, the dielectric constant is gradually reduced, the heat resistance is gradually improved along with the increase of the addition amount of the polyphenyl ether polyol with the end capped by the alcoholic hydroxyl group, and when the mass ratio is in the range, the prepared modified polystyrene material has low dielectric property and good heat resistance.
The mixing is performed under stirring, and the mixing temperature is preferably normal temperature.
The solvent is selected from one or more of tetrahydrofuran, dichloromethane, benzene, toluene, xylene, acetonitrile, N-dimethylformamide and N, N-dimethylacetamide, preferably a mixed solvent of tetrahydrofuran and N, N-dimethylformamide, more preferably the volume ratio of tetrahydrofuran to N, N-dimethylformamide is (1-2): 1.
The mass concentration of the PSAA polymer and PPOD mixed solution is 10% -40%, preferably 20% -30%.
The alcoholic hydroxyl-terminated polyphenylene ether polyol is preferably prepared by the steps of:
step a, in the presence of an alkaline catalyst, reacting double-end hydroxyl polyphenyl ether and alkylene carbonate or epoxide in a solvent to obtain a reaction mixture;
in the step a, the alkaline catalyst is selected from one or more of organic alkali, alkali metal hydride, alkali metal hydroxide, alkali metal carbonate compound and alkali metal bicarbonate compound.
The solvent is an organic solvent, preferably one or more selected from benzene, toluene, xylene, dichloromethane, chloroform, tetrahydrofuran, and N, N-dimethylformamide.
The alkylene carbonate is selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC) and Butylene Carbonate (BC), preferably one or two of ethylene carbonate and propylene carbonate.
The epoxide is selected from one or more of Ethylene Oxide (EO), propylene Oxide (PO) and butylene oxide (EB), preferably one or two of ethylene oxide and propylene oxide.
The molar ratio of the alkylene carbonate or epoxide to the double-end hydroxyl polyphenyl ether is (1-1000): 1, preferably (1-500): 1, more preferably (2-100): 1.
The molar ratio of the alkaline catalyst to the double-end hydroxyl polyphenyl ether is (0.5-100): 1, preferably (0.5 to 80): 1, more preferably (1 to 50): 1.
The reaction temperature is 50 to 200 ℃, preferably 70 to 180 ℃, more preferably 90 to 150 ℃.
The reaction time is 1 to 100 hours, preferably 2 to 70 hours, more preferably 2 to 50 hours.
And b, precipitating, washing, filtering and drying the reaction mixture to obtain the alcoholic hydroxyl group-terminated polyphenyl ether polyol.
In step b, after stopping the reaction, a precipitating agent, preferably methanol, is added to the supernatant of the reaction mixture for precipitation.
Washing is performed by adding a detergent, preferably methanol, to the precipitate.
The washing and filtering steps are repeated for a plurality of times, preferably 2 to 3 times until no reaction solvent exists in the product, and finally vacuum drying is carried out.
The drying temperature is 60-90 ℃ and the drying time is 15-30 h.
And step 3, placing the mixed solution on a die, and heating and curing to obtain the low-dielectric polyphenyl ether modified polystyrene material.
The mold is a plate mold, such as a glass plate, and the mixed solution is coated on the glass plate and then heated for curing.
The temperature rise curing system is 30-50 ℃/0.5-3h+50-70 ℃/0.5-3h+70-90 ℃/0.5-3h+90-110 ℃/0.5-3h+110-140 ℃/0.5-4h+140-170 ℃/0.5-4 h.
Preferably, the temperature rise curing system is 35-45 ℃/0.5-2h+55-65 ℃/0.5-2h+75-85 ℃/0.5-2h+95-105 ℃/0.5-2h+115-130 ℃/1-3h+145-160 ℃/1-3 h.
More preferably, the heating and curing system is 40 ℃/1 to 1.5h+60 ℃/1 to 1.5h+80 ℃/1 to 1.5h+100 ℃/1 to 1.5h+120 ℃/2 to 3h+150 ℃/2 to 3h.
The PSAA polymer produced is a polymer containing latent NCO groups (isocyanate groups). Experiments show that the PSAA polymer has high stability at normal temperature, can undergo Lossen rearrangement to be converted into a polymer containing NCO under the heating condition of 100-150 ℃, and can further react with a compound containing hydroxyl or amino; the low dielectric polyphenyl ether modified polystyrene material with compact and uniform structure and flat surface can be formed by adopting a temperature programming mode.
The invention has the beneficial effects that:
(1) The PSAA polymer prepared in the preparation process is a PS (polystyrene) copolymer containing potential NCO groups (isocyanate groups), the preparation method is simple and convenient, the polymer has the advantage of high storage stability at normal temperature, and the polymer can be converted into a PS polymer containing high-activity NCO groups under the heating condition, so that the PS can be further subjected to functional modification;
(2) The invention adopts the polyphenyl ether polyol with the end capped by the alcoholic hydroxyl group to modify the polystyrene, the polyphenyl ether polyol with the end capped by the alcoholic hydroxyl group contains aliphatic hydroxyl groups, has high reaction activity, and is introduced into the polystyrene through the reaction of NCO groups and hydroxyl groups so as to prepare the low-dielectric polyphenyl ether modified polystyrene material;
(3) The low-dielectric polyphenyl ether modified polystyrene material not only has the excellent performance of polystyrene, but also has the performance of polyphenyl ether, and the dielectric property and the heat resistance of the modified polystyrene material are effectively improved through the addition modification of the polyphenyl ether polyol capped by alcoholic hydroxyl groups;
(4) The preparation method provided by the invention avoids the phenomena of difficult control of reaction heat conduction, easy occurrence of explosion aggregation and the like in the existing polystyrene preparation method, and is simple, high in reaction controllability, short in preparation period and low in energy consumption.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not intended to limit the scope of the invention.
The preparation process of the alcoholic hydroxyl group-terminated polyphenylene ether polyol (PPOD) is as follows:
5.00g (3.13 mmol) of double-ended hydroxy polyphenylene ether (PPO, molecular weight 1600, available from Saint Foundation Ind. Co., ltd., model NorylSA90, x+y=10), 0.55g (6.25 mmol) of Ethylene Carbonate (EC) and 0.44g (3.13 mmol) of K are placed in a three-necked round-bottomed flask equipped with a reflux condenser 2 CO 3 Added to 25mL of N, N-Dimethylformamide (DMF), and the reaction was stopped by stirring at 145℃under reflux for 3h.
The supernatant of the reaction mixture was dropped into absolute methanol to precipitate, and the resulting off-white precipitate was further obtained by suction filtration and the cake was washed with absolute methanol. Repeating the vacuum filtration step, and washing with absolute methanol for 2-3 times until no reaction solvent exists in the product. Finally, the product was dried in a vacuum oven at 80 ℃ for 24h. To obtain the alcoholic hydroxyl group-terminated polyphenyl ether polyol. Its m+n=2 is characterized by nuclear magnetic hydrogen spectroscopy.
Example 1
4.94g of styrene (PS) (47.5 mmol) and 0.36g of AMAA (2.5 mmol) were weighed into a Schlenk tube, 0.01g of Azobisisobutyronitrile (AIBN) initiator and 10ml of tetrahydrofuran solvent were added, the rubber stopper was sealed, and the vacuum was pulled for 10 minutes, and tube sealing treatment was performed; then placing the Schlenk tube into an oil bath at 60 ℃, and heating and stirring for 48 hours; then the reaction solution is cooled to room temperature, precipitated and filtered in methanol to obtain white powder, and the white powder is put into a vacuum oven at 40 ℃ to be dried for 12 hours, so as to obtain PSAA polymer.
Adding 1.00g of the prepared polymer PSAA and 0.10g of PPOD into 5ml of mixed solvent of tetrahydrofuran and N, N-dimethylformamide (volume ratio is 1:1), stirring at normal temperature to completely dissolve the PSAA and the PPOD, and preparing a mixed solution of the PSAA and the PPOD;
coating the prepared mixed solution on a glass plate, and heating according to the following gradual heating program at 40 ℃/1h;60 ℃/1h;80 ℃/1h;100 ℃/1h;120 ℃/2h;150 ℃/2h to obtain the low-dielectric polyphenyl ether modified polystyrene material.
The test shows that the prepared low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.15mm, the dielectric constant of 2.45 (10 GHz), 2.42 (20 GHz) and the dielectric loss value of 1.73X10 -3 (10GHz)，2.28×10 -3 (20 GHz), the glass transition temperature was 136 ℃.
Example 2
The preparation of the low dielectric polyphenylene ether modified polystyrene material was carried out in a similar manner to example 1, except that: the amount of styrene added was 4.94g (47.5 mmoL), the amount of AMAA added was 0.36g (2.5 mmoL), and the amount of PPOD added was 0.20g.
The test shows that the prepared low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.16mm, the dielectric constant of 2.48 (10 GHz), 2.47 (20 GHz) and the dielectric loss value of 2.28X10 -3 (10GHz)，2.64×10 -3 (20 GHz), glass transition temperature was 144 ℃.
Example 3
The preparation of the low dielectric polyphenylene ether modified polystyrene material was carried out in a similar manner to example 1, except that: the addition amount of styrene was 4.68g (45 mmoL), and the addition amount of AMAA was 0.72g (5 mmoL); the amount of PPOD added was 0.05g.
Through testing, the prepared low-dielectric polyphenyl ether modified polystyrene materialHas a thickness of 0.12mm, a dielectric constant of 2.47 (10 GHz), a dielectric loss of 2.45 (20 GHz) and a dielectric loss of 1.72X10 -3 (10GHz)，2.25×10 -3 (20 GHz), glass transition temperature was 129 ℃.
Example 4
The preparation of the low dielectric polyphenylene ether modified polystyrene material was carried out in a similar manner to example 1, except that: the amount of styrene added was 4.68g (45 mmoL), the amount of AMAA added was 0.72g (5 mmoL), and the amount of PPOD added was 0.10g. .
The test shows that the prepared low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.13mm, the dielectric constant of 2.40 (10 GHz), 2.42 (20 GHz) and the dielectric loss value of 1.66 multiplied by 10 -3 (10GHz)，2.24×10 -3 (20 GHz), the glass transition temperature was 134 ℃.
Example 5
The preparation of the low dielectric polyphenylene ether modified polystyrene material was carried out in a similar manner to example 1, except that: the addition amount of styrene was 4.68g (45 mmoL), and the addition amount of AMAA was 0.72g (5 mmoL); the amount of PPOD added was 0.15g.
The test shows that the prepared low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.13mm, the dielectric constant of 2.38 (10 GHz), 2.33 (20 GHz) and the dielectric loss value of 1.70 multiplied by 10 -3 (10GHz)，2.21×10 -3 (20 GHz), glass transition temperature was 139 ℃.
Example 6
The preparation of the low dielectric polyphenylene ether modified polystyrene material was carried out in a similar manner to example 1, except that: the addition amount of styrene was 4.68g (45 mmoL), and the addition amount of AMAA was 0.72g (5 mmoL); the amount of PPOD added was 0.20g.
The test shows that the prepared low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.14mm, the dielectric constant of 2.34 (10 GHz), 2.22 (20 GHz) and the dielectric loss value of 1.65X10 -3 (10GHz)，2.16×10 -3 (20 GHz), glass transition temperature was 142 ℃.
Example 7
The preparation of the low dielectric polyphenylene ether modified polystyrene material was carried out in a similar manner to example 1, except that: the addition amount of styrene was 4.68g (45 mmoL), and the addition amount of AMAA was 0.72g (5 mmoL); the amount of PPOD added was 0.30g.
The test shows that the prepared low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.15mm, the dielectric constant of 2.51 (10 GHz), 2.37 (20 GHz) and the dielectric loss value of 2.13 multiplied by 10 -3 (10GHz)，2.34×10 -3 (20 GHz), the glass transition temperature was 148 ℃.
Example 8
The preparation of the low dielectric polyphenylene ether modified polystyrene material was carried out in a similar manner to example 1, except that: the addition amount of styrene was 4.68g (45 mmoL), and the addition amount of AMAA was 0.72g (5 mmoL); the amount of PPOD added was 0.40g.
The test shows that the prepared low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.16mm, the dielectric constant of 2.54 (10 GHz), 2.43 (20 GHz) and the dielectric loss value of 9.10 multiplied by 10 -3 (10GHz)，7.88×10 -3 (20 GHz), glass transition temperature was 152 ℃.
Example 9
The preparation of the low dielectric polyphenylene ether modified polystyrene material was carried out in a similar manner to example 1, except that: the amount of styrene added was 4.16g (40 mmoL), the amount of AMAA added was 1.43g (10 mmoL), and the amount of PPOD added was 0.10g. .
The test shows that the prepared low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.11mm, the dielectric constant of 2.38 (10 GHz), 2.39 (20 GHz) and the dielectric loss value of 1.71 multiplied by 10 -3 (10GHz)，2.27×10 -3 (20 GHz), glass transition temperature was 135 ℃.
Example 10
The preparation of the low dielectric polyphenylene ether modified polystyrene material was carried out in a similar manner to example 1, except that: the amount of styrene added was 4.16g (40 mmoL), the amount of AMAA added was 1.43g (10 mmoL), and the amount of PPOD added was 0.20g.
Through testing, the prepared low-dielectric polyphenyl ether modified polystyrene material has the thickness of 0.12mm and the dielectric constant of 2.35 (10 GHz),2.26 (20 GHz), dielectric loss value was 1.68X10 -3 (10GHz)，2.20×10 -3 (20 GHz), glass transition temperature was 145 ℃.
Comparative example
Comparative example 1
The preparation of the modified PS material was carried out in a similar manner to example 1, except that: PPOD was not added.
The thickness of the product obtained by the test is 0.16mm, the dielectric constant is 2.61 (10 GHz), 2.49 (20 GHz), and the dielectric loss value is 1.76 multiplied by 10 -3 (10GHz)，2.24×10 -3 (20 GHz), the glass transition temperature was 125 ℃.
Comparative example 2
The preparation of the modified PS material was carried out in a similar manner to example 3, except that: PPOD was not added.
The thickness of the product obtained by the test is 0.13mm, the dielectric constant is 2.59 (10 GHz), 2.49 (20 GHz), and the dielectric loss value is 1.74 multiplied by 10 -3 (10GHz)，2.18×10 -3 (20 GHz), glass transition temperature was 123 ℃.
Comparative example 3
The preparation of the modified PS material was carried out in a similar manner to example 9, except that: PPOD was not added.
The thickness of the product is 0.11mm, the dielectric constant is 2.57 (10 GHz), 2.54 (20 GHz), and the dielectric loss value is 1.71 multiplied by 10 -3 (10GHz)，2.17×10 -3 (20 GHz), glass transition temperature was 120 ℃.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A low-dielectric polyphenyl ether modified polystyrene material is characterized in that the low-dielectric polyphenyl ether modified polystyrene material is prepared from styrene, N-acetoxy methacrylamide and alcoholic hydroxyl group-terminated polyphenyl ether polyol.
2. The low dielectric polyphenylene ether-modified polystyrene material of claim 1, wherein,
the low-dielectric polyphenyl ether modified polystyrene material is prepared by reacting styrene and N-acetoxy methacrylamide to prepare a polystyrene copolymer, and then curing the polystyrene copolymer with alcoholic hydroxyl terminated polyphenyl ether polyol.
3. The low dielectric polyphenylene ether-modified polystyrene material as recited in claim 2, wherein,
the mol ratio of the styrene to the N-acetoxy methacrylamide is (1-30): 1.
4. the low dielectric polyphenylene ether-modified polystyrene material as recited in claim 2, wherein,
the mass ratio of the alcoholic hydroxyl group-terminated polyphenyl ether polyol to the polystyrene copolymer is (0.01-1): 1.
5. The low dielectric polyphenylene ether-modified polystyrene material as recited in claim 2, wherein,
the temperature rise curing system is 30-50 ℃/0.5-3h+50-70 ℃/0.5-3h+70-90 ℃/0.5-3h+90-110 ℃/0.5-3h+110-140 ℃/0.5-4h+140-170 ℃/0.5-4 h.
6. A method for preparing a low dielectric polyphenylene oxide modified polystyrene material, the method comprising:
step 1, in the presence of an initiator, styrene and N-acetoxy methacrylamide react in a solvent by heating to obtain a polystyrene copolymer;
step 2, mixing a polystyrene copolymer and an alcoholic hydroxyl group-terminated polyphenyl ether polyol in a solvent to obtain a mixed solution;
and step 3, placing the mixed solution on a die, and heating and curing to obtain the low-dielectric polyphenyl ether modified polystyrene material.
7. The method according to claim 6, wherein, in step 1,
the initiator is one or more selected from Azodiisobutyronitrile (AIBN), benzoyl Peroxide (BPO), azodiisoheptonitrile (ABVN) and benzoyl peroxide tert-butyl ester (BPB);
the addition amount of the initiator is 0.1 to 0.3 percent of the total mass of the styrene and the N-acetoxy methacrylamide.
8. The method according to claim 6, wherein, in step 1,
the reaction temperature is 40-80 ℃ and the reaction time is 24-60 h.
9. The method according to claim 6, wherein, in step 2,
the alcoholic hydroxyl-terminated polyphenylene ether polyol is preferably prepared by the steps of:
step a, in the presence of an alkaline catalyst, reacting double-end hydroxyl polyphenyl ether and alkylene carbonate or epoxide in a solvent to obtain a reaction mixture;
and b, precipitating, washing, filtering and drying the reaction mixture to obtain the alcoholic hydroxyl group-terminated polyphenyl ether polyol.
10. The method according to claim 6, wherein in step 3,
the temperature rise curing system is 30-50 ℃/0.5-3h+50-70 ℃/0.5-3h+70-90 ℃/0.5-3h+90-110 ℃/0.5-3h+110-140 ℃/0.5-4h+140-170 ℃/0.5-4 h.
CN202211649307.5A 2022-12-21 Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof Active CN116041869B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211649307.5A CN116041869B (en) 2022-12-21 Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211649307.5A CN116041869B (en) 2022-12-21 Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN116041869A true CN116041869A (en) 2023-05-02
CN116041869B CN116041869B (en) 2024-05-17

Family

ID=

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1151254A (en) * 1965-06-25 1969-05-07 Japanese Geon Co Ltd Novel High Molecular Weight Adhesive Substances
GB1208822A (en) * 1968-03-25 1970-10-14 Bexford Ltd Copolymers of vinyl halogenoesters
CN109705284A (en) * 2019-01-14 2019-05-03 上海材料研究所 A kind of polyphenyl ether resin composition of low-k and its prepreg of production
CN110003582A (en) * 2017-12-20 2019-07-12 东洋苯乙烯股份有限公司 Heat resistance styrene resin composite, molded product, extrusion sheet and food packaging container
CN114106263A (en) * 2021-12-29 2022-03-01 广东聚航新材料研究院有限公司 Methacrylate functionalized polyphenyl ether and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1151254A (en) * 1965-06-25 1969-05-07 Japanese Geon Co Ltd Novel High Molecular Weight Adhesive Substances
GB1208822A (en) * 1968-03-25 1970-10-14 Bexford Ltd Copolymers of vinyl halogenoesters
CN110003582A (en) * 2017-12-20 2019-07-12 东洋苯乙烯股份有限公司 Heat resistance styrene resin composite, molded product, extrusion sheet and food packaging container
CN109705284A (en) * 2019-01-14 2019-05-03 上海材料研究所 A kind of polyphenyl ether resin composition of low-k and its prepreg of production
CN114106263A (en) * 2021-12-29 2022-03-01 广东聚航新材料研究院有限公司 Methacrylate functionalized polyphenyl ether and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN108473758B (en) Polyphenylene ether resin composition, prepreg, metal-clad laminate, and printed wiring board
CN101885812B (en) Functionalized poly(arylene ether) composition and method
CN108641055B (en) Main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof
CN106398173B (en) Thermosetting resin composition, resin varnish, metal foil with resin, resin film, metal-clad laminate, and printed wiring board
CN113388137B (en) Preparation method of high-strength high-temperature-resistant poly (arylene ether nitrile) film
CN110818868A (en) Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof
CN110746594B (en) Low-molecular-weight fluorine-containing polyphenyl ether and preparation method and application thereof
CN116041869B (en) Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof
CN116041869A (en) Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof
US5128421A (en) Method for preparing hydroxyalkyl-functionalized polyphenylene ether with epoxy compound reactant
CN113603882A (en) Oligo (2, 6-dimethylphenylene ether), preparation method and cured product thereof
CN114031719B (en) Bismaleimide-triazine resin and preparation method and application thereof
CN114349954B (en) Phthalonitrile-terminated polyaryl ether nitrile containing methylene/methylene, crosslinked cured modified polyaryl ether nitrile and preparation method thereof
TW201912661A (en) (2,6-dimethyl-1,4-phenylene oxide)oligomer-containing benzoxazine resin, thermoset and manufacturing methods thereof
CN114957917B (en) PEN-PAQR-SiO 2 Preparation method of modified epoxy resin composite material
CN117887013A (en) Polyphenyl ether composite resin of dimensionally stable battery pack structural member and preparation method thereof
CN115160516B (en) Thermosetting polyphenyl ether material containing trifluoromethyl and preparation method and application thereof
CN115536880B (en) Polyarylether ketone-based dielectric film containing rigid annular structure, and preparation method and application thereof
CN115417986B (en) Allyl grafted polyaryletherketone oligomer, preparation method thereof, photosensitive material and application thereof
TWI830468B (en) Vinyl-containing aromatic alicyclic copolymer, resin compositions and product thereof
CN114671972B (en) Heteropoly acid type polyion liquid self-healing material and preparation method and application thereof
CN112608462B (en) LCP (liquid Crystal Polymer) high polymer material suitable for 5G product
CN115948029A (en) Low-dielectric high-hydrophobicity LCP-based LDS composite material and preparation method thereof
CN115651266B (en) Heterogeneous polymethacrylimide wave-absorbing foam and preparation method thereof
CN110128581B (en) Encapsulation process of microstrip patch antenna

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20240422

Address after: 116024 No. 2 Ling Road, Ganjingzi District, Liaoning, Dalian

Applicant after: DALIAN University OF TECHNOLOGY

Country or region after: China

Applicant after: NANYA NEW MATERIAL TECHNOLOGY Co.,Ltd.

Address before: 116024 No. 2 Ling Road, Ganjingzi District, Liaoning, Dalian

Applicant before: DALIAN University OF TECHNOLOGY

Country or region before: China

GR01 Patent grant