COMPOSITION FOR POLYURETHANE FOAMING, POLYURETHANE FOAM AND USE THEREOF

Abstract

A composition for polyurethane foaming, a polyurethane foam and a use thereof. The composition contains two different polyols with a polyethylene oxide ether structure and a polypropylene oxide ether structure, and a specific type of catalyst, flame retardant and water are added thereto; at the same time, the composition contains a small amount of a surfactant and other small molecular alcohols. The traits of the product are that it is pale yellow and transparent, and the product is not layered during long-term storage. The above-mentioned composition and polyphenylpolymethylene polyisocyanate (PAPI) produce a low-density polyurethane foam by means of a foaming machine. The foam has a good thermal insulation effect and a high rate of yield, and the foam has a flame retardant property, that is to say, same can be used for construction insulation, and can also be used for packaging a buffer material, has a good thermal insulation, adhesion and dimensional stability, and has a low odor during the process of construction, the foaming agents all use water, and do not contain chlorofluorocarbon substances that destroy the ozone layer and climate.

Claims

1. A composition for polyurethane foaming, wherein based on 100 parts by weight of the composition, it comprises the following materials in parts by weight: 10-30 parts of polyether polyol A; 20-40 parts of polyether polyol B; 10-40 parts of flame retardant; 10-30 parts of water; 1-4 parts of surfactant; 1-8 parts of catalyst; wherein, the average functionality of polyether polyol A is 4-8, the hydroxyl value is 300-700 mgKOH/g; wherein, the average functionality of polyether polyol B is 2-4, the hydroxyl value is 20-200 mgKOH/g; wherein, the flame retardant is a phosphate or a mixture of phosphates, the phosphorus content of the flame retardant is 8-40 wt %; wherein, the catalyst is a mixture of organic tertiary amines that contain hydroxyl group.

2. The composition according to claim 1, wherein the polyether polyol A is produced by the polymerization of propylene oxide, ethylene oxide and the mixture of one or more of sorbitol, sucrose, pentaerythritol, 2,4-diamino-phenol, ethylenediamine and tris(hydroxymethyl)propane in any mixing ratio as an initiator; wherein the molar ratio between the propylene oxide and the ethylene oxide is 7:3-9:1.

3. The composition according to claim 1, wherein the polyether polyol A is produced by the polymerization of propylene oxide, ethylene oxide and the mixture of sucrose, tris(hydroxymethyl)propane, sorbitol in any mixing ratio as an initiator; the average functionality is 4-5; the hydroxyl value is 400-500 mgKOH/g; the molar ratio between the propylene oxide and the ethylene oxide is 7:3-8:2.

4. The composition according to claim 1, wherein the polyether polyol A is produced by the polymerization of propylene oxide, ethylene oxide and 2,4-diamino-phenol or/and ethylenediamine as an initiator; the average functionality is 4-5; the hydroxyl value is 500-700 mgKOH/g; the molar ratio between the propylene oxide and the ethylene oxide is 7:3-9:1.

5. The composition according to claim 1, wherein the polyether polyol B is produced by the polymerization of propylene oxide, ethylene oxide and the mixture of one or more of dipropylene glycol, diethylene glycol or triethanolamine and glycerol in any mixing ratio as an initiator, and at the end of the reaction, it is blocked by ethylene oxide so that the terminal group of the polyether polyol B is a primary hydroxyl.

6. The composition according to claim 5, wherein the polyether polyol B is produced by the polymerization of propylene oxide, ethylene oxide and the mixture of glycerol and triethanolamine in any mixing ratio as an initiator, the hydroxyl value is 20-90 mgKOH/g, and at the end of the reaction, it is blocked by ethylene oxide so that the terminal group of the polyether polyol B is a primary hydroxyl.

7. The composition according to claim 1, wherein the surfactant is formed by the block copolymerization of polymethyl siloxane, propylene oxide and ethylene oxide.

8. The composition according to claim 1, wherein the catalyst comprises the mixture of dimethylamino ethoxyethanol and trimethylethoxylethylenediamine in any proportion, and further comprises one or more of N, N, N-trimethyl-N-hydroxyethyl diamino ethyl ether and trimethyl hydroxyethyl propanediamine, dimethylethanolamine.

9. The composition according to claim 1, wherein the flame retardant is the mixture of one or two of tris(2-chloropropyl) phosphate, tris(2-chloroethyl) phosphate and triethyl phosphate, wherein triethyl phosphate represents at least 40% of the total parts by weight of the flame retardant.

10. The composition according to claim 1, wherein the composition further comprises 0-3% of other additives, the other additives are selected from one or two of triethanolamine and glycerol.

11. A polyurethane foam, which is obtained from the composition according to claim 1.

12. The polyurethane foam according to claim 11, which is obtained by the reaction of the composition according to claim 1 with polyphenylpolymethylene polyisocyanate PAPI.

13. A method of using the polyurethane foam according to claim 11, wherein the polyurethane foam is used in one or more of thermal insulation filling materials, thermal insulation, sound insulation, damp proof of buildings, and the packaging of precise instrument.

14. The composition according to claim 1 comprising the following materials in parts by weight: 15-25 parts of polyether polyol A; 25-35 parts of polyether polyol B; 20-30 parts of flame retardant; 13-18 parts of water; 2-3 parts of surfactant; and 3-6 parts of catalyst.

15. The composition according to claim 1, wherein the catalyst is the composition of dimethylamino ethoxyethanol, trimethylethoxylethylenediamine and N, N, N-trimethyl-N-hydroxyethyl diamino ethyl ether in a mass ratio of 1-3:1-3:0-3.

16. The composition according to claim 1, wherein the flame retardant is the mixture of triethyl phosphate and tris(2-chloropropyl) phosphate in a mass ratio of 1-3:1-3.

Description

EMBODIMENTS

[0045] The present invention is further illustrated by the following embodiments, however, the embodiments are provided for a better understanding of the content of the present invention, and do not limit the extent of protection of the present invention.

[0046] In the present invention, unless otherwise stated, parts represent parts by weight; % represents wt %, i.e. weight percentage.

Preparation Examples 1-5

[0047] Polyether polyol 1 was a polyether polyol that was prepared by the polymerization of ethylene oxide, propylene oxide and sorbitol, sucrose, trimethylolpropane, wherein the sorbitol, sucrose, trimethylolpropane were used as initiators. The hydroxyl value was 450 mgKOH/g, and the average functionality was 4.5. The specific preparation method was as follows: 109 g sorbitol, 205 g sucrose, 268 g trimethylolpropane and 35 g catalyst were fed into a 2.5 L jacketed reaction vessel, and the temperature was increased gradually to 70 C. Stirring was started, the reaction vessel was evacuated, and excess amount of water of the raw material was removed, then the content inside the reaction vessel was replaced by nitrogen. 1000 g propylene oxide and 200 g ethylene oxide (the molar ratio between them is about 8:2) were slowly fed into the reaction vessel within 2 hours, the pressure was kept below 0.25 MPa, and the temperature was slowly increased to 100 C. until the completion of feeding. Then the temperature was increased to about 120 C. and was kept for 3 hours. After the reaction was completed, the temperature was decreased to below 90 C., the pH was adjusted, then the resulting polyether polyol was refined and filtered.

[0048] Polyether polyol 2 was a polyether polyol that was prepared by the polymerization of ethylene oxide, propylene oxide, sorbitol and trimethylolpropane, wherein the sorbitol and trimethylolpropane were used as mixed initiators. The hydroxyl value was 350 mgKOH/g, and the average functionality was 5. The specific preparation method was as follows: 364 g sorbitol, 134 g trimethylolpropane and 32 g catalyst were fed into a 2.5 L jacketed reaction vessel, and the temperature was increased gradually to 70 C. Stirring was started, the reaction vessel was evacuated, and excess amount of water of the raw material was removed. The content inside the reaction vessel was replaced by nitrogen, 1500 g propylene oxide and 300 g ethylene oxide (the molar ratio between them is about 8:2) were slowly fed into the reaction vessel within 2 hours, the pressure was kept below 0.25 MPa, and the temperature was slowly increased to 100 C. After the completion of feeding, the temperature was increased to about 110 C. and was kept for 3 hours. The temperature was decreased to below 90 C. after the reaction was completed, then the pH was adjusted, the resulting polyether polyol was refined and filtered.

[0049] Polyether polyol 3 was a polyether polyol that was prepared by the polymerization of ethylene oxide, propylene oxide, 2,4-diaminophenol and ethanediamine, wherein the 2,4-diaminophenol and ethanediamine were used as mixed initiators. The hydroxyl value was 680 mgKOH/g, and the average functionality was 4. The specific preparation method was as follows: 366 g 2,4-diaminophenol, 180 g ethanediamine were fed into a 2.5 L jacketed reaction vessel, and the temperature was increased gradually to 70 C. Stirring was started, then the content inside the reaction vessel was replaced by nitrogen. 1561 g propylene oxide and 132 g ethylene oxide (the molar ratio between them is about 9:1) were slowly fed into the reaction vessel within 2 hours, the pressure was kept below 0.25 MPa, and the temperature was slowly increased to 100 C. After the completion of feeding, the temperature was increased to about 110 C. and was kept for 2 hours. The temperature was decreased to below 90 C. after the reaction was completed, then the resulting polyether polyol was refined and filtered.

[0050] Polyether polyol 4 was a polyether polyol that was prepared by the polymerization of ethylene oxide, propylene oxide, glycerol and dipropylene glycol, wherein the glycerol and dipropylene glycol were used as mixed initiators. The hydroxyl value was 25 mgKOH/g, and the average functionality was 2.5. The specific preparation method was as follows: 645 g glycerol, 940 g dipropylene glycol and 40 g catalysts were fed into a 2.5 L jacketed reaction vessel, and the temperature was increased gradually to 70 C. Stirring was started, the reaction vessel was evacuated, excess amount of water of the raw material was removed. The content inside the reaction vessel was replaced by nitrogen, 410 g propylene oxide was slowly fed into the reaction vessel within 2 hours for a reaction, the pressure was kept below 0.25 MPa, and the temperature was kept at 90-100 C., until the completion of feeding. Then 133 g ethylene oxide (the molar ratio between propylene oxide and ethylene oxide was about 7:3) was slowly fed into the reaction vessel within 2 hours for a reaction, the pressure was kept below 0.25 MPa until the completion of feeding. Lastly, the temperature was increased to about 120 C. and was kept for 3 hours. The temperature was decreased to below 90 C. after the reaction was completed, then the resulting polyether polyol was refined and filtered.

[0051] Polyether polyol 5 was a polyether polyol that was prepared by the polymerization of ethylene oxide, propylene oxide, glycerol and triethanolamine, wherein the glycerol and triethanolamine were used as mixed initiators. The hydroxyl value was 80 mgKOH/g, and the functionality was 3. The specific preparation method was as follows: 644 g glycerol, 1044 g triethanolamine and 30 g catalyst were fed into a 2.5 L jacketed reaction vessel, and the temperature was increased gradually to 70 C. Stirring was started, the reaction vessel was evacuated, and excess amount of water of the raw material was removed. The content inside the reaction vessel was replaced by nitrogen, 438 g propylene oxide was slowly fed into the reaction vessel within 2 hours for a reaction, the pressure was kept below 0.25 MPa, the temperature was kept at 90-100 C., until the completion of feeding. Then 142 g ethylene oxide (the molar ratio between propylene oxide and ethylene oxide was about 7:3) was slowly fed into the reaction vessel within 2 hours for a reaction, the pressure was kept below 0.25 MPa until the completion of feeding. Then the temperature was increased to about 120 C. and was kept for 3 hours. The temperature was decreased to below 90 C. after the reaction was completed, then the pH was adjusted, the resulting polyether polyol was refined and filtered.

[0052] The catalyst used in the above preparation examples was potassium hydroxide.

[0053] The polyphenylpolymethylene polyisocyanate used in the following examples was PM-200 from Wanhua, Yantai, the detailed parameters were shown in the following table:

TABLE-US-00001 Acid component (%, Chlorine Viscousity Density calculated from Product (25 C.) -NCO (25 C.) based on hydrolysis brand Appearance mPa .Math. s (% Wt) g/cm.sup.3 HCL) (%) WANNATE Brown liquid 150-250 30.2-32.0 1.220-1.250 0.05 0.2 PM-200

[0054] Surfactant L-5345: Momentive high-tech materials company, Ltd., USA.

Examples 1-5

[0055] The composition of the formula shown in table 1 and PM200 of Wanhua Chemical Company were foamed using a high pressure sprayer Graco A20, the volume ratio of the two components was 1:1 (the weight ratio was 1:1.1). The polyurethane foam prepared was measured in accordance with common industry standard, and its performance is shown in table 2.

[0056] In the following table, the amounts of components are parts by weight, EO is ethylene oxide, PO is propylene oxide.

TABLE-US-00002 TABLE 1 Formula of the composition Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample Component 1 2 3 4 5 Polyether polyol 1: the 12.0 22 17.5 22 polyether polyol prepared by the polymerization of EO, PO, sorbitol, sucrose and trimethylolpropane, wherein the sorbitol, sucrose and trimethylol- propane were used as initiators, hydroxyl value 450 mgKOH/g, average functionality 4.5, the ratio between ethylene oxide and propylene oxide was about 8:2 (molar ratio, the same as below) Polyether polyol 2: the poly- 15.0 ether polyol prepared by the polymerization of EO, PO, sorbitol and trimethylol- propane, wherein the sorbitol and trimethylol- propane were used as mixed initiators, functionality 5, hydroxyl value 350 mgKOH/g, the ratio between ethylene oxide and propylene oxide was about 8:2 Polyether polyol 3: the poly- 7.0 ether polyol prepared by the polymerization of EO, PO, 2,4-diaminophenol and ethanediamine, and the 2,4-diaminophenol and ethanediamine were used as initiators, hydroxyl value 680 mgKOH/g, average functionality 4, the ratio between ethylene oxide and propylene oxide was about 9:1 Polyether polyol 4: the poly- 10.0 25.0 16.0 13.0 17.0 ether polyol prepared by the polymerization of EO, PO, glycerol and dipropylene glycol, wherein the glycerol and dipropylene glycol were used as initiators, average functionality 2.5, hydroxyl value 25 mgKOH/g, Polyether polyol 5: the poly- 10.0 15.0 15.0 13.0 15.0 ether polyol prepared by the polymerization of EO, PO, triethanolamine and glycerol, wherein the triethanolamine and glycerol were used as initiators, average functionality 3, hydroxyl value 80 mgKOH/g, Tris(2- 16 10 10 15 10 chloropropyl)phosphate Triethyl phosphate 20 15 15 15 15 Water 24 11 15 19 15 Surfactant L-5345 3 3 2 2 2 Dimethyaminoethoxyethanol 3 2 3 3 2 Trimethyl hydroxyethyl 1 1 1 1.5 1 ethylenediamine N,N,N-trimethyl-N- 1 1 1 0 hydroxyethyl diamino ethyl ether Dimethylethanolamine 0 1 0 0 0 Glycerol or Triethanolamine 0 1 0 0 1

TABLE-US-00003 TABLE 2 Foam properties Example Example Example Example Example standard Item 1 2 3 4 5 number Construction Spraying Spraying Spraying Spraying Perfusion / way Foam density, 8 12 9.5 9 9.5 GB/T6343-2009 kg/m.sup.3 Rate of yield of 115 75 95 100 90 / comprehensive construction, m.sup.3/ton Solidifying 10 10 10 10 30 / time, s heat 0.03720 0.03571 0.03660 0.03710 0.03650 GB10295 conductivity coefficient at 23 C., w/m.K aperture 94.5 92.0 93.6 94.3 94.3 ASTM ratio, % D-2856 compressive 15.9 25.1 18.8 18.0 19.2 GB8813 strength KPa Dimensional 0.1 0.3 0.2 0.3 0.1 GB3399 stability at 30 C., % Average Higher Higher Higher Higher Higher GB50404 adhesion than the than the than the than the than the strength strength strength strength strength of the of the of the of the of the foam foam foam foam foam linear <0.1 <0.1 <0.1 <0.1 <0.1 GB8811 deformation within 48 h, 30 C., % The time of 7 35 34 13 30 GB8332-2008 horizontal flame, s The range of 8 90 90 70 86 GB8332-2008 horizontal flame, mm

[0057] The above performance tests use the testing standards which are commonly used in the field, and moreover, the test method and the devices are well known and common in the field.