JPH0195118A - Preparation of novolak-type phenol resin - Google Patents

Abstract

PURPOSE:To obtain a novolak-type phenol resin having a monodisperse molecular structure and excellent flow characteristics, heat resistance, etc., and being suitable for molded items, laminated products, etc., by preparing a resol resin at first and a novolak resin thereafter. CONSTITUTION:A resol resin is prepared from a phenol (e.g., phenol) and an aldehyde (e.g., formalin) with a molar ratio (formaldehyde/phenol) of 0.5-3 in the presence of a basic catalyst (e.g., sodium hydroxide). Then, a phenol is added thereto to change the molar ratio to 0.3-0.9 and furthermore, an acidic catalyst (e.g., hydrochloric acid) is added thereto to prepare a novolak resin. A novolak-type phenol resin whose softening point is 50-120 deg.C and ratio of a peak height for a binuclear resin to that for a heptanuclear resin is 1.6-0.3 is obtd. thereby.

Description

Detailed Description of the Invention [Industrial Use Separation] The present invention relates to a method for producing novolak-type phenol stool fat that is one molecule imitation or monodisperse. Uses of well-known phenolic resins such as shaped products, laminated products, shell mold binders, resonoid grinding wheel binders, Shimarei wood binders, epoxy raw materials for sealing plates, and epoxy hardening agents. I am in charge of flight P+3.

〔Traditional'! jl technique]

General M, novolac-type phenolic fat is obtained by reacting phenols and aldehydes in the presence of acid a catalyst, but the amount of binuclear is determined by the molar ratio of molar ratio of molar ratio of molar ratio of aldehydes to phenols. (hereinafter referred to as molar ratio and road), it is determined to a certain extent, no matter how much the process progresses by 6 yen,
The molar ratio does not decrease below a certain level.
In addition, the molecular area increases and the conversion point becomes high, resulting in disadvantages such as poor redundancy of the compound.

- If the molar ratio is lowered, the polymer region will be reduced, the softening point will be lower, and the compound will have better stability, but 2
There is a drawback that the amount of nuclei is large, for example, the heat resistance of the molded product is reduced.

As described above, in the reaction method of publicly available novolac rete 1, both the oligomeric and polymeric regions are small. It is impossible to obtain a novolak-type phenol resin with a monodisperse molecular structure.
Publicly available publications include Special Publication No. 60-33124, Special Publication No. 60-33125, and Special Publication No. M60-33126, but all of these are limited to P-alkylphenol, and the process is complicated and industrially difficult. Not.

In addition, as a method for reducing the total number of 2-carrying bodies, using a side force synthesized by a normal novolac reaction treatment, for example, using a specific bathing product such as a mixture of methanol and cum,
Although there is a method of washing and sorting, the process is complicated, the yield is poor, and the cost increases, so it is not practical.

[Teruma set point to decide whether it is an invention]

From the above background, there has been a desire to develop a monodisperse novolac type phenol side d(1) that has good fluidity and exhibits heat resistance. Novolac-type phenol ff has a monodisperse molecular structure, has a small amount of μ, polymers gA and Q, and has a small amount of dinuclear substances, and has a narrow molecular weight distribution.
1 (IJH) As a result of death, those who have not released the drug are unable to create folds and reduce both the polymer region and the 2gc body and suffer from the circular mobility s+VH'tL company. A method for producing monodispersed novolak-type enol fat has been invented.

[One-shot means to solve the problem] The present invention relates to a method for using 3A of novolak-type phenol fat, which cannot be produced in a conventional manner and has a monodisperse molecular structure. ) As a result, we have invented a method for producing novolak-type phenol (1), which is monodisperse in its one-molecule structure, by first carrying out a resolization reaction and then carrying out a novolac-formation reaction.

The present invention first deals with phenols and aldehydes ■? In the method of synthesizing novolac-type phenol a (fat), the softening point of novolak-type phenol fat is 50 to 50.
120°C, and GPC (Gell Perme
ation chromatography Myo'!
Manufactured by Ikai Kogyo Co., Ltd., hereinafter referred to as GPC and Setsucho], it was found that the ratio of the peak height of the heptadonucleate to the peak height of the heptadonuclide was 1.6 to 0.3. A method for producing 7b phenol with a monodisperse molecular structure.

The phenols according to the present invention include phenol or alkylphenols such as cresol, xylenol, resorcinol, catechol, paratertiary butylphenol, offnalphenol, and phenylphenol, and also bisphenol A and bisphenol F. , bisphenol S, and mixtures thereof. Examples of aldehydes include formalin, paraformaldehyde, glyoxal, trioxane, zerioxane, and mixtures thereof.

Examples of maple-based layer media include oxides and hydroxides of alkaline metals such as sodium and potassium, alkaline earth metals such as magnesium, calcium, and barium, and triethylamine and triethanolamine. Can be used with amino acids.

Examples of acidic media include hydrochloric acid, inorganic acids such as chlorine, and
It is either a self-restraint defeat like Shuu defeat or Ajipin defeat, or it is a convenient pue Noh.

The molar ratio (formaldehydes, /phenols) of the resolized core in the present invention is 0.5 to 3.0, and is preferably 0 to 2.0. ．．
If it is less than 5, there will be more binuclear molecules and the molar ratio will be 3.
If it exceeds 0, the molecular area increases.

Further, the molar ratio tJ of the novolac formation reaction is 3 to 0.9, more preferably 0.55 to 0.75.

If the molar ratio is 0.3, the number of dinuclear molecules will be too large, and if it exceeds 0.9, the number of sieve molecules will increase.

The novolac-type phenol side according to the present invention is firstly composed of the above-mentioned phenols and aldehydes. After the resolization reaction is carried out in the presence of a basic catalyst within the molar ratio range of the resolization reaction, phenol M'Y is added to bring the molar ratio within the novolakization reaction range, and an acidic catalyst is added to carry out the novolakization reaction. Among those that are synthesized with a softening point, those with a softening point of 50~
120°C and 1.9 IC, preferably 80-105°C
It is. If the softening point is below 50°C, the product will be difficult to blow with a blower and workability will be poor; if it exceeds 120'C,
The viscosity increases, making it difficult to adapt to the manufacturing process.

In the GPC copper measurement of the novolac type phenolic resin in the present invention, the ratio of the peak height of the dinuclear substance to the peak S and height of the small heptadonucleate is 1.6 to 0.3. If it exceeds 1.6, there are disadvantages such as too many binuclear caps, lowering the softening point, and lowering the heat resistance of the molded product. In the case of a 0.3 end vortex, the polymer crack area increases and there is a risk of softening, and the molded product's maneuverability deteriorates, reducing the cutting efficiency.

GPC's pivot conditions I3, A5, I; East γ-jifji M; 1! Kogyo Co., Ltd. 4-1-HLC-802OR Column arrangement 2 G3000HLX + G2000HLX (/
lct: 0.8tny" min open 4'H
't=K: 40 e-K GK: 150-20
omy/'rit Fl 0at detection method: RI (differential intensification?r revision) [Effects of the invention] According to the present invention, a monodisperse novolac-type phenolic resin with excellent heat resistance and non-injection can be stably produced. It can be supplied to a wide variety of fields.

[Example of contamination]

The following is a detailed explanation of the present invention by way of examples, but the present invention is not limited to the examples.

Are all the "%" listed here in C2 "production amount"? Example 1゜Phenol 4709 (5 mol), 50% formalin 45
0 r (7,5 mol), sodium hydroxide 10f! Reactor C equipped with a thermometer, return hole condenser, stirring basket, and dehydrator. Then add phenol 611F (6.5 mol) and 10% salt 912, and react at 95-100°C for 3 hours to form a novolac.
80unr + Hg, heat up until the inner barrel reaches 2000℃ and hold at that temperature for 2 hours to dehydrate and remove monomer 7
Do.

◎The softening point of this resin is 95℃, and it is 2.
The peak height of the nuclear body is /゛7 The peak height of the nuclear body σ is 1.3
TC at 9.

GPC measurement of this resin is shown in Figure 1.

Lol Example 2゜Phenol 470F (50% formalin 21 in 5 mol)
0r (3.5 moles), Shu punch 30? Using the same apparatus as in Example 1, a novolak reaction was carried out under stirring at 95 to 100°C, followed by dehydration and removal of monomers to obtain a resin. This fatty axial property has a softening point of 95℃ and GPC
The height ratio of the peak height of the 2-kuma body to the peak height of the 77-nuclear body in the measurement was 1.74.

This resin is shown in GPC creation measurement-2.

4. 1'g5 reading of the drawing Figure 1 shows the GPC results of Iff according to the present invention.

Figure 2 shows the GPC results for resins other than those of the present invention.

Applicant of the waiting list: Kiyoikaji Koto Co., Ltd. Drawing's Jomon 1st W! Niseri - Output Ushito Figure 2 8 Output Ushito Procedural Amendment (Spontaneous) November 6, 1988 1, Indication of the case Patent application 1982-UJ, 273!26 Title of the invention Novolac type phenolic resin Address: 622 Oheki-cho, Takasaki City, Gunma Prefecture Representative Yes 1) Denzo 4, “Detailed Description of the Invention” column of the agent’s specification and

[Brief explanation of the drawing]

&Contents of correction (1) Page 9, line 13, r of the specification, ``Figure-1'' is corrected to ``Figure-2''. (2) On page 10, line 3 of the specification, ``Figure 2J is corrected to ``Figure 1''. (3) On page 10 of the letter of specification, line 5, "Figure-1" is corrected to "Figure-2." (4) "Figure-2" on page 10, line 6 of the specification should be corrected to "Figure-1." Patent Office non-official, small...1, FP admission - 1, Display of the case - 1932, 1936, 1st application No. 2, Part 3j, No. 2, Iku”A
qAa% Nozrakkumanfe J-R Shisha 786”f
IA method 3, relationship with the case of the person making the amendment.

Claims (1)

[Claims] Phenols and aldehydes are subjected to a resolization reaction using a basic catalyst at a molar ratio (formaldehyde/phenol) of 0.5 to 3.0, and then phenols are added to make the molar ratio of 0.3 to 0.9. In the method of synthesizing a novolak type phenolic resin by further adding an acidic catalyst to make it a novolak, the softening point of the novolak type phenol resin is 50 to 120°C, and in GPC measurement, the softening point of the novolak type phenol resin is 50 to 120 ° C. The peak height ratio of 1.6 to 0
．． 3. A method for producing a novolac-type phenolic resin.