JP2002220429A - Rigid polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an isocyanurate-modified rigid polyurethane foam which uses a polyester polyol obtained by the esterification of a phthalic acid and/or a derivative thereof as a polyol component, the rigid polyurethane foam having reduced amount of a hydrofluorocarbon(HFC) by combining a water, in which the storage stability of a formulated liquid is increased by controlling the hydrolysis of the polyester polyol. SOLUTION: The rigid polyurethane foam is obtained by mixing a polyisocyanate component, the polyol component containing the polyester polyol compound obtained by the esterification of the phthalic acid and/or its derivative, a foaming agent, a catalyst and other auxiliary to foam them. A carbon dioxide obtained by reacting the polyisocyanate component with a water is used as the foaming agent and an imidazole compound is used as the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rigid polyurethane foam, and more particularly, to foaming by mixing a polyisocyanate component and a compounded liquid obtained by mixing a polyol component, a foaming agent, a catalyst and other auxiliaries with a mixing head. A rigid polyurethane foam suitable for airless spray foaming, wherein a hydrofluorocarbon (H
The present invention relates to a rigid polyurethane foam which prevents deterioration of a compounded liquid when water is used in combination to reduce the amount of FC) used and which has improved storage stability.

[0002]

2. Description of the Related Art Rigid polyurethane foams are widely used as heat insulating materials for houses, refrigerators and the like because of their excellent heat insulating properties and self-adhesive properties.

[0003] Rigid polyurethane foams used in these applications are generally foamed by mixing a polyisocyanate component and a compounded liquid obtained by mixing a polyol component, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries with a mixing head. In this method, a good heat-insulating layer of a rigid polyurethane foam can be formed by a simple operation of directly spraying and applying to an object to be applied.

In rigid polyurethane foam, dichloromonofluoroethane (HCFC-141b), which is currently used as a main foaming agent, has a problem of ozone layer destruction. For this reason, hydrofluorocarbons (HFCs) that do not destroy the ozone layer have been proposed as candidates for next-generation blowing agents that can be used instead. HFCs include tetrafluoroethane (HFC134a), 1,
1,1,3,3-pentafluoropropane (HFC24
5fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), 1,1,1,2,3,3,3
-Heptafluoropropane (HFC227ea), among which HCFC has no ozone destructive property and
Some compounds are promising as foaming agents after their total abolition.

[0005]

However, HFCs
Since they have the problem of global warming and are expensive, it is desirable to reduce their use from the viewpoint of environmental consideration and economic efficiency.

Further, HFC has a property that it is difficult to dissolve in the polyol component and the polyisocyanate component. Therefore, when used alone, the internal pressure of the compounded liquid rises and the container ruptures or the liquid boils. Some of them are flammable and have the drawback that safety in handling cannot be ensured. In particular, in order to make the foam flame-retardant, it is indispensable to apply a polyester polyol compound obtained by subjecting phthalic acid or a phthalic acid derivative to an esterification reaction as a polyol component.
The solubility of FC was low, and the internal pressure of the mixed solution was easily increased.
For this reason, the amount of the HFC to be introduced is naturally limited, and as a result, there is a problem that the density of the obtained foam increases.

In order to reduce the amount of HFC used, increase the amount of foaming, and obtain a low-density foam, water is used, and carbon dioxide generated by the reaction between water and the polyisocyanate component is used together with HFC as a foaming agent. It is conceivable to use them in combination, but in this case, there is a problem that the polyester polyol in the compounding liquid is hydrolyzed and normal foaming cannot be performed.

In general, a compounding liquid for airless spray foaming is usually stored for a period of 1 to 2 months after being compounded until it is actually used. Very important.

However, when an attempt is made to obtain a foam having high flame retardancy by using a polyester polyol, the initial reactivity is lost in a short period of time due to hydrolysis of the polyester polyol, and the production of the foam becomes difficult.

The present invention solves the above-mentioned conventional problems and is a rigid polyurethane foam using a polyester polyol obtained by subjecting phthalic acid and / or a phthalic acid derivative to an esterification reaction as a polyol component, wherein water is used in combination. It is an object of the present invention to provide a rigid polyurethane foam in which the amount of HFC used is reduced, thereby suppressing the hydrolysis of the polyester polyol and increasing the storage stability of the blended liquid.

[0011]

The rigid polyurethane foam of the present invention is a rigid polyurethane foam obtained by mixing and foaming a polyisocyanate component, a polyol component, a foaming agent, a catalyst, and other auxiliaries. In a rigid polyurethane foam using a polyol component containing a polyester polyol compound obtained by subjecting phthalic acid and / or a phthalic acid derivative to an esterification reaction as a component, it is obtained by reacting the polyisocyanate component with water as a foaming agent. It is characterized by using carbon dioxide gas and containing an imidazole compound as a catalyst.

According to the present invention, by using an imidazole compound as a catalyst, hydrolysis of the polyester polyol when water is used in combination can be suppressed, and the storage stability of the blended liquid can be improved.

The rigid polyurethane foam of the present invention is a rigid polyurethane foam using a polyester polyol compound obtained by subjecting phthalic acid or a phthalic acid derivative to an esterification reaction as a polyol component, and thus has excellent flame retardancy. In addition, by using water as a foaming agent, the amount of HFC used can be reduced, and a low-density rigid polyurethane foam can be obtained while improving environmental safety and economic efficiency.

In the present invention, the blowing agent may be a carbon dioxide gas obtained by reacting a polyisocyanate component with water, but preferably, the carbon dioxide gas and HFC are used in combination.

In this case, the HFC is 1,1,1,1
3,3-pentafluoropropane, 1,1,1,3,3
-Pentafluorobutane, 1,1,1,2,3,3,3
One or more selected from the group consisting of -heptafluoropropane and 1,1,1,2-tetrafluoroethane can be used.

Of these, by using 1,1,1,3,3-pentafluorobutane, a foam having fine bubbles and excellent heat insulating performance can be obtained.

However, when 1,1,1,3,3-pentafluorobutane is used alone,
Since 3,3-pentafluorobutane is flammable, it may reduce the flame retardancy of the obtained foam. In addition, since the molecular weight is large, the weight required to obtain a predetermined foam density is large. For this reason, 1,1,1,
The use of 3,3-pentafluorobutane alone is not preferable from the viewpoint of safety and economy.

Therefore, when 1,1,1,3,3-pentafluorobutane is used, a rise in the internal pressure of a compounded liquid containing a foaming agent is suppressed, and a highly flame-retardant, low-density rigid polyurethane foam is used. 1,1,1,3,3 to get cheap
-It is preferable to use an HFC other than pentafluorobutane in combination.

HFCs used in combination with 1,1,1,3,3-pentafluorobutane include 1,1,1,3,3-pentafluoropropane, 1,1,1,2,3,3,3 −
Heptafluoropropane or 1,1,1,2-tetrafluoroethane is mentioned, among which 1,1,1,3,
When 3-pentafluoropropane is used, 1,
5-95% by weight of 1,1,3,3-pentafluoropropane and 9% of 1,1,1,3,3-pentafluorobutane
5 to 5% by weight, especially 1,1,1,3,3-pentafluoropropane, 20 to 80% by weight, 1,1,1,3,3-
It is preferable that pentafluorobutane is 80 to 20% by weight, and when 1,1,1,2-tetrafluoroethane is used, 1,1,1,2-tetrafluoroethane is 2 to 12% by weight, 98-88% by weight of 1,1,1,3,3-pentafluorobutane, especially 5-10% by weight of 1,1,1,2-tetrafluoroethane, 1,1,1,1
Preferably, 3,3-pentafluorobutane is 95 to 90% by weight. Also, 1,1,1,2,3,3,3-
When heptafluoropropane is used, 1,1,
1,2,3,3,3-heptafluoropropane is 2-1
It is preferable that the content of 5% by weight and 1,1,1,3,3-pentafluorobutane be 98 to 85% by weight.

The HFC is contained in an amount of 1 to 20% by weight, especially 5 to 15% by weight, based on a reactive polyurethane raw material comprising a polyisocyanate component, a polyol component, a foaming agent, a catalyst and other auxiliaries. Is preferred.

[0021]

Embodiments of the present invention will be described below in detail.

First, the raw material components used in the present invention will be described.

Polyisocyanate Component The polyisocyanate component includes aromatic polyisocyanate compounds such as diphenylmethane diisocyanate and tolylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate; and aliphatic polyisocyanates such as hexamethylene diisocyanate. One or more of these can be used. In addition,
The isocyanate index of the polyisocyanate component is 100
As mentioned above, it is particularly preferable that it is 100-200. That is, it is preferable to obtain an isocyanurate foam in the presence of a trimerization catalyst.

Polyol Component As the polyol component, one or more phthalic acids or derivatives thereof selected from the group consisting of o-phthalic acid, m-phthalic acid, p-phthalic acid and derivatives thereof are subjected to an esterification reaction. The phthalic acid-based polyester polyol obtained by this is used. By using such a phthalic acid-based polyester polyol compound containing an aromatic ring as the polyol component, stable flame retardancy can be obtained.

Examples of the hydroxy compound forming the phthalic acid-based polyester polyol include ethylene glycol, diethylene glycol, phenol and derivatives thereof, and examples of the phthalic acid derivative include diethyl phthalate and dimethyl phthalate. The preferred hydroxyl value of the polyester polyol is 150 to 450.
It is.

If the proportion of such a phthalic acid-based polyester polyol in the polyol component is too small, sufficient flame retardancy cannot be obtained, and if it is too large, the degree of the foam is reduced. It is preferably contained at 80% by weight.

As the polyol component, in addition to the above-mentioned phthalic acid-based polyester polyol, a polyether polyol obtained by subjecting phenol and / or a derivative thereof to Mannich modification (hereinafter referred to as “Mannich-modified polyol”), that is, phenol, or Nonylphenol,
A polyether polyol obtained by subjecting a phenol derivative such as an alkylphenol to Mannich modification using a secondary amine such as formaldehyde and diethanolamine, ammonia, or a primary amine, and subjecting an alkylene oxide such as ethylene oxide or propylene oxide to ring-opening addition polymerization is obtained. May be used. Since such a Mannich-modified polyol has a high self-reaction activity and a relatively high flame retardancy, by using the Mannich-modified polyol,
For example, in the case of an airless spray foaming type rigid polyurethane foam, the reaction can proceed promptly without significantly impairing the flame retardant performance at the time of spray foaming. However, when the Mannich-modified polyol in the polyol component is 8
If the content exceeds 0% by weight, the flame retardancy deteriorates. Therefore, when a Mannich-modified polyol is used, its proportion in the polyol component is 70% by weight or less, particularly 20 to 50% by weight.
It is preferred that

Further, in addition to the phthalic acid-based polyester polyol and the Mannich-modified polyol, ethylenediamine, tolylenediamine, and the like may be used within a range not to impair the object of the present invention.
A polyol compound of an initiator different from the Mannich-modified polyol such as sucrose, amino alcohol and diethylene glycol may be used in combination within a range of 30% by weight or less in the polyol component.

Catalyst The present invention is characterized in that an imidazole compound is used as a catalyst.

Specific examples of the imidazole compound include one or more of 1-isobutyl-2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole and the like. In addition, as the catalyst, a catalyst other than the imidazole-based compound that is generally used for producing a rigid polyurethane foam can be used in combination. Examples of the catalyst used in combination with the imidazole-based compound include triethylenediamine, pentamethyldiethylenetriamine, and tetramethylhexamethylene. One or two or more of amine catalysts such as diamines and organometallic catalysts such as dibutyltin dilaurate, lead octylate, stannas octoate, potassium octylate (potassium 2-ethylhexylate), and potassium acetate are exemplified.

In the present invention, water is added to the blended liquid, and carbon dioxide generated by the reaction between water and the polyisocyanate compound is used as the blowing agent. As the foaming agent, only carbon dioxide gas by the addition of water may be used, and HFC may be used in combination. In this case HF
As C, two or more kinds of HFCs including 1,1,1,3,3-pentafluorobutane may be used for the above-mentioned reason. HFCs other than 1,1,1,3,3-pentafluorobutane include 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane,
1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 1,1,1,4,4,4-hexafluorobutane, etc. And 1,1,1,3,3-pentafluoropropane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2-tetrafluoroethane Is preferably used.

When 1,1,1,3,3-pentafluoropropane is used, 5-1,95% by weight of 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3 3
95 to 5% by weight of pentafluorobutane, in particular 1,
1,1,3,3-pentafluoropropane is 20 to 80
%, 1,1,1,3,3-pentafluorobutane is preferably 80 to 20% by weight.
When using 2-tetrafluoroethane, 1,1,
2 to 12% by weight of 1,2-tetrafluoroethane,
98-88% by weight of 1,1,3,3-pentafluorobutane, especially 5% of 1,1,1,2-tetrafluoroethane
Preferably, the content of 1,1,1,3,3-pentafluorobutane is 95 to 90% by weight. Also,
When 1,1,1,2,3,3,3-heptafluoropropane is used, 2 to 15% by weight of 1,1,1,2,3,3,3-heptafluoropropane is used. , 1,
Preferably, 3,3-pentafluorobutane is 98 to 85% by weight. Beyond the above range 1,1,1,3,3
-When the amount of pentafluorobutane is large, there is a problem that the flame retardancy is reduced and the price rises. And the viscosity of the blended liquid increased.
Also, 1,1,1,2-tetrafluoroethane, 1,1,
1,1,2,3,3,3-heptafluoropropane is
It may be mixed with 1,1,1,3,3-pentafluorobutane and introduced into the liquid mixture, or may be directly mixed as a third component into a mixing head or the like.

The amount of HFC containing 1,1,1,3,3-pentafluorobutane is determined based on the polyisocyanate component,
It is preferably from 1 to 20% by weight, especially from 5 to 15% by weight, based on a reactive polyurethane raw material comprising a polyol component, a foaming agent, a catalyst and other auxiliaries. If the amount of the HFC used is less than the above range, foaming is insufficient and the density of the foam cannot be sufficiently reduced. If the amount is more than the above range, bumping of the liquid and remarkable bubbling occur, resulting in handling problems. Happens.

Foam stabilizers Any foam stabilizers that are effective for producing rigid polyurethane foams can be used. For example, a silicone-based material such as polyoxyalkylene alkyl ether can be used.

In the present invention, optional components other than those described above, for example, a flame retardant, a filler and the like can be used as long as the object of the present invention is not hindered.

In the production of the rigid polyurethane foam of the present invention, the amount of water used as a foaming agent is preferably 1 to 20 parts by weight based on 100 parts by weight of the polyol component. If the amount of water used is less than this range, foaming is insufficient and the density of the foam cannot be sufficiently reduced, and when HFC is used in combination, the effect of reducing the amount of HFC used is obtained. Is difficult. If the amount of water exceeds the above range, remarkable foaming occurs, making it difficult to handle, and also causes a problem of hydrolysis of the polyester polyol, which is not preferable. When HFC is not used in combination, the amount of water used is preferably 4 to 4 parts by weight per 100 parts by weight of the polyol component.
Preferably it is 20 parts by weight. When HFC is used in combination, it is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the polyol component, depending on the amount of HFC used.

In particular, when water and HFC are used in combination, it is preferable to use 0.5 to 10 parts by weight of water and 2 to 40 parts by weight of HFC based on 100 parts by weight of the polyol component.

If the amount of the imidazole compound used as the catalyst is too large or too small, the effect of inhibiting the hydrolysis of the polyester polyol is not obtained. In particular, excessive mixing of the imidazole compound results in high material cost. In addition, it is not preferable because it causes odor problems. Therefore, the amount of the imidazole compound is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the polyol component. In addition, when the other catalysts described above other than the imidazole compound are used in combination,
The amount of the other catalyst to be used is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the polyol component, and 1 to 10 parts by weight in total with the imidazole compound.

When the rigid polyurethane foam of the present invention is produced by airless spray foaming using a mixing head, the above-mentioned polyisocyanate component and a compounded liquid obtained by mixing a polyol component, a foaming agent, a catalyst and other auxiliaries are used. It can be manufactured by mixing using a mixing head at ５０50 ° C., spraying the mixture at a discharge pressure of 3.9 to 7.8 × 10 ⁶ Pa on the surface to be processed, and repeatedly blowing to foam to a predetermined thickness. it can.

The rigid polyurethane foam of the present invention thus obtained preferably has a core density of 20 to 45 kg / m ³ . If the core density exceeds 45 kg / m ³ , the amount of combustion components increases, the flame retardancy decreases, and the cost increases. If the core density is 20 kg / m ³ or less, the strength properties and the like become poor, which is not preferable.

[0041]

The present invention will be described more specifically below with reference to examples and comparative examples.

Examples 1 to 3 and Comparative Examples 1 to 3 According to the formulation shown in Table 1, formulation A was prepared and polyisocyanate was prepared. The raw materials used for the polyisocyanate and the mixture A are as follows.

Polyisocyanate: crude diphenylmethane diisocyanate (NCO%: 30.5) manufactured by Sumitomo Bayer Urethane Industry Co., Ltd. Polyol A: Mannich modified polyol manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Hydroxyl value: 700 mg-KOH / g Polyol B: Ethylenediamine-based polyether polyol manufactured by Takeda Pharmaceutical Co., Ltd. Hydroxyl value: 685 mg-KOH / g Polyol C: phthalic acid-based polyester polyol manufactured by Toho Rika Co., Ltd. Hydroxyl value: 240 mg-KOH / g Flame retardant: Daihachi Chemical Co., Ltd. ) "TCPP (Tris monochloropropyl phosphate)" Foam stabilizer: "L5420" (block copolymer of dimethylsiloxane and polyether) manufactured by Nippon Unicar Co., Ltd. Catalyst A: Tetramethylhexamethylenediamine manufactured by Kao Corporation Medium B: manufactured by Kao Corporation pentamethyldiethylenetriamine catalyst C: Nihon Kagaku Sangyo Co. octylate potassium solution catalyst D: Nippon Emulsifier Co. l-isobutyl-2-
Methylimidazole Catalyst E: DO of lead octylate manufactured by Nippon Chemical Industry Co., Ltd.
P solution (lead concentration 17%) Blowing agent A: 1,1,1, manufactured by Central Glass Co., Ltd.
3,3-pentafluoropropane (HFC245fa) Blowing agent B: 1,1,1,3,3- manufactured by Solvay Co., Ltd.
Pentafluorobutane (HFC365mfc) Blowing agent C: Water

The weight ratio of the mixture A and the polyisocyanate is determined so as to have a predetermined isocyanate index.
6000-9000rpm using a laboratory mixer at ℃
m for 3 seconds to foam to produce a rigid polyurethane foam.

At this time, CT (cream time) and R
T (rise time) was measured visually to determine the initial reactivity. Further, the core density (initial core density) of the obtained rigid polyurethane foam was measured to have a dimension of 30 mm × 50.
It measured about what cut by mmx50mm.

Table 1 shows the results.

Next, the mixture A was placed in a closed container,
After leaving at 0 ° C. for 3 days, CT and RT were similarly measured when the mixture was foamed with isocyanate at a liquid temperature of 10 ° C. to determine the reactivity after storage. Similarly, the core density (core density after storage) was measured.

In the case of on-site construction, the reactivity as C
T is preferably within 10 seconds, particularly within 7 seconds, and RT is preferably within 40 seconds, especially within 30 seconds. As described above, the rigid polyurethane foam has a core density of 20 to 45 kg / m2.
It is preferably in the range of ³ .

[0049]

[Table 1]

As is clear from Table 1, in Comparative Examples 1 to 3 in which no imidazole compound was used as a catalyst,
Both CT and RT after storage are slow and unsuitable for on-site construction, and the core density is large and lacks practicality. In particular,
In Comparative Example 2, the foam after storage did not cure, and was not suitable for practical use.

On the other hand, in Examples 1 to 3 using an imidazole compound, CT and RT are slightly delayed after storage, but at a practical level, and the core density is in a sufficiently preferable range.

[0052]

As described in detail above, according to the present invention,
An isocyanurate-modified rigid polyurethane foam using a polyester polyol obtained by subjecting phthalic acid and / or a phthalic acid derivative to an esterification reaction as a polyol component, wherein the rigid polyurethane has a reduced amount of HFC used by using water in combination. In the foam, the hydrolysis stability of the polyester polyol can be suppressed to increase the storage stability of the blended liquid.

For this reason, according to the present invention, a low-density rigid polyurethane foam excellent in flame retardancy, stability and practicality, while reducing the amount of HFC used to enhance environmental safety and economy, is provided. Can be provided.

Continued on the front page F-term (reference) 4F074 AA76 AA81A AA90 AD21 AG10 AG20 BA32 BA53 BB08 BC01 DA02 DA15 DA32 4J034 AA04 BA02 BA03 CA03 DF01 DF16 DF17 DF22 DG00 DG03 DG04 DG22 HA07 HC03 HC12 K22 HC35 HC04 KB05 HC17 KD11 KD12 KE02 MA16 MA24 NA02 NA03 NA05 QA01 QA02 QB01 QB16 QC01 RA10 RA14

Claims (13)

[Claims] A rigid polyurethane foam obtained by mixing and foaming a polyisocyanate component, a polyol component, a foaming agent, a catalyst, and other auxiliaries, wherein phthalic acid and / or a phthalic acid derivative are used as the polyol component. In a rigid polyurethane foam using a polyol component containing a polyester polyol compound obtained by an esterification reaction, a carbon dioxide gas obtained by reacting the polyisocyanate component with water is used as a foaming agent, and an imidazole compound is used as a catalyst. Rigid polyurethane foam characterized by the above. 2. The rigid polyurethane foam according to claim 1, wherein a carbon dioxide gas obtained by reacting an isocyanate component and water is used in combination with a hydrofluorocarbon as a foaming agent. 3. The method according to claim 2, wherein the hydrofluorocarbon is 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane,
A rigid polyurethane foam comprising one or more selected from the group consisting of 1,1,2,3,3,3-heptafluoropropane and 1,1,1,2-tetrafluoroethane. 4. The method according to claim 3, wherein the hydrofluorocarbon contains 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane. Rigid polyurethane foam. 5. The method of claim 4, wherein the hydrofluorocarbon comprises 5-95% by weight of 1,1,1,3,3-pentafluoropropane and 95-5% by weight of 1,1,1,1.
Rigid polyurethane foam containing 3,3-pentafluorobutane. 6. The method of claim 5, wherein the hydrofluorocarbon comprises 20 to 80% by weight of 1,1,1,3,3-pentafluoropropane and 80 to 20% by weight of 1,1,
Rigid polyurethane foam containing 1,3,3-pentafluorobutane. 7. The hard polyurethane according to claim 3, wherein the hydrofluorocarbon contains 1,1,1,2-tetrafluoroethane and 1,1,1,3,3-pentafluorobutane. Form. 8. The method of claim 7, wherein the hydrofluorocarbon comprises 2 to 12% by weight of 1,1,1,2-tetrafluoroethane and 98 to 88% by weight of 1,1,1,3,3.
-A rigid polyurethane foam containing pentafluorobutane. 9. The method of claim 8, wherein the hydrofluorocarbon comprises 5 to 10% by weight of 1,1,1,2-tetrafluoroethane and 95 to 90% by weight of 1,1,1,3,3.
-A rigid polyurethane foam containing pentafluorobutane. 10. The method according to claim 3, wherein the hydrofluorocarbon contains 1,1,1,2,3,3,3-heptafluoropropane and 1,1,1,3,3-pentafluorobutane. A rigid polyurethane foam characterized by the following. 11. The method according to claim 10, wherein the hydrofluorocarbon comprises 2 to 15% by weight of 1,1,1,2,3.
Rigid polyurethane foam containing 3,3-heptafluoropropane and 98 to 85% by weight of 1,1,1,3,3-pentafluorobutane. 12. The reactive polyurethane raw material comprising a polyisocyanate component, a polyol component, a foaming agent, a catalyst and other auxiliaries according to any one of claims 1 to 11, wherein the content of the hydrofluorocarbon is 1 to 2.
A rigid polyurethane foam, which is 0% by weight. 13. The reactive polyurethane raw material comprising a polyisocyanate component, a polyol component, a foaming agent, a catalyst and other auxiliaries, wherein the content of hydrofluorocarbon is 5 to 15% by weight. Rigid polyurethane foam.