MACROMONOMERIC STABILIZER, PREPARATION METHOD THEREOF, AND METHOD FOR PREPARING POLYMERIC POLYOL

Abstract

A macromonomeric stabilizer, a preparation method thereof, a method for preparing a polymeric polyol using same, and the polymeric polyol prepared. Also disclosed are a soft polyurethane foam obtained by foaming a composition of the polymeric polyol prepared and a polyisocyanate, and a molded product comprising the soft polyurethane foam. The preparation method of the macromonomeric stabilizer comprises the following steps: reacting a polyol with a tricarboxylate not comprising a polymerizable ethylenically unsaturated double bond, or a derivative thereof, to form an adduct; and reacting the resulting adduct with an epoxide comprising a polymerizable ethylenically unsaturated double bond. The macromonomeric stabilizer of the present invention has a low viscosity, comprises a plurality of active sites, and can be directly used in subsequent reactions. The preparation method of the macromonomeric stabilizer can be carried out under normal pressure, without the need for end-blocking with ethylene oxide.

Claims

1. A method for preparing a macromonomeric stabilizer, comprising: reacting a polyol with a tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or a derivative thereof, to form an adduct; and reacting the resulting adduct with an epoxide comprising a polymerizable olefinic unsaturated double bond.

2. The method according to claim 1, wherein the structure formula of the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof is ##STR00008## wherein X is a straight or branched alkane segment having 1 to 25 carbons, a cycloalkane segment having a total of 3 to 25 carbons or a straight or branched alkane segment containing cycloalkyl and having a total of 4 to 25 carbons or a cycloalkane segment substituted with straight or branched alkyl and having a total of 4 to 25 carbons, or an aromatic hydrocarbon segment having a total of 6 to 25 carbons or a straight or branched alkane segment containing aryl and having a total of 7 to 25 carbons or an aromatic hydrocarbon segment substituted with straight or branched alkyl and having a total of 7 to 25 carbons, and X does not comprise a polymerizable olefinic unsaturated double bond.

3. The method according to claim 2, wherein the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof is trimesic acid, trimellitic anhydride, or hydrogenated maleopimaric acid.

4. The method according to claim 1, wherein the polyol is a polyether polyol.

5. The method according to claim 1, wherein the epoxide comprising a polymerizable olefinic unsaturated double bond is one or more of 1,2-epoxides comprising a polymerizable olefinic unsaturated double bond, having a structure formula of ##STR00009## wherein R is selected from R.sub.1—COO—R.sub.2, R.sub.3—O—R.sub.4, or straight or branched alkyl having 1 to 4 carbons, wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently selected from H, or straight or branched alkyl having 1 to 4 carbons; T is selected from H, cyano, or branched or straight alkyl having 1 to 4 carbons.

6. The method according to claim 1, wherein the molar ratio of the polyol to the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof is 0.2:1 to 4:1.

7. The method according to claim 1, wherein the molar ratio of the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof to the epoxide is 0.1:1 to 2:1.

8. The method according to claim 1, wherein the reaction of forming the adduct is carried out in the presence or absence of a catalyst.

9. The method according to claim 1, wherein the reaction between the adduct and the epoxide comprising a polymerizable olefinic unsaturated double bond is carried out in the presence or absence of a catalyst.

10. The method according to claim 1, wherein the reaction between the polyol and the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof is carried out in a solvent-containing system or a solvent-free system.

11. A macromonomeric stabilizer prepared by the method according to claim 1.

12. A flexible polyurethane foam obtained by foaming a composition of a polyisocyanate and the polymeric polyol, wherein the polymeric polyol is prepared by a method comprising the following steps: polymerizing at least one olefinic unsaturated monomer in the presence of a base polyether polyol, a polymerization initiator, and a macromonomeric stabilizer prepared by the method according to claim 1.

13. The flexible polyurethane foam according to claim 12, wherein the olefinic unsaturated monomer is one or more selected from aliphatic conjugated diene, a vinyl aromatic compound, α,β-olefinic unsaturated nitrile, α,β-olefinic unsaturated nitrile amide, α,β-olefinic unsaturated carboxylic acid, α,β-olefinic unsaturated carboxylate, vinyl ester, vinyl ether, vinyl ketone, a vinyl halide, and a vinylidene halide.

14. The flexible polyurethane foam according to claim 12, wherein the mass of the olefinic unsaturated monomer is 20% (w/w) to 70% (w/w) of the total mass of the base polyether polyol, the olefinic unsaturated monomer, and the macromonomeric stabilizer.

15. The flexible polyurethane foam according to claim 12, wherein the mass ratio of the olefinic unsaturated monomer to the base polyether polyol is 0.1% to 250%.

16. The flexible polyurethane foam according to claim 12, wherein the base polyether polyol is a trifunctional polyether polyol having a hydroxyl value of 10 mgKOH/g to 60 mgKOH/g.

17. The flexible polyurethane foam according to claim 12, wherein by mass, the amount of the macromonomeric stabilizer is 0.3% (w/w) to 10% (w/w) of the total mass of the base polyether polyol and the olefinic unsaturated monomer.

18. The flexible polyurethane foam according to claim 12, wherein by mass, the amount of the macromonomeric stabilizer is 2% (w/w) to 5% (w/w) of the total mass of the base polyether polyol and the olefinic unsaturated monomer.

19. The flexible polyurethane foam according to claim 13, wherein the base polyether polyol is a trifunctional polyether polyol having a hydroxyl value of 10 mgKOH/g.

20. The flexible polyurethane foam according to claim 13, wherein the base polyether polyol is a trifunctional polyether polyol having a hydroxyl value of 10 mgKOH/g to 60 mgKOH/g.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0073] FIG. 1 is the SEM image of the polymeric polyol 1 prepared in Example 4.

[0074] FIG. 2 is the SEM image of the polymeric polyol 2 prepared in Example 5.

[0075] FIG. 3 is the SEM image of the comparative polymeric polyol prepared in Comparative Example 2.

DETAILED DESCRIPTION

[0076] The present disclosure will be further described hereinafter in conjunction of the specific examples. It is to be understood that the examples described below are intended to be illustrative only and are not intended to limit the scope of the present disclosure.

[0077] The materials and reagent used in the following examples of the present disclosure are sourced as follows:

[0078] Trimellitic anhydride: Shandong Xiya Chemical Industry Co., Ltd., analytical pure.

[0079] Hydrogenated maleopimaric acid: self-made, 62.5 g of Pinus massoniana rosin containing 80% abietic acid (purchased from Shanghai Sanlian Industry), 30 ml of acetic acid, and 10.2 g of maleic anhydride were mixed and then reacted. The reaction was refluxed at 110° C. for 4 hours. After the reaction was cooled, the resultant product was washed twice with acetic acid and then three times with distilled water at 80° C., filtered, and dried to obtain maleopimaric acid anhydride in a yield of 62.5%. The obtained product was redissolved in 200 ml of ethanol and catalyzed for 3.5 hours in the presence of 4 g of 5% (w/w) palladium on carbon catalyst at 65±1.5° C. under 0.45 Mpa hydrogen atmosphere. After the reaction was cooled, the filtrate was concentrated to dryness, with a yield of 92.7%.

[0080] Trimesic acid: Shanghai Macklin Biochemical Co., Ltd, analytical pure

[0081] Isopropanol: Shangdong Dadi Huapu Chemical Co., Ltd., industrial grade.

[0082] Acrylonitrile: Shanghai SECCO, industrial grade

[0083] Styrene: Tianjin Dagu Chemical Co., Ltd., industrial grade.

[0084] Azobisisobutyronitrile: Shangdong Haiming Chemical Co., Ltd., industrial grade.

[0085] Base polyether polyol: common flexible foam polyether polyol prepared by reacting glycerol with propylene oxide and ethylene oxide, Wanhua Chemical Group Co., Ltd., WANOL® F3156.

[0086] Other raw materials involved in the following examples were purchased from Aladdin Biochemical Technology Co., Ltd, if not specified otherwise.

[0087] The test method used in the present disclosure is as follows:

[0088] Hydroxyl value: GB 12008.3-2009 Plastics—Polyether Polyols—Part 3: Determination of hydroxyl value

[0089] Viscosity: GB 12008.7-2010 Plastics—Polyether Polyols—Part 7: Determination of viscosity

[0090] Solid content: GB/T 31062-2014 Polymeric Polyol

[0091] The following examples were carried out under the protection of nitrogen if not specified otherwise.

EXAMPLE 1

Preparation of Polyether Polyol 1

[0092] The specific preparation is described in CN107090064A.

[0093] In a reaction kettle, sorbitol was added as an initiator, the catalyst (KOH) which was 0.3% (w/w) of the mass of propylene oxide (PO) designed to be added was added, the reaction temperature was controlled to be about 110±5° C., the pressure was controlled to be lower than 0.15 MPa, the PO was fed, and the reaction was then carried out. After the completion of the PO feeding, the reaction continued for 2 hours, and the unreacted PO was removed for 1 hour. After the completion of degassing, ethylene oxide (EO) was fed, and with the reaction temperature controlled at about 110±5° C. and the pressure controlled to be lower than 0.15 MPa, the reaction was carried out. After the completion of material feeding, the reaction was continued for 2 hours, and unreacted EO was removed for 1 hour. At this time, the reaction stage ended. With the temperature controlled to be at 85° C. to 90° C., soft water and phosphoric acid were added to neutralize the reaction product, and the neutralized product was dehydrated, filtered, and cooled to obtain the polyether polyol 1. In this example, the mass ratio of sorbitol/EO/PO was 1.08/4.95/93.97. The hydroxyl value of the obtained polyether polyol 1 was measured to be about 28 mgKOH/g, and the molecular weight was about 12000 daltons.

EXAMPLE 2

Preparation of Polyether Polyol 2

[0094] In a reaction kettle, pentaerythrite was added as an initiator, the catalyst (KOH) which was 0.3% (w/w) of the mass of propylene oxide (PO) designed to be added was added, the reaction temperature was controlled to be about 110±5° C., the pressure was controlled to be lower than 0.15 MPa, the PO was fed, and the reaction was then carried out. After the completion of the PO feeding, the reaction continued for 2 hours, and the unreacted PO was removed for 1 hour. After the completion of degassing, ethylene oxide (EO) was fed, and with the reaction temperature controlled at about 110±5° C. and the pressure controlled to be lower than 0.15 MPa, the reaction was carried out. After the completion of material feeding, the reaction was continued for 2 hours, and unreacted EO was removed for 1 hour. At this time, the reaction stage ended. With the temperature controlled to be at 85° C. to 90° C., soft water and phosphoric acid were added to neutralize the reaction product, and the neutralized product was dehydrated, filtered, and cooled to obtain the polyether polyol 2. In this example, the mass ratio of pentaerythrite/EO/PO was 1.36/14.80/83.84. The hydroxyl value of the obtained polyether polyol 2 was measured to be about 22 mgKOH/g, and the molecular weight was about 10000 daltons.

[0095] The reactions in the following examples were carried out at atmospheric pressure if not specified otherwise.

EXAMPLE 3

Preparation of Macromonomeric Stabilizer 1

[0096] 3000 g of polyether polyol 1, 45.8 g of trimesic acid, and 180 g of acetone were mixed homogeneously, warmed to 110° C., and stirred and refluxed for 18 hours. 6.0 g of ethyl triphenyl phosphonium iodide was added and stirred to dissolve, and then 80.6 g of glycidyl methacrylate and 1.78 g of hydroquinone were added and reacted at 120° C. overnight to obtain a product as a transparent light-yellow liquid. After the solvent was removed, the product had a viscosity of 1720 mPa.Math.s (25° C.).

EXAMPLE 4

Preparation of Macromonomeric Stabilizer 2

[0097] 250 g of polyether polyol 2 and 12.5 g of hydrogenated maleopimaric acid (preliminarily dissolved with 50 g of acetone) were mixed homogeneously and heated to 100 ° C., 0.02 g of KOH was added, and then the above mixture was reacted for 4 hours. 0.59 g of tetrabutyl phosphonium bromide was added and stirred to dissolve, then 7.96 g of glycidyl methacrylate was added, and the above mixture was reacted at 120° C. for 6 hours. The acetone was removed to obtain a product as a transparent light-yellow liquid having a viscosity of 1800 mPa.Math.s (25° C.).

EXAMPLE 5

Preparation of Macromonomeric Stabilizer 3

[0098] 3000 g of polyether polyol 1 and 44.7 g of trimellitic anhydride were mixed homogeneously, heated to 120° C., and then reacted for 18 hours. 6.0 g of ethyl triphenyl phosphonium iodide was added and stirred to dissolve, then 80.6 g of glycidyl methacrylate was added, and the above mixture was reacted at 120° C. overnight to obtain a product as a transparent light-yellow liquid having a viscosity of 1600 mPa.Math.s (25° C.).

Comparative Example 1

Preparation of Comparative Stabilizer

[0099] 3000 g of polyether polyol 1 and 30.6 g of maleic anhydride were heated to 120° C. and then reacted for 12 hours. 50 g of ethylene oxide (EO) was then added, and then the reaction was continued for 4 hours. Unreacted EO was removed to obtain a product as a transparent brown-yellow liquid having a viscosity of 5500 mPa.Math.s (25° C.).

[0100] It can be seen from Examples 3 to 5 and Comparative Example 1 that with the use of the same polyether polyol as the starting material, the preparation method of the macromonomeric stabilizer provided by the present disclosure can prepare a macromonomeric stabilizer whose viscosity (lower than 4000 mPa.Math.s) was much lower than the viscosity of the macromonomeric stabilizer prepared by the prior art method.

EXAMPLE 6

Preparation of Polymeric Polyol 1

[0101] A 500 ml four-necked bottle provided with a stirrer, a heating device, a temperature control device, and a feeder was used as the reactor. 55.4 g of base polyether polyol (Wanhua WANOL® F3156, hydroxyl value: 54 mgKOH/g to 58 mgKOH/g, functionality: 3) and 5.6 g of macromonomeric stabilizer 1 were added to the reactor. The reaction system was stirred and slowly warmed to 110° C. A mixed liquid of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL® F3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile was continuously fed into the reactor within 100 minutes using a peristaltic pump. The temperature was maintained at 115° C. to 120° C., and after the completion of the feeding, the reaction was continued for 1 hour. The temperature was raised to 160° C., and the volatile organic compound (VOC) was removed in vacuo for 2 hours to obtain the polymeric polyol 1. After the index measurement, the residual styrene, acrylonitrile, and isopropanol in the obtained polymeric polyol 1 were 2 ppm, 2 ppm, and 4 ppm, respectively, and the hydroxyl value, solid content, and viscosity of the obtained polymeric polyol 1 were 29.8 mgKOH/g, 44.6% and 5049 mPa.Math.s (25° C.), respectively.

EXAMPLE 7

Preparation of Polymeric Polyol 2

[0102] A 500 ml four-necked bottle provided with a stirrer, a heating device, a temperature control device, and a feeder was used as the reactor. 55.4 g of base polyether polyol (Wanhua WANOL® F3156, hydroxyl value: 54 mgKOH/g to 58 mgKOH/g, functionality: 3) and 5.6 g of macromonomeric stabilizer 3 were added to the reactor. The reaction system was stirred and slowly warmed to 110° C. A mixed liquid of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL® F3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile was continuously fed into the reactor within 100 minutes using a peristaltic pump. The temperature was maintained at 115° C. to 120° C., and the reaction was continued for 1 hour. The VOC was removed in vacuo for 2 hours to obtain the polymeric polyol 2. After the index measurement, the residual styrene, acrylonitrile, and isopropanol in the obtained polymeric polyol 2 were 2 ppm, 1 ppm, and 3 ppm, respectively, and the hydroxyl value, solid content and viscosity of the obtained polymeric polyol 2 were 30.4 mgKOH/g, 44.5% and 4998 mPa.Math.s (25° C.), respectively.

Comparative Example 2

Preparation of Comparative Polymeric Polyol

[0103] A 500 ml four-necked bottle provided with a stirrer, a heating device, a temperature control device, and a feeder was used as the reactor. 55.4 g of base polyether polyol (Wanhua WANOL® F3156, hydroxyl value: 54 mgKOH/g to 58 mgKOH/g, functionality: 3) and 5.6 g of the comparative stabilizer prepared in Comparative Example 1 were added to the reactor. The reaction system was stirred and slowly warmed to 110° C. A mixed liquid of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL® D3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile was continuously fed into the reactor within 100 minutes using a peristaltic pump. The temperature was maintained at 115° C. to 120° C., and the reaction was continued for 1 hour. The VOC was removed in vacuo for 2 hours to obtain the comparative polymeric polyol. After the index measurement, the residual styrene, acrylonitrile, and isopropanol in the obtained comparative polymeric polyol were 2 ppm, 3 ppm, and 6 ppm, respectively, and the hydroxyl value, solid content, and viscosity of the obtained comparative polymeric polyol were 29.2 mgKOH/g, 45.0% and 5783 mPa.Math.s (25° C.), respectively.

EXAMPLE 8

[0104] Polymeric polyols prepared in Examples 6 and 7 and Comparative Example 2 were subjected to the scanning electron microscope test (SEM Test).

[0105] The polymeric polyols 1 and 2 prepared in Examples 6 and 7 and the comparative polymeric polyol prepared in Comparative Example 2 were placed in a test tube, respectively, and heated to 150° C. which was maintained for 2 hours and then cooled. After the above materials were washed with ethanol and centrifuged, the solids were collected separately and then subjected to the SEM test (SEM model: Hitachi SU8010).

[0106] SEM images of the polymeric polyols 1 and 2 and the comparative polymeric polyol are shown in FIGS. 1 to 3, respectively. It can be seen from FIGS. 1 to 3 that the polymeric polyol prepared according to the present disclosre had better thermal stability and showed no significant change in the particle appearance at high temperatures.