JP2020029572A - Polyol composition for rigid polyurethane foam, and rigid polyurethane foam production method - Google Patents

Abstract

To provide: a polyol composition for rigid polyurethane foam that has a good stock solution storage stability even for the case when HFO-1233zd is used as a blowing agent and furthermore that can suppress the poor curing and suppress the decrease in polyurethane foam physical properties; and a rigid polyurethane foam production method.SOLUTION: Provided is a polyol composition for rigid polyurethane foam, containing at least a polyol compound and a blowing agent, and that is for forming a rigid polyurethane foam by mixing with an isocyanate component comprising polyisocyanate compound, to foam and cure, and in which the blowing agent contains 1-chloro-3,3,3-trifluoro propene, and the polyol compound contains at least one selected from the group consisting of, with an amino group-containing compound as an initiator, polyether polyol P1 having at least one alkylene oxide adduct at the terminal, and with a Mannich type compound as an initiator, polyether polyol P2 having at least one alkylene oxide adduct at the terminal.SELECTED DRAWING: None

Description

  The present invention relates to a polyol composition for a rigid polyurethane foam and a rigid polyurethane foam which contain 1-chloro-3,3,3-trifluoropropene (hereinafter also referred to as HFO-1233zd) as an essential component as a foaming agent component. It relates to a manufacturing method.

  Rigid polyurethane foam is a material known as a heat insulating material, a lightweight structural material, or 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 with an isocyanate component, foaming and curing.

  As the foaming agent, a CFC-11 or other chlorofluorocarbon compound was used in the past. However, since CFC-11 caused destruction of the ozone layer, its use was banned and switched to HCFC-141b. Has been switched to HFC-245fa or HFC-365mfc, which has an ozone depletion potential of zero, but the HFC-245fa or HFC-365mfc has a problem that GWP (global warming potential) is large. Therefore, HFO-1233zd, which has a low ozone depletion potential and a low global warming potential and is nonflammable, is being developed as a foaming agent.

  For example, since a polyol composition containing HFO-1233zd has poor stock solution storage stability, attempts have been made to improve stock solution storage stability of a polyol composition containing HFO-1233zd (for example, Patent Documents 1 to 3). 4).

JP, 2011-500891, A JP 2011-500892 A JP 2011-50989 A JP-T-2013-501844A

  However, according to the conventional technology, although the reactivity delay after storage of the stock solution of the polyol composition containing HFO-1233zd is improved, when a polyurethane foam is produced using the polyol composition, poor curing is caused and the polyurethane foam is formed. The polyurethane foam sometimes shrunk. Also, immediately after the preparation of the polyol premix is mixed with the isocyanate component, even if the catalyst does not cause poor curing even when foamed, the premix is stored with the isocyanate component after storage at 40 ° C., when foamed, Poor curing occurred, and the polyurethane foam sometimes shrunk. The condition of 40 ° C. is based on the assumption of the maximum temperature of the stock solution when the drum is stored outdoors in summer.

  The present invention has been made in view of the above circumstances, and its object is to provide a stock solution having good storage stability even when HFO-1233zd is used as a foaming agent, and to further suppress poor curing and thereby suppress shrinkage of a polyurethane foam. An object of the present invention is to provide a polyol composition for a rigid polyurethane foam and a method for producing a rigid polyurethane foam.

  The polyol composition for a rigid polyurethane foam of the present invention contains at least a polyol compound and a foaming agent, and is mixed with an isocyanate component containing a polyisocyanate compound and foamed and cured to form a rigid polyurethane foam polyol composition. The foaming agent contains HFO-1233zd, and the polyol compound is a polyether polyol P1 having an amino group-containing compound as an initiator and having at least one alkylene oxide adduct at a terminal, and a Mannich-based compound. And at least one selected from the group consisting of polyether polyols P2 having at least one alkylene oxide adduct at the terminal.

  The method for producing a rigid polyurethane foam of the present invention is a method for producing a rigid polyurethane foam which is a mixture of an isocyanate component and a polyol composition, which is foamed and cured to form a rigid polyurethane foam. It is a polyol composition for polyurethane foam.

  ADVANTAGE OF THE INVENTION According to this invention, even when HFO-1233zd is used as a foaming agent, the stock solution storage stability is good, the polyol composition for rigid polyurethane foam which can suppress the curing failure and suppress the shrinkage of the polyurethane foam, and the rigid polyurethane foam Can be provided.

<Polyol composition for rigid polyurethane foam>
The polyol composition for a rigid polyurethane foam of the present embodiment contains at least a polyol compound and a foaming agent, and is mixed with an isocyanate component containing a polyisocyanate compound and foamed and cured to form a rigid polyurethane foam polyol composition. Wherein the blowing agent contains HFO-1233zd, and the polyol compound is a polyether polyol P1 having an amino group-containing compound as an initiator and having at least one alkylene oxide adduct at a terminal, and a Mannich-based product. It contains a compound as an initiator and contains at least one selected from the group consisting of polyether polyols P2 having at least one alkylene oxide adduct at a terminal. According to the polyol composition for a rigid polyurethane foam of the present embodiment, even when HFO-1233zd is used as a foaming agent, the storage stability of a stock solution is good, and furthermore, poor curing can be suppressed and shrinkage of the polyurethane foam can be suppressed. Although the reason for such an effect is not clear, it is considered as follows.

  A polyether polyol having an amine group-containing compound as an initiator and having at least one alkylene oxide adduct at a terminal, and a polyether polyol having a Mannich compound as an initiator and having at least one alkylene oxide adduct are It has higher reactivity than polyether polyol having no structure. When a foam is produced using such a polyether polyol, the internal calorific value of the foam increases due to its high reactivity. It is considered that the heat generation facilitates a cross-linking reaction, a trimerization reaction of isocyanate, and the like, and suppresses poor curing of the foam due to a decrease in catalytic activity and insufficient activity of the catalyst.

(Polyol compound)
The polyol compound has an amino group-containing compound as an initiator, a polyether polyol P1 having at least one alkylene oxide adduct at a terminal, and a Mannich-based compound as an initiator and has at least one alkylene oxide adduct at a terminal. It contains at least one member selected from the group consisting of polyether polyols P2.

[Polyether polyol P1]
The polyether polyol P1 is a polyether polyol having an amino group-containing compound as an initiator and having at least one alkylene oxide adduct at a terminal. More specifically, the initiator is obtained by addition-polymerizing an alkylene oxide to the initiator. The resulting polyether polyol.

  As the amino group-containing compound, a known amino group-containing compound used as an initiator for a polyether polyol is used. Examples of the amino group-containing compound include aromatic compounds such as 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, and naphthalenediamine. Diamine; alkylene diamines having 2 to 8 carbon atoms such as ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, neopentyl diamine, and diethylene triamine can be exemplified. Among them, ethylenediamine, propylenediamine, and diethylenetriamine are preferable, and ethylenediamine is more preferable, from the viewpoint of suppressing poor curing and suppressing the deterioration of the physical properties of the polyurethane foam.

  Examples of the alkylene oxide adduct include a propylene oxide (PO) adduct, an ethylene oxide (EO) adduct, a styrene oxide (SO) adduct, a tetrahydrofuran adduct, and the like. The ethylene oxide adduct is preferred from the viewpoint of suppressing the decrease in the amount of ethylene oxide.

  The average number of functional groups of the polyether polyol P1 is preferably from 3 to 6, more preferably from 3 to 4, from the viewpoint of suppression of curing failure and the suppression of deterioration of physical properties of the polyurethane foam.

  The hydroxyl value of the polyether polyol P1 is preferably from 300 to 1000 mgKOH / g, more preferably from 400 to 1000 mgKOH / g, from the viewpoint of suppressing curing failure and the viewpoint of suppressing deterioration in physical properties of the polyurethane foam.

Specific examples of the polyether polyol P1 include NL-300 (manufactured by Sanyo Chemical Industries, Ltd.).

[Polyether polyol P2]
The polyether polyol P2 is a polyether polyol having a Mannich-based compound as an initiator and having at least one alkylene oxide adduct at a terminal, and more specifically, phenol and / or an alkyl-substituted derivative thereof, formaldehyde, and A Mannich polyether polyol obtained by subjecting an alkylene oxide to ring-opening addition polymerization using a Mannich compound obtained by a Mannich reaction of an alkanolamine as an initiator.

  Examples of the alkylene oxide adduct include a propylene oxide (PO) adduct, an ethylene oxide (EO) adduct, a styrene oxide (SO) adduct, a tetrahydrofuran adduct, and the like. The ethylene oxide adduct is preferred from the viewpoint of suppressing the decrease in the amount of ethylene oxide.

  The average number of functional groups of the polyether polyol P2 is preferably 2 to 4 from the viewpoint of suppression of curing failure and the suppression of deterioration of physical properties of the polyurethane foam.

  The hydroxyl value of the polyether polyol P2 is preferably from 250 to 700 mgKOH / g, more preferably from 350 to 700 mgKOH / g, from the viewpoint of suppression of curing failure and the suppression of deterioration of the physical properties of the polyurethane foam.

  Specific examples of the polyether polyol P2 include DK4000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[Other polyols]
The polyol compound may include another polyol other than the polyether polyol P1 and the polyether polyol P2. Specific examples of the other polyols may include at least one polyol compound having a hydroxyl value of 300 to 1000 mgKOH / g selected from aliphatic amine polyols and aromatic amine polyols.

  Examples of the aliphatic amine polyol include an alkylenediamine-based polyol and an alkanolamine-based polyol. These polyol compounds are polyfunctional polyol compounds having terminal hydroxyl groups obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide using alkylene diamine or alkanolamine as an initiator. Known compounds can be used as the alkylenediamine without limitation. Specifically, it is preferable to use an alkylenediamine having 2 to 8 carbon atoms such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, and diethylenetriamine. Among these, the use of alkylene diamine having a small number of carbon atoms is more preferable, and the use of a polyol compound using ethylene diamine or propylene diamine as an initiator is particularly preferable. In the alkylenediamine-based polyol, the alkylenediamine as an initiator may be used alone or in combination of two or more. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. The number of functional groups of the polyol compound using alkylene diamine as an initiator is 4, and the number of functional groups of the polyol compound using alkanolamine as an initiator is 3.

  The aromatic amine-based polyol is a polyfunctional polyol compound having a terminal hydroxyl group obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide using an aromatic diamine as an initiator. As the initiator, a known aromatic diamine can be used without limitation. Specific examples include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine and the like. Among them, the use of toluenediamine (2,4-toluenediamine, 2,6-toluenediamine or a mixture thereof) is particularly preferred in that the obtained rigid polyurethane foam has excellent properties such as heat insulation and strength.

  The total of the content of the polyether polyol P1 and the content of the polyether polyol P2 is preferably 15% by weight or more in the polyol compound from the viewpoint of suppression of poor curing and suppression of deterioration in physical properties of the polyurethane foam. , 100% by weight is most preferred.

(Blowing agent)
The foaming agent contains HFO-1233zd, which has a low ozone depleting ability and a low global warming potential and is not flammable.

  It is preferable that the foaming agent further contains water. By adding water, the vapor pressure of the blowing agent of the polyol composition can be reduced. The content of water is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the polyol compound in total.

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

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

  Examples of the catalyst include tertiary amines such as triethylenediamine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, and DBU. And metal catalysts such as dibutyltin dilaurate, dibutyltin diacetate and tin octylate can be exemplified as the urethanization reaction catalyst.

  As the foam stabilizer, known foam stabilizers for rigid polyurethane foams 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 an average molecular weight of 5,000 to 8,000, polypropylene oxide, or a 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, organic phosphates, antimony trioxide, and aluminum hydroxide. In these flame retardants, for example, when an organic phosphoric acid ester is excessively added, the physical properties of a rigid polyurethane foam obtained may be deteriorated. In addition, when a metal compound powder such as antimony trioxide is excessively added, the foaming behavior of the foam may be reduced. In some cases, there may be a problem such as an influence on the temperature, and 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, and phosphonate esters. Specifically, tris (2-chloroethyl) phosphate (CLP, manufactured by Daihachi Chemical Co., Ltd.) ), Tris (β-chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical), tributoxyethyl phosphate (TBEP, manufactured by Rhodia), tributylphosphate, triethylphosphate, cresylphenylphosphate, dimethylmethylphosphonate, etc. , One or more of these can be used. The added amount of the plasticizer is preferably 5 to 40 parts by weight based on 100 parts by weight of the polyol composition. If the ratio exceeds this range, problems such as insufficient plasticizing effect and deterioration of the physical properties of the foam may occur.

  The polyol composition of the present embodiment can be used for production of continuously produced rigid polyurethane foams such as slabstock foams and sandwich panels, rigid polyurethane foam sandwich panels to be injection molded, spray foams and the like.

<Production 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 by mixing an isocyanate component and the polyol composition, foaming and curing the mixture to obtain a rigid polyurethane foam.

  As the isocyanate component, liquid MDI is used because of its ease of handling, speed of reaction, excellent physical properties of the obtained rigid polyurethane foam, and low cost. As liquid MDI, crude (crude) MDI (c-MDI) (44V-10, 44V-20L, etc. (manufactured by Sumitomo Bayer Urethane Co., Ltd.)), uretonimine-containing MDI (millionate MTL, manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like are used. You. Among these polyisocyanate compounds, the use of crude (crude) MDI is particularly preferred in that the rigid polyurethane foam formed has excellent physical properties such as mechanical strength and is inexpensive.

  In addition to the liquid MDI, another isocyanate component may be used in combination. Di- or polyisocyanate compounds well known in the polyurethane art 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 0.8 or more, more preferably 0.9 or more.

  With such a configuration, a large amount of isocyanurate bonds are formed in the resin constituting the rigid polyurethane foam, and a rigid polyurethane foam with further improved flame resistance can be manufactured.

  The method for producing a rigid polyurethane foam of the present embodiment can be used for producing a rigid polyurethane foam that is continuously produced, such as a slab stock foam or a sandwich panel, a rigid polyurethane foam sandwich panel that is injection-molded, or a spray foam.

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

<Evaluation method>

[Form density]
The foam density was determined according to JIS K7222.

[Shrinkage of foam]
The mixed and stirred mixture of the polyol composition and the isocyanate component was put into a mold having a length and width of 180 mm and a depth of 100 mm, and the foamed foam was cured at room temperature (23 ° C. ± 5 ° C.) for 10 minutes. Thereafter, the foam was taken out of the mold and cured at room temperature for 30 minutes, and the shrinkage of the foam was confirmed based on whether the foam top collapsed. When the foam top collapsed, poor curing occurred, and when the foam top did not collapse, poor curing did not occur. In Table 2, when the foam top collapsed, it was indicated by x, and when the foam top did not collapse, it was indicated by ○.

<Examples 1 to 11, Comparative Examples 1 to 5>
(Adjustment of polyol composition)
Table 1 shows the constituent materials of the polyol composition.

  The constituent materials shown in Table 1 were mixed and stirred in the composition shown in Table 2 below to prepare the polyol compositions of Examples 1 to 11 and Comparative Examples 1 to 5.

[Production of rigid polyurethane foam]
The temperature of the polyol compositions of Examples 1 to 11 and Comparative Examples 1 to 5 was adjusted to 20 ° C., and then the temperature of the isocyanate component was adjusted to 20 ° C. (Sumika Bayer Urethane Co., Ltd., crude diphenylmethane diisocyanate “Sumidur 44V-20L”, (NCO%: 31%) and an NCO / OH equivalent ratio of 1.70 were mixed and stirred with a laboratory stirrer, and foamed and cured to obtain a rigid polyurethane foam. Table 2 shows the evaluation results of the rigid polyurethane foam. In Table 2, "initial" means a rigid polyurethane foam produced using the polyol composition immediately after adjustment, and "after storage at 40 ° C for 28 days" means polyol composition stored at 40 ° C for 28 days after adjustment. Means a rigid polyurethane foam produced using a material.

  From the results in Table 2, the polyol compositions according to Examples 1 to 11 have good stock solution storage stability even when HFO-1233zd is used as a blowing agent, and are manufactured using the polyol compositions according to Examples 1 to 11 as raw materials. It can be seen that the obtained rigid polyurethane foam can suppress poor curing and suppress deterioration in physical properties even when HFO-1233zd is used as a foaming agent.

Claims (4)

A polyol composition for a rigid polyurethane foam which contains at least a polyol compound and a foaming agent and is foamed and cured by mixing with an isocyanate component containing a polyisocyanate compound to form a rigid polyurethane foam,
The blowing agent contains 1-chloro-3,3,3-trifluoropropene,
The polyol compound has an amino group-containing compound as an initiator, a polyether polyol P1 having at least one alkylene oxide adduct at a terminal, and a Mannich compound as an initiator, having at least one alkylene oxide adduct at a terminal. A polyol composition for a rigid polyurethane foam, comprising at least one member selected from the group consisting of polyether polyols P2.   The polyol composition for a rigid polyurethane foam according to claim 1, wherein the total of the content of the polyether polyol P1 and the content of the polyether polyol P2 is 15% by weight or more and 100% by weight or less in the polyol compound.   The polyol composition for a rigid polyurethane foam according to claim 1 or 2, wherein the alkylene oxide adduct is an ethylene oxide adduct. A method for producing a rigid polyurethane foam which is a mixture of an isocyanate component and a polyol composition, which is foamed and cured to form a rigid polyurethane foam,
A method for producing a rigid polyurethane foam, wherein the polyol composition is the polyol composition for a rigid polyurethane foam according to any one of claims 1 to 3.