JP6951012B2 - Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam - Google Patents

Description

The present invention comprises a polyol composition for rigid polyurethane foam containing 1-chloro-3,3,3-trifluoropropene (hereinafter, also referred to as HFO-1233zd) as an essential component as a foaming agent component, and a rigid polyurethane foam. More specifically, the present invention relates to a polyol composition for spray-foamed rigid polyurethane foam, and a method for producing spray-foamed rigid polyurethane foam.

Rigid polyurethane foam is a well-known material as a heat insulating material, a lightweight structural material, and the like. The rigid polyurethane foam is formed by mixing a polyol composition containing a polyol compound and a foaming agent as essential components and an isocyanate component, and foaming and curing the mixture. As one of the methods for producing a rigid polyurethane foam, there is a spray foaming method (for example, Patent Documents 1 and 2).

CFC-11 and other CFC compounds have been used as the foaming agent in the past, but since CFC-11 causes ozone layer depletion, their use was banned and switched to HCFC-141b. Has been switched to HFC-245fa and HFC-365mfc having an ozone depletion potential of zero, but the HFC-245fa and HFC-365mfc have a problem that GWP (global warming potential) is large. Therefore, development as a non-flammable HFO-1233zd foaming agent with a low ozone depletion potential and global warming potential is in progress.

For example, since a polyol composition containing HFO-1233zd has poor stock solution storage stability, attempts have been made to improve the stock solution storage stability of the polyol composition containing HFO-1233zd (for example, Patent Documents 3 to 3 to 3). 6).

Japanese Unexamined Patent Publication No. 2006-328172 Japanese Unexamined Patent Publication No. 2009-114288 Special Table 2011-500891 Special Table 2011-500892 Special Table 2011-500893 Special Table 2013-501844

Since the production of rigid polyurethane foam by the spray foaming method requires a rapid reaction between the polyisocyanate compound and the polyol compound, a highly active metal catalyst may be used to increase the reaction rate between the polyisocyanate compound and the polyol compound. ..

However, it has been found that the polyol composition containing the metal catalyst and HFO-1233zd has poor stock solution storage stability, and the activity of the desired metal catalyst for spray foaming may be lost during storage. If the activity of the metal catalyst desired for spray foaming is lost, the reaction rate of the polyisocyanate compound and the polyol compound decreases, which may make it difficult to produce a rigid polyurethane foam by the spray foaming method.

The present invention provides a polyol composition for rigid polyurethane foam, which contains a metal catalyst and HFO-1233zd but has good stock solution storage stability.

The polyol composition for rigid polyurethane foam of the present invention contains at least a polyol compound, a foaming agent, and a metal catalyst, and is mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam. The above-mentioned foaming agent contains HFO-1233zd, and the above-mentioned polyol composition contains calcium octylate.

According to the present invention, it is possible to provide a polyol composition for rigid polyurethane foam having good stock solution storage stability even if it contains a metal catalyst and HFO-1233zd.

<Polyol composition for rigid polyurethane foam>
The polyol composition for rigid polyurethane foam of the present embodiment (hereinafter, also simply referred to as a polyol composition) contains at least a polyol compound, a foaming agent, and a metal catalyst, and is foam-cured by mixing with an isocyanate component containing a polyisocyanate compound. A polyol composition for rigid polyurethane foam, wherein the foaming agent contains HFO-1233zd and the polyol composition contains calcium octylate.

According to the polyol composition of the present embodiment, it is possible to provide a polyol composition for rigid polyurethane foam having good stock solution storage stability even if it contains a metal catalyst and HFO-1233zd. The reason why the polyol composition of the present embodiment exerts such an effect is not clear, but it is considered as follows.

The metal catalyst reacts with fluorine derived from HFO-1233zd during storage of the undiluted solution to become a metal fluoride, which inactivates the catalytic ability. However, calcium octylate is highly reactive with fluorine, and fluorine is more reactive than the metal catalyst. Rigid polyurethane foam with good stock solution storage stability even if it contains a metal catalyst and HFO-1233zd because it can preferentially react with calcium derived from calcium octylate and prevent deactivation of the metal catalyst during storage. It is believed that a polyol composition for use can be provided.

[Polyol compound]
As the polyol compound, known polyol compounds for rigid polyurethane foam can be used without limitation. Examples of such polyol compounds include tertiary amino group-containing polyol compounds, aliphatic polyol compounds, and aromatic polyol compounds.

The tertiary amino group-containing polyol compound is an alkylene oxide, specifically, propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran, etc., using a primary or secondary amine as an initiator. It is a polyfunctional polyol compound obtained by ring-opening addition polymerization of one or more kinds.

Examples of the primary or secondary amine initiator which is an initiator of the tertiary amino group-containing polyol compound include aliphatic primary to secondary monoamines such as ammonia, methylamine and ethylamine, ethylenediamine and hexamethylene. Aliphatic primary to secondary polyamines such as diamine, N, N'-dimethylethylenediamine, aromatic primary to secondary mono to aniline, diphenylamine, toluenediamine, diphenylmethanediamine, N-methylaniline and the like. Examples thereof include alkanolamines such as polyamines, monoethanolamines and diethanolamines. The content of the tertiary amino group-containing polyol compound is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, based on the polyol compound. The tertiary amino group-containing polyol compound is effective in increasing the reactivity and expressing the physical properties, and in many cases, the increase in the reactivity is not observed when the content is less than 10% by weight, and the reactivity is high when the content exceeds 60% by weight. Too much of it may cause the foam to burn or crack.

Aliphatic polyol compounds include aliphatic or alicyclic polyfunctional active hydrogen compounds as polyol initiators, alkylene oxides, specifically propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran and the like. It is a polyfunctional oligomer obtained by ring-opening addition polymerization of one or more of the cyclic ethers, preferably PO or PO and EO.

Examples of the polyol initiator of the aliphatic polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, glycols such as neopentyl glycol, trimethylolpropane, and the like. Examples thereof include triols such as glycerin, tetrafunctional alcohols such as pentaerythritol, polyfunctional alcohols such as sorbitol and shoe cloth, and water.

Examples of the aromatic polyol compound include a polyol compound obtained by adding the above-mentioned alkylene oxide to a polyfunctional active hydrogen compound having an aromatic ring in the molecule, an ester polyol compound of an aromatic polycarboxylic acid and a polyfunctional alcohol, and the like. Will be done.

As the polyol compound obtained by adding the above-mentioned alkylene oxide to the polyfunctional active hydrogen compound, at least one of PO, EO and SO, preferably PO or PO and EO, is added to hydroquinone, bisphenol A, Mannig and the like. Specific examples thereof include a ring-opened compound.

Specific examples of the ester polyol compound of the aromatic polycarboxylic acid and the polyfunctional alcohol include an ester polyol compound obtained by reacting terephthalic acid, orthophthalic acid, isophthalic acid and the like with a hydroxyl group terminal alcohol of ethylene glycol, diethylene glycol and the like. ..

The polyol compound preferably has a hydroxyl value of 50 to 1500 mgKOH / g. Among these polyol compounds, when a tertiary amino group-containing polyol compound or an aliphatic polyol compound is used, the effect of lowering the viscosity of the polyol composition can be obtained.

The polyol compound includes ethylene glycol (EG), triethylene glycol, diethylene glycol (DEG), 1,4-butanediol, 1,6-hexanediol (1,6-HD), neopentyl glycol, diethylene glycol, and dipropylene glycol. It may contain glycol such as (DPG), triol such as glycerin and trimethylolpropane.

[Blowing agent]
The foaming agent contains HFO-1233zd, which has a low ozone depletion potential and a global warming potential and is not flammable.

The foaming agent preferably further contains water. The vapor pressure of the polyol composition can be reduced by the addition of water. The water content is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the total amount of the polyol compound.

The foaming agent may further contain a known foaming agent for rigid polyurethane foam.

The content of the foaming agent is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the total polyol compound.

[Metal catalyst]
As the metal catalyst, a known metal catalyst that promotes urethanization and urea conversion reactions can be used without particular limitation. Examples of the metal contained in the metal catalyst include tin, titanium, lead, bismuth, cobalt, and potassium.

More specific examples of metal catalysts include tin compounds such as dibutyltin dilaurate, dioctyltin malate, tin octylate and dibutyltin oxide, titanium compounds such as tetrabutyl titanate, and lead compounds such as lead naphthenate and lead octylate. , Bismus compounds such as bismuth neodecanoate and bismuth octylate, cobalt compounds such as cobalt naphthenate and cobalt octylate, and potassium compounds such as potassium octylate, potassium acetate and potassium formate. These metal catalysts can be used alone or in combination.

The amount of the metal catalyst in the polyol composition is 0.05% by weight as an active ingredient (metal salt content excluding the diluting component) with respect to 100 parts by weight of the polyol compound from the viewpoint of obtaining a desired reaction rate by the spray foaming method. The above is preferable, and 0.1% by weight or more is more preferable. However, if the reaction rate is too high, workability may be impaired due to clogging of the mixing device, etc. Therefore, the amount of the metal catalyst in the polyol composition is preferably 10% by weight or less with respect to 100 parts by weight of the polyol compound. 5, 5% by weight or less is more preferable, and 4% by weight or less is further preferable.

[Calcium octylate]
The amount of calcium octylate in the polyol composition is 0.05 parts by weight or more as an active ingredient (calcium octylate excluding diluted components) with respect to 100 parts by weight of the polyol compound from the viewpoint of stock solution storage stability. Preferably, 0.1 part by weight or more is more preferable, and 0.2 part by weight or more is further preferable. However, if a large amount of calcium octylate is contained in the polyol composition, the activity of other metal catalysts may decrease. Therefore, the amount of calcium octylate in the polyol composition is the polyol compound 100. The active ingredient (calcium octylate excluding the diluting component) is preferably 2 parts by weight or less, and more preferably 1 part by weight or less with respect to parts by weight.

[Other ingredients]
The polyol composition may contain a known catalyst other than the metal catalyst for rigid polyurethane foam, a foam stabilizer, a flame retardant, a compatibilizer, a plasticizer, a colorant, an antioxidant and the like.

Known catalysts other than the metal catalyst include N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine (Kao. No. 1), N, N-alkylpolyalkylene polyamines such as N, N', N', N "-pentamethyldiethylenetriamine (Kao. No. 3), 1-isobutyl-2-methylimidazole, 1-methylimidazole, 1,2-dimethyl Imidazole, etc., diazabicycloundecene (DBU), N, N-dimethylcyclohexylamine (polycat-8), triethylenediamine, N-methylmorpholin, bis (2-dimethyl-aminoethyl) ether (NIAX-A-1) ) And other tertiary amines can be exemplified as the urethanization reaction catalyst.

As the defoaming agent, a known defoaming agent for rigid polyurethane foam can be used without limitation. As the defoaming agent, polydimethylsiloxane and a graft copolymer or block copolymer of polydimethylsiloxane and polyalkylene oxide are usually used. As the polyalkylene oxide, polyethylene oxide having an average molecular weight of 5000 to 8000, polypropylene oxide, a random copolymer of ethylene oxide and propylene oxide, or a block copolymer of ethylene oxide and propylene oxide are used.

Examples of the flame retardant include metal compounds such as halogen-containing compounds, organic phosphoric acid esters, antimony trioxide, and aluminum hydroxide. For these flame retardants, for example, excessive addition of organic phosphoric acid ester may reduce the physical properties of the obtained rigid polyurethane foam, and excessive addition of metal compound powder such as antimony trioxide may cause foaming behavior of the foam. May cause problems such as the appearance of the problem, and the amount of addition is limited to the range that does not cause such problems.

Examples of the plasticizer include halogenated alkyl esters of phosphoric acid, alkyl phosphoric acid esters, aryl phosphoric acid esters, phosphonic acid esters and the like, and specific examples thereof include tris (2-chloroethyl) phosphate (CLP, manufactured by Daihachi Chemical Co., Ltd.). ), Tris (β-chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical Co., Ltd.), tributoxyethyl phosphate (TBEP, manufactured by Rhodia), tributyl phosphate, triethyl phosphate, cresylphenyl phosphate, dimethylmethylphosphonate, etc. can be exemplified. , One or more of these can be used. The amount of the plasticizer added is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the polyol composition. If this range is exceeded, problems such as insufficient plasticizing effect and deterioration of the physical characteristics of the foam may occur.

<Manufacturing method of rigid polyurethane foam>
The method for producing a rigid polyurethane foam of the present embodiment is a method for producing a rigid polyurethane foam in which the polyol composition and a polyisocyanate compound are mixed by a spray device and reacted to form a rigid polyurethane foam.

In the method for producing a rigid polyurethane foam of the present embodiment, since the polyol composition having good stock solution storage stability even if it contains a metal catalyst and HFO-1233zd is used, the polyol composition after storage can also be spray-foamed. Can produce rigid polyurethane foams.

As the isocyanate component, liquid MDI is used because it is easy to handle, the reaction speed is excellent, the physical characteristics of the obtained rigid polyurethane foam are excellent, and the cost is low. Liquid MDI includes crude MDI (c-MDI) (44V-10, 44V-20L, etc. (manufactured by Sumika Cobestro Urethane Co., Ltd.)), uretonimine-containing MDI (millionate MTL; manufactured by Nippon Polyurethane Industry Co., Ltd.), etc. used. Among these polyisocyanate compounds, the use of crude MDI is particularly preferable because it has excellent physical properties such as mechanical strength of the rigid polyurethane foam to be formed and is inexpensive.

In addition to the liquid MDI, other isocyanate components may be used in combination. Di-polyisocyanate compounds well known in the technical field of polyurethane can be used without limitation.

In the method for producing a rigid polyurethane foam, the isocyanate group / active hydrogen group equivalent ratio (NCO index) in the mixture of the polyol composition and the isocyanate component is preferably 1.0 to 2.2, preferably 1.1 to 2. 1 is more preferable, and 1.2 to 2.0 is further preferable.

In the production method of the present embodiment, a generally well-known spray foaming / molding apparatus for polyurethane is appropriately used to form a shape according to the intended use.

Hereinafter, examples and the like that specifically show the configuration and effects of the present invention will be described.

<Evaluation method>
[Initial gel time]
The polyol composition whose temperature was adjusted to 15 ° C. and the isocyanate component were stirred and mixed for 4 seconds with a stirrer in which the stirring blade rotates at 3000 rpm, and the gel time of the foamed polyurethane foam was measured. The gel time was defined as the time when the foam started stringing when the glass rod was inserted into the crown of the foam being foamed.

[Gel time after storage at 40 ° C for 30 days]
The polyol composition was cured in an oven set at 40 ° C. for 30 days while being sealed in a plastic container, and then the cured polyol composition and isocyanate components whose temperature was adjusted to 15 ° C. were stirred at 3000 rpm. The gel time of the foamed polyurethane foam was measured by stirring and mixing with a rotating stirrer for 4 seconds.

[Gel time delay]
After storage at 40 ° C. for 30 days, the value of the initial gel time was subtracted from the value of the gel time to obtain the time (gel time delay) in which the gel time was delayed. The smaller the gel time delay, the better the storage stability.

<Examples 1 to 8 and Comparative Examples 1 to 3>
A polyol composition is prepared with the compositions shown in Tables 2 and 3 using the raw materials shown in Table 1, and the weight ratio of the polyol composition to the polyisocyanate shown in Table 1 is shown in Tables 2 and 3. The initial gel time, the gel time after storage at 40 ° C. for 30 days, and the gel time delay were determined by the above method. The measurement results are shown in Tables 2 and 3.

As can be seen from Tables 2 and 3, it can be seen that the polyol composition containing calcium octylate has a small gel time delay, and thus the storage stability of the polyol composition is improved. On the other hand, zinc octylate had no effect.

Claims (5)

A polyol composition for a rigid polyurethane foam containing at least a polyol compound, a foaming agent, and a metal catalyst, which is mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam.
The foaming agent contains HFO-1233zd and
The polyol composition contains calcium octylate and
Wherein the metal catalyst is, Te tiger butyl titanate, potassium lead naphthenate, lead octylate, bismuth neodecanoate, bismuth octylate, cobalt naphthenate, cobalt octylate, iron acetylacetonate, bismuth neodecanoate, octoate, potassium acetate, and formate A polyol composition for rigid polyurethane foam, which is one or more selected from the group consisting of potassium. The polyol composition for rigid polyurethane foam according to claim 1, wherein the amount of the metal catalyst in the polyol composition is 0.05% by weight or more and 10% by weight or less with respect to 100 parts by weight of the polyol compound. The polyol composition for rigid polyurethane foam according to claim 1 or 2, wherein the amount of the calcium octylate in the polyol composition is 0.05 parts by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the polyol compound. The polyol composition for rigid polyurethane foam according to any one of claims 1 to 3, which is used for producing a rigid polyurethane foam by a spray foaming method. A method for producing a rigid polyurethane foam, wherein the polyol composition for rigid polyurethane foam according to any one of claims 1 to 4 and a polyisocyanate compound are mixed by a spray device and reacted to obtain a rigid polyurethane foam.