JPH02300224A - Production of liquid, stable modified aromatic polycarbonate having isocyanurate ring - Google Patents

Abstract

PURPOSE:To obtain the title polyisocyanate improved in compatibility with other resins, etc., by isocyanurating a (partially urethanized) aromatic polyisocyanate in the presence of a trimerization catalyst and an organic phosphorous ester and a surfactant to a specified degree of isocyanurization. CONSTITUTION:An aromatic polyisocyanate (A) is reacted with a hydroxy compound (B) of an MW <=2000 and a functionality <=3 at 100 deg.C, desirably 60-90 deg.C for about 2hr to react at least 10wt.% of the total NCO groups to obtain a partially urethanized aromatic polyisocyanate (C). Component A and/or component C is isocyanurated in the presence of 0.005-0.5wt.%, based on component C, component A and/or component C, trimerization catalyst (D) and 1/10-20 pts.wt., per pt.wt. component D, an organic phosphorous ester (E) as a promoter, and 0.1-2wt.%, based on component A and/or component C, surfactant at 100 deg.C, desirably 15-70 deg.C to convert at most 20wt.% of the total NCO groups into isocyanurate groups and optionally a short stop is added to the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to aromatic polyino-7 having an isocyanurate ring.
The present invention relates to modified anates, and more particularly relates to the production of modified aromatic polyisocyanates that are easy to produce, have excellent compatibility with other resins, are liquid, and have a stable isocyanurate ring.

BACKGROUND OF THE INVENTION Aromatic polyisocyanates are reacted with various active hydrogen compounds and used in various applications such as foams, elastomers, paints, and adhesives.

Such an aromatic polyisocyanate can be used after being modified into a polyisocyanate compound having isocyanurate 331.

The product obtained by reacting this polyisocyanate compound with an active hydrogen compound has the characteristics of isocyanurate such as heat resistance, flame retardance, rigidity, toughness, etc. It is used in the field of

Therefore, many isocyanurating polymerization methods for inocyanurating aromatic polyisocyanates have been implemented. For example, JP-A-54-32490, JP-A-52-
Each publication of No. 6949γ describes production methods using catalysts such as metal salts of acetylacetone and alkali metal salts of organic acids. In particular, diphenylmethane diisocyanate has a small activity ratio between the primary inocyanate group and the secondary inocyanate group, so in the isocyanurate polymerization reaction, the reaction occurs very violently, resulting in high viscosity and This is undesirable because a product having a uniform low isocyanate content and having low compatibility with other resins is obtained. Additionally, if the catalyst is inactivated to increase stability, insoluble precipitates tend to form when the reaction is carried out without a solvent, and control of the isocyanurate reaction is difficult. etc., are not fully satisfactory from an industrial perspective, and improvements are desired.

Problems to be Solved by the Invention An aromatic polyisocyanate containing an isocyanurate ring, which is easily subjected to an isocyanurate reaction, has storage stability, and has excellent compatibility with other resins. A friend who wants a degenerate body. The inventors of the present invention have conducted extensive research and study, and have achieved great results by adding a trimerization catalyst and a specific stiffening agent to aromatic polyisocyanate.
A method for efficiently producing a modified aromatic polyisocyanate containing lysocyanurate particles was discovered, and the present invention was achieved.

Means to solve problems That is, the present invention.

1. Add a trimerization catalyst, an organic phosphite, and a surfactant to an aromatic polyisocyanate and/or a partially urethanized aromatic polyisocyanate to convert 20 to 31% of all incyanate groups into isocyanurates. A method for producing a semi-modified aromatic polyisocyanate having isocyanurate jJlt-, which is characterized by adding a terminator if necessary.

Examples of the aromatic polyisocyanate used in the present invention include 2.4- or 4.4'-diisocyanate diphenyl ether, 2.4-diisocyanate, 2.6-toluene diisocyanate, and 4,6-dimethyl-1.3- Phenyl diisocyanate, 4.4'-dibenzyl diisocyanate, 9.10-anthracene diisocyanate, 3.3'-dimethyl-4,47-diisocyanate diphenylmethane, 2.6'-dimethyl-4,4'-
Examples include diphenyl diisocyanate, xylylene/diisocyanate, 2.4- or 4.4'-diphenylmethane diisocyanate, and the like.

Further, aromatic polyisocyanates particularly useful in the present invention include boramethylene poly(elbow) inocyanates represented by the general formula (1), where n = 0 to 8, and mixtures containing these.

The partially urethanized aromatic polyisocyanate used in the present invention is a product of a urethanization reaction between an aromatic polyisocyanate and a hydroxyl group-containing compound, and is prepared by a conventional method. A hydroxyl group-containing compound is added into the solution, and the reaction temperature is 1.
It can be obtained by carrying out the reaction six times at temperatures below 00°C, preferably from 60 to 90°C, for about 2 hours. In this case 100
When the temperature is increased to ζ, side reactions occur, so the viscosity of the product after the trimerization reaction increases significantly, and in some cases, an L gel-like substance is produced. This is thought to be due to the fact that by introducing the urethane group, the urethane group exhibits a cocatalytic effect and forms an isocyanurate antihydrogen bond, which significantly activates the insyanurate group. ing. Therefore, the amount of catalyst added can be reduced due to the cocatalytic effect of this urethane group. Furthermore, since an increase in the concentration of urethane groups lowers the thermal stability, which is a characteristic of the isocyanurate rings subsequently produced, it is necessary to adjust the degree of urethane groups depending on the application.

In the present invention, the urethane conversion rate is desirably 10 or less of all incyanate groups.

The hydroxyl group-containing compound for urethanization used in the present invention has a molecular weight of 2000 or less and a functional group number of 3 or less.

For example, monohydric alcohols represented by the general formula fc'OH include alkyl groups, allylalkyl groups, alkylaryl groups, aryl groups, and alkenyl groups, such as 2-ethylhexyl alcohol, lauryl alcohol, nonyl alcohol, etc. .

Also, ethylene glycol, 1,3-butanediol,
1.4-butanediol, glopylene glycol, diglobylene glycol, neopentyl glycol% 1.
Examples include dihydric alcohols such as 6-hexane glycol, 2-ethylhex/diol, and 2,2.4-trimethylbentanediol, trihydric alcohols such as trimethylolproha/glycerin, and polyester and polyether polyols. These can be used alone or as a mixture of two or more.

The urethanization reaction and the isocyanation reaction can be carried out in the absence of a solvent.

Catalysts used in the insea slate modification of the present invention include alkali metal salts of carboxylic acids having 2 to 12 carbon atoms;
Phenolates such as potassium phenolate and sodium methoxide, alcoholades, and particularly effective ones include 2.4.6-tris(dimethylaminomethyl)phenol, 2.4-bis(dimethylaminemethyl)phenol, 2.6- Ditertiary Lubdel-4-dimethylaminotrimethylsilanephenol, triethylamine, N,
M, N"-tris(dimethylaminopropyl)hexahydrotriazine, diazabicycloundece7, and other amine-based esters may be mentioned. As the organic phosphite used as a cocatalyst in the present invention, organic phosphorous esters such as Mention may be made of diesters and organic phosphorous triesters.

The hand has one to four substructures (bonded with carbon atoms). In the present invention, 1, for example, as the organic phosphite triester, tos(betachloroglobil) phosphate etc.-1tEh'), and as the organic phosphite diester, for example, (RO\P (0)H(
However, R represents alkyl having 1 to 20 carbon atoms, which may be the same or different, or 17-/1/ (aryl is, for example, phenyl) which may be substituted with alkyl having 1 to 20 carbon atoms. Exemplary compounds include, for example, di-hydrogen phosphite, diphenyl-hydrogen phosphite, and the like. Alkyl represented by the symbol R may be partially substituted with, for example, chloro, and as such,
For example, tris(2,3-dichloroglovir) phosphite. Further, the oxygen atom of the phosphite may be substituted with a sulfur atom, and examples of such a phosphite include trilafuryl trithiophosphite.

Further, for example, (14-0+3PC) where 几 may be the same or different and may be an alkyl having 1 to 20 carbon atoms or an aryl which may be substituted with an alkyl having 1 to 20 carbon atoms (aryl is, for example, phenyl). Compounds represented by: triethyl phosphite, tributyl phosphite, tris (
2-ethylhexyl) phosphite, tridefluphosphite, trilauryl phosphite, tris(tridecyl) phosphite, tristearyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di- t-butylphenyl)
There are monophosphites such as phosphites.

Further, for example, distearyl pentaerythrityl diphosphite, ditridecylbe/taerythritol diphosphite, dinonylphenylbentaerythritol diphosphite, tetraphenyltetratridecyl pentaerythrityl tetraphosphite, tetraphenyldipropylene glycol diphosphite, di-, tri-, or ketone phosphites derived from polyhydric alcohols such as tripentaerythritol triposphite, and dialkyl (01-2o) bisphenol A diphosphites,
Diphosphites derived from bisphenol compounds such as 4,4'-butylidene-bis(3-methyl-6-6-butylphenyl-di-tridecyl) phosphite;
Hydrogenated bisphenol A phos-7ite polymer (molecular weight 2
Polyphosphites such as 400-3000) can be mentioned.

In the process of the present invention, such cocatalysts are used in combination with catalysts, and the amount of catalyst used may be less than the most effective amount when used alone.

The amount of catalyst used varies depending on the activity of the catalyst, and is 0.005 to 0.5 weight i based on the raw incyanate compound.
t% is sufficient. Further, the amount of phosphite used as a promoter is about 1/10 to 20 times that of the catalyst.

In addition, the isocyanurate reaction rate is strongly influenced by the initial concentration dependence of the catalyst, and in particular in diphenylmethane diisocyanate, where the activation of two incyanate groups is close to 2, the isocyanurate reaction rate by the usual method is difficult to gel. The particles may float unevenly or, in some cases, may gel.

Therefore, in order to reduce the dependence on the initial concentration of the catalyst, it is preferable to use a method in which the catalyst is added using a diluent or the like to reduce the initial concentration. The diluent is preferably a compound that is inert or nonflammable to the rounded isocyanate and maintains the flammability and heat resistance of the resulting polymer. Examples include methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, trichlorotrifluoroethane, and the like.

By using such a catalyst, this partial polymerization can be reduced to less than 20 times the total number of isocyanate groups. By producing JI4, a liquid and stable polymer can be obtained.

When an aromatic polyisocyanate is modified to form an isocyanurate, a method has been adopted to improve the compatibility by introducing a rounded phletane group, which does not have good compatibility between the modified isocyanurate and the aromatic polyisocyanate. In the method of the present invention, by using a surfactant, isocyanurate modification can be achieved in both aromatic polyisocyanate and partially urethanized aromatic polysonanate in a solvent-free manner, and the process is free from turbidity and has a high A liquid and stable cyanurated modified product with less molecular polymer formation is available. In addition, the isocyanurate modified product produced by using a surfactant has improved phase M properties with other resins, so that the curing reaction with a compound containing active hydrogen that reacts with incyanate groups proceeds smoothly. The physical properties of the obtained cured product are also the same as above.

In the present invention, the surfactant may be added either at the initial stage of the reaction or at the latter stage of the reaction.

The surfactant used in the present invention can be used in one reaction with a polyglycol ether obtained by reacting a fulkylene/oxide such as ethylene oxide, propylene oxide, or butylene oxide, preferably with ethylene oxide, polyethylene glycol, or polypropylene glycol. It can be obtained by combining 1kJii1 with an organic compound containing a hydrogen atom. Compounds containing one such reactive hydrogen atom include alcohol, phenol,
There are thiols, primary and secondary amines. There are also nonionic surfactants consisting of polyglycol ether, carboxylic acid, sulfonic acid, and amides thereof. These include polyethylene glycol ethers. There are also surfactants which are polyalkylene oxide derivatives of the polyglycol ethers and phenolic compounds containing, for example, one or more alkyl substituents. These include polyethylene glycol nonylphenyl ether.

Furthermore, as a surfactant, there is, for example, a surfactant called a pluronic type. These are generally butylene oxide, amylene oxide, phenylethylene oxide, cyclohexene oxide, propylene oxide, or mixtures thereof; for example, 1,2-alkylene oxide or pressed alkylene oxide is polymerized in the presence of an alkali catalyst. There are nonionic surfactants obtained by preparing the corresponding water-insoluble polyalkylene glycol and then condensing it with the required number of moles of ethylene oxide. These include Gloronik L-61 and Prolonik L-62 (Asahi Denka). Furthermore, as a surfactant,
For example, it is obtained by reducing aldehydes produced by the catalytic reaction of polyolefins such as tripropylene, tetrapropylene, pentapropylene, diisobutylene, triisobutylene, tetrabutylene, propylene-isobutylene, tributene, etc., with carbon monoxide and hydrogen. There are nonionic surfactants obtained by reacting alcohol with the required number of moles of ethylene oxide.These include polyoxyethylene/ethylene alkyl ether, polyoxyethylene lauryl ether, and polyoxyethylene lauryl ether. There are ethylene, oleyl, needle, etc.

Furthermore, particularly effective surfactants in the present invention include those represented by general formula (2).

\O(asl O)y (C((Htn O)z R”
Here, Ru′, π′ are alkyl numbers of corresponding valences, p, 1
q and `` are integer values of at least 1, n is an integer value of 2 to 4, and z is an integer value of 5 or more.
-5340 (υ, C0C product), Toray Silicon S) (1
Examples include silicone surfactants such as 93 (Toshi product) and B 8424 (Goldschmidt product). The amount of such surfactant used is 0.1 to 2 weight more than the amount of aromatic polyisocyanate.

The isocyanurate ratio modification reaction in the present invention is carried out at a reaction temperature of 100°C or less, preferably 15°C to 70'C.
be. In the reaction, by using a surfactant, the isocyanurate reaction progresses effectively at a relatively low temperature, and the isocyanurate modified product produced is also uniformly dispersed in the reaction product, so the reaction can be easily carried out. The process progresses gradually and a stable and liquid isocyanurate modified product is obtained.

If the amount of catalyst is large or the reaction temperature is 100"C or higher, polymers of isocyanurate compounds or allo-77ate compounds are likely to be formed, resulting in decreased compatibility or gelation. be.

The reaction time, yield, quality, etc. of the modified aromatic polyisocyanate can be effectively controlled and adjusted by adjusting the type of catalyst and the amount thereof used. Therefore, the NCO content and viscosity of the modified aromatic polyisocyanate can be arbitrarily determined based on the NCO content at the time of termination of the reaction since it can be measured by a commonly used titration analysis.

As described above, the isocyanurate formation according to the present invention has advantages such as a small amount of catalyst and the ability to react at low temperature in a short time.

In producing isocyanurate from aromatic polyisocyanate according to the present invention, an acidic compound is used as a terminator, if necessary. For example, hydrochloric acid.

Phosphoric acid, dimethyl phosphate, trimethyl phosphate, triethyl phosphate, tricresyl phosphate, triphenyl phosphate,
Tributyl phosphate P-)luenesulfonic acid, P-)luenesulfo/dispersed methyl, xylene sulfonic acid, benzenesulfone, methanesulfonic acid, alkylbenzenesulfonic acid, dinaphthalene/disulfoy@, dinaphthalene monosulfonic acid, dinonylnaphthalene disulfone acid, dinonylnaphthalenedisulfonic acid, pen/diyl chloride,
Examples include acetyl chloride and similar compounds thereof.

The amount of the terminator used is 0.3 to 5 times equivalent, preferably 1.0 to 20 times equivalent, relative to the amount of catalyst.

When added during the isocyanurate reaction, the reaction solution also becomes cloudy. It is possible to promote stabilization of the modified aromatic polyisocyanate without causing any damage to the aromatic polyisocyanate.

This modified product is solvent-free and has stable quality, so it can be used not only for plastic foam and elastomer U4, but also for plastic foam and elastomer U4.
It is widely useful as a raw material for paints, adhesives, etc. The product obtained by reaction with p, f8 Mizuki compounds has flame retardant,
Demonstrates excellent performance in heat resistance, water resistance, toughness, etc.

Next, the present invention will be further explained in detail with reference to Examples, but the present invention is not limited to these.

In the examples, all "parts" and "chi" are "parts by weight" and "fi% by weight" unless otherwise specified.

Example, l Thermometer, stirrer, nitrogen seal Blue 1Jr: In a prepared 11-volume ground glass four-loaf flask, 500 parts of MR-200 as an aromatic polyisocyanate and L as a surfactant were added.
4.0 parts of -5340 to ancamine as a catalyst -54
1.0 part of triethyl phosphite as a cocatalyst.
0 parts, 2.0 parts of R-113 as a diluent, the catalyst was mixed with the diluent, and the air in the flask was replaced with nitrogen.
Heat to 50'Q without stirring, and after reacting for 3.5 hours, NC
The O content was measured to be 28.6%, and the reaction solution was a brown transparent liquid. 0.5 part of phosphoric acid was added as a terminator to this reaction solution, and the reaction was terminated after stirring at 50°C for 1 hour.

The obtained isocyanurate modified polyisocyanate is a brown transparent liquid with an NC0t content of 28.6% and a viscosity of 8.
A trimer was observed by infrared absorption spectrum at 50 cp/zs°C. No abnormalities were observed even after 6 months.

Examples 2 to 9 Reactions were carried out in the same manner as in Example 1 under the conditions shown in Table 1. The results are shown in Table 1 and Table 1-1.

Example 10 In a four-loaf flask similar to Example 1, MR-2001-
500 parts, 1,3-butanediol 6 as polyol
．． 1 part, replace the air in the flask with nitrogen, and
The reaction was carried out at 0°C for 2 hours. The NCO content was measured and found to be 29.4.

Next, 4.0 parts of L-5340 and -54 parts of ancamine were added.
A mixture of 0.7 parts of and 2.0 parts of FL-113 was added, 3.0 parts of triethyl phosphite was added, and the NCO content was measured after reaction at 50°C for 200 hours.26
．． It was 9%. 0.35 parts of acid was added to this reaction solution, and the reaction was completed after stirring at 50° C. for 1.0 hour.

The obtained modified isocyanurate is a brown transparent liquid with an NCO content of 26.9 and a viscosity of 4500 cP/25°C.
In this article, we introduced the triplet using infrared absorption spectra.

Regarding storage stability, no abnormality was observed even after 6 months.

Examples 11 to 18 Reactions were carried out in the same manner as in Example 10 under the conditions shown in Table 1. The results are shown in Table 1 and Table 1-1.

Comparative Examples 1 to 3 Comparative Examples 1 was carried out in the same manner as in Example 10, and Comparative Examples 2 and 3 were carried out in the same manner as in Example 1.
The reaction conditions, results, etc. are shown in Table 1 and Table 1-IK.

Notes in Table 1 below: Polymethylene polyphenyl polyisocyanate NC
O content 31.0+% Manufactured by Nippon Polyurethane Industries, product name Millionate M-200 (abbreviation 2) Tolylene diinocyanate (isomer ratio of 2,4 and 2.6 so: 20)
Manufactured by Nippon Polyurethane Industries, product name Coronate T-8
0 stands for 3) Silicone surfactant Manufactured by U, C, C, trade name 4) Polyoxygen/Propylene Glyco-#E-I2O.

Manufactured by Sanyo Chemical Industries, product name Sannix PP-200 5) Polyethylene glycol molecule t 400 Manufactured by Sanyo Chemical Industries, product name PgG 4006) Polyoxypropylene glycol molecule 1000 Manufactured by Sanyo Chemical Industries, product name Sannix PP-10000 7) Polyester polyol, hydroxyl value 265, manufactured by Schaider, trade name 8) 2,4,6-tris (dimethylaminomethyl)
Phenol Manufactured by A, C, I Company, Product Name 9 > N, N; -Chloroglopyr) Phosphate manufactured by Akzo, trade name 11)) Lichlorotrifluoroethane, manufactured by Mitsui-DuPont Fluorochemicals, trade name 12) Polyester polyol, hydroxyl value 235, manufactured by Jardil, trade name 13) Abbreviation for brown transparent liquid 14) Approximately 15) Approximately no abnormality z6) Brown transparent with some lumps occurring Approximately below margin Effects of the invention By the method of the present invention, isocyanurate can be easily and stably produced in a short time with a small amount of catalyst. A modified product can be obtained.

one! In addition, the nine modified product obtained by the method of the present invention is a polyinone anate modified product that is liquid and stable, has good compatibility with other resins, and contains an active isocyanate group at the end. By reacting these isocyanate groups with a compound having reactive activated water, a product with good workability, flame retardancy, heat resistance, and rigidity can be obtained.

Claims (1)

[Scope of Claims] 1. A trimerization catalyst, an organic phosphite, and a surfactant are added to an aromatic polyisocyanate and/or a partially urethanized aromatic polyisocyanate, and 20% by weight or less of the total isocyanate groups are added. Isocyanurate,
A method for producing a modified aromatic polyisocyanate having an isocyanurate ring, the method comprising adding a terminator if necessary. 2. As a partially urethanized aromatic polyisocyanate,
2. The production method according to claim 1, wherein an aromatic polyisocyanate is reacted with a hydroxyl group-containing compound having a molecular weight of 2,000 or less and a functional group number of 3 or less in an amount of 10% by weight or less of the total isocyanate groups.