JPH0196202A - Production of reactive polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer of low acid value, with dielectric properties, heat resistance and flame retardancy, capable of obtaining molded articles useful as substrates for setting up semiconductor elements, ICs etc., by esterification of a p-hydroxystyrene polymer under specified condition. CONSTITUTION:When the objective reactive polymer having structural unit of formula II [R is (meth)acryloyl] is to be produced by reaction of an acid halide with a p-hydroxystyrene polymer having structural unit of formula I (X is Cl or Br; m is 0-4) in the presence of a hydrogen halide eliminator, said reaction is performed under such a condition as to retain the phenolate ion index of formula III below 0.5 when the molar amount of ionized phenolic OH, molar amount of nonionized phenolic OH and molar amount of the ester group produced are denoted as a, b and c, respectively, on the assumption that the molar amount equivalent to that present of said hydrogen halide eliminator, of the phenolic OH contained in the p-hydroxystyrene polymer is totally ionized.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a reactive polymer with a low acid value by esterifying a para-hydroxystyrene polymer, and more specifically, relates to a method for producing a reactive polymer having a low acid value by esterifying a parahydroxystyrene polymer, and more specifically, a method for producing a reactive polymer having a low acid value. The present invention relates to a method for producing a reactive polymer which has excellent electrical properties, heat resistance, and flame retardancy and is useful as a material for a substrate on which electronic components such as semiconductor elements and ICs are mounted.

(Prior Art) Conventionally, as a method for forming an ester bond in phenols, various methods have been known in which phenols are reacted with an acid halide in the presence of a dehydrohalogenating agent. All of these methods relate to methods for esterifying low molecular weight phenols. In this case, the obtained product is subjected to washing, recrystallization, distillation, etc.
It is relatively easy to purify this product by removing impurities such as unreacted raw materials and by-products.

However, when a high molecular weight phenol group-containing polymer is esterified by the method described above, it is virtually impossible to obtain a highly pure esterified polymer because the purification methods described above cannot be applied. there were.

(Problems to be Solved by the Invention) Therefore, in the obtained esterified polymer, a large amount of unreacted phenolic hydroxyl groups remain, increasing the acid value of the polymer. As a result, for example, when this polymer is molded, a problem arises in that the dielectric properties of the resulting molded product deteriorate.

An object of the present invention is to provide a method for producing a reactive polymer having a low acid value without causing the above-mentioned problems even though the raw material is a high molecular weight phenol group-containing polymer.

(Means for Solving the Problems) The method for producing a reactive polymer of the present invention includes removing halo... (1
) (or represents a chlorine atom or/and a bromine atom, m represents a number of 0, 1, 2, 3.4) with an acid halide. In the method for producing a reactive polymer having a structural unit represented by the formula (wherein X and m both have the same meanings as above and R represents an acryloyl group or/and a methacryloyl group), the para-hydroxy Assuming that the entire molar amount corresponding to the amount of the dehydrohalogenating agent present among the phenolic hydroxyl groups contained in the styrene polymer is ionized, and the molar amount of the ionized phenolic hydroxyl groups is a, When the molar amount of non-ionized phenolic hydroxyl groups is s and the molar amount of generated ester groups is C.

The following formula (11) is characterized by proceeding with the reaction under conditions in which the phenolate ion index defined by τ is maintained at 0.5 or less.

In the method of the present invention, the parahydroxystyrene polymer to be esterified is a polymer consisting of a plurality of structural units shown by formula (I) chained together, and the reactive polymer according to the present invention after esterification is Makes up the skeleton.

Although the molecular weight of this polymer is not particularly limited,
Considering that the obtained reactive polymer is dissolved in an appropriate solvent to form a film and impregnated into a base material such as glass fiber to form, for example, a printed wiring board, the molecular weight is the weight average molecular weight. t,ooo~100.0
It is preferable that it is about 00.

Examples of dehydrohalogenation agents used in the method of the present invention include ammonia; primary to tertiary amines such as pyridine, N,N-dimethylaniline, triethylamine, and triallylamine; lithium hydroxide, sodium hydroxide, Alkali metal water-resistant substances such as potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; each of these may be used alone or in combination of two or more appropriately selected. Can be used in combination.

Further, the acid halide used in the method of the present invention needs to be an acid halide having an acryloyl group or a methacryloyl group. Specifically, for example, acrylic acid chloride, acrylic quasi-bromide, methacrylic acid chloride,
Methacrylic acid bromide can be mentioned. Each of these may be used alone, or two or more types may be used in an appropriate combination.

Furthermore, acid halides that do not contain polymerizable functional groups, such as acetic acid chloride, acetic bromide, propionic acid chloride, propionic acid bromide, butyric acid chloride, butyric acid bromide, isobutyric acid chloride, and isoacetic acid bromide, can also be used in combination. If the amount of these latter acid halides to be used is appropriately selected, the crosslinking density of the resulting reactive polymer can be arbitrarily adjusted when a molded article is prepared from the resulting reactive polymer.

The amount of the dehydrohalogenating agent and the acid halide to be used is a molar ratio of 1 to the phenolic hydroxyl group contained in the raw material parahydroxystyrene polymer.
The amount is preferably 1.5 times as much. If the amount of each used is less than the above range, the acid value of the obtained polymer will be high, and conversely, if it exceeds the above range, no significant effect on reducing the acid value will be observed and it will be wasted. This is because it increases costs and is uneconomical. The dehydrohalogenating agent and the acid halide may be used in equivalent amounts, and the desired esterification reaction can proceed sufficiently in this state.

The esterification reaction is carried out in a solvent. As a solvent,
For example, hydrophobic solvents such as methylene chloride, dichloroethane, chloroform, benzene, and acetic acid ester; wood-philic solvents such as methanol, ethanol, acetone, methyl ethyl ketone, dimethylformamide, and tetrahydrofuran; These solvents can be used individually or as a mixed solvent of two or more. Furthermore, the reaction can also proceed in a system where water coexists.

The reaction is carried out in a temperature range of -10 to 60°C. If the temperature is less than 110°C, the reaction takes a long time and is not industrially viable; if the temperature is higher than 60°C, side reactions such as vinyl group cleavage may occur. undesirable,
Preferably, the temperature range is -10 to 30°C.

The greatest feature of the present invention is that the reaction proceeds while maintaining the phenolate ion index, which will be described later, at 0.5 or less during the entire process of the esterification reaction, particularly from the initial stage to the middle stage of the reaction.

The phenolate ion index in the present invention is the molar amount of the phenolic hydroxyl groups contained in the parahydroxystyrene polymer that is the raw material, which corresponds to the amount of the dehydrohalogenating agent that is supplied to the reaction system. Assuming that is completely ionized, and the molar amount of the ionized phenolic hydroxyl group is a, the molar amount of the non-ionized phenolic hydroxyl group is s, and the molar amount of the generated ester group is C, It is defined as an index calculated based on the following formula 'a+÷T'.

In the reaction system in which the esterification of the present invention proceeds, first, the phenolic hydroxyl groups of the parahydroxystyrene polymer in an equimolar amount with the dehydrohalogenating agent supplied in a predetermined amount dissociate to form a predetermined concentration of phenolate ions. is formed. When acid chloride and a further dehydrohalogenating agent are added here, in addition to the phenolate ions that were already dissociated, the remaining phenolic hydroxyl groups of the parahydroxystyrene polymer are added to the system. There will also be phenolate ions generated by dissociation under the action of the dehydrohalogenating agent added later, but these phenolate ions will cause an esterification reaction with the acid chloride added at the same time. The equimolar amount of the added strict chloride disappears. Therefore, the concentration of phenolate ions within the reaction system does not substantially increase and never exceed the initial concentration as the reaction progresses.

The number of moles of ionized phenolic hydroxyl groups and non-ionized phenolic hydroxyl groups in the system decreases,
Correspondingly, the number of moles of ester groups produced increases.

In the present invention, the reaction proceeds while maintaining the previously defined phenolate ion index at 0.5 or less in the above reaction system.

If the reaction is carried out in a state where this value is larger than 0.5, the resulting polymer will have a high acid value, which is disadvantageous. It is preferable to proceed with the reaction in a state where the index is less than 0.35.

As mentioned above, before the dehydrohalogenating agent and the acid halide are allowed to coexist in the reaction system, the C value (mole amount of the formed ester group) in the above formula is zero, so the index is essentially a. /(a+b), and considering that this index does not increase during the addition process of acid halide and dehydrohalogenating agent, that is, during the reaction process, the phenolate ion index in the reaction system can be expressed as In order to maintain the value below a certain value within the above range, specifically, a predetermined amount of dehydrohalogenating agent is added to the reaction system before the addition of the severe halide, and the added dehydrohalogenating agent is The phenolic hydroxyl group of the parahydroxystyrene polymer in an equimolar amount as the agent is converted to phenolate ion, and in this state, the acid halide and the remaining dehydrohalogenating agent are added so that the addition of both is completed at the same time to carry out the reaction. Just move on.

For example, let A be the amount of dehydrohalogenating agent that is equimolar to the parahydroxystyrene polymer charged in the reaction system, and let λ be the amount of dehydrohalogenating agent that is added to the reaction system in advance before adding the acid halide. If you want to proceed with the reaction under index B, add a dehydrohalogenating agent to the reaction system in advance in an amount that satisfies B=x and A.

Alternatively, the entire amount of acid halide may be added to the reaction system from the beginning, and a dehydrogenating agent may be added thereto in an amount equimolar to the phenolic hydroxyl group of the parahydroxystyrene polymer. In this case, the phenolate ion index will be maintained at substantially zero.

Note that the acid value in the present invention refers to 11 g of potassium hydroxide reacting with 1 g of a sample of the obtained polymer, and is a measure of the esterification reaction rate of the obtained polymer. The value is determined by dissolving 1 g of the sample in a mixed solution of 1,4-dioxane and methanol (mixing ratio 1:29 by volume), and adding the resulting solution to 1/10 normal potassium hydroxide aqueous solution. This is a value measured by titration method.

In addition, a suitable process for applying the method of the present invention is a process from the early stage to the middle stage of the reaction. This is the process by which a substance is esterified.

The polymer produced as described above is obtained by converting the structural unit represented by the formula CI) of the raw material parahydroxystyrene polymer into a structural unit having an ester group as represented by the formula (I). It is something.

(Examples of the Invention) The present invention will be described in more detail below based on Examples, but the gist of the present invention is not limited in any way by these Examples.

Example 1 As a raw material, a parahydroxystyrene polymer (referred to as raw material polymer A, manufactured by Marukubi Petrochemical Company, trade name Niresin M1, weight average molecular weight: 2200) was prepared, and 36 g of it was dissolved in 300 g of tetrahydrofuran.

To the obtained solution, 35.9 g of acrylic acid chloride was added in advance, and while the temperature was maintained at 0 to 15° C., 40 g of triethylamine was added dropwise thereto to proceed with the reaction. After the addition of triethylamine was completed, the reaction system was kept at a temperature of 20 to 30°C for 1 hour, and the reaction mixture was poured into 3 bottles of water to reprecipitate the polymer, and 1 g of 35% hydrochloric acid aqueous solution was added to cool the system. After making it resistant,! Table 1 shows the yield, weight average molecular weight, and acid value of the polymer obtained by filtration, water washing, and drying.

Note that the molar ratio of 35.9 g of acrylic acid chloride and 40 g of triethylamine used to the phenolic hydroxyl group contained in the raw material polymer A was 1.32.

In this reaction, phenolate ions are generated from the phenolic hydroxyl groups of raw material polymer A by triethylamine, and at the same time, the phenolate ions are consumed by acrylic acid chloride, which has been added in its entirety, and the esterification reaction proceeds. The phenolate ion index is maintained at substantially zero throughout the entire reaction period from the start of the dropwise addition of triethylamine to the end of the reaction (the end of the dropwise addition of 40 g of triethylamine).

Example 2 240 g of raw material polymer A was dissolved in 1200 g of methanol, and 320 g of bromine was added dropwise thereto while stirring while maintaining the temperature at 5 to 10° C. to bromine raw material polymer A. Next, stirring was continued for an additional hour while maintaining the above temperature, and the resulting reaction mixture solution was poured into 6 cups of water, and the precipitated precipitate was separated in a furnace, washed with water, and dried to obtain 387 g of a polymer. Ta. The obtained polymer had a weight average molecular weight of 2950. Bromine content: 40.2%, acid value: 282 mgKOH/
It was g. This is called raw material polymer B.

860g of this raw material polymer and 300g of tetrahydrofuran
The polymer of the present invention was obtained in the same manner as in Example 1. Yield of the obtained polymer 9 Weight average molecular weight, acid value,
The bromine content is shown in Table 1.

In this case, as in Example 1, the amounts of acrylic acid chloride and triethylamine used were both equivalent to 1.32 times the molar ratio of the phenolic hydroxyl groups contained in raw material polymer B, and The phenolate ion index is maintained at substantially zero.

Example 3 36 g of raw material polymer A was dissolved in 300 g of tetrahydrofuran. First, 5 g of triethylamine was added to the resulting solution in advance.

Then, 35.9 g of acrylic acid chloride and 35 g of triethylamine were simultaneously added dropwise thereto. At this time, the respective dropping speeds were adjusted so that both finished dropping at the same time.

After the dropping was completed, the same treatment as in Example 1 was carried out to obtain a polymer of the present invention. Its specifications are shown in Table 1.

In this reaction system, the equimolar amount of triethylamine to the phenolic hydroxyl group of raw material polymer A is 40/1.3
2 = 30.3[ Therefore, 5 g of triethylamine used in advance has a molar ratio of 5/ to the above phenolic hydroxyl group.
30.3=O, corresponds to 17. And raw material polymer A
When acrylic acid chloride and triethylamine are simultaneously added to a system in which 0.17 molar amount of the phenolic hydroxyl groups already exists as phenolate ions, additional phenolate ions are added due to the action of the additional triethylamine. However, this generated phenolate ion and the phenolate ion already present before addition are subsequently annihilated by an esterification reaction with acrylic acid chloride to generate an ester group, so the phenolate ion in the system does not increase substantially and the reaction eventually proceeds without the phenolate ion index exceeding 0.17.

Example 4 A polymer was produced in the same manner as in Example 3, except that 60 g of raw material polymer B was used in place of 36 g of raw material polymer A. In this case as well, the phenolate ion index is 0.17.
is maintained so that it does not exceed. The results are shown in Table 1.

Example 5 860 g of raw material polymer was dissolved in 300 g of tetrahydrofuran. Triethylamine lo was added to the resulting solution in advance.
g was added. Next, here is acrylic acid chloride 3
5.9 g of triethylamine and 30 g of triethylamine were simultaneously added dropwise in the same manner as in Example 3, and after the addition was completed, the same treatment as in Example 1 was carried out to obtain the polymer of the present invention. Shown in the table.

In this reaction, the phenolate ion index does not exceed the value 10730.3=0.33 based on calculations similar to Example 3.

Example 6 A polymer was produced in the same manner as in Example 5, except that the amount of triethylamine added in advance was 15 g, and then 35.9 g of acrylic acid chloride and 25 g of triethylamine were simultaneously added dropwise. .

The phenolate ion index in this reaction is 15/3
0.3=0.5 shall not be exceeded.

Comparative Example 1 ° A polymer was produced in the same manner as in Example 5, except that the amount of triethylamine added in advance was 25 g, and then 35.9 g of acrylic acid chloride and 15 g of triethylamine were simultaneously added dropwise. did.

The phenolate ion index in this reaction exceeds the limit value of 0.5 and has a maximum value of 25/30.3=0.83.

Comparative Example 2 36 g of raw material polymer A was dissolved in 300 g of tetrahydrofuran, and 40 g of triethylamine was added to the resulting solution. Then, only 35.9 g of acrylic acid chloride was added dropwise thereto to proceed with the reaction.

In this case, since the entire amount of phenolic hydroxyl groups in raw material polymer A becomes phenolate ions, the maximum value of the phenolate ion index exceeds the limit value and becomes 1.00.

Comparative Example 3 A polymer was produced in the same manner as Comparative Example 2, except that 60 g of raw material polymer B was used in place of 36 g of raw material polymer A. The maximum value of the phenolate ion index at this time also exceeds the limit value and is 1.00, as in the case of Comparative Example 2.

The above results are collectively shown in Table 1.

Example 7 Para-hydroxystyrene polymer (manufactured by Maruzen Petrochemical ■, trade name Niresin M, Q weight average molecular weight: 5800) 30
0g was dispersed in an aqueous solution consisting of 300g of methanol and 900g of water, and the temperature was maintained at 5 to 10°C to remove bromine 62.
The above polymer was brominated by adding 5 g dropwise. After the above temperature was maintained and stirring continued for 1 hour, the resulting reaction mixture was filtered, washed with water, and dried. The obtained polymer had a weight average molecular weight of 9200 and a bromine content of 51.0%.
, acid value: 230 mgKOH/g. This is referred to as raw material polymer C.

60g of raw material polymer C, 300g of methylene chloride and 12g of water
It was dissolved in a two-phase solvent consisting of 0 g.

Next, 3 g of 48% sodium hydroxide aqueous solution was added in advance, and 31.4 g of methacrylic acid chloride and 48% sodium hydroxide were added in advance.
% sodium hydroxide aqueous solution was added, adjusting the dropping rate so that both drops were completed at the same time, and the reaction proceeded.

After dropping, mature at 20-30"C for 1 hour, and then
The system was made acidic by adding 1 g of 5% aqueous hydrochloric acid solution, and the organic layer was separated.

Subsequently, the organic layer was washed with water, poured into 1800 g of methanol to reprecipitate the polymer, and then subjected to furnace separation, water washing, and drying treatment to obtain the polymer of the present invention.

Here, 31.4 g of methacrylic acid chloride and 25 g of 48% aqueous sodium hydroxide solution each have a molar ratio of 1.22 times the phenolic hydroxyl group of raw material polymer C. Therefore, the equivalent molar amount of the 48% aqueous sodium hydroxide solution to the phenolic hydroxyl group of raw material polymer C is 25.0/1.22=20.5 g. Therefore, the phenolate ion index in this reaction is 3/
The maximum value is 20.5=0.15. The specifications of the obtained polymer are shown in Table 2.

Example 8 Same as Example 7, except that 6 g of the 48% aqueous sodium hydroxide solution was added in advance, and that 31.4 g of methacrylic strict chloride and 19 g of a 48% aqueous titrium acetate solution were then simultaneously added dropwise. A polymer was produced in the same manner. The results are shown in Table 2.

The phenolate ion index in this case is 6/20.5=
It never exceeds 0.29.

Example 9 Same as Example 7 except that 9 g of 48% aqueous sodium hydroxide solution was added in advance, and then 31.4 g of methacrylic acid chloride and 16 g of 48% aqueous sodium hydroxide solution were added dropwise simultaneously. A polymer was produced. The results are shown in Table 2.

The phenolate ion index in this case is 9720.5=
It never exceeds 0.44.

Comparative Example 4 The amount of 48% sodium hydroxide aqueous solution added in advance was 15 g, and then 31.4 g of methacrylic acid chloride
A polymer was produced in the same manner as in Example 7, except that a log of 48% sodium hydroxide aqueous solution was simultaneously added dropwise. The results are shown in Table 2.

The phenolate ion index in this case is 15/20.5
It never exceeds -0.73.

Comparative Example 5 A total of 12% of 48% sodium hydroxide aqueous solution was added to the reaction system in advance.
After adding 5g, methacrylic acid chloride 31.4
g was added dropwise to advance the reaction. In this case, the fyonolate ion index exceeds the limit value and reaches a maximum value of 1.00.

The above results are collectively shown in Table 2.

Example 10 The acid halide used was not only methacrylic acid chloride, but also 15.7 g of methacrylic acid chloride.

The reaction proceeded in the same manner as in Example 7, except that 14.1 g of propionic acid chloride was used. In this case, the sum of the two corresponds to 1.22 times the molar ratio of the phenolic hydroxyl groups of the raw material polymer C.

In addition, the order of dropping the halides was as follows: first, propionic acid chloride was added dropwise, and then methacrylic acid chloride was added dropwise. The specifications of the obtained polymer are shown in Table 3.

Example 11 Except that the amount of 48% sodium hydroxide aqueous solution added in advance was 9 g, and then 14.1 g of propionic acid chloride, 15.7 g of methacrylic acid chloride, and 16 g of 48% sodium hydroxide aqueous solution were added dropwise simultaneously. teeth,
A polymer was produced in the same manner as in Example 10. 3rd result
Shown in the table.

Comparative Example 6 15 g of 48% sodium hydroxide aqueous solution was added in advance, and then 14.1 g of propionic acid chloride was added.
A polymer was produced in the same manner as in Example Process 0, except that 15.7 g of methacrylic acid chloride and 10 g of a 48% aqueous sodium hydroxide solution were simultaneously added dropwise. The results are shown in Table 3.

Comparative Example 7 The total amount of 48% sodium hydroxide aqueous solution 2 was added to the reaction system in advance.
After adding 5 g of propionic acid chloride 14.1
g and 15.7 g of methacrylic acid chloride were simultaneously added dropwise to advance the reaction. The specifications of the obtained polymer are shown in Table 3.

(Effects of the Invention) As is clear from the above explanation, the acid value of the polymer produced by the method of the present invention is significantly lower than that of conventional polymers. is useful as a substrate for mounting semiconductor devices, ICs, etc., because it has very excellent electrical conduction properties and good heat resistance and flame retardancy.

Claims (1)

[Claims] In the presence of a dehydrohalogenating agent, the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X represents a chlorine atom or/and a bromine atom, and m is 0, 1, 2 , 3, or 4) is reacted with an acid halide to form the following formula:
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, X and m both have the same meanings as above, and R represents an acryloyl group and/or a methacryloyl group). In the method for producing a polyhydroxystyrene polymer, it is assumed that the molar amount corresponding to the amount of the dehydrohalogenating agent among the phenolic hydroxyl groups contained in the parahydroxystyrene polymer is fully ionized, and , where a is the molar amount of ionized phenolic hydroxyl groups, b is the molar amount of non-ionized phenolic hydroxyl groups, and c is the molar amount of the generated ester groups, it is defined by the following formula: a/(a+b+c) A method for producing a reactive polymer, characterized in that the reaction is carried out under conditions in which the phenolide ion index is maintained at 0.5 or less.