Process for production of an alkoxylated product

Abstract

The invention relates to a process for preparing an alkoxylated product. The aim of the invention is to provide aromatic polyols for preparing polyurethane-based and polyisocyanurate-based polymers, which ensure good miscibility with the isocyanate component and other components, have a good storage stability and render the end product flameproof. For this purpose, the invention devises a process for preparing an alkoxylated product by. reacting bisphenol F with propylene carbonate and/or propylene oxide as propoxylation agent and ethylene carbonate and/or ethylene oxide as ethoxylation agent, the propoxylation agent and the ethoxylation agent being used in a molar ration of 70:30 to 45:55.

Claims

1. A process for making an alkoxylated product; comprising: reacting bisphenol F, a propoxylating agent comprising propylene carbonate and/or propylene oxide and an ethoxylating agent comprising ethylene carbonate and/or ethylene oxide at conditions sufficient to produce an alkoxylated bisphenol F product, wherein the propoxylating agent and the ethoxylating agent have a molar ratio of 70:30 to 45:55.

2. The process of claim 1, wherein based on one mol of bisphenol F 1.6 mol to 0.9 mol of propoxylating agent and 1.6 mol to 0.9 mol of ethoxylating agent are used.

3. The process of claim 2, wherein the reaction is based on one mol of bisphenol F, 1.3 mol to 1 mol of propoxylating agent, and 1.3 mol to 1.0 mol of ethoxylating agent.

4. The process of claim 3, wherein the molar ratio between bisphenol F:propoxylating agent:ethoxylating agent is essentially equal to 1:1:1.

5. The process of claim 1 wherein the propoxylating agent comprises propylene carbonate.

6. The process of claim 1 wherein the ethoxylating agent comprises-ethylene carbonate.

7. The process of claim 1 wherein the reaction is effected in an alkaline medium at temperatures of 120 C. to 200 C.

8. The process of claim 1 wherein the addition of propylene carbonate and ethylene carbonate is effected at different times.

Description

(1) The invention shall be more particularly elucidated with reference to an exemplary embodiment: a) Production of alkoxylated bisphenol F (ABF) Molar ratio of bisphenol F:propylene carbonate:ethylene carbonate=1:1:1 1. 66.64 kg of bisphenol F are added into a reactor as a solid and melted at temperatures between 120 C.-160 C. 2. 0.17 kg of potassium carbonate are subsequently added with stirring at 130 C. and the reaction mixture is heated further to 175 C.-180 C. 3. 33.98 kg of propylene carbonate are then added over 2.5 h with stirring at 175-180 C. Carbon dioxide is liberated. The feed may optionally be prolonged depending on technical capability for removing the carbon dioxide. 4. 29.30 kg of ethylene carbonate are then added over 2.5 h with stirring at 175-180 C. Carbon dioxide is liberated. The feed may optionally be prolonged depending on technical capability for removing the carbon dioxide. 5. For the postreaction the temperature is held at 175 C. to 180 C. for 1-4 hours, optionally also longer, until no more carbon dioxide is formed and the reaction is complete. 6. The free water, ethylene carbonate and propylene carbonate content are optionally determined. 7. To undertake any desired reduction of the water, ethylene carbonate and propylene carbonate content the reaction mixture is distilled under vacuum for 15 minutes. 8. The reaction mixture is heated to 140 C. and 0.3 kg of salicylic acid are added. 9. When the product has cooled further (45 C. to 50 C.) it may be discharged through a filter. The product is liquid. b) Production of the alkoxylated resorcinol (molar ratio of resorcinol:propylene carbonate:ethylene carbonate=1:1.0:1.0) 1. 516.7 kg of resorcinol are added as a solid into a reactor and melted (mp: 111 C.). 2. 1.31 kg of potassium carbonate are subsequently added with stirring at 130 C. and the reaction mixture is heated further to 175 C.-180 C. 3. 479.1 kg of propylene carbonate are then added over 2.5 h with stirring at 175-180 C. Carbon dioxide is liberated. The feed may optionally be prolonged for to up to 5 h depending on technical capability for removing the carbon dioxide. 4. 413.4 kg of ethylene carbonate are then added over 2.5 h with stirring at 175-180 C. Carbon dioxide is liberated in turn. The feed may optionally be prolonged to 5 h depending on technical capability for removing the carbon dioxide. 5. For the postreaction the temperature is held at 175 C. to 180 C. for 2-6 hours, optionally also longer, until no more carbon dioxide is formed and the reaction is complete. 6. The reaction mixture is distilled for a short time under vacuum at 175-180 C. 7. The reaction mixture is cooled to 140 C. and 2.58 kg of salicylic acid are added.

(2) The alkoxylated bisphenol F produced at a) was produced using the molar ratio of propylene carbonate:ethylene carbonate=50:50. The obtained properties were recorded under heading VI of Table 1. The remaining products listed in Table 1 were produced according to procedure a), wherein the inventive ratio of propoxylating agent and ethoxylating agent was observed in the production of I, IV, V, VI and VII.

(3) The alkoxylated bisphenol Fs exhibited a low viscosity necessary for polyurethane production. These are also substantially neutral products as a result of which they are likewise suitable for use for production of polyurethanes.

(4) Also surprising was the storage stability of the inventively produced alkoxylated bisphenol F (I, IV, V, VI, VII). To this end, all samples were placed in a conditioning cabinet at 20 C. in pure form. In the noninventively produced samples II, III, VIII-XII crystallisation set in after just a few days making them unsuitable for the production of polyurethanes.

(5) The stability of the inventively produced alkoxylated bisphenol F in solvent too was demonstrably markedly better than for samples II, Ill, VIII-XII.

(6) To this end a mixture of alkoxylated bisphenol F {sample VI produced according to a)) and triethylphosphate {TEP) in a weight ratio of 80:20 was prepared and likewise placed in a conditioning cabinet at 20 C. Here too it was shown that only the inventively produced alkoxylated products provided the solution exhibiting the desired storage stability over several weeks.

(7) To complement this further mixtures of inventively alkoxylated bisphenol F {sample VIproduced according to a)), were produced in Table 2 with various solvents in the mentioned weight ratios and stored at 20 C. in a conditioning cabinet. The results are reported in Table 2 and demonstrate persuasively the storage stability of the mixtures, wherein visual assessment of crystallization was used as the measure for storage stability.

(8) TABLE-US-00001 TABLE 1 I (inv) II III IV (inv) V (inv) VI (inv) VII (inv) VIII IX X XI XII Molar 1:1.05:1.05 1:1.8:0.2 1:1.5:0.5 1:1.3:0.7 1:1.2:0.8 1:1:1 1:1.3:1.3 1:0.8:1.2 1:0.7:1.3 1:0.5:1.5 1:0.4:1.6 1:0.2:1.8 ratio BPF:PC:EC Ratio 50:50 90:10 75:25 65:35 60:40 50:50 50:50 40:60 35:65 25:75 20:80 10:90 PC:EC Viscosity 55680 280000 179200 230400 140800 130000 40960 133120 128000 140800 368640 149758 2s .Math. c [mPas] Viscosity 1260 2500 2200 2320 2040 1800 6720 1920 1720 1840 2040 1277 so .Math. c [mPas] Stability X 1 3 days about 2.5 9 weeks >9 3 days <1 week 3 days 1 day 2 days 80% in day 4 weeks weeks weeks TEP at 2o .Math. c Stability 2 1 3 days about 2.5 10 >10 3 days <1 week 3 days 1 day 2 days pure at weeks day 13 weeks weeks weeks 20 C. weeks

(9) TABLE-US-00002 TABLE 2 Storage at 20 C. [in weeks] Weight ratio 1 2 3 4 5 6 Solvent (SV) ABF:SV crystallization Triethyl phosphate 70:30 0% 0% 0% 0% 0% 0% (TEP) 50:50 0% 0% 0% 0% 0% 0% Diethylene glycol (DEG) 70:30 0% 0% 0% 0% 0% 0% 50:50 0% 0% 0% 0% 0% 0% TEP/DEG 70:30 0% 0% 0% 0% 0% 0% Ethoxylated sugar 70:30 0% 0% 0% 0% 0% 0% (Su-EO) 50:50 0% 0% 0% 0% 1% 1% Alkoxylated resorcinol 70:30 0% 0% 0% 0% 0% 0% 50:50 0% 0% 0% 0% 0% 0% 1,4-butanediol 70:30 0% 0% 0% 0% 0% 0% 50:50 0% 0% 0% 0% 0% 0% Aromat ic polyester polyol 70:30 0% 0% 0% 0% 0% 0% Stepan 1812 50:50 0% 0% 0% 0% 0% 0% Aromatic polyester polyol 70:30 0% 0% 0% 0% 0% 0% Stepan 2412 50:50 0% 0% 0% 0% 0% 0% Dibasic ester (DBE) 70:30 0% 0% 0% 0% 0% 0% 50:50 0% 0% 0% 0% 0% 0% Diphenyl cresyl phosphate 70:30 0% 0% 0% 0% 1% 1% (DPCP) 50:50 0% 0% 0% 0% 1% 1% Cresol-Resol, 90:10 0% 0% 0% 0% 0% 0% SO % in DEG 75:25 0% 0% 0% 0% 0% 0% 50:50 0% 0% 0% 0% 0% 0% Cresol-Resol, 75:25 0% 0% 0% 0% 0% 0% 50% in DEG/TEP 1:1 50:50 0% 0% 0% 0% 0% 0% Phenol-Resol, 90:10 0% 0% 0% 0% 0% 0% 50% in DEG/TEP 1:1 75:25 0% 0% 0% 0% 0% 0% 50:50 0% 0% 0% 0% 0% 0%

(10) As a result of the high aromatic proportion of the inventively produced alkoxylated product and optionally also as a result of the use of alkoxylated resorcinol which further increases the aromatic proportion, a good flame retardancy in the polyurethane end product was achieved and the compatibility with MDI/with the blowing agents was further increased as well. The additional use of halogenated flame retardants was accordingly eschewed.