POLYOL PREMIX COMPOSITION FOR RIGID POLYURETHANE FOAMS

Abstract

The present invention relates to a polyol premix composition for rigid polyurethane foams comprising a hydrohaloolefin as foaming agent, an amine catalyst and an aliphatic dicarboxylic acid. The polyol premix composition has a high initial reaction rate when it is reacted with isocyanate and shows smaller deterioration of reactivity over time.

Claims

1. A polyol premix composition for production of rigid polyurethane foams, comprising a polyol, water, a foaming agent, and an amine catalyst, and additionally a aliphatic dicarboxylic acid as reactivity- and storage stability-improving agent, wherein the foaming agent comprises a hydrohaloolefin, and the aliphatic dicarboxylic acid is present in an amount of at least 1.2 equivalents of carboxyl groups with respect to the amino groups of the amine catalyst.

2. The polyol premix composition according to claim 1, comprising the aliphatic dicarboxylic acid in an amount of at least 1.5 equivalents of carboxyl groups with respect to the amino groups in the amine catalyst.

3. The polyol premix composition according to claim 1, comprising the aliphatic dicarboxylic acid in an amount of 1.5-2.5 equivalents of carboxyl groups with respect to the amino groups in the amine catalyst.

4. The polyol premix composition according to claim 1, comprising an urethane reaction catalyst and a trimerization catalyst in a weight ratio (urethane reaction catalyst/trimerization catalyst) of 0.75-8.

5. The polyol premix composition according to claim 1, wherein the amine catalyst is selected from monoamine-, diamine-, polyamine-, and alkanolamine-based catalysts, and wherein the polyol premix composition additionally contains an ammonium salt or a non-amine type catalyst.

6. The polyol premix composition according to claim 1, wherein the aliphatic dicarboxylic acid is succinic acid, glutaric acid, or a mixture thereof.

7. The polyol premix composition according to claim 1, wherein the foaming agent is a hydrochlorofluoroolefin.

8. The polyol premix composition according to claim 1, wherein the foaming agent is 1-chloro-3,3,3-trifluoropropene.

9. The polyol premix composition according to claim 1, wherein the polyol is a mixture of a polyether polyol and a polyester polyol.

10. The polyol premix composition according to claim 1, wherein the polyol comprises an aromatic amine based polyether polyol.

11. A rigid polyurethane foam prepared by reacting the polyol premix composition according to claim 1 with an isocyanate.

12. A rigid polyurethane foam according claim 11, wherein the isocyanate comprises diphenylmethane diisocyanate (monomeric MDI) and/or polymethylene polyphenyl isocyanates (polymeric MDIs).

13. A process for producing a rigid polyurethane foam, comprising reacting the polyol premix composition according to claim 1 with an isocyanate.

14. A process for producing a rigid polyurethane foam according to claim 13, wherein the process is a spraying process.

15. The polyol premix composition according to claim 1, comprising an urethane reaction catalyst and a trimerization catalyst in a weight ratio (urethane reaction catalyst/trimerization catalyst) of 1-6.

Description

EXAMPLES

[0058] Hereinafter, typical embodiments of the present invention will be described in detail with reference to Examples but it should be understood that the scope of the present invention is not limited to these Examples.

<Raw Materials Used>

[0059] Abbreviations for the major raw materials used in Examples and Comparative Examples of the present invention are explained in Table 1.

TABLE-US-00001 TABLE 1 Raw materials used Manufacturer Abbreviation Function Chemical species product name Excenol-450SN Polyol Polyether polyol, OH-value 450 mg KOH/g Asahi Glass Co., Ltd. Excenol 450SN Z450 Polyol o-TDA based Polyether polyol, OH-value 350 mg Sumika Bayer Urethane Co., Ltd. KOH/g SBU Polyol Z450 EDP300 Polyol Polyether polyol, OH-value 750 mg KOH/g ADEKA Corp. Adeka polyether EDP300 PL306 Polyol Polyester polyol, OH-value 315 mg KOH/g Hitachi Kasei Polymer Co., Ltd. Phantol PL-306 L6988 Foam Silicone **MPMJ stabilizer Niax Silicon L-6988 Kao#10 Catalyst N,N-dimethylcyclohexylamine Kao Corp. Kaolizer No. 10 TMR2 Catalyst (2-Hydroxypropyl)trimethylammonium Air Products and Chemicals, Inc. formate Dabco TMR2 LBA Foaming 1-Chloro-3,3,3-trifluoropropene Honeywell Inc. agent HCFO-1233zd Solstice LBA iso Isocyanate Polymeric MDI, NCO % 31.5 Sumika Bayer Urethane Co., Ltd. Sumidur 44 V20L Succinic acid* Dicarboxylic Butanedioic acid Wako Pure Chemical Industries Co., Ltd. acid Glutaric acid* Dicarboxylic Pentanedioic acid Wako Pure Chemical Industries Co., Ltd. acid *The dicarboxylic acid was added as a homogeneous solution after it is dissolved in water under heat (water removed by vaporization under heat was replenished). **Momentive Performance Materials Japan Inc.

<Foaming Test Procedure>

1. Abstract

[0060] A liquid mixture of the blended polyol and LBA (foaming agent) (referred to as polyol premix) and an isocyanate were mixed and agitated with a homomixer at a particular blending ratio (referred to as reaction mixture). The reaction mixture solution is transferred immediately into a wooden box, wherein the reactivity thereof (cream time (CT), gel time (GT), and tack-free time (TFT)) was determined.

2. Foaming Test Procedure (in Detail)

[0061] 1) Polyols, additives, and others are weighed in predetermined amounts and mixed and homogenized with a homomixer (T. K. Robomix by PRIMIX Co., Ltd.), to give a blended polyol. [0062] 2) 1000.1 g of the blended polyol is weighed into a disposable cup (500 ml). [0063] 3) The foaming agent LBA is added in a predetermined amount to the blended polyol thus obtained and the resulting mixture is mixed sufficiently with a homomixer. [0064] 4) The mixture is weighed after mixing; LBA lost by vaporization is replenished and the mixture was mixed again. The mixture is then adjusted to a particular temperature (200.5 C.). After temperature adjustment, the mixture is weighed again. When the weight is smaller than a predetermined value, Step 4) is repeated to give a polyol premix. [0065] 5) The isocyanate is weighed in another disposable cup and adjusted to a particular temperature (200.5 C.). After temperature adjustment, a predetermined amount of the isocyanate was added to the polyol premix of 4. Isocyanate index is 106. [0066] 6) simultaneously with start of stop watch, the liquid mixture of 5) is mixed and agitated with a homomixer at 4000 rpm for 5 seconds (referred to as reaction mixture). [0067] 7) The reaction mixture of 6) is poured into a wooden box internally covered with a Kraft paper. [0068] 8) The following reactivities (i) to (iii) and the resin physical properties (iv) are measured. [0069] (i) Cream time (CT): period from start of mixing to until the reaction mixture becomes cloudy and creamy and starts to expand. [0070] (ii) Gel time (GT): period from start of mixing to the time when, if a wooden chopstick is inserted into and then pulled out of the reaction mixture, the reaction mixture deposited on the chopstick appears stringy. Frequency of insertion 1 time per second. [0071] (iii) Tack-free time (TFT): period from start of mixing to the time when, if a chopstick is brought into contact with the surface of the reaction mixture, the resin appears non-adhesive to the chopstick. [0072] (iv) Free density (FD): resin density (kg/m.sup.3) after free foaming (measured according to JIS K 7222 (corresponds to ISO 845)).

<Storage Stability Test Procedure>

[0073] The polyol premix of 4) is placed in a pressure bottle (model number: 5555-33) manufactured by AS ONE Corporation and stored in an oven adjusted to 50 C. for the respective period of time (see table). After it is cooled to room temperature, the reactivity thereof with isocyanate and the resin physical properties are determined according to above foaming test procedure.

Example 1

[0074] A foaming test was performed according to the foaming test procedure above, using the raw materials described in Table 1 and adding succinic acid in an amount of 2 equivalents to the amine catalyst (Kao #10). The amounts of respective components used (part by mass) and the evaluation results of the foaming test are shown in Table 2.

Example 2

[0075] A foaming test was performed according to the foaming test procedure above, using the raw materials described in Table 1 and adding glutaric acid in an amount of 2 equivalents to the amine catalyst (Kao #10). The amounts of respective components used (part by mass) and the evaluation results of the foaming test are shown in Table 2 with the results of Example 1.

Comparative Example 1a and Comparative Example 1b

[0076] A foaming test was performed according to the foaming test procedure above, using the raw materials described in Table 1 without addition of any dicarboxylic acid (Comparative Example 1a) and with addition of glutaric acid in an amount of 1 equivalent to the amine catalyst (Kao #10) (Comparative Example 1b).

[0077] The amounts of respective components used (part by mass) and the evaluation results of the foaming tests are shown in Table 2 together with the results of Examples 1 and 2. In Table 2, the addition amounts of Kao #10 and part of dicarboxylic acid are also shown by mole.

TABLE-US-00002 TABLE 2 Amounts of raw materials used in Examples 1 and 2 and Comparative Example 1a and 1b and evaluation results of foaming test Test No. Comparative Example 1b Example 1 Example 2 Comparative Example 1a Glutaric acid added in an Succinic acid added in an Glutaric acid added in an No addition of amount of 1.0 equivalents to amount of 2 equivalents to amount of 2 equivalents to dicarboxylic acid amine catalyst (Kao #10) amine catalyst (Kao #10) amine catalyst (Kao #10) Component Amount: part by mass Amount: part by mass Amount: part by mass Amount: part by mass Excenol 40 40 40 40 450 SN Z450 40 40 40 40 EDP300 5 5 5 5 PL306 15 15 15 15 (Polyol total) (100) (100) (100) (100) L6988 2 2 2 2 Dicarboxylic 0 1.04 0.00785 mol 1.86 0.0157 mol 2.08 0.0157 mol acid Kao #10 2 0.0157 mol 2 0.0157 mol 2 0.0157 mol 2 0.0157 mol TMR2 0.8 0.8 0.8 0.8 Water 1.89 1.89 1.89 1.89 (Additives (6.69) (8.24) (8.55) (8.77) total) Blended polyol 100 100 100 100 LBA 26 26 26 26 (Polyol premix (126) (126) (126) (126) total) iso 123 123 123 123 Reaction 249 249 249 249 mixture total Storage 0 After After 0 After After 0 After After 0 After After period (day) 9 days 15 days 9 days 15 days 9 days 15 days 9 days 15 days (Temperature: 50 C.) CT(sec) 7 9 10 4 5 7 2.5 2.5 2.5 2.5 2.5 2.5 GT(sec) 63 67 72 74 79 85 78 79 79 75 74 76 TFT(sec) 83 88 94 113 129 135 129 137 143 118 119 125 FD (kg/m.sup.3) 25.1 25.4 25.8 25.7 25.7 23.9 23.9 23.9 24.3 24.4 24.4
When the results of the foaming tests of Examples 1 and 2 are compared with those of Comparative Example 1a wherein no dicarboxylic acid and Comparative Example 1b wherein 0.5 mol (1 equivalence) of glutaric acid was added, that, if succinic acid or glutaric acid is added in an amount of 1 mole (2 equivalents) to the amine catalyst (Kao #10), the cream time (CT) becomes shorter and the change of CT after 15 days is mostly negligible. In addition, the differences both in gel time (GT) and tack-free time (TFT) between the initial state (day 0) and the day 15 were significantly smaller than those of Comparative Example 1a wherein no dicarboxylic acid was added, indicating that the storage stability of the polyol premix was improved.

Comparative Example 1c

[0078] A foaming test and evaluation of the results were performed similarly to Example 1, except that the addition amount of succinic acid in Example 1 was changed to 1 equivalent to the amine catalyst (Kao #10). The amounts of respective components used (part by mass) and the evaluation results of the foaming tests are shown in Table 3

[0079] A foaming test was performed according to the foaming test procedure above, using the raw materials described in Table 1 with addition of succinic acid in an amount of 1 equivalent to the amine catalyst (Kao #10).

Example 3

[0080] A foaming test and evaluation of the results were performed similarly to Example 1, except that the addition amount of succinic acid in Example 1 was changed to 1.39 parts by mass (1.5 equivalents to the amine catalyst (Kao #10). The amounts of respective components used (part by mass) and the evaluation results of the foaming test are shown in Table 3 together with the results of Example 1.

Example 4

[0081] A foaming test and evaluation of the results were performed similarly to Example 1, except that the addition amount of succinic acid in Example 1 was changed to 2.32 parts by mass (2.5 equivalents to the amine catalyst (Kao #10). The amounts of respective components used (part by mass) and the evaluation results of the foaming test are shown in Table 3 with the results of Examples 1 and 3.

TABLE-US-00003 TABLE 3 Addition amounts of raw materials and results of foaming evaluation test in Examples 3, 4, and 1 and Comparative example 1c Test No. Comparative Example 1c Example 3 Example 1 Example 4 Succinic acid added Succinic acid added Succinic acid added in Succinic acid added in an amount of in an amount of an amount of 2 equivalents in an amount of 1.0 equivalents to 1.5 equivalents to amin to amine catalyst 2.5 equivalents to amine catalyst (Kao #10) catalyst (Kao #10) (Kao #10) amine catalyst (Kao #10) Component Amount: part by mass Amount: part by mass Amount: part by mass Amount: part by mass Excenol 40 40 40 40 450 SN Z450 40 40 40 40 EDP300 5 5 5 5 PL306 15 15 15 15 (Polyol total) (100) (100) (100) (100) L6988 2 2 2 2 Dicarboxylic 0.93 1.39 1.86 2.32 acid Kao #10 2 2 2 2 TMR2 0.8 0.8 0.8 0.8 Water 1.89 1.89 1.89 1.89 (Additives (7.62) (8.08) (8.55) (9.01) total) Blended polyol 100 100 100 100 LBA 26 26 26 26 (Polyol premix (126) (126) (126) (126) total) iso 123 123 123 123 Reaction 249 249 249 249 mixture total Storage period 0 After After 0 After After 0 After After 0 After After (day) 9 days 15 days 9 days 15 days 9 days 15 days 9 days 15 days (Temperature: 50 C.) CT (sec) 4 5 7 3 3 3 2.5 2.5 2.5 2 2 2 GT (sec) 62 67 75 71 72 73 78 79 79 91 91 90 TFT (sec) 83 106 108 111 113 118 129 137 143 163 164 166 FD (kg/m.sup.3) 25.1 25.2 25.3 24.1 24.2 24.1 23.9 23.9 23.9 23.3 23.3 23.4
The results of Table 3 show that, if succinic acid is added in an amount of 1.5 to 2.5 equivalents to the amine catalyst (Kao #10), the CT of the polyol premix becomes shorter and remains almost the same even after storage for 15 days. The results further show that the changes of GT and TFT after storage of the polyol premix for 15 days are also smaller than those of Comparative Examples 1a and 1b shown in Table 2 as well as Comparative Example 1c shown in Table 3.

Example 5

[0082] A foaming test and evaluation of the results were performed similarly to Example 2, except that the addition amount of glutaric acid in Example 2 was changed to 1.55 parts by mass (1.5 equivalents to the amine catalyst (Kao #10)). The amounts of respective components used and the evaluation results of the foaming test are shown in Table 4 with the results of Example 2.

Example 6

[0083] A foaming test and evaluation of the results were performed similarly to Example 2, except that the addition amount of glutaric acid in Example 2 was changed to 2.59 parts by mass (2.5 equivalents to the amine catalyst (Kao #10)). The amounts of respective components used and the evaluation results of the foaming test are shown in Table 4 with the results of Examples 2 and 5.

TABLE-US-00004 TABLE 4 Addition amounts of raw materials and results of foaming evaluation tests in Examples 5, 6, and 2 Test No. Example 5 Example 2 Example 6 Glutaric acid added in an amount Glutaric acid added in an amount Glutaric acid added in an amount of 1.5 equivalents to of 2.0 equivalents to of 2.5 equivalents to amine catalyst (Kao #10) amine catalyst (Kao #10) amine catalyst (Kao #10) Component Amount: part by mass Amount: part by mass Amount: part by mass Excenol 450 SN 40 40 40 Z450 40 40 40 EDP300 5 5 5 PL306 15 15 15 (Polyol total) (100) (100) (100) L6988 2 2 2 Dicarboxylic acid 1.55 2.08 2.59 Kao #10 2 2 2 TMR2 0.8 0.8 0.8 Water 1.89 1.89 1.89 (Additives total) (8.24) (8.77) (9.28) Blended polyol 100 100 100 LBA 26 26 26 (Polyol premix total) (126) (126) (126) iso 123 123 123 Reaction mixture 249 249 249 total Storage period (day) 0 After 9 days After 15 days 0 After 9 days After 15 days 0 After 9 days After 15 days (Temperature: 50 C.) CT (sec) 3 3 3 2.5 2.5 2.5 2 2 2 GT (sec) 74 75 76 75 74 76 74 74 77 TFT (sec) 119 126 130 118 119 125 117 117 123 FD (kg/m3) 24.8 24.8 24.7 24.3 24.4 24.4 24.3 24.4 24.2

[0084] The results of Table 4 show that, if glutaric acid is added in an amount of 1.5 to 2.5 equivalents to the amine catalyst (Kao #10), the CT of the polyol premix becomes shorter and the change thereof after storage for 15 days is almost negligible. The results further show that the changes of GT and TFT after storage of the polyol premix for 15 days are also smaller than those of Comparative Example 1 shown in Table 2.

Comparative Examples 2-5

[0085] A foaming test and evaluation of the results were performed similarly to Example 1, except that the different acids were added in an amount amount of 2 mole equivalents to the amine catalyst (Kao #10)). The amounts of respective components and the type of the acids used and the evaluation results of the foaming test are shown in Table 5 with the results of Examples 2 and 5.

TABLE-US-00005 TABLE 5 Addition of 2.0 mole equivalents acid, amounts of raw materials and results of foaming evaluation tests in Comparative Examples 2-5 Test No. Comparative Example 1 Example 2 Example 2 Succinic acid Glutaric acid Malonic acid 2.0 equivalents 2.0 equivalents 2.0 equivalents Component Amounts: part by mass Excenol 450 SN 40 40 40 Z450 40 40 40 EDP300 5 5 5 PL306 15 15 15 (Polyol total) (100) (100) (100) L6988 2 2 2 (Di)carboxylic acid 1.86 0.0157 mol 2.08 0.0157 mol 1.64 0.0157 mol Kao #10 2 0.0157 mol 2 0.0157 mol 2 0.0157 mol TMR2 0.8 0.8 0.8 Water 1.89 1.89 1.89 (Additives total) (8.55) (8.77) (8.33) Blended polyol 100 100 100 LBA 26 26 26 (Polyol premix total) (126) (126) (126) iso 123 123 123 Reaction mixture 249 249 249 total Storage period (day) 0 After After 0 After After 0 After After (Temperature: 9 days 15 days 9 days 15 days 9 days 15 days 50 C.) CT (sec) 2.5 2.5 2.5 2.5 2.5 2.5 13 13 16 GT (sec) 78 79 79 75 74 76 108 110 115 TFT (sec) 129 137 143 118 119 125 180 196 200 FD (kg/m3) 23.9 23.9 23.9 24.3 24.4 24.4 24.7 24.4 24.5 Test No. Comparative Comparative Comparative Example 3 Example 4 Example 5 Adipic acid Pimelic acid Valeric acid 2.0 equivalents 2.0 equivalents 2.0 equivalents Component Amounts: part by mass Excenol 450 SN 40 40 40 Z450 40 40 40 EDP300 5 5 5 PL306 15 15 15 (Polyol total) (100) (100) (100) L6988 2 2 2 (Di)carboxylic acid 2.3 0.0157 mol 2.52 0.0157 mol 3.66 0.0032 mol (mono acid) Kao #10 2 0.0157 mol 2 0.0157 mol 2 0.0157 mol TMR2 0.8 0.8 0.8 Water 1.89 1.89 1.89 (Additives total) (8.99) (9.21) (10.35) Blended polyol 100 100 100 LBA 26 26 26 (Polyol premix total) (126) (126) (126) iso 123 123 123 Reaction mixture 249 249 249 total Storage period (day) 0 After After 0 After After 0 After After (Temperature: 9 days 15 days 9 days 15 days 9 days 15 days 50 C.) CT (sec) 13 13 16 13 14 17 15 18 20 GT (sec) 108 113 122 123 128 134 109 110 116 TFT (sec) 165 168 175 188 190 195 175 173 194 FD (kg/m3) 25 25.1 25.1 24.9 24.9 25 24.4 24.7 24.7
The results shown in Table 5 prove the advantageous effect of malic and succinic acid over other dicarboxylic and monocarboxylic acids with regard to CT and storage stability.

[0086] The polyol premix composition containing an added dicarboxylic acid according to the present invention gives a rigid polyurethane foam improved in reactivity and also improved in storage stability under a condition containing halogenated olefin as a foaming agent, and can thus be used in production of rigid polyurethane foams extremely superior in practical use.