JPS60208356A - Production of phenolic resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin of high heat resistance, by incorporating phenolic resin (followed by reaction, if necessary) with aminomethyl phosphonic ester condensate prepared from monoalkanolamine, formaldehyde (derivative) and trialkylphosphite. CONSTITUTION:The objective resin can be obtained by incorporating ( I ) 5- 40wt% of aminomethyl phosphonic ester condensate prepared by virtually equimolar reaction at 40-100 deg.C between (A) monoalkanolamine of formula I (R1 is 2-4C alkylene group) (e.g. monoethanolamine, monoisopropanolamine), (B) formaldehyde or its derivative (e.g. paraformaldehyde) and (C) trialkylphosphite of formula II (R<2>, R<3> and R<4> are each 1-4C alkyl) (e.g. trimethyl phosphite) to eliminate equimolar or more amount of alcohol (II) either with the manufacturing of the final phenolic resin to perform reaction or (III) in a phenolic resin varnish.

Description

[Detailed description of the invention] The present invention is an improved method for producing phenolic resin 1- It is related to.

In detail, it relates to a method for improving the physical properties of phenolic resin by 5% and flame resistance.

The flame resistance of phenolic resins that has been achieved so far has been through the addition of halogens or phosphorus compounds such as tetrabromo bisphenol, IJ cresyl phosphate, triphenyl phosphate, and ammonium phosphate; To obtain, its added violet increases,
Deteriorations in various physical properties and processability, such as a decrease in mechanical strength, electrical properties, interlayer adhesion, and punching processability, were unavoidable.

As a method to improve these, a method of adding and reacting diethyl-NIN-bis(2-hydroxyethyl) abatzmethylphosphonate (% Opening and Closing No. 56-49722)
However, because this compound has a low molecular weight and has low reactivity with phenols and aldehydes, no fundamental solution has been reached.

The present invention solves the above-mentioned problems at once by using a phosphorus compound that reacts with phenols and aldehydes, specifically, an amizmethylphosphonic acid ester condensate containing an -NH group. This is what I did.

The requirements for the structure of the present invention are that when obtaining a phenolic resin containing phenols and aldehydes as main components, the following formula (I
), formaldehyde or a derivative thereof, and a trialkyl phosphite represented by the following formula (obtained by substantially equimolar reaction, and eliminating equimolar or more alcohol) 1ro,
The purpose is to obtain a flame-resistant phenolic resin with excellent physical properties and processability by adding or reacting a condensate of agutsumethylphosphonic acid ester.

It was thought that it was impossible to economically obtain the condensate of methylphosphonic acid ester containing monoNH& used in the present invention in a yield as high as It has been found that it can be manufactured extremely easily.

Regarding the method for obtaining aminomethylphosphonic acid esters from alkanolamines, aldehydes, and alkyl phosphites, Japanese Patent Publications No. 59-19576 and Japanese Patent Publication No. 44-68
There are answers to each publication in No. 05, but they all use dialkanolamine (2vj amine) as the alkanolamine, and no specific example is given for monoalkanolamine (primary aba/). . Moreover, in these methods, only low-molecular abatumethylphosphonic acid esters can be obtained.

Examples of the 7-noalkanolamine used in the present invention include monoethanolamine, monopropanolamine, and monoalkanolamine.

Paraformaldehyde is an example of a derivative of formaldehyde. Examples of the trialkyl phosphite include trimethyl phosphite, triethyl phosphite, tributyl phosphite, dimethylethyl phosphite, and the like.

Although the molar ratio of these components used is substantially the same molar ratio, no practical problem will occur if the molar ratio is in the range of 0.9 to 1.1 molar to 1 molar of other raw materials.

1 mole of eliminated alcohol (F per mole of phosphite)
) is produced during the production of amine methylphosphonate, but
The alcohol that is further eliminated is generated by the condensation reaction, and varies depending on the type of phosphite, reaction temperature, etc. 9.0.2 to 0.8 moles (per mole of phosphite)
)) Full length is preferred. The reaction temperature is preferably 40°C to 100°C in order to convert the eliminated alcohol into a violet.

The condensate of aminomethylphosphonic acid ester of the present invention may be added and reacted during the production of phenolic resin (or may be used by being added to phenolic resin varnish).

The amount of the condensate of isomethylphosphonic acid ester used in the present invention is preferably 5 to 40%.

Moreover, other flame retardants can also be used together.

Production examples and reference examples for production of abatumethylphosphonic acid derivatives, preliminary examples for production of phenol resins, and comparative examples are shown below. Note that parts in the examples are based on weight.

[Production Example-1] Monoethanolamine 61i11 was placed in a stainless steel reaction tank, and 31.6 parts of 95% rose formaldehyde was added and reacted while maintaining the temperature at 9.55 to 65°C. The time required was 1 hour.

Next, 166 parts of triethyl phosphite was added to 5 parts at the same temperature.
The mixture was added dropwise for about an hour, and stirred for another hour at the same temperature.

The distillate was collected under reduced pressure at 60 to 70°C. The product obtained is an orange viscous liquid with a yield of 19
There were 5 parts. The fraction was 65 parts, and gas chromatography analysis showed that it was 97% ethanol and 3% water.

The amount of ethanol distilled was 1.4 mol/mol of phosphite. The product analysis values are shown in Table-1. Also, the IR spectrum of the product is shown in Figure 1.

The GPO chart is shown in Figure 2.

Analysis results and IR of the products shown in Figures 1 and 2,
Reference example below with GPO chart - 1"llI?, diethyl-N, compared with that of N-bis(2-hydroxyethyl) abatzmethylphosphonate.
It can be seen that it is a condensate of -(2-hydroxyethyl)aminomethylphosphonate.

[Production Examples-2 to 4] Production Examples-2 to 4 were produced in the same manner as Production Example-1. Table 1 shows the names of the raw materials used, their preparation, manufacturing data, product analysis values, etc.

[Reference Examples-1 to 5] Reference Examples-1 to 5 were produced in the same manner as Production Example-1. Manufacturing data, product analysis values, etc. are shown in Table-1. In addition, the IR spectra of the products obtained in Reference Examples 1 to 5 are shown in Fig. 5, Fig. 5, and Fig. 6.
The GPO charts of the products obtained are shown in Figures 4 and 7, respectively.

These production data and analytical values show that the object of the present invention cannot be obtained by known methods.

(Note) *I MKA ; Monoethanol aban MPA ; Monoinbanol aban MBA : Monoimptanol ahan DICA ; Diethanol ain *2 TIP ; ) Diethyl phosphite TMP;
) Limethyl phosphite 7ap; Tributyl viable phosphite pgp; Production of diethyl phosphite phenol laminate [Example-■] Phenol 150 parts, 57% formalin 150 parts, 26
7 parts of % ammonia were reacted for 1 hour at reflux temperature, then 57% formalin 50i1S and 40 parts of the condensate of azumethylphosphonate obtained in Production Example 1 were added, and the mixture was reacted at the same temperature for 30 minutes.

After dehydration under reduced pressure, methanol dilution and resin content of 5
Got 0% fest.

Trap this face so that the resin content is 50%, and the thickness is 0.2
5 m of kraft paper was impregnated and dried.

Seven sheets of prepreg obtained and one sheet of steel foil were laminated and heated at 160°C.
Pressure was applied at 100 kl/@2 for 1 hour to obtain a copper-clad laminate with a thickness of 4.6 g.

[Example - ■ ~ rv] (Comparative Example I) A predetermined amount of the condensate of the azutsu methylphosphonic acid ester obtained in Production Examples 2 to 4 of the phenolic resin face with a solid content of 50% and a commercially available additive type flame retardant were added. , diluted with methanol solids content 50
%.

Using this varnish, 5iIl! A steel clad laminate was obtained in the same manner as in Example-■.

The compounding amount of the common flame release agent and the test results of the obtained product 1 plate are shown below.
2. The blending amount of the flame retardant is expressed as a proportion to 100 parts of resin solid content.

[Brief explanation of drawings]

Figures 1.5.5 and 6 show Production Example 1, Reference Example 1, and
IR spectra of the products obtained in 2 and 5, section 2.4
Figures 7 and 7 are GPC charts of the products obtained in Production Example 1, Reference Examples 1 and 5, respectively. Applicant's agent Kaoru Furuya

Claims (1)

[Claims] A monoalkanol aban represented by the following formula (I). A condensate of aminomethylphosphonic acid ester obtained by reacting formaldehyde or a derivative thereof with a trialkyl phosphite of the following formula (t in ml) in substantially equimolar amounts and eliminating more than the equimolar amount of alcohol is phenol. A method for producing a flame-resistant phenolic resin that is specifically added to or reacted with the resin) N -R'-OH (II