JPH0641262A - Novolac resin and its preparation - Google Patents

Abstract

PURPOSE: To obtain an epoxy novolac resin having a low glass transition temperature and a low fusion viscosity by reacting a substance containing aromatic hydroxyl groups with an aldehyde, and extracting the obtained products with water.

CONSTITUTION: Substance including at least one aromatic hydroxyl group in each molecule represented by formula I (R is H, a halogen, hydroxyl, or a 1-9C hydrocarbon group) is reacted with a 1-14C aliphatic, alicyclic, or aromatic aldehyde at a molar ratio of 1:(0.35-0.95) in the presence of a catalyst at 90-150°C for 0.5-6 hours to obtain products. From the products, excessive amount of the aromatic hydroxyl-containing substance is eliminated, and they are extracted with water to eliminate two functional components to a content of 25 wt.% or less, thereby the objective novolac resin of formula II (A is a 1-14C bivalent hydrocarbon group; (n) is 1-10 by an average value) with quantities of two functional components reduced is obtained.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novolak resin composition which can be used for preparing an epoxy novolac resin composition having a reduced amount of bifunctional components, and a method for preparing the same.

[0002]

DISCLOSURE OF THE INVENTION High-functionality (average functionality of 5-8) epoxy novolac resin compositions have high Tg values when cured with sulfanilamide. However, it is extremely difficult to prepare them due to the high viscosity of the novolac resin composition precursor. The present invention provides high Tg values when cured with typical epoxy curing agents such as methylene dianiline, diaminodiphenyl sulfone, sulfanilamide, and the like.
On the other hand, it is an object of the present invention to provide a novolak resin composition that can be used for preparing an epoxy novolac resin composition having a relatively low melt viscosity.

One aspect of the present invention relates to a method of preparing a novolak resin composition represented by the formula below and having a reduced amount of bifunctional components.

[Chemical 5] (In the above formula, each A is independently 1 to 14, preferably 1 to
A divalent hydrocarbon group having 8 carbon atoms, each R
Is independently hydrogen, a halogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 9, preferably 1 to 4 carbon atoms, and n has an average value of 1 to 10).

This method comprises the steps of (I) in the presence of a suitable catalyst, (A) a substance having at least one aromatic hydroxyl group per molecule,
The molar ratio of (B) aldehyde and (B) :( A) was adjusted to 0.
3: 1 to 0.95: 1, preferably 0.45: 1
To II to 0.75: 1, (II) removing excess aromatic hydroxyl-containing material, and (III) the resulting product is more than what was present after step (II). Subjecting the product from step (II) to water extraction until it contains less than 25 weight percent, and preferably less than 50 weight percent, bifunctional component.

Another aspect of the present invention relates to the novolac resin composition produced by the above method. The resin composition contains both a bifunctional component and a trifunctional component, and
When R is hydrogen, they have a weight ratio of difunctional to trifunctional components of less than 1.1: 1, preferably 0.7.
Less than 5: 1, more preferably less than 0.5: 1. The novolak resin composition produced by the above method contains both a bifunctional component and a trifunctional component, and each R
Are independently a halogen atom, a hydroxyl group, or 1 to 9
When the hydrocarbon group has carbon atoms of
The weight ratio of the bifunctional component to the trifunctional component is less than 0.5:
Exists in 1. When the average aromatic hydroxyl functionality of the novolac resin composition is from 3 to about 5, it contains less than 12.5 weight percent, preferably less than 7 weight percent difunctional components. The average aromatic hydroxyl functionality of the novolac resin composition is about 5 to 1
If it is up to 2, it contains less than 9 weight percent, preferably less than 5 weight percent difunctional component.

The epoxy novolac resin composition that can be prepared from the novolac resin composition of the present invention has the formula:

[0007]

[Chemical 6]

(In the above formula, each A independently represents a divalent hydrocarbon group having 1 to 14, preferably 1 to 8 carbon atoms, and each R independently represents hydrogen, a halogen atom, A hydroxyl group or a hydrocarbon group having 1 to 9, preferably 1 to 4 carbon atoms, each R'is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and n is 1 to
The average ratio of 10) and the following conditions: (a) when bifunctional and trifunctional components are present and R is hydrogen, the weight ratio of the bifunctional component to the trifunctional component. Is less than 1.1: 1, preferably less than 0.75: 1, most preferably less than 0.5: 1, and (b) bifunctional and trifunctional components are present, and each R is independently When it is a halogen atom, a hydroxyl group or a hydrocarbon group having 1 to 9, preferably 1 to 4 carbon atoms, the weight ratio of the bifunctional component to the trifunctional component is less than 0.5: 1,
(C) When the average epoxide functionality is from 3 to about 5, the resin composition contains less than 12.5 weight percent, preferably less than 7 weight percent difunctional component,
(D) Average epoxide functionality, provided that when the average epoxide functionality is from about 5 to 12, the resin composition contains less than 9 weight percent, preferably less than 5 weight percent difunctional components. It is an epoxy novolac resin composition having a property of 3 to 12.

The term "bifunctional ingredient" as used herein refers to
It represents the part of the novolac resin composition or the epoxy novolac resin composition in which the value of n is zero.

As used herein, the term "trifunctional component" refers to
It represents the part where the value of n is 1 in the novolac resin composition or the epoxy novolac resin composition.

The term "average functionality" as used herein refers to the average number of aromatic hydroxyl groups or epoxides per molecule.

Suitable monohydric aromatic materials which can be used herein include, for example, those represented by the formula:

[0013]

[Chemical 7] (In the above formula, each R is as defined above)

Particularly suitable substances include, for example, phenol, methylphenol, ethylphenol, propylphenol, butylphenol, nonylphenol, bromophenol, chlorophenol, resorcinol, hydroquinone, catechol, or mixtures thereof.

Suitable aldehydes which may be used herein include any aliphatic, cycloaliphatic or aromatic aldehyde having 1 to 14, preferably 1 to 8 carbon atoms. Particularly suitable such aldehydes include, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde,
Or mixtures thereof.

Suitable acid catalysts that can be used herein include, for example, oxalic acid, p-toluenesulfonic acid, benzenesulfonic acid, hydrochloric acid, sulfuric acid, or mixtures thereof.

The reaction between the aldehyde and the monovalent aromatic substance is, for example, from 90 ° C to 150 ° C, preferably 100 ° C.
Any suitable temperature can be used, such as from 0 ° C to 120 ° C. The reaction is generally carried out for 0.5 to 6 hours (1800 to 21600) until the reaction is substantially complete.
Seconds), preferably 1-2 hours (3600-7200 seconds)
I can continue.

The water extraction step of the present invention may be a multi-stage batch extraction, or a continuous co-current or counter-current extraction.

The water extraction is generally carried out at temperatures from 60 ° C. to 180 ° C., preferably from 90 ° C. to 150 ° C., and the number of extraction stages or contact time gives the desired result, ie the water extraction. The number of stages or times sufficient to produce a product containing less than 25 weight percent, and preferably less than 50 weight percent of the difunctional component, than was originally present in the novolac resin composition prior to execution.

Other suitable methods for removing some of the bifunctional component are also used, such as vacuum distillation.

If desired, the efficiency of water extraction can be increased by using a small amount of one or more organic solvents with water. Suitable such organic solvents include, for example, ketones, alcohols, and glycol ethers. Particularly suitable organic solvents include
For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, amyl alcohol, monomethyl ether of dipropylene glycol, or a mixture thereof is included.

Moreover, if desired, the bifunctional novolac resin composition is extracted with a suitable organic solvent, such as those mentioned above, which is not compatible with water, together with the particularly suitable methyl isobutyl ketone. By doing so, it can be removed from the aqueous extract.

Less than 25 weight percent, preferably less than 50 weight percent, than was originally present in the original novolac resin composition prior to conducting the water extraction 2.
From a novolak resin composition having a functional product, this novolak resin composition is reacted with epihalohydrin,
Next, an epoxy novolac resin composition having a reduced amount of bifunctional components can be prepared by performing dehydrohalogenation with a substance having a basic action such as sodium hydroxide.

The epoxy resin can be cured with the novolac resin composition prepared by the method of the present invention. Suitable epoxy resins include, by way of example, glycidyl type epoxy resins of polyhydric phenols, bisphenols, novolac resins, aliphatic polyols, and nitrogen containing compounds. These and other suitable epoxy resins are commercially available from McGraw-H, 1967.
Lee and Neville published by ill
e) "Epoxy Resin Handbook (Handbo
ok of Epoxy Resins), and in detail in Chapters 2 and 3.

When curing an epoxy resin with the novolac resin composition of the present invention, the usual amounts to be used are:
Hydroxyl: epoxy ratio of 0.8: 1 to 1.1: 1
, Preferably 0.9: 1 to 1: 1. In some cases, suitable amounts to cure may deviate from these listed amounts.

The epoxy novolac resin composition prepared from the novolac resin composition of the present invention is, for example, a composite material, moldings or casti.
ngs), coatings, adhesives, and laminates.

The following examples are examples of the present invention.
It should not be construed as limiting the scope in any way.

Test Methods The following test methods were used in the examples below. molecule
Quantities were determined using a standard gel permeation chromatography (GPC) method using polystyrene standards for molecular weight determination.

The glass transition temperature (Tg) was measured using a DuPont 1090 analyzer with a Model 912 Differential Scanning Calorimeter (DSC) for Tg up to about 250 ° C.

For Tg above 250 ° C., DuPont Model 943 thermomechanical analyzer (therma).
l mechanical analyzer (TM)
A) was used.

The softening point is measured by the METTLER model FP-53 softening point app.
(MSP).

Fracture toughness measurement (G _1C ) G _1C (fracture toughness or "critical strain energy release rate (c
critical strain energy rel
The method of measuring "ease rate" is
It is a modification of E-399 from its original use for metals for plastic materials. Compressive tensile test (co
The use of the “mpact tension test” is now widespread, and the material science journal (J. Mater. Sc.
i. ) 16: 2657 (1981). Individual specimens are typically 1/8 "(3.17" thick).
5mm) flat cast pieces cut into squares approximately 1 "(25.4mm). About 1/4" in the center of one edge
Cut a dovetail notch with a depth of (6.35 mm). Next, a razor blade is inserted into this notch and lightly tapped to cause preliminary cracking. Then, place two holes in the Instron tester at the predetermined positions to pin the test piece to the AS
Drawn near its dovetail as shown in TM E-399. Next, the force required to widen the gap between the preliminary cracks is 0.02 inch / min (0.0085 mm / s).
Extend and measure the sample using the test speed of. Fit this force, along with the required sample size and actual precrack length, to the equation given in ASTM E-399,
"Stress intensifier
ation factor) "K _Q is calculated. next,
This is the tensile modulus for the sample (300,000 psi (2.
A value of 07 GPa) was used) and Poisson's ratio in combination with G _1C to determine the value. This value is generally erg / cm ² ×
Reported at 10 ⁶ . A measure comparing representative values of G _1C for various plastics and metals is the Plenum Press (New York, NY, 1983) (Ple.
Num Press) edited by K. L. Mitt
al) “Physicochemical aspects of polymer surface” Lee (L
ee), L.E. H. In the reference.

Example 1 A. Preparation of phenol-formaldehyde type novolak resin composition 2.89 parts of phenol,
1.0 part of 37% formalin, and 0.00
It was prepared by reacting 18 parts of oxalic acid to prepare a resin composition having a Mettler softening point of 74.1 ° C. and a melt viscosity of 100 cP at 150 ° C. Gel Permeation Chromatography (GP
Analysis by C) reveals that the product has a weight average molecular weight of 81.
3, number average molecular weight 583, polydispersity 1.40
Was shown. The product contains 21.26 weight percent difunctional component and is
It contained 17.10 weight percent of trifunctional components because the ratio to functional components was 1.24: 1.

B. Removal of Bifunctional Product The above prepared phenol-formaldehyde type novolak resin composition was repeatedly extracted with hot water until the content of the bifunctional component was less than about 1 weight percent.

C. Preparation of Epoxy Novolac Resin Composition 206 g of the product from Example 1-B, 925 g epichlorohydrin, 484.7 g isopropanol and 7 parts water.
It was dissolved in 8.6 g. The mixture was then heated to 70 ° C. and 360 g of 20 percent aqueous sodium hydroxide was added over approximately 45 minutes (2700 seconds). The reaction mixture was aged at this temperature for an additional 15 minutes (900 seconds). The aqueous phase was then separated and discarded. To the mixture at 70 ° C., 160 g of 20% aqueous sodium hydroxide solution is added for about 20 to 30 minutes (1200
~ 1800 seconds). The reaction solution is 15-20
It was aged for 900 minutes (900 to 1200 seconds) and then cooled. The aqueous layer was separated and the organic layer was washed repeatedly with water until free of sodium chloride and sodium hydroxide. During this wash step, an additional 462 g of epichlorohydrin was added to facilitate the separation. The product was obtained by removing excess epichlorohydrin and solvent by vacuum distillation. The semi-solid epoxy resin product has an epoxy content of 2
3.3 percent, epoxy equivalent 184.5, and hydrolyzable chloride.
The ide) content was 51 ppm.

D. Curing the Epoxy Novolac Resin Composition 35.0 g of the epoxy resin composition from Example 1-C was added to about 15
Heat to 0 ° C. and add 6.93 g of sulfanilamide. Stir this mixture until homogeneous, then 1/8 x 5 x 4 inches (0.3175 x 12.7 x 1
Pour into an aluminum mold of 0.16 cm) and then 1
Cured at 50 ° C. for 16 hours (57600 seconds), followed by 200 ° C. for 2 hours (7200 seconds), and 225 ° C. for an additional 2 hours (7200 seconds). After that, the cast product is cooled and D
Tg was analyzed by SC. The product began to exotherm, indicating incomplete cure, with a change at 273 ° C.
After post-curing at 260 ° C for 2 hours (7200 seconds), Tg was higher than 300 ° C.

E. Curing of Epoxy Novolac Resin Composition Example 1-D was repeated exactly except that 0.1 ml of a 70% solution of butyltriphenylphosphonium acetate-acetic acid complex in methanol was added along with sulfanilamide. The properties of the cured casting were such that Tg was higher than 300 ° C. and G _1C was 0.11 kJ / m ² .

Comparative Experiment A A. Curing of a commercially available epoxy novolac resin composition for comparison purposes An epoxy novolac resin composition having a nominal functionality of 3.6 (DEN.TM. from Dow Chemical Company)
Epoxy equivalent 17
9.7, weight average molecular weight 1123, number average molecular weight 61
8, polydispersity is 1.7, and 3 of 2 functional components
About 2 with a weight ratio of 1.39: 1
Contains 0.6 weight percent difunctional product) 3
Heat 5.0 g to about 150 ° C., and then Example (1-D)
7.12 g of sulfanilamide exactly as described in 1.
Mixed with. The properties of the cured resin are as follows: Tg 172 ° C, G _1C
Was 0.15 kJ / m ² .

B. Curing of a commercially available epoxy novolac resin composition for comparison purposes Comparative Experiments A-A were repeated exactly except that the catalyst described in Example (1-E) was also added. The property of the cured resin is T
g is 209.7 ° C., G _1C is 0.21 kJ / m ² , and the notched Izod impact strength is 0.
It was 18 ft · lb (9.6 J per notch meter).

Example 2 A. Preparation of phenol-formaldehyde type novolak resin composition A part of the novolac resin composition prepared in Example 1-A was used.

B. Removal of Bifunctional Product The above prepared novolak resin composition was continuously extracted with 99 ° C. water until the content of bifunctional component measured by GPC was 14.1 weight percent. As for the content of trifunctional components, the ratio of bifunctional components to trifunctional components is 0.8.
Due to 2: 1 it was 17.21 weight percent. The weight average molecular weight was 922, the number average molecular weight was 654, and the polydispersity was 1.40. The solid product has a Mettler softening point of 84.3 ° C and a melt viscosity at 150 ° C of 165 cP.
(0.165 Pa · s).

C. Preparation of Epoxy Novolac Using the procedure described in Example 1-C, a portion of the above extracted novolac resin composition prepared in Example 2-B (20
6g) to 498g of isopropanol and 80.4g
Was reacted with 925 g of epichlorohydrin in water.
After separating the aqueous phase, an additional 32 g of sodium hydroxide dissolved in 128 g of water was added in the second step. The epoxy product has an epoxy equivalent of 179.4, a hydrolyzable chloride content of 768 ppm, a Mettler softening point of 53.5 ° C., and a melt viscosity at 150 ° C. of 100 cP (0.1 Pa.
s). The weight average molecular weight was 1106, the number average molecular weight was 719, and the polydispersity was 1.54. The average epoxide functionality was calculated to be 4.0. The content of the bifunctional component and the trifunctional component was 10.50 weight percent and 12.65 weight percent, respectively, and was 0.8.
The ratio was 3: 1.

D. Curing of the epoxy novolac resin composition Part of the epoxy resin composition prepared in Example 2-C 10.
0 g was mixed with 2.76 g methylene dianiline at 150 ° C. until homogeneous and then cured for the next time period. That is, at 150 ° C. for 2 hours (7200
Second), 200 ° C for 1 hour (3600 seconds), 250 ° C for 1 hour (3600 seconds), and 270 ° C for 3/4 hours (27 hours).
00 seconds). The glass transition temperature (Tg) was 306.0 ° C. as measured by expansion using a DuPont Model 943 thermomechanical analyzer (TMA).

Comparative Experiment B A. Curing of Commercially Available Epoxy Novolac with Methylenedianiline 10.0 g of the resin composition described in Comparative Experiment AA was cured as described in Example 2-D. T measured by TMA
The g was 184.3 ° C.

B. Solvent Extraction of Commercially Available Epoxy Novolac Resin Composition A portion of the resin described in Comparative Experiment AA was treated with xylene exactly as described in Example 8 of US Pat. No. 3,928,288. . The product has an epoxy equivalent of 2
04, weight average molecular weight 2043, number average molecular weight 11
06, polydispersity 1.85, bifunctional component content 6.23
In weight percent, the ratio of bifunctional to trifunctional content was 1.12: 1.0. The average epoxide functionality was calculated to be 5.4.

C. Curing of Epoxy Novolac A portion of the resin composition from Comparative Experiment BB 10.0 g
Was reacted exactly with 2.42 g of methylenedianiline as described in Example 2-D. The Tg of the cured resin measured by TMA was 312.3 ° C.

D. Curing Epoxy Novolac Resin with Phenol Novolac A portion of 10.0 g of the epoxy novolac resin composition described in Comparative Experiment A-A was mixed with 5.76 g of the phenol novolac resin composition described in Example 1-A and tetrabutylphosphonium acetonate. This was mixed with 0.12 g of a 70 wt% methanol solution of the tart / acetic acid complex at 177 ° C. The mixture is 177 ° C. for 3 hours (10800 seconds) and 200 ° C. for 2 hours.
Time (7200 seconds), and 225 ° C for 1 hour (360
It was cured for 0 seconds. Tg of cured product measured by DSC
Was 154.4 ° C.

E. Curing of Epoxy Novolac Resin with Phenol Novolac A 10 g portion of the epoxy novolac resin composition described in Comparative Experiment A-A was mixed with 5.76 g of the phenolic resin described in Example 2-B and described in Comparative Experiments BD. Exactly what I did. The Tg of the product measured by DSC is
It was 153.4 ° C.

Example 3 A. Preparation of Phenol-Formaldehyde Novolak Resin Composition A portion of the novolak resin composition from Examples 1-4 was used.

B. Removal of Bifunctional Product The above prepared novolak resin composition was continuously extracted with water at 99 ° C. until the bifunctional component content measured by GPC was 2.55 weight percent. The weight average molecular weight of the resin composition is 1038, the number average molecular weight is 814,
The polydispersity was 1.28. The weight ratio of the bifunctional component to the trifunctional component was less than 0.5: 1.

C. Preparation of Epoxy Novolac Resin Composition Using the same procedure as described in Example 1-C, 425.9 g of the above novolac resin composition was added with 2 parts of sodium hydroxide.
Using 105.2 g of a 0 percent aqueous solution 1065.2 g.
Reacted with 1894.0 g epichlorohydrin in 8 g isopropanol. The epoxy equivalent of the epoxy novolac resin composition was 177.9. The weight average molecular weight is 1309, the number average molecular weight is 862, and the polydispersity is 1.
It was 46. The average epoxide functionality was calculated to be 4.8. The difunctional component content was 2.29 percent compared to 9.9 percent of the trifunctional product, giving a weight ratio of difunctional to trifunctional components of 0.23: 1.

D. Curing of Epoxy Novolac Resin Composition A 10.0 g portion of the epoxy novolac resin composition prepared in Example 3-C was prepared exactly as described in Example 2-D.
The reaction was carried out with 2.78 g of methylenedianiline. T
The Tg of the cured product measured by MA was 356.9 ° C.

E. Curing of the epoxy novolac resin composition Portion of the epoxy resin composition prepared in Example 3-C 34.
3 g of diaminodiphenyl sulfone 10.16 g and 1
Mix to homogeneity at 50 ° C, then degas in a vacuum oven and cast into 1/8 inch (0.3175 cm) aluminum molds. Cast products are 150 ° C for 2 hours (7200 seconds), 200 ° C for 1 hour (3600 seconds), 2
1 hour (3600 seconds) at 50 ° C and 3 / at 270 ° C
It was cured for 4 hours (2700 seconds). The properties of the cast product are as follows: Tg> 360 ° C, flexural strength 15,000 psi (10
4 MPa), bending modulus 533,000 psi (36
72 MPa).

Example 4 A. Preparation of phenol-formaldehyde type novolak resin composition In a glass reactor equipped with a stirrer, reflux condenser, addition funnel, and temperature controller, 550 g of phenol (5.8 g) was added.
5 mol) and 2.75 g (0.03 mol) of oxalic acid. The mixture was heated to 110 ° C. and 298.8 g (3.68 mol) of 37% formalin was added slowly during approximately 60 minutes (3600 seconds). The reaction mixture was refluxed during the addition of formalin and for about 60 minutes (3600 seconds) thereafter. Then vacuum was applied to remove excess phenol and water at a final temperature of 180 ° C. by vacuum distillation.

The METTLER softening point of the solid novolac resin composition was 87.9 ° C. Also, analysis by gel permeation chromatography (GPC) showed that the product had a weight average molecular weight of 1044, a number average molecular weight of 700, and a polydispersity of 1.49. The product is 16.
It contained 3 percent of the bifunctional component and the ratio of the bifunctional component to the trifunctional component was 1.2: 1.0.

B. Removal of Bifunctional Product The above prepared novolak resin composition was continuously extracted with 99 ° C. water until the content of bifunctional component measured by GPC was less than 0.5 weight percent. 2 of 3 functional ingredients
The weight ratio to the functional ingredients was less than 0.5: 1.

C. Preparation of Epoxy Novolac Resin Composition Using the exact same procedure as described in Example 1-C, Example 4
-307 g of the product from -B was added to epichlorohydrin 13
65.3 g, isopropanol 735.1 g, and water 1
207.0% aqueous caustic solution 767.0 in 18.7 g
g was used to react. MSP of the product is 81.3 ° C,
The melt viscosity measured at 150 ° C is 589 cP (0.589 Pa).
.S) and the epoxy equivalent was 186.1. Two
The ratio of functional ingredients to trifunctional components was less than 0.5: 1.

Example 5 A. Preparation of Phenol-Formaldehyde Novolak Resin Composition Phenol 150 was prepared using the procedure described in Example 4-A.
6.6 g (16.03 mol), 7.53 g (0.08 mol)
81.53 g (10.2
6 mol) of 37% formalin. The Mettler softening point of the solid product was 90.7 ° C. The bifunctional component content measured by GPC was 15.27 percent. Weight average molecular weight is 1098, number average molecular weight is 71
4 and the polydispersity was 1.54. 1 product
It contains 5.27 weight percent difunctional component, and
1 because the ratio of functional components to trifunctional components is 1.2: 1
It had a trifunctional content of 2.67 weight percent.

B. Removal of Bifunctional Product A portion of the above prepared product was measured by GPC.
It was continuously extracted with water at about 99 ° C. until the functional ingredient content was 4.26 weight percent. The Mettler softening point of the solid product was 108.9 ° C. Weight average molecular weight is 12
63, number average molecular weight 895, polydispersity 1.41
Met. The ratio of the bifunctional component to the trifunctional component is 0.
It was 40: 1.

C. Removal of Bifunctional Product A second portion of the novolak resin composition prepared in Example 5-A was continuously extracted with water until the bifunctional component content measured by GPC was less than 0.5 weight percent. did. The Mettler softening point was 128 ° C. Weight average molecular weight is 14
46, number average molecular weight is 1138, and polydispersity is 1.
It was 27. The ratio of bifunctional component to trifunctional component is
It was less than 0.25: 1.

D. Preparation of Epoxy Novolac 402.5 g of a portion of the resin composition prepared in Example 5-B
As described in Example 1-C using 1006.4 g of a 20 percent aqueous caustic solution of isopropanol 963.
Epichlorohydrin 178 in 8 g and 155.6 g of water
Reacted with 9.9 g. The epoxy equivalent of the product is 185
Met. The weight average molecular weight was 1481, the number average molecular weight was 935, and the polydispersity was 1.58. The average epoxide functionality was calculated to be 5.1. The bifunctional component content was 3.81 percent. The weight ratio of the bifunctional component to the trifunctional component was less than 0.25: 1.

E. Preparation of Epoxy Novolac 385.3 g of a portion of the resin composition prepared in Example 5-C
As described in Example 1-C using 964.6 g of a 20 percent aqueous caustic solution of isopropanol 922.7.
g and epichlorohydrin 1713.6 in 149 g of water
Reacted with g. The product was a brittle, non-sinterable solid with an MSP of 85 ° C. and an epoxide content of 23 percent (epoxy equivalent 187). Weight average molecular weight is 171
9, the number average molecular weight is 1234, the polydispersity is 1.3
It was 9. The average epoxide functionality was calculated to be 6.6. The bifunctional component content was less than 0.5 percent. The ratio of the bifunctional component to the trifunctional component is 0.2.
Less than 5: 1.0.

Example 6 A. Preparation of Phenol-Formaldehyde Novolak Resin Composition 3000 g (31.
88 moles of phenol was added to 15.0 g of oxalic acid (0.
167 mol) was used to react with 1655.96 g (20.4 mol) of 37% formalin. The obtained solid resin composition had a Mettler softening point of 92.7 ° C. and a melt viscosity of 380 cP at 150 ° C. By GPC analysis, the weight average molecular weight was 1168 and the number average molecular weight was 7.
53 and the polydispersity was 1.55. This resin composition comprises 16.67 weight percent of difunctional component and 1
It contained 3.43 weight percent of the trifunctional component. The weight ratio of the bifunctional component to the trifunctional component is 1.2.
It was 4: 1.

B. Removal of Bifunctional Product A portion of the above product was continuously extracted with water at about 99 ° C. until the bifunctional component content measured by HPLC was 0.36 weight percent. By GPC analysis, the weight average molecular weight was 1452, the number average molecular weight was 1123, and the polydispersity was 1.29. The ratio of bifunctional to trifunctional components was less than 0.25: 1.

C. Removal of Bifunctional Product A second portion of the novolak resin composition prepared in Example 6-A was continuously extracted with warm water until the bifunctional component content measured by HPLC was 0.73 weight percent. The resin composition has a weight average molecular weight of 1,427 and a number average molecular weight of 1
090 and polydispersity of 1.31. The weight ratio of the bifunctional component to the trifunctional component of the product is 0.25:
It was 1.

D. Preparation of Epoxy Novolac 425 g of a portion of the novolac resin composition from Example 6-B
Was reacted with epichlorohydrin using exactly the same reactant proportions and conditions as described in Example 5-B. The product was a non-sinterable, brittle solid with an MSP of 86.0 ° C. The melt viscosity measured at 150 ° C. was 850 cP. The epoxy equivalent weight of the product was 184.0.
The weight average molecular weight was 1775, the number average molecular weight was 1203, and the polydispersity was 1.48. The average epoxide functionality was calculated to be 6.5. The ratio of bifunctional component content to trifunctional component content was less than 0.25: 1.

E. Preparation of Epoxy Novolac Resin Composition Portion of Novolac Resin Composition from Example 6-C 425.
0 g was reacted exactly as described in Example 6-D,
A brittle solid resin composition having an epoxy equivalent of 184.6 was obtained. Weight average molecular weight is 1789, number average molecular weight is 118
7, the polydispersity was 1.41. The average epoxide functionality was calculated to be 6.4. The content of the bifunctional component is 0.
The weight ratio of 73 weight percent and the content of the bifunctional component to the content of the trifunctional component was less than 0.25: 1.

F. Curing of the Epoxy Novolac Resin Composition A portion of 35.0 g of the resin composition from Example 6-E was combined with 6.93 g of sulfanilamide and 0.2 ml of a 70 wt% methanolic solution of ethyltriphenylphosphonium acetate-acetic acid complex and 150 Mixed at ~ 160 ° C. 150
16 hours at 57 ° C (57,600 seconds), 2 hours at 200 ° C (7200 seconds), and 2 hours at 225 ° C (7200 seconds).
Sec) After curing, the Tg of the product was higher than 255 ° C.

G. Curing of Epoxy Novolac Resin Composition with Novolac Resin Composition A portion of 30.0 g of the resin composition from Example 6-E was used in Example 6
16.9 g of phenol novolac resin composition from C
And 2-methylimidazole 0.075 g and 150-1
Mixed at 60 ° C. Mix the mixture at 150 ° C. for 16 hours (5
7,600 seconds), followed by 200 ° C for 2 hours (7200
Sec) and 225 ° C. for 2 hours (7200 seconds).
The Tg of the cured product measured by DSC was higher than 240 ° C.

H. Curing of Epoxy Novolac Resin Composition A portion of 10.0 g of the resin composition from Example 6-E was mixed with 2.68 g of methylene dianiline at 150 ° C. and treated exactly as described in Example 2-D. did. Tg by TMA was 311.8 ° C.

Comparative Experiment C H. Preparation of Epoxy Novolac Resin Composition A 104 g portion of the resin composition from Example 6-A was dissolved in 462.5 g epichlorohydrin and 2.3 g of a 60 percent aqueous solution of benzyltrimethylammonium chloride was added. This solution was stirred under a nitrogen atmosphere at 70 ° C. for 72 hours (259,200 seconds), then cooled to 20 ° C. and a solution of 16% sodium hydroxide / 9% sodium carbonate 31
2.5 g was added and stirred at 20 ° C. for 90 minutes (5400 seconds). The aqueous layer is separated and an additional 312.5 g of 16 percent sodium hydroxide / 9 percent sodium carbonate solution is added at 20 ° C. for 30 minutes (1800
For a second). The aqueous layer was separated and the organic layer was washed with water until free of salt and caustic. Then 15
Excess epichlorohydrin was removed by vacuum distillation at 0 ° C. The epoxide content of the product was 24.9 percent (epoxy equivalent 172.7). The bifunctional component content was 13.4 percent. The weight average molecular weight was 1531, the number average molecular weight was 729, and the polydispersity was 1.71. The average epoxide functionality is 4.
Calculated as 2. The ratio of bifunctional component to trifunctional component was 1.30.

B. Solvent Extraction of Epoxy Novolac Resin Composition The procedure described in US Pat. No. 3,928,288 was repeated using 80.0 g of the resin composition prepared in Comparative Experiment CA.

C. Curing of Epoxy Novolac Resin Composition with Phenolic Novolac Resin Composition The procedure described in Comparative Experiments BD was repeated using the phenolic novolac resin composition described in Example 6-B.
The Tg of the cured product was 195.4 ° C.

C. Curing of Epoxy Novolac Resin Composition A portion of the resin composition from Comparative Experiment C-A 10.0 g
Was reacted exactly as described in Example 2-D with 2.86 g of methylenedianiline. The Tg of the cured resin measured by TMA was 284.2 ° C.

E. Curing of Epoxy Novolac Resin Composition A portion of the resin composition from Comparative Experiment CB 10.0 g
Was reacted with 2.41 g of methylenedianiline as described in Example 2-D. The Tg of the cured resin measured by TMA was 302.5 ° C.

F. Curing of Epoxy Novolac Resin Composition with Phenolic Novolac Resin Composition The procedure described in Comparative Experiments BD was repeated using the phenolic novolac resin composition described in Example 6-A.
The Tg of the cured product was 166.6 ° C.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Walker, Luis El. USA, Texas 77531, Krato, Barbara Drive 246 (72) Inventor McClary, Abyss El. USA, Texas 77566, Lake Jackson, Astor Lane 129 (72) Inventor Cortez, Famin M. USA, Texas 77480, Swaney, Forest Park Court 1401.

Claims (11)

[Claims] 1. The following formula, that is: (In the above formula, A is independently a divalent hydrocarbon group having 1 to 14 carbon atoms, and each R is independently hydrogen, a halogen atom, a hydroxyl group, or 1 to 9 carbon atoms. A hydrocarbon group having atoms, and n has an average value of 1 to 10), and a method for preparing a novolak resin in which the amount of bifunctional components is reduced, (A) a substance having at least one aromatic hydroxyl group per molecule in the presence of a catalyst,
The molar ratio of (B) aldehyde and (B) :( A) was adjusted to 0.
Reacting 3: 1 to 0.95: 1, (II) removing excess aromatic hydroxyl-containing material, and (III) the resulting product is present after step (II). Subjecting the product from step (II) to extraction with water until it contains less than 25 percent by weight of a bifunctional component. 2. (i) said material having an average of at least one aromatic hydroxyl group is of the formula: (Wherein each R is independently hydrogen, a halogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 9 carbon atoms), and (ii) the aldehyde is The method according to claim 1, which is an aliphatic, cycloaliphatic, or aromatic aldehyde having 1 to 14 carbon atoms. 3. (i) The substance having at least one aromatic hydroxyl group per molecule is phenol, methylphenol, butylphenol, bromophenol,
Chlorophenol, resorcinol, or a mixture thereof, (ii) the aldehyde is formaldehyde, (iii) the catalyst is oxalic acid, and (iv) the resulting product is of step (II) The method of claim 2 which contains less than 50 weight percent of the difunctional component than was present later. 4. The method of claim 3, wherein the substance having at least one aromatic hydroxyl group per molecule is phenol. 5. The process according to claim 1, wherein in step (III) a small amount of at least one organic solvent selected from ketones, alcohols and glycol ethers is used together with water. 6. A novolak resin prepared from a substance having at least one aromatic hydroxyl group and an aldehyde, having an average functionality of 3-5, 12.5.
A novolac resin composition containing less than weight percent difunctional component and having a weight ratio of difunctional component to trifunctional component of less than about 1.1: 1. 7. (i) The material having at least one aromatic hydroxyl group has the formula: (Wherein each R is independently hydrogen, a halogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 9 carbon atoms), (ii) the aldehyde is 1 to An aliphatic, cycloaliphatic, or aromatic aldehyde having 14 carbon atoms, (iii) wherein the novolac resin contains less than 12.5 weight percent bifunctional component, and the bifunctional component is a trifunctional component. The novolac resin composition according to claim 6, wherein the weight ratio to the ratio is less than 0.75: 1. 8. (i) The substance having at least one aromatic hydroxyl group per molecule is phenol, methylphenol, butylphenol, bromophenol, chlorophenol, resorcinol, or a mixture thereof, (ii) The aldehyde is formaldehyde, (iii) the novolac resin contains less than 7 weight percent difunctional component, and the weight ratio of difunctional component to trifunctional component is less than 0.5: 1. The novolak resin composition described. 9. A novolak resin prepared from a material having at least one aromatic hydroxyl group per molecule and an aldehyde, having an average aromatic hydroxyl functionality of 5-12 and less than about 9 weight percent. Novolak resin composition containing the bifunctional component of 1., and the weight ratio of the bifunctional component to the trifunctional component is less than 1.1: 1. 10. (i) The material having at least one aromatic hydroxyl group has the formula: (In the above formula, each R is independently hydrogen, a halogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 9 carbon atoms), and (ii) the aldehyde is 1 to An aliphatic, cycloaliphatic, or aromatic aldehyde having 14 carbon atoms, (iii) the novolac resin contains less than 9 weight percent of a difunctional component, and the weight of the difunctional component relative to the trifunctional component. The novolac resin composition according to claim 9, wherein the ratio is less than 0.75: 1. 11. (i) The substance having at least one aromatic hydroxyl group per molecule is phenol,
Methylphenol, butylphenol, bromophenol, chlorophenol, resorcinol, or mixtures thereof, (ii) the aldehyde is formaldehyde, (iii) the novolac resin contains less than 5 weight percent of a bifunctional component, and The novolak resin composition according to claim 10, wherein the weight ratio of the bifunctional component to the trifunctional component is less than 0.5: 1.