CN103145975B - Method for preparing polyphenyl ether with side chain containing unsaturated carbon-carbon double bond in water medium - Google Patents

Abstract

The invention discloses a method for preparing polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain in an aqueous medium. In the presence of catalysts, surfactants, basic compounds and oxidants, common phenolic monomers and Phenolic monomers containing unsaturated carbon-carbon double bonds are oxidatively copolymerized in aqueous media at 30°C to 60°C for 4 hours to 24 hours. After the oxidative copolymerization is completed, they are demulsified, filtered and washed with water. A polyphenylene ether having an unsaturated carbon-carbon double bond in the side chain is obtained. The polyphenylene ether containing unsaturated carbon-carbon double bonds prepared in the water medium of the present invention has the characteristics of less residual metal catalyst content, low dielectric constant and dielectric loss, resistance to organic solvents, high temperature resistance, and good processability. The preparation process It is green and environmentally friendly, easy to operate, safe and non-toxic, has broad development space and great market application value, and meets the requirements of sustainable development.

Description

A method for preparing polyphenylene ether with side chain containing unsaturated carbon-carbon double bond in aqueous medium

technical field

The invention relates to the technical field of polymer chemical industry, in particular to a method for preparing polyphenylene ether with side chains containing unsaturated carbon-carbon double bonds in an aqueous medium.

Background technique

Poly 2,6-dimethylphenylene oxide (PPO) is an engineering plastic with excellent comprehensive properties. It not only has good mechanical properties, but also has low dielectric constant, low dielectric loss, high glass transition temperature, Outstanding properties such as acid and alkali corrosion resistance, especially excellent electrical properties (ε=2.5-2.6, tanδ=0.0015-0.0019). However, PPO is a kind of thermoplastic resin, which cannot withstand the requirements of welding at high temperature, and is easily soluble in aromatic hydrocarbons or chlorinated aliphatic hydrocarbons. It has poor solvent resistance and poor film-forming properties. Therefore, polyphenylene ether must be modified to expand its scope of use. One method is to introduce unsaturated carbon-carbon double bonds in PPO. The advantages are: (1) Since the unsaturated carbon-carbon double bonds account for a small proportion in the entire PPO, the original thermoplastic PPO resin can be basically maintained. Excellent properties, such as low dielectric constant, high glass transition temperature, low moisture absorption, etc. (2) The solvent resistance of the PPO resin after cross-linking and curing is greatly improved. (3) The unsaturated carbon-carbon double bond is a non-polar group, which has the advantages of good dielectric properties, suitable curing temperature, and no volatile matter during curing. The PPO whose side chain is introduced into the unsaturated carbon-carbon double bond is applied in the manufacture of copper clad laminates, not only can retain its good electrical properties, but also can significantly improve its solvent resistance and soldering performance at high temperature after curing, and the process is simple It is easy to implement and can better adapt to the requirements of high-frequency printed circuit boards.

Katayo Kasei described the allylic compound developed by Asahi Kasei in Japan in the literature (Yoshiyuki ISHII, Masakatsu KURPKI, Hirozi ODA, Takeshi ARAI, and Teruo KATAYOSE. Novel Thermosettable Poly(phenyleneether). Synthesis, Blend, and Application to Copper Clad Laminates.) Alkylated polyphenylene ether (Allyl-PPO), the synthesis route includes dissolving PPO in tetrahydrofuran, using butyllithium to react with PPO, lithium replaces the hydrogen on the methyl group, and then the above product is reacted with allyl halide , so as to obtain PPO containing allyl group, the process is cumbersome and dangerous, and the structure of the obtained allylated PPO is not clear enough, because it may occur at multiple sites or at the same site multiple times in a structural unit Allylation reaction.

The traditional PPO synthesis method is carried out in organic solvents such as toluene, benzene, chloroform, pyridine, etc. The reaction not only uses a large amount of organic solvents, but also requires a highly airtight and explosion-proof reactor, which will pollute the environment. In addition, organic solvents The synthesized PPO has a large molecular weight, high glass transition temperature and is not easy to process, and due to the homogeneous reaction, the residual catalyst metal ion content in the product is relatively high, which reduces its electrical properties to a certain extent. Using water as the reaction medium not only meets the requirements of green chemistry, but the molecular weight of the product is much smaller than that synthesized in organic solvents, and the product is insoluble in water, easy to separate, and the residual copper ion content in the product is low (Catalyzedoxidative polymerization to form poly(2 ,6-dimethyl-1,6-phenylene oxide)inwater using water-soluble copper complex.Saito K,Kuwashiro N,Nishide H.Polymer2006,47,6581.), the copper ion content of synthetic PPO in the water medium is about 1ppm. In terms of research on the synthesis of polyphenylene ether using water as a medium, only the homopolymerization of 2,6-dimethylphenol has been studied, and ordinary PPO has been synthesized, while the side chain contains unsaturated carbon-carbon double The synthesis of bonded polyphenylene ether has not been reported yet.

Contents of the invention

The invention provides a method for preparing polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain in an aqueous medium. Polyphenylene ethers containing unsaturated carbon-carbon double bonds in side chains were synthesized by copolymerization of phenolic monomers.

The present invention finds: if can use the phenolic monomer containing unsaturated carbon-carbon double bond to carry out copolymerization reaction with conventional phenolic monomer in aqueous medium, then can simultaneously solve existing in the prior art " synthesis in organic solvent The PPO molecular weight is large, its glass transition temperature is high and it is not easy to process, and due to the homogeneous reaction, the residual catalyst metal ion content in the product is relatively high, which reduces its electrical properties to a certain extent. Introducing unsaturated carbon-carbon double bonds into PPO to modify polyphenylene ether and expand its use range", and the PPO synthesized in aqueous medium has a small molecular weight and is easy to process. However, the phenolic monomers will have different reactivity due to the different substituents of the phenolic hydroxyl groups, and the size of the substituents will also cause differences in steric hindrance during the reaction, thereby affecting the progress of the reaction; The research on the copolymerization of quasi-monomers is still blank, and the synthesis of polyphenylene ethers with unsaturated carbon-carbon double bonds in side chains using water as a medium has important theoretical significance and application value.

The mechanism of preparing polyphenylene ethers with side chains containing unsaturated carbon-carbon double bonds in the aqueous medium provided by the present invention is as follows: in the initial stage of the reaction, all types of phenolic monomers react with basic compounds to form water-soluble phenoxy anions. The phenoxy anion is oxidized by the catalyst to phenoxy radical, while the divalent metal ion in the catalyst is reduced to monovalent. In the presence of an oxidizing agent, monovalent metal ions are oxidized to obtain divalent metal ions again, and the oxidative coupling between phenoxy anions increases the molecular weight of the product, thereby cyclically catalyzing oxidative polymerization. With the progress of the polymerization reaction, the oligomer is insoluble in alkaline aqueous solution and precipitates out, becoming a heterogeneous system, forming stable polymer particles through the surfactant, so that the oxidative coupling polymerization reaction continues, and finally the side chain containing Polyphenylene ether with saturated carbon-carbon double bonds.

A method for preparing polyphenylene ether with side chains containing unsaturated carbon-carbon double bonds in an aqueous medium, specifically comprising the following scheme: in the presence of a catalyst, a surfactant, a basic compound and an oxidizing agent, the formula (I ) phenolic monomers shown in the structure and phenolic monomers containing unsaturated carbon-carbon double bonds shown in the structure of formula (II) were oxidatively copolymerized in aqueous medium at 30°C to 60°C for 4 hours to After 24 hours, after the oxidative copolymerization reaction is completed, the polyphenylene ether having a side chain containing unsaturated carbon-carbon double bonds represented by the structure of formula (III) is obtained through demulsification, filtration and water washing;

In formula (I), R ₁ and R ₂ are the same or different, R ₁ is hydrogen, an alkyl, haloalkyl, aminoalkyl or alkoxy group with 1 to 4 carbon atoms, R ₂ is hydrogen, and the number of carbon atoms is 1 to 4 alkyl, haloalkyl, aminoalkyl or alkoxy, R ₃ is hydrogen or halogen;

_R4 and _R5 in the formula (II) are the same or different, and _R4 is a group containing unsaturated carbon-carbon double bonds with 2 to 4 carbon atoms, hydrogen, and an alkyl group with 1 to 4 carbon atoms , haloalkyl, aminoalkyl or alkoxy, _R5 is a group with 2-4 carbon atoms containing an unsaturated carbon-carbon double bond, hydrogen, an alkyl group with 1 to 4 carbon atoms, haloalkyl , aminoalkyl or alkoxy, and at least one of both _R4 and _R5 is a group with 2-4 carbon atoms containing an unsaturated carbon-carbon double bond, and _R6 is hydrogen or halogen;

R ₁ and R 2 in formula (Ⅲ) have the same meanings as R ₁ and R ₂ in formula (I), and R ₄ and R ₅ in formula (Ⅲ) have the same meanings as R ₄ and R in formula (II), _respectively . ₅ has the same meaning; m is 15-50, n is 2-17; the weight average molecular weight of the polyphenylene ether is 4000-16000. For example, the m may be 15-22, and n may be 2-7; the weight average molecular weight of the polyphenylene ether is 4100-7400.

Preferably, the alkyl groups in the haloalkyl group, aminoalkyl group or alkoxy group are all independently alkyl groups with 1 to 4 carbon atoms, which is more conducive to the oxidative copolymerization reaction.

As a preference, the group containing unsaturated carbon-carbon double bonds with 2-4 carbon atoms is vinyl, allyl, propenyl, butenyl or butyl, which is more conducive to oxidative copolymerization reaction carried out.

The halogen is selected from halogens commonly used in the art, such as one of F, Cl, Br, I and the like.

The molar ratio composition of each raw material in the described oxidative copolymerization reaction is:

The phenolic monomer represented by the structure of formula (I) 1;

Phenolic monomers containing unsaturated carbon-carbon double bonds represented by the structure of formula (II) 0.1-0.45;

Basic compound 0.055～100;

Surfactant 0.001～0.15;

Catalyst 0.001～0.75;

Oxidizing agent Appropriate amount.

As preferably, the molar ratio composition of each raw material in the described oxidative copolymerization reaction is:

The phenolic monomer represented by the structure of formula (I) 1;

Phenolic monomers containing unsaturated carbon-carbon double bonds represented by the structure of formula (II) 0.1-0.43;

Basic compound 0.055～1.3;

Surfactant 0.0055～0.15;

Catalyst 0.001～0.75;

Oxidizing agent Appropriate amount.

The basic compound is selected from one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methoxide, sodium carbonate, potassium carbonate, potassium bicarbonate and sodium bicarbonate.

Described tensio-active agent selects anionic surfactant for use, specifically can select carboxylate surfactant, alkyl sulfate surfactant, alkylsulfonate surfactant, alkylbenzenesulfonate surfactant One or more than two.

The catalyst is selected from the copper amine complex of copper compound and amine compound, or the manganese amine complex of manganese compound and amine compound. The molar ratio of nitrogen atoms to copper ions in the copper amine complex is preferably 2 to 8, more preferably 2 to 4, or the molar ratio of nitrogen atoms to manganese ions in the manganese amine complex is preferably 2 to 8. 8, more preferably 2-4.

The copper compound is selected from a divalent copper compound, preferably one or more of copper chloride, copper bromide, copper sulfate, copper nitrate; or, the manganese compound is selected from a divalent manganese compound, preferably manganese chloride, One or more of manganese bromide, manganese iodide, manganese carbonate, manganese acetate, manganese nitrate, manganese sulfate, manganese phosphate.

The amine compound is selected from methylamine, ethylamine, 2-hydroxyethylamine, 2-methylaminoethylamine, n-propylamine, cyclobutylamine, tert-butylamine, 1,4-butanediamine, 1-hydroxybutylamine, n-pentylamine Amine, 1,5-pentanediamine, cyclopentanediamine, n-hexylamine, 4-isopropylcyclohexylamine, 1,4-cyclohexanediamine, 3-methoxyhexamethylenediamine, benzylamine, 1,6-hexanediamine, 1,8-octanediamine, 4-isopropyl-1,3-phenylenediamine, diaminodiphenylsulfone, diaminodiphenyl ether, 3,3-dimethyl benzidine, 3,3-dimethoxybenzidine, ethylenediaminetetraacetic acid, N-substituent imidazole, N,N,N',N'-tetramethyl-1,3-diamino-1 -Ethylpropane, N,N,N',N'-tetraethyl-1,3-diamino-1-methylpropane, 1,3-diaminopropane, N,N,N',N One or more of '-tetramethyl-1,3-diaminopropane.

The oxidant is oxygen, air or a mixed gas composed of oxygen and inert gas. Oxygen and inert gas in the mixed gas can be mixed in various ratios (oxygen ratio cannot be 0).

Under the action of a peroxide initiator or a photoinitiator, the product synthesized by the present invention is subjected to temperature programming or ultraviolet light irradiation, and the unsaturated carbon-carbon double bond on the side chain can undergo a crosslinking reaction to obtain a cured Modified polyphenylene ether.

The raw materials and reagents described in the present invention can all adopt commercially available products.

Compared with prior art, the present invention has following remarkable progress:

The polyphenylene ether containing unsaturated carbon-carbon double bonds prepared in the water medium of the present invention has less residual metal ion content, low dielectric constant, low dielectric loss, good processability, and the product is solvent-resistant after curing,

Good temperature resistance; at the same time, the synthesis method of the present invention is more simple and easy to implement, green and environmentally friendly, safe and non-toxic, has broad development space and great market application value, and is more in line with the requirements of sustainable development.

Detailed ways

Example 1 Preparation of Polyphenylene Ether with Side Chain Containing Unsaturated Carbon-Carbon Double Bonds in Aqueous Medium

In a reaction kettle with a stirring paddle and a thermometer, add sodium hydroxide (0.2g, 5mmol), sodium lauryl sulfate (0.1694g, 0.5mmol), 2,6-dimethylphenol (DMP, 0.4930g , 4mmol), 2-allyl-6-methylphenol (AMP, 0.15ml, 1mmol) and distilled water 100mL, after stirring evenly, raise the temperature of the reactor to 50℃, then add copper chloride (0.0086g, 0.05 mmol)/ethylenediaminetetraacetic acid (EDTA, 0.05mmol) complex, fed with oxygen, and reacted for 24 hours at a stirring speed of 600rotor/min (rev/min). After the reaction, add sodium chloride to break the emulsion, then filter, wash with water, and vacuum-dry to constant weight to obtain a solid product, that is, polyphenylene ether containing double bonds, with a yield of 78.35%, a weight average molecular weight of 6000, and a molecular weight distribution of 2.2, m= 17, n=4, residual copper ion content 0.80ppm.

Embodiment 2～3

According to the method of Example 1, polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain was prepared in the aqueous medium, the difference was that the ratio of the two phenolic monomers was changed. The polymerization results are shown in Table 1:

Table 1

Example 4

According to the method of Example 1, polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain was prepared in aqueous medium, except that 0.52 g (5.2 mmol) of potassium bicarbonate was used instead of sodium hydroxide, and the yield was 76.57%. The product The weight average molecular weight is 5900, the molecular weight distribution is 2.1, m=18, n=4, and the residual copper ion content is 0.76ppm.

Example 5

According to the method of Example 1, polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain was prepared in aqueous medium, the difference was that the oxidant was air, the yield was 76.78%, the product molecular weight was 5800, the molecular weight distribution was 2.2, m=17, n=4, the residual copper ion content is 0.81ppm.

Example 6

According to the method of Example 1, polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain was prepared in aqueous medium, except that 2,6-diethylphenol (0.5053g, 4mmol) was used instead of 2,6-diethylphenol Methyl phenol, yield 77.28%, product weight average molecular weight 6200, molecular weight distribution 2.3, m=17, n=4, residual copper ion content 0.79ppm.

Example 7

According to the method of Example 1, polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain was prepared in aqueous medium, except that 2-enebutyl-6-methylphenol (0.15ml, 1mmol) was used instead of 2- Allyl-6-methylphenol, yield 79.35%, product weight average molecular weight 6300, molecular weight distribution 2.3, m=18, n=5, residual copper ion content 0.78ppm.

Example 8

According to the method of Example 1, polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain was prepared in aqueous medium, the difference was that the reaction temperature was 30°C, the reaction time was 8 hours, the yield was 70.32%, and the weight average molecular weight of the product 4900, molecular weight distribution 2.0, m=16, n=4, residual copper ion content 0.80ppm.

Examples 9-13

According to the method of Example 1, polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain was prepared in aqueous medium, except that copper amine complexes of different concentrations were used. The polymerization results are shown in Table 2:

Table 2

Examples 14-18

According to the method of Example 1, polyphenylene ethers containing unsaturated carbon-carbon double bonds in the side chains were prepared in aqueous media, except that different copper amine complexes were used. The polymerization results are shown in Table 3:

table 3

Examples 19-23

According to the method of Example 1, polyphenylene ether containing unsaturated carbon-carbon double bonds in the side chain was prepared in aqueous medium, except that different manganese amine complexes were used. The polymerization results are shown in Table 4:

Table 4

Example 24

Dissolve 1 g of the product synthesized in Example 1 and 10 mg of the initiator cumene hydroperoxide (CHPO) in 5 ml of toluene, heat at 80°C for 1 hour under the protection of nitrogen or an inert gas, and then heat up to 180°C for 1 After hours, the cured modified polyphenylene ether was obtained. The gel content of the product was 98.6%, and the 5% decomposition temperature was 383°C. The cross-linked polymer was no longer soluble in organic solvents such as toluene and chloroform.

Example 25

Dissolve 1 g of the product synthesized in Example 1 and 10 mg of the photoinitiator TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) in 5 ml of toluene, and under the protection of nitrogen or inert gas, in Under the irradiation of 200nm ultraviolet light for 10s, the gel content of the product is 99.1%, and the 5% decomposition temperature is 392°C. The cross-linked polymerization is no longer soluble in organic solvents such as toluene and chloroform.

Claims (9)

1. the method prepared side chain and contain the polyphenylene oxide of unsaturated carbon-to-carbon double bond in aqueous medium, it is characterized in that, at catalyst, surfactant, under alkali compounds and oxidant exist, the phenol monomer containing unsaturated carbon-to-carbon double bond shown in the phenol monomer shown in formula (I) structure and formula (II) structure is carried out oxidation copolymerization in aqueous medium at 30 DEG C ~ 60 DEG C and close reaction 4 hours ~ 24 hours, after copolymerization to be oxidized terminates, through breakdown of emulsion, filtration and washing obtain the polyphenylene oxide that the side chain shown in formula (III) structure contains unsaturated carbon-to-carbon double bond,

R in formula (I) ₁and R ₂identical or different, R ₁for hydrogen, carbon number be 1 to 4 alkyl, haloalkyl, aminoalkyl or alkoxyl, R ₂for hydrogen, carbon number be 1 to 4 alkyl, haloalkyl, aminoalkyl or alkoxyl, R ₃for hydrogen or halogen;

R in formula (II) ₄and R ₅identical or different, R ₄for carbon number be 2-4 containing the group of unsaturated carbon-to-carbon double bond, hydrogen, carbon number be 1 to 4 alkyl, haloalkyl, aminoalkyl or alkoxyl, R ₅for carbon number be 2-4 containing the group of unsaturated carbon-to-carbon double bond, hydrogen, carbon number be 1 to 4 alkyl, haloalkyl, aminoalkyl or alkoxyl, and R ₄and R ₅the two have at least one for carbon number be 2-4 contain the group of unsaturated carbon-to-carbon double bond, R ₆for hydrogen or halogen;

R in formula (III) ₁, R ₂respectively with R in formula (I) ₁, R ₂there is identical implication, the R in formula (III) ₄, R ₅respectively with R in formula (II) ₄, R ₅there is identical implication; M is 15 ~ 50, n is 2 ~ 17; The weight average molecular weight of described polyphenylene oxide is 4000 ~ 16000;

Described catalyst is the copper-amine complex of copper compound and amines complexing, or is the manganese amine complex of manganese compound and amines;

In described copper-amine complex, the molar ratio of nitrogen-atoms and copper ion is 2 ~ 8, or in described manganese amine complex, the molar ratio of nitrogen-atoms and manganese ion is 2 ~ 8.

2. method according to claim 1, is characterized in that, the alkyl in described haloalkyl, aminoalkyl or alkoxyl to be carbon number all be independently of one another 1 to 4 alkyl.

3. method according to claim 1, is characterized in that, described carbon number is the group containing unsaturated carbon-to-carbon double bond of 2-4 is vinyl, pi-allyl, acrylic, cyclobutenyl or alkene butyl.

4. method according to claim 1, is characterized in that, the mol ratio that described oxidation copolymerization closes each raw material in reaction consists of:

5. the method according to claim 1 or 4, is characterized in that, described alkali compounds is one or more in potassium hydroxide, NaOH, lithium hydroxide, sodium methoxide, sodium carbonate, potash, saleratus, sodium acid carbonate;

Described surfactant is anionic surfactant.

6. method according to claim 5, is characterized in that, described surfactant is one or more in carboxylate surface active agent, alkyl sulfate surfactant, alkyl sulfonate surfactants, alkyl benzene sulfonate surfactant.

7. method according to claim 1, is characterized in that, described copper compound select in copper chloride, copper bromide, copper sulphate, copper nitrate one or more; Or, described manganese compound select in manganese chloride, manganous bromide, manganese iodide, manganese carbonate, manganese acetate, manganese nitrate, manganese sulfate, manganese phosphate one or more.

8. method according to claim 1, it is characterized in that, described amines selects methylamine, ethamine, 2 hydroxy ethylamine, 2-methylamino ethamine, n-propylamine, ring butylamine, tert-butylamine, 1, 4-butanediamine, 1-hydroxyl butylamine, n-amylamine, 1, 5-pentanediamine, ring pentanediamine, n-hexylamine, 4-isopropyl cyclohexylamine, 1, 4-cyclohexane diamine, 3-methoxyl group hexamethylene diamine, benzyl amine, 1, 6-hexamethylene diamine, 1, 8-octamethylenediamine, 4-isopropyl-1, 3-phenylenediamine, two amido diphenyl sulphone (DPS)s, diaminodiphenyl ether, 3, 3-dimethylbenzidine, 3, 3-dimethoxy benzidine, ethylenediamine tetra-acetic acid, N-substituting group imidazoles, N, N, N ', N '-tetramethyl-1, 3-bis-amido-1-triethanol propane, N, N, N ', N '-tetraethyl-1, 3-bis-amido-1-methylpropane, 1, 3-bis-amido propane, N, N, N ', N '-tetramethyl-1, one or more in 3-bis-amido propane.

9. the method according to claim 1 or 4, is characterized in that, described oxidant is oxygen, air or mix the mist formed by oxygen and inert gas.