JP2017206584A - Polyol composition for rigid polyurethane foam and manufacturing method of rigid polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition for rigid polyurethane foam containing a metal catalyst and having excellent raw liquid storage stability even if HFO-1233zd is used as a foaming agent.SOLUTION: A polyol composition for rigid polyurethane foam includes at least a polyol compound, a foaming agent and a metal catalyst, and is configured to be mixed with an isocyanate component including a polyisocyanate compound, and then foamed and hardened to produce rigid polyurethane foam. The foaming agent includes 1-chloro-3,3,3-trifluoropropene. The polyol composition includes octylic acid calcium.SELECTED DRAWING: None

Description

  The present invention relates to 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 rigid polyurethane foam. More specifically, the present invention relates to a polyol composition for spray foamed rigid polyurethane foam, and a method of producing a 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. Such a 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 then foaming and curing the mixture. One of the methods for producing rigid polyurethane foam is a spray foaming method (for example, Patent Documents 1 and 2).

  In the past, CFC-11 and other fluorocarbon compounds were used as the foaming agent, but the use of CFC-11 was prohibited because it caused destruction of the ozone layer, and it was switched to HCFC-141b. Are switched to HFC-245fa and HFC-365mfc, which have an ozone layer depletion coefficient of zero, but the HFC-245fa and HFC-365mfc have a problem that the GWP (global warming potential) is large. Therefore, development as a foaming agent of HFO-1233zd, which has a low ozone layer depletion coefficient and a global warming coefficient and is not flammable, is in progress.

  For example, since the 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). 6).

JP 2006-328172 A JP 2009-114288 A Special table 2011-500891 gazette Special table 2011-500892 gazette Special table 2011-50093 gazette Special table 2013-501844 gazette

  In the production of rigid polyurethane foam by the spray foaming method, a rapid reaction between the polyisocyanate compound and the polyol compound is required, and therefore a metal catalyst having high activity may be used to increase the reaction rate between the polyisocyanate compound and the polyol compound. .

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

  The present invention provides a polyol composition for rigid polyurethane foam having good stock solution storage stability even when it contains a metal catalyst and HFO-1233zd.

  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 polyol composition contains HFO-1233zd, and the polyol composition contains calcium octylate.

  ADVANTAGE OF THE INVENTION According to this invention, even if it contains a metal catalyst and HFO-1233zd, the polyol composition for rigid polyurethane foams with favorable stock solution storage stability can be provided.

<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 mixed with an isocyanate component containing a polyisocyanate compound to effect foam curing. It is a polyol composition for rigid polyurethane foams that forms a rigid polyurethane foam, wherein the foaming agent contains HFO-1233zd, and the polyol composition contains calcium octylate.

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

  The metal catalyst reacts with fluorine derived from HFO-1233zd during storage of the stock solution to become a metal fluoride and deactivates the catalytic ability. However, calcium octylate is highly reactive with fluorine, and fluorine is more than metal catalyst. Rigid polyurethane foam with good storage stability even when it contains a metal catalyst and HFO-1233zd because it can react preferentially with calcium derived from calcium octylate and prevent deactivation of the metal catalyst during storage It is believed that a polyol composition 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 using a primary or secondary amine as an initiator, specifically, propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran or the like. 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 that is an initiator of the tertiary amino group-containing polyol compound include aliphatic primary and 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, etc. Illustrative are alkanolamines such as polyamines, monoethanolamine and diethanolamine. The content of the tertiary amino group-containing polyol compound is preferably 10 to 60% by weight and more preferably 20 to 50% by weight in the polyol compound. Tertiary amino group-containing polyol compounds are effective in increasing reactivity and manifesting physical properties. When the amount is less than 10% by weight, the increase in reactivity is often not observed. When the amount exceeds 60% by weight, the reactivity is high. If it becomes too much, it may cause foam burns or cracks.

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

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

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

  As a polyol compound obtained by adding the above-mentioned alkylene oxide to a polyfunctional active hydrogen compound, hydroquinone, bisphenol A, Mannich or the like is added to at least one of PO, EO, SO, preferably PO or PO and EO. Specific examples are compounds having ring-opening addition.

  Specific examples of ester polyol compounds of aromatic polycarboxylic acids and polyfunctional alcohols include ester polyol compounds obtained by reacting hydroxyl-terminated alcohols of terephthalic acid, orthophthalic acid, isophthalic acid, etc. with ethylene glycol, diethylene glycol, etc. .

  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, an effect of reducing the viscosity of the polyol composition can be obtained.

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

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

  The foaming agent preferably further contains water. By adding water, the vapor pressure of the polyol composition can be reduced. The water content is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the total 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 said metal catalyst, the well-known metal catalyst which accelerates | stimulates urethanation and a urea-ized reaction can be used without 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 dibutyltin dilaurate, dioctyltin malate, tin compounds such as tin octylate and dibutyltin oxide, titanium compounds such as tetrabutyltitanate, lead compounds such as lead naphthenate and lead octylate. Bismuth 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 are 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 dilution components) with respect to 100 parts by weight of the polyol compound from the viewpoint of obtaining a desired reaction rate by spray foaming. 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, and 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 wt% or less is more preferable, and 4 wt% or less is still more preferable.

[Calcium octylate]
From the viewpoint of stock solution storage stability, 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. Preferably, 0.1 part by weight or more is more preferable, and 0.2 part by weight or more is still more preferable. However, if the polyol composition contains a large amount of calcium octylate, the activity of the other metal catalyst may be reduced. Therefore, the amount of calcium octylate in the polyol composition is determined by the polyol compound 100. 2 parts by weight or less is preferable and 1 part by weight or less is more preferable as an active ingredient (calcium octylate excluding diluted components) 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-alkylpolyalkylenepolyamines such as N, N ′, N ′, N ″ -pentamethyldiethylenetriamine (Kao. No. 3), 1-isobutyl-2-methylimidazole, 1-methylimidazole, 1,2-dimethyl Imidazole and the like, diazabicycloundecene (DBU), N, N-dimethylcyclohexylamine (Polycat-8), triethylenediamine, N-methylmorpholine, bis (2-dimethyl-aminoethyl) ether (NIAX-A-1) And the like can be exemplified as the urethanization reaction catalyst.

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

  Examples of the flame retardant include metal compounds such as halogen-containing compounds, organophosphates, antimony trioxide, and aluminum hydroxide. When these flame retardants are added, for example, excessive amounts of organophosphates, the physical properties of the resulting rigid polyurethane foam may deteriorate, and when excessive addition of metal compound powders such as antimony trioxide is added, foam foaming behavior The amount of addition is limited to a range that does not cause such a problem.

  Examples of the plasticizer include halogenated alkyl esters of phosphoric acid, alkyl phosphate esters, aryl phosphate esters, phosphonate esters, and the like. Specifically, 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, cresyl phenyl phosphate, dimethylmethylphosphonate, etc. One or more of these can be used. The addition amount of the plasticizer 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 plasticization effects and reduced physical properties of the foam may occur.

<Method for producing rigid polyurethane foam>
The manufacturing method of the rigid polyurethane foam of this embodiment is a manufacturing method of the rigid polyurethane foam which mixes the said polyol composition and a polyisocyanate compound with a spray apparatus, makes it react and makes it 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 is used even if it contains a metal catalyst and HFO-1233zd, even a polyol composition after storage can be spray foamed. Can produce a rigid polyurethane foam.

  As the isocyanate component, liquid MDI is used because it is easy to handle, the reaction speed, the physical properties of the resulting rigid polyurethane foam are excellent, and the cost is low. Examples of liquid MDI include crude (crude) MDI (c-MDI) (44V-10, 44V-20L, etc. (manufactured by Sumika Covestrourethane)), uretonimine-containing MDI (Millionate MTL; manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like. used. Among these polyisocyanate compounds, the use of crude (crude) MDI is particularly preferable in that the physical properties such as mechanical strength of the formed rigid polyurethane foam are excellent and the cost is low.

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

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

  In the manufacturing method of the present embodiment, a generally well-known polyurethane spray foaming / molding apparatus is appropriately used and molded into a shape corresponding to the application.

  Examples and the like specifically showing the configuration and effects of the present invention will be described below.

<Evaluation method>
[Initial gel time]
The polyol composition adjusted to a temperature of 15 ° C. and the isocyanate component were stirred and mixed for 4 seconds with a stirrer whose stirring blades rotated 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 foam top of the foam.

[Geltime after storage at 40 ° C for 30 days]
After the polyol composition was sealed in a plastic container and cured in an oven set at 40 ° C. for 30 days, the cured polyol composition adjusted to a temperature of 15 ° C. and the isocyanate component were stirred at 3000 rpm. The mixture was stirred and mixed for 4 seconds with a rotating stirrer, and the gel time of the foamed polyurethane foam was measured.

[Gel time delay]
After the 30-day storage at 40 ° C., the gel time value was subtracted from the gel time value to determine the gel time delay time (gel time delay). It means that storage stability is so good that there is little gel time delay.

<Examples 1-8, Comparative Examples 1-3>
A polyol composition is prepared with the composition described in Table 2 and Table 3 using the raw materials described in Table 1, and the polyol composition and the polyisocyanate described in Table 1 are weight ratios described in Table 2 and Table 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 Table 2 and Table 3, it can be seen that the polyol composition containing calcium octylate has improved gel gel storage stability because the gel time delay is small. On the other hand, zinc octylate had no effect.

Claims (6)

A polyol composition for a rigid polyurethane foam comprising at least a polyol compound, a foaming agent, and a metal catalyst, mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam,
The blowing agent contains HFO-1233zd;
A polyol composition for rigid polyurethane foam, wherein the polyol composition contains calcium octylate.   The metal catalyst is dibutyltin dilaurate, dioctyltin malate, tin octylate, dibutyltin oxide, tetrabutyl titanate, lead naphthenate, lead octylate, bismuth neodecanoate, bismuth octylate, cobalt naphthenate, cobalt octylate, acetylacetone The polyol composition for rigid polyurethane foam according to claim 1, wherein the polyol composition is one or more selected from the group consisting of iron, bismuth neodecanoate, potassium octylate, potassium acetate, and potassium formate.   The polyol composition for rigid polyurethane foam according to claim 1 or 2, wherein the amount of the metal catalyst in the polyol composition is 0.05 wt% or more and 10 wt% or less with respect to 100 parts by weight of the polyol compound.   The amount of the said calcium octylate in the said polyol composition is 0.05 to 2 weight part with respect to 100 weight part of polyol compounds, For the rigid polyurethane foam of any one of Claims 1-3 Polyol composition.   The polyol composition for rigid polyurethane foam according to any one of claims 1 to 4, which is used for producing a rigid polyurethane foam by a spray foaming method.   The manufacturing method of the rigid polyurethane foam which mixes and reacts the polyol composition for rigid polyurethane foams of any one of Claims 1-5, and a polyisocyanate compound with a spray apparatus, and makes it react.