JPS63196617A - Production of polyisocyanurate resin - Google Patents

Abstract

PURPOSE:To produce the title resin excellent in chemical resistance and heat resistance, by heat-treating a polyol containing a specified modified silicone oil and an organic polyisocyanate in the presence of a trimerization catalyst at a specified NCO index and a specified temperature. CONSTITUTION:In the reaction of an organic polyisocyanate with a polyol in the presence of a trimerization catalyst (preferably, a combination of a metal carboxylate with a tert. amine), a modified silicone oil containing active hydrogen groups is used as at least part of said polyol, e.g., silanol-terminated polysiloxane of the formula (wherein n is 1-250 and Me is methyl), and the heat treatment is conducted under conditions of an NCO index >=500 and 60-300 deg.C. As said polyisocyanate, a conventional one such as 4,4'- diphenylmethane diisocyanate can be used. A polyisocyanurate resin excellent in chemical resistance and heat resistance and excellent also in moldability, nonmountability and sliding property can be obtained. By virtue of the above properties, it can be used, for example, in resin molds, magnetic plastics, roll sliding parts, coating agents, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing polyisocyanurate resin.

[Conventional technology]

Conventionally, a method for producing polyisocyanurate resins is known in which an organic polyisocyanate is reacted with a polyether polyol such as polypropylene glycol in the presence of a trimerization catalyst.

[Problem that the invention seeks to solve]

Although polyisocyanurate resins are known to have excellent heat resistance, they have problems with chemical resistance.

[Means for solving problems]

The present inventors have conducted repeated studies to find a method for producing a polyisocyanurate resin that has excellent chemical resistance and heat resistance, and as a result, they have arrived at the present invention. That is, the present invention provides a method for producing a polyisocyanurate resin by reacting an organic polyisocyanate and a polyol in the presence of a trimerization catalyst, in which (11) a modified silicone oil having an active hydrogen-containing unit is used as at least a part of the polyol; use,(
2) The isocyanate index is 500 or more, (3) 6
This is a method for producing polyisocyanurate resin, which is characterized by heat treatment at a temperature of 0 to 300°C.

In the modified silicone oil having an active hydrogen-containing group according to the present invention, examples of the active hydrogen-containing group include a hydroxyl group and a mercapto group.

The equivalent weight (molecular weight per active hydrogen-containing group) of the modified silicone oil is usually 100 to 10,000, preferably 200 to 5,000. If the equivalent weight exceeds 10,000, chemical resistance will be insufficient, and if it is less than 100, sufficient heat resistance will occur.
cannot demonstrate.

Examples of modified silicone oils having active hydrogen-containing groups include hydroxy-modified polysiloxanes having hydroxy groups in the main chain and mercapto-modified polysiloxanes.

Specifically, the rules are as follows.

CI) Hydroxy-modified polysiloxane (1) Terminated silanol polysiloxane (a) Terminated silanol polydimethylsiloxane Molecular weight represented by the general formula (in the formula, n is an integer from 1 to 250. Me is a methyl group) usually 240 -20,000.

(b) Terminal silanol diphenyl siloxane 1) Terminal silanol polydiphenyl siloxane Compounds represented by the general formula (in the formula, n is an integer from 1 to 95; Ph is a phenyl group) are mentioned. The molecular weight is usually 850 to 20,000.

11) Terminal silanol polydimethyldiphenylsiloxane general formula (in the formula, n9m is an integer from 1 to 95. The theory is a methyl group,
Ph is a phenyl group. ) can be mentioned. The molecular weight is usually 850 to 20,000.

(iii) Bis(hydroxydimethylsilyl)benzene Compounds represented by the general formula (in the formula, n is an integer from 1 to 94, and the positive sign is a methyl group) are mentioned. The molecular weight is usually 2
26 to 20,000.

(2) Terminal alcohol polysiloxane (a) Terminal hydroxyalkylene polydimethylsiloxane General formula (wherein, n is an integer of 1 to 266 and m is an integer of θ to 225. R1 is an alkyl group having 1 to 4 carbon atoms. R2 is an alkyl group having 2 to 4 carbon atoms. The molecular weight is usually 268-82,700.

(1) Mercapto-modified polysiloxane (1) Polymercaptopropylmethylsiloxane Compounds represented by the general formula (wherein, n is an integer from 2 to sum is from 0 to 655, and is a methyl group) are mentioned. .

The molecular weight is usually 480 to 49,000.

Among the modified silicone oils having active hydrogen-containing groups, hydroxy-modified polysiloxanes are preferred.

If necessary, other polyols may be used together with the modified silicone oil having an active hydrogen-containing group.

As other polyols, polyether polyols and polyester polyols having an OH value of usually 200 or less, preferably 180 or less, and more preferably 170 or less are used.

Examples of polyether polyols include compounds having a structure in which an alkylene oxide is added to an active hydrogen-containing polyfunctional compound such as a polyhydric alcohol, a polyhydric phenol, or a polycarboxylic acid.

Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, butylene oxide,
Examples include tetrahydrofuran, styrene oxide, and epichlorohydrin.

The alkylene oxides may be used alone or in combination of two or more, and in the latter case, block addition, random addition, or a mixture of both may be used.

Examples of polyester polyols include condensed polyester polyols obtained by reacting low-molecular-weight polyols with dicarboxylic acids, and polyester polyols obtained by ring-opening polymerization of lactones.

Polycarbonate diols can also be used.

Active hydrogen-containing modified silicone oil and other polyols (
The weight ratio of polyether polyol and/or polyester polyol (polycarbonate diol) can be varied and is usually 100:0 to 20:gO, preferably 100:O to 50:50.

The amount of modified silicone oil having active hydrogen-containing groups is 2
When υ is less than 0, chemical resistance deteriorates.

As the organic polyisocyanate used in the present invention, those conventionally used in the production of polyurethane can be used. Such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding the carbon in the NGO group) [for example, 2.4- and/or 2.4- and/or 2.4-carbon atoms].
6-) Lylene diisocyanate (TDI), crude TDI
, 2.4'- and/or 4°4'-diphenylmethane diisocyanate (MDI).

Crude MDI crude diaminophenylmethane (a condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (
(e.g., 5 to 20% by weight) of a mixture with an octafunctional or higher polyamine: polyallyl polyisocyanate (PAPI), etc.): aliphatic polyisocyanate having 2 to 18 carbon atoms (e.g., hexamethylene diisocyanate, lysine diisocyanate) etc.]; carbon number 4-1
6 alicyclic polyisocyanates (e.g. isophorone diisocyanate, dicyclohexylmethane diisocyanate); aromatic aliphatic polyisocyanates having 8 to 16 carbon atoms [e.g. xylylene diisocyanate, etc.]; and modified products of these polyisocyanates (urethane groups,
Carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretonimine group, isocyanurate group.

Oxazolidone group-containing modified products, etc.): and patent application 1983
Examples include polyisocyanates other than those described in JP-199160 and mixtures of two or more thereof.

Among these, preferred are commercially readily available polyisocyanates such as 2.4- and 2.6-
- TD I, and mixtures of these isomers, crude T
DI, 4.4'- and 2.4'-■H1 and mixtures of these isomers, PA also called crude MDI
PI, and urethane groups and carbodiimide groups derived from these polyisocyanates.

Allophanate group, urea group, biuret group.

It is a modified polyisocyanate containing an isocyanurate group, and the NCO4 is usually 20 to 45, preferably 25
~80 masters.

In the present invention, the NGO index is usually 500 or more, preferably 1000 or more. When the NGO index is less than 500, heat resistance is poor.

As the trimerization catalyst used in the present invention, known ones can be used. Specifically, metal salts of carboxylic acids, e.g.
Sodium acetate, lead octylate.

Zinc octylate, cobalt naphthenate, etc.; alkoxides and hypoenoxides of alkali and alkaline earth metals, such as sodium methoxide.

Sodium phenoxide, etc.; tertiary amines, such as triethylamine, triethylenediamine.

N-methylmorpholine, (dimethylaminomethyl)phenol, pyridine, etc.; quaternary ammonium bases, such as tetraethylammonium hydroxide; imidazoles, such as imidazole, 2-ethyl-4-
Examples include methylimidazole and the like; organometallic compounds such as tin and antimony, such as tetraphenyltin and tributylantimony oxide. Among these, preferred is a combination system of a metal salt of carboxylic acid and a tertiary amine.

The amount of trimerization catalyst used is 100% of the polyisocyanurate resin.
Usually 0.01 to 10 parts, preferably 0.05 to 5 parts
Department.

In the present invention, the reaction can be carried out in the presence of other catalysts (eighth amines, organic tin compounds, organic lead compounds, etc.) and other auxiliary agents, if necessary.

Pigments, fillers, etc. can also be added depending on the amount.

In producing the polyisocyanurate resin in the present invention, the heat treatment temperature is usually 60 to 300°C, preferably 80 to 280°C, and more preferably 110 to 250°C.
It is 1. The heat treatment conditions have a great influence on the completion of the resin reaction and the microphase structure. This makes it possible to produce polyisocyanurate resins that are chemically resistant and heat resistant. The heat treatment time is usually 10 minutes to 10 hours, preferably 30 minutes to 8 hours. Heat treatment at low temperatures will result in insufficient heat resistance, and heat treatment at temperatures above 300°C will cause thermal decomposition of the resin.

The polyisocyanurate resin production method according to the present invention includes a one-shot method (a method in which an organic polyisocyanate is reacted with a polyol containing a trimerization catalyst), a prepolymer method (a method in which a stoichiometric excess of organic polyisocyanurate is reacted with a polyol), Any method (method of adding a trimerization catalyst to the reacted prepolymer having terminal NGO groups and reacting) can be applied.

The molding method for polyisocyanurate resin is vacuum molding method, RI
Although molding using the M method is useful, other molding methods can also be applied.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Parts in Examples and Comparative Examples are parts by weight.

The measurement method is as follows.

Chemical resistance (%) (Weight increase rate after 8 hours of immersion in methyl ethyl ketone at room temperature) Heat distortion temperature (according to JIS K6911. Load 18.6 A)
:9) Hair strength, hair elastic modulus (JIS K 691
1) Example 1 Diethylene oxide was added to the terminal of dimethylpolysiloxane diol of AJi5oo by a conventional method, and the equivalent amount was 985.
Obtain modified silicone oil.

20 parts of modified silicone oil, temperature controlled at 25°C, K1.3° 0.1 part of 6-tris(8-dimethylaminoprobylmohexahydro-9-)riazine, 0.1 part of potassium octylate, and silicone antifoaming. 0.05 part of agent was added. Tsuite 2
NC0126% CD modified MDI 8 temperature controlled at 5℃
Add 0 parts (NGO index 2815), mix, defoamer, mold temperature 6
It was poured into a mold at 0°C, cured at 60°C for 10 minutes, and then heat-treated at 150°C for 1 hour.

A resin with excellent chemical and heat resistance was produced.

Example 2 20 parts of dimethylpolysiloxanediol having an equivalent weight of 540 was heated to 25°C, and 0.1 part of 1.3.5-)linu(3-dimethylaminomethyltehexahydro-5-)riazine was added.
and 0.1 part of potassium octylate were added.

Then, denatured MD I of 28% NC01 was heated at 25°C.
s.

(NGO index: 1419), mixed, defoamed, poured into a mold with a mold temperature of 60°C, cured at 60°C for 10 minutes, and then heat-treated at 150°C for 5 hours.

A resin with excellent chemical resistance and heat resistance was obtained.

Example 8 To 62 parts of dimethylpolysiloxane diol having an equivalent weight of 540, 488 parts of modified polysiloxane diol with an equivalent weight of 540 and 26 parts of NCO were added (NGO index: 2867) and reacted at 80°C for 8 hours.
I got something.

The temperature of 100 parts of this prepolymer was adjusted to 25°C, and 0.1 part of 1,3°5-tris(8-dimethylaminoprobyltohexahydro-5-)riazine and 0.1 part of potassium octylate were added and mixed. The mixture was foamed, poured into a mold of type i60''Q, cured at 60''C for 10 minutes, and then heat-treated at 150°C for 5 hours.

It is coated with a resin that has excellent chemical and heat resistance.

Example 4 In Example 2, (
NGO index 7477)' A resin with excellent chemical resistance and heat resistance was obtained.

Comparative Example 1 20 parts of 112,000 polyether polyol was added to 25
The temperature was adjusted to ℃, and 0.1 part of 1,3.5-tris(8-dimethylaminoprobyltohexahydro-5-)riazine, 0.1 part of potassium octylate, and 0.05 part of a silicone antifoaming agent were added. Ta. Next, a modified MDIso part of NC042s% whose temperature was controlled at 25°C was added (NGO index 5848) and mixed.
The mixture was degassed, poured into a mold with a mold temperature of 60°C, cured at 60°C for 10 minutes, and then heat-treated at 150"C for 5 hours to obtain a resin.

Comparative Example 2 100 parts of polyether polyol with an equivalent weight of 188 was heated at 25°
The temperature was adjusted to C, and 0.1 part of diptyltin dilaurate and 0.05 part of a silicone antifoaming agent were added. 120 parts of denatured MDI containing 26 ml of NCO, temperature controlled at 25°C, was added thereto (
NCO index 108) After mixing and defoaming, mold temperature 60' (:!
After pouring into a mold and curing at 60℃ for 10 minutes,
00''CX was heat-treated for 1 hour to obtain a resin.

Test Example 1 The performance of the resins obtained in Examples 1 to 4 and Comparative Example 1.2 was tested.

The results are shown in Table-1.

〔Effect of the invention〕

The polyisocyanurate resin obtained according to the present invention has better chemical resistance and heat resistance than conventional polyisocyanurate resins, and also has excellent moldability, non-adhesiveness, and sliding properties. It will be done.

Claims (1)

[Claims] 1. A method for producing a polyisocyanurate resin by reacting an organic polyisocyanate and a polyol in the presence of a trimerization catalyst, comprising: (1) having an active hydrogen-containing group as at least a part of the polyol; Using modified silicone oil, (2) setting the isocyanate index to 500 or more, (3) 60 to 300°C
A method for producing polyisocyanurate resin characterized by heat treatment at a temperature of . 2. The manufacturing method according to claim 1, wherein the active hydrogen-containing group of the modified silicone oil is a group selected from the group consisting of a hydroxyl group and a mercapto group. 3. Modified silicone oil has an equivalent weight of 100 to 10,000
The manufacturing method according to claim 1 or 2. 4. The manufacturing method according to any one of claims 1 to 8, wherein the amount of modified silicone oil having an active hydrogen-containing group in the polyol is 20% by weight or more.