JPS6377918A - Polyurethane production catalyst - Google Patents

Abstract

PURPOSE:To obtain the title catalyst which can give a long cream time and a short mold release time, by mixing specified two compounds together. CONSTITUTION:The title catalyst is obtained by mixing 95-5pts.wt. compound (A) of formula I with 5-95pts.wt. compound (B) selected from among 1,4- diazabicyclo(2.2.2)-octane or its derivative (a) with an organic or inorganic acid (e.g., formic acid), an organotin compound (b) of formula II (wherein R1-2 are each a 1-16C alkyl and R3-4 are each a 1-20C alkyl) and an organotin compound (C) of formula III. A polyurethane is obtained by mixing 100pts.wt. polyol with a polyisocyanate, water, 0.1-10pts.wt., preferably, 0.5-5pts.wt. said catalyst and, optionally, a blowing agent, surfactant, flame retardant, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst used in the production of polyurethanes such as soft, hard, semi-hard or elastomers. More specifically, a catalyst for producing polyurethane that has an ether bond and a tertiary amino group in the molecule, has an extremely low odor and low temperature dependence, and allows the ureation reaction to proceed preferentially; The present invention also relates to a catalyst for producing polyurethane which is characterized in that it is used in combination with a catalyst for producing polyurethane which preferentially promotes a urethanization reaction with low temperature dependence.

C. Conventional technology] Conventionally, tin-based, iron-based, titanium-based, manganese-based, and other metal-based catalysts and amine-based catalysts have been used as catalysts for polyurethane production. It is already widely known that N-methylmorpholine, N-methylmorpholine,
N-ethylmorpholine, triethylenediamine, NIN
, N', N"-tetramethyl-1,3-propylenediamine, N, N, N"Nl-tetramethyl-1,6
-hexanediamine, N,N,N",N',N"-pentamethyldiethylenetriamine, bis-(2-dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine, N,
Compounds such as N-dimethylbenzylamine and N,N,N'-trimethylaminoethylpiperazine are used as catalysts for polyurethane production.

Among these polyurethane production catalysts, N, N,
N', N', N''-pentamethyldiethylenetriamine or bis-(2-dimethylaminoethyl) ether can be mentioned.

This foaming catalyst plays an extremely important role in developing the physical properties of a polyurethane compound by promoting the production of a polyurethane compound having a more homogeneous bond structure in the production of a polyurethane compound.

In addition, among the catalysts for polyurethane production mentioned above, catalysts that relatively promote the urethanization reaction (resinization catalysts) include 1.
．． 4-Diazabicyclo(2,2,2)octane, 1.4
Examples include derivatives of -diazabicyclo(2,2,2)octane with organic and/or inorganic acids, dibutyltin dilaurate, tin octoate, and the like.

This resin conversion catalyst is used in the production of polyurethane compounds.
Since it mainly contributes to the reaction of increasing the molecular weight of molecules, it plays an extremely important role in improving productivity by shortening the demolding time of products.

[Problem that the invention seeks to solve]

However, the foaming catalysts for producing polyurethane that have been developed so far have various problems. That is,
N, N, N', N', N''-pentamethyldiethylenetriamine, bis-(2-dimethylaminoethyl) ether has a pungent odor due to its high vapor pressure and extremely high volatility. This significantly worsens the working environment in the polyurethane manufacturing process.

N,N',N',N'-pentamethyldiethylenetriamine has a large temperature dependence, so at the initial stage of foaming, that is, when the reaction temperature is low (specifically, when the resin raw material temperature is around 40°C or lower), It significantly promotes the urea formation reaction (foaming reaction), but as the reaction temperature rises, it gradually promotes the urethane formation reaction (resin formation reaction), making it difficult to maintain the balance between urethane bonds and urea bonds, and Because the degree of dispersion of the urethane bonds and urea bonds formed during the initial stage and the degree of dispersion of the urethane bonds and urea bonds formed at the end of the reaction are significantly different, it is often difficult to express the designed physical properties of the resin.

Furthermore, when N, N, N', N', N'-pentamethyldiethylenetriamine and bis-(2-dimethylaminoethyl) ether are used alone at the temperature of the urethane resin raw materials, they start mixing and stirring the raw materials. Since the time (cream time) from when the foaming process begins until just before foaming begins is extremely short, the necessary amount of addition is used to ensure the desired cure time (time when demolding is possible) in the polyurethane resin manufacturing process. In this case, it becomes impossible to secure the raw material stirring time necessary for uniformly mixing the urethane resin raw materials, and the necessary resin physical properties are no longer developed.

Furthermore, even when used in combination with other tertiary amine-based urethane catalysts or metal-based urethane catalysts, the tendency for cream time to shorten remains.

For this reason, even if you try to use it in combination with a resin conversion catalyst to improve productivity, the cream time will be shortened, making it impossible to increase the amount of catalyst in the manufacturing process, and in fact, it will be impossible to increase productivity. making it extremely difficult.

Next, regarding catalysts for producing polyurethane that are considered to be catalysts for promoting ureation reactions (foaming catalysts),
-65050, the following formula RR (In the above formula, R is a methyl or ethyl group, n is 2, X is 1, y is 0 or l when X is 1, and 2 is O when y is O and 1 when y is 1), and specifically, N-2-dimethylaminoethyl-N
, N', N'-)limethyl-bis(2-aminoethyl)ether is used as a catalyst for producing polyurethane.

However, N, N, N', N', N''
-Compared to pentamethyldiethylenetriamine and bis-(2-dimethylaminoethyl) ether, it cannot be said that it has a necessary and sufficient re-time.

[Means for solving problems]

In order to solve the above problems, the present inventors have conducted intensive studies and found that a compound having two ether bonds and a tertiary amino group in the molecule has extremely low odor, and
Although it is a foaming catalyst that has suitable activity as a catalyst for producing polyurethane and promotes the ureation reaction, it does not contain the aforementioned foaming catalysts, namely, N, N, N', N'',
N”-pentamethyldiethylenetriamine, bis-(2
-dimethylaminoethyl) ether, N'-2-dimethylaminoethyl-N,N'',N'-)limethylbis(
When compared with 2-aminoethyl) ether, it was found that the ream time was sufficiently long, and a catalyst for producing polyurethane was completed.

Furthermore, this polyurethane production catalyst, 1,2-bis(2
-dimethylaminoethoxy)ethane and 1,4-diazabicyclo(2,2,2)octane, derivatives of 1,4-diazabicyclo(2,2,2)octane with organic and/or inorganic acids, dibutyltin dilaurate, octane By combining a resin-forming catalyst such as tin acid, it is possible to produce a polyurethane compound with a more homogeneous bond structure. A combined catalyst for polyurethane production has been found, which allows the amount of catalyst for polyurethane production to be increased without causing any problems.

That is, the present invention comprises 95 to 5 parts by weight of a compound represented by the following general formula, and (a) 1
．． Diazabicyclo(2,2,2) with 4-diazabicyclo(2,2,2)octane or its organic or inorganic acids
2) Octane derivative, (b) the following formula (wherein R1 and R2 are alkyl groups having 1 to 16 carbon atoms, R3
, R4 is an alkyl group having 1 to 20 carbon atoms) The present invention provides a catalyst for producing polyurethane comprising 5 to 95 parts by weight of a compound selected from the group.

(a) 1,4-diazabicyclo(2,2,2)octane or its derivative; (b); (C) organotin catalyst is a compound represented by the above formula, either alone or in combination of two or more; Can be used with.

Examples of the above organic acid or inorganic acid derivatives include formic acid, acetic acid,
Propionic acid, butyric acid, valeric acid, oleic acid, p-toluenesulfonic acid, mesylsulfonic acid, 2-ethylhexanoic acid, isodecanoic acid, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, acrylic acid, Maleic acid, dodecenylsuccinic acid, hexahydrophthalic acid, 3
．． 6-Nindomethylenetetrahydrophthalic acid, phthalic acid, lactic acid, malic acid, tartaric acid, citric acid, salicylic acid, benzoic acid, pyruvic acid, cyanoacetic acid, chloroacetic acid, phenol, cresol, xylenol, naphthol, catechol, hydroquinone, resorcinol, bisphenol Organic acids such as , pyrogallol, benzenesulfonic acid, xylene sulfonic acid, dodecylbenzenesulfonic acid, naphthalene sulfonic acid, monopropylnaphthalene sulfonic acid, dipropylnaphthalene sulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, phosphorous acid , salts of 1,4-diazabicyclo(2,2,2)octane derived from inorganic acids such as monoalkyl phosphoric acid, dialkyl phosphoric acid, nitric acid, etc., particularly preferably derived from formic acid, acetic acid, 2-ethylhexanoic acid. be done1
, 4-diazabicyclo(2,2,2)octane salts.

In the compounds defined by the above mountains) and (C),
R3 and R2 having 1 to 4 carbon atoms are particularly preferably used in the present invention, and P and R4 are particularly preferably having 8 to 12 carbon atoms.

The amount of the combined catalyst of the present invention used is preferably in the range of 0.1 to 10 parts, particularly preferably 0.5 to 5 parts, based on 100 parts of the polyol used for producing polyurethane. However, it is also possible to use it outside this range for the purpose of optimizing the polyurethane manufacturing process by controlling the amount of catalyst added.

The polyisocyanate that can be used when producing polyurethane using the novel catalyst of the present invention may be any generally known polyisocyanate, such as 2°4-tolylene diisocyanate, 2°4-tolylene diisocyanate,
．． 6-) lylene diisocyanate, 414゛-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, xylylene diisocyanate, cyclohexane diisocyanate, toluidine diisocyanate,
p-phenylene diisocyanate, o-phenylene diisocyanate, m-phenylene diisocyanate, 1.
5-naphthylene diisocyanate, 4.4'-biphenyl diisocyanate, 3.3'-dimethylbiphenyl-
Examples include 4,4''-diisocyanate, 3,3'-dimethoxybif22-4,4''-diisocyanate, and the like.

As polyols that can be used when producing polyurethane using the novel catalyst of the present invention, generally known polyester polyols, polyether polyols, etc. can be used. For example, ordinary dibasic acids and polyhydric Polyester polyols manufactured from alcohol,
Polyether polyols obtained by adding ethylene oxide or propylene oxide to polyhydric alcohols such as glycol, glycerin, pentaerythritol, trimethylolpropane, and sucrose, or triethylenediamine, tolylenediamine, 1,6-hexanediamine, 1 Examples include amine polyols obtained by adding ethylene oxide or propylene oxide to polyvalent amines such as 3-propione diamine and isophorone diamine.

Additionally, polymer polyols are organic polyol reactants that can be used in producing polyurethane foams. It is made by polymerizing one or more ethylenically unsaturated monomers dissolved or dispersed in any of the other types of polyols mentioned herein in the presence of a free radical catalyst. Representative examples of ethylenically unsaturated monomers include ethylene, propylene, acrylonitrile, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene, methyl methacrylate, and butadiene.
Such compositions generally include peroxides, versalphates, which may be used alone or in combination.
using any of the radical generating initiators including percarbonates, perborates and azo compounds at about 40°C and about 1
It is made by polymerizing monomers in a base polyol at temperatures between 50°C and 50°C.

When producing polyurethane using the novel catalyst of the present invention, additives such as CFCl3 and CHzC may be used as necessary.
Foaming agents such as lz, surfactants such as organopolysiloxane, flame retardants such as halogenated alkyl compounds and halogenated phosphorus compounds, and other additives can be used. The types and amounts of these additives can be sufficiently used within the types and ranges commonly used.

[Effect]

The present invention uses 1,2-bis(2-dimethylaminoethoxy)ethane as a foaming catalyst, and as a resinization catalyst,
By using a compound selected from 1.4-diazabicyclo(2,2,2)octane, its organic and/or inorganic acid derivatives, and organotin compounds, improvements can be made in the manufacturing process and in the physical properties of polyurethane resin products. The high-impact cream time can be extended as necessary and significantly longer than currently used catalysts for polyurethane production.

1,2-bis(2-dimethylaminoethoxy)ethane, which is used as one of the catalyst combinations for producing polyurethane of the present invention, has a relatively larger molecular weight than those previously known, and Since there are two oxygen atoms, which are considered to be highly polar, in the molecule, it has a low vapor pressure, a high boiling point, and is thought to have extremely low odor.

In addition, this catalyst has a (CL)J- group in the molecule, and has appropriate activity as a catalyst for polyurethane production, and furthermore, an oxygen atom with a high affinity for water is present in the molecule. Therefore, it is thought that it becomes a foaming catalyst that mainly promotes the reaction between isocyanate groups and water (ureation reaction).

Furthermore, 1,4-diazabicyclo(2,2,2)octane, diazabicyclo(2,2,2)octane derivatives consisting of its organic acid and/or inorganic acid, and organotin compounds,
1. Like 2-bis(2-dimethylaminoethoxy)ethane, it usually has a necessary and sufficiently long cream time when used as a catalyst for polyurethane production.
By using it in combination with 2-bis(2-dimethylaminoethoxy)ethane, it improves the ability to fill polyurethane resin into molds with complex shapes, improves resin physical properties such as dimensional shrinkage immediately after demolding and at low temperatures, At the same time, it is expected that demolding time will be shortened, that is, productivity will be improved, by increasing the amount of catalyst for producing polyurethane without causing any problems in the production process.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples.

Example 1 and Comparative Examples I~■ The mixing ratios of raw materials for producing polyurethane were as shown in Table 1, and urethane foaming was carried out according to the usual procedure. That is, polyol, water, surfactant, catalyst, blowing agent, and polyisocyanate were mixed, stirred, and poured into a paper cup kept at 20°C to form a urethane foam (the top of the paper cup was open). .

Evaluation results are shown in Tables 2 and 3.

Cream time in the table refers to the time from the start of mixing and stirring the raw materials until just before foaming begins, and gel time refers to the time when a sharp object is brought into contact with the polyurethane foam surface and then pulled away. The tack-free time is the time required for the polymerization to progress sufficiently before a thread can be drawn from the polyurethane foam, and the tack-free time is the time when the resin no longer adheres to the fingertips when the polyurethane foam is touched with a finger (tack-free time). ) refers to the time until

Table 1 $1: Aromatic amine polyol (OH
V・450) Rate 2: Sugar-based polyether polyol manufactured by Sumitomo Bayer Urethane (011V=530)*3; Glycerin-based polyether polyol manufactured by Mitsui Toatsu Chemical (OHV=
235) Umbrella 4: Surfactant manufactured by Nippon Unicar Umbrella 5: Isocyanate manufactured by Mitsui Toatsu Chemical ■ (Crude MD
Mixture of I and TDI prepolymer, NCO% = 31) Table 3 Comparison of resin physical properties of polyurethane resins molded using catalysts for polyurethane production of Examples and Comparative Examples I to ■ Note (1) Length 2 m A raw material mixture was injected into one end of the mold, and a polyurethane resin was molded under the following molding conditions. The length of the obtained panel (molded product) was defined as mold filling property. Here, the amount of the catalyst for producing polyurethane was adjusted so that the gel time was approximately 90 seconds.

Molding condition Mold: Size = 2mx12cmx3cm.

Temperature = 40°C, mold angle -3° Mixing: Lab automixer 10.000 rpm x 5 seconds Liquid temperature: 20°C Injection amount: 240g (2) Using the same raw materials, quickly remove the molded polyurethane resin from the mold. The surface hardness of the resin was measured using a Shore C hardness needle, and the time when the measured hardness reached 50 was defined as the demoldable time. Here, the amount of the catalyst for producing polyurethane was adjusted so that the gel time was approximately 90 seconds.

Molding conditions Mold: Size - 20cm x 20cm x 5
C11s temperature -40℃ Mixing: Lab Automixer 10, OOOrpm x 5 seconds Liquid temperature: 20℃ Injection amount: 50g +3 (measure this value as T (m
m).

The swelling ratio was calculated by substituting the measured value T into the above equation.

Note that 49.5 in the formula is the thickness (lIIll) of the polyurethane resin when demolding time is 30 minutes.

(4) Using the raw materials shown in Table 1, molded polyurethane resins were left in an environmental test chamber at -30°C for 24 hours, and then the appearance of the resins was visually judged.

Judgment criteria ×: The entire resin is clearly deformed.

○: Deformation or distortion is observed in a portion of the resin or in one direction.

◎: No deformation, distortion, etc. are observed.

Molding conditions Mold: Size = 20cw x 20cm x 5
cta.

Temperature = 40℃ Mixing: Lab Automixer 10, OOOrpm x 5 seconds Liquid temperature: 20℃ Injection R: 50g Demolding time: 30 minutes Example■ Odor evaluation was performed on the catalyst of the present invention and the comparative catalyst.

- Odor check test method for amine catalysts Amine-based urethane catalysts were dissolved in MN-700 (glycerin-based polyether polyol manufactured by Mitsui Toatsu Chemical Co., Ltd., molecular weight approximately 700) to a predetermined concentration, and a selected odor panel was prepared. −
It was evaluated by 50 people.

The results are shown in Table 4. The criteria for odor evaluation are as follows.

◎: Almost no odor O: Slight odor Δ: Odor ×: Strong odor Table 4 Note that the amount of catalyst added is usually 10% or less (preferably 1 to
5%), and from Table 4 it can be seen that the novel catalyst for polyurethane production of the present invention can significantly improve the working environment.

〔Effect of the invention〕

As specifically shown in the Examples, the catalyst for producing polyurethane of the present invention is a combination catalyst that has a necessary and sufficient re-time.

In cases where the filling properties of the resin greatly affect the performance of the product (for example, rigid polyurethane resin for electric refrigerator insulation), the fluidity and reactivity must be such that it can be completely filled into molds with complex shapes. is required for polyurethane raw materials, especially catalysts for polyurethane production. In general, if the reaction is carried out using only a resin-forming catalyst such as diazabicyclo(2,2,2)octane, which preferentially promotes the urethane-forming reaction (this is called a resin-forming reaction), the foaming/resin-forming reaction will occur. As the reaction progresses without the balance being maintained, the fluidity of the resin cannot be ensured, and the reaction ends before the mold can be completely filled with resin, which not only increases the defective rate of the product but also increases the Problems arise such as swelling during molding and deformation of the product due to changes over time (see Table 3, Comparative Example I).

In order to solve these problems, foaming catalysts/resinization catalysts are generally used in combination, but since the use of foaming catalysts tends to shorten the cream time, it is necessary to If a large amount is used to shorten mold time, it becomes difficult to stir the raw materials, which has the disadvantage of making it impossible to manufacture polyurethane resin due to the work process (Table 2).
Comparative Examples n, m, see Table 3 Comparative Examples n, m).

However, since the catalyst for polyurethane production of the present invention has a necessary and sufficient lead time compared to conventional products,
It becomes possible to use a large amount, and while maintaining product physical properties, demolding time can be shortened and productivity can be improved (see Example I in Table 2 and Example I in Table 3).

Furthermore, by combining a polyurethane production catalyst with a high vapor pressure, it has become possible to create a low-bromination catalyst.

As a result, the working environment in the polyurethane manufacturing process can be significantly improved.

Claims (1)

[Scope of Claims] 95 to 5 parts by weight of a compound represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼, and (a) 1,4-diazabicyclo(2,2,2)octane or its organic acid or Diazabicyclo (
2,2,2) Octane derivatives, (b) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are alkyl groups with 1 to 16 carbon atoms,
(R_3, R_4 are alkyl groups having 1 to 20 carbon atoms) (c) Organotin compound represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R_1, R_2, R_3, R_4 are the above) A catalyst for polyurethane production comprising 5 to 95 parts by weight of a compound selected from the group consisting of organotin compounds represented by (same as).